Synthesis For Fuel Ethanol Production-CRC Press (2009)
Synthesis For Fuel Ethanol Production-CRC Press (2009)
Synthesis For Fuel Ethanol Production-CRC Press (2009)
C. A. Cardona
Universidad Nacional de Colombia
Manizales, Colombia
Ó. J. Sánchez
Universidad de Caldas
Manizales, Colombia
L. F. Gutiérrez
Universidad de Caldas
Manizales, Colombia
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Cardona, C. A.
Process synthesis for fuel ethanol production / C.A. Cardona, Ó.J. Sánchez, L.F.
Gutiérrez.
p. cm. -- (Biotechnology and bioprocessing series ; 32)
Includes bibliographical references and index.
ISBN 978-1-4398-1597-7 (hardcover : alk. paper)
1. Ethanol as fuel. 2. Corn--Biotechnology. 3. Sugarcane--Biogtechnology. 4.
Biomass energy. I. Sánchez, Ó. J. II. Gutiérrez, L. F. III. Title. IV. Series.
TP339.C37 2010
662’.6692--dc22 2009035959
Chapter 1 Biofuels............................................................................................. 1
1.1 Biofuels Generalities............................................................. 1
1.1.1 Solid and Gaseous Biofuels...................................... 3
1.1.2 Liquid Biofuels......................................................... 4
1.1.2.1 Biodiesel................................................... 4
1.1.2.2 Bioethanol................................................. 5
1.2 Gasoline Oxygenation........................................................... 5
1.2.1 Tetraethyl Lead as Antiknocking Additive.............. 8
1.2.2 Ethers as Gasoline Oxygenates................................ 8
1.2.2.1 Methyl Tert-Butyl Ether (MTBE)............. 9
1.2.2.2 Ethyl Tert-Butyl Ether (ETBE)............... 10
1.2.2.3 Tert-Amyl Methyl Ether (TAME)
and Tert-Amyl Ethyl Ether (TAEE)........ 11
1.2.2.4 Di-Isopropyl Ether (DIPE)...................... 11
1.2.3 Methanol................................................................. 12
1.3 Ethanol as a Gasoline Oxygenate........................................ 12
1.3.1 Advantages of Fuel Ethanol................................... 13
1.3.2 Drawbacks of Fuel Ethanol.................................... 14
1.4 Gasoline Oxygenation Programs with Fuel Ethanol in
Some Countries................................................................... 17
References...................................................................................... 22
vii
different countries. Chapter 13 summarizes the main topics discussed in the book
in terms of perspectives and challenges in research and development for fuel etha-
nol production. Most of these chapters are supported by case studies that include
calculations and discussion of results.
The authors believe that accurate analysis and precise design as well as pro-
active government policies in fuel ethanol production will contribute to fair and
sustainable development of energy crops in the world promoting new alternatives
for poor rural areas. Finally, this book is an open and dynamic work waiting for
improvements and suggestions from the readers.
C. A. Cardona
Ó. J. Sánchez
L. F. Gutiérrez
In addition, the authors wish to acknowledge Annie Cerón, M.Sc., for her
assistance and support during the preparation of the manuscript.
xvii
xix
chips feeding small thermal plants), and transport sector (liquid biofuels produc-
tion). The hydroelectric energy is the second most important renewable resource,
whereas the contribution to the global energy consumption from such sources as
the sun, winds, tides, and geothermal energy is marginal. A 59.2% increase in
the consumption of renewable energy (corresponding to 828 million tons of oil
equivalent) is expected in the period 2002 to 2030 (IEA, 2004).
One renewable solution in the search for alternative sources of energy for the
world populace is the use of solar energy in the form of biomass (bioenergy). The
global potential of bioenergy is represented by the energy-rich crops (mostly rep-
resented by agroenergy) and lignocellulosic biomass (including the dendroenergy
from forest activities). The conversion of these feedstocks into biofuels, either for
electricity generation or for their use in vehicles, is an important option for exploi-
tation of alternative energy sources and reduction of polluting gases (Sánchez and
Cardona, 2008b), mainly CO2. The emissions generated by the combustion of
biofuels are offset by the CO2 absorption during the growth of plants and other
plant materials from which these biofuels are produced. In this way, the biomass
utilization releases the carbon dioxide that was fixed during its growth, compen-
sating the emissions generated in the current scale of time. In contrast, fossil fuel
usage releases into the atmosphere the carbon dioxide that was fixed by the plants
million of years ago, which implies a net increase in the amount of atmospheric
CO2, provoking global warming.
Energy-rich crops comprise those crops that could be exclusively addressed to
the energy production either as solid fuels for electricity generation or as liquid
biofuels that can substitute for the fossil fuels (bioethanol, biodiesel). It is esti-
mated that one hectare of energy-rich crops employed for liquid biofuel production
can avoid the emissions of 0.2 to 2.0 tons of carbon into the atmosphere compared
to the use of fossil fuels (Cannell, 2003). For the case of ethanol obtained from
sugarcane in Brazil, its use may offset carbon dioxide emissions at a rate of 2 t C/
(Ha/year) related to the oil. This substitution is more appreciable in tropical coun-
tries, whereas the offset is more effective for European countries if the electricity
is produced from biomass. Kheshgi and Prince (2005) indicate that if the CO2
released during the alcoholic fermentation is captured and injected into the sub-
soil or deeply in the ocean (where it is dissolved), ethanol production may lead to a
net carbon dioxide removal from the atmosphere (CO2 sequestration) avoiding the
emissions generated by the gasoline usage. Eventually, the environmental benefits
can be enhanced if the feedstock employed is made up of residues or wastes.
The so-called lignocellulosic biomass includes agricultural, forestry, and
municipal solid residues as well as different residues from agro-industry, the food
industry, and other industries. The lignocellulosic biomass is made up of complex
biopolymers that are not used for food purposes. The main polymeric components
of biomass are cellulose, hemicelluloses, and lignin. For their conversion into
a liquid biofuel such as ethanol, a complex pretreatment process is required in
order to transform the carbohydrate polymers (cellulose and hemicellulose) into
fermentable sugars. In contrast, for electricity generation, only the combustion of
the biomass is needed.
this case, the biomass undergoes combustion with or without coal as an auxiliary
fuel (co-combustion). The biomass can also be used as a feedstock for producing
gaseous fuels. For this, the biomass undergoes thermal treatment in the presence
of a reduced amount of oxygen (partial oxidation) or by steam. The aim of these
kinds of processes (pyrolysis, thermal gasification) is to obtain a gaseous fuel that
can be mixed in a better way with the air leading to a cleaner and more complete
combustion than is the case of the solid biomass. Moreover, the biomass can be
converted into biogas, a mixture of CH4 and CO2, using anaerobic bacteria that
assimilate the organic matter contained in the biomass forming more bacterial
cells and releasing methane and carbon dioxide as a result of the methanogenic
metabolism in absence of oxygen.
1.1.2 Liquid Biofuels
The worldwide transport sector depends almost totally on fossil fuels. While the
production of electricity is more diversified, vehicles require gasoline, diesel, or
natural gas for the mobilization. Only in specific cases, has the total substitu-
tion of gasoline with liquid biofuels been achieved, as in the case of the ethanol
obtained from energy-rich crops such as sugarcane. The advantage of liquid bio-
fuels compared to solid ones consists in their ease of transport and in the utiliza-
tion of the supply chains of fossil fuels. Biodiesel and bioethanol are the two main
liquid biofuels.
1.1.2.1 Biodiesel
Biological diesel is an oxygenated fuel obtained as a result of the transesterifica-
tion of vegetable oils and animal fats with an alcohol in the presence of a cata-
lyst (Figure 1.1). In general, the employed alcohol is methanol or ethanol. Thus,
the biodiesel is a mixture of methyl or ethyl esters of fatty acids from oil and
fats. Usually, rapeseed oil (in central Europe), sunflower oil (in southern Europe),
and palm oil (in tropical countries of Southeast Asia and South America) are
employed as a source of triglycerides. Used frying oil of animal or vegetable
origin is employed for their conversion into biodiesel as well. For biodiesel pro-
duction, acid, basic, and biological (enzymes) catalysts are used, with KOH and
NaOH being the most utilized catalysts worldwide.
1.1.2.2 Bioethanol
Bioethanol (ethyl alcohol, fuel ethanol) is the most-used liquid biofuel in the world.
It is obtained from energy-rich crops, such as sugarcane and corn. Ethanol can be
directly employed as a sole fuel in vehicles or as gasoline oxygenate increasing
its oxygen content and allowing a better hydrocarbon oxidation that reduces the
amount of aromatic compounds and carbon monoxide released into the atmo-
sphere. For this reason, fuel grade ethanol (FGE) is the market with the most
rapid growth rate in America and Europe.
The fuel ethanol can be obtained from lignocellulosic biomass as well, but its
production is much more complex. Nowadays, great efforts are being made to
diminish the production costs of lignocellulosic ethanol. It is expected that the
evolution of biomass conversion technologies will allow the massive oxygenation
of gasoline with fuel ethanol and make possible the substitution of a significant
portion of fossil fuels considering the huge availability of lignocellulosic world-
wide (Bull, 1994).
Sources: Data collected from the European Fuel Oxygenates Association (2009) and Tshiteya et al. (1991).
7
© 2010 by Taylor & Francis Group, LLC
8 Process Synthesis for Fuel Ethanol Production
Figure 1.2 Structure of some compounds with antiknocking properties in gasoline: (a)
TEL, (b) MTBE, (c) ETBE, (d) TAME.
air pollution levels in the biggest cities of the United States. This type of gasoline
should have a minimum 2% (by weight) oxygenate and benzene levels less than
1% (by volume; Nadim et al., 2001). The employing of oxygenates is aimed at
reducing the atmospheric contamination (smog during summer, CO in winter,
and toxic emissions throughout the year) because of the better combustion toward
CO2 due to the involvement of one atom of oxygen in their molecules. In addi-
tion, these additives present significant antiknocking properties. In this way, the
oxygenates play two important roles for elevating the gasoline quality. Precisely,
the most employed oxygenates as antiknocking additive in gasoline and has a
branched carbon chain like TEL (see Figure 1.2) that suggests the increase of the
octane number in its fuel blends. In this way, the oxygenates have allowed the
replacement of lead in the gasoline.
water sources contaminated with MTBE without the presence of the remaining
gasoline hydrocarbons have been reported. One of the most effective methods
for MTBE removal is by means of adsorption using granulated activated coal
obtained from coconut peels (Braids, 2001). Due to these negative features, the
use of MTBE was banned in California in 2004 and its total prohibition is pro-
jected by 2010.
gasoline, among other factors. Nevertheless, the concerns arising from the low
biodegradability and high mobility of MTBE have imposed serious limitations
to the production of this type of oxygenates in some countries, particularly in the
United States where even the usage of ETBE and TAME has been restricted in
California. A limiting factor is that the toxicological properties and the environ-
mental impacts of these ethers are not sufficiently known. It is considered that due
to the similarity in the molecular structure of the different ethers, their properties
should be analogous to those of MTBE. For this reason, contamination problems
in groundwater as a consequence of using oxygenates like ETBE, TAME, TAEE,
or DIPE are expected (Graham et al., 2000; Nadim et al., 2001).
1.2.3 Methanol
Alcohols are an oxygenation alternative for gasoline considering the environmental
disadvantages of the ethers mentioned above. The blends of alcohols and gasoline
have comparable properties related to the traditional fuels based on oil. Despite their
lower combustion heat compared to gasoline, the increase in fuel consumption when
alcohols are used as oxygenates is not significant in principle. Moreover, the possi-
bility of increasing the conversion of the blend and, therefore, the engine efficiency,
represents a great advantage for alcohol-containing gasoline. Furthermore, the emis-
sions of hydrocarbons and carbon monoxide are reduced, although a considerable
increase in the emission of aldehydes is presented (Rasskazchikova et al., 2004).
In the 1970s, several researches were carried out in countries like Japan, the
United States, and Germany aimed at the utilization of methanol (CH3OH) as an
additive for enhancing the octane number of gasoline (see Table 1.1). Ethanol was
pushed into the background due to its high comparative costs. However, despite
its high octane number, methanol usage was limited and even banned in many
countries due to its high toxicity, volatility (the highest RVP values of the ana-
lyzed oxygenates), and hygroscopicity, which generates a series of technical dif-
ficulties for the use of methanol–gasoline blends. Furthermore, the formaldehyde
formed during methanol oxidation results in the formation of a substance consid-
ered dangerous (Rasskazchikova et al., 2004).
At the beginning of the 1980s, the mixture of methanol and tert-butyl alcohol
was commercialized under the trademark Oxynol™. Nevertheless, the high vola-
tility of the blends containing methanol, due to the formation of one azeotrope
with the gasoline hydrocarbons, caused the market to refuse it (Ancillotti and
Fattore, 1998). Currently, methanol is employed as feedstock for the production
of MTBE and TAME.
Table 1.2
Main Benefits of Using Ethanol as an Oxygenate in Gasoline Blends
Emission Mix E10 Mix E85
Carbon monoxide (CO) Reduction of 25–30% Reduction of 25–30%
Carbon dioxide (CO2) Reduction of 10% Reduction up to 100% (E100)
Nitrogen oxides (NOx) Increment or reduction of 5% Reduction up to 20%
Volatile organic compounds Reduction of 7% Reduction of 30% or more
Sulfur dioxide (SO2) and Reduction Significant reduction
particulate matter
Aldehyde Increment of 30–50% (very Insufficient data
low with catalyst)
Aromatic compounds (benzene Reduction Reduction up to 50%
and butadiene)
blended with ethanol conducts electricity and its RVP is higher than nonblended
gasoline. This implies a higher volatilization rate that can lead to ozone and smog
formation (Thomas and Kwong, 2001). Although the addition of ethanol increases
the evaporation rate of organic volatile compounds, many experts consider that
the reduction of CO emissions effectively offsets the volume losses due to the
volatility increase (Ghosh and Ghose, 2003).
One of the most troubling issues regarding the utilization of gasoline blends is
the tendency of ethanol to form two liquid phases in the presence of water: one
aqueous phase with an important ethanol content and one organic phase. If water
contaminates the fuel, the water dissolves into the ethanol and disperses through
the tank. Once it exceeds the tolerance level, the alcohol–water mixture will sepa-
rate from the gasoline. Depending on individual conditions, about 40 to 80%
of the ethanol will be drawn away from the gasoline by the water, forming two
distinct layers. The top layer will be a gasoline that is a lower octane and perhaps
out of specification, while the bottom layer is a mix of water and ethanol that will
not burn (Central Illinois Manufacturing Company, 2006). To avoid the phase
separation, ethanol–gasoline blends are not directly transported by pipelines. In
general, ethanol is added to gasoline in bulk terminals (retail outlets, the end link
of the supply chain for wholesale distribution) or in tanker trucks at the terminal
immediately before delivery to the service station. In these points, reception and
storage tanks are steel-made to minimize the exposure to water that can infil-
trate into the distribution and storage systems for gasoline as well. This problem
can be overcome by using stabilizing additives such as higher alcohols, fusel oils
(mixture of higher alcohols, fatty acids, and esters), aromatic amines, ethers, and
ketones. For instance, the addition of 2.5 to 3% isobutanol ensures the stability
of ethanol–gasoline blends containing up to 5% water at temperatures down to
–20ºC. In fact, the phase stability of gasoline blends increases with high ethanol
concentrations (Rasskazchikova et al., 2004). Another approach for stabilization
of these gasoline blends is the modification of the carburetor that also can allow
the utilization of blends with higher ethanol contents (Yüksel and Yüksel, 2004).
On the other hand, ethanol, like all the alcohols in general, is highly corrosive,
depending on water content. The higher the molecular weight of the alcohol, the
less corrosive it is. To neutralize this effect, corrosion inhibitors can be added.
Among these inhibitors are hydroxyethylated alkylphenols, alkyl imidazolins,
and different oils obtained during cyclohexane production. Ethanol can have a
negative effect on rubber and plastic materials because it penetrates hoses and
tight seals, which increases fuel losses due to evaporation. Nevertheless, the cur-
rent level of development of the polymer industry makes it possible to select mate-
rials resistant to penetration of alcohols so that fuel losses are eliminated. These
new polymers are being used in the automobile parts industry (Rasskazchikova
et al., 2004).
From an economic point of view, fuel ethanol also presents some drawbacks
that depend on the situation in all countries of the world. Particularly, in the case
of the sugar sector, there exists the risk that sugar producers involved in ethanol
production can reduce the amount of ethanol produced when sugar prices are
especially high on the international market. For this reason, some governments,
like Colombia’s for instance, have adopted measures to avoid this situation by link-
ing the international sugar price to the value paid to ethanol producers. However,
several authors and nongovernmental organizations (NGOs) have expressed their
concern regarding the fact that this price structure and related tax exemptions
favor the economic groups controlling sugar markets in each country (Chaves,
2004). Another great concern, when an ethanol oxygenation program for gasoline
is being implemented, is in the pressure over food prices related to feedstocks
from which ethanol is produced, especially sugar and corn. In particular, the bio-
fuels were hardly criticized when both oil and food commodities prices reached
their historical peaks during 2008. Specifically, it was estimated that the “bio-
fuels effect” could have provoked an increase in the international price of food
commodities and crops of about 35% in that year. This statement was weakened
when the oil price fell at the end of 2008 (corresponding to the beginning of the
global financial crisis) and the price of food commodities also fell to a percentage
higher than 35%. This could indicate than the elevated value of food feedstocks
was more linked to the oil price than to the biofuels prices. However, it should be
pointed out that the price of biofuels in the international market depends on the oil
price as well. In any case, the effect of producing bioethanol and biodiesel from
agricultural resources on food and feed prices cannot be neglected and should be
thoroughly assessed. In this regard, the production of the so-called second-gener-
ation biofuels represents an important option for producing biofuels from sources
other than those related to food and feed production. In this case, bioethanol can
be produced from lignocellulosic residues or by-products, such as cane bagasse,
corn stover, or wheat straw, that have no influence on food production structure.
Considering the effect of bioethanol production on the environment, some con-
cerns have been expressed based on the fact that ethanol usage in gasoline blends
increases the aldehyde level, mostly acetaldehyde, compared to the combustion
of conventional gasoline. The aldehydes are formed during the incomplete com-
bustion of ethanol and have been linked to some potentially harmful effects on
human health. Nonetheless, it should be emphasized that all oxygenates form
higher amounts of aldehyde emission than nonoxygenated gasoline. Furthermore,
the effect on the health is negligible as proven by the Royal Society of Canada tak-
ing into account, in addition, that the catalytic convertors of new vehicles reduce
these aldehyde levels to a higher degree (Canadian Renewable Fuels Association,
2000). In the case of old automobiles that do not have this kind of convertor, the
level of formed aldehydes, although increased when ethanol is employed as the
gasoline oxygenate, is always below the permissible limits. Actually, the emission
of this type of organic compound is very low compared to other types of danger-
ous emissions (e.g., aromatic hydrocarbons), which are effectively reduced when
fuel ethanol is used (see Table 1.2).
There exists a great debate on the environmental suitability of ethanol usage
as an oxygenate, especially when blends with low ethanol contents are employed.
Reviewing various literature sources, Niven (2005) points out that gasoline blends
with 10% content of ethanol (E10) offer few advantages in terms of greenhouse
gas emissions, energy efficiency, or environmental sustainability. In addition,
this author indicates that E10 blends increase both the risk and severity of soil
and groundwater contamination, although greenhouse gas benefits for 85% etha-
nol blends (E85) are recognized. By contrast, the Argonne National Laboratory
(USA) estimates that an 8 to 10% reduction in greenhouse gas emissions per
vehicle mile traveled is achieved when biomass ethanol is used in E10 blends and
68 to 91% reduction when used in E85 blends (Wang et al., 1999). This contro-
versy has arisen in countries with an important ethanol industry, as in the case of
the United States. Authors such as Pimentel (2003) have maintained for several
years that the energy required for producing ethanol is greater than the energy
contained in the ethanol itself, particularly when starchy materials like corn are
used. This implies that important natural resources of a national economy are
being squandered by maintaining an artificial biofuels program. Nevertheless,
most studies have concluded that the energy invested in ethanol production is less
than its energy content, which allows achieving significant environmental ben-
efits. These studies have been accomplished by both independent research groups
and governmental centers and have belied Pimentel’s arguments, as shown in the
works of Shapouri et al. (2003) and Wang et al. (1999).
Table 1.3
World Production of Ethanol (in Million Liters)
Country 2008 2007 2006a 2005a References
1. USA 34,065.00 24,597.20 18,376.00 16,139.00 Renewable Fuel Asociation
(2009)
2. Brazil 24,497.28 18,997.67 16,998.00 15,999.00 Renewable Fuel Asociation
(2009)
3. China 1,899.69 1,839.51 3,849.00 3,800.00 Renewable Fuel Asociation
(2009)
4. Canada 899.69 799.77 579.00 231.00 Renewable Fuel Asociation
(2009)
5. Thailand 339.89 299.77 352.00 299.00 Renewable Fuel Asociation
(2009)
6. Colombia 300.11 283.50 269.00b 27.00b Renewable Fuel Asociation
(2009); Londoño (2007)
7. India 249.81 199.85 1,900.07 1,699.00 Renewable Fuel Asociation
(2009)
Total 64,259.48 49,024.27 44,329.07 40,199.00 Renewable Fuel Asociation
(2009)
a Industrial and beverage alcohol are included.
b These data correspond to the fuel ethanol produced in new distilleries whose construction started in
2005 (Londoño, 2007); industrial and beverage alcohol are not included.
different sources indicate that Brazil and the United States account for 82% of
world production of fuel ethanol, though this percentage is changing constantly
due to the dynamics of this biofuel on the global market. Asia and the EU are
following the large producers. China has the biggest plant for ethanol production
with an annual capacity of 320 million gallons; this plant is located in the Jilin
province and currently produces 240 million gallons per year (Murray, 2005).
