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INDEX
S.NO TOPICS PAGE.NO

Week 1
1 Lec 1 : Energy and Environment scenario 3
2 Lec 2 : Need for biomass based industries 41
Week 2
3 Lec 3 : Biomass basics 72
4 Lec 4 : Dedicated energy crops 112
5 Lec 5 : Oil cropns and microalgae 156
6 Lec 6 : Enhancing biomass properties 198
Week 3
7 Lec 7 : Basic concepts and types 242
8 Lec 8 : Feedstocks and properties 269
9 Lec 9 : Economics and LCA 308
Week 4
10 Lec 10 : Barriers and Types 342
11 Lec 11 : Dilute acid, alkali, ozone 378
12 Lec 12 : Hybrid methods 422
Week 5
13 Lec 13 : Physical Processes 453
14 Lec 14 : Gasification and Pyrolysis 499
15 Lec 15 : Products and Commercial Success Stories 550
Week 6
16 Lec 16 : Types, fundamentals, equipments, applications 594
17 Lec 17 : Details of various processes 637
18 Lec 18 : Products and Commercial Success Stories 673
Week 7
19 Lec 19 : Diesel from vegetable oils, microalgae and syngas 696
1
20 Lec 20 : Transesterification; FT process, catalysts 738
21 Lec 21 : Biodiesel purification, fuel properties 774
Week 8
22 Lec 22 : Biooil and biochar production, reactors 824
Lec 23 : Factors affecting biooil, biochar production, fuel properties

23 characterization 867
24 Lec 24 : Biooil upgradation technologies 909
Week 9
Lec 25 : Microorganisms, current industrial ethanol production
25 technology 953
26 Lec 26 : Cellulase production, SSF and CBP 989
Lec 27 : ABE fermentation pathway and kinetics, product recovery

27 technologies 1020
Week 10
28 Lec 28 : Biohydrogen production, metabolics, microorganisms 1060
29 Lec 29 : Biogas technology, fermenter designs, biogas purification 1092
30 Lec 30 : Methanol production and utilization 1126
Week 11
Lec 31 : Biomass as feedstock for synthetic organic chemicals, lactic
31 acid, polylactic acid 1154
32 Lec 32 : Succinic acid, propionic acid, acetic acid, butyric acid 1195
33 Lec 33 : 1,3-propanediol, 2,3-butanedioil, PHA 1225
Week 12
34 Lec 34 : Concept, lignocellulosic biorefinery 1250
35 Lec 35 : Aquaculture and algal biorefinery, waste biorefinery 1288
36 Lec 36 : Techno-economic evaluation 1326
37 Lec 37 : Life-cycle assessment 1359
2
Biomass Conversion and Biorefinery
Prof. Kaustubha Mohanty
Department of Chemical Engineering
Indian Institute of Technology – Guwahati
Lecture 01
Energy and Environment scenario
Good morning students. As you know, today is the first lecture of Biomass conversion and
Biorefinery. As I told you in our introduction slide, we will be covering two lectures basically
dedicated to introduction. So, today is the first one in which we will be covering world
energy scenario, consumption pattern, fossil fuel depletion and environmental issues. A bit
more elaborately I will tell you, how the fossil fuel depletion is taking place, what is the
energy requirement, how renewables are taking shape into big component in the next few
years of energy consumption as well as production and how the climate mitigation problems
are also taking shape with respect to global carbon dioxide sequestration.
(Refer Slide Time: 01:27)
So, as you know, there are institutions such as the International Energy Agency (IEA), the US
Energy Information Administration (EIA) and the European Environment Agency (EEA).
These are the three Agencies which record and publish energy data periodically. You will get
all these data, and, even whatever I am discussing today, mostly has been taken from their
records. Improved data and understanding of world energy consumption may reveal systemic
trends and patterns, which could help frame current energy issues and encourage movement
towards collectively useful solutions. The current policies scenario shows what happens if the
world continues along its present path, without any additional changes in policy. In this
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scenario energy demand will rise by 1.3 % each year till year 2040. So, basically this is how
it is being predicted.
This scenario charts a path fully aligned with the Paris agreement by holding the rise in
global temperatures to well below 2 °C. That is what the Paris agreement says about that
temperature rise should not be more than 2 °C. And they are still pursuing efforts and
convincing all the signatories of this agreement to limit it to 1.5 °C.
Electrification is emerging as the key solution for reducing emission. Now, you know that in
many developing countries and rather underdeveloped countries, electrification is still a big
issue; including India and most of the so-called Asian giants or giant/big economies. This is
however taking shape in a very nice way and increasingly it can be sourced at the lowest cost
from renewable energy. So, basically electricity from renewable energy; that is how it is
being envisaged.
There is something called tonne of oil equivalent (toe) which is a unit of energy and basically
defined as the amount of energy released by burning 1 tonne of crude oil.
4
So let us understand the energy classification or how energy is being classified. So, primary
and secondary energy, commercial and non commercial energy, renewable and non-
renewable energy. Primary energy sources are those that are either found or scored in nature,
e.g. coal, oil, natural gas, biomass, nuclear energy etc. Secondary energy is mostly converted
in industrial utilities from other sources of energy (such as) coal and oil, all these things.
So when you talk about commercial and non-commercial energy, in commercial energy it is
electricity, lignite, coal which are commercially available. Non-commercial energy is
basically fire wood, cattle dung, agricultural waste, biogas etc. It also includes wind energy.
Then comes renewable or non-renewable sources. The renewable sources are essential
inexhaustible. E.g. wind power, solar power, geothermal, tidal, biomass and hydroelectric
power. Non-renewable energy are conventional fossil fuels such as coal, oil, gas which are
basically depleting with respect to time.
5
So, if you look at the energy mix of world and India, I will be showing so many of these
statistics which are taken from these environmental energy associations and other societies.
This is from Niti Aayog. So, you can see in the energy mix of the world how much is actually
being consumed in the entire world in the form of oil and coal. So they are the most
important.
So if you look at India, 58.1 % comes from the coal and it is a very big number. The rest is
from oil and very few from hydroelectric and other sources. Now, renewables as you can see
is 2.2% and it is slowly increasing. We project that around 2035-2040 it will be more than 10
to 12%.
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Now let us understand the world total primary energy supply, consumption and demand by
source and region.
This is the world primary energy supply from 1971 to 2017 by source. If you see that round 1
(pie chart), you can see that in 2017 coal is 27%, oil is 32%. These two are more than 50%.
Rest are natural gas, bio-fuel wastes and other sources such as hydro and nuclear sources.
Similarly, if you see by source, again you can see that oil is the major one. This is the
consumption pattern by source. So oil is the major followed by natural gas, electricity and
bio-fuel.
So this is the supply in terms of region. You will see that there is something interesting. You
can see from the round 1 (pie chart) that only China accounts for 22% and OECD countries
for 38%, India actually lies in the red zone, which is non-OECD Asia. It accounts for 13.5%
out of which India is almost more than 50% which is a very significant number.
So China and India together are supplying a huge amount of energy required in the total
Global energy supply.
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So if you talk about the final consumption, again OECD is followed by China and the non-
OECD countries, the same pattern. The energy consumption pattern as well as the energy
supplied pattern is almost same.
So if you look at this particular slide, this talks about the top five countries total primary
energy supply. So, if you go by sector then you can see that the People's Republic of China
stands first followed by United States of America, India, Russian Federation and Japan. Now
if you look at the second plot that side, you can see that China’s steel consumption is actually
hugely dependent on coal followed by oil, natural gas and renewables.
And India almost follows the same pattern. However, you can see that in India the
renewables are increasing day by day. That is very interesting and that is because the
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Government of India has so much of thrust and excellent policies on actually renewables. So
if you look at this again, top 5 countries total primary energy consumption, you will see that
China’s iron and steel is followed by chemical and petrochemical, followed by non-metallic
minerals. These are basically industry based consumption patterns. And India also is
following the same trend except that the chemical and petrochemical is a very small one and
in non-specific industries it is more. Because of these non-specific, under that basically
small-scale industries comes up and you know in Indian economy small scale industries play
a very big and crucial role.
So, what if the world continues on its current path with no additional changes? So, what if we
reflect today's policy intentions and targets? This is the Stated Policies Scenario (STEPS) or
the New Policies Scenario (NPS); what we are going to adapt basically, the NPS. There is
something called the SDS, which is basically meeting the sustainable development goals. We
call it the sustainable development scenario. So, whether it is NPS and SDS or both, this is
how actually now things are being decided.
9
So, if you look at the Global total primary energy demand, that is going to have a plateau
after 2035 (projection basically), even if there is a strong population expansion as well as
economic growth. So, if you look at this, the Global total energy demand will have a
plateauing effect at 2035 or beyond 2035, primarily driven by the penetration of the
renewable energy sources into the energy mix.
As more renewables are coming into picture, they are taking a big thrust of the entire energy
supply as well as consumption pattern. So, you can understand, that is why actually there will
be a plateauing effect after 2035. So, also falling energy intensity offsets the effects of a
growing population with increasing income levels, leading to a slowdown in the energy
demand growth.
So, energy intensity actually falls as service industries take up large share of the global
economy. That is what is happening in most of the developing countries, where the service
industries are playing a big role in the economy as well as in Energy consumption basically.
10
So, if we look at how the projection looks actually; so you can see that there is something
interesting here; despite a doubling of global GDP between 2016 and 2050, the global
primary energy demand actually grows by 14%. So this is a projection towards 2050, which
you can see here. So, it is the first time in history that growth in energy demand and
economic growth are decoupled. So, this is very interesting. The first uptake of renewables is
a key driver as they often substitute for fossil fuel based generation technologies with low
efficiency.
So, renewables complemented by nuclear, nuclear power, basically, will almost double their
share in the overall energy mix (from 19% to 34%) and will provide more than half of the
electricity by 2035. So, what we understand from this particular slide is that, renewables
along with nuclear power is going to substitute almost 50% of the total energy supply after
2035 in most of the countries.
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So if you have an understanding of the total primary energy supply by 2040; this is a
prediction. You can see that, if you look at this slide, coal is continuously getting depleted.
And similarly, the natural gas though it is taking a shift after 2035. It will slowly it will come
down. Similarly, there are other sectors also.
And if you look at the sector wise, so we will understand that in a sustainable development
scenario, industry, transport, building and agriculture, these are the major shares. And if we
look at the new policies scenario, it is all the same thing; only the net amount or the net
percentage varies a little. Otherwise they easily complement each other.
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So this is the global energy demand in stated policy scenario. So you can see that, there is
something interesting, how the wood is getting decreased. Initially, long back when we
started 19th or early 18th century, so you can see that the wood was the primary source of
energy. Slowly it gets depleted and the use of coal has increased. Then oil has come into
picture and now slowly fossil fuels are depleting. So we have to depend more on the nuclear
and modern renewables. And those are taking the major amount of the energy supply and of
course demand also.
Global energy demand per fuel, if you look at, you see that in this particular plot, you see that
renewables and other fuels after 2035, here, every other thing, whether it is gas, oil or coal, it
is getting depleted or getting a plateauing effect after 2035. But renewables are increasing.
13
So, this is what it tells us that due to the policy intervention by most of the governments
across the world, there is more focus on the development of renewables.
So that is why renewables and other fuels are taking a steady curve or the curve is increasing
and not depleting.
So this is interesting. If you look at this, it is about electricity. So, if you look at this
particular slide, this and this, you just understand that 36% of oil, 14% coal, 16% of natural
gas and only 19% electricity. As you move beyond 2016, this is up to 2016. And as projected
up to 2050, you can see electricity is going to take the centre stage with 49%. See it is 50%.
Half of the main energy source will be by electricity. Followed by the modern bio-mass, bio-
energy, what we are going to discuss in our lecture, basically in this course. So you can
understand how the policies are actually driving all the Global major economies, including
the small economies also across the world to focus on the renewables and including
electricity. So mostly it will be electricity. And again, electricity can be hydropower, it can be
nuclear power and it can be from other renewables also.
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So, this particular slide tells us that India along with China emerges as the key driver for
global energy market. Another interesting observation is about Africa; the entire African
countries, in the last one (bar graph) as you can see here. You can see here, how China and
India are taking shape in 2040 (this is a projection till 2040). This is total population by
region. So in China, India and Africa (Africa means African continent and not South Africa),
you see their projected oil demand, see their natural gas demand. India is falling in the natural
gas demand because we are not yet moving into the gas natural gas. However, China has
surpassed all of us. And if you look at the renewables, you see that India is playing an
interesting role, a very big role. And of course Africa also.
15
So, we will see different energy sources, their supply, consumption and demand by source
and region. We will just quickly glance through it. So the first one is crude oil.
So you can see the world oil crude oil production from 1971 to 2018 by region. And you can
see that, OECD is of course 26.8% and Middle East (33.2%). So OECD and Middle East is
close to almost 60%. The rest is non-OECD Europe and Eurasia, then China, Asia and other
countries.
So mostly it is coming from the Gulf countries and OECD countries. If you see the final
consumption from 1971 to 2017 by sector, you can see that road, or the transportation sector
basically is almost 49.2%, followed by navigation, aviation and non-energy use sector.
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So, similarly if you see the refinery output, you can see that mostly it is coming from the
middle distillate, followed by the motor gasoline, fuel oil and then LPG, ethane, naphtha and
other products.
Let us now understand the oil demand growth, how it looks like beyond 2030-35 and till
2050. So you can see that oil demand has grown more than 1% per annum for over the last
three decades. But, this growth is expected to slow down significantly from 2020 onwards.
So from the current year onwards. The reason is due to the (fact that) more and more recent
development of the electric based systems or we are depending more on the electricity rather
than other sources of energy.
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So there is a projection of a peak in 2033. Beyond 2033 there will be a plateauing effect
again. So, by 2050 demand is projected at almost 30 million barrels per day (bpd), which is
one-third (times) below today's demand as of now. So, the chemical sector which is an
important engine of growth for the oil demand shows a slow down with respect to post 2030
projection.
Why? The reason is that, there is an increased rate of plastic recycling. That is also very
interesting now. So you know that more and more plastic recycling is happening. So that is
why there will be a plateauing effect after 2030 specially in the chemical sector.
Now when you talk about the chemical sector, more than half of the oil demand growth will
be for the next 15 years. Until 2035 chemicals is the biggest demand growth sector, and then
there will plateauing effect. So, oil use in power is the largest declining sector beyond 2030-
35. So the decline in oil demand for the road transport is modest as the EV is coming into
picture.
There are 2 things, first is EV (the electric vehicles basically). Mostly it is a huge transition in
the OECD countries. They are almost going for EV (they are already doing it). And China is
partially offset by continued use of the ICE vehicles. Though the OECD countries are going
more into the EV; however, China being one of the largest economy in Asia as well as by
population or by energy use and as well as by consumption, still China is going to continue
the ICE (that means the internal combustion engine) vehicles. So that is why in Asia it will be
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little less. Aviation growth is most prominent in non-OECD Asia and hub countries such as
Dubai.
Then, let us understand coal. So, if you look at the total final consumption from 1971 to 2017
by sector, you will see that oil is 41%, followed by electricity, natural gas and interestingly
you see biofuel, 10.7% (it’s a big one). So it is up to 2017. So understand that, beyond that
how the biomass based industries, bio-fuels that are coming from (different) other sources
(waste sources) is going to shape up our economy.
So, the world production of coal by 2018, if you look at this round one (pie chart), you can
see that China is almost half (45.6%). India comes under the non-OECD Asia (this red
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portion) (almost 30% to 35% under that is from India) and of course followed by the OECD
and other countries.
So here, if you look at this particular slide, you can understand that 40% decline in coal
demand happens despite the substantial growth of coal use in India as well as other non-
OECD Asian countries. This is basically driven by China’s decline in coal use. So that is also
very interesting right; with the decline of 53 million TJ, this is equal to two thirds of today's
total demand in China. So, all these things have driven our focus towards renewable.
Then again, we will quickly understand natural gas, the way we have discussed about coal
and oil. So Natural gas supply, consumption and demand.
20
So, here you can see that natural gas production. So, mostly it is by the non-OECD European
countries and OECD countries (close to 60%). And India has a very minimal role to play
here.
So, for the final consumption; of course industry is the most important one, followed by the
residential areas and then commercial and public services.
21
Then, when you talk about natural gas, so it is the only fossil fuel which grows its share of
total energy demand. You must understand that, among all the fossil fuels this is the only
fossil fuel (natural gas) whose demand is continuously growing for the various advantages it
has over other fossil fuels. So, particularly in short-term till 2025 and mid-term (2035) gas
demand continues to grow across all sectors led by industrial demand.
The plateauing of demand which is happening after 2035, as we can see here, almost there is
a plateauing of demand here. So, it is driven largely by the increasing competition from the
renewables. So, the Oil and Gas Industries’ own use of gas is expected to remain in line with
the total gas demand.
22
So these are certain things (points to be noted on) how the gas demand is going to take shape
up to 2035. So in the power sectors China’s gas demand growth is much higher than any
other countries (including the US). In the Middle East (previously the growth region) gas
demand peaks before 2030. Then there is chemical sector and there is transport sector.
The next (topic) is World electricity supply, consumption and demand by source and region.
So, this is the world electricity generation from 1971 to 2017 (by fuel). So, mostly it is from
coal; just like in India, it is the National Thermal Power Plant, they supply a major portion of
the electricity followed by hydro, natural gas and nuclear. In India also nuclear is slowly
taking shape.
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And (for) the electricity generation by region: if you look at (this slide), OECD is the major
(contributor) (43%), followed by China. So OECD countries and China is almost (accounts
for) more than 60%. India comes under the non-OECD Asian countries.
This is the total electricity consumption by sector. So the industry of course (consumes) close
to 42% and rest almost 50% is (consumed by) residential, commercial and public services
(sectors).
So if we talk about nuclear electricity production, you can see that close to 75% is by OECD
countries, i.e., mostly the European countries including the United Kingdom, France and
other countries and as well as the United States also. And non OECD Europe is almost 12%.
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Asia is lagging behind in this nuclear power sector, but slowly China, India and other
countries are developing their nuclear power sector.
So this is hydroelectricity (power production). Here also, you can see that OECD and China
takes the centre stage, followed by the non-OECD Asia, in which India comes into picture
and other American and African countries too.
So this is wind electricity. Again here also, OECD takes the major share. Now, what we
understand from these few slides is, basically, when we talk about renewable electricity, the
OECD countries have already taken the lead. Now China is following them and India is also
following them. And we are sure that beyond 2035 you will see a huge change in the total
energy consumption pattern as well as source.
25
So this is solar PV (photo voltaic electricity). This is one sector in which the government of
India is giving a lot of emphasis. There are a lot of subsidies available to set up a solar PV
system, including the small ones in the household sector too. Awareness is also increasing
and the Government of India is playing a big role in shaping up that particular sector.
Then, let us understand about the electrification areas across the key end uses. If you see this
particular slide, you can understand that electricity demand doubles until 2050 (this is how it
has been projected) and the policies are also like that. And it (electricity demand) grows its
(share in) total (final) energy consumption from 19% today to 29% by 2050 as demand for
other fuels are flattening (other fuels means the fossil fuels).
So, the increasing adaptation of the electric vehicles is also leading to this particular surge in
electricity demand.
26
So, in transport sector electrification is driven by strong improvements in economics of the
electrical vehicles, reaching cost parity with conventional fuel vehicles in the early 2020s.
This is what, is the actual aim of the OECD countries. They want some sort of trade mark or
cut off with the cost in comparison to adaptation of EV’s or electric vehicles. So, you can see
that, for future improvement in battery Technology, (that is that is also very important) huge
amount of research is still going on. This will enable the electrification of the heavy-duty
segments which are currently the hardest to electrify. So renewables will become cheaper
than existing coal and gas in most regions before 2030. Then you will be forced to switch
over to renewables even if you are not ready to adapt. So, that is going to happen by 2030. So
a majority of the countries will reach this tipping point in the next 5 years including India.
But anyway; in India we are already into renewables and our renewable production is also
much higher than other developing countries.
27
So as a consequence, by 2035, nearly half of the Global total capacity will be in solar and
wind, with China and India both taking the centre stage or they will become the main
contributor (that is very interesting). So solar and wind account for close to half of the Global
capacity by 2035. China, India and OECD countries are the major contributors.
Natural gas sees further capacity additions, particularly in North America and China. So
Global net additions of ~675 GW until 2035. So coal capacity declines, because in most of
the countries there is a decline in production of course, (that is true) as well as a decline in
adaptation or use. In India, the role of coal to supply and the rapid uptake in demand is much
smaller than in the earlier projections.
So that is actually good as solar in particular becomes more attractive alternative. As I told
you, that Government of India has given (emphasis on) the use of this policy as well as (the
government) giving so much of subsidies to setup solar PV systems, including the rooftop
solar PV systems for use in the households also.
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So, renewable generation accounts for more than 50% of the power supply post 2035. This is
where the NPS and SDS both complement each other. So in this particular slide, you can see,
how from 2030 onwards there is a huge increase in the Solar. You can see that yellow ones
(yellow part of the bar graphs) are the Solar and how it is increasing followed by the wind
and hydro. So this is how we are going to focus, including India. The major focus will be
mostly on the Solar PV systems. Then of course solar thermal is also there, wind energy,
hydro energy and nuclear energy. So all renewable sources.
Now let us just quickly understand (since this is introductory class) about the global
environmental issues. So we will talk about only the carbon dioxide emissions and climate
change.
29
So the trend in long-term global warming continued in 2018, which also happened to be the
fourth warmest year on record. So, you know, since the last ten or twenty years the warmest
years basically occurred in the past 22 years. And the top four were in the last four years
alone. So that is very bad. This is according to the WMO or the World Meteorological
Organisation.
The IPCC special report on the impacts of global warming of 1.5 °C reports that, for the
decade, 2006 to 2015, the average Global temperature was 0.86 °C above the pre-industrial
baseline. For the most recent decade, i.e., 2009 to 2018, the average temperature was 0.93 °C.
So it is almost going to be 1 °C.
And for the last five years 2014 to 2018 it is 1.04 °C (above the baseline). So the last four
years consecutively 2019, 2018, 2017 and 2016 are the hottest or warmest years till date. So
as a result of this, there is a huge increase in the number of cyclones that is affecting the
entire northern hemisphere and north east Pacific basins as well as Indian Ocean sides also.
So in July and August of 2018, north of Arctic circle, many record high temperatures were
registered, as well as record long periods of high temperatures. Japan and Republic of Korea
saw new national heat records 41.1 °C and 41.0 °C. These are huge temperatures; they have
never witnessed in their entire life span, (I mean) the people (of) who are currently in Japan
and Korea. Eastern Australia also experience significant drought during 2018. Severe drought
affected Uruguay and northern and central Argentina in late 2017 and early 2018 leading to
heavy agricultural losses.
30
Now British Columbia, Canada broke its record for the most area burned in the fire season
for the second successive year. The US State of California also suffered devastating wildfires.
These are the things we already know, right. These have all been reported in the news and we
know all these things. So these examples show that climate change is not a distant or future
problem, rather it is happening (now), since almost 2 to 3 decades.
And now this is the peak time that we are facing and so much of global climate change is
taking place.
Now, this slide will basically tell you the environmental impacts of various sources of
electricity generation. So coal, natural gas, nuclear, wind, solar, water (basically the reservoir
hydro power) and then again water (that is the streaming hydropower). So what are the
Environmental effects? If you look at wind, there is a potential of bird kills, the wind turbines
are highly visible and noise issue is also there.
Similarly, if you talk about solar, though it is very good, but there are issues regarding high
energy used in the manufacturing process when you make solar PV and then there is a toxic
Silicon tetrachloride waste. Similarly, flooding is a problem in hydropower dams; but you
know, all these so-called environmental impacts also can be properly minimised (mitigated)
if we take sufficient precautions. That is what is being done now-a-days by most of the
countries and they adapting the safety measures and latest technologies so that the impact on
the environment will be very minimal.
31
If you look at the world carbon dioxide emission, you will see that oil and coal are the major
emitting sectors followed by natural gas. And China and OECD again (because they are the
largest consumers of course) are the largest emitters.
So (now), if you look at the heavy industries sector, the projection from 2019 to 2060; (let us
see the from the first one 2019, 2030, 2040, 2050 and 2060), you can see that the industries
which are unlocked emissions that is increasing. See that these are all Industries which are
emitting hugely. Slowly it (emissions) is decreasing and unlocked emissions are increasing.
Then all (only) unlock emission increased (remains). And in 2050 all (other emissions) this is
gone and 2060 that is also gone (all emissions are reduced). This is how it is projected.
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So if you look at this particular slide, it says that Global carbon emissions peak in 2024 and
there is a fall by ~20% by 2050, primarily driven by the reduction in the emission from the
coal. So coal emission is gone. Once that is gone, almost 20% to 30% of the Global carbon
dioxide emission will drop immediately. So there will be an excellent balance of the carbon
dioxide that is actually being emitted by the developed and the developing countries.
So if you look at the developing economies in Asia, there is a huge percentage (statistics
wise), other developing economies and advanced economies. So these coal based plants
basically.
33
And solar is becoming the star. So you can see, this very interesting to see the how the curve
is actually increasing from 2000 to 2040 (it is prediction basically, which is going to be
absolutely true as it is). There will be absolute, the unit values may differ, but the curve will
remain so. And apart from this there are others such as wind, hydro and nuclear. Here, the
biggest problem in nuclear are the safety issues as well as the installation cost. It is a very
costly technology. But once established it is very good.
So, a carbon neutral Europe puts offshore wind in front. So this is about Europe. You see
here, in Europe there is something interesting about this bio-energy. From 2018 you see how
it is slowly increasing till 2050. Though, not a very significant jump, but the adaptation and
maintaining it is also very important. So, in Europe, the offshore wind is going to take a
major role. Solar will be less, because in Europe, you know that availability of the solar
34
power or the sunlight is much lesser than other countries, especially, with respect to the Asian
countries.
Having said that, there is no single or simple solution to reach a sustainable energy goal.
Every country is putting their efforts. A host of policies and technologies are required and it
is already there. Policies are there, technologies are also there. So to keep the climate change
targets within reach, and further technology innovation will be essential so that we do not go
beyond 1.5 °C. Though the Paris agreement says 2 °C, however most countries have agreed
that will they will try to keep it not more than 1.5 °C.
So before we end up our lecture we will quickly understand the focus of our course, i.e., the
biomass energy or the bio-energy. Let us understand what is the bio energy potential across
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world. So, you can see that in 1980 what it was, 2015 what it was, and 2050 what it will be.
This is the worlds’ primary energy demand. And this is the bio-energy demand (its
projected). 2050c and 2050d, c is based on the upper limit of the amount of biomass that can
come available as a primary energy supply without affecting the supply for food crops
(basically from agricultural residues and all).
And d (which is this one) is based on the source where a typical type of agricultural
management applied is similar to the best available technology in the industrialized regions.
So, you can understand that there is a huge upsurge in the biofuels and bioenergy based
supply.
So this is the contribution of each Biomass resource category to the Global potential of
biomass for energy use in 2050. What are these different types of feedstock. We can talk
about feedstock. So, biomass production on surplus agricultural land, bio-materials, biomass
production on degraded land, agricultural residues, animal manure (dung, where you go for
biogas basically), forest residues, tertiary residues (organic waste).
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Then you can see that energy used in the transport sector, non-fossil globally. So bio fuel is
going to take almost 73% beyond 2050. Similarly, heat production also 96% (it is a huge
number) from renewables; this is 2017 data.
Domestic supply of biomass globally; so you can see how it is. So, primary solid bio-fuel is
86%, still it is same. Slowly bio-gas and liquid bio-fuels are coming into picture. So, liquid
bio-fuels are gaining more importance because of its availability. Actually availabilities can
be round the year rather (when compared to) than Biogas. Biogas, during winter has a
depleting supply.
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So biopower generation globally; you can see that this is till 2017. You can understand that
the components that are being considered are municipal waste, industrial waste, solid bio
fuels, biogas and liquid bio fuel. You see, solid bio fuel is taking the centre stage. Now
slowly liquid bio fuel will also be coming into the picture, especially in the European
countries. Whereas, in Asia it is very less, however, slowly the Asian countries also will
catch up.
Use of biomass in electricity only plants in continents in 2017. You can see that in Asia for
solid bio-fuels again there is a huge surge. And heat generation globally.
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With this we will wind up. This is liquid bio fuel production globally. So you can see bio
ethanol, bio diesel other biofuels. So this is bio ethanol, this is biodiesel. And then other
biofuels. Other biofuels can be bio oil, it can be bio ethanol, it can be bio butanol and other
bio fuels. So what we understand from today's lecture is that, no single or simple solution
exist to reach the sustainable energy goals.
So, energy policies and adjusting to new pressure and imperatives, but the overall response is
still far from adequate to meet the energy security and environmental threats the world now
faces. The oil and gas landscape is being profoundly reshaped by shale, ushering in a period
of intense competition among suppliers and adding impetus to the rethink of company
business models and strategies.
39
Solar, wind, biomass technologies are transforming the electricity sector, but an inclusive and
deep transition also means tackling Legacy issue from existing infrastructure. Energy is vital
for the developing countries, and their Energy future is increasingly influential for global
trends as it undergoes the largest urbanisation the world has ever seen. One classic example
are the African countries. The way the urbanisation has taken place in African countries after
2000 is phenomenal.
And, all have a part to play but the governments must take the lead in writing the next chapter
in energy history and steering us on to a more secure and sustainable course.
So, thank you students. Thank you for listening. So the next class will be again introduction.
In the next class we will understand about Biomass, what is actually Biomass and what
actually bio mass based Industries looks like and bio-refinery concept. I will explain the bio-
refinery concept.
Thank you very much. In case you have anything to ask please feel free to write to me at
[email protected] or please post your questions in the NPTEL Swayam portal. I will be
happy to answer that. So thank you very much.
40
Indian Institute of Technology – Guwahati
Lecture 02
Need for Biomass based industries
Good morning students. This is lecture 2 our course. So, in this lecture, today we will discuss
about the need for the Biomass based industries under a biorefinery concept. Before
discussing (about) the biorefinery, we will try to understand the basics of biomass.
So, you know Biomass is a renewable organic material, usually which comes from plants and
animals. So, some of the important or most common (or you can say may be promising)
Biomass feedstock are: grains and starch crops such as sugarcane, corn, wheat, sugar beets
and sweet potatoes etc.; agricultural residues (such as) corn stover, wheat straw, rice straw
and all these things. Then there are food wastes, basically, coming from the food processing
industries; Forestry materials (such as) logging residues, forest thinnings; then we have
animal by-products (such as) Tallow soil, fish oil, manure etc.
Then we have dedicated energy crops, (which are specific energy crops); some of them are
switchgrass, miscanthus then we have a poplar, willow etc and of course Algae. Then, Urban
and Suburban wastes. Under this MSW comes (Municipal solid waste), lawn waste,
wastewater treatment sludge and there are many other things also.
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So what is actually the importance of the biomass energy and why we were discussing. Last
class (during our introduction) we have understood that what is the importance of biomass
based energy and Biomass based industries. So, the Global energy picture is changing rapidly
in favour of renewable energy. So, according to IRENA’s global renewable energy road map,
which is called REmap 2030 - if the realizable potential of all renewable energy technologies
beyond the business as usual implement then renewable energy will be accounting for almost
36% of the total Global energy mix by 2030. So if all the governments, according to their
policies implement it then this is going to happen. So this would be equal to a doubling of the
Global renewable energy share with compared to 2010 levels.
So then biomass has an auspicious future. So by 2030 Biomass could account for 60% of
total final renewable energy used as Biomass has potential in all sectors. So Biomass based
energy and other value added chemicals or value added products can be used across all
sectors. So that is the beauty of biomass actually. So most Biomass demand today is its
traditional used for cooking and heating.
As of now also (today) whatever Biomass is being utilised, it is basically (used) for the
traditional use (for cooking as well as heating). So in 2010 more than 60% of the total Global
Biomass demand of 53 exajoules was used in residential and commercial building sectors.
Much of this was related to traditional use of biomass for cooking and heating. Biomass
demand in the manufacturing industry is almost 15%, transport sector is 9% and the power in
district heating actually it is 8%. So this is almost about one third.
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So, Biomass applications could change over time. So, global biomass demand could double
to 108 exajoules by 2030; if all its potential beyond the business as well as usual is
implemented. So, that means nearly a third of its total will be consumed to produce power
and direct heat generation. About 30% would be utilised in biofuel production (mostly for the
transport sector) and the remainder would be halved between heating applications in the
manufacturing industry and building sectors.
So Biomass use in the combined heat and power generation (CHP technology basically) will
be key to raise its share in the manufacturing industry and power sectors. Then, estimated
Global Biomass demand according to the REmap 2030, the United States, China, India,
Brazil and Indonesia (these are the five countries, which are also five big economies of the
world) are going to account for 56% of the total Biomass demand by 2030.
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Global biomass supply in 2030 is estimated to range from 97 EJ (exajoules) to 147 exajoules
per year. Approximately 40% of this will originate from the agricultural residues. So there
lies a very important information about the agricultural and forest residues and waste
materials basically. The remaining supply potential is shared between energy crops (33 to 39
exajoules) and forest products including forest residues.
So, the largest supply potential exists in Europe and Asia (including Russia). So this is
another interesting thing that, these countries are blessed with huge biomass reserves. So that
is why they will be the potential feedstock suppliers basically. International trade of biomass
would play an important role in meeting the increasing Global demand. Trade (could)
account for between 20 to 40% of the total Global demand by 2030.
Domestic supply costs of biomass is estimated to range from as low as USD 3 for agricultural
residues to as high as USD 17 GJ for the energy crops.
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There are many challenges to be addressed in the Biomass demand and supply. Having said
that, the biomass and biomass energy is everything it’s good for the economy as a biorefinery
concept and all; everything is fine, but having said that, we need to understand that there are
many challenges that need to be addressed for the Biomass demand and supply. That is the
most important bottleneck actually.
So, its international trade as well as substitution of its traditional uses in realising such high
growth rates. So, if you keep on using Biomass for cooking purposes and heating purposes,
then this is not going to help us in a roadmap; basically if you think about the 2030-2035 road
map, which most of the countries have agreed to. So what we have to do is, basically the
bioenergy demand is estimated to be doubled between 2010 and 2030, ensuring that
sustainability of biomass will gain even more importance including environmental, economic
and societal aspects.
Now, for a sustainable and affordable bioenergy system, existing National and international
initiatives and partnerships as well as energy and resource policies need to be expanded to
address the challenges across the Biomass use and supply chain. Now, while biomass
represents an important stepping stone in doubling the Global Renewable Energy share,
potential of other renewable energy sources basically should be or must be expanded.
It should be an integrated approach rather than only Biomass and Biomass; that is not going
to help in a sustainable way, right. So for that we need to expand our work on our
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government policies including subsidising many of the installation facilities, transportation
and of course, the tax will also come into picture.
Biomass energy has rapidly become a vital part of the Global renewable energy mix and
account for an ever growing share of the electric capacity added worldwide. So, now most
importantly (last class also we have discussed that) Biomass based electricity generation is
directly feeding into the grid. So these are the upcoming things that has happened. It is
happening in many countries and will happen in India too very soon.
So, traditional Biomass primarily for cooking and heating represents about 13% and is
growing slowly or even declining. The declining is a good thing for it, but declining in the
traditional uses as well as their use in more sophisticated modern Biomass based industries, is
going to help us. So, some of the recent predictions suggest that biomass energy is likely to
make up one third of the total world energy mix by 2050.
In fact, bio fuel will provide right now almost 3% of the world's total fuel for Transport
(liquid fuel basically or maybe some gaseous fuels). So, biomass energy sources and readily
available in rural and urban areas of all countries. Biomass based industries can foster rural
development, provide employment opportunities and promote biomass regrowth through
sustainable land management practices.
This is another important thing. Let us understand, that we talked about dedicated energy
crops like as I told you maybe poplar, it may be switch grass, miscanthus, whatever it is. For
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that, when I need to cultivate them, I need to grow them, I need to plant them; so where do I
plant? So, the available land for agriculture is decreasing day by day across the world due to
more and more urbanisation. We know this. It is happening in the in India also. But we need
to understand that when I wish to grow this type of energy crops, I should not use our prime
agricultural lands, rather, I will use such land which are barren or not suitable for growing the
food crops. We can use (those lands) with a little modification, upgrade them and use for
these energy crops.
Then things will be very nice. Otherwise, sustainable Land management issue will come into
picture.
So, the negative aspects of traditional Biomass utilisation in developing countries can be
mitigated by promotion of modern waste to energy technologies which provide solid, liquid
and gaseous fuels as well as well as electricity. Another hot topic nowadays, is about
conversion of the waste to energy. You might have heard about this waste-to-energy many
times. There is another term is called water energy Nexus that also is very upcoming.
So let us talk about waste to energy. So most of the wastes of Biological nature can be
converted into energy. Now, having said that, there is one technology (of course we will
discuss in detail in one of our lectures later when we discuss about the thermochemical
aspects). So I will just tell you in a nutshell. Thermochemical conversion technologies; one
such is gasification, then we have pyrolysis. These are beautiful Technologies. If we adapt
that, we get three different types of bio fuels. One is the liquid bio fuel, one is solid bio fuel
and other is a gaseous biofuel. So these technologies are available. Only we need to upgrade
ourselves to suit a particular feedstock or rather, I can say that technology should be
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developed in such a way that they can process multiple feedstock. That is the challenge
basically. So the most common technique for producing both heat and electrical energy from
Biomass wastes is direct combustion.
Thermal efficiencies as high as 80 to 90% can be achieved by advanced gasification

technology with greatly reduced atmospheric emissions. Then of course CHP is there (the
combined heat and power system) ranging from small scale technology to large scale grid
connected facility. This is what I was telling you; just technologies are available. And now
what is the emphasis is given on? Emphasis is mostly given on how to generate electricity
from Biomass and connect it to the grid.
So, biochemical processes like anaerobic digestion and sanitary landfills can also produce
Clean Energy in the form of biogas and producer gas, which can be converted to power and
heat using a gas engine.
Now let us talk about what are the advantages of biomass energy. So, bioenergy systems
offer significant possibilities for reducing greenhouse gas emissions due to their immense
potential to replace fossil fuels in energy production. Biomass reduces emissions and
enhances carbon sequestration, since short rotation crops or forest established on abandoned
agricultural land accumulate carbon in the soil.
So this is also very interesting. That is because we know that biomass is carbon negative. The
reason is that, let us say, whatever carbon dioxide we generate by burning fuel even if it is a
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biofuel, that goes to the atmosphere. Again, we say that this carbon dioxide will be utilised by
the same feedstock materials when you are growing them. Basically it can be any energy
dedicated energy crops or any plants or maybe forest as a whole.
So, that is how the carbon cycle is supposed to be managed. And bioenergy usually provides
an irreversible mitigation effect by reducing carbon dioxide at source, but it may emit more
carbon per unit of energy than fossil fuels, unless, Biomass fuels are produced unsustainably.
So this is what we again need to understand that unless and until we produce Biomass based
fuel in a huge quantity, what will happen is that, we will be end up in producing more carbon
dioxide than we are consuming.
So biomass can play a major role in reducing the reliance on fossil fuels by making use of
thermochemical conversion Technology. I just mentioned about it (of course we will discuss
more in our subsequent lectures). So in addition, the increased utilisation of biomass based
fuel will be instrumental in safeguarding the environment, generation of new job
opportunities, sustainable development and health improvements in rural areas.
The development of efficient Biomass handling technology, improvement of agro-forestry

systems and establishment of small and large scale Biomass based power plants can play a
major role in rural development. So another important thing we need to understand is that, the
collection of such agricultural and forest wastes for the Biomass based industries is not that
easy. So rural people can be engaged for doing that. And there are many concerns about the
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transportation of such wastes to a plant where we will convert them basically to liquid and
gaseous fuels or generate electricity.
So, if we can locate the plants very near to the rural areas or the forests where these materials
are being collected, then it will be a win-win situation. So, we will save a lot of money in
transportation as well as the rural people will get some jobs and there will be some
community development also. So when compared with wind and Solar Energy, Biomass
power plant cell able to provide crucial, reliable based load generation.
This is more important. This is basically when we are talking about connecting to the grid.
There should be a proper sustainable supply. Otherwise, what will happen, today where you
are supplying one particular rate, tomorrow it will fall; that is not going to help in a
sustainable way when we talk about grid connectivity. So biomass plays a better role with
respect to wind and solar. So a large amount of energy is expended in the cultivation and
processing of crops like sugarcane, coconut and rice, which can be met by utilising energy
rich residues for electricity production.
So some of these processing, you know, use huge energy; sugarcane, coconut, rice mills (all
these things). So what is being suggested is that, there is a sugarcane waste, which is called
bagasse, then there is coconut waste, there is rice straw (all these wastes), if these wastes
which are generated at the site can be converted using suitable technologies to heat or energy,
or any such thing and maybe electricity or may be a small scale gasification plant; it can save
a lot of money basically.
So basically, it is an integrated approach. So, the waste generated at the source and treated
and converted in the same source to a value added product or you can say that, maybe to
energy. That approach will help us a lot. The integration of biomass-fueled gasifiers in coal
fired power stations would be advantages in terms of improved flexibility in response to
fluctuations in Biomass availability and lower investment costs.
So if you couple Biomass fueled gasifiers along with coal fired power station; it will help us
with 2 things; first is that, it will address the (issue of) availability of the Biomass around the
year, because coal is available to generate power. Second thing is that, we will reduce use of
coal thereby reducing the carbon dioxide generation.
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So, look at this particular biomass demand plot. This is extrapolated till 2030. Just look at the
last; look at these studies: Indonesia, then Russia, Brazil, India, China and United States. So,
these six countries mostly, even if you can consider Canada also, but I am counting these 4 to
5 countries. So just look at this particular plot. You can see that United States, China, India
and Brazil, these are the four major contributors or let us say that their demand for Biomass is
more compared to the rest of the world.
Because these countries have huge biomass reserve, as well as, they have realised the
potential of the biomass based fuels and energy and of course industries also.
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So, this is (breakdown of biomass supply) by region. Again you see Asia, the huge one here.
Basically, the contribution is coming mostly from China, India and Indonesia; then Europe
North America (in North America United States only) and then Latin America is also there.
So mostly it is coming from harvesting residues here in Asia (in which India falls). Then we
have processing residues, and of course we have fuel wood, wood residues as well as wood
waste.
Energy crops (share) is very less in Asia. However, it is so high in Europe, America and other
countries because they have started cultivating the dedicated energy crops. We are slowly
adopting it.
Then, having said about the Biomass based industries, the advantages of bioenergy and all
these things; let us now understand what are the challenges related to Biomass. So the
existing challenges of biomass supply chain related to different feedstock can be broadly
classified into four things or five things. First is operational, then economical challenge, then
social and policy and then regulatory challenges.
We will see one by one. What are operational challenges? So, feedstock unavailability;
Inefficient Resource Management and the government non-intervention approach are the key
factors hindering the expansion of the Biomass industry. Feedstock of biomass should be in
such a way that it should be available in a sustainable way throughout the year, but, can we
ensure that? Let us understand that; I am talking about rice straw or say bagasse. These are
seasonal crops. Any such crops that are seasonal, we need to understand that, of course their
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generation of waste is also seasonal. So, can we produce so much of waste, so that we can
keep it or store it for round the year application? The answer right now is, no. At least for the
Indian context, but, we need to work on that. There are policy matters, government should
interfere and make policies in such a way. And there should be Technologies, developed in
such a way that we can store these wastes for long-term use (right now that is not happening).
So, regional and seasonal availability of biomass and storage problem; this is what I already
told you. Then, pressure on transport section. Because biomass contains a huge amount of
moisture, that is why transporting waste biomass from the plantation to the production site
becomes energetically unfavourable and costly with the increase in distance. Basically
distance between the collection side and the plant.
So then, inefficiency of conversion facility, core technology and equipment shortage; now
technical barriers were resulted from the lack of standards on bioenergy systems and
equipment, especially where the energy sources are so diverse. Appropriate pre-treatment
required to prevent biodegradation and loss of heating value not only increases the production
cost, but also in equipment’s investment. So there is something called pre-treatment which
we will discuss in our subsequent lectures, what is pre-treatment and what is the importance
of it. So, we need to pre-treat the biomass according to where they are going to be used,
whether it is going to be in the thermal conversion technology or biological conversion
technology. So, depending on that we need to pre-treat the biomass. Basically fractionation
and size reduction and there are other things also.
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So then, immature industry chain; so, it is virtually impossible to get long term contracts for
consistent feedstock supply in reasonable price. So, industry will only be interested, if I am
going to supply them throughout the year in a sustainable way (the particular feedstock;
everybody is interested in a particular feedstock). So, that is not going to happen, right? But
policies should be framed and it should be implemented in such a way that industry are
favoured by implementing such techniques.
Then economic challenges; so feedstock acquisition cost; the Biomass resources are scattered
and in order to reduce the cost of transportation, biomass projects are eager to occupy land
close to the source, leading to centralisation of biomass projects. Then, limiting financing
channels and high investment and capital cost; as of now, the industries which are
implementing them, I can tell you that, there is a huge cost which is required basically for the
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capital investment; for procuring the equipment, installation, the land cost (forget about the
running cost and manpower cost). So here, the government has to intervene and make
policies in such a way that there will be GST credit, and there will be less tax on procuring
equipment. And of course there are other things apart from the subsidies.
Then social challenges; so, under social challenges there are a few things. First one is the
conflicting decision: so, decision making on selection of supplier, location, routes and
technologies is crucial and needs proper communication. So basically, which supplier you are
going to choose, whether it is reliable or not, where it is located, where is my plant located,
what are the routes or distance, how much it is going to cover for the transportation of the
feedstock from the procurement site to my plant and technologies.
So, we need to have a proper decision making system for that. So, land use issues: land use
issues lead to the loss of ecosystem preservation and the homes of indigenous people. That is
why I was just mentioning that, we should use such lands which are not at all used for the
dedicated food crops.
Then; impact on the environment: The Biomass plantation depletes nutrients from the soil,
promote aesthetic degradation, increase the loss of biodiversity. Other social impacts will
result from installation of energy farms within rural areas, like increased need of services
increased traffic etc. The potential negative social impacts appear strong enough to ignore
the benefit of new and permanent employment generation. So, if we try to develop a rural
based bio economy, then most of these issues will (should) be addressed.
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Then let us talk about the policy and regulatory challenges. At present the government is
subsidizing the domestic fuel prices which in turn makes the electricity generating cost from
conventional sources lower than the power production cost from Renewable Sources. This is
exactly what is expected from the governments. Not only from the Government of India but
from the governments of the all other countries also; that they are doing it.
So, there are no specific rules to regulate the work of utilisation of biomass resources and
there are no specific penalties for not using behaviour that should be comprehensively used.
So basically policy guidelines should be there. Governments should come up with clear cut
policies and guidelines; what is to be done and what is not to be done. If you are doing
something which is not expected, it will result in Environmental concerns on social concerns.
Then, you need to be penalized. As such, now such policies are not available. But I know that
there are coming. Soon it will be implemented in India as well as other countries also. There
is no special mechanism to manage the development of the Biomass resources industry and
there is no specialist department to manage the implementation of relevant national standards
and policies.
So all these things come under the government. These are governments’ job, basically. So I
know the government actually is coming up with so much of policies for the Biomass based
industries and there are already some existing policies, but, more needs to be done and it is
being done actually.
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Let us now understand the supply and demand framework of bio energy. You can see this
particular slide, how it is being actually depicted here. So, the land demand, land use and
energy production. So, land demand in all countries is basically based on the food demand;
for growing the food crops and of course (also) for wood demand; that means it is for either
the industrial demand for forests.
So when we talk about (land) use; so the domestic production is basically for the food and
industrial firewood and all these things plus international trade. And then, the remaining land
should be utilised for the energy crops and surplus firewood. And the energy production from
the Biomass residue, harvesting residue, processing residue, animal waste, household waste
etc.
Then primary bio energy will come from these dedicated energy crops such as sugarcane,
starch, oil crops and other cellulosic crops.
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So, if you look at the current land use and suitable area for agriculture. So this is the land use
in 2010 and that one is the potential for the crop production. So you can see that, right now
the forest is 4 billion hectares, then crop production is going on in 1.5 billion hectares. And
here, we were talking about the projection, suitable and available area that will be basically
for the dedicated energy crop production or biomass production; it will be almost around 2.7
billion hectares. So there will be a 1.4 billion hectares of surplus available land that can be
utilised.
So let us understand the relationship between the players along the value chain. This is very
interesting and very important, where you can understand that every one of us has a role to
play in this business. So all the policy makers, they will decide the policies. They may give
financial support and all these things. Then there is something called a researcher. Where
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people like me and some of you are coming into picture. What they do is, they are involved
or integrated into various sectors, whether it is a supplier, whether it is the manufacturer,
whether it is a customer.
Researcher has a big role to play in every sector. So then there is Logistics for raw Biomass
storage and transportation, and there is Logistic which is related to the bio products,
(processed products basically) for transportation and to take them to the reach of the common
people or the customers. So the researcher has a lot of role to play in the entire system; this
Biomass based industry and processing industries sector.
Let us talk about the life cycle of biomass industry. Please see where we are heading, we are
now here in the current status. You see the red one here. So that is between the initialisation
phase and the growth phase (I am talking especially about India). So we have started from the
fuel from the thermal energy sources (and) electricity. Electricity has been implemented
hugely in our country. Still there are many villages in rural areas where the electricity has not
reached.
It is going to be implemented very soon. Government of India is doing that. So then, we

move to the growth phase. In growth phase what is available? So basically there will be
increasing demand (of electricity or you can say energy) due to urbanization and
industrialization and there will be low to high value added products that will come into
picture when we pass from the initialisation phase to this particular growth phase.
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So, those products can be fertilizers, fibres, platform chemicals or other value added
products. Then we go to the maturity and decline stage. When you go to the maturity stage,
we have a constant demand. Now our demand is basically increasing. The moment you reach
here, there will be a plateauing effect and we will have a constant demand because you have
reached a mature stage.
And more or less our industrialisation or let us say the urbanisation has saturated. So, we go
for very high value added products like biochemical. Then after that there may come a
decline stage where there will be a reducing demand. And there will be no more product
innovations happening.
So here, this is the stakeholders’ interaction and role in commercialization of biomass

conversion technologies. So, in one of the slides; just 2 slides back we have discussed how
researchers are playing a role. Here also, you can see that the researchers in the top one you
see there. How they have integrated themselves into various other people basically the
supplier, customer, industry and the government.
They have completely integrated themselves along with all other stakeholders. So what do
they do? Researchers will resolve the upstream issues or harvesting issues basically. They
will provide strategies to meet the national goals as mentioned by their governments. They
provide strategies to satisfy the customer needs. And they will provide technical know-how
and expert. Then the supplier; what the supplier is supposed to do? The supplier will provide
raw material and share information.
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They provide services that meet customer need. They will obey the Regulation and policy set
and it is the long term collaboration. So, when I talk about long term collaboration that means
it’s the consistent supply. And what the government will do? The governments’ job is to
provide research funding. Governments’ job is to regulate the Biomass pricing and legal
enforcement. Then, a government must promote the importance of Sustainable development
and a government should go for financial support, whether it is an incentive, subsidy, tax
exemption like GST credit and all these things will be there.
Then there will be customer. So, the customer; what is their job? So, publicity and provide
data that (basically feedback, they should give a feedback), support green suppliers, support
green products and provide feedback on this (what I already told). And then there is the
industry, the most important. So, adapt research innovative ideas and share information, they
should have a long-term collaboration (looking for a consistent demand basically), they
should be able to beat that demand, they should generate products that meet customer needs
and obey the Regulation and policy set. So, you can understand in this particular slide, how
all the stakeholders, all of us, you, me, government, the suppliers, the industry people. So, all
of us have a role to play as a stakeholder in this particular Biomass conversion business.
Let us understand the problems of biomass large scale supply. So one of the biggest problems
related to Biomass large scale supply is the energy density. Briefly if Biomass moisture of
conventional wood is 30%, what it means? It means that every one 1 ton of wood or the
Biomass that I transport, I am transporting almost 300 kg of water. So it is huge, it is waste
basically and I am paying a heavy price for the transportation.
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So additionally, Biomass feedstock shape; so it is also very important. So whether it is
chipped, pelletized, rounded, baled, all these things will strongly influence the bulk density
and affect transportation economics. So we should also look into that. Then, in addition to the
bulk and energy density, large-scale Biomass supply is affected by a wide range of
bottlenecks, including raw material initial cost, biomass producers’ involvement and
environmental regulation and sustainability.
Now, finding solutions for all these problems means finding the solution for the creation of
the future biomass commodity in worldwide.
So are there are problems (of course), but there are solutions also. So, let us understand what
are the problems and what can be the solution. So, high quality Biomass is considerable but
limited expensive not always sustainable. So what can be the solution? Utilisation of Agro-
forestry residue; that can be a sustainable solution. High availability is there and fully
environmentally sustainable.
What is the other problem? Agro-forestry residues have lower quality and higher Micro
elements (that is true actually), calcium, magnesium and all these mineral compounds
basically. So what can be the solution? The blending of different Biomass feedstock to
arrange suitable average composition. So, do not go for a single stock. It is not going to help
us in a sustainable way. We should always go for multiple feedstock.
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So that is why, the technology should be developed in such a way that, basically our process
or equipment or let us say the process itself is capable enough to take (utilize) multiple
feedstock. So, because multiple feedstock will have different composition. So you can play
around and mix the composition in such a way that we will have an average composition that
is good enough for producing the energy or let us say, other value added products.
Availability is mainly reduced to forest areas. Now, residues have much lower costs and
dispersed and available almost everywhere. So, if you talk about the municipal solid waste,
food processing waste, industrial waste, then the dependence on only forest waste will come
down. Now; low energy density and bulk volume of fresh biomass affect storage cost and
transportation. This is what we just discussed in the previous slide.
So the activities, what we need to do is that, you go for chipping, enhance biomass storage
density, dry them, but again energy is coming into picture. So it is always advisable to reduce
the transportation cost. So how do you do that? Locate the biomass industries in such areas
where there is a huge biomass reserve. Then biomass degradability affect large distance
transport activities, long term storage.
Agro pellets production; you produce pellets from the Biomass and then it is easy to
transport, the density will come down (with low moisture and high energy density), avoiding
degradation and transportation issues. These are some of the major problems which are
associated with the Biomass and what we can and how we can address them suitably.
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So let us now understand what is a biorefinery? So I will show you 2, 3 slides to understand
what is biorefinery, then we will discuss about the Biomass based biorefinery things
(concept). So facility that integrates Biomass conversion processes and equipment to produce
fuels, power and Chemicals from Biomass is called a biorefinery. So it can be classified by
several categories: by feedstock materials, by resulting products, by technologies utilised or a
combination of all these three.
So, biomass feedstock; categorised by: chemical composition; maybe carbohydrates, lipids,
proteins, lignocellulosic materials.
So the resulting product categories may be biofuels, chemicals, biogas, electricity and heat
and technologies and unit operations employed include fermentation, gasification, pyrolysis,
hydrothermal liquefaction (It is very upcoming technology actually), hydrogenation,
hydrothermolysis and oxidation and hydrodeoxygenation.
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So some of the feedstock that has been tested (and I have just listed few there are many and
list is endless basically) are cultivated crops, agricultural waste, forest resources, urban and
industrial waste and micro algae. Algae is something interesting. We will discuss about algae
letter on; so microalgae have a great potential as a feedstock for the production of a wide
range of end products under the broad concept of biorefinery.
Algae can be used for the production of biofuels and a variety of value-added chemicals,
since they possess high amount of lipids, proteins, carbohydrates, vitamins, pigments and
enzymes.
So the importance of bio refinery for bio based industries: The International Energy Agency
Bioenergy Task 42 defined biorefining as the sustainable processing of biomass into a
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spectrum of bio based products. So it can be food, feed, chemicals and materials, as well as
bio energy that means bio fuels, power and/or heat. As refineries, biorefineries also can
provide multiple chemicals by fractioning an initial raw material (which is biomass in this
case) into multiple intermediates (so it can be Carbohydrate, protein, triglycerides) that can
be further converted into value added products. Each refining phase is also referred to as a
cascading phase. Now, biorefinery involves the enabling Technologies to make this possible,
as it allows for optimal utilisation as well as value creation of biomass. Development of
integrated closed-loop biorefineries that ensure their sustainability and economical viability
through a complete use of biomass, minimise waste, and generate the greatest possible added
value from the available sources.
What is this integrated close bio refinery? Let us say, it is a bio mass based refinery, I am
going to use one or two feedstock. I process them. Then I produce electricity or maybe liquid
bio fuels or maybe steam (if I am going for some steam based power generation) or some
other commodity products or value added products. Now thereby, I also produce a huge
amount wastewater because water is required in every stage of processing.
So having said that, you know, the fresh water availability is reducing day by day across the
globe in various places. We know that in India also, it is a huge problem in a few areas. So,
what is the need of the hour? It is that you have to treat and recycle this waste water in a
closed loop system. That means if you do that, we will be depending less on our freshwater
resources (that is what is the need of the hour).
Because a time will come when there will be very scarce water available. So how will we run
a refining process? Refining process, whether it is a bio refining or Petroleum crude based
refining, it consumes huge amount of freshwater. So we should look for an integrated closed
loop biorefinery. That means whatever waste we are generating it can be solid waste also. I
am not just talking about liquid waste (basically the wastewater), let us not talk about only
the liquid. Let us do something about the solid waste also. Whatever solid waste we generate
can we further process them to get fuels out of that, or, can we further process them to get
some value added products from that? If you do that in a closed to biorefinery circle, then the
biorefinery will become economically sustainable and will be a viable option.
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So the new you biorefinery concept overcomes the problems arising from the generation of
residues by giving them new value. This is how a significant increasee in profitability and
competitiveness over petrochemical equivalents will be achieved. Otherwise petrochemical
based fuels and products will always be low cost than whatever we produce from the
biomass. So Profitability and Competitiveness has to be taken care of also.
So we go for multiple products. What is the answer for that? We go for multiple products. Do
not aim only for the fuels or energy, but you please look for other products also. So,
biorefining is the main element in the framework of the emerging bio economy as a broad
spectrum of biomass resources offers great opportunities for a wide-ranging product portfolio
to satisfy the different needs of society.
So, as I told you, unless and until we go for multiple products, unless until we work for a
waste to energy or water energy nexus and how do we convert in-house generated waste from
the refining process, whether it is solid or liquid and get some value added products out of
that, we are not going to have a sustainable and economically viable biorefinery.
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So currently some biorefineries are operating on a commercial scale. Pulp and Paper
Industry, biofuel industry and food industry. Furthermore, many different newly advanced
biorefineries are under development. So the main characteristics of a biorefinery are: there
should be coupled generation of energy (gaseous and liquid bio fuels) as well as materials (it
can be Chemicals, food and feed). A combination of several process steps; it can be
mechanical processes, it can be thermochemical processes, it can be biochemical processes
also.
Use different raw materials; from both virgin and residual sources (that is also very
important). A common hurdle in the commercialization of biorefineries it is economic
viability. The economic hurdle starts from procuring Biomass and its logistics, technology
maturity and policy support. This is what we have already discussed.
So, the rate of commercialization of biorefineries is slow primarily due to the lack of policy
support. This I have already mentioned that the government has or should come up with
policies which will support the establishment of biorefineries. So biorefineries have to
compete with well-established petrochemical products. Policy support can drive innovation,
help technology to mature, create competitiveness to a market which in turn could reduce the
cost thus making the economic viability of biorefineries a reality. Government as a big role to
play.
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This is how it looks like basically. You have a biomass here, you process in the biorefinery,
you have downstream processing, you have separation technology. It can be catalytic
conversion or it may not be. Then we get this type of products: fuels, solvents, bulk
Chemicals, plastics, fibres, fine Chemicals and oils and what not? You can just see what not
we are getting from the biorefinery.
But again, one particular feedstock will not give me like this. So I should go for multiple
feedstock. And as well as not only virgin feedstock, but also processing feedstock, processing
with.
So before I wind up, I just quickly show you. We will glance through the different bio based
industries that are actually established and running successfully. Blue Marble Energy, so that
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is in Odessa and the Missoula. Canada's first integrated biorefinery, developed on anaerobic
digestion technology by Himark BioGas that is in Alberta, then Chemrec’s technology for
Black Liquor gasification and production of second generation of biofuels such as
biomethanol and bioDME. That is integrated with the host pulp mill and utilizes a major
sulphate or sulphite process waste product as the feedstock (completely waste product based
biorefinery).
Then Novamont has converted old petrol chemical factories into biorefinery. This is a very
interesting thing. So by just changing some of the processing things, some equipment, they
are running this refinery in a sustainable way.
C16 Biosciences they produce synthetic palm oil from carbon containing waste. Then there is
MacroCascade that aims to refine seaweed into food and fodder, and product for health care,
cosmetics, fine chemical industries and they have processed other things also. FUMI
Ingredients that produces foaming agents, heat set gels and emulsifiers from microalgae with
the help of microorganisms such as yeast and brewer’s yeast.
BIOCON, it is an Indian company. So they a processing the wood into various products.
More precisely, their researchers are looking at transforming Lignin and cellulose into
various products. Lignin based biorefineries are also there. Lignin for example can be
transformed into phenolic components which can be used to make glue, plastics and
agricultural products (crop protection). Cellulose can be transformed into clothes and
packaging.
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Now, in South Africa there is a company called Numbitrax LLC. They have bought a Bloom
biorefinery system for producing bioethanol as well as additional high return offtake products
from local and readily available resources such as prickly pear cactus plant basically. Then;
BiteBack Insect that makes insect cooking oil, insect butter and all these things.
Then there is a company called Circular Organics (it is a part of Kempen insect Valley) that
grows black soldier fly larvae on waste from the agricultural and Food Industry. So Fruit and
Vegetables surplus, remaining waste fruit juice and jam production (basically the solid
waste). These larvae are used to produce protein, grease and chitin. So, the grease is usable in
the pharmaceutical industries for cosmetics, surfactant for shower gel thereby replacing other
vegetable oil such as palm oil or it can be used as fodder also.
So with this I complete my lecture today. So thank you very much. And in the next lecture we
will start module 2. The module 2 is focused on biomass. So, we will be discussing the
availability and abundance of biomass, photosynthesis, composition and energy potential,
virgin Biomass production, agricultural, forestry waste and all these things. Their availability
and potential.
So thank you very much once again, and if you have any query, please write to me at
[email protected] or you can also write to me in the Swayam portal. Thank you.
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Indian Institute of Technology-Guwahati
Module-02
Lecture-03
Biomass Basics
Good morning students. This is module 2 and lecture 1.

So, in this entire module, basically we will be discussing about biomass and biomass
structure, its availability, then composition, their energy potential, what type of biomass are
available, what type of land requirements are there; all these things slowly we will be
discussing.
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So, let us start our lecture today. So, as you know, biomass has always been an important
energy source, considering the benefits it offers. It is renewable, widely available and carbon
neutral and has the potential to provide significant employment in the rural areas. This is
what I discussed (in the) last class also; that how biomass based industry is going to effect the
economics of the rural people.
About 32% of the total primary energy use in India is still derived from biomass. More than
70% of the country's population depends upon it for their energy needs. The current
availability of biomass in India is estimated at about 500 million metric tons per year.
So, biomass is defined as the bio residue available by water based vegetation, forest or
organic waste, by product of crop production, agro or food industries waste. Various biomass
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resources are available in India in different form. They can be classified simply in the way
they are available in nature as: grasses, woody plants, fruits, vegetables, manures and aquatic
plants.
Algae and Jatropha are also now used for manufacturing biodiesel (we will be discussing
about them in detail later on). Core distinct sources of biomass energy can be classified as
residue of agricultural crop, energy plantation and municipal and industrial waste.
So, let us have a look at this particular slide. So, (first) you can see energy crops; plants
exclusively grown to derive energy. Basically it can be fuel, liquid fuel, solid fuel as well as
gaseous fuel. So, here there are some examples, bamboo, prosopis, leuceana, then we have
miscanthus, elephant grass, switch grass etc.
Then we have agro industrial wastes. So wastes from paper mills, molasses from sugar
refineries, pulp wastes from wood processing industries, textile fibre waste etc. Then we have
agricultural waste. So, waste that is coming from farming; such as straws of cereals and
pulses, stalks of fiber crops, seed coats of oil seed (basically de-oiled cake), then crop waste
like sugar cane trash, rice husk, coconut shell etc.
Then we have MSW, which we call municipal solid waste. So, mostly they are
biodegradable, such as food and kitchen waste, green waste, paper, inert waste, like fabrics,
clothes come under that (needs to be separated basically). Forest waste; so, basically logs,
chips, barks, leaves, forest industry waste products like sawdust.
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Now, bioenergy is the largest renewable energy source globally. In 2016, total primary
energy supply of biomass resources was 56.5 Exajoules, constituting almost 70% of the share
among all renewable energy sources. So, this table will give you an idea about, what is the
total energy that is available and the biomass based energy. So, you can see that in 2016
(latest figures), if you see 80.5 is the available energy of the renewables and out of that 56.5
comes from the biomass.
In continents, the role of biomass is very prominent. In Africa more than 90% of the total
primary energy supply of renewable energy sources comes from biomass. In every other
continent, biomass is the largest renewable energy source in terms of supply and accounting
from between 40% (Oceania) to almost 96% in Africa. So, this particular table shows you
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what is the biomass fraction, basically from various continents, Africa, Americas and Asia.
The biomass is huge almost everywhere. It is more in Asia, okay followed by Africa.
So, understanding photosynthesis is the most important thing related to biomass. So,
understanding the photosynthesis of biomass began long back, in 1772 by the English
scientist, Joseph Priestley. So, he discovered that, green plants expire a life-sustaining
substance (that is basically oxygen) to the atmosphere, while a live mouse or a burning candle
removes the same substance from the atmosphere (removed meaning it is consumed
basically).
So, in 1804, the Swiss scientist Nicolas Theodore de Sausseure showed that the amount of
carbon dioxide absorbed by green plants is the molecular equivalent of the oxygen expired.
That means, he found out that, how much carbon dioxide is being consumed, is almost
equivalent (on a molecular level) to the oxygen that the plants expire. So, in this way, the
stoichiometry of the process was developed and major advancements were made to detail the
chemistry of photosynthesis, and how the assimilation of carbon dioxide takes place. About
75% of the energy in solar radiation is contained in light of wavelengths between the visible
and near infrared portions of the electromagnetic spectrum. So, that is almost in the range of
400 to 1100 nanometers.
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The light absorbing pigments effective in photosynthesis have absorption bands in this range,
particularly in that 400 to 1100 range. So, chlorophyll a and chlorophyll b, which strongly
absorb wavelengths in the red and blue regions of the spectrum, and accessory carotenoid and
phycobilin pigments participate in the process. So, photosynthesis is a biological conversion
of solar energy into sugars and starches, which are energy rich compounds.
So, in photosynthesis reaction, water and carbon dioxide molecules break down and a
carbohydrate is formed with the release of pure oxygen.
CO2 + H2O + light + Chlorophyll → C6H12O6 (Glucose) + O2
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Now, there are two reactions, light reaction and dark reaction in photosynthesis. So, in the
light reaction, the splitting of water molecule into hydrogen and oxygen is happening under
the influence of chlorophyll and sunlight. So it is a photochemical phase reaction. Under the
dark reaction hydrogen is transferred to carbon dioxide to form starch or sugar, and it is a
biochemical phase reaction.
So, let us now understand the biomass composition. I can tell you that biomass composition
is a significant property that has so much to do with biomass processing and further their
value added product generation. So, what type of composition it has? If we talk about the
lignocellulosic biomass, these basically consists of 3 primary components, first one is
cellulose, then hemicellulose, and then lignin.
Apart from that there are other components also. So, how much cellulose and how much
lignin and how much the hemicellulose is present. So, this has to be calculated a priori. So,
this comes under the physicochemical characterization of the biomass. So, you need to
characterize it and you need to find out what is the crystallinity of the cellulose.
So, there is a process called delignification in which you basically remove the lignin from the
lignocellulosic biomass, to make them more amorphous and you will get the cellulose in a
pure form. So, that can be further processed and made into sugars. So, the chemical
composition of biomass, whether it is lignocellulosic or herbaceous, can be characterized by
5 primary components: cellulose, hemicellulose, lignin, extractives/volatiles and ash. So,
these are the components which are present in almost all biomass. But, what varies, is their
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amount from biomass to biomass. In some biomass, like hard woody biomass lignin presence
will be more, the amount of lignin will be very high. And in some soft biomass like creeps
and leaves the lignin presence will be very less okay.
So, the most abundant biopolymer on the earth is cellulose. It is a polysaccharide of glucose
monomers held together by β (1 → 4) linkages (it is a bond, a glycosidic bond basically). So,
these β (1 → 4) linkages are what makes cellulose resistant to hydrolysis. That means it’s all
about the crystallinity of the cellulose. So, if it is more crystalline, then you need to process it
further, you need more energy to break it. So, if we remove lignin, then the crystallinity will
also come down (reduce).
The second major component of the biomass is hemicellulose. It is an amorphous

heteropolymer comprised of several different carbohydrates including xylose, mannose and
glucose, among others. Due to its amorphous structure hemicellulose is significantly more
susceptible to hydrolysis than crystalline cellulose. So, cellulose and hemicellulose combined
with the third major component of the biomass, that is lignin, make up about 90% of
lignocellulosic biomass and 80% of herbaceous biomass.
So, lignin is an intricate array of aromatic alcohols and it is intertwined with the cellulose and
hemicellulose fraction of the biomass structure. So, this interwoven nature of the lignin helps
provide rigidity to lignocellulosic materials such as trees. So, lignin is bound along with
cellulose and hemicellulose in a very intertwined manner. So, that is why there is a need to
de-lignify (basically remove lignin) so, that cellulose and hemicellulose may be released from
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the interlinking bond that was present previously. So, that cellulose will be more accessible
for hydrolysis purposes. The other minor components of the biomass are extractives/volatiles
and ash. While these components make up a smaller portion of the biomass composition, they
can still have a major influence on what ends up being the optimal conversion process.
So, please again note that the amount of volatiles/extractives present and the amount of ash
present plays a significant role. If there is huge ash present in the biomass, then they are not
good for certain particular processing, whether it is the thermochemical or biochemical. So,
every component has a role to play and will somehow effect the conversion technology or
conversion process.
The components comprising the extractives/volatiles include both water and ethanol solubles.
So, water soluble compounds include non-structural, sugars and proteins and ethanol soluble
compounds are typically represented by chlorophyll and waxes. Ash, which comprises the
inorganic content in biomass can be intrinsic to the biomass or added anthropogenically.
Anthropogenically means man-made (basically during the processing), so it is getting added

from the outside, it is not present inside the biomass. So, intrinsic ash includes material like
calcium and potassium ions, while anthropogenic ash is mostly silica. Silica is basically
coming from the dirt. When you are processing it in the field, it is getting dumped on the
field. So, you are taking it out. So, silica is coming into picture, that is how it is getting added
anthropogenically during harvesting.
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So, let us talk about biomass energy potential. So, biomass for energy originates from a
variety of sources classified into forestry, agricultural and waste streams. Some of the
potential sources include: crops for biofuels (dedicated crops), energy grass, short rotation
forests, woody biomass and residues, herbaceous by-products and municipal solid waste.
Globally, in 2012, the biggest share of biomass for energy came from the forests- almost 49
Exajoule out of a total supply of 56.2 Exajoule. So, the current global energy supply is about
560 Exajoule.
So, a conservative estimate of the energy potential of biomass from agriculture, forestry and
waste sectors is totalling to almost 150 Exajoule in the next 20 years. It is a huge energy
potential. About 43% coming from agricultural (so, that is residues by-products and energy
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crops), 52% from the forest (which is wood fuel, forest residues and by-products of the forest
industry like sawdust) and 5% from waste streams. Now, biomass can play an important role
in the transformation to a new energy system based on renewable energies.
Let us now understand virgin biomass production and selection, how the biomass is getting
produced, the land requirements, etc, and how do we select them. So, virgin biomass includes
all naturally occurring terrestrial plants, such as trees, bushes and grass. The manufacture of
synfuels or synthetic fuels or energy products from virgin biomass requires that suitable
quantities of biomass chosen for use as energy crops be grown, harvested and transported to
the end user or to the conversion plant.
Since at least 2,50,000 botanical species of which only about 300 are cash crops are known in
the world, which indicates that biomass selection for energy could be achieved rather easily.
Because it is a narrowed loop, it is not a very big loop. And compared to the total known
botanical species, a relatively small number are suitable for the manufacture of synfuels and
other energy products.
The selection is not easily accomplished in some cases, because of the discontinuous nature
of the growing season and the compositional changes that sometimes occur on biomass
storage.
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Many parameters must be studied in great detail to choose the proper biomass species or
combination of species for operation of the system. Some of them are growth area
availability, soil type, quality and topography, propagation and planting procedures, growth
cycles, fertilizer, herbicide, pesticide and other chemical needs, disease resistance of the
monocultures, insolation, temperature, precipitation and irrigation needs.
And there is pre harvest management, crop management and harvesting methods, storage
stability of the harvest, solar drying in the field versus in-plant drying in connection with
conversion requirements, growth area competition for food, feed, fiber and other end uses,
the possibilities and potential benefits of simultaneous or sequential growth of two or more
biomass species for synthetic fuels and foodstuffs, multiple end uses and transport to the
conversion plant gate or end-use site.
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Biomass chosen for energy applications, in the ideal case should be a high-yield, low-cash-
value species, that have short growth cycles and that grow well in the area in which biomass
energy system is located. Now, again, I am telling you, last class also we have discussed,
apart from these listed things (there are so many), one of the major costs usually comes from
the transportation of the biomass.
Now, we discussed in the last class about the biomass chipping and all, basically, the shape of
biomass and the moisture content of the biomass. So, if the moisture content is very high
almost 30% (let us say in most of the biomasses), then I am transporting almost 300 kgs of
water along with the transport of 1 tonne of biomass.
So, it is a huge thing and it is of no use, because even if you go for a thermo chemical process
or a biochemical or any other process, you need to have a dry biomass. If it is not 100%
moisture free, some moisture is okay, but you need to dry it. So, you cannot have 30%
moisture. So, you have to reduce it almost to a 5% or even less than that. Certain conversion
technologies require not more than 1%, 2% or 3% moisture.
So, then shape also plays a very important role. So, I was telling you in the last class if you
recall, that it is better for the policymakers, the implementers, industry people who are going
to set up such plants, that they must choose the location of their plant in such a way that
transportation cost should be reduced, it should be as less as possible.
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So, fertilization requirements should be low and possibly nil if the species selected fix
ambient nitrogen, thereby minimizing the amount of external chemical nutrients that have to
be supplied to the growth areas. In areas having low annual rainfall, the species grown should
have low consumptive water uses and be able to utilize available precipitation at high
efficiencies.
For terrestrial energy crops the requirements should be such that they can grow well in low
grade soils so, that the best classes of agricultural or forestry lands are not needed. After
harvesting, growth should commence again without need for replanting by vegetative or
coppice growth. So, what do we understand basically is that, lands should be chosen in such a
way to grow the dedicated energy crops, which are not been used for our traditional crops.
So, agricultural fields basically. So, most of the agricultural fields which are being utilized in
India to grow crops, cereals, pulses etc., even for vegetables production are extremely fertile.
So, in no way we are going to use those land for biomass production or let us say, for
growing energy crops or some other biomasses.
So, you must look for such lands which are either barren or are not fertile enough to grow the
energy crops. So, those types of lands are sufficiently available. So, this is one point. Second
thing is that, we should go for short rotation species. So, that means in another way I can tell
a fast growing species. There are certain species of softer bamboo which grow very fast.
So, those are being utilized or can be utilized for making bioethanol or other biomass based
products from bamboo. So, like that there are many other species which are having fastest
growth rate. And you should also take care that such species should be planted, which
required minimum attention.
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So, then let us talk about climatic and environmental factors. So, the biomass species selected
as energy crops and the climate must be compatible to sustain operation of the energy or fuel
under human controlled conditions. So, the compatibility of biomass and climate is
nevertheless essential to ensure that these systems can ultimately be operated at a profit on a
commercial scale.
The 3 primary climatic factors that have most influence on the productivity and yields of an
indigenous or transplanted biomass species are insolation (that is the solar radiation),
precipitation (rainfall & moisture), and temperature. So, we will discuss one by one.
So, natural fluctuations of these factors remove them from human control. But the
information compiled over the years in meteorological records and from agricultural and
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forestry practice, supplies a valuable database from which biomass energy system can be
conceptualized and developed. That means all these records are going to help us in choosing
and selecting a particular biomass as well as the area or land for growing this biomass.
Of these three factors, precipitation has the greatest impact, because droughts can wreak
havoc on biomass growth. And that is not only true for biomass, that is true for any plantation
or any crop. So fluctuations in insolation and temperature during normal growing seasons do
not adversely affect the biomass growth as much as insufficient water. So, ambient carbon
dioxide concentration and the availability of macronutrients and micronutrients are important
factors in the biomass production.
Having said that, we may look for such lands which are not highly fertile. But we need to
again remember that we need to supply certain nutrients (micro or macro) for the biomass
growth. However, that can be supplied in limited quantity throughout the year, in a sequential
manner so that the growth of the biomass does not get hindered.
So, let us understand insolation. So, the intensity of the incident solar radiation at the Earth's
surface is one of the key factors in photosynthesis. Except in a few rare cases, natural
biomass growth will not occur without solar energy. Insolation varies with geographical
location, time of day and season of the year, and as is well known, it is high in the tropics and
near the equator. At a given latitude, the incident radiation is not constant and often exhibits
large changes over relatively short distances.
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Although several environmental factors influence biomass productivity, there is usually a
relatively good correlation between the annual yields of the dry biomass per unit area and the
average insolation value (there is a correlation that exists).
All other factors being equal, it is generally true that the higher the insolation, the higher the
annual yield of a particular energy crop provided it is adapted to the local environment. The
approximate changes of insolation with latitude are illustrated in this table. You can have a
look in this table and you can understand that location wise what is the maximum, minimum
and average insolation at these places.
So, the next is precipitation. Precipitation as rain or in the form of snow, sleet or hail,
depending on atmospheric temperature and other conditions is governed by the movement of
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air and is generally abundant wherever air currents are predominantly upward. So, the
greatest precipitation should therefore, almost occur near the equator. The annual
requirements for good growth have been found for many biomass species to be in the range
50 centimeter to 76 centimeter.
Some crops such as wheat, exhibit good growth with much less water, but they are in the
minority (minority means when we compare with other cereals or pulses on a global scale,
they are less; that is why it is being mentioned as minority). Without irrigation, water is
supplied during the growing season by the water in the soil at the beginning of the season and
by rainfall.
So, it should be realized, though, that rainfall alone is not quantitatively related to the
productivity of terrestrial biomass, because of the differences in soil characteristics, water
evaporation rates and infiltration. The transpiration of water to the atmosphere through
biomass stomata is proportional to the vapour pressure difference between the atmosphere
and the saturated vapour present inside the leaves.
Now, having said that, we must understand that, the vapour pressure inside the leaves and the
pressure outside or the ambient pressure do play a role on controlling that stomata opening.
Transpiration is obviously affected by atmospheric temperature and humidity. The internal
water is essential for biomass growth. The efficiency of utilizing this water (we call it water
use efficiency or WUE) has been defined as the ratio of biomass accumulation to the water
consumed, expressed as transpiration or total water input to the system.
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Analysis of the transpiration phenomena and the possibilities for manipulation of WUE have
led some researchers to conclude that biomass production is inextricably linked to the
biomass transpiration. Agronomic methods that minimize surface runoff and soil evaporation
and biochemical alterations that reduce transpiration in C3 plants have the potential to
increase the WUE.
But for water limited regions fact remains that without additional water the research results
indicate that these areas cannot be expected to become regions of high biomass yields.
Irrigation and full exploitation of humid climates are of the highest priority in attempting to
increase biomass yield in these areas. So, basically in India, you know, most of our
agricultural lands till date depends on the natural rain fall. We will always be looking towards
a better monsoon this year or that year (and so on). So, as we do not have lift irrigation
system in most of the agricultural lands. Though in many areas it is there, but almost I can
say about 50% or 40% has been covered (if I am correct, according to the statistics), but still
almost 50% people completely depend upon the rainfall. Rainfall during the monsoon season
and during other season also. So, irrigation has to be done properly whether it is for the
biomass production in a large scale for the dedicated energy crops or for our usual
agricultural purposes also.
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Now, let us understand the effect of temperature. Most biomass species grow well at
temperatures between 15.6 and 32.3 degrees centigrade. Typical examples are corn, kenaf
and napier grass. So, kenaf is basically in the African continent, it is being planted for years
together for food and fiber purposes. Napier grass is another plant in grass family which is
being used for fuel production.
So, tropical grasses and certain warm season biomass have optimum growth temperatures in
the range of 35 to 40 degrees centigrade, but minimum growth temperature is still near 15
degrees. So, cool weather biomass such as wheat may show favourable growth below 15
degrees centigrade and certain marine biomass such as the giant brown kelp only survive in
water at temperature below 20 to 22 (degree centigrade).
Giant brown kelp is an algae. So, it is a big algae (which) basically looks like plant inside the
sea. So, it cannot survive at a temperature more than 22 degrees centigrade. The effect of
temperature fluctuations on net carbon dioxide uptake is a very important factor to be
considered. Ideally, the biomass species grown in an area should have a maximum rate of net
photosynthesis as close as possible to the average temperature during the growing season in
that particular area.
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So, now let us understand about different wastes one by one. So, waste biomass, municipal,
industrial, agricultural and forestry, their availability, abundance and potential. So, up to the
mid 1990s only a few commercial virgin biomass energy systems in which dedicated biomass
is grown for use as an energy resource were in operation in industrialized countries (basically
Europe and America).
So, the technology is available or under development and is slowly being incorporated into
regional, national and world energy markets. Most of the contribution of biomass to primary
energy demand in the late 1990s comes from waste biomass. Now, waste biomass is energy
containing materials that are discarded or disposed of and that are mainly derived from or
have their origin in the virgin biomass.
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So, they are lower in cost than the virgin biomass and often have negative costs, because they
are being just thrown away. So, some are quite abundant and some can be disposed of in a
manner that provides economic benefits to reduce disposal costs. So, having said that, another
most important thing we must understand and we are slowly getting aware of the fact is
segregation of the wastes. Whether segregation of the wastes is at home or in offices, whether
it is in plants where we are processing biomass, or whether it is in hotels and restaurants and
canteens. So, it is having a very big effect on the further downstream processing. So waste
biomass is generated by anthropological activities and some natural events also. So, it
includes municipal solid waste, basically urban refuse, municipal bio-solids (sewage), wood
wastes and related wastes produced in the forest and logging and forestry operations,
agricultural waste such as crop residues produced in farming, ranching and related operations,
the wastes produced by certain industries such as the pulp and paper industry and those
involved with processing of foodstuffs.
Now let us understand municipal wastes. So, there are basically two types of municipal
wastes that offer opportunities for a combined waste disposal and energy recovery. First is
the municipal solid waste that is MSW, the garbage, urban refuse and then the bio-solids, that
is coming from the sludge and sewage. So, each has its own distinctive set of characteristics
as a biomass energy resource. There are huge works already reported in literature. So, you
can refer to those.
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MSW is collected for disposal by urban communities in all industrialized countries. So, there
is no question regarding its physical availability as a waste biomass feedstock in centralized
location in these countries. The question is how best to utilize this material if it is regarded as
an “urban ore” rather than urban waste. A large portion of the MSW generated is available as
feedstock for additional energy recovery processing.
Landfilled MSW can provide energy as fuel gas for heat, steam and electric power production
over a long period of time. Surface processing of MSW can also provide energy for the same
end uses when MSW is being used as a fuel or feedstock. So, basically what we need to
understand is, how best we are going to use. Please understand that technologies are available
to process MSW, there is nothing new to be done. Available technologies are already
available.
But segregation of waste is the most important thing. Then another important thing is
basically how you are going to utilize it and where. Again you are collecting the municipal
solid waste from the entire municipal area, city, townships or even the rural areas; then you
have to transport it. Again transportation cost is a big thing. Where your plant is located, the
location of the land plant is again important thing.
So, we need to have an integrated approach thereby understanding the value of the MSW
what type of value it is. Now, please do not think that every MSWs economic value, let us
say, with respect to energy production is same. It is not so. So, the MSW from Bombay will
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have certain value, the MSW from Guwahati maybe something else. So, component wise it
may vary.
So, we have to see which MSW is best suited for what technology; that is also to be seen. So,
we need an integrated approach where MSW can be properly utilized, converted for energy
purposes as well as for other value addition also.
So, the world generates almost 2.01 billion tonnes of municipal solid waste annually with at
least 33% of that conservatively not managed in an environmentally safe manner. I am sure
this percentage 33% may be very high in Asian and African countries. So, worldwide waste
generated per person per day averages almost 0.74 kilogram, but ranges widely from 0.11 to
4.54 kilograms.
The waste generated per person from the developed countries is much, much higher than that
generated from the underdeveloped or developing countries. So, when looking forward,
global waste is expected to grow to 3.4 billion tonnes by 2050, more than double population
growth over the same period.
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Let us talk about India. Urban India about 377 million people generates 62 million tonnes of
municipal solid waste each year. Of this about 43 million tonnes (amounting to almost 70%)
is collected and 11.9 million tonnes is treated. About 31 million tonnes is dumped in landfill
sites. Now when we dump MSW in landfill sites, many a times it produces many different
types of gases, including methane and some toxic gases, thereby polluting the nearby
environment.
So, if it is not properly landfilled, then it is going to affect two things. First is the
environment in the form of leakages of gases. Second is, leaching of the components to the
groundwater sources (toxic components). Average waste is about 450 grams per person per
day (this is an Indian figure). However, there is much variability in per capita: daily
household municipal solid waste generation ranges from 170 grams per person in small towns
to 620 grams per person in large cities.
So, the trend is same; the urbanized people living in the large cities, produce more waste than
the people those are staying in the rural areas. So, waste generation will most likely increase
from 62 million tonnes to about 165 million tonnes in 2030. The associated difficulties of
MSW disposal have become a serious problem that do not bode well for the future
generations of city dwellers and the areas that have high population densities.
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So, governments often mandate the use of more environmentally acceptable methods of
MSW disposal by limiting and sometimes phasing out some of the more traditional disposal
methods. The collection and disposal costs increase and proper disposal becomes more
difficult to achieve with the passage of time. And talking about the energy potential; the
global energy potential of waste can be estimated at 8 to 18 Exajoule per year in 2010, which
could increase to 13 to 30 in 2025, if a heating value of municipal waste ranging from 6 to 14
mega joules per kg.
So, with the best estimate moving from 12 Exajoule in 2010 to 20 Exajoule in 2025, for an
average heating value of 9 mega joules per kg for waste. Some sort of estimation basically;
exact figures may vary depending upon the type of waste we are dealing with.
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So, now, let us talk about industrial wastes. So, the food industry produces large number of
residues and by-products that can be used as biomass energy sources. These waste materials
are generated from all sectors of the food industry, with everything from meat production to
confectionery producing waste that can be utilized as an energy source. Solid wastes include
peelings and scraps from fruit and vegetables, food that do not meet quality control standards,
pulp and fiber from sugar and starch extraction, filter sludges and coffee grounds. These
wastes are usually disposed of in the landfill dumps.
Now, there are liquid wastes too. So, liquid wastes are generated by washing meat, fruit and
vegetables, blanching fruit and vegetables, pre cooking meats, poultry and fish, cleaning and
processing operation as well as wine making. These wastewaters contain sugars, starches and
other dissolved and solid organic matter. The potential exists for these industrial wastes to be
anaerobically digested to produce biogas or fermented to produce ethanol (bio-ethanol), and
several commercial examples of waste to energy conversion already exist. Pulp and paper
industry is considered to be one of the highly polluting industries and consumes large amount
of energy and water in various unit operations.
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The wastewater discharged by this industry is highly heterogeneous as it contains compounds
from wood and other raw materials, processed chemicals as well as compound formed during
processing. Black liquor can be judiciously utilized for production of biogas using anaerobic
UASB technology. We will discuss about that technology later on in one of our class. So, if
you look at this particular table, you can see that this gives the domestic supply of municipal
and industrial waste. So, it is the total value and how much the industrial waste is
contributing (that is almost close to 50%).
So, this is again continent wise and understanding of the industrial waste and their energy
values. So, again, almost close to 40% here, if you look at the global data.
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Now, we are discussing about the agricultural wastes. So, out of all the wastes, my
understanding is that, agricultural waste has the greatest potential that can be utilized for
energy production or the bioenergy production, whether it is pyrolysis, whether it is
gasification, whether it is producing ethanol or use the ABE fermentation to get butanol,
biogas. Any such thing can be done using the agricultural residues, because they are very
clean and are produced in very large quantities. So, there is certainly a sustainable issue for
throughout the year getting this one (availability), but we do not have to segregate things.
Rather, technologies are now developed, where we can mix more than one type of
agricultural waste including forest waste to produce and convert them to value added
products and of course fuels.
So, the main source for energy from agricultural land is in the form of crops for biofuels and
residues for biogas, as well as use in the form of heating and cooking. In terms of area
harvested, cereal food crops, such as maize, rice and wheat, together account for more than
580 million hectares of the land use and together account for more than 80% of the area
harvested for major crops.
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So, a major indication of the significant development in agricultural practices is visible in the
increasing yield of crops around the world. Most of the major crops including cereals, oil
crops and sugar crops have shown double digit growth in yield globally, while at the same
time the area harvested for these crops has not shown similar growth. Now, some crops such
as sugar beet, barley, sorghum, etc., have reduced area harvested while at the same time
increasing yields.
So, globally, now, more food is being produced efficiently from the same area of land than
before. Thanks to the development in agricultural sector. So, high yield crops are now being
planted, which gives better yield and they are also pest resistant, thereby increasing their
overall yield.
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Crops which show a tremendous growth in area harvested include maize 45%, soybean 66%
and cassava 55%. Now, it is important to note that the use of crops for biofuels is a very
small share of the overall use of crops for food production. In terms of actual production
major crops such as maize, rice and wheat dominate the crop production globally due to their
increasing use in America (maize) and Asia (rice and wheat).
Although a minor share of maize is used for biofuel production, the potential for energy from
crops such as rice and wheat lie in their efficient use of residues such as the husk and straw,
which are currently unutilized and sometimes cause environmental concerns. In India you
know that every year there is a big problem near Delhi; from the Punjab and Haryana side the
agricultural crop residues are being burnt up. So, in huge quantities the entire polluted air
affects the National Capital Region, and breathing also becomes a problem. So, it is a very
serious problem. Now, many farmers have understood the bioenergy potential of the residues
or wastes that is generated from their crops to produce some value added products and they
have started making small plants near their agricultural lands and farms, to produce energy.
So, there are certain reports that farmers are producing energy from gasification unit and even
pyrolysis unit (small scale). So, things are happening in a very positive way, in India, as well
as in other developing and developed countries.
So, although a minor share of maize used for biofuels production, the potential for energy
from crops such as rice and wheat lie in their efficient use of residues such as husk and straw,
which are currently unutilized and sometimes cause environmental concerns. So, now, let us
talk about the oil crops. Both soybean and rapeseed production has almost doubled globally
because of their huge demand - mainly due to the extensive production of soybean in South
America (Americas itself account for 90% of the soybean production globally) and of
rapeseed in America, Asia and Europe.
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This will make you understand region wise the areas that is being utilized for harvesting
certain crops, (this is in 2017). In the worldwide figure if you see, out of all these crops,
maize, rice, wheat and soybeans constitute more than 80% (75 to 80%).
So, similarly, this will tell us, continent wise crop yield globally. Again, you can see here,
that the sugar beet and the sugarcane are the highest in yields because they are produced in an
extremely large scale in the Americas. So, this is production quantity of crops globally in
2017. Again you can see that sugarcane, maize, rice and wheat, they constitute almost more
than 75%.
So, let us talk about energy potential. Now one of the most promising sectors for growth in
bioenergy production is in the form of residues from agriculture sector. Currently, that sector
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contributes less than 3% to the total bioenergy production. However, due to the increasing
demand for replacing fossil fuels in power plants for heat and electricity with sustainable,
renewable and dispatchable energy sources, agricultural residues such as straw and husk can
form a major share of the bioenergy generation. Now, apart from replacing fossil fuels and
reducing emissions, agricultural residues also solve the environmental challenge, which can
occur due to the annual burning of harvested residues in major countries such as China and
India. This is what I just mentioned about; burning of the crop residues.
Considering the fact that 50% of the residues have to be left on the field for soil quality
purposes (basically to enhance the soil quality), the theoretical potential for utilizing
agricultural residue is still enormous. Data shows that utilizing the residues from all major
crops for energy can generate approximately 4.3 billion tonnes to 9.4 billion tonnes annually
around the world.
Utilizing standard energy conversion factors for residues by conservative moisture content
and energy content of the fuels, the theoretical energy potential from residues can be in the
range of 17.8 Exajoule to 82.3 Exajoule. The major contribution is coming from the cereals,
mainly maize, rice and wheat. So energy generation from agricultural residues could meet
about 3 to 14% of the total energy supply globally. So, this is an estimated figure for around
2030.
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So, this is the theoretical potential of the agricultural residues globally. You can see that the
first column is giving you the different types of crops, then the residues in million tonnes and
then the residues’ energy potential. You can see that maize, rice, wheat and soybean is
constituting more than 80% of the total production. And if you look at the corresponding
energy values, they are actually excellent. So, they are better and higher than other crops like
barley, oats, sorghum, olive etc.
Now, let us understand the importance of the forestry wastes. The forestry sector is the
largest contributor to the bioenergy mix globally. Forestry products, including charcoal, fuel,
pellets and wood chips account for more than 85% of the biomass used for energy purposes.
Most of the use of the forestry product is in the form of residues from pulp, paper and
sawmill industries while a significant percentage also the use of fuelwood for cooking and
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heating purposes in Africa and Asia - so called traditional fuelwood or biomass. Globally,
3.99 billion hectares of the land is classified as forest land. Most of the forest land is in the
form of other naturally regenerated forest (almost 61%), while primary forest accounted for
one third of the all forest land.
Recently, planted forests have been increasing, leading to an increasing forest land globally,
although they account for a minor share (7%). Globally, forest land has been decreasing since
2000. The decrease in forest area is noticeable in Africa (almost -7.7%), followed by America
(-3.1%) while the decrease has been compensated noticeably due to the increasing forestland
in Asia (+ 5.1%) and Europe (+ 1.4%). I can tell you that India played a significant role in
afforestation adding up to this number. So, you can see in this particular table, the forest land
area that is globally available.
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So, among continents, majority of the forest land occurs in the Americas (40%), followed by
Europe (25%) and equal share in Africa and Asia (15% each).
So, this is due to the enormous area of primary forest in the Amazon in South America,
which accounts for almost half of all primary forests globally. These primary forests are
naturally regenerated forests of native species with no visible indications of human
intervention.
So, due to significant afforestation efforts in the major economies like India and China, the
global planted forest area has increased by more than 30% during 2000 to 2017 even though
planted forests account for a minor share of the overall forest land. China and India are
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engaged in huge afforestation. So, as a result, there is a huge upsurge in the total amount of
forest area that is available, but these are basically manmade forest.
So, Asian continent accounts for 45% of all the planted forests globally. Planted forests
include those forests where the trees are predominantly of introduced species and mainly due
to human intervention.
Americas also account for the highest share of other naturally regenerated forest (34%)
globally, which are tree species that are predominately non native and do not require human
intervention to reproduce/maintain population over time. So, this particular table will tell you
about the primary forest, other naturally regenerated forest and the planted forest that is
available.
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Now, let us understand their energy potential. So, one of the primary products from forests
that are used for bioenergy production is wood fuel. Most of the wood fuel is used for
traditional cooking and heating in developing countries in Asia and Africa. Globally 1.9
billion meter cube of wood fuel was used for energy purposes - for example, fuel wood and
charcoal production.
Now, the volume includes wood removed from felling of forest or from trees killed or
damaged by natural causes. We are not supposed to cut the trees, for making any fuel. So, it
is important to note that wood fuel does not include the use of wood residues from industrial
processing of round wood, which forms a major share of the bioenergy in Europe. Among
continents, both Asia and Africa together account for three fourths of all wood fuel
production globally. India and China both adding a larger share. And the share has remained
constant in the last past 17 years, which is a good thing.
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So, woody biomass is an important source of energy and is currently the most important
source of renewable energy in the world. In 2010, global use of woody biomass for energy
was about 3.80 Gm3/year, which consisted of 1.90 Gm3/year for households fuel wood and
the similar number for large scale industrial use. During the same period, world primary
energy consumption was 541 Exajoule per year and world renewable primary energy
consumption was 71 Exajoule per year. Hence in 2010, woody biomass formed roughly 9%
of the world primary energy consumption and 65% of the world's renewable primary energy
consumption.
So, I wind up with this today and in our next class, we are going to discuss about the biomass
as energy resources. We will be discussing about the dedicated energy crops that I talked
about in today's lecture and even last lecture. So, some of those crops we’ll understand in a
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better way. How they are being grown, what are their properties and how best they can be
utilized, like maize, sorghum, sugar beet, etc. And some perennial crops such as sugar cane,
switch grass, miscanthus, etc.
So, thank you very much. And in case you have any query, please drop a mail to me at
[email protected] or feel free to log into the Swayam portal and post your query there. I
will be happy to address those. Thank you.
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Module-02
Lecture-04
Good morning students. This is lecture 2 of module 2.

And in today's lecture we will be discussing about dedicated energy crops, including some of
the annual crops like maize, sorghum, sugar, beet, hemp, etc. And then perennial herbaceous
crops like sugarcane, switchgrass, miscanthus and short rotation woody crops, like poplar,
willow, etc. Basically how they can be grown for bioenergy purposes and what is their
potential, the land availability, the energy content, all these things we will discuss.
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So, let us see this particular slide. You can see that biomass have been basically categorized
into two groups; Dedicated energy crops and Residues/Wastes. So, under dedicated energy
crops, we have the fuel wood which is basically hardwood and softwood (different traditional
fuel woods) and then herbaceous. So, there (under herbaceous) we have grain and oil crops,
and perennial grasses.
So, under residue and wastes (this we have discussed in one of our classes, this is a very large
scale quantity) we have agricultural residues, we have municipal discards, we have wood
residues. So a crop & livestock derived (under agricultural residues), wastewater/landfill and
food processing waste (under municipal discards), then urban wood waste (and primary and
secondary milling residues) (under wood residue category). So, we will discuss a few of
these.
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So, coming to the dedicated crops. Dedicated energy crops have been proposed as a strategy
to produce energy without impacting food security or the environment. As I told you in one
of the classes, one of the aims of the biofuel production is to depend on such crops or waste
materials which will not interfere, the food versus feed problem. So, it should be outside of
the food chain. Otherwise in a country like India, having huge population and huge food
demand, we are not supposed to use sugarcane directly, or let us say beet roots (sugar beet),
sorghum, corn for the bio ethanol or biofuel production. We cannot afford to do that, whereas
the same is being done in some of the developed Western countries.
So, they are grown specifically for their utilization in energy conversion processes in ways
that do not displace food production. So, they are beneficial in providing certain ecosystem
services, including carbon sequestration, biodiversity enhancement, salinity mitigation, and
enhancement of soil and water quality. So, they provide a source for the production of
renewable energy, chemicals and materials due to their composition of sugars, lipids, proteins
and fibers.
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So, crop residues and dedicated bioenergy crops together constitute 3 to 9 Exajoule of the
bioenergy potential. In general, energy crops with a larger fraction of fibrous material (the
lignocellulosic part) contain the highest calorific value making it advantageous to maximize
the yield of this plant fraction for the production of energy and fuels.
That is why I already mentioned in our previous lecture, that currently lignocellulosic
biomass are being utilized for the biofuel or bioenergy production, because of the huge
energy content in them. So, fuel wood (dedicated energy crop) produces usable heat for the
residential, commercial and power in the electric utility sector. Not all residues are available
for bioenergy production because they are needed for livestock feed and to maintain soil
fertility. So, everything cannot be converted to biofuels.
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So, they (dedicated crops) are a potentially significant source of low carbon biofuel in India.
And they have low ILUC (which is called indirect land use change, basically related to
unintended consequence of release of carbon) emissions. So, depending on where and how
they are cultivated, energy crops can be grown without creating pressure on the food market.
India supported the deployment of Jatropha, an oilseed crop, capable of being grown on
degraded lands unsuitable for conventional agriculture. The expansion of Jatropha failed to
live up to its potential for a variety of reasons, particularly its low yields.
So, I will show you this Jatropha cycle. You see these are the seeds, then they are being made
to seedlings. Then it is planted that is a (to grow into a) mature plant; then you can see plant
bearing fruits; then fruit getting dried up or ripened, and then you collect the seeds. Now from
the seed we get Jatropha oil, which is being converted to biodiesel. Now please understand
that why the Jatropha failed; it is because of this life cycle.
When you start with this seed and seedling, you plant it and you keep waiting for years
together for the Jatropha to bear fruits and ripen; then you will harvest. This is one of the
things – it is a huge time that you need to spend or you need to wait, before you get these
Jatropha seeds. And then, as I already mentioned in the previous slide, the low oil yield is one
of the major reasons why Jatropha has failed. Now nobody's talking about Jatropha anymore.
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So, the switch grass is another one (which) may offer better potential as they can often
survive under adverse conditions with little labor input and can support biodiversity and soil
carbon sequestration. With India's growing population, all currently utilized agricultural land
will likely need to be maintained or expanded by 2030 to supply sufficient food. That means
in a nutshell, we can understand that, India is no more in a position to provide its prime land
or the agricultural land for such bioenergy dedicated crops.
So, the need is to look for lands which are not cultivable. The reported yields for switch grass
and Eucalyptus, for example, range from 8 to 13 and 14 to 51 dry tonnes, respectively, per
hectare on agricultural land, but only 3 to 9 and 0 to 17 dry tonnes per hectare on marginal
land. Of course, in agricultural land the production will be very high, but the aim is not to use
the agricultural land, because that will be utilized for growing the crops. So, an estimation of
maximum of 39 million tonnes of biomass could be produced from cellulosic energy crops
grown on wastelands in India in 2030. This is a projection.
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So, if you see the biomass energy produced till 2015 percentagewise, you will see that
Finland, followed by Sweden, Austria is there, then Europe then United States. So, in the
Asian countries actually it is very less. From an energy point of view that total biomass in the
world has a potential production capacity of 33,000 Exajoule. However, currently, biomass is
partially exploited, accounting for only 14% of the primary energy in the world, standing at
approximately 56 million Terra joule per year.
Now we will discuss about the annual crops. Energy crops include plants intended for energy
production. One of their main strengths is stable production, which can ensure a large scale
long term raw material supply. In particular, new crops have significantly higher yields per
unit area than conventional ones. Now traditional crops whose final product is used to
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produce energy and biofuels are also considered as energy crops such as wheat, barley,
maize, sugar beet, sunflower, etc.
Let us understand maize. So, maize is a member of the Poaceae family. It is one of the most
popular cultivations around the world, such as in the United States, China, India and Brazil
and these 4 countries produces the largest quantities. Maize is the annual plant, wind
pollinated, both self and cross pollinated. Maize is mainly used for two reasons: (i) for the
starchy raw material content in the seeds and the material from which bio ethanol is mainly
produced; (ii) for the biomass (the crop residues) resulting from the removal of the seeds and
consisting of leaf, stems and cone of the blade.
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Maize stands out among the agricultural species with the potential to supply biomass for
energy production because it has a large acreage of approximately 177 million acres
worldwide and grain production of nearly 989.3 million tons in 2015 and 16. Now the maize
is a kharif crop and is majorly harvested from September to December. The maize Rabi is
majorly harvested in January and May.
So, in India we do twice and in other places also. So, here you can see in the left side is the
crop calendar. This is about India and in which month it is being actually planted and
harvested. So, it gives an idea about that. So, it is sowing, growing and harvesting, three
things, three phases are being shown here.
So, maize production is influenced by nitrogen application (increasing in nitrogen increases

the potential for energy generation) and inter-row spacing (very little influence). So, this
biomass presents an energy potential of 11,050 kilowatt hour per hectare. So, considering the
use of only husks and cobs it is possible to generate 2712 kilowatt hour per hectare
bioenergy. The high calorific value ranges from 15.6 to 18.3 mega joule per kg. Because of
the different energy contents and amounts of biomass produced by distinct parts of the maize
plant its potential to generate energy varies significantly.
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Then corn cobs. So, corn cobs must not be too crumbled, that is, the percentage of particles
smaller than 2 mm must be lower than 5% in which case they would be suitable for
controlled combustion. The length of corncob should be equal to 0.667 times its diameter. It
is advisable to use simple high effective chippers in order to facilitate transport of corncob
from the grinding mill to the warehouse and from the warehouse to the firebox.
You can see here; the general composition of the corn cob given in table 1; starch, cellulose,
proteins, fat and ash. You can see the starch is the highest followed by cellulose. So, this
cellulose can be basically exploited for bioenergy purposes.
Then dry corn cob. So, due to ash melting, the temperatures of ash combustion in the
fireboxes must not exceed 900 degrees centigrade. Insignificant quantity of NO X compounds
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is produced at high temperatures. You can see the proximate and ultimate analysis. So, the
moisture content is around 9.6%, the volatile matter is 80% and remaining is ash 2.16. And in
the element analysis you can see the carbon content is very high; it is almost close to 50%.
Now, the melting temperatures of ash produced from corncob combustion are: during the
early stages of sintering at 760 degrees centigrade, during the early stages of softening at 970
degrees centigrade, during the softening stage of ash at 1100 degrees centigrade, and finally,
during the melting stage of ash at 1325 degrees centigrade. So, these parameters, are very
important when somebody is going to design a particular bioenergy unit or a system or a
process.
Now, let us understand how corn is being converted to ethanol. You can see here. So, the
corn stock gets separated into flower, stem, cob and husk and leaf. All these are having
excellent bioenergy potential as it is. So, we can combine them and see what is their
bioenergy potential (that also can be done). So what you do basically, once you take it out, of
course, remove the corn, all other parts will remain. So, then you go for different
pretreatment technologies to break the recalcitrant nature of the materials. So, you can go for
dilute acid (there are many technologies), dilute acid is very common. And it is less costly,
less time consuming also. So, let us assume that we go for dilute acid pretreatment. Then
once it is done, solid residues are left. So, then you can go for the enzymatic hydrolysis, then
whatever sugar you got, it goes for the fermentation.
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So, (next is) ethanol fermentation and you get that lignocellulosic ethanol or bioethanol.
Here, in a nutshell, you can understand about the schematic of the ethanol production from
the corn stock.
Let us understand about another annual crop which is sweet sorghum. So, sorghum is the
second most important feed grain grown in the United States in terms of planting acreage,
and is also planted in India and countries of Africa. So, it contains two things, both soluble
and insoluble carbohydrate. So, in soluble we have glucose and sucrose and in insoluble we
have cellulose and hemicellulose, in almost the same quantity (soluble and insoluble in
almost same quantity) and is thus considered a good substrate for bioethanol production.
However, currently, there is only one species of sorghum that is called Sorghum bicolour,
that has the potential to mass produce ethanol. Sorghum bicolour, better known as the sweet
sorghum, has three different components which can be used for ethanol production, the grain,
the bagasse and the juice.
Now the juice extracted from plant stalks contains plenty of sugar such as sucrose, glucose
and fructose, which can be directly converted via biological fermentation process into
ethanol.
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So, approximately 50 to 85 tons per hectare of sweet sorghum stalks yields 39.7 to 42.5 ton of
juice per hectare, which upon fermentation yield 3450 to 4132 litres of ethanol per hectare.
Please note that it is a very good yield. And sweet sorghum exhibits several better
characteristics over the other energy crops. For example, drought and salt tolerance, has a
short period of growth (almost within 4 months you can take it out) and requires less water
and fertilizer leading to a low cost of production.
So, these are all very interesting features when we are thinking of growing sweet sorghum
with an aim for bio energy potential or bioenergy purposes. Now the three of the most
important traits of sweet sorghum are high biomass yield, high sugar to ethanol yield and the
ability to grow on marginal land areas. Other important traits of sweet sorghum are high
conversion efficiency of light into biomass energy, high water use efficiency and a relatively
high tolerance to soil constraints, such as salinity and water concentration.
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Sweet sorghum juice is rich in minerals, like calcium, magnesium, zinc, iron etc. After juice
extraction from sweet sorghum stalks, pulp or dry refuse left is the bagasse; and that has also
enormous potential towards bioenergy or biofuel production. So, the proximate and elemental
composition of sweet sorghum bagasse clearly indicates that it has a high carbon to nitrogen
ratio, but low amounts of nutrients.
Now, the ash consists of calcium oxide, magnesium oxide, sodium oxide, potassium oxide,
silicon oxide as well as traces of chlorine. Pretreatment, enzymatic hydrolysis and
fermentation are the essential processes (required for its) processing to ethanol.
So, you can see the composition. Basically, this is the biochemical composition of the
sorghum. You can see 35 to 50% is cellulose, 15 to 25% is hemicellulose and then rest is
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lignin. So, here the ultimate and proximate analysis is given. Fixed carbon is 16.6%, carbon is
35.5%, hydrogen, nitrogen sulfur ash is very less and volatile matter is 65.5% (huge volatile
matter content basically).
So, this scheme will make you understand, how sweet sorghum can be made into various
value added products. So, if you look about the whole plant, and then here is the plant parts;
if you look at the whole plant → make into chips; then you go for combustion, and then you
get ash for fertilizer, then you go for the pyrolysis (another thermochemical conversion
process), silage, ethanol second generation, lignin.
So, you get so many different types of products. It can be converted further into electricity
and fertilizer, some platform chemicals also. Then bagasse, leaves, sugar juice (of course, it
will go to the food and feed purposes), then the seeds will be there (that also goes for food
and feed purposes), other than that parts of juice, leaves will be converted to fertilizer and
transport fuel. So, this will make us understand about the different uses of the sweet sorghum.
And you can see that apart from other uses, it has enormous energy potential or bioenergy
potential.
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So, in India, the major factor which determines sweet sorghum as a feedstock is its likelihood
of cultivation and processing for ethanol during the non-crushing season. The Government of
India has started the Ethanol Blended Petrol Program (EBPP) in 9 states and 4 union
territories in January 2003. Now, this program encourages the blending of gasoline with
ethanol and the utilization of biodiesel obtained from non edible oils for blending with diesel
(5% blending).
Now, however, regardless of efforts, the EBPP has not taken off effectively due to unfeasible
ethanol production from molasses as well as other sources. So, though the government is
mandating that we should have almost 10% ethanol blending, however, it is not happening
due to inadequate supply, because we do not have such plants as it is. And I am happy to tell
you that Numaligarh refinery Ltd. located in Numaligarh, Assam (Indian Oil Corporation), is
basically establishing a state-of-the-art bioethanol plant. So, within 2 years, the production
will start, it is under the process now.
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So, the techno economic feasibility (carried out in India) of ethanol from sweet sorghum is
slightly lower compared to that of ethanol (from sugarcane molasses). So, sweet sorghum is
around 13 rupees, sugar cane molasses is close to 15 rupees. So, the net income from sweet
sorghum is 38% more compared to that of the sugar beets. Now, the global fuel ethanol
production in 2016 is presented in this pie chart. You can see that United States is the huge
amount (has a production of about) 57% and India is contributing only 1%. But please note
that, India is working on this particular crop and soon within three to four years or maybe
down 5 years, we will most likely double our bioethanol capacity or production capacity.
So, now understand about the sugar beet as a bioenergy crop. Now sugar beet is a man made
crop with its origin in the 19th century from table and fodder beets. Sugar beet provides an
abundance of sucrose which is easily fermented by many microbes. The amount of sucrose
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extracted per hectare is dependent on three factors. The weight of the beets harvested, the
percentage sucrose in these beets, and the amount of sucrose that is extractable.
The root of the sugar beet may contain almost 20% sucrose by fresh weight. Pulp or marc
remains after the sucrose and molasses have been extracted from the crop. The pulp
represents the 22 to 28% of the dry mass of the sugar beet root that is not solubilized during
the sugar beet extraction process. However, the amount extracted is less (if you compare that
is almost 15.3% average from the United States crop data) because some cations like sodium
and potassium or some amino nitrogen compounds like betaine and glutamine, interfere with
the extraction of the sucrose. So, thereby making the sucrose extraction a bit complicated.
So, after the sucrose has been extracted, the remaining juice is the molasses. Today, more
than 25% of the world's sugar requirement is made from sugar beet and beet sugar industry is
now well established in 45 countries spread over 4 continents of the world. For farmers, sugar
beet is important for three main reasons. First, it is a dependable cash crop. Second, it
ameliorates salt affected soils with promoting soil fertility through sound farming practices.
And third, the by-products provide nutritious cattle feed during the hot months of the year,
when green fodder is not readily available. So, this is a win, win situation for the farmers
basically. So, among sugar beet and sugar cane sugar beet accounts for only 16 to 20% area
of the world, whereas production accounts for only 11 to 13% of the world. This is a 2014
data.
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You can see this table 4, the chemical composition analysis of the sugar beet pulp. You can
see that the lignocellulosic part, that is basically hemicellulose, cellulose and lignin; they are
the highest. And when you go for sugar analysis you will see that glucose is the highest and
followed by arabinose and xylose and very minor quantity of galactose, mannose and
rhamnose.
So, the obtained values for the degree of methylation and degree of acetylation were 42.5%
and 56% respectively, which are characteristics features of the SBP (that sugar beet pulp).
The density of the sugar beet pulp is 0.596 grams per liter and the pH of 100 grams per liter
water slurry has a value of 5.14.
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So, we can further discuss little about this chemical composition analysis. The first one, table
5, tells you the chemical composition analysis of sugar beet root (dry matter basically). Then
table 6 will give you the same for sugar beet pulp and table 7 will give you that of the sugar
beet molasses. So, you can see the ash, protein, ether extracts, crude fiber and sucrose
content. You can see that the root is having the highest sucrose content, almost close to 70%.
So, sucrose is the main constituent of the sugar beet root dry matter. Protein and lipid
contents of beet pulp products are usually low. In addition, beet protein contains mainly non
essential amino acids. So, then minor carbohydrates are glucose, fructose, raffinose and some
other oligo or polysaccharides, their concentration is below 1% and it depends to a significant
extent on the manufacturing process.
And now let us understand another annual crop which is known as hemp. Hemp is Cannabis
sativa. So, there are many other species also. It is grown for various purposes of using the
fibre and seeds. It is one of the oldest non food crops in the world. Now, it is considered as an
interesting industrial plant with great uses that can be grown under a wide range of agro
ecological conditions and is more efficient compared to many other plants.
Hemp as a species also has one major drawback. It is associated with the production of illegal
drugs. So, that means you can understand that there is a controlled growing basically. So, as a
consequence, only registered hemp cultivators that are reported for the cultivation can be the
source of this valuable raw material.
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So, the main problem may be establishing a crop, because hemp is very sensitive to poor soil
structure and water shortage or excess during the early stages of growth. In terms of its
energy use, it is important that the green crop yield from hemp is on average 14.5 ton per
hectare of which 70 to 75% are hemp shives (the byproduct of the hemp processing), which
are usually left in the field constituting organic fertilizer.
Now at the same time, hemp biomass shows a significant variation in fuel properties
(calorific value, heat of combustion, ash content, ash softening temperature etc.) depending
on the season in which the harvest takes place. The heat of combustion of hemp biomass
collected in August - December is on average 18.4 mega joule per kg versus that collected in
January, April is 19.1 mega joule per kg. You can say that there is no significant or very huge
dip in that, but still there is a difference.
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So, grinding the hemp to a particle diameter of 8 mm requires an energy consumption of 117
kilowatt hour per tonne, which is about 50% smaller than the briquetting capacity of fruit
biomass at 25 kg per hour. However, compaction itself requires an energy demand of about
110 kilowatt hour per tonne, which is almost 40% more energy intensive than that of the fruit
wood.
At the same time problems related to cutting the hemp biomass are the subject of research on
reducing its energy consumption and optimizing the efficiency of this process. Literature
show that hemp has high dry matter content and good energy concentration per hectare.
Moreover, hemp is a good ratio of energy efficiency to input and is therefore an above-
average energy crop.
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So, particularly noteworthy here is the content of volatiles at the level of 69%. Please have a
look at this proximate analysis of hemp biomass, you can see that the highest constituent or
component is basically the volatile matter and if you see the ultimate analysis, the carbon is
43.36% followed by hydrogen and then of course nitrogen and sulfur, sulfur is very small
quantity.
So, you can see that by comparing this data with the possibility of growing hemp in 2019 in
the Lublin province, one can dispose of just over 100,000 tons of biomass which contains (if
you take into account its heat of combustion as per the tabulated) 1.7 PJ of energy which is
equivalent to approximately 85,000 tons of hard coal with the calorific value of 20 mega
joule per kg.
So, having said that the inherent meaning of this table data is saying that hemp is having huge
potential for bioenergy production. So, if you compared to even the hard wood also. So, since
this is outside, it is a non-food crop, and can be grown at marginal lands with little care, then
we can certainly look for such a beautiful crop for a dedicated bioenergy potential or
purposes.
So, you can see this particular slide; it will tell you about the hemp plant basically; these are
the various parts and this particular figure or the scheme will tell you what are the different
usages of hemp plant. So, you can see that there are industrial textiles and consumer textiles
fibers, agricultural benefits are there, then we can make paper, building materials okay THC,
all these things from the leafs and the bast fibers, then the hemp seed oil.
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So, seed is being used for food purposes, seed cake can go for the animal feed, the oil can go
for the personal hygienic products, for industrial products, and even for the foods also. So, it
is so much use.
So, now let us understand another crop which is called a herbaceous crop towards this energy
potential. So, herbaceous crops have the highest ranking for bioenergy production due to their
high biomass yield, high net energy gain and biomass quality that renders them suitable for
both biochemical and thermochemical conversion. Now, please understand one more thing,
among all these, whatever we were discussing, the different biomasses; biomasses are not
suitable for both biochemical and thermochemical conversion.
Some are pretty good for biochemical conversion that means fermentation to get bio alcohols,
ethanol or butanol; and some are pretty good for thermo chemical conversion, for using in
gasification, pyrolysis etc. However, there are only few noteworthy biomasses which can be
used for both the purposes and herbaceous crops are one among them.
Perennial herbaceous crops have a greater biomass production compared to woody crops,
relatively better biomass quality, low lignin content and high digestibility render herbaceous
biomass crops suitable for second generation biofuel production. Some of the native grasses
that are being developed as biomass feedstocks are big bluestem and Indian grass. So, the
first one you can see is big bluestem and the second picture is that of the Indian grass.
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Then let us discuss one of the most important crop in India and apart from India in other
countries also, i.e., sugar cane. Now sugar cane belonging to the family Poaceae is a tropical
perennial grass widely used for the sugar production. Now, the sugars extracted from sugar
cane can be easily fermented to produce ethanol. But having said that, please note that in
India we cannot afford to do that. It can be produced that is true, but, in India we are not
doing that. So, in addition the bagasse (biomass remaining after the juice is extracted from
the stalks) can be further used by sugar mills to generate steam and electricity. In India, what
we are doing is we are doing with the bagasse. Now, this bagasse is being traditionally
utilized to produce steam. And in the boilers (basically we are burning it in the boilers). And
then gasification process to generate steam and of course, feed it to the boiler and you get
electricity also. In small scale also this is being implemented in various sugar producing
industries. So, its high photosynthetic efficiency and tillering and ratooning ability make this
crop extremely attractive to be used as an energy crop. Now being a source of 70% of world's
sugar production, it is very important cash crop for cane growing countries.
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Worldwide it is grown on an area of 26.8 million hectare and its total production is 1.9 billion
tons with a fresh cane yield of 70.9 tons per hectare. Sugarcane is a C4 for plant and as a C4
for plant, sugar cane yields higher biomass than maize, miscanthus and switch grass.
Sugarcane as a feedstock has potential to become a major bioenergy source, as it has highest
yield per unit area among the agricultural commodities, thus offering possibility of excellent
energy balance than other bioenergy options.
Sugarcane and energy cane have good potential for cultivation on non fertile agricultural
lands as well. Please understand, you may be wondering what is energy cane. Energy cane is
nothing but a genetically modified version of the sugarcane and that is modified with an aim
to increase its bioenergy potential.
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So, sugarcane’s fibrous stalks are rich in sucrose, which is accumulated in its internodes.
Sugarcane industry and distilleries extract this sugar and subject it to fermentation to generate
ethanol. Now, cane derived ethanol is being used as a first generation biofuel predominantly
in Brazil where half of the total crop is used to produce ethanol. Now in Brazil, they can
afford to do so but that is not possible in India or other developing countries including most
of the Asia.
So, worldwide sugarcane is source of 21 million m 3 ethanol. And average sugarcane varieties
yield 85 to 100 kg sugar and 35 to 45 kg molasses (that is the byproduct) from 1 ton of cane
biomass, whereas, 22 to 25% ethanol recovery is obtained from molasses through
fermentation. Again, I am telling you that fermentation of molasses to produce bio-ethanol,
we are not going to use the sucrose part to produce bio ethanol.
Though it is being done in Brazil and some of the developed countries, because, for them the
availability is huge with respect to their consumption. But in other countries like India and
Asian countries, that is not possible. So, we look for basically the bagasse and molasses.
So, bagasse the other major byproduct of the sugarcane processing is mainly used as a source
of bioelectricity and also for paper, board and xylitol production purposes. So, xylitol is a
very high demand compound or component you can say. So, it’s a sugar, which is being used
mostly in the chewing gums. So, xylitol will be fermented from xylose, which is one of the
sugars present in the bagasse.
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So, presently, first generation, bioethanol is being produced from sugarcane, which involves
sucrose concentration and extraction from juice, followed by fermentation and distillation.
Now, this ethanol fraction corresponds to only a third of the cane energy and the other plant
residues corresponding to the remaining two thirds. So, by utilizing bagasse, straw, trash and
tops the other portion (that is 66%) of the sugarcane biomass, production of bioenergy from
this group can be enhanced.
Having said that, the meaning is literally that: forget about the sucrose part, that will go
basically for the production of the sugar; rest everything which is amounting to almost 66%,
every part of this, whether it is bagasse, whether it is the top, trash, straw, these all can be
converted into bioenergy or biofuels.
However, recently, focus has also been shifted to “high-fibre/high-biomass” energy cane
varieties for the production of second generation bioethanol. These are genetically modified
sugarcane which is known as energy cane. Now such cultivars are further classified into two
types. So, type one contains sugar greater than 13% and has fiber content of greater than
17%.
Whereas type two energy cane is exclusively developed for higher biomass and contains low
sugar and high fiber. Now, please understand that this energy cane, especially the type two, is
exclusively grown for bioenergy purposes because the sugar content is very less. So, we can
just use that part also as it is, if it is possible, directly to produce ethanol.
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So, energy cane also contains marginally higher lignin than the conventional type. The total
biomass and fiber contents of energy cane are significantly higher, almost 138% and 235%
more than the conventional cultivars. Such cane type easily meets all the requirements of a
renewable biomass resource.
Now, if you look at the typical features of sugarcane biomass, then table 11 will tell you the
chemical composition of the biomass and energy cane. So, you can see that basically the total
fiber content is almost 26.7 in the energy cane, cellulose is 41.6 and 43.3 in both bagasse and
energy cane. So, they are comparatively complementing each other. Lignin by percentage dry
weight is also comparable (20.3 and 21.7). And table 10 will give you the typical features of
the sugarcane biomass, the properties and the yield, the brix, fibre and fertilizer requirement
and NPK basically.
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So, table 12 will tell you about the average sugarcane energy content mostly used in
commercial sugarcane varieties; the juice, then fiber residues, sugar agricultural residue
(which is called a SCAR); and that will tell you about their mass per 1 ton of sugarcane and
the corresponding energy value.
It is very interesting; all these values they are all complementing each other. That means,
whether it is juice, whether it is fiber residue bagasse or it is SCAR, every component is
having huge bioenergy potential. So, you can see that juice is having almost 15.89 mega joule
per kg energy obtained from the sugarcane, from fiber residues it is 15.67, from sugar
agricultural residues that is SCAR, it is 15.6; all are almost complementing each other.
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So, here you can see the sugarcane production in different countries. So, you can see that
India stands here, India produces huge amount of sugarcane (a little lesser than Brazil). And
far more than that of the mainland China and other Asian countries like Thailand and
Pakistan.
So, these are the application of sugarcane biomass. You go for sugar, then filtered mud (that
is organic fertilizer), molasses (that can be converted into ethanol and animal feed), then we
have the juice (that can be converted to biofuels, pharma based products), we have bagasse
(that can be converted to ethanol), we have other renewable energy.
So, let us understand another interesting herbaceous crop, which is called switch grass. Now,
switch grass is a native warm season perennial grass indigenous, to the central and North
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American tall grass prairie into Canada. So, the plant is an immense biomass producer that
can reach heights of 10 feet or more. Its high cellulosic content makes switch grass a
candidate for ethanol production as well as, as a combustion fuel source for power
production. The use of switch grass relative to other annual row crops leads to a 95%
reduction in soil erosion and a 90% reduction in pesticide usage. So, all switch grass contains
a number of different inorganic elements, which are not useful in the conversion of this
bioresource to biofuels. And please also understand that there are different species of this
particular switch grass. There are many different varieties that are grown in India and other
countries also.
So, these elements must be treated as a side stream during the processing and conversion of
biomass to biofuels, and in order to minimize and understand their effect, it is necessary to
determine the amount of these species in the switch grass sample. Now, it can be seen that the
production of fuels from the biomass is dependent on the content and structure of the
structural components in the cell wall, as well as the inorganic constituents.
Yields of switchgrass in a study performed in Iowa state showed that they varied from 6.9 to
13.1 metric tons per hectare, with an average yield of 9 metric tons per hectare. The lowland
varieties are characterized by tall, thick stems and are generally found in heavier soils and
wetter regions.
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The upland cultivars preferred drier soils and grow better in semi-arid regions, they are also
shorter and thin-stemmed. The upland varieties of switch grass include Trailblazer,
Blackwell, Cave in Rock, Pathfinder and Caddo. These are some varieties of switch grasses.
Common low land varieties are Alamo and Kanlow. Now the elemental analysis for
switchgrass cultivars was found to be comparable to that of the hybrid poplar, another
potential biofuel feedstock.
The HHV/ the heating values are comparable to that obtained from the hybrid poplar which is
around 19 mega joules per kg and to other grasses such as the reed canary grass which has
been reported to have a value of 18 mega joules per kg.
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You can see the elemental analysis of different types of switchgrass grown in the Iowa state
in the United States. The elemental composition of biomass is a basic chemical property that
is useful in determining the potential of a given bioresource for biofuels and biopower
application. Elemental analyses for switch grass cultivars were found to be comparable to that
of the hybrid poplar and other potential biofuel feedstock.
So, this is the lignocellulosic composition of switch grass from the Iowa State. So, different
species you can see listed here. So, literature showed that the dried biomass of switch grass
contained 3400 to 4200 milligrams per kg of phosphorous and 8100 to 10900 milligrams per
kg of potassium. In general, the results show that the relative concentration of the elements in
the switch grass samples was Silicon=potassium > phosphate=calcium > chlorine > Sulphur >
Aluminium. So, the results from Kanlow do indicate that there are differences in these
components dependent on plant constituents (basically whether it is leaves, whether it is a
stem, or other parts).
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So, this particular scheme will tell you the residual biomass production for unit fuel in
different countries. So, you can see the United States top among all that followed by the rest
of Asia.
And this is the flow of biofuel production from switch grass. This is interesting, I will just
explain. So, you can see that solar energy being utilized to grow the switchgrass. So, then you
get the feedstock, then it goes for the fodder part or lignocellulosic part you just differentiate
them, then go for acid treatment, you get cellulose and hemicellulose. That is cellulose and
hemicellulose can be sccharified to sugars, hexoses and pentoses, now then can be fermented
to get biofuels. Now you can have simultaneous scarification and fermentation which is
called co-fermentation. So, that also can be possible. This is a biochemical part, now here the
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cellulose, hemicellulosic part including the lignin part can be pyrolyzed which is a
thermochemical conversion part.
Pyrolysis to what; usually highest yield is the bio-oil or you can call it pyrolytic oil and you
get some gases also. Those gases can be converted to methanol and again it can be blended,
then from bio oil we can make diesel and we can get some other co-product. It is very
interesting to note that this bio-oil, basically from pyrolysis what we get, from any
lignocellulosic biomass when you settle it, is easily settle able to 2 different phases.
One phase which is rich in the organic components, and that is the oil part, and the other part
is the aqueous part. Now, that aqueous part also contains very useful chemicals and which, if
they are present in a particular amount or in a good amount, then that can be purified to get
some platform chemicals; some value added products, nothing is waste basically.
So, then let us talk about the short rotation woody crops. The short rotation woody crops are
ideal for woody biomass production and management system because they are renewable
energy feedstocks for biofuels, bioenergy and bioproducts, that can be strategically placed in
the landscape to conserve soil and water, recycle nutrients and sequester carbon. Wood
biomass is a preferred feedstock for the pyrolytic production of bio oils because high lignin,
with its greater energy density is a desired characteristic.
The selection of species and the genetic improvement for use as a feedstock will have to take
different approaches to serve the two biofuel platforms. So, either you can go for the
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biochemical conversion using the sugars or you go for the thermochemical conversion using
the pyrolysis.
So for the biochemical platform for fuel production trees have been seen by some as a less
desirable feedstock because of the high lignin content and recalcitrance to digestion. So,
lignin has less oxygen than carbohydrates (so there is less to remove) and high energy density
meaning more energy content per ton of biomass that is processed. The first one you can see
here on the left hand side the top one is the hybrid poplar plant. And the below one is the P
deltoides. Improved woody biomass production and management systems and needed to
maintain healthy forests and ecosystem, create high paying manufacturing jobs and meet
local and regional energy demands. And these short rotation woody crops fulfill all these
criteria. So, P. deltoides has a very high growth rate (mean annual increment of 20 to 25
metre cube per hectare per year) in India.
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The genus Populus comprises (let us understand about poplar plant) 25 to 35 species of
deciduous plants native to the Northern Hemisphere. Common names used for the different
species include poplar, aspen and cottonwood. Poplar breeding mainly focuses on three
native species: Populus deltoides, Populus balsamifera and Populus trichocarpa; and two
non-native species: Populus maximowiczii and Populus nigra. So, hybrid poplars are among
fast growing trees in North America and are well suited for a variety of applications such as
biofuel production, pulp and paper applications and other bio based products such as
chemicals and adhesives.
The nominal yield of hybrid poplar species in North America is estimated to be 14 Mg per
hectare per year. The heating values for hybrid popular species are 19 megajoules per kg. The
heating values for P. deltoids species are around 16 megajoules per kg. Soil productivity
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requirements may necessitate that this valuable inorganic resource be returned to the soils.
Also, some inorganic elements, such as phosphorus, calcium, magnesium are present. So,
they have their different roles during thermochemical or biochemical conversion.
So, non structural material is often removed from biomass prior to chemical analysis. We
have solvent soluble and non-volatile compounds such as fatty acid, resins, chlorophylls and
usually that comprises a minor proportion of the biomass. For large-scale biorefinery
operation extractives can be a potential source of value added co-products. The compounds
present in the extractive fraction are a function of the solvent, which is usually ethanol,
acetone, dichloromethane or a mixture of ethanol/benzene.
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So, ethanol extractives include waxes and chlorophyll, whereas ethanol/benzene extractives
also include low-molecular-weight carbohydrates. To avoid the use of large amounts of
organic solvents on an industrial scale the extractive fraction can be effectively isolated by
using supercritical carbon dioxide or steam as the solvent. So, the ethanol extractives content
of poplar species is similar to corn stover and pine, but is much lower compared to that of the
switchgrass.
The extractive content of P. deltoides is 1.4% (the extractive content from corn is 3.9% and
switchgrass is 15.5%). So, this is very less in case of P. deltoides.
Interest in the use of willows as a feedstock for bioenergy and bioproduct has developed over
the past few decades because of the multiple environmental and rural development benefits
associated with their production and use. Depending on different estimates between 350 to
500 species of willow, basically the Salix species, are found worldwide and predominate in
the Northern hemisphere.
Although the India Himalayan region is home to 24 willow species only 10 are reported from
the Lahaul valley itself. The yield of dry oven biomass amounted on average 14.1 Mg per
hectare per year and its gain of energy is equal to 242.3 GJ per hectare per year.
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It is relatively fast growth rate and low agro-chemical requirement. It is a commercially
grown crop. You can go for the CHP, that is combined heat and power production. There are
2 potential sources of high value products from the willows. The first is the component
polymers of biomass and second is the extractives in the bark and heartwood. So, a common
misconception about willow biomass is that it makes a poor choice for the production of
different forms of energy because its energy content is lower than other woody biomass and
has higher ash content. While the energy content of willow on a volume basis is lower than
the hardwoods, due to willow’s lower specific gravity however, on the weight basis willow is
almost similar to other hardwoods.
So, the energy content of a three-year-old willow stems averaged almost 19.4 mega joule per
kg. The mean specific gravity of three-year-old stems for a different willow varieties ranges
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from 0.4 to 0.43 gram per cm3. So, this willow biomass crops are grown using coppice
management that utilizes the willows natural ability to resprout. So, this results in biomass
being produced and distributed across several stems.
The number of stems produced and maintained in this production system varies among
varieties and has ranged from 4.6 to 13.7 stems per stool after three years of regrowth
following coppicing. After the first growing season the willow is coppiced and material is
typically left in the field since first year production is very low, typically between 0.4 and 1.0
tons per hector.
So, this you can have a look. The ultimate analysis of the willow biomass; proximate analysis
and the lignocellulosic composition; you can see that the cellulose content is 42%
hemicellulose is 33% and lignin is 25%. That means it can be utilized under various
platforms to produce bioenergy, whether it is thermochemical or biochemical. So, a
significant amount of moisture is present during the time of harvest (50%), which is not good
when you go for a thermochemical conversion process. So, the high heating value of willow
biomass shows that it can be effectively used as an alternate biomass.
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So, you can see this; if you compare it with the usual petro, Naphtha (crude oil basically), the
same sort of things (products) you can get it from the biorefinery way using the willow. So,
in petrochemical way one raw material and you get diverse chemical products, whereas, in a
biorefinery way you have many raw materials and you get many different products. This is
the beauty of the biorefinery concept.
So, this will tell you about the type of solid fuels and their origin. So, from the agricultural
biomass, forest biomass and fossil fuels.
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And moisture content of different biomass varies from agricultural biomass (where it is
highest), followed by the forest and the fossil fuel. So, the moisture content in fuel causes
significant problems during ignition and combustion process. A high amount of generated
heat is lost to heating and evaporation of water which leads to a decrease in the useful energy.
So, before you process for the thermochemical conversion especially, you need to reduce the
moisture content of the biomasses.
So, with this I wind up and in the next lecture we will be discussing about the dedicated oil
crops and their biorefinery potential. Then we will also discuss about the microalgae as
feedstock for biochemicals and biofuel production. So, thank you very much and if you have
any query please feel free to write to me at [email protected], thank you.
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Module 02
Lecture-05
Oil Crops and Microalgae
Good morning students, this is lecture 3 under module 2.

In today's lecture we will discuss about the dedicated oil crops and their biorefinery potential one
by one. And then later we will discuss about microalgae. How micro algae can be used as a
feedstock for biofuels and biochemicals under a bio refinery platform.
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So, interest in the use of biofuels worldwide has grown strongly in recent years due to the limited
oil reserves, concerns about climate change from greenhouse gas emissions and desire to
promote domestic rural economies. The term biofuel is as such referred to solid, liquid or
gaseous fuels that are produced from plant matter and residues, agricultural crops, municipal
wastes and agricultural as well as forestry by-products.
Biodiesel can be derived from a variety of sources, including vegetable oils, animal fats and
waste cooking oil. So, waste cooking oil has been tried for biodiesel production since almost a
decade and it has been quite successful. Vegetable oils, also known as triglycerides, are
chemically an ester in which three fatty acid groups are attached to one glycerol molecule.
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Vegetable oils from renewable oil seeds can be used as alternate to diesel fuels. The advantages
of vegetable oils as diesel fuel are their portability, ready availability, renewability, higher heat
content (almost about 88% of number 2 diesel fuel), lower sulfur content, lower aromatic content
and biodegradability. However, the main disadvantages are the higher viscosity, higher cost,
lower volatility and the reactivity of unsaturated hydrocarbon chains.
The vegetable oils are all extremely viscous, with viscosities ranging almost 10 to 20 times
greater than number 2 diesel fuel. Blending of vegetable oils with diesel, however, reduces the
viscosity drastically. And the fuel handling system of the engine can handle vegetable oil - diesel
blends, without any problem. Initially when the blending was started, it was almost 5%. Then
gradually it can be increased. So, now government is desiring for a 10% blend in number 2 diesel
as well as in our petroleum, gasoline.
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So, over the last 30 years, the oil crop production in the world increased by 240%, while the
increase in area and in the yield was 82% and 48% respectively. The main oilseed produced in
the world is soybean whereby it represents more than 50% of total oil crop production in the
entire world. A 40% increase of growing area and an over 100% increase in total crop yield was
observed from 1989 to 2008.
The expansion was brought about by a 150% increase in oil palm acreage and additional
increases in rapeseed, soybean and sunflower acreages by 75%, 65% and 64% respectively.
Now, these data or statistics basically indicate that, there has been a huge upsurge in the
plantation as well as production of the different vegetable oils; whether it is sunflower, whether it
is soybean, whether it is rapeseed. In India mustard has also taken a significant space.
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Now annual as well as perennial oil crops was grown on a worldwide acreage of over 261
million hectares of agricultural land in total. The overall yield achieved from oil crop production
was about 72 million tons for the 2008 season; due to high difference in oil concentration
between the various crop species this translates into an estimated vegetable oil yield of 157
million tons. So, on the level of plant species, 38% of the total oil crops acreage is planted with
soybean, whereas, cottonseed and oilseed rape are grown on 12% each, followed by groundnuts
and sunflower and later on comes the oil palm (6%).
So, in terms of production, 32% of total crop yield is made up by soybean, whereas, about 28%
is from oil palm which is due to the high annual fruit of that perennial species. In the past,
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vegetable oils and fats were predominantly used for food and livestock feeding purposes,
whereas, nonfood utilization of vegetable oils in oleochemistry applications mainly focused on
particular crop species such as oilseed rape, such as canola, linseed, cotton or castor.
So, you can see these are the four pictures or images of these crops. The first one is the canola,
the second one is the linseed, third one is the cotton and fourth is the Castor. So, this situation is
currently changing due to the growing need of oil as biofuel feedstocks. Between marketing
years of 2005 and 2007, biofuel use of vegetable oils increased from 4.1% to 8.5% (almost
double) and by the year 2017, over 15% of the worldwide vegetable oil production was used as
biofuel feedstock.
So, let us look for the traditional oil crops. Most of the biodiesel is currently made from soybean,
rapeseed, sunflower and palm oils. Now having said that, kindly note that in India we are not
doing so. As I told you in the last class that whether it is in India or developing countries, when
we talk about vegetable oil to biodiesel, it comes directly under the food versus feed problem, so
we are not doing so. But having said that you have to understand that these are being done in
some of the countries in which the production is huge. And they have a huge problem of storing
the oils. So, new plant oils that are under consideration include mustard seed, peanut, sunflower
and cottonseed. Soybean oil is commonly used in the United States and rapeseed oil is used in
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many European countries for biodiesel production, whereas coconut oil and palm oils are used in
Malaysia and Indonesia for biodiesel production.
So, it is all about the supply and the production; basically, how much we are producing and how
much we are consuming. If the production of any such crops is much higher than the requirement
of a particular country, then, they can think of converting those to biofuels otherwise it is not
possible.
So, about 80% of the European Union's total biofuel production is comprised of biodiesel
produced from rapeseed and sunflower seeds (because they can afford to do that). So, soybean
oil accounts for approximately 90% of the biodiesel produced in the United States, rapeseed oil
has a 59% of total global biodiesel raw material sources followed by soybean, palm oil,
sunflower and others.
Now another thing I want you to know, that whenever we are directly showing this type of
statistics 59% of these or 28% of that, please understand that it is not only the oil that is getting
produced from that particular species but also its waste. So, let us say bagasse, the stalk, the
kernels, the husk etc. So, those are also being added to that particular statistics to produce
different types of biofuels not only biodiesel but also bio alcohols.
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So, this table will make you understand different fuel related properties of the selected vegetable
oils. So, you can see that, the first one is the different types of oil, A. indica is Azadirachta
indica, that is neem’s oil, then Jatropha, then Mahua that is Madhuca indica, then Pongamia
pinnata that is karanja and then there are other seeds. So, you can see that iodine values are very
good. However, you can (also) see that the viscosity of these oils are very high.
Especially the R. communis is extremely high, thereby, making its direct use in an engine more
difficult. And you can see there are other properties like cetane number, cloud point, pour point,
flash point all these details.
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So, the major obstacle for commercialization of biodiesel is it is cost as approximately 70% to
90% of the biodiesel production cost arises from the cost of the raw materials. Therefore,
biodiesel produced from edible vegetable oils is currently not economically feasible. Now that is
what I was just mentioning to you about, that whether it is a developing countries or developed
countries let us tell it in a sustainable way.
So, in a sustainable way producing this is not so feasible. Let us understand that in a particular
year, sunflower has been produced so large in quantities, that storing is a big problem. Now
please understand, that may not happen in the next year or next to next year. Because most of the
countries are still depending upon the season or the climate for the agricultural purposes whether
it is in India, or it is any developing countries.
And there are other factors which also govern the yield and the mass production of the crops. So,
in a sustainable way, it is very difficult to do that; whether it is in developing countries or
developed countries. So, now later has moved from the edible to non edible oil seeds. So, non
edible oil plants are easily available in all the countries and are very economical compared to the
edible plant oils.
Now the biggest thing about this non edible oil plants is that this do not come under the food
versus feed problem. And then extensive use of edible oils may cause other significant problems
such as starvation in developing countries (this is what I was mentioning). There are concerns
that biodiesel feedstock may compete with food supply in the long term. So, the sustainability
always comes into picture and economics also has to be taken care of. So, biodiesel produced
from non edible vegetable oil has a good potential as an alternative diesel fuel.
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The use of non-edible plant oils when compared with edible plant oils is very significant because
of the tremendous demand for the edible oils for food and they are far too expensive to be used
as fuel at present. Now non edible oil plants can be grown in waste lands (that is another biggest
advantage) that are not suitable for food crops and the cost of cultivation is also much lower
because these plants can still sustain reasonably high yield without intensive care. So, there are
many examples of non-edible oilseed crops such as Jatropha, Mahua, karanja, castor, neem,
rubber seed, tobacco seed, rice bran etc.
So, now we will see one by one, what are their properties and how they can contribute to this
biodiesel production. So, the first one Jatropha curcas; we have discussed about Jatropha, I
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showed you the Jatropha lifecycle in last class. So, it is a tall bush or small tree up to 5 to 7 meter
tall, belonging to the Euphorbiaceae family. Originally from Central America, Jatropha curcas
is found throughout the tropics including much of African and Asia.
So, a research study showed that one hectare of Jatropha curcas could capture up to 25 tons of
carbon dioxide from the atmosphere every year (that is a significant number of course). So,
Jatropha curcas seeds have an oil content ranging between 30% and 40%. Jatropha curcas oil
contains approximately 24.6% of crude protein, 47.25% of crude fat and 5.54% of moisture
content.
So, most of the non edible oils including Jatropha carry a high level of the free fatty acids. The
oil fraction of Jatropha consists of both saturated and unsaturated fatty acids.
So, the next one is Pongamia pinnata, which is commonly known as karanja. It is a medium
sized glabrous, perennial tree that grows in the littoral regions of South Eastern Asia and
Australia. India is full of these plants; you can see in many places. The yield of oil seed per tree
is between 8 and 24 kg.
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And the seeds of Pongamia pinnata content about 30 to 40% of oil. The oil is considered to be
less toxic and cheaper than Jatropha curcas oil, so it has become the subject of biodiesel
research.
Most of the physical and chemical properties of the Pongamia pinnata oil as similar to those of
the diesel fuel, however, this oil is more viscous and produce higher carbon residue. So,
Pongamia pinnata oil contents oleic acid (51.8%) as the major fatty acid followed by linoleic,
palmitic and stearic acid.
So, the next is also very famous tree in India which is called Madhuca indica. It is commonly
known as Mahua or butternut tree. It is a middle sized large deciduous tree which grows to a
height of 10 to 15 meter. The tree starts producing seeds after 10 years and continues for up to 60
years. An average yield of 800 kg per hectare can be expected in a mahua plantation after a
decade. So, each tree yields about 20 to 40 kg of seeds per year, mahua seed contains 35% of oil
and 16% of protein.
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Fresh Mahua oil from properly stored seeds is yellow, while commercial oils are generally
greenish yellow with an offensive odour and disagreeable taste. Mahua oil contains the high
level of free fatty acids (almost up to 20%) and a proper procedure for converting this oil to
biodiesel is very much required.
The next is Ricinus communis, which is popularly known as castor oil plant and belongs to the
family Euphorbiaceae. It originates in Africa but it is found in both wild and cultivated states in
all the tropical and subtropical countries of the world. In India also we have huge castor oil
plantation. It is a small wooden tree that can reach a height of about 6 meters. The comparitive
advantage of this plant is that, its growing period is much shorter than that of the Jatropha and
pongamia.
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So, Castor seed is an ideal candidate for production of high value industrial oil feedstocks
because of the very high oil content (almost 48 to 60% of the seed) depending upon the species,
and the extremely high levels of potential oil production (500 to 1000 liters of oil per acre) which
is a very good yield. So, the main constituent of castor oil is ricinoleic acid (which is 90%),
which contains 18 carbon atoms with a hydroxyl group position at 12.
Castor oil contains more oxygen than other oils and therefore castor oil and it is derivatives are
more soluble in alcohols during the transesterification reaction, thereby yielding a higher
biodiesel, after the reaction. So, the main disadvantage of castor oil is it is high viscosity, the
high viscosity of this oil leads to its poor atomization of the fuel, incomplete combustion,
choking of the fuel injectors and ring carbonization.
So, in India we have huge plantations of all such things, whether it is Castor, whether it is
Jatropha, whether it is Mahua. You will see Mahua and Castor especially in the eastern side of
the country. So, huge plantation is there in Odisha, Jharkhand, Bengal and Bihar. Jatropha was
planted in huge quantities. But as I told you in the last class, its sustainability has become a big
problem. Therefore, most of the Jatropha plantation has been discontinued.
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So, next is Azadirachta indica which is the neem tree. It is a member of the family Meliaceae. It
is a majestic, evergreen, tropical forest tree with a broad crown and a height of approximately 25
meters. So, it is a well established plant in at least 30 countries worldwide in Asia, Africa and
Central and South America. India is full of these trees, anywhere you go; and due to it is
environmental benefits such as purifying oxygen/air, it has been deliberately planted in the
roadsides.
So, neem seeds contain about 45% of the brownish yellow fixed soil, mainly constituted by the
oleic acid, palmitic acid and stearic acid followed by linoleic acid. Traditionally, neem oil has
been used as a fuel in lamps for lighting purposes in rural areas. And it is used on an industrial
scale for manufacturing of soaps, cosmetics, pharmaceuticals and some non edible products. And
one more important thing is that neem oil also has certain medicinal properties.
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So, next is Hevea brasiliensis, commonly known as the rubber tree. It is a fast growing tree that
belongs to the family Euphorbiaceae. It is the major source of natural rubber and is native to the
Amazon forests and is now widely cultivated in tropics across the world. In India also we have
huge rubber plantation in states like Kerala, Karnataka and many southern states.
So, normal seed production yields vary from 70 to 500 kg per hectare per year, while the annual
seed production potential in India is about 150 kg per hectare. Rubber seed contain
approximately about 40% of kernel with 20% to 25% of moisture. Apart from it is use in latex
production for foreign exchange, rubber tree produces oil bearing seed whose oil content in dried
kernel varies from 35% to 45%. Now rubber oil does not contain any unusual fatty acids and its
rich source of essential fatty acids, C18:2 and C18:3, that makes up almost 52% of it is total free
fatty acid composition.
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So, the next is Nicotiana tabacum, so it is the tobacco plant. It is an annually grown herbaceous
plant belonging to the Solanaceae family, widespread in North and South America commonly
grown for the collection of the leaves. So, the highest seed production is found in Nicotiana
tabacum varieties used to obtain the chewing tobacco, reaching 1171 kg seeds per hectare, which
corresponds to 432.9 kg oil per hectare. Now the seed oil content ranges between 33 and 40 wt%.
The major fatty acids in seed triacylglycerols are linoleic acid, followed by oleic acid, palmitic
acid and stearic acid.
The next is rice bran. Rice is the main cultivation in subtropical Southern Asia, and it is a staple
food for a large part of the world's human population especially in East, South and South Eastern
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Asia, making it the most consumed cereal grain. Rice bran is the low value co product of rice
milling which contains approximately 15 to 23% of oil. The oil fraction of rice bran consists of
both saturated and unsaturated fatty acids, cultivated in countries like China and India.
Very little research has been done to utilize this oil as a replacement for the mineral diesel. I used
to tell you that the CSIR Institute of Chemical Technology or CSIR IICT, Hyderabad. So, they
have developed an excellent process for converting this rice bran to the vegetable oil for the
human consumption. And it is in the market and has been consumed by a big number of people
in India as well as in the world.
So, the next is Moringa oleifera which is also called as drumstick tree. So, its fruit has been
consumed in India in huge quantities in South India as well as East and West India. So, Moringa
is most commonly cultivated in South India, Ethiopia, Philippines, Sudan and has been grown in
West, East and South Africa, tropical Asia, Latin America, Caribbean, Florida and Pacific
Islands.
So, Moringa seed has an oil content of between 30% to 40% depending upon the plant variety
and climate. Moringa oil contains oleic acid as the major fatty acid followed by stearic acid,
behenic acid, arachidic acid, palmitic acid, linoleic and eicosenoic acid.
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The next is Calophyllum inophyllum. It is commonly known as polanga or hone; it is a large
evergreen tree and belongs to the Clusiaceae family, widespread in East Africa, India, Southeast
Asia and Australia. So, it is a medium and large sized evergreen sub maritime tree that averages
8 to 20 meter in height, with a broad spreading crown of irregular branches. The nut kernel
contains 50% to 70% of oil and the mature tree may produce 1 to 10 kg of oil per year depending
upon the productivity of the tree as well as the efficiency of the extraction process.
Traditionally, polanga oil has been used in medicinal applications, soap, lamp oil, hair grease and
cosmetics in different parts of the world.
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Then Simmondsia chinensis; so this is commonly known as jojoba. It is a perennial shrub
belonging to the familiar Simmondsiaceae. This plant is native to Mojave and Sonoran deserts of
Mexico, California and Arizona. A 10-year-old tree yields on an average of 1 kg seeds per year.
It is unique among plants in the fact that it is seeds content about 50% of oil by weight, which is
more than the amount in soybean and somewhat more than in most of the oil seed crops.
Jojoba oil is practically colorless and odorless and it is composed mainly of straight chain
monoesters of C20 and C22 acids and alcohols with two double bonds.
The next is Sapindus mukorossi; so Sapindus mukorossi is a well known as soap nut tree. It is a
perennial tree belonging to the family Sapindaceae, indigenious to northern India. Now this plant
grows very well in deep loamy soils and leached soils. So, cultivation of Sapindus mukorossi in
such soil avoids potential soil erosion; it has been deliberately planted in most of the places to
restrict the soil erosion.
This tree can be used for rural building construction, oil and sugar presses, agricultural
implements. Sapindus mukorossi seed contains about 23% of oil out of which 92% is
triglycerides.
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Then Melia azedarach; so Melia azedarach which is also known as syringa, is a deciduous tree
that grows between 7 to 12 meter in height in the mahogany family of Meliaceae that is native to
India, Southeast Asia and Australia. The oil content of dried syringa berries is around 10 wt%.
Melia azedarach oil is characterized by a high percentage of unsaturated fatty acids, such as
oleic and linoleic acids. Other constituents that are present in greater than 1% are saturated
species such as palmitic and stearic acid.
Vernicia fordii, it is commonly known as tung tree, is an oil bearing woody plant belonging to
Euphorbecaeae family that is native to China, Burma and Vietnam. The oil content of tung seeds
and the whole nuts is approximately 21 and 41 wt% respectively and the average oil yield is
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about 450 to 600 kg per hectare. It is a good oil yield basically from this species. Its seed oil had
been conventionally used in lamps for lighting, as well as an ingredient for wood paints and
varnish. Tung oil principally contains unusual conjugated fatty acids, eleostearic acid,
octadecatrienoic acid; with linoleic, oleic, behenic acids also present in significant quantities.
Then Schleichera oleosa, it is also known as kusum. So, it is a medium sized up to almost 40
meter in height, deciduous or nearly evergreen tree belonging to the Sapindaceae family that is
native to South and South-East Asia. So, the fruits, seeds and young leaves of this plant are
edible and used for medicinal and dye purposes. The oil content of kusum seeds is 51% to 62%
but the yields are 25% to 27% in village ghanis (the oil mills) and about 36% in the expellers.
So, of course when you do a better processing or extraction technology, the yield of oil that will
come from the same seed will be much higher. Iodine value of the oil is almost 215 to 220 and it
is total fatty acid content is 91.6%.
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So, this table will make you understand the oil content in seeds and kernels of some of the non-
edible plants. So, you can see the listed neem, polanga, rubber, mahua, syringa, drumstick,
tobacco, karanja, castor, soap nut, jojoba. All those what we have actually discussed, you can
see, in most of trees (these are plants and some are shrubs), you can see this wt% seed and wt%
kernels. Let us focus on the seed only. You see that mostly they are comparative or
complementing each other (almost 20 to 30 to 40% in that range), which emphasizes that most of
these seeds can produce a huge amount of oil. And again I am telling you that extraction of oil is
a tedious job. If you are going for the traditional extraction then you may end up in getting
almost 60 to 70% or even less than that.
When you talk about chemical based or some other supercritical based extraction, then you may
go up to 80% yield. Depending upon seed, oil and in which type of soil it has been grown and
under what climatic conditions it has been grown; so many things actually affect the final yield
of the oil.
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So, this table will again make you understand the yields of various non edible feedstocks. It is
given in kg per hectare. You can see that polanga, followed by drumstick, then jatropha and
neem, so these are high yield varieties.
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Now we will discuss about microalgae. So microalgae as a feedstock for biofuels production, not
only biodiesel but how we can use microalgae in a bio refinery concept, to produce various other
biofuels apart from biodiesel as well as other platform chemicals.
Although oil crops are renewable resources, biodiesel production from oil crops in large
quantities has been deemed unsustainable. Production of crop derived biodiesel will require large
amount of arable land, which has to compete with the cultivation of food crops. Now this has led
to the controversy of “food versus fuel”. The increasing criticism of the sustainability of many
first generation biofuels has stimulated the interest in developing second generation biofuels
which are being produced from non-food feedstocks such as lignocellulosic biomass.
Now microalgae as a feedstock for biofuels has received considerable attention due to their
advantages over higher plants and other organisms. Although long term research and
development in this field have been carried out, commercial implementation of microalgal
biodiesel is still in it is infancy (there are various reasons for that). Many key technologies need
to be developed and optimized at almost all stages of microalgal biodiesel pipeline, from
screening of suitable microbial strains to downstream processing.
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So, microalgae appear to be the only promising alternative to biofuel crop plants because of the
following facts:
(a) it grows rapidly and many species contain high amounts of lipids (basically the oils) which
can provide sufficient feedstock for large scale biodiesel production;
(b) Non-requirement of arable land for microalgal culture makes their growth without conflict
with the food production.
 According to an estimate, meeting only half of the existing U.S transport fuel needs by
biodiesel would require 24% of the total cropland to grow oil palm with the highest oil
productivity. (So, you can see these are some of the algal blooms or green algal blooms).
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(A brown algal bloom is being shown here)
 On the other hand, only 2.5% of existing cropping area would be required for cultivation
of microalgae with 30% oil in biomass, which can also produce equivalent biodiesel.
 The percentage of cropping area required can still be lower, because 30% oil content in
the biomass can be achieved easily for many oleaginous microalgae.
(c) The next advantage is that, microalgal cells have photosynthetic mechanism similar to those
of higher plants to fix carbon dioxide in air and convert the carbon to carbohydrates and lipids,
with some species accumulating large amounts of triacylglycerides (TAGs - these are also
triglycerides), which are suitable for biodiesel production.
 The photosynthetic mechanism of microalgae is cost effective compared with oil
producing heterotrophic microorganisms that utilize glucose and other organic carbon
sources.
(d) So, the next advantage is that microalgae can remove large amounts of carbon dioxide
emitted by power plants and other industrial sources contributing significantly to the greenhouse
gas mitigation.
(e) From an environmental standpoint, some microalgae can efficiently treat highly polluted
municipal and agricultural wastewater that contain excess nitrogen and phosphorus nutrients.
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(f) As an attractive bioreactor system, microalgae can produce useful byproducts including long-
chain polyunsaturated fatty acids, carotenoids for foodstuffs, and other compounds used in the
cosmetic and pharmaceutical industries.
 Integrated utilization of these byproducts will make an important contribution to the
reduction of overall production costs. Now this is what I will just explain you briefly.
Now please note that, microalgae is something, each and every part of that particular
organism is being useful, it is just like a banana plant. So, the fruits we eat, the flowers
are also being eaten in India and many parts of the South East Asia. The leaves are being
used traditionally for various purposes, the trunk is also eatable. So, it is an endless thing.
Similarly, for algae also every part is being utilized. What we are talking about in these
particular slides, is about the biodiesel from microalgae; but, it is not the end of the story.
See, once you extract the biodiesel, that means the oil is extracted or lipid is extracted and
there is something left out solid, which is called lipid extracted biomass, microalgal
biomass. This will have so many other valuable things present such as a huge amount of
carbohydrates. It may have pigments, it may have other important valuable products,
such as astaxanthin, vitamins so on. So, what I mean to say is that once you extract the
lipid from the microalgae, it is not the end of the story. So, then we are going to work on
the leftover part, the solid part. So, depending upon its component analysis we can
convert it; if there is huge carbohydrate, we can go for hydrolysis followed by
fermentation thereby producing bio alcohol. We can also produce bio butanol, following
the Abe fermentation. If we see that, it has good chlorophyll content, we can extract that
chlorophyll; if it has good astaxanthin content or some different pigments, that can also
be extracted. So, vitamins also can be extracted, so we can play with it depending upon
what species it is and what is that component analysis after the oil is being extracted. So,
if we look into that perspective, in a complete biorefinery perspective, then it will become
sustainable. Otherwise, if you only talk about microalgae to biodiesel, it is not going to be
a sustainable process.
 Microalgae also produce other fuels such as alkanes, ethanol, butanol and hydrogen in a
more bio refinery platform.
(g) The use of biodiesel from microalgae results in minimal release of sulfur dioxide, nitrous
oxide and other contaminants when compared to petroleum derived diesel.
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Now let us understand the biodiversity of microalgal lipid properties. Please look at this
particular slide; you can see there are so many different types of species that has been shown
here. The picture has been taken from the European algae biomass association, you can see the
different types of algae, please do understand that algae is only green, it is not so. There are blue
green algae, there is brown algae (it is just like a plant).
So, you do not usually understand if you see with the naked eye that it is an algae. So, it is very
diverse basically. Microalgae comprise several groups of unicellular, colonial or filamentous,
photosynthetic and heterotrophic microorganisms containing chlorophyll and other pigments. So,
microalgae can grow autotrophically or heterotopically with a wide range of tolerance to
different temperature, salinity, pH and nutrient availabilities.
More than 40,000 microalgal species have been classified as prokaryotes (cyanobacteria) and
several eukaryotes including green algae, diatoms, yellow green algae, golden algae, red algae,
brown algae, dinoflagellates and others.
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Many different classes of lipids can be produced in microalgal cells. Based on chemical
structures and polarity, these lipids are divided into polar and neutral liquids. In most cases, polar
lipids function as a membrane structure component, which commonly include phospholipids and
glycolipids. So, neutral lipids include tri, di and mono acyl glycerols, waxes, isoprenoid type
lipids (for example, carotenoids), among which triacylglycerols (TAGs) are frequently found to
be accumulated as energy storage under various stress condition. These TAGs will be eventually
converted to biodiesel by the transesterification pathway.
So, although almost all types of microalgal lipids can be extracted, only TAGs are easily
transesterified into biodiesel by traditional methods. Analysis of thousands of microalgal species
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have shown tremendous difference in lipid content among different strains ranging from 1%
approximately to 85% of that dry cell weight. Microalgae produce a wide variety of fatty acids
with chain length from C10 to C24 depending on species or strains.
For example, the filamentous cyanobacterium, that is the Trichodesmium erythraeum can
synthesize C10 fatty acid accounting for almost 50% of total fatty acids. Whereas dinoflagellate
Crypthecodinium cohnii can produce docosahexaenoic acid (DHA) as high as 30 to 50% of the
total fatty acids. Moreover, for any one microalgal strain the lipid content, lipid class and fatty
acid composition fluctuate under different culture conditions.
Screening of oleaginous microalgae; due to the variation and diversity of microalgal lipids,
selection of oleaginous microalgal strains suitable for biodiesel production will require screening
large number of microalgal strains. The first large scale collection and screening of oleaginous
algae dates back to 1978, when the Aquatic Species Program was launched by the U.S National
Renewable Energy Laboratory for production of biodiesel from high lipid content algae.
With 8 years of effort about 3000 strains were collected and eventually around 300 species were
identified as oil rich algae. The main indexes determining the potential of microalgal strains as
biodiesel feedstock are growth rate, lipid content and lipid productivity.
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This table will make you understand about different microalgal species with relatively high lipid
content and productivity. So, you see that these are some of the microalgal species, here the lipid
content is given and that is the lipid productivity. You can see mostly they are complementing to
each other whereas this Pavlova lutheri giving us the highest in this particular species that is
being reported here, so followed by Neochloris sp. as well as Nannochloropsis oculata.
Both microalgae and cyanobacteria are considered as potential source of high value nutrients,
such as pigments, proteins, carbohydrate and lipid molecules. And this is what I was mentioning
about in the broad bio-refinery concept. It is not only about the lipid molecules that is being
getting extracted for biodiesel but we can play with all these things pigments, proteins,
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carbohydrates, there are vitamins and there are certain other chemicals which also can be
purified and made into the platform chemicals.
So, industrial scale production of microalgae has evolved worldwide due to human consumption
of microalgae as nutritional supplements. Apart from biomass, microalgae produce variety of
pigment molecules like chlorophyll, carotenoids, beta carotene, that are used as colorants in
cosmetic and food industry. Algae strains Chlorella sp., Dunaliella sp., Scenedesmus sp. and
cyanobacterial strains such as Spirulina sp. and Nostoc sp. are used as sources of fine chemicals
and nutrient rich foods supplements.
Further pigments; pigments are interesting class of chemicals, which can be purified from the
microalgal species. So, they are used in cosmetic industry as anti-ageing cream, refreshing or
regenerating care products for healing and repairing of damaged skin with nourishments. The
microalgae Haematococcus pluvialis (which is shown in this particular slide you can see), is
known as the natural source for the keto-carotenoid astaxanthin. Astaxanthin is one such pigment
which is of course having a lot of commercial value. Red pigment astaxanthin is the precursor
molecule for vitamin A and this pigment play important role in embryo development and cell
production in poultry as well as aquaculture firms. Moreover, astaxanthin has superior
antioxidant properties compared to those of beta carotene, alpha carotene, lutein, lycopene,
canthaxanthin and vitamin E, and therefore is becoming as popular as a human dietary
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supplement. That is what I was just mentioning about; that there is a huge commercial value of
this particular pigment.
Consequently, a number of industries such as Cyanotech, Seambiotic, Mera Pharmaceuticals and

Fuji chemical, are the producers of microalgae biomass for high value added products in
cosmetics, nutritious feed and pharmaceuticals. Selection of suitable process for pigment
extraction from the microalgae depend on several factors like biochemical features of pigments,
choice of solvents for extraction, extraction yield, duration of extraction, reproducibility,
denaturation and degradation of molecules, cost and easy operation. Now all these factors will
eventually determine how much pigments we are able to extract from a particular microalgal
species.
So, a number of processes like ultra high pressure extraction, use of supercritical carbon dioxide
for extraction, combination of techniques such as soaking in liquid nitrogen followed by buffer
extraction are currently being exploited and under research for further development to establish
energy efficient, low cost extraction technique for the pigments.
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So, microalgae are also considered as reliable rich source of the vegetable protein. Nutritional
studies on different microalgae has demonstrated that microalgae produced high amount and
high quality proteins which are the source of essential amino acids. You can see there is a
particular picture there, that picture is of the red algae Rhodophyta. These Rhodophyta and other
cyanobacterial strains produce a group of accessory photosynthetic pigment protein complexes,
for light harvesting purpose are also called phyco-billiproteins, these are high value products.
So, these proteins have a high demand in pharmaceutical industries and specific application in
the biological field as fluorophores. So, fluorophore are chemical compounds, which are
essentially responsible for emitting light. So, protein extraction from microalgae is done using
aqueous, acidic and alkaline methods followed by centrifugation, ultrafiltration, precipitation,
chromatography techniques for the recovery of the protein molecules.
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So, industrial scale extraction and purification of proteins from microalgae is not studied widely
and scalable downstream processes of microalgae for efficient extraction of proteins are still in
very high demand. So, diversity in microalgal species, variation in the cell structure, variation in
the intracellular protein content, release of protein degrading enzymes (proteases) from the cells
are major obstructions for up-scaling of the protein extraction process.
Some novel extraction techniques such as pulsed electric field, microwave assisted extraction
and ultrasound assisted extraction are employed for successful extraction of proteins from
microalgae. So, please note that the downstream processing cost usually constitute almost 40 to
50% of the entire product cost. So, that particular cost has to be brought down to a certain level,
so that the cost of the product eventually decreases.
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So, manipulation in growth conditions can enrich microalgae with high amount of carbohydrate
or polysaccharide molecules. Major components of the cell wall of algae are cellulose and
hemicellulose. Other than the cell wall algae also store polysaccharide molecules in the
cytoplasm. Marine algae produce complex sulfated cell wall polysaccharides, which have many
biomedical applications.
Some cyanobacterial strains (you see some of these are shown in this slide), are surrounded by a
matrix of polymeric substance mainly constituted by polysaccharides, which form a protective
layer between the cell and the intermediate environment.
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Biotechnological potential of the cyanobacterial extracellular polymeric matrix are attracting
increasing attention to the pharmaceutical, bio-plastic as well as food industries. Novel extraction
technologies such as enzyme assisted extraction, microwave assisted extraction, ultrasound
assisted extraction, supercritical fluid extraction and pressurized liquid extraction are currently
being applied for the extraction of bioactive molecules from microalgae.
These extraction technologies are attracting interest from the industries because of it is
advantages (such as higher yield, reduced treatment time and lower cost) compare to that of the
conventional solvent extraction techniques. A huge scope is still available for developing the
downstream processing part.
So, we will quickly go through some of the industrial products from microalgae, please see this
pigment. The product name is beta carotene, chlorophyll (chlorophyll is from green algae); this is
the structure, it is being used in the food industries, it is a natural pigment ingredient. Similarly,
beta carotene from Spirulina and, Caulerpa species; that is the structure of beta carotene and it is
found to be useful in the prevention against certain type of cancer and heart diseases.
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The next is protein; so protein powder or tablets is the form. There are different species such as
Chlorella and other cyanobacteria species such as Anthrospira. And this is the Spirulina powder
how it looks likes, this is a SEM image. It has so much of nutritional benefits, used as a
feedstock for animal and poultry. Then carbohydrate; the product name is agar, so Rhodophyta
and red algae and there are many other species.
This is how it almost consist of 70% of agarose and 30% of the agaropectin, so this is the
structure of agaropectin and agarose. So, best known application of agar is the preparation of
culture media and in petri dishes, huge application in the research lab for the growth of the
microorganisms.
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The next is carbohydrate again, Carrageenan, Fucoidan. So Carageenan can comes from the red
seaweeds. Now these are the structures, it is common food additives due to their thickening,
gelling and emulsion stabilizing properties. Fucoidan, this is the structure; it exhibits
anticoagulant abilities by enhancing the heparin cofactor II. So, they may become an alternative
to heparin due to their herbal origin.
So, the next is Alginate, carbohydrate in the form of Alginate. Different species such as
Macrocystis pyrifera, Ascophyllum nodosum, these are the structures. Alginate is a linear
polysaccharide consisting of two types of monomers. It is widely applied as a stabilizing,
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thickening or emulsifying agent in the food, cosmetic, paper and dye industries, it has so much of
medicinal applications also.
And the last one is the organic plastic, in the form of biopolymers (PLA or poly lactic acid, bio
polyethylene etc.). So, Nostoc sp., Phormidium mucicola, then Chlorella stigmaaphora and then
Chlorella vulgaris. Chlorella vulgaris is a well-known species. This is the structure, it is a
monomer and the repeating unit. So thickening agents for mobility control in water flood oil
recovery, food additive, flocculants useful in the wastewater treatment, soil conditioning, drilling
mud extenders, pet food and farm feed stabilizers. So, this is all about microalgae and I windup
today’s lecture.
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So, in the next lecture we will discuss about how to enhance the biomass properties for biofuels
and what are the challenges in conversion. So, thank you very much for listening; if you have
any query please feel free to drop mail to me at [email protected] also post your query in the
Swayam portal, thank you.
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Module 02
Lecture-06
Enhancing Biomass Properties
Good morning students, this is lecture 4 of module 2.