India is seeking to enhance its ethanol production to meet its auto biofuel pro-
gram; it has envisioned the use of ethanol not only for gasoline blends, but also for
ethanol–diesel blends and for biodiesel production (Subramanian et al., 2005).
Europe’s fuel ethanol sector was a slow starter. It took over 10 years to grow
production from 60 million liters in 1993 to 525 million liters in 2004. In the
following two years, we saw a true explosion in production. In 2005 and 2006,
there were double-digit growth levels of over 70%. However, it was not a sustain-
able growth; in 2007, production increased by only 11%. Total EU production
in 2008 was 2.8 billion liters, up from 1.8 billion liters the previous year. This
represents a significant increase of 56%. This increase was due to the growth in
French production, which almost doubled to 1 billion liters in 2008 (539 million
liters in 2007). This made France the biggest EU fuel ethanol producer in 2008,
followed by Germany that also expanded its production to 568.5 million liters,
which represented a 32.5% increase in internal Germany fuel ethanol produc-
tion. The third highest producing country was Spain with 317 million liters. In
2008, fuel ethanol production capacity increased in Belgium. Finland resumed its
production in 2008 and, in Austria, fuel ethanol has been produced for the first
complete year (European Bioethanol Fuel Association, 2009).
Many countries have implemented or are implementing programs for addition
of ethanol to gasoline (Table 1.3). Through the ProAlcool program, Brazil has
been utilizing hydrous ethanol as a fuel and anhydrous ethanol as an oxygen-
ate. This country produces ethanol from sugarcane. Although, at the beginning
of this program, concerns about the disjunction between food production versus
fuels (sugar versus ethanol) were expressed, it has been demonstrated that when
the food shelves remained empty it was caused by the destination of food produc-
tion to the export markets. In the same way, when the shelves remained full, it
was because large proportions of the population lacked the purchasing power to
buy food (Rosillo-Calle and Hall, 1987). However, due to the liberalization of
the Brazilian fuel market, the official end of the ProAlcool program, the gradual
elimination of subsidies, and the political and economic conjuncture, production
and consumption paces of fuel ethanol diminished at the end of twentieth cen-
tury, although a reactivation is expected in the coming years (Rosillo-Calle and
Cortez, 1998; Wheals et al. 1999). Brilhante (1997) indicates that the pursuit of
ethanol fuel in Brazil was not based on long-term plans with deep-set values, but
has been a response to such circumstances as a depressed sugar industry, an ambi-
tious attempt to reduce oil dependency, and more recently, “green” arguments.
Brazil is the second largest producer of fuel ethanol in the world and the first
in world’s exports (Renewable Fuels Association, 2007). Brazil is considered as
the best economical model for ethanol production in the world because it does not
implement subsidies for fuel ethanol production. However some authors consider
that the successful Brazilian ethanol model is sustainable only in Brazil due to its
advanced technology and its enormous amount of arable land available (Sperling
and Gordon, 2009). Currently, Brazil is actively seeking export markets for its
bioethanol (Thomas and Kwong, 2001), especially in Japan, which will become
a net importer of ethanol (Orellana and Neto, 2006). Brazil’s 30-year-old fuel
ethanol program is based on the most efficient agricultural technology for sugar-
cane cultivation in the world, using modern equipment and cheap sugarcane as
feedstock. The residual cane waste (bagasse) is used to process heat and power,
which results in a very competitive price and also in a high energy balance (output
energy/input energy), which varies from 8.3 for average conditions to 10.2 for best
practice production (Macedo et al., 2004).
In the case of the United States, ethanol is used either as a fuel substitute or as
an oxygenate. At present, both Ford and Chrysler offer standard models designed
to run on either 85% ethanol (E85) or gasoline. The addition of gasoline to the
E85 or E95 mixtures is done for improving cold start in engines using these kinds
of fuel. However, the best perspectives for bioethanol can be found in the oxy-
genate market. Fuel ethanol production was boosted by the passage of the Clean
Air Act in 1970, and especially by the Clean Air Amendments in 1990. Current
regulations aimed at controlling CO emissions have already produced a signifi-
cant demand for ethanol as an oxygenate. The tax credit gives oil companies
the most of these conditions, the country should produce an estimated 3,800,000
L/d of fuel ethanol by 2020 to meet the national demand and export the surplus to
new growing markets (Proexport Colombia, 2005).
The implementation of the E10 program depends on raw materials and tech-
nological limitations. For this reason and driven by the availability of the feed-
stock and the capacity of the well-structured sugar industry, the main cities of the
West Southern and West Central departments (administrative regions into which
Colombia is divided) started this program. The Cauca River valley is the major sug-
arcane production region and it is located in these departments. This region concen-
trates the best cultivable lands for sugarcane cropping (about 200,000 Ha) because
it has the most appropriate conditions: extensive and fertile alluvial valleys located
at an average of 1,000 m above sea level in tropical latitude. Currently, five etha-
nol production plants co-located in large sugar mills are operating. However, the
synergies of the sugar sector, controlled by a few economic groups, have not been
allowed to achieve a great impact on the creation of new rural jobs. According to
estimations by the Colombian Ministry of Agriculture (Ministerio de Agricultura
y Desarrollo Rural, 2006), the surface cropped with sugarcane in 2006 did not
increase compared to data obtained in 2005 (by the Columbian sugar industry).
Despite the enhancement in the production of fuel ethanol during these two years,
Colombia has not projected any increase in cane plantations. This means that the
generation of new rural jobs related to ethanol production is practically nil. In fact,
part of the cane produced is diverted to ethanol distilleries, decreasing the volumes
of sugar for export. Regulations issued by the government have included the sugar
value in the international market as a variable considered in calculating the price
of fuel ethanol produced in the country. Thus, future increases in the international
price of sugar will not discourage the national production of fuel ethanol. This situ-
ation allows the development of new commercial projects for ethanol production in
order to guarantee permanent use of ethyl alcohol for the E10 program.
The Colombian government expects that the construction of new ethanol-pro-
ducing facilities in other regions of the country will lead to real improvement
in the economic situation of the rural communities through new demands for
agricultural raw materials. Therefore, other feedstocks for ethanol production are
being analyzed considering the future growth of the fuel ethanol market. Corn,
cassava, and beets have been considered as potential feedstocks. Sugarcane is
also considered for ethanol production in zones other than in the Cauca River
valley. This encourages the cropping of cane by specific rural communities not
related to the big sugar companies. Many rural communities cultivate sugarcane
for producing noncentrifugal sugar called panela (solid brown sugar), a sweet-
ener and low-cost beverage base widely used by popular segments in Colombia.
However, the quality of life of panela producers is traditionally low within the
Colombian context. For this reason, the government is actively encouraging the
organization of the communities linked to the panela economy for them to supply
the feedstock for new projects of fuel ethanol production.
The relatively mature technology for ethanol production from corn is one
of the options to be considered under Colombian conditions because corn is an
important crop mainly cultivated in northern and eastern regions. The construc-
tion of ethanol plants using corn could offer the production of valuable co-prod-
ucts (e.g., dried distillers grains with solubles for cattle food). Furthermore, this
technology may be the base for the development of ethanol production processes
from other starchy materials such as cassava or potatoes, crops with a significant
economic importance in Colombia. Additionally, the projected signing of a free
trade agreement with the United States, the first world producer of corn, implies
the search for new markets for local corn production.
Ethanol can be obtained synthetically from coal and natural gas. The major
producer of this type of alcohol is South Africa (Thomas and Kwong, 2001). It
can be obtained by oxidation of olefins as well. However, 95% of world ethanol is
produced by fermentation from carbohydrate-containing feedstock (Berg, 2004).
The main part of ethanol is produced in batches.
Substrate concentration at the beginning of fermentation is 15 to 25% (w/v)
solids and the pH is adjusted to a value of 4 to 5 with the aim of reducing infection
risks. The process is carried out at 30 to 35ºC. Generally, yield reaches 90% of
theoretical maximum, expressed in g EtOH/g substrate. The rest of the substrate
is converted into biomass and other by-products such as glycerol and acetate.
Formed biomass can be utilized many times. Ethanol concentration at the end of
fermentation is 80 to 100 g/L (Claassen et al., 1999). In most of the distilleries,
fermentation time is 24 h, employing 6 h for yeast sedimentation in the vessels
(Pandey and Agarwal, 1993).
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Table 2.1
Steps Involved in the Development of an Industrial Process
during Its Life Cycle
Stages Features
Analysis of the chemical reaction Study of chemical synthesis
Experimental development
Selection of the best stages for the synthesis
Conceptual process design Analysis of integration possibilities
Integration of function
Heuristic design
Superstructure design
Superstructure optimization
Process development Experimental data obtained
Test reaction and separation process
Obtain kinetic and physical data
Pilot plant
Process assessment Evaluation of cost of equipment
Definition of control schemes
Detailed engineering Plant layout
Definition and construction of equipment
Pipeline design
Energy networks definition
Utilities design
Plant operation Scheduling
Stocks handling
Preventive maintenance and repave
End cycle of life Second use possibilities
Dismantle and recycle parts
not only the designers. In this way, processing features and market demands will
be taken into account during early stages of design, when the changes are easier
and less expensive to implement. Therefore, the problems, conflicts, and change
needs can be detected in time to carry out the necessary modifications with sub-
stantially less effort than by means of sequential engineering. In this framework,
concurrent engineering applied to design implies the integration of all life cycle
steps of a process in the early stages, attaining the achievements of several goals.
Thus, the research and development activities and conceptual design have to con-
sider not only the building of a plant, its operation, control, and maintenance, but
also the achievement of technoeconomic, market, environmental, and even social
objectives. Practically, and for the case of commodities, the three first stages of
the process life cycle are accomplished in a concurrent (simultaneous) way. If the
synthesis pathways for a given product are already known, as in the case of fuel
ethanol, process design procedures are focused on the second and third stages in
Table 2.1.
In this book, these two steps are analyzed for fuel ethanol production empha-
sizing the related integrated processes. In fact, concurrent engineering elements
are considered when taking into account as evaluation criteria not only technical
indexes (yield, productivity, energy consumption), but also financial and envi-
ronmental indicators in the framework of process intensification. Financial and
environmental criteria correspond to the macro and mega scale levels of analysis
(plant and unit integration and interaction between market conditions and envi-
ronmental impact, respectively), as reported by Li and Kraslawski (2004). Just
these two levels of analysis have been developed with more intensity in the past 15
years as a result of the globalization of the economy and worsening environment.
On the other hand, process and apparatus integration corresponds to the micro
scale level of analysis. At this level, process intensification through integrated
and hybrid processes with higher efficiency and less size has become the most
important development trend. This forced the change of the old paradigm of a
chemical process made up of a series of unit operations where the processes and
apparatus are coupled (meso scale). Finally, the nano scale (molecular design and
new materials) has become crucial for designing processes to obtain very high
value-added products.
The task of defining an appropriate process configuration requires the genera-
tion and evaluation of many technological schemes (process flowsheets) in order
to find those exhibiting better performance indicators. This task is called process
synthesis. In a process synthesis problem, system inputs (type, composition, con-
ditions, and flowrates of raw materials) and outputs (product flowrate and speci-
fications, effluent streams constraints) are given and the task consists of defining
the configuration of the process flowsheet or, in other words, the topology of the
technological scheme, which allows the synthesis of the product from the feed-
stocks entering the process. For this, at least one comparison criterion should be
established with the aim of evaluating different alternative process flowsheets
proposed in order to choose that with the better performance.
The configuration comprises the type and amount of unit processes and opera-
tions required by the overall process as well as their interconnection (intermedi-
ate, recycle, and purge streams) and the parameters of that configuration (mostly
those ones related to operating conditions: flowrates, temperatures, pressure,
compositions). Process synthesis procedures can be applied not only to the con-
ceptual design of new processes, but also to the retrofitting of existing ones. Some
approaches for process synthesis involve and apply fundamental concepts of ther-
modynamics as the starting point for generating new alternative process configu-
rations. Thus, energy consumption (calculated by enthalpy balances) of different
flowsheets can be helpful for selection of the best alternatives. In a similar way,
the concept of useful energy or exergy (widely employed in mechanical engineer-
ing) can also be employed as a criterion for selection of alternatives. Recently,
more global concepts from the ecology field, such as emergy, have been used for
choosing the best configuration of a process (see Section 2.2.5).
During the next step of the life cycle of an industrial process, process analy-
sis, the structure of the selected technological scheme is established in order to
improve the global process through its more comprehensive insight. The type of
problems undertaken by process analysis is summarized as follows: given the
process inputs and once determined the technological configuration of the pro-
cess that includes each one of the unit operations and processes involved, as well
as their parameters, find the system outputs. The analysis is aimed at predicting
how the given process behaves. It involves the process decomposition into its con-
stituent elements for the individual study of each unit performance. The detailed
features of the process (flowrates, pressures, temperatures, compositions) are pre-
dicted by using mathematical models, empiric correlations, and computer-aided
process simulation. Moreover, experimental methods are employed to study the
system behavior as well as validate the theoretical approach used for its descrip-
tion. It could be considered that the conceptual design stage corresponds to pro-
cess synthesis activities and the development stage to process analysis activities,
although there is no clear boundary between these two activities of process sys-
tem engineering.
Though process synthesis is carried out prior to process analysis, both tasks
interact with each other in order to achieve their goals. Thus, for evaluating the
performance of an alternative technological configuration during process synthe-
sis, mathematical models are required in order to predict the behavior of process
units. This involves a distinctive task of process analysis. Usually, aggregated
models are employed in process synthesis. Such models simplify the synthe-
sis problem in a considerable way through the representation of one aspect or
objective that tends to dominate the problem. Furthermore, short-cut models are
utilized as well. In this kind of model, the description of the units involved in
each proposed design is done through relatively simple nonlinear models with the
aim of reducing the computational costs or exploiting the algebraic structure of
the equations. During process analysis, more rigorous and complex models are
involved to predict the performance of the different units, which make up part of
a technological scheme (Grossmann et al., 2000). On the other hand, process opti-
mization plays a very important role during process design. Once the structure
with the best performance (this can, in turn, imply the employment of optimiza-
tion tools) is defined, and knowing the structure of the system components that
allow the prediction of its behavior, the optimization of the technological scheme
can be accomplished in order to find the optimal operating parameters making
possible the maximization or minimization of an objective function that evaluates
the performance of the overall system based on one or more criteria (technical,
economic, environmental).
into several subproblems (Gani and Kraslawski, 2000). In this book, these sub-
problems can comprise the following jobs applied to the production of fuel
ethanol:
To undertake this task, a series of solving strategies has been proposed. They
can be classified into two large groups: knowledge-based process synthesis and
optimization-based process synthesis. The second group of strategies is oriented
to the formulation of a synthesis problem in the form of an optimization problem.
In turn, the first group of strategies is concentrated on the representation of the
design problem as well as the organization of the knowledge required by this
problem (Li and Kraslawski, 2004), i.e., it is oriented to the development of a
representation that is rich enough to allow all the alternatives to be included, and
“smart” enough to automatically ignore illogical options. In general, the proce-
dure of generating multiple alternative process flowsheets is carried out through
different strategies implying, for instance, the combination of heuristic rules with
evolutionary strategies for process design. Heuristic methods are particularly use-
ful when very large and complex problems are dealt with. Usually, these methods
are often based on the observation of how many other problems of the same type
are solved. Knowledge-based methods imply an evolution in the learning of the
research subject as the proposed problem is being solved. This, in turn, leads to
the generation of new and better alternatives. Nevertheless, it is impossible to
ensure that the optimal structure can be achieved when heuristic methods are
employed (Westerberg, 2004). Some approaches for knowledge-based process
synthesis mostly used in process systems engineering, as well as the most innova-
tive and perspective ones, are briefly described below.
2.2.1 Evolutionary Modification
Evolutionary modification is the conventional approach for process synthesis
based on the experience of engineers and researchers. This approach condenses
this experience into a programmed set of heuristic rules intended to making deci-
sions on the process structure. Considering that this method corresponds to a trial-
and-error approximation, its main limitation consists in the difficulty of obtaining
relevant information in a way suitable for computational calculations.
2.2.2 Hierarchical Decomposition
The hierarchical heuristic method is an extension of the purely heuristic approach
that entails the evolutionary modification and combines the heuristic rules with
an evolutionary strategy for process design (Li and Kraslawski, 2004). Douglas
(1988) proposed a method by which any process can be decomposed into five lev-
els of analysis for its design. This strategy has a hierarchical sequential character
considering that in each level of analysis different decisions are made based on
heuristic rules. This allows generating different alternatives, which are evaluated
from an economic point of view using short-cut models. As the method is applied
in each one of the five levels, more information becomes available and the tech-
nological scheme of the process evolves until its completion. According to this
author, hierarchical decomposition comprises the analysis of the process in the
following levels:
• Reactor
• Separation and recycle system
• Heat recovery system
• Heating and cooling utilities
• Wastewater and effluent treatment
The design begins with the reactor selection to move toward the outer surface
of the diagram by adding other layers, such as the separation and recycle system.
These heuristic methods emphasize the decomposition strategy and screening of
alternatives, which allow the fast identification of technological configurations
often located near optimal solutions (Li and Kraslawski, 2004). However, the
main drawback of these methods is the impossibility of handling the interactions
among the different levels or layers due to their sequential character. In spite
of this, the nature of this approach allows rapidly discarding many alternative
configurations not leading to “good” designs. In addition, the analysis by design
levels permits the utilization of process simulators with which the process flow-
sheets are completed in an evolutionary way. This methodology has been mostly
applied to chemical and petro-chemical processes. Nevertheless, the utilization
of these procedures and design schemes is less frequent in the processes of the
microbiologic industry.
2.2.3 Phenomena-Driven Design
The phenomena-driven approach for process synthesis considers as a starting
point for the design, not the unit operations, but the phenomena occurring in
them at a lower level of aggregation (Gavrila and Iedema, 1996). Reactions, phase
changes, heat and mass transfer, and mixing are considered among the phenomena
included in this method. The design problem is divided (decomposed) into three
tasks: role assignment, phenomena grouping, and operating condition analysis.
The goals of these tasks can be formulated through the following questions:
• What should occur in the process in order to achieve the global design
target?
• Where should it occur?
• When and how should it occur?
In the second task, the alternative designs are proposed by grouping the phe-
nomena in units and the continuous variables are described as Boolean variables
(for instance, is the rate of a phenomenon equal to zero or greater than zero?).
In the third task, the favorable conditions in the units are defined employing
ordinal relations among quantities (dR/dt > dS/dt; Gavrila and Iedema, 1996).
This method is oriented to explore innovative units and processes in order to sup-
port the creativity during the design process. However, the method is based on
an opportunistic identification and integration of the tasks as pointed out by Li
and Kraslawski (2004). This approach has been applied to very particular cases
as in the production of methyl tert-butyl ether (MTBE) by reactive distillation
(Tanskanen et al., 1995).
2.2.4 Conflict-Based Approach
In the framework of the conflict-based approach, process synthesis is defined as
the process of decision making for identifying and handling the design conflicts
in order to satisfy multiobjective requirements (Li, 2004). Under this concept, a
design problem is decomposed into subproblems instead of applying a hierarchical
design. This allows for overcoming the drawback related to the interactions among
several hierarchical levels of analysis. The design problem is represented by the
conflicts among the interrelated design objectives or by the features of the techno-
logical scheme (Li and Kraslawski, 2004). Undoubtedly, this approach represents a
change of paradigm in process design, although some aspects should be developed,
such as the quantification of the conflicts and heuristic rules in function of their
contribution to the conflicts as well as the development of the solving algorithms.
which the user does not have direct access. Thus, the simulation is solved taking
into account the strict order of the units (from feedstocks to end products) mak-
ing up the process flowsheet. Main drawbacks of the optimization-based strategy
are related to the fact that the optimal configuration can only be found within
the alternatives considered in the formulated superstructure (Li and Kraslawski,
2004). Furthermore, this approach has the additional disadvantages of having a
significant mathematical complexity as well as the difficulties arising during the
definition of the superstructure of technological configurations, i.e., the difficulty
to ensure that the initial superstructure contains the “best” solution (Barnicki and
Siirola, 2004). In this sense only, it is possible to formulate the design problem
as a mathematical programming (optimization) problem when all the alternatives
to be considered can be enumerated and evaluated quantitatively (Westerberg,
2004). In addition, this approach presents a number of difficulties when deal-
ing with the optimization of under-defined design problems and uncertainties
that result from the multi-objective requirements of the design problem (Li and
Kraslawski. 2004).
Alternatives of
superstructure Selected diagram
MILP
algorithm
Start
Process model
NLP
optimizer
Optimal
solution
Figure 2.1 Conceptual diagram of one of the algorithms most used for optimization-
based process synthesis.
algorithm, whereas the optimal values of the operating parameters are found in
the inner loop based on NLP. The best technological configuration of the process
that maximizes or minimizes the employed objective function is identified by
repeating and executing these two loops. For this configuration, the optimal val-
ues of its operating parameters are defined as well.
The solution of NLP problems is usually based either on successive quadratic
programming (SQP) or on reduced gradient methods. Among the main solu-
tion methods of MINLP problems are the branch and bound method (Gupta and
Ravindran, 1985), generalized Benders decomposition (Geoffrion 1972), and outer
approximation (Duran and Grossmann, 1986). A new trend for solving MINLP
problems is the generalized disjunctive programming whose formulation includes
the condition that one of a set of three types of constraints should be exactly satis-
fied (Lee and Grossmann, 2005; Raman and Grossmann, 1991). The three types
of constraints comprise global independent inequalities concerning discrete deci-
sions, disjunctions that are conditional constraints involving the operator OR, and
logic pure constraints involving Boolean variables (Grossmann et al., 2000).
The formulation and solution of the main types of mathematical program-
ming problems can be accomplished in an effective way using specialized com-
puter programs, such as GAMS (Generic Algebraic Modeling System; GAMS
Development Corporation, 2007). This system requires that the models and the
formulation of the optimization problem be explicitly introduced in algebraic
form. It automatically creates an interface with the solution codes for various
types of problems (solvers). This offers a great advantage because it makes its
main efforts to formulate the problem itself and not to develop methods for solv-
ing it. GAMS has a powerful set of solvers for different optimization problems
(LP, NLP, MILP, and MINLP, among others). Moreover, it makes possible the
input of indexed equations that is very useful in the case of large-sized models.
The NLP methods ensure that the global optimum can be found if and only if
both the objective function and the constraints are convex (Floudas, 1995). If this
is not the case, the location of the global solution cannot be guaranteed. The rigor-
ous or deterministic methods for global optimization ensure an arbitrarily close
approximation to the global optimum and, in addition, carry out the verification
if this approximation has been attained. These methods include the branch and
bound method, methods based on interval arithmetic (Byrne and Bogle, 1996;
Stadherr, 1997) and generalized disjunctive programming (Lee and Grossmann,
2005), and procedures with multiple starting points in which a local optimizer
is invoked from these points (Edgar et al., 2001). In the past few years, signifi-
cant advances in the methods of rigorous global optimization have been achieved.
These methods assume that special structures in these types of problems are pres-
ent, such as bilinear, linear, fractioned, and separable concave functions. It has
been demonstrated that the algebraic models always can be reduced to these sim-
pler structures if they do not involve trigonometric functions (Grossmann et al.,
2000). Floudas (2005) points out that the most important advances in determinis-
tic global optimization belong to the following categories: convex envelopes and
convex underestimators, twice continuously differentiable constrained nonlinear
optimization problems, mixed-integer nonlinear optimization problems, bilevel
nonlinear optimization problems, optimization problems with differential-alge-
braic equations, grey-box and factorable models, and enclosure of all solutions.
Other types of techniques for global optimization correspond to nonrigorous
or heuristic search methods. These methods can find the global optima, but do
not guarantee and generally are not able to prove that the global solution is found
even if they do so. However, these procedures often find good solutions and can
be successfully applied to MINLP problems. In such cases, the heuristic method
starts with a starting solution and explores all the solutions in a certain vicinity
to that starting point, looking for a better solution. The method repeats the pro-
cedure every time a better solution is found. The metaheuristic methods direct
and improve the search with a heuristic algorithm. Tabu search, sparse search,
simulated annealing, and genetic algorithms belong to this category (Edgar et al.,
2001). In particular, stochastic methods, such as simulated annealing (Kirkpatrick
et al., 1983) and the genetic algorithms (Goldberg, 1989), have gained more and
more popularity, do not make any assumptions on the form of the functions, and
require some type of discretization, and the violation of the constraints are tack-
led through penalization functions (Grossmann et al., 2000).
2.3.2 Superstructures
One of the main challenges in the optimization-based synthesis of technological
schemes is the definition of the superstructure of alternatives that contains the
best solution. Most of the works reported have been based on the hand representa-
tion of the superstructure for each particular problem without following general
rules. To generalize this procedure, the definition of the representation type for
the superstructure is needed. Among the main types of representation proposed
are the state–task network and the state–equipment network. In the first type, two
classes of nodes (states and tasks) are used for the representation; the assignment
of equipment is dealt implicitly through the model. In the second type of repre-
sentation, the states and the equipments are employed as the nodes; the tasks in
this case are treated implicitly through the model (Grossmann et al., 2000).
Other crucial aspect during optimization of superstructures consists in how
to generate in a systematic way the superstructure so that all the alternatives of
interest are included. One of the trends in this field is the automatic generation
of superstructures, which has been developed for the case of lineal process net-
works employing an algorithm based on graphs and ensuring a search space large
enough to include the optimal solution (Friedler et al., 1993). Fraga (1998) and
Fraga et al. (2000) have developed the Jacaranda system that is able to solve a
process synthesis problem through the automatic generation of the superstructure
at the same time that it executes the search procedure. The Jacaranda system is
based on the use of an implicit enumeration procedure that generates and ana-
lyzes a directed graph representing the synthesis problem.
The level of detail of the optimization model also plays an important role for
the optimization-based approach. In general, the models can be classified into
three main classes: aggregated models, short-cut models, and rigorous models
(Grossmann et al., 2000). The first class of models employs high-level representa-
tions in which the synthesis problem is simplified by one aspect or objective that
tends to dominate the problem as mentioned above. Models for predicting the
minimum utilities and the minimum amount of units in a heat exchange and mass
exchange networks belong in this category. Short-cut models are employed in
superstructures with a high level of detail and involve the optimization of capital
and operating costs, but in which the performance of individual units is predicted
with relatively simple nonlinear models in order to reduce the computational
effort. Among the examples of this type, distillation sequences and technological
schemes can be highlighted. Finally, rigorous models are also applied in detailed
superstructures for predicting the behavior of the units as in the case of the syn-
thesis of distillation trains for separation of ideal and nonideal mixtures.
2.3.3 Hybrid Methods
Hybrid methods for process synthesis make use of mathematical programming
techniques based on optimization in combination with the knowledge-based
approach. For instance, the synthesis of heat exchange networks has been improved
by optimization employing a heuristic approach based on physical phenomena
(Gundersen and Grossmann, 1990). A method for process synthesis exploiting the
advantages of mathematical programming that uses MINLP techniques and hier-
archical decomposition maintaining the consistency of its fundamental principles
has been developed. The method consists of solving the whole technological
scheme in each decomposition level. Aggregated models (“black box” models)
are utilized for the subsystems that are in the lower hierarchical levels, evaluat-
ing in this way their interaction with the detailed MINLP problem of the current
subsystem that is being analyzed. The subsystems are: reaction, separation, and
heat integration (Daichendt and Grossmann, 1997). In this way, the solution of a
large-scale MINLP problem is avoided.
2.4 Final Considerations
The absolute majority of methods for conceptual process design have been devel-
oped for processes of basic chemical and petro-chemical industries. Most of these
approaches are especially oriented to the design of separation schemes, particularly
distillation trains. For this reason, there is a paramount interest in the application
of these methodologies to biotechnological processes, which are of a complex and
highly multicomponent nature. None of the described approaches can be applied
in a generic way to any type of synthesis problem, even more so in the case of
biological processes. Considering this, the application of a minimum of two strate-
gies or synthesis procedures is required to undertake the design of processes for
fuel ethanol production with a high technoeconomic and environmental perfor-
mance. In this way, a higher amount of possibilities can be covered allowing the
creativity during the design process that is the source of innovation. Therefore,
the employment of synthesis strategies that systematically compile and utilize the
accumulated knowledge around a research subject, such as fuel ethanol, directly
contributes to screening and filtering the best alternative process configurations.
Further, some of the approaches mentioned above were applied to the genera-
tion of different process flowsheets with a high technical, economic, and envi-
ronmental performance. Thus, both the hierarchical decomposition method and
optimization-based strategies were used for the main process steps needed for
ethanol production. For specific process steps, such as the synthesis of separation
and ethanol dehydration scheme, the analysis of the statics and the exergy balance
were also employed. These issues will be discussed in following chapters.
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3.1 Sugars
Bioethanol can be produced from raw materials containing fermentable sug-
ars, especially sucrose-containing feedstocks, such as sugarcane or sugar beet.
Sugarcane is the main feedstock for ethanol production in tropical countries like
Brazil, India, and Colombia. This feedstock can be used either in the form of
cane juice or cane molasses. About 79% of ethanol produced in Brazil comes
from fresh sugarcane juice and the remaining fraction corresponds to cane molas-
ses (Wilkie et al., 2000). Sugarcane molasses is the main feedstock for ethanol
production in India (Ghosh and Ghose, 2003). Cane molasses and different sugar-
containing streams like syrup and B-type cane juice are used for producing bio-
ethanol in Colombia. Beet molasses is the main feedstock for ethanol production
in France along with wheat (Decloux et al., 2002).
3.1.1 Sugarcane
Sugarcane (Saccharum officinarum L.) is a perennial grass cropped in tropical
and subtropical zones from Spain to South Africa. The origin of sugarcane is
in the South Pacific islands and New Guinea. The main feature of sugarcane is
that a sucrose-enriched juice is formed and accumulated in its stalk. This juice is
extracted and used for sugar production. For its growth, sugarcane requires a moist
and warm climate alternating with dry seasons. It grows better in plain or slightly
sloping lands with alluvial or clay soil with abundant luminosity. Nevertheless,
sugarcane grows in any soil of good quality provided there is appropriate humid-
ity. This crop is grown at 16 to 29.9°C and with a pH of 4.3 to 8.4 in soils with
annual precipitations of 47 to 429 mm. Cane tolerates flooding (Duke, 1998).
Sugarcane is cut every 12 months on average, although the range goes from 6 to
24 months. One plantation can last up to five years.
43
Table 3.1
World Production of Sugarcane (2007)
No. Country Production/Ton Yield/Ton/ha
1 Brazil 514,079,729 76.59
2 China 355,520,000 86.05
3 India 106,316,000 72.56
4 Thailand 64,365,682 63.71
5 Pakistan 54,752,000 53.21
6 Mexico 50,680,000 74.53
7 Colombia 40,000,000 88.89
8 Australia 36,000,000 85.71
9 USA 27,750,600 77.62
10 Philippines 25,300,000 63.25
11 Indonesia 25,200,000 72.00
12 South Africa 20,500,000 48.81
13 Argentina 19,200,000 66.21
14 Guatemala 18,800,000 83.56
15 Egypt 16,200,000 119.56
16 Vietnam 16,000,000 56.14
17 Cuba 11,100,000 27.75
18 Venezuela 9,300,000 74.40
19 Peru 8,246,406 121.75
20 Iran 5,700,000 87.69
World 1,557,664,978
Sugarcane is one of the most important crops in the world and plays a crucial
role in the economies of many developing and emerging countries. Brazil is the
major sugarcane producer followed by China and India (FAO, 2008; Table 3.1).
Brazil fielded about 5.14 million ha in 2007, while China fielded 3.55 million.
Among main cane producers, Colombia has the highest yields achieving on aver-
age 88.89 ton/ha (FAO, 2008). If considering only the cane intended for sugar
and ethanol production, the Colombian cane yield reaches more than 122 ton/ha
(Asocaña, 2006; Espinal et al., 2005b). In some developing countries, sugarcane
is cultivated by many rural communities for producing noncentrifugal sugar (solid
brown sugar), a low-cost sweetener with significant content of minerals and traces
of vitamins, widely used by the populace in those countries. This product is known
as gur in India or panela in Colombia. In particular, the Colombian government is
encouraging the use of the cane varieties normally employed for panela produc-
tion (generally, low-yield varieties) in order to utilize them for fuel ethanol produc-
tion. In this way, these communities can improve their socioeconomic conditions.
Table 3.2
Average Sugarcane Composition
Components Percentage (by Weight)
Cellulose 6.48
Fructose 0.60
Glucose 0.90
Fat 0.30
Hemicellulose 5.40
Lignin 1.42
Protein 0.40
Sucrose 13.50
Water 69.70
Nonfermentable sugar 0.35
Other reduced compounds 0.35
Organics acids 0.10
Ash 0.50
3.1.2 Cane Sugar
Sugarcane is the raw material for producing sugar. The sugar is one of the most
important commodities in the world market. Besides cane, sugar can be obtained
from the sugar beet. The sugar is extracted from these two feedstocks in the form
of sucrose crystals (Figure 3.1) with high purity. The annual worldwide production
of sugar was 163.3 million ton (raw value) in 2007, according to the International
Sugar Organization (ISO, 2008). The world sugar consumption, in turn, was 157.7
million ton (raw value) in the same year. Main producers of sugar are Brazil,
India, the European Union (EU), and China (Table 3.3). Sugar is mostly produced
CH2OH
O HOCH2 O
OH HO
HO O CH2OH
OH OH
Table 3.3
Main Sugar Producers (2007)
No. Country Production/Ton Participation/%
1 Brazil 33,200,000 17.63%
2 India 29,090,000 14.78%
3 China 13,900,000 7.38%
4 EUA 7,680,000 5.42%
5 Thailand 7,150,000 5.12%
6 Australia 4,630,000 3.65%
7 Mexico 5,420,740 3.63%
8 European Union 18,450,000 2.90%
10 Pakistan 4,360,000 2.67%
15 Russia 3,400,000 1.40%
World 149,752,383
from sugar beets in the case of the EU countries. Brazil is the main actor in the
world sugar market (first producer, third consumer, and first exporter), thus, any
change in the production in this country, due to either changes in climate or the
balance of ethanol production related to sugar, provokes changes in the inter-
national sugar price. This situation will continue in the future considering that
Brazil is expanding the area dedicated to sugarcane plantations. It is expected
that about 40 and 50 new sugar mills will be put into operation by 2010 (Decision
News Media SAS, 2006).
Mature cane is collected manually or mechanically. Hand cutting is the most
usual method. The cane is transported to the sugar mills where the sucrose is
extracted and crystallized. The first step in the production of cane sugar in mills
consists in the cane juice extraction (Figure 3.2). For this, the cane is sampled,
washed, weighed, and prepared using rotating knives to shred the stalks into
pieces. Then, the shredded cane is ground in heavy-duty roller mills, which extract
the raw juice while hot water is sprayed onto the cane bed to dissolve the sugars.
The sucrose extraction yield reaches 90 to 95% in modern sugar mills. The fiber
fraction of the cane, called bagasse, is generated in this step. This material is pre-
dried and utilized in the same sugar mill as an energy source burning it in special
Water
Sugarcane juice
Syrup
Evaporators Vacuum
pan
Cooked mass
Rotary drum
Centrifuges dryer Sugar
Molasses
Figure 3.2 Simplified scheme of the process for sugar production from sugarcane.
boilers to produce steam that generates electricity through turbo generators. The
raw juice is clarified by adding sulfur dioxide (SO2) to oxidize color substances,
destroy microorganisms, and favor the agglutination of colloids. Then, lime is
added to neutralize the juice, thus avoiding, in this way, the sucrose hydrolysis
into glucose and fructose (sucrose inversion). The limed juice is heated to 105 to
110°C in the clarifiers, to which flocculants also are added. Solid separation is
favored because the calcium sulfite formed is insoluble and precipitates removing
the suspended particles and other impurities. This precipitate (known as mud) is
mixed with flocculants, lime, and small amounts of the light fraction of bagasse,
separated from the juice, and sent to vacuum rotary filters where the filter cake
is recovered. The filter cake (press mud) is a fibrous material that can be used
for animal feed or composted to produce manure. Part of the clarified juice can
be used for ethanol production. In the evaporation step, the clarified juice is con-
centrated by removing up to 75% of the water in multiple-effect evaporators. The
removed water is used in other process steps either as steam or as condensate. The
concentrated juice or syrup contains 58 to 62% solids (about 60° Brix).
The obtained syrup is treated with direct steam to reduce its viscosity. Then,
the syrup is clarified by adding SO2, phosphoric acid, and lime. After this treat-
ment, the syrup is sent to a flotation tank where it is clarified. This clarified syrup
can be used for ethanol production. In the next step or pan stage, the sucrose con-
tained in the syrup is crystallized by removing excess water with vacuum evapo-
rators called pans. In order to increase the speed of this process, the pan stage
operates in a manner that utilizes seed crystals and a combination of products
with varying levels of sugar content to produce a range of crystal sizes and, hence,
qualities. The crystals are separated from the mother liquor in centrifuges. After
three evaporation/centrifugation stages, crystals of raw sugar and the residual
mother liquor (called C-molasses) are obtained. The molasses is one of the most
employed feedstocks, not only for ethanol production, but also for producing a
wide range of microbiological products. The sucrose crystals are dried in rotary
drum driers where the commercial raw sugar is obtained. To produce refined
sugar, the raw sugar is redissolved in clean water and treated with phosphoric
acid and saccharate to remove the remaining impurities. The clarified solution
is treated with activated carbon to remove colors and then filtered. Finally, this
mass is evaporated and crystallized in vacuum pans. The refined crystals are
washed with steam and hot water, air-dried, classified according to crystal size,
and stored.
Table 3.4
World Production of Sugar Beet (2005)
No. Country Production/Ton
1 France 29,303,000
2 Germany 25,427,000
3 USA 24,724,410
4 Russia 21,520,000
5 Ukraine 15,620,600
6 Turkey 13,500,000
7 Italy 12,000,000
8 Poland 10,972,030
9 China 7,910,000
10 United Kingdom 7,500,000
11 Spain 6,676,900
12 Holland 5,750,000
13 Belgium 5,606,025
14 Iran 4,850,000
15 Morocco 4,560,000
16 Japan 4,200,000
17 Egypt 3,429,535
18 Czech Republic 3,189,740
19 Hungary 3,108,150
20 Belarus 3,070,000
channels with circulating water. The beets are washed and passed through sys-
tems retaining diverse solid materials, such as stones, leaves, and small roots.
Once washed, the beets are transported to the choppers where they are shredded
into very thin slices (3 mm), called cossettes, and passed to a machine called a
diffuser to extract the sugar content into a water solution. The diffusers are large
rotary drums where the cossettes are put in contact with a hot water stream flow-
ing in the opposite direction. The sucrose is extracted from the vacuoles of the
beet cells into the flowing water generating the raw juice or diffusion juice. The
spent cossettes are called pulp and leave the diffuser with about a 95% moisture
content, but with low sucrose content. To recover part of the sucrose contained in
the pulp, it is pressed in screw presses reducing the moisture to 75%. After dry-
ing in rotary drums, the pressed pulp is sold as animal feed due to its high fiber
content, while the resulting liquid is added to the diffusers. The diffusion juice is
an impure sucrose solution also containing gums, pectin, amino acids, mineral
salts, nitrogenous compounds, etc. This juice has about 16° Brix and 85% purity.
It can be clarified by a process very similar to that of cane sugar. Thus, a clear
juice with 15° Brix is obtained. From this point, the process is practically the
same as for cane sugar.
Table 3.5
Composition of the Raw Sugarcane Juice
Components Percentage (by Weight)
Fructose 0.58
Glucose 0.87
Fat 0.39
Protein 0.37
Sucrose 13.37
Water 82.10
Nonfermentable sugar 0.43
Other reduced compounds 0.60
Organics acids 0.19
Ash 1.10
3.1.5.2 Sugarcane Molasses
Sugarcane molasses is a by-product of sugar processing. It is generated during
sugar crystallization by evaporation and represents the mother liquor from which
the crystals are formed. Most cane molasses used for ethanol production corre-
sponds to the C-molasses. Due to the repeated evaporation–centrifugation process,
the molasses obtained is a viscous, thick brown liquid with a higher concentra-
tion of impurities and mineral salts compared to cane juice. An example of the
Table 3.6
Average Composition of Sugarcane and Beet Molasses
Sugarcane Molasses/% Beet Molasses/%
Components (by Weight) (by Weight)
Water 18.82 18.01
Sucrose 36.70 37.50
Fructose 8.82 9.12
Glucose 6.86 7.26
Nonfermentable sugar 4.79 2.00
Other reduced compounds 4.00 3.00
Fat 0.40 0.40
Protein 3.50 6.00
Organics acids 5.00 5.00
SO2 0.10 0.10
Ca(OH)2 1.01 1.01
Ash 10.00 10.60
which acid is added in order to partially hydrolyze the sucrose and avoid its crys-
tallization (Murtagh, 1995). In this way, the sugar mills commercialize the high
test molasses as a way of exploiting the sugarcane under low sugar price condi-
tions. High test molasses contains about 70% sugars and 80° Brix that indicates
high sugar content compared to molasses. Therefore, these types of materials, as
well as the syrups, require the addition of higher amounts of nitrogen and phos-
phates when they are used to prepare the cultivation media for ethanolic fermen-
tation using yeasts. Moreover, the pantothenate content of these molasses is low
(Murtagh, 1995).
3.2 Starchy Materials
3.2.1 Starch
Starch is a polymeric carbohydrate made up of glucose units linked by glycosidic
bonds. The starch is the most abundant carbohydrate in nature after the lignocel-
lulosic complex and is present in high amounts in very important crops for human
food, such as corn, wheat, potato, cassava, rye, oats, rice, sorghum, and barley.
About 54 million tons per year of starch are produced for industrial purposes,
from which 55% comes from the United States. From the total produced starch,
44.1 million tons come from corn, 2.6 million from cassava and rice, and 2.8 mil-
lion from potato (Messias de Bragança and Fowler, 2004)
Starch is composed of two types of α-glucans, i.e., polymers based on glu-
cose monomers linked by α-type glycosidic bonds, amylose and amylopectin,
which represent 98 to 99% of the dry weight of starch kernels. The properties of
these two polysaccharides along with the ratio between them in the starch kernels
determine the properties of the starch obtained from different plant sources. This
ratio ranges from less than 15% amylose in waxy starch and 20 to 35% amylose in
normal starch to greater than 40% amylose in amylo-starch. In addition, the water
content of the starch kernels in equilibrium with the air goes from 10 to 12% in
grains to 14 to 18% in tubers (Tester et al., 2004).