In today's lecture, we will be discussing about the biomass properties, how we can enhance some of these
properties and what are the challenges in conversion of the biomass into biofuels?
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So, let us begin by discussing about physical properties of biomasses. So, some of the physical properties
of biomass affect it is pyrolysis and gasification behavior (basically the thermochemical conversion). For
example, permeability is an important factor in pyrolysis. High permeability will allow the pyrolysis
gases to be trapped in the pores, increasing their residence time in the reaction zone.
Thus, it increases the potential for secondary cracking to produce char. The pores in wood are generally
oriented longitudinally. As a result, the thermal conductivity and diffusivity in the longitudinal direction
are different from those in the lateral direction. This anisotropic behavior of wood can affect its
thermochemical conversion. A densification process such as torrefaction can reduce the anisotropic
behavior and therefore change the permeability of biomass. Hence permeability is an important property
with respect to the pyrolysis.
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Density is an important design parameter for any biomass conversion system. For a granular biomass we
can define four characteristic densities: true density, apparent density, bulk density and biomass (growth)
density. Now true density is the weight per unit volume occupied by the solid constituent of biomass. So,
it is given by total mass of biomass divided by solid volume in biomass.
The cell walls constitute the major solid content of a biomass. For common wood the density of the cell
wall is typically 1530 kg per meter cube and it is constant for most of the wood cells. The measurement of
true density of a biomass is as difficult as the measurement of a true solid volume. So, it can either be
measured with a pycnometer or maybe estimated using ultimate analysis and true density of the
constituent elements.
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Next is apparent density; so it is based on the apparent or external volume of the biomass. This includes
its pore volume or you can say the volume of all the cell cavities. For a regular shaped biomass,
mechanical means such as micrometers can be used to measure different sides of a particle to obtain its
apparent volume. An alternative is the use of volume displacement in water. The apparent density
considered the internal pores of a biomass particle but not the interstitial volume between the biomass
packed together. So this is the equation for the apparent density.
The pore volume of a biomass expressed as a fraction of it is total volume is known as it is porosity.
Apparent density is most commonly used for design calculations because it is the easiest to measure and it
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gives the actual volume occupied by a particle in a system. So, you can see the table 1 has given apparent
density of some of the wood species.
Then the bulk density; So bulk density is based on the overall space occupied by an amount or a group of
biomass particles. Bulk volume includes interstitial volume between the particles and as such it depends
on how the biomass is packed. For example, after pouring the biomass particles into a vessel, if the vessel
is tapped, the volume occupied by the particles settles to a lower value. The interstitial volume expressed
as a function of the total packed volume is known as bulk porosity.
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So, this is the bulk density equation.
So to determine the biomass bulk density, we can use standard like the American Society for testing
materials, E-873-06 standard. So, this process involves pouring the biomass into a standard sized box of a
particular size (given here), from a height of 610 millimeters. The box is then dropped from a height of
150 millimeters three times for settlement and refilling. The final weight of the biomass in the box is
divided by the box volume which gives its bulk density. This is how we can measure bulk density of the
biomass.
The total mass of the biomass may contain the green moisture of a living plant, external moisture
collected during storage and moisture inherent in the biomass. So, once the biomass is dried in a standard
oven, its mass reduces. Thus, the density can be based on either green or oven-dry depending on whether
its weight includes surface moisture or not. The external moisture depends on the degree of wetness of the
received biomass. To avoid this issue, we can completely saturate the biomass in deionized water,
measure its maximum moisture density, and specify it is bulk density accordingly.
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So, there is a relation between these three densities as given here.
Where, epsilon p is the void fraction or voidage in a biomass particle and epsilon b is the voidage of
particle packing.
So, then the next is the biomass growth density. It is specifically for biomass not for other materials. So,
the term biomass growth density is used in bioresource industries to express how much biomass is
available per unit area of land.
So, it is defined as the total amount of above-ground living organic matter in trees expressed as oven-dry
tons per unit area (that is basically the tons per hectare) and includes all organic materials: whether it is
leaves, twigs, branches, main bole, bark and the trees.
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Then we will see some of the thermodynamic properties. When we talk about gasification, which is a
thermo chemical conversion process, the thermodynamic properties of biomass heavily influence its
gasification properties (so do for pyrolysis also). So, the three important thermodynamic properties are
thermal conductivity, specific heat and heat of formation. Now what is thermal conductivity: biomass
particles are subject to heat conduction along and across their fibre which in turn influences the pyrolysis
behavior, and/or gasification behavior of course. Thus the thermal conductivity of the biomass is an
important parameter in this context. It changes with density and moisture.
So, how it changes? We will see. So based on a large number of samples, MacLean in 1941, developed
the following correlations (which is adopted from this Kitani and Hall 1989, a book is given in the page
number 877). So, K effective watts per meter Kelvin, is specific gravity in bracket 0.2 + 0.004 into m d +
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0.00238. So, this particular correlation, as you know correlations are valid for certain range, so for this
particular correlation it is only valid when your m d is greater than 40%. Now another equation which is
given by this, you can see that equation also (I am not reading it). So that is valid when m d is less than
40%.
So, two equations or correlations were proposed, the first one is when the m d is greater than 40% and the
second one is when the m d is less than 40%. So, m d is the moisture percentage of the biomass on a dry
basis. So, unlike metal and other solids biomass is highly anisotropic. Conductivity also depends on the
biomass’s moisture content, porosity as well as temperature.
Some of these depend on the degree of conversion as the biomass undergoes combustion or gasification.
Thunman and Leckner in 2002 wrote the effective thermal conductivity parallel to the direction of wood
fibre as a sum of contributions from fibres, moisture and gas in it. It is a good equation which many of us
working on the biomass sector they use it. So, K effective in watts per meter Kelvin, is G K s + F K + H
into K g + K rad for a parallel fiber.
Where, G x, F x and H x are the functions of the cell structure and it is dimensionless length; K s, K w
and K g are thermal conductivities of the dry solid (that is fibre wall), moisture and gas respectively; And
K rad represents the contribution of radiation to conductivity; it is a very nice or excellent equation which
is being adopted universally.
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So, we will see few more equations. So these components are given by the following empirical relations,
which are to be used to calculate the directional values of the thermal conductivities. Here all the thermal
conductivities are measured in watts per meter Kelvin. So, Kw is given by this equation - 0.487 + 5.887
into 10 rise of - 3 into T - 7.39 into 10 power of - 6 T square. Now K z is given by this long equation, K w
is 0.52 in perpendicular direction and K rad, so which is coming from the radiation is 5.33 e of radiation
then sigma d pore and T cube.
So, E rad is the emissivity of the pores having diameter d pore and sigma is the Stefan Boltzmann
constant, and T is the temperature in Kelvin. The contribution of gas radiation in the pores K rad, to
conductivity is important only at high temperatures.
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Now we will talk about specific heat, another important thermodynamic property. So, specific heat of
biomass is often required for thermodynamic calculations. So, it is an indication of the heat capacity of a
substance. Both moisture and temperature affect the specific heat of biomass. But density of wood species
do not have much effect on the specific heat. So, the specific heat changes much with temperature it also
depends on to some extent on the type and source of the biomass.
So, please look at this particular figure. So, you can see there are three (specific heat of a softwood
species parts) species temperature versus specific heat has been given here. So, the below one that is the
wood char, the red one is the wood bark and the blue one is the wood. So, this figure shows the increase
in specific heat of a softwood species with temperature. It also shows that bark of the wood has higher
specific heat, when it is compared to the other two species.
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Char produced from this wood has interestingly much lower specific heat. Some experimental correlation
of specific heat with temperature and moisture content is given as this Ragland et al equation 1.39 +
0.00036 T for the wood char, Gupta et al suggested for the softwood fuel 0.00546 into T - 0.524 and for
the hardwood fuel 0.0038 into 10 power of - 3 T square + 0.00598 T - 0.795.
Ragland et al., (1991): 1.39 + 0.00036 T for Wood char

Gupta et al., (2003): For softwood fuel: 0.00546T – 0.524
For hardwood fuel: 0.0038 * 10-3T2 + 0.00598T – 0.795
Now I want to say something about this so called relations; please note I do not know whether most of
you are aware of the fact or not regarding these correlations. So, let us understand what is the meaning of
correlation; why suddenly some particular number of 0.003, some x square some T square is coming into
picture. Now please understand that any correlation is an equation which is developed by doing certain
fixed number of experiments; it is all based on the experimental results.
That is why they have some specificity or limitation, like we are showing m d in the last equation. I told
you that these particular two equations, one equation is valid when the moisture content is greater than
40%, another equation is valid when the moisture content is less than 40%. So, that the reason is that this
is how the experiments are being done and this is how the equation has come from different experiments
and mostly they are average values, there is a particular way to do it. So, you need to understand that any
correlation are experimentally derived equations and has some limitations.
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So, then let us understand the heat of formation; heat of formation also known as the enthalpy of
formation is the enthalpy change when one mole of compound is formed at standard state, that is 25
degrees centigrade and 1 atmosphere from its constituting elements in their standard state. Now for
example, hydrogen and oxygen are stable in their elemental form, so their enthalpy of formation is always
zero, in elemental form.
Now however an amount of energy 241.5 kilojoules is released per mole when they are combined to form
steam, that means hydrogen and oxygen. So, the heat of formation of steam is thus - 2241.5 kilojoules per
mole that is in the gaseous form. So, this amount of energy is taken out of the system and is therefore
given a negative sign in the equation to indicate that it is an exothermic reaction. If the compound is
formed through multiple steps, the heat of formation is the sum of the enthalpy change in each process
step.
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So, gases like hydrogen, oxygen, nitrogen and chlorine are not compounds and the heat of formation for
them is zero. Values for heat of formationn for some of the compounds are given, you can see it later
water is - 241, carbon dioxide is - 393, right there are a few were given just for your understanding.
Now this is a small example problem, you can just go through it. So, find that heat of formation of
sawdust, the heating value of which is given as 476 kilojoules per mole, assume its chemical formula to
be CH 1.35 O 0.617. Now stoichiometry has to be written. The conversion of SW can be written in the
simplest term as CHO + 1.029 Oxygen will give C carbon dioxide + water 0.6575 water - 476 kilojoules
per mole of sawdust is the isothermic reaction.
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So, heat of reaction you can calculate like this, HF of carbon dioxide + 0.675 HF of water - HF of
sawdust - 1.029 HF of oxygen. So, consider the values of HF of heat of formation of carbon dioxide,
oxygen and water and substitute. So, you will get heat of reaction for the above combustion reaction -
476, it is given. So, you will calculate the heating value to be - 80.5 kilojoules per mole.
Consider the values of HF of CO2, O2, H2O (g):
The HR for the above combustion reaction is -476 kJ/mol. So,
So, the heat of reaction is the amount of heat released or absorbed in a chemical reaction with no change
in temperature. In the context of combustion reactions, heat of reaction is called the heat of combustion.
deltaH comb submits a combination, which can be calculated from the heat of formation as: methane plus
oxygen gives you 2 water plus carbon dioxide, so heat of combination will be 2 of deltaH water + deltaH
carbon dioxide - deltaH methane - deltaH oxygen.
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So, the deltaH comb, the heat of combustion of the combination for the entire fuel, can be defined as the
enthalpy change for the combustion reaction when it is a balance. So, fuel plus oxygen will give you
water plus carbon dioxide minus heat of reaction.
So, the heating value of biomass is the amount of energy biomass releases when it is completely burnt in
adequate oxygen. So, it is one of the most important properties of biomass as far as energy conversion is
concerned. Compared to most fossil fuels, the heating value of biomass is low especially on a volume
basis because its density is very low and it is high oxygen containing fuel. Higher heating value, what is
higher heating value? This is also very important to understand. So, it is defined as the amount of heat
released by the unit mass or volume of fuel, initially at 25 degrees centigrade, once it is combusted, and
the products have returned to a temperature of 25 degrees centigrade.
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It includes the latent heat of vaporization of water. HHV is also called as the gross calorific value. In
North America, the thermal efficiency of a system is usually expressed in terms of HHV, so it is
important to know the HHV of the design fuel. Then there is something called LHV or lower heating
value, so LHV is also known as net calorific value. HHV is gross calorific value and LHV is the net
calorific value.
So, the lower heating value is defined is the amount of heat released by fully combusting a specified
quantity less the heat of vaporization of the water in the combustion product, so this is the equation you
can refer to.
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So, then the next thermodynamic property is ignition temperature. So, ignition temperature is an
important property of any fuel because the combustion reaction of the fuel becomes self sustaining only
above this temperature. So, above only this temperature it will ignite basically. So in a typical gasifier a
certain amount of combustion is necessary to provide the energy required for drying and pyrolysis and
finally for the endothermic gasification reaction.
Exothermic chemical reaction can take place even at room temperature but the reaction rate being an
exponential function of temperature is very slow at low temperatures. So, when the fuel is heated by some
external means, the rate of exothermic reaction increases with a corresponding increase in the heat
generation rate.
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So, above a certain temperature the rate of heat generation matches or exceeds the rate of heat loss. When
this happens the process becomes self sustaining and that minimum temperature is called the ignition
temperature. So, the ignition temperature is generally lower for higher volatile matter content fuel because
biomass particles have a higher volatile metal content than coal. So, usually they have significantly lower
ignition temperature.
So, the inherent meaning is that, so biomass particles will ignite very fast compared to the coal. So, for
example the wheat straw has a volatile matter of 72% (daf basis, so daf is the dry ash free basis). The
ignition temperature is 220 degrees centigrade while the volatile matter of anthracite is only 7.3% but the
ignition temperature is 927 degrees centigrade.
Now we will try to understand how we will enhance the primary raw materials for the biofuels and what
are the different types of techniques that exist, including some of the genetic engineering aspects. Now
the use of plant cell wall as major energy sources would establish a virtuous industrial cycle and thus help
mitigate global warming problems as plant cell walls constitute the natural carbon dioxide sinks.
Unfortunately plant cell walls are extremely resistant to enzymatic degradation and so are difficult to
degrade into fermentable sugars. Now that is the reason why as it is mentioned here; there is a need for
the pretreatment of the biomass, (we will also discuss in our subsequent slides today itself). And due to
this recalcitrant nature of the cell wall, huge amount of energy and effort is required to make it amorphous
thus releasing the sugars which is responsible for producing alcohol.
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As a result, current dynamic area of research is the transformation and harvesting of plants. So, the
cellulose microfibrils which could be easily hydrolyzed by cellulose preparations or which could self
degrade their cellulose microfibrils by expressing a cocktail of hydrolytic enzymes. On the other hand,
now it is clear that such genetic modifications capable of conferring these novel characteristics would be
feasible only if the resultant genetically modified plants could achieve adequate public acceptance and
were able to strive in natural cropping system.
Now here I wish to tell you something very interesting. So, many of you will be knowing about this
genetic modified crops. You remember few years back in India there is a lot of hue and cry regarding the
genetic or transgenic brinjal. So, public perception about genetic modification till date is not so good. So,
they feel that if a particular species is genetically modified and being consumed, by the humans or the
animals it may have some bad effect, which I cannot give a right straightaway answer to that; we need to
do more study on that actually, I cannot say whether it is good or bad in this platform. But we need to
understand one thing, that the public perception is not so good and acceptability of such genetic crops
actually needs more public awareness and you need to convince the public about what is the importance
of this and whether there is any adverse effect if it is being consumed by the humans and/or animals. This
is first thing.
Second thing; this so called genetically modified species, plants, crops, whatever it is, they must have the
capacity of naturally cropping systems, that is one thing. There should also be able to withstand the usual
natural environment as well as the climatic conditions. So, these are some of the challenges which still
remain in the development of so called genetic engineering or genetic engineered species, crops or
transgenic plants, you can call them.
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So, the current technologies for biofuel production typically involve the pretreatment of lignocellulose
before hydrolysis with cellulase preparations. Cellulase is the enzyme which will degrade the cellulose to
glucose. So, an alternative concept is to either upregulate or downregulate hydrolases by introducing and
programming their genes in order to achieve in situ modification of the plant cell wall polysaccharides.
So, we can do in situ modification inside the plant cell itself by doing some genetic modifications by over
expressing either certain genes or certain proteins which is responsible for a particular, let us say, either
increasing the cellulose yield or carbohydrate yield or making it resistant to certain types of pathogens
attack. There are many things. It is not that genetic engineering is being done only to have a higher yield
of the biomass or have higher yield of cellulose, it is not so.
So, in principle the introduction and programming of such genes should not decrease cellulose production
levels in plants otherwise it will have an adverse effect, so our main aim is not going to be achieved.
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So, as such genetic engineering could promote the degradability of cell walls in plants bred for use as
biofuels. Although the degradative gene products in bacteria and fungi are more effective in digesting
polysaccharides than those present in plants, so plants sometimes produce pathogen related proteins such
as antibodies. So, thus it is necessary to create and improve a technical barrier to plant engineering using
trans-kingdom genes, I hope you all understand what is genes.
So, you can browse little more about these particular few slides and few of the particular words which
you may not be aware of; please read it from literature.
So, we will discuss how we can do this genetic engineering technique using the In-Fibril modification.
Now cellulose is most abundant biopolymer on the earth. An important characteristic of this biological
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polymer is that, it has a strong tendency to self-associate into microfibrils that: are not easily hydrolyzed
either chemically or biologically and that accumulate primarily in the walls of the plant cells. Now since
individual strands of cellulose are intrinsically less hydrophilic than other soluble polysaccharides,
cellulose crystals tend to form extensive intra and intermolecular hydrogen bonds with complex 3
dimensional structures. In natural crystals, for example cellulose I, the cellulose strands are parallel and
form triclinic cellulose, and monoclinic cellulose in varying proportions depending on their origins.
So, the microfibril is drawn with its chain axis as a monoclinic structure corresponding to the native
cellulose of higher plants. After strong alkaline denaturation, cellulose I forms a thermodynamically more
stable structure than that of the cellulose II with an anti parallel arrangement of strands. Therefore,
cellulose II is artificially generated from cellulose I by two industrial processes, first is called regeneration
and second is called the mercerization.
Each microfibril consist of repeated crystalline and non crystalline regions, each of which might be
relatively short (almost around 10 to 100 glucosyl residues that it contains). The microfibrils are too rigid
for cellulases to attack both the crystalline and the non crystalline regions. Lignin (another component, a
very high class compound) may bind to hemicelluloses mainly xylan, thereby associating with cellulose
microfibrils and further rigidifying them.
So, in a lignocellulosic biomass (next sometimes I will show you a structure), cellulose, hemicellulose
and lignin are bound together in a very intricate manner. So, thereby making it more rigid to the cellulase
attack, cellulase is the enzyme which we want to use for degrading the cellulose whatever is available. So,
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that is the reason why we talk about this delignification process, the pretreatment is mostly about
delignification. Not always it is delignification; but mostly, it is roughly understood as delignification.
That means removing the lignin or separating lignin from cellulose and hemicellulose. Cellulose is C 6
sugar and hemicelluloses are C 5 sugars, pentose sugars basically.
Pretreatment for decomposition of lignocellulose could represent a critical step in the conversion of
lignocellulosic biomass, as their function comprises increasing the susceptibility of plant microfibrils to
cellulase action. A noteworthy strategy for cellulose hydrolysis is not only to promote decrystallization
between the so called 1, 4 beta glucans in the crystalline regions, but also to loosen the association
between 1, 4 beta glucan and hemicellulose in the non-crystalline regions.
So, that is very important, this particular sentence is very important. So, the cellulose hydrolysis is not
only doing the decrystallization between this 1, 4 beta glucans, but it is also losing the association
between this 1, 4 beta glucan as well as others hemicelluloses in the non-crystalline regions. So, the use of
transglucosylase, such as xyloglucan endotransglucosylase (which is known as XET), is yet another
potential method for transferring glucosyl residues of 1, 4 beta glucan to another chain.
Now this can be exemplified by the action of barley XET, which catalyses the transfer of cellulose
molecules to xyloglucan and thereby forms a link between cellulose and xyloglucan.
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It is well known that the removal of lignin results in an increased level of saccharification of plant cell
walls, and this method is commonly used to facilitate the process of bioethanol production. Lignin occurs
in close association with cellulose microfibrils, it is always expected that a decrease in lignin content
would in turn increase the accessibility of the cellulose microfibrils to degradative enzymes. Lignin is an
important cell wall components, in the plants not only for water transport in xylem but also for stem
straightness and protection against pathogen attack.
So, lignin provides some sort of mechanical support also, you can say that. Therefore, it seems likely that
a dramatic reduction of the lignin content in the growing plants would result in a detrimental effects of the
plant growth, so you need to balance it. So, consequently reducing the lignin content of lignocellulosic
biofuel crops appears to be that of (little) practical use.
Let us understand that, if we want to reduce the lignin content of a dedicated energy crop in which the
lignin content is already less (let us say miscanthus, switch grass, elephant grass - they are bush type of
plants, they are grasses), then it is not going to have a much higher effect on the mechanical stability of
the plants or these bushes (because they are grasses and bush basically).
But having said that, if we are drastically reducing the in-fibril lignin, for the hardwood or softwood trees,
then we need to be careful about whether the plant can grow properly and erect and stand on the soil by
itself, by having a good mechanical stability. So that is the question basically. That is how the genetic
engineering or the engineers must ensure that there is no adverse effect on the growth of the plant.
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So, the transgenic Populus tremula overexpressing Arabidopsis cellulase (that is cell1) exhibits longer
internodes and longer fibre cells; remarkably, those characteristics translate into immediate gains in
bioconversion productivity. In addition, the enzymatic trimming of amorphous regions in the microfibrils
leads to the solubilization of some xyloglucan that is intercalated with disordered para-crystalline
domains of the microfibrils.
Xyloglucan is a key polysaccharide that is used by the plants to control the assembly of cellulose
microfibrils through cross linking. So, therefore the degradation and reconnection of xyloglucans could
induce the modification of cell wall polysaccharides in such a way, so as to further facilitate industrial
saccharification. Since adjacent cellulose microfibrils could be crosslinked to xyloglucans, the separation
of microfibrils during elongation is thought to require enzymes that solubilize xyloglucan or loosen its
binding to microfibrils.
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An additional enzyme that is an important target for plants genetic engineering is xyloglucanase, which is
called XEG, which catalyses the endo-hydrolysis of the xyloglucan backbones and exhibits xyloglucan
specific endo-1, 4-beta glucanase activity. XEG is widely distributed in nature, being present not only in
plants but also in fungi and bacteria. So, the overexpression of XEG in poplar (poplar is a plant which we
have discussed in our last class - a dedicated energy crop) resulted in the cleavage of xyloglucans
crosslinked with cellulose microfibrils, and in an acceleration of stem elongation by loosening of the wall.
The overexpression of this enzyme also causes an increase in wall density and cellulose content. So, I will
tell you in a crude way, what is the meaning of overexpression. These are genetic engineering terms. So,
as I told you please go back and read a little more about certain terms which you are not very clear about.
So, in this particular class, it is very difficult to make you understand each and every bit of the genetic
engineering aspects, so that is not the scope of this course also. So, I will be telling in a nutshell;
overexpression means making more copies of the parent protein, or gene. So, for example if cellulose
formation in wild type poplar is restricted by the entanglement with xyloglucan, the relaxation resulting
from the cleavage of crosslinking xyloglucans in the modified poplar may accelerate cellulose
biosynthesis and deposition. So, the meaning of this particular sentence is that, when we overexpress
XEG in the poplar, it has helped in cleavage of the xyloglucans which is cross-linked to the cellulose
microfibrils.
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So, by these mechanisms, the expression of XEG would promote not only cellulose degradation, but also
the production of cellulose in plants. So, the observation that overexpression of XEG in poplar results in
the acceleration of cellulose degradation by cellulase preparations is consistent with this hypothesis. Now
it is also noteworthy that the reconnection between xyloglucan molecules in the walls can be catalysed by
xyloglucan endotransglucosylase, which is called the XET, an enzyme encoded by the gene of XTH gene
family. However, XEH present in plant cell walls has not been well characterized (another class of
enzyme). So, there is possibility of some relationship and/or interaction might exist between XTH and
cellulose synthase gene expressions; it is possible that this mechanism might be leveraged to facilitate
biomass processing. More work is currently being done on whatever we have written in this last sentence
here.
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So, French bean cells habituated to grow in the presence of 2, 6 dichlorobenzonitrile formed large
amounts of soluble beta glucan and evoked the XET activity. Such inhibition of cellulose biosynthesis
would apparently not only cause the occurrence of soluble 1, 4 beta glucan but also decrease the plant
growth. While the cellulose biosynthesis pathway in plants remain unclear, there is convincing evidence
that a relationship exists between cellulose synthase, cellulase the enzyme, and the XET.
One line of research and development to facilitate the implementation of lignocellulosic biomass at a
large scale is thus to make the use of this relationship to weaken the cellulose polymers in vivo, which can
be achieved by appropriately altering the genetic makeup of biofuel crops. It is hoped that this might be
achieved in such a way that the industrial saccharification of lignocellulosic biomass could be performed
under optimal economic conditions without affecting the natural ability of these crops to grow in a natural
cropping system.
Again this is what we have already discussed in one of the slides, as I told that everything is so good
about the genetic engineering things. It has to be done in a proper way and proper understanding that if I
am decreasing the lignin content, then it should not affect the growth of the plant. This is one of the
foremost important thing.
Let us learn what is In-Planta modification. Like another genetic engineering technique. A two-pronged
strategy is required to improve lignocellulosic crops for optimal biofuel yield. So, the first one, it is
necessary to increase the yield of the cellulose production based on the plant mass, while on the other
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hand, it is also necessary to increase the conversion of cellulose into glucose. There are two things, first
you increase the yield of cellulose, by means of the genetic engineering aspect.
Second thing is that, you increase cellulose; but cellulose is bound in such an intricate fashion with
hemicellulose and lignin and their rigidity so high they are crystalline. So, that crystallinity has to be
overcome so that the cellulose can be transformed into glucose. So, improvements in the post harvest
processing in-planta were originally attempted in transgenic tobacco which constitutively produced
hyperthermophilic a-glucosidase and b-glucosidase (two different types of enzymes) from the
hyperthermophile Sulfolobus solfataricus.
So, this is one particular unicellular organism from which these two enzymes have been derived.
Transgenic plant means genetically modified plant. So, the transgene glucosidases began to accumulate in
the tobacco plant after a certain delay and were inactivate at plant growth temperature. After harvest,
however glucose could be produced from endogenous polysaccharide upon incubation at high
temperature.
I would like to say that transgenic tobacco is being farmed in many of the Western countries, because not
for the consumption of the tobacco leaves, but to purify one particular monoclonal antibody which is
present in the transgenic tobacco. Usually it is present in a very small quantity, about 6 to 7% not more
than that. Sometimes it is less than that depending upon the species, so it is a very high class antibody,
needs to be purified, for that purpose this transgenic tobacco plants are been cultivated.
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So Oraby et al in 2007, showed that cellulase expressed in rice can effectively convert the cellulose of
ammonia-fibre-explosion-pretreated rice and maize biomass into glucose. Now ammonia fibre explosion
pretreated rice, so ammonia fibre explosion is one of the pretreatment technique, we will read about more
pretreatment techniques later in our subsequent lectures. We will discuss about ammonia fibre explosion
als. So, these authors suggested that such a method of expression could be used as an environmentally
friendly technology for the hydrolysis of wasteful rice straw.
So, next genetic engineering technique is In-CRES-T modification. So, CRES-T means chimeric
REpressor silencing technology; it was developed as a novel method to silence the target genes of
transcriptional activators in plants. Transcription factor is a protein; and what is transcription? So,
transcription means in a nutshell, transferring one particular information from the DNA to the messenger
RNA or mRNA. So that process is called transcription.
You can read little more about these terminologies from the literature, so that things will be more clear. In
CRES-T, a fused gene encoding a transcriptional activator and a repression domain named as SRDX at
the carboxy terminus is expressed as an artificial chimeric repressor. The SRDX is a modified short
amphiphilic peptide of 12 amino acids derived from the plant specific transcriptional repressor known as
SUPERMAN.
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This strategy has the following advantages over the conventional genetic manipulations, such as RNAi or
gene knockout particularly in many horticultural plants which have high polyploidy and only limited
sequence information: (You know polyploidy; there is something called diploid, what is the meaning of
that? So, when an offspring is actually born, it usually carries one set of chromosomes, in their genes
from each of the parents. In polyploids, they will have two sets of genes, two from one parent and two
form another parent. You can understand in a crude way.)
i) So, chimeric repressor can dominantly suppress the expression of target genes and induce loss-of-
function phenotype, even if the endogenous paralogous genes function redundantly.
ii) Plasmid construction is very easy, what is plasmid? Plasmid is a small extra chromosomal DNA, i.e.,
not present in the chromosome itself.
iii) Cloning of the gene encoding the target transcription factor from each plant species is not necessarily
required because the construct of the model plant can be effective in other plant species.
To this date various traits of several floricultural plants have been successfully modified by the CRES-T
technique.
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Because lignin content and fermentable sugar yields are reversibly correlated, the enzymatic
saccharification rate of plants without secondary walls in their stem may be higher than that of the plants
enriched in the secondary walls. Some additional modifications may be required to utilize plants lacking
secondary walls because their total amount of cellulose is decreased, thus preventing the plants from
standing erect and making them very fragile.
Further analysis of each plant species is required to evaluate whether these disadvantages could be
compensated by the positive attributes exhibited by plants that lack secondary walls. It is particularly
worth noting that a reduced lignin content in secondary walls improves the glucose yield. That is what we
have already understood.
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Since lignin and cellulose - the major components of secondary walls - are polymers of completely
different molecular classes and result from unrelated biosynthetic mechanisms, each component of the
cell wall is likely to be independently regulated by different transcription factors downstream of the NST
genes. I am leaving it as it is, you please read this later on, if you have any query, please ask me. This
little more detail about the genetic engineering aspect, though is not so much important for this course but
I felt that I will basically write it, so you can later on read it. So, I am just moving ahead with the other
material.
So, this also the same thing, I am just leaving it to you to read. In case you have any query, please feel
free to write to me, I will be definitely happy to address those.
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Now we will try to understand what are the challenges in conversion of biomass to biofuels. There are
only few challenges. But that needs to be addressed suitably, so that we will have no problem in the
conversion. The first one is the moisture content; we have discussed it in a nutshell earlier. So, biomass
materials with high moisture content is not suitable feedstock for conventional thermochemical
conversion technologies such as gasification, pyrolysis.
High moisture can reduce the effectiveness of conversion processes. Moisture in raw biomass materials is
also undesired because fuel wood produced from these materials can contain more moisture. The fuels,
which have high moisture contents cannot burn easily. Some part of the energy in the fuel are always
consumed for the vaporization of water, which is present in the fuel. In order to maximize the heating
value of the fuel produced from these materials the moisture content biomass should be always less than
20%.
Drying the materials before being used in the conversion process is not preferable because of high cost
(because it is an energy intensive process). On the other hand, some biomass conversion processes use
biomass with high moisture content. The first one is hydrothermal conversion process. This is a beautiful
technology; it is currently being adopted in many industrial practices. So, in this particular technology, in
a high pressure high temperature system, you are going to convert the high moisture content feedstock (it
can be anything, any biomass or anything) to crude oil (basically biocrude). And in certain biological
processes such as alcohol production from carbohydrates by biomass, high moisture content does not
create any problem. So, in these processes, moisture in the biomass play an important role in the
conversion either as a major reactant or as a reaction environment.
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For example, high moisture content in biomass causes biological degradation, mold formation and losses
in the organic content during storage, that could reduce the yield of the fuel wood from these materials.
Storing biomass at less than 10% can extend the conservation time of the materials and reduce major
losses (that means losses of the sugars) during the storage period. The drawbacks of high moisture content
can be mostly solved by compressing the biomass material for more uniform properties and that process is
called densification.
So, you must have heard about densification of biomass. So increasing bulk density of biomass materials
by densification reduces transportation cost and storage volume. However, this process adds an extra cost,
densification is an added process basically. So for any added process there is a cost to it and hence the
overall cost increases.
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Then density; bulk density of lignocellulosic biomass materials is generally low. This creates difficulties
to handle such large quantities of feedstocks and increases the transportation and storage cost. The bulk
density of biomass should be between 190 to 240 kg per meter cube for efficient transport in various sizes
of trucks with approximately 25 ton loads. The size, shape, moisture content, particle density and surface
characteristics are the factors affecting the bulk density of a material. The challenge for low density and
different size and shapes of biomass can be overcome by densification process.
So, biomass in densification process; biomass materials are mechanically compressed to increase their
density and convert them into uniform shapes and sizes. You can see, how these have been converted into
particular shapes. These are powder, these are some sort of briquettes, these are some sort of rolls. You
can briquette them, pelletizing them, cubing them. So, then density of biomass can be increased ten-fold
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depending upon the biomass type, moisture content and processing condition. The costs of handling,
transportation and storage of resulted densified materials can be considerably reduced. Now because of
uniform size and shape the materials can be easily handled.
So, the next is complexity and diversity. Lignocellulosic biomass materials is mainly composed of three
components lignin, cellulose and hemicellulose. These polymers are organized in the complex non
uniform three dimensional structures and each one has different polymerization degrees. Polymerization
degree and/or structures of these biopolymers can vary among the biomass species. Cellulose is a linear
structure composite of beta 1-4 linked glucose subunits. Cellulose molecules determine the cell wall
framework.
The inter and intra chain hydrogen bonding in the structure makes the cellulose to be crystalline and this
portion of cellulose does not hydrolyze easily compared to the amorphous cellulose structure. And that is
what we have understood during the genetic modification steps that we have discussed. How the cellulose
can be available or more amenable to degradation, either by removing lignin, decrease the lignin content
or overexpressing certain cellulases (enzymes basically). So, that whatever we want that will be fulfilled.
Hemicellulose has a random and amorphous structure which is composed of several heteropolymers such
as xylan, galactomannan, arabinoxylan, glucomannan and xyloglucan.
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Phenylpropanoid monomeric units in the lignin polymer are identified as p-hydroxyphenyl, guaiacyl and
syringyl units. Composition of lignin, cellulose and hemicellulose in biomass materials significantly
differ among biomass species. For instance, some biomass materials such as hardwoods contain more
cellulose in their structures while others such as straws have more hemicellulose. Hemicellulose fractions
of softwoods mainly have D-mannose derived structures such as galactoglucomannans while
hemicelluloses in hardwoods have D-xylose derived structures.
Now this diversity among biomass material can significantly affect the conversion process for production
of biofuel and other useful products from the biomass materials.
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So, the next is recalcitrance and dissolution difficulties. Success of using lignocellulosic biomass for
biofuels and other useful chemical productions depends largely upon the physical and chemical properties
of the biomass, on pretreatment methods and optimization of the processing conditions. The
compositional changes in plant cell wall and the differences in ultra structure greatly influence the
pretreatment and hydrolysis efficiency of the biomass.
Hydrolysis is a chemical reaction that releases sugars from biomass structures. Biomass dissolution
involves both physical, chemical and/or thermochemical treatment processes. We will read more about
these techniques later on in our subsequent lectures. So, things will be clearer that time. So the
crystallinity of cellulose, hydrophobicity of lignin, and embedding the cellulose in lignin-hemicellulose
matrix and difficulties in cleavage of some linkages (for example hydrogen bonding, ether linkages
between phenyl propane units) make biomass materials resistant to hydrolysis.
Hydrolysates from biomass can be used for producing a wide range of value added products, including
biofuels (it can be ethanol, hydrogen, butanol any such things), industrially important chemicals (for
example some of the solvents) and food products (sugar and sugar alcohols).
Significant existing challenges for hydrolysis of lignocellulosic biomaterials include the following. So,
first is that existing hydrolysis methods are expensive and time consuming. Most of them are not
environmental friendly. Second is that additional steps are required, just like here pretreatment,
neutralization etc. Then third is, released carbohydrates decompose in harsh hydrolysis conditions which
is prevalent during the hydrolysis process. So these are some of the challenges that needs to be tackled.
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The major hydrolysis processes typically used for solubilization of biomass require either use of toxic,
corrosive and hazardous chemicals (for example acids, alkali) or longer retention time (for example
during enzymatic hydrolysis), which collectively make the process environmentally unsafe and/or
expensive. That is why there is a huge work right now going on across the globe to develop different pre-
treatment techniques. Basically different pre-treatment techniques; I’d rather say that efficient and
sustainable pre-treatment techniques in which the yield will be more. The techniques should be
environmentally benign. It should be a green approach.
So, huge work is going on. There are developments of hybrid techniques. We will discuss something;
hybrid means basically combining more than one unit operations together. Because in one single unit
operation, you may not achieve the yield which you are looking for; so you combine two processes. But
having said all these, three things we should note with respect to the pre-treatment:
First is that, it should be a low-cost technique and it should be done at a very faster rate. So, time is
directly related to money in industry. Second, it should result in a higher yield of the cellulose. Third is
that, it should be a greener process.
So, concentrated acid hydrolysis has been applied, but the problem with concentrated acid hydrolysis are
several. So, though they provide higher conversion, but, there are environmental concerns, corrosion and
so many other things. So, due to all these things some of these are listed here, please refer later on. Since
almost two decades’ researchers have focused their attention to dilute acid pre-treatment rather than
concentrated acid pre-treatment.
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At dilute acid pre-treatment you will see hundreds and hundreds of literature reported by various
researchers who have worked with so many different types of species and studied the pre-treatment using
the dilute acid method. So, we will of course discuss more about that.
So, subcritical water is an alternative way to hydrolyze lignocellulosic biomass but please not that when
you talk subcritical, supercritical the reactor in which we are going to achieve it, the initial investment is
very high and you are going to again use higher energy to achieve that. Now this table will make you
understand about certain breakdown methods, pre-treatment methods, alkali, acidic, enzymatic,
subcritical water and their various advantages and disadvantages. So, please refer to it later on.
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So, the presence of a weak acid in subcritical water media can also improve hydrolysis of biomass
materials. The use of carbon dioxide as a pressurizing gas also caused formation of carbonic acid that
plays catalytic role in effective solubilization of biomass. Some studies have indicated that the addition of
small amounts of hydrogen peroxide can enhance lignin removal. The differences in the content and
composition of resulted hydrolysates can change the yield of the biofuel, that is another concern again.
So, for maximum usability, biomass components in hydrolysates should be further broken down into
smaller molecular weight components with a suitable method.
So, there are other challenges also, we will just quickly go through it. So, although energy demands are
continuous, biomass materials are seasonal. So some biomass feedstocks have advantages in terms of
production, harvesting, storage and transportation compared to others. So, perennial energy crops such as
switch grass and miscanthus do not need to be replanted each year and they do not require special care
and high maintenance to grow.
On the other hand, agricultural biomass residues, whether it is a corn stover, wheat straw, rice husk, crop
peels, pulps etc. are promising low-cost feedstocks since they do not need additional land for biomass
growth and the land used for agriculture belongs to these type of biomass materials. However, high cost
of their harvesting and transportation limit their use. In addition to the advantages and disadvantages
listed above, different sources of biomass feedstocks do not have the same composition, uniform size and
shape etc. that considerably affect the efficiency of the conversion process for a specific product.
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So, there are so many things that needs to be taken care of while you go and design for a particular
conversion technology. Therefore, biomass feedstocks for a bio-refinery needs to be standardized, this is
the ultimate thing and has to be done.
So, with this I windup. So thank you very much. In the next class that will be module 3, we will start
discussing on bio-refinery. We will try to understand what is the concept of bio-refinery though in a
nutshell I have covered it in the introduction class and what are the types of bio-refinery. So, thank you
very much, if you have any query please drop a mail to me at [email protected] or please drop your
query in the swayam portal, thank you.
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Indian Institute of Science – Guwahati
Lecture 07
Basic Concepts and Types
Good morning students. This is module 3 and lecture 1. Under this module we will be
discussing about the biorefineries. And in today's class we will discuss about basic concept.
What is definition of biorefinery, how biorefinery functions, and what are the different types
of biorefineries?
Let us start. Please have a close look at this particular slide. I have deliberately added (this
slide) to make you understand the difference between Traditional oil refinery and biorefinery.
So, this is the traditional oil refinery, in which petroleum or petro crude is being processed to
fuels and energy and some platform Chemicals. The core is here; the petroleum in the core is
the crude oil.
Here the core feedstock is the Biomass. So you will have so many different types of products
from here. Fuels and energy so it can be bio-ethanol, biodiesel, biogas, hydrogen and all sorts
of liquid and gaseous fuels and even some solid fuels also. Then there can be some material
utilisation, like your basic and fine chemicals (which we call many times platform
chemicals), then Polymers and plastics. So the basic difference between Traditional refinery
and biorefineries is that, in biorefinery Biomass is the feed stock.
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There are so many different types of biomasses that can be utilised. So the feedstock can be
of n number of types. Not like in the petroleum refinery where only petro crude is being
processed. And the processes are more or less similar in the sense of their principle, whether
it is thermo chemical or sometimes bio-chemical also, and then we will have a number of
different types of products.
So the concept of the biorefinery evolved during the late 1990s. Various definitions of
biorefinery evolved by different stakeholders. Biorefinery is the separation of biomass into
distinct components which can be individually brought to the market either directly after
separation or after further (biological, thermochemical or chemical) treatment/s. Bio-refining
is the transfer of the efficiency and logic of fossil-based chemistry and substantial converting
industry as well as the production of energy on to the Biomass industries. So, these are few;
there are hundreds of such definitions provided by various stakeholders.
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Biorefinery is an overall concept of a promising plant where Biomass feedstocks are
converted and extracted into a spectrum of valuable products (this is what the US department
of energy has defined). NREL says that, biorefinery integrates Biomass conversion processes
and equipment to produce fuels, power and value-added chemical from Biomass. Then
International Energy Agency’s Bioenergy Task 42, they defined biorefining as the sustainable
processing of biomass into a spectrum of marketable bio-based products (it can be food, feed,
chemical materials) and bioenergy (biofuels, power and/or heat). And this is what is being
widely accepted by the scientists.
So, this particular definition, this NREL definition, includes the following keywords and we
will try to understand what are those:
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 Biorefinery: So here the concepts, facilities, processes and clusters of industries come
into picture.
 When you talk about sustainable; that means maximizing the economics, minimising
environmental aspects, fossil fuel replacement, socio economic aspects taken into
account.
 Then processing: upstream processing, transformation, fractionation, thermochemical
and/or biochemical conversion, extraction, separation and downstream processing.
 Then Biomass: what biomass means (with biorefining perspective). So, it can be
crops, organic Residues, agro residues, forest residues, wood, aquatic Biomass (such
as algae and all).
 Then spectrum, spectrum means more than one.
 Then marketable: A market (having an acceptable volume and prices) already exists
or is expected to become available in the near future.
 Then products: both intermediate and final products, i.e., food, feed, chemicals and
materials.
 Then energy: energy means fuels, power and heat.
So, biorefinery involves the enabling Technologies to make this possible as it allows for
optimal utilisation as well as value creation of biomass. Development of integrated closed
loop biorefineries that ensure their sustainability and economical viability through a complete
use of biomass, minimise waste and generate the greatest possible added value from the
available resources. The new biorefinery concept overcomes problems arising from the
generation of residues by giving them new value.
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This is how a significant increase in profitability and competitiveness over petrochemical
equivalents will be achieved - due to a greater efficiency derived from generating multiple
products. So biorefinery always targets for multiple products because we have to understand
that the feedstock is of low commercial value that we are going to utilise. Though its initial
value will be low. However, due to the densification and transportation cost, the cost of the
feed stock from procuring and to that of the plant will increase enormously basically.
Another thing I have already discussed and again I am telling you; feedstock sustainability is
it always a big question because most of the feedstock are seasonal. Unless and until we
standardize them for a particular biorefinery with multiple feedstocks, we cannot have a
sustainable biorefinery. And to do that, we should aim for more number of value added
products or co-products.
So, please have a look on this particular slide. Let us see what it means actually. It is a
concept. Here you can see that sustainable biomass supply. This is what I was just
mentioning; biomass supply should be sustainable. The inherent meaning of that; because
they are seasonal, so we should look for different types of biomass basically or multiple
feedstocks, so that their procurement will not face any problem throughout the year.
Then Sustainable Pre-treatment Technology. So pre-treatment technologies should be

developed in such a way that they are, efficient in handling almost all the feedstock.
Whatever maybe it? Some may be high lignin content; some may be less lignin content. How
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the pretreatment technology is going to address these issues low lignin content or high lignin
content, will depend upon what type of pretreatment technology is, being developed and
adopted.
Then you can get for different platforms: protein, Sugars, lignin, oils and fats and fibres. And
then you convert into various materials.
So separation technology is an integrated part of any refinery; whether it is a petrochemical

refinery or a biorefinery. And based on my understanding, it cost almost about 40%
(sometimes little higher than that of the entire product cost). So, you can understand that
unless and until you have a very good and low-cost separation technology, our final end-
product will be always very costly.
So, then you get so many different types of products. This already I have shown you long
back also. So, we will just quickly glance through.
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Then now there is so much of talk about circular bio economy. Meaning of circular bio
economy is that whatever we are actually producing as a final product, once they are
consumed, some waste is coming out of that. The by-products and the waste that is getting
generated during the processing should be recycled and reused in such a way that it almost
becomes a circular economy.
And also the economy of the rural people and other people who are engaged in these
industries are also being taken care of. You can see this: recycle, resources, nutrients, water
and carbon. Then renewable sources. This is the core of the circular bio economy, which is
your biorefinery. Then you get array of different products, services; use them and you
generate waste. And these wastes should also be recycled back.
I mean it should be processed into some valuable products. In one class I have given an
example of the wastewater and how water and wastewater that is being used in the Refineries
must be treated and recycled back. So, that we have to depend less on the freshwater because
freshwater resources are also depleting year by year. So then you have to recycle materials
bulk chemicals. So, it takes into account all these recycle and reuse of the materials basically.
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Let us now understand the different types of biorefinery. Two main previous attempts to
classify biorefinery systems are recognised in the literature. This is by Kamm and Kamm and
Ree and Annevelink. The corresponding citation I have given in some other slides; it will
come actually in the subsequent slides. So, several other papers mention classification
schemes for individual biorefinery set-ups such as the liquid phase catalytic processing
biorefinery and the forest based biorefinery.
So, previous classifications are based on: Raw material input (either it can be a green
refinery, it can be a whole crop biorefinery, it can be lignocellulosic feedstock biorefinery, it
can be a Marine biorefinery); Status of technology (either it is conventional or advanced
biorefinery, first and second generation biorefinery); then main (intermediate) products
produced (Syngas platform, sugar platform, Lignin platform). So slowly we will see all these
things.
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So please have a look at this particular slide where you can see that there are different types
of biorefineries listed. 9 different types and their features. So, the conventional biorefinery;
based on the existing industries such as the sugar and starch industry. The whole crop
biorefinery; it uses raw material such as cereals or maize. The green biorefinery; it uses
nature-wet biomasses, such as green grass, alfalfa, clover or immature cereals. Then 2
platform concept biorefinery; this includes sugar and syngas platforms. Lignocellulosic
feedstock biorefinery; uses nature dry raw material such as cellulose containing Biomass and
wastes. Then thermochemical biorefinery; so this is based on a mix of several Technologies,
it can be gasification, it can be pyrolysis. Then the Marine biorefinery; So that is based on the
Marine biomass (basically micro and macroalgae). Then liquid phase catalytic processing
biorefinery; this is based on the production of functionalized Hydrocarbons from biomass-
derived intermediates. Then forest based biorefinery; based on the full integration of biomass
and other feedstocks (including energy) for simultaneous production of pulp, paper, fibres,
chemicals and energy. This is all about the different types.
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We will just the conventional biorefinery what it means actually. So, many existing industries
are in fact already a sort of conventional biorefinery. So, either the sugar industry, starch
industry, vegetable oil industry, feed industry, food industry, Pulp and Paper, chemical
industry, conventional biofuel industries. Now these industries use conversion and upgrading
Technologies to separate Biomass into some main products and their residual materials.
And these Industries like the food industry already try to add some value by supplying their
by-products to other sectors. As for example, to the feed industry. However, their main
emphasis is still on producing their main products and no large efforts are made yet to
produce a broad spectrum of other value-added products like bio chemical or biofuels. That is
not happening in a large scale.
So, most of the focus is always on the main product development. However, the focus should
now be shifted to how you can generate the by-products and other wastes and convert them
into value added products. So that biorefinery will become both sustainable and economical.
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Please have a close look at this one. This is the whole crop biorefinery. In the whole crop
biorefinery this is based on dry or wet milling of biomass such as cereals: whether it is rye,
whether it is wheat, or whether it is maize. So what is being done in the first step is the
mechanical separation into grain and straw fractions, so you get a grain fraction here, so you
get a straw fraction here.
Now this grain and straw fractions will be converted. Approximately 20% is the grain
fraction and the straw is almost 80%. So both streams will be further processed separately.
The grain will deliver starch (so that is the starch platform). Then the straw (which is a
mixture of chaff, nodes, ears and leaves) represent the lignocellulosic feedstocks and may be
further processed in a lignocellulosic feedstock biorefinery.
So here, what we understand in the whole crop biorefinery is that, initially crop will be
processed into starch platform and a lignocellulosic based platform. Now that lignocellulosic
based, whatever we are getting generated, the straw basically, can be further processed in a
lignocellulosic biorefinery to other value-added chemicals and products.
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Next is Green biorefinery: Now the green biorefinery is based on the pressurization of wet
biomass such as green grasses and green Crops resulting in a fibre rich press cake and
nutrient rich press juice. The first initial step is that whatever the mechanical processing is
being done, so we will get a juice which is almost 25% and the rest 70% - 75% is the press
cake or the solid part. Now this biorefinery concept differs from others because fresh
biomasses processed here.
Advantage is that: rapid primary processing, high biomass profit per hectare and a good link
with the agricultural production. All agricultural production residues can be process here.
So this is an actual image of a pilot plant green biorefinery. So, you can see that the things are
getting processed here. So we get a protein platform, we get a fibre platform, we have a grass
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juice platform. The grass juice concentrate is here. Then this is a pilot plant biorefinery
scheme actually. And here we can get so many products like construction materials, paper,
polymer extrusions. There we get green grass protein and white grass protein. Now there are
other so many things that is happening here.
So let us understand the two platform concept biorefinery. This is based on fractionation of
biomass into mainly a sugar (basically cellulose and hemicellulose, the C6 and C5 sugar) and
a lignin fraction. Now, what is being done here is that, the Biomass, whatever it is coming, it
is converted into two things (or fractionated). One, we get a sugar platform, where sugar is
the raw material. Then it can be further processed to fuels, chemicals, polymer and raw
material.
And then you have a platform which is the Lignin platform. That lignin platform can go to
gasification (basically the thermal conversion) and you get a syngas here. Then we can have a
co-generation (CHP basically) of heat and power; and we will also get fuels and chemicals
and polymers from this platform.
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The next is lignocellulosic feedstock biorefinery. And this is most interesting because most of
the biorefineries are now looking for lignocellulosic based feedstocks. This is based on the
fractionation of lignocellulosic-rich biomass into the intermediate output streams cellulose,
hemicellulose and lignin, which can then be further processed into a portfolio of bio-based
end-products, materials, chemicals, fuels and/or heat.
Lignocellulosic-rich biomass is expected to become the most important biomass source of the
future because it will become widely available at moderate costs, and its cultivation and use
compete less with the food and feed crops. So that means, there is no food versus feed
problem here. Please understand the difference between this and the earlier one. Here we are
getting a sugar platform and then a syngas platform which is based on Lignin.
But Lignin can be converted into other things also. But in the lignocellulosic, we get
cellulosic platform and we get a lignin platform here. Now, lignin is not producing syngas
directly. It can produce whatever lignin can be used as a raw material. It is a very high value
product or it can be used for the cogeneration, which was present in the earlier this one
(Biorefinery) also. And there is a hemicellulose part also which needs to be taken care of
also.
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So then, thermochemical biorefinery. So in a thermochemical biorefinery, several
technologies could be applied such as: torrefaction, pyrolysis, gasification and HTU or HTL
(Hydrothermal upgrading or hydrothermal liquefaction). So, raw biomass and/or biomass-
derived intermediates (as for example char, pyrolysis, oil, torrefaction pellets, syngas HTU-
derived biocrude) could be conditioned and then could be introduced into these existing
capital-intensive infrastructures, substituting fossil fuels and raw materials for the sustainable
production of a spectrum of conventional petrochemical products.
Now have a close look at this particular slide. You can understand how this particular
refinery works; starting from the very source of the lignocellulosic materials, goes through
torrefaction, gasification, you remove tar, go for a scrubbing, and whatever you scrubbed out
(solid part) can be used as a fertilizer. Then you can remove carbon dioxide. You can
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concentrate carbon dioxide also. Then you can go for cryogenic distillation where we can get
acetylene and ethylene. Then we can have syngas, gaseous fuel and then the cycle goes on.
Then marine or algae biorefinery: That is more interesting now-a-days, because lot of work is
being done on this particular aspect of the algal refineries. So this is based on aquatic,
basically micro or macroalgae biomass. So microalgae can be cultivated on fresh wastewater
as well as marine water while macroalgae can only be cultivated on marine water. Here what
is happening actually; so you see this aquatic biomass that is getting cultivated here, it can be
microalgae, seaweeds, macroalgae, whatever it is. Then you go for the initial cell disruption,
product extraction (like remove the lipid content or oil whatever it is). Then, you can go for
the oil fractionation. There basically you extract oil. Then it goes to chemicals, value-added
products. You transesterify it to biodiesel. This is one of the most important aspect. Then
there are so many things left, like minerals. It can go to fertilizers and nutrients. Whatever left
out, the solid Biomass, I told you one in one of the class that it contains huge amount of
carbohydrates. Of course, the exact amount will depend upon what species we’re dealing
with. Apart from that, there will be pigments, there will be vitamins, there will be some other
important Chemicals also. The carbohydrate part can go to fermentation after hydrolysis. So
you can get alcohol based fuels, either butanol or ethanol; and other value added products like
pigments such as astaxanthin, beta-carotene; then you can also remove chlorophyll, it is a
very important class of chemicals.
So, what not we are getting from a single component or single feedstock. Now the refinery
should again be developed in such a way that you can a process different types of algae,
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whether it is microalgae, macroalgae. There are hundreds and thousands of species. So the
processes’ technology should be developed in such a way that all sorts of different species
can be converted in a single platform.
Let us now talk about, what the new biorefinery classification approach is, provided by the
International Energy Agency (IEA). So, it says that the new classification relies on the four
main features: first is the Platform; second is Products; third is Feedstock; fourth is Processes.
So, based on these four things the biorefinery has been classified. A Biorefinery system is
described as a conversion pathway from feedstock to Products via different platforms and
processes.
Now first we will see the platforms. So, the platforms are intermediates from which final
products are derived. They are the most important feature in specifying the type of
biorefinery. Platforms are intermediates which link feedstocks and final products. These
platforms are recognised as the main pillars of this biorefinery classification, since they might
be reached via different conversion processes applied to various raw materials.
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Let us see some of the platforms. The most important platforms which can be recognised in
energy driven biorefineries are the following: Biogas (A mixture of mainly methane and
carbon dioxide), it comes from anaerobic digestion; Syngas (a mixture of carbon monoxide
and hydrogen), it comes from gasification; Hydrogen from water shift gas reaction, steam
reforming, water electrolysis and fermentation (So, hydrogen come from various sources); C6
sugars (glucose, Fructose, galactose), from hydrolysis of sucrose, starch, cellulose and
hemicellulose; C5 sugars (Xylose, arabinose etc.), from hydrolysis of hemicellulose and food
and feed side streams; Lignin (phenylpropane building blocks), from the processing of
lignocellulosic biomass; pyrolysis liquid or we call it pyrolytic liquid people call it bio oil
also (So it is multi-component mixture of different size molecules), it comes from pyrolysis;
Then oil (basically triglycerides which to convert to your biodiesel), comes from the oilseed
crops, Algae and oil-based residues; then organic juice (made of different chemicals), which
is the liquid phase extracted after pressing of wet biomasses (for example grass); Then the
final one is electricity and heat, which can be internally used to meet the energy needs of the
biorefinery or sold to the grid depending upon how much you are generating basically.
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So the next is products. So biorefineries produce both energetic and non-energetic products
and can be broadly grouped into two main classes: first is energy driven biorefinery system
and the second is material driven biorefinery system.
So in energy driven biorefinery system, biomass is primarily used for the production of
secondary energy carriers. So, secondary energy carriers are basically transportation fuels,
power and/or heat. The products as feed are sold and even better can be upgraded to added-
value bio-based products, to optimise economic and ecological performance of the full
biomass supply chain. Besides electricity and heat, the energy products include the most
promising transportation biofuels until 2020: bio-ethanol, biodiesel, synthetic biofuels (FT
fuels or Fischer–Tropsch fuels and others) and maybe biomethane.
And in the material driven biorefinery systems, which primarily generate bio-based products
(like biomaterial, lubricants, Chemicals, food and feed) and process residues that can be
further processed and used to produce energy (It can be for internal use or for the outside sale
also).
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So, material products include fine Chemicals (such as amino acids, organic acids and
extracts) used in the food, chemical, pharmaceutical industry and animal feed and fibre
products among others. The selected subgroups of material products are: fertilizers; bio-
hydrogen, glycerine (it can be from transesterification of triglycerides basically); Chemicals
and building blocks (refer to the corresponding slide for examples); then we can have
Polymers and resins; we have food; animal feed; and bio materials. So, different types of
materials-based platform.
So the next is feedstock. Feedstock is the renewable raw material that is converted into
marketable products in a biorefinery. The Biomass feedstock can be subdivided into primary,
secondary or tertiary. Today renewable carbon-based feedstocks for biorefinery are typically
provided from four different sectors: (1) Agriculture (which is dedicated crops and crop
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residues); (2) Forestry (that is wood, short rotation poplar, logging residues); (3) Industry
(process residues and waste) and Domestic activities; and (4) Aquaculture (which is algae
and seaweed).
Now Biomass feedstocks, vary composition with different shares of basic components
(cellulose, hemicellulose, lignin, starch, triglycerides and proteins) and three chemical
elements: carbon, oxygen and hydrogen (plus smaller percentage of sulphur, nitrogen and
ashes). Other important characteristics are the water content, heating value, specific volume.
This is the most important thing here: different shares of basic components. This is what
doesn’t happen in the petroleum refineries. The crude which we process in petroleum
refineries, they are almost similar in composition. Of course they vary slightly depending on
from where it is; is it Indian crude, gulf crude (from where it is coming depending upon that
it varies). But not so much like Biomass. So that is why, biorefinery is extremely challenging.
So, in this classification approach, the following subgroups of biomass feedstocks are
assumed: First one is dedicated feedstock: it can be sugar crop, starch crops, lignocellulosic
crops, oil-based crops, grasses, marine biomass (like algae); The seconds is residues: oil-
based residues (It can be animal fat from the food processing industries or used cooking oil -
many times it is called waste cooking oil), then lignocellulosic residue, organic residue and
others.
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Then let us understand the processes. So, in order to produce biofuels, biochemicals,
biomaterials, food and/or feed, the feedstock is transformed into final products using different
conversion processes. Dependent on their products biorefineries can be divided in systems
where operations like fractionation/separation into polymeric products are the main processes
and systems for biofuels and biochemicals in which depolymerisation and chemical,
thermochemical and/or biochemical conversion are the major processes.
Apart from this there is an important process, which is called deoxygenation. Now
deoxygenation is important especially for those processes which are producing transportation
biofuels because the presence of oxygen may reduce the heat content of the molecules and
usually gives them higher polarity, thus decreasing blending possibilities with the existing
fossil fuels. So for the transportation sector you need to deoxygenate the liquid fuel.
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So in the biorefinery systems, several technological processes can be applied to convert
Biomass feedstock into marketable products. This classification approach identifies main
subgroups of processes such as: mechanical and physical, biochemical, chemical processes
and thermochemical. This is what we have already discussed in some of our slides of this
particular lecture.
So, you can quickly have a glance through all the things. So basically, again in a single slide
you can see the biorefinery classification based on platforms, products, feedstocks and
processes. Now you can see there are n number of processes. All these processes are not
mandatory to be present in all biorefineries; it is not so. What are the components (processes),
this will basically depend upon what is your feedstock, what products you want and what are
the platforms you are going to adapt.
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So how these 4 features with their subgroups are used for classification of biorefinery system.
This is one classical example, just have a look at this particular image. So, this is one
particular stream we can say that. It starts from feedstock, it goes for mechanical processing,
then chemical processing, platform, then biochemical processes and then we get either energy
or material products.
And if I take an example of corn, please have a look at (b), the starch crop. Corn is the
feedstock there. Then I process it, mechanically process it, basically the pre-treatment part,
then I hydrolyse it. What I will get? I will get in this platform; I will get C6 sugars. So, it is
now a sugar-based platform. The platform becomes C6 sugar platform. Then it goes to the
biochemical processing. Here the biochemical processing is fermentation and we get two or
more than two products. Bio-ethanol the most important product and then whatever other
things, for example, I have seen animal feed; there can be other products also.
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So, this is the application of new classification approach to selected biorefinery system. This
is based on the product. So, the name, one platform C6 sugars, one platform biorefinery for
biodiesel (oil based), syngas based, biogas and organic juice based, C6/C5 both and
Lignin/syngas. Please have a look later on.
So, we continue with that actually, so again coming to different platforms here. So, this is a
2-platform system (C5/C6 sugars both it is processing). Then again one-platform based on the
pyrolytic liquid. And then oil based platform and we get different types of products and the
source of other energy like heat and power whether it can be possible or not. Whether it can
be integrated into grid or not.
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So, this is based on products. I again leave it to you, please go through it later on when you
actually go through these slides. So, you can see what are the different types of platforms that
we’re using, basically sugar based. And then what are the energy output we are getting
whether it is alcohol based liquid fuel or it is electricity, heat, or it is the gaseous like bio-
methane.
So, this is a classical example, this looks very complicated, but it is not so complicated. We
can try to understand and follow actually what is actually happening. This is a network where
the individual biorefinery systems are combined. So, it is a biogas platform, we are getting
organic juice platform, syngas, hydrogen, we have C5 sugars, C6 sugars, lignin, we have
pyrolytic liquid and oil-based platform.
So, all these have been integrated. How they are integrated? This particular slide is making
you clear and make you understand. Please have a look, what are the products we are getting;
n number of products: biomethane, biomaterials, fertilizer, biohydrogen, chemicals, ethanol,
glycerine, Polymers and resins, food, feed, electricity and heat and biodiesel. This is how the
different types of materials, all the top, the green ones, they are basically the feedstock. So,
feedstock can be on organic residues here, grasses, starch crops, sugar crops, lignocellulosic
crops, then lignocellulosic residues, then oil crops, Marine Biomass, oil-based residues and
what not. Everything has been put and they have been integrated. So, it looks complicated
because of the processes here, but you can understand in a nutshell that all these different
types of feedstocks can be processed in an integrated biorefinery approach where we target
basically for not only biofuels or bioenergy but also for multiple value added end products.
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This is another example a little more simplified based on the biomass here and their
precursors. So, the Biomass and their precursors; carbohydrates, starch, hemicellulose,
cellulose, Lignin, lipid and protein which are extracted from the Biomass depending upon
what type of biomass you are using; and is the platform syngas, sugar, lignin, lipid.
And this is arranged in a little simpler way than the earliest slide. The flow is little easy to
understand here. So, you can see how they are integrated here. That means, one particular
process or feedstock is being used by different platforms as well as it is being resulted into
different end products which are again being integrated with each other to give some end-
product of high commercial value.
I think with this I will stop today's lecture. So, if you have any questions please feel free to
write to me [email protected] or do post your queries in the Swayam portal. And in the
next class the module 2 of the biorefinery module we will be discussing about the different
feedstocks, their properties and integrated biorefinery concept. Thank you very much.
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Lecture 08
Feedstocks and properties
Good morning students. This is lecture 2 under module 3 in which were discussing
biorefinery. So, in today's class we will be basically discuss about the biorefinery feedstocks,
their properties and integrated biorefinery. So, we have almost discussed feedstocks when we
discussed about the Biomass and types and all these things. But here in a biorefinery
perspective we will discuss about the different types of feedstocks that can be used, and their
properties and what it means by an integrated biorefinery.
Let us talk about the chemical composition and characterization of biomass. So, there are
various things. The first one is the elemental composition. So, plant Biomass is mostly
composed of three elements. So, it is 42 to 47% of carbon, 40 - 44% of Oxygen and around
6% of hydrogen. So, all percentages are in dry matter. This elemental composition of biomass
is followed by the so-called macronutrients which are essential for Biomass production.
So, they are and nitrogen, Phosphorus, potassium, calcium, magnesium and Sulphur.
Moreover, plants also need some additional elements in lower quantities which are known as
micronutrients and many times mentioned as trace elements. So some of them are sodium,
chlorine, iron, manganese, copper, zinc, molybdenum, nickel, Selenium and silicon. So, all
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summing together up to almost 4%. Biomass also contains, namely in the ashes, some
different elements like aluminium, arsenic, barium, cadmium, chromium, Mercury, lead,
antimony, Titanium, thallium, vanadium, tungsten. So, these are some of the heavy metals.
So, this is a classical representation of how the elemental composition of plant Biomass looks
like if you have a pictorial presentation. We will take into account the corresponding amount
of that particular element in the composition of biomass. As already mentioned you can see
the highest is of course carbon, followed by oxygen and then hydrogen, then of course
nitrogen, calcium and potassium, silicon all these things.
Then comes organic matter. Organic components can be classified into four major groups:
Carbohydrates, proteins, lipids and nucleic acids (we will see one by one). So, the first one is
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carbohydrate. These are compounds from the combination of carbon, hydrogen and oxygen to
form soluble Sugars. For example, all the monosaccharides and disaccharides and polymeric
carbohydrates such as polysaccharides.
Among the most important monosaccharides, glucose and Fructose should be mentioned.
These are the two most important monosaccharides which we’ll derive from the Biomass and
when they combine, they constitute something called sucrose, which is a disaccharide. So,
polysaccharides are formed through the aggregation of different monosaccharides which are
then used for either reserve or structural function.
Apart from that, starch and inulin (which are also starchy compound basically) are the most
important reserve polysaccharides from an energy point of view. The former is a glucose
polymer present in many seeds such a cereal grain and tubers such as potato and roots as for
example parsnip. While inulin is composed of fructose and glucose and typically found in
roots and tubers.
So, in the bioenergy context both carbohydrates can be hydrolysed into monomers and then
fermented to produce ethanol or even directly fermented with specific microorganisms.
Structural polysaccharides are used to build the cell walls and consists of four organic
compounds: cellulose, hemicellulose, pectins and Lignin. Cellulose is a polysaccharide made
up of 200 to 5000 molecules of glucose, aggregated in linear chains or bundles to build the
microfibers or we called it cellulose microfibrils and of course fibres. So, the hemicellulose
consists of polymers of pentoses and hexoses entangled among the cellulose fibres. Both
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polymers, cellulose and hemicellulose as relatively easy to hydrolyse and represent two thirds
of the lignocellulosic Biomass (they are the major component). Lignin is another major
component; is a high molecular weight insoluble plant polymer, which have complex and
variable structures made from phenylpropanoid alcohols.
Lignin is a complicated structure and it is very rigid. It requires strong acids or bases or other
hydrothermal treatments to be hydrolysed and make cellulose and hemicelluloses accessible.
That is delignification of course partly we discussed it.
This is how Cellulose, Lignin, pectins and hemicelluloses are bound to each other in a very
intricate and complex manner. So, by seeing the structure you can understand that the
cellulose and hemicellulose are very much amenable to hydrolysis, but due to this recalcitrant
nature and intricate structure, you need to remove the lignin. Once you remove the lignin or
delignify it by doing some pre-treatment methods, lignin will be removed, cellulose and
hemicellulose also becomes separated and then you can purify them and take it out for
various purposes. The feasibility and energy demand for hydrolyzing the structural
polysaccharides are essential parameters for the development of second-generation biofuels.
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Then protein: Proteins are made up of Chains of amino acids, organic compounds containing
amine (that is a -NH2 group) and a carboxyl (-COOH) group which provides plants with
enzymatic and structural functions. The production of proteins by plants require high
quantities of energy in comparison with other organic compounds. So, considering the higher
heating value of protein and cellulose the energy yield is almost 52.5% and 96.5%
respectively from protein and cellulose.
Therefore, protein rich biomasses are more interesting for food and feed production rather
than for energy uses. And for energy uses we always concentrate on celluloses and
sometimes of course hemicelluloses also.
Lipids: Lipids are heterogeneous and hydrophobic organic compounds that make up the
building blocks of the structure and function of living cells. The main lipid contained in
Biomass feedstocks are fats, oils phospholipids and waxes.
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Major components of fats or oils are tri-esters of fatty acids and glycerol which are called
triacylglycerols. According to the saturation level of fatty acids whether the containing
carbon is saturated by hydrogen atoms, double or triple bonds, they are classified as saturated
or unsaturated fats. Saturated fatty acids as contained in animal fats have a higher melting
point and thus they are solids at room temperature.
So, you must have heard many times about the saturated, unsaturated, trans fat and all these
things. So saturated fats as it is mentioned that it has the higher melting point so it is not good
to be taken in the food items. Then there are unsaturated fatty acids; vegetable lipids usually
have lower melting point because they contain fatty acids of longer chains and higher
proportions of unsaturated fatty acid and hence they are also called as oils. So, all the nuts
and all contains so much of these unsaturated fatty acids.
Waxes are esters made from the union of long chain of alcohols and acids with the aim of
acting as water proof layers and avoiding water loss in certain parts of the plants.
Phospholipids are composed of glycerol and fatty acid and a phosphate molecule to provide
structure and protection to cells.
From an energy point of view, the production of fats entails an energy demand of almost 50.5
kilojoules per gram with an energy yield of 77.2 %, if you consider a high heating value of
38.93 kilo joules.
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The next one is Nucleic acids. So, the Nucleic acids are composed of nucleotides which are
monomers made up of three components. First is a pentose group, then a phosphate group
and then a nitrogenous base. Now according to their containing sugars, there are two types of
nucleic acid: DNA (which is called deoxyribonucleic acid) and RNA (which is called
Ribonucleic acid). And they are responsible for the encoding and transcription of proteins.
Then water content and the heating value of biomass. The moisture content of biomass is the
quantity of water existing within the Biomass expressed as a percentage of the total materials’
mass. Moisture content of Biomass in natural conditions without any further processing
varies enormously depending upon the type of biomass ranging from less than 15% in cereals
straw to more than 90% as in algae biomass.
So, this is a critical parameter when using Biomass for energy purposes since it has a marked
effect on the conversion efficiency and heating value. So, in no case any Biomass is preferred
for conversion whether it is a thermochemical conversion or biochemical conversion, if it has
more than 20 to 25% or 30% of moisture, that is not desirable. It is true that last class I was
telling you that a certain high moisture containing Biomass can be converted suitably in a
biochemical platform. That is true. But more moisture containing also do create problems
while processing.
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Moreover, high moisture content entails logistic issues since it increases the tendency to
decompose that means resulting in energy loss during storage and reduces the energy and cost
balances. The heating value of biomass feedstock represents the energy amount per unit mass
or volume released on complete combustion. The heating value is referenced into different
ways: the higher or gross heating value HHB and the lower or net heating value LHV.
And we have already discussed in one of the class that LHV is the one, which is appropriate
value to assess the energy available for the subsequent use in case of bio refinery concept or
let us say if you are talking about Biomass to biofuels.
Then inorganic compounds and ash composition: Many elements are present in the Biomass
feedstocks such as Silicon, Calcium, Magnesium and there are many. As well as certain
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heavy metals such as Copper, Zinc, Cobalt, molybdenum etc. The presence of these inorganic
elements has a strong influence in the combustion process by forming gaseous and solid
emissions as well as influencing the ash melting behaviour which may add on to the
corrosion process.
While Sodium and potassium could lead to ash vitrification, high content of chlorine entails
emission of dioxins and material corrosion. The oxidation of S produces sulphur oxides
mainly Sulphur Dioxide which in combination with steam generates sulphuric acid
contributing to acid rain formation. The presence of elements such as Arsenic, barium
cadmium all these heavy metals allows the use of the generated ashes as fertilizers which
improve the environmental performance of the use of biomass for energy purpose and
additional use basically.
Then we will discuss the classification of biomass types with respect to biorefinery. So, if we
classify them according to their chemical composition. So, they can be classified as:
lignocellulosic Biomass, sugar rich biomass, starch rich biomass, oil rich biomass, protein
rich basically these types. So, lignocellulosic we have already discussed many times so it is
containing mostly the plant fibres which contains cellulose, hemicellulose and Lignin. So,
wood, starch, straw and energy grasses all this comes under lignocellulosic Biomass and this
type of Biomass is intrinsically linked to the classification of Biomass into herbaceous
Biomass and woody biomass.
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Under sugar rich biomasses, so there enriched with carbohydrates in the form of
monosaccharides mainly glucose and Fructose and disaccharides sucrose. Such as sugar beet
and sugar cane.
Then if you talk about starch rich biomasses, they have a high proportion of reserve
polysaccharides, basically starch and inulin (Inulin is a starchy compound again), such as
found in the grain cereals whether it is wheat, corn etc. or tubers, potato, artichoke etc.
Oil rich biomasses; so they have high lipid content especially in some specific parts such as
rapeseed and some micro and macro algae.
Then protein rich biomasses. So, from plant Biomass such as oil seed as for example
soybean, sunflower and legumes. As for example peas and also from animal biomasses. Pig
meat, fish and this so called this meat and fish processing industries.
Then agricultural Biomass, forest Biomass, by-products residues and waste, and aquatic
biomass. So, biomass grown in agricultural land, which includes all kinds of Agricultural
produce regardless of chemical composition, whether it is lignocellulosic, starch, oil crops
etcetera and whether it is edible or not.
So then forest biomass; wood from forest including tree plantation in forest land for energy
and woody biomass from forest management. So basically, pruning activities and thinning
activities all these things. Nobody is going to cut the healthy plants to make biofuel. So, that
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is not allowed in any country and should not be done also. So, anything that is because falling
from the tree or when we are doing this pruning and thinning business that time whatever we
are producing the wood or woody products so those can be coupled under the so-called forest
biomass.
Then by-products, residues and waste: This can be defined as biomass from well-defined
side-streams from either agricultural forestry or related industrial operations. It also includes
organic residues from Municipal solid waste, MSW.
Then comes the aquatic biomass, so it refers to any plant or animal material that has formed
in water such as algae, seaweed and aquatic plants.
Now let us talk about the biorefinery feedstocks. Broadly we can classify them as either: (1)
dedicated or non-waste feedstock; (b) residual or waste as feedstock. So, further distinction
can be made for the feedstocks according to their source of origin such as agriculture,
forestry, industry and aquaculture we have just seen that.
So (1) dedicated crops as feedstock involve a fresh carbon-based feedstock which is actually
developed for biorefinery use or purpose from the agricultural, aquaculture and forestry
sectors. This is known as primary feedstocks which is solely used for the biorefinery
purposes and are also well known as energy crops. So, they are only planted for the bio-
refinery or energy purposes. So then (2) residual feedstock involves the carbon-based
feedstocks in the form of waste or by-products or residues from the agricultural, aquaculture,
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forestry, household, organic residues and industrial sector. This is known as secondary
feedstock which is the by-product of primary processing and needed proper dispose or reuse.
So, both these are carbon-based feedstocks that are generally varied/having slight variation in
their original basic composition (of hydrogen, carbon, oxygen and other trace elements)
depending on the geographical location or position, species type, and the environment.
Moreover, they may also differ in the percentage amount of sulphur, nitrogen, phosphorous,
moisture content, micro-inorganic constituents and ashes.
They may also differ in the calorific value, heating value or specific heat, specific volume
and actual weight content. However, carbon is the main constituent of any kind of feedstock
utilised for the carbon based biorefinery.
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So, the dedicated feedstock basically involves the following types of crops: lignocellulosic
Biomasses, that is the energy crops such as forest hardwood, softwood, pine and miscanthus;
Grasses such as green plant materials, grass silage, immature cereals, herbs, bushes, plant
shoots and switch grass; Algal, or Marine Biomass such as seaweeds, sea plants and Marine
micro and macro algae; Oil crops such as rapeseed oil, coconut oil, soybean oil, palm oil,
jatropha oil and cottonseed oil and then many others; starch crops such wheat, corn, ray,
barely and maize; Then sugar crops such as sugar beet, Sorghum, potato, sweet corn, rice and
sugar cane.
The residual feedstock generally involves the following carbon-based waste or bio-products:
Residue from lignocellulosic Biomass treatment such as field crop residues, saw mill residues
such as saw dust, nonedible part of the crop and the forestry residues (which are basically left
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out after the processing); Then organic residues and by-products such as organic urban waste,
domestic waste, waste paper, food waste, compost, fruit peels, vegetable residues, cattle dung
and Swine manure; Industrial organic waste; Oil based residues such as animal fats from food
Industries, slaughterhouse waste, tanning waste, leather waste, oil cake, oil ghee waste, soap
industry waste and used cooking oil from restaurants households and others; Grass residues
and waste such as green plant materials, grass silages, silage leachate immature cereals and
plant shoot.
This is the conventional classification of feedstock. I am just telling you again. We have
discussed about the biorefinery classification. Again, the feedstock has been also classified in
the same way as the biorefineries has been classified: (1) lignocellulosic feedstock for
biorefinery; (2) whole crop feedstock for biorefinery; (3) green feedstock for biorefinery; (4)
the two platform (the two platform we have already we discussed, please understand and
don’t get confused. Again, I am repeating that this is the name here whatever listed here you
are seeing, all these has been classified as it is for the biorefinery. The types of biorefineries
we have discussed in the last class. Now the feedstock for the biorefineries are also classified
in the same manner); (5) Oleochemical feedstock for biorefinery; (6) Algal feedstock; and (7)
Organic waste feedstock. We will just quickly see what are these types of feedstocks. What
are the advantages and disadvantages and how do we process these feedstocks one by one
will quickly see.
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Lignocellulosic feedstock; Most successful, primitive, primary, and potential biorefinery
feedstock among all the biorefinery feedstock. So, it involves the nature dry lignocellulosic
feedstock such as wood material, straw, corn stover other agricultural residues, energy crops
and Municipal lignocellulosic wastes. Now this involves three major interior constituents
such as hemicellulose, cellulose and Lignin.
So, how do we process these feedstocks? So, pretreatment and dissolution of lignocellulosic
biomass (that is the first thing) using a suitable solvent. Then you separate the lignocellulosic
feedstocks into basic three components cellulose, hemicellulose, and Lignin. Once that is
done, so you take out the cellulose and then you hydrolyse the cellulose. So, you hydrolyse it
to what? To fermentable sugars or fermentable glucose.
That can be converted into sugar to biofuels or chemical intermediates like alcohol -
basically, it is an alcohol platform (whether it is methanol, ethanol and butanol) and organic
acid (succinic acid, lactic acid, levulinic acid etc.) either by chemical and biochemical
methodology. Then hydrolysis of the hemicellulose polysaccharides into the xylose sugar that
can be converted into biofuels or Chemicals like xylitol and furfurals by using chemicals and
biochemical methodology.
Lignin can be converted into value added polyphenolic aromatic compounds, bioil and value-
added Chemicals by various catalytic and thermocatalytic transformation. Lignocellulosic
Biomass feedstocks and residues can be used for co-generation of the heat and energy that
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can be used for internal processing. After complete treatment residual cake can be used as
animal feed.
Now the advantages are: they’re easily available and are of course lower cost if compared to
any other raw materials and feedstock; several product varieties - that means we get a wide
array of formation of products - can be possible from lignocellulosic Biomass by various
thermochemical and biochemical platforms. And some of these products are well marketed in
the society; So, the biorefinery products are well replaceable by the petrochemical refinery;
and natural structures of the lignocellulosic feedstock derived/extracted polyphenols are very
well preserved; And simultaneous co-generation of heat and energy is also possible from the
last cake or residual part. After processing whatever solid residues is left over that can go to
co-generation of heat and energy.
However, there are certain disadvantages also; So, dissolution is the difficult task due to the
reluctant nature of the interior complex cell wall. This we have discussed in the slide also I
have shown you have noticed how Lignin, hemicellulose, cellulose and pectins are packed
together. So, breaking it is a big job or tough job. So, you need huge amount of energy and
sometimes Chemicals. So the cost of the process is very high and sometimes it may be time
taking process also. So then costly and tedious pre-treatments are necessarily required. The
development of separation technology to separate primary components is required.
Degradation and conversion of the lignin into respective valuable polyphenolic compounds is
a very difficult task and unless and until you have achieved a proper efficiency, we cannot
have a sustainable biorefinery that functioning basically.
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So, yes in a nutshell, please have a look at this particular slide. Where it is lignocellulosic
feedstock biorefinery. LCF biorefinery we call it. So various types of feedstock; basically
first you divide them, or segregate them, or dissolve them into lignin fraction, hemicellulose
fractions and cellulose fraction. So the lignin fraction, lignin is a high value compound so it
can be used as a natural binder and adhesives. It can go as a substitute for a sub-bituminous
coal and sulphur free solid fuel. Then hemicellulose, if you hydrolyse hemicellulose, such
pentoses and hexoses (C5 sugars), so, you get Xylose, Xylite and furfural and then so many
other things, some platform Chemicals also. So you can have plant gum, can be used as
thickeners, adhesive, protective colloids, emulsifiers and stabilizers.
Now let us look to the cellulose platform. This is the cellulose platform, entire cellulose
platform. If you hydrolyse cellulose, we get glucose that is C6 sugars. So it can be fermented
and you get fuels the like ethanol, butanol and all these things and some other organic acids.
So, you also get HMF hydroxymethyl furfural, Levulinic acid (so these are very high value
component) (And HMF is also fuel additive), so then we can also get lubricants, some sort of
chemicals and Polymers and some softening agents and solvents. From this we can
understand that the lignocellulolytic biorefinery gives us a wide range of products.
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So, the next is whole crop feedstock for biorefinery: So various kinds of the cereal crops like
rye, wheat, triticale, stover, Maize and corn and these entire crops as used as sole feedstock
material. Initially seeds and grains which is amounting to 30 to 40% of what is harvested, will
be mechanically separated from the straw which is 60 to 70% of the total in the weight basis
basically.
The straw generally involves the mixture of chaff, stalk, nodes and leaves) and of course then
these seeds are processed to produce the starch and different value-added products such as
oil, biofuel, biopolymer, bio-oil, lipids and Chemicals. Whereas the straw part that can be
used to generate various value-added products. Similar to those of those of the lignocellulosic
feedstock biorefinery.
It involves dry or wet milling processes depending on the dry or wet feedstock to give the
basic fractionation, hence, feedstock is further divided into two subparts: (1) whole crop dry
mill feedstock; (2) whole crop wet mill feedstock. So the dry mill feedstock is basically entire
cereal plants as harvested. And this harvested plant Biomass is preserved, dried and stored for
long time up to their reuse in biorefinery. And the wet mill feedstock involves swelling and
soaking of the feedstock before it is processed for biorefinery purposes.
So how do you process this whole crop feedstock? So first you go for mechanical segregation
of the seeds and grains from the straw, you remove them. So, for the dry milling entire
harvested feedstock is preserved, dried and stored for long time. While wet milling involves
the primary swelling and soaking of the feedstock.
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The starch present in the cereal is then hydrolysed into glucose via chemical or biochemical
methodology to generate bioethanol or any other alcohol also and other value added side
products such as succinic and lactic acid. Further extraction of the remaining grain
components provides the polysaccharide-based bio Polymers, some drug intermediate, animal
feed and certain other value-added products.
That treated residues or agricultural residues of crops are allowed for the fractionation just
similar to that of the lignocellulosic biorefinery. Moreover, it can also be used for the
generation of the heat and electricity in the CHP platform.
So, please have a look at this particular platform. You can see that from the feeds that grains
such as cereals, corn and maize are actually procured or harvested. Then we segregate them
into the seed, this is the seed platform. And this is the straw platform. You can see the straw
when you decompose then you get the Lignin and hemicellulose and cellulose after the
pretreatment.
So then this all can go to subsequent further processing. You go for elevated gasification.
You get syngas, methanol all these things. Then seed portion can directly go to meal and can
be directly used. Then we can get starch from the seed which can also be extruded and co-
extruded go for Making bioplastics and certain other Polymers basically.
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Then if you go for a biotechnological conversion. So you get glucose, then the glucose will
go for the alcohol platform - fermentation, ethanol. So, you can also have other things also.
So then, when you go for a chemical conversion and modification, so you go for
hydrogenation, you go for some other esterification and other processes and you get you get
many different types of products.
So, in a nutshell we can understand that almost similar type of product also you are getting in
this whole crop biorefinery as we get from the lignocellulosic biorefinery. However, in case
of the lignocellulosic biorefinery the area of such value-added products that is getting
generated or produced is very large compared to other feedstocks.
The advantages are the preservation of the natural elements and structural composition is at a
greater extent and the entire whole crop is utilised for the biorefinery purpose without
creating further waste. So this is one beautiful thing. This entire thing whatever is being
harvested is being used for the biorefinery purposes. Nothing is being wasted.
So, the disadvantage is that utilisation of the expensive and specific energy crop that is
generally not economically viable. Second, this may cause increment in the prices of the
manufactured products in the market. This will happen this thing along with the agricultural
land that may be utilised to grow the energy crops. It may happen as in when this so-called
biorefinery concept is being applied and there are so many biorefineries are getting set up
whether it is in India or other countries. So, people including even the farmers will have a
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tendency to grow such energy crops which takes less time to produce and which also needs
little care during plantation.
And the yield per hectare as well as the energy value and economical value is much much
higher than that of the certain agricultural crops. That is some sort of a threat. So thats the
disadvantage. However, government should help, I have told you in one of our introduction
classes. Again, I am repeating; here comes the government which will play a big role to make
a policy so that no dedicated agricultural lands which are having high value land basically or
fertile lands, should not be utilised for growing dedicated energy crops.
So that should be the government policy because in a country like India where you have huge
population and we need a huge amount of food supply, we cannot do this.
Then green feedstock for biorefinery. So, this involves the feedstock green plant matter and
more specifically green grasses that are naturally wet to produce the variety of products. It
can include the closure fields; nature conservative grassland; Some Green crops, like lucerne
or alfalfa, clover, humid-based organic waste/compost and some immature cereals. Now
these feeds stocks are relativity of lower cost and potentially available in larger quantities.
This naturally wet green Biomass or green feedstock can be successfully converted into the
useful non-feed products such as energy, organochemicals, bioplastics and even feed
products such as animal feed by applying different chemical or biotechnological processing.
So once to do that there is something called a press cake or the leftover solid biomass. So that
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majorly consists of the cellulose, starch along with some small content of essential
components such as dyes, pigments, crude drugs and other organic compounds.
So, this press/green cake is a wide resource for the fibre production and can be used for the
production of animal feed pellets. So, it acts as a raw material for the production of wide
variety of chemicals such as monosaccharide units, organic Chemicals, acids such as
Levulinic or succinic acid and synthetic biofuels. So, press cake can be used for the insulation
material, construction panels and bio-composite materials synthesis.
This is again you please have a look to this particular slide. You can see that from the fields
we get the green wet raw material grass, lucerne whatever it is and then it can; if you are
drying it so you can get a drying material. So, then you can have so many things here. Here
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you have the press that can goes to the juice platform. We have discussed in the biorefinery
concept in the last class.
And whatever left out after the juice is getting extracted is the press cake or the solid part
which is carbohydrate rich. So, the juice can go for different platforms such as this valuable
products and enzymes, dyes all these things. And press cake can go for so many different
types of value-added material, including your biogas, syngas and fibres and solid fuels also.
And whole crops such as straw, seeds, starch etc. you pre-treat them get a carbohydrate
source then ferment you may get whatever left out and convert them to biogas and energy
generation. So integrated way, it can be operated.
So, how do you process this? So, the green biorefinery involves the primary processing
pretreatment of green feedstock or the humid organic waste. Biomass is fractionated into
fibre rich press cake and organic rich green juice. Press cake is allowed to treat for the
hydrothermal and thermochemical processing to obtain the variety of chemicals or
biomaterials. Green juice is treated by the biochemical techniques or the extraction process to
obtain the variety of miscellaneous organic compound and natural extracts.
The residue streams from the above processing can be used in anaerobic digestion for the
production of biogas to generate the heat and power for the internal use.
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Let us understand the advantages and disadvantages of this particular feedstock.
(Advantages) Multi productive system: that is a beautiful thing about this particular feedstock
and low price. And these are available in large quantities. So, grassy green feedstock is more
easily pre-treated and fractionated (the reason is because it has its contents low amount of
Lignin), so it can be fractionated into basic constituents for biorefinery processing that
ultimately reduces costing of the end product formulation when you compare it to the woody
lignocellulosic feedstock. A large variety of the secondary products can be extracted, isolated
and synthesized. Organic waste such as agricultural and forestry waste can be considered and
utilised as a green feedstock.
(Disadvantages) And if you talk about disadvantages: Isolation and separation of natural
compounds by the extraction technique needs further improvement in advanced technologies
and process economics. If you talk about the downstream processing part. Then isolation of
the natural pigments and components or constituents from the press juice is a tedious process.
Tedious process means it is time consuming and the technology also whatever it is there, the
yield is very low. Basically, we need research and more development in the downstream and
processing part.
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Now let us discuss about the Two platform feedstock for the biorefinery. So, this concept has
been implemented by the NREL (National Renewable Energy Laboratory) of the United
States. The feedstocks are separated into two different kinds of platforms, one is sugar
flatform, another is the syngas platform. Now both these platforms can offer energy and
value-added products such as Chemicals, biomaterials, biopolymers and animal food.
Use the initial complete conversion of the carbohydrate materials and then to perform further
conversion process for the syngas production and additional products. The sugar platform
biorefinery involves the production of C5 and C6 sugars from the lignocellulosic Biomass
feedstock via biochemical conversion or fermentation processes.
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The syngas platform biorefinery involves the thermochemical conversion processes that are
basically focused on the gasification reactions of the Biomass feedstock. Other processes
such as pyrolysis, hydrothermolysis, thermolysis, combusting and burning are also carried out
simultaneously. This syngas platform offers the synthesis gas and its consequent production
of fuels, power, electricity and some speciality chemicals.
So how do you process this feedstock? So initially we have to fractionate them to two
platforms basically. So, this fractionated feedstock is then biochemically applied for the
production of the C5 and C6 sugar platforms that can further be transferred into the value-
added products. So, it is a pentose and hexose platform. Then later on whatever the residual
feedstock is left out that is thermochemically treated for the syngas production or using the
gasification reactions at the higher temperatures which can be able to produce the synthetic
fuels and other speciality Chemicals.
The last remaining residues can be used for the production of biogas to generate heat and
electricity for the internal use and animal feed cake.
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If you talk about advantages and disadvantages; (Advantages) the combination of two
different platforms in one biorefinery concept offers a wide array for the production of value-
added products from the single feedstock. So, this kind of bio refinery produces the biofuels
and synthetic fuel. This biorefinery offer the complete use of the feedstock with minimum
process economics.
(Disadvantage) is that, the development of the two-platform binary refinery system and
processing is a challenging task by the means of technological development aspect. The two
platform biorefinery is specifically a sugar-based biorefinery that generally avoids the use of
the higher nitrogen and sulphur containing Biomass compounds.
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You can see this particular slide. So, this is one typical example from the wood chips. It is a
biorefinery plant concept. So the wood chips goes to the steam gasification. So, you get
syngas. So, syngas you catalytically convert using the Fischer Tropsch (FT synthesis
basically). Then when it goes to combustion, we get electricity and heat. So you further
process it (hydroprocessing basically). So, you get the Fischer Tropsch diesel and you get the
Fischer Tropsch gasoline, fractionate them.
And then whatever is left out solid part that is basically the wax. This is one of the simplest
platforms.
Then let us understand the oleochemical feedstock for the biorefinery. So, an oleochemical
biorefinery consists of the oil-rich feedstocks such as long fatty acids and esters, glycerol, oil
seed and vegetable oil crops (There are many, rapeseeds, castor seed, cotton seed we have
seen it in one of the class) which tend to produce primary speciality Chemicals such as
functional monomer, grease, lubricants and surfactants. These speciality chemicals are also
widely used in cosmetics, detergent, drug, Pharmaceuticals and household products.
Saturated C12 and C14 fatty acids are called the laurics, which are made up of the coconut,
palm kernel oil and worked as feedstock for surfactants. Then the unsaturated C16 and C18
fatty acids are called as oleics, which is worked as feedstock for the production of the
biodiesel, lubricants and certain oleochemical Polymers.
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How do you process them? So seed and lignocellulosic Biomass is separated from the oil
seed plants. The seed is allowed to extract the fatty acid ester oil content by extraction while
the lignocellulosic materials which is left of the solid parts (so basically, the oil and removed
part), is fractionated into the Sugars platform. And of course, the Lignin is generated, so the
lignin goes to various end use.
So, the seed oil is then biochemically treated for the production of the biofuel. The
fractionated lignocellulosic material is then utilised for the production of various value-added
material or products. The oil cake residues can be used as a feed for the animals. The treated
lignocellulosic residues can be used as a feedstock for the biogas plant and the generation of
the heat and electricity.
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So, if we talk about the advantages and disadvantages of this particular feedstocks.
(Advantages) It is a long chain fatty acid, so it’s a better resource to convert the raw
feedstock into biodiesel and biofuel (yield will be basically very high if we compared to other
biomasses). So, it can employ the various hydrolytic enzymes for the direct conversion of the
fatty acid esters into the biodiesel and biofuel. It will directly offer the simple fatty acid
methyl and ethyl esters by chemical and biocatalytic conversion routes that is nothing but
biodiesel.
(Disadvantages) So, disadvantages are, the extraction of the oil is a difficult task that
produces the lower yield (because of this extraction technology - need to work more on that).
So, it requires the large amount of organic solvents for the extraction process, which
increases the distillation and recovery cost. The cost of oil-based plants is much higher as
compared to that of the other lignocellulosic plants. All these oil-rich crops are edible plants
that may compete with the human food chain.
The next one is the Marine feedstock for biorefinery. So, the marine feedstock is a widely
available feeds stock in nature that can be efficiently use for the biorefinery purposes. Since it
involves the phytoplanktons which are the largest representative biomass present on the earth.
It basically involves the macro or micro algae. So more than 1 million of the species are well-
known and these algae maybe autotrophic and heterotrophic or mixotrophic.
However, species to species and according to environmental condition, the Algae are varied
in their content such as oil, carbohydrate, starch, minerals, salts and vitamins. So, they are
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recognised as the possible biggest source of the oil and carbohydrate for biofuel production.
Moreover, these aquatic plants are the major source of carbon dioxide sequestration. This is
the most interesting part of the so-called algal business macro or micro algae whatever it is,
as I told you in one of the introduction classes; why so much people are talking about algae
and algal biorefinery nowadays? Why many people across the globe working on algae? The
reason is that, it is its carbon dioxide sequestration or Carbon dioxide uptake capacity which
is almost ten times or even more than that of the Terrestrial plants. So that is one of the most
important aspect of this algal business.
So, you are growing algae, and then you are taking the biomass and you are doing the bio-
processing to get the biofuels, value added products and what not. At the same time, you are
also doing the carbon dioxide sequestration.
So how do you process them? So initially the biomass is separated or harvested from the
aquatic media. The harvesting of algal biomass is itself is very, very time taking and again
whatever (harvesting) methods are available, they are not so efficient. So, people still
working on that. So, the algal Biomass is then allowed for the filtration, centrifugation and
drying.
Then you do the cell disruption. So, you do cell disruption by so many different methods.
You can go for mechanical methods like milling, you go for autoclaving, you go for
ultrasound assisted methods, microwave radiation methods. So, (cell disruption is done) to
remove the components which are present inside the cell of the algae and take it out basically.
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So, the oil that is obtained from the algal Biomass is then treated by biochemical conversion
to obtain the biofuel and biodiesel. The algal residual cakes are a rich source of various
nutrients, like essential minerals, carbohydrates and pigments that can be efficiently isolated.
Also, this residual cake can be used as animal feed or feedstock for the biogas plant.
So, advantages are: of course the cultivation of algae is more advantages to the terrestrial
Biomass. Carbon dioxide sequestration is a biggest advantage. Then Algae are very well
known to adjust to the climatic conditions harsh or mild. So lignocellulosic biomass
possesses the complex cell wall structure while algae have simple structure. And so, you can
easily basically pre-treat them. So like terrestrial biomass, deforestation is not a problem in
case of aquatic biomass.
Algae cultivated in the lakes and oceans do not compete with the basic needs of the terrestrial
life/animals for food crops, land and freshwater for their growth. Another important aspect.
So, the growth rate of the aquatic plants or algae is much higher than the terrestrial plants.
Also, products derived from the algal biorefinery are unique since the carbohydrate sources
produced by the macroalgae are more diverse than that of the conventional plants. This is
another important aspect. Now this aquatic biomass can also be used to produce the
bioenergy products such as biofuel, bioethanol and bio-oil and treated cake can also be
utilised as a rich source for the biogas plant.
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Of course, having said that there are certain disadvantages like the high cultivation cost. So,
you know algae be needs a growth medium. It is not only water. You need to supply food to
them and apart from that they also need the macro and micronutrients. So, the existing
commercial growth media, which is available, which is BG11 or there are many others such
commercial growth media, they are very costly.
So, if you go for a raceway pond culturing and any such photobioreactor in a large scale,
then the entire cost of this cultivation becomes too much. And ultimately your product cost
will be so high that it cannot be commercially viable. So that is why the people are still
working on how to produce algae on waste water streams? Many people are working and my
group is also currently working on this particular aspect that how do we grow algae on low
cost media and different wastewaters, whether it is domestic wastewater or Industrial waste
water.
Some complicated conditions are needed for the successful and resourceful cultivation such
as high exposure of Sunlight, volume to surface area ratio, gas mixing, aeration/ventilation
etc. Economics also not so favourable right now, but so much of work has been going on and
I am sure that in the next decade algal biorefinery will take a centre stage in the entire
biorefinery business.
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So, then the last one is waste based feedstock for biorefinery. So, the waste generated is a
severe problem of the current Civilization since the rate of waste generation is much, much
greater than its actual disposal. That is why you will find waste everywhere. So, the
Civilization waste is most general a carbon based or organic waste which is ideally a nutrient
rich source for the microorganism-based biotransformation.
So, to accomplish the efficient utilisation, the renewable organic waste residues is being
categorised into the following four sectors:
(a) Organic waste from agricultural residue; (b) Organic waste from industrial residue; (c)
Organic waste from the forestry residue and; (d) Organic waste from the urban residue or
Municipal waste.
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Again, the processing is similar type: separated physically, to maintain the homogeneity of
the feedstock. You pre-treat them by various physicochemical techniques. Fractionate the
pre-treated waste into fibre rich press cake and organic content rich green juice. Then you
follow the extraction technique and other hydrothermal and thermochemical processing to get
various platform Chemicals, fuels, heat and other Polymers.
So, advantage is that: You are generally talking about waste, which is already waste. So, you
have to basically collect it, segregate it and then of course use it. So, waste biorefinery assist
to clean our society by converting the waste into value added products such as Chemicals and
energy. Hence, civilization organic waste is considered as the renewable feedstock that can
be reused for gaining several value-added products.
Having said that there is a disadvantage also, that this is available regularly in huge amount
and it needs to segregate properly according to their basic types and chemical composition
before processing. So, this segregation is a big task. The municipal solid waste contains so
many things. It contains metals, it contains plastic, polythene and all these things, food waste
then organic waste, then waste from industries and there are so many things.
So, everything together cannot be dumped to a thermochemical or biochemical platform, you

cannot do that. So, you need to segregate it. So that segregation itself is a big task and if we
educate people to segregate that at source, which is the best possible method to do that when
we generate it, then is good. Otherwise, it is very difficult.
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So, let us talk in a glance how the integrated biorefinery looks like. So have a look at this. So,
Biomass feedstock is coming (any biomass feedstock). It is pre-treated - you do the
extraction, separation and whatever it is. Then it goes for thermochemical conversion using
either combustion, gasification, or pyrolysis. You get steam, gas, bio-oil etc. and you further
get these things.
Then you basically convert it in the biochemical conversion platform using either anaerobic
digestion or fermentation. So, you get biogas and the alcohol platform (this is bioethanol,
biobutanol all these things). And all these things can be combined together to produce the
CHP or the combined heat and power and further electricity generation. So this is an
integrated approach.
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Another one, this is a biorefinery general scheme for precursor containing biomass with
preference for a carbohydrate line. So basically, with more emphasis on carbohydrate. So you
can see this soft wood, cereals, maize, sugar beet all these things, mostly carbohydrate rich;
you fractionate them. Lignin, carbohydrates, fats and protein. So, lignin part can come to
syngas and syngas can be converted to methanol, gasoline and all these things.
Some of the Biomass precursors like straw, bagasse etc. can be converted to energy by
gasification, pyrolysis. Then the carbohydrate platform goes to glucose, then ethanol, ethene
all these things. Certain organic acids will come here. Fats, proteins will also go for so many
other products like enzymes, some animal feed etc.
So, another one. This is an integrated biorefinery emerged from a paper mill: basic product
and their applications. So, this is an example of a thousand kilogram of wood. So, wood yard,
then it is digester, then there is a Bleaching Plant, and it is going to drying machine. Then the
ethanol plant, where we are getting almost 50 kg of ethanol per 1000 kg of the wood
processed. Then Vanillin, it is a very high value product. Three kg vanillin, so it’s a very
small amount with respect to 1000 kg of the wood that is processed and the Lignin. You see
the amount of the Lignin. So for hard wood the Lignin content is very high. Its almost 40%
straight away; for 1000 kg wood processed we get 400 kg of Lignin. And remember, this is a
huge amount of lignin and if we can have a lignin biorefinery here further that side, then this
entire concept of this integrated biorefinery along with this Pulp and Paper Mill will be a
sustainable biorefinery process. You get so many products of course.
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This is one last slide I wish to show you. So, this is the system integration for a waste
biorefinery concept combining biochemical and thermochemical processes to produce
platforms for biofuels and chemical products. So, have a look at the organic waste and
biomass, if it is having algae, it goes to hydrothermal liquefaction, one of the most important
technique will learn about this later on.
So, you get the biocrude. This crude if I process and distil I will get the similar cuts I get in a
traditional refinery - petroleum, diesel, naphtha all these things. Beautiful technique, please
try to understand, you will be wondering where did the plastic emerge from? So, this plastic
is an add-on thing. So, if I can mix plastics with these algae (We have also done some work
on that), it will produce excellent quality of biocrude and the quality of the fuel that will
come from this biocrude will be much, much better than the “only algal” biocrude. And in
this way we are also taking care of the plastic utilisation or waste plastic utilisation. So, then,
the high lignin materials will go to pre-treatment. Then lignin, this is the lignin platform, then
whatever solid that is left out, you can anaerobically digest it.
So, you get basically the volatile fatty acid (VFAs). So then yeast fermentation - you get oil.
Esterification and hydrogenation we get ethanol, butanol, propanol. Again, this is the alcohol
platform. Now anaerobic digestion - we get biogas, biogas can be converted into energy
generation. It can be directly integrated to the grid also, by adopting proper technology. Heat
and electricity from the biorefinery.
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Now, whatever hydrothermal liquefaction residues will be there (very less) that can also be
combined with this anaerobic digestion process to produce electricity. So, do you understand
it is a beautiful process and a complete integrated refinery concept in which a particular waste
can be segregated and another waste like plastics also can be integrated to take care of the
solid waste management or plastic waste management problem. And so as to get a better fuel
quality also.
So, another one just quickly will go through. It is an integrated 4-platform (biogas, green
juice, green fibres and electricity and heat) biorefinery using grass silage and food residues
for bioplastic, insulation material, fertilizer and electricity. So, the grass silage - process it
and separate, you get green juice. And then green juice can be anaerobically fermented.
Separate, you get fertilizer, biogas platform this is you get heat and electricity. Natural gas
also can be combined with this. This is another integrated four platform bio refinery concept.
With this I conclude and thank you very much. If you have any query, please write a mail to
me at [email protected]. You can also drop your query in the Swayam portal. And in the
next class which is module 3 and lecture 3 we will discuss about the economics and life cycle
assessment of the biorefineries. Thank you very much.
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Lecture 09
Economics and LCA
Good morning students, today is lecture 3 under module 3 and you know that we are
discussing about biorefinery and concepts under this module. So today we will be discussing
about the economics and the life cycle assessment of biorefineries. So, let us begin.
The development of a new bio refinery, its design and construction, requires huge
investments; cost estimation are often Paramount for deciding the economic viability of
biorefineries and must be performed on a case-by-case basis. However, it is possible to make
a rough estimation based and data from demo plants, process Modelling and/or literature at
various stages of the biorefinery development. A Biorefinery system include the harvesting,
storage and transport of the products as well as the biorefinery itself. Innovative new
conversion Technologies usually follow a development pathway from the lab, to piloting,
then demonstration and finally the construction of a commercial plant. The number of years
for a bio-based product to reach commercialisation depends heavily on the economics and
hence on drop-in versus non-drop-in (which means existing demand and infrastructure), type
of conversion technology and supply chain integration.
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Total cost can be divided into two things: one is a capital expenditure, which is called as
CAPEX and then the other one is the operating expenditure, which is called OPEX. CAPEX
can be subdivided into mainly two things, one is plant cost and off-site cost and another cost
also we can add on which is called engineering cost. So, the plant cost represents the capital
necessary for the installed process equipment with all the auxiliary and accessories that are
needed for the complete process operations. So, including from the piping, instrumentation,
insulation, foundations, site preparation everything. Whereas off-site costs are not directly
related to the process operation. They rather include costs of the addition of the site
infrastructure, for example power generation units, boilers, pipelines, offices etc. OPEX
consists of fixed and variable cost. Variable costs comprise cost of feedstock and supplies,
waste management, product packaging, finished and semi-finished products in stock etc.
Fixed cost comprises salaries, taxes, licence fees, interest payments, marketing cost etc. This
gives us a rough idea about what are the different types of costs involved in a biorefinery.
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So, if you represent it in a schematic, we can understand in a better way, please have a look.
You can see that 20% to 30% of the cost comes under the capital costs, which are investment
cost basically. Equity, interest rate, life time etc. Then the major cost, 40% to 70%, is the
consumption related cost. So, these are feedstock cost, auxiliaries (like electricity requirement
- energy basically, chemicals), disposal cost etc.
Then the next is 10% to 25% is the operation related cost, which takes into account the
manpower cost, insurance cost, cost of services etc. All these things, these three are basically
the cost of the entire biorefinery process. So minus if you do the revenue, then that will
become your profit.
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So, estimations for the cost of biorefinery products are affected by a range of drivers that
could change in direction and importance over time. So, some of these include: supply cost,
market price and demand, competing, non-energy markets for Biomass, preferences of
farmers and Woodland owners, Success of alternative waste recovery and recycling,
production cost, storage costs, distribution cost, access to market.
The first one, supply cost is basically feedstock supply cost. So how the feedstock is getting
procured from the source and getting transported and all these things will come into that.
Then again, the market price of the feedstock and market price of the product that you are
eventually going to sell off all these things comes under that, with respect to demand for that
particular product.
Then the second is, competing non-energy markets for the biomass. One of the most
important thing that we need to understand at this point also that these bio-based products’
acceptability has to be increased. So, a public awareness and campaigning is required to do
that. So, right now even when somebody going to install a biorefinery, it is of paramount
importance that they should also work on increasing the awareness of the bio-based products.
Then preferences of farmers and Woodland owners. So this is for both the things: one, is that
feedstock procurement and all these things; then second, to whom you are selling the
products. So, in both the cases farmers are of course stakeholders and the Woodland owners.
The next one is about the success of alternative waste recovery and recycling. As I told you in
one of our class that recycle and reuse is one of the most important factors that is associated
with the so-called bio refinery concept. So, unless and until we are looking for a value-based
product from the waste that is getting generated from the biorefinery itself, we cannot have a
sustainable economy. So that needs to be done. For that you have to develop the process
technologies also. Production cost is of course very important that has to be taken care of, so
then storage cost also important cost. You are you are going to store 2 things. First is that
storing of the feedstocks; second is that storing of the finished products. And apart from that
in between also storing of this waste and all, till they get recycled and converted. So then
distribution cost and access to markets, all these will impact the entire costing of the
biorefinery system.
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So, main economic factors are capital cost, Plant capacity, process technology, raw material
cost and chemical costs. The major economic factor to consider for input cost of biodiesel
production is the feedstock, which is about 75 to 80% of the total operating cost. This is for
an example that let us understand that if biodiesel is a prime product or the main product
from a particular bio refinery, then what is the situation.
So, other important costs of course labour, methanol and catalyst which must be added to the
feedstock with respect to biodiesel. Using an estimated process cost exclusive of feedstock
cost US dollar 0.158 per litre for biodiesel production and estimating a feedstock cost of US
dollar 0.539 per litre for the refined soy oil and overall cost of US dollar 0.70 litre for the
production of soy-based biodiesel was estimated. So, I have given the reference at the bottom
you can refer to it later on.
Palm oil is the main option that is traded internationally and with potential for import in the
short-term basis.
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So, the oil in vegetable seeds is converted into biodiesel through oil extraction, oil refining
and transesterification. And as I told you in last class even last to last class, we have
discussed that extraction technology should be developed in such a way that they are very
efficient as well as they are low cost. And the cost of biodiesel can be lowered by increasing
feedstock yields, developing novel technologies and increasing economic return on glycerol.
Please understand that glycerine is one of the most important by product from the
transesterification reaction or biodiesel production. Glycerol is a very high value product but
the problem right now is that the amount of glycerol that is produced across the globe and
that is converted into useful products, there is a disparity. So you have huge surplus of
glycerol. Unless and until we develop technologies to convert glycerine to other value added
products rather than what is right now being used commercially then the sustainability of a
bio diesel a based biorefinery is still in question.
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Let us look at Biomass cost which is one of the most significant cost associated with the
biorefinery. The biological fraction from waste generated in developing countries is 50%
higher when compared with developed nations. So, waste based biorefineries play a vital role
in the economy of developing countries. In India the most common feedstock for bioethanol
biorefineries is molasses.
Because there is a huge by-product that is coming from the sugar processing industries,
mostly based on sugarcane. So, the market price of molasses fluctuated from 18 to 92 US
dollar per tonne in the last decade. And market price fluctuated between US dollar per tonne
for rice straw is between 11 to 13, bagasse 12 to 14 and rice husk is 22 to 30. Now in India
food grain straw is mainly used as a cattle feed, followed by its use in industry as a packaging
material, construction materials, straw board and paper and hardboard units. Cost of
Agricultural and Forestry Residue is dependent on various parameters such as biomass
production, pre-processing, handling and transportation. So, when you talk about biomass
cost, all these costs are coming into picture.
Cost of residues fluctuated between 14 to 34 US dollar per tonne, minimum being for the
bajra straw and the maximum for the arhar stalks. In another scenario when the travel
distance was 100 KM from the farms cost fluctuated from US Dollar 36 to 55 per tonne for
bajra straw and arhar stalks respectively highlighting the influence of transportation on
market price of the residues.
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We have discussed about this travel cost in one of our lectures previously that the
transportation cost is a significant cost with respect to the Biomass procurement cost. The
cost of the Biomass as it is will be very low because any way when it is getting procured
from forest resources, agricultural field or anywhere, municipal waste also, its price or cost is
very less. But when we keep on transporting it the transportation cost increases significantly
due two things.
First is, where is the Plant located, how far it is from the source, that is source of procurement
and what is the density and shape and size of this biomasses. If it is low dense, then it is
basically very high-volume and transportation becomes difficult as well as it becomes costly.
So, India is known for its biomass diversity which can be categorised as grasses, woody
plants, fruits, vegetables, manures, aquatic plants and what not there are so many. So,
biodiesel manufacturers have also started using algae as feedstock. These available biomass
sources can be broadly divided into three categories: energy crops, agricultural crop residues,
municipal and industrial wastes. And we have already discussed this significantly in a few of
our classes.
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So, let us now understand what contributes to the logistics cost. So, one of the bottlenecks
involved in commercialization of biorefinery is the cost involved in logistics, which include
several discreet processes. Harvesting and collection of biomass and site that is from the
cultivation field or forest. Storage of biomass is a significant cost, so proper storage of
biomass is of paramount importance to ensure round the year availability even though they
are harvested at different times of the year. Because most of the crops are seasonal. Location
of the storage space can be at the collection site, biorefinery, or at any place in between the
two sites. So the location will eventually decide about the transportation. Then biomass
storage at the collection site is a low-cost option, but that is not always a Win-Win situation
because there are certain disadvantages associated with it such as the loss of biomass material
due to degradation; uncontrolled moisture content of biomass leading to processing
difficulties; chances of contamination due to spore formation or fungal infection; and finally
low storage period as the farmers need the land for cultivation of next crop. So, biomass
storage is a critical stage in the biomass supply chain, hence, the location and facilities should
be decided based on the holistic analysis of respective storage unit.
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Processing of biomass: So, low energy content of Biomass in comparison to fossil fuels
coupled with low density means that comparatively large amount of biomass is required to
obtain a similar amount of energy. So, this poses severe handling and transportation
problems. Compacting of biomass through several processing or pretreatment steps is
advantageous as it reduces the volume of biomass as well as improve the storage, handling
and transportation efficiency.
Though densification techniques (we have discussed that how do you densify this, you make
into briquettes, pellets and all these things) the harvested biomass can be processed into bales,
pellets, cubes, pucks, briquettes and wood chips. Technically processing can be undertaken at
any stage. However, the advantages are maximized if it is done after harvesting or collection
stage.
Transfer of biomass from the collection point to a common point from where the
transportation can be initiated is also very important. It also involves loading of biomass into
the transportation vehicles and unloading them once the Biomass reaches the biorefineries; so
for each and every step there is a cost associated.
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Transportation: biomass feedstocks have geographically varied locations, low energy content
and density, which makes transportation the cost-intensive step of the entire supply chain.
Cost input during transportation is dependent on travel distance, travel time and bio mass
density. Travel distance affects the cost involved in the fuel purchased for vehicles and also
the travel time involved. Then travel time in turn affects the cost involved in hiring
manpower, maintenance of the vehicles and insurance. Manpower is required for basically
loading and unloading the Biomass in the transportation vehicles. So, travel time includes the
time spent on a round trip and the waiting time during the loading and unloading of biomass
at the site and biorefinery respectively. Hence, the larger the distance between the two sites,
larger the travel time and higher is the capital allocation and manpower and maintenance; so
these things needs to be optimised.
Another factor affecting the transportation cost is the Biomass density. The low density of
biomass means a large volume of biomass needed to be transported, hence more number of
vehicles required or multiple trips to be undertaken by limited number of vehicles.
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Economic viability of biorefinery system. So in economic viability of biorefinery systems, we
will see a case study of bioethanol. Bioethanol plants and sugar cane mills are well
established processes, where the biorefinery concept can be implemented little easily since
sugarcane bagasse is a feasible feedstock to produce fuels as well as certain chemicals.
Techno economic analysis of Ethanol production using mild liquefaction of bagasse plus
simultaneous saccharification and co-fermentation shows a minimum selling price between
50.38 and 62.72 US cents per litre which is comparable with the market price.
The production of xylitol, citric acid and glutamic acid from sugarcane lignocellulose that
includes bagasse and harvesting residues each in combination with electricity have been
evaluated. The three biorefinery systems were simulated to be annexed to an existing sugar
mill in South Africa. The case study is there, please read the references that have been given
at the bottom. You can please refer to those and read in details from the manuscripts.
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The production of xylitol and glutamic acid has shown economic feasibility with an internal
rate of return of almost 12.3% and 31.5% exceeding the internal rate of return of the base
case which is 10.3%. Likewise, the production of ethanol, lactic acid or methanol and
ethanol-lactic acid from sugarcane bagasse have been studied. Lactic acid demonstrated to be
economically attractive by showing the greatest net present value almost it ranges from 476
to 1276 million dollars.
In the same way the production of ethanol and lactic acid as co-product was found to be a
favourable scenario. Since this acid has applications in pharmaceutical, cosmetic, chemical,
and food industry.
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Let us now understand the biodiesel. So as for biodiesel production this industry also has the
potential to integrate bio refinery system to convert residual biomasses and waste into
biofuel, heat, electricity and bio-based green products. Glycerol is the main co-product in
biodiesel production and can be transferred into valuable products through chemo catalytic
technologies.
The valorization of glycerol for the production of lactic acid, acrylic acid, allyl alcohol
propanediols and glycerol carbonate has been evaluated; all glycerol valorization routes
shown to be profitable, being the most attractive the manufacture of glycerol carbonate. Palm
empty fruit bunches are abundant lignocellulosic residues from the palm oil biodiesel
industry. The conversion of this residue into ethanol, heat and power, and cattle feed were
evaluated according to the techno economic principles.
So, the economic feasibility of bio oil production from the EFB via fast pyrolysis using a
fluidized bed technology was studied. Crude bio oil can potentially be produced from the
EFB at a product value of 0.47 dollar per kg with a payback period and return on investment
of 3.2 years and 21.9% respectively, which is considered as almost a moderate range. So, the
integration of microalgae and Jatropha as viable route for the production of biofuels and
biochemical has also been analysed in the United Arab Emirates context.
Three scenarios were examined; in all of them, biodiesel and glycerol is produced; in the first
scenario biogas and organic fertilizer is produced by anaerobic fermentation of Jatropha fruit
cake and seedcake. And in the second scenario the production of lipids from Jatropha and
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microalgae to produce biodiesel was evaluated and the production of animal feed, biogas and
organic fertilizer was also integrated. In the third scenario that involves the production of
lipids from microalgae for the production of biodiesel, as well as hydrogen and animal feed
as final product (from the lipid extracted from algae basically); so this is the first scenario
which was almost profitable compared to other scenarios.
So now we will understand about the life cycle assessment. Now, whenever we are going to
develop a process technology or let us say refinery, biorefinery or any industry whether it is a
waste biomass-based industry or any other feedstock-based industry we need to carry out a
life cycle assessment plus the techno economic evaluation. So, we have discussed about the
cost, in a nutshell we understand what are the different types of cost that are associated in
setting up a biorefinery. Now we will try to understand what is the meaning of a life cycle
assessment (LCA).
LCA provides a quantitative estimation of the potential environmental problems of an

examined system in terms of environmental indicators proposing concurrently ways to
overcome the environmental burdens thus addressing thoroughly the issue of sustainability.
The LCA results could provide the basis for decision to support establishing new
technologies, processes or products for industrial applications and policy-making for
mitigation of Climate Change or fossils resources dependency.
Based on the biorefinery system the assessment of parameters related to its implementation
potentials (for example feedstock availability), feasibility and stability add valuable aspects
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of the new products and production Technologies. Moreover, these results constitute the
cornerstone of robust conclusions and future oriented recommendations for the industries.
So, let us understand how it happens actually. So in step 1, we have to define the goals. So in
the step 2 we will talk about the inventory data collection. In step 3 it is the impact
assessment and in step 4 it is the results interpretation. So, the method of choice for deriving
environmental indicators for biorefinery is life cycle assessment based on the ISO 14040
methodology encompassing the 4 steps as mentioned here (refer slide).
So, if all necessary input and output streams cannot be collected within the framework of life
cycle inventory due to a lack of valid data, this can result in a retroactive redefinition of the
system boundaries. The sensitivity analysis can also show the necessity to refine the system
boundaries.
When you define the goal in the step 1 basically you are talking about the system boundaries.
You define the system boundaries, functional units, and what are the environmental impacts,
that is going to arise from the processing of the feedstocks, handling them and when you
convert them to value added products. In the second step it is about inventory Data Collection
where experimental and literature data will be collected and stored, then databases will be
accessed and you have to take the help of certain LCA software.
In the third step, it is impact assessment, where the data processing for the environmental
impact will be basically carried out to understand whether there are any environmental effects
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at all from the biorefinery perspective when you are processing the Biomass and converting
them to the value-added products. And in the final step, that is the result interpretation, you
basically elaborate what are the results we have actually received. Then, based on that, what
are the recommendations for reducing the environmental impact and/or mitigation. So, these
are the essential 4 steps which are required to carry out the basic LCA study. There are so
many other things also but, in a nutshell, let us try to understand what is LCA.
So, in the course of evaluation and interpretation, it can be determined that additional data
must be generated in order to arrive at a representative result. Therefore, the data required for
the life cycle inventory is of particular importance within the LCA. The representativeness of
data and factors needs to be verified in a case specific way for every biorefinery pathway
assessment.
The life cycle steps are implemented in different modules of the assessment - From the
feedstock generation to the standardized products. Furthermore, the modules gather the
input’s consumption and calculate the emissions of the three main greenhouse gases - carbon
dioxide, Methane and Nitrous oxide and primary energy demand. So, the parameters that are
considered for each production step of the biorefinery as input factors for the assessment are:
agro inputs, field work, field emission, use of the Fossil energy resources, conversion inputs
transport efficiencies, emissions from steam production, Electricity production, multi product
outputs and the residues.
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So, two categories of input parameters: emission driving parameters and process parameters.
For example, the input of the field emission needs the process parameter of the field work to
calculate the exact amount of emissions. So, you have to basically collect so much of field
data and then analyse them to understand the value of emission. The emission driving
parameters are linked to emission coefficients. Applying representative emission factors is a
significant challenge and application of default values and non-specific data, for example on
energy-mixes, can impose strong divergences concerning the representativeness of results.
The use and disposal phase can only be partly covered as operators and developers have only
limited data and influence on the use and disposal of products. Based on these limitations, the
results can only be interpreted as estimates. Further, the overall emissions of the different
biorefinery operations and process steps can be calculated, and a second step the emissions
are converted to a specific value with regard to the functional units like for example the
annual product quantity.
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The handling of cut-off rules must also be very carefully considered as these lead to
considerable uncertainties in the result if too many material and energy flows are excluded
from the LCA. So non-relevant life cycle stages, including the associated material and energy
flows are excluded based on these cut-off rules. Cut-off criteria should ensure that this
procedure is not purely arbitrary.
Life cycle thinking is referring to a maximum balancing scope, for example cradle-to-grave
(the meaning of cradle to grave here is basically you start from the feedstock and end up in
the finished goods or finished product. The entire lifecycle, so that is basically from cradle-
to-grave. That’s what it means.), as bio-based products strongly reveal their positive
environmental potential especially in the use phase by substituting Fossil-based reference
products and services or end of life phase related to the biogenic origin of product bound
carbon.
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So, let us look at this, particular generalized system boundaries of a biorefinery LCA
approach. This is a complete system boundary that is defined for a particular value-added
biofuel based biorefinery. So, you start with the Biomass production chain basically, inputs,
energy, fertilizer etc. to grow biomass, procure, transport, process. Then in that case there
will be emissions and that will be the residues.
Now to make a sustainable biorefinery we also should convert these residues into value added
products that is basically the recycling of the waste. Then the biomass goes to the Processing
Unit, the plant, in which you are processing into value added products. So, when you are
doing that there is an enormous amount of emissions that is coming out. And of course, again
another set of by-product.
That by-product also should be taken into consideration to convert to value added products
and basically minimise the waste and recycle them. Inputs are energy, Chemicals, nutrients
and enzymes and there may be many things and the biofuels and other value-added products
in terms of energy, electricity, and platform chemical. So, this is the complete system
boundary and it’s an entire system.
Now I can take some small boundaries here also (refer to the corresponding slide for
explanation @time 28:05 min). This is a generalized one. So, I can take one by one
processes, one system boundaries, find out what are the emissions and also, we can do the
techno economic assessment also by defining the system boundaries. So, this is how actually
the boundaries have been defined for a biorefinery LCA approach.
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Let us now understand the current challenges of assessing biorefineries. Considering life
cycle assessment as an established method, to assess the environmental impacts of a product,
based on the ISO 10400 criteria, the choice of allocation is one of the most discussed issues.
Additionally, the choice of functional unit, system boundaries and whether the LCA is
accounting or consequential are the key issues for the LCAs of biorefineries.
So, functional unit and allocation: Let us understand what it means. So, the functional unit is
often reflected by reference material flows (for example, the amount of output) rather than
the function (for example, the heat value). Biorefineries producing multiple outputs increases
the difficulty of identifying one main function. The importance of the choice of functional
unit for comparing and interpret results is unquestionable. Multifunctionality of biorefinery
concepts are also leading to the common challenge of allocating the environmental impacts to
various outputs.
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Different outputs from a biorefinery can actually have different functional units and physical
attributes leading to a core question in the LCA for biorefineries. The partitioning method is
an ideal choice for biorefinery which is based on artificial splitting up of multifunctional
processes into a number of independently operating monofunctional process. So, it is easier
to assess basically if you do like that. It is necessary to distinguish between processes with or
without an underlying physical relationship between the outputs and the emissions.
Now, let us understand system boundaries. So, the choice of system boundaries or balancing
the scope strongly influences the result of value based biorefinery quality evaluation. So, you
can go for an entire cradle to grave life cycle. However, from a practical point view due to
limitations in data availability especially in terms of the use and the end of life phase, the
assessments of one follow cradle-to-gate or gate-to-gate approach. So these are midsegment
approaches.
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The considered life cycle stages include: Biomass cultivation; process steps upstream and
inside the biorefinery; consumer use of biorefinery products; and product disposal. Although
there is a distinction between bio based and non-bio-based value chains, it is worth noting
that a purely bio-based value chain may have connections and interactions in common with
non-bio-based value chain. The system boundaries of the case studies in the reports are
mostly cradle-to-gate.
The use and disposal phase is often not covered as operators and developers of biorefineries
have only limited data and influence on the use and disposal of products.
This is an interesting slide where we can understand, what is this cradle-to-Grave, cradle-to-
gate and gate-to-gate system boundaries under LCA concept. Look at the Cradle-to-Grave, so
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it starts from the Biomass cultivation and extraction everything to recycling and disposal you
get it? So it is the entire bio refinery system. Now let us understand cradle-to-gate which is
intermediate boundary. It starts from Biomass cultivation and extraction, let us go to the
production, processing, intermediate product and let us say till production or processing. It is
not sacrosanctly defined like this. You can either take it that side or you can bring it this side
also. You can end anywhere. It depends upon what type of data is available with you and how
easily you can proceed with the availability of the data basically. Then, if you understand
about gate-to-gate it is basically a single process. Let us see this. Production and processing
of the biomass. This is one gate-to-gate approach. It can be production and processing of the
intermediate product. Again, gate-to-gate approach. So, this is how the system boundaries has
been defined for LCA analysis. So, the second one is a non-bio-based value chain and top one
is the bio-based value chain.
So, now let us take a case study of the technical, economic and environmental assessment of
a biorefinery. So, we are talking about a 2-platform biorefinery, where there is a C5 and C6
sugar platform to convert it to bioethanol and the Biomass is corn stover. So, the raw material
is corn stover, the platform is the sugar platform, both C5 and C6, the process is a
lignocellulosic biomass conversion.
The product and the major end material is ethanol. There may be the other by-products also.
Product energy is electricity and heat. Concept according to the VDI 6310 is the
lignocellulosic biorefinery and the balancing scope is cradle-to-gate.
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This case study is characterizing a lignocellulosic biorefinery using residual corn stover to
produce ethanol as fossil fuels substitute. So, it has on-site process energy generation via
Lignin combustion in a boiler and Electricity production with steam from combustor. So, the
inherent meaning of this particular sentence is that whatever lignin is getting generated
during the pretreatment or delignification of the Biomass is getting burnt to produce
electricity.
Additionally, biogas is generated on-site by the anaerobic digestion of wastewater. No

external energy supply is needed, every energy that is required for the biorefinery is getting
generated on-site. So, the lignocellulosic bio refinery has on-site cellulase enzyme production
facility also. So, the bio refinery process described is designed for a capacity of
approximately 104 tonne corn stover operating 24 hours 6 days a week. This corresponds to
approximately 7,500 plant operating hours per annum.
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So, this is the overview of the techno economical assessment: the process pathways of
ethanol synthesis from corn stover. So, these are the agrochemicals requirement. How much
it is required it is written there. The energy, how much it is getting consumed in the form of
electricity, steam and how much electricity credit you are generating. Then the operating
materials like cost of the corn steep liquor, sulphuric acid, diammonium phosphate, some
other solvents all these things and of course, the water (it is a huge requirement and a huge
cost).
So, then it goes to the cultivation of the corn stover, you get let us say 3883 kilograms per
hectare per year and it goes to the lignocellulosic biorefinery (biomass productivity), comes
to the biorefinery and you get almost 834 kilograms per hectare per year of the ethanol. Then
of course there are other things. So you can refer it and get an understanding that how that
TEE looks like.
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So then lignocellulosic ethanol biorefinery pathway. Ethanol is produced based on corn
stover. The milled corn stover is pre-treated in a dilute acid pretreatment process. So, 18
milligrams of sulphuric acid per gram of dry mass is optimised requirement. Enzymatic
Hydrolysis is used to convert the hemicellulose and cellulose into monomeric C5 and C6
Sugars and lignin which are the platform inside the described ethanol biorefinery.
Cellulase is produced on site. The C5 and C6 sugars are fed into fermentation tanks. The
fermentation uses metabolically engineered strains of the Saccharomyces cerevisiae
microorganisms that are capable of co-fermenting xylose and glucose to ethanol. So, this
particular Saccharomyces cerevisiae, which is the engineered strain, can co-ferment both C5
and C6 Sugars to ethanol whereas, a separate hydrolysis and fermentation processes applied,
SHF process.
So finally, the fermentation broth is fed into a distillation process. Distillation columns and
Molecular sieves are used to produce 99.5% ethanol. It is a very great purity. So again, you
can see here, whatever Lignin is coming from this hydrolysis after the delignification step, is
being fed to the boiler. So, lignin is burnt basically and you generate electricity and heat in a
CHP platform.
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So, this is the biorefinery and reference system – a value chain case study with reference to
cradle-to-gate approach. So, the Biomass - corn stover – transport - biorefinery - we get
ethanol, Lignin - converted to energy, whatever left out can be converted to fertilizer. It is not
that fertilizer is the only thing, it can be any other things also. So crude oil – extraction –
transport – refinery - gasoline, naphtha, aromatic etc. This is your general refinery. This is a
bio refinery.
So, the key characteristics of the case study based on the 2 platform C5, C6 sugars and Lignin
bio refinery to produce bioethanol, electricity and heat from corn stover is that; so, the state
of technology is almost commercial. Country is United States; the main data source is from
literature. The products are ethanol and Electricity, these are the costs given in a million
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Euros - investment, feedstock, operating, labour and all these costs and then auxiliaries,
feedstock, conversion rates are also given.
So, if you look the mass balance case study; so you can see, these are the different things -
waste water, conversion loss, Lignin (converted to CHP), ethanol, water, corn stover, and
Chemicals. Have a look here, the input - the major input cost is of course that of the water,
followed by the Biomass that is corn stover, and the small amount is due to the Chemicals.
Now, if you talk about the output, so the major cost is wastewater.
So, this was what I was mentioning that waste water needs to be treated. Recycle in-house so
that our dependency of freshwater will come down. Followed by the conversion losses, huge
amount of conversion that is getting lost and then this yellow (z)one you can see, that is the
lignin - of course it is value added because it is getting converted to electricity and heat;
followed by this brown (z)one, which is the ethanol production. See the cost in terms of the
mass balance.
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So, when you talk about the sharing of the cost, it is again in the same manner - raw material
supply, followed by auxiliary and operating material, followed by the imputed interest, then
the next is the write-off cost and there are some other costs like insurance and auxiliary and
operating material.
So, if you look at the sensitivity analysis of the cost structure in a case study, you can see this
red one is the raw material supply and the blue one is the total investment (the entire
investment cost) and the line which is horizontal you can see that is the other costs. So, based
on the self-sustained energy supply within the biorefinery, especially no effect on the
sensitivity of the overall cost structure is related to the energy cost. So that is what is
understood from this particular slide.
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So, value chain environmental assessment in case study. So, this is an overview of the TEE
assessment results cases study. So, the greenhouse gas emissions. This was estimated after
the LCA study or TEE study. Raw material sourcing corn stover is almost 2651 tons of
carbon dioxide equivalent; so the biorefinery 35017, reference system 368751 tonnes and
savings is 331083 tonnes. Then this is the cumulated energy demand in terms of the terra-
joule, then these are the other costs in terms of the million euros.
If we talk about the greenhouse gas emissions of biorefinery compared to reference case
study, you see, this is the second-generation ethanol biorefinery. And this is the greenhouse
gas emission. You see the gas (emission), this is nothing when you compared to the fossil
reference. So, this is quite understood from this particular slide, when you talk about
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biorefinery concept that Greenhouse gas emissions is far less compared to the Fossil fuel
emissions.
So, the next is cumulative energy demand of biorefinery compared to reference. So again you
can see that the energy demand for biorefinery compared to the fossil fuel reference, with
respect to renewables, it is little higher. But then you have to understand, what is the output in
terms of every aspect including the environmental aspect. It is not about only the energy
demand or energy requirement.
This is the cost and revenue, the final one. You can see, this is the input cost basically and
this is the final value of the ethanol selling price. So, you can see that it is marginally higher
than all the input cost and everything is being accounted here, whether it is water supply,
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disposal, raw material, insurance, maintenance, everything. So, we can understand from this
particular slide that, the ethanol cost (the annual selling price) of the total amount that is
produced is higher than the input cost or the production costs. That means we are in profit.
So, let us conclude this LCA discussion. So, today's biorefinery processes still show
significant optimisation potential while the production processes of fossils-based products are
technically mature and optimised. Technical developments in the biorefinery sector continue
to generate new knowledge and as they are commercialized and deployed, these are likely to
lead to further improvements via economies of scale. As a result, it is expected that the
production cost for bio refinery products will decline in the near future and that the product
will become more competitive over time. Until this is achieved, bio refinery pathways will
continue to rely on targeted policy measures and public transport programs to drive the
development.
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The wide implementation of biorefinery technologies requires that a large number of possible
products meet the quality and price requirement of the market. So, basically price is one
factor, another is the awareness of the bio based products and their acceptability by the end
users. So in addition it is necessary to identify and optimise the site-adapted biorefinery
technologies and recycling paths from the multitude of potentially available raw materials
and conversion paths.
So, with this I wind up today's lecture; in case you have any query, please feel free to write to
me at [email protected] or post your query in the Swayam portal itself I will definitely
answer those. In the next module we will be discussing about the biomass pre-treatment
technologies. What are the different types of biomass pretreatment techniques that is
available? What are their pros and cons and how they can be carried out? So, thank you very
much.
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Lecture 10
Barriers and Types
Good morning students. Today's class is lecture 1 under module 4 and in this module we will
be discussing about the Biomass pretreatment. So, this is one of the most important aspect of
the entire Biomass conversion or biorefinery concept. So, in today's class we will discuss
about what are the barriers that exist for the lignocellulosic Biomass conversion and what are
the different types of pretreatment technologies that are commercially adapted one by one.
Lignocellulose is the most abundantly available, inexpensive and renewable raw material.
Lignocellulosic Biomass is being investigated as a promising feedstock for the production of
alternative fuels, Chemicals and materials. The production of commercially valuable
Chemicals and biofuels using lignocellulose based processes has the potential to decrease
Greenhouse gas emissions, bring benefits to rural economy, and promote energy security.
The composition of lignocellulosic biomass varies with biomass source. So hard wood, soft
wood, agriculture residue, energy crops, municipal solid waste all these things and is affected
by the origin, age, climatic conditions, harvesting and storage processes. Some of these things
we already know; during our subsequent classes we have discussed this.
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Now, please have a look at this particular table, where the chemical composition of various
lignocellulosic Biomass has been listed and the source has also been given. You can later on
see. It is basically listed under three different categories: cellulose, hemicellulose and Lignin.
Please understand that, apart from these there are some other materials also, there are
proteins, there are volatile materials, ash all these things.
The main chemical building blocks of lignocellulosic biomass that includes actually cellulose
- almost about 35 to 50%, hemicellulose - 20 to 35% and Lignin which vary from 15 to 20%.
Now the composition varies and depends on cultivation conditions, geographical location and
the age of plants. Now let us see, this corn straw or oat straw. You see this it is almost 39-42
in that range is the cellulose, and hemicellulose is from 27-21 in that range, and Lignin is 10
to 20 in that range.
Now, you come to bagasse, here the cellulose little more. Now you come to Aspen (this
forestry residues) cellulose amount is increased basically, there are so many things. Now if
you come to solid cattle manure, you can see the cellulose, hemicellulose and lignin all the
three major components are very less. There are other components which are more
predominantly in that particular material.
So likewise, the understanding is that, the cellulose, hemicellulose and Lignin varies apart
from other materials. And the process or the technologies for converting this Biomass,
including of course, the pre-treatment technologies, should be developed in such a way that
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any process can consider or can take the various multiple feedstocks rather than developing a
process for a single or two feedstocks.
Please have a look at this particular slide. You see that, one class long back I think we have
discussed how the cellulose, hemicellulose and Lignin actually intricately bind together. This
again it is telling, you please see that the cellulose is the blue part. Lignin is the green part,
and the hemicellulose is the red part or the orange whatever it is will be visible from your
side. So these are intricately bound together. So that is the reason why we are talking about in
today's class pre-treatment.
Why the pre-treatment is required? Because I want or we want this cellulose and
hemicellulose to be disintegrated. Because it is bound together - cellulose, hemicellulose and
Lignin all are bound together and you need to disintegrate them. Then you need to take out
the cellulose and hemicellulose part. We will go for hydrolysis, we will get C6 and C5 sugar,
then that will be fermented to Bioethanol, alcohol platforms and other chemicals.
Now lignocellulosic Biomass is composed of cellulose and hemicellulose, tightly packed and
protected by phenol aldehyde Lignin polymer. And the polysaccharide fractions of
lignocellulosic biomass, including cellulose and hemicellulose can be broken down into sugar
monomers. They are then converted into biofuels, biogas and biochemicals through
biotechnological platforms such as anaerobic digestion and fermentation.
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Lignocellulosic Biomass consists of carbohydrate fraction such as cellulose and
hemicellulose and non-carbohydrate functions like lignin, protein and other extractives or
volatile matters. So, cellulose and hemicellulose which are polysaccharides in the biomass
can be converted to bioethanol, biobutanol and other fermentation products through various
biological pathways. They can also be transformed into furan based chemicals and other
organic acids by thermochemical pathways. Either it is pyrolysis and gasification or any such
processes.
For effective conversion of these carbohydrates, it is necessary to overcome and/or reduce the
recalcitrance of biomass prior to the conversion process. Bio recalcitrance is defined as the
natural resistance of plant cell walls for its biological conversion mainly caused by the
complexity and heterogeneity of biomass.
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The recalcitrant nature of lignocellulosic biomass presents a technical challenge for releasing
fermentable sugars from the Biomass and a major hurdle in its use in biorefinery. Several
phenotypes of biomass have been evaluated as recalcitrance factors. So, some of these are
listed here. First is the chemical composition and second is the molecular weight of lignin,
lignin syringyl or guaiacyl unit (we will discuss about this later on little), Cellulose
crystallinity, then degree of polymerization of cellulose and cellulose accessibility.
Let us talk about cellulose. So we will try to understand what are the various components,
and their composition, and their role in the recalcitrant nature of the lignocellulosic biomass.
Now you know cellulose is one of the most abundantly available material on the earth
(natural material). So, the composition of lignocellulosic biomass varies with plant species,
age, stage of growth and season; this is well understood.
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Cellulose is a linear polymer composed of D-glucose units linked together by the β-(1-4)
glycosidic bonds. This is a classical structure of the single cellulose molecule. The degree of
polymerization is approximately 4000 to 6000 glucose in Woody Biomass. Polymers of
cellulose are interlinked through hydrogen and van der Waals bond to form a microfibril and
present in crystalline and amorphous form. These microfibrils are covered by hemicellulose
and Lignin and intricately actually pegged.
So, crystalline cellulose fibre parts attached to each other by non-covalent hydrogen bonding,
which provides 3 to 30 times lower degradability as compared to the amorphous part. Now
cellulase, that is the enzyme which will degrade cellulose, is readily able to hydrolyse more
accessible amorphous cellulose but it is not effective at degrading the less accessible
crystalline portion. That is the reason why we are going for pre-treatment.
Now, let us understand hemicellulose. So, this is a classical structure of hemicellulose

molecule. So, hemicellulose, the second most abundant heterogeneously branched polymer, is
composed of pentoses (D-xylose and L-arabinose), hexoses (such as D-Glucose, D-mannose
and D-galactose), apart from these sugar units, there are certain acetyl groups and uronic
acids.
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So, the degree of polymerization is as high as 50 - 300 monosaccharide units. Hemicellulose
lacks a crystalline structure owing to its branched structure and the presence of acetyl group
and is easily degradable owing to its amorphous nature. This is the basic structural difference
between cellulose and hemicellulose. Where cellulose is more recalcitrant in nature and
hemicellulose is little less than cellulose in recalcitrance.
So, the composition of hemicellulose varies with plant species. Soft wood hemicellulose
components are galactoglucomannan and arabinoglucuronoxylan, while glucuronoxylan is
the main component of hemicellulose in hardwood. Hemicellulose acts as a physical barrier
and restricts the accessibility of cellulase to cellulose. Removal of hemicellulose with
pretreatment methods such as acid or steam hydrolysis and the addition of enzymes increases
the cellulose hydrolysis.
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So then Lignin. Lignin is the most complex amorphous polyphenolic polymer composed of
three o-methoxylated p-hydroxypenyl propanoid units (which are known as a monolignols as
for example of p-coumaryl, coniferyl and sinapyl alcohol). So, you can see the structure of
the p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol and that of the lignin. So, these
monomer units give rise to p-hydroxyphenyl (H), guaiacyl (G) and syringyl (S) subunits
when incorporated into a lignin polymer.
So, this H, G and S they are intricately bound together and linked together to form the
complex lignin molecular structure. So, depending on the biomass source, lignin composition
varies with the change in the ratio of different monomer units. So, gymnosperms or you can
say that soft wood plants and Fern Lignin are generally composed of G as the main
component followed by a small amount of H unit.
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Now contrastingly in angiosperm that is hard plants, Lignin is mainly composed of S units
followed by G units. So more of S followed by less of G. So, the main lignin components of
herbaceous crops are G followed by H and S. So, from this statement we will understand
basically that this H, S and G, depending up on how much amount they are present, the
softness or hardness is basically decided.
So various monomer units are linked through this β-O-4 aryl ether bonds and lignin acts as
glue around the cellulose and hemicellulose fibres. And its main function is to provide
mechanical strength and support for the formation of vascular tissue for the transport of
nutrients and to promote resistance against microbial attack. This is the main function of
Lignin in plants. And Lignin makes Biomass recalcitrant by restricting the accessibility of
cellulase enzyme to cellulose and by preventing the deactivation of enzymes by various
lignin derived compounds.
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This is the figure which will tell about this main component of lignocellulosic biomass, how
intricately they are actually bound together. So, the Biomass, this is a typical plant cell
microscopic image. This is the Macro fibril and this is the microfibrils. In the microfibril you
can see that how Lignin, which is this rod shaped green shown here, then cellulose and
hemicellulose (this brown portion), so you can understand that, that looks like scattered but
they are intricately bound together with each other.
So, we need to actually disintegrate this entire structure. So that we get cellulose and of
course hemicellulose also.
Lignocellulosic biomass recalcitrance is the natural resistance of plant cells against microbial,
degradation, animal attacks and other environmental conditions. Now along with the
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structural components, there are other factors that influence recalcitrance. So, some of them
are acetyl groups and proteins and the porosity of the biomass. In table 2 we will learn more
about that. So acetyl groups bind hemicellulose via covalent ester bonds and deacetylation of
biomass may increase lignocellulose degradation by 5 to 7 times.
This recalcitrance property is a bottleneck in industrial utilisation of lignocellulosic biomass

and various pre-treatments are required to overcome this issue. Proteins also have negative
and positive influences on recalcitrance.
Some proteins help to break hydrogen bonds between polysaccharides which improves
degradation while some proteins inhibit the activity of various hydrolases. So, hydrolases are
the enzymes that are responsible for doing the hydrolysis. So, to overcome the inhibitory
effects of various proteins, usually dried lignocellulosic materials are used in the bio refinery,
as drying and storage of biomass denature protein.
So, the physical structure which includes the accessible surface area (We call it ASA),
particle size and pore volume of the material plays an important role in the biomass
recalcitrance. Higher ASA provides more surface area for enzymes during hydrolysis.
Ultrafine grinding leads to smaller particle sizes leading to changes in polymerization and
porosity and enhances enzymatic hydrolysis. When you are grinding them to finer particle
size, basically you are increasing the surface area and thereby resulting in more degradation.
The pore size of the Biomass also has an important role, as enzymes which can only enter the
pore of specific size, because enzyme has a certain size.
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So, this is the table 2. Let us understand what is being given here and this is the reference of
this particular table. So, effect of lignocellulosic biomass composition and physical structure
and recalcitrance. So, this is the pre-treatment method: chemical method and physical
method. So the components are Lignin, hemicellulose, acetyl group, proteins. Then under
physical we will be talking about crystallinity, degree of polymerization, particle size, pore
size and surface area. This is what we have already discussed.
So, in a nutshell whatever we have discussed is represented in this particular table. So please
refer to it later on; we will just quickly glance through it. So, lignin acts as a physical barrier
and restricts accessibility to cellulose. Lignin derived compounds have inhibitory effects on
hydrolysis. That is very important. So, when you do this hydrolysis, and there are certain by-
products that will be created which are not required at all and which are many times are toxic
to the entire process.
We need to get rid of them. So lignin plays a very important role in making such or
generating such by-product. That is why lignin has to be removed completely. Hemicellulose
acts the physical barrier and restrict the accessibility of cellulase enzyme to cellulose. Acetyl
group interferes with enzymes recognition. Proteins will have both positive and negative
effects on hydrolysis.
Crystallinity tells us that hydrolysis rate of amorphous cellulose is almost 30 times higher
than the crystalline cellulose. That is why more crystalline the cellulose, we need to have a
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better pre-treatment technology and we need to spend the more energy, Chemicals and all
these things to make the higher crystalline cellulose amenable to hydrolysis; and other things
please go through it later on.
Now, we will discuss about the pre-treatment of lignocellulosic biomass, the different
methods. The conversion of lignocellulosic biomass requires pre-treatment to transform the
Biomass for the fermentation process. Pretreatment is also needed to break the rigid structure
of Lignin and hemicellulose and to release cellulose for the enzymatic hydrolysis.
Pretreatment will cause changes in both micro and macro structure of lignocelluloses and
initiate modifications in the chemical composition of lignocelluloses.
The pre-treatment methods aid in the alteration of the natural structure of lignocellulose for
the microbial attack in the decomposition process. Pretreatment process helps breakdown
Lignin and hemicellulose that surround cellulose to release cellulose from the cell.
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The process involves the removal of Lignin and the degradation of hemicelluloses which
causes the alteration in cellulose crystalline structure and subsequently it releases cellulose.
This process helps the interaction of enzyme and substrate which enhances the hydrolysis
process. The pretreatment process ought to be straightforward, environmental friendly,
economical and efficient. It has to be like that. Otherwise it will not be a sustainable process
and cannot be a part of the biorefinery.
Additionally, the pretreatment method must not cause in the rise of inhibitory compounds.
This is what I was just mentioning. So, these inhibitory compounds formation should be
restricted by choosing a particular pre-treatment method which will not create a greater
amount of such inhibitory compounds.
Up to date, no synchronised pre-treatment approach that matches the whole variety of