The amylose is a linear polysaccharide made up of D-glucopyranose units
linked by α(1,4) glycosidic bonds, although it has been established that some
molecules present several branching points due to the presence of α(1,6) (Buleón
et al., 1998). These branching points are present in an amount of 9 to 20 per mole-
cule (Sajilata and Singhal, 2005). The molecular weight of amylose is in the range
1×105–1×106 Da with a polymerization degree of 324 to 4,920 (1,000 on average).
These variations depend on the starch origin. The basic structure of amylose is
depicted in Figure 3.3. Two ends can be distinguished: one end with intact gly-
cosidic hydroxyl (corresponding to the glucose residue of the right-hand side of
Figure 3.3) called the reducing end, and the end with the glucose residue whose
glycosidic hydroxyl is participating in the glycosidic bond with the following glu-
cose residue (the left-hand side of Figure 3.3) called the nonreducing end. These
ends are very important during the process of enzymatic hydrolysis of starch.
The amylopectin is a highly branched polymer made up of chains of
D-glucopyranose units linked by α(1,4) bonds, but with 5 to 6% α(1,6) bonds
leading to branching points (Buleón et al., 1998). These branching points occur
every 15 to 30 glucose units on average. The amylopectin has a greater molecular
weight than amylose (1×107–1×109 Da) with a higher polymerization degree of
9,600–15,900 (Tester et al., 2004). Because of the branches, the amylopectin pres-
ents an elevated amount of chains that are differentiated by their inner or outer
character. As in the case of amylose, the nonreducing ends of amylopectin can be
distinguished (see the left-hand side of Figure 3.4a). The single reducing end of
the amylopectin molecule can be observed on the right-hand side of Figure 3.4b.
The amylose and amylopectin are located in the starch kernel in a radial way in
the form of concentric layers where there exist crystalline and amorphous zones
of these two polysaccharides. This implies that kernel degradation, the first stage
in the solubilization of starch in water, is very difficult at low temperatures. To
achieve this goal, it is necessary to break the starch kernels through a hydrother-
mal treatment involving the adsorption of hot water by the kernels and their swell-
ing and destruction with the corresponding release of amylose and amylopectin
in a soluble form. This process is known as starch gelatinization and has a crucial
(a)
(b)
Figure 3.4 Amylopectin: (a) Structure of amylopectin, for outer chains a ≈ 12-23 and
for inner chains b ≈ 20-30; (b) simplified diagram of an amylopectin structure.
3.2.2.1 Corn
Corn (Zea mays) is the most employed feedstock in the world to produce starch
either for the food industry or for ethanol production. Corn is a crop whose origin
is in the Americas. Its stalks can reach 4 m in height and does not have branches.
Its seeds are the structure with the highest value of starch in this plant and are the
base for human food in many communities in Central and South America. The
starch accumulates in the endosperm of corn seeds. Corn requires a temperature
of 25 to 30°C and an important degree of sunlight for its growth. Corn can toler-
ate minimum temperatures down to 8°C. At 30°C, the adsorption of nutrients and
water can be difficult. This crop is exigent in water, but adapts itself very well to
all kind of soils preferring those with a pH of 6 to 7. Similarly, corn requires deep
soils rich in organic matter (Infoagro, 2007).
Corn is the most cropped grain in the world, followed by wheat and rice. The
United States is the major corn producer, followed by China and Brazil (FAO,
2008), as shown in Table 3.7. The United States reported the planting of 35.02
Table 3.7
World Production of Corn (2007)
No. Country Production/Ton
1 United States of America 332,092,180
2 China 151,970,000
3 Brazil 51,589,721
4 Mexico 22,500,000
5 Argentina 21,755,364
6 India 16,780,000
7 France 13,107,000
8 Indonesia 12,381,561
9 Canada 10,554,500
10 Italy 9,891,362
11 Hungary 8,400,000
12 Nigeria 7,800,000
13 South Africa 7,338,738
14 Egypt 7,045,000
15 Philippines 6,730,000
16 Ukraine 6,700,000
17 Romania 3,686,502
18 Spain 3,647,900
19 Thailand 3,619,021
World 784,786,580
Table 3.8
Composition of the Main Starchy Crops
Used for Ethanol Production
Component Corn Wheat Cassava
Humidity 15.50 13.70 70.00
Starch 60.59 57.25 26.50
Protein 8.70 14.53 0.80
Lipids 3.64 3.50 0.30
Fiber 8.31 7.79 0.60
million ha in 2007; China, 28.07 million ha; and Brazil, 13.82 million ha. The
U.S. yield is very high (about 9.48 ton/ha), although Kuwait has the maximum
yield (21.0 ton/ha), but it has a very small annual production: 1,050 ton in 2007
(FAO, 2008). In the United States, both private and public sectors have been sys-
tematically investing in research and development of corn cropping oriented to the
production of sweeteners for the food sector and ethanol for transportation sector.
In addition, the U.S. government has granted certain tax exemptions to farmers in
order to support corn production, which is considered a strategic crop. It should
be noted that the powerful lobby of corn producers has confronted the big oil
industry supporting the implementation of renewable fuels from corn. In fact,
most ethanol-producing plants in the United States employ corn as a feedstock. In
2007, 22.5% of U.S. corn production was dedicated to ethanol production (FAO,
2008; Renewable Fuel Association, 2009; Sánchez and Cardona, 2008b). China
also has been increasing its ethanol production from grains including corn. This
fact, along with the expected increase in ethanol production in the United States,
has been pushing corn prices upward. This has had direct effects on the costs of
corn-containing foods in such importing countries, such as Mexico.
Starch is the corn component that is directly used for ethanol production.
Likewise, starch is corn’s main component, as seen in Table 3.8 from data com-
piled by Cardona et al. (2005). There exist two technologies for using corn starch
as a feedstock for fuel ethanol production. One technology employs the separation
of starch from all the other components of the corn kernel and this is called wet
milling. In this way, during the wet milling process, the corn kernel is separated
into its components: starch, fiber, gluten, germ, and oil. The other technology
does not involve the separation of starch. By contrast, the whole milled grain
enters into the ethanol production process directly (dry milling).
The corn wet milling process allows the production of a series of value-added
co-products that offset to a certain degree the fuel ethanol production costs. These
co-products are directly related to the structure of corn grain. Starch represents
60% of the grain and is located in the endosperm. Grain proteins are concen-
trated in the gluten. Corn oil is located in the germ and represents 4% of the grain
Corn
S
Steeping KS Centrifugation
(H2O + dil. H2SO4) Grinding Screening/HSP
Crushing/ Filtration/
Evaporation Extraction Drying
Corn oil
HSW Corn gluten meal
Drying
Corn gluten feed
Figure 3.5 Simplified block diagram of corn wet milling. HSP: hydroclonic sepa-
ration. Streams: CSL—corn steep liquor, HSW—heavy steep water, KS—corn slurry,
S—starch.
(Gulati et al., 1996; U.S. Grains Council, 2007). The overall wet milling process
is depicted in Figure 3.5. The first step in the corn wet milling process is the
steeping of the grains in large tanks that can process from 1,500 to 6,000 bushels
of corn, according to the typical volumes of starch industry in the United States
(U.S. Grains Council, 2007). Steeping is carried out during 30 to 50 h at 49 to
54°C in water containing 0.1 to 0.2% sulfur dioxide. The sulfurous acid that is
formed contributes to the separation of the starch and insoluble proteins, break-
ing the protein matrix of the endosperm through the destruction of disulfur bonds
in gluten proteins. During this step, about 6% of dry matter is dissolved in the
liquid containing the corn steep liquor. These dissolved components provide the
nutritional value to the corn extractives that are condensed and fermented after
the partial dehydration of steeping in water.
After grain steeping, the swelled corn grain contains about 45% water. This
soft grain is ground and the germ is removed by flotation. The germ is cracked
and its oil is extracted using hexane as a solvent. The corn oil is refined while the
solid residue of the germ is dried to prepare the corn germ meal. Once the germ
is removed, the resulting material undergoes milling that crushes starch particles
and releases the fiber. This fiber is separated from the starch and gluten proteins
by using a screen. The thick mixture of starch and gluten is pumped to a rotary
disk column where these two components are separated by applying centrifugal
force. In this centrifugal separator, the product that is obtained contains approxi-
mately 60% protein. This product is concentrated, filtered, and dried to obtain the
corn gluten meal. The starch is separated again to reduce its protein content down
to 0.3% (U.S. Grains Council, 2007). The fiber in the first part of milling is added
to the evaporated corn steep liquor. The stream from this process evaporates in
order to produce the corn gluten feed, as illustrated in Figure 3.5.
The co-products obtained are mostly intended for animal feed. The corn gluten
meal has a high protein and energy content and is a good source of the amino acid
methionine. This co-product is used for cattle feed as a protein supplement (about
60% protein) as well as for feeding poultry and pigs. Corn gluten feed contains
about 20% protein and a reduced amount of oil and fats. This material is also used
as a protein supplement, although it has a lower nutritive value in comparison to
corn gluten meal. It can be used for poultry and pig feed and even for ruminants
due to its significant content of digestible fiber. Corn oil is utilized for human
food. In general, from each 100 kg of corn processed by this technology, 2.87 kg
corn oil, 4.65 kg corn gluten meal, and 24.09 kg corn gluten feed can be obtained.
According to the U.S. Department of Agriculture, the average price per tonne of
these products is as follows: US$357 for corn gluten meal, US$88 for corn gluten
feed, and US$662 for corn oil (Bothast and Schlicher, 2005).
3.2.2.3 Cassava
The cassava (Manihot esculenta) is a perennial bush achieving 2 m by height
and is native to South America. The main feature of this plant is its edible roots,
thus the plant is uprooted after one year of growth in order to obtain its better
conditions for its consumption. The cassava root is cylindrical and oblong and
can reach up to 100 cm in length and 10 cm of diameter. Its pulp is firm and
presents high starch content. Cassava tubers are consumed in a cooked form and
represent a crucial component in the food of more than 500 million people in
America, Asia, and Africa. The cassava is not a very exigent crop, but it should
be grown no higher than 1,500 m above sea level. For cassava cropping, the soils
should be porous because the root requires sufficient oxygen levels to grow; it also
requires good drainage. The cropping temperature should be in the range 25 to
30°C (Agronet, 2007). For this reason, cassava is one of the most important tropi-
cal crops in the world. Once planted, cassava roots can be harvested after seven
months and stay in the soil for three years (Alarcón and Dufour, 1998).
The world’s largest cassava producer is Nigeria, followed by Brazil, Indonesia,
and Thailand (FAO, 2007b). As can be observed in Table 3.9, major cassava
producers are located in Africa, Southeast Asia, and South America. The most
Table 3.9
World Production of Cassava (2007)
No. Country Production/Ton
1 Nigeria 45,750,000
2 Brazil 27,312,946
3 Thailand 26,411,233
4 Indonesia 19,610,071
5 Democratic Republic of Congo 15,000,000
6 Ghana 9,650,000
7 Vietnam 8,900,000
8 Angola 8,800,000
9 India 7,600,000
10 Mozambique 7,350,000
11 United Republic of Tanzania 6,600,000
12 Paraguay 5,100,000
13 Uganda 4,456,000
14 China 4,370,000
15 Benin 2,525,000
16 Madagascar 2,400,000
17 Malawi 2,150,000
18 Côte d’Ivoire 2,110,000
19 Colombia 2,100,000
20 Cameroon 2,076,000
World 222,138,068
elevated cassava yields among the main producers are from Thailand (20.28 ton/
ha) and Brazil (13.63 ton/ha; FAO, 2007a). In general, more than 90% of cas-
sava production is directed to human food, while the balance is used for produc-
ing starches and snacks. The substitution of corn with cassava flour has been
proposed for animal feed production taking into account its high energy content
(Espinal et al., 2005a). The importance of cassava cropping from the viewpoint
of its agro-industrial applications lies in its high potential for energy production
in the form of starch (see Table 3.8). Espinal et al. (2005a) report that the use of
improved seeds and fertilizers, and a suitable weed control allows production of
20 to 30 ton/ha of fresh roots and 10 to 12 ton/ha of dried cassava in zones where
other starch-producing crops like corn, sorghum, or rice do not reach yields above
4 or 5 ton/ha.
There exist two main methods for industrial production of native cassava
starch: the traditional method employed in India and some Latin American coun-
tries, and the modern method of the type used by the company Alfa Laval for
large-scale production. In the traditional process, fresh roots are washed and
debarked before crushing in a rotary rasper. Starch is separated from the crushed
pulp before passing through a series of reciprocating nylon screens of decreasing
mesh size (50250 mesh). The resultant starch milk is settled over a period of four
to eight hours using a shallow settling table or a series of inclined channels laid
out in a zigzag pattern. Settled starch is sun-dried on large cement drying floors
for approximately eight hours. During this period, the moisture content reduces
from 45 to 50% down to 10 to 12%. To achieve efficient drying, sunny conditions
are required with ambient temperatures of more than 30°C and relative humidity
of 20 to 30%. Dried starch is ground to a fine powder and packaged for sale (FAO
and IFAD, 2004). In the modern Alfa Laval–type process, roots are washed and
debarked, sliced and then crushed in a rotary rasper. Starch pulp is passed through
two conical rotary extractors to separate starch granules from fibrous materials,
and then fed via a protective safety screen and hydro cyclone unit to a continuous
centrifuge for washing and concentration. The concentrated starch milk is passed
through a rotary vacuum filter to reduce water content to 40 to 45% and then flash
dried. The flash drying reduces moisture content to 10 to 12% in a few seconds,
so starch granules do not heat up and suffer thermal degradation.
3.3 Lignocellulosic Materials
The lignocellulosic complex represents the most abundant biopolymer on Earth
and constitutes the main component of a great variety of wastes and residues
from domestic and industrial activities of man. Moreover, it is present in profuse
biological materials, such as wood, grass, straw, and forage. Due to its immediate
origin in a biological process, this biopolymer complex has received the name of
lignocellulosic biomass. Being the most plentiful material in the biosphere, the
use of the lignocellulosic biomass will allow the production of a valuable biofuel
like bioethanol as well as the economic exploitation of a wide range of potential
feedstocks resulting from domestic, agricultural, and industrial activities.
CH2OH OH CH2OH OH
O O
O OH O OH
O OH O OH O
O O
OH CH2OH OH CH2OH
Cellobiose unit
COOH
O
OH
H3CO O
OH OH
O O O
O O
OAc OH OH OAc OH
O O O
O O
OH OH OAc
(a)
COOH
O OH
OH HOH2C
H3CO O O
OH OH
O O O
O O
OH OH OH OH O
O O O
O O
OH OH OH
(b)
1. Agricultural residues
2. Agro-industrial residues
3. Hardwood
4. Softwood
5. Herbaceous biomass
6. Cellulosic wastes
7. Municipal solid waste
C CH CH
CH CH CH
OH OH OH
Lignin Cellulose
Hemicellulose
Microfiber of celullose
65
© 2010 by Taylor & Francis Group, LLC
66 Process Synthesis for Fuel Ethanol Production
volume of residues, among which the straw should be highlighted. The straw
is the dried, crushed or not crushed material coming from plants of the family
Gramineae once it is separated from the grain. The straws most evaluated for
ethanol production purposes are wheat straw, rice straw, and barley straw. The
agro-industrial residues refer to the by-products and wastes generated during the
commercial transformation of agricultural crops. The bagasse should be listed
among these residues. The most studied agro-industrial residue is the sugarcane
bagasse, the fibrous residue obtained after juice extraction during the milling step
of sugarcane. Other promising residue is the sweet sorghum bagasse. Other mate-
rials belonging to this category are corn stover and olive stone and pulp.
The materials having origin in hardwood constitute a separate group of ligno-
cellulosic feedstocks. These materials comprise not only the wood itself, but also
its derivatives like sawdust, shavings, and the collected biomass resulting from
forestry activities, such as branches, stalks, and trunk pieces. The wood obtained
from trees of the angiosperm species—poplar, eucalyptus, aspen, oak, maple,
birch, rosewood, and mahogany—belongs to hardwood. The softwood, in turn,
comprises the wood of conifers. The wood from trees of the gymnosperm spe-
cies, such as pine, fir, spruce, larch, and cedar, can be included in this group.
Softwood has higher lignin content than hardwood.
The herbaceous biomass refers to the materials coming from herbaceous
plants, i.e., those plants not generating wood. The grasses are plants that present
neither woody stems nor woody roots. In general, their stems are green. The most
studied herbaceous biomass for ethanol production purposes comprises differ-
ent types of grasses like switchgrass, used in North America for hay production,
alfalfa hay, reed canary grass, coastal Bermuda grass, and timothy grass that
covers almost two-thirds of the livestock meadows in the United States. These
herbaceous plants have a great importance because they grow very fast and have
reduced nutritional requirements. Thus, these plants are excellent candidates for
their exploitation as crops dedicated to bioenergy production.
Among the cellulosic wastes are residues resulting from industrial activities,
mostly related to paper processing, which have an elevated content of cellulose
compared to other types of lignocellulosic biomass. As examples of this group,
newspaper, waste office paper, and paper sludge, one of the effluents of plants for
paper recycling, should be highlighted. Finally, the organic fraction of munici-
pal solid wastes are composed of materials with high lignocellulosic content like
wasted paper, cardboard, fruit and vegetable peels, garden residues, and wood
items, among others.
The composition of lignocellulosic biomass, expressed as the proportion of
cellulose, hemicellulose, and lignin, depends on its origin, though some simi-
larities can be observed independent on the group to which all material belongs.
The composition of several representative lignocellulosic materials is presented
in Table 3.11. As can be observed, hardwood presents high cellulose content mak-
ing it very promising regarding the production of second generation bioethanol.
In this sense, the hydrolysis of cellulose allows the formation of glucose, which
in turn can be transformed into ethanol by fermentation. Likewise, the cellulosic
67
© 2010 by Taylor & Francis Group, LLC
68 Process Synthesis for Fuel Ethanol Production
wastes have high cellulose contents. On the other hand and due to its high lignin
content, softwood has a more difficult transformation process increasing the com-
plexity of fuel ethanol production.
From the large variety of lignocellulosic materials that have been proved for
fuel ethanol production, those with higher availability and production volume
have been defined as the most promising. Logically, this selection is made based
on the context of each region and country. Thus, the corn stover along with pop-
lar wood has become the most potential feedstocks for bioethanol production in
the United States. In Europe, the straw of different cereals is the most promising
material. In fact, wheat straw and barley straw are the feedstocks defined for the
first commercial plant for production of cellulosic ethanol whose construction
started in 2005 and will open soon in Salamanca (Spain; Abengoa, 2008). In the
case of South American countries like Brazil and Colombia, the most promising
feedstock for second generation (lignocellulosic) ethanol is cane bagasse because
it has great availability and production volumes. In addition, the participation of
the sugar sector could provide the necessary financial resources needed for the
implementation of these technologies at industrial level.
3.3.2.1 Sugarcane Bagasse
The sugarcane bagasse is one of the most produced lignocellulosic materials in
the world and represents the residue of cane stems after crushing and juice extrac-
tion. It is a by-product of the sugar industry and is almost exclusively utilized in
sugar mills as a fuel for steam generation. In the past few years, the research on
the economic utilization of bagasse to produce electricity, paper and paper pulp,
and fermentation products has intensified. For instance, the Colombian sugar sec-
tor already produces paper from bagasse at an industrial level and commercializes
15 MW of electricity obtained from this material in the national interconnected
electric network (Asocaña, 2006). The technologies for production value-added
products by fermentation employing bagasse are currently under development. In
general, these technologies are oriented to the application of solid-state fermen-
tation to produce animal feed, enzymes, amino acids, organic acids, and phar-
maceuticals, among others (Pandey et al., 2000). The pretreated bagasse can be
used as a substrate in submerged fermentations for production of xylitol, flavors,
single-cell protein, cellulases, ligninases, and xylanases (Aguilar et al., 2002;
Cardona and Sánchez, 2007; Pandey et al., 2000). In addition, sugarcane bagasse
can be the feedstock for producing activated carbon with an exceptionally high
adsorptive capacity (Cardona and Sánchez, 2007; Lutz et al., 1998).
The percentage of the main biopolymers in cane bagasse is quite similar to
that of hardwood (see Table 3.11). In chemical terms, cane bagasse contains about
50% α-cellulose, 30% pentosans, and 2.4% ash. Due to its low ash content, the
bagasse presents a better performance during fermentation than other residues,
such as rice straw and wheat straw, which contain 17.5% and 11.0% ash, respec-
tively. Moreover, the bagasse can be considered as a valuable means for accumu-
lating solar energy due to its high yield (80 ton/ha) compared to wheat (1 ton/ha),
grasses (2 ton/ha), and trees (20 ton/ha; Pandey et al., 2000). In general, great
amounts of energy can be obtained from cane bagasse. By burning the bagasse in
co-generation systems, the total amounts of process steam and electricity required
to adequately cover the energy needs of sugar mills can be obtained, with an
energy surplus that can be sold to the grid. Nevertheless, different energy and
economic analyses indicate that more benefits can be achieved if the bagasse were
used for ethanol production (Cardona and Sánchez, 2006; Moreira, 2000). To this
regard, it is necessary to take into account that the electricity can be obtained
from a great number of primary fuels, while the liquid fossil fuels for transporta-
tion can be substituted only by a reduced amount of renewable fuels (bioethanol
and biodiesel; Moreira, 2000).
The global production of cane bagasse can be estimated at 373 to 416 million
tonne per year considering data of 2004 and yields from 280 kg bagasse per tonne
of cane (Moreira, 2000) up to 312 kg/ton (Kim and Dale, 2004). The ethanol
yields of bagasse depend on the conversion technology employed, which will be
discussed in the following chapters. In a preliminary way, a yield of 140 L EtOH/
ton bagasse can be assumed based on the efficiency reported by different trials
carried out in the National Renewable Energy Laboratory in the United States
(Golden, CO), which has been used by Kim and Dale (2004). Considering the
mentioned yield, the global potential for producing ethanol from cane bagasse
reaches 58.2 million L/year, an amount greater than all the ethanol produced in
the world in 2007.
different local conditions (Kim and Dale, 2004). Taking into account this factor,
the amount of corn stover that can be collected in a sustainable way in the United
States has been estimated at 80 to 100 million ton (dry basis) per year. Only a
small portion of this amount (about 20 million ton) has the potential to be used
for purposes other than ethanol production, such as, for instance, the production
of agglomerates, pulp, or furfural. In this way, the production of 11 million L
of fuel ethanol will imply the utilization of only 40% of collectable corn stover
(Kadam and McMillan, 2003). The global potential for ethanol production from
this material reaches 72.45 million L. Undoubtedly, the implementation of a pro-
gram for fuel ethanol production from corn stover would reduce the pressure
over corn prices.
in the case of wastes from marketplaces. In this case, the presence of discarded
fruits with different maturity degrees provides the starch, which can be hydrolyzed
using enzymes that degrade this polysaccharide and the cellulose coming from the
lignocellulosic biomass present in these residues as well (Cardona et al., 2004).
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by weight and not by volume. Considering that the specific gravity of molasses
is 1.416, a liter of molasses would have 1,413.95 grams. In addition, the sugar
content of molasses to be diluted should be taken into account due to the varia-
tions in compositions during each processing batch. Thus, the final concentration
of sugars after the dilution of molasses down to 25° Brix is not always the same.
For instance, the cane molasses in Colombian sugar mills contains 48 to 55%
total sugars on average, whereas the North American molasses is poorer in sugars
(46%). In general, diluted molasses containing sugar concentrations up to 18% can
be used. If more concentrated molasses is employed, the ethanol formed during
fermentation will make the microorganisms have a lower growth rate that leads
to more prolonged fermentation times. Alternatively, a first portion of molasses
diluted down to 18° Brix can be used to favor a faster yeast growth and, once
the cultivation medium reaches 12° Brix, the second portion of molasses diluted
down to 35° Brix is added to this medium (Murtagh, 1995).
The ash content of molasses is another important factor to be considered. If
this content is greater than 10%, incrustation problems can arise in pipelines and
distillation towers in the subsequent process steps. The incrustation represents
the accumulation of certain salts, mostly calcium sulfate, which are formed as a
consequence of using sulfuric acid for conditioning the molasses. The addition of
sulfuric acid is intended to separate the sucrose hydrolysis into its two constituent
sugars: glucose and fructose. Although the yeasts synthesize the enzyme required
for such hydrolysis, the invertase, the previous breakdown of this disaccharide
allows a faster fermentation. Furthermore, the acid addition allows adjusting the
pH of the cultivation medium based on molasses in such a way that the yeast
growth is increased and the development of other undesired microorganisms,
mainly bacteria, is avoided. The calcium ions come from the clarification pro-
cess of both cane juice and syrup. The incrustation can be prevented through
sedimentation systems in the dilution tanks of molasses, fermenters, storage tanks
for wine before distillation, and stillage storage tanks before its concentration.
Special chelating agents can be employed in order to remove the solids causing
incrustations from the molasses (Murtagh, 1995).
Different studies to neutralize the effect the osmotic pressure has on process
microorganisms have been done. One approach is the development of special yeast
strains with higher resistance to the salts contained in molasses, i.e., strains more
tolerant to elevated osmotic pressures. Nevertheless, the most common approach
to offset the negative effect of salts is the conditioning of molasses by adding dif-
ferent organic and inorganic compounds. Some of the substances employed for
conditioning sugarcane molasses (that can be applied to beet molasses as well)
are presented in Table 4.1.
The presence of metal traces in beet molasses also affects the ethanolic fer-
mentation using yeasts. The employed agents for cane molasses, for example,
EDTA (ethylene diamine tetraacetic acid), ferrocyanide, and zeolites have dem-
onstrated their usefulness during the conditioning of beet molasses (Ergun et al.,
1997). In the particular case of zeolites, it has been suggested that they can act
as a pH regulator, which has been verified in fermentations with high glucose
Table 4.1
Some Ways for Conditioning and Supplementation of Sugarcane Molasses
for Ethanolic Fermentation Using Saccharomyces cerevisiae
Additive/Supplement Function Remarks References
H2SO4 Precipitation of Removal of calcium Murtagh (1995)
calcium salts; pH salts avoids scaling
adjustment during distillation
Synthetic zeolites Removal of 1–20 g/L medium SivaRaman et al.
inhibitory (1994)
substances; changes
in flocculation
behavior of the
yeast
Unsaturated lipids, soy Protection against SivaRaman et al.
flour, Aspergillus the inhibitory (1994)
oryzae proteolipids effects of substrate
and product
Chitin Protection against 2 g/L medium; Cachot and Pons
the inhibitory reduction of (1991); Patil and Patil
effects of substrate fermentation time (1989)
and product
Skim milk powder Protection against 2 g/L medium Cachot and Pons
the inhibitory (1991); Patil and Patil
effects of substrate (1989); Patil et al.
and product (1985)
EDTA, potassium Binding of inhibitory EDTA: 50 mg/L Pandey and Agarwal
ferrocyanide, sodium metal ions K4Fe(CN)6, NaK (1993)
potassium tartarate tartarate: 1.5 g/L
Alumina beads Growth promoting 2 g/L medium Cachot and Pons
effect (1991)
Yeast extract Source of amino 2 g/L medium Cachot and Pons
acids (1991)
Urea, diammonium Sources of nitrogen Murtagh (1995)
phosphate and phosphorous
Enzymatic complex of Conversion of Commercial Acevedo et al. (2003)
amylases, cellulases nonfermentable preparation
and amylopectinases substances into Rhizozyme: 35 ppm
assimilable
compounds
Source: Adapted from Sánchez, Ó.J., and C.A. Cardona. 2008. Bioresource Technology 99:5270–
5295. Elsevier Ltd.
Process
water
Process Liquefying
water heater enzyme Liquefied
paste
Recycled condensate
Liquefaction
Ground grains Hot water tank
Coolers
tank Flash
tank
Backset
Cooker
Steam
Figure 4.1 Scheme of cooking and liquefaction steps of ground corn grains.
dry-milling process generates co-products with lower value than the wet-milling
process, this technology offers higher ethanol yields that can be in the range
419.4 to 460.6 L/ton (Gulati et al., 1996). Furthermore, the dry milling has lower
capital and labor costs.
The dry milling of corn is made up of washing and milling the grains until they
reach 3 to 5 mm. Then, some impurities are removed (Cardona et al., 2005). The
milling is generally accomplished with the use of hammer mills. The starch from
the ground grain should be gelatinized since the granules of native starch are not
susceptible to enzymatic attack. To carry out this process, a starch suspension con-
taining no more than 45% solids is prepared and cooked. To start the cooking pro-
cess, the suspension is prepared in hot water (88°C). Madson and Monceaux (1995)
emphasize that one of the key issues during the design and operation of production
processes for ethanol production from starch is the elimination of contaminating
bacteria which requires the maintenance of sterile conditions along the production
line until the fermentation step. The decisive factor during the design of cooking
systems is not that the starch cooks itself, but the elimination of bacteria. The over-
all process for cooking and liquefying ground corn grains is presented in Figure 4.1,
which is based on information provided by Madson and Monceaux (1995).
Considering that the conditions needed to reach the sterility are different from
the cooking conditions, the preliminary cooking of the suspension of ground
grains should be accomplished with minimum solubilization of the potential
fermentable substances in order to avoid undesired reactions. These substances
should be released only during the subsequent steps of liquefaction, saccharifica-
tion, and fermentation. This is explained taking into account that a premature
solubilization can lead to the risk of undesired reactions involving fermentable
substances, such as sugars contained in the corn fiber. These secondary reactions
can provoke the retrogradation of starch (crystallization of soluble starch after
have not been effectively published in the open literature. This fact limits the
quality of the related simulations and the possibility of involving a more detailed
description of these steps during the application of process synthesis procedures
to elucidate the best conditions for fuel ethanol production.
Lignin
Hemicellulose Pretreatment
Cellulose
Amorphous Crystalline
region region
and its composition adds a factor implying even more variability exhibited by
these materials regarding their digestibility (Mosier et al., 2005b). Therefore, the
pretreatment step of the lignocellulosic complex has the following goals:
Source: Adapted from Sánchez, Ó.J., and C.A. Cardona. 2008. Bioresource Technology 99:5270–5295. Elsevier Ltd.
87
© 2010 by Taylor & Francis Group, LLC
88
Table 4.3 (Continued)
Physical–Chemical Methods for Pretreatment of Lignocellulosic Biomass for Ethanol Production
Methods Procedure/Agents Remarks Examples of Pretreated Materials References
Ammonia fiber 1–2 kg ammonia/kg Ammonia recovery is required Aspen wood chips Dale et al. (1996); Holtzapple et al.,
explosion dry biomass, 90ºC, 0–60% hemicellulose hydrolysis in Bagasse, wheat straw, barley straw, (1994); Lynd et al. (2002); Sun and
(AFEX) 30 min, p = dependence on moisture, >90% rice hulls, corn stover Cheng (2002)
1.12–1.36 MPa olygomers Switchgrass, coastal Bermuda grass,
Source: Adapted from Sánchez, Ó.J., and C.A. Cardona. 2008. Bioresource Technology 99:5270–5295. Elsevier Ltd.
T − Tref
log R0 = log t exp (4.1)
14.75
If the steam explosion process is carried out under acidic conditions (which
increases the efficiency of cellulose hydrolysis), an additional term should be intro-
duced in Equation (4.1) to consider the effect of pH on the combined severity (CS):
CS = log R0 − pH (4.2)
The pH can be calculated from the amount of sulfuric acid added to the material
and its water content (Söderström et al., 2003).
An important factor to be considered when pretreatment methods are used
(including steam explosion) is the particle size of the lignocellulosic materials.
The conventional mechanical methods require 70% more energy than steam
explosion in order to achieve the same reduction in the particle size. During steam
explosion, some inhibitors of the subsequent biological processes (enzymatic
hydrolysis, fermentation) are formed. Inhibitors formation during the pretreat-
ment requires the washing of pretreated biomass. This decreases the global yield
of the saccharification due to the removal of sugars generated during the hemi-
cellulose hydrolysis. Typically, 20 to 25% of the initial dry matter is removed by
the washing water (Sun and Cheng, 2002). For this reason, the use of very small
particles in some cases (e.g., herbaceous wastes) is not desirable if taking into
account the economy of the process (Ballesteros et al., 2002).
Steam explosion is recognized as one of the most efficient methods for hard-
wood (poplar, oak, birch, maple) and agroindustrial residues, but it is less efficient
for softwood (pine, cedar; Sánchez and Cardona, 2008). For instance, an increase
of 90% in the efficiency of the subsequent enzymatic hydrolysis of poplar chips
pretreated by steam explosion was reported compared to 15% efficiency when pre-
treatment of chips is not carried out (Sun and Cheng, 2002). In the case of cane
bagasse pretreatment, Kaar et al. (1998) determined the conditions that maximize
sugars concentration by varying the temperature within the range of 188 to 243°C
and residence time within the range of 0.5 to 44 min. These authors concluded that
these conditions strongly depend on the composition of the lignocellulosic mate-
rial and it demonstrated the formation of furfural. On the other hand, it has been
reported that the susceptibility of the pretreated substrate to the action of cellulases
is highly influenced by the steam pressure and vaporization time during the pre-
treatment, as was demonstrated for rice straw. In particular, a steam pressure of
3.53 MPa during a short vaporization time (2 min) significantly increases the enzy-
matic hydrolysis without any observable inhibitory effect (Moniruzzaman, 1996).
For the case of softwood that has an increased lignin content and is more
difficult to degrade, a two-stage steam pretreatment has been proposed. In the
first stage, the operating conditions are defined in such a way that the maximum
amount of sugars derived from hemicellulose is obtained. In the second stage,
more severe conditions are employed to degrade the solid fraction resulting
from the first stage achieving a partial hydrolysis of cellulose. In both stages,
the softwood sawdust is impregnated with dilute sulfuric acid. Shahbazi et al.
(2005) propose a fractionation procedure for softwood based on steam explo-
sion and alkaline delignification in order to produce ethanol and related co-
products. An analogous fractionation procedure was utilized by Belkacemi
et al. (2002) where the captured hemicellulose-rich liquor was enzymatically
treated to produce xylose-rich solutions. Regarding the enzymatic hydrolysis
of hemicellulose, Saha (2003) points out that there are no suitable commercial
hemicellulase preparations that can efficiently hydrolyze feedstocks like corn
fiber to monomeric sugars. This author also briefly reviews the microorganisms
and enzymes that could be useful for degrading hemicellulose. Other analogous
schemes involve two hydrolysis stages (Nguyen et al., 1999) or an initial treat-
ment by steam explosion followed by an acid hydrolysis to completely degrade
the xylans with a further acid recovery (Saska and Ozer, 1995).
One of the methods with better indexes is the pretreatment with liquid hot
water (LHW) or thermohydrolysis. Laser et al. (2002) mention that under optimal
conditions, this method is comparable to the dilute acid pretreatment, but with-
out the addition of acids or production of neutralization wastes. In addition, this
method presents elevated recovery rates of pentoses and does not generate inhibi-
tors (Ogier et al., 1999). Nevertheless, solid load for this method is much less than
for the steam explosion method, which is usually greater than 50%.
Another physical–chemical method is the ammonia fiber explosion (AFEX)
process whose function is similar to steam explosion. The pretreatment with
ammonium does not generate inhibitors for subsequent biological processes, so
the washing with water is not necessary. In addition, a small particle size is not
required. For this method, Dale et al. (1996) report experimental data correlat-
ing conditions of the AFEX process, enzyme doses during cellulose hydrolysis,
and the corresponding yields for several agricultural and lignocellulosic residues.
Similarly to the AFEX method and steam explosion, CO2 explosion uses the
same principle, but the yields are relatively low compared to the other methods
(Sánchez and Cardona, 2008; Sun and Cheng, 2002).
Source: Adapted from Sánchez, Ó.J., and C.A. Cardona. 2008. Bioresource Technology 99:5270–5295. Elsevier Ltd.
93
© 2010 by Taylor & Francis Group, LLC
94 Process Synthesis for Fuel Ethanol Production
Source: Adapted from Sánchez, Ó.J., and C.A. Cardona. 2008. Bioresource Technology 99:5270–5295. Elsevier Ltd.
none of the processes can be discarded as less reliable. Milling has been suggested
as a sole pretreatment method before the cellulose hydrolysis since the required
equipment is less expensive than the equipment needed for other pretreatment
methods such as steam explosion or ammonia fiber explosion (AFEX) process,
which can account for 6 to 20% of the capital costs of the process. In contrast,
milling equipment accounts for about 1% of these costs. However, it is considered
that milling has elevated energy costs. Alvo and Belkacemi (1997) point out that
milling of perennial grasses requires much less energy that milling of wood. These
authors consider that milling as a unique pretreatment method should not be dis-
carded as an option taking into account the advantages of this configuration: toxic
products of degradation are not formed, soluble carbohydrates of the initial biomass
are not destroyed, and many rural communities can acquire an easier way to mill in
comparison to other expensive pretreatment equipment. This alternative should be
evaluated in depth, utilizing simulation and optimization tools in the design step.
Dilute-acid pretreatment is the most studied method in the world along with
steam explosion since they have a major probability of being implemented at an
industrial scale in the near future. In fact, the utilization of dilute acids is con-
sidered one of the most mature technologies compared to the rest of biomass
pretreatment methods. The NREL (National Renewable Energy Laboratory)
of the U.S. Department of Energy, which is one of the institutions leading the
research and industrial development of technologies for fuel ethanol production
from lignocellulosic materials in the United States, has chosen the dilute-acid
pretreatment as the best model process to have been developed in the past years
and offered to the industry (Aden et al., 2002; Wooley et al., 1999). The main
advantage of this method compared to steam explosion is the higher recovery of
sugars derived from the hydrolyzed hemicellulose. In the case of hardwood, about
80% of sugars can be recovered using dilute sulfuric acid while this recovery does
not reach 65% when steam explosion is used (Lynd, 1996). The higher the sugars
recovery, the greater the monosaccharide content in the liquid fraction resulting
from the pretreatment. This liquid fraction can be employed as a culture medium
for pentose-assimilating yeasts, or can be added to the bioreactor where the fer-
mentation of cellulose hydrolyzates is accomplished as an additional sugar source
(see the following chapters).
Another prospective method is the pretreatment by LHW. In particular, steam
explosion and LHW processes have been compared in the case of poplar biomass
obtaining better results for the latter method (Negro et al., 2003). In general,
it is considered that the most efficient and promising methods are dilute-acid
pretreatment, steam explosion with the addition of acid catalysts, and the LHW
method (Ogier et al., 1999). To this regard, the evaluation of the global process
for fuel ethanol production from lignocellulosic materials has been performed
by Hamelinck et al. (2005) and the above-mentioned promising pretreatment
methods should be noted. These authors selected one of the three pretreatment
methods and diverse biological conversion technologies according to three differ-
ent stages of technological maturity and development of the operations involved.
For this, they employed spreadsheets and commercial simulators to study the
HO OH OH HO
OH OH OH OH
O OH
OH OH O
O O OH
OH OH OH
OH HO OH HO
Xylose Mannose Galactose Glucose Phenolic
compounds
Figure 4.3 Main inhibitors formed during the pretreatment of lignocellulosic biomass.
fermentation process are formed (Sánchez and Cardona, 2008). Inhibitory sub-
stances are generated as a result of the hydrolysis of extractive components,
organic and sugar acids esterified to hemicellulose (acetic, formic, glucuronic,
galacturonic), and solubilized phenolic derivatives. In the same way, inhibitors are
produced from degradation products of soluble sugars (furfural, hydroxymethyl-
furfural [HMF]) and lignin (cinnamaldehyde, p-hydroxybenzaldehyde, syringal-
dehyde), and as a consequence of corrosion (metal ions; Körner et al., 1984; Lynd,
1996; Palmqvist and Hahn-Hägerdal, 2000b), as shown in Figure 4.3.
In general, the liquid stream resulting from pretreatment undergoes detoxifica-
tion. This stream basically represents the hemicellulose hydrolyzates. The solid
fraction containing cellulose and lignin is washed with water in order to remove
all the soluble substances including the inhibitors. The resulting washing water is
mixed with the hemicellulose hydrolyzates to obtain a liquid medium that can be
employed for alcoholic fermentation or for producing other substances by micro-
organisms. If this liquid medium is employed to produce ethanol, the fermentation
of the pentoses and hexoses released from the hemicellulose hydrolysis during the
pretreatment can be accomplished in a parallel way to the fermentation of glucose
formed during the cellulose hydrolysis. Another option is the unification of the cel-
lulose hydrolyzate and the hemicellulose hydrolyzate for their joint fermentation. In
both cases, the previous detoxification of the hemicellulose hydrolyzate is required
especially when parallel fermentations are carried out. This is explained by the fact
that pentose-assimilating yeasts are very sensitive to the presence of inhibitors.
The methods used for detoxification can be physical, chemical, or biological.
As reported by Palmqvist and Hahn-Hägerdal (2000a), these methods cannot
be directly compared because they vary in their degree of neutralization of the
inhibitors. In addition, the fermenting microorganisms have different tolerances
to the inhibitors that increase the complexity of this process.
101
© 2010 by Taylor & Francis Group, LLC
102
Table 4.6 (Continued)
Physical Methods for Detoxification of Pretreated Biomass
Methods Procedure/Agents Examples Microorganism Remarks References
Supercritical solvent in Dilute-acid S. cerevisiae Solv.: supercritical CO2; 98% Persson et al. (2002b)
countercurrent with the spruce hz. yield of ref. fermn.; removal:
hydrolyzate, 20 MPa, 40ºC; then, 93% furfural, 10% HMF
depressurization
Source: Adapted from Sánchez, Ó.J., and C.A. Cardona. 2008. Bioresource Technology 99:5270–5295. Elsevier Ltd.
Note: HMF = hydroxymethylfurfural; hz. = hydrolyzate. Reference fermentation (ref. fermn.) refers to fermentation carried out in a glucose-based medium without
inhibitors.
103
© 2010 by Taylor & Francis Group, LLC
104
Table 4.7 (Continued)
Chemical Methods for Detoxification of Pretreated Biomass
Methods Procedure/Agents Examples Microorganism Remarks References
Combined alkaline KOH, pH = 10, then pH Bagasse hz. Pichia stipitis Reduction of ketones and Palmqvist and Hahn-Hägerdal
detoxification adjustment to 6.5 with aldehydes, removal of volatile (2000a)
HCl and addition of 1% Dilute-acid hz. of S. cerevisiae compounds when hydrolyzate is Palmqvist and Hahn-Hägerdal
sodium sulfite spruce heated at 90ºC (2000a)
Willow hz. Recombinant Palmqvist and Hahn-Hägerdal
E. coli (2000a)
Source: Adapted from Sánchez, Ó.J., and C.A. Cardona. 2008. Bioresource Technology 99:5270–5295. Elsevier Ltd.
Note: Reference fermentation (ref. fermn.) refers to fermentation carried out in a glucose-based medium without inhibitors; hz = hydrolyzate.
Source: Adapted from Sánchez, Ó.J., and C.A. Cardona. 2008. Bioresource Technology 99:5270–5295. Elsevier Ltd.
Note: hz = hydrolyzate.