lignocellulosic biomass, and the process of pre-treatment varies according to the type of
lignocellulosic biomass and preferred products. This is what I was mentioned in the
beginning of the class. You have to note; it is a very serious thing actually. When we are
talking about these pre-treatment processes or when we are talking about the entire
biorefinery concept, we need to understand that the pretreatment cost is almost 40%, if you
talk about the entire cost of the product. Now, why it is 40% right now or almost in that
range? The reason is that; first thing is that whatever pre-treatment techniques are available,
these are suitable for certain particular types of biomass. So no pretreatment technology, not a
single one or hybrid Technology has been developed which will take into account so many
different types of multiple feedstocks; because different feedstocks will have different
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components. Some will have higher cellulose, and some will have very low amount of
hemicellulose, some will have high amount of lignin; so it all depends. That is the reason why
we need to work more to develop more efficient pre-treatment technologies, which will be
economical, which will also take less time, which will not be energy-intensive and then
which will be sustainable. And which will again, I am telling you that, must be able to take
into account multiple feedstocks or it will be able to process multiple feedstocks, that is very
important.
So, the following criteria lead to an improvement in the enzymatic hydrolysis of

lignocellulosic materials: The first is increasing the surface area and porosity which can be
done by doing the mechanical processing; modification of the lignin structure (modification
of the lignin structure can be done by genetic engineering - in one of our class we have
discussed that); you have to remove Lignin, so this is a delignification process (you call this
one pretreatment also); partial depolymerization of the hemicellulose (So, you have to release
hemicellulose also or depolymerize so that hemicellulose which is bound to cellulose will be
disintegrated); then remove hemicellulose, because hemicellulose also can be hydrolysed and
converted to the sugar; and then reducing the crystallinity of the cellulose.
So, once you do the pre-treatment (you can see how it is intricately bound); so, this is the
lignin, green one is cellulose and this thread type whatever it is being shown here is
hemicellulose. You disintegrate, that means you treat it, delignify it and it will be
disintegrated into something like this: hemicellulose pure, lignin in the purest form and
cellulose in the purest form.
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Let us understand the pretreatment methods. So we have two different broad categories of
pretreatment methods: first one is biological and second is a non-biological. So, in the
biological we have fungi based pretreatment methods, we can have bacteria based or Archae
based. And under non biological we have varieties of pretreatment methods: some are
physical, some are chemical and some are physico chemical. So in today's class we will
discuss few of them and some we will discussion in our next class.
These are some of the methods I have listed, there are many which are not listed here also.
Physical: under physical it can be milling, microwave, ultrasound, pyrolysis. Under chemical
it is acid treatment, alkali treatment, ozonolysis, organosolvent process and ionic liquids. And
ionic liquids are excellent class of green solvents. And then physico-chemical: hot water
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treatment, steam explosion, Ammonia based treatment, wet oxidation and carbon dioxide
explosion.
Some of these physico chemical treatment and chemical treatments are of course, they are
costly.
Now this particular slide will show you whatever I have just told you in the earlier slide. It is
presented in a better way here. So, classification of the lignocellulosic Biomass pre-treatment
methods in detail. Physical: extrusion, pulsed electric energy based, liquid hot water,
pyrolysis, irradiation (basically the microwave treatment), Mechanical milling, grinding,
chipping.
When you come to chemical: It is again acid, alkali, solvolysis (that means using organic
solvents), oxidative (using either oxygen, ozone, hydrogen peroxide), then ionic liquid -
different types of ionic liquids are there, and hydrotropes like sodium benzoate and salts -
certain metal salts.
Then we have physico-chemical. So, steam explosion, Ammonia fibre explosion (AFEX) - It
is a very interesting and very efficient technique. But you have to do it in a proper way.
Otherwise there are risks associated with that - anyway will discuss later on. Ultrasound-
assisted chemical pre-treatment - this is one of the most efficient processes. But however, it
has its own limitation. Now beyond certain limit, it cannot work and it’s a low-cost
technology though a certain amount of energy is required. Then microwave-assisted chemical
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treatment. Not only microwave, but microwave assisted chemical pre-treatment. Then
microwave-assisted pyrolysis. Then combined pre-treatment. So, this is called hybrid - more
work is being done here. So, it is a combination of one or two different pre-treatment
methods. Then biological; based on enzymes, microorganisms and development of suitable
microbial consortium to take care of the pretreatment.
So, this is the bioconversion of lignocellulosic biomass into value added products with the
inclusion of the pretreatment steps. So this is your biomass and this is the structure. So you
pre-treat here. Biological, chemical, physical, physico-chemical, anything we get and that
will result in something, the disintegration of the structure of the Lignin, cellulose and
hemicellulose.
Then you convert them: cellulose and hemicellulose will be basically purified. So, you
hydrolyse them. So, then you can (subject to) any bio chemical or bio technological platform
such as fermentation, anaerobic digestion, so you get alcohol platform. It can be bio-ethanol.
It can be bio butanol. Then we can get biogas also. Next is lignin, so lignin either it can go for
pyrolysis, gasification with or without the presence of catalysis.
So, we can get biopolymers, we will get aromatic hydrocarbons and other value-added
chemicals.
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So, physical methods of biomass pre-treatment we will discuss. So, in general physical pre-
treatment is responsible for the changes in specific surface area, particle sizes, crystallinity
index and polymerization degree of biomass. Physical pre-treatment avoids the use of
chemicals thus reducing the generation of waste and inhibitors for subsequent reaction. Now
mechanical, microwave or ultrasound pretreatments are the most common techniques carried
out in order to improve the efficiency of the main steps in biomass processing.
So, let us understand mechanical pretreatment. The advantages of mechanical pretreatment of

lignocellulosic materials are: reduction of particle size, increase of specific surface area and
bulk density and reduction of the amount of chemical waste. So higher bulk density helps
with handling of biomass after harvesting, storage and transport. In turn lower particle sizes
as well as an increase in the specific surface area makes the chemical or physical processing
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easier due to: (1) development of a phase boundary between lignocellulosic material and
chemicals and; (2) elimination of heat transfer limitation. So, the main disadvantage of
mechanical pre-treatment is the high energy consumption which contributes to high
processing cost of lignocellulosic materials.
These are some of the schematic representation of the mechanical pre-treatment processes.
This is a hammer mill where milling is done. This is an extruder for the extrusion process.
That is a ball mill where small balls are present to disintegrate or reduce the size of the
Biomass. This is an Air mill and that is a roll mill. All are mechanical operation process
basically.
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So, where do we apply this actually. So the effectiveness of milling, chipping and mashing of
pre-treatments of Norway spruce (it’s an example here) were compared for enzymatic
hydrolysis of this feedstock into when it is being converted into biobutanol. So pre-treatment
with ball milling gave the lowest particle size of the spruce in comparison to mashing or
chipping but resulted in low hydrolysis efficiency.
Now application of extrusion has a large potential in the pretreatment of lignocellulosic

materials for biogas production. Researchers have applied twin screw extruder in vine
trimming shoots pre-treatment for Methane production in anaerobic digestion. Now treated
samples generated around almost 15 to 21% of more biogas compared to untreated material.
So, it is a very good finding with physical treatment.
So, it was observed that an extrusion reduces the amount of hemicellulose fraction by around
50% simultaneously increasing the fraction of soluble Chemicals like carbohydrates proteins,
lipids, minerals and vitamins which are rapidly converted by methanogenic microorganisms
hence, increasing Methane production. However, this investigation proved that use of ball
milling has only a small impact on the process efficiency.
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This is the selected examples of the studies concerning mechanical pretreatment. So, I leave it
to you. Please have a look later on. So, you can see that there are different types of biomasses
are listed here, different types of pretreatment methods are listed here, a mechanical one.
Then pretreatment conditions. How much time and all these things are given here. And what
is the efficiency of the process?
So, we will just see the first one. The Douglas fir residues. So, the hammer milling, air
classifier milling, ball milling, chipped, mashed all these things has been compared. So, the
time of residence inside the mill is basically 7 to 30 minutes. The result is that, highest yield
of glucose and xylose/mannose and was obtained after 30 minutes of ball milling. So ball
milling decreases the cellulose crystal from 40.73% to 11.7% which is a significant decrease.
Please have a look later on.
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Now the next one Microwave and its application. So, Microwave is a type of electromagnetic
non-ionizing radiation with frequency between the infrared and radio waves. Microwave
radiation absorbed by matter has appropriate energy to excite the vibration of molecules, but
its energy is too low to break chemical bonds. The electric field of microwave transfer their
energy to molecules which leads to the generation of thermal energy.
The main advantages of microwave heating versus conventional heating are: lower energy
consumption, shorter reaction time and avoided contact with the feedstock. On the other
hand, the prolonged time of microwave treatment increases degradation of polysaccharides.
So researchers have demonstrated advantages of the application of microwave in the increase
of the yield of biogas in biomethanation of organic matter.
This is just one of the researches which I have listed here, there are many works. So,
Microwave generated heat increases the solubility of Lignin, released soluble compounds and
improved the rate of hydrolysis due to cellular disruption. However, the effectiveness of
biogas production depended on the time of exposure and power of irradiation. A longer
exposure time can lead to fractional degradation of reducing Sugars and the generation of
inhibitors negatively affecting the biogas formation.
Nevertheless, appropriate time of microwave irradiation of biomass increased cell frangibility

and improved enzymatic hydrolysis by disruption of biomass complex structure. It is a good
process, it is easy to operate and not too energy-intensive also.
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So, let us talk about one of its application for converting the switchgrass and miscanthus into
alcohol platform. So, microwave pretreatment was effectively applied to reduce the
recalcitrance of complex biomass feedstock structure of switchgrass and miscanthus to
enhance their solubility in subcritical water in the hydrogen production in aqueous phase
reforming. It was the done for the hydrogen production process.
So, this was possible owing to the action of microwaves on oxygenated polar functional
groups present in the biomass structure. Additionally, the temperature pretreatment above
200 degrees centigrade accelerated the deconstruction of polymer complexes leading to
delignification as well as partial removal of hemicellulose. It enhances solubilisation
switchgrass and miscanthus however this negatively affected the gasification efficiency.
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So, this table will again let us understand what are the different types of studies that concerns
about the application of microwaves. You can see again switchgrass, is there and miscanthus,
and then Cauliflower and cabbage is also mentioned here. So there are direct pre-treatment
and then domestic microwave oven at different microwave power. This is a domestic
microwave oven which is being used here. Time of residence is 15 to 30 min. You can see
that highest increase in biogas production emerged in microwave power of 350 watts in 25
minutes.
And another in very interesting fact about microwave treatment is that, it is a very faster
process. So, time is money in industries. So, we should choose such processes which are
faster. So please have a look later on.
The next one is ultrasound and its application. Application of ultrasound as a green
Technology plays a positive role in the efficient production of added value Chemicals or
biofuels by effective decomposition of recalcitrant lignocellulosic materials. The main
advantages of ultrasound pre-treatment are: shorter processing time, lower operation
temperature and finally a lower amount of chemicals used during further valorization.
Additionally, it has potential to be combined with other technologies.
However, the effect of the ultrasound treatment differs depending on the type of
lignocellulosic material.
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One example of grape pomace has been listed here. So, the influence of ultrasound pre-
treatment on the efficiency of biomass processing was tested for Methane production from
grape pomace among others. So, increases of Methane yield and kinetic constant of the
hydrolysis after the application of ultrasound by all most 10% and 35% respectively were
observed in comparison to untreated material.
Moreover, pretreatment of grape pomace reduced the amount of hemicellulose and Lignin
and slightly increased the content of soluble ingredients compared to control samples. It is
almost by 13%, 6% and 5% respectively. So, the positive effects of ultrasounds on both
chemical composition and yield to Methane were explained by the presence of the formed
Cavitation bubbles which mechanically disrupted the cell wall structure of the lignocellulosic
material.
So, it is an interesting technology actually technique. So simple one, where the Cavitation
actually happens by the formation of bubbles and it will do the disruption of the cellular
structure.
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So, we will see one of the applications on the Agava leaves. So, researchers, showed the
effect of ultrasound pretreatment on the physico chemical properties of the Agava leaves. The
use of ultrasound for 30 minutes resulted in an increase in the content of holocellulose and
Lignin and a reduction of extractives and ash in the analysed material. Now holocellulose is
the amount of water non-soluble carbohydrates basically.
So, moreover the agava leaves treated for 30 minutes showed enlarged pores and damaged
cellular structure. As a result, Polymers were more accessible for further processing. The use
of ultrasound resulted in mechanical breaking down of the complex structure of leaves which
led to fracturing of bonds binding Lignin and cellulose and hemicellulose. An increase in the
sonication time to 60 minutes, caused the decrease in the amount of holocellulose and Lignin
which was related to the fractionation or breaking down of Lignin and hemicellulose
molecules.
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So this particular table has given examples of studies concerning the application of
ultrasound. You can see again that grape pomace and Agava leaves are being ultra sound
treated and the different pretreatment conditions are given. You can see the efficiency of the
process. So, the first one in case of grape pomace less than 25 degree centigrade almost 40 to
70 minutes is the time of Residence. So, ultrasound treatment reduced yield of hemicellulose
and Lignin by 13.3 and 6.3% respectively. Ultrasound pre-treatment provided increase in
Methane production compared to untreated sample. Moreover, pre-treatment of grape pomace
slightly increased the amount of soluble ingredients compared to the control sample.
Similarly, in case of the Agava leaves pre-treatment resulted in the production of inulinases
and cellulases and a reduction in the amount of extractives and ash; these are the enzymes.
So, ultrasound pre-treatment for 30 minutes, results in 1.5 to 2 times higher specific
enzymatic activity which is known as SEA of inulinases, but reduces SEA for other enzymes.
So, these are some of the classical findings from the ultrasound-based treatment.
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So now we will discuss the biological approaches to hydrolyse lignocellulosic structures.
Biological pretreatment using microorganisms is a promising approach to degrade
lignocellulose structure extracellularly thus increasing the sugar conversion rate of the
biomass. Now they have several attractive traits such as eco-friendly and simple operation,
low capital cost, low energy requirement and almost no chemical requirement.
However, the major drawback are the long pre-treatment time and strict microbial growth
conditions. So, the extraction of Lignin degrading enzymes from microorganisms to be used
directly on the Biomass emerges as an alternative approach to eliminate the above problems.
However, efforts in reducing the cost of enzyme extraction are necessary to make it a viable
process.
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So, this is the schematic representation. So, here the lignocellulosic Biomass. Any such
lignocellulosic Biomass, treat it with microorganisms. It can be a single strain
microorganism. It can be a microbial consortium also; depends on what you are deciding
actually. Then again actually it goes for the Lignin degradation, and the cellulose
decrystallization.
So, from cellulose to reducing sugars using the cellulase enzyme. So then of course you can
further ferment them to alcohol platforms.
So, cellulolytic and ligninolytic microorganisms. So, the commonly used microorganisms are
bacteria and filamentous fungi (for example Ascomycetes, Basidiomycetes), which are found
ubiquitous in soil, living plants and lignocellulosic waste material. The fungi can be classified
into brown rot, white rot and soft rot fungi. These microorganisms secrete enzymes that are
capable of selectively degrading Lignin (they are known as the ligninolytic fungi) or
hydrolyse cellulose (they are known as the cellulolytic bacteria). Now biological pretreatment
using microorganisms and enzymes extracted from them also offer a great opportunity to
produce various high value-added Chemicals from the waste-by-product lignin. Among the
microorganisms, white rot fungi have been extensively studied and proven to be one of the
most effective lignin degrading species. However again I am telling you that it is a time-
consuming process.
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Let us talk about the applications. So during their growth most white rot fungi, whether it is
Pleurotus ostreatus, whether it is Trametes versicolor, whether it is Phanerochaete
chrysosporium, produce extracellular Lignin modifying enzymes including laccase, Lignin
peroxidase (which are known as LiPs) and manganese peroxidases (which are known as
MnPs). Now these are enzymes.
Now these enzymes exhibit specificity for Lignin and catalyse enzymatic cleavage of Lignin
aromatic rings through oxidation processes. And these are all slow processes. So, as a result
the linkages between polysaccharides and Lignin are broken down thus liberating the
cellulose component and enhancing the hydrolysis of lignocellulose. In addition, some of the
white rot fungi as mentioned here, for example the Phanerochaete chrysosporium, secrete
cellulolytic enzymes known to hydrolyse cellulose thus increasing its enzymatic digestibility.
So, it is happening simultaneously basically you can say in that spirit.
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So, some of the different types of fungus and bacteria and the feedstock and the operating
conditions and what has happened after the pre-treatment process. So we will see one thing;
the white rot fungus T. versicolor. Cow manure and selected cereal crops were being
considered. Operation condition is 25 degrees centigrade, 135 RPM rotations per minute, 6
days, 75% MC. and pH is 4.2. So, the result is 80% increase in cellulose degradation. It is an
excellent result.
But it has taken time, you can understand that it is 6 days’ time. So, 10 to 18% increase in
methane yield. So if you look at this particular table in a proper way you will understand that
efficiency is not an issue. The only issue is that it is very time consuming and then since we
are dealing with live organisms, we have to ensure each and every day that their growth
conditions are maintained.
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So ligninolytic enzymes. In an alternative approach to microorganism incubation, ligninolytic
enzymes extracted from the fungal and bacterial cultures can be purified and used directly on
the biomass as pre-treatment. Here what we are talking about that, instead of using the
microorganisms directly we extract the enzymes which is responsible for this pre-treatment,
delignification or disintegration, can be extracted and purified and then it will be used.
So now in this case, we are done away with the growth condition of the microorganisms.
Only we have to maintain proper conditions for the enzymatic attack on to the plant cell or
the biomass cells basically. But please understand that, it is a better technique. However,
extracting and purifying enzymes from microorganisms is a very tedious job and is time-
consuming as well as it is a high cost matter.
So, these ligninolytic enzymes are capable of catalysing various biochemical reactions to
degrade selectively Lignin with minimal cellulose consumption. The direct application of
enzymes on the Biomass eliminates the long growing period of microorganisms thus
significantly reducing the pretreatment time. So, 15 to 40 days to almost 6 to 24 hours. That
is fine, but again, the cost has a bigger role to play.
So as a result, enzymatic pre-treatment can accelerate bioenergy production at minimal

environmental impacts, no chemical addition and lower energy.
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Modified Lignin after enzymatic pretreatment can also be recovered for effective uses in fast
pyrolysis to produce biooil. This is one of the significant works. So, common enzymes used
for prre-treating lignocellulosic Biomass are mostly commercialized products from leading
companies such as DuPont, Novozymes and DSM. So these are some of the companies, the
enzyme making companies basically and very well known.
The capability to identify microorganisms and growth conditions to cost-effectively produce

and purify high amount of stable ligninolytic enzymes is critical for this pretreatment to be
commercially viable.
So major ligninolytic enzymes such laccase, LiPs which is called Lignin peroxidase and
MnPs - Manganese peroxidase have been evaluated for their efficiency in delignifying
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lignocellulosic biomass. Up to 50% lignin removal was attained by pre-treatment with P.
ostreatus laccases for high Lignin content biomass (29% and 33% for coffee silverskin and
potato peel respectively).
The pre-treatment of wheat straw using a P. cinnabarinus laccase achieved 37% Lignin
removal, leading to an increase of 60% in glucose yield after the enzymatic hydrolysis.
Sugarcane bagasse pre-treated with ligninolytic enzyme extracted from P. ostreatus IBL-02
strain containing laccase, LiPs and MnPs also reported 34% delignification and ethanol
production of 16 grams per litre after the fermentation process.
This table lists some of the properties of the important ligninolytic enzymes. So, you can see
three enzymes are listed here: laccase, LiPs and MnPs. And different types of plant materials.
What are the characteristic features, and what is the substrate specificity. So, you please go
through it later on when you go through the lecture note. So, with this I conclude today's
lecture.
And tomorrow we will be discussing dilute acid, alkali hydrolysis and Ozone treatment
pretreatment methods. If you have any query, please feel free to write to me at
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[email protected] or please register your query in the Swayam portal. So, thank you very
much.
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Lecture 11
Dilute Acid, Alkali, Ozone
Good morning students. Today is lecture 2 under module 4 and as you know that this module
is dedicated to our Biomass pretreatment and we have discussed basics in the last class.
Today we will discuss some of the most important pre-treatment processes such as dilute
acid, alkali based pre-treatment, auto hydrolysis, Ozone based pre-treatment and few others.
Let us start. As you know that pre-treatment of lignocellulosic biomasses can be carried out
by various methods: chemical, physical, combined and physico-chemical. So, some of these
we have discussed; some we’re going to discuss today. So, under chemical: it is acid pre-
treatment, alkaline, organosolv, ionic liquids, deep eutectic solvents. All these things we will
be discussing today; physical we have already discussed.
So, in the combined pre-treatment it is actually with Microwave based pre-treatment, then
Microwave with the alkali, Microwave with deep eutectic solvents, then ultrasound with ionic
liquids, like this, basically a combination of two pre-treatment technologies. And then
physicochemical: steam explosion, Ammonia fibre explosion, liquid hot water these things
also we’re going to discuss today.
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So, the goal is again the same as we have already discussed; it is to release or defragment
cellulose, Lignin and hemicellulose. So, remove Lignin and purify cellulose and
hemicellulose so that they can be converted into various value-added products.
Let us talk about chemical pre-treatment. This particular image is a beautiful image from the
perspective that it can tell us how different types of chemical pre-treatment are there and how
they overlap each other in a doing a particular job. Now, let us look at this particular green
one. The green boundary here. You can see, that is almost taking into everything except little
part of the acid pre-treatment.
With this green boundary pertains to the lignin removal. All these processes under this green
they will do Lignin removal more efficiently than other processes. Similarly, if you see this
red one, so that one is for the cellulose removal, whether ionic liquid or deep eutectic
solvents, alkaline pretreatment, even part of little organosolv pretreatment also. Similarly,
oxidative, acid pretreatment and alkaline. This takes care of the hemicellulose removal.
This type of pretreatment uses chemical reactions to change the recalcitrant structure of
lignocellulosic materials. Most commonly used are acid, alkaline, ionic liquids, oxidizing
agents and organosolv pretreatment. Now depending upon the chemical substances used
during pretreatment various mechanisms of the Biomass decomposition can occur.
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Let us understand acidic pretreatment: So, pretreatment of lignocelluloses with acids is one of
the most effective method of solubilizing the hemicellulose making cellulose more
accessible. Now acid pretreatment involves the use of concentrated and dilute acid both, to
break the rigid structure of the lignocellulosic materials. The main reactions during acid
pretreatment at the hydrolysis of hemicellulose and condensation and precipitation of the
solubilized Lignin.
The most commonly used acid is the dilute sulphuric acid which has been commercially used
to pre-treat a wide variety of biomass types whether it is switchgrass, cronstover, Spruce and
poplar. So, this list is basically endless. If you see just type dilute acid pretreatment of
lignocellulosic biomass there are hundreds and hundreds of excellent research papers
available.
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Dilute sulphuric acid has traditionally been used to manufacture furfurals by hydrolysing the
hemicellulose to simple sugars such as xylose which continues to convert into furfurals.
Other acids have also been studied such as hydrochloric acid, then Phosphoric acid and nitric
acid. Due to its ability to remove hemicellulose acid pretreatment has been used as part of
overall processes in fractionating the components of lignocellulosic biomass.
Acid pretreatment followed by alkali pretreatment results in relativity pure cellulose. Now,
please give little more emphasis on this particular sentence, which I have highlighted in blue
colour. So, acid pretreatment which basically talking about the removal of hemicellulose in a
more efficient manner than that of cellulose and Lignin followed by alkalis. Alkali is more
predominantly will be doing the role to remove lignin.
So, if you combine this it becomes a hybrid process. Dilute acid followed by Alkali so both
hemicellulose and Lignin will be removed and whatever left out is cellulose. So, the
disadvantages of acid pretreatment are corrosive environment of reaction and possible
formation of inhibitors like HMF (hydroxymethylfurfural) and acetic acid during further
processing. Now when you talk about corrosive environment of the reaction that means you
have to use a very sophisticated reactor of a particular material so that it can deal with the
corrosive environment. So, glass is better. But you know that glass you cannot makeup in
very big size reactors. It is very difficult to do that. This basically adds on to extra additional
cost to the entire process. HMF is a very high value material or solvent. So, it is a fuel
additive also.
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So, it was reported that the concentration of 2 grams per litre of HMF and 3 grams per litre of
Acetic Acid formed during acidic pretreatment of lignocellulosic feedstock can result in the
loss of the efficiency of further fermentation process. The meaning of this particular sentence
is that for certain cases as for example dilute acid pretreatment of few biomasses, it has been
noticed that beyond 2 grams of HMF and 3 grams per litre of Acetic Acid the process and the
fermentation is not proceeding in a proper direction because this HMF and acetic acid is
becoming toxic for the fermentation to proceed.
Strong acid treatment allows to obtain high sugar yield at mild temperatures during
hydrolysis of cellulose. Although strong acid hydrolysis is very efficient and independent
from the feedstock source the reaction medium is highly toxic and corrosive which requires
the design of resistant and robust reactors; that affects the cost of biomass processing. So that
means adding additional cost.
So, the solution that reduces cost while maintaining the high process efficiency is the
application of the dilute acid. If you talk about dilute acid also, the problem of corrosiveness
also comes down to a lesser extent. So, the advantages of dilute acid treatment are: high
reaction rates of hemicellulose and cellulose hydrolysis and limited formation of inhibitors.
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See few examples. The first one is application of dilute acid pretreatment in enzymatic
hydrolysis of Bananas pseudostem. Shimizu et al studied the effect of sulfuric acid
concentration on the chemical composition of products and glucose yield in enzymatic
hydrolysis of Banana pseudostem so this the image. So, the sulphuric acid in concentration up
to 25% broke glycosidic bond which resulted in random and effective removal of
hemicellulose and an increase in the cellulose and Lignin content in comparison to the
untreated material.
Removal of hemicellulose from the studied feedstock was accompanied by growth in both
external and internal surface area of the treated biomass which exposes the cellulose fraction.
On the other hand, aggressive acidic environment that means sulphuric acid with the
concentration of above 25% completely remove hemicellulose from the banana pseudostem
and lead to cellulose degradation.
And that is what also we do not want. So as a result, lower glucose yield in enzymatic
hydrolysis was obtained; because cellulose was degraded. Now, for all such a processes
whether it is dilute acid pretreatment, then enzymatic hydrolysis, fermentation you need to
optimise the process parameters so that you get a proper yield of the cellulose and then it gets
converted to glucose.
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So, another application on Elephant grass. The effect of sulphuric acid treatment on
crystallinity index, solid recovery and chemical composition of elephant grass was studied by
Santos et al. It was demonstrated that acid effectiveness during the pretreatment depended on
the part of the plant that has been treated. Acid pretreatment removed hemicellulose from
samples proportional to the acid concentration used additional increasing the amount of
glucan and Lignin.
Moreover, the pretreatment resulted in the removal of a higher amount of solid from leaf and
whole plant rather than from the stem. The yield of enzymatic hydrolysis decreases in the
following order: Leaves, whole plant and stem fraction.
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So, another one application on the Agava leaves. Effect of the type of acid whether sulfuric
acid or hydrochloric acid on the yield of reducing Sugars obtained from Agava leaves was
tested by Avila-Gaxiola et al in 2018. So, you can refer that reference has been given. A
slightly higher yield of reducing Sugars was observed after pretreatment in the presence of
oxoacids. An increase concentration of acids regardless of the type led to a reduction in the
amount of sugar produced which is associated with their degradation to furfurals or
hydroxymethylfurfural.
The best results of the treatments applied in the lignocellulosic materials were sulphuric acid
at only 0.5% volume by volume basis, very diluted concentration. Sugars released is 68
grams of reducing sugar per 100 grams of Agava powder, which is actually very good yield.
No inhibitory compounds were detected; that’s because the concentration of the sulphuric
acid is very low.
So, another application on green landscaping waste. Dilute phosphoric acid was used for
obtaining high quality value-added cellulose Acetate from Green landscaping waste. So, the
performed investigation showed that wood structure after exposition to phosphoric acid
degrades in lower temperature than untreated sample. And the crystalline fraction of the
cellulose increased, while the amorphous one decreased after the use of the phosphoric acid.
Such treatment improves the separation of hemicellulose from the feedstock degrading the
bonding of Lignin and cellulose. As a result, the yield of cellulose acetate obtained from the
solid fraction increased.
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This particular table, please refer to this one. So here it is given that selected samples of the
studies concerning acid pretreatment. This list is only a representative in nature. There are
many. This has been taken from a particular reference which is listed here. You can refer to it
later there are many. I just quickly explain to you. Banana pseudostem we have already seen.
Let us see this Sisal fibre. So different concentration, say 0.5 to 1.5%, so different
concentrations of sulphuric acid has been tested.
The condition is; temperature is around 100 degrees to 120 degrees’ centigrade; time of
residence is of course not mentioned and the efficiency is that the highest xylose
concentration of 0.132 gram per litre of the fibre was obtained at 120 degrees centigrade with
2.5 % volume by volume of sulphuric acid. Like similarly, I do not want to read out all these
things you can refer it later on and I deliberately added all these things so that those (of you)
who will be working on Biomass related topics for their academic interest or otherwise for
doing some research, it will be helpful for them to get some first-hand information about the
different effects of the dilute acid pretreatment. Similarly, this is continuing, so you can see
the Agava plant which we have discussed, this is cornstover dilute phosphoric acid 50 degree
centigrade, 10 hours. So you can see that it substantially decreases the gaseous product
formation, but increase the amount of liquid fraction in the pyrolysis process. This is
particularly done, pre-treated cornstover with an aim to pyrolyze it.
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The next one is alkaline pretreatment: Alkaline pretreatment involves the use of bases such as
Sodium, Potassium, calcium and ammonium Hydroxide for the pretreatment of
lignocellulosic biomass. The use of an alkali causes the degradation of Ester and glycosidic
side chains resulting in structural alteration of Lignin and cellulose swelling, partially de-
crystallization of cellulose and partial solvation of hemicellulose.
Sodium hydroxide has been used extensively by researchers for many years and it has been
shown to disrupt the lignin structure of the Biomass increasing the accessibility of enzyme to
cellulose and hemicellulose. Another alkali that has been used for the pretreatment of
biomass is the lime. Lignocellulosic feedstocks that have been shown to benefit from this
method of pretreatment are cornstover, switchgrass, bagasse, wheat, rice straw and the list is
actually end less there are many other. Just a few are listed here.
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So, pretreatment of biomass with the use of bases can be carried out at room temperature and
its yield depends on the lignin content. Pretreatment is most efficient for lignocellulosic
materials characterized by low lignin content. The advantages of this particular alkaline
treatment are: (a) use of cheap chemicals: actually that means the low-cost chemicals; (b)
mild reaction conditions; (c) Effective removal of Lignin and xylan and (d) possibility of
biomass fractionation. However, the biggest disadvantage of that particular process is the
long process time it requires and difficulties in neutralization of the post treatment mixture.
So that means you have to neutralize after the processes is over. There will be still so much of
Alkaline content in the reaction mixture.
So, you need to take out your Lignin and cellulose, hemicellulose. So, you need to neutralize
it. So that neutralization also adds some another cost. So, you have to add some acid to
neutralize it. The most important thing is of course the long process time. So that is the
disadvantage and in commercial or industrial applications we have to have the processes
which are faster and as well as low cost.
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This is an excellent slide. You see this is a flowchart of a pretreatment process using the
alkalis. What it does. This is a representative one. It is not true for every biomass. So let us
just understand. A biomass - so, you give alkalis to pre-treat it, so whatever you get is
(subjected to) a filtration. So, it is a solid residue - you wash it - then whatever the solid
residue that is obtained is nothing but the cellulose enriched residues.
So, you can further process it to get pure cellulose out of that. So, the brown liquor after the
alkali pretreatment. So, alkali pretreatment will result into two things. One is this solid rich
leftover mass. So that is basically Cellulose rich and another is a brown liquor liquid. So that
brown liquor when you do the further processing by adjusting its pH and all these things it
goes for precipitation – centrifugation - then again, you will get a solid part - wash it - you get
hemicellulose. And from here this particular process whatever the solid part is come down as
hemicellulose whatever liquid part remain it has become by the time colourless liquid. That
goes to further processing of evaporation - centrifugation - washer - lyophilization and you
get lignin. Here actually during this evaporation what is evaporated is this alcohol.
So this alcohol or in this case ethanol will be again recycled back to this particular space.
Now you can see and understand that from this particular process that in three subsequent
steps we are getting cellulose rich residue, then hemicelluloses and Lignin by alkali
pretreatment.
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So, few applications we will see, application on bamboo. Yuan et al investigated in detail the
effect of sodium hydroxide concentration on the chemical composition of bamboo which can
be used as a potential feedstock for the production of Sugars and alcohol. Additionally, they
showed that post treatment liquor can be a source of high-value Lignin and silica. It was
demonstrated that severe conditions can lead to degradation of cellulose and hemicellulose
monomer hence decreasing the sugar yield.
And effective removal of sugar from the solid fraction resulted in their larger share in the
liquid fraction. Furfural and hydroxymethylfurfural potential inhibiter for further processing
were not detected in liquid fraction. So that is a good thing actually. So we will get more
bioethanol.
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Application on banana pseudostem. So, by again Shimizu et al. Influence of sodium
hydroxide in the range of 5 to 30% was studied for the yield of glucose. Alkaline
pretreatment in the range of 5 to 25% concentration of sodium hydroxide gradually removed
hemicellulose and Lignin from the Biomass structure. However higher alkaline concentration,
that is 30% and above led to a decrease in the cellulose content as compared to 25% Sodium
Hydroxide suggesting cellulose degradation.
So, this is what is I was talking about optimisation. So, you have to take different
concentrations and to see at what concentration of sodium hydroxide or alkali, you are getting
the best result, the higher yield of reducing sugar. So, glucose yield is increased gradually
with increasing concentration of sodium hydroxide achieving the highest value after
treatment by 25% sodium hydroxide.
So, high glucose yield resulted from solubilization of Lignin and hemicellulose fractions
caused by the alkali pretreatment; this is the reason for high yield.
So then application on commercials Xylan. An important issue in the alkali pretreatment is

the presence of impurities like potassium, sodium, calcium and magnesium ions that affect
the initial decomposition of the organic Biomass components. Giudicianni et al in 2018
investigated the effect of the presence of calcium and sodium ions in commercials Xylan on
the composition of gaseous and liquid products formed during its pyrolysis.
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So, a comparison of the chemical composition of the demineralized and raw Xylan prove that
incorporation of the metal ions into the Xylan structure affect the mechanism of its
decomposition. Metal ions decrease the initial decomposition temperature of Xylan. The
presence of metals results also in the reduction in the amount of furfural (being a product of
depolymerization of Xylan chain, rearrangement and dehydration reactions) and an increase
in the content of furfuryl alcohol and other low molecular weight products.
So, this is again another table which gives selected examples of studies concerning alkaline
pretreatment. So, you can see so many are mentioned here actually if you look at literature,
there are hundreds of papers on alkali pretreatment of different Biomass. So here we have
listed Banana pseudostem, wheat straw, Zizania latifolia, commercial Bamboo chips, peach
tree, miscanthus and giganteus and then many. So, you please refer to it later on, I am not
going to read this table.
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And we will move into the next pretreatment method which is a very important class of
pretreatment methods known as organosolv method. The organosolv is a method of biomass
pretreatment that uses various organic and aqueous organic solvent mixture to solubilize
hemicellulose and extract Lignin. Please understand acids are out of this; no acids and alkalis
are covered under this.
So organic solvent such as methanol, ethanol and Acetone, ethylene glycol, Triethylene
glycol and tetrahedrofurfuryl alcohol are the most commonly used solvent for the organosolv
pretreatment process. Organic acids such as Oxalic, salicylic and acetylsalicylic acid are
catalyst to organosolv solvation process. So, they act as catalyst, they are not the main
solvents. So the organosolv pretreatment of lignocellulosic materials with the use of alcohol
leads to the hydrolysis of the internal bonds of Lignin and hemicellulose as well as hydrolysis
of ether and Ester interpolymer bond between them resulting in lignin removal and almost
complete solubilisation of the hemicellulose.
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The presence of organic acids in the organosolv process leads to the formation of hydrogen
ions, which facilitate delignification of biomass and dissolution of Lignin. So, this the
mechanism. So, the optimal temperature of the process is in the range 100 degree to 250
degree centigrade and depends on the type of biomass. However, the use of a catalyst (so that
includes any organic or inorganic acids) allows the process to be run effectively at lower
temperature.
So, you use catalyst the temperature will come down. Then addition of an inorganic acid to
the reaction mixture causes hydrolysis of hemicellulose which significantly increases the
availability of cellulose for further process. The solvents used in the process are open
inhibitors for further reactions of fermentation or enzymatic hydrolysis, so they must be
removed after the pretreatment process.
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The advantages of the organosolv pretreatment are: high efficiency, mild conditions, easy
solvent recovery, and the possibility of its recycling and relatively high purity of biomass
fractions and the possibility of their separation. The disadvantages are: high cost of solvent
and their recovery but also, the cost of a process related to the specific requirement of the
used equipment due to the use of volatile solvents.
So again, you need specific type of sophisticated equipment to carry out this particular
pretreatment.
So, we will see alcohol pretreatment under organosolv. Alcohol, especially the lower
molecular weight aliphatic alcohols are the most frequently used solvents in the organosolv
pretreatment. Regarding the type of alcohol, it was found that normal primary alcohols were
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better agent than the secondary or tertiary alcohols for delignification. Although the mixtures
of n-butyl alcohol water appeared to be the most efficient in removing Lignin from the wood.
However, due to the low cost and ease recovery methanol and ethanol seems to be the most
favoured alcohol for alcohol based organosolv pretreatment.
On the other hand, some polyhydric alcohol also can be employed for the pre-treating
Biomass under atmospheric pressure with or without catalyst.
So, let us see this process flowchart for methanol and ethanol pretreatment. So the
lignocellulosic Biomass, you use either ethanol or methanol water. You pre-treat it, so
whatever you get is basically the unwashed pulp. So that you filter it then again go for warm
solvent washing so you get the solvent washes, again it goes to the solvent recovery process.
You need to recover the solvent because solvents are costly.
Then again, followed by a warm water washing, solid fraction, you will be getting and this
goes to the enzymatic hydrolysis or SSF. So, whatever spent liquor you are getting here that
goes to the solvent recovery process and the solvent is again feed back into the pretreatment
process. So, this is from here again, you can see that. From the solvent recovery you will get
something a concentrated Black Liquor.
So that is rich in lignin fraction. So, you need to recover Lignin. So, you go for the different
processes such as dilution with water followed by precipitation filtration. So then again, you
see water washing, drying and you get organosolv lignin fraction. And then here again the
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water washing and filter again recovery and the reuse of this process. This is one simple
system where you can see that we are getting the solid fraction which can be processed for
the enzymatic hydrolysis or SSF. And then we get a lignin there apart from that some other
solvents.
So, the main products from pretreatment are the following. First one is the cellulosic fibres.
So which contain the original cellulose component and varying amounts of hemicellulose and
little residual Lignin which could not be taken out. The second part, solid Lignin obtained
after removal of the volatile solvent from the black liquor by distillation. It may contain
lipophilic extractives from the original lignocellulosic feedstock. And the third one is an
aqueous solution of the hemicellulose sugars, which consists mainly of xylose in the case of
hard wood or agricultural residues. You do not get xylose every time. It depends which
Biomass you are using. This solution is the filtrate of the previous solvent-evaporated liquor
in which the lignin fraction was precipitated.
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So, we will see 1 or 2 applications. So, application on wheat straw. An ethanol treatment of
straw remove both lignin 14% and hemicellulose 51%. Partial delignification and significant
loss of hemicellulose fraction resulted in a 15% increase in cumulative biogas production
compared to the untreated sample.
Another application on bagasse, para rubber wood sawdust, Palm and cassava fibre. So, the
studies of Inkrod et al of the extraction of Lignin from Bagasse, para rubber wood sawdust,
palm and cassava fibres in the presence of a solvent mixture of methyl isobutyl ketone,
ethanol, water, and sulfuric acid showed that the highest efficiency in Lignin removal was
obtained for the bagasse sample that is 88% in 160 degree centigrade.
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Other lignocellulosic materials revealed a similar yield of Lignin in the range of 67 to 71%.
The Lignins extracted from bagasse and para rubber wood sawdust had the highest purity of
89% and 87% respectively while purity of Lignin present in other samples was in the range of
64 to 78%. And it is a good process and quite efficient.
Another application of this process on Pinu radiate. So, in another work it was demonstrated
that the conditions of the organosolv process have a strong impact on the thermal stability of
Lignin extracted from Pinu radiate. It was observed that severe process conditions like high
temperature or to a lesser extent process time lead to a decrease in the thermal stability of
Lignin due to the degradation of its macromolecular structure. Lignin is a very complex
molecule. So, we have seen the structure. Though it is a very rigid structure, however too
harsh treatment will result in the lignin degradation.
So, this is selected examples of some of the studies concerning the organosolv method. You
can see that some of the Biomasses like sugarcane, barley, straw, oak sawdust, wheat, pinus
all these things are there and different pretreatment processes. Ethanol 50% volume by
volume here acetone and water is mixed in 50-50 ratio, and sulfuric acid concentration of 10
to 35 moles per dm cube.
That is very small amount. It acts as catalyst. As I mentioned that in the alcohol adding acid,
acid is actually working as a catalyst. So then ethanol 50% and then again ethanol 60% by
weight 40 to 60% of Ethanol in water. There are so many different types of pretreatment
processes and then followed by their conditions. Again, I am telling you for your
understanding whatever you are seeing here; let us say the time of residence to 50 to 60
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minutes, temperature 130 to 670 degree, these are the range and they have varied, like 15, 20,
30, 40, 50, 60 like that they might have varied. I am just telling you for your understanding.
That you will understand how to optimise the process. Temperature again, 130, 140, 150,
200, 300, 500 up to 670. So this is the range they have varied and they might have got an
optimised condition. And let us see the optimised condition he has given here for one
particular optimal condition; 160 degrees centigrade, 10 minutes and 0.5% concentration of
sulphuric acid for 50% ethanol water mixture.
This is what is called the optimised process condition for the most efficient or the highest
reducing sugar yield you can say.
So, the next class of solvents are ionic liquids. Ionic liquids are considered as the green
solvents owing to their unique solvation properties. So Ionic liquids shows high thermal
stability and low toxicity and required low vapour pressure. This ionic liquid selectively
remove the Lignin and hemicellulose part of biomass to provide pure cellulose for further
hydrolysis. The IL pretreatment process can be operated more efficiently in continuous mode
with high biomass input.
However, the main challenges are IL toxicity, pH compatibility, costliness - Ionic liquid still
whatever it is commercially available most of them are very costly - and process complexity.
Low cost and environmentally friendly IL’s have been synthesized using Lignin and
hemicellulose derived compounds. The reduced amination of Lignin monomers, furfural,
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vanillin, and P-anisaldehyde followed by treatment with phosphoric acid has generated ionic
liquids including this.
So, these are some of the ionic liquids which are actually being generated from Lignin and
lignin derived products.
How do you prepare ionic liquids? It is very simple, mix this and this; representative am
telling you. what is that? These 4 on the top are all cations. These 4 on the bottom are all
anions. So, any cation and any anion you fuse them together you get an ionic liquid. It is not
so easy to do that. It can be done in the lab scale but you need further processing. Fusing
together at certain conditions is fine.
But then the purity comes into picture. So, it may be 50%, 60%, 70% pure but then you need
to purify to 80% 85% 90% it is again a challenge. So, these are different types of ionic liquids
cations and anions; imidazolium based, pyrrolidinium based, Piperidinium based and based
on ammonium. And these are some of the anions; hexafluorophosphate, dicyanamide, tetra
chloroaluminate and ammonium.
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So, there are 2 ways you can do. The path one is fractional dissolution of lignocellulose or
pulping and path 2 is dissolution and reconstruction of cellulose.
Which is being explained in more detail in such a nice schematic representation, but let us
first understand what is Path 1. So, ionic liquids are used as solvents in the process owing to
their good solubilizing power and Ultra low Vapour pressure and therefore negligible loss
into the environment. Moreover, used IL’s like N222 HSO4, BMIM HSO4, BMIM Cl are
quite cheap. I can tell you, see let us look at this, BMIM is your cation and HSO4 is anion,
like that you can understand.
So that BMIM is the cation and Cl is the anion. So high degree of Lignin removal leaves
behind the cellulose with quite porous structure that can easily be transformed into hexoses in
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high yield. Further fermentation can afford bioethanol is fuels. Alternatively, chemical
pretreatment that can also be done in ionic liquid can transform sugar into platform chemical
such as a HMF or Levulinic acid.
Part 2 is dissolution and reconstruction of cellulose. So, some ionic liquids like EMIM OAc,
EMIM DEP are good solvent for the dissolution of wood - hardwoods basically - dissolving
all of the wood constituents whether it is cellulose, hemicellulose and Lignin. Now, this
dissolved cellulose can be reconstructed in amorphous state by addition of water, spun into
fibres, transformed into composites, films, nanoparticles or chemically modified for further
use.
So how these two things have been done here, we will try to understand. So, this is the
lignocellulosic Biomass. So, you add ionic liquid to it. Then follow the proper protocol how
to do it. There are steps and process conditions. Now the first one use EMIM DEP or EMIM
OAc, you got, this is the part 2 basically which we have discussed, dissolved cellulose. Now
this dissolved cellulose can be purified into cellulose.
It goes for further processing like cellulose derivatives, HMF, Levulinic acid and
fermentation to Sugars, ethanol, this is alcohol or biofuel platform. So, then this dissolved
cellulose can be further spun into fibres, nanoparticles, films and composite and you can use
them. Now in the part 1 which discussed if you use N222 HSO4 and similar other ionic
liquids so you are getting for a fractionalization.
So, you pre-treat and pretreatment process, then you get cellulose and further processing and
whatever precipitation is remaining that is rich in Lignin basically, deep brown in colour.
You can see the colour is also been shown here. Again, you further process it so you get 2
things hemicellulose rich fraction to be purified to get hemicellulose and lignin rich fraction
you get lignin. So, you are getting cellulose, hemicellulose and Lignin in ionic liquid
pretreatment process and all are in a better yield.
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So, this table is showing you selected examples of the studies concerning application of the
ionic liquids. So again, I am not going to read out this. So please refer to it later. So, the
temperature, residence time, efficiency of the process, what are the Chemicals, what are the
different types of ionic liquids being used and these are the different types of biomass.
Similar table with different Biomass again.

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So next class of solvent is Deep Eutectic Solvents. So deep eutectic solvents come in the
picture as a result of certain disadvantages of the ionic liquids. So, DES, these are two or
more components mixture in which one is a hydrogen bond acceptor, which is known as
HBA, another is a hydrogen bond donor (HBD). So, you fuse together a hydrogen bond
acceptor like ChCl or hydrogen bond donor like urea in a molar ratio that you decide.
So, you will get ChCl urea, which is the deep eutectic solvent. It is just like ionic liquid you
are fusing one cation and anion. Here we are talking in terms of hydrogen bond acceptor and
hydrogen donor. So, an application of the DES for pretreatment of biomass is an alternative
to conventional IL’s especially due to their lower cost. In comparison to the IL’s the synthesis
of DES is easier and DES can be obtained from widely available and inexpensive ingredients.
So, for example your quaternary ammonium salt and metal chloride; these are less costly than
the ionic liquids.
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The other advantages of DES are low-volatility, wide liquid range, low toxicity
biodegradability and enzyme compatibility. Biodegradability is very important feature for a
solvent to be extraordinarily green solvent. So, the ability to remove Lignin and
hemicellulose from Biomass structure during pretreatment is determined by the capacity of
the dissociation of protons by this DES.
Strong electron withdrawing groups of HBD’s - hydrogen bond donors - can enhance process
performance while hydroxyl or amino groups of the hydrogen bond donors negatively
influence the process efficiency. So, strong acidic DES can effectively remove Xylan from
rice straw structure. As a result, cellulose is more available for enzyme despite the presence
of Lignin in the structure of biomass.
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So, we will see one application in Sago waste. So 3 types of DES differing in HBD choline
chloride that is ChCl urea and ChCl citric acid and ChCl glycerol was synthesized and used
for the pretreatment of sago waste in the enzymatic hydrolysis into sugar. So, basically three
different types of Deep eutectic solvents are prepared. A more acidic or alkaline character of
the hydrogen bond donor increases sugar yield due to more efficient disrupting of the
lignocellulosic structure.
The neutral HBD in ChCl glycerol pretreatment resulted in low glucose yield. Moreover,
ChCl urea DES deep eutectic solvent behaves like a conventional alkaline reagent that breaks
down the Lignin and facilitate excess of enzymes to the Biomass.
So, another application on rice straw. Xing et al presented a novel type of DES that uses the
dihydrogen bonding donors, a mixture of formic acid and acetic acid with ChCl, which
effectively removes Lignin and hemicellulose increasing the amount of cellulose.
Pretreatment of rice straw with a dihydrogen bonding DES showed significant abrasion and
splitting of fibres as well as some delamination and peeling as a result of partial
decomposition of hemicellulose.
This increased the total sugar yield in comparison to the use of DES containing single
hydrogen bond donor. This is a very good work. I have given you the reference. It is a
published work in chemical engineering journal. Those who are interested please refer to this.
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And again, one more table in which listed are the studies concerning application of the
different Deep eutectic solvents with respect to different Biomass like say rice straw, Sago
waste, herbal residues, what are the Chemicals and HDB’s all that is being used, what is the
temperature, time of residence and what is the efficiency. So please refer to this later on.
Again, this is continuing with switchgrass and rice straw.

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So will move to the next class of treatment which is called oxidative pretreatment. The
oxidative pretreatment is based on the treatment of lignocellulosic materials with oxidizing
agent. So, what are those? Those can be Ozone, hydrogen peroxide, oxygen or even air. The
processes mainly involve removal of Lignin from the Biomass structure and increase the
accessibility of cellulose. Unfortunately, Biomass oxidation is not a selective process and the
removal of Lignin is often accompanied by the loss of hemicellulose and Cellulose.
The effectiveness of the delignification process is the result of the oxidation of the aromatic
rings in the presence of an oxidizing agent to Carboxylic acids. Other reactions of the
delignification process that take part during oxidative pretreatment include electrophilic
substitution, displacement of sides chains, and cleavage of alkylaryl linkage. So, these are the
other type of reactions.
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Let us understand the Ozone oxidation to promote delignification. Ozone is a promising
reagent for the oxidation of lignocellulosic biomass due to its selective reactivity lignin. Its
powerful oxidising property target compounds with functional groups with high electron
density such as Lignin and overlook cellulose and hemicellulose. Thus, no significant losses
of Carbohydrates occur and the Sugars’ accessibility to enzymes and microbes is increased
due to the destruction of lignocellulosic biomass structure.
Advantages include: no production of toxic residues, mild operating conditions - basically

room temperature and pressure, easy onsite production - that is reduced transport cost,
chemical supply and storage problems. On the contrary Ozone production requires high
energy inputs (36 megajoule per kg of Ozone) and high doses for pretreatment (example, 9kg
Ozone per tonne of dry biomass to produce 63 kg of ethanol).
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This is a schematic of the Ozone oxidation process. So, basically you have an Oxygen gas
tank here - then by flowmeter it goes to a unit, which is basically Ozone generator. So, you
maintain standard temperature and pressure. Now this ozone will be fed to a packed bed type
of column which is having this lignocellulosic Biomass.
And you have a micro bubble diffuser - so the Ozone will be diffused and it will come in
contact with the lignocellulosic Biomass, then whatever the Ozone is getting or moving out
of this column has to be passed through an Ozone destructor. So again, convert Ozone to
oxygen. So, this is very simplest way - this can be done in a large scale very easily. No harsh
pretreatment condition and no requirement of sophisticated instrumentation only you need a
Ozone generator and oxygen cylinder.
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So, studies have been conducted to explore the application of Ozone oxidation in
lignocellulosic bio-refinery. It has been used to pretreat a wide range of lignocellulosic
biomass to generate biogas, bioethanol and biohydrogen. This table again list out selected
examples of biofuel production from lignocellulosic Biomass pre-treated with Ozone
oxidation. So, MC is moisture content. So you can see it is written 45% w/w MC that is
moisture content.
So, it is biogas. The target is biogas production, bioethanol production, biohydrogen

production. So, please refer to the slide later on.
So, we will talk about the physicochemical pretreatment methods. This category of
pretreatment includes methods that combine physical changes and chemical reactions during
the processing hence the name physicochemical. Generally, lignocellulosic Biomass is treated
at high temperature and under pressure with an inorganic compound which leads to
disruption of its recalcitrant structure. As a result the basic components of biomass are
fractionated, which facilitates further processing.
We will see one example, one such pre-treatment method which is steam explosion method
or auto hydrolysis. So, Steam explosion is one of the most commonly used methods of
physicochemical pretreatment of lignocellulosic biomass. So, this method is based on the
treatment of the biomass by high pressure saturated steam, which is rapidly lowered. That is
why it is causing explosion. Causing the explosive decompression.
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So typical conditions of the steam explosion process are temperature 160 to 240 degree and a
pressure of 0.7 to 4.8 Mega Pascal. The purpose of the vapour explosion is to solubilize
hemicellulose and improve the accessibility of cellulose while avoiding formation of
inhibitors for further enzymatic processes. The steam explosion pretreatment results in partial
hydrolysis of hemicellulose by released acetic acid.
Lignin is removed only to a limited extent, but melting, depolymerization and

repolymerization reaction causes its redistribution on the surface of the fibre. The main
advantages of the steam explosive pretreatment are residence time is very short - so, it is
good for commercial application, low energy consumption and lack of chemicals used. So the
entire process is very economically justified.
However, there are certain issues, like poor lignin removal, deconstruction of Xylan into
hemicellulose and possible generation of inhibitors affecting further processing. Again this
HMF and acetic acid and all this. So, if you go for a high temperature application.
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So, we will see one application on bagasse. So, steam explosion was used in the pretreatment
of bagasse in the extraction of cellulose nanofibrils. The pretreatment result in partial removal
of hemicellulose from Biomass increasing the crystallinity index. In addition, the processing
stripped middle lamella and primary wall separated the closely packed fibres in the bagasse
structure.
Another application on hardwood, soft wood and agricultural residues. Priyanto et al, this is a
very good study published in ACS Sustainable Chemistry engineering. So, what they did
actually they used moisture from Biomass as a source of steam in order to improve properties
of feedstock pretreatment. This is very interesting study. Hardwood, softwood and
agricultural residues with different moisture content from 45% to 75% were treated in a
specially designed reactor.
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The process called self-steam explosion effectively reduced the grain size (almost average
below 1 mm) of feedstock increasing the heating values and hydrophobicity. It was suggested
that such a type of pretreatment can be economically efficient reducing processing cost more
than half compared to the conventional milling.
This table is giving you selected examples of some of the studies concerning application of
the steam explosion method. Various types of biomass, their pretreatment conditions and the
efficiency has been listed, please refer to it later on.
So, we move ahead to one of the again more studied method which is called AFEX that is
Ammonia fibre explosion method. So here, it is similar to the steam explosion. So here it is
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based in the pretreatment of lignocellulose with liquid Ammonia at elevated temperature.
With the pressure around 0.7 to 2.7 mega pascal. The process conditions and the presence of
ammonia causes the swelling of the biomass, increasing the available surface area, the
degradation of hemicellulose to oligomeric sugars and the change of the lignin structure.
Basically, the mechanism is that, the ammonia is swelling the Biomass making it more
porous and they will be more accessible to the enzyme. So an important disadvantage of this
AFEX process is the low efficiency of the process as in the case of acid pretreatment, the
corrosive reaction and environment also.
So, for this reason the process requires the use of appropriate reactors and hence again
additional cost come into the picture.
We will see some of these AFEX study. So the AFEX process was used as a pretreatment
method of Corn stover, prairie cord grass and switchgrass before the pyrolysis process. All
this has been used for pyrolysis but before that they are pre-treated with AFEX to increase the
pyrolytic product yield. The impact of the treatment was negligible and did not significantly
improved the properties of tested materials.
Parameters such as moisture content, volatile matter, ash content or heating values were
almost the same before and after pretreatment. However, the AFEX process increased pellet
durability and decrease the temperature of the sample degradation, not much effect has been
actually reported. During the pyrolysis process the yield just increased for biochar from 22 to
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25% and for the bio-oil it is 46 to 48% after the AFEX pretreatment which is very, very
marginal actually not significant.
This is again selected examples of the studies concerning application of the AFEX method.
Various biomass is like cornstover, grass, switchgrass, which we just saw. Agava, bagasse
and leaf, Agava salmiana bagasse. So please see the different chemical that is listed. The
conditions, time of residence and the efficiency of the process, please refer to it later.
And we will see one of the most important class of this pretreatment process, which is called
liquid hot water and hydrothermal liquefaction methods. In hydrothermal process water is
used for the pretreatment of lignocellulosic biomass. No catalyst or chemicals other than
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water are used. So that it is called hydrothermal method. So, depending on the process
temperature hydrothermal processes are divided into 5 types.
(a) The first one is the hot water extraction; (b) second one is pressurised hot water
extraction; (c) Third one is the liquid hot water pretreatment; (d) forth one is hydrothermal
carbonization or HTC; and, (e) hydrothermal liquefaction or HTL. HTC and HCL are widely
studied since last decade and have lot of applications and excellent studies have been
reported. So, the low-temperature process in which the process temperature is below the
boiling point of the water (less than hundred degree centigrade) is used to extract some of the
water-soluble Biomass components such as pectin and tannin.
Due to the temperature range of the process, the target of each is different. So that we need to
understand. Here whatever is being listed you’re seeing, everything has a certain different
temperature. The temperature, temperature range depending upon their product whatever
coming out will also be different. We will see. So in the pressurized hot water extraction, it is
carried out in the 150 to 180 degree centigrade in that range and can be used as a pretreatment
of the pulp dissolving process and for the reduction of hemicellulose content in the forest bio
refineries samples.
In the liquid hot water process the applied temperature is 140 to 230 degree centigrade is little
or a we can say slightly higher than the PHWE. So this process leads to partial dissolution of
hemicellulose and Lignin and reduction of the durability of the structure. In turn in the HTC
or the hydrothermal carbonization, which is carried out at 180 to 250 degree centigrade is
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used to convert Biomass into modern carbon materials with specific physicochemical
properties.
High quality carbon can be prepared that is why the name is actually hydrothermal
carbonization. Then during the HTC process hydrolysis, dehydration, decarboxylation,
polymerization, aromatization and condensation reaction takes place. As a result of the high-
temperature starting from 280 degree centigrade in the HTL process, a biocrude that is oil
like product can be obtained. We will discuss HTL later on, its a very good process actually.
Whatever we have discussed this has been given in this particular some sort of schematic
representation of graphical abstract type you can see. Biomass, the treatment method. You
can see this. The first one is the hydrothermal liquefaction HTL which was discussed at the
end. So that converts, you will get Carbon, you get bio-oil and you get water soluble
degradation products.
Apart from that you get carbon dioxide, carbon monoxide, hydrogen and methane. When you
go for the liquid hot water pretreatment, you get hemicellulose and extracted biomass here.
The solid biomass can be fractionated again into valuable products. For hot water extraction,
which is below 100 degree centigrade we get extracted biomass which can be for the
processed to again value-added products and we get the polysaccharides and polyphenolic
compounds.
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So, this is the lowest in the lowest range of the hydrothermal processes and HTL is the
highest range in terms of the temperature and the uses.
So, a table line gives you the studies concerning application of the hydrothermal method. So
again, I am telling you that you please refer to it later on. So different Biomass are listed,
different pretreatment conditions and their efficiency of the process has been listed. So, this
will help you if at all going to do some work on Biomass fractionation or biomass
pretreatment.
We will see this the characteristics of the lignocellulosic pretreatment techniques. This is an
overall idea. So, you can see this, different pre-treatment methods like microorganisms - the
biological one, followed by ligninolytic enzymes, alkali method, acids or dilute acids method,
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Ozone oxidation, ionic liquids and deep eutectic solvents, you have mechanical - this is a
mechanical and physical method milling and grinding, then irradiation using using
microwave, ultrasound, hydrothermal - like hot liquid and steam explosion. So, I will leave it
to you for read and referred to it later on. There is not much to again describe or there is no
much point in reading. Whatever being listed here we have already discussed throughout our
today's lecture. This in a single table is this has been compared. So, you can understand what
are the advantages, disadvantages of a particular process for a particular biomass.
So, with this I conclude my today's lecture. So please feel free to post your query in the
Swayam portal as well as drop a mail to me at [email protected]. I shall be happy to
answer and in the next class that is the third of the module 4 we will be discussing about
hybrid methods and the role of pretreatment in a biorefinery concept. Thank you very much.
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Lecture 12
Hybrid Methods
Good morning students. Today is lecture 3 under module 4. In this module as you know that
we are discussing about the Biomass pre-treatment. Today we will discuss about the hybrid
methods of pre-treatment and what is the importance of pre-treatment in a biorefinery
concept.
So, based on the drawbacks of single pre-treatment methods researchers have been trying to
combine these methods to overcome the problems and increase efficiency. If you recall one
of my class, I emphasized that why do we basically need a hybrid system; because you know
any process has its own limitations in terms of the efficiency, yield or such parameters,
restricted to maybe 70 to 80% depending upon the type of technology or process it is.
So, in any single step process it is very difficult to achieve a very higher yield and that is the
reason why there are many operations or processes that can be combined together with the
sole aim to increase the yield. So that is how actually the hybrid methods came into picture.
Since many years ago many studies have been carried out by a combination of various pre-
treatment methods.
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Combinations of one or more pre-treatment methods to improve the pre-treatment process
may be a possibility to find process designs that will be suitable for enhanced fractionation of
the raw material. This could be for instance, to yield process streams which are optimised for
hemicellulose while others streams are optimised for other compounds.
The implementation of several different pre-treatment methods comes with an additional cost
if the methods are dissimilar. So cost is a very important aspect when you talk about
commercialization. So that also need to be taken care of. So, it would not be advisable to
apply widely different pre-treatment methods. Nevertheless, pre-treatment is commonly
preceded by size reduction step which can be regarded as a mechanical pre-treatment. If the
size reduction is Thorough.
The reverse operational procedure is also a possibility. Now Microwave and Ultrasound
technique in combination with other pre-treatment techniques such as pre-treatment using the
deep eutectic solvents, acids, alkalis (these are all that we have discussed in our last class)
have been widely used as a part of the hybrid process of pre-treatment. Please understand that
this is whatever written here, the hybrid is not only restricted to this. There are many numbers
of studies. We will just discuss few of them to get an idea about actually a how and why this
hybrid processes have been adopted.
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So, we will see the microwave-assisted method, which is one of the most common and a low-
cost method and faster process also we will discuss that. So microwave technology can be
combined with other pre-treatment technologies to increase the efficiency of the process. So,
Microwave Technology has been successfully applied along with deep eutectic solvents pre-
treatment, DES, Alkali pre-treatment and acid pre-treatment usually dilute acid pre-treatment.
Let us have a look at this hybrid technology application in the switchgrass, corn stover and
miscanthus feedstocks. Microwave technology combined with the use of DES pre-treatment
was applied to ultrafast fractionation of switchgrass, corn stover and miscanthus feedstocks.
The combination of Microwave irradiation and ChCl and lactic acid over only 45 seconds
resulted in a highly effective lignin and hemicellulose removal and left the cellulose intact.
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Please understand it is very faster process 45 seconds only. Now this kind of pre-treatment
allowed the removal of more hemicellulose than lignin. Additionally, microwave
significantly improve the efficiency of the pre-treatment by DES. So overall we can say that
it is an excellent hybrid system.
So, the electromagnetic field of microwaves led to the breakdown of the biomass structure
mainly due to molecular collision caused by dielectric polarization. In addition, microwave
radiation increases the molecular polarity of DES which enhance the efficiency of the pre-
treatment. Pre-treated biomass showed a 2 to 5, fold increase in digestibility during
enzymatic hydrolysis in comparison to the untreated feedstock.
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Now, please have a look at this particular schematic of the microwave assisted DES pre-
treatment. So, this is the lignocellulosic Biomass whatever it can be miscanthus, corn stover
whatever we have discussed, switch grass. So, then it has been put it under a microwave
reactor. Along with that DES in different concentrations of course because you need to
optimise it, the process parameters.
So, you can see within 45 seconds they have degraded and result into 2 two different
fractions. So, one fraction is basically pre-treatment liquor which is thick, viscous and brown
in colour this colour. And then another one is the solid residue. That solid residue basically
contain glucose and Xylan; basically you can say that it contains your carbohydrates. And
this part which is dark in colour it contains lignin mostly.
But depending upon the efficiency of the process. It will always happen that some of the
carbohydrates remains here and some of the Lignin also remains there.
So, microwave technology combined with acid pre-treatment. So, one application is in with
Jabon tree Biomass. So, Microwave with the presence of the acid, intensified the
decomposition of biomass during the Jabon tree pre-treatment which allowed obtaining
higher yield of sugars. Despite the increased efficiency in removal of Lignin with the time of
irradiation the formation of side products occurs, which affected further processing.
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Then a microwave combined with alkali pre-treatment. Application in brewers’ spent grains
(BSG). So, microwave assisted alkali was found as the most effective pre-treatment among
others studied techniques such as your steam explosion, Ammonia fibre explosion, then dilute
acid, organosolv used for reducing sugar production by enzymatic hydrolysis of brewers
spent grains that is called BSG.
After treatment with the combination of Microwave and alkali the surface of the BSG
increase due to disruption of the structure of the investigated material which resulted in larger
sugar yield in comparison to the use of the other pre-treatment methods.
So, the process is described here in brief. So, a domestic Microwave with the maximum
output power of 800 watts was employed for this purpose. 1% weight by volume biomass
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was loaded to 0.5% Sodium Hydroxide weight by volume in a stoppered flask and subjected
to microwave irradiation at varying power settings of 400 watts, 560 watts and 800 watts for
different residence times varying from 30 second, 60 seconds and 120 seconds.
Please understand again I am telling you that the microwave techniques at superfast
techniques. It is very faster than any other pre-treatment processes, even if you are combining
two processes or talking about a single process also. After pre-treatment the Biomass
thoroughly washed with distilled water till pH 6 and dried in air. The dried solid Residue was
used for enzymatic hydrolysis and composition analysis because the that dried solid residue
contains most of the carbohydrates.
Comprehensive studies on the effect of microwave alkali pre-treatment on the crystallinity

index, specific surface area and morphology of BSG were also performed by Kan et al. This
particular publication has been referred here. So, it is an interesting work. So those who wish
to read more can please refer to this particular citation, which is given below. So, it was
shown that the pre-treatment of BSG caused removal of Lignin from the feedstock structure
and significant growth of the specific surface area from 9 m2/g for raw Biomass to 162 m2/g
for treated samples. A huge surface area increase.
The treatment of the investigated samples with alkali in the presence of microwave assures
effective removal of hemicellulose and Lignin from the lignocellulosic materials. However,
the presence of a large amount of sodium hydroxide resulted in degradation of the crystalline
and part of cellulose, while the high microwave power and extended treatment time led to
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degradation of the organic fraction of cellulose which reduced the efficiency of further
processing.
So, we will see the systems this hybrid process application in Cassava stem hydrolysis. So,
similar observations were noted for combined microwave alkali pre-treatment of cassava
stem for sugar production which depended on reaction time, base concentration, solid to
liquid ratio and microwave frequency. So, microwave frequency was found to be the most
significant factor affecting the sugar yield.
And the importance of other parameters decreases in the following order, reaction time, solid
to liquid ratio, base content. So, the authors have varied basically the 4 different types of
parameter. The first one is of course the microwave frequency which was found to be the
most important parameter that is affecting the sugar yield followed by the others like reaction
time, solid to liquid ratio and the base content. So, Microwave with alkali treatment increases
the crystallinity index of cassava stem removing all its amorphous parts.
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And now we can discuss the comparison of acid and alkali assisted microwave pre-treatment
in cassava bioconversion. So, you have seen the individual processes clubbed with
Microwave. Now, we will discuss about the comparison. So, the methods of microwave pre-
treatment with alkali and Microwave with acid were compared for efficiency in cassava
bioconversion. In both methods the microwave power and the process time were indicated as
the main factors providing high efficiency of the initial treatment.
It was exhibited that the yield of Sugars during enzymatic cassava hydrolysis was 52% higher
after microwave-assisted Sodium Hydroxide treatment in comparison to the microwave
assisted sulphuric acid treatment. Differences in the performance of two types of pre-
treatment results from the presence of inhibitors of enzymatic hydrolysis, which are
generated during the microwave acidic method.
In general, the acid solubilizes the hemicellulose whereas the base solubilizes lignin. So, this
the mechanism. And the application of microwave is only intensifying the chemical
processing.
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Now we will discuss about the ultrasound assisted methods. So, ultrasound technology can be
combined with other pre-treatment technologies to increase the efficiency of the process.
Now Ultrasound Technology has been successfully applied with ionic liquids pre-treatment,
alkali pre-treatment and enzymatic pre-treatment. For your information I am telling you can
read little more about ultrasonication processes. In a nutshell I am telling you that this is also
one of the very good technology or the process which is also a faster process compared to
other such pre-treatment processes. And it is also low cost.
We will see the ultrasound Technology combined with IL’s treatment in its application in the
sugarcane bagasse and wheat straw. So, ultrasound combined with the ionic liquids
effectively improve the process of saccharification of sugarcane bagasse as well as wheat
straw. Ionic liquids by forming hydrogen bonds with cellulose disrupted its crystalline
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structure while ultrasound treatment through the mechanical effect opened the biomass
structure and intensified the chemical interaction of the ionic liquids.
The combined method significantly improves the efficiency of enzymatic reduction of Sugars
compared to Biomass treated only with ionic liquid.
So, we will see in brief the process how it was carried out. So, 1 gram of biomass anything
either bagasse or wheat straw was dispersed in 20 grams of ionic liquids (so, in this case the
[Bmim] Cl or [Bmim] OAc) in a double jacketed beaker. Sonication was performed by a
single frequency counter current flow ultrasound reactor. The sonication system was operated
at 5 frequencies 20, 28, 35, 40 and 50 kilo hertz.
Five different probes with diameters of 1.34, 3.61, 3.05, 2.03 and 1.05 (cm) were used for the
frequencies of 20, 28, 35, 40 and 50 kilo hertz respectively. After completion of the reaction
2 volumes of deionized water were added to the reaction mixture. The mixture was stirred at
600 RPM by using a magnetic stirrer and filter under suction to remove as much liquid as
possible. The filtered biomass was soaked in ethanol, filtered again, washed 3 times with
deionized water, dried to a constant weight and kept further analysis.
So, this is a nut shell I just told you about the process how ultrasound-assisted ionic liquid
pre-treatment method was carried out. So, one beautiful thing about the entire hybrid system
is that as you know that there are so many different types of ionic liquids available or one can
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tailor make ionic liquid in the lab. So, as I told you in the last class you need to take a cation
and you need to take anion and fuse them together to obtain a ionic liquid.
So, if you can study the chemistry little more - chemistry of the Biomass, its structure and all,
so then we can understand that what type of ionic liquid will be better suited for that
particular biomass. So, with that type of study we can include those for doing the
experimentation with ultrasound-assisted ionic liquid pre-treatment.
Now, the next one is ultrasound Technology combined with enzymatic hydrolysis. So we will
discuss its application in peanuts shells, coconut shells and pistachio shells. The mechanical
effect of ultrasound treatment on the Biomass structure and intensify the Sodium Hydroxide
performance during the combined pre-treatment of peanut shells, coconut shells and pistachio
shells before enzymatic hydrolysis to sugars.
Ultrasound enhance the rate of the delignification by morphological changes caused by

intense turbulence and shear effects. In addition, ultrasound created free radicals in water
taking part in the cleavage of Lignin and Xylan structure. The use of this combined process
besides intensified delignification reduce the time of the process and the amount of alkali
leading to the higher sugar yield.
As such this was proved to be a very good hybrid process. It has resulted in a more
delignification. It has reduced the time of the entire process and the amount of alkali that is
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being used earlier, or if you compared to the single alkali pre-treatment process so thereby
resulting in a higher sugar yield.
This is the experimental setup for ultrasound assisted alkaline pre-treatment in 100 ml batch
reactor. This is a reactor simple reactor chemical reactor. So, this is the ultrasound generator,
and this is the ultrasound gun or probe whatever you can say. This is the reactor and this is a
jacketed reactor - you need to cool it in case the heat is evolving, and it is a stirred reactor.
Stirring will further enhance the mass transfer or the rate of reaction. And it is a simple
system and can be done in lab easily.
Now we will discuss about the comparison of the ionic liquid and alkali assisted ultrasound
pre-treatment for eucalyptus. Wang et al compared the effect of the ultrasound-assisted ionic
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liquid and alkaline pre-treatment methods on the structure and chemical composition of
eucalyptus and the yield of its enzymatic saccharification. It was found that ultrasound in
combination with ionic liquid was much more efficient in the delignification process while
ultrasound in combination with alkaline was a more efficient in removal of the hemicellulose
from the eucalyptus structure.
So, in addition ultrasound combined with ionic liquids remove the amorphous fraction during
the pre-treatment more effectively than alkali combined with ultrasound. As a consequence,
higher yield of Sugars could be obtained in the first case that means ultrasound followed by
ionic liquids.
So, we will see some of these results which are reported in Literature and I have tabulated
here. The reference is given here from where this table have been taken. These are some
selected examples where studies concerning the applications of the combined methods or
hybrid method. So, all type of biomass, the different treatment method, the chemicals that are
being used, then the predetermined conditions very important - this last class also I discussed,
again I am telling so this is actually very important. You need to optimise the process
parameters. You need to vary the range of reaction time or residence time, the temperature -
if at all it is there, the amount of chemicals you’re using, the amount of energy, the type of
solvents, all these things are there and the efficiency of the processor. Let us see one thing we
have not discussed about this one Jabon tree craft pulp.
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So, it is a microwave of almost 1000 watts plus acid, in which they have used only 1%
sulphuric acid and the conditions are - temperature 180 degrees centigrade, 190 and 200
degrees, that is what they have varied, three different sets of temperature and three different
sets of residence time 5 minutes, 7 minutes and 10 minutes. So, the result is very interesting.
So optimal temperature they found it is 190 degrees centigrade and reducing sugar yield
increases of around 40 grams per 100 gram of dry pulp, which is a good yield.
Please understand the yield of sugar is directly related to type of biomass because first of all
every Biomass are distinct in their composition. So, if the carbohydrate fraction is more, then
we are going to get more sugar. And if the lignin is more, compared to carbohydrates, the
reducing sugar yield will be of course less. Let us move ahead.
There are many I have listed here. So, if you see this sugarcane bagasse, wheat straw which
was ultrasound with ionic liquids. So, they have used 20 - 50 kilo hertz, in that range they
have varied. 1-Butyl-3-methylimidazolium chloride (Bmim Cl basically) and they have used
also Bmim Acetate (OAc) and the temperature is 80 degrees centigrade, time of residence is
30 minutes. So that is again in this case that are optimised.
So, they have put that optimal condition 30 minutes, 80 degrees centigrade, 20 kilohertz and
with the glucose yield of 40% and 53% for bagasse and wheat straw respectively, which is
again very good in terms of glucose yield. So similarly, there are so many things as listed
here. So, what I request is that you can please go through all these things.
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We are still continuing; these are some of the more different types of hybrid treatments given
here. So, corn stover Biomass alkaline oxidative treatment (AlkOx it is called). So the
chemical used is 10 molar sodium hydroxide, along with the hydrogen peroxide. Temperature
is 60 degrees centigrade, time of residence is 5 hours; so it takes long time. So, it was found
that combined method dissolves 93.4% and 83.5% of Lignin and hemicellulose respectively,
which is a very good result.
Now then ultrasound followed by AlkOx (sugarcane bagasse), then steam alkali pre-treatment
(debarked white birch chips), then steam and hydrogen peroxide combined (sugarcane
bagasse). Now we have discussed certain hybrid pre-treatment technology in today's class.
There are many, everything it is not possible to discuss in a single class and is also out of the
scope of this particular course. So the idea is to make you understand that how the hybrid
processes works and it is always not true that you can just combined two any different
processes and a look for that.
You can do some experiment to find out which is good or which is bad but there should be
some theoretical understanding that which particular two different pre-treatment methods
should be combined and why and how they will be combined. So, I hope you get an
understanding about the different hybrid processes.
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So, we will just discuss briefly about other combined treatment methods. So, alkaline pre-
treatment combined with mechanical extrusion. So, as mentioned earlier the alkaline pre-
treatment method is one of the most commonly used methods for pre-treatment of
lignocellulosic materials. However, alkaline treatment combined with mechanical extrusion
enhance noticeably the removal of Lignin and hemicellulose from the corn stover structure.
The use of a combined mechanical alkaline method increases the yield of Sugars by about
25% in comparison to the yield obtained after alkaline treatments only.
Both methods ensure destruction of the corn stover structure. The combination of mechanical
and alkaline treatment allows for not only disruption of the recalcitrance of the Biomass
structure, but can also be useful in further processing.
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Alkaline pre-treatment in the presence of hydrogen peroxide. It is called AHP. So AHP is an
oxidative pre-treatment process. It acts in the delignification of the lignocellulosic Biomass
which allows a greater efficiency to be achieved in the recovery of Sugars in the liquid phase
of enzymatic hydrolysis since the presence of Lignin makes it difficult for the enzymes to
attack the substrate.
The hydrogen peroxide is very unstable in alkaline conditions and decomposes very fast. So
that generate hydroxyl radicals and superoxide it can result in an increase in the efficiency of
delignification of biomass. The effectiveness of the alkaline pre-treatment with hydrogen
peroxide depends on the reaction conditions such as the amount of biomass to be treated,
time, temperature and concentration of peroxide and base.
This type of pre-treatment has low energy consumption and does not generate inhibitors like
hydroxymethylfurfural and furfurals. So, this is one of the best take-home-message from this
particular AHP study, that, they do not generate the inhibitors; because this inhibitors HMF
and furfurals and then some other intermediates they have a very bad effect on the further
fermentation process.
So, we will see its application in corn straw and gooseweed. The use of a combined sodium
hydroxide and hydrogen peroxide pre-treatment (the AHP pre-treatment) of corn straw result
in the removal of 93% of Lignin and 83% of hemicellulose from the structure of the raw
material. Effective treatment of the main components of lignocellulose during the enzymatic
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hydrolysis allowed the achievement of 61% conversion of cellulose to glucose and 69%
conversion of hemicellulose to xylose.
And on the other hand, alkali and hydrogen peroxide did not make any difference to sugar
yield obtained in Gooseweed pre-treatment before bioethanol production. Combined sodium
hydroxide and hydrogen peroxide treatment released an equal amount of sugar in comparison
to the use of the alkaline pre-treatment method. Therefore, the researchers have indicated that
it is more economically justified to use only an alkaline pre-treatment method.
So, the next combined method is sequential acid and alkaline pre-treatment. This is a very
interesting study reported in Bioresource technology, the reference is given if you are
interested to learn more in detail, please refer and read. So, a combination of dilute acid pre-
treatment with alkaline pre-treatment makes the removal of hemicellulosic Sugars and Lignin
from the lignocellulosic Biomass possible in order to enhance their enzymatic digestibility
and fermentability.
Most processes involve the use of dilute sulphuric acid pre-treatment with subsequent
alkaline Lignin extraction using Sodium Hydroxide followed by further enzymatic digestion
and fermentation. Besides sulphuric acid and sodium hydroxide, sequential hydrochloric acid
and lime pre-treatment has also been applied to corn stover achieving maximum glucose and
xylose yields of 89.5% and 97% respectively with the cellulase doses of 10 filter paper units
per gram of substrate.
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So, the solid material that is resulting out of the sequential pre-treatment shows a higher
crystallinity index, as the amorphous contributions from hemicellulose and Lignin were
removed. In addition, depending on the severity of the alkaline treatment cellulose
crystallinity is decreased due to the polymorphic transformation of cellulose from type 1 to
type 2. This phenomenon results in higher enzymatic digestibility of cellulose rich material.
So, these are the process conditions and the schematic. So Biomass is (subjected to) a process
standard acid hydrolysis. So, you get pentoses or the C5 sugars. Then the acid treated bio
masses is being send to a alkaline extraction system where you get actually Lignin as the
bottom or the product which are there in the liquid fraction and you get the crude cellulose in
the solid fraction. So, this is the different process condition.
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So here the authors actually have studied four different types of biomass. First one is soybean
husk, second one is oil palm empty fruit bunches, third is Pinus species straw and the fourth
one is Eucalyptus straw. Now a different process conditions both for Acid hydrolysis and
alkaline conditions are given here. So, you can have a look later on.
So, the applications of this particular technology and its result we will discuss. Some
investigation evaluated sequential alkaline acid pre-treatment. The sequential alkaline and
acid pre-treatment using a 14.49% solid to liquid this yield was applied to corncobs. The
maximum reducing sugar yield obtained after enzymatic hydrolysis of the cellulose rich
material was 0.99 gram per gram.
In another study on cotton stalks first applied on alkaline pre-treatment removing 52.48% of
the lignin with sugar loss of 3.5 %. A subsequent 2 stage dilute acid treatment using sulphuric
acid of the delignified Biomass release 29.4 grams per litre of sugar, 63.5% Hollocellulose
hydrolysis in the hydrolysate along with 2.18 and 1.32 grams per litre of phenolics and
furfurals respectively.
Again, you see that there are some inhabitance and that is being resulted which is actually not
warranted. We are always supposed to develop pre-treatment processes in such a way that
one of the aims is to get rid of these inhibitors.
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So finally, detoxification of the hydrolysate by over liming and adsorption with activated
charcoal reduce the furfurals and phenolics. To remove the formation or to reduce the
formation of this inhibitory compounds like these furfurals, activated charcoal adsorption was
used and it resulted in a good removal of this furfurals and phenolics. However, in sequential
alkaline acid process, considerable amount of hemicellulose is removed together with lignin,
resulting in a loss of fermentable sugars as the Lignin present in the Black Liquor inhibits
microbial metabolism and Xylose consumption.
So, 2 different references have been listed here. So those who are interested to read more
these are classic studies and very good results, so please refer to them.
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So, finally we will see the comparison of an acid, alkali and hybrid acid alkali what we have
discussed in a nutshell. So, you can see this mild acid biomass pre-treatment, Alkaline
industrial pulping process, and Sequential acid and alkaline based pre-treatment. So, these are
the advantages given here and these are certain disadvantages. So, in the case of mild acid
biomass pre-treatment the advantages are high recovery yields of each Biomass production,
possibility to use all Biomass fractions, low energy demand, low chemical cost, low
concentration of toxic compounds. And there are certain disadvantages long processing time,
two processing steps required to recover the three main biomass constituents, and greater
equipment requirement to handle the corrosive environment, and more research demands to
enhance the whole process, more research also demanded to enhance the utilisation of the
Biomass constituents.
Then let us talk about the alkaline industrial pulping process. So short processing time,
simple processing steps, efficiency in obtaining cellulose pulp and defined processing
technology are some of the advantages. Now if you talk about the disadvantages, then it is
highly concentrated processing media, low yields of cellulose, high volumes of liquid
residue, generation of polluting residues and high production of toxic compounds.
Now let us understand the sequential acid and alkaline biomass pre-treatment. So, recovery of
hemicellulose, Sugars, Lignin and cellulose with greater efficiency is one of the advantages.
Then enhanced enzymatic digestibility, and fermentability. But there are few disadvantages
also which are additional processing steps, more research demands to enhance the entire
process and more research also demands to enhance the utilisation of biomass constituents.
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Now will discuss about the role of pre-treatment in the biorefinery concept. We have already
discussed in a nutshell, that how the pre-treatment and why the pre-treatment is required, we
will discuss in a biorefinery concept. A biorefinery can be defined as the renewable
equivalent of a petroleum refinery. The main differences being raw material. In the
biorefinery biomass can be converted into a wide range of chemicals and energy carriers.
And it can also contribute to the development of a circular economy. The concept is based on
the model that lignocellulosic materials which were used to generate bio-based products can
be recovered to a certain degree and be recovered and recycled. The International Energy
Agency, Bioenergy Task42 defines biorefining as the sustainable processing of biomass into
a spectrum of marketable bio-based products, Chemicals, material etc and bioenergy. So, it
can be biofuels, power and heat.
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So, if you see in a nutshell that this is a schematic representation of a biorefinery for
production of energy carriers and chemicals. So, you see that lignocellulosic crops or
lignocellulosic waste, it can be Municipal solid waste also are pre-treated, followed by
hydrolysis. So, we get 3 different fractions. So, the first fraction is rich in Lignin content, the
second is rich in C6 sugars, third is rich in C5 sugars.
So, they can be further processed and fed to different reactors, or let us say further processed
either thermochemically or biochemically or physico-chemically to get different products
such as biodiesel, Methane and hydrogen, ethanol certain chemical building blocks, food and
feed, Polymers and resins and other biomaterials.
So, some important considerations have been suggested for the biorefinery concept to
become a path forward towards a less Fossil dependent society. The development of
biorefineries is a vital key for integration of food, feed, Chemicals, fuels and energy
production in the future. Combinations of physical and biotechnological processes for the
production of proteins but also for platform chemicals such as lactic acid will be of
importance in the future.
That is most important thing. We have been discussing this during our many lectures that a
biorefinery will become sustainable if at all we will recycle and reuse the waste that is getting
generated. Second, most of the by-products when they are converted into some valuable
products must be marketable. And there should be acceptability by the people also. There are
so many things we have discussed during biorefinery.
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So, Biomass can mitigate to some extent the high atmospheric levels of carbon dioxide by
replacing fossil fuels. So, this precisely is telling that Biomass sources are carbon dioxide
sequesters. So, they help in carbon dioxide sequestration. In addition, in many countries
around the world the concept may be important to secure domestic energy carriers and the
supply of chemicals. Most lignocellulosic feedstock is generally much more Complex and
recalcitrant than the currently used starchy materials, for example, the ethanol industry,
which poses a great challenge.
One of the major challenges that the biorefinery concept faces to become successful is to find
suitable raw material. It is likely that second grade or waste material will be the main raw
material supply in a biorefinery. When we discussed about the Biomasses for biorefinery we
have discussed about the waste material and different lignocellulosic materials. So this
includes straw, bagasse, tree root, branches, forest thinning etc. to name few, there are many
more.
However, large part of the published research that deals with Woody materials are often
based on wood chips of high quality. Now this wood chips even including the wood sawdust
also having a huge commercial value. So, when you talk about using them for converting in
Biorefinery perspective to other valuable products. So, there is a challenge to it. So, this is in
direct competition with, e.g., the interests of the pulp producers. This is what I was just
mentioning because the pulp producers need more than in a biorefinery.
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Because it has a direct commercial value, well-established marketable end product. So, on the
other hand the residue from agricultural operations are in so many cases available for
conversion to other valuable products and are not at all in high demand. So thus, it calls for
very robust and versatile production methods to be able to handle raw materials of different
origin. It is not likely that a biorefinery will be capable of processing all sorts of
lignocellulosic materials.
Now till today. We understand that a single biorefinery, unless and until fitted properly with
robust and versatile production method and technologies, it cannot process multiple
feedstocks. And unless and until multiple feedstocks are processed a biorefinery cannot be
sustainable.
So, the purpose of the Biomass pre-treatment step somewhat shifted during the last decades.
Previously the main interest was to use lignocellulosic materials mainly for bioethanol
production. If you go back to some 10-15 years back researches, you will see that whatever
pre-treatment methods were being studied and reported all are aimed to get C5 and C6
Sugars. Mostly C6 sugars convert them to glucose, then convert them to and then process
them in a ethanol platform to get bioethanol or sometimes may be biobutanol.
Now since few years there is a change in this attitude that researchers have looked for pre-
treating the Biomass for other thermochemical conversion processes, whether it is a pyrolysis
or whether it is gasification. So today it is of great importance to find ways to maximize the
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overall yield of the valuable compounds that make up lignocellulosic materials. Pre-treatment
methods that enable efficient recovery of Carbohydrates as well as lignin are desired.
However, this all depends on the situation and the final product. The energy requirement in
the production processes must be met under any circumstances either by internal or external
integration of high energy streams, such as in a mill producing pulp where the excess Lignin
is the main process energy supply.
So pre-treatment is a step that is included as one of the first steps in the process to elevate
access to the raw material. It is difficult to define the best pre-treatment for all situations and
raw materials. However, it is vital that some important features of the pre-treatment methods
are fulfilled, such as high recovery of the individual Polymers and other compounds in the
lignocellulosic materials. In addition, the formation of toxic or inhibiting compounds must be
low (as low as possible) to decrease the risk of negative effects in the enzymatic hydrolysis
and fermentation steps if they are part of the process.
It is not true that always they will be a part of the process. If you are talking about
thermochemical conversion after the first treatment, then you do not have to worry about this
particular formation of toxic inhibiting compound. It is well known that too severe condition
during pre-treatment because greater degradation of hemicellulosic sugars which can cause
formation of highly toxic compounds such as furfural, HMF and other organic acids.
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The energy requirement is another most important aspect of the entire pre-treatment process.
It must be as low as possible. So, it is also an advantage if energy integration between the
pre-treatment step and other parts of the production facility can be implemented, such as
utilisation of a low-grade steam for distillation purposes. It has also been established that
economic success of a biorefinery is heavily dependent on the solid content of the pre-treated
materials.
So, if too dilute solutions are produced, the energy cost for purification may be prohibitively
very high which can cause an otherwise well-functioning treatment method to be discarded.
So, it is very important that if your pre-treatment processes have resulted in a too much of
dilute solution, then that dilute solutions will be full of aqueous part or water rich part. You
need to purify your sugar.
So that is the downstream processing part, that part will take on almost 40% of the entire
product cost (40 to 45%). So, you need to decrease that. So that is why if the solid content is
more in the resultant product then it is always good.
So effective pre-treatment of available lignocellulosic Biomass contribute to the generation of

sustainable biorefineries and the decrease in Environmental impacts caused by organic waste
disposal. The polysaccharide fractions of lignocellulosic biomass, including cellulose and
hemicellulose can be broken down into sugar monomers. They are then converted into
biofuels, biogas and biochemicals through bio technologies such as an anaerobic digestion
and fermentation.
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Efficiency and cost effectiveness of the bio conversion process depend on the transformation
of polysaccharides to monomers sugars. Commercial applications of lignocellulosic biomass
are hindered by the resistance of polysaccharides into hydrolysis, and the presence of
recalcitrant Lignin.
So, a range of pre-treatment methods have been developed and employed to increase
conversion efficiency. The pre-treatment of lignocellulosic biomass aims to decrystallise
cellulose structure through lignin removal, increase the cellulose and hemicellulose solubility,
increases accessible surface area to enzymes and Chemicals and minimises the loss of sugars.
So, the anticipated end products also determine the choice of pre-treatment method as each
method induces different effects on different types of lignocellulosic biomass.
Various by-products generated through this processes can be recovered and utilised for other
by biochemical productions. The success in identifying and applying effective pre-treatment
to lignocellulosic Biomass can increase the socio-economic impacts and resolve the global
problems involving sustainable energy and development.
So, with this I conclude today's lecture. So, we have completed this module 4 in which we
have discussed about the pre-treatment methods. The next module this module 5 we will be
dealing with physical and thermal conversion processes and the class 1 and lecture 1 of
module 5 will discuss about the types, the fundamental principles, equipment and
applications of thermochemical conversion processes. So, thank you very much if you have
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any query, please register your query in the Swayam portal or drop a mail to me at
[email protected], thank you.
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Module 05
Lecture-13
Physical Processes
Good morning students, today is lecture 1 under module 5. And under module 5 we will be
discussing about the physical and thermal conversion processes. In today's lecture, we will
discuss about the physical conversion of biomass. So, let us begin.
There are numerous aquatic and terrestrial virgin biomass species and many types of waste
biomass that are potential fuels or feedstocks. With the exception of microalgae and some high
moisture content biomass, essentially all are solid materials. Now some of the compositional
differences already exist and we have discussed that also in some of our earlier classes.
So, the aquatics, municipal bio-solids, and animal manures are high in moisture content. The
terrestrial species contain relatively small amounts of moisture. On a moisture and ash free basis
the heating value of most biomass is in the same range, but on a dry basis, these materials can
exhibit wide variation. Because of these broad differences, many of the possible feedstock
process energy product combinations are not feasible.
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So, such feedstocks do not support self sustained combustion under conventional conditions
unless the moisture is reduced by a considerable amount, a high cost process in wastewater
treatment plants. Bio-solids are more suited for microbial conversion in aqueous systems, where
a liquid water medium is essential. In contrast, woody biomass is often suitable for direct use as
a solid fuel or as a feedstock for thermochemical conversion (such as pyrolysis, gasification
which we are going to discuss under this module). The physical processes are employed to
prepare biomass for use as a fuel or as feedstock for a conversion process. The processes
examined are dewatering and drying, size reduction, densification and separation. So, these are
the things which we are going to discuss under the physical conversion of biomass today.
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So, first let us understand about the dewatering and drying. So, dewatering and drying the basic
difference between these 2 is that in the first case that is in dewatering, it is basically the removal
of all or part of the contained moisture from biomass as a liquid. And while drying, it is the same
thing except that the moisture that is getting removed is removed as vapour. So, open air solar
drying is the one which is very much in practice in most of the countries to process biomass.
So, that is the low cost drying method and can be used. So, raw materials that are not sufficiently
stable to be dried by solar methods can be dried more rapidly using industrial dryers, such as
spray dryers, drum dryers and convection ovens if cost permits. Here the cost is basically the
equipments are not so costly, the cost is the energy costs. The key biomass property that should
be obviously examined in addition to conversion process requirement is the moisture content of
the fresh biomass.
The method available for its partial or total removal and the effects, if any on the properties of
the remaining biomass. So, moisture content, the amount of moisture present in the initial phase
of the biomass when it is getting procured is of utmost important. Because that is finally going to
decide about which conversion process you are going to use, and what will be the resultant
product.
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So, the moisture content of biomass is as variable as the multitude of biomass species available
as potential feedstocks.
The water content in the untreated municipal bio-solids is high because of the nature of the
collection system. That is dilution with water to facilitate localized disposal and transport in
municipal lines to wastewater treatment plants that is what is being practiced in all municipalities
across the world. So, in the table 1, some of the species are mentioned along with their water
content.
Aquatic plants, you can see almost 95%, untreated municipal bio-solids also 95, farm animal
waste 80%, terrestrial biomass 40 to 60%, agricultural crop residues 15%, municipal solid waste
30%. The terrestrial biomass is considered as a potential biomass and it includes most
herbaceous species, softwoods and hardwoods. The agricultural residue that have been exposed
to open air solar drying contain less moisture content. Straws are good example of this particular
process. These potential feedstocks include most herbaceous species, softwoods as well as
hardwoods.
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About one half of the solar energy falling on the leaves supplies the energy to facilitate
transpiration which is necessary for the photosynthesis to occur. Wood also absorbs moisture
from humid air and is equivalent of an elastic gel that exhibits limited swelling as water vapor is
taken up from the air. Two different mechanisms are operative: one is adsorption; another is
absorption.
In adsorption moisture is transferred from air to the wood surfaces and results from the attraction
between polar water molecules and the negatively charged surfaces of the wood. The negative
charges involve functional groups on the surface that can carry full or partial negative charges or
organic molecules that can exist as dipoles with the negative ends clustered on the surface. The
amount of moisture adsorbed on wood surface is relatively small, it ranges up to about 5 to 6
weight percentage of that wood at 20 degrees centigrade and 100% relative humidity.
So, I was talking about this here you can see that functional groups. Now functional groups are a
certain type of groups that are present on any surface. So, any material you can say whether it is
a living material, nonliving material and in most of the applications. Now I can tell you a
classical example of a membrane or even a catalyst. So, I can make a membrane - tailor make
basically - So, that means for a particular intended application, so let us say I want to remove
some cations or anions from a particular aqueous stream. So, I will use a membrane which is
doped with or let us say which is fused or topped with certain functional groups of negatively
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charged ions. So, if I want to remove cations, I can have anions, if I want to remove anions I can
have cations, in that way.
So, basically it will attract negative charges attracts and then it will be retained on the surface of
the membrane, other low molecular weight compounds and solvents will pass through it.
Similarly, to make a intended and a particular synthesis, chemical reaction or a better yield we
can sometimes dope different functional groups on the surface of a catalyst, so as to increase its
catalytic activity.
So, functional groups can be easily found out by FTIR technique - the Fourier transform infrared
techniques, spectroscopic technique and there are many other analytical techniques also
available.
So, in absorption, water molecules are drawn into the permeable pores of the wood by sponge
like processes due to diffusional and osmotic forces followed by capillary condensation. So, a
large number of fine capillaries in the wood fibres facilitate this. So, you can read a little more
about capillary condensation. So, I can say in a nutshell that how and what happens? So, it is
very predominant when you talk about porous materials - it can be catalyst, it can be membrane,
it can be similar type of materials which contains distinct pores.
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So, let us say, something is getting, adsorbent basically, here we are talking about adsorption and
absorption. So what is happening? Suppose, you are adsorbing some gaseous component on the
surface of the adsorbent let us say, I am just giving an example to understand capillary
condensation. So, it will adsorb on the surface then when you decrease the pressure it can go
inside the pore of the catalyst or adsorbent whatever it is.
So, after the adsorption, you do desorption the reverse of the process, so you decrease the
pressure. Once you decrease the pressure what will happen whatever the material or gaseous
molecules are inside the pore they will try to move out. So, when they will try to move out, so
they will form a meniscus on the surface of the pore, something like this and that is due to
resultant capillary condensation or capillary forces.
So, due to this the rate of adsorption and rate of desorption are quite different, they do not fall on
the same line though ideally they should have; and this is due to capillary condensation
phenomena, so and this process in adsorption is called hysteresis. And so you can read little more
about capillary condensation if you are more interested from any mass transfers books.
So, the amount of moisture absorbed within the woody structure depends upon the pore
diameters and distribution of the capillaries. In spruce wood pulps, for example, the amount of
water vapor absorbed at 20 degrees centigrade and 100% relative humidity is almost about 25
weight percentage. The maximum total amount of water taken up from air at ambient conditions
by absorption and adsorption is about 30 wt% of the wood but can reach almost 200 weight
percentage if the woody is soaked liquid water.
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Dry biomass burns at higher temperatures and have higher thermal efficiencies than wet biomass.
For example, the flame temperatures of greenwood containing 50 weight percentage moisture
and dry wood in conventional combustor that supply boiler heat are about 980 degrees centigrade
and 1260 to 1370 degrees centigrade respectively. Flame temperature is directly related to the
amount of heat necessary to evaporate the moisture content in the wood.
The lower the moisture content, the lower the amount of energy needed to remove the water and
the higher the boiler efficiency. With the exception of suspension firing units for which the
moisture content of the fuel is usually in the 20 weight percentage range, the maximum moisture
content range is 55 to 65 weight percentage.
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Indeed, combustion of biomass containing 65 weight percentage moisture in conventional grate
type systems can result in lowering the adiabatic flame temperature to the point where self
sustained combustion does not occur. Many of the large scale biomass combustion systems for
producing heat, hot water or steam accept biomass fuels containing relatively large amount of
moisture and are operated without much apparent concern for the effects of moisture content of
the fuel on the combustion process itself.
One of the largest biomass fuel power plants equipped with travelling grates operates very well
with the wood chips containing an average of 50 weight percentage moisture. Although a few
initial handling and storage problems caused by high moisture fuel supplies had to be solved.
The fluid bed combustors are excellent systems which are designed to operate with the fuel
having a variable moisture content up to about 50 weight percentage, so they are excellent. So,
they are fluidized bed combustors basically.
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So pre-drying of biomass has sometimes been justified in the past only for the large scale
operations, or where low cost energy is available as waste heat. It is important to realize
however, that the absence of any capability to pre dry feedstock for thermochemical conversion
has sometimes caused severe operating problems, particularly for gasification processes. In one
of the early fluid bed gasification plants fueled with wood chips and sawdust to produce low
energy gas as an onsite boiler fuel, it was very difficult to control combustion.
The industrial gas burners installed in the plant did not function satisfactorily with the product
gas. These problems were attributed to large variations in the quality of the gas caused by
accepting wood feedstock at any moisture content up to 50 weight percentage which in turn
resulted in large swings in gas heating values from about 3 to 8 mega joule per meter cube.
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So, let us now understand the drying methods. The mechanism of water uptake by trees suggests
several methods of drying terrestrial biomass. The most obvious method is to expose biomass to
circulating low humidity air that is heated. So, the final moisture content of the air dried biomass
is usually in the 35 weight percentage range or less. The advantage of this partial drying method
is that it is low in cost, so mostly it is adopted even in commercial scale.
So, that disadvantages are however several, the process is slow and it depends on the local
climate. Some labor is required to arrange the freshly harvested biomass in suitable piles or
windrows to facilitate exposure to sunlight and air circulation and then if there is rain then there
is a big problem. So, forage crops have traditionally been partially dried in open air to this
moisture level. So, they can be removed from the field and stored without significant
deterioration and loss of nutrient value. Solar drying also facilitates densification of hay by
baling.
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There is another technology which is also adopted in large scale in industry, it is called Kiln
drying. So, under this kiln drying controlled conditions is commonly employed to improve the
stability and physical characteristics of lumber products used as materials of construction or for
manufacturing furniture, whereas open air drying is traditionally employed for the curing or
seasoning of tree parts and round woods to be used as fuel.
A kiln drying promotes the removal of moisture by circulating heated air by natural draft or with
fans or blowers through the wood, which is carefully piled in the kiln to promote the drying
process. Heat is transferred from hot air, heated by steam coil supplied by a boiler or from hot
stack gases heated by the burning of waste biomass or other fuels through manifolds. Kiln drying
is rapid compared to the rate of open air solar drying, but it is too slow for some continuous
thermo chemical conversion processes, unless the dryers and storage facilities are sized to handle
the demand for pre dried feedstock. So, essentially the meaning is that when we are preparing a
feedstock for a thermo chemical conversion like biomass pyrolysis, which are large in scale. So,
unless until we have such a similar scale kiln drying, so you cannot supply a biomass to
thermochemical conversion process, the quantity it is required using the Kiln dryer.
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So, this is one image of the kiln drying system or dryer. So, it is rapid compared to the rate of
open air solar drying but too slow for some continuous processes. So, the use of superheated
steam for drying other than burning of some of feedstock as heat source may allow further
improvement in efficiency. The direct heat systems are generally lower in cost than the indirect
heat systems, if commercial drying units are used and these are not very expensive systems also.
So, thermochemical conversion reactors can also be designed, so that incoming fresh feed is
dried to the desired level by heat transfer from the hot reaction products. So, that means this is
essentially talking about the heat that is getting generated from the thermochemical conversion
processes and are basically getting wasted, so some sort of waste heat recovery.
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So, that heat can be used to dry the feedstock which is going to be used in the thermochemical
conversion systems. The simple addition of enclosed drying tunnels for passages of hot air or
stack gases over and through incoming fresh feed can sometimes suffice to reduce moisture to
the desired level and preheat the feed without the need to install the industrial driers.
Note, however, that stack gases from biomass fired boilers contain about 15 weight percentage of
moisture and that temperatures below 250 degrees centigrade only a small amount of additional
moisture can be absorbed before the gas becomes fully saturated. So, this is the equation WG
equals to 2940M by T i minus T 0, where WG is the drying gas weight in kilograms per hour, M
is the water evaporated in kilograms per hour, T i is the temperature of drying gas that is entering
in degrees centigrade and T 0 is the temperature of the drying gas leaving in degrees centigrade.
Now this equation indicates that large fans and motors are required for circulation of the drying
gases when low temperature gas is used as the drying medium. To obtain sufficient heat for
drying purposes, some of the stack gas may have to be extracted upstream of the boiler heat
recovery equipment, which can have an adverse effect on the steam generation. For most
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thermochemical conversion system that process green biomass, a balance is usually struck
among the optimum moisture range that is needed for the conversion, the feedstock demand rate,
the drying requirements, the size of the feedstock storage facility, feedstock stability on storage
and the cost of supplying pre dried feedstock. Whenever it is necessary to remove moisture from
virgin or waste biomass feedstocks, air drying, mechanical dewatering and drying with waste
heat or stack gases should be evaluated first.
So, the entire idea of this discussion is that when you talk about a sustainable bio refinery
perspective, basically whatever the heat that is getting generated from one or the other processes
and are being wasted. So, should not be wasted basically that is what is the message. So, you
need to go for the waste heat recovery systems. There are excellent waste heat recovery systems
that are being designed and are being implemented in most of the petroleum refineries, where the
process streams that comes out is at very elevated temperature and we basically use some
selective heat exchanger type of units to recover the heat. And that heat can again be used for
drying purposes or for something else where the heat and/or energy is being required. Energy is
very important in any process industries that takes the major amount of the cost, one of the major
amount of the cost. So, it is always important that energy whatever it is being getting into wastes
should be recovered and reused.
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So, now let us discuss about size reduction. So, we have understood little about size reduction
during in some of our earlier classes, that we need to reduce size to increase it is surface area and
all. So, let us just quickly glance through the same thing once again in a little elaborate manner.
So, reduction in physical size is often required before biomass is used as a fuel or feedstock.
Size reduction techniques are employed to prepare biomass for direct fuel use, fabrication into
fuel pellets, cubes, briquettes and/or conversion. Now smaller particles and pieces of biomass,
reduce its storage volume, facilitate handling of the material in the solid state and transport of the
material as a slurry or pneumatically and sometimes permit ready separation of components such
as bark and whitewood.
The size of the pieces or particles can be critical when drying is used. Because the exposed
surface area which is a function of physical size, can determine drying time and the methods and
conditions needed to remove moisture. There are a few exceptions where size reduction is not
needed, such as in whole tree burning, but nobody is doing all these things nowadays so, because
that takes more amount of energy to start the burning.
So, particle size should satisfy the requirements of supplying feedstocks to the conversion reactor
and of the conversion process itself. For combustion systems, the combustion chamber and heat
exchanger designs, the operating conditions and the methods of delivering solid fuel and
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removing the ash, determine the optimum size characteristics of the fuel. For thermal gasification
and liquefaction processes, particle size and size reduction can influence the rate of conversion,
the operating conditions of the process and product yields and distributions. Biological processes
are also affected by the physical size of the feedstock. In general, the smaller the substrate
particles the higher the reaction rate because more surface area is exposed to the enzymes and
microorganisms that promote the process.
So, this is one of the application size reduction machine basically, so it is the hammer mill. So,
dry shredders are commercially used for reducing the size of biomass. The most common types
of machines are vertical and horizontal shaft hammer mills. Metal hammers on rotating shafts or
drums reduced particle size by impacting the feed material until the particles are small enough to
drop through the grate openings.
So, hammer mills are commonly used in the MSW, MSW means here municipal solid waste,
MSW processing systems to reduce the size of the components before separation of RDF, RDF is
the refuse-derived fuel or you can say that combustible fraction of the municipal solid waste.
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So, there is another machine which is called a hydro pulper. So, hydro pulpers are wet shredders
in which a high speed cutting blade pulverizes a water suspension of the feed over a perforated
plate. So, you can see this is a tank and which is holding this, this is the extraction plate and
extraction box here, then air plunged seal here, there is a gearbox motor that is rotating actually.
So, the pulped material passes through the plate and then non pulping materials are rejected.
Anything that is mostly you can say that semi-solid form or in a paste form or basically the pulp
that will pass through smoothly through that extraction plate and rest everything will be retained
on the surface of the plate and will be rejected. The action is similar to that of a kitchen waste
disposal unit.
So, the hydro pulpers can also be used for the simultaneous size reduction and separation of the
combustible fraction of the municipal solid waste from the inorganic materials. Experimental
studies have shown that hydro pulpers can also supply good feedstocks for microbial processing
from other biomass. Maintenance cost wet shredders are lower than those for the dry shredders.
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Chipping has been the traditional mechanical method of size reduction to prepare wood fuels for
direct combustion. It is an energy intensive operation, but it does improve bulk density, handling
and transportation cost. So, it is a good technique, now also being widely used. Disc chipping
and hogging at the 2 preferred means of preparing the wood fuels. A hammer hogs with free
swing hammers break the feed into small pieces, whereas knife hogs cut the feed with blades.
So, the 2 way basically either you cut it otherwise you just hammer it. So, the least desirable
option seems to be chipping in the field at the time of harvest, which requires that a power
chipper accompanying the harvester through the field. So, this particular thing is very interesting,
we have discussed this when we discussed about this bio refinery details. So it is always
important that whatever processing of the biomass you are doing you please do at the source, it is
always not possible but it is important for more sustainability. If you do the processing in the
field, then the transportation cost also reduces significantly. Among the other options that can be
considered for producing wood or chunking, billeting and crushing. Crushing is carried out by
passing the stems between 2 or more metal rolls of varying size, at different rotational speed and
the different types of surfaces.
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So, the crushing and brunching of wood may offer significant advantages over chipping, this is a
biomass crusher grinder. So, this technique is flexible and is able to process lengthy stems to
yield bolts of crushed wood that exhibit relatively rapid drying. For reactor feeding purposes,
however further size reduction would be necessary. The feedstock characteristics required for the
combustion or conversion process used determine which of these methods of size reduction
maybe applicable.
Next is the size reduction in using steam explosion. See, we have understood steam explosion in
detail in our one of the last module classes when we discussed pretreatment processes
physiochemical pretreatment processes. So, the treatment of wood chips with steam at elevated
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pressures and temperatures for shorter time periods followed by rapid decompression, this is
what is the principle of steam explosion, changes the physical state of the woody structure by
defibration.
Although some chemical changes occur with the hemicelluloses and lignin in this process, the
particle sizes are reduced and surface areas and pore volume is increased. The commercial
process involves pressurization with saturated steam at pressure to about 7 megapascals. The
process has also been proposed for the pretreatment of lignocellulosic feedstock in the
production of fermentation ethanol because of the large increase in accessibility of the cellulosic
fraction to enzymatic hydrolysis. So, studies on steam explosion suggests that the technique can
be used for several different biomass applications, ranging from modifying the fibrous structure
and particle sizes alone at the low temperatures to a combination of physical and chemical
changes at the higher temperatures.
Next is densification, so baling has long been used to densify hays, straws and other agricultural
crops such as cotton to simplify removal from the field and to reduce storage space and
transportation costs. Baled straw has a density of 70 to 90 kilograms per meter cube at 10 to 50
weight percent moisture content, whereas bulk density of piled straw is about 5 to 15% of this
density range.
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When straws are compressed to form pellets, briquettes or cubes in specially designed dies and
presses the density can be increased to 350 to 1200 kilograms per meter cube. In contrast, dried
wood has a density of 600 to 700 kg per meter cube and a bulk density of about 350 to 450 kg
per meter cube, whereas the bulk densities and densities of wood briquettes are 700 to 800
kilograms per meter cube and up to 1400 kilograms per meter cube respectively.
Biomass densification appears to have the greatest use for upgrading agricultural and forestry
residues that might otherwise be lost, or that require disposal at additional cost. High Density
fabricated biomass shapes simplify the logistics of handling and storage, improve biomass
stability, facilitate the feeding of solid biomass fuels to furnaces, and feedstocks to reactors, and
offer higher energy density, cleaner burning solid fuels that in some cases can approach the
heating value of coals.
The heating value depends on the moisture and ash contents of the densified material, and is
usually in the range of 15 to 17 mega joules per kg. Numerous commercial processes for
production of densified fuels in the form of logs, briquettes, and pellets from a wide range of
biomass provide domestic fuels for space heating, industry uses the pellets and briquettes as
boiler fuels.
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Numerous devices and methods of fabricating solid fuel pellets and briquettes from a variety of
biomass, especially RDF, wood and wood and agricultural residues have been developed and
patented. The pellets and briquettes are manufactured by extrusion and other techniques. A
binding agent such as a thermoplastic resin may sometimes be incorporated during the
fabrication.
A ring die extrusion or a die and roller mill is the most widely used machine type in wood
pelleting, although punch and die technology has been developed. Other types of pelleting
machines include disk pelletizers, drum and rotary cylindrical pelletizers, tablet presses,
compacting and briquetting rolls, piston type briquetters, cubers and screw extruders. There are
so many different types of units are available for doing this densification.
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An exemplary method for production of pellets was developed in 1977. A raw material of
random particle size such as sawdust or wood residue from which rocks, tramp metal and other
foreign materials are removed is conveyed to a hammer mill where particle sizes is adjusted to a
uniform maximum dimension that is about 85% or less of the minimum thickness of the pellets
desired.
The milled product is then dried in a rotary drum dryer to a moisture content of about 14 to 22
weight percent and fed through a ring shaped die capable of generating pressure between 55 to
275 megapascals to afford the desired shape and diameter. The pellet mill die and roller
assembly must be capable of producing sufficient compression within the die to raise the
temperature of the material to about 162 to 177 degree centigrade.
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The products from the mill have a low uniform moisture content, a maximum cross sectional
dimension of 13 mm, a density of 400 kilograms per meter cube and a heating of 19.8 to 20.9
mega joules per kg. It is not necessary to add a binder to the particles, providing the pressure
during the pelleting produces the necessary temperature increase. During extrusion, the lignin in
biomass migrate to the pellet surface and form a skin on cooling that protects the pellet from
shattering and from any rapid change in the moisture content before use. Briquettes are formed
by similar procedures, except the products are usually larger in diameter and length then the
pellets.
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These are images of some of the briquettes. So briquetting is described to consist of subjecting
wood residues containing 8 to 15 weight percent of moisture at a maximum particle size of 0.5 to
1 centimeter to a pressure of about 200 megapascals, which increases the temperature about 100
to 150 degrees centigrade. The major machine types used to manufacture briquettes are impact,
extrusion, hydraulic, pneumatic and double roll presses and die presses that can also be used for
pellet production.
Briquette production rates are 200 to 1500 kilograms per hour for impact presses, but some
models can produce 2000 to 6000 kilograms per hour, 500 to 2500 kilograms per hour for
extrusion presses and up to 5000 kilograms per hour for hydraulic and pneumatic presses.
There is something called a Biotruck 2000, so this is the image of biotruck 2000, so what is this?
This is a unique commercially available system, it is a truck , transportation vehicle, so what it
does? So, it is a moving vehicle of special design, so that continuously perform all the operations
in the field, so it has to be taken to the field. So, from harvesting agricultural virgin biomass to
pellet production.
So, what it will do is that, it will do the harvesting of the agricultural crops as well as at the same
time after harvesting of the cereals and grains whatever the left out biomass straw or whatever it
is , it will convert on the field itself to pellets. So, the operating sequence consists of the
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integration into one machine of continuous crop harvesting, size reduction of about 0.6 mm
pieces, heating the pieces to a temperature between 80 to 120 degrees centigrade using the waste
heat of the engine, and compressing the heated pieces in a toothed wheel pelleting press.
Now this is again very interesting, you can see this using the waste heat of the engine, what
about the heat that is getting generated when the engine is running, that heat is being captured to
do the process. So, no binder is used. The production rate of the pelletized cereal crops is about
8000 kilograms per hour, it is a huge amount. And the bulk density is about 500 to 700 kilograms
per meter cube, so the transportation becomes easy.
So, another unique example of densification is the production of high density, moisture resistant
briquettes from wet wood residues without pre drying or the use of binders. The briquettes do not
disintegrate when wet and retain a maximum of about 40 weight percent moisture after
immersion in water. They are made from wood and bark alone and from mixtures in the pilot
extruder at operating pressures typically ranging from 30 to 50 megapascals at a maximum
surface temperature about around 210 degrees centigrade.
Moisture resistant briquettes were made in tests from the Western hemlock sawdust, a mixture of
50:50 Western hemlock and red cedar sawdust and Western hemlock bark hog fuel, this is just an
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example. So, the feed contains up to about 65 weight percent moisture and must be sized, so that
maximum size is less than 80% of the barrel diameter.
So, let us understand the economical factors or economic factors of the densification process.
The wholesale cost in the United States of wood waste pellets is in the range of 85 to 140 dollars
per ton, so that was in mid 1997. Now this cost range effectively precludes their use as a
feedstock for most conversion processes, and it limits residential fuel applications. The
production cost exclusive of biomass cost is estimated to be about 30 to 60% of the wholesale
cost, and depends on production rates and the amount of processing needed.
For example, in Spain the increase in electric energy consumption required to mill wood waste to
5 to 8 mm sizes is almost totally compensated for by the decrease in electrical energy
consumption during the densification process itself.
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Exclusive of wood cost, the cost of manufacturing densified wood residues in small units
operated by one person is about 22 dollar per ton at a production rate of 1250 tons per year.
Smaller particles in the 2 mm size range can increase production rates by 50% or more, but the
energy cost is excessive. Industrial manufacturing cost in Spain of densified wood wastes
exclusive of wet wood costs are about 30 to 200 dollars per ton at a production rates of one ton
per hour.
So, in Finland the cost of producing straw fuel pellets on farms in small portable pelletizers is
estimated to be about 54 to 84 dollar per ton. Biotruck 2000, described as earlier for producing
pellets or briquettes from agricultural waste in Europe has a production rate of about 8 ton per
hours in the field and cost about 400,000 dollar.
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Now we will discuss about the separation. It is sometimes desirable to physically separate
potential biomass feedstocks into 2 or more components of different applications. So, the subject
is quite broad in scope because of the wide range of biomass types processed and the variety of
separation methods that are used. Examples are the separation of agricultural biomass into
foodstuffs and residues that may serve as fuel or as a raw material for synfuel manufacture.
The separation of marine biomass to isolate various chemicals and the separation of oils from
oilseeds. Now common operations such as screening, air classification, magnetic separation,
extraction, mechanical expression under pressure, distillation, filtration, and crystallization are
often used, as well as industry specific methods characteristic of farming, forest products, and
specialized industries - depending upon your biomass, you need to choose a particular separation
process.
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So MSW, the municipal solid waste, is a complex mixture of inorganic and organic materials.
Efficient separation and economic recovery of the RDF - the refuse derived fuel and the
components that can be recycled is the ultimate challenge to engineers who specialize in
designing resource recovery equipment for the large scale processing of solid waste generated by
urban communities.
One of the first comprehensive resource recovery plants in the world was built in Dade County,
Florida in United States. A brief description of this facility when it was in full scale operation to
recover recyclables and RDF is very, very informative. You can read more by Google searching
the name of the place. The plant was designed to process 2720 tons per day of MSW, but it
frequently processed over more than that, close to 4000 tons per day. And it could process up to
5000 tons per day if only household garbage were received.
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So, it was designed to accept in addition to household garbage, a wide variety of solid wastes,
including trash, garden clipping, trees, tires, plastics, pathological wastes, white goods - As for
example stoves, refrigerators, air conditioners, and industrial, commercial and demolition wastes.
RDF and shredded tires approximately 1000 per day were burned for onsite power generation in
a 77 megawatt power plant and glass, aluminum, ferrous metals as well as materials including
the ash and fly ash were recovered and sold.
The plant achieved a 97% volumetric reduction compared to as received MSW. Only about 6%
of the total incoming MSW remained as unsalable residue and was disposed of in a proper
manner using landfill technology. The plant also conformed to all effluent, leachate, emissions,
noise and odor requirements, so the environmental clearance basically from the environmental
agencies. So, impressive results such as this dependent on the availability and reliability of the
efficient separation methods, this is an very good, classic success story of the MSW treatment.
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Simplified description of the first comprehensive materials recovery facility of its type in the
United States illustrates how one plant was designed to accomplish some of these separations.
The plant called Recovery 1 was built in New Orleans, Louisiana to process 590 tons per day of
municipal solid waste.
The waste was delivered and unloaded at one of the 2 receiving pit conveyers and transported by
conveyers to the first separation unit, a 13.7-meter-long by 3-meter diameter rotating trommel
that contained circular holes 12 centimeter in diameter. So it is a perforated trommel, rotating
trommel. So, plastic and paper bags tumbling in the trommel were broken upon by the lifters.
The smaller and heavier objects such as heavy metal, glass bottles, even some of the plastics, that
fell through the holes were transported directly to a magnetic ferrous recovery station and an air
classifier. So, air classifier is a unit in which air is being used to fluidize the MSW. So, based
upon their density, so they will be separated. The larger and light materials such as paper, textiles
and aluminum containers that pass through the trommel were conveyed to a 746 kilowatt primary
shredder.
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This shredded material was then conveyed to the ferrous recovery station and the air classifier. In
the air classifier a high speed air current blows the light materials out of the top of the classifier.
This fraction RDF which is the refuse fuel consist of shredded paper, plastic, wood, yard waste
and food wastes. The heavy fraction is essentially glass, aluminum and other non-ferrous metals
and some organic material, it was routed to the recovery building for further processing.
A secondary 746 kilowatt shredder system handled oversized bulky wastes without passage
through the trommel. The output was also conveyed to the air classifier where RDF was obtained
as the overhead and the heavy fraction was conveyed to the recovery building. Each shredder
was sized to process around 590 ton of the MSW in about 12 hour to ensure operating reliability.
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Three modules were located in the recovery building, the first module consisted of a vibrating
screen to separate the shredded material by particle size, a drum magnet to separate residual
ferrous material, an eddy current separator to remove the non magnetic aluminum and other
nonferrous metals, and a small hammer mill to further shred the aluminum fraction to increase it
is bulk density.
The output from the first module consisted of the ferrous fraction, the aluminum fraction and a
fraction that contained primarily glass and some non ferrous metals. The glass fraction,
containing some residual non ferrous metal was conveyed to the secondary recovery module
which consisted of a crusher, another vibrating screen, a rod mill and a two-deck, fine mesh
vibrating screen. The glass fraction was then crushed and screened in the second module.
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The smaller fraction was treated with a pulsed water stream that separated the light fraction
which was discarded. The heavier glass fraction was pumped as slurries to the bottom deck of
the fine mesh second screen to separate the larger particles for crushing in the rod mill.
Recycling of the milled material back to the top deck of the fine mesh screen yielded a glass
cullet fraction for further treatment in the third module, and a non ferrous metal fraction which
was removed from the second screen.
In the third module contained a hydro cyclone, a froth floatation tank and a glass dryer. The glass
cullet fraction from the second module was mixed with clean water in the pre float tank to
remove any remaining organic particles, separated from the slurry through centrifugal separation
and froth flotation and conveyed to the loadout building for shipment.
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So, you can have a close look at this MSW processing. Municipal solid waste. So, three things it
has been shown here, first one is the thermal conversion process, second is the biological
conversion, third one is the landfilling. So, look at this thermal conversion process, this is what
we are going to discuss in this module. So, different types of process, incineration, pyrolysis,
gasification and RDF the refused derived fuel.
So, what it gives us, heat and power, gas, oil, charcoal, syngas, heat and power everything is
energy. Then biological fractions, basically 2 things anaerobic digestion which gives us biogas,
methane rich biogas maybe sometimes hydrogen also in more quantity depending upon what is
the feedstock and composting, so you get compost. Again we are talking about energy, then
landfill with gas recovery and that landfill gas can also be collected and can be converted to the
energy systems and landfill without gas recovery.
So, RDF was recovered from the air classifier and the ferrous, aluminum and glass fractions
were recovered from the bottom of the classifier, this is a simplified description of how MSW is
separated into recyclables and fuel. There are many refinements of these operations, this is just a
simple understanding that what processes can be used to convert municipal solid waste into
energy.
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Now we will understand the separation of the virgin biomass. The production of virgin biomass
for food and feed has progressed from the very labour-intensive, low-efficiency agricultural
practices over the 1800s and 1900s to what some now consider to be a modern miracle. Now the
invention of numerous agricultural machines in the late 1800s that can seed the earth and reap
the harvest with minimum labour and energy inputs made it possible to continuously produce
biomass in quantity to help meet the massive demand for foodstuffs and other farm products
caused by the growing population.
Eli Whitney’s cotton gin, so this is the Eli Whitney’s cotton gin machine it is a classic example
of this type of machine which will do the virgin biomass separation. And the Cyrus
McCormick’s reaper, you can see this, it is a reaper which is being used in the field. And these
are the 2 devices that helped mechanize agriculture and change the course of history by
providing non labour intensive methods of physically separating the desired products - cotton
and grain for these particular inventions from biomass, these units actually made history. So,
earlier everything was completely labour-dependent, after these discoveries less labour-
dependent processing of the entire agricultural product was possible basically.
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Simultaneously with the advancement of agriculture, although not via the same pathway, new
hardware and improved methodologies were developed for the planting, managing and
harvesting of trees that made large scale commercial forestry operations more economic and less
dependent on labour. Better methods of land clearing, thinning and growth management and
improved hardware for harvesting such as feller bunchers which were first used in the early
1970s, resulted in modern forest products industry that supplies commercial and industrial needs
for the wood and wood products. As the use of trees for energy and feedstock expands, it is
expected that much of the existing commercial hardware and improvements will be applied to
meet these needs.
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A few of the non manual separation methods used for woody biomass processing that have use in
energy applications are briefly described. Delimbing and debarking of trees is an old technology.
For the smaller trees where fibre in the form of white wood chips is the desired product, the trees
can be debarked and delimbed by the use of chain flails which will remove the outer bark layer,
leaving the white wood behind. Hammer milling then yields a homogenous product. Basically
white board, white chip whatever it is.
So in most thermochemical energy applications however, separation of the bark and wood is not
necessary. But where it is necessary to remove the bark, some efforts have been made to recover
the residues for fuel from flail machines by using them together with tub grinders.
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A tub grinder operating simultaneously with a chain flail was successfully used to comminute the
residues. The green weight of the fuel residues was about one-fourth to one-third of the total
clean chip plus fuel weight. In a few installations that burn hogged wood, disc and shaker screens
have been employed to separate preselected, oversized pieces for subsequent size reduction and
return to the fuel stream.
Finely divided wood fuels such as sawdust and sander dust are sometimes screened to remove
the larger pieces. By-product hulls from the production of rice, cotton, peanuts, soybean and
similar crops that have outer shells covering small seed of fruit are sometimes used directly as
fuels or feedstocks.
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So, you can see this is the virgin biomass processing actually, so the biomass that is getting
generated by the use of solar energy and the carbon dioxide that is getting used during the
photosynthesis are being collected and chipped and processed into various by-products. Then it
goes to the biomass power plant where it is basically converted into energy.
And after the shells are fractured most of the hulls can be separated with vibrating screens or
rotating trommels having appropriately sized openings. The by-product hulls that have high ash
content and bulk density present a few difficulties on direct combustion or gasification, but
specially designed systems are available to eliminate these problems.
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So, now we will discuss about the extraction. Solvent extraction is the age old technique and it is
still in practice whether it is in the lab scale or in the commercial scale. So, solvent extraction of
biomass, its derived ash or biomass parts such as the seeds has been or being currently used
commercially to isolate and separate certain chemicals or group of related compounds that are
present. Inorganic salts are found in some biomass species at concentrations that may justify
extraction and purification.
Aqueous extraction of the ash from giant brown kelp and the spent pulp of sugar beet and
fractional crystallization of the extract, for example, were commercial processes for the
manufacture of potassium compounds in the early 1900s. Examples of the some of the organic
compounds that are extracted with solvents are trigycerides, terpenes and lignins. Water and
water in mixtures with polar solvents have been used for extraction of several of the low
molecular weight water soluble sugars.
Aqueous organic solvents are effective for the selective extraction of lignins in biomass. Lignins
can also be extracted from biomass by the use of dilute aqueous alkali under mild conditions but
aqueous alcohols alone such as 50% ehanol solubilize lignins in wood leaving relatively pure
undecomposed cellulose. Deciduous trees are delignified by aqueous ethanol extraction to a
greater extent than conifers.
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Lignin is also readily extracted by mixtures of butanol or amyl or isoamyl alcohols with water.
Separation of the lignins from the extracts yields tarlike substances that become brittle on
cooling.
Since one of the prime objective of producing chemical pulps from wood is delignification,
without changing the cellulosic fibres the data accumulated on the solvent extraction of wood
suggests that high quality paper pulps could be manufactured by solvent extraction of hardwoods
and softwoods as well as other biomass species. The lignins in the extracts might provide the
starting point for the production of new lignin derivatives and polymers. As you have understood
that lignin is a by-product and having high commercial value. Solvent extraction of biomass
under relatively mild conditions to remove lignins by a strictly physical process without the
addition of other chemicals would seem to offer several advantages of a chemical pulping
methods.
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Solvent recoveries approaching 100% should permit solvent recycling with minimal losses. A
continuous process for the pulping of wood with aqueous n-butanol which was found to be the
most effective solvent has been proposed for the pulping of wood and the separation of lignins.
So, this type of process which would be expected to be environmentally benign, does not seem to
have been commercialized to any extent by the pulp industry.
So, with this I windup today, so today we have discussed about the physical conversion of the
biomasses and tried to learn how this happens basically. In the next class we will be discussing
about the gasification and pyrolysis process, the fundamentals and how gasification and
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pyrolysis actually can be conducted. So, thank you very much, in case you have any query please
submit it in the swayam portal or drop a mail to me at [email protected].
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Module 05
Lecture-14
Gasification and Pyrolysis
Good morning students this is lecture 2 under module 5. And as you know that we are discussing
biomass physicochemical and thermochemical conversion in this module. And today's class is an
important one in which we will be discussing about 2 most important thermochemical
conversion processes, one is gasification and another is pyrolysis, so let us begin.
So, gasification is a partial oxidation process that converts biomass into carbon monoxide and
hydrogen with less amount of carbon dioxide and water. Now this process occurs at high
temperatures (above 700 degrees centigrade) without combustion, with a controlled amount of
oxygen and/or steam. Gasification typically uses only 25 to 40% of the theoretical oxidant - it
can be either pure oxygen or air - to generate enough heat to gasify the remaining unoxidized
fuel producing syngas or producer gas which are used as fuels.
Gasification generates lower amounts of some pollutants such as SOx and NOx in comparison to
combustion. Now basically combustion is a full oxidation process in which all the biomass is
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completely oxidized, whereas in gasification, we use less than theoretical oxygen that is required,
for the partial oxidation process.
So, biomass gasification processes are generally designed to produce low or medium energy fuel
gases for the manufacturer of chemicals or hydrogen. More than one million small scale, air
blown gasifiers for wood and biomass derived charcoal feedstocks were built during World War
II to manufacture low energy gas to power vehicles and to generate steam and electric power.
A significant number of biomass gasification plants have been built but many have been closed
down and dismantled or mothballed. The pyrolytic gasification of biomass has been interpreted
to involve the decomposition of carbohydrates by depolymerization and dehydration followed by
steam carbon or steam carbon fragmentation reactions. So, pyrolytic gasification is a type of
gasification process.
I would like to say during this discussion is that, pyrolysis, though it is a separate
thermochemical conversion process, but whenever gasification is actually happening, so the
second step is the pyrolysis reaction. So, before the gasification reaction really begins, so
pyrolysis happens. We will discuss in our subsequent discussion today, when we will talk about
the reaction mechanisms, then it will be a little more clear.
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So, some of the coal gasification processes are also suitable for biomass feedstocks. Since the
conditions required for coal gasification are more severe than those needed for biomass, some
coal gasifiers can be operated on biomass or biomass-coal feedstock blends. Indeed, some
gasifiers that were originally designed for coal gasification are currently in commercial use with
biomass feedstock because coal is being depleting day by day.
The chemistries of coal and biomass gasification are quite similar in terms of the steam carbon
chemistry, and are essentially identical after a certain point is reached in the gasification process.
Note, however, that biomass is much more reactive than most of the coals. Biomass contains
more volatile matter than coal, and the pyrolytic chars from biomass are more reactive than
pyrolytic coal chars.
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The thermodynamic equilibrium concentrations of specific gases in the mixture depend on the
abundance of carbon, hydrogen and oxygen, the temperature, as well as the pressure. Biomass is
gasified at lower temperatures than coal because its main constituents, the high-oxygen cellulose
and hemicellulose, have higher reactivity than oxygen-deficient carbonaceous materials in the
coal.
In addition of co-reactants to the biomass system, such as oxygen and steam, can result in large
changes in reaction rates, product gas compositions and yields and selectivity as in coal
conversion. Biomass feedstocks contain a high proportion of volatile materials 70 to 90% for
wood, compared to 30 to 45% for typical coals.
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A relatively large fraction of most biomass feedstocks can be devolatilized rapidly at low to
moderate temperatures, and the organic volatiles can be rapidly converted to gaseous products.
The chars formed on pyrolytic gasification of most biomass feedstocks have high reactivity and
they gasify very rapidly. For biomass and waste biomass, steam gasification generally starts at a
temperature near to 300 to 375 degrees centigrade, again depending upon the type of feedstock.
Undesirable emissions and byproducts from the thermal gasification of biomass can include
particulates, alkali and heavy metals oils, tars and some aqueous condensates.
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It is important to avoid gas turbine blade corrosion and corrosion by removing undesirable
particulates that maybe present. The removal of tars and condensable gases may also be
necessary. Furthermore, utilization of the sensible heat in the product gas improves the overall
thermal operating efficiencies. Non turbine applications of the gas may also be able to take
advantages of the process that provide clean, pressurized hot gas such, as certain downstream
chemical syntheses and fuel uses.
So, what happens, basically when the gasification is happening in a gasifier any type of gasifier
we will also discuss in our class today, what are the different types of gasifiers available and of
course, pyrolysis reactors are pyrolysers. So, there are many obnoxious byproducts that actually
getting formed including some of the tar also. So, these needs to be removed frequently
otherwise it will create a problem inside the reactor.
So, the reactor vessel will corrode if there are some corroding elements present and if you do not
take it out from for a prolonged time and they keep on presenting then there cannot be a proper
reaction will proceed basically. So, research on thermal biomass gasification in North America
has tended to concentrate on medium energy gas production, scale-up of advanced process
concepts that have been evaluated at the PDU scale, and the problems that need to be solved to
permit large scale thermal biomass gasifiers to be operated in a reliable fashion for power
production, especially for advanced power cycles. So, PDU means the power distribution unit.
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So, this is a typical scheme please have a look. The first one here, it talks about the gasification
routes, the second one is about the gasification reactions, we will discuss that in detail in our next
slide. So, let us understand this is what I was telling you that pyrolysis is a part of the entire
gasification process if you stop here and do only pyrolysis then it becomes a pyrolysis reaction
and then subsequent products.
But then if you go on for the next step, that step is basically the gasification process, let us
understand. So, biomass needs to be dried for any thermochemical conversion process, we have
discussed last class in one of the pretreatment classes, we have discussed that biomass needs to
be dried to a particular moisture level otherwise the reaction may not proceed in a proper
direction, so it is dried then it goes for pyrolysis.
So, after pyrolysis there may be so many different types of things you can see that gases, liquids,
oxygenated compounds and solid is basically the char. So, if you go for a gas phase reactions
like cracking, reforming, combustion, water gas shift reactions, you get carbon monoxide,
hydrogen, methane, water, carbon dioxide and some other smaller components. If you go for the
char gasification reactions, so you get carbon monoxide, hydrogen, methane, water carbon
dioxide, residual carbon.
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So, if you talk about the product, the product from the gasification is mostly the syngas/synthesis
gas or maybe producer guess. So, these are the some of the reactions that happens actually the
carbonation reaction, oxidation reaction, water gas shift reaction - water gas shift reaction takes
place at very high temperature, then methanation and steam reforming. So, this is given in detail
we will see in the next slide the reactions.
So, 4 to 5 different types of reactions happen. The first one is the dehydration or the drying
process as I have shown you here, the drying process. So, that occurs at around 100 degrees
centigrade, so the resulted steam is then mixed into the gaseous flow and maybe involved with
subsequent chemical reactions predominantly the water gas reaction if high temperature actually
exists.
So, after that the biomass or whatever the vapor that is getting generated actually that goes to the
pyrolysis step, which is called as devolatilization state. So that occurs between 200 to 300
degrees centigrade, sometimes up to 350 degrees also. This process releases the volatiles, thereby
producing char as an effect almost 70% weight loss. So, char is getting produced because there is
severe weight loss almost approximately up to 70%.
The process is, however dependent on the properties of the biomass which eventually determines
the structure and composition of the char. Then in the next step it goes to the combustion
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reaction. So, the char then undergoes the combustion reactions to primarily form carbon dioxide
and small amounts of carbon monoxide that provides heat for the subsequent gasification
reactions.
So, you can see that here the fuel, let us understand it is a dry fuel or after the drying fuel, then
when the devolatilization or the pyrolysis reaction is proceeding we get char. And some of the
tars and hydrogen, some methane, some gases - you can trap it or you can leave it depending
upon how much you are producing. Then this char subsequently goes for the combustion
reaction and gasification reactions.
So, the gasification process occurs as the char reacts with steam and carbon dioxide to produce
carbon monoxide and hydrogen. Now there is a reversible gas phase water shift reaction which
we talked in the step one also. And this happens at very high temperatures, and this reaction,
water gas shift reaction reaches equilibrium very fast when the temperature is very high thereby
balancing the concentrations of carbon monoxide, steam, carbon dioxide and hydrogen.
The major product of syngas or synthesis gas is of course carbon monoxide and hydrogen, and if
certain amount of carbon comes into contact with a proper amount of oxygen and get combusted
then it will result in some amount of carbon dioxide.
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So, let us understand the different types of gasification process variations. So, the primary
products of biomass pyrolysis under conventional pyrolysis conditions are gas, oil, char and
water. As the reaction temperature increases, gas yield increases. That means what
predominantly it means, when you stop during pyrolysis - at the pyrolysis reaction that the entire
thermochemical conversion process becomes pyrolysis process.
Then you will get gas, oil, char and water, that is what we get from the pyrolysis reaction. But
when we are proceeding in a gasifier and doing the gasification reactions, so then we will get the
gases - there will be more gaseous product yield. So, it is important to note that pyrolysis may
involve green or pre dried biomass and that product water is formed in both cases.
Water is released as the biomass dries in the gasifier and is also a product of a chemical reaction
that occur even with bone dry biomass, even if the dry biomass is almost close to 95, 98% or
close to 99% dry. So, unless it is rapidly removed from the reactor, this water would be expected
to participate in the process along with any added feed water or steam. One or one of the more
innovative pyrolytic gasification process is an indirectly heated fluid bed system, we will discuss
about that later.
Now this system uses two fluid bed reactors containing sand as a heat transfer medium. Now
sand holds the heat for a long time and it is a good medium for doing the heat transfer. So, that is
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why it is being used and it is low cost readily available can be recycled back. So, combustion of
char formed in the pyrolysis reactor takes place with air within the combustion reactor. The heat
released supplies the energy of pyrolysis of the combustible fraction in the pyrolysis reactor.
Heat transfer is then accomplished by flow of hot sand from the combustion reactor at 950
degrees centigrade to the pyrolysis reactor at 800 degree centigrade and then the sand can be
returned back or recycled back to the combustion reactor. So, this configuration separates the
combustion and pyrolysis reactions, that means predominantly instead of a single gasifier under
which drying pyrolysis, gasification, combustion everything is happening you have 2 different
reactors.
In which in one reactor pyrolysis is happening and another reactor combustion is happening. And
it yields a pyrolysis gas that can be upgraded to a high energy gas, which is a substitute natural
gas is called SNG by shifting, scrubbing and methanation with regard to nitrogen separation. So,
there are certain the shifting, scrubbing, methanation are the polishing steps.
So, let us have a look at this particular 2 bed fluidized reactor system which is being used to
produce methane. So, you can see this, this is the fluidized bed combustion process, this is the
fluidized bed pyrolysis process, both are using the sand. The sand is as a heating medium and the
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sand is getting interchanged or recycled between these 2 beds. So, when the air is supplied to
combustion reactor, whatever you get is the combustible products.
Then this one, under the pyrolysis reaction, the shredded feed organics are being actually fed
your feedstock, so and whatever you get is basically the gas and char. Now under there is a
separator, the separator actually separates that char and the gas phase, so the gas phase means the
pyrolysis gas phase. Then it goes to the some shifting reactions, carbon monoxides, scrubbing to
remove carbon dioxide, then methanation reaction to get methane, pure methane, you have to
purify it and part of the pyrolysis gas is being recycled to maintain the reaction conditions inside
the pyrolysis reactor. And the char is getting fed to the combustion reactor where it is undergoing
the gasification reaction. So, the pyrolysis gas with hybrid popular feedstocks typically contains
about 38% carbon monoxide, 15% carbon dioxide, 15% methane, 26 mole percent of hydrogen
and 6% of C2S.
Now this is a medium energy gas having a higher heating value of about 19.4 mega joule per
meter cube. The projected gas yields are about 670 meter cube of pyrolysis gas or about 200
meter cube meter of methane per dry ton of feed is SNG is produced, substitute natural gas. It is
a very nice process.
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So, many thermal conversion processes can be classified as partial oxidation processes in which
the biomass is supplied with less than the stoichiometric amount of oxygen needed for complete
combustion. When the oxygen is supplied by air, low energy gases are formed that contain
higher concentrations of hydrogen, carbon monoxide and carbon dioxide than medium energy
gases.
When we use pure oxygen or oxygen enriched air or even air also gases with higher energy
values can be obtained. In some or certain partial oxidation processes, the various chemical
reactions may occur simultaneously in the same reactor zone. Most of the time you will
understand that the gasification process is being done in a single gasifier, in a single reactor let us
called it single reactor all sorts of reactions are happening there are different zones.
But what we have discussed is just before this last slide about the 2 fluidized bed systems that
has essentially done to produce when you look for 2 different things, one is this syngas, producer
gas whatever it is and one is the pure methane. So, that was particularly aimed to produce
methane as well as the usual syngas, so then you go for a 2 bed systems.
Otherwise if you are looking for a syngas whether high quality energy carrier or low energy
carrier gas whatever it is depending upon the feedstock and other process conditions a single
gasifier is more than enough. So, in others the reactor maybe divided into zones that is what I
was just telling - a combustion zone that supplies the heat to promote the pyrolysis in a second
zone, and perhaps a third zone for drying, the overall result of which is partial oxidation.
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So, this is another example of the partial oxidation process, so here the production of synthesis
gas in a three zone shaft reactor furnace. Please understand that it is a three zone shaft reactor,
but it is a single reactor. Now let us understand, so the three zone, so here you feed the biomass.
So, the biomass is being feed, this is that zone which is responsible for the first reaction that is
that drying zone.
Then comes the second zone that is the pyrolysis zone, then it comes to the third zone where
oxygen or air enriched with oxygen is being fed to do the combustion process in a of course less
than theoretical demand. So, whatever you get is basically the molten slag, then it goes to feed
quenching and the gas will be recovered here on the top of the reactor.
Then it goes to water scrubbing and you get a downstream part of that or the bottom product is
being separated and recycled. So, this is the fine liquid that is getting recycled, the wastewater is
again treated and then discharged. And whatever is coming here is the almost pure gas after the
water scrubbing, then it goes to electrostatic precipitation to remove fly ash and other certain
components.
Then you cool it and you get product gas and whatever during the cooling process certain
amount of moisture whatever it is actually still remains in the gas phase will condense and then
that can be fed back to the separation unit. So, in this process, coarsely shredded feed is fed to
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the top of the furnace. As it descends to the first zone the charge is dried by the ascending hot
gases which are partially cleaned by the feed.
So, please try to understand what is happening here, you feed it, so when you feed initially here
drying is happening. So, the drying is happening then pyrolysis combustion, when the pyrolysis
and combustion reaction is happening at the bottom portion, the gas is moving upward. So, this
gas is also doing the drying process, correct, do you understand this? So, that means in a single
thing you do not have to supply extra energy or heat to take care of the drying process.
The product gas whatever is producing that is doing the drying. So, the gas is reduced in
temperature from about 315 degrees centigrade to the range of 40 to 200 degrees centigrade. The
dried feed then enters the pyrolytic zone in which temperature ranges from 315 to 1000 degrees
centigrade. Again depending on what feed you are using, for different feedstocks the temperature
may vary.
So, the resulting char and ash then descend to the hearth zone, where the char is partially
oxidized with pure oxygen, the hearth is that the bottom zone basically. Slagging temperatures
near 1650 degrees centigrade occur in this zone, and the resulting molten slag of metal oxide
forms a liquid pool at the bottom of the hearth. Continuous withdrawal of the pool and
quenching forms a sterile granular frit.
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The product gas is processed to remove fly ash and liquids, which are recycled to the reactor. A
typical gas analysis is almost 40 mole percent of carbon monoxide, 23 mole percent of carbon
dioxide, 5 mole percent of methane, 5 tool percent of C2S and 20 mole percent of hydrogen. This
gas has higher heating value of about 14.5 mega joule per meter cube.
An example of the gasification of biomass by partial oxidation in which air is supplied without
zone separation in the gasifier is the molten salt process. In this process, shredded biomass and
air are continuously introduced beneath the surface of a sodium carbonate containing melt which
is maintained at about 1000 degrees centigrade. As the resulting gas passes through the melt the
acid gases are absorbed by the alkaline media and the ash is also retained in the melt.
The melt is continuously withdrawn for processing to remove the ash and is then returned to the
gasifier. No tars or liquid products are formed in this process. Thus, with about 20, 15, 75% of
the theoretical air needed for complete oxidation, the respective higher heating values of the gas
are about 9, 4.3, 2.2 mega joules per meter cube.
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Basically, biomass gasifiers can be categorized into several reactor design groups. A descending
bed of biomass often referred to as a moving or fixed bed with counter current gas flow updraft
and a descending bed of biomass with counter current gas flow that is called downdraft. A
descending bed of biomass with crossflow gas, a fluidized bed of biomass with rising gas and
entrained flow circulating bed of biomass and a tumbling beds, there are various types of
arrangements can be possible.
So, some of the designs that are being tested and are commercialized are fixed bed, moving beds,
suspended bed, fluid bed reactors, entrained feed solid reactor, stationary vertical shaft reactors,
inclined rotating kilns, horizontal shaft kilns, high temperature electrically heated reactors with
gas blanketed walls, single and multi hearth reactors, ablative, ultrafast and flash pyrolysis
reactors and several other designs.
You can see that there are so many different types of designs of the reactors that is already been
tested. There are clearly numerous reactor designs and configurations for biomass gasification
probably more than in the case of coal gasification systems because of the relative ease of
thermal biomass conversion.
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So, let us now understand the different biomass gasifier design, we will just try to understand in
a glance, how this looks like. This you can see in this particular diagram, I have shown 2
different type of fixed bed gasifiers. One is the updraft gasifier another is the downdraft gasifier.
Now a fixed bed gasifier can be either updraft, that means what is happening in the updraft.
The fuel is getting dropped from the top, gasifying agent from the bottom. And the downdraft, so
both fuel and gasification agents occurs from the top, it is a co-current flow, here the flow is
counter current. In updraft gasification, the char at the bottom of the bed meets the gasifying
agent first and complete combustion occurs producing hydrogen and carbon dioxide and raising
the temperature to almost 1000 degrees centigrade.
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So, the hot gases percolate upwards through the bed driving endothermic reactions with
unreacted char to form hydrogen and carbon monoxide with consequent cooling to 750 degrees
centigrade. The gases pyrolyze the dry biomass which is descending and also of course near the
top of the reactor and also dry the incoming biomass. Updraft gasifiers typically produced
between 10 to 20 weight percent tar in the produced gas which is far too high for many advanced
applications, it is not a good thing of course.
The allowable tar levels depend on the downstream application. These are around 0.05 grams
normal per meter cube, 0.005 gram normal per meter cube 0.001 gram normal per meter cube,
for gas engines, gas turbines and fuel cells applications respectively. In contrast to an updraft
gasifier in a downdraft gasifier which is the closed loop, the gas flows co-currently with the fuel.
A throated gasifier has a restriction partway down the gasifier where air or oxygen is added and
when the temperature rises to 1200 degree to 1400 degree centigrade, and the fuel feedstock is
either burned or pyrolyses.
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The combustion gases then pass down over the hot char at the bottom of the bed where they are
reduced to hydrogen and carbon monoxide. The high temperature within the throat ensures that
the tar formed during pyrolysis are significantly cracked, that is the homogeneous cracking with
further cracking occurring as the gas meets the hot char on the way out of the bed, heterogeneous
cracking leading to a less tarry off-gas.
Some disadvantages of a throated gasifiers are, the constriction at the throat affects the type of
biomass that can be successfully gasified, a low moisture content is required almost 25 weight
percent. Ash and dust are significantly present in the exhaust; tar can still be up to 5 grams
normal per meter cube needing further cleanup.
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Biomass gasifier designs. So this is a bubbling fluidized bed system. So, the biomass is fed from
the side, you can see this is the main bubbling fluidized bed. Here the biomass is being fed using
a hopper and a feeding screw, there is a screw system which is slowly actually feed in a
particular rate. There are grids here, this is the fluidized bed, then whatever the gasification
product is going basis the gas phase, that needs to be separated from the fly ash and other
components. So, that will be done using a cyclone separator, then you get the hot product gas and
whatever it is remain the solid fractions will again come down to the bottom of the reactor. So,
either they will be burned again or they can be collected from the bottom. So, the biomass is feed
from the side and/or below the bottom of the bed and the gasifying agent’s velocity is controlled
so, that it is just greater than the minimum fluidization velocity of the bed material, the product
gas exits from the top of the gasifier and ash is either removed from the bottom or from the
product gas using a cyclone.
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So, next design is a circulating fluidized bed. So, circulating fluidized bed known as CFB
systems use 2 different integrated units. In the first unit, there are 2 systems you can see, this is
one column there is another column here. So, the first unit is called the riser the second unit is
called the downcomer. Now in the first unit, which is known as the riser the bed material is kept
fluidized.
So, this is the main reactor where the fluidization is happening by the gasifying agent. So, you
see that we feed the biofuel feed or the feedstock is being fed here somewhere and from the
bottom you collect the ash. And then when the gas goes out and there is a downcomer here, here
you basically do some processing some other things are also there, you collect the product gas
here.
So, there is air pre heater and then part of that gas is also being recycled back. So, in the riser, the
biomass is fluidized by the gasifying agent with a higher velocity that then found in the bubbling
fluidized bed the BFB, which we discussed. Now this allows the bed material to be fluidized to a
greater extent than the BFB and the overall residence time is higher due to the circulation, which
is effected by passing the product gas and entrained bed material through a cyclone which
separates the product gas from the bed material which is re-circulated back to the riser.
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So, we will now discuss about a special gasification technique which is called supercritical water
gasification. Water above it is critical point which is 374.12 degree centigrade and a 221.2 bar is
termed as supercritical. Now under these settings, the liquid and gas phase do not exist, it is a
phase between a liquid and gas phase, it is called supercritical phase. And in that phase
particularly the water shows distinctive reactivity and solvency characteristics.
So, the water in supercritical phase will have both the properties of a gas phase as well as a liquid
phase. Solubilities of organic materials and gases which are normally insoluble are enhanced
with a decrease in solubility for inorganics. So, supercritical water gasification has been applied
to wet biomass without the need for pre drying. So, this technology is being actually developed
to take care of the wet biomasses.
Please understand that when the biomasses are highly wet or has high moisture content, then you
need a significant amount of energy to basically dry them before you feed them to a gasifier or a
pyrolysers. So, if you go for a supercritical water gasification system, then whatever the water or
moisture is present inside the biomass will actually behave like a reactant? So, this is the major
advantage and this is the aim of developing the supercritical water gasification system.
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So, product gas from this SCWG is mainly comprises hydrogen, carbon dioxide, methane and
carbon monoxide. The carbon monoxide yield is comparatively low as carbon monoxide
transforms into carbon dioxide through the water gas shift reaction.
So, this is the unit. So, this supercritical water gasification the main reactor is of course very
costly, you can think about the high temperature and high pressure required to make the water
into the supercritical stage. So, here the main reaction is happening then whatever you are getting
here the product it goes through some heat exchanger and there is a phase separator, you get
clean water and you get the product gas.
And whatever portion from this is a combustion air and methane is recycled and being collected
as a flue gas or maybe used for other purposes. So, by employing the supercritical water
gasification process, even liquid biomass such as olive mill water can be utilized with the
production of low tar hydrogen gas. It is a very nice technology, the only problem is the cost and
special types of reactors of course, and that is why it leads to the extra or additional cost.
Tar and coke formation are curtailed by rapid dissolution of product gas components in
supercritical water. Wet biomass treatment without pre drying, liquid biomass treatments such as
olive mill wastewater, high hydrogen yield, high gasification efficiency and low tar formation
are the main advantages of this particular technology.
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We are just further discussing about that particular technology only. If you look at this particular
slide, you can see that hydrogen, this is the blue one is the hydrogen production. You can see that
it enhances exponentially after the 600 degrees centigrade. So, up to 600 degrees centigrade it is
almost in a saturated stage the production is happening. The moment we cross 600 degrees
centigrade, there is an exponential increase in the hydrogen gas production.
While the carbon monoxide, the carbon monoxide is the red one, it decreases after 600 degrees
centigrade, it is almost after 660 or 650 you can say that. So, methane decreases to 540 degrees
centigrade and then remains almost constant when even the temperature is increased. Major
limitations include requirements of high pressure, high temperature resistance and rust resistant
materials, consequently increasing the investment cost and high energy requirements.
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The major motivation behind biomass gasification is to exploit a large variety of waste materials
as feedstock, to increase resource efficiency and to reduce adverse climate change via carbon
dioxide mitigation. Although gasification is a key technology to utilize biomass waste, it poses
many potential kinds of risks, which have a significant impact on society and the environment at
large.
One of the main problems is the potential emissions of particulates. Some are dioxins, PAH,
carbon monoxide, SOx, NOx, and some volatile organics. These pollutants can interact with
humans through inhalation, ingestion, and dermal contact and thus pose a grave threat to human
health. Ash and tars are noteworthy elements which have potential for environmental
contamination, should be properly disposed off.
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So, gasification is a system which has an inherent risk for fire and explosion vulnerability,
especially since the gasifiers operate at high temperature and pressure. This probability enhances
significantly when hydrogen is the desired product; it is highly flammable and therefore
necessitates a great amount of caution. The waste streams formed require a suitable disposal
system to be implemented that meets all the legislative guidelines, especially these
environmental guidelines.
Techniques like low temperature circulating fluidized bed, which can produce ash with
negligible PAH impurity pose little threat to the environment, meaning that this ash can also be
used as a fertilizer or soil enhancer basically.
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So, next is we will discuss about pyrolysis. So, biomass pyrolysis can be described as the direct
thermal decomposition of the organic components in biomass in the absence of oxygen to yield
an array of useful products, liquid or solid derivatives and fuel gases. Eventually, pyrolysis
processes were utilized for the commercial production of a wide range of fuels, solvents,
chemicals and other products from biomass feedstocks.
Knowledge of the effects of various independent parameters such as biomass feedstock type,
composition, reaction temperature and pressure, residence time and catalyst on reaction rates,
product selectivities and product yields has led to the development of advanced biomass
pyrolysis processes.
The accumulation of considerable experimental data on these parameters has resulted in

advanced pyrolysis methods for the direct thermal conversion of biomass to liquid fuels and
various chemicals in higher yields than those obtained by the traditional long residence time
pyrolysis methods.
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So, the main product from pyrolysis, there is I already told you in the beginning of the class that
pyrolysis is a step inside the gasification. However, when you only go for pyrolysis reaction, our
main aim is mostly to produce the bio oil or pyrolytic oil, which can be further processed and can
be blended as a transportation fuel and it can have several other users also.
So, let us understand pyrolysis with different types of reaction conditions. So, a biomass is
mainly composed of long polymeric chain of cellulose, hemicellulose and pectin and some other
components - volatiles. Now the proportion of each end product depends on the temperature,
time - residence time, heating rate and pressure, types of precursors that we are using, and the
reactor design and configurations.
We can see how the reactions proceeds. So less than 200 degrees centigrade what is happening,
that is called as dehydration, drying or removal of the moisture, we call it dehydration. The
moment you proceed beyond 200 and within that 200 to 280 degrees centigrade you can see this
first hemicellulose will start degrading, so hemicellulose decomposes. So, it will result in some
amount of syngas and a minor quantity of bio oil, then we proceed further to beyond 280 degrees
centigrade and in the range of almost 300 degrees centigrade.
The broad range of 240 to 350 degrees centigrade, the cellulose degrades, when the cellulose
decomposes, it again produces some amount of syngas some more amount of bio oil, and minor
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amount of the bio char, that is the solid residue that will be left out. You proceed further beyond
350 degrees centigrade up to 400 or 500 degrees centigrade here lignin decomposes, lignin
decomposes mostly to the bio char and certain less amount of bio oil, so this is how the pyrolysis
reaction happens.
So, this is the yield of the pyrolytic products, you can see the yield of the bio char this decreases
as and when we proceed with the pyrolysis reaction or we increase the temperature. So, this is
the yield of bio oil, you can see that the most amount of the highest yield is about this 500
degrees centigrade you beyond that it decreases. Because beyond that lignin is decomposed,
lignin is not resulting more into bio oil, it is getting converted more into your bio char.
Then there is gas and water also. So, a modern technology was developed to extract maximum
possible energy from biomass using combustion, which is exothermic reaction, gasification
which is another exothermic reaction and pyrolysis which an endothermic reaction. Pyrolysis can
be considered as part of gasification and combustion, this is what I already mentioned you.
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So, these are some of the end products and the temperature and the type of reactions. So, less
than 350 moisture loss, depolymerization we get carbonyl and carboxyl group production, this is
what I have already described, but this is given in a tabular format for a better understanding. So,
between 350 to 450, you get breaking up glycosides chain of polysaccharides. So, tar production
begins that contains levoglucosan, anhydrides and oligosaccharides. Above 450 dehydration
rearrangement and fission of sugar units happens, you get acetaldehyde, glyoxalin, acrolein
production and some other components. Above 500 degree centigrade a mixture of all the
processes reactions that is happening and mixture of all the above products also being produced.
So then condensation reaction happens. So, unsaturated products condense and cleave to the
char, a highly reactive char residue containing trapped free radicals is the end product.
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So, conventional pyrolysis consists of the slow irreversible thermal degradation of the organic
components in biomass, most of which are lignocellulosic polymers, in the absence of oxygen.
So, pyrolysis is happening without oxygen, whereas gasification is happening which happens
after the pyrolysis with a less amount of theoretical oxygen, which is required for the combustion
process.
So, slow pyrolysis has traditionally been used for the production of charcoal. Short residence
time pyrolysis which are flash pyrolysis, ultra pyrolysis of biomass at moderate temperatures can
afford up to 70 weight percent yields of the liquid products. So, they are very good in producing
higher amount of bio oil. Pyrolysis conditions can be used, that provides high yields of gas or
liquid products and char yields of less than 5%.
One configuration of an advanced biomass pyrolysis system, for example, involves an ablative
vortex reactor for pyrolysis at biomass residence times of fractions of a second coupled to a
downstream vapor cracker.
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Overall, the pyrolysis process can be classified as slow and fast depending upon the heating rate.
In slow pyrolysis process, the time of heating the biomass substrate to pyrolysis temperature is
longer than the time of retention of the substrate at characteristic pyrolysis reaction temperature.
However, in fast pyrolysis, the initial heating time of the precursor is smaller than the final
retention time at pyrolysis peak temperature.
Based on medium, pyrolysis can be another 2 types namely hydrous pyrolysis and hydro
pyrolysis, what medium is being used. So, a slow and fast pyrolysis is usually carried out in inert
atmosphere, whereas hydrous pyrolysis is carried out in the presence of water and hydro
pyrolysis occurred in the presence of hydrogen.
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So, this table gives you the types of pyrolysis process with resultant products. So, a fast pyrolysis
the retention time is extremely low, less than 2 seconds, rate of heating is very high, final
temperature is around 500 degrees centigrade and the major product that you get is the bio oil.
The highest yield is of course bio oil. Flash pyrolysis less than one second extremely fast, high
rate of heating less than around 650 degrees centigrade. And again the major product is bio oil
and certain chemicals and maybe gas - less amount of gas. Ultra-rapid - less than 0.5 second,
very high rate of heating; the temperature required is 1000 degrees centigrade, you get chemicals
and gases. Vacuum pyrolysis, you get bio oil. Hydro pyrolysis less than 10 seconds, high rate of
heating, temperature required is less than 500 and the major product is bio oil.
And carbonization - this is the slow pyrolysis which was initially used so many years before to
produce that char - charcoal. So, the resultant product is charcoal and less than 400 degrees
centigrade. Conventional is about 5 to 30 minutes, (heating rate) low, many times we can call it
as an intermediate pyrolysis, so the maximum temperature we can go depending upon the type of
feedstock is 600, you get so many different types of products in a certain proportion - char, bio
oil and gas. However, again depending upon the type of feedstock, maximum yield is of course
of the bio oil.
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So, fast pyrolysis. So, during the fast pyrolysis process, biomass residues are heated in absence
of oxygen at high temperature using higher heating rate. Based on the initial weight of the
biomass fast pyrolysis can provide 60 to 75% of the liquid bio fuels with 15 to 25% of the
biochar residues. So, the process is characterized by small vapor retention time, however quick
chilling of vapors and aerosol can ensure higher bio oil yield, so this is another further step.
So, you get a pyrolysis oil here, non condensable gases - can be processed through the gas
burner. And you get the heat - again that heat can be used in the pyrolysis here. So, the pyrolysis
oil you can see that so many different types of processing here, synthesis and extraction to
biobased chemicals. I can tell you again we have already discussed once, the major product from
the fast pyrolysis or any pyrolysis of course, is the oil, that is the major aim.
Whenever we generate oil, so you just leave it or settle it under gravity, allow it for some time,
you see that 2 distinct phases, one top phase and bottom phase, there is phase separation. The one
phase is containing the oil rich phase that is the organic components and that is if we decant it
properly and take it out and further process that is the bio oil.
And there are other portion which is aquatic phase, that aquatic phase contains so many different
types of chemicals and some of these chemicals can be of very high value depending upon what
is the feedstock you are using, that can be processed. You get that type of platform chemicals
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here. Upgrade you get advanced bio fuels, if you can go for some sort of distillation process.
Feed to turbine engine you get a clean power here.
Boiler you get heat and whatever the biochar that leaves, it can either be burnt in a boiler to
produce the heat - maybe steam at certain cases or if the quality of the char is poor it can be used
as a soil enhancer.
Fast pyrolysis technology is getting implausible acceptance for producing liquid fuels due to
certain technical advantages, so some of them are listed here. So, it can ensure preliminary
disintegration of the simple oligomer and lignin portions from the lignocellulosic biomass with
successive upgrading. The scaling up of this process is economically feasible. It can utilize
second generation bio oil feedstock such as forest residues, municipal and industrial wastes.
It provides easy storability and transportability of liquid fuels. It can ensure secondary
transformation of motor fuels, additives or special chemicals.
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Then is flash pyrolysis. So this is a flash pyrolyser or flash pyrolysis reactor. So, flash pyrolysis
process of biomass can give solid, liquid and gaseous products. The bio oil production can go up
to 75% if you use this particular technology. This procedure is carried out by speedy
devolatilization under inert atmosphere using higher heating rate with high pyrolysis temperature
around 450 to 1000 degree centigrade.
So, in this process, the gas residence time is less than 1 second - is too little. Nevertheless, the
process has poor thermal stability. Due to catalytic effect of the char, the oil becomes viscous
and sometimes it contains some solid residues also which is not desirable but you can further
process it to take out the solid part.
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Then slow pyrolysis. Slow pyrolysis can yield good quality charcoal using low temperature as
well as low heating rates. The vapour residence time can be around 5 to 30 minutes in this
process. The volatile organic fractions present in vapor phase continue to react with each other to
yield char and some liquid fractions. The quality of bio oil produce in this process is very low.
So, if your aim is to produce bio oil it is recommended not to use slow pyrolysis, you can better
go for an intermediate pyrolysis where you get a good amount of bio oil. And if you only want
higher bio-oil yield then you can go for the fast pyrolysis or flash pyrolysis. So, the longer
residence time in slow pyrolysis initiates further cracking to reduce the yield of bio oil.
The process suffers from low heat transfer values with longer retention time leading to enhance
the expenditure by higher input of energy. The stoichiometric equation for a production of
charcoal is shown by this equation :
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Then let us understand catalytic pyrolysis. A mixture of hydrocarbon was produced earlier from
methanol over zeolites like ZSM-5. Another patent suggested passing the vapors from pyrolyzer
over a bed of zeolite ZSM-5 to produce short chain hydrocarbons. It was reported that the
catalyst of ZSM-5 can convert bio oils generated from the pyrolyzer to alkylated benzene. The
disadvantage of using ZSM-5 as catalyst was coke formation.
However, these disadvantages can be overcome by using a circulating fluidized bed technology,
where the fluidized bed can be prepared using different types of catalyst instead of sand. So, this
CFB whatever we have discussed under the gasification, the same reactor can be used. Catalyst
can be mixed with lignocellulosic substrate earlier to pyrolysis process or separately with the
gaseous reactants to obtain desired products.
So, this statement you will see many times. You will come across 2 different terminologies, one
is called ex-situ catalytic pyrolysis, one is called in-situ catalytic pyrolysis; where the in-situ
catalytic pyrolysis the catalyst is physically mixed with the biomass, then we go for the pyrolysis
reaction. In ex-situ pyrolysis reaction what happens that there is a fixed bed type of reactor, it
can be fluidized bed also. There the biomass is not mixed with the catalyst, so the catalyst is kept
in a separate section and the when the vapour is getting generated after the pyrolysis reaction
from the feed biomass, that passes through a bed of catalyst. So, the catalytic cracking is
happening for the vapor phase, so you can call it vapor phase catalytic cracking.
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That is better because this catalyst can be regenerated and reused. Whereas, if you mix with the
feedstock then you cannot separate the catalyst from the biomass and it will be waste basically.
And you know the catalysts are extremely costly, most of the catalyst or commercial catalyst. So,
it was revealed that parting of the catalyst and biomass was more operative for the
transformation of the required products.
So, catalytic hydro pyrolysis. So catalytic hydro pyrolysis is a kind of catalytic pyrolysis where
pyrolysis is carried out using fluidized bed reactor under the flow of hydrogen. In this process
the fluidized bed is replaced by a transition metal catalyst. It was reported that the replacement
inert sand with nickel based catalyst under atmospheric pressure can convert the bio oil into low
molecular weight hydrocarbons within short contact time.
Recently, Gas Technology Institute in Illinois, United States reported a new process where the
overall process is carried out under 7 to 34 bar pressure. Due to high pressure C1 and C3 gases
are evolved which after reforming produce large amount of hydrogen. However, the system is
also very complex as it is a combination of hydro-pyrolysis and reforming. Overall the
establishment of this process is very costly.
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So, we will see certain types of reactors. The first is the fixed bed reactor. So, this is a very
simple technology that gives priority to the production of bio oils which are relatively uniform in
size with low fines content. So, it is made up of 2 basic components; that is the gas cooling
compartment and the cleaning system by filtering through the cyclone, wet scrubbers and dry
filters.
So, here this is a gas distributor which is distributing the sweeping gas, here you feed your
biomass through a feeder and it is a fixed bed pyrolysis reaction happens; the heat is being
supplied and whatever the resultant is the vapor, gas and aerosol.
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So, during reaction, the solid sample is allowed to pass through a vertical shaft where it
encounters an upwardly moving counter current gas stream product. This reactor can be made
using either steel, firebricks or concrete and composed of the feeding unit, a unit for removing
the ash and the gas escape unit.
The reactor, which has it is priority for applications involving small scale heat and power, has
high ability to conserve carbon and can operate for long time for solid residence, low gas
velocity and of course with a low ash carry-over. It has it is own limitation in the problem is
usually encountered during the tar removal.
Then fluidized bed system, the unit looks like similar - it is a schematic. Here it can be little
something conical like shape maybe, there are different designs available. But the bed is
fluidized it is not a fixed bed, the remaining things are same, so this reactor consist of a mixture
of 2 phases the solid and the liquid and usually accomplished by passing a pressurized fluid
through the solid material.
Now there are different types of fluidized bed reactors which include bubbling fluidized,
circulating fluidized, ablative reactor, vortex reactor, rotating disk reactor, vacuum pyrolysis
reactor and rotating cone reactor, there are many different designs are available and this is the
simplest schematic.
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So, the advantages of fluidized bed are: The provision of heat transfer is very rapid. It has a good
grip of pyrolysis reaction and vapor holding time control. It has sufficiently high surface area for
contact between the 2 phases in the mixture, because, the biomass is in suspended medium. The
heat transfer in the system is exemplary and the relative velocity between the phases is very high.
So, then the next is bubbling fluidized bed reactor. So, the high presence of solid density in the
bed ensures a better temperature control, smooth contact between gas and solid, good transfer of
heat and excellent storage capacity. The biomass is heated in an environment devoid of oxygen
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and decomposed into gas, vapor, aerosols and char and these components are finally collected
from the reactor.
While the charcoal is collected using the cyclone separator and stored, the vapour is cooled
rapidly and condensed into high quality bio oil and stored with about almost 70% yield of the
biomass weight - dry weight basically.
Then next is the circulating fluidized bed. So you can have a close look at the image, you can see
that there are 2 different sections. The first one is the fluidized bed here, the main reactor here
and this is the combustor. So the features of this reactor is similar to that of a bubbling fluidized
bed reactor described above except the fact that residence time for the vapors and char is shorter.
This makes the gas velocity and the content of char in the bio oil to be higher. However, it has a
large throughputs advantage, single and double type of these reactors are also available.
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Then next is vacuum pyrolysis reactor. This is a slow pyrolysis reactor with heat transfer rate
very low. This results in a lower bio oil yield usually in the range of 35 to 50 weight percent. The
design is highly complicated and requirement for investment and maintenance is always high
thereby making the technology uneconomically suitable. The biomass is conveyed into the
vacuum chamber with a high temperature with the aid of a conveyor metal belt with periodical
stirring of the biomass by mechanical agitation.
The heat carrier is usually made of a burner while the biomass is melted by heating inductively
using molten salts. So, it has the ability to process larger particle size biomass but requires
special solid feeds, special discharging devices in order to have an effective seal all the time.
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Then rotating cone reactor. Unlike the fluidized bed reactor the rotating cone reactor requires the
mixing of biomass and hot sand mechanically and does not require the use of inert gas. The feed
and the hot sand are fed in from the bottom of the cone while they are transported to the lip of
the cone during spinning using a centrifugal force and as they get up to the tip, the vapour
generated is condensed by the condenser and then you can collect the condensable part.
The char and the sand are combusted with the sand being heated up again and reintroduced to
mix the fresh feedstock at the bottom of the cone. So you take out the char. And char if it is
getting converted and fully combusted, so you basically end up with a certain ash and the ash is
having a low density and it can be easily separated. And the sand which is already containing
high amount of heat can be recycled back. Though the design of this reactor might be complex,
its high bio oil yield makes it extremely desirable.
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So, the 2 different designs which we have already discussed - this is the vacuum pyrolysis
reactor and that is the rotating cone reactor. So, you can have more different stages in the
vacuum pyrolysis reactor, you can have a single stage also, you can have multiple stages also.
Then whatever it is coming out - biomass is usually fed from the top or if it has different distinct
stages, so you can feed from this side also.
There is a condenser which condenses the liquid and you get the liquid here and the char can be
collected from the bottom. Again in the rotating cone reactor also biomass as well as the hot sand
which is carrying the heat is being fed from the top and the cone is rotating.
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So, we will just summarize. So advantages and disadvantages of different pyrolysis reactor. If
you look at fixed bed reactor, the advantages are simplicity in design, reliable results and
biomass size is independent, no fixed biomass size is required. However, the disadvantages are
high carbon conservation, long solid residence time, low ash carry-over and difficult to remove
the char.
If you talk about bubbling fluidized bed, the advantages are the design is simple and easy
operational procedures. However, it suffers from good temperature control and suitable for large
scale application, small particle sizes are needed. There is a small mistake here actually the good
temperature control will come to the advantages.
And for the circulating fluidized bed, the advantages are: well understood technology, better
thermal control, large particle sizes can be processed, disadvantages large scale production
difficulty, complex hydrodynamics and char is very, very fine. So, that char cannot be utilized
for any better purposes you can restrict itself to only soil amendment.
Rotating cone, advantages are: centrifugal force circulates hot sand and biomass substrate, no
carrier gas is required. Difficulty is that: operational processes are (difficult) having
disadvantageous position, smaller particle sizes needed - otherwise you cannot circulate them
and they will deposit on the bottom, large scale application is difficult.
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If you talk about vacuum pyrolysis, the advantages are that: the oil that you get from this
particular reactor is very clean. Can process larger particles of 3 to 5 centimeter, no carrier gas
required, lower temperature required, condensation of liquid product is very easier. The
disadvantages are that: it is a slow process, solid residence time is too high, requires large scale
equipment, poor heat and mass transfer rate and it generates more water.
So, we will talk about the pyrolysis mechanisms. Many dehydration, cracking, isomerization,
dehydrogenation, aromatization, coking and condensation reactions and rearrangements happen
during the pyrolysis reaction. So, the pyrolysis reactions are very complex and predicting them
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for a particular biomass is too difficult. The products are water, carbon oxides, other gases,
charcoal, organic compounds, tar and polymer.
When cellulose is slowly heated at about 250 to 270 degree centigrade, a large quantity of gas is
produced consisting chiefly of carbon dioxide and carbon monoxide. Initially, small amounts of
hydrogen and hydro carbon gases and large amount carbon oxides are emitted. The hydrocarbon
in the product gas then increase with further temperature increases until hydrogen is the main
product. The carbon oxide and most other products owe their formation to the secondary and
further reactions.
(Refer Slide Time: 1:00:10)
Pyrolysis of cellulose yields the best known of the 1, 6-anhydrohexoses, β-glucosan or

levoglucosan, in reasonably good yields. A novel technique based on flash devolatilization of
biomass and direct molecular-beam, mass spectrometric analysis has shown that levoglucosan is
a primary product of the pyrolysis of pure cellulose. However, the yield of levoglucosan on
pyrolysis of most biomass is low even though the cellulose content is about 50 weight percent.
Also, when pure cellulose is treated with only small amount of alkali, levoglucosan formation is
inhibited and a different product slate composed of furan derivatives are produced.
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So, this is the reaction you can see of the β-glucosan formation during pyrolysis. This is from the
β-D-glucose, it’s a mixture, here it can be from cellulose or starch. So, levoglucosan is also
obtained directly on pyrolysis of glucose and starch. The compound has the same empirical
formula as the monomeric building block of the cellulosic polymers.
So, with this I wind up and thank you very much, so in the next class we will be discussing about
the thermal conversion products, what are the different types of products, their composition, their
applications and some certain commercial success stories about the gasification and pyrolysis,
thank you very much. If you have any query please feel free to register it in the swayam portal or
drop a mail to me at [email protected], thank you.
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Module 05
Lecture-15
Products and Commercial Success Stories
Good morning students, this is lecture 3 of module 5. And in this lecture as you know that we are
discussing about the thermochemical processes. Today we will discuss about the thermal
conversion products and some commercial successful stories. So, let us begin.
Food waste can be classified into four major groups by source generation as residential,
institutional, commercial and industrial. So, we have discussed about different types of
biomasses which includes this type of wastes also. And we will try to understand that how this
food waste has been commercially used to generate different types of value added products
including the biofuels.
Now from these type of food waste, commercial (which takes into account agricultural waste,
supermarket waste), and industrial (for example, food processing industry). So, these food wastes
can be classified as pre-consumption food waste, and whereas residential and institutional like
cafeteria, hospital etc, these wastes are considered to be the post-consumption food waste.
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So, mixed food waste sources from post consumer groups are characterized by high moisture
content almost 60 to 90% very, very high moisture content, including also high organic content
almost 95% dry matter. Along with that there is high salt content and rich nutrition which are
very valuable for recycling and valorization.
The mixed characteristics of postconsumer waste make it more challenging to convert into
energy, bio based materials and high value chemicals. In addition, post consumer institutional
waste generation from cafeterias and hospitals is often contaminated by plastic utensils, because
you know that we have a habit of carrying all these materials in plastic. So, when we consume
the food, we just dump it along with the rest of food waste, so that creates a big problem.
So, by comparison pre consumer food waste is more homogeneous than post consumer mixed
waste. So, post consumer waste is always a mixed waste, so it comes with mixing up
polyethylenes that means plastics as well as paper and some other materials also. So, literature
reports that commercial and industrial food waste are less susceptible to quick deterioration
compared to mixed food waste from residential and institutional waste.
Now food waste conversion into power, heat, fuels and bio-products varies based on the specific
feedstock and is generally categorized into 2 major conversion pathways either biochemical or
thermochemical.
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So, let us understand the thermochemical conversion products of the food waste. Now this
schematic will make you understand that how the different food waste can be converted by both
the routes, one is biochemical as well as thermochemical. So, let us see the first one, biological
one. So, you can go for anaerobic digestion, which will yield me biogas enriched with methane,
you can ferment it.
So, after taking the carbohydrate parts and again do hydrolysis to get glucose. We will get an
ethanol platform, so bio-ethanol apart from small carbon dioxide. So, then coming to
thermochemical, so we can have incineration, incineration will give me heat and electricity. If
you go for pyrolysis and gasification it gives me bio oil, char which is coming from the pyrolysis
and syngas which is a product from gasification, this we have discussed in our last class.
So, another important thing is hydrothermal carbonization. So, that will give me hydrochar or
char and some gases. Now this makes an understanding that food waste having enormous
potential to be converted into so many different types of value added products apart from the
energy either using the biological route or your thermochemical route.
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Let us understand the thermal conversion of post consumer mixed food waste by gasification. So,
postconsumer food waste from residential, institutional and some commercial sectors is
represented by heterogeneous chemical characteristics. So, because they include carbohydrates,
lipid, amino acids, phosphates, vitamins and carbon, but also containing other substances. In
addition, postconsumer mixed waste may have a high moisture content.
Now it has been reported that average proximate analysis of food waste is 80% volatile matter,
50% fixed carbon, 5% ash. So, this is just a generalized statistic for most of the so called
postconsumer mixed waste. However, research on thermal decomposition of mixed food waste
suggests that with a moisture content higher than 45%, a steam gasification approach would be
viable because the water vapor liberated in the pyrolysis test can be used in the gasification stage
and therefore, the energy consumed to evaporate moisture can be recovered.
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Generally, the char gasification stage is slower than the prior pyrolysis stage and that is why it is
the rate limiting step. And understanding the catalytic effect of char on the overall efficiency of
gasification is essential. Because of the presence of inorganic constituents in the food waste, char
from the initial pyrolysis step was found to have a catalytic effect. If you recall our last lecture,
then I precisely told you that when you talk about pyrolysis and gasification, please understand
that pyrolysis is also a part of gasification.
This is what we are talking about here also. So, when gasification proceeds or starts, so the initial
step is your dehydration or let us we can say that removal of the moisture around up to 150, 200
degrees centigrade beyond that your pyrolysis reaction starts in, so in the pyrolysis we will get a
char. So, the resultant is char and very small amount of gas and other materials will come into
picture.
Now this char with the help of either steam or air will be converted or let us say will be gasified
with less than a theoretical amount of oxygen that is required to do combustion is required for
the gasification process. So, that much amount of oxygen will gasify either it can be oxygen or it
can be a steam. So, another important thing which here also we are mentioning that the char may
contain several different types of inorganic materials.
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So, these inorganic materials have a vital role to play during the gasification process. So, they
may act as a catalyst during the gasification process thereby enhancing the rate of reaction and
also increasing the yield. So, char reactivity increased with the degree of conversion. Research
on post-consumer mixed food waste considered pre-processing the food waste by dehydrating,
grinding and palletizing due to the heterogeneous properties of the waste.
Comparison of simulated gasification results with direct combustion indicated that, although
combustion of pelletized food waste is energetically comparable to wood combustion,
gasification results are also in agreement with other biomass gasification literature.
So, this is the schematic of the thermal conversion of post consumer mixed food waste through
gasification. So, unprepared food, so this is the food preparation, so you can see the spoilage,
unserved excess, so this is pre consumer waste. So, then of course water is hugely consumed
during the processing of the food.
So, then prepared food, that goes to the food service, so you get consumed food and whatever
served excess plate waste all these different types of wastes are being mixed. Plastics, then some
cutlery things, your paper napkins all these things come into this, so that is post consumer waste.
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Now let us talk about the another very important product of the gasification that is, the syngas.
So, the immediate near-term opportunities for lignocellulosic biorefineries use lignin for the
process heat, power and steam. However, there are other opportunities to consider for lignin that
would be implemented in the 3 to 10 years’ timeframe. Although these opportunities have
technical challenges, they have few technology barrier, and R & D support can be largely limited
to process engineering, recovery and integration refinements.
Lignin combustion is practiced today in paper mills to produce process heat, power, steam and to
recover pulping chemicals. For lignocellulosic biorefineries, there will be technical challenges
around material handling, and overall heat balance and integration.
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Lignin gasification produces syngas which is enriched with carbon monoxide and hydrogen. The
addition of a second step employing water gas shift technology allows production of a pure
hydrogen steam with co formation of carbon dioxide. Now hydrogen can be used to make
electricity, for example in fuel cell applications or for hydrogenation and hydrogenolysis
applications.
Now syngas can be used in different ways; technologies to produce DME that is the methanol/
dimethyl ether is well established. The products can be used directly or maybe converted to
green gasoline via the methanol to gasoline that is called MTG process or to olefins via the
methanol to olefin process which is known as MTO. So, these processes are very well
established and commercially adapted also.
Now because of the high degree of technology development in the methanol DME catalysts and
processes, the use of lignin derived syngas could be readily implemented. Now the technology
needs include the economic purification of syngas and demonstration that gasification can
proceed smoothly with biorefinery lignin.
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The FT technology, the Fischer Tropsch technology to produce green diesel represents another
use of lignin derived syngas. For example, Sasol has a extensive technology in this area. The
technical needs for the FT include economical purification of syngas streams and catalysts and
process improvements to reduce unwanted products such as methane and higher molecular
weight compounds such as waxes.
So, there are a lot of technology development has happened since last 2 decades for the FT
technology. So, that all these, such drawbacks which has been mentioned would be overcome.
The conversion of syngas to mixed alcohols has not been commercialized, it would allow the
production of ethanol and other fuel alcohols or high value alcohol chemicals. A major challenge
for this technology is catalyst and process improvements to increase space time yields.
So, the catalysts are lacking in selectivity and rate and that is the reason so many academicians
and scientists are working day and night on developing different types of catalysts, which will
have a better selectivity as well as rate for different processes, it is not about FT also, there are
many other processes. In chemical reaction engineering, in energy production in other
environmental application, in so many different areas.
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Although syngas production via gasification is a well developed technology for coal and natural
gas, there is continuing controversy over gasification economics at the scale anticipated for the
lignocellulosic biorefinery. Because see if you remember we have discussed all these things, one
of the most important aspect of the entire biorefinery or if you precisely talk about
lignocellulosic biorefinery is that unless until we aim and get or we produce, let us say we
produce different high value products which comes out or derived from the byproducts as well as
from the waste, then the lignocellulosic biorefinery cannot be sustainable. And one more
important part lignocellulosic biorefinery aspect is that, the different types of feedstocks that
required to be treated in a single biorefinery without changing the equipments, process streams
or maybe with a little modification or less interference in the process dynamics.
So, these are the challenges already exist, and people are working day and night to overcome
this. So, a better understanding of this issue is needed which may lead to identification of
specific improvements needed in overall gasification technology. Gasification of different lignin
sources may also differ; this is what I was just mentioning. For example, gasification a black
liquor a byproduct of pulping has been problematic within industry, that has due to the
concentration as well as also the viscosity also played a big role during conversion.
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So, this is a thermochemcial standalone gasifier, where it fits into a biorefinery in numerous
ways. For example, this is a standalone process where the biomass residues would be fed directly
into the gasifier, the resultant syngas would then be converted to products such as FT liquids.
That means we can call it green fuels, methanol or mixed alcohols.
So in another example, the gasifier is integrated into a biochemical lignocellulosic biorefinery.

Now in this particular example, the biochemical or thermochemical integrated biorefinery, the
lignin rich residues from lignocellulosic feedstock are fed into the gasifier. Now sugars are
primarily converted to ethanol while the lignin is primarily converted into the syngas products.
So, this is also very simplified and highly adapted technology across various biorefineries.
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So, now let us understand the pyrolysis products. So, among all the different types of pyrolysis
which we have discussed in last class, fast pyrolysis is readily adaptable by most of the
industries, because of it is high yield of bio oil or pyrolysis oil. So, fast pyrolysis is a method that
converts dry biomass to a liquid product known as pyrolysis oil or bio oil.
As produced bio oils are generally quite unstable to viscosity changes and oxidation, which
makes their use for chemicals and fuels problematic. So, pyrolysis oils could be incorporated into
various petroleum refinery processes provided they are appropriately pretreated and stabilized.
So, the outcome, would be displacement of a fraction of imported petroleum and the production
of green fuels and chemicals.
Now technology needs include preconditioning, the pyrolysis oil before stabilization, then
catalyst and process development to stabilize the pyrolysis oil for storage and transport from a
bio refinery to a petroleum refinery. Then validation of the stabilized pyrolysis oil compatibility
with current petroleum conversion catalysts and processes.
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Now let us look at this particular pyrolysis integrated with gasification technology process. So,
the pyrolysis technology could be the basis for a standalone biorefinery, that is integrated into a
biochemical or thermochemical refinery. So, you can see here, so the forest residue is pyrolyzed,
this is a pyrolysis technology here. So, whatever the pyrolytic lignin is left out that goes to the
hydrotreating or hydrocracking, where we get green gasoline, green diesel, this type of fractions.
Then water soluble pyrolysis oil, because I told you and again I am repeating, that whenever we
talk about bio oil, pyrolytic oil, pyrolysis oil, please understand that it has a huge amount of
aqueous fraction and that needs to be decanted, because the oil is the only organic phase that is
useful for us. So, that goes to reforming, then syngas, then alcohol synthesis, then we get a
ethanol or we may get methanol, n- propanol, n-butanol and n-pentanol.
So, the fast pyrolysis needs a dry precursor, absolutely dry precursor, dry feedstock, 0.5 second,
500 degrees centigrade, 1 atm - very fast process and it needs inert atmosphere and solid particle
heat carrier, so this is what is required. So, products are pyrolysis oil, aqueous phase. So aqueous
phase as I told you, again I am telling you that it may contain different types of valuable
chemicals, now depending upon what is the feedstock.
And if their concentration in this aqueous phase is good enough, and it is a high value product
then it should be purified. But please again note that purification that is the downstream
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processing part is a very costly affair. So in commercial applications are liquid, smoke, resins,
mixtures, there are so many applications.
So, this is the biochemical thermochemical pyrolysis biorefinery. So, here the feedstock is corn
stover. So, the corn stover is being processed into the ethanol platform where ethanol is being
produced as one of the product whatever left out is the lignin residues goes to pyrolysis. Then it
again another stage where we are hydrotreating or hydrocracking it to get green gasoline. And
the coal also can be used to do the steam generation and steam as well as power and it is a
integrated part of the entire biorefinery system, where both gasification and pyrolysis are taking
place .
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So, the next example is the bio oil derived products’ selective hydro deoxygenation. Now mild
hydro deoxygenation is of interest to remove oxygen functional groups and produce olefins as
reactive hydrocarbon feedstock. Now please note that, bio oil usually contains a huge amount of
oxygen which are not desirable, if we are going to use in any engines, where the fuel is getting
burnt, so it has to be removed. So, to do that hydro deoxygenation is one of the technology.
So, for example, mild hydro deoxygenation of acetone can produce propylene that can be used to
produce valuable C3 chemicals. As for example acrylic acid and acrylates, acrylonitrile, pyridine
propylene oxide and 1, 2-propane diol, and the most consumed polymer is polypropylene.
Aliphatic and cyclic ketones are common oxygenate compounds found in bio oil and a lot more
in upgrading of the bio oil by ketonization process. The direct reduction usually leads to
formation of paraffin and alcohol when drastic and/or mild condition is used respectively.
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A catalytic system designed for mild hydro deoxygenation of ketone to olefin was investigated.
Hydrogenation of ketone to alcohol was accomplished over metal catalyst, various types of
metals has been studied - nickel, copper, iron, cobalt, platinum and their alloys - at low
temperature. The alcohol produced was then dehydrated over acidic catalyst. Hydrogenation and
dehydration were separately studied in order to understand the role of each catalytic function.
Now that integrated hydrogenation-dehydration over double bed, physical mixed bed and bi-
functional catalyst bed were then optimized to allow only essential amount of hydrogen
consumption in the first stage.
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This is one schematic of how selective HDO ketone is being carried out. So, this is the reference
of this particular paper has been given here, you can go through it later, Catalysts science and
technology; it is a very nice interesting work. So, what is happening here you can see this is
ketonization. So, your bio oil is getting impregnated over the catalyst surface here it is copper.
So, resulting in a corresponding alcohol, now that alcohol will be dehydrated using another
catalyst which are basically acidic catalyst. So, a rapid dehydration synergistically prevents
reversible dehydrogenation of alcohol while excessive olefin hydrogenation can be limited over
selected metal. So, you can read a little more and about this particular work.
So, let us now discuss about furfural, which is one of the most important platform chemicals
from such biorefineries. Now furfural identified as one of the top 30 platform chemicals derived
from biomass is an important fuel precursor, which can be converted to hydrocarbon fuels and
fuel intermediates. With current global production greater than 200,000 tonnes annually it is
currently a high value commercial commodity chemical produced primarily from agricultural
waste, such as oat hulls, corn cobs and sugarcane bagasse.
Industrial processes for furfural production were developed as early as 1921 when the Quaker
Oats batch process was developed to produce furfural from oat hulls. Since then many alternative
batch and continuous processes have been developed, with most of the batch operations
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primarily using sulfuric acid as a homogeneous acid catalyst, and temperatures ranging between
160 to 200 degrees centigrade.
High operating costs and low energy efficiency coupled with low furfural yield, on the order of
less than 50% resulted in the closure of batch plants in 1990s. So, another significant industrial
continuous process for furfural production was developed by Quaker Oats which was operated
for 40 years in Belle Glade in Florida until 1997. Now the continuous process utilized a
traditional horizontal screw style reactor similar to the 1 ton per day horizontal reactor system
which was installed in Metso, used at the NREL laboratory for diluted acid pretreatment. A
slightly improved furfural yield of about 55% was obtained in the continuous process developed
by the Quaker Oats using a residence time of one hour. While this process was technically
successful, the plant ultimately shut down due to the high maintenance cost of the continuous
reactor system. So, with this you can understand it is not about only the technology, the
processing cost is very important.
The yield is important, the entire cost whatever you are actually going to have it during the
processing of this any product is very much important. So, in industrial parlance the most
important thing to decide is about the cost. The cost means several different types of costs, which
we have already discussed.
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So, improving furfural yield beyond 55% in industrial production has been the subject of much
research since last 100 years. This is a difficult task because furfural once produced, rapidly
degrades through resinification and condensation reactions. So, furfural resinification is a
reaction in which furfural reacts with itself, while condensation reactions occur when furfural
reacts with xylose or one of the intermediates of xylose to furfural conversion to form furfural
pentose or di-furfural pentose.
Now resinification is, you can say some sort of autonomous process. The loss of furfural by
condensation is significantly greater than those by resinification. Much research has been
conducted in recent decades to try to minimize degradation and improve furfural yield.
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The main focus of the process improvements to achieve higher furfural yield can be categorized
into three ways. First is by improving furfural removal efficiency using steam or an inert gas, for
example the Suprayield process which uses nitrogen stripping. Second is that by extracting
furfural using a secondary organic phase in a biphasic reaction, for example using cyclopentyl
methyl ether CPME 26, o-nitortoluene, tetrahydrofuran, and/or γ-valerolactone.
So, another technique is by using different homogeneous or heterogeneous solid catalyst, for
example maleic acid27, formic acid21, metal salts and or Amberlyst70.
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Now production value of added chemical furfural from biomass you can understand, this is just a
schematic. A corn stover has been shown, it has to be pretreated, pretreated is very important we
have discussed how it has been carried out in one of our module exclusively that dedicated to
this. Then it will give us pentose sugars, now this pentose sugar under dehydration will give me
furfural.
The first furfural production plant was a batch process originally developed by Quaker Oats in
1920s in the United States. In this process, biomass was treated with acid, aqueous sulfuric acid
or phosphoric acid and steam at 153 degrees centigrade in a hydrolysis step, which could convert
the pentosans in the biomass to pentoses. The generated pentoses were then converted into
furfural in a subsequent stage, and then furfural was recovered by steam stripping from solution.
However, the drawback of this process was very low yield - less than 50% based on mono
sugars, substantial steam requirements, steam is a very costly product in any process industries,
then high effluent production. High effluent in this case is very acidic wastewater and high
operating costs which lead to the closure of the plants in developed countries till 1990s.
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The rather low yield of this process was attributed to the fact that the first step that was the
hydrolysis reaction was 50 times faster than the second step that is the dehydration. So, there is a
mismatch about the rate of reaction of both the steps. So consequently a significant number of
side reactions occurred because of the high availability of mono sugars in the process, which
ultimately reduce the quantity of mono sugars available for furfural production.
Recently, Westpro has modified the Quaker Oats technology process in China into a continuous
process, and it has been quite successful process. Now this method uses fixed bed reactors and a
continuous dynamic azeotropic distillation refining process, which led to a 4 to 12% production
yield with respect to the initial weight of dry biomass used, corn cobs, rice hulls, flax dregs,
cotton hulls, sugarcane bagasse, wood, so many different types of feedstock has been tried.
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SupraYield is another modification of the Quaker Oats technology process introduced in the late
1990s. In this technology lignocelluloses are hydrolyzed in one stage and then pentoses are
converted into furfural in the aqueous solution at it is boiling point with or without phosphoric
acid as a catalyst. The solution containing furfural is then adiabatically flash distilled, which
facilitates the transfer of the furfural formed from the aqueous phase to the vapor purpose. This
process has a production yield of 50 to 70% and is less expensive than the traditional process
described above.
So, now we will see some of the commercial success stories. First in the world biorefinery
producing wood based renewable biodiesel is the UPM biofuels. So, UPM biofuels is a big
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company in Finland, has developed an innovative production process from the crude tall oil, a
natural wood extract and a residue of pulp making process, to biofuel for transportation. So, their
product is known as UPM BioVerno, is a unique wood based renewable diesel resembling
almost the fossil diesel, suitable for current distribution systems and all diesel engines without
any modification. The greenhouse gas emissions are reduced significantly over 80%, it is a very
significant result. And in addition, tailpipe emissions such as NOx and other particles are
reduced significantly. Converting that crude tall oil - many times called Talal also - to biofuel is
an innovative way to use an own process residue without changing the main process that is the
pulp production.
So, this bio refinery has been integrated to the original pulp production unit, where you are using
the pulp production waste and converting it to diesel.
So, the key success factor is certified sustainability, it is very interesting. So, feedstock is wood
based non food origin with no increase in harvesting or land use. So, no question of any food
versus feed problem, and the greenhouse gas emission reduction is significant. Distributors value
the high stability of this high quality oxygen free hydrocarbon fuel as it functions as direct
replacement for fossil diesel.
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There are no blending limitations like in the first generation bio diesels. As a result UPM
produces a cost competitive high quality transport fuel that truly decreases emissions. During
2017, production efficiency has increased significantly and energy consumption was reduced by
25%. Another significant improvement in that entire integrated biorefinery technology.
Currently, UPM biofuels is evaluating growth opportunities for a possible second biorefinery in
Mussalo, that is in Kotka, in southeastern Finland with a planned capacity of 500,000 tons.
This is a photo of actually the UPM Biorefinery, UPM Biorefinery is also an excellent example
of innovation in the forest industry, as it utilizes the residue of pulp production, does not increase
harvesting of forest, but provides an environmentally friendly option for the transport. In
addition, tailpipe emissions such as NOx and particles are reduced significantly, so it is a win-
win story basically.
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So, this is their refinery production process, let us quickly glance through it and understand, this
is being given in a nutshell. So, this is the crude tall oil, a residue of chemical pulping process
containing the natural extractive components of the wood which they have used as a feedstock.
Now this goes to that pretreatment. So, crude tall oil is purified, so the salts, impurities, solid
particles and water are removed.
And this is a quite energy intensive and cost intensive process, then it goes to the hydro
treatment. So, in the hydro treatment pretreated crude tall oil is fed together with makeup and
recycled hydrogen to the reactor where the chemical structure is modified. So, the reaction water
is separated and directed to wastewater treatment plant. They have a very good in-house and very
efficient wastewater treatment plan also, where they recycle water.
Then it goes to the fractionation, so here the remaining hydrogen sulfide and uncondensable
gases are removed, the remaining liquid is distilled to separate renewable diesel. Then you get
the renewable diesel and otherwise renewable naphtha both way they produce. So, fantastic
technology and a very nice integrated biorefinery.
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So, next is our own Indian success story. So that DBT-ICT, 2G Ethanol Technology, so DBT is
the Department of biotechnology, Government of India and ICT, the Institute of Chemical
Technology mostly, many of few may be knowing it as a UDCT it is in Mumbai, India. So,
DBT-ICT 2G Ethanol Technology has been validated and demonstrated at a scale of 10 ton
biomass per day at India Glycols limited site at Kashipur, Uttarakhand.
The technology and plant designed at feedstock flexible that is the beauty of this technology, any
biomass feedstock from hardwood chips and cotton stock to soft bagasse and rice straw can be
processed and has been processed. The technology employs continuous processing from biomass
size reduction to fermentation and converts biomass feed to alcohol within 24 hours compared to
other technologies that take anywhere from 3 to 5 days, another significant milestone achieved.
So, the plant design with a low footprint also has unique features such as advanced reactor
design and separation technologies with slurry flow rapid reaction regime operations.
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So, this is what in a nutshell we can describe it. The process outline, lignocellulosic biomass as I
told any biomass soft, hard does not matter. It will be pretreated, the first step is always
pretreatment, then it will goes to saccharification, that separation, fermentation and purification,
you get sugars, lignin, alcohol can further be processed into other products.
So, fractionation to sugars, lignin, rapid and efficient process less than 24 hours, high
conversion, enzyme and chemical that is whatever being used are recycled. So, zero waste
almost zero waste technology we can say and silica and inorganic recovery is also being carried
out, especially when you are using this rice husk and other bagasses which contains some
amount of silica in it, so excellent technology.
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So, this is how they have processed, this you see lab scale process 1 kg per day, 2009 it was
developed in the lab scale in ICT. So, then it goes to a pilot scale 1 ton per day in 2010 to 13 that
they have tested. And then it goes to a pre commercial scale 10 ton per day in March 2016, now
it is a full scale plant.
So, the achievements, if you talk about achievements, that technology has several novel features
and achievements, that marks it apart from other globally promoted technologies. The first is 2
steps alkali soda-nitric acid fractionation. Second, slurry flow systems with recycle and reuse of
water, alkali and acid. Then next feedstock agnostic technology, this is the most beautiful part of
this entire technology. Any biomass feedstock from hardwood chips and cotton stalk to soft
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bagasse and rice straw can be processed. Lowest enzyme dosage on account of enzyme reuse
over weeks. No fancy metallurgy hence low capital expenditure.
Low cost of production with recycling of enzymes, chemicals and water, low consumption of
power and water. And demonstration plant ran smoothly from the first run without any problem
related to solid handling and other issues that plague other technologies, so excellent technology.
So, challenges that this technology addressed are scalable technology to a wide range from 100
tons biomass per day to 500 ton per day as the technology can find decentralized deployment in
the Indian agricultural heartland not only providing biofuel options for India, but positively
impacting farm revenues for farmers. Creation of jobs, net reduction in import of crude oil and
reduction in carbon emissions, thereby fuelling India's green economic growth engine, so it is a
fantastic technology.
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So, based on the data generated at the 10 tons per day plant basic and detailed engineering has
been carried out for a 450 ton per day rice straw processing plant to produce 100 kilo liter per
day fuel grade ethanol. This plant shall come up and start operations in 2020. The 10-ton
biomass per day plant was scaled up in one go from a 1-ton biomass per day plant. The scale up
went without any hitch and the plant could be operated end to end from size reduction to
fermentation, including all the continuous flow system in a single week.
So, DBT-ICT technology is feedstock agnostic, however as per the biomass availability survey
in Bathinda region rice straw and cotton stalk will be used as raw material in their Bathinda
plant. So, feedstock capacity is 450 tons biomass processing per day.
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Next such commercial adaptation is the biomass technology group BTG. So, here the pyrolysis
has been adapted. Pyrolysis offers the possibility of decoupling, time, place and scale, easy
handling of the liquids and a more consistent quality compared to any solid biomass. With fast
pyrolysis a clean liquid is produced as an intermediate suitable for a wide variety of applications.
BTG's fast pyrolysis process is based on the rotating cone reactor developed by the University of
Twente in Netherlands.
Biomass particles at room temperature and hot sand particles are introduced near the bottom of
the cone where the solids are mixed and transported upwards by the rotating action of the cone.
In this type of reactor rapid heating, and a short gas phase residence time can be realized. The
initial work of the University of Twente has been the basis for BTG to further develop pyrolysis
reactor and the overall process. Since 1993, BTG has been involved in numerous projects on fast
pyrolysis.
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Biomass particles are fed near the bottom of the pyrolysis reactor together with an excess flow of
hot heat carrier material such as sand where it is being pyrolyzed. We have already seen that how
sand can be used as a heat carrier. So, the produced vapors pass through several cyclones before
entering the condenser, in which the vapors are quenched by re-circulated oil.
The pyrolysis reactor is integrated in a circulating sand system composed of a riser, a fluidized
bed char combustor, the pyrolysis reactor and a down-comer. So, these are the parts of the unit.
Now in this concept char is burned with air to provide the heat required for the pyrolysis process.
Oil is the main product, non condensable pyrolysis gases are combusted and can be used as for
example to generate additional steam. Now excess heat can be used for drying the feedstock.
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Two test facilities are available in BTG’s lab, a small unit 2 to 3 kg per hour to enable rapid
screening of potential feedstock and a 100 to 200 kg per hour pilot plant. Due to large amounts
of oxygenated compounds present the oil has a polar nature and does not mix readily with
hydrocarbons. The degradation products from the biomass constituents include organic acids like
formic acid, acetic acid, giving the oil its low pH.
Water is an integral part of the single phase chemical solution. The hydrophilic bio oils have a
water content of typically 15 to 35 weight percent. Again as you know that this depends upon
what feedstock you are using and how much initial moisture content that feedstock is having. So,
typically phase separation does occur when the water content is higher than that of the 30 to
45%.
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So, BTG’s full scale plant takes into account 2 tons per hour fast pyrolysis process and it was
constructed, designed and delivered to Malaysia. In the factory located closely to an existing
palm mill where what they are using actually the empty fruit bunches or you can say the empty
palm fruit bunches are converted into the pyrolysis oil. Usually the wet EFB where the moisture
is about 65% are combusted on-site yielding only ash which can be recycled to the plantations.
The palm mill produces about 6 ton per hour of this wet EFB, empty fruit bunches. So, the empty
fruit bunches can be converted into pyrolysis oil using BTG’s fast pyrolysis technology. Prior to
feeding it to the pyrolysis plant the EFB is further sized and dried. In a dryer the moisture
content is reduced down to about 5 to 10%. In this way, all the wet EFB from the palm is
converted into approximately 1.2 ton per hour pyrolysis oil.
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This is their technology, very simple technology, but nicely integrated, so that the yield of the
pyrolytic oil is very high. You can see this biomass is fed to this circulated sand based reactor
where actually the pyrolysis is happening here. So, the gas or the vapors, what is coming out of
the pyrolysis is being feed to a tower which is basically cooler , where it is the condensable part
is condensed and you get the oil here.
Now what about non condensable gases - that can be collected and burnt. Similarly you can see
that the sand along with the char whatever left out is from the pyrolysis reactor is being fed to
another unit where the sand has been recovered and again can be processed or fed back to the
main pyrolyzer or the pyrolysis reactor. And whatever the gas is still left out that can be fed to
another cyclone, where the ash can be collected. Because of the due to the density difference and
that gas can go to steam production. So, you can see this is a very nice integrated approach.
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So, in Hengelo, the Netherlands a 5 tons per hour pyrolysis plant is planned. This unit will
convert wood into pyrolysis oil, process steam and electricity. The main advantages for the BTG-
BTL’s technology in comparison to other pyrolysis technologies are: high biomass throughput
per reactor volume resulting in compact reactor design. Absence of inert carrier gas resulting in
minimum downstream equipment size.
Maximum calorific value of pyrolysis gas actually, very simple process, no gas cycle required.
High flexibility for feedstocks, so waste material, large particle size, all these feedstocks can be
actually processed. Low amount of solids in the oil.
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The compact design of the modified rotating cone reactor makes scaling up straight forward to
capacities larger than 5 tons per hour. Now BTL standard design includes recovery of excess
heat in the form of steam which can be used for the industrial or local heating applications and
electricity production. Now depending on local conditions, energy efficiencies of 85 to 90% can
be achieved, so that is based on biomass and oil, heat, electricity out.
So, because of the feed flexibility, BTL’s technology can also handle biomasses with low ash
melting temperature, such as palm derived EFB’s. Now BTL’s technology can process particles
with a thickness of up to 3 mm. So, 2 beautiful things about this particular technology is that it
can just like our DBT-ICT 2G ethanol technology. Now this technology also can process
different types of feedstock materials not only different types of feedstock also different size of
feedstock also.
Fluid bed technologies may use similar sized particles, while CFB technology must use smaller
ones as a residence times are limited, CFB with the circulating fluidized bed technology.
So, this is the BTG-BTL plant process flow diagram. So, you can see that wet biomass right
now, once it comes it is being fed to some sort of dryer where air is being used and the moisture
is taken out. So, the biomass is getting dried then it is collected somewhere. Now here there is a
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conveyer system you can see that which is basically taking the biomass up and put it in the
somewhere in the top where there is the feeder.
From here the biomass is slowly fed to the main reactor, here the pyrolysis is happening. Now
from the main reactor, it goes to the separator and air is being fed also here. So, what it is
separating is the sand and char, the solid part. So, the sand and char is being separated and char is
being fed to the char combustor, where the flue gas is being taken away from the top and is being
used for steam generation and some other purposes.
And the oil whatever it is getting converted from here the condensable part that goes straight to
the condenser, where the oil is getting condensed and collected and further processed. So, this is
a simple and nicely integrated technology by the BTG-BTL technology, and the yield is very
high. And as we have already discussed that it can process any type of feedstock as well as
different sizes of the feedstock particles also.
So, the next is again an Indian success story it is about the Praj biorefinery, so Praj second
generation biomass to bioethanol technology which is named as enfinity and biomethanation of
stillage to biogas and renewable CNG, is a beautiful technology which is actually being praised
by most of the western countries also. So, it is located in Pune, Maharashtra, and the plant’s
capacity is 1 million liters per annum.
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The principle feedstocks are rice straw, sugar cane bagasse, wheat straw, corn cobs, corn stover,
cotton stalk and saw dust, and please understand there are many more also, these are the
principle feedstock of course. The feedstock capacity is more than 4000 metric tons per year on a
bone dry basis. So, feedstock supply arranged through local farmers and biomass suppliers from
different parts of India.
Praj’s state of the art second generation ethanol pilot plant facility is operational since 2009. This
facility has tested more than 450 metric ton of biomass such as corn cob, cane bagasse and other
things. Empty fruit bunches, rice straw also has been processed. Rigorous testing and 800,000
man hours of technology development efforts enabled Praj to scale the Enfinity to 1 million liters
per annum capacity.
Multi-product, so the plant is designed to produce bio-ethanol, bio-gas or bioCNG, bio-fertilizer

and there is also provision for production of biochemicals, Iso-butanol to jet fuel. End to end
technology demonstration from feedstock processing till end product and wastewater treatment.
Zero process liquid discharge, that is very interesting actually. Process integration for
optimization of energy and water consumption.
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Efficient pretreatment technology developed after extensive screening, enzymatic hydrolysis
optimized after numerous cocktails. Behavior of different feedstocks were studied by applying
different process treatment. Enzymatic hydrolysis reactor based on CFD modeling studies, the
fermentation process using robust co-fermenting yeast strain was developed. Strain development
involved both classical and targeted techniques for improved yields and titer. Residue which is
rich in lignin used as fuel for boiler to generate steam and electricity.
So, this is Praj’s smart biorefinery concept, so the first generation and second generation it has
both it is taking to account. Molasses, juice, grain, lignocellulosic, municipal solid waste. So, it
goes to the smart biorefinery processing where we get this multiple products such as fuel grade
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ethanol, pharma grade ethanol also, then iso-butanol, biochemicals and bio jet fuel. And left out
can be used as biofertilizers, biogas it can be converted to biogas, bio CNG and lignin cake,
lignin cake can be further pyrolysed also.
So, this is the entire schematic process, this is the business model for their energy production
from biomass. So, the biomass pretreated, pretreated slurry coming to enzymatic hydrolysis, it is
getting fermented, you get purification distillation process, dehydration you get the ethanol,
ethanol is stored here. So, the lignin cake from here the liquid solid separation process can be
processed in this platform. It is a co-generation platform where you can use gasification,
pyrolysis any other things to again generate the power, in a CHP platform module. And that is
you can see the utility of the existing distillery process and the 2G bolt on moduler, here it is
pretreatment, enzymatic hydrolysis. This is hydrolyzed slurry that goes to fermentation process,
so this is a very nice and beautiful technology which was developed by Praj.
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So, the Praj process actually it ensures healthy lives and promote well-being of all at all ages:
Smoke produced due to the burning of the agricultural crop residue deteriorated the human
health, by using residue in the process to produce bioethanol will avoid the burning of crop
residue, resulting in improving air quality and human health, one of the most important aspect.
Second is, they ensure a sustainable consumption and production patterns. It ensures the
sustainable crop production and economical development of the society. Crop residue generated
is going to be consumed by such projects, it assures crop production and its utilization pattern.
Ethanol produced from such projects will also help to meet the demand of ethanol blending
target of the said state.
So, it further ensures access to affordable, reliable, sustainable and modern energy for all. So,
production of ethanol from crop residues and making it available for transport fuel ensures
affordability reliability to the society.
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So, with this I end my today’s lecture. So, if you have any queries please feel free to register
your query in the swayam portal or else you can drop a mail to me at [email protected]. So,
in the next module that is module 6 we will discuss the microbial conversion process, so thank
you very much.
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Module 06
Lecture-16
Types, Fundamentals, Equipments, Applications
Good morning students. Today we are starting module 6, and under module 6 we will be
discussing about the various microbial conversion processes. So, in today’s lecture we will be
discussing different types of microbial conversion processes, then the fundamentals basically
and what are the equipments that are being used for the microbial conversion processes and
few applications. So, let us begin.
So, biochemical conversion processes allow the decomposition of biomass to available

carbohydrates, which could be converted into liquid fuels and biogas as well as different
types of bioproducts using biological agents such as bacteria and enzymes etc. Now, in this
process, various soluble and gaseous metabolites including alcohols, volatile fatty acids,
methane, carbon dioxide and hydrogen can be produced through pure and complex
microorganisms.
Some of the processes that are having tremendous commercial application are anaerobic
digestion, fermentation, microbial fuel cell or microbial electrochemical systems and
composting.
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So, we will see all of these briefly. So, first one is anaerobic digestion. Now, anaerobic
digestion is a multi-step biological process that is useful not only for proper waste
management, but also for generating renewable energy. It consists of 4 basic stages:
hydrolysis, acidogenesis, acetogenesis and methanogenesis. Now, during the whole process,
there are a series of chemical reactions occurring through natural metabolic pathways enabled
by microorganisms in an oxygen free environment.
So, anaerobic digestion means basically, the entire process is happening without oxygen.
Now, these reactions break down the organic macromolecules into simpler molecules,
leading to the generation of biogas. So, biogas basically here, it is a mixture of methane and
carbon dioxide, as well as traces of other gases and digestate.
Now, the feedstocks commonly used for this type of processes include sewage sludge,
agricultural residues, the municipal solid residue and animal manure. Anaerobic digestion can
be carried out at the mesophiclic which is basically from 20 to 45 degrees centigrade, or
thermophilic range from 45 to 60 degrees centigrade conditions.
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Many factors including hydraulic retention time, organic loading rate and substrates can also
affect the fermentation performance. Now, substrates containing excessive inhibitors such as
ammonia, sulphide, metals and organics may make the fermentation process more instable
resulting in a low yield of bio-methane.
Actually, what happens during an anaerobic digestion process? So, when the process is
happening, there are many byproducts that are produced. Now, some of these are actually not
required for that particular environment. So, we can call them that, they are inhibitors or toxic
compounds. Now, what way they are inhibiting basically? So beyond certain limit, if they are
getting produced and again let us say produced and remained in the environment or in the
process equipment itself, then they will hamper the growth of the microorganisms and their
metabolic activities. Now, so, that is not good. So, in any such fermentation process,
including anaerobic digestion, when such type of inhibitory compounds are getting formed, it
is required that these compounds needs to be removed frequently. So, as to maintain their
concentration inside the equipment, at a very small level, so that they are not going to inhibit
the metabolic activity of the microorganisms.
Apart from that, if we go for a short hydraulic retention time, so that might lead to the risk of
wash out of microbial communities. So, retention time basically means how much time the
feed is going to be spent or going to be processed inside a particular reactor. So, a high OLR
that means organic loading rate will boost the acidogenesis stage. So, that means the
feedstock is very much enriched with the organic compound.
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So, if you have a high OLR, so it will boost the acidogenesis stage of easily degradable
substrates and the excessive accumulation of volatile fatty acids may further inhibit the
activity of microorganisms. So, precisely this means that if you have a high organic loading
so there will be faster degradation of the easily degradable substrates, basically during the
acidogenesis stage, which usually results into the volatile fatty acids.
And even though volatile fatty acids are important, but beyond certain limit again, they will
inhibit the activity of the microorganisms. The biogas produced possesses an energy content
of 20 to 40% lower than the heating value of the raw material. Now, the process is ideal for
organic waste with a moisture content ranging between 80 to 90%. One of the advantages of
the process lies in the potential of the final biogas to be used directly in ignition gas engines
and gas turbines.
The overall conversion efficiency of the process is 21%. Residual heat from the engines and
turbines can be recovered through an exchange. So, I told you in the last class or even last to
last class when we were discussing about thermochemical conversion process, I told you that
when any such conversion processes whether it is thermochemical, biochemical or any other
unit operations are going on, so, usually there is some heat generation. Now, that heat
generation even if it is not so high also, if we can harness that heat generation by some waste
heat recovery process and recycle back it to some other unit which requires the heat, maybe
for steam generation, maybe for drying the biomass, then it will be a very good thing or we
can say it will help us in a sustainable bio-refinery approach.
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We will see the reaction steps. The first one is hydrolysis. So, hydrolysis represents the initial
phase of the process. Biomass that consists of very large organic polymers such as fats,
carbohydrates and proteins are converted into smaller molecules such as fatty acids, simple
sugars and amino acids. It should be noted that most of the large molecules are further
decomposed in the acidogenesis stage. On the other hand, other by-products resulting from
the hydrolysis stage including hydrogen and acetate are used in the final stage of the process
that is methanogenesis.
The second step is acidogenesis. Acidogenesis is the second stage of the anaerobic digestion
through which acidogenic microorganisms basically fermentative bacteria, further decompose
the products of the hydrolysis stage producing ammonia, carbon dioxide, hydrogen, hydrogen
sulphide, alcohols, lighter volatile fatty acids, carbonic acid and certain alcohols.
Acidogenesis process only partially decomposes the biomass, therefore for the final
production of methane, the acetogenesis process is required.
Now acetogenesis, this step employs acetogenic microorganisms catabolizing the products
created in a acidogenesis phases into acetic acid CH3COOH, carbon dioxide and hydrogen.
Now acetogens finalize the breakdown process of the biomass facilitating the action of the
methanogenic archaea to produce methane as biofuel.
Then the last step is the methanogenesis. And now this is the final stage of anaerobic
digestion during which as mentioned earlier, methane is generated from the main products of
acetogenesis that is acetic acid and carbon dioxide through hydrogenotrophic methanogenesis
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and/or acetoclastic methanogenesis as given below. So, 2 different types of reactions take
place:
Have a look at this particular slide, this is the basic concept and steps for the anaerobic
digestion process. So, whatever we have discussed it is given in a schematic representation
here. So, the 4 degradation steps that what we just discussed - hydrolysis, acidogenesis,
acetogenesis, methanogenesis. So, doubling time is 1 to 48 hour. This is again the second step
is 1 to 48 hour. Acetogenesis takes more time 9 to 120 hours and methanogenesis is 18 to 120
hours.
So, the polysaccharides, proteins, fats. So, that gets converted to monomers, that again get
converted to fatty acids, lactate, alcohols, acetate, hydrogen, carbon dioxide, formate. So, this
is the methanation step, that is the hydrolysis steps. So, ultimately, we get methane and
carbon dioxide by the final 2 reactions, which we just discussed in the previous slide.
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So, the next is fermentation. So, fermentation is an enzyme catalyzed metabolic process
whereby organisms convert starch or sugar to alcohol or an acid or hydrogen, anaerobically,
releasing energy. Now, fermentation is an anaerobic biochemical process. In fermentation the
first process is the same as cellular respiration, which is the formation of pyruvic acid by
glycolysis where 2 net ATP molecules are synthesized.
So, you can see this scheme, here nicely it is represented. So, that glucose goes through that
glycolysis step and it provides the pyruvic acid, so this is the same as the respiratory cycle.
And here 2 net ATP molecules are synthesized. Now then in the next step pyruvate is reduced
to lactic acid. So, in this step, so pyruvate to lactic acid and ethanol plus carbon dioxide and
other products.
So, here NAD+ is formed which is reutilized back in the glycolysis process. So, you can see
the reaction here and NADH + H+ it gives us NAD+. Now, this NAD+ is again goes back
here that means, whatever it is getting produced here will be consumed in that glycolysis
step.
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So, on the basis of the end product formed, fermentation can be categorized as acid
fermentation, alcohol fermentation and hydrogen fermentation. So, we will see one by one
what are those. Let us first discuss about the acid fermentation. So under acid fermentation
lactic acid fermentation. So, lactic acid is formed from pyruvate produced in glycolysis.
NAD+ is generated from NADH. Enzyme lactate dehydrogenase catalyze this reaction. So,
lactate dehydrogenase is the enzyme that catalyzes this reaction. Lactobacillus bacteria
prepare curd from milk via this type of lactic acid fermentation. Now, during intense exercise
when oxygen supply is inadequate muscles derive energy by producing lactic acid, which
gets accumulated in the cells causing fatigue and all of us have noticed this when we get
stressed up.
So, the muscles basically pain and if you go for a this one some sort of we can say intense
exercise, most of us have felt this lactic acid production and this lactic acid production inside
the muscles actually causes the fatigue and sometimes pain also. So, when we go for a
massage for the muscles, so, it basically it removes or disperses this lactic acid which is
stored in a particular area of the muscles, thereby reducing the fatigue and pain.
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So, the next one is acetic acid fermentation. Vinegar, which is one of the most widely used
product, in the food and beverage and this one restaurant industries is produced by this
process. So, this is a 2 step process. The first step is the formation of ethyl alcohol from sugar
anaerobically using yeast and in the second step ethyl alcohol is further oxidized to form
acetic acid using acetobacter bacteria. Now microbial oxidation of alcohol to acid is an
aerobic process.
So, the next one butyric acid fermentation. Now, this type of fermentation is characteristics of
obligate anaerobic bacteria, genus Clostridium. This occurs in retting of jute fiber, rancid
butter, tobacco processing and tanning of leather. Butyric acid is produced in human colon as
a product of dietary fiber fermentation, it is an important source of energy for colorectal
epithelium.
Sugar is first oxidized to pyruvate by the process of glycolysis. And then pyruvate is further
oxidized to form acetyl coenzyme A by the oxidoreductase enzyme with the production of
hydrogen and carbon dioxide. Now, this acetyl coenzyme A is further reduced to form butyric
acid, this type of fermentation leads to a relatively higher yield of energy, a 3 ATP. We have
seen that in glycolysis, it is 2 ATP, here in this case it is 3 ATP.
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So, the next is alcohol fermentation. So, we have discussed about acid fermentation. So, we
will now discuss about alcohol fermentation. So, this is used in the industrial production of
wine, beer, biofuel etc. The end product is alcohol and carbon dioxide. Pyruvic acid breaks
down into acetaldehyde and carbon dioxide is released. In the next step ethanol is formed
from acetaldehyde.
NAD+ is also formed from NADH utilized in glycolysis. Enzyme pyruvic acid decarboxylase
and alcohol dehydrogenase catalyzes these reactions. So, these are 2 enzymes which are
responsible for doing these reactions. Now, microorganisms commonly used to carry out the
process are Saccharomyces cerevisiae, while the feedstock used for this type of process are
categorized into 3 different classes, sugars, starch and lignocellulosic structures.
In detail the theoretical yield of the processes is 51.14 gram of ethanol and 48.86 grams of
carbon dioxide from 100 gram of hexoses or pentoses. So, this is the reaction:
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So, in addition to ethanol and carbon dioxide glycerol and carboxylic acids are also produced
as by-products. The quality and yields of the process depends on various factors such as
feedstock, temperature, pH, inoculum and fermentation time. The conversion of sugars into
ethanol could take place through different metabolic pathways depending on the starting
substrate.
More specifically from hexoses such as glucose through glycolysis or EMP pathway - the
Embden-Meyerhof pathway and from pentoses through a pentose phosphate pathway, which
is known as PPP pathway. So, the conversion reactions of the hexoses are faster than those of
the pentoses. At the end of the conversion process ethanol is distilled and dehydrated in order
to obtain concentrated alcohol while the solid residues can be used as fuel in boilers for the
production of gas or can be used as feed for livestock.
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So, you can see this particular schematic representation how glucose is getting converted to
pyruvic acid. Pyruvic acid is getting converted to different types of these are here the
different types of organisms are written. And here the fermentation products are written, you
can see the pyruvic acid depending upon the different types of organisms are going to give us
different types of products.
If you are using the Escherichia or Acetobacter we will get acetic acid, that is vinegar.
Pyruvic acid will be converted to lactic acid, Cheese, yogurt, soya sauce further processing, if
we use as Aspergillus, Lactobacillus, Streptococcus, all these organisms. So, pyruvic acid can
be converted to propionic acid, if we use Propionibacterium. So, further if you use
Saccharomyces you will get ethanol plus carbon dioxide, if you use Clostridium, you will get
acetone , isopropanol and butyric acid.
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The next is hydrogen fermentation. Now, hydrogen is a potential alternative energy source
due to its cleanliness and high energy density by mass. It can be produced by various routes
through using different types of microorganisms, including dark fermentation via hydrogen
producing bacteria, photo fermentation via photosynthetic bacteria and direct bio-photolysis
using green microalgae or indirect bio-photolysis using cyanobacteria.
Now, dark fermentation can be considered as a sub process derived from anaerobic digestion,
in which the methanogenesis stage is hindered by the inactivation of the methanogenic
archaea. Now in terms of photo-fermentation and this photosynthetic bacteria, the
photosynthetic bacteria can degrade low molecular weight organics, including sugars,
alcohols and volatile fatty acids to hydrogen and carbon monoxide under an anaerobic
environment.
So, this is more or less similar to the anaerobic digestion process, this particular step. So, the
hydrogen production is a natural response of the cellular need for the releasing of the excess
of electrons and is always coupled with volatile fatty acids and/or alcohol production.
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The stoichiometric yields are 4 moles of hydrogen for each mole of glucose, when acetic acid
is the co-product and 2 moles of hydrogen if butyric acid is produced. So, many times what
happens if you are looking for pure hydrogen production, then you have to suppress the path
to produce butyric acid, we will always go for the acetic acid pathway where we will get
more hydrogen yield per mole of glucose.
In practice the hydrogen yields are within the range of 10 to 20% of the COD the chemical
oxygen demand, which is equivalent to 1.17 to 2.3 moles hydrogen per mole of glucose.
Now, production of dark fermentative hydrogen is a ubiquitous phenomenon that occurs in
most of the anaerobic natural environments. It consists in an obligate cascade of reduction
oxidation or redox reactions that must be kept in balance.
Now dark fermentation can involve any type of organic molecules, glucose being the most
common substructure investigated in literature. Many biological pathways have been
proposed using glucose as model substrate. I will show you the next figure. And photo
fermentative hydrogen production involves the conversion of organic compounds into carbon
dioxide and hydrogen in the presence of light as an energy source with no oxygen evolution.
Photo fermentation can completely convert organic compounds into hydrogen even with a
relatively high hydrogen partial pressure.
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So, this is the pathways for the hydrogen production by dark fermentation from glucose under
anaerobic conditions using mixed cultures. So, let us try to understand, so the glucose that is
getting degraded to this PEP using NAD + and NADH that cycle. So, then it gives to
fumarate and succinate. Now when it comes in the glycolysis pathway, this straight forward
here, so, 2 ATPs are being produced.
So, it is getting converted to pyruvate. Now this pyruvate can be converted to lactate and
again propionate, this is another pathway. Now when we come down here and we go for this
acetyl coenzyme A production. Now this acetyl coenzyme A can further be converted to
acetate to ethanol or butyryl coenzyme A via different, different pathways.
Now Pyruvate formate lyase, which is known as PFL, is the common pathway in the
facultative anaerobes. So, pyruvate-ferredoxin oxidoreductase, which is known as PFOR, is
the common pathway in strict anaerobes. Additional hydrogen production by hydrogenases at
low hydrogen partial pressure less than 60 Pascal is also happens.
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So, next is we will try to understand the basic concepts about the microbial fuel cell or
microbial electrochemical systems. Now, microbial electrochemical systems exploit the
metabolism of microorganisms to bio-electrochemically convert low grade chemical energy
stored in biodegradable substrates to high grade energy, that is electricity and value added
chemicals like hydrogen and methane.
As a rapidly evolving technology, this microbial electrolytic electrochemical system has been
successfully implemented to treat wastewater for electricity generation using microbial fuel
cells, and in bio-refinery facilities using microbial electrolysis cells and microbial
electrosynthesis. Now, specific applications include wastewater treatment, power sources for
remote sensors, research platforms for electrode-bacteria interaction and value added
component production.
Compared with other biological processes, this MES show higher versatility and lower sludge
production making them very promising in practical applications. In many other applications,
if there is a high rate of sludge production, then sludge disposal is an another issue which
needs to be tackled because that sludge has to be properly disposed, otherwise where you will
keep the sludge.
So, that is of course, there are many applications of the sludge nowadays. So, many value
added products are being produced, depending upon of course, the quality of the sludge. The
substrates used in MES can vary greatly from glucose, acetate, lactate and dyes to domestic
wastewater containing complex species.
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Typically, these biodegradable substances are electro-oxidized at the anode via bacterial
metabolism to produce electrons and protons. Then the electrons are conducted to the cathode
and are accepted by oxygen nitrate and metal ions. After decades of research and
development, the performance and stability of MES have approached industry standards. It is
predicted that MFCs can potentially produce 23.3 and 40 terawatt hour of electricity from
wastewater in India by 2025 and 2050 respectively.
So, this is a projection or prediction you can say. The long term operational stability has also
been verified. So Zhang et al installed and operated 2 microbial fuel cells in a municipal
wastewater treatment plant for about 400 days. These 2 microbial fuel cells showed great
durability in the COD removal and fluctuation tolerance, demonstrating the long term
effectiveness of this technology outside the laboratory.
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So, the next important microbial conversion process is composting. Composting is a preferred
and environmentally sound method whereby organic waste is reduced to organic fertilizer and
soil conditioners through biological processes. It involves 3 phases, and uses diverse
microflora such as bacteria, fungi and mesophiclic and as well as thermophilic eventually
converting organic waste to humus.
During the first phase there is an increase in carbon dioxide along with the temperature, the
substrate is reduced due to the degradation of sugar and proteins by the action of mesophiclic
organisms. The second phase leads to an increase of the temperature in the compost piles
from 45 degrees centigrade to approximately 70 degrees centigrade and the mesophiles are
replaced by thermophiles.
Large number of pathogenic individuals are degraded during this time; the third phage begins
with the decrease of the temperature of the compost pile. Various parameters including the
carbon nitrogen ratio, composting temperature, pH of the finished product, moisture content
are important during the composting process.
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Now, let us understand the different equipments, those are essentially required to accomplish
the microbial conversion processes. So, bioreactors, especially are closed bioreactors can
provide the ideal milieu for the microbial growth and metabolism, because why we are
talking about closed bioreactors, because we can easily control all the parameters in a closed
system.
A bioreactor represents the equipment in which biological reactions and microbial cell
reproduction occur using enzymes or living cell as bio-catalyst. Microbial biofuel conversion
is mainly divided into an upstream treatment process that includes fermentation for microbial
growth and product generation and a downstream treatment process that includes product
purification, isolation and collection.
In order to improve energy conversion efficiency, the specifications of the bioreactor should
integrate not only the correct structural configuration, but also precise operational control for
optimized multiphase flow as well as heat and mass transfer in the reaction solution.
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Due to their adaptable operating conditions, bioreactors are widely used in different types of
microbial biofuel conversion processes, such as biogas production by anaerobic digestion,
hydrogen production by photo-fermentation or dark fermentation, alcohol production by
fermentation and fatty acid production by microalgae. During the microbial conversion
processes, microbial cells are sensitive to variations in their surroundings and any instability
is detrimental to their growth and product synthesis.
In bioreactors the environmental parameters there are many. So, some of these are noted here
like temperature, pH, medium composition, retention time, mass and heat transfer rate. So,
this can be maintained at near optimal ranges to enhance microorganism growth and product
accumulation. So, whenever we are going to start a process using a bioreactor and a particular
microorganism, a single strain or a mixed strain and the different types of substrates, you
need to optimize the various process parameters which are written here in the last sentence
and we have just discussed. So, this optimization is required because at that particular
optimized conditions probably will get the highest yield of the product which is your desired
product.
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So, let us now discuss about the bioreactors for anaerobic digestion and their configurations.
Bioreactor design is usually conducted on an experimental basis considering influencing
factors like gas-liquid-gas multiphase flow, mass and heat transfer balance and energy
conversion efficiency. A bioreactor with superior performance requires a watertight structure,
high heat and mass transfer efficiency, good mixing performance, low energy investment and
high product output.
The most commonly used configurations are: convectional anaerobic reactor, such as the
anaerobic sequencing batch reactor, the continuous stirred tank reactor and the anaerobic plug
flow reactor. Then, in the second category it is the sludge retention reactor, such as anaerobic
contact reactor, the up-flow anaerobic sludge bed reactor, the up-flow anaerobic solid state
reactor, the anaerobic baffled reactor and the internal circulation reactor.
And in the third category it’s an anaerobic membrane reactor, such as the anaerobic filter
reactor, the anaerobic fluidized bed reactor and the expanded granular sludge blanket.
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The conventional anaerobic reactor is a single-tank system that utilizes the same tank for
substrate treatment and fermentation. It is the single equipment or the single reactor in which
all sorts of reactions are happening. All steps of microbial biofuels conversion take place in a
single tank, which means that downstream treatment process as well as the intermediate
byproducts can have significant negative influences on the upstream treatment processes
because in a single reactor it is happening.
So, when there is product formation that the amount of product as well as the inhibitory
compounds that form due to certain secondary reactions, they are all retaining in the same
reactor. So, it will further inhibit the growth of the microorganism and even stop the further
reactions. Thus, efficient approaches to avoid the interactive effects of different reactions are
essential to enhance bioreactor performance.
The configuration of sludge retention reactors is relatively complex compared to the

conventional reactors, sludge retention reactors usually contain 2 main components, the
liquid phase reaction module and the solid phase recycling or gathering module.
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Anaerobic membrane reactors are constructed with a supporting membrane to enhance
contact between wastewater and the bacterial microorganism. Now when there is the growth
of this bacterial biofilm. So, it grows on the supporting membrane causing a separation
between the bacterial biomass and the wastewater in the reactor. So, in the anaerobic
fluidized bed reactor inert particles like fine sand and alumina are provided for the thin
bacterial biofilm to grow on. The configurations of anaerobic membrane reactor enhance the
resistance of the microbes to inhibitors, thereby improving biofuel production.
We will see the bioreactor functions. So, in that microbial conversion process bioreactors
provide fine control of operating conditions for microorganisms’ growth, metabolism and
product synthesis thus improving the biofuel production. For example, the pH can be
maintained at suitable levels by adding buffer solutions and the temperature can be controlled
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by a thermostatic water bath or the hydraulic retention time of wastewater can be controlled
by regulating the inward feeding rate.
Now, different structural characteristics are required for different applications of a bioreactor,
for example the leakage resistance of a bioreactor is critical when applied to biogas
production. The function of conventional anaerobic reactors is to supply relatively stable
operating conditions in an established temporal sequence. Owing to its simple structure the
sequencing anaerobic reactor has the advantages of operational simplicity and low cost. The
major function of sludge retention reactor is the recycling of microbial biomass thus,
avoiding biomass washout.
Some configurations of sludge retention reactors can have special functions. For example, in
the anaerobic baffled reactor, the flow patterns of waste influents can be regulated by
arranging the baffles, serving to separate acidogenesis and methanogenesis along the vertical
axis of the reactor and allowing different bacterial communities to develop under
independently suited conditions.
The function of the anaerobic membrane reactor is based on the supporting membrane
material used for microbial biofilm formation, which serves to separate influents from the
microbial biomass. By generating this microbial biofilm biomass washout can be avoided.
So, this is one of the greatest advantage of using a solid membranes. And the microbes have a
longer retention time than hydraulic retention time.
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As a result the mechanical mixing and sludge settling that occur in sludge retention reactors
can be avoided in anaerobic membrane reactors. So, these are very important class of
membrane reactors.
Now, let us understand the influencing factors for the bioreactors for anaerobic digestion.
Reactor size and shape usually influence biofuel output capacity increasing the size of the
container can improve biofuel production to some extent, but can also cause biomass
concentration gradients in the reactors, which further hinders the biofuel production.
Bioreactors operated at low temperature are less prone to thermal instability and degradation.
However, since some thermophilic bacteria prefer high ambient temperatures of up to 65

degrees centigrade, bioreactors must maintain the standard of thermotolerance. Generated
byproducts can dissolve and accumulate in the bioreactor over time inhibiting microbial
growth and metabolism. Thus, in order to maximize the efficiency of microbial biofuel
conversion, bioreactor design must incorporate some mechanism to quickly remove such
byproducts.
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Let us understand the bioreactors for fermentation. So, their configuration. So, bioreactors for
fermentation process are also termed as fermenters. Two types of fermenter vessels are used.
So, the small scales are usually made up of glass and for the industrial purposes, we use
stainless steel. So, glass is non toxic and corrosion proof, it is easy to examine the interior
reaction what is happening inside the vessel.
Sterilization is easily done with the autoclaves. So, these are very small fermenters with a
diameter of around 60 centimeter. Then stainless steel is mostly used for large scale
fermentations, these vessels have the potential to resist pressure and corrosion, the
sterilization is achieved in situ. So, heat in the fermenter vessel is produced due to microbial
activity and agitation.
Temperature in the vessel is maintained by either adding or removing heat from the system.
So, we can have jacketed system. I will show you one of the figure in which we can
understand this. So, thermostatically controlled baths or internal coils of generally used to
provide heat while silicon jackets are used to remove excess heat.
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So, it has doubled silicon mat with heating wires sandwiched between the mats. Now, if the
size is exceeded, resulting in covering the surface by the jacket heat removal is tedious and
then in the internal coils cold water has to be circulated to maintain the exact temperature, it
is always easy if you have an outside temperature control. Now, that is possible only when
you have a smaller reactors or fermenters.
If we have large reactors or fermenters then some inside internal coiling facility has to be
integrated, but that again creates problem for the proper mixing of the fermentation broth.
Then next is sealing assembly. So, it is used for sealing of the stirrer shaft to offer proper
agitation and it can function for a longer period aseptically. There are 3 types of sealing
assembly in the fermenter.
Packed gland seal: so in this the shaft has been sealed with several packing rings of asbestos,
pushed by gland against the shaft. To prevent insufficient heat penetration packing rings have
been regularly checked and replaced. The second one is mechanical seal and the third one is
magnetic drives. So, in the mechanical seal it consists of 2 portion, stationary portion in the
bearing and rotating portion for the shaft. Two parts are pushed together with the help of
springs. Under the magnetic drives, these are again of 2 types of magnets that is driving and
driven magnet, the driving magnet will be seized on the external part of the head plate in
bearing and associated to the drive shaft and another that driven magnet will be located at the
end of the impeller shaft and seized in the bearings on the head plates’ inner surface.
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Now, let us see this particular schematic representation of a usual fermenter, it can be a lab
scale fermenter, it can be industrial scale fermenter. Let us see. So, you can see that this is the
reactor: there is a motor and this is the impeller. This is the impeller; you can see these are the
small plates which are there. So, please understand that impellers there are so many different
types of impeller designs are available, it is not that only this has to be used, this is a
particular design.
Now, what impeller design you will choose that is the job of the engineer or the scientist who
are basically designing the fermenters, that based on what type of substrate you are going to
use inside the fermenter. So, this is about impeller. So, this whatever you were seeing here,
this is an external jacket. So, that job is to remove the heat that is produced inside the
fermenter.
So, how do you do that? So you can send in the cooling water - ice cold water and it will take
away the excess heat what is being produced in the fermenter and not required and you will
get the cooling water out here. So, it will have elevated temperature depending upon what
temperature is there. Now, there is a sparger that is provided. Again I am telling you sparger
there are so many different types of sparger designs are there.
You can use a single nozzle sparger, you can use 10 perforated whole plates, you can use 100
perforated whole plates or you can have different types of designs. Again you have to decide
what is your requirement and whatever you are seeing this is a culture broth then we can have
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baffles. Now baffles are not mandated everywhere, the necessity arises that if baffles are
there the mixing will be good inside this.
So, impeller will be there, it is very slow, it will move very slowly. But if it moves too slow
then the microorganisms will start depositing on the surface of the impeller plates. So, that is
also not correct. So, there are so many other things are there you can see that steam can be
put here. So, that the reason the steam is required to sterilize one particular batch is over, then
you need to sterilize it in the big systems.
Or if it is a small fermenter that glass type, you can take it out remove the heads shaft, motor
and everything and all accessories, take it and put it in autoclave where we can go for
sterilization there. So, baffles are there, impellers, disc turbines, variable pitch open turbine. I
have already told what is the job of baffles and impellers. So, let us move ahead.
So, sparger provides proper aeration in the vessels so that sufficient oxygen is supplied to the
microorganisms for metabolic process. Three types of spargers are used porous spargers,
nozzle spargers and combined spargers and agitator. In the porous spargers these are made up
of ceramic or sintered glass and used in non-agitated vessel on the laboratory scale. Nozzle
sparger has opened or partially open single pipe.
Now, this type of sparger is generally used because they do not get blocked and provide
lower pressure. So, in case of combined sparger and agitator they introduce air by hollow
agitator shaft and release it from the holes of the drill disc to connect to the base of the main
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shaft. When the agitator is operated at the range of RPM, the deliver good aeration in a
baffled vessel.
Then there are feed ports, which are tubes made up of silicon. They are used to add nutrients
and acid/alkali in the fermenter, in situ sterilization is performed before removal or addition
of the product. Then, another very important thing for the fermenters are foam controller.
Now they have 2 units foam sensing and control unit. In the fermenter a probe has been
inserted through the top and set at a distinct level above the broth surface.
Now when the form level rises and touches this probe tip a current will be passed through the
circuit. So, this current will activate the pump and antifoam will immediately be released to
combat that situation, because foaming is not beneficial for the fermentation.
Then different types of valves are used in the fermenter to control the movement of liquid in
the vessel, like globe valve, butterfly valve, ball valve and diaphragm value. Now globe
valves are suitable for general purposes but they do not regulate flow. Butterfly valves are not
suitable for aseptic conditions and are used for large diameter pipes which operate under low
pressure. Ball valves are essentially suitable for aseptic conditions. They handle mycelial
broths and are operated under high temperature. Diaphragm valves help in flow adjustment.
Then apart from that we have safety valves. So, they are built-in in air and pipe layout to
operate under pressure. With the help of these valves the pressure is maintained within the
safe limits.
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Now let us discuss about the types of fermenters. We will quickly discuss about the basics of
the few fermenters which are essentially adapted in the lab scale as well as commercial scale.
There are many types. So, the first one is the continuous stirred tank reactor, then we have
airlift reactor, we have fluidized bed reactor, we have packed bed reactors, we have
photobioreactors, membrane fermenters and bubble column fermemter.
So, we will see quickly all these reactors in a glance. So, the first one you can see the image.
So, that is the stirred tank fermenter the simplest one. So, one of the most conventional
bioreactors is the stirred tank bioreactor used in the lab scale as well as in the commercial
scale also. The core component of the stirred tank bioreactor is the agitator or impeller which
performs a wide range of functions.
So, it does the heat and mass transfer functions that means it helps in enhancing the heat and
mass transfer rate, it does aeration also and it does mixing of the fermentation broth.
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Second one is airlift fermenters. So, these are classic fermenters and are being used in
industrial scale as well in the lab scale also. So, airlift reactor is generally for the gas liquid or
gas liquid solid contacting devices. They have different fluid circulation, which is a definite
cyclic pattern via built channels. Stream of air or other gases provides agitation to the content
inside channels.
The gas stream helps swap over the material between the gas phase and the medium, oxygen
is usually transferred to the liquid. Products formed after the reactions are excreted when the
gas phase is inserted. Two types of airlift reactors are there: one is called the internal loop
you can see the first image and then there is a second one which is called external loop. Now
in the internal loop and in both the systems we have there are 2 things.
First one is called riser column, another is called downcomer. See this riser and downcomer
differentiation you can easily understand in the external loop reactor where the downcomer is
outside the main reactor. And here it is inside. So, you can you can see 2 pipes, big pipes.
One big diameter pipe inside that a small diameter pipe if it is placed like that.
So, the inside one will be the riser through which the flow is basically happening like this and
then it is coming. It is a circulating flow like this. And when it is in outside that is the external
loop airlift reactor, most of the reactions are happening in the riser section and this is what
helps in a proper heat and mass transfer rate as well as to maintain the microorganism
growth. And some other activities like that you can talk about the HRT, OLR and all these
things.
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So, the next is bubble column fermenter. So, these are very classical reactors, which are used
in many chemical, petrochemical and biochemical industries. Now, these reactors are simple
in construction, they are easy to maintain and they have low operating costs. So, these are
cylindrical in shape with a ratio of 4 is to 6 : height to diameter ratio basically and at the base
of the column air or gas is introduced via perforated pipes or plates or metal microporous
sparger.
So, you can see that, so, this is a column it is a big column, it can be made up of a glass, it
can be made up of perspex, it can be any other material also. So, here there is a sparger that is
provided – multiperforated/multiple hole sparger you can see, you can use different types of
sparger also. So, gas is being passed through like this and through this particular sparger the
gas will be pushed through and when it will come in contact with the fermentation broth, it
will result in small, small bubbles.
Now, the concept in the entire the bubble column is that how the bubbles are getting created.
The size that matters, and how they are getting coalesced with each other because bubbles has
a tendency to coalesce with each other, so they will form a small to big bubbles. Now these
big bubbles under agitation, mechanical agitation or any sorts of agitation inside the
fermentation broth will again be ruptured into smaller bubbles.
So, what is the idea is that it is a continuous generation of bubbles, coalescence and again
break down into smaller bubbles will create high mass transfer area. So, that is the basic
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concept in the bubble column reactor. So, flow rate of air or gas is maintained accurately so
that the proper oxygen transfer or mixing is achieved. Perforated plates are attached in the
fermenter to improve the performance of the reactor.
So, the next is packed bed fermenter. Now, packed bed fermenter reactors are also called as
fixed bed reactors, which are used in many chemical processing applications like absorption,
distillation, stripping, separation processes and catalytic reactions. It consists of partition like
tube or channel which has catalytic particles of pellets on to which liquid flows through the
catalyst.
Chemical composition of the substance gets altered when the liquid reacts with the catalyst.
This reactor has many advantages as its conversion rate is high for the catalyst, easy to
manage and build, more efficient contact between reactant and catalyst is made compared to
other types of reactors, product formation is more due to the increased contact of
reactant/catalyst. Please understand, if this is only one of the reactor in which there is
intimate contact between the reactant and the catalyst.
So, the entire amount of the catalytic surface will be covered with the reactants, so, that there
will be more product formation. So, these reactors work effectively even on high
temperatures and pressures.
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So, the next is another class of fermenters which are also industrially used and adapted. So,
are called fluidized bed fermenters. Now, design of the reactor must be proper so that fluid
flow rate is sufficient to suspend the catalyst particles. So, catalyst is laid on the bottom of the
reactor and the reactants are pumped into reactor via distributor pump to make the bed
fluidized.
If the reactant is liquid then bed expands uniformly and make homogeneous fluidization and
if it is gas then bed expands non uniformally to make aggregative fluidization. During this
whole process the reaction between the reactant and catalyst led to the formation of new
products which are retrieved continuously during the course of time.
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So, the next is photobioreactors. So, the main application of photobioreactors are in
photosynthetic processes involving vegetable biomass growth or microalgae growth under
restricted conditions. Now, the introduction of more complicated cultivating methods of
microalgae with higher production value and capable of providing sterile conditions which is
accessible by different types of close photobioreactors applied outdoors.
So, here whatever you are seeing now. So, in general, if you talk about the laboratory scale
photobioreactors they are artificially illuminated because we need to provide light for the
photosynthesis. So, here whatever you are seeing, so, this is an image of a (open/outdoor)
raceway pond. These raceway ponds can also be constructed in-house where we can supply
this one artificial lighting.
But this is an open to atmosphere and open to sunlight raceway pond. Now, these are plate
type algal photobioreactor, these are tubular photobioreactors. Now, here this, this and this,
these 3 are closed systems. So, as I told you that during this discussion this closed systems
are always good because we can easily control the different process parameters inside a
closed system and they are not susceptible to any other infectious bacteria, virus or this such
environmental problems.
Whereas this type of raceway pond are always susceptible to environmental conditions -
sometimes rains, let us say the rain happens it will immediately increase the amount of the
broth inside the reactor. So, everything gets diluted, which is not happening here and here and
here. Now, this is easy to maintain, the cost is low. However, these are initially very costly
processes, but once you have this, so then you can maintain it easily and control it easily. So,
that the yield will be better.
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So, next is these are latest development in the environmental and energy sites actually the
membrane bioreactors. So, it basically combines traditional treatment with filtration via
membranes, resulting in the removal of organic and suspended solid matters that are also
removes high level of nutrients. Now, membrane bioreactor systems are submerged in an
aerated biological reactor. The pore size of the membrane ranges from 0.035 microns to 0.4
microns.
Membrane bioreactor system is widely used in treatment of wastewater from several sources.
However, membrane fouling is a chief obstacle to the extensive application of membranes.
So, you can see here 2 different images are there. So, here what is happening the membrane is
outside. So, this is the bioreactor. So, membrane is used as separate. This is a 2 different unit
operations; bioreactors, here everything is happening all the reactions, product formation,
then you need to remove product and other value added products or inhibitory compounds
use a membrane reactor. So, it will remove the effluent and the retentate can be recycled.
This is one system.
In another system where we have this activated sludge ponds and such type of units the
membrane bioreactors can be directly placed inside the aerobic ponds. So, it has its own
advantages and disadvantages, this has its own advantages disadvantages. This is easy to
control. Here the clogging and concentration polarization can be an issue, if we are putting it
directly inside - because microorganisms will start growing on the surface of the membrane.
So, there are issues into that but both are used.
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So, then we will talk about the bioreactors for microbial fuel cell and microbial electrolysis
systems their configurations. At the heart of an MES lies the bioreactor where biodegradable
substrates are converted to electrical current. The current is utilized directly in the MFCs or
conducted to the cathode for further reaction in case of the MECs.
Now, therefore, the performance of an MES is dictated by the performance of the bioreactor
within where scientific disciplines like microorganism ecology, biomaterial science,
mechanical engineering and control strategy meet multiphysics phenomena like biofilm
formation, multiphase flow, heat and mass transfer and bioelectrochemical conversion
complicated systems.
So, many different types of parameters needs to be controlled and taken care of. A typical
MES consists of 2 chambers the anode chamber for electron production and the cathode
chamber to close the circuit and the yield of the final products. MES have evolved from
typical 2 chamber configurations to single chamber and hybrid designs. Novel modes of
operation like the up-flow mode have also been developed.
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In a 2 chamber MES aqueous and gaseous substrates are bioelectrochemically degraded to
produce electrons in the anode, these electrons are transferred to the cathode resulting in
electricity production or product generation. Liu et al demonstrated the first single chamber
MFC in which atmospheric oxygen can passively diffuse into and react with the porous
hydrophobic cathode.
Plain anode and cathode can also be used to form a single chamber MES bioreactor. Single
chamber MFCs are capable of treating wastewater with a high concentration of nitrogen,
although ammonia inhibition was still observed. So, ammonia whatever is getting produced,
if it is again produced a certain amount which is beyond a tolerable amount then it will
suppress all the metabolic activities.
So, the maximum power density decreased from 6.1 to 1.4 watts per meter cube when TAN
concentration increased from 3500 to 10,000 milligrams per liter. So, TAN is the total
ammonia nitrogen. So, one concern for the single chamber MFC is that a large percentage of
the organic substrate is lost without contributing to the electricity production.
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From a geometric perspective, both the single and double-chamber MESs can be engineered
to form a tubular configuration. Now, this configuration is considered very promising due to
increased sludge rentention time and reduced hydraulic retention time. Tubular MESs can be
readily integrated to fit into existing facilities. Ye et al developed tubular 2 chamber MFCs
using PMMA (polymethyl Methacrylate) tubes of different diameters; the inner tube and
interspace served as the anode and cathodic chambers (respectively).
Five of these MFCs were integrated into a sink drainpipe for kitchen wastewater treatments.
It is a very nice work. I have referred it down. Please read if you wish to read and learn more
on this particular technology.
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So, these are the configurations of the microbial electrolytic systems. So, the first one
whatever you are seeing, this this schematic and prototype of the first single chamber MFC.
So, it is a very simple system. And the second one, where it says a single chamber MFC with
a plain anode and a cathode. So, this is the cathode here, Air cathode this is the anode here,
you can see the organic matter and microorganisms start depositing on the surface of the
anode.
In the third one so, it is a tublar 2 chamber MFC. Here in this case the 5 MFCs were
connected to form a stack and integrated into a sink drain pipe. You can set the cascading
basically or multistging.
Now, let us understand the system integration of the bioreactors for MFCs and MES. So, the
output of a single bioreactor is usually insufficient for most of the applications. One
promising approach to this problem is to combine several bioreactors to form a stack, which
improves productivity and efficiency. For example, several MFCs can be hydraulically and
electrically connected to form an MFC stack.
This approach does not affect the columbic efficiency of individual fuel cells, but can
increase the total power output and COD removal efficiency. Ledezma et al demonstrated the
first self sustained MFC stack that is not only self sufficient in terms of feeding, hydration,
sensing and reporting, but can also produce sufficient net power output to run peristaltic
pumps.
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So, peristaltic pumps are required to feed different types of materials, whether it can be your
substrate, whether it can be different types of nutrients, even supplying buffers also. MFC
configuration as well as the hydraulic and electric connections in stacked MFCs have to be
properly engineered to avoid short circuiting and to fulfill the requirements of the desired
application.
One major challenge for MFC stacks is voltage reversal. When one or more MFCs reverse
polarity. So, this results in severe deterioration of the MFC system as a whole. Capacitors can
be integrated into a serially connected MFC stack to accumulate charge, which should
prevent voltage reversal and enhance power output. So, bioreactors do not serve as stand-
alone devices, they need to be integrated with other MES and even other energy systems for
maximum performance and energy efficiency.
In a classical study Liu et al proposed an integrated MFC-SBR (SBR is sequencing batch

reactor) for the activated sludge process. The MFC was submerged inside this SBR, synthetic
wastewater was fed to the MFC first and the resulting effluent was processed by the SBR.
The oxygen for the aeration process was shared by the MFC biocathode to further recover
electrical energy and reduce the cost of operation.
MESs can also be coupled to renewable energy sources like solar, wind and geothermal
energy to maximize the energy production of the entire system.
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With this I conclude today's lecture. In our next lecture, we will be discussing about the
details of the various microbial conversion processes. So, if you have any query regarding
this lecture, please feel free to post your query in Swayam portal or drop a mail to me at
[email protected]. Thank you.
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Module 06
Lecture-17
Details of Various Processes
Good morning students, today is lecture 2 under module 6. As you know that we are
discussing various microbial conversion processes and in the last class we have discussed in
brief the different processes and different types of equipments and the products under that
lecture. So, in today's class we will be basically discussing about the processes in little detail
- anaerobic digestion and fermentation. So, let us begin anaerobic digestion.
Anaerobic digestion is a series of biological processes in which complex organic materials

are broken down into their simpler chemical components by various microorganisms without
the presence of oxygen. It is a multi-step biological process that is useful not only for proper
waste management but also for generating renewable energy like various types of biofuels. It
consists of 4 basic stages hydrolysis, acidogenesis, acetogenesis and methanogenesis.
During the entire process there are series of chemical reactions occurring through natural
metabolic pathways enabled by microorganisms in an oxygen free environment. Now these
reactions break down the organic macromolecules into simpler molecules leading to the
generation of biogas which is a mixture of methane, carbon dioxide and traces of other gases
like hydrogen and carbon monoxide.
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And apart from that the digestate or the solid part. So, the feedstocks that are commonly used
in this type process include sewage sludge, agricultural residues, municipal solid residue,
animal manure and there can be many other feedstocks also.
Now the process is ideal for organic waste with a moisture content ranging between 80 to
90%. One of the advantages of the process lies in the potential of the final biogas to be used
directly in ignition gas engines and gas turbines. The overall conversion efficiency of this
process is 21%, residual heat from the engines and turbines can be recovered through an
exchanger. Now the process can be summarized in 4 main stages.
First is hydrolysis. So, in hydrolysis the complex organic materials for example proteins,
lipids and carbohydrates - they are broken down into low molecular weight compounds such
as amino acids, fatty acids and simple sugars. Under acidogenesis the acidic bacteria promote
a process of fermentation producing the volatile fatty acids. Apart from volatile fatty acids
there are alcohols, hydrogen and carbon dioxide also get produced. Then acetogenesis, here
acetic acid, carbon dioxide and hydrogen are formed from the volatile fatty acids by acid
forming bacteria, they are known as also acetogens. And in the last which is the most
important step is the methanogenesis, here the methanogenic bacteria continue the
consumption of the volatile fatty acids and produce the methane gas.
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We will try to see in a nutshell - if you recall last class I have shown you one sketch, here this
is little in an elaborate way it is being presented. So, let us quickly glance through it. So, the
first step is hydrolysis here. The organic materials you can call them, group them and term
them as biopolymers - they are getting converted under lipids, carbohydrates and proteins to
various routes.
If you look at the first route the lipids are getting converted to LCVFA- the low carbon
volatile fatty acids and glycerine. Now that can be converted to organic intermediates and
alcohols, lactic acid - further to acetic acid by the step 2 and step 3. So, up to this. Now
carbohydrates can be converted into mono and disaccharides and then they also can be
converted either into organic intermediates or inorganic intermediates.
Similarly, the proteins get converted to polypeptides and again peptides and then again these
peptides can be converted to either organic intermediates or inorganic intermediates. Now
please understand that when I am telling that this conversion is happening it depends upon
what type of microorganism is being present and what they are converting. So, that is the
most important thing apart from other things.
Now before you come to the last one which is called the methanogenesis. So, you can see that
methanogenesis can happen via 2 different routes, one is this acetate route - acetic acid route,
another is the carbon dioxide and hydrogen route. So, either acetic acid can convert to
methane and carbon dioxide via this reaction or the carbon dioxide plus hydrogen can be
converted to methane plus water.
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So, please understand that the final reaction again proceeds mostly by the methanogens via 2
different routes. Now if we use the acetotropic methanogens - so mostly this is for the 70% of
the methane that is getting produced, this is the route, then we get the acetate route. And if we
are using the hydrotropic methanogens then the next 30% of the entire methane that is being
produced is coming from this particular route. So, the entire scheme is again presented there
in a very a brief way.
So, now we will try to understand the microbiology of the entire anaerobic digestion process.
So, let us first talk about the general scheme. So, 3 different forms of bacteria are active
during the AD process. So, they are fermentative bacteria, they are acetogens and
methanogens. So, these are the main microflora which are responsible for the entire anaerobic
digestion process for different reactions.
Now the hydrolyzing and fermenting microorganisms are responsible for the initial attack on
polymers and monomers found in the waste material and produce mainly acetate and
hydrogen, but also varying amounts of volatile fatty acids such as propionate and butyrate as
well as some alcohols. Now the obligate hydrogen-producing acetogenic bacteria convert this
propionate and butyrate into again acetate and hydrogen. So, 2 groups of methanogenic
archaea produce methane from the acetate or hydrogen respectively.
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So, this is again we will try to understand. This is a schematic representation of how the
carbon is flowing in the anaerobic environment with methanogen. So, this is for with
methanogens and this is without methanogen. So, let us try to understand what is happening
with the methanogens. So, when the complex organic materials are getting degraded in the
presence of methanogens then 3 things will happen.
So, usually if you see this particular route from this side the left side, you can see 51% is
getting converted through this route. So, the organic materials are degraded to acetate, acetate
is degrading to methane. So, as I told you 2 slides before that the 70% of the methane that is
produced from the anaerobic digestion comes via this route - acetate. Apart from that 51%,
30% is again converted to propionate and butyrate, which are further again converted to
either acetate or hydrogen and carbon dioxide depending upon the process condition as well
as depending upon the type of microorganisms present. And the next 19% is directly getting
converted to hydrogen and carbon monoxide and this 30% of the entire methane that is
getting produced coming via hydrogen plus carbon dioxide reaction. Now this entire scheme
is when the methanogens is present.
Now when methanogens are not present then what is happening to the carbon cycle? So, here
the complex material are getting converted to acetate, intermediates and hydrogen and carbon
dioxide in various of course percentage and further processing is not happening because there
are no methanogens available which will degrade these compounds into methane and carbon
monoxide.
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Now this scheme we have understood; now we will go ahead and try to understand in a gist
that what the scheme is all about. So, the major part of the carbon flow in a well operating
anaerobic reactor occurs between the fermentative microorganisms and the methanogens.
Only between 20 to 30% of the carbon is transferred into intermediary products before these
are metabolized into methane and carbon.
So, this is what I have shown you - the intermediate products are propionate, butyrate etc.
Now again these will be converted either to acetate or hydrogen and carbon dioxide route.
Before finally being converted to methane. Now a balanced anaerobic digestion process
demands that, the products from the first 2 groups of microbes responsible for hydrolyzing
and fermenting the material to hydrogen and acetate, simultaneously are used by the third
group of microbes for the production of methane and carbon dioxide. So, this is very
important. Now the first group of microorganisms can survive without the presence of
methanogens but will under these conditions form an increased amount of the reduced
products such as volatile fatty acids. The second group does however rely on the activity of
methanogens for removing hydrogen to make their metabolism thermodynamically possible
as their reactions are endergonic under standard conditions and only occurs when the
hydrogen is kept below a certain concentration. Now endergonic reactions are such reactions
in which the heat is actually absorbed. So, the net change of free energy is always positive.
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The relationship between the volatile fatty acid degrading bacteria and the hydrogen utilizing
methanogens is defined as syntrophic due to the dependent nature of this relationship and the
process is called interspecies hydrogen transport. Now syntrophic is a process or we can say
that it is a technique by which even the microorganisms especially in such anaerobic
digestion process coexist.
So, in this process let us say there are 2 different types of microorganisms are present in a
syntrophic relationship; then basically they are syntrophic because they are co-feeding each
other. So, the products are generated by one microorganism is being consumed by the other
microorganisms. So, they are interdependent on each other, they are not actually parasite,
they are interdependent and both are actually feeding on the products of each other. So, the
interspecies hydrogen transfer actually affects the entire carbon cycle - I have mentioned
here.
So, methanogens can participate in the interspecies hydrogen transfer combining hydrogen
and carbon dioxide to produce methane. So, besides methanogens, acetogens and sulphate
reducing bacteria can also participate in the IHT. So, the lower the hydrogen concentration,
better are the thermodynamics of the volatile fatty acid degradation. So, the distance between
the VFA degrader and the hydrogen utilizer that eventually affects the thermodynamics of the
process.
Therefore, the conversion is improved in granules and flocks compared to a situation where
the microbes are distributed freely in liquid solution. Essentially what is the meaning of that?
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Microorganisms are grown in granules and flocks and when they are suspended freely in the
liquid solution without forming flocks, the entire thermodynamics inside the process and the
hydrogen utilization, actually the IHT is getting affected.
Two partners have to share a very small amount of energy and the conditions for ensuring
energy for both microbes is very strict and can only be met within a narrow range of
hydrogen concentrations.
So, this is a schematic representation of the biomass anaerobic digestion scheme. It is a

general representation. So, you can see just we will quickly glance. So the biomass, it has to
be pre-processed - so you may have to sometimes chop it - mechanical pre-processing, then
you can go for some slight thermal pre-processing where you remove moisture and all.
Bring them to a desired particle size and bring them to a desired moisture content before you
feed them to the digester. Then they are made into slurry. Now you do not dump the entire
solid biomass under the digester. So, you usually make them into a slurry. This slurry goes to
the digester. Now here the anaerobic digestion is happening, so you have to give inoculum, if
required, you have to supply certain other micro nutrients or nutrients and maintain the
proper temperature inside the digester so that the anaerobic digestion happens. And it’s
strictly anaerobic process - dark fermentation. Now once the process starts happening, slowly
you will see that day 3, day 4, day 5 and after that so biogas will start coming. Now this
biogas whatever will come will be collected in a biogas storage vessel. From here you can
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either convert it to liquid fuels by compressing it or you can send it to the gas turbine system
where you can generate electricity directly.
And whatever left out here - the digestate or semi solid type of with having some moisture in
that - it can go to a separator where you get the filtrate liquid, this also can be converted to
some other value added products and then the fiber or solid again we can process it under
thermochemical conversion process or you can use as cattle feed and some other value added
products.
The second thing is that, this is what we talked about with the general scheme. Now we are
discussing about the syntrophic acetate conversion process. Now the syntrophic relationships
have also been found to be importance for the conversion of acetate when the acetate
degrading methanogens are inhibited by concentrations of ammonia or sulfite. So, we
discussed syntrophic for the IHT - interspecies hydrogen transfer.
Now we are discussing that, syntrophic relationship also having some importance when we
talk about acetate conversion. Now under these conditions the acetate utilizing methanogens
are inhibited and other groups of microbes replace them to obtain energy from the oxidation
of acetate to hydrogen and carbon dioxide. Due to thermodynamic constants this reaction
proceeds much better at increased temperatures and is the way of acetate transformation
when the temperature is usually higher than the 60 degree centigrade.
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So, that is the upper limit of the thermophilic acetate utilizing methanogens. So, in
accordance to this, the population of Methanosarcina species which is one of the methanogen
species disappeared more or less instantaneously from a biogas reactor operated on manure
when the temperature was increased from 55 to 65 degree centigrade. Now concurrently the
acetate concentration first increased and then stabilized at a level somewhat higher than that
found in the 60 degree centigrade.
So, clearly telling us that beyond 60 degree centigrade some of these thermophilic activities
are happening and the acetate utilizing methanogens are inhibited.
So, this coincided with a significant increase in the population of hydrogen utilizing
methanogens indicating that this group had become dominant in the overall conversion. So,
there will be more hydrogen production. When the concentration of acetate is low, syntrophic
acetate conversion is the major process for acetate transformation. However, when the
concentration of acetate is above the threshold level for the specific population of acetate
utilizing methanogens in the reactor, these will be the major group active in the system.
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The next is enzymatic ability to degrade substrate. Now bacteria degrade substrate through
the use of enzymes. Enzymes are proteinaceous molecules that catalyze biochemical
reactions. Two types of enzymes are involved in the substrate degradation: endoenzymes and
exoenzymes. Now a large and diverse community of bacteria is needed to ensure that proper
types of exoenzymes and endoenzymes are available for the degradation of the substrates
present.
The relative abundance of bacteria within an aerobic digester often is greater than 1016 cells
per millilitre. This population consists of a saccharolytic bacteria, proteolytic bacteria,
lipolytic bacteria and methane-forming bacteria. So, the table below gives an understanding
about that substrates to be degraded, different types of exoenzyme that is required and
examples.
Now we can see one case. Let us see the first one, the polysaccharides. So, this is the
substrate that is getting degraded and the exoenzyme you need to degrade this substrate is
saccharolytic exoenzyme. An example is cellulase. Cellulase is exactly it is the enzyme, that
will do the degradation and the bacterium that is required is the Bacillus species, the
Cellulomonas species and the product will be the simple sugar. So, similarly it is there for
proteins and lipids which will be converted into amino acids and fatty acids by Bacillus and
Mycobacterium species.
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Next is acetate forming bacteria. Acetate forming bacteria or acetogenic bacteria grows in a
symbiotic relationship with methane forming bacteria. Acetate serves as a substrate for
methane forming bacteria. For example, when ethanol is converted to acetate, carbon dioxide
is used and acetate and hydrogen are produced. So, this is the reaction:
When acetate forming bacteria produce acetate hydrogen is also produced. If the hydrogen
accumulates and significant hydrogen pressure occurs, the pressure results in the termination
of activity of acetate forming bacteria and loss of acetate production. So, this has to be
controlled in the fermenters. However, methane forming bacteria utilize hydrogen in the
production of methane and significant hydrogen pressure does not occur:
Acetate forming bacteria are obligate hydrogen producers and survive only at very low
concentrations of hydrogen in the environment, they can only survive if their metabolic waste
that is hydrogen is continuously removed or consumed by other microflora. Now this is
achieved in their symbiotic relationship with hydrogen utilizing bacteria and/or methane
forming bacteria.
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So, the next is sulphate reducing bacteria. So, SRB are also found in anaerobic digesters
along with acetate forming bacteria and methane forming bacteria. If sulphates are present,
then SRB such as Desulfovibrio disulfuricans multiply. So, this is one type of sulfate
reducing bacteria. Their multiplication or reproduction often requires the use of hydrogen and
acetate the same substrates used by the methane forming bacteria methanogens.
When sulfate is used to degrade an organic compound, sulphate is reduced to hydrogen

sulfide. Hydrogen is needed to reduce sulfate to hydrogen sulphide. The need for hydrogen
results in competition for hydrogen between 2 bacterial groups SRB and MFB. When SRB
and MFB compete for hydrogen and acetate, SRB obtain hydrogen and acetate more easily
than MFB under low acetate concentrations.
At substrate-to-sulfate ratios less than 2, SRB out compete MFB for acetate and at substrate-
to-sulfate ratios between 2 and 3, competition is very intense between the 2 groups and when
substrate-to-sulfate ratio is greater than 3, the methanogens are favoured.
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So, the hydrogen sulfide produced by SRB has a greater inhibitory effect at low
concentrations on MFB and acetate forming bacteria than acid forming bacteria. This is one
of the simple representation scheme that how the sulphate reducing bacteria and methane
forming bacteria are surviving in a synergistic relationship between them - symbiotic. So, you
can see that the sulphate is being reduced by the sulphate reducing bacteria to hydrogen
sulfide.
And they are also consuming the hydrogen and acetate that is getting produced from the
methane forming bacteria, as we have understood, then beyond certain limits of the hydrogen
inside the fermenter or anaerobic digester the methane forming bacteria will cease to do their
methanogenic activities. So, the hydrogen has to be continuously removed. Now in this
symbiotic relationship the hydrogen is getting consumed by the sulphate reducing bacteria to
hydrogen sulfide and the level of hydrogen is maintained in such a way that the
methanogenesis reaction is getting favoured.
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So, next is methane forming bacteria. MFB are some of the oldest bacteria and are grouped in
the domain Archaeabacteria. MFB are oxygen sensitive, fastidious anaerobes and are free
living terrestrial and aquatic organisms. Coenzymes that are unique to MFB are coenzyme M
and the nickel containing coenzymes F 420 and F 430. Coenzyme M is used to reduce carbon
dioxide to methane.
The nickel containing coenzymes are important hydrogen carriers in the methanogens. So,
MFB obtain energy by reducing simplistic compounds or substrates such as carbon dioxide
and acetate. MFB grow as microbial consortia, tolerate high concentrations of salt and are
obligate anaerobes. MFB grow well in aquatic environments in which strict anaerobic
condition exists.
The anaerobic condition of an aquatic environment is expressed in terms of it ORP or which

is called the oxidation reduction potential. MFB grow best in an environment with an ORP of
less than - 300 millivolt. Most facultative anaerobes do well in aquatic environments with
ORP between + 200 and - 200 millivolt. So, facultative anaerobes are a group of
microorganisms which do actually their metabolic activity in the presence of oxygen.
But when we deplete oxygen and they can also go for their metabolic activity without the
presence of oxygen also. So, they are that is why called facultative anaerobes.
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The reproductive times or generation times for MFB range from 3 days at 35 degrees
centigrade to 50 days at 10 degree centigrade. Because of the long generation time of MFB
high retention times are required in an anaerobic digester to ensure the growth of a large
population of MFB for the degradation of organic compounds. At least 12 days are required
to obtain a large population of MFB.
MFB obtain their energy for reproduction and cellular activity from the degradation of a
relatively small number of simple substrates including hydrogen, 1 carbon compounds and
acetate as the 2 carbon compound. 1 carbon compounds include formate, methanol, carbon
dioxide, carbon monoxide and methylamine. Other one carbon compounds that can be
converted to substrate for MFB include dimethyl sulfide, dimethylamine and trimethylamine.
Several alcohols including 2-propanol and 2-butanol as well as propanol and butanol may be
used in the reduction of carbon dioxide to methane.
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The most familiar and frequently acknowledged substrates of MFB are acetate and hydrogen.
Acetate is commonly split to form methane while hydrogen is combined with carbon dioxide
to form methane. So, these reactions we have seen many times, again it has been just reported
here for the easy understanding and to maintain the flow.
So, each methane forming bacterium has a specific substrate or group of substrates that it can
degrade. So, you can see here there are only 5 methanogens are being listed, there are many
others. So, if you see the first one the Methanobacterium formicicum. So, what it does, its
substrate is carbon dioxide, formate and hydrogen. If you talk about the last one
Methanosarcina bakerii, so for it the substrate is acetate, carbon dioxide, hydrogen, methanol
and methylamine.
Now there are 3 principal groups of methane-forming bacteria. So, these groups are
hydrogenotrophic methanogens, acetotrophic methanogens and methylotrophic methanogens.
Broadly grouped into 3 different types.
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Let us see the hydrogenotrophic methanogens. The hydrogenotrophic methanogens use
hydrogen to convert carbon dioxide to methane. By converting carbon dioxide to methane
these organisms help to maintain a low partial hydrogen pressure in an anaerobic digester that
is required for the acetogenic bacteria to do this reaction:
Now the acetotropic methanogens split acetate into methane and carbon dioxide. The carbon
dioxide produced from acetate may be converted by hydrogenotrophic methanogens to
methane. Some hydrogenotrophic methanogens use carbon monoxide also to produce
methane. So, this is the reaction:
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So, the acetotropic methanogens reproduce more slowly than the hydrogenotrophic
methanogens and are adversely affected by the accumulation of hydrogen. Therefore, the
maintenance of a low partial hydrogen pressure in an anaerobic digester is favourable for the
activity of not only acetate-forming bacteria, but also acetotrophic methanogens. Under a
relatively high hydrogen partial pressure acetate and methane production are reduced.
Now let us talk about the methylotrophic methanogens. The methylotrophic methanogens
grow on substrates that contain the methyl group CH3. Examples of these substrates include
methanol and methylamines. Group 1 and group 2 methanogens produce methane from
carbon dioxide and hydrogen, whereas group 3 methanogens produce methane directly from
the methyl groups and not from the carbon dioxide.
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So, the use of different substrates by MFB results in different energy gains by the bacteria.
For example hydrogen consuming methane production results in more energy gain for
methane-forming bacteria than acetate degradation. Although methane production using
hydrogen is the more effective process for energy captured by methane forming bacteria, less
than 30% of the methane produced in anaerobic digester is by this method only.
Approximately 70% of the methane produced in an anaerobic digester is directly derived

from the acetate pathway. The reason for this is the limited supply of hydrogen in an
anaerobic digester. So, the majority of the methane obtained from acetate is produced by 2
genera of acetotrophic methanogens that is Methanosarcina and Methanothrix.
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Now we will discuss about the fermentation process in a bit more detail than what we
discussed in our last lecture.
So, the term fermentation was first used by Louis Pasteur to define respiration in the absence
of free molecular oxygen. Fermentation can be broadly defined as respiration that occurs in
the dark and not involve the use of free molecular oxygen or nitrite ions as the final electron
acceptors of the degraded organic compounds. Therefore, respiration may occur through
several fermentative pathways including sulfate reduction, mixed acid production and
methane production.
Fermentation is a form of anaerobic respiration. The bacteria that perform fermentation are
facultative anaerobes. So, I have already explained what is facultative anaerobes.
Fermentation involves the transformation of organic compounds to various inorganic and
organic products. During fermentation a portion of an organic compound may be oxidized
while another portion is reduced.
It is from this oxidation-reduction of organic compounds that fermenting bacteria obtain their
energy and produce numerous simplistic and soluble organic compounds.
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Fermentative bacteria are capable of performing a variety of oxidation-reduction reactions
involving the organic carbon dioxide, carbon monoxide, molecular hydrogen and sulfur
compounds. Fermentative bacteria include facultative anaerobes, aerotolerant anaerobes and
strict anaerobes. Some fermentative bacteria such as Clostridia and Escherichia coli produce
a large variety of products, whereas other fermentative bacteria such as Acetobacterium
produce a very small number of products.
As environmental and operational conditions change for example the pH and temperature the
bacteria that are active and inactive also change, because the environment has a huge effect
on the different types of microorganisms. These changes in activity are responsible for
changes in the types and quantities of compounds that are produced through fermentation. Let
us see these 2 small tables are listed here.
The first one is the fermentative products of Clostridium species. You can see that organic
products like acetate, acetone, butanol, inorganic carbon dioxide and hydrogen. And this one
the second one is the fermentative products from E. coli or Escherichia coli, acetate, ethanol,
formate everything under organic and under inorganic carbon dioxide and hydrogen.
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So, we can have a look at the different types of fermentation, this is presented in a nice
scheme. So, different pathways are when you degrade hexoses, for example, glucose and
fructose through different fermentative pathways. So, these are the different paths. So, when
you go for the lactate fermentation you get lactate, ethanol and carbon dioxide. When you go
for the alcohol fermentation it is ethanol and carbon dioxide, when you go for butyrate
fermentation you get butyrate, butanol, isopropanol, ethanol, carbon dioxide and when you go
for this butanediol fermentation you get butanediol and carbon dioxide.
Similarly, the propionate fermentation will give you propionate, acetate and carbon dioxide.
And mixed acid fermentation will give you acetate, ethanol and carbon dioxide along with
some formate, formic acid. Now there are several types of fermentation which are classified
according to the major end products obtained in the fermentation process. Now these types of
fermentation include acetate, alcohol or basically ethanol, butyrate, lactate, mixed acid,
mixed acid and butanediol, propionate and succinate, sulfide and methane. So, these are
different types of fermentation pathways we will see one by one.
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So, the first is acetate fermentation. Acetate is produced in several fermentative pathways. A
large diversity of bacteria collectively known as acetogenic or acetate forming bacteria
produces non gaseous acetate. These organisms include bacteria in the genera
Acetobacterium, Clostridium and Sporomusa. Some acetogenic bacteria are of course
thermophilic, but not all.
Several biochemical reactions are used by acetogenic bacteria to produce acetate. Most
acetogenic bacteria produce acetate from hydrogen and carbon monoxide while some
produce acetate from water and carbon monoxide by this particular reaction:
Some acidogenic bacteria produce acetate from carbon dioxide and methanol and often 6
carbon sugars or hexoses are degraded to acetone. Even propionate is converted to acetate.
So, these are the reactions:
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Then we will talk about the butyrate fermentation. Butyrate is a major fermentative product
of many bacteria. Strict anaerobes in the genera of Clostridium and Butyrivibrio ferment a
variety of sugars to produce butyrate. Under low pH values almost less than 4.5 several
clostridia species produce small amounts of acetone and n-Butanol. Now n-Butanol is highly
toxic to bacteria because of its interference with the cellular membrane functions. So, the
hexose that is getting converted to butyrate:
The next is lactate fermentation. A common product of many fermentative reaction is lactate.
The production of lactate is achieved by the aerotolerant, strictly fermentative lactate forming
bacteria and they are highly saccharolytic.
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There are 3 biochemical reactions for lactate production from sugar such as glucose:
The above reactions depend on what type of bacterial species it is being used. So, these are
some of the bacterial species are being shown in the other side of the slide. So, in addition to
the glucose other sugars fermented by lactate forming bacteria include fructose, galactose,
mannose, saccharose, lactose, maltose and some pentoses.
The next is propionate and succinate fermentation. Anaerobic Propionibacterium or

propionate-forming bacteria ferment glucose and lactate. Lactate the major end product of the
lactate fermentation is the preferred substrate for the propionate forming bacteria. Although
succinate usually is an intermediate product of the fermentation some succinate is produced
as an end product.
The above reactions depend upon which species is converting it or degrading it. These are
some of the species responsible for doing these conversions of glucose and lactate to
propionate is being listed there. So, propionate is a major substrate for acid fermentation that
can be converted to acetate and then used in methane production. Propionate increases the
relatively high concentrations under adverse operational conditions.
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Then the next is mixed acid fermentation and it is sometimes combined with that of the
butanediol production. Now a large variety of bacteria in the genera Enterobacter,
Escherichia, Erwinia, Salmonella, Serratia and Shigella are responsible for the mixed acid
fermentation. These organisms ferment sugars to a mixture of acids such as acetate, formate,
lactate and succinate.
Carbon dioxide, hydrogen and ethanol are also being produced. The prevalence of acids
among the products of mixed acid fermentation account for the name of the fermentation
process. Bacteria in the genera Enterobacter and Erwinia also produce 2, 3 butanediol in
addition to acids. The production of butanediol increases when the pH is decrease that means
less than 6.
So, in anaerobic digester acid production takes place simultaneously with methane
production. Although several acids are produced during acid fermentation, acetate is the
primary substrate used for methane production in an anaerobic digester.
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We will see the next one which is the methane fermentation. Three types of methane-forming
bacteria achieve methane for production, 2 groups of obligate chemolithotrophic
methanogens and one group of methylotrophic methanogens. Chemolithotrophic
methanogens produce methane from carbon dioxide and hydrogen or formate by this
reaction:
Now carbon monoxide also may be used by some chemolithotropic methanogens in the
production of methane, by this reaction:
Now methylotrophic methanogens produce methane by using methyl group containing

substrates such as methanol, methylamine and acetic and these organisms produce methane
directly from the methyl group and not via carbon dioxide by these 2 following reactions:
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Then next is sulfide fermentation. Sulfate is reduced to sulfide by bacteria for 2 purposes. So,
first is that bacteria use sulfate as the principal sulfur nutrient. Now this is done by enzyme
systems that reduce sulfate to sulfide. The reduction of sulfate to sulfide and its incorporation
as a nutrient into cellular material is termed as a assimilatory sulfate reduction. Second is that
during sulfide fermentation or desulfurification, sulfate is reduced to sulfide as organic
compounds are oxidized.
Because the sulfide produced through fermentation is released to the environment and not
incorporated into the cellular material, sulfide fermentation is also known as dissimilatory
sulfate reduction. There are 2 groups of sulfate reducing bacteria first group is called
incomplete oxidizers and the second are complete oxidizers.
Incomplete oxidizers degrade organic compounds to new bacterial cells, carbon dioxide and
acetate, ethanol, formate, lactate and propionate, whereas complete oxidizers degrade organic
compounds to new bacterial cells and carbon dioxide. So, you can see that the incomplete
oxidizers actually produce so many different types of products.
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So, the table list actually genera of sulfate reducing bacteria. So, you can see different genus
of sulfate reducing bacteria there and it is mentioned whether they are the species of
incomplete oxidizers or they fall under the species of complete oxidizer. So, the
Desulfobacter the first one. This is a complete oxidizer. The second one is Desulfobulbus, it
is a incomplete oxidizer. Like similarly there are others also mentioned.
So, the next fermentation type is the alcohol or ethanol fermentation. Though alcohol
fermentation is the domain of yeast, so mostly the Saccharomyces, alcohol is also produced
by several species of bacteria in the genera of Erwinia, Sarcina and Zymomonas. Now these
organisms produce ethanol from the anaerobic degradation of hexoses such as glucose.
At relatively low pH value less than 4.5, alcohol is produced by the bacteria in the genera
Enterobacter and Serratia, by this reaction:
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So, now we will quickly understand and the different methods of fermentation. Now
fermentation has been classified into liquid fermentation, submerged fermentation or solid-
state fermentation mainly based on the level of water used during the fermentation. So, SmF
which is the submerged fermentation exploits or utilizes free flowing liquid substrate broths
and molasses.
The bioactive compounds are secreted into the fermentation broth. The substrates are utilized
quite rapidly and hence need to be constantly replaced or supplemented with nutrients. This
fermentation method is suitable for microorganisms such as bacteria that need high moisture
content. An additional choice of this technique/method is that purification and refining of
products is easier. SmF is mainly used in the extraction of secondary metabolites that
necessitate to be used in the liquid form.
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In contrast, SSF utilizes the solid substrate like bran, bagasse and paper pulp. The main
interest and advantage of using this substrate is that nutrient-rich waste materials can be
easily or efficiently recycled as substrate. In this fermentation method or technique, the same
substrate can be used for a long fermentation period and can be utilized very slowly and
steadily.
Henceforth, this technique supports controlled release of nutrients. SSF is best suited or
adapted for fermentation techniques including fungi and microorganisms that depend on
limited moisture content. Nevertheless, it cannot be used in fermentation process involving
organisms they require a very high aw value (aw is the water activity value) such as most of
the bacteria. So, bacteria and yeasts are equally involved in SmF and SSF, whereas fungi are
mostly concerned with the SSF processes.
The roles of bacteria and yeast in SMF are mostly related to food and beverage processing
industries. Filamentous fungi are best suited for SSF owing to their physiological,
biochemical and enzymological properties and dominate in oriental foods, ensiling and
composting processes.
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So, this is a table which gives us information about the different factors, the liquid substrate
fermentation and the solid substrate fermentation. So, if you see the second one under aseptic
condition; so the liquid substrate fermentation, there will be heat sterilization and aseptic
control and the solid substrate fermentation, vapour treatment and non-sterile conditions.
So, when you talk about let us say the inoculation here - so easy inoculation and continuous
process under the liquid substrate fermentation and under solid state fermentation spore
inoculation and it is a batch process. Because mostly it is being done by the fungi. So, you
can go through the table later on.
So, I am moving ahead. So, we will try to understand what are the different fermentation
modes, how it can be done? Essentially there are 3, one is the batch one which is very much
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is being practiced in most of the lab scales, then the fed-batch and then the continuous
culture. Now what is batch? Now here you can see nicely I have depicted this particular
figure - given this particular figure, from here you can directly understand what is a batch,
what is the fed-batch and what is a continuous process from this. There is an inlet, there is
outlet, you can see that under batch inlet and outlet both are strike down, what does it mean?
So, this means that no extra feeding is used from the beginning to the end of the process.
Once the substrate is fed to the batch reactor and the microorganisms and other necessary
things are being supplied it is being closed and reaction will proceed. Once the reaction stops
the products are formed you will open the reactor. So, this is what is batch.
Now what is fed-batch? So, you can see that outlet, there is no outlet, but there is intermittent
inlet. So, once you supply the feed then you can intermittently also supply the feed. What
does it mean? So, fed-batch is a process where feeding with substrate and supplements can
extend the duration of a culture for higher cell densities or to switch metabolism to produce a
recombinant protein for example. So, intermittently you are feeding.
The next is the continuous culture where inlet and outlet both are open throughout the
process. That is why it is a continuous process. Continuous feeding and continuous taking out
of the reaction products. So, it is mostly adapted in the industries. So, continuous culture
where either the feed rate of a growth limiting substance keeps cell density constant (that
reactor is called a chemostat) or cell density determines the fed rate of the substrate (That
reactor is called a turbidostat). Now cell retention can offer another very productive option,
that is called perfusion. The incoming feed rate matches the rate of the removal of the
harvest. The balanced nature of the feeding allows a steady state to be achieved which can
last for days to months. This state is good for studying microbial metabolism or long-term
production.
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Now this is again described nicely under this particular schematic representation which tells
us the salient features of various fermentative modes. We will quickly go through it. The
batch, fed-batch and continuous. Let us see the batch. So, it is commonly used, relatively
slow substrate utilization rate and low risk of contamination and strain mutation because it is
a closed system. There is no feeding, there is no taking out of the products.
In the fed-batch it is best during substrate inhibition. When there is substrate inhibition you
feed little more again the dilution factor actually increases inside the fermentation and it will
dilute the inhibitory products. So, that inhibitory products under dilution will not more serve
as inhibitory substances (the inhibitory effect will be diminished) and it has prolonged log and
stationary phase of the microorganisms (growth phase we are talking about). So, when you
compare fed-batch, we can say the effectiveness of fed-batch over batch due to concentrated
substrate utilization and large metabolites production during stationary phase. Now this is the
advantages of fed-batch with batch respectively.
Now let us talk about the continuous system. Now here less sterilization and re-inoculation is
required because we are continuously feeding the substrate as well as continuously taking out
the substrate. Less maintenance cost and fastest substrate utilization rate. Now if you
compare continuous with fed-batch or batch we can say that it is more effective due to high
productivity and reduce product inhibition. So, this is all about fermentation and how we can
do the fermentation via various types of reactors or the various types of mode.
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So, with this today I conclude my lecture and in our next lecture under this module we will be
discussing about the various products of the microbial conversion processes and their utilities
and some of the commercial success stories. So, thank you very much and if you have any
query please register it under the Swayam portal or drop a mail to me at kmohanty.iitg.ac.in.
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Module 06
Lecture-18
Products and Commercial Success Stories
Good morning students. This is lecture 3 of module 6. As you know that in this module we are
discussing about the microbial conversion processes. In today's lecture, we will discuss about the
different types of microbial conversion products and few commercial success stories related to these
products. So, let us begin.
So, the first and foremost important microbial conversion product is of course, biogas which is
coming from the anaerobic digestion. So, AD of municipal sludges results in the production of a
mixture of gases. Collectively these are referred as either digester gas or biogas. The only gas of
economic value that is produced in an anaerobic digester is methane. Now, methane can be used as a
source of fuel.
It is a natural flammable gas, methane is odourless and burns cleanly. Pure methane has a heat value
of around 1000 British thermal unit per feet cube. Typically, biogas production in municipal
anaerobic digesters is between 10 to 25 feet cube per pound of volatile solids degraded or 0.75 to 1
meter cube per kg of volatile solids. The heat value of biogas is approximately 500 to 600 Btu per feet
cube, much lower than that of the methane because of the dilution of the methane by carbon dioxide.
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Now, with an increase in the quantity of carbon dioxide in the biogas, its heat value will be
decreasing. So, if the carbon dioxide content of the biogas becomes too large, biogas will not allow
for a self sustained burn and supplemental fuel will be required. So, that means if carbon dioxide will
be too much, then biogas will not ignite and you need to have some secondary fuel to do the ignition.
So, if the carbon dioxide fraction in the biogas increases above 30%, the acid concentration in the
sludge increases and the pH drops below 7. And at pH values below 7 significant acid fermentation
occurs. Now that is not good for the anaerobic digestion, when we are talking about biogas or
methane formation. Now numerous gases are produced in an anaerobic digester. The gases produced
in largest quantities are methane and carbon dioxide by volume methane is about 60 to 65% and
carbon dioxide is 35 to 40%.
Most of the municipal wastewater treatment plants use biogas to heat digesters to around 32 to 35
degrees centigrade. The biogas may also be used to heat buildings. Biogas not used to heat digesters is
simply flamed up. So, the organic compounds include methane and volatile organic compounds. The
VOC contains different types of other components such as volatile fatty acids, nitrogen containing
compounds and volatile sulfur compound VSC.
The production of nitrogen containing VOC and VSC is usually due to the degradation of
proteinaceous wastes that is present in different types of wastes like municipal solid waste. Now of
the inorganic gases produced in an anaerobic digester, hydrogen sulfide is the most undesirable. The
reason is that if the biogas contents too much of hydrogen sulfide, the gas may damage the digester
equipment, this is basically due to the corrosion.
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So, hydrogen sulfide can be scrubbed from biogas, but the scrubbing process is expensive, usually,
you go for a chemical scrubbing. So, means you are adding more cost to the entire process.
So, let us look at this particular slide where I have given the organic gases that is produced through
microbial activity. So, this particular table gives the different types of organic gases. And here we
have different types of inorganic gases. So, you can see that inorganic gases are basically ammonia,
carbon dioxide, carbon disulfide, carbon monoxide, hydrogen sulfide, nitrogen and nitrous oxide. And
organic gases are so many - acetate, butyrate, caproic acid, formate, propionate, succinate and there is
a big list basically.
So, the inorganic gases like molecular nitrogen and nitrous oxide are produced through anoxic
respiration, the process is called denitrification in the anaerobic digester. Now, anoxic respiration can
occur with the transfer of nitrate ions, to the digester with sludges or the addition of nitrate containing
compounds, such as sodium nitrate to increase the digester alkalinity.
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So, the next product is lactic acid. So, lactic acid is an organic acid. It has molecular formula
CH3CH(OH)COOH. It is white in solid state and is miscible with water. While in liquid state that
means in the dissolved form, it is a colourless solution. Fermentation has virtually waived chemical
synthesis of lactic acid. The lactic acid is produced anaerobically with a 95% w/w yield based on
carbohydrate, a titer of over 100 grams per liter and a productivity of over 2 grams per liter. Now, this
is comparable to process employing the lactic acid bacteria.
Lactobacilli produce mixed isomers, whereas Rhizopus forms L –(+)- LA exclusively, lactic acid
exclusively. So, Rhizopus oryzae is favoured for formation since it makes only the stereochemically
pure L plus lactic acid. In a homolactic fermentation, one mole of glucose is ultimately converted to 2
moles of lactic acid and under a heterolactic fermentation yields we get carbon dioxide and ethanol in
addition to lactic acid in a process called the phosphoketolase pathway.
Now, lactate dehydrogenase that is the enzyme responsible for lactic acid formation, catalyzes the
interconversion of pyruvate and lactate with concomitant interconversion of NADH and NAD +. So,
if you are interested, you can read a little more on the phosphoketolase pathway to understand the
entire process in a better way.
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So, here we are trying to understand in brief what are the different types of products and of course,
their end uses and other necessary things ascribed to these products. So, Griffith and Compere these 2
scientists in 1977 described a fixed film system for continuous lactic acid production from the
wastewaters which contained readily recoverable sugar polymers from the pulp, paper and fibreboard
industries.
Now their fixed film unit (it is 2 inches x 6 inches small one), was seeded with Lactobacilli and
lactose fermenting yeast. So, usually the kefir culture we many times called it kephir. So, kephir. So,
kefir culture is a symbiotic mesophilic mixed culture, where bacteria and yeast are both present in
symbiosis. Now the wood molasses substrate wastewater concentrate was pre-treated with cellulase,
diastase and hemicellulases. So, these are the enzymes.
Now with a continuous feed rate of 60 gram per gram wood molasses over the seed(ed) fixed film
unit, 31 to 32 grams per gram per lactic acid yield was obtained, which is pretty good. So, the
production of calcium lactate from molasses by Lactobacillus delbrueckii has also been reported by
Tewari and Vyas in 1971. So, 2 of the most common applications of lactic acid fermentation is
production of yogurt, and sauerkraut.
Now, yogurt all of us know and sauerkraut is a cabbage based product which is fermented - the
cabbage is basically sliced into very thin strips and then fermented using the lactic acid bacteria. So,
lactic acid is found primarily in sour milk products such as koumiss, laban, yogurt, kefir and some
cottage cheeses. The casein in fermented milk is coagulated (curdled) by lactic acid. Lactic acid is
also responsible for the sour flavour of the sourdough bread.
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So, then acetic acid. Acetic acid can be produced by biomass fermentation in 5 different well known
methods. So we will see one by one. The first one is anaerobic gasification of biopolymers to methane
and carbon dioxide, followed by methanolic carbonylation to acetic acid. Now, this method
essentially involves an anaerobic digestion to produce methane, followed by introduction of the
methane gas into a standard methanol carbonylation facility.
So, the second one is anaerobic yeast fermentation of hydrolyzed biopolymers to ethanol followed by
oxidation to acetaldehyde and then to produce acetic acid from acetaldehyde. Now, in this case,
oxygen enriched air and acetaldehyde are fed into a reactor at around 66 degrees centigrade and 101.3
kilo Pascal, where they undergo a 3 step chain reaction. Now, this process is about 95% efficient with
very few byproducts.
The next process is anaerobic yeast fermentation of hydrolyzed biopolymers to ethanol followed by
aerobic bacterial fermentation to acetic acid. So, in this single process both aerobic and anaerobic
processes are used. This is the third method, and the process is currently used for vinegar production,
it is very widely adapted process for vinegar production. We will just discuss in a little more detail.
So, in this process molasses, nutrients and 1% ethanol are used to start a submerged aerobic
fermentation. That is the seed you can say, first, the primary feedstock.
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Now, the concentration of ethanol is kept about 1% until the acetic acid concentration nears to 10 to
11%. Now this mixture of extractant and acetic acid is then put through a distillation chain to recover
both. A major drawback to this process for acetic acid production is the energy intensive distillation
step, which adds substantially to the cost of acetic acid production.
Then the fourth process is anaerobic bacterial homo-fermentation of biopolymers. So, that has
generated much interest in recent years. In this fermentation, hydrogen is oxidized and carbon dioxide
is reduced to acetic acid.
In the next method that is an anaerobic bacterial hetero-fermentation of biopolymers with

simultaneous production of ethanol and other acids. Now hetero-fermentation of carbohydrates to
acetic acids present several purification problems. Now these problems are multiplied in hetero-
fermentation by the presence of other organic products and the concomitant lower yield of acetic acid
is usually reported.
So, we understand that there are 5 different processes through which we can produce acetic acid. So,
we have discussed in a brief about this 5 different processes and their pros and cons.
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So, the next important class of product from the microbial conversion is alcohol - so ethyl alcohol. So,
ethyl alcohol is a primary metabolite that can be formed from fermentation of a carbohydrate or sugar
or a polysaccharide that can be depolymerized to a fermentable sugar. Now it has lower toxicity and is
easily biodegradable. It is soluble in water, harmless to the environment and does not generate
greenhouse gases.
Mostly, yeasts are preferred for these fermentation. Saccharomyces cerevisiae is the well known yeast
to do alcohol fermentation. But the species used depends on the substrate employed. Again, I am
telling you, it is very important, which species you are going to use, Saccharomyces different strains
are available. Now, that will depend on what is your substrate. For example, Saccharomyces
cerevisiae is used for the fermentation of hexose, whereas Candida species or Kluyveromyces fragilis
species may be employed if pentose or lactose is used as a substrate for the ethanol production.
Now, ethanol is produced in Brazil from cane sugar at 12.5 billion litres per year and is used as 25%
fuel blend or as a pure fuel. With regard to beverage ethanol, some 60 million tons of beer and 30
million tons of wine are produced each year. Now, having said that, please understand that we are
talking about Brazil here, sugar production from the sugar, sugar to ethanol in Brazil and various
other countries.
Now, this we have already discussed when we discuss about bio-refinery fundamentals and concepts,
we have discussed that we cannot do it in India and other developing countries because there is a food
versus feed problem. So, in India, we cannot talk about or think about producing ethanol from this but
certainly we can think about producing it from the waste, whether it is lignocellulosic waste from our
agricultural product forest tellings and all or even molasses and other wastes.
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Now, the uses of ethanol are many, including the use as a solvent in beverages, in food and feed via
single cell protein - which is very well known as a SCP, hydrocarbon synthesis via ethylene, as a
gasoline dilutant as gasohol. So, gasohol is almost 10% ethanol plus 90% gasoline. And for biological
energy generation, that is ATP and that happens during the metabolic pathway. So, the basic steps for
ethanol production from grain, cellulose or waste materials consists of 3 steps.
The first one is the conversion of the gram starch or cellulose to fermentable sugar. So, then, this
fermentable sugar is fermented to alcohol. And the third and one most important step is the separation
of the resulting fermentation beer, which contains 6 to 12% ethanol into substantially water-free
ethanol. So, sugars for ethanol production may be obtained from any feedstocks, such as grains,
watermelon, and fruits, sugar beets, sugar cane, sweet sorghum, and potatoes and from cellulosic
residues of corn, small grain straws, wastepaper, sawdust, wood chips, grasses or forages and
cellulose containing municipal waste.
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So, the next product is or we can say that, many times say it is a byproduct, is glycerol. So, we have
discussed about glycerol earlier that glycerol is one of the most important byproduct having lots of
commercial application from the biodiesel industries. But glycerol does produce during the microbial
conversion process also. So, glycerol is used in almost all chemical industries due to its particular
combination of physical and chemical properties.
The majority goes into the manufacturing of synthetic resins and ester gums, drugs, cosmetics and
toothpastes because glycerol is a good solvent for many compounds. So, one of the biochemical
processes that produce glycerol is aerobic fermentation with osmophilic yeast. Glycerol is
accumulated in the yeast as a compatible solute during the adaptation to high osmotic pressures or
high sugar concentrations.
Saccharomyces cerevisiae uses glycerol as its sole compatible osmolyte. The process usually
decreases the specific growth rate because of the limited oxygen transfer rates of industrial
bioreactors. Candida krusei is another osmophilic yeast which can ferment glucose into glycerol.
DuPont corporate and Genencor these are the 2 important industries which work on producing
different types of enzymes and enzyme producing microorganisms.
So, they have different cocktails of enzymes also. So, these 2 companies have engineered biosynthetic
pathways into an industrial strain of E. Coli to directly convert glucose to 1-3 propanediol, a route not
previously available in a single microorganism. So, this is an important breakthrough in enzyme
technology you can say.
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So, the next class of products are polymers and biodegradable plastics. So, a lot of emphasis is being
laid on biodegradable plastics due to various reasons of the plastic pollution and has been in market
since almost a decade, the biodegradable plastics. So, bio based polymers include various synthetic
polymers derived from renewable sources. So, biopolymers it can be nucleic acids, polyamides,
polysaccharides, polyesters and polyphenols and their derivatives and their blends and composites.
So, they are applied in the food, pharmaceutical, chemical and petroleum industries and are used as a
emulsifying agent, stabilizing agent and flocculating agents. Lactic acid produced from fermentation
has been used to synthesize biodegradable plastics. So, that is polylactic acid - PLA. Biodegradable
plastics have a high demand because they are thermoplastic and environmentally degradable and help
to reduce the disposal problem of the non degradable plastics.
Several polyesters with properties comparable to conventional plastics such as polybutylene

succinate, polyester carbonate, poly-D-3-hydroxybutyrate, polypropiolactone - PPL and poly-L-lactic
acid (actually polylactic acid – PLA) are used as biodegradable plastics.
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Many of these bio polymers such as polylactic acid and polyglycolic acid, have been accepted for use
in the medical industry as medical devices or cell culture matrices. Poly-glutamic acid produced by
genus Bacillus can be used as the basis in drug delivery applications for cancer therapy. Now PGA
conjugation can provide more stable and water soluble drugs, which control drugs’ exposure to
tumour cells. Polyhydroxyalkanoate, is one of the largest group of thermoplastic polyesters
synthesized by numerous bacteria as an intracellular carbon and energy storage compound and
accumulated as granules in the cytoplasm.
PHA is regarded as a potentially useful alternative to petroleum derived thermoplastics because it is

biodegradable and biocompatible. PHA has been industrially produced by pure cultures of Alcaligenes
latus, Azotobacter vinelandii, Pseudomonas oleovorans, Ralstonia eutropha, recombinant Alcaligenes
eutrophus and recombinant E. Coli.
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So, apart from all these products that we have discussed, which are actually the major products, there
are other various products which are being produced in very small or minor quantities. So, some of
these are having high industrial and commercial value, like microbial polysaccharides. So, xanthan
gum, Dextrans, Mannans, Pullulan, and Cellulose. Then amino acids - L-Alanine, L-Aspartic acid,
then L-Lysine, L-Phenylalanine, and L-Threonine.
Antibiotics such as Aminoglycosides, then Bacteriocin, β-Lactam, Nisin, Tetracyclines. Enzymes

such as alkaline proteases, α-Amylases, and there are many others and few vitamins like beta-
carotene, Provitamin D 2, vitamin B 12 and Riboflavin.
So, we will now see and discuss the different commercial success stories, how the microbial
conversion process has been commercially adapted to produce different products. So we will see 2 or
3.
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So, the first one is that Solrod biogas plant in Denmark. So, the Solrod biogas plant was taken into
operation in 2015 - very recently started. The plant was established and is operated by Solrod biogas
company founded in May 28, 2014 with Solrod Municipality as the shareholder. The idea is to build a
biogas plant in Solrod emerged from the need to find a sustainable solution to the community’s odour
problem, which is basically caused by the seaweed fouling the beach.
So, what happens in this particular province or the town of Solrod is that this huge amount of
seaweeds is coming and getting deposited on the sea shore. Now, slowly, they are degrading under the
attack of sunlight and of course water and they are getting degraded. So, when they are getting
degraded, they started producing obnoxious gases, I am not telling it is toxic, but they are creating
huge odour nuisance.
So, the people in the municipality of Solrod, they wanted to get rid of this odour in a permanent way.
So, then this idea has started that how to convert these seaweeds into valuable products, so that they
can get rid of this odour as well as they can produce some valuable products. So, then the story begins
actually. So, simultaneously the Solrod Municipality also wish to take concrete action concerning
climate change challenges by producing green energy.
So, the biogas plant has a treatment capacity of 200,000 tonnes feedstock per year, the biogas
produced is used directly for the CHP generation in a large gas engine - combined heat generation
system/cycle. So, the power is sold to the grid and the heat is supplied to the local district heating
system, which is operated by a particular company like Vestegnens and owned by 12 municipalities as
stakeholders.
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So, if you look at that input output system of the particular plant, so the treatment capacity is 200,000
tons per year, methane that is getting produced is 6 million meter cube per year, electricity production
is 23 gigawatts hour per year, heat production is basically the district heating is again at 28 gigawatts
hour per year. Now, if we talk about biomass feedstocks, the major feedstock is of course, the
seaweed which was the initial target actually.
So, seaweed contains various types of Zostera maritima, Pilayella littoralis and Ectocarpus sp. So,
usually 7400 tons, the share of biogas is about 0.5%. So, contribution to the value of the project is
nutrient supply and improved sea water quality. So, this is very interesting the last column and then
manure is being added of course, CP Kelco - that is a pectin, then Chr Hansen. So, altogether adds on
to 200,000 tons, but if you see the shares so you can see that from the pectin the share of biogas is
huge.
Seaweed, is not the major contributor however, in this way, they got rid of the entire odour creating
problem and simultaneously produced fuels. So, if you talk about manure so it is contribution to the
value of project is terms of gas production and process stability. Pectin, major contribution to the gas
production booster and Hansen actually, again, nutrient supply and gas production booster.
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So, if you talk about investment and economy, the Solrod biogas has a share capital of 16 million
Danish kroner consisting of a cash contribution of 6.08 million Danish kroner and 9.92 million Danish
kroner as assets, other than the cash. So, investment is 85 million DKK which is excluding the CHP
unit. Then the European Union grant is 0.5 million euro and the annual revenue that is coming right
now is around 30 million Danish kroner. So, this is quite a success story, and it is been recently
implemented.
So, if you talk about the estimated benefits related to the Solrod biogas plant, so it is 60 gigawatt hour
per year in renewable energy production, which is a very good amount, 104 local jobs are being
created out of which 14 are permanent jobs, 40,100 tons of carbon dioxide equivalent is almost saved
per year, which is almost 51% of the municipality target for the 2025. The next is sustainable waste
treatment and lower cost of the waste transport, production of digestate as bio-fertilizer for farmers.
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So, this is another success story from this particular biogas plant, where the digestate or the solid part
left out after the fermentation is being used as the biofertilizers and it is sold to different farmers. So,
reduced leaching of nitrogen to aquatic environment by almost 62 tons per year - So, 70%
requirement for the Koge Bay and reduced leaching of phosphate to the aquatic environment by 9 tons
per year - 100% of requirement of the Koge Bay. So, reduced odour nuisance from the beach and
seaweed which was their major target, then improved sea water quality and higher recreational value
of the maritime coastal area.
So, the next success story that we are going to discuss is about the Lantmannen Agroetanol, Sweden.
So, Lantmannen is a Swedish agricultural cooperative owned by 25,000 Swedish farmers, providing
food, feed and fuel nationally and internationally. Now since 2001 Lantmannen has produced fuel
ethanol at a facility in a Norrkoping in the South-Eastern Sweden, based on wheat and other grains as
well as residues from the food industry.
The plant was initiated to develop new markets for agricultural products. Thanks to the efficient
processes, the use of renewable process energy from adjacent biomass fuel CHP and important co-
products in the form of protein rich feed and biogas, the fuel ethanol produced reduces the greenhouse
gas emissions by more than 90% compared to the fossil fuels. Now this is the major outcome of this
entire project.
So, from 2015 onwards Lantmannen is also marketing a renewable ethanol fuel for the diesel engines
known as Agro Cleanpower 95, that is the trade mark which reduces the greenhouse gas emissions by
up to 90% compared to the fossil diesel. A noteworthy co-product here is the biobased carbon dioxide
that is sold as an industrial raw material to customers in the food processing and packaging industry,
that is an example of the biobased carbon capture and use.
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Yet the ethanol production at the Lantmannen plant has had significant problems in terms of business
performance. However, beginning in the second half of 2015, the plant has become profitable as a
result of increased ethanol volumes exported instead of used within the Sweden. So, actually what
happened when they were using whatever the ethanol that is being produced inside the Sweden in the
initial years, then they are not making profit.
Because of the policy problems that was there or existed that particular duration in the Sweden. Now,
so they decided to sell it off. So, export it to various other countries. So, once they started doing that,
their revenues have jumped like anything. Now, later on the Swedish government has also changed its
policy so that this Lantmannen ethanol was being again now marketed inside Sweden.
So, this was actually as I told that there was policy problem. So, in Germany, the policy measures
towards renewable fuels depending on the greenhouse gas emission reduction potential, whereas the
Swedish policy currently do not. But this has made Lantmannen’s ethanol highly competitive in other
European markets and has resulted in substantial profits. However, in 2018 Sweden introduced similar
policy measures as Germany.
So, Agroetanol has an annual capacity to convert 600,000 tons of grains to 230,000 meter cube of
ethanol with 200,000 tons of protein feed as co-product mainly for cattle and 200,000 tons of carbon
dioxide which is collected, liquefied and turned into green carbonic acid. So, that mainly goes for the
beverage production.
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So, this is all about the Lantmannen biorefinery which is located at the Norrkoping in Sweden. So,
this is the plant top aerial view. So, the grains residues from the food industries, then cellulose from
agricultural and forest tailings and forest residues are processed. So, they are into 3 distinct streams,
the one is starch rich stream, another is a protein and fiber rich stream another is a carbon dioxide, the
gas basically which is coming from the pre-processing.
Now, the starch goes to the ethanol platform, which gives us biofuels, green chemicals and packaging,
again the solid whatever is left out. Then the protein and fiber goes to the DDGS platform where it is
converted to feed and food. Then carbon dioxide, it goes to the carbic acid platform where it produced
food, industrial applications and of course carbon dioxide also goes for this greenhouse gas emission.
It is a bio based carbon dioxide capture and sequestration cycle basically you talk about.
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Then the year of implementation of this plant is 2005. But again, it is updated in or upgraded in 2015.
Location is of course Norrkoping in Sweden. The technology is ethanol biorefinery. So, the location
of ethanol plant close to biomass based CHP ensures deliveries of renewable electricity and process
heat. So, this is one of the most important take home message from this particular plant. Principle
feedstocks are wheat and other grains as well as starch rich residues from the food industry.
If you talk about Products and markets, then fuel ethanol and co-products in the form of protein rich
feed. A further co-product here is the biobased carbon dioxide that is captured and sold as industrial
raw material to customers in the food processing and packaging industry. So, if you talk about the
TRL the technology readiness level: it is TRL 9 - So, that is the actual system proven in operational
environment and it is quite a success story.
So, the next one is Biowert grass biorefinery, that is for the biobased plastics located in Germany. So,
Biowert industries was founded by Michael Gass in 2000 as a Swiss-German company. The first
Biowert grass refinery is started operation in 2007 and is located in Brensbach, Germany on an 18,000
m2 site. The main products based on grass from permanent pastureland and arable land for crop
production are grass fibre insulation (AgriCellBW is the trademark name), natural fibre reinforced
plastic (AgriPlastBW is the trademark name) and fertilizer made from digestate (AgriFerBW that is the
trademark name). So, the facility has an annual throughput of about 2000 tons dry matter equivalent
to 8000 tons grass per year at 25 to 30% dry matter content. The integrated biogas plant produces
13,40,000 m3 of biogas annually, which is used in combined heat and power facilities, which in 2012
produced 5.2 gigawatt hour (GWhel) electricity.
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Now, the first step after ensiling includes mechanical treatment of the grass silage and isolation of
grass fibres through pulping, drying and pressing processes. The grass fibres are further processed
into AgriCellBW and AgriPlastBW synthetic granules. AgriPlastBW contains 30 to 50% grass fibres and
50 to 70% recycled polyolefine and is used for injection moulding for a range of uses.
The grass juice remaining from the mechanical pretreatment of grass silage is used as a substrate in
the biogas plant together with local co-substrate such as food waste and slurry. The heat and
electricity derived from the biogas facility is used to satisfy the energy in the biorefinery and excess
electricity is exported to the electricity grid. Wastewater that is arising from the process is reused for
pretreatment of the grass silage. Digestate from the biogas plant is further processed to a concentrated
and a liquid biofertilizer used by the local farmers. Now, this closes the nutrient cycle in the circular
economy.
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So, if you closely look at this particular plant and how it happens, this is the aerial view of the
Biowert plant, these are the different types of agri-based products. Now, let us have a look here this is
interesting actually. This is a cycle which is Biower cycle, which talks about the circular economy.
So, there is a complete nutrient recycle here in this. If you start from the grass - Meadow grass, it is
harvested, then it is delivered, processed in the grass factory.
So, the solid parts go to the fibre production in a name of AgriCell, then whatever the other products
that comes here is again processed and granule into different products named as AgriPlast. Then the
slurry - grass slurry, that goes to the biogas reactor - basically for the anaerobic digestion. Here the
different other biomass also can be co-feeded. So, the co-feedstock process here. So, whatever comes
out is nothing but your green power.
Then whatever left out this can be used as AgriFerBW agri fertilizer basically the slurry it can be
concentrated and made into your solid fertilizer also. Now, you can see that fertilizer is being again
used as fertilizer in plantation to grow Meadow grass. So, thereby the nutrients which are present in
the grass are getting recycled again. So, it is a complete nutrient recycle and circular economic
concept.
So, if you look at the input and output for this particular plant, - the input is biomass and then
electricity demand. So, biomass is about 8000 tons per year. And electricity demand is 2.5 to 3
gigawatt hour per year. And the biogas and CHP plant that produce actually grass juices - 1942 ton
per year - that is required as a feedstock to be fed to the digester and then the co-substrates in biogas
facility around 15,260 tons per year.
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So what is the output? Outputs are this actually: AgriCellBW and AgriPlastBW, the solid by-products
which are being converted into 2 different trade names and being marketed - and then biogas
(approximately 13,40,000 m3 per year of the methane concentration). And then of course, there is 5.2
gigawatt hour electricity generation. Now, please understand that - whatever it is getting produced
here, the electricity, almost 50 to 60% of that is being utilized in the entire plant and the rest either is
being sold or directly fed to the electricity grid.
So, with this, I conclude today's lecture. So, in the next module, that is module 7, we will be
discussing about bio-diesel. So, thank you very much in case you have any query please feel free to
register your query in the Swayam portal or you can drop a mail to me at [email protected], Thank
you.
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Module-07
Lecture-19
Diesel from Vegetable Oils, Microalgae and Syngas
Good morning students, today is lecture 1 of module 7. And this particular module is dedicated
to biodiesel. So, in today's class we will understand diesel from different vegetable oils,
microalgae as well as syngas. So let us begin.
The depleting trend of conventional, non-renewable, fossil based fuel has triggered research and
development of an alternative energy. So, biodiesel is one of the most promising renewable
energy in this century. In addition, biodiesel has many superior properties as compared to
petroleum diesel such as lower exhaust emissions, it is biodegradable, non-toxic, renewable, and
it is almost free of sulfur.
Since biodiesel is renewable and environmentally friendly, the use of this fuel is a shift towards
the sustainable energy. So, in the figure 1 here, you can see the different types of oils and their
yield per hectare. So, you can see soybean oil, then cameline oil, safflower, sunflower, rapeseed,
castor oil, jatropha, palm oil and algae oil. So, you can see that among all, algae, per hectare
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yield is very high. So, anyway we will be discussing about most of these oil sources and what are
the major composition of all these oils.
So, let us again, go to that. So, the history of biodiesel is as long as that of diesel engine itself.
The use of vegetable oils was investigated as early as the era when diesel engine was developed
by Rudolf Diesel - who has actually invented the diesel engine. So, when he invented and tested
the diesel engine; he used peanut oil as a fuel for his engine. So, many vegetable oils were
investigated during the historic times, which include palm oil, soybean oil, cottonseed oil and
castor oil etc.
The feedstock for biodiesel production can be categorized as lipid feedstock and alcohol
feedstock. Now lipid feedstock includes vegetable oils, animal fats, and more recently other plant
like organisms such as the cyanobacteria and algae. The vegetable oils used as lipid feedstock for
biodiesel production are highly dependent on regional climate. So, some of them are rapeseed oil
in European countries and Canada, Soybean oil predominantly in the United States, and palm oil
predominantly in the tropical countries such as Malaysia and Indonesia.
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Coconut oil is another lipid feedstock used for synthesis of biodiesel in coastal areas. Potential
non edible oils used as lipid feedstock in India include Jatropha oil and karanja oil. Now this
table will give you an understanding about the different oil seed plants, their oil content, their oil
seed production and average oil seed price and average oil price - given in US dollars and the
yield per kg per hectare per year.
So, you can see that rapeseeds, soybean, sunflower seed, palm, cottonseed, peanut, copra and
coconut all are listed. So, this gives us an understanding about that we have plenty options of oil
seeds available in the world. And most of these here listed are almost the vegetable oils which
can be used for the cooking purposes, but not all. Now that is why if you recall our discussion
during biorefinery, I have been telling you many times that in India and other developing
countries we cannot use such vegetable oils, or say anything, any feedstock that comes under
food. So, that is why in India our focus is initially when this biodiesel has started, our focus was
completely shifted to the Jatropha, Jatropha curcas. And in one of our class I have told you that
why Jatropha is not become sustainable, it could not fit to the sustainable; then moreover
economy is also a problem with such Jatropha based biodiesel.
So then, we have shifted our attention to other non food based seed oils, we can call them as non
edible oil seeds and in our lecture perhaps 5, we have discussed about various types of non edible
oil seeds, whether it is mahuya, karanja, neem and there are many.
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Soybean oil dominates the world oil seed production while rapeseed production is second only to
soybean oil. The oil content in soybean and rapeseed is 21% and 35% respectively. Despite the
lesser availability, palm oil is an interesting source for biodiesel production due to it is lower
price and relatively high oil content, it is almost 40%. So, oil seeds contain droplets of lipid
which can be extracted as vegetable oils.
But extraction, many times, is an energy intensive as well as a cost intensive process. So, the
major component of vegetable oil is triacylglycerol - which is called as TAG, or triglyceride,
which is called as TG - which is a molecule composed of three esters of fatty acid chain attached
to the glycerol backbone, so basically the glycerol group. So, when 1 and 2 acyl groups are
replaced by hydroxyl groups, it is called diacylglycerol – DAG, or diglycerides – DG; or
monoacylglycerol – MAG, or monoglyceride - MG respectively.
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Now this table will give you the understanding about the molecular structure of the triglyceride,
diglycerides and monoglyceride. So, the fatty acid chains usually range from 10 to 24 carbon
atoms. These fatty acids are frequently represented by a symbol such as C18:1, which indicates
that a fraction consists of 18 carbon atoms and 1 double bond. So, typical fatty acids attached to
TAG found in vegetable oils are presented in the table 3.
That means this table; so you can have a glance through this. So, it tells us about the structures of
common fatty acids found in vegetable oils. So, three different groups are presented here. The
first one is saturated, second is mono-unsaturated and third one is polyunsaturated. So, this is
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their common name and then this is the symbol and then the formula and double bond position -
where the double bond is located, which carbon atom basically.
So, naturally occurring fatty acids in vegetable oils have a cis-formation whereas, unnatural
trans-isomers occur due to partial hydrogenation process. And in cis-isomer, hydrogen atoms are
attached on the same side causing a “V” shape of the fatty acid chain. Now when two hydrogen
atoms are attached on the other side of each other, trans-isomer is formed and the molecular
structure is linear.
So, the shape of the configuration determines stacking of TAG molecules, proximity between
molecules and intermolecular forces between the molecules. Now all these factors are key
parameters for determining properties of various vegetable oils, such as crystallization and
melting temperature. The major difference between various vegetable oils is the type of fatty
acids attached in the triglyceride molecule.
Fatty acid composition is of utmost importance, as it determines fuel properties of biodiesel