107
© 2010 by Taylor & Francis Group, LLC
108 Process Synthesis for Fuel Ethanol Production
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5.1 Starch Saccharification
In Chapter 4, the use of α-amylase during starch liquefaction was mentioned. It is
worth emphasizing here some general issues related to the enzymatic hydrolysis of
starch. The utilization of enzymes to break down the starch has some advantages
over the hydrolysis using acids. In the latter case, strong conditions are required
to achieve the degradation of starch (150°C, pH of 1.5 to 1.8). The amylolytic
enzymes work under milder conditions (temperatures lower than 110°C, neutral
pH) with the corresponding energy savings. In addition, the enzymatic process
does not generate compounds resulting from degradation or oxidation of sugars
due to the very high specificity of the enzymes (Lopez-Munguía, 1993). For these
reasons, the sweeteners industry does not use the acid hydrolysis of starch. This
process has been taken over by the fuel ethanol industry in order to obtain the
fermentable sugars needed for yeast cultivation.
Main amylases employed for starch hydrolysis at the industrial level are
from bacterial and fungal origin though some plant enzymes are eventually
used (Table 5.1). The enzyme α-amylase obtained from thermophilic bacteria
or produced by a recombinant microorganism using the gene obtained from a
thermophilic organism is one of the most used amylases. This enzyme randomly
hydrolyzes the α(1,4) glycosidic bonds within the chains of both amylose and
amylopectin. For this enzyme to attack the starch, the previous gelatinization of
starch should have been carried out. Thus, the broken starch granules release the
amylose and amylopectin and the enzymatic action can be started. The α-amylase
can support high temperatures of up to 110°C while keeping its activity, thus
it is ideal for starch liquefaction process. The molecular weights and optimum
temperatures of enzymatic activity of the α-amylases most commonly employed
for starch processing are shown in Table 5.2. Apar and Özbek (2004) provide
information about the effects of operating conditions on the enzymatic hydroly-
sis of corn starch using commercial α-amylase. In general, the optimum pH of
115
Table 5.1
Main Enzymes Used for Starch Hydrolysis
Bond
Enzymes Source Hydrolyzed Products Mechanism
α-amylase Bacillus licheniformis α(1,4) Dextrines, Endoenzyme
B. subtilis maltodextrines,
maltose
β-amylase Asergillus oryzae α(1,4) from Dextrines, Exoenzyme
Bacillus cereus nonreducing maltose
Barley ends
Glucoamylase A. niger α(1,4) from Glucose Exoenzyme
(amyloglucosidase) Rhizopus sp. nonreducing
ends and α(1,6)
Pullulanase B. acidopullulyticus α(1,6) Maltodextrines Endoenzyme
Klebsiella pneumoniae
Table 5.2
Origin and Properties of Different α-Amylases and Glucoamylases
Molecular Optimum
Microbial Source Weight Temperature/ºC Optimum/pH References
α-amylases Nigam and Singh
Bacillus subtilis 54,780 80 5.6 (1995); Pandey et
Bacillus 49,000 70 al. (2000a)
amyloliquefaciens
Bacillus licheniformis 62,000 90 6.0–6.5
Glucoamylases Nigam and Singh
Aspergillus awamori 83,700–88,000 60 4.5 (1995); Pandey et
Aspergillus niger I 99,000 60 4.5–5.0 al. (2000a)
Aspergillus niger II 112,000 60 4.4
Aspergillus oryzae I 76,000 60 4.5
Aspergillus oryzae II 38,000 50 4.5
Aspergillus oryzae III 38,000 40 4.5
Aspergillus saitoi 90,000 4.5
Cephalosporium 26,850 45–62
eichhormonie
Lipomyces 811,500 50
kononenkoae
Mucor rouxianus I 59,000 55 4.7
Mucor rouxianus II 49,000 55 4.7
Penicillium oxalicum I 84,000 55–60 4.6
Penicillium oxalicum II 86,000 60 4.6
Rhizophus delemar 100,000 40 4.5
the α-amylase is about 6. For this reason, the pH of the cooked starch should be
adjusted before the enzyme addition during the liquefaction process.
Glucoamylase (amyloglucosidase) is the other most employed enzyme in starch-
to-ethanol process. This enzyme is generally obtained from Aspergillus niger or a
species of Rhizopus genus (Labeille et al., 1997; Nigam and Singh, 1995; Shigechi
et al., 2004). The glucoamylase is an exo-enzyme that hydrolyzes the α(1,4) bonds
from the nonreducing ends of amylose or amylopectin chains forming glucose.
Unlike α-amylase, most glucoamylases have the ability to hydrolyze the α(1,6)
bonds in branching points of the amylopectin, though the hydrolysis rate of this
bond is 15 times lower than for the α(1,4) bonds (López-Munguía, 1993; Pandey
et al., 2000b). This feature allows this enzyme to convert the dextrins formed dur-
ing the liquefaction step into glucose. The optimum temperatures of enzymatic
activity for glucoamylases are lower than those of α-amylases employed during
starch liquefaction (see Table 5.2). Consequently, the cooling of liquefied starch is
needed to ensure an appropriate conversion toward glucose. In some commercial
formulations of amylases, the enzyme pullulanase, which specifically hydrolyzes
the α(1,6) bonds, is also employed. Finally, the β-amylase is mostly employed in
the brewing industry and for production of maltose syrups.
The process of hydrolysis (or saccharification) of the stream exiting the lique-
faction tank is aimed at obtaining a glucose-rich solution for its later fermenta-
tion. This stream is adjusted at a pH of 4.5 and cooled down to 65°C in order to
ensure the optimum conditions of the hydrolysis process (Bothast and Schlicher,
2005). The saccharification product is called corn mash if this cereal is the feed-
stock employed or saccharified starch if starch is the feedstock employed, as in
the case of wet milling.
The steps related to the starch degradation are responsible for 10 to 20% of the
energy consumption of the ethanol process in the case of fuel ethanol produced
from starchy materials. One potential option to minimize this high amount of
energy is the substitution of enzymatic hydrolysis technologies in liquid media at
high temperatures with technologies involving the starch hydrolysis using amy-
lases working at low temperatures in solid phase. This approach would make pos-
sible the “cold hydrolysis” of the native starch (Cardona and Sánchez, 2007). For
this, the discovery and characterization of new enzymes displaying these prop-
erties are required (Robertson et al., 2006). Some microorganisms, such as the
bacterium Clostridium thermohydrosulfuricum, have the ability to digest nonge-
latinized starch and convert it into ethanol at 66°C. However, the productivities
attained are too low (Mori and Inaba, 1990).
5.2 Hydrolysis of Cellulose
The yeast Saccharomyces cerevisiae and the bacterium Zymomonas mobilis are
not able to directly utilize the cellulose for ethanol production. In general, these
microorganisms have the highest probability to be used in an industrial process
for conversion of lignocellulosic biomass into fuel ethanol. For this reason, a
Crystalline
Amorphous
Exoglucanases
Crystalline
Glucose
Cellobiose
Endoglucanase
β-glucosidase
Cello-oligosaccharides
these particles in combination with their size and shape determines if β-glycosidic
bonds are or are not accessible to enzymatic attack (Zhang and Lynd, 2004). This
makes the hydrolysis process slower in relation to the enzymatic degradation of
other biopolymers. For comparison, the hydrolysis rate of starch by amylases is
100 times faster than the hydrolysis rate of cellulose by cellulases under indus-
trial processing conditions. Apparently, this difference in hydrolysis rates can be
explained to a greater extent by the higher accessibility of the enzymes to the
substrate, which is more limited in the case of the cellulose, than by the fact that
the β(1,4) bond of cellulose is more difficult to hydrolyze than the α(1,4) bond of
starch. In the case of the pretreated lignocellulosic complex, the cellulases can
bind in a reversible way not only to the cellulose particles, but also to the lignin that
reduces their effectiveness. In addition, the cellulases can bind in an irreversible
way to the substrate provoking a progressive loss of enzymatic activity. It has been
postulated that the addition of surfactants to the reaction mixture can improve the
effectiveness of enzymatic cellulose hydrolysis due to the reduction of enzyme
loss through irreversible binding to the substrate. The surfactant increases the rate
of hydrolysis as well as prolongs the enzyme life. This allows the reduction of
enzyme dosage to 50%. It has been reported that the usage of Tween-80 improved
sugar production for any given particle size of cellulose when milled newsprint
was used as a feedstock. Similarly, the use of sophorolipid increases by 67% the
hydrolysis of steam-exploded wood (Duff et al., 1995; Helle et al., 1993).
One nonconventional approach for saccharification that demonstrates the
diversity of trends for research and development of cellulose hydrolysis is the
enzymatic hydrolysis in biphasic media, by which higher glucose concentrations
can be attained. The goal of replacing part of the water with organic substances is
explained by the need of ensuring the necessary rheological properties to accom-
plish saccharification using higher substrate loads taking into account that glu-
cose does not migrate to the organic phase. Cantarella et al. (2001) employed this
approach for saccharification of steam-exploded wheat straw employing a medium
with 25% (by volume) aqueous phase and 75% organic phase (acetates). Higher
glucose concentrations (measured in the aqueous phase) were obtained compared
to the case when only the aqueous phase was used. These concentrations reached
about 150 g/L. However, when the aqueous phase was fermented using S. cer-
evisiae, an increase in the lag-phase and a small reduction in ethanol yield were
observed (nearly 86 to 92% of the theoretical maximum). Another approach to
cellulose hydrolysis consists in the design of hydrolyzing agents, which are dif-
ferent from mineral acids (that degrade the formed glucose) or enzymes. Mosier
et al. (2002) have systematically studied several organic acids in order to assess
their cellulose hydrolysis and glucose degradation characteristics in comparison
to sulfuric acid. Their results indicate that maleic acid presented the best char-
acteristics. In particular, this acid does not degrade the formed glucose. These
studies are aimed at developing a nonprotein catalyst that mimics the action of the
cellulases. In this way, maleic acid is a suitable catalytic domain for the synthesis
of such enzymatic mimicry.
* Filter paper units (FPU) allow the indirect quantification of enzymatic activity of cellulases. One
FPU is equivalent to the cellulase amount needed to form 1 μmol glucose in one minute measured
as reducing sugars (or to form 0.10 mg glucose in one minute) during the cellulose hydrolysis reac-
tion employing as the substrate Whatman No. 1 paper filter under determined conditions (pH = 4.8,
0.05 M sodium citrate buffer, 50°C). See Ghose (1987).
The increase of the thermal stability of cellulases is important since the tem-
perature increase implies an increase of the cellulose hydrolysis rate (Mielenz,
2001). The augment of specific activity, in turn, can lead to significantly reduced
costs. It is estimated that a 10-fold increase in specific activity could lead to nearly
16 cents (U.S.) savings per liter of ethanol produced. Among the strategies to
attain the increase of specific activity are the increase in the efficiency of active
sites through protein engineering or random mutagenesis, augment of thermal
tolerance, improvement in the degradation of the crystalline structure of cellu-
lose, enhancement of the synergism among the cellulases from different sources,
and reduction of nonspecific bindings (Cardona and Sánchez, 2007; Sheehan and
Himmel, 1999).
In general, the costs of cellulases are considered high. According to prelimi-
nary evaluations of the National Renewable Energy Laboratory (NREL) cited
by Tengerdy and Szakacs (2003), the cost of cellulase production in situ by sub-
merged culture is U.S.$0.38/100,000 FPU. Hence, cellulase costs make up 20%
of ethanol production costs, assuming them at U.S.$1.5/gallon. On the other hand,
commercial cellulase cost (U.S.$16/100,000 FPU) is prohibitive for this process.
In contrast, these authors indicate that the cost for producing cellulases by solid-
state fermentation of corn stover would be U.S.$0.15/100,000 FPU that would
correspond to U.S.$0.118/gal EtOH, i.e., nearly 8% of total costs. The analysis of
process integration via simulation of not only the technological scheme, but also
the costs structure, can provide key elements allowing a deep evaluation of all of
these alternatives in order to choose the more convenient option for in situ cellu-
lase production. On the other hand, the mathematical description of cellulase pro-
duction can allow the definition of useful relationships to assess the performance
and quality of the production of such enzymes using different process analysis
approaches. These approaches undoubtedly will contribute to the definition of
strategies to lower the costs of cellulases. This is the case of cellulase production
in a soluble form after starch cooking. In contrast, during the first steps of ligno-
cellulosic hydrolysis, the cellulases are added to a suspension of cellulose and
lignin particles. The Langmuir model is widely used for description of adsorption
processes involving cellulases taking into account the good adjustment to experi-
mental data in most cases (Cardona and Sánchez, 2007). In addition, it represents
a simple mechanistic model that can be used to compare kinetic properties of
various cellulase–cellulose systems. Kadam et al. (2004) employed a Langmuir-
type isotherm to describe the enzymatic hydrolysis of cellulose for the case of
dilute-acid pretreated corn stover. In this model, the inhibition effect on cellulases
of other sugars present in the biomass hydrolyzate as xylose was considered as
well as the effect of temperature (through the Arrhenius equation) and the dosage
of β-glucosidase. In an early work, Bernardez et al. (1993) studied the adsorption
process of complexed cellulase systems (cellulosomes) released by the anaerobic
thermophilic bacterium Clostridium thermocellum onto crystalline cellulose,
pretreated wood, and lignin employing the Langmuir description. Nevertheless,
some experimental data indicate that the negative effect of lignin content in the
hydrolyzate is not principally due to the enzyme partitioning between cellulose
and lignin, suggesting that lignin hinders saccharification by physically limiting
the enzyme accessibility of the cellulose (Meunier-Goddik and Penner, 1999).
Hence, more structure-oriented modeling is required to gain insight on biomass
hydrolyzate’s hydrolysis and its optimal operating conditions. Other models have
been proposed since the union of the cellulases to the cellulose does not meet all
the assumptions inherent to the Langmuir model. To this end, two-site adsorption
models, Freundlich isotherms, and combined Langmuir–Freundlich isotherms
have been proposed (Zhang and Lynd, 2004). Lynd et al. (2002) present in their
wide review about the microbial cellulose utilization, a compilation of values of
adsorption parameters for cellulases isolated from different microorganism and
for diverse substrates. In that work, the kinetic constants for cellulose utilization
by different microorganisms are reported as well. On the other hand, it has been
shown that the intensity of the agitation in batch reactors has little effect over cel-
lulose hydrolysis when cellulose particles are suspended. Based on the analysis of
the kinetic constants and on experimental data, it was concluded that the external
mass transfer is not a limiting factor of the global process of hydrolysis. However,
when the internal area is much greater than the external one, as in the case of
most cellulosic substrates, it is probable that cellulases can remain entrapped in
the pores provoking lower hydrolysis rates (Zhang and Lynd, 2004). These con-
siderations are essential when mathematical representations of cellulose saccha-
rification are developed. On the other hand, some kinetic studies for cellulose
hydrolysis highlight the significant effect the enzyme dosage has on glucose yield.
In particular, Schell et al. (1999) accomplished the saccharification of dilute-acid
pretreated Douglas fir and obtained data from which was derived a useful empiri-
cal model to calculate the glucose yield as well as to formulate a kinetic cellulose
hydrolysis model.
Zhang and Lynd (2004) reviewed in detail the works concerning the model-
ing of cellulose hydrolysis and point out that most of proposed models for the
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131
Table 6.1
Main Types of Microbial Metabolism according to Their
Catabolic Features
Metabolism Energy Source Carbon Source Feed Kind
Fermentative Organic compounds Organic compounds Organotrophic
Respiratory Organic compounds Organic compounds, Organotrophic
Inorganic compounds CO2 Autotrophic
Methanogenic Organic compounds Organic compounds, Organotrophic
Inorganic compounds, H2 CO2 Autotrophic
Phototrophic Solar radiation Organic compounds, Photoorganotrophic
CO2 Photoorganotrophic
Glucolysis
Glucose
Dihydroxiacetone-P Glyceraldehyde-3P
NADH
NAD+
Glycerol-3P
Glycerol Pyruvate
Acetaldehyde
Alpha-acetolactate
NADH
ADHI
NAD+
Dihydroxyvalerate Diacetyl
Ethanol
Acetoin
Alpha-ketoisovalerate
2,3-Butanediol
Valine
Figure 6.1 Main metabolic pathways involved in the biosynthesis of ethanol and other
related metabolites during alcoholic fermentation using Saccharomyces cerevisiae (ADHI
= alcohol dehydrogenase).
135
© 2010 by Taylor & Francis Group, LLC
136 Process Synthesis for Fuel Ethanol Production
6.2.1 Yeasts
The most employed microorganisms for fuel ethanol production are the yeasts
of the Saccharomyces cerevisiae species that convert hexoses, such as glucose
and fructose, into pyruvate through glycolysis, which is finally reduced to etha-
nol generating two moles of ATP for each molecule of consumed hexose under
anaerobic conditions (Claassen et al., 1999) as shown in Figure 6.1. This micro-
organism also has the ability to convert hexoses into CO2 by aerobic respiration.
One of the two processes may be favored depending on the oxygen concentration
in the culture medium and the carbon source. In the latter case, mainly biomass
is formed and it is the base for large-scale production of baker’s yeast. In addition
to their ability to be grown under anaerobic conditions, yeasts have the advantage
of tolerating relatively high concentrations of ethanol (up to 150 g/L). Below a
concentration of 30 g/L the inhibition is negligible (Kargupta et al., 1998). The
yeast Schizosaccharomyces pombe has the additional advantage of tolerating high
osmotic pressures (high amounts of salts) and high solids content (Bullock, 2002;
Goyes and Bolaños, 2005). In fact, a fermentation process using a wild strain of
this yeast has been patented (Carrascosa, 2006).
Other yeasts having the capability of growing under thermophilic conditions
have been evaluated from an industrial viewpoint. Increased fermentation temper-
ature accelerates metabolic processes and lowers the refrigeration requirements.
For this reason, one of the yeasts that is most studied for ethanol production is
Kluyveromyces marxianus, which can be cultivated at temperatures higher than
40°C (Ballesteros et al., 2001). This condition makes this yeast very promising
in the case of cellulose conversion schemes for ethanol production by the simul-
taneous accomplishment of hydrolysis and fermentation (Ballesteros et al., 2004)
because the cellulases have greater activity at temperatures much higher (50 to
60°C) than those of conventional fermentations.
One of the main problems during ethanol production from lignocellulosic mate-
rials is that S. cerevisiae can ferment only certain mono- and disaccharides, such as
glucose, fructose, maltose, and sucrose. Nevertheless, this microorganism cannot
Xylose
Glucose
XR NAD(P)H
NAD(P)+
Pyruvate
Others TAC
metabolites
Ethanol
Figure 6.2 Main metabolic pathways involved during ethanolic fermentation using
microorganisms assimilating both hexoses and pentoses. (Glu-6P = glucose-6-phosphate,
Fru-6P = fructose-6-phosphate, Eri-4P = erithrose-4-phosphate, Gly-3P = glyceralde-
hyde-3-phosphate, Sed-7P = sedoheptulose-6-fosfato, TAC = Krebs cycle, XR =: xylose-
reductase, XDH = xylitol-dehydrogenase, XI = xylosa-isomerase, TAL1 = transaldolase,
TKL1 = transketolase)
biomass utilization rate. As a rule, the microorganisms prefer the glucose over
the galactose, followed by the xylose and arabinose (Gong et al., 1999), which is
explained by the catabolic repression the glucose exerts on the consumption rate
of xylose and other pentoses as in the case of C. shehatae. In addition, ethanol
productivity achieved using xylose-assimilating yeasts is lower than that of micro-
organisms fermenting only hexoses. Thus, their ethanol production rate from glu-
cose is at least five times lower than that observed in S. cerevisiae. Moreover,
their culture requires oxygen and ethanol tolerance that is two to four times lower
(Claassen et al., 1999). Most xylose-utilizing yeasts are mesophiles, i.e., they are
cultivated at temperatures near 30°C; likewise S. cerevisiae, though there exist
reports about the methylotrophic yeast Hansenula polymorpha cultivated at 37ºC
in a xylose-containing medium (Ryabova et al., 2003).
6.2.2 Bacteria
Some bacteria have the capacity to produce ethanol in significant amounts mak-
ing them potential microorganisms for industrial purposes (see Table 6.2). Among
bacteria, the most promising microorganism is Zymomonas mobilis. This facul-
tative anaerobe presents higher ethanol yields than yeasts, which is related to
the metabolic pathways involved. Z. mobilis makes use of the Entner–Doudoroff
pathway converting 1 mol of hexose into 2 mol of ethanol, but releasing only 1 mol
of ATP (Jeffries, 2005; Figure 6.3), unlike S. cerevisiae that uses the Embden–
Meyerhoff–Parnas pathway (i.e., the glucolytic way) but forms two molecules of
ATP (see Figure 6.1). This fact implies a lower cell yield due to the lower energy
yield of this bacterium, increasing the amount of ethanol that can be obtained
from the same amount of substrate compared to yeasts. There have been reported
ethanol yields of 97% of the theoretical yield from glucose. Furthermore, this
bacterium has a more rapid fermentation due to its higher ethanol production
rate (three to five times higher than in S. cerevisiae) and substrate consumption
Glucose Ethanol
ATP
ADP 2 NAD+ 2 CO2
2 NADPHP + 2 H+
Glucose -6P
NADP Pyruvate
NADPH + H+ NADPH+ H +
2 ATP
Glucono -1,5- lactone-6P 2 ADP
NAD+
H2O P1
Glyceraldehyde – 3P
2-dehydro – 3 deoxy
6-phosphogluconate gluconate – 6P
Figure 6.3 Main metabolic pathway involved during ethanol biosynthesis by the bac-
terium Zymomonas mobilis.
rate. Additionally, this bacterium has a high ethanol tolerance (100 g/L) and a
higher optimal production temperature. Z. mobilis requires no controlled addition
of oxygen and is much more susceptible to genetic manipulations to enhance its
yield or transfer new traits than is the case of yeasts.