derived from corresponding vegetable oils. Fatty acid composition also determines degree of
saturation, unsaturation and the molecular weight of vegetable oils. Fatty acid compositions of
various vegetable oils are shown in table 4. So, in the next table I will show you.
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So, this table gives us the fatty acid composition of vegetable oil. So, the vegetable oils common
name, species is given, and then fatty acid composition by weight percentage. So, we can see
one; let us see the soybean; the usual soybean or Glycine max. So, you can see that 10 weight
percent is to 0 fatty acid composition, so 16 carbon atoms and no double bond basically.
Then if you proceed again, you will see that 18 carbon atoms no double bond is 4.3 weight
percent. Then 18 carbon atoms and 1 double bond is 22.3%. So, similarly so many other
vegetable oils and their fatty acid composition has been listed, so you can go through it later.
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So, we will move ahead. So, the degree of saturation/unsaturation and molecular weight of
vegetable oils can be calculated by two things, first is something called an iodine value and
second is called saponification value (respectively). Now higher iodine value and saponification
value indicates higher degree of unsaturation and lower molecular weight of the corresponding
vegetable oils. Iodine and saponification values of selected vegetable oils are shown in the table
5.
So, you can see few oils are being listed, so rapeseed oil, soybean, palm, and sunflower
cottonseed, linseed, rice bran and their corresponding saponification value and iodine values
have been listed.
Now we will quickly glance through the different types of vegetable oils that has been used in
many places to produce biodiesel. So the first one is soybean oil; soybean or soya is referred to
as Glycine max which is found only under cultivation and is a member of the Papilionaceae
family. The origin of soybean is not very clear, for the genus Glycine has two major gene
centers; Eastern Africa and Australia.
So, many literatures will tell us that this soybean has been originated from Eastern Asia, but
there is no proper proof for that. So, based on historical and geographical evidence, north eastern
China has been considered as the region of origin of soybean domestication. So, today soybean is
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world's largest oil seed in terms of total production and in international trades. The oil content in
soybean seed ranges from 15 to 22%, depending on environmental conditions during the seeds
maturity. The major fatty acids are oleic acid, which is C18:1, we can say that 18 carbon atoms
and 1 double bond and linoleic which is having two double bonds.
The next is rapeseed oil, mustard, oil and canola oil. So, the word “rape” is originated from the
Latin world “rapum” which means turnip. Now this belongs to Brassica family including turnips,
mustard, cabbage, rutabagas, broccoli and kale. Now these seeds have oil content over 40%, in
which the dominant fatty acids include oleic acid, linoleic acid and erucic acid. Now when
rapeseed has erucic acid content higher than 5%, it is called HEAR, it is called high erucic acid
rapeseed. While a low erucic acid rapeseed which is known as LEAR is referred to as rapseed
having erucic acid concentration less than 5%. Now under Canadian Agricultural Product
Standards (CAPS) Act, canola oil is defined as oil extracted from rapeseeds of B. napus and B.
campestris species with low level in both erucic acid and glucosinolate content. The erucic acid
content in canola oil shall not exceed 5%, that is weight by weight.
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The next is palm oil. The origin of palm oil is believed to be in Africa, but most productive
regions are located in Southeast Asia especially Malaysia and Indonesia, which together account
for around 80% of the world production. There are generally two types of oil derived from the
palm, so palm oil from the mesocarp and then the palm kernel oil from the kernel inside the seed.
Palm oil is more saturated than soybean oil and rapeseed oil, as it is major fatty acids include
palmitic, stearic, oleic, and linoleic acids.
Now palm oil can be fractionated at ambient temperatures in Palm olein or oleic-rich oil and
palm stearin or stearic-rich oil. So, that is the solid fraction and the earlier one that is the oleic
rich oil is the liquid fraction. Now due to the saturated fatty acids contained in this oil, it has
superior oxidation stability as compared to other vegetable oils.
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The next is sunflower oil. So, Helianthus annuus is the botanical name of the common sunflower
species for which it is a member of the Compositae of flower plants growing throughout the
world. The name stems from Greek word helios meaning sun, and anthos meaning flower.
Sunflower originated in South-West United States and Mexico areas. Sunflower seeds are edible
and often crushed for oil extraction. The major fatty acids in sunflower oil are oleic and linoleic.
Sunflower is considered as one of the most ancient oil seed species as it is cultivation can be
traced back to 3000 B.C. Sunflower was once the world top rank oil producing plant prior to the
advent of soybean boom after World War II.
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The next is rice bran oil. So, rice bran is the main source of the rice oil. Lipid droplets can be
extracted from the rice bran using extruder, expander and expeller to form a bran flake or pallet
followed by solvent - usually hexane is being used for the extraction process in the extraction
bed. The majority of the oil components are triacylglyceride with palmitic, oleic and linoleic as
the major fatty acid present in the rice bran oil.
Diacylglyceride, monoacylglyceride and sterols may be present in minor amounts in rice bran
oil. Rice bran oil is used widely in Asian countries due to it is delicate flavour and odor. It is
recently gaining interest as healthy oil since it helps in reducing serum cholesterol. Recently rice
bran has been widely adopted in India and sub continents. And one of our premier research labs
in India which is CSIR Indian Institute of Chemical Technology has formulated an excellent rice
bran oil and that has been commercially produced now.
The next is Jatropha, now we are coming to the non-edible oils. Jatropha curcas is the member
of the Euphorbiaceae family. It originated in America but is harvested mainly in Asian countries
especially in India. Jatropha is well adapted to arid and semi arid conditions and it shreds it is
leaves in order to survive during the drought seasons. So, it can be grown on non cultivated and
degraded wasteland, and therefore is considered as one of the most promising feedstock for
biodiesel production.
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Oil derived from Jatropha is non edible due to curcin, a toxic compound that is found in the
seeds. The oil content ranges from 35 to 40% in the seed and 50 to 60% in the kernel with oleic
and linoleic as it is major fatty acid content. Having said that, you know we have already
discussed that why again in India, let us talk about Indian context. Now you do not see Jatropha
plantation anywhere in India because of the sustainable problem which we have already
discussed when we discussed about the Jatropha curcas cycle.
The next is karanja oil. So, karanja is a member of the Leguminaceae family with Pongamia
pinnata as it is botanical name. It is an oil seed bearing tree native to humid and subtropical
environments, such as those in Philippines, Indonesia, Malaysia, Myanmar, Australia, India and
the United States. It is highly tolerant to salinity and can be cultivated on degraded wasteland on
a variety of soil types, ranging from clay to sandy or stony.
The oil droplets extracted from Karanja appear yellowish orange to brown and are not edible due
to the presence of toxic flavonoids. Oil content varies from 9% to 46% with oleic and linoleic
acids major fatty acids.
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So, let us talk about biodiesel production. So under this module, in our next class that is a lecture
2 of module 7, we will be discussing in detail how do you produce biodiesel by
transesterification process, the reaction mechanism - how the reaction happens, how you conduct
it in a lab scale - All these things we will be discussing in our next class. Today in a gist we will
just go through and in detail we will discuss in our next class.
So, transesterification is the most common method used to reduce viscosity of vegetable oils and
produce biodiesel. In addition to transesterification of TAG biodiesel can be produced from free
fatty acids through esterification. Since ester is characterized by RCOOR group (R = alkyl group,
R is alkyl group), TAG is a type of ester and reaction that converts TAG into biodiesel is
therefore known as transesterification, that means transforming the ester.
In contrast, free fatty acid is not an ester and therefore the reaction to produce biodiesel from free
fatty acids is called esterification, that means making ester. Transesterification is the reaction
between glycerides with short chain alcohols and is comprised of three consecutive reactions
starting from TAG to DAG, DAG to MAG and from MAG to glycerol. We will discuss this in
detail in our next class.
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In each step, the reaction consumes one mole of alcohol and produces one mole of ester. In total,
one mole of TAG reacts with three moles of alcohol to produce three moles of ester that is
biodiesel and one mole of glycerol. So, glycerol is one of the most important byproducts having
a lot of commercial value and application from the biodiesel industries. So, in general the
reaction performance is influenced by various parameters such as type of alcohol, alcohol to oil
molar ratio, free fatty acid content, water content, reaction temperature, reaction duration and the
type of catalysts that you are using.
Now let us talk about the diesel that is coming out from microalgae. We have discussed about
microalgae in one of our previous classes that why microalgae suddenly become a big bloom and
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of research interest for many of the scientists and academicians across the globe. So, today we
will discuss how diesel can be produced from microalgae. So many microalgae, in particular the
green algae and diatoms can accumulate significant quantities of neutral lipids primarily as
triacylglycerols - TAGs.
Now these lipids can then be extracted from the biomass and converted into biodiesel or green
diesel as substitutes for petroleum derived transportation fuels. So, having said that, I am telling
you that, once you produce biodiesel, it needs some further processing, which we are going to
discuss in our subsequent lectures under this module, maybe in the lecture 3 under module 7. So,
you need to purify it, it is not that you produce and directly it can be used in the engines, it is not
so. We will discuss how this will eventually happen.
So the lipid content is the significant prerequisite determining the aptness of the microalgae for
commercial biofuel production. In general, microalgae cell contains 30 to 80% lipid. Lipids are
in general soluble in non-polar solvents but insoluble in polar solvents due to the presence of
hydrophobic chain. Therefore, they are easily extractable using organic solvent extraction
method. They are further categorized into neutral and polar type.
So, this particular table will make you understand or give you some information about some of
the typical microalgal species with relatively high lipid content and productivities which can be
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used or has been used for the biodiesel production. Please understand that we have more than
200,000 species of microalgae and out of that almost 50,000 might have been tested.
Please note that all species do not contain a huge amount of lipid which can be grown and
harvested for the biodiesel production, it cannot be. So, these are some of the already well tested
microalgal species which are having very high lipid content. So like C. protothecoides, then
Chlorococcum, Chlorella sorokiniana, D. salina all these things, there are so many different
types of species, even the Scenedesmus species also.
You can see that the first one, it comes under the Chlorophyceae genus; it has a lipid content
about 15 to 58% again depending upon the species (w/w). And the lipid productivity, if you talk
about the productivity in milligrams per litre per day, so it is the highest almost among those are
listed 1214. And one of the most important species is the Scenedesmus species; it can be grown
easily, it is very widely adapted, climatically adapted species along with even Chlorella vulgaris
and all other. So, it has also a good lipid content and a very nice lipid productivity.
So, during the last decade considerable attention is drawn towards algae for the economic
possibilities in their mass growth. It is not about only biodiesel, but there are various other
applications of the microalgae which I have already told you - what are the different types of
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components or the value added products that can be extracted from microalgae or further process
to make directly commercial products.
So, the biofuel synthesis from algae proceeds through the following 5 steps. First is that you need
to culture the algae; second is harvesting the algae or dewatering algae. So, this is right now also
this is one of the most important steps, because it consumes energy and it takes time also. So,
when you have huge amount of algae that needs to be dewatered and harvested; so, you have to
have a proper technology, which should be faster as well as it should be low in cost.
The third is the extraction of algae from oil (oil from algae). So, you can either go for this
chemical based extraction or physical extraction, it depends on what type of species it is, what is
the oil content. So, there are so many other parameters to be thought of, but again extraction is
also a cost intensive process. Then purification of the algal oil, so the downstream purification
you need to remove whatever water content, glycerol and any other components which are not
the fuel components needs to be removed. And the last one is the processing of oil into biofuels.
So, please have a look at this particular flowchart. This is the flowchart for biofuel production
from the microalgae. So, it starts from the strain selection - the first and foremost important thing
that which strain you are going to use for the biofuel production. So, now let us say I am in
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Guwahati, in Guwahati in my group alone we have strain, we have almost more than 100
different strains which we have screened for different purposes.
It is not only for the biodiesel production; we have used it for different purposes. And we have
seen that certain strains are naturally having very high lipid content. So, we can use those strains
for the biodiesel production. So the strain selection is very important. So, after that you have to
go for cultivation strategy, what type of cultivation strategy was going to add up? Suspended
cultures, immobilized cultures, hybrid systems, how we are growing them?
In raceway ponds, photobioreactors, open, closed so many things are coming into picture. Then
the sitting options, so wastewater treatment, aquaculture, carbon dioxide sources; it is again some
sort of hybrid digestion you can tell that. If you talk about wastewater treatment - in one of the
class I have already told you that if we can grow algae in wastewaters, then it is a win-win
situation.
Because it will purify the wastewater or let us say it will treat the wastewater, as well as the
microalgal growth will be there, so of course, you can harvest it. So, two things are happening in
a single thing, and you will be depending less on the amount of freshwater. So, thereby you can
recycle the harvested water after maybe some minor treatment back to the raceway pond or
bioreactors.
Then resources like of course, this is capital cost that is coming into picture. Then cultivation,
different factors will be there growing medium, light, carbon dioxide, nutrients. Then harvesting,
then it goes for the conversion process, what type of conversion process you are looking for?
Fractionation extraction technology, lipid extraction, extraction of carbohydrate, other things,
proteins; then conversion, photobiological, fermentation, anaerobic digestion, gasification,
pyrolysis, liquefaction and the last transesterification for the biodiesel production.
Then, once you do that, so you get majorly 2 different types of products - the biofuels, like solid
also dry biomass - that de-oiled cake you can say, charcoal. Under liquid we may get ethanol
from the carbohydrate platform, then butanol also from the carbohydrate platform, diesel coming
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from the lipid. Then jet fuel and gaseous if you talk about hydrogen, methane, syngas maybe
from anaerobic digestion and FTA and other processes. Then other various bio products like
cosmetic, fertilizers, bio plastics, antibiotics, vitamins and so many other things.
So, culturing up algae or algaculture. So, algal culture refers to the growth of algae similar to that
of aquaculture. The growth expectation of algae is very simple and affordable, that is, sufficient
light, naturally available dissolved nutrients and carbon dioxide is what the algae needs to grow.
Unialgal growth without contamination of other eukaryotic or prokaryotic organisms and axenic
culture (that means bacteria free) is challenging, especially when you are growing it openly.
So, the growth rate of algae is spectacularly high, it is almost doubling in 24 hours, unlike plants
as their energy is not spent on the growth of their parts. There are two kinds of algae culture
classified based on the growth characteristics are either batch culture or continuous flow culture,
BC and CFC.
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Now let us see the BC. The inoculation of algal cell in a container when the abundant resource is
available, follows the sigmoidal curve in the batch culture. The loss of medium slays the culture
and this could be subdued by introducing small volumes of fresh medium into the existing
culture. Then comes the continuous flow culture, CFC. The regulated addition of adequate
volume of fresh medium rich in nutrients to the culture medium to attain steady state is
performed in the CFC method.
A steady state is the uniform cell density where the birth rate is equal to the death rate. This is
the definition of steady state with respect to the CFC. Now this is done proportional to the
growth of algae in special culture technique known as Turbidostat culture or Chemostat culture.
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Now Turbidostat culture is the fresh addition of medium to the culture when the growth reaches
a certain limit, whereas, chemostat culture is the introduction of fresh medium to the culture at a
predetermined rate. So, let us now understand the major physical parameters that affects the
growth of the algae. The first and foremost important thing is pH, I have told you many times
whenever you deal anything with the aqueous medium pH always plays a big role.
The total collapse of algal cell wall occurs with the un-optimized pH level; so you have to be
very careful of the pH. And the proper cell growth happens in the pH range of 8.2 to 8.7 and
supplement of carbon dioxide into the medium enables the attainment of the optimized pH. Then
illumination, another important factor. Illumination needs to be concentrated in adequate
photoperiod and intensity.
These depend on the density of the culture and depth of the vessel in use. The important
strategies with respect to illumination are:
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Fluorescent lamps, photoperiod and light intensity. So, in fluorescent lamps the radiation in 380
to 500 nanometer usually the blue light and 600 to 700 nanometer usually the red light is
preferred for the algal growth. Photoperiod, the illumination period is expected to be around 16
to 18 hour for the appropriate culture maintenance. Again these so many things which we are
discussing all the parameters that also depends on a particular species.
Light intensity; algae growth differs with the intensity of light ranging from 5% to 10%. Mostly
the light and dark cycles are followed as the cells do not grow in continuous illumination. The
next is temperature, temperature of the culture medium varies with respect to the temperature
zone of the regions. Algaculture in countries like India and United States (basically temperate
zones) operates at 10 degree centigrade to 25 degrees centigrade.
And in tropical countries, especially Brazil and Singapore the temperature of action is below 20
degrees centigrade. The temperature beyond 35 degree centigrade leads to destructive algal
growth.
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Then the medium of culture; the medium is responsible for the contamination of culture and it
creates a hindrance in the sterilization also. The quality of water used in media has significance
and sea water with unpredictable contaminant is a serious issue in culturing medium. So,
seawater may contain vitamins, chelating agents, buffers, soil extract etc. and sometimes it needs
to be purified.
So, three major types of culturing are practiced worldwide and are discussed in this section, we
will try to understand in a nutshell. So, open pond system: algae usually grow in lakes and
copying this similar pattern is known as the open pond system for algal culturing. The ponds are
of one-foot depth and alga cultivation could be from one acre to several acres. The types of open
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pond system are raceway ponds (which are the most common), natural ponds (so they are the
shallow lagoons and shallow ponds), mixed ponds, circular open ponds mixed with center pivot
mixer. In raceway ponds, a closed loop with recirculation channel is designed with paddles for
better mixing, laminar flow and circulation of carbon dioxide. But it also has a high peril of
contamination with low rates of production due to it is sensitivity to the environmental
fluctuation.
The next are photobioreactors or closed loop culturing. Intensive research on algae production
compelled the idea of the closed loop reactor systems. Photobioreactor is a worth substitute for
OPS for it is massive productivity rate and high quality of algae. So, everything is good in
photobioreactors, that is because it is a closed system, it is very easy to control all the parameters
and there is no problem of this contamination also.
Now researchers have created many versions like tubular, bubble, christmas, plate, horizontal,
foil and porous photobioreactors. The tubular bioreactor is the common photobioreactor type
used in the algal culture and it comprises of tubular solar arrays, biomass unit, exchange column
to exchange gas and pump. The tubular solar arrays basically mean the tubular photobioreactors
which are placed under the sunlight in open atmosphere.
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The vertical column tubular photobioreactor offers good gas exchange while the horizontal
column tubular photobioreactor gets better access of light and also possess higher surface area.
However, the negatives of the vertical tubular photobioreactor is the low surface to volume ratio,
and horizontal column tubular photobioreactor is the low mass transfer leading to difficulty in
carbon dioxide elimination and excessive heat generation.
So, this is the closed photobioreactor - actually a schematic. So, the algae, carbon dioxide, then
water or wastewater whatever, the nutrients are all mixed in the feeding vessel, then it goes to the
photobioreactor where it is cultured; proper amount of carbon dioxide and light is being given.
And a proper light and dark cycle has been maintained, then you see that it goes for the
harvesting, the separator where the algal slurry has been separated.
And the secondary water can be used - treated and fed back to the photobioreactor or the
raceway pond whatever it is. Then the slurry is being centrifuged, so you will get the biomass,
the solid biomass which can be further processed, you can extract the lipid, make it biodiesel and
other parts also whatever left out in the solid residue can be used for various other platform
chemicals or other value added products.
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Disappointingly, in general photobioreactors suffer from their high capital cost (this is one of the
most important thing actually which hinders its application in large commercial sector) which
exceeds the output due to it is complexity and exclusive erection materials. Further, it suffers
from improper carbon dioxide and oxygen balance, control in temperature and biofilm formation
- fouling.
So, the next is hybrid systems. Synergizing the effectiveness of the open pond system and
photobioreactor can be achieved by the hybridization of both the systems. The two stage hybrid
cultivation system is the advanced version of the alga culture, where the cell medium is
transferred from the open pond system to the raceway pond system when the nutrients are found
to decline.
The feasible separation of biomass from the lipid accumulation and least possibility of
contamination strike the positive note. The hybrid system can be of small PBRs with big ponds
or ponds with large PBRs, anyone of these combinations.
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The hybrid system comprises of two stages. Stage I: PBRs are chosen as phase I to reduce the
lipid accumulation and contamination in the culture. The density of biomass can be increased in
the closed PBR system; once it is done you transfer it to the raceway ponds. In second, stage II:
the selection of OPS in the stage II increase the economic compatibility of the process. The two
most significant at the phase II after the completion of I phase helps to promote rich
carbohydrates and lipids in the algae.
So, then we will talk about increase of lipid content by alternative nitrogen supply. The trial of
reducing the nitrogen environment retards the growth of the culture. The latest research shows
the supply of nitrogen at the beginning of the culture growth and then deprive it after the
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considerable dense biomass raises the lipid production, this is called nitrogen starvation, or
nitrogen shock. So, the nitrogen starvation disrupts the cell and directs the carbon towards
carbohydrate and lipid production. Nannochloropsis gaditana and Chlorella protothecoides are
the few algal species that produced good results in the switch over of nitrogen sources. So, this is
one of the widely studied problem or we can say the aspect of the microalgal culture and growth.
So, then brine condition; now this methodology is reverse to the nitrogen supply mechanism.
Better products are produced only with two stage cultivation process compared to single stage
cultivation.
Enhancement of algal growth is observed with saline condition and the gradual increase of
salinity lowers the metabolism. The lower salinity level improves the lipid and carbohydrate
generation in algae. Chlorophyceae species indicates the effect of salinity in their growth in stage
II cultivation.
724
Then harvesting or dewatering of algae. The cultured algae needs to be dewatered in order to
access the lipid profile. The dewatered algae looks like an interim of solid-liquid medium instead
of a liquid which flows easily. The experiments prove that only 0.1% of dry matter is available in
1 litre of the culture media. Filtration and centrifugation are the processes involved in removing
water from algae.
Many advanced mechanics are explored under these categories. Flocculation and membrane
filtration is effective in drying the algae. Methods involved in filtration are pressure, vacuum,
deepbed sand, cross flow and magnetic filtration. Huge amount of work is still going on, on this
particular harvesting technology.
725
So, then algal oil through lipid extraction from dry algal mass. The biological micro species has
multilayered cell wall made up of polysaccharides and cellulose synthesized from silicic acid.
The cell wall envelopes the lipid or fatty acids and the removal of algal oil is known as that lipid
extraction. The specific extraction of lipids is also performed by solvent extraction using
methanol and chloroform.
Interest is on microwave, grinding, bead beating and ultrasound mechanical methods for
extraction. This method does not require extra chemicals and the subsequent extraction step
becomes easier. Mostly, bead baiting is done to disturb the cell walls of microbes in small scale
level with beads made up of ceramics or glass.
726
In recent years, research is directed towards extraction free from solvents. The supercritical fluid
technique accomplishes the demand by producing safe and good quality end products. The
efficacy of this method in extracting specific components from a complex biological species is
worth enough. The oil extracted using n-heptane by Soxhlet extraction method is much lower
than that of the supercritical fluid extraction.
But please understand that supercritical fluid extraction is a costly process because of the huge
capital investment, it requires. So, lipid extracted from various microalgae and the method of
application is given in this particular table. You can see the different types of microalgal species
here, Chlorella vulgaris, Cyanobacteria, Scenesdemus, again Chlorella and Chlorophyta.
Different types of extraction technologies: Ultrasonification, microwave, using a virus, then
Soxhlet extraction. So you can see the type of algal oil it is given there, 16%, somewhere it is
49%, then almost 10 to 11%, and the last one it is 18%.
727
So, now we will discuss biofuel synthesis from algae by transesterification process. So, algae
competes the fellow contestants in the biodiesel synthesis market which gives an insight for the
future oil demand. Algal oil displays a remarkable tendency to get converted into diesel range
esters. Transesterification is the reaction between one mole of triglyceride molecule which is a
complex ester and 3 to 4 moles of alcohol to produce simple esters, that is called biodiesel.
The transesterification technique is often catalyzed by several acid catalysts, namely sulphonic
acid and sulfuric acid and base catalysts such as sodium hydroxide, potassium hydroxide, sodium
methoxide, sodium ethoxide and K2CO3. Now with several classes of catalyst in action, porous
catalyst Hβ and mixed oxide of nickel and molybdenum turns to be veracious materials. The
biodiesel yield in the presence of these catalysts almost reaches 100%.
So, that is excellent yield using this particular catalyst. Lot of research is still going on in
developing low cost and high yielding catalyst, which will basically lower the final product cost
of the biodiesel.
728
Potential of nano carbon particles is also being used to convert lipids onto biodiesel. The
conventional transesterification uses inorganic catalyst and has the demerit of polluting the
environment due to it is disposal hitches. Therefore, green substitutes like enzymes can act as a
better auxiliary. Biological catalysts, which are treated for the biodiesel formation and out of
them lipases have created a niche in the industry.
Immobilized lipases on metal oxide nanoparticles have fine thermal stability, corresponds to
good selectivity and also can be easily separated. Biodiesel yield was as high as 90% with
enzyme concentration of only 1 to 3.5%.
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Now we will discuss about diesel from syngas. So, in today's class, as I told you in the beginning
we are discussing diesel from three various sources. First is vegetable oil, that we have discussed
and understood. Second is from the algae, we have understood in detail how algae can be grown,
how it can be cultured, what are the parameters that affect? And the third and last one is the
diesel from a syngas.
So, diesel powered heavy duty trucks and more efficient diesel cars have been widely used in
industrialized nations, especially in the European countries with the number of diesel engines
being increased to 1.1 billion by the year 2020. Increasingly stringent environmental regulations,
however dictate the need for a super clean diesel that is a carbon neutral fuel with low emissions
and a high internal combustion efficiency.
As an alternative fuel to the conventional crude oil based diesel, the FT diesel which is called the
Fischer-Tropsch diesel, has a high cetane number and almost zero sulfur content, has been
proven to be effective dramatically reducing the emission of sulfur dioxide, nitrous oxides,
nitrogen oxides and particulate matter - all the Sox and NOx all these things - as compared to the
conventional fossil fuel diesels.
Now consequently automobile manufacturers worldwide are increasingly viewing Fischer

Tropsch diesel as a feasible alternative diesel engine fuel given its two primary differentiating
attributes. The first: high fuel efficiency and the second: a low impact on the existing distribution
infrastructure. That means you do not have to modify the engines for the biodiesel or the FTD.
730
So, FT diesel can be obtained from syngas via the Fischer Tropsch synthesis process which
industrially usually consist of 3 steps. The first is the gasification or reforming into syngas of the
carbon containing materials such coal, natural gas or sustainable biomass. Second is the catalytic
Fischer Tropsch synthesis. The third: a product work-up, usually involves a mild hydrocracking
step.
So, this is a classical syngas biorefinery schematic presentation, let us understand. So, it can be
natural gas, coal, biomass, mostly since we are talking about biodiesel, so it is biomass.
However, coal and natural gas also can be co-feeded. Then we produce hydrogen and carbon
731
monoxide - the syngas. So, when you talk about the Fischer Tropsch synthesis if you go for the
FT synthesis then further refining will give us gases, LPG, naptha, kerosene, diesel all the cuts.
Then finally lubes and waxes. And, as it is also we can use hydrogen and methane. Then if you
go for the methanol synthesis route - we get DME or the dimethyl ether; so it can further be
converted to propylene, ethylene, gasoline, acrylic acid and further some oxygenating
compounds.
So, the FT synthesis converts syngas into hydrocarbons mainly alkane and alkene through
catalytic hydrogenation; the process can in principle be expressed by the following chemical
reactions in their simplified forms:
The hydrocarbon formation reaction:
The water-gas shift (WGS):
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Now, in these equations the CH2 group represent the chain type hydrocarbons ranging from
methane to heavier waxes. These reactions are in principle, very important due to their
applications in converting syngas derived from coal, natural gas or biomass based carbon
containing materials into several of the useful hydrocarbons that has served as the backbone of
modern motor fuels and the feedstock of chemical plants.
The hydrocarbons produced from the FT synthesis are mainly straight chain alkanes and alkenes,
although small amounts of isomers and oxygenates are also produced in addition to the primary
byproducts, water and secondary carbon dioxide.
733
So, this is an interesting process flow schematic for the biodiesel production from the syngas. So,
the raw gas from the gasification unit that is coming - it goes to the water gas shift reaction. Then
it goes to the acidic gas removal where carbon dioxide has been removed and you can have the
sulfur recovery coupled with that carbon dioxide removal process. And part of the carbon
dioxide also can be recycled back to other processes like this tail gas treatment.
Then this purified syngas which is having a sulfur content of almost less than 50 PPB goes to the
Fischer Tropsch synthesis loop. So, where the FTS is being after the process is over, we will get
the FTS crude. So, which will further be processed or maybe we can say that upgraded to give us
diesel almost 70% and naphtha 20%. Then the dry gas part of that FT gas can be sent back to the
tail gas treatment unit and again the lighter hydrocarbons can be recycled back.
And whatever is coming out from the tail gas treatment unit is nothing but the LPG - 6% around.
And from the water treatment plant also which is coming from the FTS loop the water based
actually. So, it will get oxygenating compounds almost 4%. So, this is the usual process
schematic for the biodiesel production from the syngas.
So, we will try to understand the process in a better way. Let us go through it. So, a simplified
flowchart of the Fischer Tropsch process that is what we have already seen it. From this diagram,
it is clear that the FT synthesis process for processing syngas is rather very straightforward
734
irrespective of the syngas source. Within the process boundary limits assumed here, part of the
inlet raw syngas stream from the gasification unit is first shifted in a water gas shift reactor to
adjust the hydrogen carbon monoxide ratio to approximately 1.6 to 2.
It is very important to do that otherwise your reaction will not proceed in the proper direction.
The raw syngas is subsequently subjected to a purification process to remove contaminants in
order to maintain sulfur concentration below 50 ppb - parts per billion. So, the acid gas stream
with high concentrations of hydrogen sulfide and other sulfur compounds exiting from the gas
purification unit is sent to a sulfur recovery unit to collect the elemental sulfur.
So, this is the sulfur recovery unit, just I was mentioning about that, it is also very important part.
Because you anyway you are recovering the sulfur out of that even if it is a small amount of
sulfur that is present in the entire process streams, you can understand that the amount of
feedstock the plant is processing per day. So, it is a quite significant amount of sulfur that is
needs to be recovered. So, in order to meet the quality specification, purified syngas must have a
hydrogen + carbon dioxide volumetric content above 98%.
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So, once this level of purity has been reached, the syngas thus generated is fed to the FT
synthesis reactor to produce the hydrocarbons, so gaseous, liquid, wax and of course water. Since
a significant amount of reaction water is generated which usually dissolves the FT synthesis
oxygenates, a dedicated water treatment unit in the FT synthesis process is therefore required.
So, this is the water treatment unit which we are right now talking about which is directly
coming from the FTS loop the Fischer Tropsch synthesis loop.
The light condensate recovered is then combined with the major wax and condensate stream
from the FT synthesis reactor and subsequently sent to the product processing unit for upgrading
into end products such as diesel, naphtha and liquid petroleum gas.
736
So, students, with this I windup today’s lecture. So, in the next lecture we will discuss about
transesterification, the FT process and catalysts. So, basically we will understand the
transesterification reactions including the esterification reaction in detail. And we will also
understand what is the importance of catalyst and what are the various types catalyst that are
being used for transesterification and FT processes including the homogeneous and
heterogeneous catalyst all.
So, thank you, and in case you have any query please register your query in the swayam portal or
you can drop me a mail directly at [email protected].
737
Module-07
Lecture-20
Transesterification FT Process, Catalysts
Good morning students, this is lecture 2 under module 7. As you know that we are discussing
biodiesel under this particular module. Today we will discuss about transesterification reaction in
detail, the various reaction mechanisms basically. As well as the Fischer-Tropsch process and we
also discuss about the catalyst and the reactors which are required to carry out such reactions. So,
let us begin.
So, transesterification gained much acceptance in recent years for the conversion of the vegetable
oils into products with technically more compatible fuel properties. Transesterification is an
imperative process for biodiesel production, as it can reduce the viscosity of the feedstock
vegetable oils to a level closer to the conventional fossil based diesel oil. It represents an
important group of organic reactions during which interchange of the alkoxy moiety results in
the transformation of one ester to another as per this particular scheme.
738
You can see this, this is the simplest reaction glyceride + alcohol with a presence of a catalyst, it
can be any acid type catalyst, basic type catalyst or homogeneous, heterogeneous anything. So, it
will result us ester + glycerol, this is the general reaction scheme. So, we will learn about the
detailed mechanism later.
So, transesterification is an equilibrium reaction describing the alcoholysis of carboxylic esters

usually performed in the presence of a conventional catalyst (sodium hydroxide, potassium
hydroxide) for valuable acceleration of the equilibrium adjustment to achieve a higher yield of
esters. Chemically vegetable oils are triglyceride molecules with structural differences in their
glycerol bound alkyl moiety.
739
Now transesterification of these triglyceride molecules with short chain alcohols in the presence
of suitable catalyst results in fatty acid methyl esters and glycerol. Now these fatty acids (FAME)
are your biodiesel. Now a sequence of 3 consecutive reverse reactions illustrates the overall
transesterification process.
So, this is how it happens actually, this is the overall reaction mechanism of a biodiesel
formation. Now we have a triglyceride that reacts with methanol to give us diglyceride and one
methyl ester. Now what you see that, we are getting series of methyl ester R 1, R 2, R 3 different
R groups and a series of methyl esters. So, these reactions are happening simultaneously.
740
Now that diglyceride is again reacting with another methanol molecule to give us a
monoglyceride and another methyl ester. This monoglyceride is further reacting with methanol
to give as another methyl ester and glycerol. So, glycerol is the final byproduct of
transesterification reaction.
741
So, let us understand the chemical transesterification reactions. Chemically biodiesel can be
synthesized either by acid catalyzed or base catalyzed transesterification of the feedstock. Now
we will discuss both. So, acid catalyzed transesterification reactions: acid catalyzed
transesterification reactions are mostly carried out by Bronsted acids, preferentially sulfuric,
hydrochloric and sulfonic acids.
So, this name bronsted acid, bronsted base many times you will come across in such type of
reactions. So, bronsted acid is something which actually is ready to give a proton, and bronsted
base is one which is ready to accept a proton. So, this is the general understanding of bronsted
acid and base. So, the mechanism of acid esterification is described in scheme 3, so in the next
slide it is there.
742
So, let us see what is this reaction, I will try to make you understand. So, here you can see there
is one catalyst is there, so H+ is a protonated catalyst. So, here carbocation reaction II results
from the carbonyl group protonation of the ester as a first step followed by a nucleophilic attack
of an alcohol producing a tetrahedral intermediate. So, let me make you understand this reaction
mechanism.
So, here this is first getting protonated, now this protonated is going to make as a carbocation
molecule. Now what is a carbocation molecule? So, this is a carbocation molecule. So a
743
carbocation molecule is something in which the carbon atom is positively charged. So, it is a
carbon cation basically. The carbon atom here is positively charged, and it has 3 bonds, you can
see 1, 2, 3. Now this carbocation group is reacting with the alcohol to give as an intermediate
complex.
Now this intermediate complex, when we remove glycerol molecule from this intermediate
complex, then we will get the methyl ester. And the catalyst will be again further deprotonated.
So the deprotonated catalyst will have more active surface areas to further carryout the reaction.
So, this is an overall simplified understanding of how the esterification of the monoglyceride can
be extended to diglyceride and triglycerides, so this is a series of reactions.
Now, the presence of water may decrease the alkyl ester yield due to the formation of the
carboxylic acids by reaction with carbocation II; therefore, competitive carboxylic acid
formation can be avoided using water free feedstock. Although high yields of alkyl esters can be
achieved using acid esterification, certain disadvantages, that is slow reaction speed, high
temperature requirement and difficult glycerol recovery render it unfit for use.
Mostly acid esterification is recommended as a pre step for biodiesel production via base
catalyzed transesterification where an acid value lesser than 2 to 4 milligrams potassium
hydroxide per gram is required which can be easily achieved by acid transesterification of the
744
feedstock. Now chemical transesterification reactions catalyzed by acids are highly beneficial for
the feedstock with higher free fatty acid content. So, those, feedstock which have a very high
free FFA content they can go for the acid catalyzed reaction.
So, acid catalyzed reaction results in better yield, although the reaction is time consuming, slow
and requires higher temperature conditions. Acid esterification is well accepted as a pre step for
the base catalyzed transesterification reactions to esterify free fatty acids if higher than 2%, if
they are present higher than 2%. The acid catalyzed transesterification therefore helps in
reducing the levels of the free fatty acids to a level compatible with alkaline transesterification.
For acid esterification of feedstock with higher free fatty acids, sulfuric acid is a more effective
catalyst compared with others including hydrochloric acid, formic acid, nitric acid and acetic
acid. Inadequacy of base catalyzed transesterification reactions for the vegetable oils with high
free fatty acid content is also reported by various researchers.
745
Now we will discuss about the base catalyzed transesterification reaction. So, alkaline catalyzed
transesterification reactions are much faster than acid catalyzed esterification reactions and have
gained much attention. Substantially anhydrous feedstock with the least free fatty acid content
gives the best results regarding ester yield using base catalyzed transesterification. Now because
of the less corrosive nature of the alkaline catalyst compared with acid catalyst, at industrial scale
alkaline catalyzed transesterification is usually preferred, because it is anyway a faster reaction.
Now the most commonly employed alkaline catalyst are sodium and potassium hydroxides and
alkoxides. These catalysts are well accepted for industrial scale biodiesel production, because
these are low cost and easy to transport and store. Comparatively, sodium and potassium
methoxides are preferably being used to catalyze continuous flow processes for the production of
the biodiesel.
746
The only disadvantage associated with the base catalyzed transesterification is the additional
purification requirements of biodiesel and glycerol for the removal of the base catalyst. To avoid
this drawback, researchers have investigated heterogeneous catalyst for their potential to catalyze
transesterification. Simple filtration can separate heterogeneous catalyst from the end products
and thus can be reused.
Now some important heterogeneous catalyst investigated by scientific community to catalyze

transesterification reactions include Hb-zeolite, zinc oxide, titanium dioxide, zirconium dioxide,
zeolites, alkaline earth oxides, then ion exchange resins, dolomites, sodium aluminate, then
calcium oxide and magnesium oxide. So, there are many more; I have just listed a few. More or
less these are tested, gave high selectivity and also readily available and many of them are also
low cost.
747
So, now let us understand the mechanism for the base catalyzed transesterification reactions.
Now, base catalyzed transesterification of vegetable oil starts with the reaction of alcohol with
alkaline catalyst resulting in the generation of alkoxide along with the protonated catalyst. A
tetrahedral intermediate is then formed as a result of nucleophilic attack of alkoxide on carbonyl
moiety of the triglyceride. Let us see how; actually in the next slide it is there.
So, there are 4 steps being shown here. The first one, the alcohol is reacting with the catalyst, B
is the catalyst. So, the B is getting protonated, so BH and we will get a carbonyl moiety of the
triglyceride. So, here you can get a carbonyl moiety, so when it is again reacted, so we get
another intermediate product. Now that intermediate product is again decomposed into 1 anion,
748
this is 1 anionic group and plus here ester. Now this anionic group is further reacted with the
protonated catalyst to give as a methyl ester and deprotonated catalyst. Now this deprotonated
catalyst is having free or active more surface area which can carry out further reactions, so
simple reaction mechanism.
749
So, we will try to understand the experimental steps for biodiesel synthesis. Two step synthesis
of biodiesel from feed with high free fatty acid. Different steps of the process include: First is
that mixing of appropriate amount of oil, methanol and catalyst in a reaction vessel. Catalyst can
be homogeneous or heterogeneous acidic catalyst. Heterogeneous catalysts are preferred over
homogeneous as the later one is associated with disadvantage such as reactor corrosion and
difficulty in separation.
Now second, raising the temperature of the reaction mixture to the desired reaction temperature
and stirring the mixture for the desired reaction time at that temperature. Once the reaction is
finished and the desired free fatty acid level is reached, the mixture can be centrifuged to
separate the catalyst from it. That is why you can use the heterogeneous catalyst, so you can
remove is using centrifugation and filtration.
750
The separated esterified product can then be directly used for the transesterification process or
after removing the excess solvent from the product at reduced pressure in a rotary evaporator.
For the transesterification process the esterified product is mixed with appropriate amount of an
alcohol and a suitable base catalyst. The temperature of the mixture is then raised to the desired
reaction temperature at which it is mixed for the desired reaction time.
After completion of the reaction the excess solvent either methanol or ethanol is then separated
at reduced pressure by using a rotary evaporator. The solid catalyst is separated from liquid
product by centrifugation. The liquid mixture is then kept in a separating funnel where the
byproduct glycerol is separated as the bottom product. So, I hope you understand and I have
listed entirely the experimental procedure how to produce biodiesel.
751
So, this is the direct transesterification of the feed with low free fatty acid content. So, we can
see that, so vegetable oil or animal fat less than 2.5% free fatty acid, so you can add catalyst and
alcohol, so you can go for the transesterification. Here the vegetable oil and animal fat which are
having greater than 2.5 weight percent of free fatty acid will be esterified first.
So, try to understand the two different processes. Here if the free fatty acid content is less than
2.5 weight percent then you can directly add a catalyst and alcohol and you go for the
transesterification. Now if the free fatty acid content is higher than if you remember we have just
discussed that when the free fatty acid content is higher we usually go by the acid catalyzed
reaction. So, that is a pre step before the base catalyzed reaction so then you are just going to do
that.
So, esterification by the acid catalyst, then you get oil with free fatty acid content which is less
than 2.5 weight percent then you go for the usual transesterification route. Then you go for the
solvent recovery, catalyst separation, crude biodiesel and remove the glycerol. So, glycerol can
be further purified by base neutralization and you get the biodiesel. So, this is the schematic or
flow chart you can say of the biodiesel production.
752
Then we will try to also understand the biochemical or enzymatic transesterification reactions.
So much of work has already been done and reported (you can see the literature) on enzymatic
transesterification reactions. Now compared with the use of acids or alkalis to catalyze
transesterification reactions for biodiesel production, enzymes with significant advantages are
attracting the researchers.
The advantages associated with enzymes are: they have huge specificity, reuse ability, mild
reaction conditions requirement, and efficiency improvement by genetic engineering, whole cell
immobilization, capacity to accept multiple substrates, they are natural and their thermal stability
to catalyze green reactions. Now enzyme based catalyst reaction system is time consuming as
compared to the conventional catalyst reaction process.
We have learnt that basic catalyzed reactions are extremely fast, so they are industrially being
adapted. So, lipases extracted from different microbial strains have been utilized as biocatalyst
for the production of biodiesel by researchers.
753
High stability and repeated use of immobilized lipases were revealed to be the superior
characteristics compared to the free lipase for biodiesel production. Anyway in one class we
have discussed about the importance of immobilization. So, immobilized lipases can be reused
for many times rather than free lipases, and they have other advantages also. So, different
immobilization methods have been reported by different researchers but of these the most
appropriate method was found to be lipase entrapment on sol-gel matrices with hydrophobic
nature and lipase adsorption on hydrophobic carriers such as polypropylene.
Whereas lyophilized powders and immobilized preparations are the recognized commercially
available lipases. In the recent years, researchers have investigated different reaction systems for
conducting the best lipase catalyzed transesterification reactions. Solvent free system, organic
solvent medium with hydrophobic nature, hydrophilic reaction medium and ionic liquid medium
are among the well considered reaction systems for biodiesel productions.
754
So much of work has already been reported and some of them are fantastic works. So, this is I
am trying to show you the process flow schematic for the biodiesel production from the
vegetable oils. So, what you are going to do is that, you are adding methanol and catalyst to the
vegetable oil feed to the reactor. So, here the reaction is happening then you go for the separator,
so here you remove basically the glycerol.
So, almost close to 50% yield. So then you go for acidulation and separation, you are just adding
acid. So, you get the free fatty acid whatever unconverted free fatty acids here, then again you go
for your methanol removal here, so you get the methanol removal method, so you get the crude
glycerol which is almost 85% yield. So, the methanol can also be recovered and goes to the
methanol water rectification unit, so you can basically recover the methanol.
So, from here the methyl ester, your biodiesel part, goes to the methanol removal part, here
methanol is removed and again fed back to the rectification unit. Then it goes to the
neutralization and washing step which are just the finishing steps. So, you go for drying then you
get the finished biodiesel. So, you may need acid, water and all these things to do that in this
process.
755
So, please understand that this is the simplified schematic representation of the biodiesel
production from vegetable oils. There are many small unit operations and many small operations
are there which are not being shown here in industrial scale what is being required actually.
So, let us understand the process; alcohol catalyst and oil are combined in the reactor and
agitated for approximately an hour at 60 degree centigrade. Smaller plants often use batch
reactors but most, larger plants greater than 4 more million liters per year production, use
continuous flow processes involving continuous stirred tank reactors CSTR or plug flow
reactors.
Now let us understand the glycerol separation; following the reaction glycerol is removed from
the methyl esters. Due to the low solubility of glycerol in the esters this separation generally
occurs quickly and maybe accomplished with either a settling tank or a centrifuge. So, when you
talk about a huge amount of feedstock you are dealing with that, you cannot go for a centrifuge,
so you have to go for settling tank.
Now the excess methanol tends to act as a solubilizer and can slow the separation. However, this
excess methanol is usually not removed from the reaction stream until after the glycerol and
methyl esters are separated because the transesterification reaction is reversible and the methyl
756
esters may recombine with glycerin to form the monoglycerides. So, that is one of the biggest
disadvantage and you have to take care of that.
So, the glycerol stream leaving the separator is only about 50% glycerol, it contains some of the
excess methanol and most of the catalyst and soap. The first step in refining the glycerol is
usually to add acid to split the soaps into free fatty acid and salts. The free fatty acids are not
soluble in the glycerol and will rise to the top and where they can be removed and recycled. The
salts remain with the glycerol although depending upon the chemical compounds present some
may precipitate out.
After acidulation and separation of the free fatty acids the methanol in the glycerol is removed by
a vacuum flash process or another type of evaporator. The glycerol refining process takes the
purity up to 99.5% to 99.7% using vacuum distillation or ion exchange processes.
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Then methanol separation; after separation from the glycerol the methyl esters pass through a
methanol stripper usually a vacuum flash process or a falling film evaporator before entering the
neutralization step and water washing. Acid is added to the biodiesel to neutralize any residual
catalyst and to split any soap that may have formed during the reaction. Soaps will react with the
acid to form water soluble salts and free fatty acids. The salts will be removed during the water
washing step and the free fatty acids will stay in the biodiesel.
Then washing the biodiesel; a water washing step is intended to remove any remaining catalyst,
soap, salts, methanol or free glycerol from the biodiesel. Neutralization before washing reduces
the water required and minimizes the potential for emulsions to form when the wash water is
758
added to the biodiesel. Following the wash process, any remaining water is removed from the
biodiesel by a vacuum flash process.
Now let us understand the FT synthesis, the Fischer Tropsch synthesis, though we have
discussed about Fischer Tropsch earlier also. We will again see the reactions and other process
conditions and reactors in detail. So, in FTS syngas, that is carbon monoxide and hydrogen is
catalytically converted into a spectrum of hydrocarbon chains, so this is the reaction, this we
have already discussed earlier.
But again to maintain the reading properly, so I have again given these reactions. So, the 4 main
metals considered for Fischer Tropsch synthesis are iron, cobalt, ruthenium and nickel.
Ruthenium the most active is impractical due to it is high cost and low abundance, it is a very
costly metal. Nickel although inexpensive is plagued by coking and typically considered a
methanation catalyst.
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Thus cobalt and iron are the essential active industrial metals for the Fischer Tropsch synthesis.
The cost of iron based FT catalyst is estimated to be 10 to 40 dollar per pound, whereas cobalt
based FT catalyst can cost about 60 to 100 dollar per pound. And are more susceptible to the;
marketplace due to increasing demands in the aerospace and batteries. Each FT catalyst
developed to date has their, own yield structure.
Cobalt based catalyst produces more water and water cleanup is required whereas iron based
catalyst active for the WGS produces even carbon dioxide which can be sent to a (WGS is the
water gas shift reaction) shift reactor. So, iron catalyst can be used in a wider variety of
feedstocks compared to cobalt catalyst, however, economics still is the driving source and
finding the cheapest available feedstock. Another advantage of iron, spent cobalt catalyst needs
to be reclaimed whereas iron catalyst can be land filled.
760
This is just a schematic understanding of the sources for the synthesis gas for the Fischer
Tropsch synthesis process. So, it can be coal, it can be biomass, it can be natural gas, now those
can be converted to syngas, carbon monoxide and hydrogen and further go for the Fischer
Tropsch process and you get your fuel. Similarly, carbon dioxide from the atmosphere or from
the flue gas and electricity also can help to produce carbon dioxide and hydrogen. And this also
can be further processed by the Fischer Tropsch process to generate fuel.
Now let us understand little more about the FTS catalysts. Structural and chemical promoters are
usually added on iron based catalyst. Binders such as silica are usually added to improve the
structural rigidity of iron catalyst. Alkali metals are electronic promoters that facilitate
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carburization, increase the FTS activity and improve the selectivity to high molecular weight
hydrocarbons.
Promoters such as copper are added in part to facilitate the reduction of iron oxides. Because
cobalt is expensive, to increase the number of cobalt atoms exposed at the surface, cobalt nano-
particles are dispersed on carriers such as metal oxides, zeolites, carbon materials, manganese,
ceria, silica carbide, and various other number of materials. Many of these supports originally
thought to be inert, are now being used to promote a specific selectivity.
Unlike iron, promoters used for cobalt do not significantly increase the turnover frequency;
rather these metals aid in increasing the percentage of reduction of cobalt oxides to cobalt metal.
Whether it promotes methanation depends on the nature of the promoter. Lastly, unlike cobalt
and ruthenium where the metallic surface is deemed active for the Fischer Tropsch synthesis,
several species of iron carbide exhibit Fischer Tropsch synthesis activity.
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So, we will try to understand the mechanism now. So, ninety years have passed since discovery
of the Fischer Tropsch synthesis process. However, many details regarding the mechanism
remains speculative. Interactions between the active metals with carbon monoxide or hydrogen
are still being investigated to elucidate specific dissociation pathways, and their kinetic effect on
hydrocarbon chain growth.
Carbon monoxide may dissociate directly or with assistance of hydrogen in a concerted manner.
Two different mechanistic families have been proposed to explain initiation and chain growth
steps during the Fischer Tropsch synthesis, first is carbide mechanism, second is carbon
monoxide insertion mechanism.
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So, in carbide mechanism first proposed by Fischer and Tropsch, carbon monoxide dissociatively
adsorbs to form carbide and surface oxygen. Carbide species are partially hydrogenated to CHx
intermediates which serve as a chain growth monomer. Termination occurs by abstraction of
hydrogen to form olefins or by addition of CH3 species or hydrogen to form paraffins. Whereas
in carbon monoxide insertion mechanism; carbon monoxide directly inserts into the growing
hydrocarbon chain prior to carbon oxygen scission manner.
Micro kinetic models, isotope tracer studies and steady state and transient kinetic investigations
lend support to this mechanistic scheme, where C-O scission is the key step.
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So, tuning; since both carbon monoxide and vinylic intermediates are π-accepting based ligands,
both are susceptible to electronic back donation from the catalyst surface.
So, we will see a mechanism here. So, this is FTS mechanism, it is a balancing act controlled by
the localized electron donating capability of the active surface. So, you can see this, you can see
that carbon monoxide dissociation rate. Here this side it is decreasing where the electrons are
withdrawing, here it is increasing where the electrons are donating. Various catalyst like nickel,
cobalt, ruthenium, iron carbide, iron, all these are being used.
And different catalyst depending upon the different dissociation rate and what is the active
surface and what type of bonding is happening, you will get different types of products. Let us
go back; so this, whatever I have shown, is a Dewar-Chatt-Duncanson model and is a base model
used to describe how localized back donation from the metal will specifically affect how these
species will interact.
So, if the localized sp2 character is retained, both carbon monoxide and C2 will be weakly bound
to the surface and the C = C will be observed in the IR is remarkably similar to the free C = C.
So, it is specifically talking about this and the position is also very important. Now in contrast to
weak back donation, if too strong carbon takes one more sp3 character as a metallocyclopropane
species.
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Vibrational observations then reveal that C-C bond weakened to resemble a single bond X2, this
one. So, you can see here it is a double bond, here the bond is weakened, it is a single bond here.
So, vibrational observations reveal that C-C bond we can to resemble a single bond marked by
the X2 in the image. Thus, a balance for the back donation of FTS is of great importance and if
not held could lead to inferior and pore catalyst.
Now in general based upon the figure 3, different major scenarios can be identified. So, we will
discuss what are the 3 different scenarios that can happen while this carbon monoxide
dissociation is happening?
The first one is route A, weak back donation. So, carbon monoxide is adsorbed molecularly as
the scission of carbon bond with H+ is not kinetically favored. If carbon monoxide is weakly
adsorbed then the vinylic intermediate species will be an L configuration weakly bound to the
surface, this one. They will be in this type of configuration L configuration.
Thus the intermediate is susceptible to hydrogenation reactions and high selectivity to methane
and light hydrocarbons are observed. As carbon monoxide dissociation is difficult, carbon
growth from the weakly bound L configured vinylic intermediate could be through the carbon
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monoxide insertion. Moreover, the carbons of the vinylic intermediate exhibit sp2 hybridization,
that is electrophilic in nature because of the weak back donation from the metal.
Now consequently, chain growth can occur at either C position, resulting in internal olefins,
branched paraffins, and oxygenated materials through a pseudo hydroformylation series of steps.
This configuration has been proposed for the un-promoted iron carbide. So, basically we
discussed about this, we can see the n-paraffins, branched olefins, 1-olefin, 2-olefin, acids,
ketones and esters all these things will be produced in this route weak back donation.
Now route B is the semi strong back donation. Now carbon monoxide adsorbs in an associative
manner followed by H dissociation on the active side. As adsorbed carbon monoxide is stable, so
is the vinylic intermediate as an X2 configuration. Now we are talking about this configuration,
we can call this as a semi strong back donation happening here, thus this is the metallic surface
of the catalyst.
So, these species are suitably stabilized on the active surface to favor chain growth solely at the
Cx position, resulting in a fingerprint of primarily linear paraffins and 1-olefins as observed for
cobalt and ruthenium catalyst, usually cobalt and ruthenium based catalyst are being used.
Potassium promoted iron catalyst can also be included in this configuration.
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Now route C, the last one is the strong back donation. Now as carbon monoxide rapidly
dissociates the vinylic intermediate, that is the π-acceptor, will also easily dissociate forming a
carbidic phase. The X2 configuration though present will not possess sufficient stability and will
dissociate to an active carbidic phase which will convert to methane or inactive graphite carbon.
Now this usually happens with nickel catalyst. So, you can see that the same X2 configuration,
with the nickel catalyst will result as methane and coke formation will happen, so due to the
strong back donation scheme. After carbon monoxide was decomposed on further surface of the
nickel or silicon dioxide immediately after hydrogen and unlabeled carbon monoxide produced
methane and carbon dioxide, suggesting that methanation involves a Cs intermediate, which
basically happens due to the strong back donation.
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So, we will try to understand now and learn about the different reactors that are essential for the
FT synthesis reaction. So, slurry bubble column reactor, the SBCR. The development of a low
temperature slurry phase FTS process began in 1938 by Kolbel and Ackermann and the
technology attained a production rate of 11.5 tons of hydrocarbons per day. In a typical slurry
bubble column reactor synthesis gas enters from the bottom of the reactor and thoroughly mixes
with the liquid phase containing the catalyst.
The reaction takes place on the catalyst surface and the product gas exits from the top with
heavier hydrocarbons being recovered from the bottom using an appropriately sized metal filter.
Cooling tubes remove the heat produced by the reaction; the major issue with the slurry phase
reactor was product separation from the catalyst. Since some breakthrough of the catalyst occurs
activity declined.
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A problem with the conventional SBCRs is the scale up. In most cases the initial reactor design
is solely based on the reactor results from the laboratory and/or pilots plant scale studies.
Assumptions made based on preliminary testing of the slurry bubble column reactors at small
scale may not apply at the industrial scale due to the differences in the reactor hydrodynamics.
So, SBCR technology has been adopted by both industry as well as academia because of the
simplicity of the operation compared to the fixed bed reactors. Exxon and Sasol have
independently developed SBCRs as shown in figure 4 a and 4 b.
We will see these 2 reactors. So, the A design is done by the Exxon company and B design is by
the Sasol. So, you can see that there is little difference between the design. So basically you can
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see that in the B you have cooling coils that is inserted inside the reactors. So, that the cooling
can be done very fast, if you have it outside the reactor, so it will take time and cooling effect
may not be so good.
But if you put it inside the reaction, but there are problems also maintenance and all these things
is a big issue, so but the cooling can be faster. So, here you can see the reaction, this is the main
reaction zone and there are integrities given here. Mostly both the designs have been well
adapted by industrial sector, and are still in practice.
Then is the fluidized bed reactors which are also very common. Sasol has employed circulating
fluidized bed reactors commercially for many years. One drawback is that high temperature
operation is required to achieve high productivity. Now this precludes the use of typical high
surface area catalyst which would otherwise undergo attrition under such harsh conditions, thus
lower surface area, attrition resistance, catalysts are used.
Other problems include an energy requirement to circulate the catalyst and the pressure drop.
The Sasol fixed fluidized bed reactors have replaced circulating based reactors. So, this is a
typical circulating fluidized bed reactor.
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So, then we will discuss about the fixed bed and compact bed reactors. Now the fixed bed reactor
configuration offers high throughput with plug flow behavior, lower maintenance cost and
reduced losses due to attrition and wear. Moreover, they are easily tested at small scale using a
single tube. So, you can see that there are many tubular tubes are here, so you can have single
tube, you can have multiple tubes.
It is basically a design how much feed you are processing, that is very important. So, multi-
channel fixed bed reactors are much smaller in size as they are complicated to fabricate, but they
are more mobile useful for reaching standard resources. You can carry it them and install it any
other places. So, the catalytic activity in micro channel reactor can certainly be higher because of
the better heat transfer. However, there is also the reactor cost which is part of the capital cost
and has less impact on the economics unless the difference is huge.
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So, with this I wind up today's lecture. So, in the next lecture which is again under module 7
lecture 3 under biodiesel, we will discuss about the techniques to purify biodiesel and we will
also discuss about the biodiesel fuel properties. So, thank you very much, in case you have any
query, please register, it on the swayam portal or you can drop a mail to me at
[email protected].
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Module-07
Lecture-21
Biodiesel Purification Fuel Properties
Good morning students. Today is lecture 3 under module 7 and as you know that we are
discussing biodiesel under module 7. Today we will be discussing about the biodiesel
purification and fuel property. So, let us begin.
Transesterification of triglycerides with short chain alcohols, that is either methanol or ethanol in
the presence of an alkali catalyst has been most widely used to obtain biodiesel or essentially we
can say that fatty acid alkyl esters. So, glycerol is an important byproduct of the
transesterification reaction which needs to be separated from the biodiesel phase.
So, if you recall in our last class, we have discussed extensively how transesterification reactions
happen, what are the different types of reactions, acid catalyzed, base catalyze and everything.
So, depending upon the regional regulation biodiesel needs to meet certain characterization prior
to reaching the market. Regional regulations essentially means every country has their own
regulations and fuel standards, so that you have to meet.
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So, even though the densities are biodiesel and glycerol are distinct enough from one another to
be separated via gravitational settling and centrifugation, further purification is required to
remove impurities? So what are those impurities? Now the remaining vegetable oil, alcohol,
catalyst, a little bit quantity of the soap and the free fatty acids which are not purified and meet
the standard specification introduced in the ASTM D6571 or EN 14214. So, ASTM is the
American Society for testing and materials, and EN is the European standards, any one of these.
Low quality biodiesel due to impurities cannot only compromise the engine performance, but
also complicate the storage and transportation of the fuel. Biodiesel purification techniques
include wet washing using water, you can use acidified water also, some organic solvents or
ionic liquids, the ionic liquids are a bit costly. Or else you can use dry washing via adsorption or
ion exchange and membrane separation.
Now biodiesel purification method has been characterized based on the nature of the process
such as either equilibrium based, affinity based, membrane based, solid-liquid or reaction
separation based.
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So, as shown in the figure. So, this figure I will explain you. You can see this, this is the classical
representation of how the biodiesel can be purified, so as to get high purity biodiesel. So, 4
things have been shown here, 4 different types or distinct separation processes equilibrium
based, so it is distillation. You can see that crude biodiesel, impurities are present, so the
biodiesel mixed with solvent, then it will be purified.
Then affinity based is basically adsorption, so AD. So, here you will use different types of
adsorbents to remove the impurities. So, all the impurities will be adsorbed either in the surface
of the adsorbent or it may get inside the pores also. So, then you or you can have ion exchange
also. So, either you can have cation exchange bed, you can have anion exchange bed, so it is a
packed bed system, where the impurities will be attached to the ion exchange resins and
biodiesel will be purified.
Then membrane based: Membrane has often taken a very important role in most of the process
industries using chemicals, pharmaceuticals, then food and beverage industries. Now in this case
also biodiesel also can be purified using different types of membrane system maybe
ultrafiltration, nanofiltration and others where the beauty of the membrane separation is that you
can tailor make membrane to target a specific separation.
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So, either you can retain them on the top, all the impurities, or you can pass them to the permeate
side depending upon the pore size. Then the last one is reaction based which is called reactive
distillation. So, reactive distillation is a distillation process where reaction and distillation both
are happening in the same chamber or the same unit, we will discuss this in detail later on or we
can have membrane bioreactor.
So, here feed is being processed, feed is being fed to the membrane bioreactor where the
biodiesel is getting produced as well as getting purified in a single system. So, we will discuss
one by one.
So, let us discuss the first one which is equilibrium based separation process. So, absorption and
distillation as well as supercritical fluid extraction and liquid-liquid extraction are some of the
most common equilibrium based separation processes. Absorption is commonly utilized for
separating particles and impurities from a gaseous mixture, therefore it does not have a major
application in the biodiesel separation which is a liquid phase process.
Let us talk about distillation. So, distillation is the most common method for separation of more
volatile compounds from heavier substances in a liquid mixture. There are different distillation
techniques including conventional distillation, which are ordinary, vacuum or steam distillation
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or azeotropic distillation - if at all the feed streams have formed azeotropes (close boiling point
mixtures basically) or you can go for extractive distillation or molecular distillation.
Now conventional distillation and evaporation are perhaps by far the most common methods
used in biodiesel purification to remove the remaining alcohol or water from the crude biodiesel.
Typically, the unreacted alcohol is separated from biodiesel prior to further purification. In
molecular distillation carried out under high vacuum the molecules’ free path is longer than the
evaporation and condenser surface distance; therefore, most of the evaporated molecules reach
the condensing surface without being deflected on collision with foreign gas molecules resulting
in a higher separation yield. Literature reported that molecular distillation was used to purify
biodiesel obtained from waste cooking oil to achieve a 98% separation yield at the evaporator
temperature of 120 degree. So, if you look at the literature, you will find there are plenty of
works when biodiesel has been purified.
Basically the glycerol has been removed. Glycerol is already removed, when you are talking
about purification stuff we are just removing the unconverted vegetable oils, some free fatty
acids, then alcohol - very important. So, all these things are being very successfully removed by
distillation process. Now in certain cases, it has been also observed that distillation followed by
another unit operation where it can be treated as a last polishing step to further sometimes you
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may have to dehydrate it and some other polishing steps are necessary, so as to get a purified
biodiesel.
So, then is LLE which is called liquid-liquid extraction. So, it is also known as the solvent
extraction - is a well-established separation technique to extract desirable components from a
liquid feed to a specific solvent. So, this process is the most common method used for biodiesel
purification that encompasses all the techniques developed for wet washing. The use of
deionized water to remove soap, catalyst, alcohol and other contaminants of biodiesel is one of
the most common biodiesel purification methods.
So, water temperature and volume are the key factors in improving purification of the biodiesel
phase. So, I will show you one table where we will see the negative effects of contaminants on
biodiesel and engines and why we are talking about purifying it?
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So, you can see that the methanol remains in a quantity which is more than that is desirable. Of
course, it is desirable that you remove all methanol, water, any catalyst, free fatty acids
everything. So, if methanol is present, then the deterioration of the natural rubber seals and
gaskets, lower flash points, problem in storage basically corrosion of pieces of alumina and zinc,
all these things will happen.
If water will remain in more quantity, then it will reduce the heat of combustion, corrosion of
system components, formation of ice crystals, bacteriological growth will also happen if water is
present. Then if the catalyst or soap remains then it will damage the injectors, it will pose
corrosion problems in engines, plugging up filters and weakening of the engines. If free fatty
acids are present then it will reduce the oxidation stability, it will also create corrosion problem
in the vital engine components.
Similarly, glycerides and glycerols, so all these things will lead to crystallization, decantation,
storage problems and has to be removed.
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So, let us now understand the wet washing technologies. So, production of biodiesel is usually
followed with soaps formation and water production especially when low quality feedstock and
alkaline catalysts are used as shown in the figure. So, this is a fatty acid, so you are using sodium
hydroxide as the catalyst, you get the sodium soap and then water.
So, feedstocks would be dried to control water content, which causes hydrolysis of fats and oils
to free fatty acids. The presence of free fatty acids leads to soap formation, thus interfering in the
products purification process.
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Consequently, feedstocks with high amount of water and free fatty acids molecules could easily
interfere with the transesterification reaction, resulting in soaps formation thereby affecting the
purification of crude biodiesel and lowering the yield of the alkyl esters. The commonest
effective technique to remove glycerol and methanol from biodiesel production mixture is by
water washing, since both glycerol and methanol are highly soluble in water.
Biodiesel wet washing technique involves addition of certain amount of water to crude biodiesel
and then agitating it gently to avoid formation of emulsion, you have to be very careful beyond
certain rpm or rotations per minute. If you do that, then there will be a emulsion formation
because it is oil and water will mix with each other and it will form an emulsion. You can
observe in the naked eye also, some whitish or milky color formation will start, so that is not
actually required.
So, you have to be very careful about the agitation speed. So, the process is repeated until
colorless wash water is obtained, indicating complete removal of the impurities.
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So, wet washing process usually requires a lot of water approximately water wash solution at the
rate of 28% by volume of oil, and 1 gram of tannic acid per litre of water. The use of large
quantity of water generates huge amount of wastewater and incur high energy cost, because
again you need to process this wastewater. So, wet washing is mostly conducted through
washing with deionized water, washing with acid (5% usually phosphoric acid) and water and
washing with organic solvent and water.
Anyone you can do, either with pure deionized water or with the 5% phosphoric acid mixed
water or organic solvent and water mixture. So, let us talk about that deionized water washing
technology. Water washing has been traditionally used to purify crude biodiesel after its
separation from glycerol. It was reported that air was continuously introduced into the aqueous
layer, while gently stirring the mixture of crude biodiesel and water. In one of the significant
work for which the reference has been given here.
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So, this process was continued until the ester layer becomes clear. In addition, after settling the
aqueous solution was drained and water alone was added at 28% by volume of oil for the final
washing process. Water washing is the most problematic step in biodiesel production, although
water washing involves heated, softened water, wastewater treatment and water methanol
separation, but the process of water application provides an avenue for the addition of acid to
neutralize the remaining catalyst and remove the salts formed.
Though it has certain drawbacks as we have mentioned, but it is still preferred because of the low
cost and it is efficiency, it is a benign process, it is easy to carry out. So, if you talk about
applications, literature reported that after transesterification crude biodiesel and glycerol can be
phase separated within the first 10 minute, and a complete separation could be achieved in 2
hours after stirring is stopped.
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Also alcohol can be removed through distillation and evaporation and that care must be taken to
ensure zero water accumulation in the recovered alcohol stream. Authors reported that after
phase separation deionized water is added to crude biodiesel at the rate of 5.5% by volume of the
feedstock and the mixture is stirred for a period of 5 minutes and allow to settle for glycerol
removal.
This is the procedure which is reported in this particular reference which is given here. The
removal of complete glycerol is an indication of high quality biodiesel production. Also literature
noted that washing two times is enough to get rid of impurities from the methyl esters. The crude
methyl ester produced was washed and distilled under vacuum at 30 to 80 degrees centigrade and
133 Pascal.
The product was then dried at 80 degrees centigrade for 10 minute to remove traces of moisture
and the methyl ester yield was found to be 97 to 99% which is an excellent yield. So, you can
please refer to this particular reference, which is reported in the industrial engineering chemistry
research journal in 1998, long back but it is a classic study.
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So, then acids and deionized water washing technology. Acids such as phosphoric acid, sulfuric
acid and hydrochloric acid are mostly used in the purification of crude biodiesel. This process is
followed with the use of distilled water to completely remove biodiesel impurities. For the
purpose of immediate use on diesel engines and long term storage purified biodiesel is properly
dried.
If you talk about applications, then literature noted that after one-step transesterification reaction,
the crude methyl esters produced was purified with hot water at 70 degrees centigrade and 5%
phosphoric acid at 50 degrees centigrade. The authors dried the methyl ester layer in a vacuum
and checked with ceric ammonium nitrate reagent for glycerol removal and the reference has
been given here. It is also a very interesting work reported in the fuel processing technology
journal in 2008.
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Another work stated that water have to be reduced to a limit of 0.05% volume by volume to meet
the ASTM D6751 standard specification. The authors washed biodiesel with water at a pH 4.5,
the process helped in neutralizing the catalyst and converting the soap formed to free fatty acids,
thus reducing it is emulsifying tendencies. So, one of the major aim of this work is to reduce the
emulsification.
So, further vacuum dryer wash used to reduce the residual water from initial value of 2.4% to a
final value of 0.045%. The water removed via drying was recycled into washing operation. As
well, to reduce the cost of production, the glycerol produced was also refined to a concentration
level suitable to the market value, that is approximately 80 weight by weight percent.
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So, the next is organic solvent washing technology. Organic solvents such as petroleum ether has
been used to purify crude biodiesel. Now this process is usually followed with the use of the
large amount of demineralized water to remove residual soap and catalyst. So, let us talk about
some applications. The fatty acid methyl esters was distilled under vacuum at 180 degrees
centigrade, when the temperature reached 240 degrees centigrade, that distillation was assumed
to be completed.
The crude FAME was separated after acidic transesterification and then purified with petroleum
ether and washed with hot water until the washing reached a neutral pH. n-Hexane was also used
for the extraction of crude biodiesel at 1 : 1 ratio at room temperature, the mixture was washed
three times using distilled water and the final yield obtained was 93 weight percent. So, the
references also been given, it is also an excellent work published in energy conversion
management journal in 2007.
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So, let us go ahead and talk about other separation processes. We will talk about affinity based
separation process. So, adsorption and ion exchange are the most common affinity based
separation processes, also known as that dry washing methods for biodiesel purification. In these
processes an appropriate adsorbent is used to selectively adsorb certain impurities from the liquid
phase onto it is surface.
As you know that adsorption is a very selective process and you can also make certain
adsorbents, so as to target a specific impurity. Dry washing offers several advantages over wet
washing which includes the ease of integration into an existing plant, shorter purification time,
no water consumption and wastewater production and smaller unit sizes. The absence of water in
purification of biodiesel during dry washing results in biodiesel with acceptable water content,
which is less than 500 ppm that is based on the ASTM D675 standard.
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This is a simple schematic diagram of the biodiesel by dry washing technology. So, you can see
this unrefined biodiesel which is produced. So, then it goes to the residual alcohol, removal.
Initially you will remove alcohol, most probably this will be a distillation unit. Then you mix it
and goes for a mixing unit, so at 65 degrees centigrade for 20 to 30 minutes with a certain
agitation speed which should also take care that emulsification should not happen, so the speed
should be less than that.
Then you can add the adsorbent here, basically it can be magnesol ion exchange resins, activated
carbon. It can be in a suspended mode, in the liquid phase or you can go for a packed bed.
Usually many commercial scale applications are all packed bed units. Then whatever it is
coming out from the stream that goes to a filter section where you get the refined biodiesel, and
here spent adsorbent can be recovered and regenerated and can be reused back.
So, it is the simplfied system again, as I told you many times that whenever I am showing any
sketches, so there in between so many small, small unit operations and steps, which are not
usually shown in that schematic diagram because it is easy to understand in nutshell if the
schematic representation is concentrated only the major unit operations.
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So, let us talk about adsorption. Adsorption is the process by which atoms, ions or molecules
known as adsorbate, from a substance mostly liquid or gas adhere to a solid surface called as
adsorbent. Adsorbents are natural or synthetic materials of amorphous or micro crystalline
structures, owning basic and acidic adsorption sites, where polar substances such as glycerol and
methanol can be adsorbed and filtered out of the biodiesel.
Adsorption loading, selectivity, regenerability, kinetics, compatibility and cost are the most
important criteria that need to be considered for adsorbent selection. Silica based adsorbents such
as Magnesol and Trisyl, bio-based adsorbents such as lignocellulosic substrates and activated
compounds, including the famous activated carbon, then you have activated fiber and activated
clay are among the most common adsorbents for this process.
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So, silica based adsorbents. So, silica is one of the key elements in different types of industrially
available adsorbents including silica gel, zeolites and molecular sieves. It is an amorphous
inorganic mesoporous adsorbent produced via polymerization of the silicic acid. Silica gel owns
a hydrophilic surface due to the presence of hydroxyl group, which makes it a proper adsorbent
for water, alcohol and other polar molecules.
Silica showed a great potential for removal of glycerol from biodiesel synthesized from waste
cooking oil. Silica gel could effectively remove glycerol and monoglycerides from biodiesel, and
the presence of small amounts of water and soaps does not influence that adsorption of glycerol.
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Silica gel could effectively remove glycerol and monoglycerides from biodiesel and the presence
of small amounts of water and soap does not influence the adsorption of glycerol. However, the
presence of alcohol usually methanol negatively affects glycerol adsorption and decrease the
effective saturation capacity by about half due to the affinity effect of the methanol on silica
surface and glycerol in liquid phase.
One of the most important thing let me tell you about this entire adsorption phenomena is that
whenever we talk about adsorption and a system or a process that we are carrying out where
there are more number of impurities to be removed - It is not a single one or two there are many
then these impurities will try to adsorb on the surface of the adsorbent which is known as a
competitive adsorption, due to their inherent physiochemical properties as well as the
physiochemical properties of the adsorbent.
So, in this case, let us say if the methanol is trying to get adsorbed on the surface of the adsorbent
more than that of glycerol, so then that creates a problem. So, we have to choose adsorbent
selectively in such a way that initially either glycerol will be adsorbed or methanol or some other
impurities, then we can have successive columns. So, one will remove that glycerol completely
another will remove methanol completely - like that. But please understand that this also adds on
cost, as an as more unit operations you are adding that means you are increasing the cost of the
final product, so that also has to be taken care of.
So, the presence of water at severe conditions results in vegetable oil and glycerol hydrolysis to
free fatty acids which need to be separated during the biodiesel refining process. Magnesol is one
of the common commercially available silica based adsorbents used for biodiesel purification.
It is in fact an inorganic matrix of magnesium silicate and anhydrous sodium sulfate offering a
great potential for selective adsorption of hydrophilic impurities of the crude biodiesel.
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Similar to other adsorbents, biodiesel needs to be thoroughly mixed with the magnesol powder
for a certain period of time. The mixture is then subjected to filtration to separate magnesol from
the final Fuel. Faccini et al in one of the very important work, so they have evaluated different
types of adsorbents for biodiesel purification, where 1% magnesol and 2% silica salt showed
promising results.
The soap, methanol and water content of the crude biodiesel were about 1670 ppm, 2.13% and
1300 milligrams per kg, respectively. Those values correspondingly decreased to 60.85, 0.19%
and 500 milligrams per kg after purification by 1% magnesol which is good purification result.
So, this adsorbent also successfully decrease the free and total glycerol from 0.71 and 0.26 to
0.28 to 0.02 respectively, the reference has been listed below.
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We will talk about biomass based adsorbents; so cellulosic and lignocellulosic substrates were
also found to be effective adsorbents for the biodiesel purification due to the enormous cost of
most of the synthetic adsorbents focus has been more on developing low cost or readily
available, renewable biomass based adsorbent. So, people have concentrated more and more on
lignocellulosic substrates.
These materials are abundant and inexpensive in addition to their advantages as renewable,
biocompatible and non toxic materials. This method is widely and simply used in small scale
biodiesel plants, and the biomass that adsorbs the impurities is burned for heating after saturation
and refilled with a fresh biomass. Gomes et al in 2015 use different types of starch with various
morphologies along with cellulose as a natural adsorbent for biodiesel purification.
Corn starch and rice starch own a polyhedral structure while potato starch and cassava starch
have ellipsoidal and semi spherical structures respectively.
795
The eucalyptus bleached kraft cellulose with a tape format was also used for biodiesel
purification. The dry washing was performed via admixing, 1 to 10% of the adsorbent in
biodiesel for 10 minutes at room temperature and 150 rpm followed by filtration using a filter
paper. Regardless of the adsorbent type and content the acidity index decreased after purification
with the aforementioned biomasses.
The free glycerol content of the biodiesel was about 0.13% which was completely removed using
the following substrates - 5% potato starch, 1 to 2% cassava starch and 1% rice starch. The
purified biodiesel with 2% corn starch could also meet the standard specification for free
glycerol. Turbidity, showing the presence of impurities in the biodiesel was also significantly
decreased in the case of using 5% potato starch or 1 to 2% cassava starch.
796
Rice husk ash showed promising performance in biodiesel purification up to 5% dose. The
adsorption capability of the rice husk ash is attributed to it is high silica content and the presence
of meso and macropores in its structure, so it is a very good adsorbent. Although the water
content of the purified biodiesel with RHA was still above the acceptable value, it was
significantly lower than that of the purified biodiesel using acidified water, 1% phosphoric acid
actually and magnesol using 1% magnesol.
Then activated compounds: So, activated carbon activated fiber which is known as carbon fiber
and activated alumina are among the most common adsorbents in industrial applications.
Activated carbon which owns a large porous volume and high surface area can be manufactured
797
from any carbonaceous organics. As for example, sawdust, petroleum coke, wood, charcoal,
peat, fruit nuts, bituminous coal, lignite and coconut shells.
The porous structure is activated through either steam or chemical activation. Two types of
activation usually done, steam activation is also called as physical activation. And chemical
activation use some sort of chemicals, either acids or bases to do the activation. So, in the case of
steam activation, the substrate is heated to 400 to 500 degree centigrade in an oxygen free
atmosphere to remove the volatile components, that step is called the carbonization step.
That is followed by the oxidization step using the steam or carbon dioxide at 800 to 1000 degree
centigrade. So, the chemical activation is performed via impregnation of the substrate with a
strong dehydrating agent, usually phosphoric acid or zinc chloride. But many times zinc chloride
is being not considered because it is little toxic. So, followed by heating to 500 to 800 degree
centigrade, then followed by washing, drying and grinding.
Thermal dehydration of hydrated alumina and recrystallization is the most common method used
to produce activated alumina. The presence of Lewis acids sites on the surface of activated
alumina makes it suitable adsorbent for polar compounds and oxygenates such as alcohols,
aldehydes, ketones and carboxylic acids. You know Lewis acid are the acids which are ready to
give electrons, they are ready to donate electrons, electron pairs you can say.
798
And Fadhil and Dheyab in one of the significant work - the references given here below -
compared the performance of activated carbon prior to and after acid treatment either with
sulfuric acid or hydrochloric acid for purifying biodiesel synthesized from spent cooking oil and
spent fish frying oil. So, the activated carbon purifications led to a better biodiesel yield usually
91.5 to 93.75%. It is a significant yield actually with respect to water washed product which is 86
to 89% on both of the feedstock.
In case of the spent fish frying oil, the modification of activated carbon with acids, improved its
performance especially in the case of activated carbon modified by sulfuric acid, which resulted
in a biodiesel yield of 93.75%. On the other hand, the untreated activated carbon led to the best
purification result for the spent cooking oil biodiesel, so almost you get 93.4% yield.
799
So, the next category is ion exchange. So, ion exchange is the process of exchanging the ions
between the solution and a proper solid phase due to a stronger affinity, basically the electrostatic
force between the target species and the functional groups on the surface. Ion exchangers consist
of a matrix with excess charges localized in specific sites of the structure. Ion exchangers resins
are one of the most common types of exchangers typically produced via fictionalization of the
polymer obtained from copolymerization of styrene crosslinked with divinylbenzene.
The ion exchange resins are categorized based on the functionality and yet divided according to
their strength (basically density of the charge) to strongly acidic cation, weakly acidic cations,
strongly basic anion and weakly basic anion exchange resins. So, basically 4 distinct types of
resins.
800
The presence of sulfonic acid groups (sulfonated polystyrene basically) in the matrix leads to the
formation of strong cation exchange resin as the protons can easily be exchanged with other
cations. On the other hand, carboxylic groups are usually incorporated in the exchanger’s matrix
to produce a weak cation exchange resin. The strong anion exchange resins are usually obtained
by insertion of the quaternary ammonium species into the matrix structure while the presence of
radicals of secondary or tertiary amines leads to the formation of weak anion exchangers.
The structural properties, that is degree of crosslinking, porosity and particle size exchange
capacity, stability, type and density of the charges need to be considered in order to choose a
proper ion exchange resin.
801
Let us discuss about applications. So, Boris and Skelton studied the performance of PD206 and
BD10 dry ion exchange resins which are strong acid cation resins for purification of biodiesel
produced from used cooking oil and rapeseed oil. Although the resins showed promising
performance for soap and glycerol removal, the methanol removal was not satisfactory. Lewatit
GF202, on the other hand showed a great potential for the methanol removal, along with it is
capability to decrease the soap and glycerol content in the purified biodiesel.
The reusability of this resin was an additional advantage. Now again, as I told you just few
minutes before, again I am telling you that in case of whether it is adsorption, ion exchange, ion
exchange resins or absorbent, no single species will purify the entire amount of different types of
impurities that we used to remove - that is not possible. Therefore, there is a need that we
develop different systems with higher efficiency to remove one particular component, either
glycerol, then followed by methanol, followed by water, soap and free fatty acids like that. So,
you need to fine tune and optimize your process in such a way that we will have minimum
number of columns to achieve that in a stage wise separation also can be done. So, this is where
the design engineers play a vital role in designing a low cost purification step otherwise the final
product cost will be too high.
802
So, now let us talk about the membrane based separation technologies in biodiesel purification.
So, these are the latest developments; some of these are also been commercialized. By stark
contrast to the high water content involved in typical water washing methods, membrane
technology has emerged as a low or no water alternative in the purification of crude biodiesel.
So, as well as the cost advantages associated with the lack of wastewater, this method avoids
potential emulsion in the product facilitating two phase separation.
Since we are not using water, so there is no question of any emulsion formation. So, micro
filtration which is basically 0.1 to 10 micron in that range, ultrafiltration between 1 to 20
nanometer and nanofiltration maximum pore size is of almost 1 nanometer. So, all these types of
membranes are all used depending on the characteristics of the feedstock. So, in the next figure, I
will show you a schematic of the micro and ultrafiltration experimental unit which was used by a
Atadashi et al and published in 2015 in a very good work.
803
So, it’s a simplified membrane based biodiesel purification unit. So, this is a feed tank, from here
the feed is getting pumped, these are rotameters and all and this is your membrane unit M1. So,
M1 is the membrane module, it is a hollow fiber membrane module here. So, it can be
ultrafiltration, it can be any other membrane separation, nanofiltration and all. So, whatever you
get the concentrate that concentrate goes back to feed tank again.
And the permeate can be recovered and the membrane separation units are very easy to handle.
And they are simple to design also, not much unit operations and much other accessories are
required. And energy requirement is also very, very low compared to other energy intensive
processes. Here whatever the energy is required is just the pumping cost, the membrane itself
does not need any energy to do the purification. You can refer particular work in this particular
journal which is published in 2015, it is a nice work.
804
Then we will talk about organic and polymeric membranes. The organic membranes employed in
biodiesel purification include Polysulfone, polyamide, and polycarbonate, regenerated celluloses,
polyvinylidene fluoride which is known as PVDF and polyacrylonitrile with varying success.
These organic membranes can be sorted according to their hydrophilicity and corresponding
hydrophobicity.
A hydrophilic membrane is less susceptible to fouling from a variety of biorefinery feeds due to
the water content but is more susceptible to deformation due to pH and temperature swings. A
hydrophobic material is more useful for the separation of oils. So, based upon the hydrophobicity
you can choose actually what is your intention and what you are going to remove? Are you going
to remove alcohol, are you going to remove glycerol and where you want to remove?
You want to pass them to the permeate side or you want to retain them on the surface of the
membrane? All these things has to be pre decided before you go for designing of a membrane
unit.
805
So, let us talk about applications. He et al directly compared polysulfone and polyacrylonitrile
membranes in obtaining high purity biodiesel as well as using water and acid washing for
comparison. While all methods were able to produce high purity biodiesel (almost 97.5%), only
the membrane extraction method was successful in decreasing ester losses, endemic to water and
acid washing methods.
So, 10.1 weight percent esters were lost even at the optimum temperature of 50 degrees
centigrade with distilled water due to emulsification. The polysulfone and polyacrylonitrile
membranes by contrast, were able to purify biodiesel with only 8.1 weight percent and 10.3
weight percent ester losses. However, the poly acrylonitrile membrane allowed for higher water
content in the final biodiesel product than any other methods making it perhaps unsuitable for the
biodiesel refining.
806
The polysulfone membrane additionally led to the highest purity of biodiesel at roughly 99%
without additional steps. Comparisons conducted between ultrafiltration poly ether-sulfone and
microfiltration cellulose ester membrane demonstrated successful separation of glycerol from the
final biodiesel product. This particular work reference is also given below it was published in
Renewable Energy.
And with nominal molecular weight cutoff of 10 kilo Dalton, the ultrafiltration poly ether-
sulfone membrane alone could reach 0.02% weight percent glycerol in the permeate, meeting
international standards. Additional success with ultrafiltration polyacrylonitrile membranes have
been experienced for glycerol separation from a biodiesel product. Saleh et al found a 63%
reduction in glycerol content in the permeate upon adding 1 weight percent water by mass
reaching a level of 0.013 weight percent glycerol in the permeate side.
807
So, we will talk about inorganic and ceramic membranes. So, there is a substantially less variety
in inorganic membranes versus their organic counterparts. Because they are generally focused on
either alpha alumina support structure, usually with titanium oxides or zirconium oxides, we are
talking about commercially available ceramic membranes. Now these membranes have
numerous positive qualities over organic membranes, such as increased fouling, temperature, pH
fluctuation resistance, a longer time on stream.
This allows inorganic membranes to deal more effectively with the base catalyst used in the
transesterification reactions endemic to the biodiesel production. Now these increased resistances
additionally lend to usefulness in a continuous process in which a FAME rich permeate flow is
separated from an unreacted retentate as transesterification occurs down the length of a
membrane bioreactor.
With a 0.05 micron ceramic membrane at 25 degrees centigrade, Saleh et al successfully met
ASTM standard for glycerol in the final biodiesel product. So, less than 0.02 weight percent - the
reference has been given here.
808
And this is the schematic representation of the ceramic membrane unit for biodiesel purification
process. So you can see that the crude acid alkyl esters - the biodiesel, it goes to the inorganic
membrane, then whatever is coming to the permeate side, that is nothing but the removal of the
glycerol, alcohol and other contaminants. Alcohol can be stored for further processing, you get
the recovered catalyst, you get purified glycerol for sale to other industries.
Please understand, again I am telling this is not a single unit, there are multiple units here but it
was shown to simplify the process. And from the inorganic membrane, you get the purified
biodiesel mostly in the retentate side and which can go for further drying and further processing
some polishing step before it is getting stored.
809
So, this table will give you a comparison of polymeric and different inorganic membranes. So, if
you talk about inorganic membranes, the advantages are - they having long term durability, you
can use them for many months and years. High thermal stability, they can withstand more than
200 degrees centigrade temperature which the polymeric membrane cannot. Chemical stability in
wide pH range they can handle; they can handle high structural integrity also.
Disadvantage is that they are very brittle. So, you have to be very careful otherwise it will break
very easily. It is expensive, that is one of the most or you can say the biggest disadvantage right
now and as some ceramic membranes have low hydrothermal stability. So, if you talk about
current status, so some small scale applications are already going on, and surface modifications
to improve hydrothermal stability is also being undertaken.
So, let us talk about polymeric membranes the advantages are that cheap or low cost. You can
produce them in mass larger scale productions. So, usually available in large quantities and they
have good quality control. However, the disadvantage is that they are structurally weak, not
stable, so we are talking about the mechanical stability. And temperature is also they cannot
withstand more than 100 - 120 degrees centigrade.
810
Prone to denature and be contaminated separation and they have a short lifespan; you have to
replace them frequently. The current status is that wide applications in aqueous phase and some
gaseous phase.
So, if you look at this particular table, here the advantages and disadvantages of the different
refining technologies which we have discussed till now. So, basically the three, one the first one
is the wet washing, then the dry washing and the membrane purification. Of course membrane
also a part of your dry washing you can say that because you are not using water. So, all the
advantages and disadvantages which we have already discussed have been given in a single
slide, so you can refer to it later on. So, we will go ahead.
811
So, now we will talk about the reaction based separation processes in biodiesel purification. In
the case of reversible reactions, the process yield is limited by the equilibrium. To overcome this
limitation a separation process that should be integrated with the reaction to separate the
substrate, that is basically product and keep it is concentration from the equilibrium
concentration. Hybrid reaction, membrane separation as for example, membrane bioreactor,
reactive distillation and adsorptive distillation are some of the common reaction based separation
methods.
So, let us talk about reactive distillation. The integration of chemical reaction and a product
separation that is the purification step in a single multifunctional process is known as the reactive
distillation. That means, in a single column you are doing the reaction as well as the separation.
So, this integration declines the chemical equilibrium limitations, avoids the potential necessity
of auxiliary solvent and increases the selectivity.
812
Therefore, reactive distillation has the potential to improve the efficiency of the process, while it
needs a lower capital investment, operation cost and energy consumption. However, this process
also has it is own operational challenges and economic limitations, especially in case of the gas
liquid reactions at severe operating conditions of very slow reactions. In fact, a large column is
required to provide a reasonable residence time in case of very slow reaction which compromises
the feasibility of the process. And again, it will increase the operational and fixed cost.
So, if you talk about applications Wang et al in a classical work reported that 10% saving in
energy consumption along with 50% higher productivity for methyl acetate hydrolysis using
reactive distillation compared with the conventional process using fixed bed reactor followed by
a distillation process. So, it is a significant work that reported 10% energy saving as well as 50%
higher productivity in a single unit where reaction as well as purification has been carried out.
813
Reactive distillation using acid catalyst has a potential to be used for biodiesel production or
pretreatment of feedstock with a very high free fatty acid content. Various designs have been
studied to maximize the reaction rate and biodiesel yield. It is noteworthy that the downstream
alcohol recovery step can be avoided in the case of biodiesel production using reactive
distillation.
So, let us talk about membrane bioreactors for biodiesel processing. In optimizing the inorganic
membrane for bioreactor technology three factors have thus far been studied. First is the amount
of catalyst, second is the appropriate residence time for the complete conversion and third is the
methanol to oil ratio. Baroutian et al in 2011 tested potassium hydroxide catalyst loadings up to
814
250 milligram per centimeter cube at temperatures of 50 and 70 degree centigrade in a packed
bed reactor system using activated carbon as the adsorbent.
So, for loading of 37.5 milligram per centimeter cube the conversion reached no higher than
89.3% at 70 degree centigrade - further increases to 143.75 milligrams per centimeter cube
yielded conversions up to 93.5% at same temperature 70 degree centigrade. Now beyond this the
conversion dropped slightly to a maximum of 91.5% at 250 milligram per centimeter cube and
70 degree centigrade due to soap formation. The reference has been listed down, it is a very good
work published in bioresource technology in 2011.
So, let us talk about biofuel properties. So, this particular table will give you the free fatty acid
composition of vegetable oils. I think we have discussed this when we discussed about vegetable
oils and all. But I have again added, so that you can understand while we are discussing about the
biodiesel purification, so the properties of the fuel, biodiesel as a fuel. So, you can see the fatty
acids different types of fatty acids are listed here, lauric, mysteric, palmitic, palmioleic, stearic,
oleic, linoleic all these things and this is the formula C by D ratio.
And this is the different sources - algae, soybean, sunflower, corn, cotton seed, canola, olive,
safflower, hazelnut and rapeseed. So, this is nothing to discuss here, so I leave it to you to refer it
815
later on when you go through the video, so you please see this and the reference has also been
given here.
In the next table the properties of the biodiesel from all vegetable oils are listed here. So, the
properties like the ester content, flash point, water and sediment, kinematic viscosity, density,
cetane number, CFPP, carbon residue, free glycerine, acid number, distillation temperature,
everything all the fuel properties. So, please have a close look here all different types of
feedstocks are been listed like algae, soybean, safflower, corn, cotton seed, all the vegetable oils.
So, you can understand that which particular feedstock has is having better fuel properties.
816
So, let us talk about the cetane number, it is one of the most important fuel property. The cetane
number which is an indicator of a diesel fuel self ignition quality, allows the fuel to be easily
ignited and burn quickly. It can be defined as the measure of knock tendency of a diesel fuel. The
cetane number is related to the ignition delay time which is the time interval between the start of
injection and the start of combustion.
As the cetane number increases the ignition delay decreases and the main combustion phase that
is the diffusion control combustion increases. Similar to low cetane number high cetane number
too is inconvenience as well. If the cetane number of diesel fuel is too high this fuel may ignite in
a short distance to a injector nozzle and causes excessive heating of the injector which is not at
all desirable.
817
As a result of the intense heating, cooked fuel properties inside the injector may plug the injector
nozzle. Because of this the cetane number of diesel fuel should not be higher than 65. The cetane
number of all biodiesel fuels are measured and their relation with the degree of unsaturation
levels of their feedstocks is depicted. So, this particular figure you can see how the cetane
number is changing with respect to the degree of unsaturation of the particular base oil.
Where it is olive oil, hazelnut oil, this red one is algae basically you can see the cetane number is
highest for the algal oil because of the very good amount of free fatty acids that is available with
the algal oil. The quality is actually good compared to other oils.
818
So, we will talk about cold filter plugging point CFPP. So, in the literature three main
characteristics are generally defined to characterize the cold flow properties of the fuel. First is
the cloud point, second is the pour point hence third is the cold filter plugging point CFPP. Cloud
point can be defined as the first temperature at which the cloud layer which is the indicator of the
onset of crystallization on the fuel surface is seen when the fuel is cooled.
The pour point can be expressed as the lowest temperature at which the fuel still maintains it is
fluidity. At temperatures lower than this value the fuel is no longer in a liquid state due to
excessive gelling. These two definitions are insufficient for automotive fuels, because the fuel
that can be pumped by the fuel pump (namely not yet reached to it is pour point) may plug the
fuel filter and therefore the vehicle may not start.
Because of this, the use of the CFPP value is more useful for determining the cold flow quality
of an automotive fuel. CFPP is the lowest temperature at which the fuel can pass through the fuel
filter without causing plugging problem. And in this sense, the CFPP of all the biodiesel fuels
were correlated with the parameter long chain saturated factor which is known as LCSF, which
was calculated taking into account the composition of the saturated fatty acids and lending more
weight to the composition of fatty acids with a long chain.
819
The correlation between CFPP values of produced biodiesel fuels and LCSF levels of the
vegetable oil feedstocks was depicted in figure 7, in the next figure I will show you. As can be
seen the biodiesel fuels with the lowest CFPP were from algae, corn and canola oil. As I just
mentioned you that biodiesel lipid content or the free fatty acid content is very good.
So, that is why you always get better fuel properties. So, you can see in the figure 7, the change
of the CFPP value of the biodiesel along with the LCSF; you can again see that here the CFPP
value is better for the sunflower oil and also for some other base oils.
So, the next one oxidation stability; oxidation stability is one of the most critical fuel properties
affecting the long term storage and uses of a biodiesel fuel. It indicates the fuel’s resistance to
auto oxidation. The temperature, the amount of oxygen and the material of the container where
the fuel is stored are the decisive parameters on the oxidation reactions.
820
The changes in oxidation stability of the produced biodiesel with the viscosity and acid numbers
are given in the figure, next figure here.
So, you can see from these 2 figures how the oxidative stability is changing with respect to the
acid number the below figure and the viscosity the top figure for the different oils. So, if you go
back we can see that, it is seen that the biodiesel fuels obtain from the safflower, olive and algae
had the highest oxidative stability. Again algae is supposed to be good in terms of oxidative
stability also.
821
In addition, it is seen that the viscosity and the acid number values of these biodiesels are higher
than those of the other fuels. In the figure 9, the change of oxidation stability of the produced
biodiesel with total unsaturation level - TUS of the feedstock can be seen. As illustrated in the
graphic, it is determined that oxidative stability exhibited an increase with the increase in the
TUS level.
So, this is in this figure you can see here, how the change of the oxidation stability is happening
with the TUS number for different types of vegetable oils even the algae. You can see that algae
it is good and followed by the hazelnut oil, the stability is better and even for the olive oil also.
822
So, with this I conclude today’s lecture. In case you have any query please register your query in
the swayam portal or you can drop a mail to me at [email protected], thank you very much.
823
Module 08
Lecture-22
Biooil and Biochar Production Reactors
Good morning students. This is lecture 1 under module 8. In this lecture, we will be
discussing about biooil and biochar production, then the factors affecting biooil and biochar
production and about the reactors. So, let us begin.
Biochar is mainly produced through thermochemical conversion processes, such as slow

pyrolysis, fast pyrolysis, torrefaction and gasification, under various process parameters.
These processes irreversibly change the physical state and chemical composition of biomass
into biochar in the absence or limitation of oxygen supply under specific temperatures and
pressures.
Biomass decomposition generally occurs during the primary decomposition to form solid
char at 200 to 400 degrees centigrade, which is responsible for the largest degradation of
biomass; the secondary reactions proceed to take place within the solid matrix with further
rising of the temperature. As you know that in our earlier class also we have discussed that
biooil and biochar are the 2 most valuable and important products of the thermochemical
conversion.
824
So, there are various types of processes that can be used or techniques that can be used
starting from gasification, pyrolysis, torrefaction, hydrothermal liquefaction, there are many
thermochemical conversion processes, which we have already discussed. Now, it has always
been seen that whenever you eye apply for a higher biooil production, then the process and
the reactor process parameters will be a little different than when you are eying the biochar as
the main product and that we are going to discuss today also.
If you look at biochar production from biomass using the thermochemical conversion
technologies - so, we can have 4 different classes of processes. The first let us begin with the
fast pyrolysis; so, this particular slide will make you understand that what are the process
conditions that is required to produce biochar and of course, even biooil also. So, in fast
pyrolysis the reaction conditions are little different. So, it is around 350 to 700 degrees
centigrade in the absence of air and target is actually biooil. So, fast pyrolysis is always used
to produce biooil. The biochar that you get, the quality is not so good. So, the byproducts are
biochar and combustibles.
So, then, slow pyrolysis. In slow pyrolysis, the reaction conditions are again 300 to 700
degrees centigrade, the temperature is almost more or less the same in the absence of air, but
the target product here is majorly the biochar. Apart from that, you may get some biooil and
combustible gases.
Now, the next is gasification. Here the reaction conditions are a little different. So, around
700 to 1200 degrees centigrade, partial air is there - we have discussed about gasification in
825
detail earlier. Here the target product is of course, syngas, byproduct is by biochar and tars.
Now, here the biochar whatever we are getting is okay, moderately quality is fine or
moderate we can say.
Then torrefaction, here the reaction conditions and temperatures are very less compared to
other processes around 200 to 300 degrees centigrade in the absence of air, but the major
product is biochar and we get no byproducts from this torrefaction process.
So, let us understand one by one all the processes. So, first is the slow pyrolysis. So, slow
pyrolysis is a process in which biomass undergoes decomposition at a relatively moderate
temperature 350 to 500 degrees centigrade, which provides the sufficient residence time for
biomass pyrolysis vapour and increases its secondary cracking level as much as possible.
“Slow” in the slow pyrolysis process indicates low heating rate and meanwhile, the optimum
char formation temperature region is also a crucial factor influencing the quality and yield of
biochar.
For instance, biochar obtained from the pyrolysis of wood at a higher temperature 750 to 900
degrees centigrade and long residence time greater than 30 minutes is claimed to be much
better char material to substitute for coal and coke in steelmaking. Higher pyrolysis
temperature is essential for improving the quality of biochar in slow pyrolysis processes since
more volatiles are removed from biochar increasing its carbon content.
826
Then gasification: Gasification usually takes place at 700 to 1000 degrees centigrade, in
which biomass undergoes an incomplete combustion with various gasifying agents, such as
air, pure oxygen or steam and oxygen to produce a gaseous product. The quality of biochar
produced from biomass gasification is closely related to its carbon content. It is mainly
affected by the gasified parameters which increase the equivalence ratio – ER, then feedstock
properties, gasifying agent and of course pressure.
Now among these parameters the equivalence ratio is regarded as the most important factor
that affects the gasification process. And the optimum value is usually 0.25 to 0.28 according
to the physicochemical properties of the biomass. Generally, it has been seen that when you
increase the ER, that leads to an increase in the gasification temperature, which affects the
quality of the biochar that is produced.
827
So, in a significant work Yao et al reported that char yield decreased from 0.22 to 0.14
kilogram per kilogram of biomass with increasing ER from 0.1 to 0.6. Meanwhile, carbon
content of the produced biochar slightly decreased from 88.17% to 71.16%. So, it indicates
that higher ER value needs more oxygen that is required to be fed into the gasifier, which
results in both positive and negative impacts for the quality of the biochar.
On one hand, it strengthens the heterogeneous reactions to convert more carbon from the
solid phase into the gaseous species, facilitating the formation of the micropores and further
increasing the specific surface area of the biochar. On the other hand, more oxygen molecules
in the gasification process may cause the strong ablation of biochar reducing its mechanical
strength and yield as well as increasing its ash content.
828
Let us now understand about torrefaction. So, in a typical torrefaction process, biomass
feedstock is heated directly and/or indirectly to temperatures between 200 to 300 degrees
centigrade in an inert atmosphere at a low heating rate - lower than 50 degrees centigrade per
minute - and a relatively long residence time 20 to 120 minute. The production of the dark
brown solid fuel containing 90% of the initial energy content is the target product of this
process, which is known as the torrefied biochar, and an energy densification of about 1.3 can
be achieved. Now, in order to obtain high energy density of the torrefied biochar, high
torrefaction temperature and long residence time are essential in the torrefaction process,
which result in the reduction of the quality and energy yield of the torrefied biochar. If you
understand, then the main product of torrefaction is biochar. So, it does not produce any other
byproducts. Of course, it will result in some gas, which is of no use or no commercial
application.
829
So, according to Niu et al the optimum torrefaction condition of biomass may be to maintain
the solid yield in the range of 60 to 80%, in order to obtain relatively high higher heating
value and mass energy density of the biochar and the energy yield. So, another important
thing is that biomass physicochemical properties such as moisture content, higher heating
value, ash content. So, these properties significantly affect the quality of the torrefied biochar.
Among these, moisture content should be the most crucial, because due to that, it actually
determines the energy that is required to carry out or even initiate the torrefaction process.
So, more the moisture content, the more amount of energy will be required to carry out the
torrefaction process. The yield of the biochar from hemicellulose torrefaction is the lowest
among the 3 major components.
The 3 major components mean hemicellulose, lignin and cellulose. So, with the increase in
the torrefaction temperature and residence time, the content of hemicellulose and cellulose
decreased in the torrefied biochar while the content of lignin increased correspondingly.
830
So, you can see these are the biochars from different biomass sources, these are just
representative to make you understand how they look like actually. So, these are 4 different
types of biomasses. Hardwood, rice hulls, switchgrass and bagasse and they are
corresponding biochar. And this is the mechanism of the primary and secondary pyrolysis of
biomass, the pyrolysis reaction.
So, you can see that when there is a dry fuel. So, whatever you actually are taking as the
feedstock, whether it is lignocellulosic biomass or say any such material, so, you need to dry
it to remove its moisture content to certain level otherwise you cannot put it in the pyrolyser
or pyrolysis reactor. Here whatever is happening after the drying basically the primary
pyrolysis here fragmentation and sinkage is happening.
So, you can see that water, tar and permanent gas and char like this are getting generated
during the primary pyrolysis reactions, then when it goes to again further higher temperature
and you move towards secondary pyrolysis reactions. So, you get again water, tar, permanent
gas and char consisting of different molecules and there are different stages.
And again, it is very important to note that pyrolysis is very complex. There are so many
reactions primary and secondary, which are being simultaneously happening and it is very
difficult to predict exact mechanism. But having said that, people have already studied
pyrolysis reaction mechanism in detail and they have also told that there are various reactions
which are simultaneously happening including the reforming, dehydration, cracking,
oxidation, water gas shift, gasification and polymerization.
831
So, now let us understand the factors that affect the biochar chemical properties, we will be
talking about biochar properties, 2 different types of properties, first is the chemical
properties and second is the physical property. So, let us start with the chemical properties.
Atomic ratio: So, the process of carbonization involves changes in the chemical structure of
the fuel mostly by detachment of functional groups. The release of these hydrogen and
oxygen containing groups results in a decrease in the respective ratios with carbon.
There is something called Van-Krevelen diagram. So, you can read more about this - the
references given here below. So, Van-Krevelen diagram presented by Dirk van Krevelen in
1950 can be used to show the evolution of the 3 main fuel components that is carbon, oxygen
and hydrogen during carbonization.
A variation of only about 100 degrees centigrade may decrease the oxygen carbon ratio from
0.7 to 0.3, but it takes another 700 degrees centigrade to achieve a further reduction from 0.3
to almost 0. Now, it should be noted that the temperature range of 250 to 350 degrees
centigrade leads to the highest decrease in atomic ratios. The further release of almost all
hydrogen from the char requires very high treatment temperatures.
832
So, this is a classical Van-Krevelen diagram for the natural carbonization process. You can
see that it is plotted between O by C ratio mol by mol and H by C ratio, again mol by mol.
So, hydrogen to carbon ratio and oxygen to carbon ratio. Now, you can see that it lies from
anthracite coal and then this is another type of coal, then we have lignite here, we have peat
overlapping.
Then you can see that green one is the biomass. And from there the last one is the cellulose;
here the lignin degradation will happen. So, from here we can get an understanding about
what are the different temperatures also that is required and what is the O by C and H by C
ratio that will give us an insight about the various reaction mechanisms also.
833
So, next is elemental composition. So, one main goal of biochar production is the change in
chemical composition compared to that of raw biomass, most of all the increase in the carbon
content. Now, this is due to the detachment of functional groups containing oxygen and
hydrogen. Therefore, an increase in reaction temperature leads to an increase in the carbon
content while resulting in a lower content of hydrogen and oxygen.
The carbon content of untreated woods is typically slightly above 50% and the oxygen
content is just over 40% that is basically by weight, dry ash free basis. The most significant
changes during biochar production occur in the temperature range of 200 to 400 degrees
centigrade. At higher temperatures both approximate asymptomatically the extreme values
that is 100% carbon and 0% of oxygen.
High temperature biochars may each carbon contents of more than 95% and oxygen content
of less than 5%. The hydrogen content of wood varies between 5% to 7% and is decreased
during pyrolysis to less than 2%. So, when you go beyond or almost touching about 700
degrees centigrade or even below 1% for very high treatment temperatures more than 700 to
800 degrees centigrade.
However, the values are much more scattered and large differences can be seen for chars
produced at the same temperature. Again please note that whatever we are talking about,
these are generalized statements and process parameters and result will vary depending upon
what is the feedstock and feedstock composition - it is better to say that feedstock
composition. So, the carbon content of the untreated straw and grass is typically just below
834
50%. The oxygen content is in the range of 40 to 45%, a little more than the woody biomass.
Carbonization can increase the carbon content to around 90% and reduce almost the entire
amount of oxygen and hydrogen.
At short residence times of a few minutes, even relatively high temperatures might be
insufficient to achieve complete conversion. In this time range, the influence of the residence
time is important. However, the typical production conditions of biochar especially in a
commercial scale involves slow heating rates and residence times of many minutes,
sometimes hours and even days also.
Because the main aim is to produce as much as amount of biochar having excellent or let us
say having the highest carbon content. Now, for these conditions, the influence of the
residence time on the elemental composition is small. At moderate temperatures, even a
significant increase in residence time, you can say from 60 to 180 minute results only in a
decrease in carbon content of few percent. So, there is hardly any effect of the residence time.
So, as the biochar will never be utilized in its, ash free from but as an entity with the
inorganics, it seems more reasonable to give the composition based on the total matter instead
of the dry or ash free matter.
835
So, the next is energy content. So, as a result of the higher carbon content in the biochar the
energy content increases with temperature. The most significant increase in energy content
takes place at temperatures between 250 to 350 degrees centigrade, within this range of only
100 degrees centigrade, the heating value is raised from less than 20 mega joules per kg to a
value of 25 to 30 mega joules per kg.
So, beyond 400 degrees centigrade, the change in energy content is not significant.
Prolonging the residence time also has a positive impact on the heating value, leading to a
further increase. However, the effect is rather small compared to that of the temperature. In
the torrefaction range, prolonging the residence time from 1 to 2 or even 3 hours increases the
heating value by only a few mega joules per kg.
836
So, next is fixed carbon and volatile matter. The carbon content that remains in the solid
structure after the volatile components are driven off is referred to as the fixed carbon. Some
biochar applications, especially metallurgical require very high fixed carbon contents of
almost more than 90% or even 95% in order to substitute for the fossil carbon carriers. The
fixed carbon content of raw biomass is in the range of 10 to 30% and undergoes no
significant change before the torrefaction range. So, which is actually 200 to 300 degrees
centigrade in that range. So, between 250 to 350 degrees centigrade, the amount of fixed
carbon is increased to about 50 to 60%. It is again on ash free basis. Now, even though the
small temperature range shows to have the most effect on the fixed carbon content, fixed
carbon content of more than 90% required temperatures of approximately 700 degrees
centigrade.
The increase in the fixed carbon content is a direct result of the devolatilization process and
hence, decrease in the amount of volatile matter. So, when you are heating it with a higher
temperature basically more than 400, 500 close to 700 degrees centigrade, almost all the
volatile matters will escape. That is why the process is called devolatilization, resulting in
higher amount of fixed carbon.
Then we will talk about functionality. So, the main process during carbonization is the
thermal decomposition of the biomass structure, resulting in the detachment of functional
groups and the release of oxygen and hydrogen. As a result, biochars with low hydrogen to
carbon ratios, so that corresponds to a higher degree of carbonation contain less functional
groups and more aromatic structures then low temperature chars.
837
Aromatic structures have a high thermodynamic stability and are therefore important for
some applications such as soil amendment or metallurgical purposes, where long term
stability of the biochar is required. So, the aromaticity of biochar increases rapidly between
200 to 500 degrees centigrade, the most significant changes are observed in the temperature
range of torrefaction. That is again, if you recall 200 to 300 or 350 degrees centigrade
maximum.
The maximum is reached between 500 to 800 degrees centigrade. So, in this temperature
range, the entire carbon of some biochars may be bound in the aromatic structures. The type
and the amount of functional groups influence the biochar’s alkalinity, the ability to
neutralize acids in the soils. The partial detachment of functional groups leads to unpaired
negative charges and hence the ability to accept protons.
These functional groups include for example, carboxyl and hydroxyl groups. Several
categories of alkalinity can be distinguished like surface organic functional groups, soluble
organic compounds, carbonate and other inorganic alkalis. An increase in the treatment
temperature also leads to an increase in the alkalinity.
838
So, next we will talk about ash content and the composition. Many parameters for example,
elemental composition or fixed carbon content are typically given on a dry and ash free basis.
The water is completely driven off during pyrolysis. The ash however, largely remains in the
solid product. It is important to know the ash content of the biochar, because the amount and
type of inorganics can determine possible applications.
A high ash content may also inhibit the use in high grade industrial applications. The increase
in ash content may intensify ash related problems during the thermochemical conversion of
biomass. The ash content of biochar is largely dependent on the ash content in the parent
biomass. This varies greatly depending on the type of biomass and also on the harvesting
techniques also.
839
Biomass contents noteworthy amounts of alkali and alkaline earth metals. It is called AAEM,
significantly more than other fuels. So, these are mostly sodium, potassium, calcium and
magnesium. A comprehensive review of the composition of biomass presented by Vassilev et
al, - the reference is given below - shows that the main components (given as oxides) of
biomass ash are silicon dioxide, calcium oxide and potassium oxide.
And other noteworthy amounts include this one P2O5 - especially in the animal residues it is
present - and then Al2O3 - which is alumina and magnesium oxide. A number of studies have
also shown that AAEM are partly released into the gas phase during the thermochemical
conversion. The release is both as a result of the decomposition of cellulose, hemicellulose
and lignin as well as the interaction between the volatiles and the char and can be observed
over the entire temperature range of pyrolysis.
However, the dominating release occurs during the 2 temperature ranges either below 500
degrees centigrade or at higher temperatures above 800 degrees centigrade. Here I want to
tell something, you can see the interaction between volatiles and the char. Now, when the
process begins initially at lower temperature, so, the dehydration is happening. So, the
moisture whatever is left is getting out then devolatilization started.
Now, at the same time the char formation is happening. Now, when the volatile components
are getting escaped and still inside the reactor and the char which is getting produced, they
are interacting with each other. Now, this leads to some secondary and tertiary types of
different reactions and thereby resulting in different products, it can be tar, it can be smaller
molecular weight compounds and it may also result in fractions of different types of biooil.
Now, this cannot be stopped, because it is inherently happening inside the reactor which you
cannot control. Because you are heating something inside a closed environment in a
controlled atmosphere. And whatever is getting produced that gas is again reacting with the
feed what is getting converted or getting either gasified or getting either torrefied or getting
either pyrolyzed.
840
So, now we will talk about the physical properties, factors affecting the biochar physical
properties. The first and foremost important are density and porosity. So, if you recall, we
have talked about density of biomass, how it is going to happen, how it is going to affect the
transportation, storage and other things. Now we will talk about the biochar properties. So,
the density of any bulk material is an important property for the design and operation of all
handling and processing facilities, the storage, transportation, all these things.
While the weight-based energy density of biochar increases with the treatment temperature,
the bulk density shows the opposite trend. As the gases devolatilize from the solid biomass
structure, during pyrolysis, they leave a porous char behind, the higher the porosity the lighter
the char per unit volume becomes. The density can be distinguished either as bulk density,
envelope density or particle density.
While all densities bear some information about structural changes of the biomass during
carbonization. The bulk density is the most important design parameter for shipping and
handling, where planning might be based on volume rather than on (or in addition to) weight
basically.
841
The most significant reduction in bulk density is achieved by drying, which may be a separate
step or an integral part of pyrolysis, reducing the bulk density of green wood from about 700
kilogram per meter cube to roughly 400 kilogram per meter cube. A subsequent carbonization
process at temperatures above 300 degrees centigrade reduced the bulk density further to 300
to 330 kilograms per meter cube.
However, a strong temperature correlation cannot be seen in this example. Generally, the
higher the bulk density of the parent biomass is, the higher the bulk density of the produced
char. The carbonization process leads to a slight decrease in the particle density with
increasing temperature. The true density which considers the solid structure only,
disregarding of all the pores increases with increasing the degree of carbonation.
842
So, the next one of the most important parameter of the biochar is the surface area. The
porosity changes as a result of the escaping volatile gases during the carbonization process
and so does that total surface area of the biomass. A large surface area is connected to a
number of other biochar properties, as for example, cation exchange capacity or water
holding capacity and therefore prerequisite for a number of biochar applications.
While a large surface area is characteristic of biochars from pyrolysis, the residues of
hydrothermal carbonization have a very low surface area. The surface area is usually
determined by BET analysis. An increase in residence time leads to a further increase in
surface area, but even a very long residence time of many hours is less efficient in raising the
surface area compared to an increase in temperature.
For most biomasses, a surface area of several 100 meters square per gram can be achieved
under suitable carbonization conditions. For sewage sludge however, the surface area
seemingly remains below 100 meters square per gram regardless of the paralysis conditions.
After an initial increase, the surface area of biochars may decrease again at high
temperatures. Whether this trend is solely due to the heating rate, or also due to the residence
time at higher temperatures, which is an inevitable result of the heating rate, actually, it is not
so clear. The decrease in surface area at high temperatures is likely the result of a shrinking
solid matrix.
843
So, now we will discuss about the various reactors that is required for the biochar production.
So, under slow pyrolysis, biochar yield between 25 to 35% can be reproducibly produced.
During slow pyrolysis the residence time of the feedstock is longer and the temperature are
lower than 700 degrees centigrade. This allows all the volatile components to escape leaving
a chary solid behind.
A pyrolytic gasification is an example of indirectly heated process which utilizes an external

vessel to burn portion of the fuel and uses the heat to pyrolyze the biomass producing
medium energy gas with significant fraction of tars. If you recall, we have discussed this
during our gasification discussion. So, such a design has a great prospect for modification to
produce biochar, because the movement of the ignition front leaves the char behind.
Autothermal reactors provide the necessary heat of reaction by means of partial oxidation of
the biomass within the reactor. The heat produced is sufficient to drive the endothermic
reactions within the reactor to produce biochar, biooil and syngas.
844
So, this is a typical schematic representation of the biomass gas stove. So, air is generally
employed as the oxidation agent. The yield largely depends on the reactor design, operating
conditions and physicochemical properties of the biomass. So, such designs include one of
the most significant design which was being used by many - is called top-lit updraft gasifier
(TLUG) and natural draft.
So, TLUG is a “tar burning, char making” gasifier which has the advantage that tar is much
lower due to the flaming pyrolysis of the biomass and the gases then passing through a layer
of the charcoal on the top. So, you can see that you are passing basically the air here, the
forced air, here primary air is getting inside your reactor. So, here the combustion is
happening. So, the bed of charcoal is present here.
And then secondary air is there and it is a very simple design. So, TLUG are easily adaptable
and can be used for small scale char production, because of their ease of operation simple
technology with ease of fabrication, as well as the ability to generate a substantial char yield.
845
So, Auger pyrolysis reactors are getting increased attention from many small and midsize
industries. In an auger reactor, biomass is continuously fed to a single or twin-screw and then
the auger rotation moves the product along the axis until the end of the heating zone.
So I will show you this image, this is the hopper; it is a feed storage we can say. From here,
through a screw conveyor type of belt rotating system which is rotating. So, it is the feeding
system. It is coming to the reactor. So, this is a single auger reactor. Here also you can see
some sort of screw and belt rotation system that is rotating. And the rotation speed also plays
a very vital role in determining - the residence time - how much time the feed is spending
inside the reactor is all determined by this rotation speed.
846
Then, you get the solid fraction here, all the volatiles can be condensed and gaseous fraction
can be collected if it is useful, otherwise other condensable parts can be condensed if
required. So, as the biomass decomposes, gases and organic volatiles leave the reactor and
the biochar is collected at the bottom. Auger pyrolysis reactors are simple to operate, require
little or no carrier gas and consume little energy.
Moreover, one advantage of auger reactor is that, the residence time of biomass in the heated
zone can be controlled easily by varying the rotation speed; this is what I just told you - speed
of the screw or the flight pitch. Vapour residence time is much longer in auger reactors than
in the fluidized bed reactors and hence increases the likelihood of the secondary reactions and
consequently increases the yield of the char to the detriment of the yield of biooil. So, yes,
this we have already discussed.
And now we will discuss about biooil. So, till now we have just discussed about the biochar.
We will now focus our discussion on biooil which is another significant product of interest
especially from the pyrolysis. So, fast pyrolysis is a high temperature process in which
biomass is rapidly heated in absence of oxygen. As a result, it decomposes to generate mostly
vapours and aerosols and some charcoal.
Liquid production requires very low vapour residence time to minimize secondary reactions
of typically one second, although acceptable yields can be obtained at residence times up to 5
second, if the vapour temperature is kept below 400 degrees centigrade. After cooling and
847
condensation, a dark brown mobile liquid is formed which has a heating below about half of
that of the conventional fuel oil.
Both residence time and temperature control is important to freeze the intermediates of most
chemical interest in conjunction with moderate gas/vapour phase temperatures of 400 to 500
degrees centigrade before recovery of the product to maximize organic liquid yields.
So, this is the typical graphical abstract of the pyrolysis of the biomass. So, the biomass. so
you talk about the particular size, moisture, composition, these things we have discussed
already and then it goes to the pyrolysis reactor, you can have different types of pyrolysis
reactors, we have already discussed about that. So, the feed rate, reaction time, gases flow
rate, temperature, heating rate, all this will affect the quality of the biochar or biooil that you
are going to produce.
So, you get a char here. Then all the volatile components go to a condenser, whatever
condensable will be condensed as a liquid phase, which you get as biooil and whatever non-
condensable - It will be left off. Now, it also contains some of the important gaseous
components. If required, it can be also captured and converted to value added fuel.
So, whatever biooil you get here, there are many things that you need to do - we will discuss
about the fuel properties, calorific value, viscosity, water content, all these things are very
important features of the biooil. Now, whatever biooil you get here are usually containing a
848
huge amount of the aqueous phase. So, if you leave it under the density separation, it will be
separated into 2 distinct phases.
One phase is your organic rich phase - the heavier part, which is actually the oil part and the
another part is the more aqueous part the lighter part, but please remember in one class I have
already told you again I am repeating that even that lighter part also contains so many
valuable chemicals. Now, again what type of chemicals that depend upon the what type of
biomass we are using.
And some of the chemicals, some are rare - we have also done some work in this thing. And
there are various interesting works already reported in literature you can see. Depending upon
that biomass we get very different types of platform chemicals and some chemicals are of
very high value like D-glucose and all. So, those can be purified even if it is in small
quantity, you are producing in a large quantity biooil then you can do some downstream
processing, purify it. And it can be used as different value added products.
So, we will talk about the essential features of a fast pyrolysis process, towards biooil
production as you understand that for biooil production, the most important pyrolysis is the
fast pyrolysis process. So, very high heating and heat transfer rates, which usually requires
finely ground biomass feed; carefully control pyrolysis reaction temperature about 500
degrees centigrade in the vapour phase, with short vapour residence times of typically less
than 2 second; rapid cooling of the pyrolysis vapours to give the biooil products.
849
So, all these are very important. The main product biooil is a miscible mixture of polar
organics, this is what exactly I was mentioning just one slide before, it is about 75 to 80% by
weight and rest is water requires about 20 to 25%. So, very short residence times results in
complete depolymerization of the lignin due to random bond cleavage and the interaction of
the lignin macromolecules resulting in a less homogeneous liquid product. While longer
residence times can cause secondary cracking of the primary products, reducing yield and
adversely affecting biooil properties.
As fast pyrolysis for liquids occurs in a few seconds are less, heat and mass transfer processes
and phase transition phenomena as well as chemical reaction kinetics play important roles.
The critical issue is to bring the reacting biomass particles to the optimum process parameter
and minimize their exposure to the lower temperatures that favor formation of charcoal.
Another possibility is to transfer heat very fast only to the particule surface that contacts the
heat source, which is used in ablative processes. Fast pyrolysis process includes drying the
feed to typically less than 10% water in order to minimize the water in the product liquid oil,
grinding the feed to give sufficiently small particles to ensure rapid reaction, then fast
pyrolysis, rapid and efficient separation of solids - that is also very important part (basically
solid means char here) and rapid quenching and collection of the liquid product (often
referred to as the biooil).
850
So, this particular plot or graph will make you understand about the broad spectrum of
different types of pyrolysis products. So, you can see here we have compared this fast,
intermediate, slow carbonization, gasification and slow torrefaction. So, let us see the fast
paralysis here. In the fast pyrolysis the amount of the gas is very low - you can see this is the
black one – gas, followed by the char.
The second portion here is the char, then this is your water and whatever the rest all left out
till the 100% is all your organic compounds. So, you can understand that we are getting more
amount of biooil in the fast pyrolysis - it is quite clear. So, if you compare to intermediate,
slow and all these things, you can see that the gaseous components are increasing in the
gasification of course, the product is syngas. So, that is why the gaseous component is
highest. And in the slow torrefaction, you can see that the char, there is no organics and water
phase, it is either little gas phase here and the rest everything is char. So, in all cases, a
commercial process comprises 3 main stages from the feed reception to the delivery of one or
more of the useful products. So, these are the different steps or we can say stages.
The first one is the feed reception, storage handling, preparation and pre-treatment. The
second is the conversion of solid biomass by fast pyrolysis to a more usable form of energy in
liquid form, which is known as biooil and the third is the conversion of this primary liquid
product by processing, refining or cleanup (or we many times call as upgradation) to a
marketable end product such as electricity, heat, biofuels and/or different platform chemicals.
851
Now, we will talk about the heat transport. So, there are 2 important requirements for heat
transfer in a pyrolysis reactor. The first is that transfer of heat to the reactor heat transfer
medium. So, it is solid reactor wall in ablative reactors, gas and solid in the fluid and
transport bed reactors and gas in the entrained flow reactors. And the second is, from the heat
transfer medium to the pyrolysing biomass.
Now, the important feature of the ablative heat transfer is that, the contact of the biomass and
the hot solid abrades the product char of the particle exposing fresh biomass for reaction.
Now, this is actually not good. So, attrition of the char from the pyrolysing particle can also
occur in both fluid and circulating fluid beds due to the contact of the biomass with in-bed
solids where the solid mixing occurs.
The important feature of the ablative heat transfer is that the contact of the biomass and the
hot solid abrades the product char of the particle exposing fresh biomass for reaction.
852
Char removal is an essential requirement for the larger particles especially if it is greater than
2 mm to avoid the slow pyrolysis reactions. Now, the low thermal conductivity of biomass
gives low heating rates through larger particles which lead to increased char formation and
the hot char is known as the catalytically active char. Since the thermal conductivity of
biomass is very poor, reliance on gas-solid heat transfer means that biomass particles have to
be very small to fuel the requirements of rapid heating to achieve high liquid yields.
It is recommended that the water in the feed should be discounted in the final pyrolysis
products with only the water of pyrolysis being quoted, because that is what is getting
produced during pyrolysis, the biomass is not having that water content. So, that is known as
water of pyrolysis. And the product yields expressed on a dry feed basis. As a rule of thumb,
the water of pyrolysis is typically 12 weight percent of the dry feed.
853
So, the next is heat supply. The high heat transfer rate that is necessary to heat the particles
sufficiently quickly imposes a major design requirement on achieving the high heat fluxes
required to match the high heating rates and endothermic pyrolysis reactions. The 2 dominant
modes of heat transport in the fast pyrolysis technologies are conductive and convective.
Other possibilities to achieve the pyrolysis temperature and heat transfer rates necessary have
included vapour condensation such as sodium, induction heating of the reactor wall and the
use of the contact electrical heaters.
In a circulating fluid bed the majority of the heat transfer will be from the hot circulating
sand, typically at a sand to biomass ratio of 20 which therefore requires an efficient sand
reheating system.
854
Next is feed preparation. The cost of size reduction in financial and energy terms is clear
qualitatively but data is not available to define such a penalty associated with the small
particle sizes demanded of fluid bed and circulating fluid bed system. Drying is usually
required to less than 10 weight percent water unless a naturally dry material such as straw is
available.
As moisture is generated in fast pyrolysis, biooil always contains at least about 15% water at
an assumed product yield of around 60 weight % organics and 11 weight % reaction water.
This water cannot be removed by conventional methods such as distillation. Now, selective
condensation may reduce the water content of one or more fractions, but at the expense of
operating problems and a possible loss of low molecular weight volatile components.
855
Then temperature of reaction. Now it is necessary to understand that there is a distinction
between the temperature of reaction and the reactor temperature. The latter that is the reactor
temperature is much, much higher due to the need for the temperature gradient to do the heat
transfer. For fast paralysis the lower limit on wood decomposition is approximately 435
degree centigrade for obtaining acceptable liquid yields of at least 50% with low reaction
time.
Again that particular temperature which is mentioned here may vary slightly this side or that
side depending upon the type of biomass. The effect of temperature is well understood in
terms of total product yield with the maximum typically about 500 to 520 degree centigrade
for most forms of woody biomass. The other crops may have a maximum at different
temperatures.
But as I have mentioned you again I am telling you that it is not so significant difference
maybe 25, 30 degrees or something like that sometimes may be 50 not more than that. At
prolonged residence times (>1 second) the lignin derived fraction may be further
depolymerised to produce more homogenous liquid. This is also influenced by the reactor
configuration.
856
The next is vapour residence time, one of the most important parameter. The effect of vapour
residence time on organic liquid yield is relatively well understood, although the interaction
of temperature and residence time is less understood. It is believed that at temperatures below
400 degree centigrade secondary condensation reactions occur and the average molecular
weight of the liquid product decreases.
Boroson et al have demonstrated that average molecular weight decreases with degree of
secondary reaction that is basically increasing the residence time and temperature. The
reference is given below. There is no definition of product quality in terms of physical or
chemical properties or composition and this area needs further or need to be addressed as
more applications are tested and alternative supplies of bio fuel oil become available.
857
Then the next one is how do you collect the liquid basically? The pyrolysis vapours have
similar properties to cigarette smoke and capture by almost all collection devices is very
inefficient. The product vapours are not true vapours but rather the mist or fume and typically
present in an inert gas at relatively low concentrations which increases the cooling and
condensation problem. They can be characterized as a combination of true vapours, micron
size droplets and polar molecules bonded with water vapour molecules.
It is a complex mixture basically. Now this contributes to the collection problem as the
aerosols need to be impinged onto a surface to permit collection, even after cooling to below
the dew point temperature.
858
Electrostatic precipitators are effective and are now used by many researchers, but can create
problems from the polar nature of the product and arcing of the liquid as they flow, causing
the electrostatic precipitator to short out. Larger scale processing usually employs some type
of quenching or contact with cooled liquid product which is effective. The rate of cooling
appears to be very important.
Now slow cooling leads to preferential collection of the lignin derived components which
results in a viscous liquid and it can also lead to the blockage of the heat exchange equipment
and liquid fractionation. Very rapid cooling of the product has been suggested to be effective
as occurs typically in a direct contact quench. Transfer lines from the reactor to the cyclones
to the liquid collection system should be maintained at more than or greater than 400 degree
centigrade to minimise the liquid deposition and collection.
Then the next one is the char separation. Now some char is inevitably carried over from the
cyclones and collects in the liquid. Subsequent separation has proved difficult, because they
are very fine and it is very difficult to separate them from a very high viscous liquid. So,
liquid filtration has also proved difficult as the liquid can have a gel like consistency
apparently due to some interaction of lignin derived fraction with the char.
Now this aspect of char reduction and/or removal will be increasingly important as more
demanding applications are introduced which require lowered char tolerances in terms of
particle size and total quantity. Possible solutions include changing process conditions to
859
reduce the nature of the pyrolytic lignin, increasing the degree of the depolymerization of the
lignin derived fraction of the liquid or adding chemicals to the liquid.
For example, to improve the handling properties or reduce the char lignin interaction, some
sort of additives - chemical additives.
So, now we will talk about the reactors for biooil production. So, this is one classical
circulating fluidized bed. You can see that it is a simplified schematic representation. So,
circulating fluid bed and transport bed reactor systems have many of the features of bubbling
bed except that the residence time of the char is almost the same as for vapours and gas.
And the char is more attrited due to the higher gas velocities. So, you can see that biomass
that is dried and made into the desired particle size is being fed through some Hopper
mechanism to the pyrolyser. So, this is the pyrolyzer. Then whatever the gas that is coming -
the volatiles, the vapours, that is passing through the cyclones either 1 cyclone, 2 cyclone, or
multiple cyclones and it will remove the sand and char.
Then this sand, then it goes to another system or it is another cyclone where the hot sand will
be recycled back to the pyrolyzer and the ash will be collected here. And the vapours that is
coming will go to a quenching facility or we can say that a condensing facility where the oil
will be basically separated and some of the gas whatever is left out it can be taken out or can
be recycled back to the system depending upon what it contains basically.
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So, heat supply is usually from recirculation of the heated sand from a secondary char
combustor which can be either a bubbling a circulating fluid bed. Now in this respect, the
process is similar to a twin fluid bed gasifier except that the reactor temperature is much
lower and the closely integrated char combustion in a secondary reactor requires careful
control to ensure that the temperature, heat flux and solid flow match the process and feed
requirements.
Heat transfer is a mixture of conduction and convection in the riser. All the char is burned in
the secondary reactor to reheat the circulating sand. This is you can say that the secondary
reactor - the combustor - to reheat the char and all the char is burned in the secondary reactor
to reheat the circulating sand, so there is no char available for export unless an alternative
heating source is used. If separated, the char would be a fine powder, but this fine powder
biochar is of no much commercial value. However, it can be used for some processes like soil
amendments and all.
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So, this is another reactor which is also been widely adapted. It is called a rotating cone
reactor. So, the rotating cone reactor - it was invented by the University of Twente and
developed by the BTG group, is a relatively recent development and effectively operates as a
transported bed reactor but with transport effected by the centrifugal forces in a rotating cone
rather than gas. So, this is the cone - will explain.
So, how it happens? So, some of the key features. So, the centrifugation drives hot sand and
biomass up a rotating heated cone; vapours are collected and processed conveniently. So, this
is a cone you can see that this is a cone is rotating basically. So, here saw dust (this is written
sawdust, but it can be any biomass) and sand is being fed to the cone, now it is rotating and
here the temperature is maintained.
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So, the pyrolysis gases and vapours are escaping from here. This is the large view. This is the
reactor. Then the sand and char can be collected and recycled back. The vapours goes to a
condenser where the uncondensable gas will be left out and whatever you get is the biooil
storage. Anyway you get aqueous fraction mixed with that and you need to do further
processing of that.
The char and sand drop into the fluid bed surrounding the cone, whence they are lifted to a
separate fluid bed combustor where char is burned to heat the sand which is then dropped
back into the rotating cone. So, basically we are talking about this one. So, where the char
and sand are getting separated and the sand is again re-circulated back. Char is burned in a
secondary bubbling fluid bed combustor. The hot sand is re-circulated to the pyrolyzer;
carrier gas requirements in the pyrolysis reactor are much less than for the fluid bed and
transported bed systems.
However, gas is needed for the char to burn off and the sand transport. Liquid yields of about
60 to 70% on dry feed are typically obtained in this type of a rotating corn bed pyrolysis.
So, then we will talk about ablative reactor. Ablative pyrolysis is substantially different in
concept compared to other methods of fast pyrolysis. In all the other methods the rate of
reaction is limited by the rate of heat transfer through the biomass particles which is why
small particles are required. In fast pyrolysis, slow pyrolysis whatever you talk about. So, the
mode of reaction ablative pyrolysis is like melting butter in the frying pan.
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So, the rate of melting can be significantly enhanced by pressing the butter down and moving
it over or spreading it over the heated pan surface. So, similar things happen actually. So, in
ablative pyrolysis heat is transferred from the hot reactor wall to melt wood that is in contact
with it under pressure. As the wood is moved away the molten layer then vaporizers to a
product very similar to that derived from the fluid bed system. The pyrolysis front thus moves
uni-directionally through the biomass particle.
As the wood is mechanically moved away the residual oil film both provides lubrication for
successive biomass particles and also rapidly evaporates to give pyrolysis vapour for
collection in the same way as other processes.
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So, you can have a look here, this is how the ablative reactor looks like. So, you can see this
is the reactor heating zone, this actually moves like this. So, from here starting to the end. So
the entire reaction or the heat transfer zone is moving along with the wood particles. So, the
vapors will be collected here and it will be further condensed to get the biooil and the char
will be taken out from that side.
There is an element of cracking on the hot surface from the char that is also deposited. The
rate of reaction is strongly influenced by the pressure of the wood onto the heated surface; the
relative velocity of the wood and the heat exchange surface; and the reactor surface
temperature. As reaction rates are not limited by heat transfer through the biomass particles,
larger particles can be used and in principle there is no upper limit to the size that can be
processed. The process, in fact, is limited by the rate of heat supplied to the reactor rather
than the rate of heat absorption by the pyrolysing biomass as in other reactors.
There is no requirement for inert gas so the processing equipment is smaller and the reaction
system is thus more intensive. In addition, the absence of fluidising gas substantially
increases the partial pressure of the condensable vapour leading to more efficient collection
and smaller equipment. However, the process is surface area controlled so scaling is less
effective and the reactor is mechanically driven and is thus more complex.
The char is a fine powder which can be separated by cyclones and hot vapour filters as for the
fluid bed reaction system. Aston University has developed an ablative plate reactor - which I
just showed you - in which pressure and motion is derived mechanically obviating the need
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for a carrier gas. Liquid yields of 70 to 75 weight percent on dry-feed basis are typically
obtained. So, this we have already discussed.
So, with this I conclude today's lecture and in our next class we will discuss about the fuel
property characterization. And the most important aspect of the biooil production is a biooil
upgradation technology. How do you upgrade the biooil so that you can use the major
transportation fuel or at least as a blending agent. Thank you very much. If you have any
query please register your queries in the swayam portal or drop a mail to me at
[email protected].
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Module 08
Lecture-23
Factors Affecting Biooil, Biochar production, Fuel Properties Characterization
Good morning students. This is lecture 2 under module 8. As you know, we have been
discussing biooil and biochar. Under this lecture we will be discussing about the various fuel
characterization techniques. I will tell you the details about the procedures which will help
you immensely later when you try to carry out such analysis for the biofuel that you are going
to produce - especially the liquid biofuels. And then today we will also talk about the biooil
upgradation technologies. So, let us begin.
Biodiesels from different sources like vegetable oil and animal have become popular over the
last few years. Although the main constraints of applications of biodiesel are their high
market price and need for many of their feedstock as food sources, the other important factor
to restrict them from being used more is that they can damage the engine parts due to some of
their properties and thereby reduce the engine life.
The threats of pollution due to the use of conventional and non conventional fuels are
becoming evident. It is found that biofuels including biodiesels are more eco-friendly than
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petro-diesel. Only the NOX emissions from the combustion of biodiesels have been reported
to be little more than that of the petro-diesel.
So, this table will tell you the different types of fuel properties, the testing apparatus and the
respective standard. Now there are 8 here we have listed which are the standard
characterization parameters that needs to be carried out for any biodiesel or biooil that you
actually produce. So, the first is acid number, the testing apparatus require is a burette and
pipette, it is very simple.
Then next is calorific value, you need a digital bomb calorimeter for that and the plain bomb
calorimeter digital or not digital is not an issue actually. So, then kinematic viscosity you
need a viscometer. Relative density you can calculate it using pycnometer. Flash and fire
point using the respective apparatus. Cloud and pour point using the respective apparatus.
Ash content you need a muffle furnace it is a simple thing. Carbon residue, also you can carry
out using a carbon residue content apparatus.
You can see the standards are given the international standards ASTMs and all these things.
So, the properties of the biodiesel give an indication of whether it would be suitable or not for
the performance, life and emission of the engine. Some of the properties we have already
discussed under this table.
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So, we will see one by one. The first is acid number. Titration method is used to estimate the
acid number of the biodiesel. Usually 0.1 to 0.5 ml of biodiesel is taken in a conical flask. A
50 ml of the solvent mixture which is usually 95% ethanol and diethyl ether in 1 : 1 ratio is
added to it and mixed thoroughly. Now this solvent oil mixture is titrated against 0.1 molar
KOH using a 1% phenolphthalein indicator.
So, you can find out the acid number from this formula. So, 56.1 into normality of the KOH
solution into volume of KOH used divided by weight of the sample taken.
Now besides the quality control of biodiesel the acid number plays a significant role in the
quality control of the feedstock also. Additionally, increasing acid numbers when compared
to the initial acid number of the biodiesel can point to ongoing fuel degradation or the
intrusion of the water. So, which actually happens by the hydrolysis of the free fatty acids.
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Then the next is calorific value. Biodiesel about 0.5 gram in a container is placed in the bomb
and the 8 centimeter cotton thread hanging from an 8 centimeter nichrome wire is dipped into
the biodiesel. The bomb is then filled with oxygen at 400 psi. Then it is placed inside the
insulated container containing distilled water and the fuse wires are placed in their position
on the bomb. The nichrome wire is stuck to 2 sticks attached to the fuse wires.
The initial temperature is noted and then it is reduced to 0 degree centigrade. The fire button
is pressed to make a short circuit on the nichrome wire and ignite the biodiesel. The
temperature kept on increasing for a certain time. The temperature is noted when it was
stable. So, the calorific value in kilo joules per kilogram can be calculated by this equation.
So, weight of the water plus water equivalent into temperature rise into specific heat of water
divided by weight of the sample.
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Then kinematic viscosity: The biodiesel is poured into the heat chamber of a Redwood
viscometer and heated up to 40 degree centigrade. The stopper of the viscometer is displaced
to let the heater biodiesel drain out of it and be collected in a measuring cylinder placed
underneath. As 50 ml of the biodiesel is collected in the measuring cylinder the stopper is
placed again to stop the flow of the biodiesel.
The time taken for the collection of 50 ml biodiesel is noted. So, you can calculate the
viscosity using this equation A into time - B by time. So, here A and B are 2 constants for the
specific redwood viscometer A = 0.26 and B = 179, when the time taken is less than 100
second and A becomes 0.24 and B becomes 50 when the time taken is more than 100 second.
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So, the next is relative density. The pycnometer is kept inside a refrigerator after filling them
up with biodiesel. They are taken out of the refrigerator when the temperature of the biodiesel
reached 15 degrees centigrade. The mass and volume of the biodiesel are measured and the
density of the biodiesel is calculated. The formula for measuring the density is as follows. So,
the relative density in kilograms per meter cube equals to mass of the pycnometer containing
the biodiesel minus mass of the empty pycnometer divided by the volume of the biodiesel.
So, then we will talk about the flash point, fire point, cloud and pour point. These are very
important properties for any liquid fuels. So, flash and fire point: the biodiesel is kept inside
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the flash and fire point apparatus and a cotton thread is placed in it. The biodiesel is heated
with a gas stove; another ignited cotton thread is dragged on the surface of the former thread.
The temperature at which the spark came out of the first thread is noted as the flash point of
the biodiesel. And the temperature at which the thread started burning is noted as the fire
point of the biodiesel. These are very simple experiments.
Then similarly cloud and pour point: the cloud and pour point apparatus is filled up with ice,
the glass vessels of these apparatus filled up with biodiesel are placed in their slots of the
apparatus. The temperature at which the paraffin in the biodiesel started solidifying and
cloudiness appeared in the biodiesel was noted as the cloud point. The temperature at which
the biodiesel becomes semi-solid is noted as the pour point of the biodiesel.
Then ash content: The sample (5 gram) is taken in a pre-weight quartz crucible and placed
inside a muffle furnace usually at 450 degrees centigrade preheated. After half an hour when
the biodiesel burnt completely to ash the crucible is taken out. The crucible is weighed again
when its temperature drops to room temperature. So, you basically keep it in a desiccator.
The formula for calculating the ash content is given below. Ash content of biodiesel in
percentage equals to initial weight of the crucible minus final weight of the crucible divided
by weight of the biodiesel into 100.
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Then the another one is the carbon residue content. So, what you do is that you take 5 gram
of biodiesel and put it inside a pre-weighed heat proof glass bulb and place inside the carbon
residue apparatus, preheated at 450 degree centigrade and kept there for half an hour. The
weight of the bulb is measured after its temperature drop to room temperature. So, the carbon
residue content of the biodiesel in percentage can be calculated by this equation: Initial
weight of the bulb minus final weight of the bulb divided by weight of the biodiesel taken
into 100.
So, another very important parameter for any liquid fuel is the water content determination.
Water contamination of biodiesel plays a significant role in the quality control of the
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feedstock and the end product. Biodiesel although considered hydrophobic, can contain as
much as 1500 parts per million (ppm) of dissolved water excluding that of the suspended
water droplets.
Now the presence of water in biofuels reduces the calorific value, enhances corrosion,
promotes the growth of microorganisms and also increases the probability of oxidation
products that are formed during long term storage. Additionally, water cleaves the ester bond
of the FAMEs via hydrolytic degradation. The same applies for the glycerides in the
feedstock also.
The liberated free fatty acids consume the added sodium hydroxide thereby forming soaps
and emulsions that increase viscosity and seriously hinder the phase separation of the
glycerine. But due to these all materials used in the biodiesel production process should be
essentially anhydrous.
Several methods exist for the determination of water, so like loss on drying, reaction with
calcium hydride, Karl Fischer titration which is the most adapted one, then Fourier transform
infrared or Raman spectroscopy and dielectric measurements. Now among these the KFT or
the Karl Fischer titration is certainly the method of choice when trace amounts of free
emulsified or dissolved water have to be accurately determined in a reasonable time.
The principle of KF titration is based on the Bunsen reaction between the iodine and sulfur
dioxide in an aqueous medium. A primary alcohol can be used as the solvent and a base as
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the buffering agent. The alcohol reacts with sulfur dioxide and base to form an intermediate
alkyl sulphide salt which is then oxidized by iodine to an alkyl sulfate salt. So, this is the
reaction.
The reactive alcohol is typically methanol or 2-2 ethoxyethoxyethanol or another suitable

alcohol. Water and iodine are consumed in a 1 : 1 ratio in the above reaction. Once all of the
water present in consumed the presence of excess iodine is detected by the titrators indicator
electrode that signals the end point of the titration. The amount of water present in the sample
is calculated based on the concentration of iodine in the KF titrating reagent that is titre and
the amount of KF reagent consumed in the titration.
In most cases of the KF titration the sample can be directly injected into the KF solution and
xylene can also be injected in order to improve biodiesel solubility. However, as many
biodiesel fuels contain additives or impurities that can undergo side reactions during titration
they should not be injected directly.
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So, now we understand the different types of the fuel properties that needs to be actually
characterized for a biodiesel or biooil. Now we will talk about the biooil which is the major
product from the pyrolysis of biomass and as we have discussed many times that biooil
suffers so many different types of drawbacks like high water content, high oxygen content,
higher viscosity, there are many other things also we will discuss now.
So, there is a need to upgrade the biooil. So, now we will discuss the different biooil
upgradation techniques and how they can be performed. So, why there is a need to upgrade
the biooil? Now biooil can be upgraded in a number of ways, so we can do it either
physically or chemically or catalytically. So, there are number of objectives for upgrading of
which the main ones are: first one is the most important of course the improvement of the
biooil quality to overcome or reduce one or more of the fuel quality deficiencies.
And the second is, towards the production of chemicals and if you remove oxygen then you
can produce hydrocarbon biofuels. So, the most important properties that inhibit the
widespread use of biooil are - first is the phase separation. So, phase separation from use of
wet feedstock and or secondary cracking of vapours leading to high water content in the
liquid product. Phase separation cannot be reversed except though relatively high additions of
co-solvents such as ethanol.
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Then incompatibility and immiscibility with conventional fuels from the high oxygen content
of the bio-oil. So, if you cannot do that then the problem is that you cannot blend it with the
petrol fuels. And then high solids content that affect the catalyst and utilization in engines and
burners. High viscosity that hinders pumping and combustion and which cannot readily be
controlled by raising temperature as for heavy fossil fuels due to the temperature sensitivity.
Now high water content that lowers heating value but also lowers viscosity. Chemical or
thermal instability which limits the use of the higher temperatures for controlling properties.
And again another one is the high acidity which actually leads to corrosion in storage and
utilization. So, as you understand from these so many drawbacks you have to understand
what is the intention?
So, the intention of producing biodiesel and upgrade it to a certain quality so that its fuel
properties matches to that of the petrol-diesel, if it matches then only you can blend it or you
can directly use it in the engines which were used to burn actually the petro-diesel. So, to
achieve that there are various upgradation technologies available, so we will discuss one by
one.
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So, the first one physical upgradation of the biooil using the simple filtration mechanism.
Now the most important properties that may adversely affect biooil fuel quality are
incompatibility with the conventional fuels, from the high oxygen content of the biooil, high
solids content, high viscosity and chemical instability. Now hot vapour filtration can reduce
the ash content of the oil to less than 0.01% and the alkali content to less than 10 ppm much
lower than reported for biomass oils produced in systems using only cyclones.
Now this gives a higher quality product with lower char however accumulated char on the
filter medium is catalytically active and potentially cracks the vapours, reduces yield by up to
20%, reduces viscosity and lowers the average molecular weight of the liquid product. Now
there is limited information available on the performance or operation of hot vapour filters
but they can be specified and perform similarly to hot gas filters in gasification processes.
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So, this is a classical study. In the below you can see that the reference is given. So, it is ACS
sustainable chemistry and engineering and it is a nice work, what they have done here? They
have performed the catalytic hot gas filtration with a supported heteropolyacid acid catalyst.
So, the diesel engine test performed on crude and hot filtered oil showed a substantial
increase in burning rate and a lower ignition delay for the latter due to the lower average
molecular weight of the filter oil.
Liquid filtration to very low particle sizes of below around let us say 5 microns is very
difficult due to the physicochemical nature of the liquid and usually requires very high
pressure drops and self cleaning filters. Although improvement is claimed with filter pores of
around 10 micron.
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So, the next physical upgradation is solvent addition and emulsions. Polar solvents have been
used for many years to homogenize and reduce the viscosity of biomass oils. The addition of
solvent especially methanol showed a significant effect on the oil stability. Diebold and
Czernik found that the rate of viscosity increase or we can say that due to the ageing actually
for the oil with 10 weight percent of methanol was almost 20 times less than that of the oil
without additive.
Now use of co-solvents to compatibilize biooil with other sustainable liquid fuels as blends is
tested. Pyrolysis oils or biooils are not miscible with hydrocarbon fuels but they can be
emulsified with diesel oil with the aid of surfactants. A process for producing stable micro
emulsion with 5 to 30% of the biooil in diesel has been developed at CANMET. So, the
reference is given below.
So, this is what they have done actually. This was done at the University of Florence, Italy.
So, they have been working on emulsions of 5 to 95% biooil in diesel to make either a
transport fuel or a fuel for power generation in engines that does not require engine
modification to dual fuel operation. Now there is limited experience of using such fuels in
engines or burners but significantly higher levels of corrosion erosion were observed in
engine applications compared to biooil or diesel alone.
A further drawback of this approach is the cost of surfactants and the high energy required for
the emulsification. So, what they have done? It is a simple experiment. So, the biooil if it is
not suitable for emulsification basically the heavier fraction whatever the lighter fractions are,
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can be emulsified, will be mixed with different emulsifying agents like these surfactants -
tween 60, span 80 and all these things and diesel in different proportions.
So, once that is done so you can get something like this is the mixture, this is the stratified
one, this is the stable one. So at different proportions or you can say the different blends
using different surfactants so different mixtures were prepared, their stability is tested and
their engine performance is also carried out. So, a further drawback of this approach is the
cost of the surfactants and the high energy required for the emulsification.
So, the next one is physical upgradation using the blends. So, more recently some success has
been achieved through production of blends of biooil with a variety of co-solvents and other
sustainable or green fuels as well as conventional transport fuels. Therefore some exploratory
work was initiated in 2012 to produce homogeneous blends of biooil with biodiesel and an
alcohol co-solvent.
So, both ethanol and butanol were tried. A key result was that single phase and stable blends
of biooil, biodiesel and either ethanol or butanol could be prepared which utilize the whole
biooil including the water content. So, this is one of the best things regarding this blending
actually. So, use the entire biooil that is coming out of the pyrolysis reactor including that of
the water part or aqueous part.
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So, a key requirement is to maximize the use of biooil, maximize the sustainability of the
resultant blend by use of renewable solvents and satisfy marine oil specifications of which
flash point above 60 degree centigrade is the key.
So, this is the overview of the fast pyrolysis upgrading technologies. So, another important
upgradation method. So, this is the direct route of the fast pyrolysis and this is indirect route.
So, under the direct route biomass undergoes the fast pyrolysis so the cracking is happening,
so part of that directly goes to refining and part of that again further processed using the
hydro processing. And you then refined and you get these hydrocarbons, SNG, diesel,
gasoline etcetera or various different fractions.
The liquid biooil part can be modified as for example to esters and can be used as chemicals
and also part of that can be refined to get the biofuels. And you can prepare directly the
blends and use as fuels. Under the indirect routes you can use the gasification that means the
syngas and then convert it using the Fischer Tropsch synthesis to different types of alcohols
and then you can get another fuel platform here or from here the FT synthesis directly goes to
the refining platform and you get the different types of biofuels.
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Then catalytic upgradation of the biooil so natural ash in biomass. Before considering
catalytic upgradation of biooil it is important to appreciate firstly that biomass contains very
active catalyst within its structures. So, these are called the alkali metals that form ash and
which are essential for nutrient transfer and growth of the biomass. The most active is of
course potassium followed by sodium.
Now these act by causing secondary cracking of vapours and reducing liquid yield and liquid
quality and depending on the concentration the effect can be more severe than even the char
cracking. Ash can be managed to some extent by selection of the crops and harvesting time
but it cannot be eliminated from growing biomass. Ash can be reduced by washing in water
or dilute acid and the more extreme the conditions in temperature or concentration
respectively the more complete removal of the ash will happen.
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However as washing conditions becomes more extreme, firstly hemicellulose and then
cellulose is lost through hydrolysis. Now this reduces the liquid yield as well as the quality.
In addition, washed biomass needs to have an acid removed as completely as possible and
recovered or disposed of and the wet biomass has to be dried again. So washing is therefore
not considered as a viable possibility, unless there are some unusual circumstances such as
removal of the contaminants.
Another consequence of high ash removal is the increased production of levoglucosan which
can reach levels in biooil where recovery becomes an interesting proposition. Although
commercially market needs to be identified and/or developed. You know levoglucosan is one
of the most important chemical that forms during pyrolysis directly as a decomposition
product from the carbohydrates starch and other things cellulose and hemicellulose whatever
it is.
Now levoglucosan is also an important chemical it has various widespread application - one
of the most important application is its use as a tracer. So, there are many other applications
also.
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The next is hydrocarbon biofuels. Now direct production of high yields of liquids by fast
pyrolysis inevitably caused attention to focus on their use as biofuels (basically looking
towards the sustainable transport fuels) to supplement and replace fossil fuel derived
transport fuels. However, the high oxygen content of biooil and the non miscibility or
incompatibility with hydrocarbon fuels have prevented simple adoption of biooil as a
transport fuel at least as a blend.
Now the main methods for upgrading biooil to transport fuels are the first one is
hydrodeoxygenation. So, hydrodeoxygenation of biooil to a substantially deoxygenated
product, then catalytic vapour cracking of fast pyrolysis vapours in a closed coupled
atmosphere to aromatics that can be followed by hydrodeoxygenation and/or introduction
into a refinery for further processing basically. So, partial upgrading by hydrodeoxygenation
followed by introduction into a refinery direct introduction of crude biooil into a refinery.
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So, hydrotreating is another option actually for upgradation. So, hydro-processing rejects
oxygen as water by catalytic reaction with hydrogen. This is usually considered as a separate
and distinct process to fast pyrolysis that can therefore be carried out remotely. The process is
typically high pressure up to 20 mega pascal and moderate temperature up to 400 degree
centigrade and requires a hydrogen supply or source.
Full hydrotreating gives a naphtha-like product that requires orthodox refining to derive
conventional transport fuels. So, you basically distilled it to different cuts. So, a projected
typical yield of naphtha equivalent from biomass is about 25% weight or 55% in energy
terms excluding the provision of the hydrogen. Inclusion of hydrogen production by
gasification of biomass reduces the yields to around 15 weight percent or 33% in terms of
energy.
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The process can be depicted by the following conceptual reaction. So, CHO + 0.77 hydrogen
gives CH 2 + 0.43 water.
The catalyst originally tested in 1980s and 1990s were based on sulfided CoMo or NiMo. So,
cobalt molybdenum or nickel molybdenum supported on alumina and aluminosilicate and the
process conditions are much similar to those used in the desulphurization process.
Now you know this CoMo, NiMo catalysts are the desulphurization catalyst which are used
in the petroleum industries. However, a number of fundamental problems arose including that
the catalyst supports of typically alumina or aluminosilicates were found to be unstable in the
high water content environment of biooil and the sulfur was stripped up from the catalyst
requiring constant re-sulfurization.
So, this is a big problem. More recently attention turned to precious metal catalyst on less
susceptible supports and considerable academic and industrial research has been carried out.
One of the most important aspect of this type of catalyst is that how the catalyst is supported
on the base material? In this case alumina aluminosilicates, they should not come out when
the processing is happening.
When the water content is higher so there is a huge chance that though the catalyst will be
dug up. So, that is why there is a need to look out for the proper doping methods as well as
there should be a proper susceptible supports which will take care of this problem.
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Tests have been carried out on both batch and continuous flow processes focusing on an
initial low temperature stabilization step followed by more extensive catalytic deoxygenation
using different metal catalyst and processing conditions to give a range of products including
that of the petroleum refinery feedstock. Now remaining challenges include complete
deoxygenation especially of phenols without saturation with the hydrogen.
A key aspect is of course the production of hydrogen very important. Since the hydrogen
requirement is significant it should be renewable and sustainable. Having said that the
meaning of renewable and sustainable it is a complex you can say some sort of biorefinery
concept, where the requirement of hydrogen whatever it is should be made from in-house
hydrogen production, you cannot buy hydrogen from outside its very costly and
transportation also makes it not feasible.
So, few refineries have a hydrogen surplus, so this has to be provided. There are many ways
of providing hydrogen such as gasification of biomass followed by shifting to hydrogen, then
scrubbing the carbon dioxide.
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Product biooil or the aqueous phase from the phase separated product can be steam reformed
to hydrogen or hydrogen can also be generated locally by the electrolysis of water preferably
using the renewably produced electricity. Again we are talking about the renewable
electricity because the electricity has to be generated in house so as to meet the energy
requirement as well as the make the entire process sustainable.
Supply of the hydrogen from external sources is unlikely to be feasible due to the very high
cost of storage and transport. The necessary purity of hydrogen is unknown but some carbon
monoxide shifting may take place in the hydroprocessing reactor removing the need for
dedicated shift reactors. The high cost of hydrogen means that unused hydrogen would have
to be recovered and recycled as only a fraction of the hydrogen would be utilized due to the
need for high hydrogen partial pressures.
Recovery and recycling of unused hydrogen is both technically and economically very, very
challenging and lot of work has been going on this particular aspect.
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There is increasing interest in supercritical processing of biooil, another important study has
been done, to either improve the properties of the biooil or to deoxygenate into a hydrocarbon
fuel. The supercritical fluid studied included water, carbon dioxide, methanol, ethanol,
butanol and cyclohexane using traditional CoMo type catalyst, precious metals such as
platinum, palladium and ruthenium on inert support such as carbon or cracking catalyst
including the HZSM-5.
Now the results are mixed with no clear conclusions on the efficacy of this route. High
pressures are still required as well as the recovery of the fluids involved. There continues to
be an interest in use of model compounds even though it is impossible to adequately
represent the complexity of biooil with single compounds or even groups of so called
representative compounds.
891
The next important one is of course using the zeolite catalyst to crack the biooil. So, you have
biomass. So use the fast pyrolysis process you get liquid then it comes to 2 different fractions
- of course liquid directly goes to catalysis and you get the upgraded product. You go for the
volatilization, again catalysis and you get upgraded product. Vapour can be directly
catalyzed. The vapour catalytic cracking, you get upgraded product or you can have an
integrated catalytic fast pyrolysis approach also which is now more recently been adopted in
many of the industries.
So, we will discuss about the catalytic vapour cracking in a closed loop scenario. Cracking
usually over zeolites, rejects oxygen as carbon dioxide as well as water, summarized in the
conceptual overall reaction below. So, this CHO + 0.26 oxygen gives 0.65 CH + 0.27 water +
0.34 carbon dioxide.
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The process takes place in 2 stages. Firstly, cracking which deposits carbon or coke on the
catalyst surface which is then burned up in the second reaction.
This deposition of coke on the surface of catalyst is a very bad phenomenon but however it
has been noticed that the amount that get deposited on the surface of the catalyst is actually
very low. So, in this case the oxygen is ultimately mostly rejected as carbon dioxide with
some water from burning of the carbon on the coked catalyst. Now this lowers the carbon
efficiency of the process compared to the hydro deoxygenation but avoids the need for
hydrogen and pressure. So, there is a good thing about that. That you do not need hydrogen at
higher pressure.
So, cracking takes place at atmospheric pressure either with in-situ catalyst or in a closed
coupled process. There is no requirement of hydrogen or pressure. So, the projected yield is
around 18 weight percent aromatics and the process is understood to be the basis for the
recently abandoned Kior process. Now this process is believed to have been based on the first
stage of zeolite cracking, possibly modified with metals followed by hydrotreating to deliver
hydrocarbon transport fuels.
Early work by NREL added a closed to secondary reactor to the fast pyrolysis process in
which vapours pass through a closed coupled fixed bed of ZSM catalyst, this has the
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advantage of providing independent control of the temperature and residences of pyrolysis
vapours over the catalyst.
Among cracking catalyst ZSM-5 has attracted most attention due to its shape selectivity to
aromatics with promoters such as gallium or nickel. A key disadvantage is that catalyst
rapidly cokes which requires frequent regeneration as in a fluid catalytic cracking unit in a
conventional refinery, the FCC unit. Oxygen is thus substantially removed as carbon
monoxide and carbon dioxide even as well as water also a minor fraction compared to solely
water in hydrodeoxygenation.
Production of aromatics is also likely to be of significant interest to the chemical sector where
aromatics are the second largest global petrochemical sector. A complementary approach is
to incorporate catalyst cracking in the pyrolysis reactor which offers a more compact reaction
system, but there is a catch. So, you have to compromise between the 2 things. First is the
optimum pyrolysis condition and there is also an optimum catalysis conduction.
So, anyway somewhere you have to make a compromise so by optimizing both the process
parameters simultaneously and to see that you are getting a moderate yield.
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So, this is one of the continuous fast pyrolysis process, that was developed for the lignin
actually and a direct upgradation of pyrolysis vapour by the HZSM-5 catalyst which is by
producing the renewable aromatics. So, you can see this is a screw feeder where the lignin is
being fed to the pyrolysis centrifuge reactor, the pyrolysis has been happening in a separate
one and the vapour whatever it is coming from the pyrolysis reactor, it is getting cracked in a
separate reactor where the catalyst in the fixed bed system are being provided.
So, the bed is made up of the HZSM-5 catalyst, then you get the aromatic hydrocarbons
olefins and all these things. So, although some advantages result in improvements to yield
and quality of the liquids the catalyst has to operate at the same temperature as pyrolysis or
vice versa and the necessary contact time for the fast pyrolysis are not optimal for catalytic
cracking.
So, there is a catch, this is what I was just mentioning you that, kindly understand that the
optimized process parameter for pyrolysis, lignin pyrolysis or biomass pyrolysis is quite
different than the optimized process parameters for the vapour catalytic cracking. Now if both
you want to have in the single reactor then you have to compromise on the optimized
parameter for one, either you go for this or you go for that. Then you can further see that
what type of yield and the quality of fuel, quality of the product you are achieving or getting.
Now however this could operate as the first step in a multi stage process followed by
secondary vapour process utilizing process conditions more suitable for the vapour phase
cracking. So, whatever has been done here - if you do that then the question of putting them
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together in a single reactor in which both your pyrolysis as well as vapour catalytic cracking
will be carried out is not required. So, you can have 2 different stages.
Then we will talk about supercritical fluid, we have just touched that supercritical fluids; we
will discuss in detail. So, a fluid is considered supercritical when its temperature and pressure
go above its critical point. Supercritical fluids possess unique transport properties. So, they
have properties of both gases as well as liquids. So, they can effuse through solids like a gas
and diesel materials like a liquid.
That is what I was telling that the supercritical fluid possesses the properties of both gas and
liquid. In particular, supercritical fluids have the ability to diesel materials not normally
soluble in either liquid or gaseous phase of the solvent and hence to promote the gasification
or liquefaction reactions. Supercritical fluids have been recently used to improve oil yield and
quality and have demonstrated a great potential for producing biooil or biocrude with much
higher calorific values and lower viscosity.
Water is the cheapest and most commonly used supercritical fluid in hydrothermal processing
but utilizing water as the solvent for liquefaction of biomass has the following drawbacks.
The first is that lower yields of the water insoluble oil product, second is that it yields a biooil
that is very viscous with a high oxygen content.
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To enhance the oil yield and qualities the utilization of organic solvents such as ethanol,
butanol, acetone, 2-propanol, n-hexanol, 1,4-dioxane, and methanol has been adopted. Now
all these solvents have shown a significant effect on biooil yield and quality although super
critical fluids can be produced at relatively lower temperature and the process is
environmentally friendly these organic solvents are too expensive to make it economically
feasible on a large scale.
In a significant work - the reference has been given below - crude glycerol, the low value
product of the biodiesel production has also shown very promising results for being used as a
substitute for the supercritical solvents, traditional organic solvents. Minami and Ska have
reported that 90% of beech wood was successfully decomposed in supercritical methanol.
The above mentioned supercritical organic solvent fluids are predominantly used in HTL
process to improve the biooil yield and quality. Besides, it was also used to upgrade the
pyrolysis biooil.
897
Next is gasification of synfuels. A recent concept that has attracted much interest is the
decentralized production of biooil or biooil char slurries for transportation to a central process
plant for gasification and synthesis of hydrocarbon transport fluids, by for example the FT
processing, FT synthesis or alcohols. Although there is a small energy penalty from the lower
pyrolysis energy efficiency, transportation energy and additional biooil gasification stage, this
is more than compensated by the economies of the scale achievable on a commercial sized
gasification and transport fuel synthesis plant. Now although the concept of very large
gasification plants of 5 gigawatt or more has been promoted based on the importation of
biomass on a massive scale to an integrated plant, for example that was already established at
Rotterdam, there are significant obstacles to be overcome.
898
Decentralized fast pyrolysis plants up to 100,000 tons per year or 12 tons per hour are
currently feasible and close to being commercially realized. Biooil gasification in an
entrained flow oxygen blown pressurized gasifier is also feasible such as a Texaco or Shell
system with the added advantage that feeding a liquid at pressure is easier than solid biomass,
offers lower cost and the gas quality under such condition is likely to be higher than from the
solid biomass.
Finally, transport fuel synthesis at 50,000 to 200,000 tons per day is also commercially
realizable from the extensive gas to liquid plants currently operational around the world.
Synthetic hydrocarbons include diesel, gasoline, kerosene, LPG and methane. These liquid
fuels are entirely compatible with conventional fuels in all proportions but are much cleaner.
At least in the medium term, these are likely to be the biofuel of choice due to the ease of
assimilation into the market place.
We will now discuss about fast hydropyrolysis. Fast hydropyrolysis is the decomposition of
an organic material under high heating rates almost about 500 degree centigrade per second
in a hydrogen environment. It can only be performed in systems that allow short vapour
residence time, few seconds only, such as fluidized bed reactors, cyclone reactors, micro
pyrolysis systems such as the Py-GC/MS (Pyroprobe).
The hydrogen may be the only gas or may be diluted in an inert gas such as nitrogen. Fast
hydropyrolysis was performed for coal in the past. The hydrogen partial pressure is variable
and it usually ranges from atmospheric to about 30 bar, though studies with 54 bar have been
899
also reported. The process can be catalytic or non catalytic however in order to ensure proper
level of deoxygenation, some groups have employed a hydrotreating unit right after the fast
hydropyrolysis reactor, so that the volatiles coming from the first reactor are immediately
upgraded in the second unit.
Fast hydropyrolysis generates 2 liquid phases; one is that organic phase containing the
mixture of hydrocarbons which is the target product or the biooil part and then the aqueous
phase along with the char and permanent gases. If a catalyst is used, then coke on the catalyst
surface may also be produced though it has been reported that the amount of coke formation
is small.
A fluidized bed reactor is basically chosen for this illustration. All the configurations are
discussed: non-catalytic fast hydropyrolysis, catalytic fast hydropyrolysis, non-catalytic fast
hydropyrolysis with ex-situ hydrotreating and catalytic hydropyrolysis with ex-situ
hydrotreating.
900
I will show you the schematic representation of these 4 systems what we have just mentioned.
The first one. So, this is fast hydropyrolysis, here whatever you are seeing that is a pyrolyzer
or pyrolysis reactor; the biomass is being fed and you use some sort of inner particles bed
basically to carry out the fluidization, they are not catalyst. So, hydrogen is being fed and you
get the oxygenated volatiles.
Now in the second case - b, it is catalytic fast hydropyrolysis; so instead of having the inert
particles here we have fluidized catalytic bed particles here. So, and hydrogen is being fed
and you carry out this. Now in the third case there is a separate hydrotreating unit without
catalyst. So, you do not have a catalyst here, again it is the inert particles to carry out the
fluidization process. And you have a secondary unit which is hydrotreating unit, but that
hydrotreating unit is having catalyst. Now in the last one you have a catalytic pyrolyzer as
well as you have a catalytic hydrotreating unit. So, both the units contain catalyst. So, 4
distinct cases have been studied and the reference is also given below.
901
So, if an HDO catalyst is present in the reactor it is called catalytic fast hydropyrolysis.
Catalytic hydropyrolysis often performed at elevated pressure to increase the driving force for
the HDO. Now this approach has been more successful in achieving the high energy recovery
and biooil with low oxygen content. Both non-catalytic and catalytic fast hydropyrolysis can
be coupled with downstream HDO, performed in a fixed bed reactor for vapour phase
product upgrading.
An advantage of not having a catalyst in the pyrolysis reactor - scenario a and c here, these 2
are non catalytic, the optimal temperature of 500 degrees centigrade for fast pyrolysis can be
applied without having to also consider what might be optimal for the catalytic HDO
reactions. Note, however that without HDO catalyst the hydrogen used in the fast
hydropyrolysis typically does not enable significant HDO. So, this is one of the disadvantage.
So, it is always better to have a catalytic HDO.
902
Therefore, the advantage of in-situ HDO is not obtained here and it becomes crucial to have a
short residence time before the downstream HDO reactor to avoid secondary reactions such
as polymerization. For concepts with a catalyst in the fluid bed - scenario b and d - where
catalyst is used both in the pyrolysis reactor as well as in the hydrotreating units the choice of
catalyst becomes very crucial.
A too reactive catalyst also may crack all species to light gases and no oil phases form. So,
you do not get oil. So, the catalyst selection is very important, this was observed by Dayton et
al, that initially most gaseous products were obtained but due to catalyst deactivation a liquid
product was obtained after 20 hours on stream.
903
So, this is a proposed process diagram for the H2 biooil concept. The reference is given here.
The fast hydropyrolysis and downstream catalytic HDO. So, what is happening is this, here
the hydropyrolysis reactor here the biomass is being dried, then fed directly to the
hydropyrolysis reactor. So, hydrogen is being fed here, then whatever you get here so it goes
through the series of cyclone separators.
So, in the first one the cyclone will separate the sand and char. Now this sand and char will
be fed to a combusting unit and whatever is coming out in this combusting unit is being fed to
another cyclone separator where the sand will be re-circulated back to the pyrolyser, sand is a
heating medium. Now the gases, the pyrolytic vapours now those from here actually it goes
to the temperature adjustment, then catalytic HDO process.
Then it can go to the gas liquid separator and condensor. Now again I am telling you that
there can be many small, small unit operations involved in the entire scheme which are not
being shown here. Let you understand that what are the main units that are responsible for
carrying out this H2 biooil process.
So, a process referred to as the H2 biooil involved fast hydropyrolysis at elevated pressure
and downstream HDO of the pyrolysis vapours. The process combines fast hydropyrolysis
with vapour upgrading to produce a biooil compatible with the current transportation fuel
infrastructure. The pyrolysis gas may be recycled to the pyrolysis reactor or utilized in a gas
turbine and the char is combusted or gasified to provide heat and/or hydrogen for the process.
904
The H2 biooil concept was partly verified by an experimental investigation using pure
cellulose as biomass and inverted cyclone fast hydropyrolysis reactor operated at 550 degree
centigrade and a fixed bed HDO reactor with alumina, platinum alumina or ruthenium
alumina as catalyst operated at 375 degree centigrade with 9 bar hydrogen partial pressure
and 27 bar total pressure. So, this is a very good study and this has been commercially
adapted, the H2 biooil process.
Now the degree of deoxygenation obtained in those experiments were only 14 to 27%. In a
follow-up study the HDO catalyst was improved by using platinum molybdenum support on
multi walled carbon nanotubes. Now you understand that the significance of the catalyst - the
selection of catalyst is very important. The residence time in the HDO reactor was more than
double and the conditions adjusted to 480 degree centigrade in the pyrolysis reactor, 300
degree centigrade is the HDO reactor and 25 bar hydrogen pressure resulting in close to
100% deoxygenation using both cellulose and popular wood as biomass.
So, this is a case study, you can use other biomass. No liquid oil was recovered, only an
aqueous phase, so the biooil composition and yield was only based on the GC analysis of the
gas phase. Overall it appears that to realize biomass to hydrocarbon fuels using a fast
pyrolysis based process, fast hydropyrolysis at elevated pressure using a high partial pressure
of hydrogen is a possible method.
905
So, centralized plants are more favourable in terms of the hydrogen requirement which is
significant for both catalytic fast hydropyrolysis and catalytic HDO -hydrodeoxygenation,
and it is clear that hydrogen consumption should be addressed in the development of a
commercially attractive process. One option is to reform the light gases produced in the fast
hydropyrolysis into carbon dioxide and hydrogen which can then be fed to the pyrolysis
reactor. And carbon dioxide can be recycled back for other processes.
Additional hydrogen could potentially be produced sustainably from the electrolysis of water
using electricity from wind and solar power making entirely the production of hydrogen as
sustainable and green. Hydrogen could potentially also be produced from the gasification of
char. Another utilization strategy for the light gases could be conversion into synthetic natural
gas by using the methanation process. Now techno-economic analysis and life cycle
assessments can be used to evaluate whether a process is economically viable and allows for
comparison of the different processes.
906
Such analyses have been performed for various fast pyrolysis and catalytic upgrading
processes. For example stating the transportation of solid biomass is viable within a radius of
less than 170 kilometre. The economics has to be taken into consideration. So, LC and TA
studies are very important. As these analyses are based on a complex network of data and
assumptions as for example agricultural yields, energy prices, process efficiencies and yields,
it is recommended to interpret the results with caution, especially if an uncertainty and
sensitivity analysis is left out.
Investigation of catalytic fast hydropyrolysis of solid biomass directed at minimizing coke

formation and cracking and stabilizing reactive oxygenates. The influence of various
operating conditions for catalytic fast hydropyrolysis, for example temperature, hydrogen
partial pressure, space velocity, gas flows, etcetera should also be investigated to optimize the
oil yield, deoxygenation and energy yield in the produced oil.
907
So, with this I conclude today’s lecture. So, in the next lecture that is the last lecture of the
module 8 we will be discussing about the applications of biochar and how you do you also
characterize the biochar. So, as you know that biochar also is an important value added
product or byproduct or side product from the pyrolysis of the biomass. So, if you have any
query please register your query in the swayam portal or you can drop a mail to me at
[email protected], thank you.
908
Module-08
Lecture-24
Factors Affecting Biooil, Biochar production, Fuel Properties Characterization
Good morning students. Today is lecture 3 under module 8. And in today's lecture we will be
discussing 2 main important things. One is the biochar characterization and another is the
biochar applications. So, let us begin.
Biochar is produced by carbonization of biomass and the derived organic materials.

Carbonization is a pyrolytic reaction occurring when biomass is heated under the exclusion of
oxygen and involves processes such as condensation, decarboxylation, demethylation,
oxidation and reduction. Although the carbonization process reduces the heterogeneity of
carbohydrates, biochar characteristics are largely determined by the properties of the original
feedstock and the carbonisation conditions.
The use of biochar to mitigate climate change by sequestering carbon is already being
experimented and it is a very interesting topic of research since almost 2 decades, many
excellent works have been reported and some are also being implemented. Recently, many
beneficial applications of biochar are developed, ranging from use as a growing media, a
bulking agent for composting, soil amendment to improve soil fertility (another important
909
class of application of biochar), then as feed additive in livestock farming and for remediation
of contaminated soils.
Finding the most appropriate application of biochar depends on its composition and
characteristics. Biochar parameters include pH, organic carbon content, volatile compound
content, ash content, elemental composition, nutrient content, plant available nutrients, bulk
density, pore volume, porosity, surface area, water holding capacity, cation exchange
capacity, iodine number, surface functional group, sorption properties, nutrient release
dynamics and stability.
Some of these parameters are challenging to assess. Now, the need for standardizing biochar
characterization is very evident. Besides most analytical characterization is conducted on
freshly produced biochar. It is known that certain biochar properties such as volatile or
aliphatic carbon content and CEC content changes over the time. So, that means when you
are storing it during its aging this aliphatic carbon content CEC content will change.
Now, given the long residence time of biochar in soils, the relevance of certain initial biochar
characteristics which are likely to change over time remains debatable. So, hardly there are
any reports on the biochar once it is applied to the soil or some other application and how its
properties are changing with respect to time is not much studied.
910
Identification of biochar through modern analytical techniques is likely to result in variation
in its surface properties, such as surface area, surface charge, functional groups, pore volume
and distribution. Applicability and performance of biochar depend upon the type of
contaminants, environmental conditions, remediation goals and land use purpose in general.
The main objective of characterization is to differentiate biochar from soil organic matter and
other forms of black carbons yielded from various biomasses.
Some of the modern techniques - such as solid state NMR, FTIR, XRD, XPS, SEM, TEM,
TGA-DTG, GCMS and NEXAFS - that most effectively differentiate various types of
biochar can also be used to characterize individual biochar waste, or you can say the
collection of fragments recovered from both soil and solution system. So, we will discuss one
by one these things.
911
And before that, let us try to understand the biochar benefits. The major utilization of biochar
is found in 4 major areas, where biochar is being used in environmental management which
includes soil improvement, waste management, climate change mitigation and energy
generation. The biochar influence on chemical properties of acidic soil is steady with their
chemical configuration and application of alkali biochar significantly raises the sorption of
phosphorus and decreases the obtainability of the adsorbed phosphorus.
Biochar, the product of different biomasses can provide an alternative source of long term
carbon storage in soil to minimize climate variation by an enhancement in the biogenic
carbon collection, decreases the greenhouse gas emissions, restore soil fertility, amend soil
physical properties such as pH, pore structure, surface area and mineral matter, enhances the
crop yield and productivity and reduces the nitrogen emissions and leaching.
So, these are basically biological and environmental applications or the benefits when we are
using a biochar in soil.
912
So, let us understand the generalized analytical techniques for the biochar analysis - the
characterization techniques. Clearly it has been seen that structural analysis of biochar will
influence its flexibility in the environment and its interactive function with the soil
hydrologic cycle and appropriateness of being a biological role for soil microorganisms.
However, the broad range of biochar structural characterization caused its challenging to
study methods and appropriate to connect the fundamental physical properties of density and
porosity to environmental benefits.
Biochar has similarities with activated carbon in many aspects, such as mutual production
during pyrolysis and medium to large surface areas. Also, the biochar surrounds a non
carbonized fraction that may undergo change with soil impurities. Specially, the level of
oxygen containing carboxyl, hydroxyl and phenolic surface functional groups in the
biosphere could efficiently hold together the soil contaminants.
913
We will see one by one some of the analytical techniques to characterize the biochar. The
first is solid state nuclear magnetic resonance (ssNMR) spectroscopy. Solid state C NMR
spectroscopy is used to estimate the carbon chemistry of biochars generated from different
feedstock at operating temperatures with a range of 350 to 600 degrees centigrade. Now,
solid state magic angle spinning the MAS NMR spectra are obtained at a frequency of 100.6
megahertz on a Varian unity INOVA 400 NMR spectrometer.
So, this is one of the spectrometer model please do not understand that only this has to be
used there are many. This is just taken from literature. Now carbon solid state NMR spectra
are attained by utilizing cross polarization as well as direct polarization techniques. The
observability of C in the biochar for the DP spectra is higher than the CP spectra. Now, this
can be partly attributed to the low hydrogen content of the condensed aromatic units that
form the bulk of chars’ molecular structure.
Then ferromagnetic and paramagnetic mainly the iron minerals can also affect NMR
observability of the char materials. The iron contents are higher for the biochars produced
from bamboo and food feedstock and this likely to have contributed to the very low CP for
the bamboo and food at 600 degree biochars. So, the inherent meaning of this entire
discussion is that what is the composition of your biochar, mineral composition including that
if you have more iron content, then your CP DP value is going to change.
914
So, this composition also makes effect or impact when you are analyzing the biochar in a
particular analytical tool whether it is ssNMR, whether it is XRD, whether it is XPS all such
spectroscopic and IR methods.
So, this is one typical solid state NMR spectra CP and DP NMR spectra of the biochars
produced from the wood feedstocks at production temperatures between 350 and 550 degrees
centigrade. So, this is oak wood at 350 and it is 450, you can see that there are changes in
peaks. Now, I am, in detail not telling you why the peak has changed and all these things; that
actually will take so much of time even out of our discussion with respect to this particular
course.
But this is just to make you understand that how actually NMR peaks looks like and what you
can infer from it. Similarly, the below one is the pinewood at 450 and 550. So, the peaks at
what range actually this is in ppm, you can see the x scale, the peaks are coming. So, from
that you have to analyze the peaks; there are standard library available to analyze the peaks.
So, you can use that and making use of a software you can analyze it.
So, the quantification of aromaticity from the C NMR spectra of the different biochar is
compromised by 2 main factors. The first is the presence of the large spinning sidebands –
SSB - that overlap with the non aromatic signal and the second is the low CP observability
for all the biochars and the low DP observability of a minority of the biochars.
915
Now, aromaticity in biochar is generally easier to assess than the degree of the aromatic
condensation. In particular, the determination of elemental composition, the spectroscopic
assessment of functional groups, the measurement of the aromatic molecular markers and
measuring the structural density the Pycnoindex basically, can yield insight into the
proportion of the aromatic carbon in biochars.
Then, the Fourier transform infrared spectroscopy. So, FTIR is used for the structural analysis
and characterization of the functional groups present on the biochar surfaces. The FTIR
spectral peak tasks are understood based on characteristic vibrations for those produced from
the wood and grass feedstock, dairy manure, biooil yielded during pyrolysis of manures
occurring at higher rates, natural organic matter and bacterial surfaces and what not.
You can use any materials to find out the functional groups present on the surface of it, using
the FTIR spectroscopy. FTIR also described the stretching of carbon hydrogen bands that are
associated with aliphatic functional groups. The presence of hydrocarbons is confirmed
through FTIR for the better understanding of biochar structural properties. For the feedstock,
the broad band near 3300 centimeter inverse is attributed to the stretching vibration of the
hydrogen bonded hydroxyl groups.
The symmetric and asymmetric carbon hydrogen stretching are linked with aliphatic
functional groups. The carbon oxygen double bond stretching for carboxyl, aldehyde, ester,
and ketone are identified in the bandwidth 1740 to 700 centimeter inverse.
916
So, in addition to a carbon oxygen double bond stretching vibration bands for amides are
noted at 1645 to 1653 centimeter inverse. So, these are wave numbers. So, absorption band of
amide in these region likely results from the carbonyl stretching vibration in the peptide bond
rather than C-H stretching and N-H bending that appear at lower wave number. The FTIR
analysis confirms the high quality of nitrogen, oxygen, hydrogen, alkane and cyclic alkene
having functional groups on biochar surfaces in addition with a strong peak that could denote
sulfur, amine or ester groups.
Infrared spectroscopy is a promising technology that is used for different nitrogen functional
groups in organic matter in addition to being instantaneous and non-destructive. Mid-IR
spectroscopy has been used to develop calibrations for nitrogen, carbon and fiber contents in
manure. For that manure is scanned in the mid-infrared wavelength from 2500 to 25,000
nanometer. So, that correspond to 4000 to 400 centimeter inverse using KBR as reference.
FTIR analyzes physicochemical variations and similarities.
917
The next is the scanning electron microscope SEM. So the SEM is mostly used for
characterizing biochar and effective for detecting biochar macropores, SEM is a surface
characterization technique. So, however microscopy and computerized tomography go
through a difficulty such as choosing representative samples and viewing orientations,
development of image analysis protocols to quantify porosity and definition of edges between
solid and pore.
Now, SEM is used to study the ultimate composition and surface morphology of biochars
before and after sorption such as iron impregnated biochar, MPB and BPB, magnetic biochar,
magnetic and non magnetic energy cane biochar, ZVI biochar, clay biochar, carbon
composites etcetera. So, basically biochar, when you produce it and then after its application,
you again have to see and see what are the changes in the surface.
So, SEM images give the data of surface morphology, which is a significant factor in
adsorbent-adsorbate connection. So, when you are talking about adsorption so, the surface
morphology plays a significant role. That is why it is very important to characterize the
biochar using SEM.
918
So, this is a typical image of the SEM. So, you can see that this is the original macadamia nut
shell, which was used to prepare the biochar. So, then B is actually after the pyrolysis, the
biochar is produced, this is the original feedstock, this is after the pyrolysis the biochar is
produced, then this is the original cells of the scanning electron microscopy image and this is
the inner view.
So, from here you can understand that how actually the scanning electron micrograph of a
biochar looks like. So, the short residence time partially destroys the original wood cell
morphology. So, that means when we are talking about pyrolysis conditions. The surface
morphologies of the nanocomposite are non smooth with some porosity due to the inherent
nature of biochar.
SEM has detected the soil black carbon occurrence as well as defined and amorphous
particles. Lignocellulose biomass is converted from amorphous C structures to poly-aromatic
graphene sheets with rising temperature while at low temperature BC is likely to be a
complex combination of these 2 main carbon forms.
919
So, next is TEM, transmission electron microscope; So the TEM is exceptional for its quality
to give data about size, morphology, composition, crystallinity and electronic state of sample
all with a very high spatial resolution. Because a thin specimen is actually required for the
TEM analysis specific sample preparation techniques such as ultra-microtomy, iron milling
or electro-polishing are sometimes needed.
Tiny particles, fines and colloidal suspensions are also dispersed on TEM grids often, this
method could lead to improve a variety of adsorptive remediation processes. So this is a
representative image of a TEM micrograph of a corn stover biochar at 200 nanometers.
So, then is XPS and Raman spectroscopy. So, XPS also referred to as the electron
spectroscopy for chemical analysis ESCA. And it has been used in surface analysis because it
920
can be applied to higher range of materials and delivers valuable quantitative as well as
chemical state information. XPS is typically proficient by preparing the sample surface to
their excited state with mono energetic Al k alpha X-rays, causing photoelectrons which are
released on the surface of the sample and an electron energy analyzer is used to compute the
photoelectrons energy released. XPS is the best tool for the analysis of the significant change
in the proportion of aromatic carbon of fresh and aged biochar. Furthermore, the increased
carbon defect population pursued by XPS gives an additional support to the Raman findings.
The proportion of aromatic carbon is higher in the light fraction of the biochar that is
produced at 550 degrees centigrade amended soils than in the corresponding biochar that is
produced at 450 degrees centigrade amended soils.
This is a typical spectrum of the biochar XPS spectrum. So, 2 things have been shown here.
One is the biochar and other is the magnetic biochar. So, the biochar is denoted by that black
curve and the red curve actually denotes the magnetic biochar. So, you can see the magnetic
biochar the peak has been reduced here, wherever here it has been broadened or you have a
larger peak here.
And in case of here the Fe2p. So, biochar do not have a peak whereas magnetic biochar due
to the presence of iron. So, you can see that there is a huge peak. So, XPS to set a modest and
easy way to activate method for cost efficient sorbent yield and removal ability and determine
the sorption mechanism of metals by surface analysis. For the further examination of metal
sorption mechanism of the different metal impregnated biochars. Binding energy shifts for
carbon, iron, oxygen and metals and that can be observed using the XPS.
921
So, then next is Raman spectroscopy. So, Raman spectroscopy is very valuable tool for the
characterization of the carbon based nanostructures. The Raman spectra of pristine and
treated multi walled nanotubes is excited with the range of 514.5 nanometer laser line. So,
Raman usually consists of 3 characteristics bands, the D band at approximately 1338
centimeter inverse, it shows the presence of amorphous carbon in their samples.
Then, the G band which originates from the tangible stretching of the carbon-carbon bonds in
graphene sheet and then the D band which is a weak part of the G band again. So, basically 2
D band and G band. So, you can see this is a representative spectra of the fresh and an ancient
biochar sample, ancient means the old biochar samples. So, you can see that the D band
corresponding to 1338 centimeter inverse here, it is appearing. Then the G band is appearing
later on. So, it is also a very good technology especially when you are talking about
nanostructures.
922
Then XRD, X-ray diffractometer: XRD examines crystalline material structure and size. For
that a computer controlled X-ray diffractometer equipped with a stepping motor, a graphite
crystal monochromator and a CuK alpha radiation source are used. As grain size decreases
hardness would be increased and peaks become broader. The Debye-Scherrer equation which
is designed in 1918 for the determination of the mean size of the single crystal nanoparticle or
crystallite in nano-crystalline bulk material in the form can be written as l = k alpha beta cos
theta.
Where K is the shape factor with a value of about 0.9, small k is the X-ray wavelength, beta
is the line broadening at half of the maximum intensity in radians, and theta is the Bragg’s
angle, l is the mean size of the ordered or crystalline domain.
923
Using the X-ray diffraction techniques and Bragg’s law to derive the structure of crystals and
show the exact position of atoms, you can use this equation n lambda = 2d sine theta.
Where n is the integer determined by the order given, k is the wavelength of X-ray, d is the
spacing between the planes in the atomic lattice and h is the angle between the incident ray
and scattering planes.
Some unknown peaks emerged in the XRD pattern signifying the existence of a small amount
of other minerals, which are commonly detected for biochars formed from agricultural and
forest residues at high pyrolytic temperatures with the increase of reaction time, noticeable
changes in the relative intensities of the XRD peaks are observed and the difffraction peak
becomes stronger and stronger.
924
This is one typical representative image of the XRD analysis of the biochars produced at
different temperatures. So, 3 different temperature biochars are plotted here you can see that.
The green one corresponding to 250 degrees centigrade and the red one corresponding to 450
degrees centigrade and the blue one corresponding to 350 degrees centigrade, 3 different
types of biochars.
And you can see that different types of peaks and corresponding this one composition. So,
this is a Apophyllite, then you can see that graphite peak here, fluoride peak, then chlorite,
then gabbsite, bayerite and all these things. So, XRD is a very important technique to find out
the crystallinity index of the biomass or biochar or any such material you can find out
whether it is amorphous or crystalline. And you can also find out the molecular structure..
925
So, then we will talk about TGA and DTG, which is basically thermal analytical technique.
So, thermogravimetric and derivative thermogravimetric analysis. TGA in actual sense is
applicable for thermal analysis in which changes in physical and chemical properties of
materials are measured as a function of increasing temperature. Now, temperature can be
responsible for data about physical changes such as phase transition.
Adsorption kinetics of carbon dioxide is determined using a TGA instrument at a flow rate of
50 ml per minute, you can vary the flow rate. So, this is just an example. So, it is found that
the existence of nitrogen functionalities on carbon surface generally enhance the carbon
dioxide adsorption capacity. It is important to reference that elemental analysis here only
analyzes the nitrogen, carbon, sulfur and hydrogen content of the carbon.
The oxygen content is assessed by difference assuming that only 5 element C, H, N, S, O

could be gasified from the carbon samples. So, oxygen is always by difference. Proximate
analysis is carried out with the aid of TGA to determine the amount of ash and volatile
matter.
The pyrolysis characteristics are described by TG and derivative thermogravimetric curve of

the raw biomass under anaerobic conditions. The variations in elemental composition and
decomposition process of raw biomass in TG-DTG, specifying that increasing pyrolytic
temperature produces biochar with decreases in surface acidity, polarity and increase in the
aromaticity.
926
The water holding capacity of the biochar is further evaluated with the TG analysis of the
water saturated biochars. It is a very important information or let us say the characterization
of the biochar especially when you are going to use it in the agricultural purposes, water
holding capacity is very important parameter. Though the various information that obtained
from TG analysis, tells the story of the stability of different samples of biochar. These results
further confirm the association of the metal particles with biochar surfaces.
So, this is one typical representative image of the TG and DTG curves of the biomass and the
biochar. So, you can see the solid black line is corresponding to that DTG and TG of the
original biomass whereas, the dotted and blue line corresponding to the biochar. So, this
curve you can see which is coming like here. So, this is the thermogravimetric analysis curve.
So, initially what we are doing here is that we are measuring the TG percent is basically the
weight loss with respect to temperature and time of course. So, we are not plotting time here
it is temperature. So, you are increasing temperature of course, the weight loss will increase.
So, initially the moisture will be removed then other components like volatile matters and
some decomposition started, then slowly you are seeing that we are reaching around 550
close to 550, 530.
So, then it is almost become saturated, so, no more weight loss is being noticed. And DTG is
the derivative of the TG plot. So, whatever the TG data you are getting from this instrument,
you can plot it by taking the derivative and plot it. So, you get some more information about
the phase transition and other things from this plot.
927
So, the next is near edge X-ray absorption fine structure spectroscopy which is called as
NEXAFS. So, in soil biogeochemistry black carbon has a significant role. Its complexity,
mainly within environmental matrices presents a challenge for researchers primarily as a
result of techniques, which may favour the detection of certain functional group types instead
of capturing total sample carbon.
Now, characteristic resonance in the NEXAFS spectra showed direct molecular speciation of
the total carbon chemistry of the potentially interfering and reference materials and
environmental matrices that are obtained from an earlier biochar and different feedstock trial.
NEXAFS shows high aromaticity values at low temperature range for unaltered feedstocks
and showing decreasing aromaticity with increasing temperature.
928
So, next we will discuss about the biochar benefit to the environment. This is a classic slide
or representative slide, where you can understand that how biochar can be used in various
forms or various applications. So, you can start from the adsorption, then pathogens control,
moderate organic and inorganic contaminants removal or again, it is one form of adsorption
only, increased soil nutrients, soil amendment purposes.
So, these both are for the agricultural purposes, good absorption site for the NOx, nutrient
absorber again agricultural applications, improved soil fertility again agricultural application,
then enhance soil capacity again agricultural applications. So, you can understand that
biochar has huge application in the agricultural field as well as in environmental applications.
929
So, a biochar as a soil amendment for remediation. Although biochar has the capacity to
increase soil water holding capability, its hydrophobicity can significantly affect this ability.
Biochar with a high pH value would cause a significant rise in the soil pH with neutral to
basic properties, but only a slight increase in soil with acidic pH. The outcome of the biochar
on the exchangeable cation capacity value of the soil repeatedly displays correlation with the
fluctuations of the calcium present and the rise in the pH value.
Acidic soil such as peat benefited from an increase in the pH but the rise of pH in neutral soil
as those soils in a temperate climate inhibit the growth of pH sensitive microbes.
So, this is a slide where you can understand the possible effects of biochar on plant nutrient
uptake. So, you can see this is the plant; here the plant roots are taking the nutrients. So, here
the biochars which are helping in holding the nutrients in a manner so that they are available
in a particular site. Then slowly it is getting released, nutrient holding and nutrient releasing
and the plant is taking it up.
So, this can be nitrogen, phosphorus, potassium, calcium, magnesium, manganese and so
many things. Apart from this biochars also helps in holding water in a better way than the
usual soil. So, when you hold water, when the water holding capacity of the biochar which is
applied to the top surface improves. So, it aids in a better plant growth. So, this is the idea.
930
So, let us discuss the biochar’s effect on soil properties. So, biochar occurrence on top soil
has a substantial outcome on the natural surroundings, depth, porosity, affected texture,
structure, consistency and all through the process of altering the pore size distribution,
surface area, packings, particle size distribution as well as bulk density. It, however, changes
the features of soil which directly affects the growth of the plant.
Biochar existence has an effect on permeability, the reaction of soil to water, swelling
shrinking, its aggregation and soil preparation workability to ambient temperature variations.
It alters soil physical nature, triggering an increase in the total specific surface area of the
soil, which definitely increases the aeration and structure of the soil.
931
Biochar stimulates the working of mycorrhiza fungi as follows: changing the soil physical
and chemical structure, tortuously altering the mycorrhizae, which affects the
microorganisms of the soil in the environment, intruding with a plant fungus signalling and a
allelochemical detoxification, providing refugia from fungal grazers. Now biochar porosity
improves the habitation of mycorrhiza fungi as well as the soil quality.
Now it boosts the anion and cation exchange capacities of the soil, which improved soil
properties thereby cause increasing the pH and total P and N, boosting better root
improvement and reducing aluminium that may be present. However, biochar reduces
drought by increasing the moisture content of the soil, thus reducing soil erosion and nutrient
leaching.
Consequently, biochar surface comprises of several chemically active groups. They include
ketones, diols, carboxylic acid etcetera, which produces vast potential for the adsorption of
noxious elements, such as manganese, aluminium in acidic soils, lead, cadmium, arsenic,
nickel and copper in heavy metal polluted soils. Some particles that exist in biochar causes a
significant rise in the porosity of the soil, and thus promote airflow through the landfill cover.
And thus increased oxygen diffusion that arises inside the landfill cover, which may lead to
high degrees of microbial degradation. As a soil conditioner, biochar increases the
biophysical features of the soil, for example, soil nutrient retention and water holding
capacity while stimulating the growth of a plant.
932
Biochar has several advantages and can be used in reducing the tensile strength of the soil,
increasing pH and soil structure, increasing the efficiency of the fertilizer use. Biochar further
decreases the leachate of soil nutrients, thereby improving nutrients available for plant as well
as decreasing the bioavailability of the heavy metals. Research has shown that between 350
to 450 degrees centigrade at low temperature biochar produced become acidic in nature.
Whereas the biochars that are produced at high temperature of around 750 degrees centigrade
gives alkalinity. Now if the soil envisioned for biochar use is acidic, the biochar produced at
750 degrees centigrade or above may be effective in neutralizing the soil and thus increasing
its fertility. So, do you get it? From this statement you can understand that biochar can be
custom made to suit a particular type of soils amendment or increasing the soil fertility.
So, if you have a acidic soil, you can produce alkaline biochar. If you have alkaline soil, you
can produce acidic biochar, vice versa. So, biochar is a prospective material used to increase
the soil quality and minimize harmful effects of heavy metals at the site of storage dynamics.
933
Biochar reactions in soil: Biochar is used to improve potential carbon sink and soil carbon
storage, increase nutrient in soil retention and availability of nutrient, reduction of nutrient
leachate and sustain the stability of the ecosystem of the soil, thereby adding aromatic
structure and humus soil. Current research has expressed the best application rates and
procedures, properties of adding biochar to the soil carbon sequestration and accumulation of
nutrients over a long period.
Furthermore, biochar intermingling with soil microbial communities and the long term fate,
stability and toxicity in soil requires further study. Biochar application to soil should increase
soils sorption capacity of the anthropogenic organic pollutants, as for example herbicides and
pesticides in a systematically different way, then the unstructured organic matter. Factors
such as food, climate change, low soil fertility, food security are the driving forces behind
new technologies that are being introduced in the farming sector.
934
Soil amendment helps in risk reduction of contaminant transfer to water receptor organisms.
Biochar amendment is very useful, especially in its high stability against decay, thereby
prolonging its lifespan in the soil which enriches the soil properties. It also helps to retain soil
nutrients, soil quality by increased pH, microbial flora etcetera. Other benefits of biochar for
soil amendment include decrease of carbon dioxide production, by the addition of biochar
concentration between 4 and 62%, reduces nitrogen oxide production, levels higher than
25%.
Biochar reduces the bacterial wilt in tomatoes, study shows that these biochar are obtained
from municipal organic waste and it suppresses the disease in Ralstonia solanacearum
infested soil, it is a bacteria. So, biochar helps in adsorbing nutrients, minerals present in the
soil and pesticides thereby preventing the uptake of these chemicals into water bodies and the
degradation of these waters from agricultural activities.
935
Let us talk about the release of nutrient from biochar. So, several researches show how
biochar affects nutrient availability positively, which makes it a great prospect as a slow
release fertilizer in the soil. So, it is very important to note that one of the way how the
biochar is enhancing the fertility of the soil is this, that it not only store or withhold the
nutrients but also helps in slow releasing the nutrients to the soil, so that those can be uptake.
So, if it releases everything and too much of nutrients available, then it is not going to serve
the purpose for the plant growth. So, when nutrients from biochar are released especially the
adsorbed nutrients, it is solely influenced by its desorption characteristics. So, some of the
features may have a major impact on the nutrient desorption from biochar. It was reported
that the rates of desorption of ammonia from hardwood biochar rise from about 19 to 29%
due to a decrease in the pyrolyzed temperature range from 650 to 450 degrees centigrade.
Now, what is the meaning of this? The meaning of this is that the pyrolysis condition to
produce the biochar finally affects the adsorption and desorption rate of the nutrients to the
biochar surface. So, considering black soil the minimum percent of the P desorbed over lower
P loads around let us say 19 milligrams per liter, rises from 35 to 40% with the rise in biochar
application rates ranging from 1 to 11%.
936
Researchers specified that above 66% of the P adsorbed by biochar was released at a higher P
loadings, almost 105 and 250 milligrams. So, that means, when you have more loading, there
is the chance of desorption becomes higher. Now, this shows that the percentage of
desorption may increase by enhancing biochar application rates and P loadings. Furthermore,
cacao shell biochar desorbed 1487 milligrams per kg phosphate and corncob biochar
desorbed 175 milligrams per kg of phosphate.
So, consequently, biochar desorption properties solely depend on the pyrolysis temperature,
feedstock type and the rate biochar application. Thus, it is believed that several biochar types
should be able to accomplish different soil nutrients in the same soil, or can be used
differently in the soil to obtain the anticipated nutrient supply effects.
937
So, we will quickly go through some of the other applications of biochars. So, biochar used in
the building sector. So, 2 of the biochar’s properties are extremely low thermal conductivity,
and its ability to absorb water up to 6 times its weight. Now these properties mean that
biochar is just the right material for insulating buildings and regulating humidity in
combination with clay, but also with lime and cement mortar biochar can be added to clay at
a ratio up to 50% and replace sand in lime and cement mortars.
This creates indoor plasters with excellent insulation and breathing properties able to
maintain humidity levels in the room at around 45 to 70% during both summer as well as
winter. Thus in turn prevents not just dry air, which can lead to respiratory disorders and
allergies but also dampness and air conditioning on the walls, which can lead to mold
developing.
Biochar mud plaster adsorbs smells and toxins, a property not just benefiting smokers.
Biochar mud plasters can improve working conditions in libraries, schools, warehouses,
factories and agricultural buildings. Biochar is an efficient adsorber of electromagnetic
radiation meaning that biochar mud plaster can prevent electrosmog. Biochar can also be
applied to the outside walls of a building by jet spray technique. mixing it with line applied at
a thickness up to 20 centimeter, it is a substitute for the Styrofoam insulation.
House insulated this way become carbon sinks, while at the same time having a more healthy
indoor climate. Should such a house be demolished at a later date, the biochar mud or biochar
lime plaster can be recycled as a valuable compost additive. So, this is a win-win situation.
938
So, biochar application in gas remediation. Biochar is very active for the remediation of the
poisonous substances from the gas, biochar from rice hull, bamboos, sludge, hardwood chip,
and manure from pig effectively eliminated hydrogen sulfide from biogas with adsorption
capacity between 110 to 370 milligram hydrogen sulfide per gram of biochar, which is
efficiency removal of about 96%, excellent removal efficiency actually.
So, adsorption of hydrogen sulfide was essentially assisted by the biochar moisture content
which is almost greater than 85% volume by weight, pH greater than 8, existing surface area
and chemical bonding with surface radical groups. For example, the OH and COOH groups,
functional groups. Hydrogen sulfide, intermingling with alkali biochar surface through ionic
interaction with OH and COOH functional groups in the presence of oxygen and water which
result to the formation of K and sodium sulfate, maybe bioavailable as sulfate to plants.
939
Biochar obtained from peanut shells and soybean straw at pyrolyzed temperatures between
350 to 750 degrees centigrade was tested for trichloroethylene abstraction. This is a typical
example which is reported in literature. So, this PBC and SBC are obtained at a high
pyrolyzed temperature were more efficient than those obtained at low pyrolyzed temperature
for trichloroethylene elimination and were compared to the marketable activated char
/activated carbon.
So, the rate of application of 0.28 grams per liter PBC 700 was better compared to that of the
activated biochar with removal efficiency greater than 88% up to the trichloroethylene
concentration of 9 milligrams per liter. The efficiencies elimination of the biochar was
credited to enhance the hydrophobicity and surface area and reduce the polarity of the biochar
in comparison of the PBC and SBC that is produced at 300 degrees centigrade.
940
So, biochar and greenhouse gases. The key cause of changes in the climate is the increase in
the greenhouse gases and the global warming, but carbon dioxide emissions contribute over
almost 77%. The carbon dioxide emission over soil respiration is about 10 times higher
compared to that produced from the burning of fossil fuels. Furthermore, it is essential to
decrease carbon dioxide contaminants from agricultural soil to moderate climate change.
Biochar is essentially used to increase soil carbon sequestration and reduces nitrous oxide
emission as well as methane emission. Current research has shown that biochar could
possibly decrease the greenhouse gas emissions which are liable for global warming, nitrous
oxide and methane also from the soil, which have major impacts on the climate change.
941
Example of this can be shown in biochar obtained from paper mill waste, bio-solids and
green waste poultry litter reduces nitrous oxide emission from an acidic Ferro sol. This shows
that several biochar types have an effect on the greenhouse gas emissions from soils in
several ways. It is evident that water content in the soil, type of feedstocks of biochar and
biochar pyrolyzed temperature affects biochar potential to reduce greenhouses gas emissions.
There are steps that encompass the reduction of greenhouse gas emission by using biochar
which is multifaceted and becoming clearer methodically. From studies biochar provides
great adsorption sites for nitrogen oxides, nitrogen due to the large surface area thus reducing
the release of these gases from the soil ecological unit.
So, let us talk about biochar as a potential source of toxicants. So, presence of combustion
driven toxic organic compounds such as polynuclear aromatic hydrocarbon, chlorinated
hydrocarbons and dioxins is often suspected in the biochar products. So, PAHs consists of
fused aromatic rings and generally occur in coal, oil and tar deposits and are by-products of
the burning of fossil fuel or biomass.
They are of a concern due to the carcinogenic, mutagenic and teratogenic nature of some of
these compounds. Dioxin is a general term for a large group of polychlorinated dibenzo-p-
dioxins PCDDs and polychlorinated dibenzofurans PCDFs. While the exact mechanism of
formation of these toxicants during combustion of biomass are unclear, these are speculated
to be synthesized through a catalytic assembly of dioxin structures from carbon, oxygen and
942
chlorine at a temperature window of 300 to 325 degrees centigrade and other multi step
reaction processes in the post combustion zone.
Moreover, since highly hydrophobic compounds are strongly served by the biochars the
current extraction procedure may need to be modified to get a more accurate estimation of
that total load of such contaminants on biochars. Even if these are not readily actually
bioavailable. So, some biochars may be reach in metal contents and may be of concern if
applied to soil without due consideration.
For example, zinc contents of the E. Saligna wood and poultry litter biochars are found to
range from 1312 to 1661 milligrams per kg and from 1449 to 1642 milligrams per kg which
is a very huge load actually. Soil application of these biochars are at high rates could build up
soil zinc levels that could potentially toxic to plants and soil microorganisms and should be
avoided.
Now, the levels of toxic metals in biochars depend on the original content of the metals in the
feedstock and processing condition and the potential impact on soil would depend on the soil
type and their ability to immobilize and detoxify the contaminants. So, what we understand in
a nut shell is that, having said so many good things about biochars, there are certain
drawbacks also, just we talked about zinc.
Let us understand that if we are producing biochar, which can inherently contain some toxic
compounds. See certain compounds are toxic beyond certain level, it is not that they are
943
always toxic, for example, zinc. Now, zinc is very essential for human growth and any living
organism growth, but if you are keep on eating zinc, so, it will not result in our developing
immunization, it will rather become toxic to the cell and it will create other problems.
Similarly, the same thing is for the plants also. So, when we are loading the soil with biochar
having certain compounds which can be toxic in nature beyond certain range, then we have to
be very cautious and to apply such biochars for the agricultural purposes. One example that
we have discussed is about zinc. There are similar other examples also.
So, waste management is one of the attractive elements associated with the biochars
technology. Therefore, the feedstock source especially when biochar are produced from
waste material - let us for example, the municipal solid waste, it can be sewage sludge or
industrial waste, may influence the nature and extent of contaminants present in the final
biochar product and/or formed during the production process.
MSW is a complex mixture of varying components consisting of cellulose or lignin derived.

Numerous studies highlighted the potential of contaminants to be present in the pyrolysis
products and the importance of careful choice of waste as a feedstock. The makeup of the
waste used as a feedstock may content precursors for other toxicants that may be formed
during the pyrolysis process.
944
Generally, organic compounds become less bioavailable with time in soils or sediments. In
this context, the presence of highly microporous hydrophobic sorbents such as biochars may
be particularly effective in reducing their bioavailability with time. Indeed, the
physicochemical characteristics of sorbent matrix have been shown to have profound effects
on the bioavailability of organic compounds.
For example, tests with model sorbents showed that with glass and polystyrene beads,
phenanthrene was rapidly mineralized, whereas with porous polystyrene beads little of the
compound was desorbed and only less than 7% of the sorbed phenanthrene was mineralized.
Microporosity of biochar, therefore is expected to influence the bioavailability of
agrochemicals.
945
So, let us understand the impact on transport of agrochemicals and contaminants including
the persistent organic pollutant POPs. So, POPs produced and used in industrialized nations
are a cause of great concern globally due to their persistent, bio-accumulative and toxic
nature as well as their propensity to travel long distances to affect even remote and
uninhabited parts of the globe.
So, the partitioning process plays a crucial role in determining their environmental fate,
transport, accumulation, impact on biota and food safety. If soil application of biochars
become a common practice the distribution of POPs may be altered even more and may
require an understanding of the potential impact of the biochar applications to soil on the
accumulation and distribution of the POPs. Biochar particles can potentially serve as the
vehicles for off-site transport of the agrochemicals.
The importance of colloidal transport as a pathway of off-site migration of relatively

hydrophobic contaminants is well recognized. It is also known that colloids (being richer in
organic matter and greater sorption affinity) often get enriched in contaminants such as
nutrients and pesticides during their overland transport. Soil application of biochar may
facilitate increased off-site migration of agrochemicals through at least 2 mechanisms.
The first one is that due to the low specific gravity the freshly produced biochar particles are
erosion prone and are likely to get easily entrained in the surface runoff. Second the
extraordinary ability of the biochar to sorb chemical is likely to lead to a greater enrichment
of the residues on the colloids during their transport. However, whether these contaminants
946
would remain bioavailable to potentially exert an effect on the organisms in the receiving
environment is not so clear. So, much work is currently going on this particular area.
See, if you could talk about the ecotoxicological effect on soil organisms. A variety of
organic compounds including the biooils, ash, pyroligneous acids, volatile matter may remain
on biochar surfaces immediately following pyrolysis. However, the fate of these compounds
with time in soil after biochar application is not known. So, it is expected that the water-
soluble components such as acids, alcohol, aldehydes, ketones and sugars that are easily
metabolized by soil microbes may have a positive effect.
Whereas, the presence of compounds such as PAHs, cresols, xylenols, formaldehyde,

acrolein, and other carbonyl compounds depending on the of course pyrolysis process
conditions, may have a bactericidal or fungicidal activity. Earthworms are useful indicators of
soil health as they are highly mobile and sensitive to soil contamination.
947
Copper contents of some poultry biochars have been found to be as high as 1000 milligrams
per kg. Earthworms can exhibit sublethal toxic response at relatively low concentrations
almost less than 30 milligram per kg of copper in soil. Now you can understand that if you
have huge copper content in the biochar and you are applying it to the soil for the agricultural
purposes than the earthworm will have a toxic response.
So, therefore care must be taken in soil application to avoid the accumulation of toxic levels
of the copper. Biochar may also indirectly influence the soil environment for earthworms it
has also been suggested that increasing pH of acid soils through the application of charcoal
can benefit earthworm population. However, alkaline biochars if applied at high rate can also
adversely affect the soil environment conditions for the earthworms.
948
So, will finally conclude by talking little about the biochar and the bio-economy. So, bio-
economy implies the exploration and exploitation of the bio-resources which involves the use
of biotechnology to create new bioproducts of economic value. In this case the feedstock is
the bioresources while the bioproduct is a biochar which is a very important feature of the
bio-economy. Several bioproducts can be produced from any versatile bioresource to add
value to the bioresource promptly.
In essence the production, marketing, awareness campaigns and commercialization are

imperative for the sustainability of the bio-economy. In addition, quality, safety and quantity
of the bioproduct have a significant effect on the bio-economy. As for biochar, effective large
production will result in agronomic and economic benefits. For instance, the yield of the
crops to which the biochar is applied and the profit made because of surplus harvest
determines the economic balance.
Bio-economy has been a viable strategy to refine and upgrade bioresources in developed
countries while there is need to create awareness in most developing countries and encourage
bio-product production. Biochar is a marketable bioproduct which can be used in agriculture
industry and energy sector. Some researchers demonstrated that the carbon dioxide
sequestration payments could play a vital role in biochar profitability.
So, there should be a policy. So biochar can be promoted by introducing a policy on carbon
dioxide sequestration payment. In the meantime, agriculturalist may find it lucrative to use
biochar for cultivation of cash crops that will yield high returns. So, biochar is an additive to
949
soil last long and does not need to be added every year when compared to agricultural
fertilizers, thus it is cost effective.
So, if you look at this particular slide you can understand the economic importance of the
biochar. These are the different types of materials or feedstocks from which the biochars have
been produced and these are the typical things, you can see the colours, the blue one is the
biochar feedstocks percentage actually your economic consideration or importance. Red one
is the transport and spreading, green one is the soil effect.
Then light blue is the heat generation and offset and the orange one is that of the soil
sequestration. So, in a different biochars that is produced from different feedstocks have
different economic consideration.
950
So, transportation is considered a major factor in the economics of biochar production. The
production of biochar is gaining attention due to its promising potential in energy and
environment. Literature reported that the economic assumption results for the production of
biochar in Selangor at 532 US dollar per year and the total revenue from biochar sale was
8012 US dollar per year.
It was demonstrated that yard waste was confirmed to be promising biomass feedstock for the
production of biochar with the net margin of 69 dollar and 16 dollar for the high and low
revenue scenario of the carbon dioxide equivalent including livestock manures, cattle, and
horse. Therefore, biochar production can be attractive if the proceeds of the above values
offset the economic cost of raising, harvesting, hauling and storing the biomass feedstock,
alongside those of employing pyrolysis, transportation and application of the biochar. So, the
entire cost of procuring biomass to the final biochar production.
951
So, with this I conclude today’s lecture, in case you have any query please register in the
swayam portal or you can also drop a mail to me at [email protected], thank you very
much, in the next module that is module 9 we will start talking and discussing about the bio-
ethanol and bio-butanol, 2 of the most important class of products from the fermentation
pathway, so thank you.
952
Indian Institute of Technology - Guwahati
Lecture – 25
Microorganisms, Current Industrial Ethanol Production Technology
Good morning students. Today is lecture 1 under module 9. And as you know that in this
module 9 we will be discussing basically about bioethanol and biobutanol, so two of the most
important products from the fermentation pathway. So, let us begin our class today.
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So, we will talk about corn ethanol first. So, as you know maize or corn is a grain plant from
the family Poaceae and the genus Zea, originated in Mexico but widespread to all continents.
Maize crops currently occupy about 147 million hectares worldwide being extensively used
as human or animal food due to their nutritional properties. The period of growth and
development of this grain is limited by water, temperature and solar radiation.
If you recall we have discussed about maize when we discussed about different types of
biomass, lignocellulosic biomasses and other biomass which has been used for conversion.
So, drought, extreme temperatures lower than 10 degrees centigrade and higher than 30
degrees centigrade and low light intensity affect negatively corn productivity. Taking as basis
the world's largest maize ethanol producer that is United States, harvesting processes carried
out mechanically where the corn cob is separated from the culm so that grains are extracted
while the cob with the straw are left in the field to improve the soil fertility.
So, this is a table which will make you understand about the global corn production and the
yield from 2015 and 2017 in million metric tons. If you see the world is around actually
projected if you look at projected to 1036.90 million metric tons that is the production in
2017 and 18 and it has been increased, but I could not find actually the updated statistics. So,
I am presenting you the old one. This is taken from the Foreign Agricultural Services of the
USDA office.
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And you can see that apart from United States, China, Brazil, the entire European Union is
clubbed into one group, Argentina, Mexico and even India is contributing towards the global
production in a substantial way.
So corn undergoes many preprocessing steps before it can be considered ready for
fermentation for ethanol production. However, as a basic first step post harvest corn is shelled
to remove kernels from the cob, followed by separation from the impurities such as stones
and sticks by screeners or scalpers before getting stored in the silos. Subsequently, a
commercially well-established large-scale biotechnological process is employed via 3 broad
steps.
So, the first step is the conversion of starchy feedstocks into fermentable sugars. So, this also
happens via 3 major sequential unit operations namely milling, liquefaction and enzyme-
based saccharification. Now, the second one is fermentation where the yeast metabolically
converts these sugars into ethanol and then finally followed by the purification where the
ethanol thus generated is separated out from other byproducts and impurities by distillation
before it gets stored or transported to market.
Now, please understand that this is the basic scheme for any corn ethanol production or we
can say ethanol production. So, this and this is well understood, anyway we are going to
discuss and in purification step distillation is the one which is being commercially adapted in
many corn ethanol refineries. But please understand that only distillation is not going to serve
the purpose, there are many other recovery methods also there.
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Depending upon what is your yield of the corn ethanol in the fermentative product basically,
what is the concentration and what are the other byproducts present, so that will decide
eventually whether you are going to have only distillation, a series of distillation or you will
have to combine some other unit operations along with distillation so as to have a hybrid
recovery process.
Milling is the very first unit operation in the biotechnological process described earlier. So,
based on how the grain is milled for ethanol production, this step is categorized into 2
methods. First is wet milling and then dry milling. So, we will discuss in detail about these
two. So wet milling is what? If the grain is first soaked into water to fractionate it into its
individual components such as starch, fiber and germ which are then processed separately,
then it is called wet milling process.
And what is dry milling? Now if the whole grain and the residual components are separated
at the end instead of the beginning of the process then it is called the dry milling process. So,
this is the basic difference between two milling processes. The wet milling process results in
production of a number of co-products such as gluten feed, gluten meal, food-grade corn oil
and distillers’ grain with solubles which is called as DGS. It could separate individual
components of corn grain prior to processing.
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So, this is the schematic where you can understand that how the fuel ethanol is being
produced along with the various unit operations. So, let us just glance through it in a quick
way. So, this is the grain storage. Then it goes for milling. Now, this milling can be dry
milling or wet milling. Then you go for cooking, liquefaction, then the fermentation. This is
the main fermentation bioreactors.
Once it is done, so then you will go for distillation where your fuel ethanol will be recovered
and you will get the solid residues and apart from that certain value-added components which
are present as byproducts, but not essentially require in the fuel ethanol components. Then
you go for storage and fuel to market. These solids products we can also make value added
products out of these. So, you dry them, then it goes to DDG which is called a dry distillers
grain and also can be sold out as a product.
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So, let us understand wet and dry milling in a better way again. So, in the wet milling the
corn kernel is soaked in water and diluted sulfuric acid almost 24 to 36 hours at 52 degrees
centigrade before grinding the kernels into mash in order to facilitate the grain components
segregation. Now, this soaking separates the germ, gluten, fiber and starch being the first
component processed into corn oil or sold to oil producers.
And the other separated from starch using centrifugal, screen and hydroclonic separators. The
remaining liquor is concentrated and dried with the fiber component resulting in the corn
gluten which is sold as feed to the livestock industry. The gluten component that is protein is
filtered and dried to produce the corn gluten meal product. The starch is sent to the
saccharification process and then to the subsequent steps of ethanol production. The usual
steps followed by fermentation, distillation and all.
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And in the dry milling process, the whole corn kernel is ground into a fine powder and mixed
with water to form a mash in which the liquefying enzymes such as amylase are added to
break down the starch into simple sugars. Now, ammonia is also added for pH control and as
nutrient for the yeast in the posterior fermentation step. The mash is then cooked to avoid
bacterial contamination and proceed to saccharification step in which liquefied starch is
hydrolyzed to glucose with saccharifying enzymes such as glucoamylase. So, after cooling
the mash is sent to subsequent steps for ethanol production. Co-products of the dry milling
process include distillers grain which is used as an animal feed, also known as the distillers’
dried grain with solubles or its short form is DDGs and carbon dioxide.
So, this is the flowchart showing various steps of the dry milling and wet milling process. So,
corn flour production and mash formation in the dry milling process it starts, then it followed
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by saccharification, fermentation, distillation and then DDGS formation. Now, similarly in
the wet milling also we start with steeping. Now steeping followed by grinding and
separation where you remove starch and separate starch.
And then others are gluten and fiber components which can also be converted to animal feed.
Now this starch again whatever it is there so it can go to fermentation, distillation and the
usual process. So, from here down it is the usual common processes in both the wet milling
and dry milling and the differences we have already discussed.
The glucose-rich mash obtained after saccharification step regardless of the milling type
actually proceeds to the fermentation process which normally takes about 30 to 40 hours at
mesophilic temperatures. Now in order to reduce the residence time of reactors, the
application of simultaneous saccharification and fermentation which is known as SSF is
widely where glucoamylase and yeast usually Saccharomyces cerevisiae are added
simultaneously.
The resulting mixture containing about 15% ethanol and solids from the grain and added
yeast is pumped to a multi-column distillation column where the ethanol is separated from the
remaining stillage. This liquid stream is centrifuged to obtain the thin stillage which is often
recirculated in the process for better exploitation of sugars. From distillation 93 to 95% pure
ethanol is obtained, which is dehydrated to approximately 99% pure ethanol in a molecular
sieve system.
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What this molecular sieve will do? Let us understand. So molecular sieves are composed of a
microporous substance in which the water molecules are only trapped and adsorbed inside
their molecular structure whereas the larger ethanol molecules will flow around them. So that
means it will not adsorb them. So ethanol is then denatured with 1.76 to 5% natural gasoline
that is being added actually to render it undrinkable.
So that is free of beverage alcohol tax and stored in large tanks for eventual shipment. A
representative scheme for the corn ethanol is being shown in the figure, we will try to
understand.
So, again two different processes. The wet milling is this side, the dry milling is this side and
this particular porition is dedicated to the processes which are common to both. So, again you
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can see that steeping followed by degerm and defiber followed by the starch separation, then
liquefaction, then it goes to saccharification, fermentation, distillation, dehydration and
whatever solids you get that can be either corn gluten feed or can be DDGS.
Then you get here ethanol. Similarly, in the dry milling process it is milling - the mash
formation actually - followed by liquefaction and then the usual process. So, this is an overall
schematic representation of how corn ethanol can be produced using two different milling
processes dry and wet.
Now, we will discuss about lignocellulosic ethanol production. Among the components of
biomass, lignocellulose is the most abundant with the production of almost 170 billion metric
tons per year. The different sources of lignocellulosic biomass are agricultural residues,
agrowastes, forest biomass, forest wastes, industrial wastes, municipal solid waste, etc. Now,
if you recall we have already discussed about lignocellulosic biomass, different types of
biomasses, their characteristic features everything earlier. So, we just quickly go through
again in a nutshell. So, lignocellulosic biomass consists of the following three major
components. Cellulose around 40 to 60%, hemicellulose around 20 to 40% and lignin is the
rest 10 to 25% which are intertwined together to form a lignine carbohydrate complex which
are also called as LCC.
To date, most commercial biorefinery processes focus on the exploitation of cellulose and
hemicellulose whereas the lignin fraction is still treated as a waste product. But if you recall,
we have already discussed about how and why lignin should also be treated at par with other
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components such as cellulose and hemicellulose because lignin is a very high value
commercial chemical.
Now that lignin can be converted to various other components, it can be converted to fuel
also and apart from that other chemicals via lignin biorefinery which we have already
discussed. I hope you can recall that, right.
So, this is the different types of lignocellulosic biomasses, we have already discussed this in
one of our subsequent classes, but I feel that it is better to show you once again in a nutshell
so that the flow of this particular lecture will be retained. So, just quickly we are going
through. We have different types of biomasses and what are listed under them. So dedicated
whole plants, agricultural residues, agro-wastes, forest waste, industrial waste, municipal
solid waste.
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And this table 2 gives a brief description and bioethanol potential of different lignocellulosic
biomass sources. So, if you look at quickly perennial grasses, so the potential can be 0.9 to 37
tons per hectare that is the biomass growth and you can see the potential ethanol yield is
almost 160 to 460 litres per ton. Though not very good, but it is okay. So, because whenever
you talk about lignocellulosic biomasses we never depend upon the single biomass.
So, there are various types of biomasses that can be combined together and processed so that
entire biorefinery will become sustainable. If you look at the agricultural residue, so the
ethanol production is almost 235 to 450 litres per ton. Similarly, municipal solid waste the
amount is of course less 154, but again you need to understand that we are converting
municipal solid waste which is already a waste into some value-added products.
So, it is always a win-win thing, only we need to take care of the process economics and
sustainability.
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The production of second-generation bioethanol starts with the collection of lignocellulosic
feedstock and then its transportation to the plant site. If you remember again recall, let me tell
again - the transportation is one of the major costs that contributes to this lignocellulosic
bioethanol production. Now, depending on the feedstock and appropriate pre-processing step,
either grinding, milling, so all these mechanical pre-processing steps is realized to obtain the
adequate feedstock particle size so that you can transport easily - something to do with your
bulk density and all. So, after this pre-processing, second-generation bioethanol is produced
using a process involving the following primary steps. So, the first is pretreatment followed
by hydrolysis to sugars, then fermentation and product and product upgrading.
Now, there is a pre-treatment which is not present in the corn ethanol production. So you can
tell sometimes that milling is a type of pre-treatment, but it is not separately grouped under a
pre-treatment category. So, this biethanol production includes a separate hydrolysis and
fermentation which is known as SHF. Now, using SHF process, the temperature for the
enzymatic hydrolysis and fermentation temperature can be optimized independently.
So, this is one of the most important thing. Moreover SHF also permits to recycle the yeast
fermentation, which is not the case with the other alternative like your SSFs because you are
carrying out the entire thing in a single reactor system.
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This is the process flow diagram for the cellulosic ethanol production from the beginning that
is from the biomass procurement and storage to that of end fuel. So, lignocellulosic biomass
that is procured, then stored, then transported. Transported to this biorefinery. Then you grind
it, pre-treat it, enzymatic hydrolysis, then you go for fermentation, then go for distillation
where you purify ethanol. Then ethanol storage and subsequent use.
Now lignocellulosic biomass pre-treatment. If you try to recall we have discussed in

extensively. I have told you what are the different types of pre-treatment methods, what are
the pros and cons of each of the pre-treatment methods. So, we’re are not going to discuss it
once more. We will just quickly in a single sight try to understand what are the different
pretreatment methods and try to recall it.
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So, the physical: You can see under physical extrusion, pulsed electric energy, liquid hot
water which is one of the most important one, mechanical, irradiation and pyrolysis. Then
under chemical: so alkali, acid. So these are very important class of pre-treatment methods
especially acid which is dilute acid. Solvolysis, oxidative processes, hydrotropes, ionic liquid,
salts. Then we go for a combination of physical and chemical which is called physico-
chemical.
Steam explosion, AFEX - the ammonia fiber explosion, ultrasound assisted chemical
pretreatment, microwave assisted chemical pretreatment, microwave assisted pyrolysis which
is also gaining a lot of research interest nowadays, combined pretreatment. Then we have
biological. So biological pre-treatment processes they are benign process, they are good. The
only thing is that they take long time.
So, when you are actually talking about a biorefinery concept, then biological somehow do
not fit if you talk about the process time it takes. So enzyme based, microorganism based and
of course you can have microbial Consortium.
Let us talk about the detoxification. Although pretreatment is an essential step for converting
the lignocellulosic biomass into ethanol, it has a major side effect on the overall process due
to generation of lignocellulose derived byproducts under the pretreatment conditions that act
as inhibitors for enzymes and fermenting microorganisms in the subsequent steps if their
accumulation is sufficiently high.
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The byproducts produced during pretreatment include sugar acids, acetic acid, formic acid,
levulinic acid, HMF and furfural. You know HMF is one of the very high value chemical, it
is a fuel additive. And other products are also having certain commercial value. Now, most of
the lignocellulose derived inhibitors are produced when hemicellulose and lignin degraded
during pretreatment.
Whereas cellulose and extractives of the biomass may be the source of inhibitors being
affected unintentionally by the pretreatment conditions. I will show you it in figure 7, so the
next I will show you. So, the pretreatment inhibitors can be categorized into three major
groups based on their origins. So, first is the aliphatic acids, then furan derivatives and
phenolic compounds.
You can have a look here. So, this is the different types of inhibitors that is generated from
degradation of different compounds in the lignocellulosic biomass after the pretreatment
under acidic conditions. So, arrows indicate tentative formation pathways. So, you can see,
let us look at this cellulose first. So, cellulose is giving us oligosaccharides and disaccharids,
hexose sugars like glucose, mannose and all these things which we need actually.
Hemicellulose is giving us pentose and all, furans and then aliphatic carboxylic acids.
Hemicellulose also degrades to these type of compounds which can be grouped as uronic
acids. Now lignin, so lignin gives us benzoquinones, phenylic compounds, the major
component of actually lignin, Lignin also can degrade and gives us certain very few amount
of course uronic acids. Then apart from that we have extractives and ash.
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So, this is a broad understanding that how different byproducts are getting generated and
what is their pathway. So it is very complicated. It is not so easy and various researchers have
tried to actually simulate then study the pathway through which actually these different
byproducts are forming.
So certain strategies have been suggested to counteract the problems with inhibitors that
include both alternative measurements for the conversion process and the treatment of the
pretreated biomass to remove or neutralize inhibitors using biological, physical and chemical
methods. However, type and quantity of inhibitors depend on the pretreatment methods
applied and it is taken into consideration prior to selecting a detoxification method.
Detoxification may be essential if strongly inhibiting hydrolysates are fermented, high

quantity of inhibitors accumulate in the fermentation broth due to recirculation of streams or
when a fermenting organism with low inhibitor tolerance is used. The detoxification methods
should selectively remove inhibitors and be cheap or low cost we can say and easy to
integrate into the entire process scheme.
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So, this table make you understand about the strategies and techniques to overcome the
inhibitors problem during ethanol production from LCB. So, if you look at the strategy the
first one is feedstock selection and engineering. So, what is the approach? Approach is that
selection of biomass with less recalcitrance and those generate less inhibitors during
pretreatment. So, this can be done when you screen biomass for fermentation.
So, remarks is that the drawbacks can be something like that the limitation of using broad
range of LCB. There are many n number of LCBs, how many you are going to screen. So,
this is an experimental screening you have to do to make you understand. Then the option for
short rotation crops dedicated to biorefining through sugar platform process, this is one of the
important outcome. Let us talk about one more, chemical additives.
So, treatment of the pretreated biomass. So, if you talk about alkalis, then more chemicals
needed and reducing agents such as dithionite and all. So some methods require additional
process step, to purify certain other chemicals. So, if you talk about then liquid-liquid
extraction, so you use ethyl acetate, supercritical fluid extraction, though it is costly but it is a
very good process, trialkylamine. So, requirement of additional chemicals and time. So, every
strategies and techniques need to be fixed based upon what is your feedstock. Now, in
lignocellulosic biorefinery the feedstocks keeps on varying. So, you have to optimize the
process parameters again and again when you are actually mixing or changing a whole range
of biomass from one particular biomass composition to another biomass composition that can
also be done and it has been practiced also. Otherwise, you cannot have a sustainable
biorefinery.
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Then the next step is hydrolysis. So, cellulose and hemicellulose present in the lignocellulosic
biomasses are required to convert into fermentable sugars through a process called
hydrolysis. In most cases, the outcomes of the pretreatment process are two fractions such as
first is the water-insoluble solids, so they contain mainly cellulose and lignin. And then a
liquid fraction that contents the hemicellulose.
Now, based on the pretreatment method and conditions, hemicellulose may be either almost
completely hydrolyzed into its monomeric sugars and then can be converted into ethanol
during the fermentation without further hydrolysis process or it can be converted into
oligosaccharides if it undergoes complete depolymerization and require further hydrolysis
prior to subjecting to the fermentation process.
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The dominant sugars in hemicellulose are mannose in softwoods and xylose in hardwoods
and agricultural residues along with a small amount of arabinose and galactose. Even though
a small portion of cellulose may also be converted into glucose under the pretreatment
condition, most of this carbohydrate remains unreacted and requires further hydrolysis.
On the other hand, liquid fraction contains monomeric sugars or oligosaccharides of

hemicellulose. In general, conversion of hemicellulose and cellulose into their monomeric
sugars involves either acid or enzymatic hydrolysis.
So, we will talk about acid hydrolysis. Acid hydrolysis can be done via two approaches such
as dilute acid treatment at high temperature and pressure with a short reaction time ranging
between seconds and minutes and then a concentrated acid treatments at low temperature and
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it takes a long time. The major problem with acid hydrolysis are the requirements of either
recovery or neutralization of the acids prior to conducting fermentation and production of
large amount of wastes.
Mostly sulfuric acid is used in either approaches of acid hydrolysis, although other inorganic
acids such as hydrochloric acid, nitric acid, trifluoracetic acid, phosphoric acid have also been
reported for use for this purpose.
Dilute acid hydrolysis is generally applied for the purpose of hemicellulose hydrolysis and as
a way of pretreatment of cellulose to make it more accessible to enzymes. However, both
carbohydrate polymers can be hydrolyzed with dilute acid requiring a two-stage hydrolysis
process where the first stage is carried out at low temperature to maximize the hemicellulose
conversion. On the other hand, the second stage involves high temperature range between
230 degrees centigrade to 240 degrees centigrade to convert cellulose into glucose.
The major drawbacks of cellulose hydrolysis using acid are the requirements of high
temperature and high risk of the production of inhibitors through degradation of sugars. The
most commonly used concentrations of sulfuric acid and temperatures during dilute acid
hydrolysis ranges from 0.5 to 1.5% and 120 to 160 degrees centigrade. So, this is the range.
You need to optimize it for a particular biomass.
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Then the next is the concentrated acid hydrolysis. Now, this can be applied for
depolymerizing both hemicellulose and cellulose. So, this is the advantage of this process.
Like dilute acid hydrolysis, sulfuric acid, hydrochloric acid or TFA can also be used in
concentrated acid hydrolysis in a concentration range between 41% for HCl and almost 100%
for the TFA.
Now, reaction times in this kind of acid hydrolysis are generally much longer than the times
required for dilute acid hydrolysis. However, concentrated acid offers a complete and rapid
conversion of cellulose to glucose and hemicelluloses to five carbon sugars. Again this is one
of the best thing about this concentrated acid hydrolysis. So, this process has been shown
interest due to its moderate process temperature and without requiring costly enzymes.
However, corrosion of the equipment with high concentration of acid is a major drawback of
this hydrolysis technique. So, you need to invest a so much about the equipment.
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Then the enzymatic hydrolysis. Now, this has been considered as one of the most promising
green and effective process due to enzyme specificity to the substrate working at relatively
lower temperatures and generation of minimum inhibitors. So, the major enzyme systems
used in the hydrolysis of lignocellulosic biomasses include cellulases, hemicellulases such as
xylanase and ligninases.
So, cellulase is a mixture, it is a cocktail of enzymes, mixture of enzymes that acts

synergistically on cellulose and converts it into glucose. So, you need at least 3 enzymes to
make the cellulase cocktail - are required in a typical cellulase system for the bioconversion
of cellulose into glucose. So, that include endo 1-4 beta glucanase or carboxymethylcellulases
or then exoglucanase or cellobiohydrolase and beta glucosidase. So, these 3 are minimum
required.
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So, unlike cellulose, hemicellulose is chemically quite complex and its degredation requires
more specific and multiple enzyme systems. A typical hemicellulose system includes endo 1,
4 beta xylanase or endoxylanase, xylan 1, 4 beta xylan esterases. Then there are so many
other enzymes which are being listed here.
Now, the major enzymes of lignin degradation are lignin peroxidases, manganese peroxidases
and laccases. So, enzymes involved in the enzymatic hydrolysis of cellulose, hemicellulose
and lignin so I have shown, you a picture you can see this.
So, these are the different types of enzymes that are involved in the enzymatic hydrolysis of
cellulose, hemicellulose and lignin. So, the first one here this is cellulose, here this is
hemicellulose structure and this is lignin. You can see different types of enzymes such as
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endoglucanases, cellobiohydrolase, beta glucosidase for the cellulose hydrolysis. Here for the
hemicellulose hydrolysis there are so many different types of enzymes are there and how they
are actually targeting.
So, these are components you can understand. So, this particular component corresponds to D
xylose which is present in the hemicellulose. Similarly, this small one where the red enzyme
is being shown - the red enzyme is basically acetylxylan esterase and this particular
component is an acetyl group. And lignin is a very complex structure. So lignin is also being
degraded using different enzymes such as lignin peroxidase, then versatile peroxidases, you
can have a cocktail also and manganese peroxidase and of course laccases.
So, then the next is fermentation. So after pretreatment and hydrolysis of the lignocellulosic
biomasses, simple sugars are produced as a result of depolymerization of cellulose and
hemicellulose that are then fermented by relevant microorganisms and converted into ethanol.
The overall process is referred to as the fermentation. Ethanol fermentation can be done
either by submerged or solid state fermentation.
And what is the difference we will try to understand. So in submerged fermentation, water is
an important liquid that is used to make fermentation mash by mixing a predefined solid with
water. On the other hand, solid state fermentation is the bioconversion of the LCB in its
natural state. So in a solid state fermentation, LCBs are moistened and with a thin layer of
water on the surface of the biomass using weight ratios of water to lignocellulose -
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approximately 1 : 1 ratio or 10 : 1 ratio in that, again varies for the different types of
biomasses.
So the next is product recovery which is one of the most important steps. The reason is that
this step consumes lot of energy, chemicals and almost 40% of the entire production cost
belongs to this particular product recovery strategies. So, there is a lot of work is still going
on how to reduce the cost of this particular process, the product recovery process. So, ethanol
is recovered from the fermentation broth by distillation or distillation combined with
adsorption.
It may be membrane also, now a lot of work has been reported with membrane. So,
distillation is a mature process for ethanol recovery The first part is distilling the fermentation
broth to separate ethanol from water to reach an ethanol concentration of around 95% and the
bottom liquid contains residual lignin, unreacted cellulose and hemicellulose, ash, enzyme,
organisms that means the microorganisms and other components and are send to the
wastewater treatment.
So, there you can again recover some of the components. These materials may be
concentrated and burned as fuel to power the process or converted to various co-products, the
bottom part.
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So, we will try to understand the different microorganisms which are required in the
fermentation process for the corn based ethanol products. So, the most important is of course
the Brewers’ yeast which is Saccharomyces cerevisiae - the most widely used for commercial
fuel ethanol production from sugar and starchy feedstocks. Saccharomyces cerevisiae has
dominated this sector as the biocatalyst of choice mainly because of the advantageous
attributes it has acquired during natural evolution process over the other ethanol producing
microorganisms. So, what are these attributes? So, major are extremely high ethanol
tolerance, this is the most important part of this Sacchromyces cerevisiae use. It can grow
under stringent anaerobic conditions, is least affected in the presence of oxygen. So, these are
very important attributes.
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So, the best known strains of Saccharomyces cerevisiae isolated so far and used industrially
can convert almost 95% of the sugar directly into ethanol. So, Saccharomuces cerevisiae is a
naturally adapted ethanol fermenting microorganism with a very high tolerance to ethanol
almost 150 grams per liter and chemical inhibitors compared to other well-known natural
ethanol producing organisms such as Zymomonas mobilis.
So, you can have a look at this particular table which gives us a comparative analysis of the
Saccharomyces cerevisiae versus Zymomonas mobilis. So, let us see the first one
Saccharomyces cerevisiae, so the sugars that is utilized you can use any of these glucose,
fructose, maltose, sucrose, etc. The fermentation condition is anaerobic almost 30 to 37
degrees centigrade. Ethanol tolerance 150 grams per liter. Other attributes is up to 95% of the
theoretical yield.
If you use Zymomonas mobilis again the same sort of sugars that it can depolymerize. So, it is
anaerobic around 30 degree centigrade, more or less same. Ethanol tolerance is a little less
than that of the Saccharomyces cerevisiae around 100 grams per liter, but it can produce up to
97% of the theoretical yield. Now please understand this is theoretically, practically how
much is getting produced that depends upon your process optimization and how nicely or
how best you can do the process optimization.
So, we will understand the role of microorganisms in fermentation of lignocellulosic

hydrolysates. Many bacteria and yeasts can ferment soluble sugars in the absence of oxygen,
which results in the production of ethanol. Now these microorganisms can be obtained from
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yeast, bacteria and filamentous fungi. However, filamentous fungi produce ethanol at low
rates and have limited tolerance to ethanol.
Although a good number of microorganisms can play roles in the fermentation, the efficiency
and feasibility of all microorganisms as ethanol fermenter are not equal. Commercial
exploitation of these microorganisms is also limited and only a few are used on large scale
ethanol production.
The most common and widely used microorganism for ethanol fermentation is of course
yeast which has been proved to be robust and well suited to fermentation of lignocellulosic
hydrolysates. It can efficiently ferment 6 carbon sugars but hardly pentoses due to the lack of
enzymes that convert xylose to xylulose. The common bacterial species used for ethanol
fermentation is a gram negative bacteria which is this Zymomonas mobilis.
Some thermophilic anaerobic bacteria such as Thermoanaerobacter ethanolicus. Clostridium,

then Thermoanaerobacter mathranii, Thermoanaerobium brockii, Clostridium
thermosaccharolyticum, so these are all investigated for lignocellulosic ethanol production.
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The performance of any microorganism as ethanol fermenter can be evaluated based on the
efficiency under the different process conditions. This I was talking about, process
optimization condition and all these things. So these are the parameters that need to be
optimized. Wide temperature range, pH range, ethanol tolerance, growth rate, ethanol
productivity, osmotic tolerance, specificity, ethanol yield, genetic stability and inhibitor
tolerance.
The characteristic of an ethanologenic microorganism to be involved in lignocellulosic

ethanol production includes its capability to utilize multiple sugars - that is the very important
thing because when you talk about LCB, we talk about cellulose, hemicellulose both. We
want to convert both these sugars. So, then high ethanol yield. It must tolerate to high ethanol
concentration.
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It should have high ethanol productivity. Good growth in simple and inexpensive media.
Capability to grow in undiluted fermentation broth with resistance to inhibitors and ability to
retard contaminants under the growth condition.
So, this particular table will tell you about the potential of some of the selected
microorganisms in lignocellulosic biethanol production. So, you can have a look at it later.
The font sizes are very small. So, if you take a screenshot and then you can read later on. So,
all species are listed here, mostly which had been used commercially also. Saccharomyces
cerevisiae, then recombinant Saccharomyces cerevisiae that means genetically modified.
Zymomonas mobilis, E. coli, recombinant E. coli and there are many others also and their
characteristics features, their contribution, where it is being used, only fermentation or
fermenters plus hydrolysis both. And then what is the major feature and role.
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So, then let us discuss about the industrial processing pathways for the ethanol production.
So, in general three main ethanol conversion technologies can be distinguished. So, the first
one is the first generation process, then second generation process and the integrated of first
and second generation conversion process. If you recall, the biofuels have also been known as
like that. First generation biofuels, second generation biofuel, third generation biofuels, all
these things.
So the first generation industrial processing is the conversion of sugar and starch rich biomass
crops to ethanol. In sugar based first generation industrial processes, I will show you the
figures later in the next slide, sugarcane, energycane or sweets sorghum is shredded and
milled to extract the sugar rich juice. The sugar juice is treated and concentrated by
evaporation before entering the fermentation step.
During fermentation which is an exothermic process, sucrose is converted to glucose and

fructose which are converted to ethanol, carbon dioxide and byproducts like alcohols, organic
acids, etc.
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So, the fermented broth is fed to a centrifuge to enable yeast separation and recovery. The
fermentation gases are fed to an absorber for ethanol recovery. Both the ethanol recovered
from the centrifuge and absorber are fed to a distillation column. So, actually the similar
process of saccharification followed by fermentation, distillation and the usual procedure.
The distillation product is fed to a rectification column which produces hydrous ethanol.
After further dehydration anhydrous ethanol is formed. So, for first generation technologies,
cane bagasse and cane trash are fed to a cogeneration facility to produce process steam and
process surplus electricity. So in a closed loop birefinery concept.
So, this is the schematic of the possible ethanol conversion concepts for the first generation
technology. Quickly we will go through this. So, the sugary rich crops like sugarcane and any
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other starchy crops. So, you extract the juice and the juice is getting treated. Then fermented,
distillation and rectification, So, you get ethanol. So, whatever the residue is coming here it
goes to the combined heat generation process, heat and power generation unit.
So, you get a steam. The steam is being used for other processes like distillation and all. And
then you can also have electricity. And whatever surplus electricity after you use it in the
entire scheme can also be send to your grid or can be sold out.
So, the next is the second generation industrial processing. So, here the conversion of
lignocellulosic biomass to ethanol happens. So, due to the complex structure of
lignocellulose, the biomass needs to undergo treatment for embedded sugars that are
available for the fermentation to ethanol. In a second generation industrial process,
lignocellulosic biomass feedstock is pretreated and the hemicellulose and very little cellulose
are hydrolyzed followed by fermentation and ethanol separation.
Hydrolysis combined with fermentation is more complex than fermentation of simple sugars.
Many different techniques to pretreat and hydrolyse the lignocellulose biomass have been
researched to improve ethanol yield and to reduce ethanol production cost. Currently, steam
pretreatment followed by enzymatic hydrolysis is considered as one of the most viable
options for lignocellulosic ethanol production.
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So, this is the scheme actually. So the feed handling, so basically you go for pretreatment and
all these things. In mechanical preprocessing, then you go for the pretreatment. Any one the
pretreatment process that we have already discussed. Hydrolysis, fermentation, distillation,
the common steps. Then whatever the residue, solid residue it goes to a CHP unit. Again
steam is being used here, electricity being used here, whatever produced surplus electricity
can be taken back and sold out.
One of the important feature here is of course the enzyme that is required - you can have to
produce it in a mass or large scale. So, the industrial processing residues of the second
generation process which mainly consists of lignin and the unreacted cellulose from
hydrolysis are fed to the cogeneration facility. So, the CHP unit basically.
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So, another possibility is to integrate first-and-second generation process that is the
lignocellulosic residues of the first generation process as for example your bagasse and trash
are fed to the second generation process. How it happens? So, whatever it is the
lignocellulosic residues coming from the first generation - this is the first generation, this is
the second generation - are being fed to the second generation process because they are
lignocellulosic rich component. And the entire rest process schemes are same.
So, the cogeneration unit fed with residues of the second generation process supplies the
steam and electricity for both the processes. So, you have a basically a combined CHP unit,
single CHP unit. This is the advantage of combining or integrating both the first generation
and second generation that you can have a single CHP unit which will produce enough steam
and electricity which will be sufficient for managing both first generation and second
generation processes together.
So, I think with this I conclude today's lecture. In case if you have any query, please register
it in the Swayam portal and I will answer it. You can also drop a mail to me directly at
[email protected]. So, thank you very much. And in the next class, we will be discussing
about cellulases - that is the enzymes and their role in hydrolysis, concepts of SSF -
simultaneous saccharification and fermentation and CBP - the consulated bioprocessing and
then advanced fermentation technologies. Thank you.
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Lecture – 26
Cellulase Production, SSF and CBP
Good morning students. This is lecture 2 under module 9. As you know that we have been
discussing bioethanol and biobutanol under this particular section. So, we will learn today
about cellulases - the enzymes - their role in hydrolysis, concepts of SSF and CBP and
advanced fermentation technologies. So, let us begin.
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Cellulases and their role in hydrolysis. Though we have discussed, but we will again quickly
go through the cellulose structure. Cellulose first discovered by the French scientist Anselme
Payen in 1838 is a high molecular weight homopolymer consisting of D-anhydro-
glucopyranose units joined together by beta 1, 4 linkages and is a major fraction of the total
carbohydrate in lignocellulose.
Cellobiose is the repeating unit in the long chains that contain 2 glucose units rotated by 180
degree relative to each other which provides conformational stability to the cellulose
structure. The glucose chains in the cellulose have one reducing and one non-reducing end.
The reducing aldehyde can get exposed by opening the hemiacetal bond.
So, the number of glucose molecules which we call as the degree of polymerization in one
chain can vary from 100 to more than 10,000 depending upon the origin of the cellulose. The
glucose molecules in the cellulose are connected by numerous inter-chain and intra-chain
hydrogen bonds that cause the crystallinity in the cellulose structure and make it insoluble in
water. The smallest unit in the cellulose structure is considered as elementary fibril, a bundle
of around 30 to 36 cellulose chains bound by hydrogen bonding. Now, many elementary
fibrils are bundled into a unit called as microfibril. I will show you the image in next slide.
Cellulose molecules are very tightly packed inside the microfibril and do not allow
penetration of even small water molecules. Thus, accessibility of enzymes is mainly restricted
to the surface molecules only.
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You can see this is the schematic representation of the cellulose structure. Now, this we have
discussed earlier also, but we will just as I told you that just to understand the role of
cellulases it is also very important to again understand the cellulose structure. So you can see
this. The green color things these are actually the cellulose fibrils and lignin is this brown
color one and the blue color small lines which have been indicated here everywhere are
hemicelluloses.
So cellulose, hemicellulose and lignin are very intricately interlinked or bound together. So, if
you see here how it looks like, let us consider a small microfibril and this is expanded here,
you will see that whatever is written in G, these are actually glucose chain and this is a single
elementary fibril. So the red color, the glucose molecules in red color represents the
crystalline region.
Whatever it is mentioned in the black color are amorphous region. So, in crystalline region, it
is difficult for the enzymes to act on. So, usually they first act on the amorphous region, then
start the cleavaging. So this we will discuss.
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Let us discuss about the enzymatic cellulose hydrolysis. Cellulose can be hydrolyzed to
glucose monomers using chemicals, commonly using strong acid or biological catalysts. Acid
hydrolysis is a quick process. However, it suffers from several limitations such as high
energy requirement, high capital cost, corrosion resistant equipment, high disposal cost and
degradation product formation.
Now, enzymatic hydrolysis is an alternative to acid hydrolysis that addresses several of these
limitations and has been the focus of research in the last several decades. The major enzyme
systems used in the hydrolysis of the lignocellulosic biomass include cellulases,
hemicellulases for example xylanase and ligninases; ligninases and the enzymes that will
degrade lignin.
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Cellulase is a mixture of enzymes, it is a cocktail basically, that acts synergistically on
cellulose and converts it into glucose. At least 3 enzymes are required in a typical cellulase
system for the bioconversion of cellulose into glucose that include and that must include
these 3: Endo-1-4-beta-glucanase or Carboxymethylcellulases; Exoglucanase or
Cellobiohydrolase – CBH; then Beta-glucosidase. Every single enzyme has their different
role and we will discuss what is their role.
Now for example, endoglucanases mainly act in the amorphous region on the surface glucose
chains of the cellulose and hydrolyze the beta 1-4 linkages in a random manner. So we will
see how it works.
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So, this is a very typical representation of how the different enzymes act on glucose
microfibril. So, this is you can see endoglucanase, this is CBH 1, this is CBH 2, then this is
beta glucosidase. Now, endoglucanase as I told that it is working only on the amorphous
region. So, you can see that it is working on the amorphous region which is represented by
the black lines. Let us go back. So, this random hydrolysis of bonds in glucose chain results
in a rapid decrease in the degree of polymerization of the cellulose.
Now, we will understand what is the role of exoglucanase. Now, these enzymes act from the
chain ends like CBH 1 from the reducing end and CBH 2 from the non-reducing end in a
processive manner. So, that means they move along the same chain after hydrolyzing the
bond and produce mainly cellobiose as the product.
So, let us see how it happens. This end is the reducing end, this is the non-reducing end and
you can see that here CBH 1 is acting on the reducing end and CBH 2 is acting on the non-
reducing end. From this side and from this side they keep on doing the clevage or acting on
that particular chain. What is the product? So, product is cellobiose, cellobiose is a
disaccharide.
So, beta glucosidases hydrolyze the soluble oligomers or cellobiose to glucose and complete
the hydrolysis process. Now, the last one to act is actually this beta glucosidase. So, this
works on the cellobiose that is being produced by this CBH 1, CBH 2 and the oligomers. You
can see here how it is working and then they form the glucose.
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So, we will try to understand the cellulase system of the Trichoderma reesei which is one of
the most widely adapted filamentous fungi for the production of the high amounts of cellulase
and their cellulase are the most studied cellulase systems. The reasons for the focus on this
particular microorganism are because of its high levels of enzymes secretion, it is almost 0.14
to 0.38 grams protein per gram of carbon source which is very good actually and the
effectiveness of the biomass degradation.
So, this cellulase system of the Trichoderma reesei consists of two cellobiohydrolyases (so
CBH 1 and CBH 2), five endoglucanases and two beta glucosidases. Now, some amounts of
xylanases have also been identified along with cellulase enzymes in the crude mixtures. CBH
1 is the major fraction of the crude enzyme mixture and accounts for up to 60% of the total
protein.
So, this particular slide will make you understand about the different types of enzymes that is
being produced from the Trichoderma reesei and what is their role. So, you can see that this
is the CBH 1, this is CBH 2. As you know that CBH 1 progressively acts from the reducing
end, CBH 2 progressively acts from the non-reducing end. Then endoglucanase,
endoglucanase 1 and endoglucanase 2 - so that acts nonprocessively on cellulose surface and
produce short chains, very short chains. Whereas endoglucanase 2 acts nonprocessively on
cellulose structure and produce again the short chains, but different actions. Then we have
beta glucosidases, they hydrolyze soluble cellodextrins and cellobiose to glucose - that is the
final cleavage.
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So, most of the cellulase enzymes contain two independent domains or modules. The first one
is the catalytic domain which is sortly known as CD and the second one is the CBM which is
carbohydrate-binding module. Now, these domains are joined by a peptide linker. In the case
of CBH 1 cellulose is degraded from the reducing end by the cooperative action of these two
domains. CBH 1 and CBH 2 have tunnel-shaped catalytic domain structures formed by
disulfide bridges.
CBM helps in hydrolysis by bringing the high local concentrations of enzyme close to the
surface and providing more time for the enzyme in close proximity of the substrate.
Cellobiose is the main product of the cellulose hydrolysis by CBH action. The tunnel-shaped
catalytic domain structure of CBH prevents the rearrangement of glucose chains and the
formation of many different products.
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Now CBM is not present in all of the endoglucanases and the need for its presence for
enzymatic activities, that is the catalytic efficiency, is not very well understood. Some
endoglucanases such as EG 3 of the Trichoderma reesei and EG 1 and EG 3 of Humicola
insolens, that is another thermophilic fungus, they hydrolyze cellulose efficiently although
they are lacking CBM.
Now, it has been suggested that the lack of CBM mainly affects the hydrolysis of the
crystalline insoluble cellulose and the hydrolysis efficiency of soluble cellulose remains
almost the same. Only a few enzymes that are part of cellulosomes contain CBM. However,
often multiple CBM domains are present on the scaffolding protein to which these cellulases
are bound.
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So, now let us move ahead and discuss what is SSF. So, we have discussed in a nutshell SSF
long back, so let us try to understand how it works actually. Simultaneous saccharification
and fermentation is a process that combines enzymatic hydrolysis with fermentation to obtain
value-added products in a single step; underline single step, very important. Now, this
process is based on the use of an enzymatic complex to hydrolyze cellulose and obtained
sugars.
These sugars are later used by the microorganisms and are converted into value-added
products. This process is often effective when combined with dilute acid or high temperature
hot water pretreatment. SSF has an enhanced rate of hydrolysis, needs lower enzyme loading,
results in higher bioethanol yields and reduces the risk of contamination.
Now, this is the classical schematic representation of an SSF process and mostly SSF follows
this route for the bioethanol production or ethanol production. Now, let us understand how it
happens. So, the raw material biomass - it undergoes pretreatment. It can be different types of
pretreatment depending upon what the biomass is. Then the hemicellulose part and you take
it out.
The cellulose and lignin goes to another unit where cellulose is actually again basically
recovered and fed back to the simultaneous saccharification and fermentation reactor, it is a
single reactor. Now, you will have to add enzymes. Now, enzymes can be externally
produced or it can be in-situ produced also. And whatever the yeast that is being used to
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degrade this hemicellulose can also be used here, either externally produced or also can be
supplied.
So, once the saccharification and fermentation happens, both the reactions, then the product
can be taken out and it goes to a separation unit - usually distillation in case of ethanol. So,
then you get a lignin product here, basically lignin rich product and you get a pure ethanol
there. You may need some intermediate steps which are not shown here as I told you many
times. This is just to try to understand what are the basic units or unit operations that is
required for SSF process.
SSF consolidates enzymatic cellulose hydrolysis and hexose fermentation in one reactor.
Cellulases are added to the pretreated materials to hydrolyze the cellulose fraction to glucose,
while the fermentative microorganism converts glucose into biofuels in the same reactor.
Given that glucose - an inhibitor of cellulase, is converted by the fermenting microorganisms
into ethanol, SSF can efficiently remove or reduce the inhibitory effect of glucose on
cellulases, thus achieving faster biomass hydrolysis rates and higher ethanol yields. So this is
one of the most important factor of SSF or you can say the advantage of SSF. SSF requires
compatible fermentation and saccharification conditions with a similar pH, temperature and
optimum substrate concentration which is again a little drawback or disadvantage of the SSF
system because you need to optimize it properly.
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Two things are happening, saccharification and fermentation, and their optimized process
parameters may differ, but when you are carrying out both in a single reactor you have to
optimize in such a way that both the processes are efficiently happening to a certain extent.
Now, in many cases the low pH as for example lower than 5 and high temperature for
example greater than 313 Kelvin may be favorable for enzymatic hydrolysis, whereas the low
pH can surely inhibit the lactic acid production and the high temperature may affect adversely
the fungal cell growth. Trichoderma reesei cellulases which constitute the most active
preparations have optimal activity at pH 4.5 and 328 Kelvin temperature.
Similarly, for Saccharomyces cultures, SSF are typically controlled at pH 4.5, but the
temperature is a little low at 310 Kelvin. A typical fermentation will usually take 5 to 7 days
depending on the accessibility of the cellulose and initial solids loading of the fermentation.
The long residence time make contamination control difficult in a continuous process, but
may be manageable when you go for a batch process.
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So, let us look for the advantages of this SSF. Now, there are many advantages. So, the first
one is increase of hydrolysis rate by conversion of sugars that inhibit the cellulase activity.
This is one of the most important thing when you talk about fermentation perspective. Now,
lower enzyme requirement, higher product yields, lower requirements for sterile conditions -
since glucose is removed immediately and being consumed and bioethanol is produced,
shorter process time and less reactor volume. The major advantage of SSF is that the
immediate consumption of sugars by the microorganisms produces low sugar concentrations
in the fermenter which significantly reduces the enzyme inhibition.
However, the major disadvantages are the pH and temperature of the process - this is what I
was mentioning - since the optimum temperature of enzymatic hydrolysis is typically greater
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than the fermentation temperature. Therefore, it is necessary to find an equilibrium point
where the process works properly that means both fermentation and saccharification.
The main disadvantages of SSF lies in the different temperature optima for saccharification, it
is 323 Kelvin and fermentation 308 Kelvin. So, some intermediate range you have to ensure
so that both are happening in a particular efficient manner.
So, then another system which is called CBP, the consolidated bioprocessing. Now, ethanol
production from cellulosic biomass involves 5 unit operations. What are those? First is
pretreatment, second is cellulase production, third is enzymatic hydrolysis, fourth is the
microbial fermentation and fifth is product recovery. Now, consolidated bioprocessing
combines the 3 biologically mediated steps. What are those?
Cellulase production, enzymatic hydrolysis and microbial fermentation into a single

operation - please underline single operation. So, that means 3 microbial processes are
clubbed together, pretreatment is separate and your product recovery is separate. Now, CBP
has outstanding potential for providing a breakthrough solution for the biological conversion
of cellulosic biomass into ethanol.
The implementation of CBP requires microbes that can produce a functional cellulase system
while generating ethanol at high yields and concentrations.
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This is a typical schematic representation of the CBP system. Biomass, so of course it
undergoes here, we have not seen here. So, biomass of course will undergo some different
pretreatment processes. Then the next step is enzymatic production, hydrolysis and co-
fermentation. Next is distillation and dehydration where you purify bioethanol and the
distillage which is enriched with lignin can be converted and further processed to recover the
lignin as you know that lignin is a high value product.
So, let us understand the economic benefits of the CBP process. Now, CBP features a high
level of process consolidation and lacks a dedicated step for cellulase production. A model
developed at the National Renewable Energy Laboratory to analyze the advances in biomass
processing systems indicated that increasing levels of process consolidation can result in
greater cost reductions.
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And CBP offers the largest cost reduction of any process improvement considered to date.
The costs savings realized by CBP result from the reduction of capital costs and operational
costs that occur when that dedicated cellulase production step is eliminated. In addition, CBP
can potentially achieve higher process efficiency, which can also lead to lower processing
cost.
The CBP configuration can potentially lead to more efficient biomass hydrolysis. Two
features of the CBP, one is the microbe-enzyme synergy and the other one is the use of
thermophiles, may lead to savings in both capital cost and operational cost by yielding higher
biomass hydrolysis rate which in turn lead to reduced reactor volumes and shorter processing
cycles. Now we will try to understand the effects of the microbe-enzyme synergy in the CBP.
In the SSF system, cellulose hydrolysis is accomplished using a cellulose enzyme system. In
a CBP configuration using anaerobic bacteria with a complex cellulase system, cellulose
hydrolysis is accomplished by a tertiary cellulose-enzyme-microbe system which is called as
CEM in addition to the CE system. So CE is just a cellulose-enzyme system, CEM is
cellulose-enzyme-microbe system.
Now according to a qualitative analysis conducted by Lu et al in 2006, the cellulose

hydrolysis rates mediated mainly by the CEM complex plus CE in a CBP setup could be 2.7
to 4.7 times greater than the rates achieved by CE complex in SSF. So that is the beauty of
CBP.
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Now this microbe-enzyme synergy requires the presence of metabolically active adherent
cellulolytic microorganisms and is believed to result from the microbe’s preferred access to
hydrolysis products, local high celulase concentrations and the removal of hydrolysis product
from the fermentation broth. Now, these increased hydrolysis rates suggest that a CEM
system may be an efficient way to decrease enzymatic hydrolysis cost.
Now we will try to understand the another important feature of the CBP which is the use of
the thermophiles. Some of the cellulolytic microorganisms of potential use in CBP have
optimal growth temperatures in the range of thermophiles. For example, C. thermocellum has
an optimal growth temperature of 65 degrees centigrade whereas Caldicellulosiruptor species
has an optimal growth temperature of 80 degrees centigrade, temperatures at which
substantial solubilization of lignocelluloses can be achieved without pretreatment.
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Now, the advantages of using a high-temperature system include - higher reaction rates,
reduced sensitivity to contaminants, then lower cooling requirements and the possibility of
recovering ethanol directly from the fermentation broth because it is at an elevated
temperature and mostly it is in the vapor phase. Easy to collect it. Now, the advantages
reduces the inhibition effect and the downstream separation cost.
So, let us then understand the different types of fermentation processes. So, Submerged
cultivation; now submerged cultivation of microbial cells in bioreactors guarantees a
controlled environment for the efficient production of high quality end products and to
achieve optimal productivity and yield. Industrial bioreactors operated in batch, fed-batch and
continuous mode are utilized to culture different types of microorganisms producing a wide
range of products.
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So, we will discuss these 3 briefly. Batch cultivation: Now batch culture represents a closed
system in which the medium, nutrients and inoculum are added to the bioreactor mostly
under aseptic conditions at the beginning of cultivation. The volume of the culture broth in
the bioreactor is theoretically constant during the cultivation.
So, fed-batch cultivation: Now fed-batch culture represents a semi-open system.

So, let us see the schematic representation. So this is batch, this is fed-batch and this is
continuous. So, in the batch no inlet, no outlet. It is fed and closed, right. It is a completely
closed system, volume is constant. And here in the fed-batch there is no outlet, but you
supply intermittently the feed. Volume is not constant, right. In a continuous system
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cultivation you have a continuous supply of feed and continuous withdrawal of the product,
volume is maintained constant.
So, the fed-batch culture represents a semi-open system in which one or more nutrients are
aseptically and gradually added to the bioreactor while the product is retained inside. The
volume of the culture broth increases with time. Now, the main advantages of fed-batch over
batch culture are that the possibility to prolong product synthesis; the ability to achieve higher
cell densities and thus increase the amount of the product which is usually proportional to the
concentration of the biomass; the capacity to enhance yield or productivity by controlled
sequential addition of nutrients and; the feature of prolonged productive cultivation over the
unprofitable periods when the bioreactor would normally be prepared for a new batch.
Continuous cultivation: Now continuous culture represents an open system in which nutrients
are aseptically and continuously added to the bioreactor, and the culture broth that contains
cells and metabolites that is moved at that same time. Now, the main advantage of continuous
culture which is known as the chemostat over the batch mode are: the possibility to set up
optimum conditions for maximum and long term product synthesis; The ability to achieve
stable product quality - that is the steady state is characterized by a homogeneous cell culture
represented by a constant concentration of biomass and metabolites and; a distinct reduction
in unprofitable periods of the bioreactor operation.
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Let us move and discuss about the different other advanced fermentation technology. The
first one is the solid state fermentation. The term solid state fermentation or solid substrate
cultivation is used for systems where microorganisms are cultured on the surface of a
concentrated water insoluble substrate (usually containing polysaccharides as a carbon and
energy source) with a low level of free water.
Now, this technique was developed in the Eastern countries where it has been used for
centuries for the production of traditional foods such as soy sauce, koji, miso or sake using
different substrates and microorganisms. However, in the Western countries it has not been
widely exploited and its application is limited mainly to the production of industrial enzymes,
certain food products and feed supplements.
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There are several advantages of this SSF over the conventional submerged technology such
as: the use of the concentrated medium resulting in a small reactor volume and lower capital
investment costs; The lower risk of contamination with yeasts - that is one of the most
important thing - and bacteria of course due to low moisture levels and substrate complexity;
The simplicity of the technology and low production of effluent water from the process
(underline, that is very important, low production of effluent water); The higher product yield
and easier product recovery and; the use of agricultural wastes as substitutes for certain
applications. As for example feed supplements and cellulolytic enzymes.
We will then discuss about the microorganisms and the substrates that are used in this SSF
process. Filamentous fungi are preferred for this SSF processes mainly due to their abilities to
grow on the substrates with the reduced water activity, penetrate their hyphae into the solid
substrate and produce exoenzymes - for example amylolytic or cellulolytic enzymes, which
decompose the polysaccharides - that is the main carbon source often present in the solid
substrates.
The efficiency of SSF is highly influenced by the selection of solid substrate. The substrate
suitable for SSF should ideally meet the following requirements. First it should have a porous
solid matrix with a large surface area per unit volume almost in the range of 103 to 106 meter
square per centimeter cube. It should sustain gentle compression and mixing. It should
contain biodegradable carbohydrates. Its matrix should absorb water in the proportion of one
to several times its dry weight.
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And also should have a relatively high water activity on the solid/gas interface to support
microbial growth and should absorb the additionally added nutrients such as nitrogen sources
ammonia, urea and peptides and mineral salts. Let us understand the limitations and
challenges of the solid substrate fermentation. Although SSF has many advantages over
liquid cultivation, the main challenges are poor heat and mass transfers within the substrate.
And limited potential to monitor, online and key cultivation parameters as for example
temperature, pH, dissolved oxygen, nutrient concentration, water content, etc. Thus, an
inability to precisely control the microbial environment.
To overcome this, immobilization has been studied widely for bioethanol production. Now
immobilization seems to be one of the most significant trends in the biotechnology industries.
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Cell immobilization can be defined as the physical confinement or placement of unbroken
cells to some area with keeping preferred catalytic activity.
Biological catalysts as for example enzymes, microorganisms are generally immobilized by

involving several various methods such as entrapment within a porous matrix, adsorption on
the solid carrier surface, crosslinking and encapsulation. Kyriakou et al indicated that yeast
cells can be immobilized in various types of carriers such as calcium alginate, chitosan,
carrageenan, pre-polymers and cellulose.
Wirawan et al have recently studied continuous co-fermentation to produce ethanol from

alkaline pretreated sugarcane bagasse using polyvinyl alcohol immobilized Zymomonas
mobilis ATCC 29191 and suspended P. stipitis BCRC 21775. These are the strains. Now, it
was concluded that two-stage process enabled high ethanol yield from glucose by the
immobilized Zymomonas mobilis as well as ethanol production from xylose by P. stipitis
obtaining the final overall yield of almost 70.65% in SHCF and 81.18% in SSCF systems,
quite a significant improvement. Now Cao et al investigated yeast-immobilized catalytically
active membrane to effectively remove extracellular ethanol and thus improve ethanol
productivity in the pervaporation membrane reactor. It is simultaneously getting removed so
that there will be less inhibition.
Now, the authors revealed that immobilized yeast on the membrane demonstrated better
fermentation capacity in high substrate concentrations almost 800 grams per liter of glucose
in comparison with free yeasts.
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Now, another process which is known as Very high gravity fermentation process, VHG
process. Now, in the recent years brewing and bioethanol industry have been more focused
on implementing cost cutting measures to remain profitable during the economic downturn.
One such measure is the adaptation of emerging very high gravity fermentation technology
owing to its process productivity-enhancing and effluent-minimizing capabilities.
Very important is that effluent minimizing - because if you reduce your effluent so much
downstream processing part and wastewater treatment steps can be eliminated. Now, this
technology aims to decrease process water requirements and hence reduce associated
distillation cost, effluent and its treatment cost which comprises a major portion of the overall
energy cost which in turn accounts for about almost 30% of the total production cost. VHG
thereby achieves increased productivity through higher ethanol concentrations in the final
broth without major additional investment or infrastructure requirement.
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The potential benefits of VHG fermentation technology over conventional approaches
include a considerable savings of water, more yield of alcohol and reduced labour as well as
energy needs, less capital cost and also minimize bacterial contamination.
So, let us understand the VHG bioethanol fermentation. So VHG fermentation is an emerging
versatile one among such technologies offering great savings in the process water and energy
requirements through fermentation of higher concentrations of sugar substrate and therefore
increased final ethanol concentration in the medium. VHG ethanol fermentations have been
carried out using media containing simple sugars, like glucose, sucrose, etc., as well as
complex carbohydrates also such as starch, dextrin, etc. A glucose-containing medium with
more than 300 grams per liter of dissolved solids along with other nutrients such as free
amino nitrogen, yeast extracts, sterols, etc., is typically used for the VHG fermentation to
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study ethanol production. Rapid fermentation and high final ethanol concentration are of the
major importance in the ethanol industry.
So, this table will make you understand the ethanol production via VHG fermentation using
different starch substrates. You can look at closely for different substrates such as wheat,
maize, hull-less barley, oats, rye, then sweet and grain sorghum, then corn mash, potato
mash, sweet potato mash. You see that just go to the third one, third column you can see the
maximum ethanol produced.
You can see in percentage it almost varies from 14 to 17%. One or two cases it is 23.8% in
case of wheat mash, where the concentration of dissolved solids is 37.9% and fermentation
time is 130 hours. So enhanced fermentation time or more or less the maximum ethanol that
is produced is in that same range volume by volume almost 15 to 17%.
1015
So, then the next is syngas fermentation route. Now, the production of bioethanol from
syngas is an emerging technology that can utilize a wide variety of biomass and it fits exactly
very nicely in a biorefinery concept. The route of ethanol production has the advantage of
utilizing the entire biomass including the lignin content, which is usually difficult to break
down and it is not so in case of your SSFs or CBP.
Now, biomass is converted into syngas via a process called gasification (which we have
discussed in detail earlier), a process in which solid or liquid carbonaceous material such as
biomass, coal or oil that react with air, oxygen and/or steam to produce a gas product called
syngas or producer gas that contains carbon monoxide, hydrogen, carbon dioxide, methane
and nitrogen in various proportions. Biomass syngas can then be converted into biofuels such
as methanol, ethanol and hydrogen via the metal-catalytic or biocatalytic methods.
1016
Let us understand the process. The initial stage is ethanol production via syngas is biomass
gasification. Cleaned gas is cooled to the normal ambient temperature and stored at a high
pressure. Cooled and cleaned gas is fed into an ethanol conversion chamber where microbes
ferment the gas into ethanol and acetic acid. After fermentation is complete, the liquid is
distilled to separate ethanol from other products.
The ethanol produced is then dehydrated to produce fuel quality ethanol. I will show you the
figure 7, then we can understand it better. The cell mass can be recycled to the gasifier while
it is not approved as animal feed in case. Now, a large number of bacterial strains have been
isolated that have the ability to ferment producer gas to ethanol, acetic acid and other useful
liquid.
1017
Now, this is the schematic of the production of ethanol by microbial fermentation of the
biomass-derived syngas. So, you can see the biomass. Then we have the pretreatment, any
sorts of physicochemical pretreatment processes. Then it goes to the gasification. Now, after
the gasification is over, the gas goes to the gas cleaning and conditioning step where the heat
can be recovered to generate power for the process and again being reused in this process.
Carbon dioxide rich waste gas may be supplied for the cleaning purposes. Then whatever you
get the syngas or waste gas it goes to the fermentation here. This is the fermenter. Then you
do the ethanol recovery. Part of ethanol can be feedback. Then you go for what you can call
the downstream processing part - distillation and other processing - to get the fuel graded
ethanol.
So, Clostridium ljungdahlii was the first organism recognized as able to form ethanol from
components of producer gas. The organism favors the production of acetate at a higher pH,
but ethanol is the dominant product at pH between 4 and 4.5. Some optimization needs to be
done. Now recently, an additional clostridial acetogen was isolated and was shown to
produce ethanol from producer gas generated from biomass.
Other organisms that can produce ethanol from producer gas although not as the major
product include Butyribacterium methylotrophicum and Clostridium autoethanogenum.
1018
So with this, I conclude today's lecture. In our next lecture that is lecture 3 under module 9,
we will be discussing about biobutanol that is the ABE fermentation pathway, its kinetics and
how do you recover biobutanol. So in case you have any query, please feel free to register it
in the Swayam portal or you can drop a mail to me at [email protected]. Thank you.
1019
Lecture – 27
ABE Fermentation Pathway and Kinetics, Product Recovery Technologies
Good morning students. This is lecture 3 under module 9. And in today's lecture we will be
discussing in detail about the ABE fermentation, one of the most important fermentation
processes that actually produces acetone, butanol and ethanol, but the major aim can be to
produce butanol as a fuel additive. So let us begin.
1020
So, recent concerns about depleting crude oil reserves, environmental impact of fossil fuels
and national security threats have prompted increased interest in the development of
alternative fuels. Biobutanol derived from sustainable renewable sources such as
lignocellulosic biomass has emerged as a promising renewable drop-in fuel. In comparison
with bioethanol, biobutanol has a higher energy density and can be used in 100% blends,
while being less hygroscopic that facilitates its transport via pipelines.
Biobutanol can be produced by a bacteria of genus Clostridium in a process known as the

Acetone-Butanol-Ethanol fermentation - in short ABE fermentation. It was developed by
chemist Chaim Weizmann and was the primary process used to produce acetone, which was
needed to make cordite, a substance essential for the British war industry during the World
War 1.
The ABE fermentation is a biphasic process that converts sugars into acids, basically your
acetate and butyrate, and then solvents acetone, butanol and ethanol. During the first phase
which is also known as the acidogenesis phase the primary products are the acidic
metabolites. As the metabolism shifts to solventogenesis, the acids are assimilated into the
ABE solvents.
While this metabolic shift is associated with changes in the extracellular pH and the onset of
sporulation, its exact mechanism is not well understood. Recent experiments have shown that
enzyme regulation plays a key role in the phase shift. The ABE fermentation is also
1021
dependent on various culture conditions such as pH, nutrient shortage, product inhibition,
media composition as well as the redox state.
The most prevalent Clostridium bacteria for the ABE fermentation are Clostridium
acetobutylicum and Clostridium beijerinckii, though the more recent species mentioned here
the Clostridium saccharoperbutylacetonicum N1-4 strain garnered a lot of interest due to its
high butanol yield capacity.
So, we will discuss about the fermentation pathway and the kinetics of the ABE fermentation
route. The metabolic pathway I have shown here, we will just go to the next slide.
1022
You can have a close look here. So this is the metabolic pathway of the ABE fermentation
that is the Clostridium acetobutylicum strain image, microscopic image. So, this is the acid
fermentation phase here where we are getting acetate and butyrate and here the yellow
portion is the solventogenesis phase or the solvent fermentation phase in which we are getting
the solvents of our interest ethanol, acetone and butanol.
So, let us discuss how it is happening basically. So, initially the substrate glucose is converted
to acetate and butyrate as the metabolism undergoes the acidogenesis. Due to the generation
of the acidic metabolites, the external pH of the culture decreases until the cellular
metabolism shifts to solventogenesis, a phase in which the acids are assimilated into acetone,
butanol and ethanol.
Although the shift is associated with an external pH drop, its exact mechanism is not fully
understood. As solventogenesis proceeds, the solvents eventually become toxic to the
Clostridium strain. Now in particular, butanol begins to disrupt the cellular membrane fluidity
at concentration levels of just 8 to 10 grams per liter. So, let us see how it happens actually.
This is the main metabolic pathway.
So the glucose get converted to fructose 6-P with the help of ATP, the adenosine triphosphate
energy molecules and it again generates ADP. Now in the second phase, the fructose 6-P is
getting converted to glyceraldehyde 3-P again with the help of ATP. And similarly that
glyceraldehyde 3-P is getting converted to pyruvate the most important molecule of this
fermentation pathway.
The pyruvate gets converted to acetyl coenzyme A with the help of enzyme coenzyme A and
it produces two carbon dioxide molecules. Now this acetyl coenzyme A can get into different
pathways. So, one pathway is this where we get actually the acetate and butyrate which is
known as the acidogenesis path. Now, if you see this also there is a shift to here. Now, all
these things depends upon the process conditions your pH and other parameters.
So, that goes to the solventogenesis phase where you get the ethanol, acetone and butanol.
Now acetyl coenzyme A part also can be converted to acetoacetyl coenzyme A, then 3-
hydroxybutyryl CoA, crotonyl coenzyme A and then finally butyryl coenzyme A. Now, this
1023
butyryl coenzyme A again goes back to two different pathways. So, one is solventogenesis
pathway where we directly get butanol and here you get butyrate under the acidogenesis path.
So, the toxicity of butanol to Clostridium poses a key challenge since it limits the product
titre. In fact, all the major products in the pathway that is the acetate, butyrate, acetone,
butanol and ethanol are toxic to the Clostridium species, but only butanol and butyrate are
typically at high enough concentration levels throughout the fermentation to cause substantial
inhibition. Because your acetone and ethanol, the rate of formation of those two are much
less compared to that of the butanol.
Now, running the ABE fermentation in a continuous culture helps alleviate product inhibition
since products can be continuously removed from the culture. Product removal enables
achieving a higher product titre since the reactions are shifted towards the products and this is
what actually we wish to happen. So, continuous culture of course solves that problem.
However, it has also some inherent issues.
1024
Now, in the continuous ABE fermentation, the shift to solventogenesis can be induced by
changing the external pH from a very high approximately 5.5 to 6 to a low almost around 4.5
level. Now, although there are 100 different genes that are upregulated after the switch to
solventogenesis, the primary enzymes relevant to solventogenesis are encoded by the genes
acetoacetate decarboxylase which is known as the adc, alcohol aldehyde dehydrogenase
(adhE) and then butyrate-acetoacetate CoA transferase (ctfA/B). Now, these enzymes are
responsive to the pH of the culture and change their expression accordingly. So, please
understand pH plays a very important role in the entire ABE fermentation process. Now, at
acidogenic pH levels, the enzymes are present at low concentration level. The enzymes are
expressed more strongly when the fermentation switches to solventogenesis.
1025
As the solvent production is dependent on the concentration of the undissociated acids in the
culture, it is often desirable to initially perform the continuous fermentation in the acidogenic
stage so that the sufficient butyrate is produced. Biomass growth is also impacted by the
phase of metabolism. During acidogenesis, Clostridium grows exponentially. As the
metabolism shifts to solventogenesis, Clostridium begins to sporulate and reaches a stationary
phase.
Now, because the metabolic shift can be induced by changing the external pH, one common
approach to avoid washout of biomass is to have a two-stage chemostat, two-stage continuous
process basically in which the first stage is operated at an acidogenic pH level and the second
stage at a solventogenesis pH level. Now if you do like that, then what will happen is that you
can freely maintain the optimum culture conditions or environment for both acidogenesis as
well as the solventogenesis.
So, in a single fermenter it is very difficult to maintain that. So, somewhere you have to
optimize or while you are optimizing that in a single this one (fermenter) somewhere you
have to make compromise.
Now, growth during (both) phases is inhibited by the toxic acids and solvents produced
during the fermentation. In addition to disrupting the cell membrane, butanol decreases the
glucose uptake by Clostridium acetobutylicum. Now, Ballongue et al in 1987 have reported
that biomass growth rate decreased by 50% when either acetate or butyrate reaches 4 grams
per liter, that becomes toxic beyond that limit.
1026
And that the biomass growth stops when that total concentration of acids reaches
approximately 5 grams per liter. You can see such a narrow range. Now since butyrate is
typically at a higher concentration level than acetate, it has more deleterious effect on the
biomass concentration.
So, let us understand the general cell cycle of the Clostridium acetobutylicum with its
different cell forms and the major products during the acidogenesis and solventogenesis. How
it actually happens that growth phase of the Clostridium species? So we can start that. Let us
say the carbohydrate that is being fed to the vegetative cells which are of the Clostridium
species. Then it goes in this cycle.
So, the cell differentiation and granulose production happens. We will get the Clostridial
stage cells, then initiation of the sporulation. Now, at this stage acetone and butanol are
getting formed. Now their growth is happening, so they started doing the sporulation. So, you
can see the forespores here. Now, after that we have the spore maturation stage that will
come. Now once that happens, then the spores will come out and then spore germination will
happen, eventually they again get converted to vegetative cells.
Now in a secondary way, we can say that this vegetative cells are also dividing themselves
during their growth. And when that is happening, you are getting acetate and butyrate. So,
now I hope you can understand that how the cell division and the cell growth of the
Clostridium species is happening and in the same time when they are producing basically our
1027
product of interest acetone, butanol of course even acetate and butyrate to carry out their
metabolic pathway.
Let us talk about the mass balance equation and the reaction rates. Under the assumptions that
the continuous Clostridium acetobutylicum culture has a constant volume and temperature,
the kinetic model of the metabolic pathway as depicted in the figure 1 consists of a dynamic
mass balance equations for all metabolites in the pathway. Whatever I have shown starting
from your glucose, then it goes to pyruvate, from pyruvate to acetyl coenzyme A and then
butyrate and all these things.
Now, glucose is the only metabolite that is fed to the culture. Hence, that dilution rate D, the
inlet glucose concentration and the pH of the culture comprise the inputs to the continuous
culture. These are the main important parameters. The kinetic rate expressions for all the
metabolic reactions are given in table 2 in the next slide with the kinetic parameters are also
given in that table 3.
1028
So, you can refer to this. I have listed this. This is taken from a very interesting work by
Buehler and Mesbah. It is already given, you can see the reference also. Now, the mass
balance equations for all the metabolites in the continuous Clostridium culture according to
the figure 1 which we have shown. So glucose mass balance equation, then fructose,
pyruvate, lactate, butyrate, carbon dioxide, acetate, ethanol everything is given.
So, you can refer to it later on. So, we are not going to discuss this kinetics in detail, but I just
thought that I will give this information so that you can understand that what actually is
happening in a nutshell.
So, most of the reactions in the metabolic pathway are represented by the typical enzyme
substrate reaction scheme. So, what is that? E + S, E is the enzyme, S is the substrate, so that
1029
when they react, the kinetic constant is k1 and k –1. So it is a reversible reaction. So, they
form ES, ES is the intermediate complex. Now when the ES undergoes further reaction, it
gives us E + P, so P is your product.
So, this is the usual enzyme substrate reaction. Now, the rate expressions we can do by the
famous Michaelis-Menten kinetics, MM kinetics. So, you can write d by dt of P = V max S
by K s + S, now where S and P denote the concentration of the substrate S and product P
respectively in millimoles and V max is the maximum reaction rate, h inverse or the hour
inverse and K s is the Michaelis-Menten constant.
Now table 2 gives the reaction rates in the metabolites’ mass balance equations as listed in
the table 1. So, R 1, R 2, R 3 all these and the corresponding equations. So, here the F, you
can see there is F, so the F actually describes the effect of the glucose inhibition. In the
equation 2 it is mentioned. In all equations V is the maximum reaction rate, K is the
Michaelis-Menten constant, alpha is the kinetic parameter as described in the equation 4, kd is
the first order biomass death constant and µ is the specific biomass growth rate.
1030
So, table 3 gives us the estimated kinetic parameters and their 95% confidence intervals. All
the parameters K 1, K 6, K 7, K 9, K i, V 1, V 9, alpha 8, alpha 10, mu max and r ah plus. So,
let us move ahead.
So, to describe the effect of glucose inhibition on the pathway dynamics, an on-off switch
which is denoted by F in the kinetic rates is applied to reactions that utilizes glucose as their
energy source. Now, these reactions involve the energy sources that is ATP, adenosine
triphosphate, adenosine diphosphate, and nicotinamide adenine dinucleotide and NADH - the
hydrogen, the availability of which is dependent on the glucose concentrations.
So, all these ATP, ADP, NAD, NADH these are the energy carriers. Now the on-off switch
describing the glucose inhibition effect is defined by the piecewise constant function. So, F
1031
you can see that F =1 when G is greater than 2 millimolar, F = 0 when G is much less than or
equal to 2 millimolar where G denotes the concentration of the glucose.
The reaction rate expressions that have not been described by the MM kinetics include the
rate of the biomass growth, the death as well as the rate of the enzyme regulation reactions all
these which are already there in the tables; R 8, R 10, R 11, R 13 and R 15. So, let us talk
about the biomass growth and death. The dynamics of the biomass concentration in the
continuous Clostridium acetobutylicum culture are governed by the biomass growth rate R x
and the detath rate R d.
The biomass death kinetics are described by a first order expression. On the other hand,
biomass growth is dependent on the metabolic phase of the fermentation and consequently on
the culture pH as well as the concentration of the inhibitory metabolites.
1032
The biomass growth is described by the Monod kinetics expression R x = mu G X by K x +
G,
where the observed specific growth rate of the biomass mu is defined by mu = mu max F T, F
is a function basically of the B n, B and pH.
Now, mu max being the maximum specific growth rate and the function of that function of F
T of that B n, B and pH being the total inhibition function that accounts for the inhibitory
effects of the butanol, butyrate and the culture pH.
So, this function tells us the inhibitory effect of the three components. First is the butanol,
second is the butyrate and third is the pH on biomass growth. So, the total inhibition function
is defined as F T = F B n, F B and F pH
where F B n, F B and F pH denote the inhibition functions for the butanol, butyrate and pH
effects respectively independently.
1033
Let us now discuss about the enzyme regulation. Since the upregulation of the enzyme adc,
adhE and ctfA/B is dependent on the pH, the metabolic reactions involving these enzymes
cannot be described by the MM kinetics. Now, it is assumed that the total enzyme
concentration in the culture does not remain constant. The mass balance for each enzyme is
written as d by dt of E = r E + r E +H – D E
now where E bracket denotes the concentration of the enzyme, r E and r E+ are the constants
and H is the smoothed switch function denoted by H = 1 – tan hyperbolic 5 pH –4.5.
1034
So, in equation 3 the value of 4.5 represents the pH at which the switch occurs and the
constant 5 determines the sharpness of the switch function. At low pH levels that is
approximately 4.5, the switch has a value of 1 and at high pH values greater than 6 the switch
has a value of 0. Once the concentration of the enzyme is determined, the kinetic rates for the
metabolites created from the enzymatic reactions can be described by d by dt of P = – alpha S
E where alpha = k 1 k 2 divided by k –1 + k 2.
These are the rate constants. P, S, and E denote the concentration of the product, substrate
and enzyme respectively; k 1, k –1 and k 2 are all reaction constants as we have defined
already in the equation 1. Now, this expression is derived using the pseudo steady-state
approximation for the enzyme-substrate reactions with variable enzyme concentration.
1035
Now, we will talk about the product recovery technologies, the challenges also. See, let me
tell you that when you talk about this ABE fermentation, please understand that ABE
fermentation is not at all similar to that of when we talk about the SSF and SHF all these
things to produce bioethanol basically. There are our target is to produce only bioethanol and
whatever inhibitory compounds are produced we can control them easily.
Because their metabolism and their metabolic pathway is lesser complicated than this ABE
fermentation. Now here in ABE, we are having 3 different types of products, the final
products acetone, butanol, ethanol. Now, mostly butanol production is much higher than that
of the acetone and your ethanol; this you can also regulate by doing the cleaving and
changing the metabolic pathway in a particular direction so as to get more acetone than that
of the ethanol or butanol.
See these things can be done, but the entire metabolic pathway of the ABE fermentation is
quite complicated. And again you need to understand that a Clostridium is a strict anaerobic
species, you have to maintain strict anaerobic conditions, otherwise your products will be
something else. You do not get a proper yield of the product and the efficiency of the process
will come down.
Now, let us come into the discussion of what we going to right now discuss is about the
product recovery technology. So, as we have discussed it many times that once a certain
product is produced in a fermentation pathway, there is much challenge because in a
1036
fermentation broth there are so many things, the cells are also there, live cells. Apart from
that there are metabolites and there are so many inhibitory compounds.
Now with that the product of interest is actually present in a aqueous phase. The recovery of
that particular product of interest is extremely challenging when we are talking about a much
more complicated process like that of the ABE fermentation. But there are excellent works
have been reported and there are many processes which are being commercialized, but still a
lot of scope exists to do more research on this particular product recovery technologies of
even ethanol production also during your SSF, SHF and here also in the ABE fermentation
also. So, let us discuss.
So, many processes are there. I have listed few which are mostly commercialized or going to
be commercialized soon. Distillation, adsorption, gas stripping, liquid-liquid extraction,
pertraction, reverse osmosis, membrane distillation, thermopervaporation, sweep gas
pervaporation and vacuum pervaporation.
Let me tell you that these 4 are the classic unit operations. These are practiced in most of the
refineries and biorefineries. So much of work has been done and these are commercial
processes. When we start about from 5 onwards, all these, starting from pertraction, RO and
all these things, these are all latest developments and these are all membrane based systems.
We will quickly discuss about all these things. We will try to understand the basics.
1037
So, first is distillation. Now distillation is one of the well-known separation techniques in
which separation occurs due to the difference of volatilities of the separated component. So,
the vapour liquid equilibrium plays the important role. When a mixture containing substances
of various volatilities is brought to boiling, the composition of the vapours released will be
different than that of the content of solvents in the boiling liquid.
Now, there are several possible modes of distillation. We can have continuous flash
distillation. We can have batch distillation. We have fractional distillation. We can have
steam distillation. There are many other distillations also. Now, aqueous acetone-butanol-
ethanol mixture is a complex system in which the water-organic azeotropic mixtures can be
formed during the distillation. How it forms let us understand this.
If you talk about the water-n-butanol system, the azeotrope is quite heterogeneous. The
temperature of zeotrope lies between 91.7 to 92.4 (°C) and the water content in azeotrope is
38%, it is quite a high amount. When you talk about the water-ethanol azeotrope it is a
homogeneous mixture. The temperature is around 78.1 (°C) and water content is very less
4.4. Now this gives us an excellent information this table that was should be my recovery
strategies.
Now, if you understand that you see here the water is more, so the target should be to the
move the other component. So, here the water is very less, so if possible we can target that
water has to be dehydrated so that other components 95-96% are anyway remains pure. So,
then there are ways to deal with the azeotropes.
1038
Thanks to the heterogeneous water-n-butanol azeotrope, a simple two-column distillation
system can be used. This is what I was telling that the table gives us a lot of information
about which type of process or unit operations has to be choosen and no additional compound
has to be added to separate the mixture. Conventional distillation for recovery of the ABE
fermentation products from batch fermentator was described by Roffler et al in 1987.
Now acetone, n-butanol and ethanol are heated to 100 degrees centigrade by heat exchange
and are removed from broth by the stream of vapours. Obtained vapours contain about 70
weight percent of water and 30 weight percent of the acetone, butanol and ethanol.
Subsequently, vapours are separated in the series of four distillation columns.
1039
In the first column operating at 0.7 atmospheric pressure about 99.5 weight percent of
acetone is removed, whereas residual bottom products of the first column are transported to
so-called ethanol column operating to 0.3 atmospheric pressure a 95 weight percent ethanol is
obtained in this step. Subsequently, the bottom products of ethanol column and overhead
streams are redirected to the decanter where water and n-butanol are separated.
The water phase with 9.5 weight percent of n-butanol content is transported to water stripper,
whereas n-butanol rich phase with approximately 23 weight percent water content is
redirected to n-butanol stripper. In the n-butanol stripper 99.7 weight percent n-butanol is
obtained. I hope you got a understanding of how this distillation can help us to remove and
purify acetone, butanol and ethanol.
Now, this is a process flow diagram of the batch fermentation for production of butanol,
acetone and ethanol. So, the molasses that goes to the feed mixture tank and you supply the
required amount of water and other nutrients which are much more important, some
micronutrients for the fermentation. So, you need to do some sterilization, then it goes to the
batch fermenter. From here, the broth surge tank, whatever it is there it is being fed into a
stripper. Now from the stripper, this stillage, there are stillage evaporators, so it goes through
a series of evaporators and finally we get dried stillage storage. It can be also a value added
product if you go for further processing. Now, whatever is the top portion is being collected
from the stripper, so this goes to different types of unit operation.
1040
So, in the first water stripper it can be stripped and then whatever we get is the butanol rich
phase that can go to another butanol stripper and you get the butanol, pure butanol. Similarly,
the other fraction goes to the acetone and ethanol column from where you get ethanol and
acetone, purified acetone and ethanol.
So, the next is flash fermentation. So, Mariano et al described the flash fermentation that is
the continuous fermentation with the integrated ABE recovery. Now, in this particular design,
a bioreactor worked at atmospheric pressure whereas broth was continuously circulated to a
vacuum chamber. You can see this, this is a much simpler process than that of the what I
have shown you the earlier slide.
See, this is your fermenter. Here continuous feed is there, continuous fermentation is
happening. Then it goes to the vacuum section or vacuum chamber, where whatever we are
getting that is in that top section is the ABE enriched vapor and fermentation gases. And
whatever the liquid product that is getting condensed is the liquid steam depleted in ABE. It
can be recirculated back to the fermenter and can be used while preparing for the
fermentation media.
Now whatever the ABE enriched vapours, this goes to the absorber tower. Please understand
that it is not a single absorber, there may be multiple absorbers. So, you get carbon dioxide
and hydrogen from the top and whatever you are getting actually from the bottom product
that goes to the series of distillation towers where you can purify your acetone, butanol and
ethanol.
1041
So, the bioreactor worked at atmospheric pressure whereas broth was continuously circulated
to a vacuum chamber. In the vacuum chamber, acetone and butanol and ethanol were boiled
up and condensed. Proposed technology allowed to produce 30 to 37 grams per liter of n-
butanol which is a good yield.
So, distillation is nowadays the most popular technique used in the industry for ABE
fermentation product recovery. However, this technique possesses several disadvantages. The
first and foremost important thing is high investment cost. The capital investment is very
high. High energy consumption because you need to produce steam to do the distillation and
of course the selectivity is low. Now due to this fact, other product recovery techniques are
also being investigated.
1042
The next one is adsorption; it is also a very important unit operation. So, it is described as a
process in which particles from a liquid or a gas mixture are preferentially attached to a solid
surface. So Levario and co-workers investigated adsorption of ethanol and n-butanol on
mesoporous carbons with surface areas ranging from 500 to 1300 meter square per gram.
It was found that n-butanol was adsorbed more efficiently compared to ethanol on each of the
tested mesoporous carbons. It was also found that capacity of alcohol adsorption increased
with an increase of the adsorbent surface area. Moreover, applied mesoporous carbons were
thermally and chemically stable during perform measurements.
Wiehn et al in 2014 applied expanded bed adsorption method which is widely used in some
of the biorefineries and refineries of course for the in-situ removal of the butanol from ABE
1043
fermentation broth. If you recall, we just discussed that the process dynamics should be in
such a way that if you continuously remove butanol, then butanol will not inhibit the
fermentation pathway. So macroporous hydrophobic polystyrene-codivinylbenzene resin was
used in this study as butanol adsorbent.
After that 38.5 hours of the process 27.2 grams per liter and 40.7 grams per liter of butanol
and total solvents were produced, which is a little less compared to other one, but it is a good
yield. Now, efficiency of the total solvent production was improved in expanded bed
adsorption method almost 2.3 fold compared to the traditional batch fermentation. Now at the
same time, butanol production was increased to 2.24. Authors recovered 81% of butanol from
fermentation broth using the EBA technique recovery.
Now, although adsorbants used in adsorption technique possesses high selectivity towards
butanol over water, there are several problems during ABE fermentation products recovery
by adsorption. One of them are difficulties in desorption of organic compounds previously
adsorbed on the sorbent.
Several separation methods should be used to realise this process. Additionally, bacteria can
also adhere to the adsorbent and decrease the adsorption efficiency especially if the adsorbent
is recycled. Anyway you have to regenerate the adsorbent and recycle it to take care of the
entire process economics.
1044
So, the next one is gas stripping. Now, gas stripping is a separation method which enables
selective removal of volatile components from the ABE fermentation broth. Now, in this
technique gas is passed into the fermenter and volatiles are condensed and subsequently
recovered from the condenser. Application of this technique is possible due to the volatile
properties of the ABE.
The gas stripping process possesses several advantages over other removal techniques such as
the simplicity and low cost of operation and its efficiency is not disturbed by fouling or
clogging due to the presence of biomass. Moreover, gases produced during the fermentation
that is carbon dioxide and hydrogen can also be used for the ABE product recovery by the
gas stripping.
1045
Only volatile products are removed from fermentation broth and due to this fact the reaction
intermediates which is your acetate and butyrate are not removed from the fermentation broth
and are converted almost entirely into ABE, which is a win-win situation actually. However,
one of the disadvantages is that that tiny bubbles which are produced during the gas stripping
create excessive amounts of foam in the bioreactor, so much of foaming takes place.
Now, such a process results in the necessity of addition of anti-foaming agent which can be
toxic to bacteria. So, these are complicated issues. But you have to add the anti-foaming
agent at a certain concentration so that it will not create a toxicity problem for the bacteria.
Now, this in turn results in overall lower productivity of the ABE fermentation. These are the
issues that needs to be taken care of.
Now Ezeji et al in 2005 tested the influence of various parameters such as the presence of
acetone and ethanol, gas recycle rate, bubble size on the performance of ABE recovery from
the fermentation broth. It is an excellent work, reference is given in the bottom of the slide. It
was found that the application of sparger gas stripping mode resulted in creation of much
amounts of foam in the bioreactor, which caused the necessity of the addition of more anti-
foaming agent in comparison with the impeller module. When you sparge the gas, you are
sparging to create bubbles that is the reason why the foaming will be more, but when he used
impellers which are mechanically driven impellers basically, then the foaming will be less.
But when you talk about the gas stripping mode, it is always preferred mode when you do not
have a, what you can say, a live system or fermentation.
1046
If you are only carrying out some chemical reaction and all, so it is much more advantageous
because you continuously generate bubbles, the bubbles squirls, then they break. Again they
squirls, they break - in that way they create huge mass transfer area. So, that is the advantage
actually, but not so good when you talk about fermentation. Now, the consequence of
antifoam addition is reduced production of the fermenttation products, which is explained as
a toxic effect of the anti-foaming agents to the microbes. Authors found that gas recycle rates
of 80 centimeter cube per second at a constant gas stripping rate of 0.058 per hour are
sufficient to maintain the n-butanol concentration below toxic levels during the run of the
ABE fermentation.
This is a schematic diagram showing the in-situ butanol recovery. It is a simplified schematic
just to make you understand that how the in-situ butanol recovery is happening using the gas
stripping by the gas sparger system. So, this you can say the B is actually the bioreactor and
A is the gas recycle pump with variable speed, you can control it. And the C is your
condenser and D is the condensed vapour.
This is what we are collecting that is the condensed ABE vapours. Now please understand
that it contains ABE, it further needs to be distilled out. And E is the cooling apparatus with
the coolant. So this is simple system, can be practiced in the lab scale also, many people work
like that. It has so many advantages, but at the same time you have to take care of this
foaming issue.
1047
Now, let us talk about the liquid-liquid extraction, another most important product recovery
technology. LLE is a method used to extract a dissolved substance from the liquid mixture in
a certain solvent by using another solvent. So, Kurkijarvi et al in 2014 applied non-
biocompatible solvents such as 1-heptanol, 1-octanol and 1-decanol during continuous
extraction of the ABE fermentation products in dual extraction process with solvent
generation.
So, you can see this there is a dual extraction system here as proposed by this particular
authors. That means two different extracting units. So, distribution coefficients of butanol
recovery obtained during the experiments performed at 37 degrees centigrade were equal to
11.26, 9.95 and 7.17 for 1-heptanol, 1-octanol and 1-decanol respectively. The authors
claimed that with this method the energy consumption of the ABE fermenters and product
recovery can be lowered to less than 4 mega joule per kg - it is a good process basically.
1048
So, comparing to the other separation techniques high capacity of the extractant and and high
selectivity of n-butanol water separation can be obtained from the liquid-liquid extraction.
The main disadvantage of using direct extraction in fermentation products recovery is the
creation of emulsions and the extractant fouling. So, such phenomena can result in problems
with phase separation and consequently in significant contamination of aqueous streams with
chemicals.
Now, from this slide onwards whatever we will be discussing these are all based on the
membrane separation processes. So, first one is pertraction, the membrane extraction
basically. So, it can be described as a liquid-liquid extraction technique in which a porous
membrane is placed between the two phases. Now, pertraction is a membrane process based
1049
on the same separation mechanism as extraction, where both extraction and stripping of the
solute are realized in one unit.
Member extraction requires the installation of membrane area, which separates extracting
liquid from the extractant. Qureshi et al investigated pertraction mode coupled directly with
the fermenter at 35 degrees centigrade. Silicone membrane as selective boundary and oleyl
alcohol as extractant were used. Butanol production in the first cycle was 8.89 grams per liter,
whereas in the second operation cycle butanol productivity increased to 10.29 grams per liter.
So, although recovery of butanol was efficient, acetone removal from fermentation broth was
poor, almost close to 1.62 grams per liter in the first cycle. Now, pertraction possesses some
limitations such as lower mass transfer coefficient compared with liquid-liquid extraction and
the instability of the hollow fibre modules in contact with the solvent. Now, on an industrial
scale problems with extraction of membrane solvent may occur due to the relatively high
viscosity of extractants.
Such difficulties resulted in pressure losses and mass transfer limitations in the solvent phase.
The major advantage of the pertraction method is that the dispersion of the extractant in the
solvent phase is unnecessary. Using the membrane pertraction it is possible to connect
selective membrane properties with the capacity of extractant.
1050
Now, I wish to say that I have also run a course last time actually last semester this NPTEL
course, MOOCS course on membrane technology. Now under which I have discussed about
all this what we are going to discuss like this pertraction in detail. Now, if anybody is
interested to learn more on such processes whether it is pertraction, reverse osmosis, then let
us say pervaporation or membrane distillation which we are going to discuss in our
subsequent slides.
You can also refer to my course which is available now free in YouTube. And again, I also
wish to say that this course will be redone in the January to May session in the 2021. If you
wish you can also register for that course. Now, for this particular lecture on pertraction, you
can see this link.
1051
So, the next is RO, reverse osmosis. Now, RO is a membrane based technology commonly
applied in desalination of water and production of potable water. In RO, semi-permeable
membrane separate a feed solution into two streams: permeate - which is a purified water -
and concentrate - solution with salts and retained compounds. Polyamide membranes were
described as good materials for the butanol recovery in RO so with a rejection rate almost
less than equivalent to 85%.
Garcia et al in 1986 obtained rejection rates in the range of 98% and the optimal rejection of
butanol in the ferment liquor occurred at recoveries of 20 to 45%. Flux varied in the range of
0.05 to 0.6, dm cube meter square minute inverse.
Diltz et al in 2007 utilized RO method for a post-treatment of an anaerobic fermentation

broth. Experiments were performed at 25 degrees centigrade using six organic model
compounds; ethanol, butanol, butyric acid, lactic acid, oxalic acid and acetic acid. Efficiency
of the butyric acid, lactic acid and butanol rejection was greater than 99% at a pressure of
5515.8 kilo Pascal.
Whereas acetic acid, ethanol and oxalic acid were rejected with efficiency in the range of 79
to 92% at the same pressure, Now, the rejection of organic components was improved when
the fermentation broth was used as a feed stream comparing with RO experiments performed
for each component individually.
1052
So, this is a process flow diagram for the RO test unit. So, you can see that this is the feed
tank. From the feed tank the feed has been pumped to a pre-filter where you remove the
suspended particles and other things whatever present and should not go to the RO system.
Then a high pressure pump will pump it to the RO unit. Now, from where you get the
permeate as well as the concentrate - permeate is the desired product. So, that is basically
your purified water and the concentrate will have more salts and other components.
So, RO has been discussed in detail in NPTEL course on membrane technology. The link is
there. So, in this particular link the entire membrane technology course is there, so you can
choose the respective RO because it is not a single lecture, there are many.
1053
So, the next is membrane distillation. Now, membrane distillation is a process in which a
microporous, hydrophobic membrane is applied to separate aqueous solutions at different
temperatures. Membrane distillation process is similar to conventional distillation, requires
heating of the feed solution in order to obtain the necessary latent heat of vaporization and
MD is based on the vapor-liquid equilibrium just like the distillation.
Now, the temperature difference between both sides of the microporous membrane results in
a vapour pressure difference. Thanks to that vapour molecules are transported through the
membrane from the high vapour pressure to the lower vapour pressure side of the membrane.
Membrane used in membrane distillation process should be highly porous, of course almost
close to or more or greater than that of the 70%. Moreover, membrane wetting cannot occur
1054
and only vapour should be transported through the pores of the membrane. Five various
membrane distillation modes are described in literature and it is there in my lecture also.
Those who are interested, I have given the link in the next slide you can refer.
First is called DCMD, the direct contact membrane distillation, then the vacuum membrane
distillation, then air gap membrane distillation, sweeping gas membrane distillation and
osmotic membrane distillation. Most of the membranes used in MD are manufactured from
highly hydrophobic polymers such as PVDF, PTFE, then polyethylene and polypropylene.
So, this is a schematic representation of the experimental apparatus of the membrane

distillation. Now, Gryta et al in 2000 tested properties of the batch fermentation producing
ethanol with membrane distillation recovery method. The authors used porous capillary
polypropylene membranes to separate volatile organic compounds from fermentation broth,
which was supposed to increase productivity or efficiency of the fermentation process.
The efficiency of fermentation broth combined with membrane distillation was 0.4 to 0.51
grams ethanol per gram of sugar and the production rate of 2.5 to 4 gram ethanol per dm cube
hour.
1055
So, again I have given the link here of the membrane distillation. It is a single lecture.
So, next is pervaporation. Pervaporation is a membrane separation technique for the

separation of binary or multicomponent liquid mixtures, mostly organic components. And the
transport through the membrane occurs owing to the difference in the chemical potentials
between the both sides of the membrane. The difference in chemical potentials can be created
by the temperature difference - which we can call the thermopervaporation, application of
sweep gas on the permeate side - it becomes sweep gas pervaporation and the pressure
difference - it becomes a vacuum pervaporation. So, basically between the both sides of the
membrane, upstream and downstream side.
1056
So, this is a schematic representation of a thermopervaporation process. So,
thermopervaporation is the least studied mode of the pervaporation. Feed mixture is in direct
and continuous contact with the membrane selective layer, whereas permeate is condensed on
a cold wall at atmospheric pressure. Transport in the TPV can be facilitated by increasing
temperature difference and decreasing the distance between the membrane and the cold wall.
Franken et al in 1990 proposed polysulfone membrane to be used for ethanol recovery by

thermopervaporation. Total flux obtained during experiments with this polysulfone
membrane was equal to 14.4 grams per meter square hour whereas separation factor was 10
and at 16.5 degrees centigrade difference and 35 weight percent of the ethanol in the feed.
1057
So, the next is the sweeping gas pervaporation. So, now this system in this way or this mode,
the permeant partial pressure on the permeate side is decreased by the sweeping gas that takes
out the vapours with an inert gas system. So, basically on the downstream side you use a
sweeping gas. So, hollow fibres are applied in SGPV, which allows obtaining a large surface
area per volume ratio.
Plaza et al in 2013 applied sweeping gas membrane pervaporation for n-butanol recovery.
Membranes prepared by gelation of an ionic liquid 1-butyl-3methyl imidazolium
hexafluorophosphate which is known as the bmim PF6 in the pores of the
polytetrafluoroethylene hollow fibers were used in the experiment. Partial flux of n-butanol
was equal to 1300 grams per hour meter square at 500 ppm n-butanol content in the feed.
Next is vacuum pervaporation. In vacuum pervaporation mode a driving force is created by

vacuum on the permeate side of the membrane. So, basically the permeate side or the
downstream side of the membrane module is being connected to a vacuum pump. So, Liu et
al provided a list of membrane used for ABE fermentation products recovery by vacuum
pervaporation.
So, PDMS, PDMS filled with silicate, ethylene propylene diene rubber, styrene butadiene
rubber, PMS and PTMSP were used. Now PDMS can also be applied in sweep gas
pervaporation mode as well as porous polypropylene and porous polytetrafluoroethylene
membranes. Liu et al in 2014 tested properties of in-situ crosslinked polydimethylsiloxane/
brominated polypropylene oxide membrane for n-butanol recovery by pervaporation.
1058
During PV experiments with PDMS/BPPO membrane in contact with n-butanol-water
mixture, total flux of 220 grams per meter square hour and separation factor of 35 were
obtained.
So, again details of the pervaporation can be found from this link.
So, with this I conclude today's lecture. So, next class we will be starting our module 10
which is dedicated to hydrogen, methane and methanol. So if you have any query, please
register your queries in the Swayam portal or you can also write a mail to me at
[email protected]. Thank you.
1059
Lecture – 28
Biohydrogen Production, Metabolics, Microorganisms
Good morning students. We are starting lecture 1 under module 10 today. So this module is
dedicated to hydrogen, methane and methanol. So, three most important value added products
from the fermentation and even other processes also. And today we will be discussing
exclusively on biohydrogen generation, its metabolic pathways, basics and what are the
different types of microorganisms that carry out this biohydrogen production. And we will
also learn about facultative anaerobes, thermophilic microorganisms and microbial fuel cell.
So, let us begin.
1060
Fossil fuels are not renewable and are a limited energy source. The utilization of fossil fuels
is also causing serious environmental pollution. Therefore, there is a need for the replacement
and development of new fuels for energy. Hydrogen does not generate pollution and is
considered as an environment friendly source of energy. In addition, hydrogen also has a very
high energy content per unit weight.
So, almost 142 kilojoules per gram. At present, hydrogen is mostly produced from fossil fuels
including natural gas, heavy oil sand naphtha as well as coal also. Now, it is also produced by
electrolysis of water and only 1% is being currently produced from the biomass. Therefore,
the future use of hydrogen as an energy source requires that more be produced from
renewable biomass, not from the fossil fuels.
So most of the research is now concentrated on development of biomass based hydrogen

production and its further utilization.
(Refer Slide Time 02:09)
1061
Using biological conversion processes, hydrogen can be produced from renewable sources
such as water, waste streams and energy crops. The process is conducted under ambient
temperature and atmospheric pressure conditions. Hence, it has the advantage that it is less
energy intensive and it does not cause environmental problems. The biohydrogen can be
converted into power via proton exchange membrane fuel cell.
Among the various biofuels biohydrogen has a high conversion efficiency to power and high
energy density and without the generation of pollutants. So when its gas is used as fuel, it will
not produce pollution to the air but it produces only water as its end product when it burns.
So biohydrogen has been mostly produced from microorganisms and can be subdivided into
3 major categories. So biophotolysis of water using green algae or cyanobacteria, which are
1062
also known as blue green algae. Photodecomposition or photofermentation of organic
compounds using photosynthetic bacteria and dark fermentation from organic waste or
energy crops using fermentative bacteria.
Now, the first 2 methods use light for the production of hydrogen, but the last method uses
the fermentative process that is not dependent on light. A new hybrid biological hydrogen
production process has been developed very recently by use of the electrochemical process.
Now these processes include the electrolysis, which is based on the concept and practice of
microbial fuel cell. This method needs to be added with electrical potential generated by a
microbial fuel cell so as to achieve sufficient strength to release protons to hydrogen.
So, we will discuss one by one these 3 processes. The first is the biophotolysis of water by
microalgae. The most ideal method for hydrogen production is one which utilizes resources
that are abundant on earth such as water and light from the sun. Algae and photosynthetic
bacteria use sunlight for the production of hydrogen. Algae use greenhouse gases that is
carbon dioxide as the carbon source for hydrogen production.
So there is no requirement of adding substrate as nutrients. However, you may need to give
some substrate or supply nutrients and micronutrients for its growth. Now, the advantage of
this method is the simultaneous removal of carbon dioxide during the production of
hydrogen. Algae which perform biophotolysis can be divided into green algae and
cyanobacteria.
1063
And each produces hydrogen from direct biophotolysis and indirect biophotolysis
respectively. The algal system is potentially a very ideal system. However, the disadvantage
of this system is the low light conversion efficiency and the expense of the photobioreactor.
Hydrogenases plays a vital role in biophotolysis of cyanobacteria and green microalgae.