Among the drawbacks of Z. mobilis, the too narrow range of fermentable sub-
strates (glucose, fructose, and sucrose) should be noted (Claassen et al., 1999;
Hawgood et al., 1985). Other disadvantage of the use of this bacterium for fermen-
tation of sugarcane syrup and other sucrose-based media is the formation of the
polysaccharide levan (made up of fructose units), which increases the viscosity of
fermentation broth, and of sorbitol, a product of fructose reduction that reduces
the efficiency of the conversion of sucrose into ethanol (Doelle and Doelle, 1989;
Grote and Rogers, 1985; Lee and Huang, 2000). In addition, preculture conditions
have a significant influence on bacterium performance, especially on sucrose
hydrolysis rate. Hence, the addition of invertase to the culture medium has been
proposed (Doelle and Doelle, 1989). Lee and Huang (2000) studied batch ethano-
lic fermentation using Z. mobilis through nonstructured models based on meta-
bolic analysis. These models allowed the use of ethanol and sorbitol formation
during cultivation on a medium containing glucose and fructose or on a sucrose
medium supplemented with immobilized invertase.
Other bacteria that have been investigated in order to implement processes of
direct conversion of lignocellulosic biomass into ethanol are thermophilic and
saccharolytic clostridia. Clostridium thermohydrosulfuricum, C. thermosaccha-
rolyticum, and C. thermocellum can synthesize up to 2 mol EtOH/mol hexose.
Likewise, these bacteria may transform pentoses and amino acids into ethanol.
Having saccharolytic properties, these microorganisms have the ability to grow
on a wide variety of nontreated wastes. C. thermocellum can even directly con-
vert lignocellulosic materials into ethanol (McMillan, 1997). In this way, ethanol
can be directly obtained from pretreated lignocellulosic biomass without the need
of adding costly cellulases. Moreover, the cultivation of these microorganisms at
high temperatures offers the possibility of an easier ethanol removal by distilla-
tion or pervaporation and reduced cooling expenditures (Claassen et al., 1999).
Clostridium thermocellum has been the most studied thermophilic clostridium
because it has the capacity to produce cellulases, hydrolyzing the cellulose and
fermenting the glucose forming ethyl alcohol. On the other hand, the possibility
of employing C. thermosaccharolyticum to produce ethanol from pentoses result-
ing from hemicellulose degradation during the pretreatment of biomass has been
shown (Wyman, 1994).
The main drawback of these bacteria consists in their very low ethanol toler-
ance compared to yeasts. Consequently the maximum reached ethanol concentra-
tions are lower than 30 g/L. In addition, they exhibit a reduced ethanol yield due
to the formation of fermentation by-products like acetic acid and lactate that make
the final ethanol concentrations very low and cultivation times prolonged (3 to
12 days) (Baskaran et al., 1995; McMillan, 1997; Szczodrak and Fiedurek, 1996;
Wyman, 1994). Process integration can play a crucial role for evaluating the most
optimal configurations in order to implement them at an industrial level.
6.3.1 Mutagenesis
By applying random genetic modification techniques, also called mutagenesis,
mutations in the microbial DNA are induced through employing physical or
chemical agents (mutagens). The mutations are produced randomly in the DNA
chain and lead to the production of mutant microorganisms that can transfer
these changes in the genome to the subsequent generations. Among the most
used physical agents, ultraviolet radiation (usually with a wave length of 260 nm)
is highlighted. This radiation is absorbed by the double bonds of pyrimidines
composing the DNA chain. As a result, DNA photoproducts are obtained that
provoke drastic changes in the nucleic acids. This process is not directed and
leads to the death of most irradiated cells. However, a small number of cells
survive and even acquire some desirable traits as a higher product yield. The best
mutants are selected by screening procedures and are irradiated again in order
to obtain mutants with better yields. Besides ultraviolet radiation, x-rays and
ionizing radiations are also employed though these agents can cause the death of
all the irradiated cell population. Among the most employed chemical mutagens
are the nitrogenated base analogues (5-bromouracile, 2-aminopurine), deami-
nating or hydroxylating agents (nitrous acid, hydroxyl amine), alkylating agents
(mustard gas, ethyl-ethanesulfonate, ethyl-methanesulfonate, nitrosoguanidine),
intercalant agents (acridine orange, ethidium bromide, proflavine), and pairing
blocking agents (benzopyrene, aflatoxine B1; Crueger and Crueger, 1993). The
selection programs of industrial microorganisms by mutagenesis are very pro-
longed, tedious, and expensive, but can cause significant increases in the yield
of the overall process.
In the case of fuel ethanol production, the development of mutant cells has
been oriented, besides increasing ethanol yield, to the enhancement of tolerance
to salts and impurities contained in the medium (e.g., for the case of yeasts culti-
vated on molasses) or to the acquiring of flocculating properties. This latter trait
allows the ready separation of yeast cells during schemes of continuous fermenta-
tion or by repeated-batch regimes (see Chapter 7) because the cells agglomerate
and settle (or float) allowing their rapid removal from the cultivation broth.
Vector (plasmid)
Recombinant
vector
Host chromosome
Vectors replication
Cell reproduction
145
© 2010 by Taylor & Francis Group, LLC
146
Table 6.3 (Continued)
Some Examples of Recombinant Microorganisms with Potential Use for Fuel Ethanol Production
Host Expressed Enzymes Gene Donor Feedstock/Medium Remarks References
E. coli FBR3 Pyruvate Z. mobilis Mixed sugars Batch process; 72 h Dien et al. (1998)
147
© 2010 by Taylor & Francis Group, LLC
148 Process Synthesis for Fuel Ethanol Production
Pentoses
[Hemicellulases]
Hemicellulose
Hexoses Lactate
LIGNOCELLULOSIC BIOMASS
HC Pentoses Pentoses
Acetic Acid
Hexoses Hexoses
C5 Fermentation
A
Ethanol
C6 Fermentation
C Cellulose Glucose
[Complexed cellulase system] iti
on
or hib
In
[non-complexed cellulases]
L Lignin Lignin
to produce cellulases (Cardona and Sánchez, 2007). The second strategy is con-
sidered more difficult due to the complexity of cellulases system (Béguin and
Aubert, 1994). Currently, the production of cellulases by bacterial hosts produc-
ing ethanol at high yield such as engineered E. coli, K. oxytoca, and Z. mobilis
and by the yeast S. cerevisiae has been studied. For instance, the expression of
cellulases in K. oxytoca has allowed an increased hydrolysis yield for microcrys-
talline cellulose and an anaerobic growth on amorphous cellulose. Similarly, sev-
eral cellobiohydrolases have been functionally expressed in S. cerevisiae (Lynd et
al., 2005). Undoubtedly, ongoing research on genetic and metabolic engineering
will make possible the development of effective and stable strains of microorgan-
isms for converting cellulosic biomass into ethanol. This fact will surely lead to a
qualitative improvement in the industrial production of fuel ethanol in the future
(Cardona and Sánchez, 2007).
One of the bottlenecks of ethanol production from biomass is the high cost
of enzymes, as noted above. The current cost of producing lignocellulolytic
enzymes by submerged fermentation mainly using T. reesei, is about US$0.40 to
0.60/gal ethanol, but an increase in the specific activity of the enzymes or in the
efficiency of their production through genetic engineering can be expected. This
would allow an eventual cost reduction of the enzymes to US$0.07/gal ethanol, as
suggested by (suggested by Tengerdy and Szakacs, 2003). However, these authors
consider that the genetic improvement of fungi producing these enzymes by solid-
state fermentation could have a greater potential than the genetic improvement of
fungi synthesizing the same enzymes by submerged fermentation, considering
the fact that fungi growing on the surface of biomass have enzymatic complexes
with optimal characteristics and proportions for the hydrolysis of lignocellulosic
materials. On the other hand, the U.S. Department of Energy has contracted
with the world enzyme-producing leaders, Novozymes (Denmark) and Genencor
(USA), with the aim of developing research for improving cellulase systems and
reducing their costs. The research must be oriented not only to the enhancement
of yield, stability, and specific activity of cellulases, but also to the development of
an enzyme mixture that will remain active under hard conditions related to such
steps as acid pretreatment (Mielenz, 2001).
Undoubtedly, if the worldwide use of fuel ethanol uses the development of
the technology of lignocellulosic biomass utilization, genetic engineering will
be called to supply the “tailored” microorganisms needed to meet the exigen-
cies of this new technology. From this, the importance of the metabolic pathway
engineering is inferred. Metabolic pathway engineering is aimed at establishing
metabolic pathways and production hosts, which are capable of delivering opti-
mal flow of carbon from substrate to final product at high yields and volumetric
productivities. In particular, pathway engineering can achieve the integration of
the process at the molecular level through the optimization of the primary meta-
bolic pathways for the synthesis of the targeted product (Chotani et al., 2000).
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155
for both cell growth and ethanol production. Although these yeasts have the abil-
ity to grow under anaerobic conditions, small amounts of oxygen are needed for
synthesis of such substances as fatty acids and sterols. In the case of continu-
ous cultures, cell concentration, cell yield from glucose, and yeast viability are
enhanced by increasing air supply while decreasing ethanol concentration under
both microaerobic and aerobic conditions. Inhibition of cell growth by etha-
nol decreases at microaerobic conditions related to fully anaerobic cultivation.
Specific ethanol productivity is stimulated with the increase of oxygen percentage
in the feed (see, for example, the work of Alfenore et al., 2004). In the case of
fed-batch cultures, Alfenore et al. (2004) show that higher ethanol concentrations
(147 g/L) can be obtained in cultures without oxygen limitation (0.2 vvm) in only
45 h in comparison to microaerobic conditions. In addition, a 23% increase in
the viable cell mass was achieved. Similar studies for fed-batch cultures were
performed for assessing the synergistic effect of temperature and ethanol content
on the behavior of S. cerevisiae cultures (Aldiguier et al., 2004). Best results were
found at 30ºC and 33ºC for around 120 g/L of ethanol produced in 30 h. Slight
benefits for growth at 30ºC and for ethanol production at 33ºC were observed.
These data suggest the possibility of designing two-stage, high-cell-density biore-
actors. One proposed method to reduce the inhibition by ethanol of yeast cultures
is the preadaptation to a medium with an initial content of ethanol. In this way,
yeasts could be acclimatized to acquire ethanol tolerance by serially transferring
them into a medium with ethanol. Vriesekoop and Pamment (2005) point out that
this approach has not provided important success because which preadaptation to
ethanol causes a decrease in the rate of yeast death, it does not prevent it. These
authors showed that the addition of acetaldehyde to preadapted cultures of S. cer-
evisiae eliminates the long lag-phase of yeasts caused by the sudden exposure to
initial ethanol concentrations as high as 50 g/L.
fermentation for batch regime or contained in the feed stream for continuous
regime. This indicator can be expressed in percentage. It is worth emphasizing
that substrate conversion implies that the microorganisms consume the substrate
not only for ethanol biosynthesis, but also for formation of new cellular biomass
and other substances generated as fermentation by-products. S. cerevisiae is the
most employed microorganism for industrial ethanol production from sucrose-
based media.
Molasses or Yeast
sugarcane juice propagation Yeast reutilization
Fermenter
Adjustment wort
Weighing and Fermentation Decantation and Wine
sterilization Brix degrees centrifugation
Figure 7.1 Schematic sequence of operations during batch industrial process for etha-
nol production from sugarcane.
to a productivity higher than that obtained for the conventional process with yeast
recovery (Navarro et al., 1986). Shojaosadati (1996) highlights that yeast reuse
results in a decrease in new growth with more sugar available for conversion
to ethanol and a corresponding increase in ethanol yield of 2 to 7%. For etha-
nol production from beet molasses, this author obtained 8% lower consumption
of the feedstock employing cell recycling. Traditional productivities reached by
batch fermentation are in the range of 1 to 3 g/(L × h). However, if a significantly
high concentration of yeasts (44 g/L) and a high supplementation of yeast extract
(28 g/L) at low ethanol content (approximately 60 g/L) are employed in a glu-
cose-based medium, ethanol productivity as high as 21 g/(L × h) can be achieved
(Chen, 1981). This value is comparable to those obtained during continuous culti-
vation, as shown in Table 7.1.
The recirculation of stillage from a previous batch to the current fermentation,
as schematically illustrated in Figure 7.2, has also been proposed. The stillage
represents one of the distillation product streams during the subsequent ethanol
recovery step that contains a significant amount of water and a much-reduced
amount of ethanol. The addition of stillage to the culture broth can lead to lower
water consumption and the reduction of stillage volume to be treated.
7.1.2.2 Semicontinuous Fermentation
Fed-batch fermentation is one of the most employed cultivation regimes when
process microorganisms present catabolic repression, i.e., when high substrate
concentrations inhibit specific metabolic processes like those related to cell
growth rate. For this reason, the microorganisms grow faster at low substrate
concentrations. In fact, the cultivation of S. cerevisiae to produce baker’s yeasts
is accomplished by this process. Nevertheless, the application of fed-batch culti-
vation to ethanolic fermentation has also offered important results by maintain-
ing low substrate levels as ethanol is accumulated in the medium. This type of
cultivation regime along with the cell recycling is the most utilized technology in
Brazil for bioethanol production due to the possibility of achieving higher volu-
metric productivities (Sánchez and Cardona, 2008). To implement such a process,
conventional batch fermentation is performed though using a less-concentrated
medium. Once the sugars have been consumed, the bioreactor is fed with por-
tions of fresh medium or by adding a small amount of medium permanently until
the end of fermentation. This continuous feeding of the medium can be done in
a linear way (with a constant feeding rate) or according to a more complex func-
tion defining the rate with which the fresh medium is added to the fermenter,
e.g., by an exponential feeding rate. Control of flow rate of medium feeding is
quite advantageous because the inhibitory effect caused by high concentrations of
substrate or product in fermentation broth is neutralized. It was observed that the
addition of sucrose in a linear or exponentially decreasing way leads to 10 to 14%
increase in ethanol productivity (Echegaray et al., 2000). It has been reported that
immobilized yeast cells have better performance in fed-batch cultures regard-
ing ethanol production (Roukas 1996). Aeration is an important factor during
this fermentation regime as well. For fed-batch cultures, Alfenore et al. (2004)
Source: Modified from Sánchez, Ó.J., and C.A. Cardona. 2008. Bioresource Technology 99:5270–5295. Elsevier Ltd.
159
© 2010 by Taylor & Francis Group, LLC
160 Process Synthesis for Fuel Ethanol Production
Culture broth
Dilute Ethanol
Molasses
Yeast recycle
Yeast-free
wine
1 2
3
Stillage recycle
Figure 7.2 Reutilization of yeast cells and stillage during batch fermentation: (1) fer-
menter, (2) separation of cells by centrifugation, (3) distillation column.
have shown that higher ethanol concentrations (147 g/L) could be obtained during
cultivation without oxygen limitation (0.2 volumes of air per volume of broth in
1 min or vvm) during only 45 h in comparison to microaerobic conditions.
In the case of multiple or repeated batch fermentation, the use of flocculating
strains of yeasts is of great importance. In this type of culture, after starting a
conventional batch, the yeasts are decanted in the same vessel where they were
cultivated and then the clarified culture broth located in the upper zone of the
fermenter is removed. Then, an equal amount of fresh culture medium is added
for the following batch. In this way, high cell concentrations are reached and inhi-
bition effect by ethanol is reduced without the need of adding flocculation aids or
using separation or recirculation devices. These repeated batches can be accom-
plished until the moment when the activity and viability of culture are lost as a
consequence of a high exposition to fermentation environment. When this occurs,
the system should be reinoculated (Sánchez and Cardona, 2008). Some factors,
such as agitation, allow flock size to be optimum for reaching higher ethanol
concentrations. Even small levels of dissolved oxygen in the medium can facili-
tate the neutralization of inhibition effect by ethanol, as suggested by Hawgood
et al. (1985). Maia and Nelson (1993) point out that the addition of unsaturated
fatty acids can reduce or eliminate the need for microaeration because the oxygen
requirement is related to the synthesis of these acids. These authors evaluated the
supplementation of sucrose-based medium with fatty acids sources (soy and corn
flours) in repeated-batch cultures obtaining best results with corn flour and justi-
fying the traditional and empiric use of this component during the fermentation
step by the small Brazilian distillers. Some examples of fed-batch and repeated
batch fermentations for bioethanol production from sugarcane molasses can be
observed in Table 7.1.
V, X, S, P V1 V2 Vn
(a) (b)
consumed and yields are reduced. In general, in commercial processes for etha-
nol production, although the productivity is important, it is more relevant for the
substrate conversion considering that the main part of the production costs cor-
respond to feedstocks (Gil et al., 1991). On the other hand, aeration also plays an
important role during continuous ethanolic cultivations. Cell concentration, cell
yield from glucose, and yeast viability may be enhanced by increasing air supply,
whereas ethanol concentration decreases under both microaerobic and aerobic
conditions. Cell growth inhibition by ethanol is reduced at microaerobic condi-
tions compared to fully anaerobic cultivation, and specific ethanol productivity is
stimulated with the increase of oxygen percentage in the feed stream (Alfenore et
al., 2004; Sánchez and Cardona, 2008).
An important feature of continuous processes is related to the diminution of
the product inhibition effect. Through cascade of continuous reactors, ethanol
obtained in the first reactors is easily transported to the next ones reducing in this
way its inhibitory effect (see Figure 7.3b). On the other hand, other configurations
employing one fermenter can contribute to the reduction of product inhibition. In
particular, the Swedish company Alfa Laval implemented a continuous process
for producing 150,000 L EtOH/d in Brazil by Biostill technology (Kosaric and
Velikonja, 1995). This process is based on yeast cultivation carried out in a fer-
mentation vessel from which a liquid stream is continuously withdrawn to be sent
to a centrifuge. From the centrifuge, one concentrated yeast stream is continu-
ously removed and recycled back to the fermenter. The other yeast-free stream is
directed to a distillation tower. From this tower, concentrated solution of ethanol
and stillage are removed. A portion of the stillage is also recycled back to the
fermenter in order to maintain the mass balance necessary for conserving steady-
state conditions according to the original configuration patented by Alfa Laval
(Ehnstroem, 1984), which is shown in Figure 7.4. In this process, there is signifi-
cant savings in process water, which reduces stillage volumes and low residence
times (3 to 6 h) in the fermenter can be achieved. A modification to this process
using no recirculation stream from a distillation column and reaching yields of
96% of theoretical has been patented as well (Da Silva and Vaz, 1989).
Other alternatives of continuous fermentation have been proposed, but many
of them still have not reached the commercial level. Some of them require the
use of highly flocculating yeast strains similar to the tower and fluidized-bed
reactors. These types of reactors allow much higher cell concentrations (70 to
100 g/L) and ethanol productivities, and have a long-term stability due to the
self-replenishing of fresh yeasts. Moreover, these fermenters do not require stir-
ring devices or centrifugation (Gong et al., 1999). S. uvarum is one of the most
promising yeasts to be employed in these configurations thanks to its flocculating
properties. All of these efforts have been directed to the increase of productivity
and yield, as can be seen in Table 7.1. Another approach for increasing process
productivity is the continuous ethanol removal from culture broth during fer-
mentation by means of a vacuum or membranes. These configurations enhance
efficiency of the process remarkably well, but imply an increase in capital costs.
The use of vacuum flash coupled with continuous fermenters could eliminate the
Conc. EtOH
Gas Outlet
Feed
Distillation
Unit
Fermentor
Centrifuge
Yeast
discharge
Figure 7.4 Biostill process for continuous ethanol production: (1) yeast recycling loop,
(2) stillage recycling loop.
need of heat exchangers and increase the productivity (Costa et al., 2001). These
types of configurations involving the application of reaction–separation integra-
tion are discussed in Chapter 9.
Effluent Effluent
Fixed Moving
particles particles
Feed Feed
(a) (b)
Figure 7.5 Most employed configurations for bioreactors with immobilized cells: (a)
fixed-bed reactor, (b) fluidized-bed reactor.
165
© 2010 by Taylor & Francis Group, LLC
166 Process Synthesis for Fuel Ethanol Production
(1999) claim that the simple addition of a small fraction of solids in submerged
cultures facilitates cell anchorage. This kind of adhesion enhances the metabolic
activity and is an easier and more economical method than the immobilization of
cells. In batch flasks cultures, these authors showed that materials, such as river
sand, delignified sawdust, chitin, and chitosan, make possible the adhesion of S.
cerevisiae cells leading to higher ethanol production in comparison to free cells.
Thus, the application of these techniques of “passive immobilization” to continu-
ous cultures should be experimentally tested. Nowadays, most of the configura-
tions using immobilized cells are, so far, used in commercial operations. Hence,
preliminary design and simulation of this type of process could become a very
useful tool for defining new research lines at pilot and semi-industrial levels con-
sidering the overall bioethanol production process (Sánchez and Cardona, 2008).
fermentation increases the throughput rate of an ethanol plant without the need of
increasing the plant capacity. These authors provide a theoretical method for pre-
dicting the maximum concentration of ethanol in fermented mash that takes into
account changes in the weight and volume of mash during fermentation. Bayrock
and Ingledew (2001) designed and tested a system that combines the multistage
continuous culture fermentation and the VHG cultivation for feed containing 150
to 320 g/L of glucose using S. cerevisiae. The maximum ethanol concentration
obtained in the process was 132.1 g/L indicating the feasibility of implementing
this technology in the industry, particularly in the continuous production of etha-
nol from wheat starch (Sánchez and Cardona, 2008).