Hydrogenases are the enzymes responsible to carry out hydrogen production. They were
classified according to the metals thought to be at their active sites. So 3 classes of
hydrogenases were recognized. The first is the iron only - iron-iron hydrogenases, then the
nickel-iron hydrogenases and then metal-free hydrogenases.
Among the 3 types of enzymes most commonly found in algae are the iron hydrogenases and
nickel-iron hydrogenases except for the metal-free hydrogenases found in some of the
methanogens. Iron-iron hydrogenase is an enzyme which plays a vital role in anaerobic
metabolism which is produced by green algae and become more efficient catalyst
hydrogenases. Iron-iron hydrogenase is able to catalyze the reversible oxidation of the
molecular hydrogen.
Now, coming to the nickel-iron hydrogenase; produced by the cyanobacteria consist of the
center of several metals that includes nickel and iron bimetallic sites active, iron-sulfur and
magnesium ions. Now nickel-iron active site is located inside the protein molecules and
functions as the bidirectional hydrogenases that involve a number of lines in the catalytic
reaction route such as route of the electron transfer, proton transfer lines as well as the gas-
access channel.
1064
Now we will discuss about the direct biophotolysis. Direct biophotolysis is a biological
process that can produce hydrogen directly from water using microalgae photosynthesis
system to convert solar energy into chemical energy in the form of hydrogen. The reaction is
given as two water plus solar energy under photosynthesis process will produce 2 molecules
of hydrogen and oxygen.
The advantage of this process is that even in low light intensities, green algae and anaerobic
conditions are still able to convert almost 22% of the light energy by using the hydrogen as
an electron donor in the process of fixation of carbon dioxide. Hydrogen production by green
microalgae takes place in anaerobic conditions in the dark to induce activation of enzymes
involved in the hydrogen metabolism. Green microalgae have the genetic machinery,
enzymatic, metabolic and electron transport to photoproduce hydrogen.
1065
So, you can see this is the schematic representation of the direct biophotolysis of water for
hydrogen production. I will explain this. So, green algae uses a photosynthetic mechanism.
So, it can be photosystem 1 and photosystem 2 both basically to obtain protons and electrons
from water and hence produce hydrogen from direct biophotolysis of water. You can read
little more about photosystem 1 and photosystem 2 in a nutshell, I will just tell you that.
Photosystem 1 and photosystem 2, there are so many differences. The basic difference is that
what type of light energy they are absorbing. So photosystem 1 basically absorbs higher
wavelength or longer wavelength lights around 700 nanometer whereas photosystem 2
absorbs shorter wavelength around 630 nanometers a little less than that. And another
differentiation is that photosystem 2 actually generates the electron e- directly from the water.
Whereas photosystem 2 gets its electron from the process of the photosystem 2. So,
chloroplast in algae receives visible light and degrades water directly, then produces protons
and electrons. This is happening in the PS 2. Now, the electrons flow from the water through
the two photosystem, PS 1 and PS 2 to the hydrogen producing enzyme, here in this case is
hydrogenase, via an electron carrier (here it is ferredoxin) which is denoted by Fd, you can
see that here. So, here from the water we get the electrons. Now, this electron is being used
for the hydrogenase also and even the PS 1 also gets the e minus from the PS 2. And with the
help of ferredoxin the hydrogenase is able to produce hydrogen. Now, this enzyme uses
protons and electrons in its catalytic process for hydrogen production. The major enzyme
needed for that direct biophotolysis of water is hydrogenase. However, this enzyme is very
sensitive to oxygen.
1066
Now, hydrogenase sensitivity to oxygen is a big challenge for this method, so that further
research is needed to develop engineered hydrogenase so that it is not sensitive to oxygen
inactivation. Since oxygen is extremely sensitive for the hydrogenase mechanism, whatever
oxygen is getting produced has to be scrapped out. Having said that it is not so easy to do
that.
So to prevent the inhibition of hydrogenase the partial pressure of oxygen has been lowered
using inert gas sparging; however, these methods still have practical problems in that they
require a high cost. You are additionally making some mechanical enrichment of sparging
gas, so of course you need pump or tank, sparger and all these things. So, you are adding cost
to the entire process.
Now, to remove the produced oxygen, an oxygen absorber and respiratory oxygen uptake by
microalgae have been attempted, but resulted again in an increase in the cost and decrease in
the hydrogen concentration, not very effective. Now, only insignificant amounts of hydrogen
can be produced during the night. Therefore optimization of the daylight and night dark cycle
for enhanced production of hydrogen has been performed and enhanced hydrogen production
has been reported through mutagenesis for the development of less oxygen sensitive
hydrogenase enzymes.
1067
Now, we will discuss about indirect biophotolysis. Indirect biophotolysis is a biological
process that can produce hydrogen from water using a system of microalgae and
Cyanobacteria photosynthesis to convert solar energy into chemical energy in the form of
hydrogen through several steps. Now, what are those steps? Essentially 4 steps. First is the
biomass production by photosynthesis. Second is biomass concentration.
Third is dark aerobic fermentation which produces 4 glucose mol hydrogen per mol in the
algal cells together with 2 moles of acetate, acetic acid and (fourth) conversion of 2 moles of
acetic acid into hydrogen. Now, this process can be classified into two distinct groups one of
which is dependent on the light and the other is not depending on the light. So the reactions
you can see that 6 water + 6 carbon dioxide in the presence of light will give us glucose + 6
oxygen. Now this glucose + 2 water will give us 4 moles of hydrogen + 2 acetic acid and 2
carbon dioxide. Now these 2 acetic acid plus water plus light will again be converted to
hydrogen and carbon dioxide.
So overall reaction can be written as 12 water in the presence of light will give us 12 moles of
hydrogen plus 6 moles of oxygen.
1068
Cyanobacteria or the blue green algae uses photosynthesis to degrade water to oxygen,
simultaneously fixes carbon dioxide from the air to synthesize macro cell material inside the
cells and then produces hydrogen from the cell material by anaerobic fermentation. The key
enzyme for hydrogen production in this process is the nitrogen fixation enzyme nitrogenase
which produces hydrogen in the oxygen and nitrogen deficient systems.
Heterocystous cyanobacteria are composed of two different cell types where the oxygen
production activity and the hydrogen production activity spatially separated. The
photosynthetically generated oxygen needs to be separated from the nitrogenase for the
higher production of hydrogen, otherwise it will inhibit basically.
The nitrogenase system of cyanobacteria is less efficient than the hydrogenase system of
green algae because of the low turnover number, usage of the ATP that is continuously
produced and getting used, the necessity for differentiation and maintenance of heterocysts
which requires a lot of energy.
1069
Cyanobacteria contain not only nitrogenase but also uptake hydrogenase which consumes the
hydrogen. Thus hydrogen production is getting low. Now, in order to resolve these problems,
the uptake of hydrogenase function should be removed from cyanobacteria. An uptake
hydrogenase deleted mutant and replacement of gas phase with argon gas was previously
sought to enhance the production of hydrogen.
In indirect biophotolysis separated oxygen production and hydrogen production was

attempted with the aim of preventing inhibition of the hydrogen production activity. Cell
material is produced by carbon dioxide fixation and biphotolysis in stage 1, and then the cell
material is converted to hydrogen by anaerobic fermentation in stage 2.
1070
I will show you this. So, indirect biophotolysis, it consists of two distinct steps. This is
actually more or less we can say that photosynthesis and this is your anaerobic fermentation.
So, again the same which we have shown during the direct photolysis PS 2 and PS 1,
photosystem 2 and photosystem 1 are doing their job. PS 2 is getting the electron directly
from the water, then PS 1 it is getting it from the PS 2 system.
Then with the help of ferredoxin and hydrogease, the cell material is getting converted. Then
it goes to the anaerobic process where fermentation is happening. And again this PS 1,
whatever the ATP is getting generated that ATP is being used by the nitrogenase as well as
the hydrogenase enzymes with the help of ferredoxin to convert biomass into hydrogen and
of course other products little.
Chlamydomonas reinhardtii has been the main microorganism for the indirect biophotolysis.
The hydrogenase system of Chlamydomonas reinhardtii was investigated to increase the
hydrogen production rate and to remove the oxygen which inhibits the hydrogen production
activity. This is the overall reaction. So 8 hydrogen + 8 electron + 16 ATP will gives 4 moles
of hydrogen + 16 ADP + 16 Pi.
1071
So, another attempt was the development of a system for hydrogen photoproduction based on
the dilution method by transferring the Chlamydomonas reinhardtii from where it is first
grown, usually in the sulfur-replete medium to either sulfur-limited medium or sulfur-free
medium or sulfure deprivation. Now, sulfur deprivation in this system gradually inactivates
the photosynthetic oxygen evolution and leads to the establishment of anaerobiosis in the
medium for the hydrogen production which is required, anaerobic condition basically.
However, this system must satisfy the anaerobic and aerobic conditions alternatively at each
stage. Even though various studies have been performed, the economic viability and low
hydrogen production still remains the major obstacles in the commercialization of these
methods.
Even if these problems are resolved, low light conversion efficiency, the gas separation
problem of hydrogen and oxygen, intricacy of the design and high cost of photobioreactors
needs to be solved for the commercialization to be successful.
Now, we will discuss the fundamentals of biological hydrogen production processes by the
fermentation pathway. Now, there are a variety of biological production processes.
Fermentation is one of the most effective method because it can be operated and produce
hydrogen continuously without the need for light. When compared with hydrogen production
through biophotolysis, the hydrogen production by fermentation process has a higher stability
and efficiency.
1072
In industrial scale, the fermentation process is more appropriate to use because it uses a
simple control system so that the necessary operational costs are minimized. And it can be
integrated with other anaerobic process - that is one of the biggest advantages. One of the
advantage of the hydrogen production by fermentation process is using a variety of organic
waste as substrate - this is what I was telling.
When we are talking about the waste conversion, you can always couple waste conversion in
the form of fermentation so that you can produce biohydrogen. So, it plays a dual role of
waste reduction and energy production. So, basically waste to energy. Thus, hydrogen
production through fermentation process has received extensive attention from the
researchers and scientists in recent years.
Biohydrogen production by fermentation process by using carbohydrates as substrate has

received significant attention from the researchers and scientists in the recent few years.
So, here are some reactions of hydrogen production by fermentation of glucose shows that
the most desirable end product is acetate, acetic acid. With the production levels of 4
hydrogen mole per mole of glucose. So C 6 H 12 O 6 + 12 water will give us 6 HCO 3 minus
bicarbonate + 12 moles of hydrogen and 6 H+. Similarly, I am not reading the reactions. You
can go through later on. You can also see that delta G which given in the first one is 241
kilojoules per mole. For other all the 3 reactions it is negative –48, –137, –97.
1073
So, theoretically the maximum 33% of chemical oxygen demand can be converted from
glucose to hydrogen, The rest of the energy is released as acetate. Based on the theory as
shown in the reaction the first equation above, 12 moles of hydrogen can be produced from 1
mole of glucose, see this is theoretical.
But production of 12 mole of hydrogen is thermodynamically unfavorable. So it is never

getting produced because you have to maintain the thermodynamic equilibrium. So in
contrast to the former reactions, production of propionate decreases the production of
hydrogen.
So, we will now discuss about photo-fermentation. Photo-fermentation is a fermentative

conversion of organic substrates by a diverse group of photosynthetic bacteria that use
sunlight as energy to convert organic compounds into hydrogen and carbon dioxide. For
example photo-fermentation with a purple non-sulfur bacteria, which is well known as PNS
bacteria, can be used to convert fatty acids into hydrogen and small molecules between the
products of other gases, namely carbon dioxide.
1074
Now, this process takes place in anoxic or anaerobic conditions and by using photosynthetic
bacterium and sunlight as energy. There are several types of bacteria that can be used in
photo-fermentation processes such as Rhodobacter sphaeroides, Rhodopseudomonas
palustris, Rhodobacter capsulatus, and Rhodospirillum rubrum. Now by using small
molecule organic acids such as acetate, lactate and butyrate as carbon and energy source of
light, it can change the carbon source to produce hydrogen.
In the photo-fermentation process, PNS bacteria is a group of photosynthetic bacteria that has
some advantage over cyanobacteria and algae. Now, these bacteria use enzyme nitrogease to
catalyze nitrogen fixation for reduction of molecular nitrogen to ammonia. Nitrogenase has
interesting property that it can evolve hydrogen simultaneously with nitrogen reduction.
Stressful concentrations of nitrogen are therefore required for hydrogen evolution.
Photo-heterotrophs make use of energy from sunlight to oxidize organic compounds and
generate the electron potential needed to drive hydrogen production. By utilizing energy from
the sun to drive thermodynamically unfavorable reactions, PNS bacteria can potentially divert
100% of electrons from an organic substrate to hydrogen production. In these processes,
photo-heterotrophs typically utilize the smaller organic acids that are often produced but not
metabolized during the dark fermentation.
Thus, waste streams from photo-fermentation obtained contain fewer byproducts as the
organic compounds are fully reduced to form hydrogen and carbon dioxide and that is one of
the most important aspect of this entire process.
1075
In principle, photo-fermentation able to convert fully organic compounds into hydrogen even
against a relatively high hydrogen partial pressure because hydrogen evolution is driven by
the ATP dependent nitrogenase and ATP formed is capture light energy through
photosynthesis. Now, you can have a look at this particular image. Now, in the figure we can
see that the non-sulfur photosynthetic bacteria can carry out photosynthetic anaerobic purple,
then captured using solar energy to generate ATP and high energy electrons through electron
flow through which then reduces ferredoxin. Now, reduction of ATP and reduced ferredoxin
drive the hydrogen protons with nitrogenase. The organism is unable to obtain electrons from
water and therefore they use organic compounds usually organic acids as substrates.
1076
And now we will discuss about dark fermentation. Dark fermentation is the fermentative
conversion of organic substrate and biomass materials to produce biohydrogen which takes
place in anaerobic conditions and without the presence of light. It is a complex process
manifested by various groups of bacteria by involving a series of biochemical reactions. Dark
hydrogen fermentation has several advantages compared with other biological methods of
hydrogen production, such as, photosynthetic and photo-fermentation because of its ability to
produce hydrogen continuously without the presence of light, higher hydrogen production
rate, process simplicity, lower net energy input and utilization of low value waste as raw
materials. Dark fermentation can also produce hydrogen from organic waste as shown in the
following equation. So, the organic waste plus water can give us CH 3 COO – H+ + 4
bicarbonate + 8 hydrogen.
So, in order to increase the yield of more hydrogen in the dark fermentation process, it is
necessary to control several parameters namely pH, organic food, nutrition feed rate,
temperature, solid retention time and the partial pressure of hydrogen. One of the most
important parameters of hydrogen production is pH, because pH has a direct influence on the
activities of the enzyme hydrogenase.
Several studies reported that the hydrogenase activity are directly correlated with dark
fermentation of hydrogen. This indicates that pH plays a very important role on the hydrogen
1077
production. Anyway, as I told you many times that pH always plays a very important role
whether it is a biological system or whether it is a non-biological system, especially when
you are dealing with some aqueous medium reaction.
Now, in general pH value was maintained at a pH range of 5.5 to 8 either by adjusting the
initial pH, by using the buffer or by using an automatic pH controller. Now by applying these
techniques, the maximum conversion efficiency has been increased by 60 to 70%. Several
studies have been conducted for the hydrogen production using a batch reactor, anaerobic
sequencing batch reactor, fed batch reactor, fluidized bed reactor and continuously stirred
tank reactors and continuous dark fermentation with different types of raw materials.
Extensive studies are being reported. So those who are interested to learn more under dark
fermentative biohydrogen production please look for literature.
So, we will explain the hydrogen production metabolic pathway in the dark fermentation.
Essentially you can see these, I will explain. Two different pathways. One is the first one this
one - which is called the pyruvate. In this pathway, particularly the pyruvate is converted to
formate and acetyl coenzyme A by pyruvate formate lyase, so PFL system. We call it as a
PFL system in facultative anaerobes.
Whereas in case of the B it is a PFOR system; here the pyruvate is converted to carbon
dioxide and acetyl coenzyme A by pyruvate ferredoxin oxidoreductase, PFOR and this is
reduced to ferredoxin by strict anaerobes. So, you can see this, the first one the PFL system
1078
here the glucose is getting converted to pyruvate, pyruvate is getting converted to formate as
well as acetyl coenzyme A.
Now formate is getting converted to hydrogen and carbon dioxide. In case of PFOR system
here the glucose is converted to pyruvate. Now this pyruvate is getting converted to carbon
dioxide and acetyl coenzyme A and both these in the presence ferredoxin along with the
hydrogenase is getting converted to 4 moles of hydrogen.
So dark fermentation by strict anaerobes: Hydrogen production by strict anaerobes is usually

performed using Clostridium species. We have discussed about Clostridium when we
discussed about ABE fermentation. Now, these processes are very sensitive to oxygen hence
minimizing the contact with exterior oxygen is vital. Therefore, reducing agents are usually
added to the medium.
The enzyme involved in the hydrogen production by strict fermentative microorganism is

hydrogenase. This enzyme is very sensitive to oxygen. Hence, anaerobic conditions that do
not allow contact with oxygen at utmost necessary. The hydrogen yield from this process is
generally higher and is closer to the theoretical yield in comparison with the facultative
anaerobes. Very strict anaerobes isolated from sewage sludge or earth soil have been used to
increase hydrogen production.
Three are being listed here. Clostridium thermolacticum - so 3 moles of hydrogen per mole of
lactose; Clostridium acetobutylicum - so 1.97 moles of hydrogen per mole of glucose; and
1079
Clostridium butyricum - 9.95 millimoles of hydrogen per gram of COD from starch. You can
see the first one is perhaps one of the best.
So, then dark fermentation by facultative anaerobes. Hydrogen production using facultative
anaerobes is usually conducted using the Enterobacter species. The advantages of facultative
anaerobes are that they are less oxygen sensitive and hence there is no need for the addition
of expensive reducing agents to the medium. The process itself is simple and scale up is easy.
However, the hydrogen production yield is lower in comparison with the strict anaerobes.
Despite this, this process is widely used because of its high hydrogen production rates and
simplicity in operation. Now, these facultative anaerobes as mentioned above produce
formate via the PFL system and hydrogen and carbon dioxide are produced from formate by
FHL. It was reported that there also exists an NADH pathway where the hydrogen is getting
produced via re-oxidation of NADH produced during the glycolysis pathway.
So, Enterobacter cloacae IIT-BT 08, this is developed by Professor Das group in IIT
Kharagpur Biotechnology Department - 6 moles of hydrogen per mole of sucrose.
Enterobacter aerogenes E82005 has given 3.5 moles of hydrogen per mole of molasses.
Enterobacter aerogenes, HU-101 has given 6 moles of hydrogen per mole of glycerol. So
excellent works are being reported and many works are being also commercially adapted in
few biorefineries.
1080
So then we will discuss about the dark fermentation by thermophilic microorganisms. Now,
thermophilic microorganisms may provide a solution for the problem of low hydrogen
production yield. Basically, thermodynamic limitations are what prevent mesophilic
microorganisms from producing a high yield of biohydrogen. Even though thermophilic
microorganisms have disadvantages such as a high culture temperature over 45 degrees
centigrade and slow cell growth, hydrogen production yield is higher.
And byproducts are much lower than for the mesophilic microorganisms. The theoretical
maximum yield of hydrogen production is 4 moles of hydrogen from 1 mole of hexose. Now
thermophilic microorganisms that have been used for the production of hydrogen include
Thermococcales, Thermotogales and Caldicellulosiruptor. Now they have glycan-degrading
enzymes that function as effective scavengers of starch and cellulose-based biomass.
Therefore, the high temperature process using thermophiles can greatly reduce the number of
biomass pretreatment steps and improve the hydrogen production.
1081
Moreover, the high temperature process can inhibit hydrogen-consuming methanogens in
mixed culture because the growth of mesophilic methanogen is inhibited by high
temperature. Both Caldicellulosiruptor saccharolyticus and Thermotoga elfii produced yields
of 3.3 moles of hydrogen from 1 mole of hexose which is 83% of the theoretical maximum
yield and is very good.
So, the maximal production rate of hydrogen of each microorganism was 8.4 millimole per
liters per hour and 4.5 millimole per liter per hour which are excellent values. Thermococcus
kodakaraensis produced a yield of 1.1 mole hydrogen from 1 mole of hexose and a specific
hydrogen production rate of 24.9 to 59.6 millimol per gram cell per hour.
C. saccharolyticus resulted in a yield of over 3.1 mole hydrogen per mole of glucose from
glucose in continuous mode and hydrogen production rate of 4 to 11 millimol per liter per
hour, which is also a good one if you compare with other such microorganisms.
1082
So, we will now discuss about photo-dark fermentation. The main problem faced by using a
dark fermentation biohydrogen production is the low yield and energy efficiency. For
example in dark fermentation for 1 mole hexose can only produce 2 to 4 moles of hydrogen
with acetate and butyrate again as byproducts. Now, byproducts contain many organic acids,
which lead to energy waste and environmental pollution.
While in photofermentation, organic acids can be used side by photosynthetic bacteria for
further processing and then converted into hydrogen production. Now, various efforts have
been done so that new approaches such as byproduct of organic acid produced by
fermentation for further methane and hydrogen production in other processes. The best
solution to solve this problem is by using sequentially between dark fermentation process and
photofermentation.
So, basically you operate sequentially dark fermentation and photofermentation in separate
units. Now, this concept is very promising for the production of biohydrogen because
hydrogen production is greater than the dark phase of the fermentation process or a single
photofermentation.
1083
So, the two stage process combining dark and photo fermentation can improve the hydrogen
production theoretically from to 4 to 12 moles of hydrogen per mole of hexose and from 2 to
10 moles of hydrogen per mole of pentose. During the dark fermentation of carbohydrate
containing substrate is converted to organic acids, carbon dioxide and hydrogen by
mesophilic and thermophilic bacteria.
In the second stage, dark fermentation waste containing organic acids such as acetic acid and
lactic bacteria used in photofermentation by photosynthetic or PNS bacteria for hydrogen
production further.
So, hybrid biological hydrogen production by electrochemical processes. Electrochemical

methods offer some advantages over traditional chemical treatments. So, what are those?
1084
Now less coagulant ion is required, less sludge is formed and electrocoagulation equipment is
very compact. Thus, it is suitable for installation where the available space is rather limited.
Furthermore, the convenience of dosing control only by adjusting current makes automation
quite easy.
Electrocoagulation is an electrochemical method of treating polluted water whereby

sacrificial anodes dissolve to produce active coagulant precursor usually aluminum or iron
cations into the solution. Additionally, electrolytic reaction evolve gas usually the hydrogen
in the form of bubbles at the cathode that can enhance the process. This effect is known as the
electroflotation.
Hydrogen is a main byproduct of the electrocoagulation process as it is generated at the

cathodes by water electrolysis. With an effective gas-liquid-solid separation process, high
quality hydrogen can be recovered from the electrocoagulation process and used as an energy
source or as a reactant for industrial processes. Production of hydrogen by the
electrochemical process is not limited to carbohydrate as in the fermentation process actually,
because any biodegradable dissolved organic matter can theoretically be used in this process
to produce hydrogen from the complete oxidation of organic material. Electrocoagulation is
one way to produce hydrogen as well as an alternative treatment method for the wastewater.
So, basically, we can again say that water energy in excess or waste to energy.
1085
So, this is the representation that how actually it happens. So, this is the anode where
oxidation is happening. This is the cathode. So, you can see that when the electric current is
applied to both the anode and cathode, so the current flows through, the pollutants rises to the
surfaces and are getting converted slowly by the available microorganisms to various
products and byproducts.
Now, occurrence of electrocoagulation method is to separate water into hydrogen and oxygen
elements by passing an electric current between the two electrodes in the water.
Electrocoagulation is a complex process occurring via electrolytic reactions at electrode
surfaces and formation of coagulants in the aqueous phase. Electrocoagulation process is
based on the formation of thickeners, so basically hydroxyl metals in wastewater by
dissolving the anode as shown in the figure.
1086
So, reaction that occurs in electrocoagulation using alumunium electrode are as follows. You
can use other metal as a electrode also. So, for aluminum electrodes Al + 3 e gives Al 3+. So,
in the anode in alkaline medium Al 3+ + 3 OH gives us Al OH 3. So, in case of acidic
medium in anode we will get Al OH 3 that is in the form of solid plus 3 H+. Now, for iron
electrodes, the ion plus 2 e will give us Fe 2+. Now, in alkaline medium we will get Fe OH 2
and in case of acidic medium we get 4 moles of Fe 3+ and 4 moles of OH minus. Now,
subsequent reaction of oxygen that is getting generated by this reaction 2 water 4 e will give
us oxygen + 4 H+. At cathode subsequent reaction of oxygen happens which is this 2 water +
2 e will give us hydrogen + 2 OH minus.
Now, you can understand so many different types of reactions are happening simultaneously.
So, controlling is of course an important issue. So, a bioelectrochemical system is an
alternative technology using microorganisms as electrochemical catalysts. Microorganisms
are capable of catalyzing the oxygen reduction reaction at the anode and cathode electrodes.
Bioelectrical systems are divided into two major groups which are microbial fuel cells and
microbial electrolysis cells, MFCs and MECs.
1087
So, we will just in a glance understand about microbial fuel cell. MFC consists of two
electrodes, anode and cathode, where bacteria grows on organic materials dissolved in the
anode chamber in anaerobic conditions. Due to activities of the bacteria, chemical energy
from organic matter in the wastewater is converted into electrical energy. Microorganisms
oxidize substrates to produce electrons and then transport to the anode.
As a result, electrons flow through an external circuit to the cathode and produce a
measurable electrical current. If you recall we have discussed MFC earlier also, but just to
maintain the flow of this entire lecture we are discussing in a nutshell. So, by
electrochemically augmenting the cathode potential in MFC circuit, it is possible to directly
produce hydrogen from protons and electrons produced by the bacteria.
This approach greatly reduces the energy needed to make hydrogen directly from organic
matter compared to that required for hydrogen production from water via electrolysis.
1088
In a typical MFC, the open circuit potential of the anode is usually 300 millivolt. If hydrogen
is produced at the cathode, the half reactions occurring at the anode and cathode with acetate
being oxidized at the anode are as follows. So, at anode C 2 H 4 O 2 + 2 water will give us 2
moles of carbon dioxide, 8 electrons and 8 protons. At cathode 8 proton + 8 electrons again
getting reacted to gives us 4 moles of hydrogen.
Now, producing hydrogen at the cathode requires a potential of at least –410 millivolt at pH
7. So, hydrogen can theoretically be produced at the cathode by applying a circuit voltage
greater than 110 millivolts that is in the range of 410 to 300 millivolt. This voltage is
substantially lower than that needed for the hydrogen derived from the electrolysis of water
which is theoretically 1210 millivolt at neutral pH that is very high actually if you compare
with this process.
In practice, 1800 to 2000 millivolt is needed for water hydrolysis under alkaline solution
conditions due to over potential at the electrodes. It is shown here that this biochemical
barrier can be circumvented by generating hydrogen gas from acetate using a completely
anaerobic microbial fuel cell.
1089
More than 90% of the protons and electrons produced by bacteria from the oxidation of
acetate were recovered as hydrogen gas with an overall Coulombic efficiency - that is the
total recovery of electrons from acetate - usually at around 60 to 78%. This is equivalent to an
overall yield of 2.9 moles of hydrogen per mole of acetate if you assume 78% Coulombic
efficiency and 92% recovery of electrons in the form of hydrogen.
Now, this bio-electrochemically assisted microbial system if combined with hydrogen

fermentation that produces 2 to 3 moles of hydrogen per mole of glucose has the potential to
produce 8 to 9 moles of hydrogen per mole of glucose at an energy cost equivalent to 1.2
mole of hydrogen per mole of glucose, which is excellent actually.
1090
So, we will wind up our discussion talking about this MEC/microbial electrolytic cell: MEC
is a slightly modified MFC, where a small amount of electricity is applied to the anode
chamber to suppress the production of methane and oxygen is kept out of the cathode
chamber to assist bacterial oxidation of organic matter present in wastewater to produce
hydrogen.
While MEC has tremendous potential, the development of this technique is still in its infancy.
Information about the anode materials and microorganisms used in MFCs are also applicable
to MEC systems due to their similar anodic processes. Yet, efficient and scalable designs are
required and investigated by biologists for the successful applications of the microbial
electrolysis process.
So with this, I wind up today's lecture. So in the next lecture, we will be discussing about the
fundamentals of biogas technology, fermenter designs and biogas purification processes. So
if you have any query, please feel free to register it in the Swayam portal or you can always
drop a mail to me at [email protected]. Thank you.
1091
Lecture – 29
Biogas Technology, Fermenter Designs, Biogas Purification
Good morning students. Today is lecture 2 under module 10. As you know that we are
discussing hydrogen, methane and methanol in this particular module. And in today's lecture
we will be basically discussing about the fundamentals of biogas technology that includes the
different types of microorganisms, what are the process conditions, then what are the
different types of fermenters that can be used or has been used and how do you purify biogas
once it is produced, because as you know that you cannot use directly the biogas that is
getting generated into some application. So let us begin.
1092
Fundamentals of the biogas process. So, biogas is an energy rich gas mixture that is created
during the natural decomposition of organic material without the presence of air or we can
say precisely oxygen. The major and important component of biogas is the combustible
methane. Depending on the substrates used, methane content varies between 50% to 65%.
In addition, there is also carbon dioxide with a proportion of almost 35 to 50%, the second
major component after methane of course. Apart from carbon dioxide, there are other
ingredients also which are present in very minuscule quantities such as nitrogen, water,
oxygen and hydrogen sulfide. Especially hydrogen sulfide creates lot of problem but it is
present in low concentrations. However, for certain applications you need to scrap it.
Now, biogas can be converted into electricity, heat, gas or fuel. What remains with the
fermentation product is a high quality fertilizer - that means after the gas is produced
whatever left out is the solid residue that is actually a good quality fertilizer. It is very rich in
humus-forming substances and nutrients. Liquid or dried, they are used in agriculture, in
landscaping and horticulture as well as in private gardens as organic fertilizers or soil
improvers or soil enhancers.
1093
Natural gas consists of 98% methane. Now, in order to be able to feed biogas into a natural
gas network, it must have the same methane content as the natural gas that means 98%. Now
for this purpose biogas is washed and the carbon dioxide is removed so that methane content
increases. Now, if biogas has a methane content of 98%, it is called biomethane. You must
have heard about biomethane many times.
Many people get confused about what is the difference between biogas and biomethane. So
essentially if biogas contains 98% methane we can call it biomethane. Now this can be fed
into the existing gas network and for example taken from the pump of a gas filling station. A
biomethane vehicle reduces carbon dioxide emissions by up to 90% compared to a
comparable petrol engine and cost the user only half of the fuel cost per kilometer.
The processing of biogas into biomethane began at the end of 2006 with the biogas plant in
Pliening near Munich in Germany. So if biomethane is liquefied into liquefied natural gas
that is LNG, it can also be used for trucks and ships due to its high energy density.
1094
Now, we will try to understand the characterization of the substrates; what type of
characterization they require for the substrates or we can say basically the feedstocks for the
biogas plants. So the term substrate refers to any biomass suitable as an input material
(feedstock) for the biogas plants. Not all the constituents of the substrates are biodegradable
in an anaerobic fermenter.
Most of the biomass consists of water, and minerals form another fraction of the biomass. So
although all organic matter is considered biodegradable, the reaction velocities of the
degradation of various organic compounds differ considerably. The substrate may contain
easily biodegradable material likes sugar, starch, alcohols, and so on; then medium
biodegradable materials such as protein, cellulose, fats, oils, and so on.
And then heavily biodegradable materials like lignocellulose and lignin. Now, both
decompose very slowly that means the lignocellulose and lignin and sometimes not at all and
therefore the retention time instead of the fermenter becomes very long due to the slow
decomposition of these particular components.
1095
How to characterize the composition? First a defined amount of substrates should be dried at
105 degrees centigrade until the mass remains constant. So I am just trying to explain the
procedure to characterize the substrates. Mainly water will be lost but also some substances
such as alcohols, aldehydes, ketones, carboxylic acid, etc., all organic components, having
low vapour pressure they will be disappear.
Now, this residue is called total solids or dry matter. So, you can write either TS which is
more appropriate or many times people write dry matter also. Now, after ashing for 6 hours at
550 degrees centigrade, only the minerals will remain. It is assumed that the difference
between the mass of the total solid and the mass of the ash, so as to speak, the loss of ignition
is the mass of the organic dry matter that was decomposed thermally or was burned down.
Sometimes, this organic dry matter is also called the volatile substances (VS) or volatile dry
matter. In most of the cases, the biogas yield or the methane yield refers to the mass unit of
organic dry matter such as meter cube per kg of oDM, oDM is organic dry matter. Further
differentiation of the biodegradability requires either the van Soest test for the more detailed
characterization of the substrate or the so called standard fermentation test, which delivers the
biogas yield directly.
1096
So, for the metabolism of the microorganisms, macronutrients like nitrogen, phosphorus,
potassium, sulfur as well as certain micronutrients such as trace elements of chromium,
cobalt, selenium, tungsten, magnesium, iron, zinc, nickel, molybdenum and so on are utmost
necessary. A ratio of C:N:P:S of 500-1000:50-20:5:3 is usually sufficient. Now, the balanced
composition can be obtained by adding raw straw if the C by N ratio is too low or by adding
manure if this ratio is too high.
So, we are learning actually how do you prepare the feedstock material and charge the
fermenter so that the anaerobic digestion can proceed. A mixture of trace elements needs to
be added only in the case of mono-fermentation of biogas crops. While in the case of co-
fermentation of plants and manure, an addition of trace elements is usually not necessary.
It should be pointed out that high concentrations of the nutrient as well as that of the trace
elements could have an adverse, even toxic effect on the metabolism of the microorganisms
those are responsible for producing biogas. Now, despite all progresses in research, the role
of the trace element has not been discovered completely yet. Especially for the new
substrates, the necessity of adding nutrients and trace elements should be analyzed
experimentally.
1097
Now, this is a very interesting slide in which the authors, actually I have given reference here.
You can see this, you can download and read later on of course. This is very interesting, in a
single schematic representation, the authors have tried to make us understand that what are
the different types of characterization processes and what temperature it will be carried out.
So, if you see this, the temperature is increasing in this direction and there the total mass is
100% and the mass is getting decreased in this direction or you can say that unit. So, if you
see, most of the percent is almost 34 to 35%. So, this is entirely actually if you see it is 35%,
so rest 65% is the water loss or the moisture loss or loss due to bound and unbound moisture
you can say. Then small portion, this yellowish portion almost 2 to 3% that is due to the
volatile compounds.
And volatile suspended or dissolved solids (VSS) again another 15 to 20% in that range.
Then while we come down, so almost 24% here this is coarsely dispersed volatile matter,
heavily or non biodegradable organic matter. So, this takes into account some lignocellulose
and basically your lignin is also there. Then ash content which is usually 0 to 4%, depending
upon the biomass feedstock again.
So, ash content can be carried out using this pyrolysis in a closed recipient at 950 degrees
centigrade. So, you can understand that in a single slide that what are the different
characterization techniques can be done with respect to the thermal decomposition basically.
1098
So, now we will try to understand the basic processes and the process conditions that are
essential for the biogas fermentation. The decomposition of the substrate and the formation of
biogas involves at least 4 distinct steps. So, we will see one by one. The first is the
decomposition of the solid organic matter by extracellular enzymatic reactions into water-
soluble chemical compounds takes place. This is called hydrolysis - the most important step
of the biogas process. Now this hydrolysis by fermentative bacteria is the conversion of
polymers into monomers and brings about a wide variety of substances like glycerol, sugar,
amino acids, alcohol, aldehydes, ketones, ester, higher carboxylic acids, and so on.
Now in the second step, these substances are converted by the acidogenic bacteria into
carboxylic acids, such as propionic acid, butyric acid, acetic acid, valeric acid, caproic acid
and so on. Simultaneously, hydrogen and carbon dioxide are produced as byproducts but at a
very low amount. Third step is that here the acetogenic bacteria convert the carboxylic acid
into acetic acid. In the fourth and final step, it is a methanogenesis step when methanogenic
bacteria produce biogas from acetic acid as well as from the molecular hydrogen and carbon
dioxide. The latter conversion seems to be much more important than previously assumed.
1099
So, this is a slide where you can understand what are the different types of bacteria those are
involved in the 4 distinct steps. So we will just quickly go through. The first is the
fermentative bacteria. Here actually solid biodegradable materials such as hydrocarbons, fat,
proteins they are getting converted to monomers. So, hydrolysis step. Now, then you go
ahead. These steps are happening in sequence, but once they start these are all happening
simultaneously.
Then we have acidogenic bacteria, which are carrying out the a acidogensis. Here amino
acids, fatty acids, sugar, alcohol, glycerol all these things will be converted into different
types of acids like carboxylic acids. Then when we move ahead and you can see from here
also little amount of molecular hydrogen, carbon dioxide and little amount of acetic acid also
formed during this hydrolysis process.
Now, we go for acetogensis process where acetogenic bacteria are converting the acetic acid
and molecular hydrogen, carbon dioxide formally into methane and carbon dioxide. So, that
is the getting converted using the methanogenic bacteria. So, you can understand the 4
distinct classes of bacteria that are responsible for carrying out 4 distinct and necessary steps
inside the biogas fermenter.
1100
All the four steps run in parallel at the same time forming a serious problem of process
control. Now, the stability of the process depends on the equilibrium between the acid
formation (that is by step 1 to until step 3) and acid consumption (that is step 4). So, there
should be a balance between these 3 steps where the acids are getting produced and this is the
final step where the acid is being consumed and they are getting converted into methane and
carbon dioxide.
So, since methanogenic bacteria can exist in a pH range between approximately 6.8 and 8.2
only, any overproduction of acids may lower the pH below this limit, thereby killing or at
least inhibiting the methanogenesis bacteria - which is not good. Now, once the pH has fallen
below the limit, the collapse of the process cannot be reversed and the whole content of a
fermenter must be disposed of.
The control of the feed rate of substrate is the most important technical measure to keep the
process properly running. Hydrolysis, that is step 1, is the bottleneck of the entire biogas
production process. Now, the enzymatic degradation of polymers into monomers determines
not only the overall biogas yield but also the process intensity. Having said that, the meaning
why that is the bottleneck, because hydrolysis is the step where the polymers are getting
degraded into monomers.
So, more efficiently the polymers are degraded into monomers, more amount of methane will
be produced. It is as simple as that, more amount of monomers so more amount of methane.
1101
Efforts in research and development focus mainly on the intensification of this particular
hydrolysis step.
The necessary microorganisms for all four steps are ubiquitous. Now, the addition of
inoculating microbes is not needed but could shorten the fermentation period. This refers
especially to the methanogenic bacteria, which have lower rates of cell division than other
bacteria. Other bacteria means, other acidogenic bacteria. Now, a continuous feed of
inoculate has not proven successful because the whole system adapts itself permanently to the
process conditions.
This refers mainly to step 1 to 3 of the fermentation process described earlier as well as to the
use of waste as substrate which carries a wide variety of microbes into the process. Similar
principles for ecological system also apply here: that is the higher the biodiversity, the more
stable is the system. It is again understood. So, instead of keeping fermenters clean and free
from strange microbes, it is better to offer a high biodiversity of microorganisms. For
example, by occasionally adding compost or sewage sludge or manure.
1102
The microbial variety is substrate controlled primarily and secondly controlled by the process
conditions. Microorganisms grow and settle according to the environmental conditions,
mainly according to the available nutrients to the temperature and to the pH value. This not
only refers to the input substrates, but also significantly to the intermediate substances of the
biodegradation process.
Now, due to the higher number of available species for the step 1 and step 2, hydrolysis and
acidogenesis, these two steps, they may run in a wide temperature range between
approximately 20 degrees centigrade to more than 60 degrees centigrade. Now for the
methanation, the temperatures should be either around 37 degrees centigrade it is the
mesophilic temperature or 55 degrees centigrade which is thermophilic temperature
depending upon what type of microorganisms are present in your biogas plant. The higher the
temperature, the higher the process intensity (vid. Arrhenius’ law), but less is the process
stability. Even higher reaction temperatures are possible. So, you can talk about a super or
hyperthermophilic temperatures which are usually greater than 60 degrees centigrade, but
applied seldom yet due to the instability problems. Maintaining temperature is always an
issue.
1103
The microorganisms, especially the methanogenic bacteria together with acetogenic and
acidogenic bacteria form a biocenosis (Biocenosis means a consortia of bacteria), preferably
as biofilms on solid surface or as floccules. So, there is a very intensive transport of
intermediate products between the different microorganisms called the interspecies mass
transfer that greatly affect the process intensity and stability.
The microbes are embedded in the extracellular polymeric substances which are popularly
known as the EPS. They are composed of polysaccharides, proteins, nucleic acids, lipids and
other biological macromolecules. Now, EPS provide a highly hydrated gel matrix in which
the microbes can establish stable synergistic consortia. So, the biocenosis is very sensitive
against high flow velocity gradients.
Hence intensive agitation or high flow velocities may destroy it and must be avoided also.
Gentle agitation is advisable because some form of agitation enhances the rate of mass
transfer, therefore to keep the flow patterns at very low Reynolds number, almost below 10.
1104
This is another interesting slide which is taken from this particular reference, you can refer to
it later on. So, this is what I was just mentioning that how the biocenosis actually keeps itself
in two forms. First is this film; as a film over some solid surface. They are getting attached.
So, this is a schematic representation, otherwise in the form of floccules. So, let us see two.
So, you can see that, please do not think that exactly it looks like that or it appears like that,
some sort of floccules you can imagine.
So, this is an imaginary representation. So, the first red one is composed of acidogenic
bacteria, microorganisms. The middle one consists of a acetogenic bacteria and the yellow
one the core one that consists of the methanogenic bacteria. So, similarly, it is the same thing,
the representation is the same way. You can see that when we are talking about a film
attachment, film type of growth over a solid surface.
You can see that here we have methanogenic bacteria which is present immediately on the
surface of the host or you can say the solid surface. Above that acetogenic bacteria and above
finally acidogenic bacteria which is exposed to the bulk or you can say that to the feed. More
or less, the film getting represented whatever it is here represented, more or less it is being
seen in the similar way distinct, but there is no clear distinct. You cannot cut and get them,
taking them separately that I will remove this part of acetogenic bacteria, only
methanogenesis and you cannot do like that. So, this is a schematic representation as I told
you that they exist in a very beautiful way either in floccules or in film development in an
entirely synergistic way. They have a very good synergism between all of them and the
intermediate products, let us look at what about the fatty acids that is being consumed here?
1105
This is the step where the polymers are getting converted to monomers. Now, apart from that
please understand that small amount of acetic acid, small amount of molecular hydrogen and
carbon dioxide are also formed. Now, all these are getting transported in this direction you
can understand. So, that here the acetogenic bacterias will convert all these monomers into
different acids. Now, these acids are the source for the methanogenic bacteria which will
eventually pass through this.
Mass transfer is happening in this direction and mass transfer is happening in this direction.
So, what is happening is this as I was telling that the acids, now these acids are the source or
the substrates for the methanogenic bacteria which eventually convert them into methane and
carbon dioxide that is happening in the final core one. And then methane and carbondioxide
will come out.
So, we will try to understand the process disturbances. It is very important because operating
the plant though looks simple, but it is not so simple we need to take care of many things. We
will try to understand what are the things that create disturbances and how to address them.
So, it is said among experts, but not published officially, that the overall availability of biogas
plants in Europe amount of 50 to 60% only with respect to the design capacity.
Apart from combined heat and power plant failures, major reasons are the following. The first
is too fast increase of the feeding rate. So, if you do that after commissioning of a biogas
plant due to the limited growth rate of methanogenic bacteria due to the necessary adaptation
1106
of the microorganisms and due to the time needed to establish the biocenosis too fast increase
of the feeding rates are not going to serve any purpose. Now, why?
Organic acids might be produced faster than it is consumed, this is what we do not want
because it will inhibit the entire process. As a result pH value falls rapidly and inhibits or
even kills the methanogenic bacteria those are very sensitive. Now, what should you do? The
recommendation says that the feedings should be increased stepwise under permanent
monitoring of the pH. So a fed batch system is always a better system. So be patient.
Bioprocesses need space and time, do not be in a hurry. It may take 2 years until a new
process runs at its optimum. So, you need to be very patient. The growing rate of the
microorganism determines the hydraulic retention time at least in single stage reactors. So, if
the volumetric feed rate is too high, microorganisms will be washed out unless they are fixed.
In practice, the retention time should not fall below 12 days, minimum retention time.
Then some substrates like proteins especially when coming from the slaughter waste, food
waste, expired food, blood, etc., then legumes, some types of manure like chicken manure
and all these things may contain high concentrations of nitrogen which is converted into
ammonia or ammonium depending upon the process conditions. Now ammonia leads to an
inhibition of methane bacteria.
So, again, I am telling you please understand that methanogenesis bacterias are extremely
sensitive to environmental conditions. So, you have to be very careful. So, the limit
1107
concentration depends on pH and temperature and is approximately 3000 ppm under
mesophilic conditions at pH 7. Now, heavy metals which act as trace elements at lower
concentrations and stimulate the bacterial activity may have a toxic effect at higher
concentrations.
So, any such metals beyond certain limit always they are toxic. It is same for us also, human
beings also. So, usually, the concentrations of such metals will not rise fast. Hydrogen sulfide
a byproduct of the fermentation process chemically bound and precipitate some metals. Other
metals can be removed by complexing agents for example polyphosphates and lose their
bioavailability.
On the other hand, missing trace elements reduce the biogas production that is also an issue
and need to be added if the analysis of the inventory of the fermenter indicates scarcity. You
need to keep on monitoring every day, even certain hours basis so as to find out the heavy
metal concentrations. Then you will find out whether you need to supply them or they are
already present in sufficient amount.
So most of the hydrolysis and acidifying are facultative anaerobic bacteria. Strong anaerobic
conditions are not necessary for them. But methanogenic bacteria are obligatorily anaerobic
or anaerobes. The inhibition starts at low concentration of 0.1 ppm oxygen. So it is very low,
you can understand then how sensitive this methanogenic bacterias are. Recently, it was
found that methanogenics could even adapt to higher oxygen concentration of more than 1%
and will not be inhibited.
1108
Nevertheless, strong anaerobic conditions should be maintained inside the fermenters at any
conditions. Then biowaste as well as industrial biodegradable waste could contain high
concentrations of sulfur. Hydrogen sulfide could be created during hydrolysis and
acidification as well as during methanation. An inhibition of methanation process begins at
concentration of approximately 50 ppm in case of dissociated hydrogen sulfide and a pH
greater than 6.8.
Now undissociated hydrogen sulfide causes inhibition of the process at concentrations of 200
ppm and above. Gaseous hydrogen sulfide emitted from storage tanks or together with the
biogas is highly toxic to human beings that is another problem. So it may also affect the
engine oil of the CHPs and should therefore be removed from the biogas process plants.
So now we will talk about different types of fermenter designs for the biogas production. The
fermenter design is based on some fundamental parameters and equations as illustrated in the
figure. So I will just show the figure and then we will come back again.
1109
So this is the design parameters for anaerobic digestion. So, I will just try to explain quickly.
So 3 things. First is this is the input, feed substrate whatever it is. This is the output, liquid
residue and then this is the biogas that is the final product output. So, you can see that the
load parameters are given here. The performance parameters are given here. So, the load
parameters like hydraulic retention time HRT in terms of days.
So, V R by V in. So, V in is your input of mass flow rate and V R is your output mass flow
rate. So, organic load OLR, then sludge load rate SLR. Sludge is also required but it is in a
very minute quantity depending upon the capacity also and the condition. So, performance
parameters are biogas yield, methane yield, biogas productivity and specific gas productivity
unit in meter cube per kg day. So, the equations are valid only for steady state operation.
Load parameters describe the physical load of the reactors. The simplest is the hydraulic
retention time. It describes the statistical average residential time of a defined amount of
matter inside the reactor, which has a defined volume when a certain volumetric flow rate
flows through the reactor. Then, the next is the OLR organic load rate. It is the mass of the
dry organic matter or we can say the volatile matter fed to the reactor per unit of time and per
unit volume of the reactor.
It is one of the most important parameters to describe the capacity of a fermenter. For most of
the conventional biogas plants, the organic load rate lies between 0.5 and 5 kilograms per
meter cube day. Exhausting the optimization potential in total for example by installing
1110
reactors with fixation of active biomass and OLR of more than 30 kg per meter cube day
seems to be possible. It is recommended actually.
The most important performance parameter is of course the biogas or the methane yield. It is
the ratio of the total biogas produced with respect to the converted organic dry matter. The
biogas productivity explains how much biogas is produced by unit volume of the reactor per
unit amount of time. By rearrangement of the equations according to the given data and to the
need, almost all important design parameters can be calculated.
But it should not be neglected that some data must be found experimentally by long lasting
and repeated experiments. So, they become more reliable data then.
1111
So, the desired biogas digesters should meet the following specifications. Absence of water
or gas leakages, operating temperature of 35 degrees centigrade which is the mesophilic
condition for the methanogenesis bacteria, high corrosion resistance, easy to maintain, low
cost and affordable. The biogas digester was designed to withstand pressures subjected
during the operation. The maximum shear stress on the digester was adapted from a classic
work by Gere and Timoshenko.
The reference is given below. Let the design pressure be 10% above the operating pressure
that is what is basically recommended by the designers. So, design pressure equals to 10% of
the operating pressure plus 2.4478 bars. So, that 2.4478 is the maximum shear stress, so that
is 2.7 bars. Hence, the calculated design pressure is 2.7 bars, so 0.27 Newton per mm square.
Now, we will quickly discuss few of the digesters which are commercially being adopted and
used and installed in many places. So, first is the Plug Flow Digester. Now, this is a type of
anaerobic digester that uses a long narrow horizontal tank in which a material or manure is
added at a constant rate and that force other material to move through the tank and be
digested. No mechanical or any form of agitation inside.
Typically, a plug flow digester vessel is five times longer than it is wide. It is insulated and
heated and is made of reinforced concrete, steel or fiberglass. A plug flow digester has no
means of agitation. The term plug flow means that the manure in principle flows through the
1112
digester vessel literally as a plug, so gradually being pushed out to the outlet as the new
material is being added.
So, the main advantage of the plug flow design is that it is simple and economical to install
and operate. However, it is not as efficient or as consistent as the completely mixed
fermenters.
The next one is fixed dome digesters. So a well and a dome are made out of cement concrete
basically. Fixed dome digesters are usually built underground. The dome is fixed and hence
the name is given to this type of plant is fixed dome type of biogas plant. The function of the
modified fixed dome digester plant is similar to that of the floating holder type biogas plant.
The only difference is the fixed top part of the digester. You can see here, this portion, it is
fixed, it is not floating.
I will show you floating one in the next slide. So, the used slurry expands and overflows into
the overflow tank. Now disadvantage is that special sealants are required for this type of fixed
dome digesters, high technical skill are required for construction and gas pressure fluctuate
which causes complication of the gases; because the gas is continuously getting generated.
And in case of the fixed dome here what is happening, when the gases are continuously
getting generated, you should have a proper headspace to hold the gas. Now, even if you have
a proper headspace also, when the gas is continuously formed and getting concentrated here it
will create too much pressure inside the tank. And if they are not continuously getting
removed at a particular flow rate, thereby maintaining the pressure inside the fermenter that
1113
the fermenter may also get cracked or burst. So, these are the disadvantage of the fixed dome
process.
Now to overcome that we have floating drum digester. So, this is a classic design. It was done
by Jashu Bhai J Patel in India in 1956. So, he has designed a floating drum biogas plant
popularly known as the Gobar gas plant in India. In 1962, Patel's design was approved by the
Khadi and Village Industries Commission of Government of India popularly known as the
Khadi Commission. And this design soon became popular in India and the entire world.
It is divided into two parts. One side has the inlet from where the slurry is fed to the tank. The
tank has a cylindrical dome made up of stainless steel that floats on the slurry and collects the
gas that is generated. So, this is a beautiful design. What is happening here is that the top
portion is floating. So, as and when the gas is getting formed and the gas is becoming more
the amount of gas that is generated, so the dome that top portion which is floating will move
upward.
So, depending upon the amount of gas that is getting generated as well as the pressure that is
getting developed, the head will float. It will move up and down like this. It is a beautiful
design. So, the slurry is made to ferment for about 50 days. More gas is made by bacterial
fermentation leading to the pressure inside the gas collecting dome to increase. Now the gas
can be taken out through an outlet pipe. The decomposed matter expands and overflows into
the next small holding tank.
1114
So, now we will talk about the biogas purification. As I told you in the beginning of the class
that once we produce biogas as we have understood that biogas consists of so many different
types of components starting from the major component of methane to carbon dioxide,
carbon monoxide, nitrogen, hydrogen, hydrogen sulfide and other compounds.
Now, you need to purify them for a particular application. Suppose I am talking about
preparing biomethane then I have to scrap all carbon dioxide and everything else so that at
least I have 98% enriched biogas, then I can call it a biomethane which can be directly used
in the vehicles. Let us try to understand how it can be done.
So, in order to obtain biogas in a productive and profitable way, it must be processed before
use. Thus prior to use, raw biogas is subjected to conditioning or we can call it as purification
operations resulting in the properties required by the users. Biogas purification is the
operation of retention of unwanted biogas component before it is used in the combustion
process. Whatever the ultimate way of using biogas, it is impossible to use it in the raw state.
The only recyclable component is the methane. To enable the use of biogas by cogeneration
the substances to be eliminated are water, organohalogens, carbon dioxide and sulfur. The
most important reasons for improving the quality of biogas include the need to meet the
requirements of the installations in which it is used as for example engines, boilers, fuel cells
increasing its calorific value, but also for standardizing the quality.
1115
During the conditioning process, the compounds that inhibit the combustion process are
reduced in quantity or totally eliminated depending on the final use of biogas. Most
commonly used methods of biogas, conditioning pressure adsorption, biogas purification with
water under pressure, physical and chemical absorption, membrane separation and cryogenic
separation.
So one or two specific and most widely used applications we will discuss just now. Now
these methods largely involve the removal of hydrogen sulfide, carbon dioxide and water
vapor. The principle of cleaning techniques used currently includes adsorption, biofiltration,
water scrubbing which is an absorption process and refrigeration. So, these will discuss.
1116
So following table highlights the biogas components that are removed depending on how
they are being used. So what are the components? The major components being listed here.
Hydrogen sulfide, carbon dioxide and water. So, if you talk about the biogas use in gas
station, so, hydrogen sulfide must be less than 1000 ppm, carbon dioxide removal not
required, water removal not required.
Let us talk about the stove, so cooking gas. So, hydrogen sulfide removal has to be, complete
removal is required and carbon dioxide removal is not essential, water has to be removed
otherwise ignition will not proceed. Then if it is being used in cogeneration of heat and
electricity in the CHP plants, so hydrogen sulfide must be less than 1000 ppm, carbon dioxide
no need to remove whereas water has to be removed.
Again, it will create problem of combustion. If you are going to use it for fuel for cars, you
can see that everything needs to be removed whether it is hydrogen sulfide, carbon dioxide or
water. And if you talk about a biogas used in the fuel for the gas network, then you can see
that everything else needs to be removed whether it is hydrogen sulfide, carbon dioxide or
water.
So we will quickly discuss few cleaning process. First is the biofiltration. Now, biofiltration
relies upon the natural biological metabolism of sulfur oxidizing bacteria species to convert
hydrogen sulfide into elemental sulfur or sulfate. So these systems are designed to ensure a
high-density microbial community and maximize contact between the microorganisms and
the feed gas. A biological filter combines water scrubbing and biological desulfurization.
1117
As with water scrubbing, the biogas and the separated digestate meet in a counter current
flow in a filter bed. The biogas is mixed with 4 to 6% air before entry into the filter bed.
Biofiltration systems can be set up in three different configurations. Bioscrubber, biofilter and
biotrickling filter. In a bioscrubber, pollutants are absorbed into liquid flowing counter-
currently through an absorption column similar to that of a water scrubber. The liquid is then
sent to a bioreactor for the microbes to degrade the contaminants.
A biofilter consists of a packed bed of organic material that stimulates biofilm growth
through which humidified biogas is pumped. Contaminants in the biogas adsorb into the film
and interact with the microbes and then eventually they are degraded. Biofiltration systems
are effective for treating low and high hydrogen sulfide concentrations from almost 50 to 100
ppm to 2000 to 4000 ppm, resulting in a hydrogen sulfide removal of 89 to 99.9% at a rate of
20 to 125 gram hydrogen sulfide per meter cube per hour, which is excellent actually. Now,
most bacteria grow and function optimally at a temperature about 35 degrees centigrade and
neutral pH. So this process conditions you need to maintain.
1118
Next is adsorption. Now adsorption is the adhesion of compounds onto the solid surface.
When biogas is flushed through an adsorbent bed, contaminant molecules will bind to the
adsorbent’s surface removing the contaminants from the gas stream. Effective adsorbents are
generally high porous with a high surface area which greatly increases their removal capacity.
Pressure swing adsorption is a method for the separation of carbon dioxide from methane by
adsorption/desorption of carbon dioxide on zeolites or activated carbon at alternating pressure
levels. Commonly used adsorbents are zeolite, carbon molecular sieve, silica gel and
activated carbon due to their low cost, large specific area and pore volume and excellent
thermal stability.
These adsorbents are designed to have a specific pore size thus enabling selective adsorption
of molecules that are smaller than the design pore size. The adsorbent must be replaced once
it is filled or can be regenerated a limited number of times. This however contributes to extra
operational cost.
1119
In a PSA System, pressure swing adsorption process, biogas is compressed to a pressure
between 4 to 10 bar and is fed to a vessel where it is put in contact with the material that is
the adsorbent you can see there, activated carbon, zeolite or active carbon molecule sieve (the
etched portion), a representation, that will selectively retain the carbon dioxide. The
adsorbent a porous solid normally with high surface area.
Recent research and experimental demonstrations have shown that adsorption technology
paves the way for scaling up the biogas upgrading process with high energy efficiency.
Moreover, PSA systems can be deployed in any part of the world since they do not depend on
the availability of cold or hot sources.
1120
Next is pressurized water scrubbing. Purification of biogas by pressure water is one of the
most widely used biogas treatment methods. Pollutant compounds can be physically adsorbed
or dissolved in a liquid solution. To enhance the absorption of carbon dioxide and hydrogen
sulfide, biogas is usually compressed to 900 to 1200 kilo Pascal, and the high surface area
packing media is usually used.
Inside the scrubber, biogas flows counter currently to water that is sprayed from the top of the
scrubber and the absorption primarily occurs on the surface of the packing media. The raw
biogas is introduced at the bottom of the column and flows upward while fresh water is
introduced at the top of the column flowing downward over a packed bed. The packed bed
which is typically a high surface area plastic media allows for efficient contact between the
water and gas phases in a countercurrent absorption regime.
So, this is the process flow diagram of a high pressure water scrubbing. You can see two
columns. One is the absorption column, one is the desorption column. So, here the raw biogas
compressed and fed to the absorption column. In between there is a flash tower. So, upgraded
biomethane you will get here. When you go for the desorption column, air will be utilized to
do the desorption.
And whatever is coming, the bleed water and make-up water is being added and it is basically
pressurized and fed to the absorption tower. Now, it is important that hydrogen sulfide be
removed prior to the removal of the carbon dioxide. As hydrogen sulfide is highly corrosive
and would result in decreased life and higher maintenance of the subsequent compressors, it
1121
is required that before the carbon dioxide is removed, hydrogen sulfide must be removed.
Cleaned biogas can contain almost greater than 96% of methane after drying.
So, the next one is refrigeration and chilling. Now refrigeration or gas cooling provides a
simple means for removing moisture from the gas. When the gas is cooled, so typically to
between -18 to 2 degrees centigrade, water vapor condenses on the cooling coils and can be
captured in a trap. Some ammonia will also be removed given the high solubility of ammonia
in water.
Insignificant trace amounts of other compounds may also be absorbed into the water. At low
temperature of less than –73 degrees centigrade, volatile organic components will condense
and can be removed too. At –70 degrees centigrade, 99% removal of siloxane can be
achieved as well, but it is costly to operate at such a low temperature. Hydrogen sulfide
should be removed prior to refrigeration to significantly lengthen the life of the refrigeration
unit.
So you must understand that every cleaning step you go, the final polishing step, hydrogen
sulfide must be removed before that. It is the most notorious component present in the biogas.
1122
So, these are the contaminants that is removed by different biogas cleaning technologies. So,
it is just a comparative understanding. So, look at adsorption. Hydrogen sulfide will be
removed. VOCs, ammonia, siloxanes, and water all will be removed. So high removal. So, if
you talk about water scrubbing again hydrogen sulfide, VOCs, ammonia, siloxanes will be
highly removed.
And if you talk about biofiltration the same thing. And in refrigeration also ammonia and
siloxane and water will be removed completely apart with other components will be removed
partially.
So, before I wind up I will just like to mention that, each renewable source of energy whether
it is wind, biomass, whether it is solar or any such thing has its specific strength and carry out
1123
different tasks. Now, this is the only way to ensure a stable and efficient power supply from
renewable energies in the long term in a sustainable and also in an economical way. Though
wind and solar are available in plenty without being paid for them, they are not always
available.
In the future, technologies thus must be developed that provides solution when wind is not
blowing and the sun is not shining, we have to take care of all these things. Now, this is
where biogas comes into picture. Biogas can be reliably and continuously generated and
stored. Biogas plants are therefore perfect gap fillers in the renewable energy transition
system.
A power supply that combines climatic protection with reliability and low costs can only be
achieved in the long term if the various renewable energies interact. Having said that, I just
wish to mention that we have discussed about different types of renewable sources though
our focus is on biomass in the beginning lectures. You must understand that a single source
of renewable energy is not sufficient.
So, we should have multiple sources of energies. Wherever it is possible solar plus biomass,
wind plus biomass, solar plus wind, something like that. There are other sources also. I am
just telling the major three sources. So they need to be integrated in such a way that
generation of power, electricity, everything that is possible from different multiple sources
without any hindrance so that there is no shortage of power supply.
And this is now being practiced in many European countries, slowly other developing
countries have also adopted this model and things are moving in a right direction.
1124
So, I conclude and in the next class under this module, we will be discussing about methanol
production and utilization. So, if you have any query, please register it under the Swayam
portal or you can always drop a mail to me at [email protected]. So, thank you very much.
1125
Lecture – 30
Methanol Production and Utilization
Good morning students. Today is lecture 3 under module 10 and today we will be discussing
about methanol production and utilization. So, let us begin.
Methanol as an alternative biofuel for internal combustion and other engines has gained interest
since last few years. Methanol is being used as fuel either in combination with gasoline or
1126
independently. Methanol or methyl alcohol is an organic compound CH3OH with a molecular
weight of 32.042. Nowadays, it is one of the main competitors to hydrogen as a clean fuel.
The use of hydrogen appears to be most promising from an energy point of view. In fact, it has
the highest energy content per unit weight of any known fuel, 142 kilojoules per gram. It is a
very big energy content you can say and in comparison to the other natural gases it is
environmentally safe.
At present, the problems related to the use of hydrogen as a new energy resource are the costs
of purification process and the difficulties linked to the infrastructure for storage and transport.
You must be aware that huge work across the entire world is going on for hydrogen storage,
still many things are unanswered and people are working day and night to make it successful.
There are interesting works already being commercialized also.
One of the most important competitor appears to be methanol, which has an octane number of
113 and a density that is about half that of gasoline. Among several uses, methanol can be
mixed with conventional gasoline without requiring any technical modification in the vehicle
fleet. So, that is the most interesting part of methanol blending. So, most of the methanol fueled
vehicles use M85.
So M85 is nothing but a mixture of 85% methanol and 15% of unleaded gasoline. Furthermore,
methanol can be used as a convenient energy carrier for hydrogen storage and transportation,
as an easily transportable fuel, and also in the chemical industry as a solvent and as a C1
1127
building block for producing intermediates and synthetic hydrocarbons including polymers and
single-cell proteins. Methanol is an extremely valuable solvent for most of the chemical
industries.
For all these reasons. methanol is considered to be the transition molecule from fossil fuels to
renewable energies. It is only slightly soluble in fat and oil and represents one of the most
important chemical raw materials. Indeed, the primary use of methanol is in the chemical
industry as either a feedstock solvent or a cosolvent. Methanol is less expensive to produce in
comparison to ethanol (as a fuel when we talk about ethanol uses of fuel) however, it has a
lower energy density and it is a little more toxic than ethanol. Now methanol may be made
from hydrocarbons or renewable sources, in particular natural gas and biomass respectively.
That is why we are discussing it under this course. It can also be synthesized from carbon
dioxide and hydrogen. For direct engine application, usually a blend of methanol, ethanol and
petroleum is anytime preferred than individual fuels.
1128
So, if you talk about the methanol produced and its use, approximately 65% of methanol
produced worldwide is consumed for the production of acetic acid, vinyl and methyl acetates,
methyl methacrylate, methylamines, MTBE that is methyl tert-butyl ether, fuel additives and
other chemicals. The remaining portion is converted into formaldehyde and the resulting
products as shown in the following figure. You can see that if you go by percentage
formaldehyde is the highest.
So, methanol was first produced by destructive distillation or we can call it as pyrolysis of
wood and was known as wood alcohol by the British scientists. During the OPEC 1973 oil
crisis, methanol was produced from coal as a proven fuel with a well-established manufacturing
technology and sufficient resources to replace gasoline. Later on in 1986 Swedish Motor Fuel
1129
Technology Corporation extensively reviewed the use of alcohols and alcohol blends as motor
fuels.
So, they reported in detail the methanol production from natural gas, very heavy oils,
bituminous shales, coals, peat as well as biomass. Slowly then methanol’s use as a fuel started
gaining interest basically as a blend. In 2018, Government of India announced that if feasible,
passenger vehicles will run on 15% methanol mixed fuel. At present vehicles in India use up
to 10% of ethanol-blended fuel. If approved by the government it is estimated to cut monthly
cost at least by 10%.
Now we will discuss about the various ways to produce methanol. So, the first one is methanol
from natural gas. Many technologies have been developed over the years to produce methanol
from different sources. In fact, it can be synthesized from several carbon containing feedstocks
including natural gases. It could even be produced right at the gas well by oxidative
transformation - that means production at source, which looks good from the economical point
of view, then coal, biomass or carbon dioxide, the latter directly recovered from the
atmosphere.
Currently about 90% of methanol is produced from natural gas. The process route for the
production of the simplest alcohol is relatively straightforward involving the three following
basic steps. The first one is the production of syngas or synthesis gas, Second is the conversion
of syngas into the crude methanol. Third and one of the most important aspect is of course
distillation of the crude methanol to achieve the desired purity.
1130
The process of converting syngas into crude methanol occurs at a pressure of 50 to 100 bar and
a temperature of 200 to 300 degrees centigrade. The main reactions involved in methanol
synthesis are shown below. The first one is hydrogenation of carbon monoxide. So carbon
monoxide plus 2 hydrogen gives us methanol. Then it is divided into two consecutive steps.
The carbon monoxide plus hydrogen gives us formaldehyde, formaldehyde plus hydrogen
gives us methanol. Again the last one hydrogenation of carbon dioxide, so carbon dioxide plus
3 hydrogen gives us methanol plus water.
So, you have to understand that these all reactions are happening simultaneously. So, in
addition the conversion of synthesis gas is subjected to a thermodynamic equilibrium that limits
the process to a lower conversion per pass and, therefore, implies a large recycle of the
unconverted gas.
The resulting recycle and cooling duty are largely responsible for the investment cost of the
process segment. Over the years, several solid catalyst have been developed in order to
maximize methanol yield and selectivity and minimize byproduct formation.
1131
So, this is a conventional methanol production a schematic representation. So, we will try to
understand in a nutshell the flow diagram, the block diagram basically. So, steam plus natural
gas they are fed to a reformer. The first reformer looks something like this in industrial scale.
So, you get a fuel gas here and you can also partly supply the natural gas or fuel. Then what
you get is basically the syngas or synthesis gas, carbon monoxide plus hydrogen or carbon
dioxide plus hydrogen.
These are the two reactions that will happen inside the methanol converter. Now from the
methanol converter, we will get the hydrogen purge. So, we can again purify this hydrogen and
it can go to burners or to the hydrogen consumers depending upon what is the purity. And this
is how it looks like a methanol converter in the real life industries.
Then the methanol water mixture it goes to a distillation unit (it looks something like this),
where it is purified to get an almost 99% pure methanol and the leftover water can further be
recycled to various processes.
1132
And next is the BASF. It is a German company developed process. It is a high pressure method.
Now, a great variety of oxides and metals have been tested as hydrogenation catalysts
excluding only the eighth group of the periodic system, almost all have been used. So, all
reactions were carried out at high pressure 250 to 300 bar and high temperature 320 to 450
degrees centigrade.
So among all, two catalysts which has given a very extremely high selectivity and the best
results in these reaction conditions were zinc oxide/Cr2O3 and zinc oxide/copper oxide
catalysts. So bimetallic catalyst basically. So, on this basis many studies have been done to
investigate the reaction mechanisms of methanol production in presence of the above
mentioned solid catalysts.
These are solid catalysts because these heterogeneous catalysts are easy to recover from the
liquid phase stream and you can regenerate and reuse it. Homogeneous catalysts we cannot do
it. So, as shown below two different ways are proposed both involving the adsorption of carbon
monoxide and hydrogen on the surface of the catalyst. So, this is the mechanism A and the
second one is shown in the next slide.
So, the mechanism A shows that the reaction takes place in four consecutive hydrogenation
steps. So, there are four consecutive hydrogenation steps. You understand that this is the
surface of the catalyst, carbon monoxide, then hydrogen is getting attached on the surface or
adsorbed on the surface of the catalyst. So, in four subsequent steps so you get methanol.
1133
Then in the second one, this is mechanism B. Here in the mechanism B, both carbon monoxide
and a hydroxyl group on the catalyst surface are involved. So, in the mechanism A only carbon
monoxide and hydrogen were involved, here one carboxylic group, you can see that C double
bond O, this carboxylic group is coming into picture and it is getting adsorbed on the surface
of the catalyst and then the reaction proceeds in this way.
So, the first step, it takes place by insertion of a carbon monoxide to (form a) formate
intermediate. So, the formate intermediate is this COOH. Subsequent hydrogenation and
dehydration leads to the formation of methanol passing through a methoxide intermediate.
Now, it is noteworthy that these two mechanisms proposed, differ not only for the intermediates
formed, but also for the way in which they are bonded to the catalyst surface, that is with a
carbon atom in the mechanism A and with oxygen in mechanism B. So, that is the basic
difference between these two mechanisms. As a result, catalytic cycles of the zinc oxide /Cr2O3
and zinc oxide/copper oxide catalyst were proposed and they have been found to be extremely
selective.
1134
So, the next is the Imperial Chemical Industries process which is a low-pressure method. In the
1960s, the BASF high pressure method was overcome by a low-pressure method created by
ICI. Now it is Johnson Matthey. So, they developed a new route for methanol synthesis in a
pressure range equal to 35 to 54 bar, much lower than that of the BASF method, and a
temperature ranging from 200 to 300 degrees centigrade, again a lower temperature range than
that of the BASF.
Now, this was made possible not only by the discovery of a new more active and selective
copper based catalyst (copper/zinc oxide/alumina Al2O3), but also by the development of a new
advanced purification process for synthesis gases, which allowed them to use sulfur-chlorine-
free syngas. Now, I have told you many times that any such processes when you talk about the
biomass conversion into value added products; purification step after the product is formed,
either that is in the gaseous phase or in the liquid phase maybe sometimes in solid phase also,
the purification phase is the most time consuming, energy consuming as well as it is a costly
affair. Almost 40% of the product cost goes to the purification. So, if you have an excellent
purification process which is economical, then the product price will come down and as well
as you will get a higher purity product.
That is what it has happened in the ICI method. Despite the fact that the catalytic power of
copper zinc catalyst in methanol synthesis was already well known. This was not exploited
commercially due to their low lifetime and the low thermal stability mostly caused by their
deactivation by poisoning. So, very quickly they get deactivated, so that is once they deactivate
we call them catalyst poisoning, so they are no more taking part in the reaction.
1135
Now, these problems were overcome thanks to the addition of alumina, which increases the
stability of the copper zinc oxide catalysts and inhibits the thermal formation of the copper
crystallites.
So the next and most important process is of course methanol from coal and biomass. The use
of biomass and char represent another route for methanol production. Nowadays, new
industrial research is trying to solve the triple problem of energy demand, waste management
and greenhouse gas emissions. Waste to energy technologies convert solid waste into various
forms that can be used to supply energy which can be derived by the thermochemical processes.
The latter is a better route than biochemical conversion due to a higher amount of feedstock
transfer and a faster conversion rate. The production process for obtaining methanol from coal
and biomass is similar to that for the production of methanol from natural gas, subdivided into
the following 3 steps. Syngas production, synthesis of the crude methanol and purification.
In the first step, coal or biomass is converted inside a gasifier into the gaseous products which
consists of biogas that is methane and carbon dioxide, syngas (hydrogen, carbon dioxide and
carbon monoxide), pure hydrogen and maybe some alkaline gases.
1136
Now, the gasification process is a thermochemical conversion technique which we have
discussed in detail in our previous classes that allows the conversion of solid biomasses into
gaseous mixtures with the help of gasifying agent. It can be air or oxygen, steam and flue gases.
Now, this process using high temperatures in the presence of oxygen aims for a large scale
development to overcome the current limits that is the low hydrogen production and high tar
content in the syngas.
In fact, the unwanted tar may cause the formation of tar aerosols and polymerization into more
complicated structures, which are not favorable for hydrogen production through steam
reforming. For this reason, several research groups have focused their studies on maximizing
the hydrogen quantity produced and minimizing that of tar.
Under typical gasification conditions, oxygen levels are restricted to less than 30% of that
required for complete combustion and carbon monoxide and hydrogen are the major products.
Methanol is produced from syngas utilizing conventional gasification of biomass at high
temperatures almost at 800 to 1000 degrees centigrade and it can be made with any resource
containing carbon such as coal or solid wastes.
1137
Now, we will look for the reactions. The conversion of gaseous products involve many
reactions. So 5 main reactions have been listed here. The char gasification reaction, so carbon
plus water gives carbon monoxide plus hydrogen. Then water shift gas reaction, so carbon
monoxide plus water gives carbon dioxide plus hydrogen. Steam reforming of methane,
methane plus water gives carbon monoxide plus 3 hydrogen. Boudouard reactions, so carbon
plus carbon dioxide reacts to give us 2 moles of carbon monoxide. Then methanation reaction,
here the carbon plus 2 hydrogen gives us methane.
Now again the same methane gets converted to carbon monoxide. So, all these are going on
simultaneously. However, unconventional gasification processes applied to biomass do not
always produce a syngas with the quality that is required for methanol synthesis.
So, please note that any syngas that is produced through biomass gasification cannot be used
to convert it to methanol, we need certain purity. So, one of the biggest problem in the
gasification of biomass is the formation of tar and char via the reduction of the carbon oxides.
Now, the synthesis gas for methanol production should only contain a small proportion of inert
gas components.
1138
In fact, the use of air as a gasification agent always results in a syngas with a high nitrogen
content which is not actually desirable when you talk about methanol conversion.
So, for methanol synthesis the optimal hydrogen carbon dioxide molar ratio in the syngas is
greater than 2. And then the gasification of biomass always results in a gas with a too low
hydrogen to carbon dioxide ratio. So, this is a problem with biomass to methanol. So, usually
the water gas shift process is the most frequently used process for ensuring a suitable ratio of
carbon dioxide carbon monoxide hydrogen and mainly to convert the carbon monoxide to
carbon dioxide.
If carbon monoxide is present when the syngas is combusted in gasification, the carbon dioxide
removal efficiency will be limited since the carbon monoxide in syngas will be converted to
carbon dioxide during the combustion process. The reaction temperature for the water gas is
375 degrees centigrade and the pressure is 40 bar. Carbon monoxide is converted to carbon
dioxide and hydrogen.
The carbon dioxide produced during the water gas shift process must be separated from the
syngas in order to ensure a suitable ratio of the carbon dioxide carbon monoxide hydrogen for
the commercially available methanol production catalyst required minimum to be 5:28:63 in
that ratio. So, sulfur must be removed from the syngas as sulfur is very hazardous for the
catalyst used for methanol production as well as during the water gas shift reaction.
1139
So, now we will discuss about the methanol from catalytic hydrogenation of carbon dioxide.
Carbon dioxide is a linear molecule that is very stable and needs extra efforts to make it
reactive. Owing to its high stability, a substantial energy input, optimized reaction conditions
and a catalyst with high stability and activity are required for converting carbon dioxide into
value-added chemicals.
Converting 1 mole of carbon dioxide to methanol requests an energy input of about 228
kilojoules and 6 electrons to reduce the carbon 4+ of carbon dioxide to C 2- of methanol. So,
the carbon oxygen bonds are very strong and high energy is required for breaking them. For
this reason in order to convert carbon dioxide into methanol, a very good catalytic system is
the utmost need.
So, the reaction of this catalytic conversion of carbon dioxide into methanol by hydrogenation
is given below. So, carbon dioxide plus 3 moles of hydrogen will give us methanol plus water.
1140
The next one is methanol biosynthesis way. The catalytic conversion of methane to methanol
is effected by enzymes including methane monooxygenase. So these enzymes are mixed-
function oxygenases, that is, oxygen is coupled with the production of water and NAD+. So
this is the reaction: methane + oxygen + NADPH + hydrogen gives us methanol + water +
NAD+.
Both iron and copper dependent enzymes have been characterized. Intense but largely fruitless
efforts have been undertaken to emulate this reactivity because of various process optimization
things as well as the yield.
1141
Now we will talk about the various uses of methanol. So the first one and one of the most
important is of course methanol to various platform chemicals such as formaldehyde, acetate
or acetic acid and MTBE - methyl tert-butyl ether. So methanol is primarily converted to
formaldehyde which is widely used in many areas, especially polymers. The conversion entails
the oxidation reaction 2 moles of methanol plus oxygen will give us 2 moles of formaldehyde
and water.
So, methanol and isobutene are combined to give MTBE the methyl tert-butyl ether. So, MTBE
is a very important class of chemical and it is a major octane booster that is getting used in
gasoline. So acetic acid can be produced from methanol via following the Cativa process. It is
a very well known process and has been well adapted also. The Cativa process is a method for
the production of acetic acid by the carbonylation of methanol.
The process is similar to the Monsanto process and was developed by the BP chemicals. It is
based on an Iridium containing catalyst such as this complex Ir CO 2 I 2 complex, so it is the
Iridium based catalyst.
So let us see how it happens. I will explain you in the next two slides. You can just have a look
at this particular cycle how it is happening, I will explain this. So, please look at the first second
third and fourth four different intermediate steps. So, the base molecule is nothing but methanol
from where we are producing various products. So this is your starting material methanol. We
will come back to that inner cycle later on. So, let us start with the one.
1142
So methanol is converted to methyl iodide. Methanol is getting converted to methyle iodide
how it is I will explain it in the next slide. So, methyl iodide is the starting reaction you can say
that. So, the reaction of methyl iodide with the square planar active catalyst species 1. So this
is the species 1 with iridium in the center to form octahedral iridium 3 species in the section 2
you can say here. Again you can see that Ir 3.
Now, the next is this oxidative addition reaction involves the formal insertion of the iridium
center into the carbon-iodine bond of the methyl iodide. So, after the ligand exchange, that
means iodine for carbon monoxide, so in the next phase what is happening here iodide is getting
replaced with a carbon monoxide. So, you can see that one more carbon monoxide is coming
here.
The migratory insertion of carbon monoxide into the iridium based carbon bond in the step 3
to step 4 results in the formation of a square pyramidal species with a bound acetyl ligand. So,
this is a square pyramidal species with acetyl ligand here C double bond O.
Now, the active catalyst species 1 is regenerated by the reductive elimination of acetyl iodide
from 4 and via a de-insertion reaction. So, you can see that I- is getting removed from here and
this particular complex is getting converted to the first species, which is the starting reaction
species. Now, the acetyl iodide is hydrolyzed to produce the acetic acid product in the process
generating hydroiodic acid, which is in turn used to convert the starting material that is
methanol to the methyl iodide used in the first step. You can see how it is happening and
1143
formerly you are getting your product of interest. This is the inner circle where this particular
pathway is responsible for forming methyl iodide from methanol. So, this is the process detail.
So, the next is methanol to DME - dimethyl ether. In the last 10 years, one of the most
promising technologies is the use of methanol as a C1 building block in the petrochemical
industry and a wide part of its production is consumed in the manufacturing of DME as an
alternate fuel. Now, DME has the an octane number and ignition temperature close to that of
diesel fuel that is why it is so important.
Now, it leads to lower NOx emission, less smoke, less engine noise than the conventional diesel
engine and furthermore can easily be transported. DME can also be used as a chemical
feedstock for manufacturing of many products such as short olefins, for example ethylene and
propylene, gasoline, hydrogen, acetic acid and dimethyl sulfate.
1144
So, the current DME manufacturing process is a double-step indirect synthesis one in which
methanol synthesis carried out by one of the above mentioned technologies is followed by
dehydration, 2 moles of methanol gives us CH 3 O CH 3 plus water.
Another developing process involves the direct synthesis of DME from syngas. Now, in this
process syngas carbon monoxide and hydrogen with 1 : 1 molar ratio are converted to DME in
the presence of a catalyst. So 3 moles of carbon monoxide plus 3 moles of hydrogen in the
same ratio will give us DME plus carbon dioxide.
1145
Now hydrogen production from methanol, we will discuss a few processes. The first one is
methanol decomposition. So, methanol decomposition is an endothermic reaction to produce
hydrogen and carbon monoxide from methanol. So, methanol is giving us CO + 2 H 2 you can
see that delta H is 90.1 kilojoules per mole.
And this is applicable to the recovery of waste heat of around 200 degrees centigrade from
industries. For the development of a heat-recovery system, new catalysts that can be active
even at temperatures below 200 degrees centigrade are indispensable. Usami et al in 1998 for
example have tested 15% wet palladium/zirconium oxide, then Pd/Pr2O3 and PdCeO2 catalyst.
Now, these catalysts, prepared by coprecipitation can produce high catalytic activity in the
selective decomposition of methanol to carbon monoxide and hydrogen at a temperature as low
as 200 degrees centigrade. It is a beautiful work, the reference is given here, you can read more
if you are interested.
The next one is methanol-water solution electrolysis. Another way to produce hydrogen from
methanol is by methanol-water solution electrolysis using an electrolytic cell. Now, generally
electrolysis of water is the best option for producing very pure hydrogen and that too very
quickly. As in the electrolysis of water, in the methanol-water system the hydrogen produced
is very pure almost 95.5 to 97.2 mol percent.
1146
But the theoretical voltage of the system is much lower than that of the water electrolysis
process, 1.23 volts in water electrolysis compared to 0.03 volt (very less it is in methanol-water
solution electrolysis). So, in methanol-water solution electrolysis, hydrogen is produced by
applying DC voltage to the electrolytic cell.
So, in this system the overall reaction can be written as that methanol plus water gives us carbon
dioxide plus 3 moles of hydrogen.
The reaction at anode and cathode are like this: methanol plus water is carbon dioxide + 6
proton + 6 electron that is in anode, then 6 proton + 6 electrons gives us 3 moles of hydrogen
at cathode.
Now, at the anode methanol reacts with water to produce carbon dioxide, so exhausted outside
the anode basically and protons and electrons. Now, the protons produced by the anode reaction
move to the cathode of the electrolytic cell through the proton exchange membrane. There is a
PEM membrane in between and the electrons produced by the anode reaction move to the
cathode through the external circuit containing the DC power supply. This is how it happens.
1147
So you can imagine, it is a schematic representation simplified one. You can see that this is
anode part, this is a cathode part and here this is your PEM - proton exchange membrane, it is
a membrane, solid membrane. Now, you can see that when in the anode these reactions are
happening, the protons are passing through the proton exchange membrane PEM membrane to
the cathode side where it is combined with the electrons and resulting in hydrogen.
So, at the cathode protons supplied from the anode react with electrons supplied from the
anode. Hydrogen production by methanol-water solution electrolysis is suitable for only
portable power applications because methanol-water solution electrolysis can start up and shut
down in a moment and can produce hydrogen at a lower temperature, very fast quick, but for
the smaller applications. The voltage needed in methanol-water is three times lower than that
of the water solution electrolysis.
1148
So, next one is methanol steam reforming. The production process that is much used in the
production of hydrogen is the methanol steam reforming, popularly known as the MSR
pathway. Now compared to the other fuels, methanol presents several advantages for hydrogen
production. In fact, the absence of a strong carbon-carbon bond facilitates the reforming at low
temperatures, a range of temperature that is very low when compared to other common fuels.
The overall reaction for the MSR to the production of hydrogen is expressed as methanol plus
water is carbon dioxide plus 3 moles of hydrogen. The delta H is a little lower here compared
to other reaction, 49.7 kilojoules per mol.
1149
Then the next is partial oxidation or ATR autothermal reforming. So unlike MD and MSR,
partial oxidation of methanol is an exothermic reaction. So, no additional heat is needed.
However, the temperature control can become difficult. The addition of steam into POM leads
to the ATR of methanol. Now, the addition of steam in ATR intensifies hydrogen production,
but it lowers the reaction temperature and thereby the reaction rate. In contrast to MSR and
methanol ATR, relatively less hydrogen is produced from POM.
The POM can be expressed as methanol plus half oxygen is 2 moles of hydrogen plus carbon
dioxide with a delta H 192.3 kilojoules per mol and it is a higher delta H you can see if you
compared to other reactions.
Now by virtue of more heat released from POM being employed for chemical reactions, POM
is kinetically faster than the MSR and methanol ATR implying that a smaller reactor is
achievable or it will be good for carrying out the POM.
Now, we will discuss about the methanol fuel cells. So, one type of proton exchange membrane
fuel cell is the DMFC which is direct methanol fuel cell; that uses methanol or methanol
solutions as fuel and works at an ambient temperature. Now, this is the reaction. So methanol
plus 1.5 oxygen gives us carbon dioxide plus 2 water.
1150
The structure of the DMFC consists of two porous electrolytic electrodes on both sides of a
solid polymer electrolyte membrane. The thermodynamic reversible potential for the overall
cell reaction is 1.214 volt, Methanol and water are oxidized in the anode catalyst layer (known
as ACL) and release electrons and protons according to this reaction. So methanol plus water
gives us carbon dioxide + 6 protons + 6 electrons.
You can see how it happens into subsequent representations. This is the overall representation
where you can see that this is the chamber. Here you can see that methanol is getting fed to the
chamber. And this part is anode, this is cathode. The electron is getting flown like this way
from anode to cathode. Then you have to supply oxygen. So, it will result in carbon dioxide
this side, water that side and this is a more elaborate way of representation.
Now, these electrons are transported through an external circuit to the cathode, while the
protons penetrate the electrolyte membrane to the cathode. So, in the cathode catalyst layer the
CCL layer, the oxygen from the ambient atmosphere reacts with electrons and protons and
generates water. So 6 protons + 6 electrons + 1.5 moles of oxygen will give us 3 moles of
water.
So, you can see here, both are same, here it is written in a better expressive way. So you can
see that methanol is getting converted to carbon dioxide. The electron is getting circulated via
1151
the load, from anode to the cathode. This is how it flows, it is very nicely represented there.
And the hydrogen is getting transported via this membrane, the solid electrolyte membrane and
getting to the other side, where oxygen is getting converted with the help of a proton that is
coming from this side to that side and with the help of electrons to water. It is very simplified
system and it has a lot of applications.
Now DMFC was initially developed in the United States by several organizations including
NASA during the 1990s. So, it operates at a temperature range of 60 to 130 degrees centigrade.
Current DMFCs are limited in the power they can produce (basically they produce small
amount of power), but it can still store high energy content in a small space, so that is the beauty
of DMFCs. This means that they can produce a small amount of power over a long period of
time, sustainability.
This makes them-ill suited for powering large vehicles, but they are very ideal for smaller
vehicles such as forklifts and tuggers. Now DMFCs are thus used where the power requirement
is modest such as mobile electronic devices or chargers and portable power packs. Military
applications of DMFCs are an emerging application since they have low noise and thermal
signatures and they have absolutely no toxic effluent.
1152
So with this, I wind up today's lecture. So if you have any query, please register it in the
Swayam portal or you can always feel free to drop a mail to me at [email protected]. The
next module that is module 11 is dedicated to the organic commodity chemicals from biomass.
So various types of platform chemicals that are being produced from biomass we will learn
about that. And so thank you very much.
1153
Lecture – 31
Biomass as Feedstock for Synthetic Organic Chemicals, Lactic Acid, Polylactic Acid
Good morning students. Today is lecture 1 under module 11. And as you know that module
11 is dedicated into 3 lectures and we will be actually learning about organic commodity
chemicals that are being manufactured from the biomass. And in today's lecture we will talk
about synthetic organic chemicals such as lactic acid and polylactic acid (PLA). So, let us
begin.
1154
So, biomass is utilized worldwide as a source of many naturally occurring and some synthetic
speciality chemicals, as well as cellulosic and starchy polymers. High-value, low-volume
products including many flavorings, drugs, fragrances, dyes, oil, waxes, tannins, resins,
gums, rubbers, pesticides, and specialty polymers are commercially extracted from and
produced by conversion of biomass feedstocks.
However, biomass conversion to commodity chemicals which includes the vast majority of
commercial organic chemicals, polymers and plastics is used to only a limited extent.
Biomass can serve as a source of large volume organic chemicals that retain the basic
structural characteristics of biomass and either are or have the potential of becoming
commodity chemicals.
One such is actually very famous which is a dextrose or you can say D-glucose from the
hydrolysis of starch or cellulose, high-fructose corn syrup from the enzymatic isomerization
of dextrose hydrolysate and D-Xylose from the hydrolysis of the hemicelluloses - these are
commodity products.
1155
Biomass feedstocks present several opportunities for varying product distributions as a
function of market demand and other factors or in which an optimum mix of products is
chosen based on feedstock characteristics. Mild acid hydrolysis of hemicellulose in wood for
example affords a solution that is predominantly either xylose or mannose depending on the
type of wood and a cellulose-lignin residue.
Now acid treatment of this residue yields a glucose solution which can be combined with
mannose for alcoholic fermentation and lignin residue. If you recall, these things we have
discussed when we had discussed about fermentation products and all these things, but here
we will discuss about speciality chemicals in detail. Now, phenols can be made from this
residue by hydrogenation.
And 2-furancarboxyaldehyde, that is furfural, can be made from xylose by strong acid
treatment. The commodity chemicals obtained from the primary biomass feedstock, C5 and
C6 sugars and lignins in this system design are ethanol, furfural and phenols.
1156
Other compounds that can be produced directly from biomass in good yields, but which do
not retain the basic structural characteristics of biomass are classified as commodity
chemicals. So, examples are many, as in the beginning of the class I told you. Some of the
major important things are acetic acid, methane and synthesis gas. Now they are not
manufactured in large volume from biomass because fossil fuels are the preferred feedstocks
in commercial production systems.
But as you know that fossil fuel is depleting and there is a need to look for alternate fuels and
of course a route for producing even commodity chemicals, so biomass has taken a center
stage of research since almost 20 to 30 years. Now, technically, biomass can serve as a
feedstock for production of the entire range of commodity organic chemicals presently
manufactured from fossil fuels.
Naturally occurring organic chemicals have long been extracted from a variety of biomass
species. Alkaloids, steroids, vitamins, amino acids, proteins, enzymes, oils, gums, resins,
waxes and other complex organic chemicals are isolated and marketed as specialty products
or used for the conversion to other specialty products.
1157
So thousands of examples exist. Just something I have written here, we will go through it.
The glycoside digitonin used in heart medicine from the purple foxglove plant. The narcotic
morphine from the opium poppy plant. The antimalarial quinine from the tropical trees of the
Cinchona species. The chemotherapeutic agent taxol from Pacific yew tree members of the
genus Taxus. The algins and alginic acids from the ocean kelp Macrocystis pyrifera.
The high-erucic-acid canola oil from the rapeseed. The lesquerella oils that are high in
hydroxy-unsaturated fatty acids from cruciferous Lesquerella species. The B vitamins from
various biomass species, the alkaloid scopolamine from the belladonna plant. The enzyme
cellulase in certain bacteria that catalyzes the hydrolysis of cellulose to glucose, etc. Now all
of these specialty products are organic or organometallic compounds.
And most are normally marketed as high value and specialty products. Now, having said that,
we just try to understand actually that these are some of the names only, there are many, but
again I have told you many times that what happens when you produce something from the
biomass. Biomass itself is extremely complex in nature we have learned that.
So, when you degrade it, try to make some value-added products out of them, does not matter
whether you use thermochemical conversion process or you use biochemical conversion that
is fermentation, the major problem is of course the downstream processing. Another problem
is of course the extraction of that particular compound from which you are going to make
some value-added products. This is first step.
1158
Second is the purification or downstream processing part so which is extremely, we can say
that it is costly with respect to the chemicals required, the equipment that is being required
and of course the energy. So, people are working day and night on those aspects. We have
already learned some of the latest developments of downstream processing part and again we
will also discuss in future about downstream processing.
So, these commodity chemicals, their structures are complex, only a few are semisynthetic or
synthetic products. The retention of chirality by natural organic chemicals used as
pharmaceuticals, dietary supplements and biological agents is beneficial because
physiological activity depends on it. Now, the majority of complex organic chemicals that
occur naturally in biomass will therefore continue to be obtained by extraction of suitable
species.
This is what I was just mentioning. The need for development of a particular protocol to
extract suitable species and that too in a cost beneficial or economical way when the cost of
synthesis from the biomass feedstocks is acceptable and competitive. So, cost is very
important that has to be taken care of when you go for making commercial products. Now,
chemicals from wood or silvichemicals are in class by themselves.
So many silvichemicals are commercially available. Natural polyisoprene rubbers from trees
that are members of the genus Hevea continue to be harvested and marketed - that is in large
scale. Now turpentine supply fragrances, perfume ingredients, aroma chemicals, flavorings,
1159
and a large number of terpene intermediates for the synthesis of high-value chemicals such as
vitamins.
Synthetic terpene resins prepared by cationic polymerization of terpene hydrocarbons are

used in hot-melt and pressure-sensitive adhesives. Wood pulps are sources of specialty sugars
used in drugs, sweeteners, plasticizers and surfactants. In addition to the commercial
regenerated cellulose described previously, wood pulps are used for production of cellulose
esters such as the acetates and butyrates for fibers, films and moldings and for production of
ethers such as ethyl cellulose, carboxymethylcellulose and hydroxyethyl cellulose for use as
gums and thickening agents. The alkaline pulping liquors are usually combusted to recover
the pulping chemicals and energy for recycle but the alkali lignins are also separated for use
in formulating resins, rubbers and emulsions.
Dimethyl sulfide, dimethyl sulfoxide and dimethyl sulfone are recovered from the volatile
fraction of the kraft black liquors from the sulfate pulping. The sulfonated lignins in sulfite
pulping liquors are a source of semisynthetic vanillin and are separated for use in formulating
adhesives, binders, dispersants, tanning agents and similar products.
1160
The alkaline pulping liquors yield fatty and resin acid salts that on acidification afford tall-oil
fatty acids for conversion to dimer acids, polyamide resins and other products that are used in
inks, resins, adhesives and surface coatings. Now phenolic acids and waxes extracted from
various barks are used in a variety of resin applications. In the midst of the fossil fuel era, the
less complex commodity organic chemicals are preferentially manufactured from petroleum
or natural gas.
Whereas complex speciality chemicals are derived from biomass. But commodity organic
chemicals are open to entry by biomass feedstocks if they can provide economic advantage.
Again the same thing that economic advantage is coming into picture. So, when you talk
about economic advantage vis a vis biomass, again I am just trying to repeat it that two things
are very important, the species which you want to extract from the biomass that step has to be
economical.
Then second is that, once that is produced, mostly they will be in aqueous phase, then you
have to go for purification that is the downstream part. So, both these steps are the major
contributor to the overall cost of the final product. So, note that many of the routes described
here to commodity chemicals from biomass were in commercial use in the past, are still in
commercial use, have recently been commercialized or have been developed and are
available for commercial use.
1161
So this is actually you can see what are the different types of products or value-added
products that can be derived from the biomass. These are all commodity chemicals only, we
are not talking about other things like directly used biofuel and all. So, you can see that C 5
sugar, C6 sugar, cellulose, lignin and other things, nitrogen and carbon. So, from the C5
sugars we can have furfural and xylitol.
From C6 sugars you can have so many things, ethanol and so many other things of course,
ethanol of course goes to your biofuel production, but we are discussing about commodity
chemicals. So, you can see all the chemicals here, the different types of acids, we can have
glycerol and all these things as their byproduct can also be converted to some other value-
added products. Then you can have fructose very important.
Similarly from cellulose we can have different types of acids, esters, nitrates, ethers. Then
from lignins, the main thing is of course phenol, phenolic compounds and vanillin and lignin
sulfonate, then there are so many other things also. So the primary building blocks and the
main processing methods for production of the more important biomass derived chemicals
are given here.
1162
So, we will see the different commodity chemicals by various routes. First, we will talk about
the thermochemical synthesis. Consideration of the building blocks for most organic
chemical commodities, the synthesis gas, the light olefin, ethylene, propylene, butadiene and
BTX and the chemical structures of the principal biomass component suggests some of the
routes that might be developed to provide improved thermochemical processes for biomass
feedstocks.
With the exception of synthesis gas, each of these building blocks is a hydrocarbon, whereas
the principal components in biomass, the polysaccharides, are polymers in which each carbon
atom is bound to an oxygen atom. Depolymerization and carbon-oxygen bond scission are
therefore necessary on a large molecular scale to synthesize the same building blocks. Such
brute force degradation can be achieved at elevated temperatures.
But there are opportunities to employ thermally balanced processes and energy conservation
and to transfer the carbon and chemical energy in the feedstock to the desired products at a
near theoretical yield.
1163
Low-moisture-content feedstocks are clearly preferred for thermochemical processes. This
we have understood earlier also when we discussed about thermochemical conversion
processes in detail such as gasification and pyrolysis. Now, also the costs of producing the
basic building blocks from biomass feedstocks by thermochemical methods are usually more
than the costs from petroleum and natural gas and that is the problem.
Now, this situation is expected to change as the fossil fuel era approaches its end. Now, when
that happens, you will never think about cost. However, cost is always an important factor
when you talk about commercial production in a sustainable way. Now thermochemical
gasification of biomass to high yields of synthesis gas or syngas can be carried out with most
biomass feedstocks without regard to the structure of the biomass components.
All of the organic components are thermochemical gasified under conditions that yield the
desired syngas composition. Syngas in turn can be converted to a large number of chemicals
and synthetic fuels by established processes; such as, you can see the scheme such as the
Btu’s, hydrogen, methanol, SNG, ammonia, oxoalcohols and different types of hydrocarbons.
1164
The gasification technology for conversion of biomass to syngas has been developed and
scaled up from the laboratory to the pilot plant to full-scale systems. If you recall, we have
discussed some of the success stories, how it has been adapted in India as well as other
countries. Now, it has been commercialized for fuel production, but not for the manufacture
of syngas derived chemicals.
But there is no technical reason why commercial syngas processes cannot employ biomass
feedstocks. Time has come that it has to be done. Now, the competitors for biomass
feedstocks and natural gas and petroleum feedstocks, which are currently preferred in most
countries for syngas production and conversion to methanol or high-hydrogen streams for
other applications.
The direct thermochemical production of the intermediate light olefin building blocks from
biomass can be achieved by rapid pyrolysis at temperatures above those normally used to
maximize liquid yields. Maximum liquid yields occur near temperature of 500 degrees
centigrade. The volatile matter formed by biomass pyrolysis begins to participate in
secondary gas phase reactions at temperatures exceeding about 600 degree centigrade.
1165
Using gas-phase residence times of 0.5 to 1 second at temperatures above 500 degrees
centigrade, the apparent rates of gas production from cellulose were measured for seven gas
species. Carbon dioxide, hydrogen, carbon monoxide, methane, C2H4, C2H6 and C3H6. Now
fast pyrolysis of biomass by RTP process for example provides reasonably good yields of
light olefins at reactor temperatures and residences time 700 to 900 degrees centigrade and of
course 0.03 to 1.5 seconds. You can understand very fast.
Now the gas yield can exceed 90 wt% of the biomass. Optimum yields of ethylene, total
gaseous unsaturates and total gaseous hydrocarbons from woody feedstocks were 8,15 and
25% by weight of the feedstock. BTX and syngas are the byproducts. Another method for
production of ethylene and propylene from biomass feedstocks is via syngas and the
synthesis of Fischer-Tropsch hydrocarbons.
Now, if this technology is commercialized on a large scale at some future time, the resulting
hydrocarbons can be readily converted to these olefins and that is going to happen in near
future.
1166
So, almost any paraffinic or naphthenic hydrocarbon heavier than methane can be steamed
cracked to ethylene and propylene in good yields. Now, the lower molecular weight paraffins
normally afford higher yields of ethylene, whereas the higher molecular weight paraffins
yield products that have higher propylene to ethylene ratios. An approach to the production of
ethylene from biomass that does not involve pyrolysis is of course your ethanol dehydration.
The catalytic conversion of syngas to ethanol from low-grade biomass or even fossil fuel
feedstocks and fermentation ethanol via advanced cellulose hydrolysis and fermentation
methods which make it possible to obtain high yields of ethanol from low-grade biomass
feedstocks as well. It is a good process or technology. So, what is important is that these
processes are expected to make large quantities of low-cost ethanol available for chemical
uses that include ethanol conversion to ethylene as well as acetaldehyde and acetic acid. Once
this technology is operational for the production of these chemicals, an entire commodity
chemicals industry founded on low-cost ethanol can follow. A complete biorefinery approach
you can say, sustainable biorefinery.
1167
So, markets forces will determine which low-cost ethanol technology is superior. Each is
anticipated to be capable of providing ethanol at market prices in the same price range as
methanol derived from natural gas. Butadiene is manufactured in the petroleum industry by
the catalytic dehydrogenation of the butanes and butenes and by the direct cracking of
naphthas and light oils.
The overall butadiene yield by catalytic dehydrogenation, the most common industrial
process is as high as about 80% at selectivity of about 90%. The yields and selectivity of
butadiene by direct thermochemical conversion of biomass are nil and the various routes to
C4 hydrocarbons from biomass are not a practical. A few options exist for butadiene
synthesis by alternative methods. Processes based on each of these routes to butadiene have
been developed and commercialized.
1168
Butadiene is obtained by the following chemical reactions. Ethanol is the key reactant in
equation 1 and also in equation 2 because it is readily converted to acetaldehyde. The
processes based on equation 1 was developed in Russia and the process based on equation 2
was developed in the United States. These are the 2 reactions you can see. The yield of
butadiene for the Russian processes about 30 to 35%. It is about 70% if the mixture of
ethanol and acetaldehyde are employed as in the US process.
1169
Equation 3 represents a process that involves 2, 3 butylene glycol, a product from the
microbial conversion of the biomass. The process is carried out in two sequential steps via the
glycol diacetate in overall yields to butadiene of about 80%. The process of equation 4 starts
with a biomass derivative, the cyclic ether tetrahydrofuran and can be carried out at high
yields. When this process was first operated on a large scale in Germany, acetylene and
formaldehyde were the raw materials for the synthesis of intermediate tetrahydrofuran.
In commercial practice, the aromatic building blocks for the synthesis of commodity organic
chemicals particularly benzene and p-xylene are extracted from BTX. BTX is a mixture of
the monocyclic aromatic hydrocarbon benzenes, toluene, ethylbenzene and xylene produced
in the petroleum industry by the dehydrogenation of naphthas using catalytic reforming and
by the thermal reforming and catalytic and thermal cracking of middle distillates.
Coal tars and coke oven gases also yield BTX. In modern coal coking process more than 90%
of the benzene and toluene obtainable from coal is collected by scrubbing coke-oven gas. The
direct thermochemical conversion of biomass to an equivalent BTX product however is not
1170
feasible under conventional conditions. Only a small amount of the monocyclic aromatic
hydrocarbons are formed on pyrolysis or the thermal cracking of biomass feedstocks.
The pyrolysis of pure cellulose yields many different liquid products including a few
substituted phenolic compounds and phenol, only trace to small amounts of BTX are formed.
Pyrolysis at atmospheric or reduced pressure of the lignins, which are highly aromatic
structures because of the abundance of the substituted phenly propane units yields phenols
instead of the BTX type of products. The hardwoods generally yield phenols in the
pyrocatechol and pyrogallol series whereas softwoods yields phenols in the pyrocatechol
series.
Now a few of the aromatic compounds that have been identified in lignin pyrolysis products
are phenol, eugenol, pyrocatechol, pyrogallol 1, 3 dimethyl ether, o-cresol, guaiacol,
vinylguaiacol and propyl guaiacol. Now most of the methanol formed on pyrolysis of woody
biomass might be expected to be derived from the large number of methoxyl groups in the
lignin fraction. But a substantial portion is also believed to be formed from the methoxyl
groups present in the hemicelluloses too.
1171
Two basically different methods were found to maximize BTX formation during direct
thermochemical conversion of biomass feedstocks. One is the hydrogenolysis of the
substituted phenolic compounds that are formed from woody feedstocks and the other is
aromatization of intermediates. The noncatalytic hydropyrolysis of hardwood maple chips at
670 degrees centigrade and 1.02 mega Pascal shows that aromatic compounds are formed in
substantial yields on fast pyrolysis in hydrogen atmospheres.
The liquid product yield is about 17 weight percent of the feed, one-ring aromatic compounds
make up about 39 weight percent of the liquid product and the yield of phenol is about 26
weight percent It is evident that to increase the yield of BTX, hydropyrolysis at greater
severity or hydrocracking and hydro-dealkylation should be used to aromatize more of the
phenolic compounds. This is just to increase your BTX yield.
The organic vapors formed on fast pyrolysis of either woody biomass or RDF can be
upgraded with selective zeolite catalysts to selectively yield either BTX or C2-C5 olefins. It
has also been found that biomass pyrolysis oils can be catalytically upgraded to high BTX
liquids after formation and collection.
1172
Products containing 23 to 38 weight percent BTX and 19 to 35 weight percent aliphatic,
gasoline-range hydrocarbons are obtained by thermal treatment at atmospheric pressure and
330 o 410 centigrade. The selectivity for benzene is about 90% of the BTX with
aluminosilicate catalyst. Molecular sieve and similar shape selective catalysts exhibited high
selectivities for toulene, the xylenes and other alkylated benzenes.
An alternative approach to BTX from biomass discovered in the 1980s employs fast pyrolysis
of woody biomass in methane atmospheres that is methanolysis. So, preliminary studies of
the methanolysis of dry fir wood particles in the presence of silica flour at 1 to 3 second
residence time, temperatures of 1000 degrees centigrade and pressure of 0.34 Mega Pascal
converted 12% of the available carbon to BTX, 21% to ethylene and 48% to carbon
monoxide without net methane consumption.
Thus, the building blocks for synthesis of commodity organic chemical-synthesis gas, the
light olefins, ethylene, propylene and butadiene and BTX can be obtained from biomass
feedstocks by thermochemical conversion.
1173
And now we will discuss about some of the pentose-derived commodity chemicals. An
example is of course xylitol, the pentahydric alcohol that is manufactured by the
hydrogenation of the aldehyde group in the xylose. Now one of the unique reactions of the
pentose known since the 19th century is cyclodehydration to yield furfural. Xylose for
example is dehydrated by acid treatment through one or two intermediates to form the furan-
substituted aldehyde in quantitative yield of the xylose.
The reaction is industrially significant because it made the furans available on a large scale
from biomass feedstocks such as corn cobs, oat hulls and rice hulls. Now many other
feedstocks has also been used and reported. Now the two principal furans from which many
derivatives available are the tetrahydrofuran and tetrahydrofurfuryl alcohol, both of which
are manufactured from furfural.
1174
Furfural is converted by catalytic decarbonylation to furan, by catalytic hydrogenation of the
aldehyde group to furfuryl alcohol, on further hydrogenation of the furan ring to the
tetrahydrofurfuryl alcohol, and by oxidation of the aldehyde group to furoic acid. Now, furan
is converted to tetrahydrofuran by catalytic hydrogenation and undergoes a large number of
substitution and addition reactions.
Tetrahydrfurfuryl alcohol undergoes catalytic dehydration and rearrangement to the

dihydropyran which can be hydrogenated to tetrahydropyran. Tetrahydrofurfuryl alcohol is
also converted to levulinic acid - it is one of the most important commodity chemical - on
treatment with dilute acid. Tetrahydrofuran has been converted to adiponitrile and adipic acid
precursor in a commercially two-step process via dichlorobutane.
1175
Tetrahydrofuran has also been converted to n-butanol in high selectivity which simplifies and
reduces the cost of purification and to 1, 3-butadiene via dehydration and dehydrogenation.
Both furan and furfural have been converted to maleic anhydride another important class of
platform chemicals with the former producing better yields and fewer byproducts. Four major
carboxylic acid such as acetic acid, formic acid, glyceric acid and lactic acid are formed
under mild alkaline oxidation conditions from xylose.
So we will now discuss about some of the chemicals from the hexose derived; that is derived
from the hexose basically. Several hexose sugars, sugar syrups and starches are marketed as
commodity chemicals, but only a few derivatives such as the disaccharide cellobiose, a
glucose 3 glucoside, which is synthesized not from glucose but by careful hydrolysis of
cellulose, are marketed.
The hexoses yield a wide range of esters, ethers, anhydro derivatives and they undergo
numerous rearrangement, substitution, isomerization, cyclodehydration and reduction-
oxidation reactions to further produce value-added chemicals. Glucose is converted to
gluconic acid by oxidation of the aldehyde group to a carboxylic group and to the hexahydric
alcohol, sorbitol by hydrogenation of the aldehyde group (or to sorbitol and mannitol when
invert sugar is used in place of glucose), then to a large number of ethers by elimination of
water such as 1, 6-anhydroglucose, 2, 4-anhydeoglucose and 2-hydroxymethylofurfural. The
hexoses can also be converted directly to levulinic acid and formic acid on acid treatment
without isolation of the 2-hydroxymethylfurfural.
1176
Levulinic acid is a versatile chemical intermediate that can be converted through proven
routes to higher value chemicals such as diphenolic acid, succinic acid, pyrrolidines,
pyrrolidones and the agricultural chemical 3-amino levulinic acid. Gluconic acid, glucono
and lactone from this acid, then sorbitol, sorbitol esters, sorbitans, mannitol, mannitol esters,
copolymers of fatty acid sorbitol esters and alkylene oxides and a few other derivatives are
currently marketed as commodity chemicals derived from the hexoses. Vitamin C that is L-
ascorbic acid is perhaps one of the best example of a commercial derivative of the D-glucose
that is manufactured primarily by chemical synthesis.
Now we will talk about some of the lignin-derived chemicals. Now commodity lignin
chemicals and their salts and derivatives are complex mixtures of compounds obtained from
the spent liquors of the wood pulping industry. The lignins are sold for a variety of industrial
1177
and speciality applications including adhesives, binders, dispersing agents, emulsifiers,
cement and gypsum board manufacture, oil well drilling and road stabilization formulations.
A few pure commodity chemicals are synthesized from the lignins. Synthetic vanillin, a
member of the catechol series is one such example. The compound, a pharmaceutical
intermediate and flavoring and perfume agent. Among the synthetic methods are the alkaline
air oxidation of the spent sulfite liquor from pulping operations, then the oxidation of the
coniferyl alcohol from pine trees, the conversion of guaiacol from catechol or wood pyrolysis
oils.
Then some lipid-derived chemicals. Lipids or fats are found in seed and vegetable oils and
the fruit pupls and of course animal tallows and greases also. The vast majority are
triglycerides, C 6 to C 24 fatty acid esters of the trihydric alcohol glycerol. Smaller amounts
of the mono and diacylglycerides and unesterified fatty acids are also present. Alkaline
hydrolysis of the glycerides provide large amount of glycerol and the fatty acids as
commodity chemicals.
The fatty acids of most industrial significance as commodity chemicals from fat hydrolysis,
or as derivatives are usually esters that includes the saturated lauric, myristic, palmitic,
stearic, arachidic, behenic acid, the C 18 monounsaturated oleic and ricinoleic acid and the
polyunsaturated C 18 linoleic, linolenic and eleostearic acids. Now glycerol forms acetals,
aldehydes, amines, ethers, esters and halides and can also be converted to acrolein and other
derivatives.
1178
Glycerol is thus a versatile chemical that is useful in hundreds of applications, the most
important of which are in alkyd resins and the manufacturer of the explosive nitroglycerin,
glyceroltrinitrate. So the ester is synthesize from oils such as cottonseed or soybean oil by
transesterifying the glycerides in the oil with a methanol to yield the methyl esters of the fatty
acids in the same manner that methyl biodiesel fuel is manufactured.
The methyl esters are isolated and then transesterified with sucrose to yield a sucrose
polyester in which 6 to 8 fatty acid molecules are bonded through ester linkages to the
hydroxyl groups in the sucrose molecule. The liberated methanol is removed. The synthetic
ester has many of the characteristics of and is a low-calorie replacement for natural fats.
Unlike the glycerides in natural fats, digestive enzymes are unable to metabolize the synthetic
ester, it passes through the body unchanged.
1179
Now we will talk about some of the protein-derived chemicals. Proteins are widely
distributed in plants and animals and consist of one or more polymeric chains of amino acids
that are bound in peptide linkages. Usually more than 100 amino acids are linked in the
natural polypeptide. The polypeptide chains are converted to the amino acids by acid, alkali
and enzyme catalyzed hydrolysis.
More than 30 amino acids have been isolated from protein hydrolysates. The most common
amino acids are the neutral acids glycine, alanine, serine, cysteine and then cystine, threonine,
valine, methionine, leucine, isoleucine, phenylalanine, then tyrosine, proline, hydroxyproline,
tryptophane and asparagine. The basic acids include arginine, lysine, hydroxylysine,
glutamine, histidine and ornithine.
And the acidic acids are aspartic and glutamic acids. Glycine, alanine and methionine are
chemically synthesized. Proline, hydroxyproline, cysteine and cystine are obtained from the
protein hydrolysates. Proline and hydroxyproline from the gelatin normally of animal origin
basically from the collagen and cysteine and cystine from keratin protein of the animal origin.
1180
Now we will talk about biopolymers. Now excluding the polyisoprenes that is the natural
rubbers found in several biomass species, the main biomass constituents, the natural
cellulose, hemicellulose and lignins as well as the proteins and nucleic acids are biopolymers.
Some are chemically modified and marketed. Some are marketed as natural products.
The major classes of biopolymers include the cellulose esters and ethers, chitin and chitosan,
then hyaluronic acid, polyhydroxyalkanoates, silk and other natural polypeptides, starch
esters, xanthan, dextran, and other polysaccharides, synthetic polypeptides and polymers
synthesized from primary biomass derivatives such as glycerol and other polyols and fatty
acids.
Several of these polymers are biodegradable plastics useful in packaging, molding and
extrusion applications, yield biodegradable detergents, furnish films and coatings that are
selectively permeable to specific gases and are highly water absorbing materials useful for
moisture removal, or lend themselves to medical uses.
1181
Microbial (Bio)synthesis: Microbial processing by direct fermentation of primary biomass
derivatives such as glucose can be used to synthesize a large number of organic chemicals.
The cellular components that facilitate these processes are enzymes, the protein catalysts
produced by the microorganisms. It is evident that most of the common chemicals listed are
commercially available from the non-biomass sources.
The molecular structure of the products range from simple compounds such as ethanol to
complex compounds such as penicillins to polymeric products such as
polyhydroxybutyrates/PHB. Suitable substrates are generally monosaccharides and
disaccharides and their original sources such as molasses, starch, and cellulose hydrolysates.
1182
A wide range of biomass feedstocks is used for commercial fermentation systems. Examples
are glucose for many different chemicals and products, beet sugar molasses for citric acid,
hydrolyzed starch for citric acid, itaconic acid and xantham gum, thinned starch for
ionophores and alkaline proteases, vegetable oil for terramycin, corn steep liquor for
penicillin, soybean meal for Vitamin B12.
Some naturally occurring and mutant strains of Arthrobacter, Corynebacterium,

Brevibacterium and Nocardia species have been known to excrete large amounts of certain
amino acids into the medium. An intensive research effort has been carried out over the last
few decades to isolate and characterize enzymes generated by microorganisms and to produce
and market cell-free enzymes for use as catalysts in the synthesis of commodity and
speciality chemicals.
Among the commercial preparations are amylases, proteases, cellulases, glucose isomerases
and oxidases, pectinases, invertases and cofactors.
Now we will discuss about lactic acids and of course then polylactic acids, the two most
important commercial or commodity chemicals. Lactic acid is an important commodity
chemical, an intermediate for producing alkyl lactates, propylene glycol, propylene oxide,
acrylic acid and of course PLA the polylactic acid. Lactic acid has found applications in food,
pharmaceuticals and cosmetics.
1183
In general, it can be stated that there is a need to develop new catalytic process for synthesis
of lactic acid not only from carbohydrates, but also from the lignocellulosic material, which is
cheaper and more abundant compared to the carbohydrates. Since lactic acid can be made
from different reagents such as lignocellulosic material, cellulose, carbohydrates, sugars,
trioses, glycolaldehyde and glycerol, and the reaction conditions are relatively demanding, it
can be easily observed that these reactions are usually complex involving several types of
transformations such as aldol condensation, retro-aldol condensation, dehydration, 1, 2-
hydride shift, etc.
Lactide synthesis can be summarized as follows. It is principally performed in two steps. First
polylactide prepolymer is generated in the first step via dehydration followed by thermal
depolymerization in the second step, which gives lactide. Besides consideration of lactic acid
as a platform for commodity chemicals, the interest in lactic acid arose sharply with the
development of the biodegradable polylactides that is the PLA/ olylactic acid produced by
polymerization of the dilactide derivative derived by self-esterification of the lactic acid.
Now, we will discuss how a PLA is also getting produced. Now lactic acid is commercially
produced by fermentation of biomass, starting typically, for example, from corn derived
glucose. Fermentation processes suffer from low productivity along with costly separation
and several purification steps.
That is the usual drawback of any fermentation process. Now lactic acid and alkyl lactates
can be catalytically, produced from lignocellulosic raw material, cellulose and sugars as well
1184
as from trioses which are intermediates formed from sugars. If water is used as solvent,lactic
acid is formed whereas in alcohol solvents lactates are generated.
Lactic acid has been catalytically produced using metal salts either under subcritical
conditions or at lower temperatures. Furthermore, strong alkali was used as a catalyst under
subcritical conditions in the production of the lactic acid. Several feedstocks has been applied
(for example) Lignocellulosic feedstock, cellulose, disaccharides as for example, sucrose,
monosaccharidic sugars, trioses, C2-containing glycolaldehyde, even glycerol.
Trioses, dihydroxyacetone and glyceraldehydes are formed via retro-aldol condensation from
sugars whereas glycolaldehyde is formed from the degradation of the glucose to C2 and C4
aldoses. Glycerol is a particularly interesting feedstock being a byproduct from the biodiesel
production with currently low value. There are a lot of discussion about how to convert
glycerin to a value-added products. We have already discussed it.
Now typically, lactic acid production in high yields is more demanding from the
lignocellulosic feedstock than from the sugars. Lactic acid has been produced directly from
the lignocellulosic biomass under subcritical water in the presence of homogeneous metal
ions. Under subcritical temperatures in the presence of metal ions, organic material is
dissolved, since water is ionized and act as a Bronsted acid.
1185
Cellulose transformations to lactic acid have been investigated using several types of
heterogeneous catalysts, zeolites, sulfonated carbon, sulfonated zirconia, tungstated alumina
and heteropolyacids. The reaction mechanism for formation of lactic acid from cellulose
proposed by Holm et al., consists of cellulose autoprotolysis to soluble oligomers in the first
step. Now, this implies that at 190 degrees centigrade the pKw of water, the ionization
constant of water, is low.
And thus due to autohydrolysis water acts as a Bronsted acid. Thereafter solid Lewis acid
sites interact with the C3 hydroxyl in the oligomeric glucose unit leading to dehydroxylation.
In the final step, the Lewis acid is cleaved away. Since high reaction temperatures and
pressures are needed for the cellulose transformation to lactic acid, the catalyst stability is a
very crucial factor.
Several carbohydrates and sugars have been transformed to lactic acid using either harsh
conditions with subcritical water or milder conditions and homogeneous metal salts as
catalysts.
1186
Lactic acid has also been produced from trioses either under hydrothermal conditions with
the aid of metal salts or alkali or alternatively using heterogeneous catalyst at lower
temperatures such as 140 degree centigrade. Trioses are intermediates in the production of
lactic acid from biomass formed during a retroaldol condensation of sugars. Hydrothermal
conditions in the presence of metal ions have been applied in the transformation of trioses to
lactic acid.
High yields of lactic acid were obtained also from the pyruvaldehyde under hydrothermal
conditions in the presence of metal ions. Heterogeneous catalysts are more attractive
compared to homogeneous ones (we have understood that, we have discussed why it is so)
from the industrial point of view. There are several heterogeneous catalysts which have been
reported to be efficient for the production of lactic acid from trioses, such as Sn-beta, Sn-Si-
CSM carbon mesoporous silica hybrid material and H-USY. Lactic acid formation from
glyceraldehyde which is an isomer of dihydroxyacetone is slower than from
dihydroxyacetone as the substrate when the yields of lactic acid within the same reaction time
are compared.
1187
Alkyl lactates have been produced using both homogeneous and heterogeneous catalysts. The
reaction involves dehydration of triose to pyruvaldehyde followed by esterfication of
pyruvaldehyde hemiacetal, which thereafter can form either methyl lactate or alternatively the
dimethyl acetal of pyruvaldehyde. Now lactic acid is an attractive raw material for its
conversion to various chemicals.
The primary classes of these reactions are hydrogenation, dehydrogenation, dehydration,

condensation, esterification, polymerization and substitution at the alcohol group. Lactic acid
serves as a highly attractive building block for the synthesis of such chemicals such as acrylic
acid, pyruvic acid, 2, 3-pentanedione, lactic acid esters and 1, 2-propanediol.
1188
So, now we will discuss about polylactic acid. The quality of the monomers of lactic acid and
lactide as well as the chemical changes induced during polymerization and processing are
crucial parameters for controlling the properties of the resulting PLA products. The recent
growing interest for the manufacture of the biodegradable plastic necessitates a high demand
for lactic acid as the raw material for PLA production.
Much research effort is currently focused on the modification of polylactide to make it

suitable for a wide range of applications. Optically pure lactic acid is necessary to obtain high
crystalline polylactic acid which leads to the high strength, chemical and heat resistance
properties of the polymer. So PLA is the first commodity polymer produced from annually
renewable sources.
PLA is a representative bio-based plastic that is used in packaging, stationary, containers, etc.
In addition, the utilization of the polyester has been expanded to medical field for drug
delivery, resorbable sutures, and as a material for medical implants and other related
applications.
The rate of degradation of PLA depends on the degree of crystallinity. As the lactide content
increases, the degradation of the graft polymer decreases. The PLA is a semi-crystalline
polymer with a glass transition temperature between 55 to 59 degrees centigrade and a
melting point of 170 to 180 degrees centigrade. It shows good mechanical stiffness, high
Young's modulus, thermal plasticity and has a good processability.
1189
PLAs are basically synthesized via three processes. Production of lactic acid by microbial
fermentation. Second, purification of lactic acid and preparation of its cyclic dimer that is
lactide. Then third polycondensation of lactic acid or ring-opening polymerization of lactides.
So, next figure shows the reaction mechanism for both the polycondensation of LA and the
ring-opening polymerization of lactides.
In direct condensation, a solvent is used and higher reaction times are required. The resulting
polymer is a material with low to intermediate molecular weights. Lactide is obtained by the
depolymerization of low molecular weight PLA under reduced pressure to give L-lactide, D-
lactide or meso-lactide.
So, let us understand what is this scheme basically. It is a schematic representation of the
PLA synthesis. We will start with the lactic acid. So, two routes have been shown here.
Condensation it gives low molecular weight prepolymer and upon addition of the chain
coupling agents it gives the high molecular weight PLA.
Another route is the lactic acid to condensation, then it gives the low molecular weight
prepolymer, upon depolymerization then it gives lactide - that is what we just discussed. Now
this lactide when you ring opening it; so undergo the ring-opening polymerization reaction it
gives 2 PLA, high molecular weight PLA.
1190
The different percentages of the lactide isomers formed depend on the lactic acid isomer
feedstock, temperature and catalyst. Polylactic acid can undergo cationic ring-opening
polymerization. It has been found that trifluoromethane sulfonic acid and methyl
trifluoromethane sulfonic acid are the only cationic initiators to polymerize lactide. The
polymerization proceeds via triflate ester end groups instead of the free carbenium ions which
yield at low temperatures an optically active polymer without racemization.
Now chain the growth proceeds by cleavage of the alkyloxygen bond. The propagation
mechanism begins with positively charged lactide ring being cleaved at alkyl-oxygen bond by
an SN2 attack by the triflate anion. The triflate end group reacts with the second molecule of
the lactide again in an SN2 fashion to yield a positively charged lactide that is opened. Then
the triflate anion again opens the charged lactide and polymerization proceeds.
1191
Anionic lactide polymerization proceed by nucleophilic reaction of the anion with the
carbonyl and the subsequent acyl-oxygen cleavage. This produces and alkoxide end group
which continues to propagate. Ring-opening polymerization of the lactide needs a catalyst but
it results in a PLA with a high molecular weight. Depending upon the monomer used and the
reaction conditions, it is possible to control the ratio and sequence of the D and L lactic acid
units in the final polymer, some sort of process optimization of the reaction conditions.
The ring-opening polymerization of the lactide can be carried out in melt or solution by
cationic, anionic and coordination mechanisms depending on the initiator utilized. The most
considered active initiator for the L-lactide ring-opening polymerization is the stannous
octoate which causes a low degree of racemization at high temperatures. It is catalyzed by
transition metals such as tin, aluminum, lead, zinc, bismuth, iron and yttrium.
1192
PLA is chemically synthesized by heavy metal catalyzed ring-opening polymerization of
lactide, which in turn is derived from fermentation lactate. However, the trace residues of the
heavy metal catalyst are unfavorable for certain applications, in particular medical and food
applications. For this purpose, enzymes are attractive targets because they are natural non-
harmful catalysts that can drive the reactions under mild conditions.
In addition, highly specific enzymatic reaction and/or whole cell systems bearing them may
be capable of synthesizing polymers with a fine structure from inexpensive raw materials.
The appropriate strategy would be the discovery of a PLA producing microorganism. There is
no information available on PLA production using natural strains. People are still working on
this particular aspect.
However, engineered strains have been used extensively for producing LA based polyesters.
In that case, the Lactobacillus strains could be useful in establishing the one step process for
the synthesis of the LA based polyesters.
1193
So with this, I conclude today's lecture. So in our next class, we will be discussing about
succinic acid, propionic acid, acetic acid and butyric acid. So thank you very much. In case
you have any query, please register in the Swayam portal or you can always drop a mail to
me at [email protected].
1194
Lecture – 32
Succinic Acid, Propionic Acid, Acetic Acid, Butyric Acid
Good morning students. Today is lecture is 2 under module 11. As you know that in this
module we are discussing the various organic commodity chemicals that can be produced
from biomass and in today's lecture will cover essentially three of them - succinic acid,
propionic acid and acetic acid as well as butyric acid. So, let us begin.
1195
First we will discuss about succinic acid. Succinic acid, a four carbon dicarboxylic acid is one
of the end products of anaerobic fermentation and is also an intermediate of that TCA cycle
that is tricarboxylic acid cycle. Now, various important chemicals including 1, 4-butanediol,
tetrahydrofuran, gamma butyrolactone, N-methyl-2-pyrrolidone and adipic acid can be
synthesized from succinic acid.
When the US Department of Energy identified succinic acid as one of the 12 promising
fundamental chemicals to be produced through biotechnology in 2004, it was suggested that
bio-based succinic acid will become competitive with the petrochemical process only if its
productivity approaches 2.4 grams per liter per hour. So, this is the target they have faced .
Because some sort of techno-economical evaluation they have carried out and found out that
if it is more than 2.5 grams per liter per hour the productivity of the succinic acid from the
biological materials then it will become competitive. A number of succinic acid producing
microorganisms have been isolated or developed together with the fermentation and recovery
systems.
Escherichia coli and natural succinic acid producers such as Anaerobiospirillum

succiniciproducens, Actinobacillus succinogenes, Mannheimia succiniciproducens have been
metabolically engineered to achieve higher yield and productivity.
Many available and cost-competitive carbon and nitrogen sources have been investigated for
each succinic acid producers for the efficiencies of growth and succinic acid production. In
1196
addition, various mixed and semipurified carbon and nitrogen sources including the cane
molasses, corn steep liquor, soybean floor, wood hydrolysate, yeast extract, polypeptone as
well as crude glycerol mostly from the biodiesel production industry have been examined for
succinic acid production.
In parallel with the development of the fermentation process of succinic acid production,
several different downstream processes for the separation and purification of succinic acid
from culture medium have also been investigated and developed. For example, ultrafiltration
was used widely for the removal of cells and cell debris as an initial separation step.
If you recall even our yesterday's discussion, I was giving a more emphasis that when we
produce certain commodity chemicals using the biotechnological routes and even
thermochemical routes also, once they are produced, they will be mostly in the aqueous
phase. Then you have to carry out the downstream separation part that means that is basically
purification.
So, usually 7%, 10%, 15 to 20% will be the initial concentration of the commodity chemicals
in the fermentation broth or in the aqueous medium when you talk about thermochemical
conversion. So, you need to purify it up to 70%, 80% so that you can use it as a bulk
commodity chemical. So, here that is the catch. So, the downstream processing part is
supposed to be very costly, still it is very costly.
With the invention of membrane and all these things process cost is coming down slowly and
more work is yet to be done and people are doing day and night so much of research on this
particular aspect that how to develop low cost as well as sustainably economical downstream
processing part for purification of commodity chemicals once they are produced. Membrane
has been tried a lot.
Apart from membrane there are other processes and we have also discussed that how hybrid
processes has also been taken into account and had been successful for certain chemical
purification. So additional steps in the downstream processes including precipitation, reactive
extraction and electrodialysis have been developed to selectively separate succinic acid from
the fermentation mixture. Ion exchange and crystallization procedures were adapted to further
purify and crystallize succinic acid.
1197
We will talk about some of the carbon sources from where succinic acid can be produced.
Various kinds of carbohydrates are metabolized to succinic acid by diverse succinic acid
producers. A. succiniciproducens is able to catabolize several carbohydrates that include
glucose, sucrose, fructose, lactose, soluble starches as well as corn syrups while M.
succiniciproducens can utilize sucrose, fructose, lactose, xylose, maltose, mannitol and
arabitol as efficiently as glucose.
Now moreover, many kinds of carbohydrates including glucose, sucrose, fructose, lactose,
arabinose, galactose, maltose, mannitol, mannose, xylose. soluble starches and corn syrups
can be used for succinic acid production by A. succinogenes. Further more reduced carbon
sources such as glycerol can be utilized by A. succiniciproducens and M. succiniciproducens.
1198
In the fed-batch fermentation of A. succiniciproducens with glycerol as the carbon source,
high succinic acid yield of 1.6 gram was achieved with the low accumulation byproducts.
Now in the same manner by using the sorbitol as a carbon source, succinic acid yield was
increased compared to glucose using E.coli. The reason is that glycerol and sorbitol are more
reduced than glucose and provides more reducing power.
In another study employing carbohydrates using a transport system other than the
phosphotransferase system was demonstrated to increase the succinic acid yield because
more carbon flux could be directed towards the oxaloacetate formation at the PEP node. In
addition, co fermentation of fructose, xylose or galactose with glucose was studied for E. coli
as well as A. succiniciproducens by various researchers.
Some of the references are given. If you are interested to learn more, you can please browse
through these particular references, these are classical works.
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Instead of employing purified carbohydrates as carbon sources, some cost-effective
feedstocks such as wood hydrolysates, cane molasses, cheese whey and straw hydrolysates
have been used for bio-based succinic acid production. In 2000 and 2003, Lee et al
investigated anaerobic fermentation process for succinic acid production from whey and
wood hydrolysates by A. succiniciproducens.
In the batch fermentation with 20 grams per liter of non-treated whey and 7 grams per liter of
glucose, the yield and productivity of succinic acid of 0.95 gram per gram and 0.46 gram per
liter per hour respectively were obtained. When wood hydrolysate that is almost equivalent to
27 grams per liter of glucose was used as carbon source, the succinic acid yield of 0.88 grams
per gram was obtained.
So, what you can see from this particular slide is that the succinic acid which is being
reported is extremely low when you talk about the 2.5 grams per liter per hour productivity.
However, these are classical works which has led a new path or you can say opened up new
avenues to work on bio-based succinic acid production whereas we are now using genetically
engineered strains to increase the yield as well as productivity.
In the case of M. succinicproducens, whey and wood hydrolyzates-based medium were

utilized as economical carbon sources to produce succinic acid. So very important 2 papers
which are given below you can browse through them if you want to learn more. They are
excellent work in this particular field.
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Then using corn steep liquor containing whey-based medium, the succinic acid yield of 0.71
gram per gram and productivity of 1.18 grams per liter per hour was obtained in batch
fermentation. Now, this is batch fermentation. Of course, when you talk about batch
fermentation and compare with continuous one it is always less, but it has its own
advantages.
Now, continuous fermentation resulted in succinic acid yield of 0.69 grams per gram and
productivity of 3.9 grams per liter per hour You have just notice that the productivity is
almost a double, 1.18 to 3.9 - when we go for batch to continuous fermentaion mode. Now by
using wood hydrolysates based medium, the succinic acid yield 0.56 per gram and a
productivity of 1.17 gram per liter per hour were obtained in batch fermentation and 0.55 per
gram and 3.19 grams per liter obtained in continuous fermentation.
Again you see that from 1.17 to almost double 3.19 gram per liter per hour the productivity
has enhanced when we went for continuous fermentation using the wood hydrolysates. So,
various studies utilizing the inexpensive carbon sources such as corn fiber hydrolysates, cane
molasses, cheese whey, wheat milling byproducts and straw hydrolysates by A. succinogenes
have been carried out to examine the possibility for cost-effective succinic acid production.
You will see that there are many, I could not report here also, just those which are very
important results we have listed here. So, much of work you will see from succinic acid
production using two very different approaches. First different types of low cost biomass.
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Either it is low cost or it is almost no cost, just like waste only you have to segregate and then
little preprocessing and then you can use it.
Second using different types of strains. Mixed strains have also been reported. Then
genetically engineered strains have been reported. So, these are the two ways on which most
of the succinic acid production research has been carried out.
Now let us talk about propionic acid. Propionic acid is a colorless naturally occurring
carboxylic acid with a slightly unpleasant odor. It is soluble in water, organic solvents as well
as alcohols. As a speciality chemical, propionic acid is mainly used as a preservative in food
and grains about almost 52% of what is being produced worldwide, bakery and dairy
products 18% and in herbicide 16%, cellulose acetate propionate, another classical
commodity chemical 10%. Now, sodium propionate can also be used in treating dermatoses,
wound infection and conjunctivitis. In addition, esters of propionate are used in artificial fruit
flavors as for example citronellyl and geranyl propionate and of course in plasticizers as for
example glycerol tripropionate and phenyl propionate.
Propionate esters are also good substitutes for volatile solvents such as xylenes and certain
ketones classified as hazardous air pollutants. In the past 10 years, the US market for
propionic acid continue to grow at an annual rate of 2.3% with a sale price reaching 0.92 to
0.97 dollar per pound in 2009.
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Current industrial production our propionic acid is mainly through the petrochemical process.
Mostly it is from ethylene, carbon monoxide and steam which is the Reppe process or ethanol
and carbon monoxide which is the well-known Larson process. And of course, both are
carried out in the presence of catalysts. Now, due to the non-renewable feedstocks derived
from the increasingly expensive crude oil and environmental concerns of the petrochemical
processes, there is a great interest in producing bio-based propionic acid via fermentation
using the propionibacteria, which are widely used in industry for the manufacturing of the
Swiss cheese and vitamin B12. Propionic acid fermentation using renewable biomass such as
agricultural residues and industrial wastes as feedstock is sustainable and environmentally
friendly. The bio-based propionic acid is also more appealing to the consumers for uses in
foods and cosmetics.
However, conventional propionic acid fermentation is uneconomical due to the low

productivity yield. It is very low 0.5 grams per gram and the productivity is also less than 1
gram per liter per hour and product concentration which is less than 40 grams per liter caused
by the end-product inhibition.
1203
So let us talk about some of the propionic acid bacteria which are being used by various
researchers even in the commercial scale to produce propionic acid. Many bacteria are
capable of producing propionic acid. I am just showing you the table 1. You can see here.
Here are some propionic acid producing bacteria and then general characteristics are given,
we will come back to it later. Among them, Propionibacterium can produce propionic acid as
the major product in that dicarboxylic acid pathway.
Figure 1, I will show you again what is this dicarboxylic pathway the first one and then
acrylic acid pathway of the Clostridium species. Anyway, we will come back to it. And is the
most widely used genus for the propionic acid fermentation. Another species of interest is
that Clostridium propionicum which can ferment lactate, alanine, serine and threonine to
produce propionic acid and acetic acids via the acrylic acid pathway.
The second pathway, we will go to that. Some species in the genera of Bacteriodes,
Fusobacterium, Megasphaera, Selenomonas and Veillonella can also produce propionic acid
but not all of them can use sugar or carbohydrate as carbon source. So far, propionic acid
fermentation research has focused on Propionibacterium because of their better fermentation
performance and broader substrate spectrum compared to other genera.
1204
Yes, this is the table 1. Please have a close look at this table. You can see that, what are the
different types of the species of (bacteria) that are being used to produce propionic acid.
Whether they are gram positive or gram negative? What are the substrates they could
degrade? What are the products? What are the optimum pH and temperature? So we will just
go, one or two I will just tell you, rest you can see later on when you go through the lecture.
The first is the Propionibacterium acidipropionici and the class of propionibacterium species.
So, they are gram positive stains. They can degrade various types of substrate whether it is
glucose, sucrose, lactose, lactate, even glycerol also. Now the product is propionate, acetate,
succinate and carbon dioxide, of course at different proportions. Optimum pH is 6.5 to 7.
Optimum temperature is 30 to 32.
So, if you look at some other one, let us say the last one the Fusobacterium necrophorum. It
is a gram negative bacteria and it will only degrade lactate. It is a lactate based bacteria which
will produce propionic acid. The end products are acetate, propionate and butyrate, again at
different proportions, pH has to be maintained at less than 7.5 that is the optimum and
temperature is slightly higher it is 39. Now, there are others also, you can go through it later
on.
1205
This, I showed you a few minutes before. So, this is the classical propionic acid fermentation
pathway, basically 2 different pathways. First is the dicarboxylic acid pathway of the
Propionibacteria. Second is the acrylic acid pathway of the Clostridium species, Clostridium
propionicum. So, let us try to understand what is happening in that dicarboxylic acid pathway
of the Propionibacteria.
So, you can see that here the substrate is glucose, it can be something else also. So, glucose is
getting converted to 3 phosphoenopyruvate, it is a pyruvate cycle again. Then it is finally
degraded to pyruvate. Now, this pyruvate can result in three different products, again using
different pathways. Now, when you talk about this particular pathway where the acetyl
coenzyme A is getting produced, you remember this we have discussed during fermentation
also, a little different right? So, this pathway we have discussed. Now that gives an
intermediate product which is called a Acetylphosphate and that finally being degraded to
end product which is a acetate. Now, similarly pyruvate can go through a 2 different other
pathways. So, one is that oxaloacetate pathway, one is the methymalonyl coenzyme A
pathway.
So, if you go through methymalonyl coenzyme pathway it will give you succinyl coenzyme
A and finally 2 succinate. And here also if you talk about methynyl coenzyme A, it will go to
the propionyl coenzyme A and 2 propionate. Now, 2 methymalonyl coenzyme A is also
coming partly from the 2 succinate. Now, this 2 succinate is also getting converted in a
backward cycle to 2 succinyl coenzyme A and then methymalonyl coenzyme A.
1206
And if you look at the oxaloacetate pathway, so it gets converted to malate, fumarate. Now,
this fumarate is getting converted to succinate. So, this is your dicarboxylic acid pathway of
the Propionibacterium.
Now, let us talk about the acrylic acid pathway of the Clostridium species. Now here you can
see that if we start with alanine. So alanine is getting converted to pyruvate. Now pyruvate to
acetyl coenzyme A, acetyl coenzyme A to acetylphosphate, acetylphosphate to acetate. Now
pyruvate to lactate. Lactate is getting converted to lactyl coenzyme A, then acrylyl coenzyme
A, then propionyl coenzyme A and finally propionate. So, these are the 2 major pathways to
produce the propionic acid.
So, propionic acid production from the renewable feedstocks. We will try to understand what
are the biomases that are being used. As the raw material cost usually accounts for a major
portion of the final product cost in fermentation production of the oxychemicals including
propionic acid, it is important to use inexpensive or low cost feedstock for a propionic acid
fermentation to make it more favorable to compete with the chemical synthesis route.
There are a large amounts of wastes or byproducts generated from food, agricultural and
other industries including cheese whey from the dairy industry, cane molasses and sugarcane
bagasse from the sugar industry, corn fiber and CSL (corn steep liquor basically) from the
corn milling industry and glycerol from the biodiesel industry which may be used as low cost
feedstock for fermentation process.
1207
Now, these wastes containing fermentable sugars or carbon sources have low value but high
biochemical oxygen demand and chemical oxygen demand, the BOD and COD, posing an
environmental threat if they are not treated properly. So it is something you can say that
waste to value-added products.
Thus, the application of these low-cost and renewable wastes as an alternative feedstock to
produce value-added chemicals such as propionic acid has attracted large interest from both
industry as well as academia. Some fermentation studies using low-cost biomass feedstock
are summarized in the table 2. So, you can see that the different types of substrates here,
processes, the titer, the productivity, the yield and the respective references. Now, this table
has been taken from this particular reference, you can browse through later on. So let us just
see one or two.
Whey permeate: Recycle-batch with fluidized bed process. So, the titer is 65 grams per liter,
productivity is 0.2 to 0.68. It is of course less compared to the theoretical one. Yield is 0.5
grams per gram. Similarly, if you go to corn meal, this is a batch process with again a
fluidized bed operation. The titer is 40 grams per liter, however the productivity is higher in
this case 2.12 grams per liter per hour and the yield is 0.58 gram per gram. Similarly, if you
look at some other things you can see Jerusalem artichoke, a lot of work has been done on
this, sugarcane bagasse, glycerol, then glycerol and potato juice and respective productivities
as well as the yield.
1208
The US dairy industry annually generated more than 80 million tons of whey as a byproduct
from the cheese manufacturing process. The main components of cheese whey are whey
protein and whey lactose, which makes up to about 75% of the whey total solids and are
currently in a large surplus with limited uses. Propionic acid production from whey lactose
and whey permeate by Propionibacteria has been extensively investigated.
In general, high productivity 0.22 to 0.68 grams per liter per hour and yield a 0.5 grams per
gram lactose with a high propionic acid concentration of 65 gram per liter can be obtained
from the concentrated whey permeate. Calcium propionate produced from whey can be used
as a natural preservative in bakery and dairy products.
1209
Corn fiber and corn steep liquor are two low-value byproducts from the corn wet milling
industry. They are currently used mainly for the animal feed purposes but with the large
surplus because of the rapid expansion of the corn ethanol industry in recent years, they are
being unused. Corn steep liquor is rich in amino acids and trace elements just like some of the
metal ions and vitamins and is a good nitrogen and nutrients source for industrial
fermentation.
A high final titer of propionic acid, almost 46 grams per liter, has been reported by using corn
steep liquor medium in a continuous Propionibacteria fermentation. In another study, Huang
et al reported a high yield and high productivity almost 2.12 grams per liter per hour of
propionic acid in a recycle batch fermentation process using the hydrolyzed corn meal as
substrate.
Molasses is a byproduct of the sugar refining industry and its major component is sucrose,
glucose and fructose. Propionibacterium is capable of converting all these three sugars into
propionic acid.
A propionic acid fermentation process with non-treated or hydrolyzed molasses as carbon

source reached a high propionic acid concentration of 92 grams per liter with a yield of 0.46
gram per gram and a productivity of 0.36 gram per liter per hour as reported by Feng et all in
2011. Respective references are given below, if you wish you can browse through them later
on.
1210
Sugarcane bagasse is another cheap and abundant byproduct of sugar refining, which can be
hydrolyzed into glucose and xylose and then used as carbon source for propionic acid
production achieving a titer of 51 gram per liter, yield of 0.43 gram per gram and a
productivity of 0.71 gram per liter per hour. Corncob molasses, a hemicellulose hydrolysate
containing glucose, xylose and arabinose was used as a carbon source from the P.
acidipropionici.
Now the three sugars in the corncob molasses are simultaneously converted to a propionic
acid titer of 71.8 grams per liter with the productivity of 0.28 grams per liter per hour in a
fed-batch fermentation system with an initial cell density of 14.8 gram per liter. I think you
can recall that we have discussed about what is a batch process, what is the fed-batch process,
what is a continuous process. So, fed-batch process has its own advantages, the productivity
actually increases.
In addition to the above food crop residues, non-food crops can also be used as low-cost
biomass feedstock in the biorefineries. For example, Jerusalem artichoke hydrolysate
containing mainly fructose was also used for propionic acid fermentation achieving a final
titer of 68.5 grams per liter, yield of 0.48 grams per gram and a productivity of 1.55 grams
per liter per hour.
In addition to the agricultural and food processing wastes mentioned above, crude glycerol as
a low-value byproduct from biodiesel production has also become an attractive substrate for
propionic acid fermentation. Glycerol has a higher reduction level compared to glucose,
1211
sucrose and lactate and is thus beneficial to intracellular redox balance and propionic acid
production. In general, a high P/A ratio of greater than 10 to 20 can be obtained with glycerol
in propionic acid fermentation.
High propionic acid production of 106 gram per liter was obtained in immobilized-cell
fermentation in a fibrous bed bioreactor with glycerol as sole carbon source. The
fermentation performance with crude glycerol was comparable to that with pure glycerol
indicating Propionibacteria was not inhibited by the impurity components such as methanol,
fatty acids and salts present in the biodiesel wastes.
So, this is the best part of this particular research work that is reported by Zhang and Yang
and the reference is given below. Himmi et al in 2000 reported a propionic acid yield of 0.64
per gram per gram and a productivity of 0.42 gram per liter per hour from glycerol with P.
acidipropionici ATCC 25562 strain. Ruhal and Choudhary also reported the production of
propionic acid and trehalose using the P. freudenreichii subspecies shermanii and crude
glycerol from the biodiesel waste.
1212
Liu et al in 2011 reported propionic acid yield and productivity 0.57 gram per gram and 0.15
gram per liter per hour respectively from the mixture of glycerol and glucose at a mass ratio
of 2 with P. acidipropionici ATCC 4965. So it is a very important work in which actually
they used two different types of substrates as a carbon source - a mixture of glycerol as well
as glucose.
Although free-cell fermentation of glycerol usually suffered from low productivity due to the
in vivo NADH imbalance, a notably high productivity of 1.44 gram per liter per hour was
reached by continuous fermentation with immobilized cells. So, what is being done and
reported by Dishisha et al is that, to balance the NADH inside the fermentation media, they
have gone for the continuous fermentation process with the immobilized cells of the
propionic acid bacteria.
So, in summary abundant low-cost renewable feedstocks are available for propionic acid
fermentation and they offer an opportunity to reduce the cost of the bio-based propionic acid.
1213
So, now we will discuss about the acetic acid, another very important commodity chemical
and that is being now manufactured in a large scale from different biomasses. Acetic acid is a
colorless and weak organic acid with sour taste and pungent smell. Acetic acid is an
important raw material in the chemical industry. The largest industrial application of acetic
acid consists of the production of the vinyl acetate monomer, acetic anhydride and various
esters.
Acetic acid is also used as a solvent in chemical reactions such as the production of
terephthalic acid, the raw material for the polyethylene terephthalate. The global demand for
acetic acid is around 6.5 million tons per year of which approximately 1.5 million tonne per
year is recycled, the remainder is manufactured from petrochemical feedstock or from
biological sources.
The biological sources of course it is less than that of the petroleum or chemical stock, but as
we have discussed it has to increase. So, about 75% of the acetic acid in the chemical
industry is produced by carbonylation of methanol with carbon monoxide, the chemical
pathway, chemical process. Only about 10% of acetic acid is only produced by the
fermentation mainly as vinegar.
1214
So, let us talk about the microbial production of the acetate. Acetic acid is produced naturally
as the sole or main fermentation product by anaerobic homeacetogens and aerobic acetic acid
bacteria. Acetic acid bacteria content 12 genera belonging to the family Acetobacteraceae.
They are aerobic, gram-negative or gram-variable and ellipsoidal to rod-shaped microbes
which oxidize ethanol to acetate in aerobic vinegar fermentation.
A high acetate concentration of up to 20% weight by volume can be obtained in aerobic

vinegar fermentation with about 60% weight by weight yield from sugar. The process
generally involves 2 steps. The first one is that fermentation of sugar to ethanol by yeasts
such as Saccharomyces cerevisiae and Kluyveromyces fragilis and second step is oxidation of
ethanol to acetic acid by the species of Acetobacter.
In contrast, anaerobic homoacetogens produce only acetate from sugar at a theoretical yield
of 3 mol of acetate per mole of glucose with an actual fermentation yield of higher than 85%
weight by weight.
1215
So table 3 has listed the different types of homoacetogens and their optimal growth
conditions and the respective substrates they could degrade to produce acetic acid. So we will
go through one or two. So Clostridium thermoaceticum. So it can degrade fructose, pyruvate,
glucose, xylose, lactate, even carbon dioxide and hydrogen. So, the optimal conditions is
around 60 degrees centigrade and the pH is 7.
Similarly, there are many Clostridium aceticum, Clostridium formicoaceticum, Clostridium

magnum. So all those can again degrade fructose, pyruvate, pectin, lactate, then malate,
xylose, citrate all these things and their respective optimal conditions are also given. So, just
we can understand that there are many different types of microorganisms are there and they
are also efficient enough to degrade various types of subtrate at a particular optimal
condition.
1216
Now, we will talk about butyric acid. So, butyric acid is a four carbon carboxylic acid present
as an oily colorless liquid that is soluble in water, ethanol and ether. Butyric acid has an
unpleasant smell and acidic taste. It is naturally found in butter, parmesan cheese, vomit and
as a product of some anaerobic fermentation. Butyric acid and its derivatives have been
widely used in food, chemical and pharmaceutical industries.
The acidic form is used to enhance the butter like flavor in food and the ester form can serve
as a flavor in the food and perfume. Butyric acid can also be used to synthesize cellulose
butyrate plastics for the textile fiber production. As butyrate can provide protection against
colon cancer and colitis, various butyrate derivatives are considered as antineoplastic drugs
for treating hemoglobinopathies, cancer and gastrointestinal diseases. It has a wide medicinal
application.
1217
Butyric acid producing anaerobic bacteria have also been proposed as a novel probiotic
treatment for inflammatory bowel disease. Moreover, acids produced from a fermentation
process are more favorable than chemically synthesized counterparts for applications in food
and pharmaceutical industries. There are many bacterial strains producing butyric acid which
belong to the genera Clostridium, Butyribacterium, Butyrivibrio, Sarcina, Eubacterium,
Fusobacterium, Megasphera, Roseburia, and Coprococcus.
The genera Clostridium, Butyribacterium and Butyrivibrio are the most studied butyric acid
producing microorganisms. However, the preferred strains for potential commercial uses are
in the genus Clostridium. The reason is that they have high and stable productivity
performance. The next table gives us the butyrate producing Clostridium species with their
substrates and the fermentation products. They are gram-positive, chemo-organotrophic, strict
anaerobes and spore formers.
1218
You can see that various types of Clostridium species producing butyrate as the major
product, we will just see one or two. The first one Clostridium aminobutyricum. So gamma
aminobutyrate is the substrate. The products are acetate, butyrate and ammonia. Similarly, if
you will come down and see Clostridium barkeri, so it can degrade glucose, fructose, ribose,
mannitol, pyruvate and finally produce butyrate, acetate, lactate, propionate and hydrogen.
So, there are many others also there. So you can later on go through it and have a feeling that
what are the different types of Clostridium species have been used to produce various
products such as acetate, butyrate from different types of substrates.
Most butyric acid producing clostridia ferment glucose, xylose, lactose, starch and glycerol
for the cell growth and butyric acid production. Other substrates such as cellulose and carbon
1219
dioxide can also be used for butyrate production, Clostridium carboxidivorans and
Butyribacterium methylotrophicum can utilize carbon monoxide and carbon dioxide and
hydrogen to produce butyric acid.
Clostridium cellulovorans, then Clostridium carboxidivorans, Clostridium

polysaccharolyticum and Clostridium populeti can use cellulose for butyrate synthesis.
Similarly, Clostridium kluyveri can produce butyric acid as a major product from ethanol and
acetate as substrates. Most Clostridium species produce butyrate and acetate along with
additional products such as ethanol and lactate, but they are in very low concentration.
Some Clostridium species such as Clostridium acetobutylicum, Clostridium saccharolyticum,

and Clostridium thermocellum can be manipulated to form either solvents or acids as the
main product depending on the culture conditions. Several species including Clostridium
butyricum, Clostridium tyrobutyricum and Clostridium thermobutyricum can produce
butyrate as the main product with a relatively high productivity and yield and they are thus of
high interest for potential industrial production of butyrate.
The optimal temperature and pH for the Clostridium butyricum and Clostridium
tyrobutyricum are 30 to 37 degrees centigrade and 4.5 to 7 respectively. Clostridium
thermobutyricum is a moderate thermophile with the optimal growth temperature of 55
degrees centigrade and a pH of 7. Clostridium butyricum is classified into non-toxigenic and
toxigenic species. Only non-toxigenic C. butyricum can be used for butyric acid production.
1220
Butyric acid bacteria can use a wide variety of carbon sources. To date, various feedstocks
have been studied for butyric acid production by fermentation. It is presented in table 5, we
will come back to it later. So butyric acid production from cheese whey, a byproduct from the
cheese manufacturing containing mainly lactose and whey protein by Clostridium beijerinckii
at pH 5 gave a final concentration of 12 grams per liter (it is a very good concentration
actually), yield of 0.25 gram per gram and a productivity a 0.6 gram per liter per hour.
Cane molasses, a byproduct of the sugar industry containing approximately 45 to 50% weight
by weight total sugars was used as substrate to produce 26.2 grams per liter butyric acid with
a yield of 0.47 gram per gram and a productivity of 4.13 grams per liter per hour, it is a very
good productivity.
Corn meal after hydrolysis of starch with amylases was used for butyric acid production by
Clostridium tyrobutyricum immobilized in an FBB at 37 degrees centigrade, pH 6 giving a
high butyric acid productivity of 6.78 grams per liter per hour and a yield of 0.45 gram per
gram and a final concentration of 46 gram per liter.
1221
Yes, so we can go through this table which lists some of the butyric acid production from
different substrates, the strains, the concentration, productivity and yield. Let us see the
cheese whey by using the Clostridium beijerinckii. So, the concentration is 12 grams per liter,
productivity is 0.6 gram per liter per hour, yield is 0.25 grams per gram. So, if you look at the
third one the cane molasses using the Clostridium tyrobutyricum you can see the
concentration is 26.2, productivity has increased many fold 4.13. Similarly, if you look at
cornmeal, again the same Clostridium species, you can see that productivity has increased
many fold again 6.78 grams per liter per hour. So, these are some of the classical works that
are reported by various authors and the main references given here Yang et al. So, you can
browse it if you are interested more in detail. So, let us move ahead.
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So, butyric acid production from wheat flour gave a high final butyric acid concentration of
62.8 grams per liter, productivity of 1.25 grams per liter per hour and a yield of 0.45 gram per
gram of glucose. Jerusalem artichoke after treating with dilute acid to hydrolyze its
carbohydrate, mainly inulin, to fructose and glucose was used for butyric acid production in
repeated batch fermentations.
The butyric acid productivity, yield and final concentration from the fermentation were 2.75
grams per litre per hour, 0.44 gram per gram and 27.5 grams per liter respectively. Most of
the Clostridial species are also capable of fermenting pentose such as xylose. Butyric acid
fermentation with corn fiber hydrolysate containing glucose, xylose and arabinose as the
carbon source and corn steep liquor as the nitrogen source gave a high butyrate yield of 0.47
gram per gram and the productivity of 2.91 gram per liter per hour.
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In addition, butyric acid production from brown algae treated with dilute sulfuric acid for
hydrolysis of its polysaccharides mainly the galactan have also been studied. It is also a very
classical work. These studies demonstrated that butyric acid can be produced from various
biomasses including processing waste and agricultural residues. However, further
improvements in the fermentation processes are needed for economic production of the bio-
butyric acid.
So with this, I wind up today's lecture. If you have any query, please register it in the
Swayam portal or you can always drop a mail to me at [email protected]. In our next
lecture under this module, we will be discussing about 2-3 more such commodity chemicals;
1, 3-propanediol, 2, 3-butanediol and the PHA. Thank you very much.
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Lecture – 33
1, 3-Propanediol, 2, 3-Butanediol, PHA
Good morning students. This is lecture 3 under module 11. As you know, we are discussing
about the commodity chemicals from biomass. Today, we will discuss about precisely 3 very
important commodity chemicals: 1, 3-Propanediol, 2, 3-Butanediol and then PHA. So, let us
begin.
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We will start our discussion about 1, 3-Propanediol. 1, 3-Propanediol can be used as an
essential monomer to synthesize a new type of polyester that is polytrimethylene
terephthalate (very well known as PTT), and as an ingredient in other polymers, cosmetics,
foods, lubricants and medicines. 1, 3-Propanediol is a 3 carbon diol with hydroxyl groups at 1
and 3 carbon positions, that is why the name is 1, 3-Propanediol. It is one of the oldest known
fermentation products described as early as 1881 by August Freund in the glycerol-
fermenting anaerobic culture containing Clostridium pasteurianum.
Having two functional groups, 1, 3-Propanediol is a high-value speciality chemical in

polymer synthesis, in particular as a monomer for polyesters, polyethers and polyurethanes.
For instance, polyester associated with 1, 3-Propanediol exhibits unique features such as the
elastic recovery of nylon and superior stretching which are difficult to obtain from other
glycerol based products.
1, 3-Propanediol has been produced mainly from petroleum derivatives such as acrolein,
using hydration and hydrogenation catalytic reactions (the well known Degussa-DuPont
route) and ethylene oxide using the hydroformylation and hydrogenation catalytic reactions
(the well known Shell route). Now, in addition to the chemical catalytic processes DuPont
and its collaborator Genencor International have developed the glucose to 1, 3-Propanediol
biological process after an extensive effort was undertaken to make metabolically engineered
Escherichia coli. So, Genencor is a well known company which manufactures different types
of enzymes. So, what they have done is that they have metabolically engineered the E. coli
and both DuPont and Genecor have developed the process of making 1, 3-Propanediol using
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a biological route from glucose. Considering problems with the conventional chemical
process for the 1, 3-propanediol production (so those are petroleum based material for
sources, high pressure and temperature in processes as well as environmental aspects caused
by the toxic chemicals and the intermediates), the fermentation based 1, 3-Propanediol
production as an economically competitive chemical process has been recognized as one of
the novel biological processes representing a paradigm shift from the petroleum products to
biomass based renewable products.
So, this is actually true for all other chemicals which we have been discussing since last 2
classes that due to the problem, mostly environmental problems, then the depletion of the
fossil based resources there is a need to look for biomass based platform to develop or
produce such platform and commodity chemicals.
So, considerable attention has been paid to 1, 3-Propanediol production other than from
glucose, especially glycerol because it is a huge amount as we have been discussing many
times and you will recall that glycerol is one of the most important byproducts from the
biodiesel processing unit. Only 10% has been used for some value addition, rest is a waste.
So there is a huge demand to make the glycerol as a value-added product.
So a large amount of raw glycerol is generated in the range of almost 10% weight by weight
of biodiesel during the production of biodiesel. Unlike the chemical conversion of glycerol to
1, 3-Propanediol, the biological conversion of glycerol to 1, 3-Propanediol is an
environmental friendly and economical process due to the low energy requirement with mild
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reaction conditions compared to that of chemical processes because in chemical processes
you go for high temperature, pressure.
And there is also a higher yield of 1, 3-Propanediol than that is achieved via the chemical
reaction; that can be one of the most significant result of this biological route. Now, 1, 3-
Propanediol can be produced naturally under anaerobic as well as microaerobic conditions by
various microorganisms including the genera Klebsiella, then Clostridia, Enterobacter,
Citrobacter and Lactobacilli group.
Now, this is the classical general metabolic pathway of the glycerol degredation. So, we can
see how it actually happens. So, we can start with glycerol there. So, this is the usual route to
produce butanol, acetate, ethanol, etc. from the glycerol. Now if we go for a dehydration
reaction, then glycerol will result in 3-hydroxypropionaldehyde and that upon degradation
will give us 1, 3-Pripanediol, this is the route.
Now, this is the standard route of metabolic pathway through which we get many different
types of products. So, glycerol is getting converted to phosphoenolpyruvate then to pyruvate
using these particular steps. Then pyruvate to lactate, otherwise pyruvate straightaway to
acetyl coenzyme A. Similar thing we have discussed during our fermentation pathway
discussion. Now acetyl coenzyme A again goes back to acetoactyl coenzyme A.
And this pathway will give us n-Butanol as well as Butyrate. Now acetyl coenzyme A also
can be converted to acetate and acetaldehyde to ethanol. This is the usual route for the
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eternal. Now pyruvate also can convert to acetoin and 2, 3-Butanediol. So, I hope you will
understand that with glycerol itself only we are getting so many different types of products.
But having said that please note that all these products whatever components, the chemicals
that is being generated are produced from glycerol using this metabolic pathway are not in
sufficient quantity. So, their concentrations will vary and some will be in higher
concentration, some will be extremely low concentration that it is very difficult to purify.
Now having said that metabolic pathway can also be engineered in such a way that you can
target to produce 1, 3-Propanediol if you suppress this particular route.
Those technologies are already established and it has been done. Suppose you do not want 1,
3-Propanediol you can directly suppress this, you can go for any one of these. If you suppose
you want ethanol, we can try to suppress this particular route. There will be some production
of n-Butanol and butyrate, but we need to suppress the route. Similarly, any one of the
product.
So in addition to 1, 3-Propanediol, the genera Klebsiella can produce ethanol, 2, 3-

Butanediol, acetate and Clostridia can produce butanol, butyrate, ethanol and acetate. Now,
we just saw that from glycerol we can get so many different products, but what are the
products and all that again depends upon the type of species that you are using. The best
known 1, 3-Propanediol producing wild-type bacteria to date belongs to the genera Klebsiella
and Clostridium because of the high tolerance to 1, 3-Propanediol and their high yields and
productivity. So other bacteria such as Clostridium freundii, Lactobacillius brevis,
Clostridium pasteurianum can also produce 1, 3-Propanediol but at relatively low
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concentrations as well as low productivity. There are two important enzymes involved in the
1, 3-Propanediol synthesis in Klebsiella pneumoniae, so one is glycerol dehydratase which is
written as GDHt. So it is vitamin B12 mediated dehydration that is the route converting
glycerol to 3-hydroxypropionaldehyde.
And then the next enzyme is 1, 3-Propanediol oxidoreductase/PDOR. What it does? It

reduces 3-hydroxy propionaldehyde to 1, 3-Propanediol subsequent steps. Now, the
accumulation of the 3-hydroxypropionaldehyde, a microbial precursor of the 1, 3-Propanediol
has been known to inhibit 1, 3-Propanediol production because of the toxic effects.
Now the next class of the commodity chemical is 2, 3-Butanediol. 2, 3-Butanediol is also of
commercial interest as an anti-freezing agent due to its low freezing point and as a feedstock
for the formation of methyl ethyl ketone by dehydration, which can be used as a liquid fuel
additive. 2, 3-Butanediol is a 4-carbon diol with hydroxyl groups at 2 and 3 carbon positions.
This compound is also known as 2, 3-butylene glycol, 2, 3-dihydroxybutane or

dimethylethylene glycol. Now, 2, 3-Butanediol has a high boiling point of 177 degrees
centigrade and a low freezing point of –60 degrees centigrade, so the levoform of 2, 3-
Butanediol and basically, and is a promising anti-freezing agent. Now, there are 3 different
stereoisomeric forms of 2, 3-Butanediol, one(L)plus, d minus and a mesoform.
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So, you can see this. These are the 3 different forms. So, this form is that 2, 3-Butanediol, it is
the levorotatary form. And this is L+ 2, 3-Butanediol, this is dextrorotatory form. And this is
the optically inactive form.
2, 3-Butanediol is an industrially useful chemical with numerous applications in the

manufacture of printing inks, synthetic perfumes, softening and moistening agents, a solvent
resins and lacquers and a carrier for drugs and pharmaceuticals. Furthermore, the derivatives
of 2, 3-Butanediol such as methyl ethyl ketone and 1, 3-butadiene have attracted much
attention recently.
Because those chemicals which are now produced by a petroleum refinery process can be
produced from biologically produced 2, 3-Butanediol. Methyl ethyl ketone can be produced
from 2, 3-Butanediol by dehydration. It is a simple process and it can be used as an effective
fuel additive because of a higher heat of combustion than ethanol. An interest in 1, 3-
butadiene production from 2, 3-Butanediol increased significantly during World War 2.
Because 1, 3-butadiene is an essential monomer for synthetic rubber. In addition, 1, 3-

butadiene can be converted to styrene by dimerization which is an important aromatic
building block for polymer.
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Due to the shortage of fossil fuel supplies and rising oil prices, the biotechnology for the
production of 2, 3-Butanediol has received much attention recently. Numerous
microorganisms have been known to produce 2, 3-Butanedoil from a variety of carbohydrates
such as glycerol, hexose and pentose as well as lignocelluloses through a microbial
fermentation processes.
These include a number of species of the genera Klebsiella, Enterobacter, Bacillus and
Lactobacillus. Klebsiella oxytoca and Klebsiella pneumoniae are facultative anaerobic
bacteria which obtain the energy for growth and maintenance through aerobic respiration and
anaerobic fermentation.
The Klebsiella species is also found to utilize various substrates including glycerol, glucose,
xylose, mannose, galactose, arabinose, and lactose making it feasible to produce 2, 3-
Butanediol with cheap substrates or low cost substance such as biodiesel waste,
lignocellulosic waste, etc.
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Usually, 2, 3-Butanediol is synthesized as a mixture of two isomer types of 2, 3-Butanediol
by different microorganisms. For example, Bacillus subtilis can produce the d form and
mesoform in almost equal amounts. Whereas on the other hand, Bacillus polymyxa produces
only the optically active form of 2, 3-Butanediol. There are only a few reports on
stereoisomer analysis of 2, 3-Butanediol produced from different microorganisms.
During the fermentation, microorganisms produce 2, 3-Butanediol along with other

byproducts such as ethanol, lactic acid and acetic acid. It is crucial to use all of the available
cheap substrates for the cost effective production of the biofuels and bio-based chemicals
because the cost of raw material significantly influences the final cost of the product.
Wood and agricultural biomass mostly the lignocellulosic materials are popular candidates
for low-price biomass resources and that has been an increased interest in research on their
use for 2, 3-Butanediol production.
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Among components in lignocellulosic materials, cellulose is a polymer of glucose and
hemicellulose contains hexose and pentose. According to previous results, 2, 3-Butanediol
can be produced from various types of carbohydrates including hexose and pentose sugars
which are liberated from lignocellulosic materials by hydrolytic method. Each hexose and
pentose or mixed substrate has been examined for 2, 3-Butanediol production.
Among them, glucose has been the substrate most often examined for 2, 3-Butanediol
production. Aerobacter aerogenes NRRL B199, this is the strain name, yielded 0.45 gram of
2, 3-Butanediol per gram of glucose at the initial glucose concentration of 195 grams per
liter. Then Bacillus polymyxa utilized glucose as a carbon source for the production of 2, 3-
Butanediol.
The inhibition of growth occurred at substrate concentration exceeding 150 grams per liter.
These are very classical studies. The references are given, you can browse through later on if
you are interested to read more into detail.
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Bacillus licheniformis produced 2, 3-Butanediol from glucose when grown either in air or
under nitrogen. After 72 hours of fermentation on a 2% weight by volume glucose at pH 6
and 37 degrees centigrade, the optimum yield of 2, 3-Butanediol was 47 gram per 100 grams
of glucose. In addition to glucose, the use of various pentoses and hexoses has been examined
for 2, 3-Butanediol production.
Jansen and Tsao reported that Klebsiella pneumoniae was able to utilize various pentoses
including xylose, arabinose, mannose, galactose and cellobiose for growth and 2, 3-
Butanediol production. The maximum specific growth rate of 1.05 per hour occurred at a
xylose concentration of 20 grams per liter by Klebsiella oxytoca under aerobic conditions.
Janssen et al performed a 14-batch fermentation for 2, 3-Butanediol production and simulated

2, 3-Butanediol production with respect to the oxygen transfer rate and initial xylose
concentration.
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With an initial xylose concentration of 100 grams per liter and an oxygen transfer rate of
point 0.027 moles per liter per hour, the average 2, 3-Butanediol production rate was 1.35
grams per liter per hour. The production of 2, 3-Butanediol from lignocellulosic wastes other
than purified hexose and pentose has been considered as an economical method.
Laube et al attempted to use acid-hydrolyzed aspen wood, larchwood and oat spelts; but only
a low 2, 3-Butanediol yield was obtained even with the additional xylose implying that there
was an inhibitory effect of hydrolyzate on 2, 3-Butanediol production. As you know that
beyond certain concenteation, all the products as well as substrates can inhibit the entire
fermentation process, so that care must be taken. Frazer and McCaskey investigated the effect
of the selected components in acid-hydrolyzed hardwood on 2, 3-Butanediol production by
the Klebsiella pneumoniae species.
According to their result, sulfate up to 0.2% weight by volume and furfural up to 0.2% again
weight by volume did not affect growth, but sulfate reduced 2, 3-Butanediol by 30% while
furfural induced growth slightly. So phenolic compounds including syringealdehyde and
vanillin significantly inhibited growth and 2, 3-Butanediol production to as low as 0.1% and
0.05% respectively.
So both these components synringealdehyde as well as vanillin are great inhibitors in the
entire fermentation process to produce 2, 3-Butanediol using this particular strain.
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Grover et al used wood hydrolysate after neutralization with calcium hydroxide and filtration.
In flask cultures, 2, 3-Butanediol was produced at 12 grams per litre with a yield of 0.27 gram
per gram of sugar. Glycerol is also considered to be a cost effective and efficient carbon
source for the production of 2, 3-Butanediol. Klebsiella pneumoniae DMS 2026 has been
known to be a 1, 3-Propanediol producing strain as well as a 2, 3-Butanediol producing strain
using glycerol.
This is what we have already seen when we discussed at the beginning of our class about the
1, 3-Propanediol production. So this Klebsiella pneumoniae GT1 produced 2, 3-Butanediol
from glycerol at low pH and microaerobic conditions. When the pH was lowered stepwise
from 7.3 to 5.4 in a continuous culture, 2, 3-Butanediol formation started at pH 6.6 and
reached a maximum yield at pH 5.5 under microaerobic conditions, while production of
acetate, ethanol and 1, 3-Propanediol decreased.
This is what we want. I was just talking if you recall our discussion during metabolic
pathway, so if you want to maximize 2, 3-Butanediol production then you have to suppress
the production of other components, whether it is acetate, ethanol, 1, 3-Propanediol or any
other such components, like even butanol also.
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So while this Klebsiella pneumoniae can produce 1, 3-Propanediol and hydrogen only under
strictly anaerobic condition, the microaerobic conditions caused little 1, 3-Propanediol
production, and higher 2, 3-Butanediol production in the presence of oxygen and glycerol.
There is a very interesting study. Fed-batch culture of this particular strain was carried out by
Petrov and Petrova.
By optimizing the medium conditions without pH control, 49.2 grams per liter of 2, 3-
Butanediol was produced at an initial pH of 8 under microaerobic conditions with the
concentration of glycerol about 30 grams per liter. The addition of organic acids such as
acetic acid and succinic acid has been demonstrated to be advantageous for 2, 3-Butanediol
production.
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The addition of succinic acid at 10 grams per liter to the medium containing xylose was
found to improve 2, 3-Butanediol productivity from xylose by Klebsiella oxytoca, but higher
concentration of succinate were inhibitory. Then Nakashimada et al., investigated the effect
of organic acids on 2, 3-Butanediol production of Bacillus polymyxa and found that 150
millimolar of acetate gave the highest 2, 3-Butanediol yield, that is 0.87 moles of 2, 3-
Butanediol per mole of glucose which is a very good actually, and the concentration of 248
millimolar in a batch culture. When glucose and acetic acid were fed together in the ratio of
0.35 mole acetate per mole of glucose in the fed-batch cultures 2, 3-Butanediol production
reached 637 millimolar and 566 millimolar at pH 6.8 and pH 6.3 respectively.
Now we will talk about the other one of the most important commodity chemicals, PHA, that
is polyhydroxalkanoate. So, PHAs are a family of bio-polyesters synthesized by many
bacteria for energy and carbon storage purposes. The natural polymers can be melted and
molded like petrochemical thermoplastics but degraded completely into benign metabolic
products by microorganisms in the environment. P3HB is the most common PHA.
More than 100 hydroxyalkanoic acids have now been identified as the possible PHA
monomers. They are usually 3-hydroxyalkanoates with R configuration resulting in high
stereoregularity and optical activity of the biopolyesters. The monomeric hydroxyalkanoates
can be roughly divided into 2 groups: Short-chain length hydroxylalkanoates with 3 to 5
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carbons and medium-chain-length hydroxyalkanoates with 6 to 14 carbons. The size of side
chain can to a great extent affect the material properties.
Small side chains such as methyl and ethyl groups of scl-P3HAs result in a stiff material with
high crystallinity, high tensile modulus and low ductility whereas large side chains of mcl-
P3HA make the material more elastic with lower crystallinity, low melting temperature as
well as high ductility. So, actually the length of the side chains matters. So controlling the
size and content of the side chains in P3HA copolymers can therefore make a bio-polyester
with desired properties.
So, basically you can tailor make a particular PHA. The material properties can also be
modified by incorporating longer monomers such as 4-hydroxybutyrate and 4-
hydroxyvalerate in the PHA backbone. For instance, as the 4HB content in a copolyester, that
is P3HB4HB, increases, the crystallinity of the copolymer declines and its ductility increases.
In microbial PHA biosynthesis, precursors of 4HB are supplied either as the sole carbon
source or as a co-substrate of glucose.
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PHA bio-polyesters, because of their biodegradability and biocompatibility have attracted
great research and industrial interest. They have been produced via microbial fermentation
from various renewable feedstocks such as glucose, starch, sucrose, vegetable oils, animal fat
and food processing residues. The production cost however is still relatively high in
comparison with petrochemical plastics. It is attributed to the cost of raw materials, microbial
fermentation and polymer recovery.
Cellulosic biomass such as corn stover and cane bagasse is a potentially inexpensive and
renewable feedstock for bio-based fuels, chemicals as well as materials. Compared to starchy
grains, cellulosic biomass contents much less glucan, more hemicellulose, lignin and other
plant components. A substantial amount of organic residues are left from ethanol
fermentation, posing a high treatment cost or environmental liability to the biomass refining
processes.
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A general PHA bioprocess consists of three basic operations. What are those? The first is the
biomass pretreatment, second is the microbial synthesis, and then third is the polyester
recovery and purification step. Now, microbial synthesis or bio-polyesters are complex and
many times inhibitory substrates play a key role in the PHA bioprocess. Under controlled
conditions, bio polyesters are accumulated inside the cells as inclusion bodies that may
account for 60 to 80% of the dry cell mass.
Glucose is a popular carbon source for PHA fermentation in laboratory as well as in industry.
In a laboratory fed-batch culture a very high productivity of 4.6 grams P3HB per liter per
hour and a high P3HB content up almost 80 weight percent was achieved. It was a very
significant report actually. The reference is given below, you can browse through it if you are
interested to learn more.
This high-cell density culture however may be impossible in biomass refining because of a
much lower glucose concentration and presence of other inhibitory substances in the feeding
solution. Fed-batch fermentation is a useful tool in controlling substrate inhibition for high-
cell density cultures. If you recall our discussions during fermentation, I have clearly told you
how fed-batch is an advantageous mode of operation with respect to batch operation or batch
mode of fermentation.
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So, this is the classical schematic PHA biosynthesis from glucose, xylose and luvulinic acidic
route. So, let us understand. Glucose and xylose, so both are giving acetic acid. So, xylose is
giving an intermediate before it goes to acetic acid, xylulose. So, now this acetic acid is
getting converted to 2-Acetyl coenzyme A, then to Acetoacetyl coenzyme A, then to 3-
Hydroxybutyrul coenzyme A, then poly 3HB-3HV-4HV.
And you can see that this is the main metabolism pathway which has not been described here,
and has been left out. So, this particular component is giving again to the 3-hydroxyvaleryl
coenzyme A. And from the levulinic acid also that particular step is going through two
different intermediate compounds and finally we are getting poly 3HB-3HV-4HV as the
product. Now there are some intermediate steps which have been skipped here. This is just a
simple understanding of the schematic biosynthesis pathway.
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The inhibitory compounds in hydrolysates solution however may not be utilized by microbial
cells and could be accumulated with feeding resulting in quick deterioration of the microbial
activity. A continuous feeding system consisting of two bioreactors in series may provide a
solution. So, how it can help us basically? In the first bioreactor, you grow the cells. The cells
grow with a balanced nutrient supply, basically you are growing the biomass.
And in the second one PHA is fromed under limited nutrient conditions at constant level of
inhibitory compounds because what happens when you are growing and producing PHA
simultaneously in a single reactor, during the cell growth, there are some inhibitory
compounds production that actually inhibit the growth of the cell as well as inhibit that PHA
formation. So, that will not happen if you are going to use a continuous feeding system
having two separate bioreactors in series.
For example, one system operated at a dilution rate of 0.08 per hour produced 1.23 gram
P3HB per liter per hour with a yield of 0.36 gram P3HB per gram of glucose. The PHA
content was 72 weight percent of the dry cell mass. Xylose is a predominant hemicellulosic
sugar of biomass hydrolysates. Because of its poor utilization by yeast, it may also be a
primary residual sugar in ethanol fermentation.
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An early study demonstrated P3HB accumulation on xylose and arabinose in Pseudomonas
pseudoflava. In a well-controlled bioreactor the specific P3HB formation rate, cell yield and
polymer yield on xylose were 0.03 grams per grams per hour, 0.17 gram per gram and 0.04
gram per gram respectively in comparison with 0.11 gram per gram per hour, 0.36 gram per
gram and 0.08 gram per gram respectively on glucose.
Two problems are encountered in the PHA biosynthesis on levuliniv acid. The first is the acid
toxicity and the second is the composition control of the co-polyesters. With a strain of
Alcaligenes species grown on levulinic acid and glucose, this PHA that is P3HB3HV was
formed with about 40 mole percent of the 3HV. The cell growth and PHA synthesis were
inhibited at a low concentration of levuliniv acid that is 1 gram per liter.
So this fact indicates that the acid has a higher toxicity than propionic acid does, and a
popular precursor substrate of the 3HV.
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A strain of Ralstonia eutropha, so formerly it was known Alcaligenes eutropha, was inhibited
with levulinic acid at concentrations from 0.5 to 8 grams per liter. The co-polyesters
P3HB3HV formed on fructose and levulinic acid contains 35 mole percent of 3HV or lower.
No 4HV is detected in the polyster backbone from its precursor levulinic acid. PHA with the
high mole percentage of 4HV (almost 19 to 30%) could be synthesized on levulinic acid with
a recombinant strain. So the two references are very classical studies particularly on the PHA
formation from the levulinic acid. So, if you are interested to learn more you can go through
it.
So, this table tells you about the monomer composition, average molecular weight, IR
absorbance of the PHA formed on glucose, valeric acid as well as levulinic acid. So, 3
different carbon sources are given, their molecular weight, how much 3HV is getting formed.
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You can see from glucose it is 100% 3HB, 0 3HV, 0 4HV. When you come to valeric acid
you see that 3HB is less whereas 3HV is more and no 4HV.
And when you talk about levulinic acid there is a balanced formation of 3HB as well as 3HV.
So although the average molecular weight of PHAs formed on 3 different carbon sources is
quite similar, the monomeric composition varies. A homopolymer P3HB is formed on
glucose. On valeric acid, a co-polyster that is P3HB3HV is formed with 3HV being the
predominant monomer. You can see that 78.2 mole percent and 3HB is the only secondary
monomer, roughtly it is 22%.
On levuliniv acid, this P3HB3HV4HV is formed in which both 3HB and 3HV are the
predominant monomers while 4HV is a minor monomer. The IR absorption intensity at
wavelength number around 1180 centimeter inverse is reversal to the crystallinity of the PHA
matrix. The IR absorbance at wave number 1380 centimeter inverse is attributed to the
vibration energy of methyl group of bio-polyesters and often used as a reference.
P3HB is a well known brittle PHA because of its high stereoregularity and high crystallinity,
almost 60 to 70%. Its relative IR absorbance is 0.93, the smallest among all the 3 PHAs. The
copolymer P3HB3HV has a lower crystallinity and higher ductility than the P3HB does, but
the effect of the second monomer on matrix crystallinity and material ductility is not high
because of co-crystallization of the 3HB and 3HV.
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The terpolyester P3HB3HV4HV has the lowest crystallinity and highest relative IR
absorbance because of the content of 3HV as well as the irregularity caused by the 4HV.
Indeed, the cast film of this terpolyester exhibit a very high elongation at break close to 500%
in comparison with P3HB which is less than 5% and P3HB3HV which is less than 50%. The
melting point of the terpolyester is between 120 to 130 degrees centigrade in comparison with
the two other things.
Like P3HB is 170 to 180, 3HB3HV is 150 to 160 degrees centigrade, almost similar. So, in
addition to glucose, xylose and levulinic acid, many organic hydrolysates exist in the
solutions of biomass refining. They may not be primary carbon source because of relatively
low concentrations, but can apply a great inhibitory effect on the PHA fermentation.
For instance, Pseudomonas pseudoflava is able to grow and form P3HB on xylose and
arabinose or the hydrolysates from hemicellulosic fraction of the poplar wood. The strain
however is inhibited completely in hydrolysates solution of high concentrations, almost
greater than 30% volume by volume.
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The toxicity of hydrolysates depend on the three factors. First is cell density, then
hydrolysates concentration and the inoculum preparation. A high initial cell density ranging
from 3 to 6 gram per liter could effectively relieve the inhibitory effect of the hydrolysates.
The hydrolysates and glucose are simultaneously utilized with cell growth and PHA
formation.
So with this, I wind up today's class and we are done with our discussion on commodity
chemicals production from the biomass. Though biomass gives us so many different types of
commodity chemicals, I have restricted our discussions to only those which are commercially
being produced and are of high value. So, thank you very much. In case you have any query
register in the Swayam portal. You can always drop a mail to me at [email protected].
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Lecture – 34
Concept, Lignocellulosic Biorefinery
Good morning students. We are starting module 12 today and as you know this is the last
module of our course and this module is dedicated to integrated biorefinery. So, in today's
lecture, we will be discussing about the concept of integrated biorefinery. If you recall, we
have already discussed about biorefinery.
We will try to learn what is integrated biorefinery and few examples of already
commercialized integrated biorefinery. That will include corn, soybean and sugarcane-based
biorefinery as well as lignocellulosic biomass based biorefinery. So, let us begin our
discussion.
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If you recall, we have discussed this, but I am just trying to make you aware again that what
are the first generation biorefinery and second generation biorefinery. So, this is your first
generation biorefinery in which corn, wheat, soy grains, then sugarcane, sorghum cane, sugar
beet, cassava all these were being used to produce valuable products. It can be biofuel, some
platform chemicals and other value-added products from these biomasses.
Now, when we look for the second generation biorefinery, so there the focus is entirely
switched to mostly the lignocellulosic biomass wastes. Perennial grasses, herbaceous crop
residue, forest biomass, industrial biomass waste all these things that includes even the
municipal solid waste. So, if you look at the first generation biorefinery conceptually what it
means actually? So, let us understand that the base or the platform is actually the
sugar/glucose.
So, when we go for our microbial fermentation, we get fuels, alcoholic fuels, ethanol, butanol
and all these things, plus chemicals i.e., lactic acid, propionic acid, succinic acid. We have
discussed all these in detail previously. And then you go for catalytic conversion, so you get
chemical precursors. You again further convert them to different types of upgraded fuels and
chemicals.
So then we have a decentralized biomass processing. It is very much required, especially if

we are talking about the wastes including the lignocellulosic biomass. So biomass milling,
pretreatment, pellet production. Then it goes to the processing like hydrolysis, fermentation,
product separation. Then we have either fuels and chemicals and we can also centralize
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biomass processing where all these operations like the pretreatment operation, mechanical
aspects as well as hydrolysis, fermentation, product operation, everything is carried out in a
centralized way.
So, let us try to again understand about the integrated biorefinery. So, the concept of
biorefinery was originated in the late 90s as a result of scarcity of fossil fuels and increasing
trends of use of biomass as a renewable feedstock for the production of non-food products.
That term green biorefinery was first introduced in 1997 as: “Green biorefineries represent
complex to fully integrated systems of sustainable, environmentally and resource friendly
technologies for the comprehensive material and energetic utilization as well as exploitation
of biological raw materials in form of green and residue biomass from a targeted sustainable
regional land utilization”. This is what looks to be a big actually terminology, but this is what
it was coined as the definition of green biorefinery.
Then American National Renewable Energy Laboratory, the NREL, defined biorefinery as:
“A biorefinery is a facility that integrates biomass conversion processes and equipment to
produce fuels, power and chemicals from biomass.”
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Biorefinery was classified into 3 types. Phase 1, Phase 2 and Phase 3 based on the conversion
technologies to produce various bioproducts. So phase 1 biorefinery has a fixed processing
capability. So it uses grain as feedstock to produce fixed amounts of ethanol, other feed
products and carbon dioxide. The low capacity dry mill primarily build for manufacture of
ethanol is an example of the phase 1 biorefinery.
The current wet milling technology with more processing flexibility is considered as phase 2
biorefinery. So phase 2 and phase 1 the difference is that in phase 1 it is fixed processing
capability, but in the phase 2 we have more processing flexibility. So, it also uses grain as
feedstock to yield assembly products such as starch, high fructose corn syrup, ethanol and
corn oil depending on their demands and price.
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The phase 3 biorefinery which takes into account the whole crop, green and LCF (LCF is the
lignocellulosic feedstock) uses mixture of biomass to produce multitude of products using
combination of technologies. So in phase 3, we have different types of biomass plus different
types of conversion technology plus different types of products. So the phase 3 is most
advanced form of biorefinery.
The whole-crop biorefinery uses entire crops such as cereals, rye, wheat and maize as raw
materials to obtain useful products. The cereals are first mechanically separated into corn and
straw. The cellulosic straw is further processed in the LCF biorefinery. The corn is either
converted into starch or meal by grinding. The meal is then converted into binder, adhesives
and filler by extrusion.
Starch is further processed through plasticization, chemical modification and biological

conversion via glucose as per the need and demand of course. The green biorefinery uses
natural wet biomass such as grass, green plants or green crops. It is a multi-product system
that handles its refinery cuts, products and fractions according to physiology of the
corresponding plant materials.
The USDOE, the United States Department of Energy and NREL further described biomass
conversion technologies based on 5 platforms. So what are those? The first is the foremost
important from where all these biorefinery started is the sugar platform biorefinery. The
second is thermochemical or syngas platform. Third is biogas platform, basically anaerobic
digestion.
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Fourth is the carbon-rich chains platform and fifth is the plant products platform; so entirely
LCF based. So SPB produces ethanol and other building block chemicals through
fermentation of sugars. The syngas platform uses technology of biomass gasification to
produce syngas and liquid fuels. The biogas platform is useful for production of cooking gas
by anaerobic digestion, which is very famous in Asian countries including that of India.
The carbon-rich chains platform converts vegetable oils into biodiesel by transesterification
with methanol for application as liquid fuel. The plant products platform performs biorefining
in biological plants itself rather than in the industrial plants.
So, the present classification of biorefinery covers whole ranges of biomass and is based on
the known conversion technologies. Please look at this particular figure. This is a proposed
model for integration of extraction, biochemical and thermochemical processes into a single
biorefinery internally recycling the energy and extraction solvent required. So that is what it
is integrated biorefinery.
You have multiple feedstocks, we have multiple conversion technologies and you have
multiple products. And whatever waste is coming again you are recycling them in the same
biorefinery in various forms that is what is integrated biorefinery. So, let us try to understand
this wheat straw. It is going through densification, extraction. When you extract, you find
some sort of chemicals, useful chemicals.
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Whatever the residue left that is being processed in an integrated biorefinery way. It can be
converted to chemicals and materials. Then biochemical processing, thermochemical
processing both will give us fuel. Now, further conversion we get energy. So, whatever
carbon dioxide you are seeing now, whatever carbon dioxide is that is getting generated
during the entire processing is again being used or consumed by the wheat to grow itself.
So, this is why the biomass of lignocellulosic biomass play safe or we can say that plays a
role in environmental benign technology. So, however conversion technologies and platform
chemicals are expected to be expanded in near future in response to further scientific
advancements and discovery of novel feedstock. The individual integrated biorefinery will be
developed based on specific type of feedstock with the goals to produce certain ranges of
products using specific conversion technologies.
For example, lignocellulosic biorefinery can be developed through gasification, fast

pyrolysis, ethanol butanol or other chemical intermediates.
Now, we will discuss few integrated biorefineries. The first one is integrated corn-based
biorefinery program. So, through a $38 million partnership with the US Department of
Energy, DuPont initiated the integrated corn-based biorefinery program in 2003 to develop a
cost effective technology package for cellulosic ethanol from entire corn plants, please note
down again entire corn plant, and in the future any biomass.
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So, they wish to develop such a protocol which they have already developed so they can
process multiple feedstocks. So, through this a $38 million partnership with the US
Department of Energy DuPont initiated the integrated biorefinery program for any biomass.
Unlike traditional corn grain ethanol, the ICBR technology will use the entire corn plant that
is stalks, cobs and leaves left in the field after harvest as opposed to only the corn kernel.
So if you remember the Phase I biorefinery or the corn-based biorefinery used to have only
this kernel as their feedstock. Now in the integrated system we have the entire plant, so this is
the difference. So, ultimately the use of corn stover and similar agricultural residues will lead
to lower production costs and expand the potential for new biorefineries.
So, the ICBR concept relies on biotechnology to convert corn stover into fuel ethanol. Dry
cornstover is milled into smaller pieces to generate more consistent bulk feedstock. Then the
stover is pretreated to separate the lignin from the plant cellulosic backbone to make cellulose
more accessible for future processing. So, this milling and pretreatment, so these are the
processing, preprocessing things.
You can see the agricultural inputs, plant feedstocks. So, they have to be milled and
pretreated. Then the second part is conversion of sugars, so we are doing the saccharification.
Then the fermentation will begin. Fermentation process, then the separation which is many
times I have told you that this is one of the most energy intensive as well as a costly process
the downstream part. So you get biofuels and biochemicals.
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So enzymes can now break the cellulosic material down to fermentable sugars in a process
called saccharification. Novel fermentation technologies enable the conversion of both
glucose and xylose from cellulose and hemicellulose effectively converting nearly all of the
useful sugars into ethanol. In a series of separation steps, ethanol is isolated from the
fermentation broth and refined to a fuel-grade product and it is very energy intensive as well
as costly process.
So in the past, harsh pretreatment conditions and high temperatures were used in an attempt
to break down the cellulose matrix to its individual sugar components. The ICBR technology
is designed to break down cellulosic biomass into fermentable sugars through natural enzyme
based processes replacing less efficient petrochemical processes.
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So resource depletion, global warming and potential impacts on agricultural ecosystems
emerged as the most relevant environmental issues. For practical purposes, metrics used to
guide a technology development effort should meet the following 3 criteria. So first one is the
metrics should address the key issues and they should also be quantifiable. The metric should
be derived from process data, modelling data.
The metric should relate to other metrics commonly used in research and business decision
making processes. Now, cradle-to-gate fossil energy consumption is the aggregated
consumption of fossil fuels at the biorefinery itself and also in operations upstream such as
feedstock production and energy generation.
The benefits of process efficiency are magnified in the cradle-to-gate view. Furthermore, the
cradle-to-gate approach highlights the benefits of avoiding material inputs with a large
environmental footprint. Cradle-to-gate fossil energy consumption relates closely to various
aspects of the environmental footprint. So it is a direct measure of the depletion of the fossil
resources.
Emission of anthropogenic carbon dioxide, considered a major contributor to climate change,

are also linked directly to fossil energy consumption. The extraction, refining, transportation
and ultimately combustion of fossil fuels are major causes of emission to air, water and land.
Therefore, fossil energy consumption can be considered a leading indicator for many other
environmental impacts such as the green house gas emissions, water consumption, smog
formation, acid rain or heavy metal emissions.
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The cradle-to-gate fossil energy footprint to produce a gallon of bioethanol is well below the
lower heat value of the fuel, so that is the energy ultimately delivered to a vehicle. Both
stover-to-ethanol cases have a smaller cradle-to-gate fossil energy footprint than grain-to-
ethanol case. Compared to corn grain, corn stover comes to the biorefinery with a smaller
fossil energy footprint.
Primarily because producing stover and grain on the same field does not require much
additional effort compared to producing grain only. Conventional corn grain ethanol plants
receive their process heat and power from fossil fuels such as natural gas and coal. Cellulosic
ethanol plants are primarily designed to be self-sufficient in heat and power supply with non-
fermentable residue serving as a renewable fuel for on-site cogeneration facilities, the CHP
facilities. We have already discussed about that.
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And this puts cellulosic biorefineries at an advantage even when the feed co-products from
grain ethanol facilities are rewarded with energy credits for displacing other types of animal
feed. Moreover, cellulosic ethanol facilities will probably produce surplus electricity. The
ethanol plant would be an exporter of electricity, which potentially displaces grid electricity.
In-depth analysis of the contributors to the cradle-to-gate fossil energy consumption also
illuminate trade-offs among process alternatives. However, the implementation of recycle
loops may come at the expense of additional energy and water consumption. It is common to
underestimate the energy consumption of the separation steps required to return the chemical
back to the process at a required purity level.
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So, now we will talk about another biorefinery technology/integrated biorefinery that is based
on soybean. So, integrated soybean-based biorefinery technology. Soybean accounts for 60%
of world's oil seed production followed by cotton seed which accounts for 10% of the global
production. Global soybean production in 2016 was 324 million tons, a significant increase of
17% compared to 2013.
The United States, Brazil and Argentina are the largest soybean producers in the world with
the production that occupies more than 80% of the world production of this oilseed. Brazil is
the country with the greatest potential for expansion of the cultivated area, being the largest
producer and exporter of soybeans and their derivatives worldwide. In general, 78 to 80% of
the grain is transformed into bran and 18 to 20% of the grain results in oil, the remainder
being fibrous material from the low value-added shell used as feed. Soybean seeds contain on
an average 40% protein, 20% lipids, 35% carbohydrates both soluble and insoluble fraction
and 4.9% ash.
The soybean refining is composed of a set of processes that aim to transform crude oil into
the edible oil. The refining process improve the appearance, odor and flavor of oil, which
occurs with the removal of certain components of the crude oil. Now, there are two types of
refining process. The first is chemical and second is the physical one and these definitions are
related to the process for the removal of the fatty acids in the oil, which are considered as
unwanted components when you talk about final consumption. So, in the chemical refining
saponification of the acids occur through an alkaline solution which dilutes the soaps
generated in water for the later removal of the process by various separators. In turn, the
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physical refining is characterized as a process that separates the acids using the difference of
their volatility in relation to that triglyceride present in the oil.
The main steps involved in the refining process are degumming - which is actually hydration,
the neutralization - which is a deacidification step, bleaching - which is a clarification
process, and then deodorization. The removal of traces of components responsible for
undesirable odors and flavours occur in the stage called deodorization. The operation takes
place in a stripper where the steam usually 1 to 3% is injected into the soybean oil under low
pressure (almost 1 to 6 mmHg) and sufficient temperature to vaporize the fatty acids and
odoriferous ferrous compounds and to remove them from the oil. So, they are more volatile
and they will immediately vaporize. The deodorization temperature is variable because it
directly affects the vapor pressure of the volatile constituents to be removed and thus directly
affects the removal rate of these components.
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So, this is a simplified flowchart for the refining of soybean oil. So, you can see that this is
the preprocessing step. Soybean goes through a mechanical preprocessing steps like crushing,
milling, whatever it is. Then the crushed seeds go to the extraction unit. Usually hexane being
used as the extracting solvent. So you get the crude oil. Now, that crude oil goes to the
refining purposes. So, various steps are there.
This is only shown in schematic only the main steps. Under that refining there are various
steps. Extraction also not single extractor, there may be many series of extractors. Then the
neutralized oil, it goes to the bleacher where bleaching is taking place. Then whatever you get
is pure oil without color. Now, this is finally being fed to a distillation unit where we get the
distillate product and refined oil. So, this is the process called actually deodorization.
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So the usage of oil for the fuel synthesis is based on the transformation of triglycerides in
esters. The most common ways to synthesize those substance is by the transesterification of
the refined oil. Although the regular transesterification process provides high conversion rates
and have a relatively operational simplicity, some problem comes along such as low energetic
and production efficiency; need to adjust the raw material; the use of high toxicity
intermediate products - very big problem the third one; then the generation of a significant
byproduct volume as for example glycerol - with a level of contamination that requires high
investment to its use or discharge; the use of methanol, which besides toxic needs fossil fuels
as raw material to be produced in the form of energy; difficulty in recycling the catalyst,
again it is a challenge still remains mostly for the engineering people including the chemical
engineers; need to remove the glycerol from biodiesel; and, high environmental impact that is
associated with this entire processing.
So in this regard, the biorefinery concept fits perfectly because in addition to using residual
raw materials, it manages to generate value-added products, not only one but many which
help the lucrative process. However, waste oils demand different technologies than the usual
ones. And in this case, one of the solutions for technically and economically viable biodiesel
production is the use of processes that use solvents under supercritical and subcritical
conditions.
But again, I am telling that supercritical systems is a costly process, subcritical is fairly less
costly than that. Thus one of the steps for a biorefinery would be the production of esters and
glycerin with low level of contaminants. The objective is the esterification of residual raw
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materials in super and subcritical environments to obtain esters and glycerin for the synthesis
of propene and various other polymers.
The second integrated process is the extraction of high value-added waste products from the
refining of vegetable oils. Using the SODD, which has significant amount of free fatty acids
that is it can become a potential source to produce esters, then tocopherols which are widely
used in the cosmetic industry, then sterols used in the formulation of vitamin supplements in
cosmetic industry, biorefinery is a great generator of high value-added products.
A process which separates the products efficiently and with high purity will provide raw
material for the synthesis of esters and quality raw materials for the cosmetic and medicinal
sectors. The separation with supercritical fluid, mostly carbon dioxide being used as the fluid,
allows to obtain products without the contamination of solvents, thus allowing a
commercialization of the same with greater purity.
The fatty acids obtained are used for the synthesis of esters in a subcritical environment and
contemplate the third part of the biorefinery.
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The main residue produced by the refining process are gums, soap stocks, spent bleaching
earth that is called as the SBE, deodorizer distillate product, and another one is lecithin that
can be obtained from the gum residues. Biodiesel can be produced from the soap stock and
spent bleaching earth. Concentrated tocopherols are obtained from deodorizer distillate, and
the electrical energy is produced from the soybean molasses generated during the
concentration of proteins from soybean meal.
After the hull and straw removal, the soybean flakes are sent to the soybean oil extraction.
Now, in this step the most common method used to extract is the direct solvent extraction
with hexane as solvent which I have already shown you in that schematic diagram. Now, it
consists of 3 basic steps. The seeds preparation, oil extraction and oil/meal desolventizing.
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So, this is the overview of the main steps and residues in a soybean biorefinery. You can see
this figure. Soybean goes for harvest, of course then you get the straw out of that. It can go to
the LCF, lignocellulosic based biorefinery. Then the soybean seeds, it goes through sort of
physicochemical processing steps, you get flakes. Now the flakes are sent to the extraction,
so where you get crude oil and hexane. So, from here two separate processes.
So, extraction and most of the value-added products. Crude oil plus hexane we get
evaporation, hexane recycle. Crude oil then it goes to degumming, you get degummed oil.
You send to neutralization, you get neutralized oil. Goes to bleaching, you get bleached oil.
Deodorising, you get the final refined soybean oil. Now, the defatted flakes, that means the
flakes from which the oil has already been removed but few amount of oil will always be
present depending upon what is the process, plus hexane. It will go to evaporation where
hexane will be recycled back. It will be recovered and recycled back. Then you get the
defatted soyabean meal. You can go for some isolation steps and okara, whey and all these
things and you get some soy protein isolate maybe it is in a lower quantity. Then if you go for
concentration, you get the soybean molasses which can further go for producing energy and
you get the soy protein concentrate.
From this, basically you get the soy protein concetrate. Now, the next main step is the
chemical refining of the soybean oil which aims to remove the unwanted oil components with
minimal impact on triacylglycerols and minimal loss of the desirable components. After the
oil extraction, the protein content in the meal becomes even more concentrated and for an
achieved concentration of 65 to 72% dmb it can be sold as soy protein concentrate.
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So, this is an overview of the main steps and residues in soybean biorefinery. So, whatever
we have discussed is put in a single slide. So you can go through it later. Here basically what
is being done is that entire process; suppose, this is a refining process, this is the oil
extraction unit. So, oil extraction, seed preparation, oil extraction, decentralizing, this
miscella desolventizing. Then you get the oil, it goes to refining.
Degumming, neutralizing, bleaching, deodorising, you get the refined oil. And apart from
that there are so many other processes are also happening together. So, you can see this. This
is what is basically different types of byproducts that is coming out when this refining
process is going on. All this can be converted into various products. Just see the products, so
many different types of products, glycerol, biodiesel. And then we can have other different
types of chemical sources and plus energy.
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So with the technological advance and increased investment in this area, many bio refineries
are already in operation to minimize the problems caused by traditional refineries. In
addition, it is demonstrated that the use of soybean raw materials or biomass in a biorefinery
presents numerous environmental and economic advantages as high-value added products are
formed. These products can be applied in different sectors of the chemical, pharmaceutical,
cosmetic and food industries, thus, contributing to the use of the production generated. It is
important to note that in this highly evolved integrated biorefinery model, the added benefits
of operational and administrative synergies will emerge over time. So, the implementation of
the integrated biorefinery of soybeans, especially specifically in the Brazil is very interesting
considering the country's expertise regarding the biofuel technology that is already applied to
soybeans.
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Now, next we are going to talk about the integrated sugarcane-based biorefinery technology.
So, this is an overall schematic diagram of the experiments of the sugarcane-based
biorefinery. We will discuss. So, let us say you start from here. The sugarcane bagasse/SCB.
You go for hydrothermal fractionation. So, you get the liquid part which is composed of the
hemicellulose plus lignin here.
Now that goes to the lignin extraction. So, whatever lignin you extract that can be pyrolyzed.
So, you get bio-oil and other carbon microsphere. So, you process it using ionic liquid plus
hemicellulose, basically ionic liquid based pretreatment. So, you go for some anti-solvent
extraction. You will have the ionic liquid recovery, you will have precipitated hemicellulose.
The hemicellulose can futher be converted into ethanol, butanol or any other such uses. So,
whatever solid part that is left after removing the liquid one you will have the cellulose. Now,
this cellulose can go for hydrolysis. Then we get the glucose, oligosaccharides. It can be
converted into various other products such as fuels, basically alcoholic based fuels. So,
different types of solid catalysts are being required for this entire processing, heterogeneous
catalyst.
So, some of the names are here there, but it is not only these catalysts, there are many
catalyst. So, you can develop catalysts characterize. One of the most important part of the
entire biorefinery business or even the refinery business is the development of novel catalyst,
effiecient catalyst, which is still going on. So, sugarcane bagasse, a solid residue from the
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sugar industry is a renewable resource with high feasibility for use as a precursor for biofuels
and bio-based materials and chemicals.
In the biotechnological conversion of lignocellulosic biomass to sugars, the pretreatment and

the hydrolysis steps are the bottleneck and the energy intensive process that result in high
operating costs.
So, this is a sugarcane biorefinery. This is put in a more understandable way. So, you can see
that how each process during sugar production yields different products. This is very
interesting. So, let us start with this. Sugarcane washing, milling. After milling it is liquid
part, it goes to the filtration but the bagasse or the solid part is coming here. It can directly go
for power generation, gasification.
Then, if not, you process, you saccharify it, you pretreat it. You get hemicellulose, it
produces xylitol. Lignin; lignin can be pyrolized to get various products and bio-oil.
Cellulose; you get MCC, NCC. Then whatever the byproduct from milling to filtration, the
press mud, it can have so many different things; hythane, methane, hydrogen, struvite and
VFA/volatile fatty acids. You do filtration, you get sugar.
Sugar based platform we can start, alcholic fuels and other things. Molasss; the molasses can
be fermented and distilled and further things. Otherwise we can have food additives, citric
acid, soil conditioner and succinic acid; so many products. Then if you do distillation, you get
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alcoholic fuel here, alcohols. Whatever carbon dioxide is being generated from here that can
go to the algal cultivation.
Algal cultivation ponds, it is an integrated refinery approach. So, many things are happening
in a single way. Nothing is being wasted. Whatever byproduct is getting generated, whatever
be their quantity, will be converted into some other valuable products. By doing that we
generate so many other products or byproducts like let us say waste products like carbon
dioxide, water that has to be recycled.
Carbon dioxide, very difficult to trap it. So you can trap it and fed to the algal raceway ponds
or photobioreactors. So, you get vinasse from here, so cattle feed, yeast and all these things.
Spent wash can be further processed to get hydrogen, methane, hythane and VFA just like the
press mud doing here. So, sugarcane processing industry’s waste could be valorized to
produce multiple biobased products.
This is a classic example by the Novozymes. Novo Nordisk up to a level corresponding to the
wastewater of an ordinary household. So this is a very interesting process where each and
every byproduct is getting converted to some valuable products.
The treated wastewater is pumped from Novozymes (Novozyme is a company that produces
enzymes) to the treatment plants of the Kalundborg Municipality where a final treatment
process takes place. The major achievements in the KIS are reduced consumption of
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resources and a significant reduction in the environmental strain. Now this symbiosis
approach resulted in an annual savings of 635,000 tons of carbon dioxide.
Huge one, you can understand that because that carbon dioxide is being utilized whatever is
being generated by the algae. Now 14.1 million Euro in socioeconomic savings and 24.2
million Euro in business economics savings, so huge savings. By working together,
exchanging water, materials and energy streams and waste, KIS has set out an important
sustainable route to attain environmental, economical and industrial development.
It is a very classic case study for this integrated sugarcane based biorefinery. Adoption of
industrial symbiosis helps to increase resilience and economic gains, create sustainable
growth, utilization of resources in a better way, while successfully reducing environmental
impact and carbon dioxide emissions.
So, these are the two figures. You can see that the first one is the simplified flowchart of
products. So boxes in orange they are products. for a sugarcane biorefinery. So, you start with
sugarcane. Harvest it, so culm and straw. So, let us see the culm part. Milling, you get
bagasse, broth. So from bagasse to bioelectricity. Now bagasse can produce ethanol 2G
through the fermentation pathway.
It can produce syngas through gasification. It can produce heat directly with combustion.
Now, the broth can be converted into various one. So, you can get sucrose basically by
crystallization, again further organic synthesis you get chemicals with high value, alcohols
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and organic acids. Now, 1G ethanol to monomers for green polymers and 1G ethanol before
that also go and can be converted to the vinasse, so that we will get biogas and biofertilizers.
And whatever left out after taking the culm is basically the straw and tips. So, you can
produce ethanol, 2G ethanol and organic matter for soil recovery. So, what we understand is
that how many different types of products are getting produced from a single lignocellulosic
biomass. So, this is what has actually been described here, but it is written there. So, the
target compound, precursor, the route, the status.
So, let us see one. Succinic acid, precursor is the xylose from hemicellulose. The route is the
fermentation and what is the status, the status is in development. Improvement of
microorganisms and yields is that requirement. Then let us talk about 2G ethanol. So, the
precursor is glucose from cellulose, xylose from hemicellulose both. Route is fermentation,
So, the status is in production but with the improvement of enzymes, microorganisms, yields
and cost reduction is required.
Now, let us talk about 5-hydroxymethylfurfural. It is a very important HMF chemical, it is a

fuel additive. So its precursor is cellulose. Its route is organic synthesis. And what about
status? It is an established industrial process, still needing to improve catalyst, yields, and
others. Then the last one is xylitol. I have skipped some, you can go through later. So, the
precursor is the xylose from hemicellulose. Route is organic synthesis. It is in development
process stage, improvement of catalysts, yields and others are required.
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So, chemical processes are those based exclusively on chemical reactions (forming or
breaking). Usually a biomass component is extracted and purified and subsequently used as
starting material in a synthetic route. Catalysts are often used to increase the yield of product
of interest and to decrease the reaction time. The chemical processes are chemo-catalytic. In
the case of utilization of cellulose and hemicellulose from lignocellulosic waste, especially
bagasse and straw, first these polymers and their constituent sugars must be obtained.
Especially the glucose or hexose or xylose or pentose respectively to obtain products of

industrial interest such as 2G ethanol. With lignin, the breaking of its molecular structure is
initially attempted to release mainly phenolic compounds, which may be tested for example
as monomers for various routes of preparation.
So, obtaining building blocks and synthesis intermediates is the usual approach used by the
R&D projects to add greater value in bioenergetic chains in a biorefinery. You can see some
are listed here. So, the raw materials are sucrose, bagasse, straw and vinasse that is the
aqueous effluent. Main composition is glucose and fructose. Usage is commercial sugar,
ethanol, renewable chemicals.
Similarly bagasse you get the main composition is the lignin, cellulose, hemicellulose,
inorganic and water. So it can go for animal food, bioelectricity production, renewable
chemicals, 2G ethanol, fibres and polymers, so many more. So building blocks such as
furfural and xylitol and 5-hydroxymethylfufural (HMF), among others can add great value to
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carbohydrates which can be extended to derivatives of lignin. The reason is that they are
high-value chemicals.
(Refre Slide Time: 35:41)
So the biochemical process in figure 10, so we will just go back to figure 10, this one, this
process, are fermentation for the production of first generation ethanol and other chemicals
such as alcohols and other organic acids and anaerobic digestion for the production of biogas
and biofertilizer, that is, the mineralized fraction. Enzymatic catalysis contributes to increase
the rate of metabolic reactions involved in biochemical conversion routes.
Biochemical processes have major operational similarity to chemical processes with respect
to the stages of compositional analysis and characterization of the feedstock, pretreatment
whenever necessary, structural identification and study of industrial potential. The main
feature of these processes relates to the use of microorganisms either fungi, bacteria and yeast
which have the biochemical mechanisms that allows the synthesis of organic chemicals such
as ethanol.
For example, production of ethanol whether it is 1G or 2G by the yeast, Saccharomyces

cerevisiae by means of fermentation of sucrose also produces carbon dioxide.
1277
Anaerobic fermentation of organic matter present in the vinasse mainly produces methane
and carbon dioxide as well as mineral residue rich in inorganic salts of nitrogen, sulfur and
carbon. In this case, bacterial consortia are used formed by Acinetobacter, Arthrobacter,
Bacillus and Brevbacterium among some of the various other species. The bacteria
Lactobacillus delbrueckii can be used for the production of lactic acid via fermentation of
glucose.
And Anaerobiospirillum succiniciproducens for the production of succinic acid through

fermentation of pentoses and hexoses. However, despite the high potential for production of a
large amount of chemicals, the slow rate of reaction (that is very important, the kinetic
conversion, kinetics part is still very ill understood) and the difficulty in separating final
products (the downstream step) can in some cases limit the use of bioprocesses in sugarcane
biorefineries for products other than ethanol. Again, for the reason same is that they are
energy intensive and costly.
1278
So this is the integrated sugarcane-soybean based biorefinery. Please understand two things
here, both sugarcane and soybean are being combined together. So, you can see this is the
graphical abstract of the integrated sugarcane-soybean biorefinery process. The
implementation of a sugarcane-soybean biorefinery requires consideration of its agricultural,
industrial, logistic, geographic, process stream, equipment, administrative and marketing
aspects.
So many things has to be taken care of. So, you can see this sugar gets converted to biodiesel,
cellulose, nanocrystal, nanofibrils, glycerols, then soymeal, hulls and lecithin, electrical
energy, biogas, ethanol. So, this is in combination with various other processes and is a
classical integrated refinery in which there are two substrates basically.
1279
So, this is the simplified design of the integrated sugarcane-soybean refinery. So, this is the
agricultural stage. This is 1G ethanol stage. This is the sugar stage and finally is the combined
heat and power generation stage - the CHP stage. So, you can see this is the sugarcane being
cultivated, it is being taken away. Then soybean you get the oil extracted. Then the sugarcane
goes for the ethanol processing. Again here the soy oil also partly can go for the ethanol
processing.
And huge amount of biodiesel can be produced after the transesterificatioin and you get so
much of glycerol. Glycerol can be converted into various value-added products catalytically.
So, then you get, this is the 2G ethanol stage. Then you have also cellulose nanomaterials
stage. So, you get unhydrolyzed biomass, delignification, hydrolysis, purification you get
cellulose nanocrystals. So, this is a classical example of how soybean and sugarcane can be
processed simultaneously in an integrated biorefinery.
So, this is another classical example which is integrated lignocellulosic based biorefinery
technology. The LCF that is the lignocellulosic feedstock can be processed directly through
thermochemical processes such as combustion, gasification, liquefaction and fast paralysis or
any other pyrolysis slow or medium also. The LCF can also be processed through the
biological routes like fermentation, digestion and microbial processing or chemical routes
such as aqueous phase dehydration/hydrogenation.
1280
Have a look at this particular figure. This is a potential avenues of lignocellulosic biorefinery.
So just see there, so many products. Now lignocellulosic feedstock, pretreatment. You go for
hydrolysis. This is the sugar platforms and this is the lignin one. Lignin, then pentose, then
hexose. Lignin can get converted to so many things. Gasoline, phenolics, aromatics. Of
course then pentose sugars and hexose sugars they can produce the alcohols and other
chemicals, furfural.
Then the ABE fermentation - acetone, butanol ethanol. C1 to C6 alkanes, aromatics, coke,
then hydrogen, liquid fuels, 5-HMF/hydroxymethylfurfural and levulinic acid. Then the
waste part it can go to the combustion, gasification, fast pyrolysis, liquefaction. We get bio-
oil, synthesis gas, electricity, heat. Bio-oil can be further refined because they are not suitable
for direct use, can be upgraded to aromatics, hydrocarbons, cokes and different types of fuels
apart from hydrogen.
So, first process is the combustion and gasification So, the combustion of neat biomass or
together with coal is an established technology for the production of heat or combined heat
and power using the Rankine cycle, the CHP. The suitability of biomass combustion in
micro, small and medium scale makes this technology is an ideal choice for decentralized
biorefinery. Alternatively, the LCF is gasified by sub-stoichimetric amounts of air at higher
temperatures (almost 1073-1173 Kelvin) to produce syngas for application as a source of
hydrogen in chemical industries or for conversion to fuels and organic chemicals by the
Fischer Tropsch synthesis, FTS. However, presence of tars and methane in the resulting
syngas mandates complex downstream processing making biomass gasification gigantic in
1281
nature and economically unviable. The catalytic biomass gasification enhances the efficiency
of biomass gasification to the extent of almost 10% only.
The second is fermentation and anaerobic digestion. The LCF is recalcitrant in nature because
of the protective plant cell wall composed of lignin. The LCF is therefore subjected to
pretreatment to disrupt the cellulose, hemicellulose, lignin networks. We have studied and
understood this earlier. The pretreatment thus enhances accessibility of the carbohydrates of
LCF for subsequent hydrolysis and fermentation.
The solid residue containing mainly cellulose and remaining hemicellulose and lignin
recovered from pretreatment are subsequently hydrolyzed either enzymatically using
cellulases that is for cellulose or hemicellulases, these are the enzymes, for hemicellulose or
chemically using sulfuric acid or other acids to monomer sugars. The hexose sugars are easily
fermented to either ethanol by the Baker’s yeast or butanol by the ABE fermentation using
the Clostridia acetobutylicum bacterial species.
1282
Ideally, pentose sugars should also be fermented to ethanol or acetone-butanol-ethanol either
in separate reactors or together with hexose sugars in the same reactor using two different
microorganisms called that co-fermentation process. However, limited availability of suitable
strains together with slower fermentation rate compared to hexose sugars prohibits their
proper utilization for alcoholic bio-fuels so far.
At present, the cost of ethanol from the LCF is almost double compared to that of the corn
ethanol due to the expensive pretreatment step. Now, this restrains widespread acceptability
of the lignocellulosic feedstock for a production of alcoholic biofuel so far. The economics of
cellulosic ethanol however can be improved by two different approaches. First is the
integration of cellulose hydrolysis and fermentation in single reactor, commonly known as
simultaneous saccharification and fermentation. Second is consolidated bioprocessing where
cellulase and hemicellulase production, hydrolysis of carbohydrates and co-fermentation of
hexose and pentose sugars are integrated in a single reactor.
1283
The third one is the lignin conversion. The huge quantities of lignin are produced as a
byproduct during the conversion of the LCF to alcholic bio-fuels or value-added organic
chemicals. The overall economics of the LCB can be improved by proper utilization of such
low value but high volume lignin to valuable products. The lignin can be converted to
gasoline range fuel additives or phenolic building block chemicals by either simultaneous
lignin depolymerization, or hydrodeoxygenation in a single reactor, base catalyzed lignin
depolymerization followed by hydrodeoxygenation in two different reactors or solvolysis
using hydrogen donating solvents. The world's most abundant aromatic polymer lignin can
also be upgraded to aromatic feedstock by zeolite upgrading using HZSM-5 catalysts.
Then is platform chemicals. Almost all organic chemicals and finished products
manufactured in petrochemical industry are derived from a set of few building block
1284
chemicals. The biorefinery in principle should also produce similar kinds of building block
chemicals from biomass to meet societal needs of organic chemicals and polymer commonly
known as platform chemicals.
With the exception of glycerol and isoprene, all other platform chemicals are essentially
produced from sugars only and that being derived from various sources of carbohydrates by
biological, chemical or enzymatic means. The paradigm shift from hydrocarbons based
building block chemicals in petrochemical industry to highly oxygen-functionalized bio-
based platform chemicals will generate notable opportunities for chemical processing
industries.
The use of oxygenated platform chemicals will eliminate the need for several capital
intensive oxidative processes used in the petrochemical industry. It will reduce the overall
cost. The new chemistry based on these oxygen-functionalized platform chemicals is
however unsuitable with existing petrochemical industry infrastructures, so this is another
problem.
FDCA is another important platform chemical. It finds widespread application as precursor

for industrial plastics including bottles, textiles, food packaging, carpets, electronic materials
and automotive applications. Avantium is currently operating pilot plant at Chemelot campus
in Geleen, the Netherlands to produce methyl levulinate, FDCA and polyethylene furanoate.
1285
So PEF polyesters offer plenty of opportunities as fibres, films and other applications.
Together with the partners that is Coca-Cola, Danone and ALPLA, the company is currently
engaged to make PEF bottles as commercial success. The technology involves catalytic
dehydration of carbohydrates in methanol to methoxymethyl furfural and methyl levulinate.
The methoxymethyl furfural is subsequently transformed to FDCA by catalytic oxidation in
acetic acid.
FDCA is further polymerized with ethylene glycol to produce PEF. Sugar alcohols, xylitol
and sorbitol, are generally used in pharmaceuticals, oral and personal care products and as a
precursor for value-added chemicals. The xylitol and sorbitol are currently produced
commercially by catalytic hydrogenation of xylose and glucose respectively over nickel
catalyst under high temperature and precursor.
1286
So with this, I conclude today's lecture. In our next class that is under module 12 lecture 2,
we will be discussing about aquaculture and algal biorefinery, waste biorefinery, hybrid and
chemical and biological conversion processes. Thank you very much. So if you have any
query, please register in the Swayam portal or you can always drop a mail to me at
[email protected].
1287
Lecture – 35
Aquaculture and Algal Biorefinery, Waste Biorefinery
Good morning students. This is lecture 2 under module 12. And as you know that we are
discussing integrated biorefinery concept and few examples. In today's lecture, we will
discuss about aquaculture and algal biorefinery, that how aquaculture and algae biorefinery
are clubbed together. Then we will also discuss a little about the waste biorefinery though
few things we have already discussed in our module 2. Then we will talk about hybrid,
chemical and biological conversion processes in the biorefinery concept. So, let us begin.
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So, as you can see from this particular slide, this is about the co-processing of algal and
cellulosic feedstock. You can see this algal feedstock, so once you grow it, then you harvest
it. You harvest, then harvested algal biomass. There are 2 things. First is that biomass you
take it out. Second thing is that after you harvest biomass the culture water will remain. So,
basically it is a wastewater. So, culture water containing cellulose and hemicellulose.
So that can go to some recovery unit and then finally it can also be used for the enzyme
cocktail storage tank and residual culture water for the recycling and reuse purposes. So, the
harvested algal biomass, once you separate the oil or the lipid content of that, so you get algal
meal. So algal oil having so many different types of contents like AA, PUFA, then omega-3
and all these things, so that can be separated.
So you can get various products, not only fuels, but also some platform chemicals and others
glycerin, biodiesel, 1, 3 propanediol and the list is endless, there are many. Similarly, if you
talk about the cellulosic feedstock, once you harvest the crop, so compaction, transportation,
pretreatment, detoxification, solid and liquid separation, then you go for the enzymatic
hydrolysis of cellulose and hemicellulose after you remove the lignin part.
Then once that is done, so you can go for the fermentation. So, you get bioethanol, mostly if
you talk about the fermentation pathway you get bioethanol. And other than biethanol, we
have so many other products, some acids and some other products as the coproducts. They
are also value-added products. Now, this is in a nutshell we try to understand how the algal
biorefinery tried to clubbed with other systems.
1289
So one classical example we will discuss is about aquaculture and algal biorefinery. So, based
on the unique advantages in productivity and the potential to avoid competition for arable
land or biodiverse landscapes, algae have been considered as one of the most promising
resources for biofuels and biomass. So, this we have discussed during our discussion on algae
long back. So although they are not superior to higher plants with respect to photosynthetic
efficiency, the microalgae have extremely high growth rates and yield more oil than any
higher plants. So, a plant takes time to grow and do its photosynthesis and other things.
However, algae can grow very fast. So, algae can make use of waste stream as a nutrient
source, which have great potential for wastewater. bioremediation. So, this is most interesting
part actually particularly if you talk about algae vis-a-vis about other terrestrial plants.
So, more importantly algae are the basis of the food chain supporting over 70% of the world's
biomass. With concerns of sustainability issues for the over utilization of marine resources,
aquaculture is regarded as a future sustainable source of quality protein for the planet's
growing population.
1290
Fish and shell fish mariculture thereby have become an important food sector globally and
hold great promise for closing the nutritional gap of many people worldwide. However, at
present the vast majority of aquaculture feed is sourced from wild fish populations. While
reducing use of fish oils in aqua feed, an apparent challenge in aquaculture is to produce the
final products or sea foods with high levels of omega-3 fatty acids, that is the health
promoting agent for the consumers.
Now this growing concern is also a driving force for the marketing of non-fish omega-3 oils
and alternative feed ingredients in aquaculture. Now, there are some aesthetic issues. Many
consumers do not like to consume omega-3 that is derived from the fish oils. As algal omega-
3 oil can be recovered from the extracted lipids intended for biofuel production, policy
initiatives for the meaningful integration of algal biofuel production with the aquaculture
industry has to be done and thereby it will provide many economic and sustainable outcomes
to the society at a large.
1291
So, the discharged water from aquaculture could match the requirement for algal growth. So
it has some nutrient content. So algae can grow fantastically over that discharge water. So
similar has also been implemented in the aquaponic system that aims to simultaneously grow
fish and vegetables in a single system; that has been very popular since few years, the
aquaponic system.
So in fact disposal of aquaculture wastewater has become a major task to further improve
production efficiency and decrease the environmental impacts of the aquaculture industry.
However, this process is not so straightforward due to the cost associated with the nutrient
removal, that process is very costly. So, the effluent from aquaculture production and
facilities contains large amount of nitrates and phosphates which are also essential nutrients
for the algal growth in production.
Therefore, the benefit of the ancillary industries between aquaculture and algal biofuel can
offset energy and greenhouse gas emissions in the algal production and also reduce
investment for the wastewater management in aquaculture. So, you save a lot of money in
that.
1292
So, let us concentrate on this proposed scheme. So, this scheme talks about, this is the flow
sheet for the microalgae biorefinery aiming at producing omega-3 fatty acids, animal feed
and biodiesel as the main products simultaneously. So, algae grow with the presence of light,
water and fertilizer or some nutrient source. While you are cultivating algae, so you can use
wastewater and even carbon dioxide from different sources like power plants, the flue gas.
So, then you harvest algae biomass, so you get algal oil that can convert to omega-3 fatty
acids. Remaining oil can be converted to biodiesel. You get glycerol. Glycerol can be
converted to 1, 3 propaneiol through different routes. This we have already discussed how to
do it, catalytically or biologically. Whatever meal that is left out, algal meal that is the
residual biomass after the oil is extracted you can either convert into biogas or ethanol
depending upon the process you choose thermochemical or biochemical.
You can have the animal feed also or other valuable products also can be found out from that.
So an algae can produce proteins, carbohydrates, lipids and other valuable components for
example pigments, antioxidants, fatty acids, vitamins, recombinant proteins. The concept of
an algal biorefinery has to explore the possibility of large-scale parallel and complimentary
production streams of these bioproducts from industrially grown algae.
1293
So, let us look at the potential of an algal biorefinery in aquaculture. The main applications of
microalgae for aquaculture are associated with nutrition as a sole component or as a food
additive to basic nutrients. Microalgae are required for larval nutrition during a brief period
or even for adults, either for direct consumption in the case of mollusk or penaeid shrimp or
directly or indirectly as food for the live prey fed to the small fish larva.
The use of microalgae in fish hatcheries is required for both production of live prey and
maintaining the quality of the larva-rearing medium. A significant growth rate can be
obtained with microalgae supplemented diets in many species such as prawn, oyster, abalone
and scallop. The nutritional value of the dietary algae is not only dependent on the chemical
composition, but also on factors such as the capability of the animal to ingest and digest the
algae and to assimilate their nutrients.
1294
As aquafeed additives, algal biorefinery products have been shown to have positive effects on
the immune system of the developing fish larvae and the regulation of immunity, gene
expression as well as signalling. For example, feeding guppies with optimal concentration of
a neutral lipid extract of the green microalgae Parietochloris incisa containing beta carotene
and arachidonic acid as the major highly unsaturated fatty acids significantly reduced
infection with the protozoan parasite, Tetrahymena species.
This is a very interesting work actually. So an additive effect of this P. incisa derived beta
carotene and AA rich triacylglycerol TAG was evidenced by increased guppy survival under
acute salinity stress. So as use of antibiotics in aquaculture is banned in many countries. algal
aquafeed could be a more profitable venture rather than nutrient input alone. A lot of work
has been going on on this particular aspect.
1295
The most frequently used aquaculture feed species are Chlorella, Tetraselmis, Isochrysis,
Pavlova, then Phaeodactylum, then Chaetoceros, Nannochloropsis, Skeletonema and
Thalassiosira. So, combination of different algal species provides better balanced nutrition
and improves animal growth better than a diet composed of only one algal species.
In addition to providing protein and energy, they provide other key nutrients such as
vitamins, essential polyunsaturated fatty acids, pigments and sterols which are transferred
through the food chain. Protein and vitamin content is a major factor determining the
nutritional value of microalgae. In addition, omega-3 PUFAs mainly consisting EPA, AA and
DHA content is of the major importance as it has lot of commercial value.
1296
So, please have a close look at this particular slide. Here the aquaculture and algal biorefinery
has been shown to stress that how algal biorefinery can be coupled with the aquaculture
system. So, you see that the first one this is the aquaculture is going on. So, the fish feed
aquaculture is going on. So, algae cultivated with that wastewater. Then once you take the
algal biomass it can go for so many different types; biofuels, bioplastics, then other value-
added products and many.
Let us not again go back to that, we have already covered it many times. Then whatever the
water that is coming out after the algae is harvested you need to treat it a little further. So that
it can be recycled back to either here or to here. Similarly here if you can see this is the
schematic representation of a multiproduct algal biorefinery model. So, you grow algae in
different systems.
So, this is how the algae has been cultivated either raceway pond, photobioreactors, indoor,
outdoor anything. You get it, so it can go for feed and supplements that same thing can be
used as in the aquaculture system. So, the residual biomass can be converted to biofertilizer,
bio oil, biogas, so many other things, so even pharmaceuticals and high value natural
products. So, this is how algal bioculture and aquaculture can be combined together for a
win-win situation.
It has been estimated that the production of microalgae for aquaculture could be more than
1000 tons, so 62% for mollusks, 21% for shrimps and 16% for fish. The worldwide annual
production of algal biomass is estimated to be 5 million kg per year with a market value of
1297
about 1.25 billion US dollar per year. Its huge, every day it is growing. So, approximately
one-fifth of this biomass is used to nourish the fish and shell fish that are cultivated in
aquaculture hatcheries.
However, valuable extractable chemicals as above could be obtained from biofuel

biorefineries. By producing various coproducts such as omega-3 fatty acids and biodiesel in a
sequential biomass processing algal biorefineries have a strong potential to match the
challenge in aquaculture to generate end products, seafood with high levels of health-
promoting nutrients for human consumption as well as it takes into account the aesthetic
issues also without further depleting naturally occurring fish stocks.
So, let us try to understand the trends in algal biorefinery with reference to the aquaculture
systems. So with increased demand of second and third generation biofuels, private
investment has sprung up now far exceeding public funding. Currently, no algal biorefinery is
commercially operating. However, significant improvements to commercialization have been
reported by companies like Sapphire Energy, CEHMM and Cellana.
Although algae have been recognized as a promising biofuel feedstock, it is worth noting that
there are also some obstacles hindering the development of the microalgae biofuels. For
instance, with current available photo-bioreactors the production cost of algal biomass is
eight times higher than that of the fossil fuels. So, therefore maximizing the value derived
from algal biomass feedstock seems to be essential for the algal biofuel development.
1298
So as and when you produce more and more different value-added products from the algal
biorefinery system, the price of the algal biofuel will come down significantly.
At present, many other algal products are more profitable than biodiesel and these products
will be important to establish profitable algal biorefineries. However, it can be anticipated
that demand for these products will be much more easily satisfied which will influence the
price than the demand for biodiesel, which aims to replace large proportions of fossil fuels.
At present, the productivity of microalgal biomass on average can reach 80 ton per hectare
per year obtained from a microalgae plant.
If biofuel content accounts for 30% of the biomass, it is roughly into that range, the non-fuel
production can easily exceed 50 tons per hectare per year. So this is a direct mass balance you
can say taking into account 30% of the biomass goes for the biofuel production. So, vice
versa the ongoing research of microalgae biofuels will likely continue to alleviate the
production cost which is also a desirable criteria for the algal biorefinery.
1299
So, let us understand what is the future direction. Requirement of high cost and energy for the
large-scale production of microalgae has been the major constraint for its commercial
utilization. Reduction of excessive power expenditure through optimization of different
methods and technologies for agitation, harvesting, drying of biomass is one of the key
directions of future research as all these are energy intensive processes and costly.
Now moreover, efficient strain selection, genetic engineering and utilization of the
wastewater and carbon dioxide for biomass production should be taken into consideration.
So, microalgae species and strain selection is determined by many factors. Some of them are
growth rate, optimal temperature range, lipid accumulation, harvesting properties and
response to nutrient deprivation.
1300
Unsaturated fatty acids constitute the major proportions of lipids in microalgae, raising
concerns for storage of biodiesel as the acids are prone to oxidation. One corrective measure
is the partial catalytic hydrogenation of the oil. However, higher levels of polyunsaturated
fats lower the cold filter plugging point, the temperature at which the fuel starts to form
crystals or you can say solidifies and blocks the fuel filters of an engine.
It can be seen that the extent of unsaturation in oil lowers its melting point. Therefore, colder
climates require a higher unsaturated lipid content to enable the fuel to perform at low
temperatures. Linked to the cost of cultivation, the process byproducts as for example the
exhausted growth medium and exploited biomass should be recycled or be considered as new
substrates for other processes in an integrated biorefinery system with higher value and
commercial suitability.
For example, as fertilizer costs for nitrogen and phosphorus are likely to increase due to the
high energy cost and depletion respectively, it can be envisaged that unwanted biomass can
be used for biogas that is methane production whereby nutrients from the sludge can be
recirculated. Similarly, fish waste can be used to create additional revenue streams through
the growth of algae for biofuel and methane which is also called the Aqua-Sphere system.
To this end, the issue of bioaccumulation of heavy metals and bioactive chemicals need to be
considered if animal feed is to be produced repeatedly. Furthermore, it is important to search
for native microalgae species both for biofuel production and aquaculture due to the
environmental and economic benefits they offer.
1301
In aquaculture, it has been already reported that native species exhibited superior survival
than laboratory species in in larval P. magellanicus. However, the process of isolating and
testing new species of algae is extremely labor intensive and hatcheries are unlikely to adopt
new algal species without well-established culture methods and proven long-term success.
The enrichment of live algal feeds by altering culturing conditions and by adding
supplements to the culture water may be a very fruitful area of research.
Many researchers are working on this particular aspect. However, little is known about the
effect of this modified feeds on larval performance. More research is required on this aspect.
Moreover, the direct addition of dissolved organic components such as sugars, amino acids
and fatty acids to larval culture tanks may be a very direct and simple way to supply essential
nutrients to larva, although little research has been done in this particular area.
1302
Now, we will talk about waste biorefineries. I think we discussed about waste biorefineries in
one of our classes long back, but we are discussing this in an integrated biorefinery context.
So, a waste biorefinery is a means to valorize waste as a renewable feedstock to recover bio-
based materials and energy through sustainable biotechnology. Now, this approach
holistically integrates remediation and resource recovery.
You can see this is the petroleum based linear economy and this is the bio-based circular
economy. Whatever you get the environmentally clean and renewable energy. It is a
sustainable process, and this is a non-sustainable process. So it is ecologically and
environmentally friendly, this is not so. Now if you come to here, we talk about an integrated
waste biorefinery where different types of wastes can be recycled, reused as a feedstock for
the waste biorefinery to have various value-added products.
Now we can have more than one different types of conversion process whether it is biological
or thermochemical. And we can have different processes, unit operations inside a single
integrated waste biorefinery basically as we have learned about integrated biorefinery.
Integrated biorefinery is one in which we use different types of feedstocks, use different types
of conversion technology and what we get is different types of products.
So, waste valorization has become vital necessity where biodegradable organic fraction of the
wastes are treated employing biocatalyst under specifically maintained operating conditions.
Now, this is a need of the hour. This is nothing more fancy nowadays, this is the need of the
1303
hour. So, we get biofuels, we get water that is treated can be recycled back to the process
unit, we get different types of bio-based products including bioplastic and we get bioenergy.
So, traditionally waste remediation processes are intended to remove, reduce pollutants to
safeguard the environment. Now, no more that is the case. The current pressing need to find
alternative feedstocks has led to a transition from remediating waste towards refining waste
to recover valuable resources. Any waste whether it is solid, liquid or gaseous has an inherent
net positive energy that can be recovered and reused to produce bio-based products and
biofuels through a closed loop bioprocesses cascading system (more than one process)
enabling the shift towards a circular and low-carbon bioeconomy. The possibility is evident
that bio-based products which include platform chemicals, biofuels, bio-commodities can be
derived from waste at a scale that is sufficiently large.
Approximately 9 GT of carbon dioxide, 650 kilometer cube of wastewater and 2.2 GT of

solid waste at generated each year making it possible to substantially satisfy both the current
feedstock crisis and future sustainability requirements and creating independence from the
fossil-based precursors.
1304
The integrated approach encompasses multifunctional bioprocesses in an optimized sequence
to mine every constituent of waste (nothing is waste, everything can be converted into some
valuable product by a particular technology), with the objectives of maximizing the
productivity of mercantile intermediates and products and making the process more
economical.
Bioprocesses that utilize waste as a substrate for producing bio-based products require
appropriate technologies including acidogenesis, bio-electrogenesis, photosynthesis and
proto-fermentation, etc. In this scenario, acidogenic fermentation is evolving as a focal
process that enables a cascading progression of hydrolysis, acidogenesis, solventogenesis as
well as methanogenesis.
Current research is focused on navigating the acidogenic process to obtain specific high-value
products instead of solely producing methane if the reaction progresses to completion. So,
nobody is talking about only methane production. When you produce methane, you are also
producing other valuable chemicals, it is already being produced, nobody has ever thought of
that, we have to trap them and further refine them to get a value-added product, now that is
being done.
1305
Metabolically versatile acidogenic bacterias utilize various wastes along with carbon
monoxide and carbon dioxide to produce a variety of high-value products including short and
medium chain fatty acids, alcohols, biohydrogen biomethane, esters and other products
depending on the process parameters and of course operational conditions. A systemized
interlinking of bio processes is the key to constructing a waste biorefinery.
Effluents from acidogenic bioprocess could be used as substrates by photo biocapture clusters
- which are very commonly known as PCCs - comprising photosynthetic organisms to
advance treatment efficacy, assimilating gaseous waste basically as well as recover secondary
products. Now, these photo biocapture clusters have shown notable progress in the
production of biofuels and commercially viable bioproducts owing to their photosynthetic
and chemoautotrophic machinery.
1306
Microalgae with malleable metabolisms can be cultivated in autotrophic and heterotrophic
modes of nutrition utilizing carbon dioxide and the organic fraction of waste as their carbon
sources. Because they can consume various feedstocks, microalgae can be employed to yield
biodiesel, biomass or high-value chemicals such as pharmaceuticals, nutraceuticals,
antioxidants, food supplements and biofertilizers.
Photo-bacteria have been widely applied to waste remediation through photo-fermentation to

produce platform chemicals, bioelectricity, biohydrogen and biopolymers through photo-
anoxygenesis. Although there are certain challenges, the carbon dioxide bio-capture cluster
has the innate potential to solve energy and climate change issues in a unified approach or in
a more sustainable way also.
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The success of these technologies relies on the versatile metabolism of the biocatalysts and
their ability to utilize waste. More work has been done on this particular development of the
biocatalyst and many people are still working day and night to develop efficient biocatalyst.
Tailoring syntrophic biocatalyst into synthetic consortia that means comprising several
different organisms with this specific objective could escalate their potential to overcome
their individual limitations and maximize their productivity.
In addition to producing various bio-based products, the reducing equivalents that is protons
and electrons generated during the acidogenic process can be harvested as electrical energy in
the presence of an electrode assembly in a microbial fuel cell through a process called bio-
electrogenesis. We have already discussed about microbial fuel cell. Now, although the
achievable power densities with MFCs are low at present, they can be improved with
technological interventions combined with process optimization.
In addition to power, MFCs have many other applications such as bio-electrochemical

treatment for treating waste, microbial electrosynthesis and microbial electrolysis cell for
producing high-value products as well as biofuels. Electro-fermentation is closely associated
with the MES for steering fermenters and in a bio-electrongenic environment wherein, the
reducing equivalents in the anodic chamber are channelized to synthesize high-value
electrochemicals in the cathodic chamber through a defined circuitry control. Bio-cathodes
are being introduced to bio-electrochemistry to balance the drawbacks of MFCs providing
economic feasibility and higher power outputs.
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Synthesis of various products including short, medium and long-chain fatty acids, alcohol,
esters and diols are being researched using specifically enriched bacteria in microbial
electrochemical systems. Integrating PCCs with MES hypothesized to enhance the
photosynthetic efficiency leading to increased biomass and greater synthesis of light induced
bio-products including biodiesel, nutraceuticals, antioxidants, pigments and colorants through
that transport electron flux.
Photosynthetic bio-cathodes with their ability to produce oxygen develop a strongly

electronegative environment for enhanced proton transport, thereby concurrently increasing
the power output.
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Progressively retuning MFC configurations could make microbial electrochemical
technologies a viable option for the waste remediation, high-value product synthesis and
carbon dioxide sequestration in the context of a waste biorefinery, in turn ensuring
environmental sustainability and establishing a viable bio-electro economy.
Innovative and optimized process integrations to mine wastes to recover marketable products
can begin to reform the current linear economy leading to environmental biofactories.
Reconfiguring the current mindset to make the closed-loop approach a social norm will help
to transition from the petroleum refinery to waste biorefinery comprehensively addressing
sustainable development goals.
Food waste is one of the most commonly generated bio-waste in developing and developed
countries. The disposal of food waste pollutes the environment and results in a loss of
valuable nutrients. In order to conserve natural resources and to meet the environmental
discharge standards, the management of food waste for the production of high value-added
products has grown rapidly.
Food waste biomass has been mostly used for the production of biofuels with the aim of
partially or completely replacing highly polluting fossil-oriented fuels. The major
disadvantages by these traditional treatment technologies are excessive time, poor feasibility,
high cost, the emission of greenhouse gases and sludge production. The integration of a
biorefinery is the most promising technology used to convert food waste into value-added
products.
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So, this is a slide where integrated biorefinery concept diagram using food waste as the
substrate or feedstock has been presented. So, you can see that so food waste, so we can have
anaerobic fermentation. We get biohydrogen, biomethane, biohythane, VFA the volatile fatty
acids and biofertilizers the leftover. From microbial electrolysis cell also you get all these
things. We can have animal feed the left out things.
Yeast fermentation you get bioethanol, biodiesel. Bio-electriochemical process you get
biochemicals, biopolymers. So, after this whatever the effluents is left out just look at this,
the effluents basically the wastewater so you can further treat it to grow algae over that. What
we have discussed a few minutes before, so algal growth. Biodiesel, biomass, nutraceuticals,
animal feed. Again, the same thing whatever we are getting, of course a different product.
Then you go for anoxygenesis, you get bioplastics.
You can use it in the microbial fuel cell you get bioelectricity. So then effluents, again
whatever it is coming from this secondary effluents can be treated little more and can be
directly used for agricultural and farming processes. The concept of biorefinery is the
bioconversion of food waste into biofuels, power, heat and bio-products with the effective
utilization of the food waste. The complexity of integrated biorefineries is based on the
factors such as feedstock, byproducts and the applied technologies.
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Conventional biorefineries are designed around separate unit operations such as processing of
feedstock, fermentation and post fermentation recovery of the biofuels. For instance, the
processing of feedstocks such as corn or corn starch needs hydrolysis, followed by batch
fermentation and then recovery of product. These individual processes necessitate improved
principal and operational cost and production cost.
However, the progress made with these new technologies can permit these unit operations to
be integrated as hard as possible, increasing the viability of the existing biorefineries. In the
system, food waste and waste cooking oil are converted into biogas and biodiesel by
anaerobic digestion and transesterification processes respectively. And this is the established
protocol. Digested residue from the AD process can be further used as stand-alone fertilizer
or as a coenzyme in the composting process.
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Integrated food waste recycling by means of cultivation of the Rhodotorula glutinis and
anaerobic digestion for the fuel precursors. It was reported that dominant fatty acid methyl
esters such as palmitic, stearic and oleic acids were found to be perfect for the biodiesel
production. The maximum yield of methane was achieved from the anaerobic digestion of the
derived residual solids.
As mentioned in the previous section, AD is a complex sequential process and shows a

balanced equilibrium that involves accumulation of the volatile fatty acids within the digester
system. The over accumulation of fatty acids inhibits the methanogenic process. Therefore,
integrating hydrogen and methane production through two-stage fermentation is the possible
route.
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The blend of hydrogen and methane gas with a composition of 10 to 15% hydrogen and 50 to
55% methane and 30 to 40% carbon dioxide is called bio-hythane which is produced using a
two-stage anaerobic fermentation process. The raw materials used for the production of
hydrogen are sugar, starch and carbohydrates. Bio-hythane is considered as an energy carrier
with a higher energy conversion efficiency with the replacement of fossil fuels by the
biological processes.
The addition of a lower amount of hydrogen extends the flammability range of methane due
to its higher mass specific heating value than methane. The burning speed of hydrogen is
about seven fold higher than methane thereby reducing the burning time of the engine.
Furthermore, the presence of hydrogen reduces the emission of greenhouse gases into the
atmosphere with decreased carbon dioxide gas production.
Bio-hythane is considered to be an environmental friendly gas. Basically, what is done is that,

you know hydrogen and methane both are clean fuels. Hydrogen is a much more clean fuel,
but it has its own limitations. Methane has its own limitation. So, if you combine them in
different proportions and find some optimized proportion, then you can have a win-win
situation that you have advantageous things from both the fuels.
And you are clubbing together so that the bio-hythane can be used without any limitations,
which are already present with our hydrogen or otherwise methane if we talk about a
standalone.
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So, hydrogen is produced from food waste rich in starch and cellulose. Dark fermentation
produces hydrogen during the acidogenic stage of the anaerobic digestion of organic matter,
which is considered to be a promising technique relative to the conventional chemical process
because the need for chemical energy is less and it is therefore more ecofriendly. Based on
energy recovery, the output of energy is 7 to 9 times greater by the combined production of
hydrogen and methane than conventional hydrogen production alone and 10 to 12% higher
than that of the production of methane alone. Therefore, a two-stage fermentation plays a
significant role in maximum recovery of energy from the food waste substrate. Effective
biomethane production from non-gaseous fermentation products could make biological
production of biohydrogen economically attractive.
Numerous investigations have been carried out employing food waste as substrate for bio-
hythane production. The generation of bio-hythane has been investigated both in lab scale
and semi pilot scale extent. In the first stage, a higher hydrogen production of 66.7 liter per
kg VS was obtained. Whereas in the second stage a higher biogas production of 0.72 meter
cube per kg VS was obtained as distinctive bio-hythane composition.
One study executed a two-stage fermentation process for the enhancement of bioenergy from
the food waste. The results revealed the maximum yield of methane was observed by
utilizing effluent from the first stage. In addition, COD removal of 70 to 90% was obtained
under optimum conditions. The overall reaction rate and the yield of biogas were improved
by the production of combined hydrogen and methane in a two-stage process related to the
conventional two-phase process.
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Adapting older Biotech achievements such as bioethanol from sugarcane or beets into a
biorefinery could make them more efficient. However, biorefineries using food crops suffer
from the same sustainability issues as the first generation biofuels. Of course, much of the
hype surrounding biorefinery is the possibility and the technical challenge of using the
biomass waste or at least biomass resources that are sustainable.
The field’s close relationship with agriculture is one of the reasons there are so many
incentives. So, there is the hope that biorefineries could regenerate rural areas. So, one
example of company working towards this end is Matrica, which relies on plantations of the
thistle across Sardinia in previously uncultivated plots of the land, so unaerable lands
basically.
From the oil rich thistle flower and plant biomass, Matrica produces not only energy, but also
a wide range of products, perhaps unfamiliar to the normal consumer but essential to much of
our daily life, chemical intermediates, plasticizers, lubricants, components of cosmetic
products and there are many more..
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Meanwhile, Norway has Borregard which describes itself as the world's most advanced
biorefinery. Listed on the Oslo Stock Market with a market cap of over 800 million euro
Borregard specializes in using wood as a raw material. The resulting speciality chemicals are
used in fields as diverse as construction and pharmaceuticals. But it is not only wood that is
desirable raw material. In green biorefineries, grasslands are used instead.
For example, Biowert was founded in 2005 in Germany and now sells both bio-based plastics
and the grass green juice from which amino acids and proteins can be extracted and used as
flavoring agents or in cosmetics.
This is another success story. This is Billund Biorefinery process that is in Denmark. Then let
us talk about the waste, how waste can be converted. This is a classical success story. In this
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area Ynsect that is in France, a particularly curious case, so instead of enzymes or microbes,
it uses insects for the bioconversion steps in the refinement process. Insects eat the
agricultural waste such as fruit that did not meet the standards of supermarkets.
And the waste is then transformed into products from aquaculture feed to nutraceuticals. And
then in Denmark the Billund Biorefinery goes after other waste energy that is sewage.
Besides treating the water, this biorefinery utilizes the organic waste to produce biogas,
fertilizer and bioplastics.
So, now we will talk about the hybrid chemical and biological conversion process with
respect to the integrated biorefinery concept. So, hybrid biomass conversion technologies
have both biochemical and thermochemical steps. For example, heterogeneous catalytic
processes for converting aqueous phase sugars into hydrocarbons have been developed. The
overall process still requires a clean sugar stream generated from the pretreatment and
enzymatic hydrolysis of lignocellulosic biomass, but uses supported metal oxide catalysts to
make aromatic hydrocarbons instead of yeast to ferment sugars to ethanol. Now, if you recall
many times I have told you during our other lectures that this catalyst, supported metal oxide
catalyst has a huge role in the biorefinery concept. You talk about any other catalytic
conversion process, you need an efficient catalyst.
Now, at present also the catalysts which are commercially available are extremely costly. So,
there is a lot of research going on how to develop efficient catalysts from different types of
waste, industrial waste, biowaste and other wastes. Another hybrid under development uses
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the gasification to deconstruct lignocellulosic biomass to produce syngas, then a biochemical
conversion step to ferment the intermediate syngas to produce ethanol or other chemical.
Syngas quality is still a challenge as impurities can adversely affect the fermentation
microorganisms, but the process is less sensitive to syngas composition, that means the
hydrogen to carbon monoxide ratio, carbon dioxide and nitrogen concentration. Syngas gas
compression is also not needed for the ambient pressure process, but optimizing mass transfer
is critical for efficiency.
The main disadvantage of biochemical degradation and conversion process is their inability
to process the lignin fraction of the biomass feedstock. This inherently results in a loss of
carbon and thus an inefficient feedstock use. Purely thermochemical conversion processes on
the other hand are characterized by their own low product selectivity and thus relatively low
yields.
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This is a syngas fermentation process flow chart where the feedstock is being gasified here.
Then the syngas, there are many other processes as I told you many times this is just a simple
schematic to make you understand, it goes to the fermenter. The syngas is getting fermented.
Then it goes to a distillation column where you get ethanol is the distillate. Now, hybrid
biorefineries employ both previously introduced bioconversion platform that is biological and
thermochemical conversion platforms simultaneously.
By using a thermochemical degradation step like pyrolysis or gasification followed by a

biochemical conversion step, the usage of the biomass feedstock and the production of the
desired products is significantly increased. Now, these characteristics make the two platform
biorefinery perhaps the most integrated design as of now.
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So, the fermentation of syngas from biomass gasification is another possible route for ethanol
production from woody biomass. In this process, the ethanol synthesis is realized by a
biological fermentation. So far only very limited information is available about complete
process analysis for biomass derived syngas fermentation. Now, this process is realised in 5
major process steps discussed below or shown here.
Gasification, first we are getting flue gas and all these things. Then we have a gas cleaning.
So, the gas goes to the gas cleaning process. From here it gets to the compressor where there
is a fermentation happening here. From fermentation, one stream goes to the product
separation part, we get ethanol, acetic acid and all these things. This is a distillation column,
series of distillation columns. Another part goes to the compressor.
And basically to the CHP / combined heat and power generation unit. So we have
gasification, we have gas cleaning unit, we have fermentation unit, we product separation as
well as heat and power production unit. So, this is a classical flow sheet of the
thermochemical conversion with gasification and syngas fermentation So, thermochemical
conversion process is here, biochemical conversion process is here, both are integrated, This
is what is the integrated biorefinery is all about.
So, the gasification and gas cleaning is based on the same technology compared to the
gasification and synthesis process. Like in the catalytic synthesis, methane present in the
producer gas coming from the steam gasification process cannot be used within the syngas
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fermentation. In the present analysis, carbon dioxide is not regarded as a critical component
of syngas fermentation.
Therefore, no carbon dioxide removal process is assumed in the gas cleaning section. This
may not hold true for the layout of the fermentation reactor. Large fractions of carbon dioxide
present in the syngas will increase fermenter volume and power consumption for gas
compression. Furthermore, significant amounts of carbon dioxide will be present in the water
phase because of the significantly higher solubility compared to hydrogen and carbon
monoxide.
Ethene, ethane, tars, particulates, sulphur and nitrogen compounds may have an inhibiting
effect - not fully investigated yet. Thus further gas cleaning steps may be necessary.
For the fermentation of synthesis gas to ethanol, different bacteria are known so far. Beside
ethanol, these microorganisms produce acetic acid as a byproduct. In the syngas fermentation
process, carbon monoxide is consumed primarily by microorganisms, hydrogen is consumed
to a lower extent and methane present in the producer gas cannot be converted.
With a conversion efficiency of approximately 85% of the carbon monoxide content of the
syngas, the recycling of the unconverted gas does not appear promising because the partial
pressures of the main substrates - carbon monoxide and hydrogen - would be reduced in the
fresh feed leading to decreased mass transfer rates and increased fermenter volume. In syngas
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fermentation, the conversion is mainly limited by the mass transfer of hydrogen and carbon
monoxide in the aqueous phase.
So, Pardo-Planas et al in 2017 presented an Aspen Plus model of the production of ethanol
and acetic acid with the use of syngas fermentation. The reference is given below. The
considered biomass feedstock is switchgrass. The modelled process consists of a gasification
unit, a fermentation unit and a downstream processing unit. The model for the gasification
unit was based on an Auger gasifier.
Auger gasifiers have distinguished drying, pyrolysis and combustion zones. This allows for a
tight control of how much feedstock carbon is converted into char. The fermentation module
was modelled in Aspen Plus with the use of a stoichiometric reactor.
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So the reactor operates at ambient pressure and 37 degrees centigrade. Acetogenic bacteria
like Clostridium ljungdahlii, Clostridium carboxidivorans, then Alkalibaculum bacchi were
present in the reactor and catalyzed the following reactions. 4 carbon monoxide + 2 water
gives us CH 3 COOH + 2 carbon dioxide. Carbon dioxide + 4 hydrogen gives us CH 3
COOH + 2 water. 6 carbon monoxide + 3 water gives us C 2 H 5 OH + 4 carbon dioxide.
Then 2 carbon dioxide + 6 hydrogen reacts to give us again C2 H 5 OH and 3 water.
And in another work Michailos et al in 2019 developed another Aspen Plus model of a
syngas fermentation process, but modelled the gasifier as a circulating fluidized bed reactor
and used a CSTR reactor for the fermentation process.
The considered acetogenic bacterium was Clostridium ljungdahlii which converts

respectively 70 and 50% of the carbon monoxide and hydrogen present in the syngas to
ethanol. References are given below. If you are interested more, so please go through this
interesting work.
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So, with this I conclude my today's lecture and next lecture will be our last lecture for this
course. In that lecture, we will be covering about one of the very important thing, everybody
is talking about today, you develop some process what you will do with that? You have to
study the techno-economical aspects as well as the lifecycle of that, especially if it is a
biological system.
So, we will be discussing about that and we will wind up our course with that particular
lecture. So, thank you very much. If you have any query, please register in this Swayam
portal or you are always free to drop a mail to me at [email protected].
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Bomass Conversion and Biorefinery
Lecture – 36
Techno-Economic Evaluation
Good morning students. This is lecture 3 under module 12. And as you know that this is the
last module and we are discussing integrated biorefinery and today's lecture and the next
lecture, there will be one more lecture, is focused on two very important aspects of the entire
biorefinery concept. First one is the techno-economical assessment or analysis or evaluation,
so popularly known as TEA; that is what we are going to discuss today.
And in our next subsequent lecture and the last lecture of this course we will be discussing
about the life-cycle assessment. So, let us try to understand what is the techno-economical
analysis. Why it is required? How it can be done? Then I have taken a case study which is
recently published in one of the peer-reviewed international journal. So, that reference is also
given. So, you can download the paper and read later on after the class. So, it will make you
understand the entire lecture in a better way. So, let us begin.
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Techno-economical analysis and life cycle assessment are tools that can be used to evaluate
whether or not an existing or proposed chemical process is truly sustainable. How we will do
that? Now by assessing the economics of the scale and there are broader impacts. Now LCA
will take care of environmental things and others that is what we are going to discuss in the
next class. But today's lecture is completely dedicated to the techno-economic analysis.
Wherein we will be discussing about the economics So, techno-economical modelling is that
well established process which when developed in concert with technology ensures that
market driven prices can be achieved. So, whatever technology you develop and whether it is
a refinery, biorefinery, new industry, may not be necessarily a biorefinery, so you need to go
for this TEA and LCA.
So, you start with a feedstock or the base material from which you are trying to develop your
product or you are making the product. Then it goes through various processes, conversion
processes, purification processes, polishing steps, there are many, then finally you get your
purified product and you will end up in getting it in a certain value, the price of it. Now, that
price should eventually be related to the already available such products in the market on a
commercial scale.
Then only the entire process can become sustainable or economical. Otherwise, it is not going
to help the industry. So, typically this part of the stage-gate process in product development
and related research. So, applying techno-economic modelling at the beginning of a project
can greatly assist in reduction of unnecessary cost and investment risk. So, when somebody
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wants to start a industry or let us say biorefinery, he or she must be convinced that what are
the risks.
One of the risk is basically of course this investment risk where somebody is investing. And
another is of course the risks that are associated with the environmental concerns. Now, such
modelling provides cost and performance boundaries that actually assist in the creative
process that is forcing scientific teams to work within these confines, leads to new thought
processes as well as solutions.
Now, these process models integrating technical, economic and process engineering
information are versatile and precise tools that serve as a common language across technical
and financial fields, thereby allowing these 8 different types of parameters. The first one is
the definition of a project scale and scope for economic value. Second one is evaluation and
comparison of the alternative processes. Third is evaluation of alternative technologies for
relative value.
Fourth is for more informed project, process, technology decisions throughout the project.
Then fifth is providing a framework for test, analysis and a basis for continual processing
improvement. Sixth is evaluation of equity investment opportunity, returns and risk. Seventh
is sensitivity to changes in prices and efficiencies on project worth. And eight and last one is
calculation of the credit requirements, risks and other conditions.
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So if you closely look at this particular techno-economical analysis, it is a typical flow sheet.
So as I was telling you in the beginning of the class, so we start with raw material. Now raw
material means what basically? So you look here, the raw materials and what are the things
that is actually related to its cost. The first one is the market cost. If the raw material is
directly available in the market so that you can procure it, buy it directly, then it has a cost.
Even if it is not so you are going to collect it from some sources. Let us talk about our
biorefinery, biomasses, then what you are going to do? You need to procure it from forest,
agricultural field. So, it is a different model altogether, but there is a cost associated. Second
is that pretreatment. We have extensively discussed about pretreatment. What is the need of
pretreatment?
And you know that there is a huge cost associated with the pretreatment. And third is the
transportation, another major cost. So, all these costs together will get inside to the raw
material cost. Second is the process. Now, what is processing cost? There are 2 different
types of processing cost, capital cost and then second is the operating cost. Now, capital cost
is basically the equipment cost.
The equipment that is required for converting the biomass into value-added products. Now,
that equipment cost will be decided by three factors. First is the size. So what is that type of
reactor? 5 liters, 10 liters, 100 liters what is that? Then pressure and temperature. So, all these
things will (operating pressure and temperature) subsequently decide about the cost of the
equipment. Second is the operating cost.
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Now, operating costs have two major things. I am only telling you the major things, there are
small ancillary costs also. So, operating cost is first is energy the most important one, second
is the labor cost. But third, there are chemicals consumable cost also associated, but when
you compare it with energy and labor that is very small, so here it has not been written. Then
third is product. Now product disposition.
So, what is the product yield? What is the value of the products and what are the byproducts?
Now, this is very important. We have been discussing in our entire course that byproducts or
many times people call it waste products are literally not waste. They have certain value
addition. So we need to purify it, recover it, and again make it into a marketable product so
that it has some value addition.
So the standard and comprehensive approach for performing a financial and economic
analysis is a cost benefit analysis. It is called as CBA. So a CBA consists in monetizing all
major benefits and all costs generated by the investment and presenting their streams over the
lifetime of the technology expressed usually in number of years, which is known as cash
flow. Now, costs and benefits can then be directly compared between different scenarios as
well as with reasonable alternatives to the proposed project.
Generally speaking, a project is considered viable if the sum of expected incremental benefits
is larger than the sum of all costs accrued in project implementation. And now this can be
assessed through profitability indicators and there are various parameters to do that. Now, in
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general CBA provides four main indicators. The first is the NPV which is the net present
value. The second is the IRR, which is known as the internal rate of return.
Third is B by C ratio, which is benefit by cost ratio. And the fourth is the payback time. Now,
these indicators assess attractiveness of investment by comparing the present value of money
to the value of money in the future, taking the time value of money, so that is the discount
rate basically, and returns on investment into account.
Now, therefore these indicators are important decision making tools for investors, national
government as well as for donors and IFIs, the international financial institutes. Now net
present value: so NPV indicator is determined by calculating the cost (negative cash flow)
and benefits (that is the positive cash flow) for each period of an investment and by
discounting their value over a periodic rate of return.
Now, NPV is defined as sum of the results when the initial cost of the investment are
deducted from the discounted value of the net benefits. So, basically revenue minus the cost.
Then next one is the IRR, internal rate of return. Now IRR indicator is defined as the discount
rate at which the NPV equals 0. Now, this rate means that the present value of this positive
cash flow for the project would equal the present value of its cost.
So, how it actually accounts into you can understand from this next sentence that, if IRR
exceeds cost of capital, project is worthwhile that is it is profitable to undertake, otherwise it
is not so.
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So then the benefit by cost ratio. So B by C indicator is the ratio of the present value of
benefits to the present value of costs over the project lifetime. The B by C ratio provides
some advantages when a ranking of alternative investment project is needed under budget
constraints. So if B by C is greater than 1, the project is accepted. If it is less it is not
profitable, so there is no question of accepting the project.
Then, one of the most important one is the payback time PBT. So the PBT measures the time
required for the net cash inflows to equal the original capital outlet. So it is the number of
years required for the discounted sum of annual savings to equal the discounted investment
costs or in other words the time span after which the investment will start to pay back. So,
you generate profit basically.
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So, before performing financial and economic cost-benefit analysis, the investment must be
contextualized into an economic, institutional, social and technical framework to identify
relevant barriers and constraints. So, the first step is the identification and description of both
the benchmark scenario and the investment scenario. Now, the second step is the
identification of the investment’s outcomes including the capital and operating costs and the
monetized benefits.
Then the third step is the determination of the project’s incremental net flows, which results
from the comparing costs and benefits of the project with costs and benefits of the benchmark
scenario. Now, with these elements it is possible to calculate the financial project profitability
indicators. So, the next one is converting market prices into economic or shadow prices.
Removing transfer payments that is taxes and subsidies and quantifying positive and negative
externalities to calculate the economic flows. Perform sensitivity analysis in order to deal
with the main risks and uncertainties that could affect the proposed project. I will talk about
sensitivity analysis in the fag end of today's lecture.
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Let us look at this particular schematic representation of the overall framework for LCA and
TEA analysis. LCA we are going to discuss in next class in detail. So, you can see that capital
expenditure. Purchase cost, installation cost, engineering and construction cost, then there are
financing costs, then there are operating costs. It is written as CapEx and OpEx. So, raw
materials, energy, labor. This is what we discussed in the figure 1 first.
So, all these things to be taken into account when you discuss that techno-economical
analysis or evaluation. Apart from that, the material processing and fabrication cost, then
LCOE and GHG that will come under LCA, the greenhouse gas emission and all that we will
discuss next class. Then upstream, logistic, conversion process emission inventory, this also
comes under LCA. So, TEA is restricted to different types of costs.
LCA also takes into this type of material processing and fabrication details into its account.
So, this is understanding of the overall framework of the LCA and TEA how it can be done
together and both are done together actually for any new project that you are going to start.
So, I have taken a case study, it is an interesting one, a small work actually. So, there are big
works which are reported, big in the terms of number of processes and all.
So, this I have to chosen so that we can discuss it in our class and you can get an
understanding that actually how it works. Once you learn the nitty gritties, then you can
always go and read more details if you are interested to do so. So, I have taken mango
processing waste biorefinery case study which is reported in one of the very good work in the
1334
industrial crops and products journal. So, I have given the reference, you can later on see So,
let us start.
So techno-economical evaluation of an integrated mango processing waste biorefinery. So

techno-economical evaluation is mandatory for a novel process to be upgraded for
commercialization. It provides useful data including profitability. Now, these data serve as a
directive for emerging and changing capital spending plans, for evaluating operating and
maintenance cost, for forecasting profitability, and for guiding future research and
development efforts of the process. The success of a biorefinery model depends on the
availability of the raw material. Therefore, the search for the resources that are generated in
large quantity becomes important. Mangoes are one of the major agricultural commodities
mostly in the tropical countries and India ranks among the first in the world's mango
producing countries.
The production of fruit in India accounts for 52.6% of the global mango production. So, you
can understand that how much of waste we actually generate and why there is a need to talk
about the mango processing waste biorefinery.
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Now mangoes are popular choices for processing because of their succulent taste, richness in
carotenoids, ascorbic acid and a greater availability during the summer seasons. The growing
popularity of fresh and processed mango products may be estimated from the fact that India
exported 36,000 tons of fresh mangoes and 129,000 tons of mango pulp during the year
2015-16. So, this is the statistics which I got from the manuscript.
I am sure this statistics has been increased and we may have added more tons to whatever
being written here. So, processing units purchase mangoes from market yeards as they are
assured of large quantities to run the unit continuously till the mango season is over that is
very important. So, processing of mangoes leads to generation of almost 25 to 40% of the
fruit as a waste.
Peels are the major byproduct of mango processing which contains valuable nutrients such as
polyphenols, pectin, sugars and natural pigments. Pectin is a bioactive hydrocolloid that has
major applications in food and pharmaceutical products.
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Mango peel polyphenols were explored in literature for potential applications such as
antioxidants and preservatives. Mango peel fibres were found to be a good source for soluble
fibres, which later exhibited pre-biotic properties also, so that is very interesting actually. So
that is why a lot of work has been going on on this conversion. The other methods of
utilization of the peels may include livestock feed, biochar and preparation of compost.
That utility peels as livestock feed is limited by the presence of tannins which may act as
anti-nutrients and interfere in the growth of the animal, but it depends on how much tannin is
present. So mango kernels are mainly reported for the recovery of the lipids and starch.
Mango kernel lipids that contains about 9 to 13% of lipids on dry basis were classified into
neutral lipids that is almost 94%, then phospholipids 4% and glycolipids 2%.
Now, the uniqueness of lipid composition was highlighted in many recent studies, especially
the application of mango kernel oil as a cocoa-butter replacement because cocoa-butter is
very costly.
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So, food industries in particular are searching for the cocoa-butter alternatives due to the high
price and demand. Mango kernel contains significant quantities of linoleic acid that is an
Omega-6 fatty acid, is a good fatty acid, and small quantities of alpha linolenic acid which
are essential fatty acids required in the human diet. Now, the mango processing waste is
available as a local raw material in western part of India and rich in potential bio-active
compounds.
It may therefore be utilized in a biorefinery model for the recovery of many valuable
products. The chemical properties of mango processing waste are primarily controlled by 5
key components. First is peel to seed ratio, then pectin and cellulose content in the peel,
starch and oil content in the second kernel.
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An understanding of how pre and post harvesting operations and natural variability effect
physical and chemical properties of the feedstock would help one develop strategies to
sustainable extraction and production of high value products. In India, there are more than 30
popular varieties of mango, but when it comes to processing there are only handful varieties
that are preferred by the processing industries.
More than 80% of mango processing market in India is contributed by Alphonso, Totapuri
and Kesar varieties. So, we have so many varieties in India of the mango. So, there are
certain regions in India where a particular type of varieties processed at a very large scale.
For example, in the state of Maharashtra processing Alphonso variety is most popular.
Alphonso is mostly being produced only in Maharashtra. And in Chittoor district of Andhra
Pradesh, Totapuri variety is processed at a very large scale.
So, the unique selling point of the proposed biorefinery is that variation due to varietal
differences could be avoided by decentralized approach of procurement of waste unlike
agricultural residue biomass supply chain where feedstock is sourced from multiple locations
and residues of multiple different crops. So, I hope you understand this. This we are talking
about the supply chain management system.
When you talk about a biomass based refinery, you need to procure it from different parts of
the agricultural fields and forest. When we are talking about mango waste refinery, please
understand that mangoes are already coming to that mango processing plant and we are
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getting the waste entirely directly from the processing unit and we can also set up the small
scale biorefinery plant itself along with the mango processing unit.
So that is also doable and if that is done then it will save a lot of other cost also, logistical
cost. Now procurement of 20 kilometer radius of mango processing unit ensures that mango
processing waste would have similar traits. Even though procurement of raw material can
happen for multiple suppliers, consistency of feedstock can be ensured by accepting only a
single variety to minimize variations in chemical composition.
Standardization of raw material quality is possible with mango processing waste because top
grade mangoes are procured by mango processing units and they need to pass stringent
quality criteria before they can be pulped for export purposes.
Except composting and biogas generation, there is no commercial facility for valorization of
mango processing waste into value-added products. However, there are studies available for
separation of individual components such as mango seed oil, pectin and total polyphenol.
Feedstock availability in large quantity is feasible when proposed plant is located within 20 to
30 kilometer radius of pulping facilities or else I just told you what will happen - Then your
transportation and logistic cost will increase. In Indian context, if we consider large mango
processing units, they process between 60,000 to 100,000 tons of mangoes in just 3 to 4
months which essentially means that each plant produce about 25,000 to 40,000 tons of waste
during this 90 to 120 days of operation. It is a huge waste. Average pulping waste collected
from a medium scale mango processing industry is about 50 to 100 tons per day.
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So, some regions have more than 10 units within 20 to 30 kilometer radius. Therefore,
collection of even 500 to 1000 tons of waste per day is feasible in Indian context. So, this is a
very interesting observation. This is already reported in literature and we know it is a fact that
most of these so called mango processing units are usually located in the state of Maharashtra
as well as in Andhra Pradesh and other states also where like West Bengal and few other
states.
So, they are located in close proximity or almost 15, 20, 30 kilometer radius. Let it be 50
kilometer also, no issue. So, what is the inherent meaning of this? So, if they are actually
located inside this 20 to 30 kilometer radius, then collection of these waste from this
particular area is a viable alternative or sustainable alternative in terms of economics.
Otherwise, suppose you are collecting from 100 kilometer, 200 kilometer distance.
Then the handling cost, transportation cost will add on so much than whatever a procurement
of the waste you are doing that cost of the procurement from the source and getting it to the
biorefinery will be so high that even if you process also your final product like pectin and
other things are not going to be economical. So, an assumption therefore is to take lower side
of the processing capacity for a biorefinery plant so that supply chain remains feasible for
smooth plant operation.
Supply chain is the most important aspect of any biorefinery. Since mango pulping is a
seasonal business and pulping continues only for 3 to 4 months, it is assumed that plant
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operates 24 hours per day and 180 days per year. So, keeping dried material in inventory for
2 months that is an assumption with collection of 240 tons per day waste per day as a base
case, which could easily be procured within 20 kilometer radius of the proposed facility.
So, your location a biorefinery should be in such a way that all the mango processing units
are located within 20 to 30 kilometer radius. So, an exhaustive biorefinery involves many unit
operations, therefore the cost incurred in the process also goes up quite significantly which
becomes a bottleneck for the process.
Let us understand how it happens actually. So, the first one, the part one A which is here this
side, your left hand side is the mango processing waste biorefinery schematic representation.
The B, the second one talks about the pectin production from the mango peel production
which is the most important product from this particular waste biorefinery. Let us see this
one.
So mango processing waste. So, there are two different things, one is the mango peel, another
one the seed. Let us see what is there in the peel. So peel that gets a drying, again huge
amount of energy is required. Then you go for some mechanical preprocessing, again energy
is required, size reduction basically. So then you extract polyphenols using ethanol. There is a
cost involved. Then the peel residue goes for drying, again energy intensive process.
Then you finally remove the pectin or you extract pectin using water plus mineral acids.
There are other things. Then you precipitate it using ethanol. Then finally it goes to dryer and
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you get the dry powder pectin. Now, similarly, the mango seed. Now mango seed has 2
different things. One is the seed coat, another one is the mango kernel which is inside. Now
you just send it to electricity production.
Usually it contains some cellulose, hemicellulose very small quantity and mostly lignin and
some extractive materials will also be there. Let us talk about mango kernel. So, it goes to
steeping, size reduction, fractionation that it contains lots of oil that we have already
discussed - different types of oils actually. So, you remove the oil. So, whatever left out is
basically starch and there is some amount of protein rich meal - the final cake or the waste
material or what you can say the solid part after removing everything it has certain protein
content. So that can be used as cattle feed and some other applications. This is all about
mango processing waste biorefinery concept. Now let us talk about the pectin production
from the mango peel waste. So the dry peel powder. So use ethanol to remove it. Then you
have ethanol recovery unit here.
It is an integrated system approach. So, then it goes to, there is a membrane, so you remove
that ethanol, then whatever the peel powder that is left out the solid one, you go for drying.
Then pectin extraction happens. After the extraction, you have a pectin rich layer. You have a
liquor plus residue here. Pectin goes for drying and then you collect it. The liquor plus
residue, finally you get a peel residue and a liquor.
Now, that peel residue finally can be utilized for some other purposes like cattle feed and you
can also go for some pyrolysis to produce activated carbon or biochar out of this. So, this is
an overall understanding of the mango processing waste biorefinery concept as well as how
do we produce pectin from the mango peel waste.
(Refer Slid e Time: 25:42)
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So, mango peel processing. Extraction of polyphenols. The mango peels are dried in a rotary
dryer and pulverized using a ball mill to prepare a fine powder for extraction of polyphenols.
I am just talking about how this processing is happening. We will just briefly discuss. There
are several alternatives available such as hammer mill, vibratory mill, ball mill, knife mill,
two roll mill and disk mill for biomass size reduction, mechanical processing.
The ball or vibratory ball mills are universal types of disintegrators and can be used for either
dry or wet materials. Choice of mill essentially depends on two major factors. First is the cost
of the equipment and second is the energy requirement in comminution. Now, energy
requirement for size reduction is influenced by initial particle size, moisture content, material
properties, feed rate of the material and machine variables.
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In case of dried mango peel if the moisture content is less than 10%, chopping and grinding
could be integrated to optimize grinding energy and get better results. The particle size of
mango peel waste certainly plays very important role in pectin and polyphenols extraction. It
is known fact that the specific energy requirement for grinding biomass increases with a
decrease in the screen size or degree of fineness of the grind.
So, it would be better to maintain particle size near Mesh 20. So, another important factor to
be considered is to observe the particle size distribution pattern and evaluate the maximum
likelihood of particles falls within a narrow range that is consistent particle size distribution
should be known to minimize chances of process variations. Extraction process involves
refluxing up 95% ethanol solution with solid solvent ratio of 1 is to 20.
After refluxing for 4 hours, the liquid stream is transferred to distillation unit to concentrate
polyphenols and recycle ethanol water mixture in the process. Subsequently, extract is spray
dried to obtain polyphenols extract powder. For encapsulation of polyphenols, maltodextrin is
widely used as a wall material. The core material for encapsulation is homogenized with the
wall material, then mixture is fed into the spray dryer and atomized with a nozzle.
This causes rapid evaporation of moisture from atomized droplets. Peel powder residue that is
saturated with 95% ethanol is then dried for subsequent pectin extraction process and ethanol
water mixture is recovered as condensate which goes back to the process as a recycled
stream. Thus, more than 98% of ethanol is recovered in the system.
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Now, the different parameters on the basis of which the economic analysis was conducted are
as follows. The first one is the capital investment cost. So an economic analysis was
conducted to estimate the NPV, IRR and PBP respectively which is based on the capital
investment and an operating cost of the refinery. Model for integrated biorefinery was
constructed in this Superpro designer, so it is a software, it is a tool to carry out such TEA
analysis.
So, capital investment costs are estimated based on the purchase cost of each piece of
operating equipment. The purchase cost for the major equipment items were based on
budgetary quotations from the equipment suppliers. The mass and energy balance outputs
from the processing model were used to evaluate the capital and operating cost.
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Equipment cost information was derived from literature, equipment suppliers and the
Superpro Designer software database. All currency used in the models are in US dollars
adjusted to the year 2017. So, the new cost that is the base cost into new size by base size to
the power of 0.6.
So this is being used to calculate the cost. So, direct fixed capital cost is the sum of the direct
cost, indirect cost and other costs of contractor’s fee and contingency.
Now the DC that is the direct cost estimated from the Superpro Designer is based on the total
equipment purchase cost using a distributed set of EPC factors. So, these are some in-built
features in this particular software Superpro Designer. So, the plant considered here is
assumed to be financed without any external loans and thus no amortized loan repayment is
required. Now, the plant has a 15 year lifetime with salvage value at the end.
Then the operating cost: Operating costs of mango processing waste based biorefinery
consists of raw material cost, utility cost, labor, laboratory cost, consumables and the waste
disposal cost. Now, these costs are based on the literature survey, communication with
industries, market prices observed in 2017 in Indian context. Mango processing waste has no
formal price mechanism in Indian market and is largely thrown away in dumping yards and
landfills.
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Waste which fetches no value from processing plants at present, it will no longer be available
for zero cost if proposed plant comes into being. Considering very high moisture in the waste
and assumption is that mango processing waste can be procured from processing plants at 25
dollar per metric ton as basis that is the basis actually.
So, there is no overhead on transporting raw material as material is assumed to be delivered

at plant gate by aggregators at 25 dollar per metric ton price. Since 6 months of plant
operation necessitates 2 months of raw material storage, cost of storage has been included in
the raw material cost and spread across all 6 months in the calculation. So without storage,
the price point at plant gate was assumed to be 21.7 dollar per metric ton, which is at par with
the price of the biomass procured for power plants in India, at par with that. So, storage cost
of 10 dollar per metric ton was considered for 2 months period. Therefore, for fifth and sixth
month cost would be 31.7 dollar per metric ton of mango processing waste. When cost of
storage was included in the raw material cost itself and spread across all 6 months, it comes
out to be 25 dollar per metric ton.
This is how it is actually being calculated. So, water tariff structure is not consolidated at
national level in India and states are responsible for choosing tariff structures and it varies.
So, it is very difficult to consolidate something on that.
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Since water access is scarce in India, price of water is on the rise and considered on the
higher side in this study, we have considered 0.7 dollar per kilolitre. Fixed operating costs are
generally incurred in full regardless of whether the plant is producing at full capacity. For this
study, electricity tariff is considered to be 0.35 dollar per kilowatt hour which is significantly
higher when compared to countries such as United States or United Kingdom, where the
energy price is very less.
Now, contrary to the developed countries labor cost in India is moderately low. So, we are
offsetting in that labor cost, labor cost is very high in the developed countries. So, based on
data procured from Indian industries 10.5 dollar per hour was assumed as the labor cost. It
may vary depending upon the area where you are locating it. So, it may be ten 10, it may be
11 something like that.
So for the proposed plant, steam is assumed to be generated through coal. With boiler
efficiency of 85%, steam cost is estimated to be 17 dollar per metric ton. Now, other costs
include labor, laboratory, consumables and water treatment charges which cumulatively
contribute to about 21% of the total operating cost.
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So, this talks about the total capital investment cost for the PEP, PSEP and WMB, the 3
different processes in the mango waste processing birefinery concept. So, total plant direct
cost, equipment purchase costs, installation cost, process piping, instrumentation, insulation,
electrical cost or charges, building cost, building cost is almost 40% you can see. So, yard
improvement, then total plant direct cost.
Engineering is 60%, construction 85%. Then total plant cost is TPIC these two + TPDC. So,
you get this amount. Then contractor’s fee and contingency, the contractor’s fee and
contingency has been separated here. If you add all these things, you get the direct fixed
capital cost equals to TPC + CFC. So, this gives us an understanding about what is the actual
values.
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So, table 2, this gives us an understanding of the economical evaluation parameters of the
mango processing waste biorefinery model. So, these are the time parameters. Analysis year,
project life, construction period, then startup period (months 4), inflation rate 4%. Then we
have financing parameters like equity, 100% equity here in this case. Depreciation method, a
straight line depreciation method was used. Then depreciation period; here it has been taken
to be 10 years. Income tax has been assumed as 35%.
It also varies every year, you know that. Discount rate have been fixed at flat 10%. So, then
there are annual operating cost, start up cost, salvage value. And construction plan value like
first year how much percentage, second year how much percentage, third year how much
percentage, the construction also goes on but you start the operation at certain unit. So, it is
an ongoing process. So, it has been assumed that within 3 year all sorts of construction will
be over.
So, then this table gives us an understanding about the annual operating cost and material cost
for mango processing waste biorefinery. So, if you closely look, the costs are basically the
raw material cost, labor, laboratory costs, consumables, waste disposal, utilities, all these
things. So, if you talk about the raw materials directly as a component, so there is the ethyl
alcohol, hexane, mango peel, mango seed, mineral acid, RO water, potassium metabisulfite
and water, not much is required.
So, all these costs are tabulated here. So, the fixed capital cost of the biorefinery plant with
the base capacity was estimated to be 41.8 million dollars. However for PEP and PSEP
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processes, FCC was estimated to be 23.2 and 24.9 million dollars respectively. This is about
almost 55 to 59% of the FCC incurred by the mango biorefinery process.
Now, the purchase and installation of a rotary dryer, extraction unit, storage tank and
centrifuges were the major contributors to the total capital fixed cost which was the main
contributor to the total capital investment. So, this is basically the the instruments or
equipment.
Then operating and production cost. The mango biorefinery plant required higher annual
operating costs due to its complex unit operations for multiple products and energy recovery.
The unit operating costs per PEP and PSEP are comparable. Now, the annual operating costs
for the process were $6,997,000 for PEP; $7,582,000 for PSEP and $10,427,000 for the
WMB respectively in dollars.
So, the largest contributor to the annual operating costs are the utilities costs, so that is almost
are 63.4%, 68.7%, 68.3%. So, mostly they are comparable and they are of the same scale of
the total operating cost. The electrical power consumption cost is very significant almost
58%, 65%, and 69% of the total utility cost for the different processes. Among the utilities
and raw material contribute only 14 to 17% of total operating cost.
Steam is the second largest required energy resource in the process accounting for about 20 to
28% of the total utility costs. Significant amount of steam is used to provide heat in the
distillation and evaporation unit operations.
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So the last one what I am going to talk about is the sensitivity analysis. Now plant capacity
was found to be a dominant player in changing the economics of the plant in most influential
way. The second dominant factor that influenced the economics of the plant was days of
operation. Considering the seasonality of the fruit that is 3 months in a year (for the mango
we are talking about), it was assumed in base case that waste would be collected during peak
season and enough material would be kept as an inventory for total plant operation for at least
continuous 6 months. In worst case scenario, waste processing time was considered same as
mango pulping period of 3 months and no inventory was considered at all. One of the
consequences for such approach would be that plant stands idle for the rest of the year, which
is not good.
So, in this I wish to say something. So, we have discussed about biorefinery in detail. So
many different types of biorefinery, different models, we have all discussed. Now, I hope you
can understand that, why this particular plant will keep idle for 6 months; that is not
sustainable. What will happen to the human resources that are engaged in this particular
mango waste biorefinery?
So, there is a need to look for such other waste which can also be processed in the same type
of equipment whatever we have already installed for the mango waste biorefinery processes.
It is a very holistic thinking that you can run the plant for the entire one year. There is no
question of any shutdown and sit for idle for 6 months. So that is anyway not going to
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become sustainable because once you shutdown the plant, starting it up is also a costly affair
and it is a time consuming process.
So, refinery whether it is small scale, large scale must continue its operation throughout the
year, 24 x 7; even if it is not 24 x 7 also. Then only it will become sustainable. So, the only
approach is to look for other waste which can be processed in the similar unit operations,
which are already installed for the mango waste biorefinery.
So to make the best use of the facility plant should run as long as possible. To evaluate this,
it was assumed that processing waste must be dried to a safe moisture level, less than 10%,
for the storage purpose and plant should run for 270 days in a year. Long term storage greater
than 4 months may lead to the loss of polyphenols. The quality of pectin and lipids may also
change with time. In order to minimize the processing related challenges, perishable
inventory management becomes very important.
Even though longer period seems to be an attractive option, quality aspects of products must
be considered before storing the perishables. One important barrier for developing countries
such as India is the lack of an enabling environment, that is institution, support services and
infrastructural facilities. The availability of skilled people and laboratory facilities must be
considered for better quality management.
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A stable process is characterized by stable and high products yield, low process variations
and less impact on product quality. Effect of price variation in product prices is also quite
significant from plant economics viewpoint. The base case price for mango oil and pectin is
considered as 8 dollar per kg and 10 dollar per kg respectively, which is somewhat modest
when compared against international market.
Now, it has to come down further, to make it more commercially successful products. Now,
for sensitivity analysis lower bound on seed oil price was assumed to be 4 dollar per kg and
the highest international market price was assumed to be 12 dollar per kg; that is quite offset,
so that you can look for a very good profit. So, it was found that NPV increased linearly as
price of the product increased.
A similar trend was followed when pectin price changed from 10 dollar to 14 dollar per kg.
On the lower side, pectin price was assumed to be 6 dollar per kg, NPV reduced by 40%.
When price increased to 14 dollar per kg, NPV also increased linearly, $61 millions. So, this
is just an understanding about how it will happen when we talk about the sensitivity analysis.
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So, the peel to seed ratio in mangoes are affected by the change in variety. Considering the
variations in the peel percent in the waste, it was observed that effect on NPV was negligible.
One of the most crucial problems faced by biomass based projects in India is the
sustainability of a good quality raw material supply at a reasonable cost throughout the year.
I have been telling this, that the supply chain management issue is the most important factor
that should be tackled or looked into before anybody starts any biomass based biorefinery
anywhere in India. So hence, it is imperative to understand how variation in raw material
price would affect overall economics of the plant. One of the ways to foster the supply chain
of mango processing waste is to incentivize supply chain players by offering attractive price
for the raw material.
It is interesting to note that shift of raw material purchase price from 25 dollars per ton to 45
dollars per tonne did not have any significant effect on the NPV. I hope you get a message
and understanding that how this economical evaluation is basically being carried out, what
are the typical cost, capital cost, operating cost? So, I deliberately chose a short case study so
that we can quickly understand. There are very excellent works reported in literature. If you
are interested, you can just download and read more into that.
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So minimum capital investment and maximum returns is ideal for a business. Operating days
is another important parameter for plant economics. It is expected that plant should be
utilized to the maximum capacity, but challenges such as unavailability and storage of
seasonal perishable raw material for longer period becomes a bottleneck. So, this is a
bottleneck for any biomass based industries.
Compositional variations could pose another challenge for the plant economics. Based on
available data in Indian context, 3 to 6 months plant operation seems feasible which requires
storage of raw material up to 3 months. Overall, the techno-economical model shows that
huge quantum of mango processing waste that is currently been disposed of in many parts of
the world could be used as an excellent feedstock for the recovery of multiple products.
So, as I told you many times unless and until in a single biorefinery you look for multiple
products, then your biorefinery is not going to become sustainable and economical.
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So, I hope you get an understanding about what is the techno-economical evaluation analysis
is all about. In our next class. I will talk about the life-cycle assessment and then we will
close the course. And thank you very much. And if you have any query, you can always drop
a mail to me at [email protected] or please register your query in the Swayam portal, we
will answer it. Thank you.
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Lecture – 37
Life-Cycle Assessment
Good morning students. As you know, today is the last lecture of this module as well as for
this entire course. And under this particular lecture, under this module named integrated
biorefinery, we are going to discuss about the life cycle assessment with a case study. As you
know that last class we have discussed about the techno-economical evaluation or
assessment; even in one of our previous modules we have discussed briefly about the TEA
and LCA.
But in this module we are going to discuss in detail about both TEA and LCA. TEA we have
discussed, LCA we are going to discuss today. I will also take an example or we can say a
case study that how LCA has been done or carried out for that particular biorefinery. So, let
us begin.
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Life-cycle analysis also known as life-cycle assessment is a primary tool used to support the
decision making for a sustainable development. According to the US Environmental
Protection Agency, LCA is a tool to evaluate the potential environmental impacts of a
product, material, process or activity. Crucially, an LCA is a comprehensive method for
assessing all direct and indirect environmental impacts across the full life cycle of a product
system, from materials acquisition, to manufacturing, to use, and to final disposition or you
can say disposal or even reuse. The application of LCA helps to promote the sustainable
design and redesign of products and processes leading to reduced overall environmental
impacts and the reduced use and release of non-renewable or toxic materials.
So, if you recall our earlier discussions, LCA mostly relate itself to the environmental
concerns; how a product which we are making in an industry, it can be any product, how it
performs in its entire lifecycle. So that means we begin with the feedstock, then feedstock has
been processed, converted to some product, it is purified, polished to a final product, then
there are so many waste streams that comes out. Various types of waste, it can be solid, liquid
gas. How those wastes are being actually treated? How those wastes are being recycled and
reused? And all these things are being covered in a life cycle assessment. So, it tells us a
comprehensive and overall view of how a product, once it is formed, is going to have a broad
environmental impact during the use as well as after the use also.
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So, LCA studies identify key materials and processes within the products’ life cycles that are
likely to pose the greatest impacts including the resource demand and human health impacts.
Now, these assessments delineate the full benefits and costs of a product or process which
allows decision makers to select the most effective solution. The LCA process is a
systematic, phased approach and consists of 4 components
What are those 4 components? The first and foremost one is the goal definition and scoping.
What is the scope? And how you define it basically? Second is inventory analysis. Third is
impact assessment and last one is the interpretation. Now, all these things we will discuss in
subsequent slides today itself and when I take a case study, it will be more clear to you. So,
life-cycle assessment is a cradle-to-grave approach for assessing products, processes,
industrial systems, and the like.
Cradle-to-grave begins with the gathering of raw materials from the earth to create the
product and and ends the point when all materials are returned to the earth. So, this is a more
holistic approach when you talk about cradle-to-grave. It starts from a point where it ends in
the same point basically. So, it is a cycle.
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So LCA evaluates all stages of a product's life from the perspective that they are
interdependent, meaning that one operation leads to the next. LCA enables the estimation of
the cumulative environmental impacts resulting from all stages in the product life cycle and
as a result allows selecting the path or process that is more environmentally preferable. LCA
approach has developed over decades coming from product-oriented model used to evaluate
environmental impact to a bigger framework that elaborates on a wider environmental,
economic as well as social scale. Social is also very important. Now at the current stage, LCA
is being transferred into life cycle sustainability analysis which people call it a LCSA, which
links the sustainability questions with the knowledge and research needed to address them.
Now by including the impacts throughout the product life cycle, LCA provides a
comprehensive view of the environmental aspects of the product or process and a more
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accurate picture of the true environmental trade-offs in product selection. Specifically, LCA
is a technique to assess the environmental aspects and potential impacts associated with a
product, process or service by: compiling an inventory of relevant energy and materials
inputs as well as the environmental releases; Second, evaluating the potential environmental
impacts associated with identified inputs and releases; Third is interpreting the results to help
make more informed decisions. So, all these points are going to help us when we carry out
this LCA or LCSA.
So, you can have a look at this figure 1. So, this describes the phases of a life cycle
assessment. It was adapted from US EPA. So, goal, scope and definition, inventory analysis,
impact assessment and interpretation. Now, all these things are interrelated with each other.
So, that means once the goal and scope definition can be interpreted and then that same can
be used by inventory analysis.
Inventory analysis, data can be interpreted that same can be used to do the impact assessment.
That means basically the meaning is that all these 3 parameters, the basic parameters, they are
interdependent on each other. So, the term life cycle refers to the major activities in the
course of product's life span from its manufacture, use, maintenance and final disposal. Now,
the final disposal again as I told you earlier also that including the raw material acquisition
required to manufacture the product.
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The LCA process is a systematic, iterative, phased approach and consists of 4 components.
Goal definition and scoping, inventory analysis, impact assessment and interpretation. Now,
sometimes this also calls improvement analysis.
So, let us understand what are these 4 parameters. So, Goal definition and Scoping: now
define and describe the product, process or activity. Establish the context in which the
assessment is to be made and identify the boundaries and environmental impacts to be
reviewed for the assessment. Then, next is the Inventory Analysis: Now here you identify and
quantify the energy, water and materials usage and environmental releases. As for example
air emissions, solid waste disposal, wastewater discharge, all these things. Then third is the
Impact Assessment: Now, assess the human and ecological effects of energy, water and
material usage and the environmental releases identified in the inventory analysis. And the
last one is Interpretation: Now, here you evaluate the results of the inventory analysis and
impact assessment to select the preferred product, process or service with a clear
understanding of the uncertainty and the assumptions used to generate the results.
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Now, please have a close look at figure 2, this is the logical flowchart of the LCA based
approach proposed by Juan et al and this is International Journal of Life Cycle Assessment.
So, this is being taken from one particular paper which is given below. So, what it says
basically? So, it is telling us about the 3 different steps. So, step 1 which basically talks about
the existing building, current state that is the diagnostic approach, then possible retrofit
solutions.
Now, in the step 2, it is the multi-criteria approach. Here the life cycle cost analysis is there,
life cycle assessment analysis, life cycle social analysis, and structural performance, again
buildings. Now, the third one is, which out of all these, when we collect data and analyze
them, analyze the impact, analyze how they are going to create problems for environmental
effects and all these things, then we can think about the different types of solutions.
Now out of that you have to go for a best solution. Then extended building life time. And as
you know that all these, again I am telling you, they are all interdependent on each other. One
particular parameters’ data will have an enormous impact on the subsequent conversion
processes, subsequent wastewater treatment processes, subsequent energy requirement and all
these things.
And from the upstream side also when you talk about procuring, raw material processing,
then making into a particular shape, size, density so that it can be stored properly and can be
used for further conversion. So all they are related to each other.
1365
So let us understand the benefits of the life-cycle assessment. Now LCA can guide decision
makers to help select the product or process that results in the least impact to the
environment. Now, this information can be used in conjunction with other factors such as
cost and performance data to select a product or process. Now again, I am telling you there
are two important things.
If you remember in our TEA discussion I was telling you, it is very important to understand
that if somebody goes for development of a process and technology, then find out whether it
is technically valuable or not that is the technical part. Then the second is that whether it is
techno economically valuable or not or sustainable or not and third is the life-cycle
assessment. So, all these 3 things you have to do.
First is technical challenge, second is the techno-economical challenge or let us say the cost
of the product and the process and third is the life cycle which takes into account also a part
of that processes which I have discussed earlier. So, all these things will be taken into
consideration when somebody goes for building up a new biorefinery or refinery or any
process industries or any industry per se.
So, the ability to track and document shifts in the environmental impacts can help decision
makers and managers fully characterize the environmental trade-offs associated with the
product or process alternatives. Now, by performing an LCA users can, what they can do?
Basically it is listed out. Now develop a systematic evaluation of the environmental
consequences associated with a given product.
1366
Then analyse the environmental trade-offs associated with one or more specific product or
process to help gain stakeholders as for example state, community acceptance for a planned
action. Third is quantify environmental releases to air, water and land in relation to each life
cycle stages and/or major contributing process. Fourth is assist in identifying significant
shifts in environmental impacts between life cycle stages and environmental media.
Then next is assess the human and ecological effects of the material consumption and
environmental releases to the local community, region as well as the world. Next is compare
the health and ecological impacts between two or more rival products/processes or identify
the impacts of a specific product or processes. And the last one is identify impacts to one or
more specific environmental areas of concern.
1367
Now, let us talk about the limitations of conducting an LCA. Now performing an LCA can be
resource or time intensive. Depending upon how thorough a LCA the users wish to conduct,
gathering the data can be problematic and the availability of data can greatly impact the
accuracy of the final results. So it results in voluminous data.
There are unfavorable economical conditions that needs to be taken into consideration, long
durations of operation basically that results in unreliable data. Therefore, it is important to
weigh the availability of quality data, the time necessary to conduct the study and the
financial resources required against the projected benefits of the finished assessment.
Now, let us take a case study. So here, I have taken a life cycle assessment of orange fruit
peel waste biorefinery. You remember we had also taken a case study when we discussed
1368
about the technico-economical assessment in our last class. So, let us see how LCA has been
carried out for this particular waste biorefinery. So fruit and vegetable processing, packing,
distribution and consumption generate a huge quantity of fruit and vegetable waste.
For example, approximately 1.81, 6.53, 32.0 and 15.0 million tons of fruit and vegetable
waste are generated in India, the Philippines, China and the United States respectively with
the majority being disposed of either by composting or dumping in the landfills and rivers
causing environmental pollution because many components leach out. Then they also
produce toxic gases.
Now, instead of using fruit peel waste for a single application, it would be beneficial to
develop an integrated approach for multiple applications, which assures economical
feasibility. Now, this integrated approach is summed up as biorefinery and we have been
discussing about biorefinery in many of our classes. So by 2020, it is anticipated that a
majority of chemicals produced through chemical routes would shift to bio-based processing
with agro industrial waste, municipal and forestry waste as the primary feedstock.
However, bio-based products are subjected to many environmental drawbacks like increased
land use, more reaction time and high eutrophication potentials. In addition, the indirect
emissions caused because of using auxiliary processing units and chemicals for biorefinery
also add up to the total environmental burden. Hence, the environmental impacts resulting
from the various processing step in a biorefinery should be evaluated during the initial design
phase itself using tools like life cycle assessment.
1369
Economic feasibility of a biorefinery can be achieved by producing a combination of low-
volume high-value products. As for example, essential oils, pectin, phenolic compounds. And
also low value high volume products as per example compost, cattle feed, methane which are
produced in high volume or large volume.
So this figure 3 gives us a generalized scheme of the valorization of the fruit peel waste. It is
a generalized scheme. It has been divided into 2 approaches. First is a direct approach or
direct utilization, second is the biorefinery approach. Let us see what is the difference. If you
go for a direct utilization you can have animal feed, you can have energy production, you can
have some sort of medicinal uses and nutritional food components.
So, mixing with existing food, briquette, then there are different things which are noted
down. So, if you talk about the biorefinery approach, then we go for various types of multiple
products. So, it is again divided into 3 distinct groups. First is bio-energy, biochemicals and
then bio-materials. In bio-energy we can have solid lignin, coke, briquette, direct burning of
solid fuel basically. So, you can have liquid ethanol, methanol as well as bio-oil which comes
from pyrolysis. So, this is under bio-energy.
Let us see about (bio)chemicals. Now you can have proteins, enzymes, phenolic compounds,
aroma compounds, different types of cosmetics. Then bioactive compounds like polyphenols,
dopamine, etc. Fatty acids, organic acids and some speciality chemicals like flavonoids. Now
bio-materials, we can have different types of nano-materials. We can have metal-carbon
1370
composite. We can have bio-polymers, we can have bio-fertilizer, we can have activated
carbon and adsorbents, adhesives, dyes, pigments, inks, so many things. You can see the list
is endless actually in a biorefinery perspective. And we have learned in this particular course
that whenever you talk about biorefinery, it should have multiple feedstocks, it should have
also multiple products, then only it will become sustainable.
The citrus waste is hydrolyzed with dilute acid explosion process followed by expansion to
separate the limonene. Now I am just going to discuss that how this has been carried out that
means how the biorefinery study has been done and what are the assumptions has been taken
all these things we are going to discuss. So, the liquid hydrolysate is fermented to obtain
ethanol.
Whereas the remaining stillage along with the solid residue is sent to digester for methane
production, basically anaerobic digestion. Now, based on the process simulation using Aspen
Plus and actual experimentation, a detailed inventory analysis was performed to obtain 390
kg of ethanol, 558 Nm cube of methane and 125 kg of limonene by treating 2.5 tons per hour
of citrus waste.
Now, the gate to gate LCA was performed according to the ISO 14040:2006. The 4 major
steps for LCA is goal and scope, life cycle inventory, life cycle assessment and interpretation.
This we have already discussed. Now, the processes available in the Indian database of the
GaBi Education Software were used for the process modeling.
1371
Now, this is the proposed generalized scheme for the fruit peel waste biorefinery. Now, you
can see that the fruit waste storage, it goes to drying, then size reduction - mechanical
operation basically. Then you go for solvent extraction where you take out the phenolic
compounds. Then whatever left out that goes to flashing. So, again you get essential oils as a
byproduct from that side.
You steam here, then it goes for the hydrolysis part. Here we you use acid and water and then
you filter it. Once you filter there is a liquid part, there is a solid part. The solid part goes to
anaerobic digestion, you get methane. Part of that can also be gasified to produce syngas.
Now the liquid product can be fermented then you get ethanol distillation and recovery,
basically you are producing ethanol, distill it; finally ethanol.
Then part of the fermentation broth, the stillage can be fed to anaerobic digestion. It has so
many valuable components which can be used as source of nutrient during anaerobic
digestion. So, this is a simplified schematic representation of the fruit peel waste biorefinery.
1372
Now, this process flow diagram tells us about the citrus waste biorefinery. Here you can see
that hydrolysis and flashing, it has just been expanded little from that side. Citrus waste,
steam, your acid and water - dilute sulphuric acid treatment. You carry out hydrolysis and
flashing, you get limonene one of the major component of this particular waste biorefinery.
Then whatever left out has been filtered. The solid goes to anaerobic digestion, the liquid
goes to fermentation, distillation, ethanol using the yeast Saccharomyces cerevisiae.
Now, let us talk about the goal and scope for this particular waste biorefinery. Now, the scope
includes the following processes. Hydrolysis and flashing, filtration, fermentation and
distillation, then anaerobic digestion. The 4 major processes. Now besides these steps,
production of utilities such as electricity and steam, and raw materials such as sulfuric acid is
considered in the LCA. The functional unit used in the study is 2500 kg of citrus waste.
1373
Now, assumptions and limitations. The following attributional LCA modeling approaches are
to certain assumptions and limitations. The results would obviously change with the change
in assumptions. First is the health impacts of the CW are not considered in this study. Second,
emissions pertaining to the generation of CW are not a part of the study.
Third, to accommodate environmental emissions due to transportation of the raw materials,

all raw materials travel a distance of only 100 kilometer to reach the processing site. Fourth,
the wastewater treatment plant is not within the scope of the study, the ETP, effluent
treatment plant. The unreacted raw materials carried along with water are assumed to be
emissions to freshwater.
1374
So, the table lists the different types of unit operations and processes of the FPW biorefinery
and products. If you talk about steam distillation/flashing, the product is essential oil.
Hydrolysis, the product is pectin and starch. Solvent extraction, we get polyphenols and
antioxidants. Fermentation, we get organic acids and alcohols like ethanol. Gasification and
pyrolysis we get syngas. Composting we get biofertilizer. Size reduction and blending, we get
cattle feed and dietary fiber.
Now, CW is considered to have no environmental burden as it is regarded as waste. The

geographical location of the processing setup is assumed to be India and hence an Indian data
set is used to model background processes such as thermal energy from hard coal, electricity
and steam from hard coal. Water is assumed as the direct input to the process and water
processing unit is out of the scope of this study. With specific concentration to Indian
subcontinent, the Indian database is used for process modeling.
Then let us talk about the life cycle inventory. The first one is feedstock. Now the citrus
waste generated after extraction of juice has 20% dry matter with significant amounts of
pectin 25%, hexosans almost 26% and pectosans 7%. The CW thus obtained is used for
further processing without any drying or grinding. Hence drying and grinding processes are
out of the scope of this particular study.
The feedstock is sourced from nearby area as it would decrease the cost of procurement and
reduce the chances of its degradation before processing. Hence the feedstock and other raw
1375
materials are assumed to travel a distance of 100 kilometer to reach the processing site to
incorporate transportation emissions in the study.
Then, the next method is dilute acid hydrolysis and flashing. Now hydrolysis is carried out in
an autoclave using steam. 2500 kilogram of CW was mixed with water, 1742 kilogram of
steam and 49 kilogram of sulfuric acid for hydrolysis. The hydrolysis conditions were
considered in such a way so as to maximize the sugar content. The power required for the
agitator was calculated using the CheCalc software.
The separation of limonene is generally carried out by steam distillation. The CW is

subjected to boiling water or steam. The peels release the essential oil through evaporation
and condense to form two layers, aqueous layer and organic layer in a decanter.
1376
Another method of removal of essential oil is cold pressing of peels. The watery emulsion
formed due to cold pressing is centrifuged to separate out the essential oil. The obtained
hydrolysate from hydrolysis section is flashed in an expansion tank. The vapors thus
produced content 99% limonene from the CWs. Now, these vapors are condensed and
limonene that is 100 kg is separated from water using a decanter. The residual hydrolysate
from the expansion tank is used for the next step.
Filtration: The residual hydrolysate is filtered to separate the soluble and insoluble
components. The insoluble component around 1500 kilogram is washed and sent to the
anaerobic digester and the soluble portion is sent to fermenter for further processing for
anaerobic digestion to be carried out actually.
1377
Now, the liquid hydrolysate is sent to a fermenter in which 6 kilograms of Saccharomyces
cerevisiae is used for fermentation under anaerobic conditions. The power of agitator
required for fermentation was calculated using the CheCalc software. The ethanol that is 390
kg is distilled out from the mother liquor. The stillage obtained from the process is digested
to obtain methane and carbon dioxide.
Then the next one is the anaerobic digestion. The insoluble solids obtained by the filtration of
hydrolysate are mixed with the stillage obtained from the bottom of the fermenter and the
slurry is sent to the anaerobic digester to produce methane, 558 Nm cube per hour and carbon
dioxide is almost 803 Nm cube per hour.
Now the CML 2001 impact assessment method is used to evaluate the environmental impacts
of the CW biorefinery. This method restricts quantitative modelling to early stages in the
cause-effect chain to limit uncertainties. Results are grouped in midpoint categories according
to common mechanism say for example climate change or commonly accepted grouping say
for example ecotoxicity The results are reported in five different midpoint indicators:
First, is global warming potential that is measred in kilograms of carbon dioxide equivalent.
Second, is acidification potential, it is measured in kilograms per sulphur dioxide equivalent.
Third is eutrophication potential, it is measured in kilogram of phosphate equivalent. Fourth
is ozone depletion potential, it is measured in kilograms R11 equivalent. And the final one is
photochemical ozone creation potential, it is measured in terms of kilograms per ethene
equivalent. So, these 5 major parameters are very important.
1378
So, this table will give you an understanding about the environmental indicators for this
particular CW biorefinery. You can see that global warming potential, so kilogram carbon
dioxide equivalent per 2500 kilograms of CW that is processed. So, from the hydrolysis and
flashing it is 565. Filtration and washing step it is 15.3. Fermentation and distillation is 357.
Total is 937.3. That is 937.3 kilograms of carbon dioxide equivalent per 2500 kilograms of
CW that is processed.
Now, let us talk about this eutrophication potential. So, it is 0.5, very small, for again 2500
kilograms of CW processed. If you talk about the photochemical ozone creation potential, it
is 0.4 kilogram ethene equivalent for 2500 kilogram of the CW that is processed. So, this
gives you an understanding about how different types of these processes are generating
different types of parameters which we have measured in exclusively 5 different indicators.
The next is interpretation. Now the table 5, I think there is a mistake here it will be table 2.
Table 2 shows the contribution of each process to the overall environmental indicators for the
production of 390 kg of ethanol and 558 meter cube of methane from 2500 kg of CW. The
GWP of the CW biorefinery is found out to be 937.3 kg carbon dioxide equivalent.
1379
So, if you look into this particular figure 6, it tells us about the percent contribution of
processes in overall environmental impacts, again for these 5 different indicators. A high
contribution of anaerobic digestion is attributed to a large amount of biogenic carbon dioxide
emitted in the process. You can see that during anaerobic digestion it is more.
Then the AP for CW biorefinery is observed to be 8.64 kilogram sulfur dioxide equivalent.
The high contribution of the fermentation and distillation steps in AP, EP, ODP and POCP is
attributed to the use of steam and electricity obtained by combustion of fossil fuels.
So, figure 6 shows the percent contribution of each process to the overall midpoint indicators
of the process. It is observed from this figure that hydrolysis and flashing that contributes
only 14.3% of ODP of the entire CW biorefinery is one of the major contributors to other
1380
environmental indicators of this particular biorefinery. Hydrolysis and flashing contribute to
around 60% of the overall AP and EP of the CW biorefinery.
A high contribution of the fermentation and distillation step, almost 77%, to overall ODP is
attributed to the use of electricity and process steam obtained from fossil fuels. It is evident
from figure 6 that all the steps considered contribute significantly to different environmental
indicators with process intensification, the contribution of the steps can be decreased
significantly.
The overall GWP is 937.3 kilograms of carbon dioxide equivalent for 2500 kilogram of CW
processed. Such an evaluation would help in calculating the overall sustainability of the
process. Steps and measures would be directed towards decreasing the overall environmental
indicator value. A high contribution of hydrolysis and flashing is attributed to the use of
process steam obtained from the hard coal.
During the design phase of a biorefinery, it is important to identify the steps that contribute
significantly to overall environmental impacts. Such environmental hotspots can be worked
upon from process intensification viewpoint to decrease the environmental loading of the
process. Process intensification offers a number of avenues to enhance the energy utilization
efficiency and thereby the associated environmental impacts.
1381
So to elucidate the reduction in environmental impacts due to process intensification,
processes such as microwave-assisted essential oil extraction, microwaves and ultrasound-
assisted extraction of pectin and phenolic compounds respectively are compared with the
conventional methods. The use of microwave-assisted technologies for hydrolysis and
essential oil extraction not only avoid the use of steam, but also has a better efficiency and
processing time than the conventional setup like steam distillation. The use of more
sophisticated technologies might appear as an environmentally benign option, however such
technologies often have significant indirect emissions associated with it.
It can be concluded that individual contribution of various processing steps may vary for
different indicators. Therefore, more attention should be paid on the use of such processing
steps or decreasing the environmental loading of processing during the process development
of such biorefineries.
So, I hope that you got an exclusive idea about what is LCA, how LCA can be carried out.
So, with this, I conclude today's lecture as well as the entire course. I am hopeful that you
have understood the concepts of how biomass can be converted using various techniques.
Then what is a biorefinery, what are the different types of biorefineries that exist or are being
planned with reference to the sustainable development goals. Then also we have discussed so
many different success stories for different conversion technologies. We have also discussed
different success studies which are commercially actually running biorefineries.
1382
Then in the fag end of the lecture, we have discussed about the techno-economical
assessment and evaluation as well as the life-cycle assessment and evaluation. So, I am
hopeful that this course will be very useful for your academic and research purposes or even
somebody wishes to set up industries that is basically biomass based industries also, this
course will be very helpful for them.
So thank you very much. If you have any query, you can feel free to write to me at
[email protected] or register your query in the Swayam portal itself. So, thank you very
much.
1383
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IS NOT FOR
SALE
NOR COMMERCIAL USE
(044) 2257 5905/08

nptel.ac.in
swayam.gov.in
1384

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INDEX

S.NO TOPICS PAGE.NO

2 Lec 2 : Need for biomass based industries 41

4 Lec 4 : Dedicated energy crops 112

5 Lec 5 : Oil cropns and microalgae 156

6 Lec 6 : Enhancing biomass properties 198

8 Lec 8 : Feedstocks and properties 269

9 Lec 9 : Economics and LCA 308

11 Lec 11 : Dilute acid, alkali, ozone 378

12 Lec 12 : Hybrid methods 422

14 Lec 14 : Gasification and Pyrolysis 499

15 Lec 15 : Products and Commercial Success Stories 550

17 Lec 17 : Details of various processes 637

18 Lec 18 : Products and Commercial Success Stories 673

21 Lec 21 : Biodiesel purification, fuel properties 774

Lec 23 : Factors affecting biooil, biochar production, fuel properties

24 Lec 24 : Biooil upgradation technologies 909

26 Lec 26 : Cellulase production, SSF and CBP 989

Lec 27 : ABE fermentation pathway and kinetics, product recovery

29 Lec 29 : Biogas technology, fermenter designs, biogas purification 1092

30 Lec 30 : Methanol production and utilization 1126

33 Lec 33 : 1,3-propanediol, 2,3-butanedioil, PHA 1225

35 Lec 35 : Aquaculture and algal biorefinery, waste biorefinery 1288

36 Lec 36 : Techno-economic evaluation 1326

37 Lec 37 : Life-cycle assessment 1359

Thermal efficiencies as high as 80 to 90% can be achieved by advanced gasification

The development of efficient Biomass handling technology, improvement of agro-forestry

It is going to be implemented very soon. Government of India is doing that. So then, we

So here, this is the stakeholders’ interaction and role in commercialization of biomass

Good morning students. This is module 2 and lecture 1.

CO2 + H2O + light + Chlorophyll → C6H12O6 (Glucose) + O2

(Refer Slide Time: 07:00)

The second major component of the biomass is hemicellulose. It is an amorphous

Anthropogenically means man-made (basically during the processing), so it is getting added

Good morning students. This is lecture 2 of module 2.

So, maize production is influenced by nitrogen application (increasing in nitrogen increases

Good morning students, this is lecture 3 under module 2.

Consequently, a number of industries such as Cyanotech, Seambiotic, Mera Pharmaceuticals and

Good morning students, this is lecture 4 of module 2.

(Refer Slide Time: 02:59)

Ragland et al., (1991): 1.39 + 0.00036 T for Wood char

Consider the values of HF of CO2, O2, H2O (g):

The HR for the above combustion reaction is -476 kJ/mol. So,

(Refer Slide Time: 14:46)

(Refer Slide Time: 15:34)

(Refer Slide Time: 16:55)

Then Sustainable Pre-treatment Technology. So pre-treatment technologies should be

So separation technology is an integrated part of any refinery; whether it is a petrochemical

So, everything together cannot be dumped to a thermochemical or biochemical platform, you

(Refer Slide Time: 01:42)

LCA provides a quantitative estimation of the potential environmental problems of an

Additionally, biogas is generated on-site by the anaerobic digestion of wastewater. No

Now, let us understand hemicellulose. So, this is a classical structure of hemicellulose

This recalcitrance property is a bottleneck in industrial utilisation of lignocellulosic biomass

Up to date, no synchronised pre-treatment approach that matches the whole variety of

So, the following criteria lead to an improvement in the enzymatic hydrolysis of

So, let us understand mechanical pretreatment. The advantages of mechanical pretreatment of

Now application of extrusion has a large potential in the pretreatment of lignocellulosic

Nevertheless, appropriate time of microwave irradiation of biomass increased cell frangibility

So as a result, enzymatic pre-treatment can accelerate bioenergy production at minimal