VHG technology has been tested with successful results for oats, barley, rye,
and triticale, as cited by Wang et al. (1999). The pretreatment of feedstock can play
an important role when process integration is analyzed during this type of fer-
mentation processes. Wang et al. (1999) propose the integration of a pretreatment
process, pearling by abrasion of cereal grains such as rye or triticale, with VHG
fermentation technology. The pearling of cereals removes approximately 12% of
grain dry matter, which increases its starch content to 7 to 8%. This increase in
starch content combined with the employment of high concentrations of sugars,
which is the main feature of VHG fermentation, allows the increase in the final
ethanol concentration of 64% in comparison to the use of nonpearled grains in
conventional fermentations.
Lignocellulosic Cellulases
biomass
Figure 7.6 Block diagram of fuel ethanol production from lignocellulosic materials by
separate hydrolysis and fermentation (SHF).
Solid residues
(co-products)
Figure 7.7 Block diagram of separate hydrolysis and fermentation (SHF) process for
fuel ethanol production from lignocellulosic biomass without parallel fermentation of
pentoses.
MSW has been already patented (Titmas, 1999) and some strategies for improv-
ing the fermentability of acid hydrolyzates of MSW have been defined. Nguyen et
al. (1999) employed a mixed solids waste (construction lumber waste, almond tree
prunings, wheat straw, office waste paper, and newsprint) for producing ethanol
by SHF using yeasts. In this process, the recycling of enzymes was implemented
through microfiltration and ultrafiltration achieving 90% cellulose hydrolysis
using a net enzyme loading of 10 filter paper units (FPU)/g cellulose.
S. cerevisiae has demonstrated its elevated resistance to the presence of inhibi-
tors in the lignocellulosic hydrolyzate. In the case of the more productive continu-
ous regime, one way to enhance this resistance is the increase in the cell retention
to prevent washout and maintain high yeast cell density. Brandberg et al. (2005)
employed a microfiltration unit to recirculate the cells under microaerobic condi-
tions achieving sugar conversion up to 99% for undetoxified dilute-acid pretreated
hydrolyzates of softwood (spruce) supplemented with mineral nutrients, although
the productivity was low.
Table 7.3
Some Examples of Co-Fermentation of Lignocellulosic Hydrolyzates Using
Nonrecombinant Microorganisms
Feedstock/
Technology Bioagent Medium Remarks References
Co-fermentation Saccharomyces Glucose and Batch and Laplace et al.,
(mixed culture) cerevisiae xylose continuous 1993
mutant+ cultures; 100%
Pichia stipitis glucose
conversion and
69% xylose
conversion
Respiratory Steam— Continuous Delgenes et al.,
deficient S. exploded and culture: EtOH 1996
diastaticus + enzymatically conc. 13.5 g/L,
P. stipitis hydrolyzed yield 0.25 g/g,
aspen wood productivity
1.6 g/(Lh);
100%
conversion of
glucose and
xilose
Isomerization of S. cerevisiae + Nonpretreated Batch process; Chandrakant and
xilose and xilose spent sulfite yield 0.41 g/g; Bisaria, 1998;
fermentation (glucosa)– liquors, 51–84% xilose Lindén and
isomerasa acid- utilization Hahn-Hägerdal,
hydrolyzed 1989
wheat straw
Source: Extracted from Cardona, C.A., and Ó.J. Sánchez. 2007. Bioresource Technology 98:2415–
2457. Elsevier Ltd.
Stochastic Deterministic
models models
Mathematical
Time models of Hydrodynamics
regime fermentation
Static Segregated
models Kinetics models
Non-structured Structured
models models
depending on cell age. If probabilistic functions are not considered in the model,
the description becomes deterministic and other types of distribution can be used,
such as the distribution of the average age of cell population as a function of
time. In the simplest case, the age of the entire population corresponds to the cur-
rent time in a batch fermentation process. When the time regime of a cultivation
process is considered, the corresponding models can be either dynamic or static.
Dynamic models are used to describe discontinuous and semicontinuous pro-
cesses as well as to assess the dynamic behavior of continuous processes that are
the bases for developing control schemes for fermentation. In these models, the
time derivatives are important. If those derivatives are equal to zero, the model
becomes static and the process is analyzed under steady-state conditions.
When the hydrodynamic features of the cultivation process are taken into
account, it is necessary to employ segregated models considering, for example,
the existence of cell aggregates or zones inside the fermenter with poor agitation.
In these cases, the models can consider derivatives with respect to one or more
of the three space coordinates (models with distributed parameters). If the hydro-
dynamic transport phenomena are not considered, the mentioned derivatives are
null (models with nondistributed or concentrated parameters) and the models
are nonsegregated. Actually, this type of models is used for description of the
bioreactor rather than the cultivation process itself. Finally, to study the kinetic
behavior of the cell culture, the models can be either structured (sometime, also
called deterministic) or nonstructured (unstructured). In the former case, the
internal structure of the biological system is considered, i.e., its constituent com-
ponents and the interactions between them. Some fermentation processes have
been described through structured models by considering several key intermedi-
ate metabolites (like RNA, ATP, NAD+, etc.) besides the substrates and products.
This approach has been applied to the analysis of metabolic pathways (metabolic
flux analysis) leading to the biosynthesis of ethanol (for instance, see the work of
Çakır et al., 2004). However, these models are complex and the determination of
their parameters is quite difficult. In contrast, the nonstructured models simplify
the description of fermentation behavior by considering the cells as black boxes
with some “average” composition that is characterized through the overall cell
biomass concentration.
For process design of technological configurations involving fermentation pro-
cesses, especially when process synthesis procedures are applied, the utilization
of complex structured segregated models are not desirable due to the considerable
increase in computational effort and mathematical complexity of the calculations
required to define the performance of the overall process at a plant scale. For this
reason, nonstructured, nonsegregated models without consideration of cell distri-
bution by age are preferable. However, these simplified models should reflect the
main phenomena inherent to the description level defined. Thus, to evaluate etha-
nolic fermentation kinetics, such mathematical models should accurately describe
at least the cell growth, consumption of the main substrate, and ethanol produc-
tion. In the simplest case, ethanologenic fermentation can be described using a
stoichiometric approach, which is useful for calculation of mass and energy bal-
ances of the cultivation process during both batch and continuous processes.
Lin and Tanaka (2006) reviewed the classical generic models for the description
of ethanolic fermentation. These authors point out that the nonstructured models
are frequently used during the routine control of fermentation processes, whereas
structured models should be used for optimization and control of ethanol fermenta-
tion. The main limitation of these models is that they do not consider simultane-
ously the four factors affecting ethanol concentration (substrate limitation, substrate
inhibition, product inhibition, and cell death). Most of the models reviewed by
these authors are related to the simple ethanol fermentation, but it is also neces-
sary to analyze other models, which apply to more complex processes, such as co-
fermentation and simultaneous saccharification and fermentation (SSF).
Other specific models have been developed for special configurations of bio-
reactors or for specific fermentation conditions (Cardona and Sánchez, 2007).
Gilson and Thomas (1995) developed a model for a fluidized-bed reactor with
yeast cells immobilized on alginate beads. It was shown that the observed reduc-
tion in ethanol yield compared to free yeast cells was caused by substrate restric-
tions inside the beads and not by changes in the metabolic rate of the immobilized
cells. Borzani (1987) derived a Monod-based model for evaluating the maximum
value of the mash-feeding rate to be used in order to have a completely fermented
medium during the fed-batch fermentation of molasses for ethanol production.
Converti et al. (2003) provide a simplified modeling of the kinetics of fed-batch
fermentation of sugarcane molasses that allows the prediction and control of the
performance of this regime of cultivation. Certainly, this tool is very useful for
the simulation of the entire process. Tsuji et al. (1986) evaluated the performance
of continuous alcoholic fermentation using a vector-valued objective function.
This analysis considered the trade-off among three criteria (ethanol productiv-
ity, the ethanol concentration in the broth, and the substrate conversion) on the
basis of the noninferior set defined in a vector-valued function space. Costa et al.
(2001) used an intrinsic model that took into account cell volume fraction and the
dependence of kinetic constants on temperature for continuous vacuum fermenta-
tion using yeasts. With the help of this model, the process was optimized using
response surface analysis that allowed the determination of operational condi-
tions maximizing high yield and productivity. In the same way, dynamic simula-
tion was performed using the concepts of factorial design in order to determine
the best control structures for the process. Maia and Nelson (1993) presented a
model of gravitational sedimentation intended to describe the recycling of cells
to the bioreactor using a parallel plate sedimenter during continuous fermenta-
tion. This model allowed the optimization of the operating conditions in order to
efficiently recycle yeasts at high cell density.
Table 7.4
Some Kinetic Models Describing Specific Cell Growth Rate during
Ethanologenic Fermentations Employing Glucose-Based Media
No. Model of Growtha Observations Ref.
1. S Saccharomyces Aiba et al., 1968
µ = µ max e− k1P cerevisiae, k1 shift for
KS + S
continuous culture
2. S S. cerevisiae alginate Birol et al., 1998
µ = µ max (1 − K PX P ) inmovilization, ≥
KS + S
10% sugars
3. S. cerevisiae, some Luong, 1985
S P
α
S Ki P X
rX = µ max 1 − 1 − X
K S + S K i + S Pm X m (7.1)
where S, X, and P are the concentrations (in g/L) of substrate (glucose), cell bio-
mass (S. cerevisiae), and product (ethanol), respectively, µmax is the maximum
specific growth rate (in h-1), KS and Ki are the semisaturation and substrate inhibi-
tion constants, Pm is the maximum product concentration, and Xm is the maximum
cell biomass concentration in the medium. The models describing the substrate
consumption rate (rS) and product formation rate (rP) are represented by the fol-
lowing equations:
1
rS = − rX (7.2)
YX /S
1
rP = rX (7.3)
YP
where YX/S is the cell biomass yield from substrate (in g cell/g substrate) and
YP = YX/S /YP/S (in g cell/g EtOH); YP/S is the product yield from substrate (in g
EtOH/g substrate).
Substrate consumption rate and product formation rate for the bacterium Z.
mobilis were selected according to the model 5 of Table 7.4, which was slightly
modified to consider cell biomass recirculation as follows:
n
S P X
rX = µ max 1 − 1 − X
K S + S Pm X m (7.4)
1
rS = − rX − mX (7.5)
YX S
rP = αrX + βX (7.6)
The yeast cells are assumed to have a “molecular formula” that is derived
from the elemental analysis of cell biomass. Despite its simplicity, this approach
has the advantage of providing suitable relationships to perform mass and energy
balances required to simulate the alcoholic fermentation process. Moreover,
other transformations can be considered by adding more stoichiometric reactions
describing, for example, the formation of fermentation by-products like acetalde-
hyde and glycerol:
rx = [αrx ,1 + (1 − α )rx ,2 ] X
S1 P − Pix ,1 K ix ,1
rx ,1 = µ max,1 1−
K sx ,1 + S1 Pmx ,1 − Pix ,1 K ix ,1 + S1
S2 P − Pix ,2 K ix ,2
rx ,2 = µ max,2 1−
K
sx ,2 + S 2 Pmx ,2 − P ix ,2 K ix ,2 + S2
S1 P − Pis,1 K is,1
rs,1 = −αqs,max,1 1− X
K ss,1 + S1 Pms,1 − Pis,1 K is,1 + S1
(7.7)
S2 P − Pis,2 K is,2
rs,2 = −(1 − α )qs,max,2 1− X
K ss,2 + S2 Pms,2 − Pis,2 K is,2 + S2
rp = [αrp,1 + (1 − α))rp,2 ] X
S1 P − Pip,1 K ip,1
rp,1 = q p,max,1 1 −
K sp,1 + S1 Pmp,1 − Pip,1 K ip,1 + S1
S2 P − Pip,2 K ip,2
rp,2 = q p,max,2 1−
K sp,2 Pmp,2 − Pip,22 K ip,2 + S2
where rx is the overall cell growth rate, rx,1 and rx,1 are the cell growth rate from
glucose and xylose, respectively; rs,1 and rs,1 are the glucose and xylose consump-
tion rates, respectively; rp is the overall ethanol production rate; rp,1 and rp,1 are
the ethanol production rates from glucose and xylose, respectively; X, S1, S2, and
P are the concentrations (in g/L) of cell biomass, glucose, xylose, and ethanol,
respectively; α, µmax,1, µmax,2, qs,max,1, qs,max,2, qp,max,1, qp,max,2, Ksx,1, Ksx,2, Kss,1, Kss,2,
Ksp,1, Ksp,2 , Pmx,1, Pmx,2, Pms,1, Pms,2, Pmp,1, Pmp,2, Kix,1, Kix,2, Kis,1, Kis,2, Kip,1, Kip,2, Pix,1,
Pix, Pis,1, Pis,2 , Pip,1, Pip,2 are the kinetic parameters.
120 2.5
100
2.0
80
S1, S2, P [g/L]
1.5
X [g/L]
60
1.0
40
0.5
20
0 0.0
0 10 20 30 40 50
Time [h]
25
20
15
0.10 0.12 0.16 0.19 0.21 0.24
Dilution Rate, 1/h
dX v
= (µ v − µ nv − µ d − D ) X v
dt
dX nv
= µ nv Xv (µ d − D ) X nv
dt
dX d
= µ d ( X v − X nv ) − DX d (7.8)
dt
dP µ v X v
= − m p X nv − DP
dt Yx / p
dS µ v X v
= − mS X nv − D(S0 − S )
dt Yx / S
where X, S, and P are the concentrations of cell biomass in the effluent stream,
S 0 is the concentration of substrate in the feed stream (in kg/m3), D is the dilution
rate (in h-1), µ is the specific growth rate (in h-1). The subindexes v, nv, and d refer
to viable, nonviable, and dead cells, respectively. The biomass growth (death) rate
expressions are as follows:
S P S
µ v = µ max 1−
K1 + S Pc K 2 + S
S P S
µ nv = µ max 1− − µv (7.9)
K1 + S Pc K 2 + S
µd = µv
where µmax, K1, K2 , and Pc are kinetic constants, which can be found in the original
work of Jarzębski (1992).
In a previous work (Restrepo et al., 2007), the simulation of the continuous
system using the available information and parameters reported by Jarzębski
(1992) was performed, but the results were not satisfactory because there was
no appropriate correspondence with the experimental data reported by Perego et
al. (1985) for continuous fermentation using sugarcane molasses as a feedstock.
Using the software Matlab™ (Mathworks, Inc., USA), the curves corresponding
to the dynamic behavior of such fermentation system were obtained (Figure 7.11).
Nondynamic analysis (bifurcation analysis) is a powerful tool to study the oscil-
latory behavior of continuous ethanolic fermentations. This tool was used in the
previous mentioned work in order to assess whether the model can describe the
dynamic behavior of the system. For the analysis of the fermentation system stud-
ied, the software MatCont developed in the University of Gent (Belgium) was
employed as a toolbox in Matlab package. The results of bifurcation analysis for
the Jarzębski’s model are shown in Figure 7.12. From this diagram in the zone hav-
ing a physical sense (positive dilution rates), it can be observed that the dynamic
system behaves in an ordinary way and presents no sustained oscillations (Hopf
bifurcations). In the zone of negative dilution rates, limit point (LP or node-saddle
bifurcation) and Hopf bifurcation are present indicating that the model does have
the possibility to represent the oscillations.
For representing the sustained oscillations and the instability of the contin-
uous fermentation, the Jarzębski’s model was modified and adjusted in such a
way that the model represents not only the oscillatory fermentation reported by
Perego, Jr. et al. (1985) appropriately, but also the data for continuous nonoscil-
latory fermentation obtained by these same authors. The modification consisted
in the simplification of the nonviable biomass growth rate (µ nv) considering that
the inhibition of cell biomass is mainly due to the high ethanol concentration. In
addition, the expression describing the biomass death rate (µ nv) was changed in
such a way that this rate was proportional to a fraction d of the viable biomass
growth rate (µ nv). Therefore, the model modified comprises the system (7.8) and
the following rate expressions:
4
Dead biomass
Experimental data of Perego
et al. (1985)
2
–2
0 10 20 30 40 50 60 70 80 90 100
Time (h)
60
40
20
0
0 10 20 30 40 50 60 70 80 90 100
Time (h)
S P S
µ v = µ max 1−
K1 + S Pc K 2 + S
S P S
µ nv = µ max 1− − µv (7.10)
K1 + S Pc K 2 + S
µ d = − dµ v
60
50
BP
40
S (g/L)
30
BP
20
H
LP H
BP
10 BP H
H
0
–0.04 –0.02 0 0.02 0.04 0.06 0.08 0.1 0.12
D (1/h)
Figure 7.12 Bifurcation diagram of the continuous ethanolic fermentation using the
model of Jarzębski (1992) for an inlet substrate concentration (S 0) of 137.5 kg/m3. H =
Hopf bifurcation, BP = bifurcation point, LP = limit point.
5
Xt, Xv, Xnv, Xd (kg/m3)
0
0 10 20 30 40 50 60 70 80 90 100
Tiempo (h)
(a)
55
50
45
40
35
S (kg/m3)
30
25
20
15
10
0 10 20 30 40 50 60 70 80
Time (h)
(b)
Figure 7.13 Dynamic simulation using the proposed modified model (continuous
curves). The continuous curves were calculated using the model proposed. The experi-
mental data were taken from the work of Perego et al. (1985). (a) Cell biomass behav-
ior: total biomass ( ), viable biomass (---), nonviable biomass (---), dead biomass (···),
experimental data for cell biomass (□). (b) Substrate behavior: substrate ( ), experi-
mental data for substrate (□).
Table 7.5
Values of Kinetic Parameters Obtained by Adjusting the Experimental
Data according to the Proposed Modified Model
K1/kg m–3 K2/kg m–3 µmax/h–1 µ’max/h–1 Yx/p/kg kg–1 Yx/s/kg kg–1
0.0842 6.2479 0.2623 0.2218 0.1817 0.0647
2.5
Hopf bifurcation
Xv (kg/m3)
1.5
0.5
Branching Branching
0
0 0.05 0.1 0.15 0.2 0.25 0.3
D (1/h)
Figure 7.14 Response diagram of the continuous ethanolic fermentation process for
viable cell biomass in dependence on the dilution rate D.
When the bifurcation analysis has been performed based on the modified model,
a Hopf bifurcation can be noted in the response diagram near D = 0.089 h-1 for
the viable biomass in dependence on the dilution rate (Figure 7.14) indicating the
appearance of the oscillatory fermentation. Similarly, the point with the maximum
concentration of viable cells was also established. This point matches with the max-
imum ethanol concentration and corresponds to an inlet substrate concentration of
137.5 kg/m3. Finally, through bifurcation analysis, it is possible to delimit the zones
of the operating diagram S 0 versus D (Figure 7.15). In particular, the parameter S 0
has demonstrated a strong influence on the fermentation behavior. Small changes in
the nutrient composition of the culture broth entering the continuous fermenter can
provoke significant changes in the response variables (concentrations of biomass,
ethanol, and residual substrate). Knowing these zones, the task of operating the
fermenter in the stable zones becomes easier. Moreover, the design of the control
250
Unstable zone
200
S0 (kg/m3)
150
Stable zone
50
0
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1
D (1/h)
Figure 7.15 Operating diagram of the continuous ethanolic fermentation for inlet sub-
strate concentration (S 0) and dilution rate (D).
structure can be based on these nonlinear analysis tools. Therefore, the modified
model can predict when the instability of the fermentation will occur. At this point,
the instability of the system can be considered during the early step of conceptual
design, which permits a better design of the automatic control system. This issue is
of great importance during the operation of industrial ethanolic fermentations.
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199
• Nonfermented sugars
• Oligosaccharides resulting from the incomplete saccharification of
starch or cellulose
• Ground and spent cereal grains
• Lignin (in dependence on the biomass pretreatment method)
• Other fermentation products like glycerol
• Lactic acid produced from contaminant bacteria
• Small amounts of acetic acid released during hemicellulose hydrolysis
• Dissolved carbon dioxide, salts, and excretion products from microbial
cells metabolism
• Other compounds and materials
However, the two main components are water (80 to 90%) and ethyl alcohol.
Making use of the higher volatility and lower boiling point of ethanol, the unit
operation used as a rule for its separation is the conventional distillation at a pres-
sure equal or higher than atmospheric pressure.
Usually, two distillation columns are utilized to elevate the ethanol concentra-
tion up to 90 to 92%. Concentrations higher than 95.6% (or 89.4 molar %) are
impossible to obtain by conventional distillation due to the similar composition of
both the saturated vapor and saturated liquid achieved in the top of the distillation
column. This composition is named azeotropic and is one of the main thermo-
dynamic limits imposed on ethanol purification process. To produce anhydrous
ethanol (99.5% or more), nonconventional separation technologies are required
(see Section 8.2).
The technological scheme of the concentration and rectification steps of the
ethanol contained in the culture broth is shown in Figure 8.1. During fermentation,
carbon dioxide is generated as a result of the microbial metabolism. In the gas
outlet stream and, along with CO2, small amounts of volatilized ethanol, as well
as even much smaller amounts of water and other volatile substances, can be
found. To avoid the ethanol loss, this gaseous stream is fed to a scrubber where a
counter-current stream of water absorbs more than 98% ethanol. The scrubber is
filled with a plastic-packed bed favoring the contact between the rising gaseous
stream and the downward liquid stream. The gaseous ethanol-stripped stream is
released into the atmosphere while the liquid stream containing about 2.5% etha-
nol is unified with the culture broth coming from fermenter in order to be fed to
the distillation column (Wooley et al., 1999).
The first distillation column is called the concentration or beer column. This
column has a determined number of plates that can be of various types. It has
been suggested that the fixed-valve Nutter-type plates are the most suitable to
handle streams containing solids exhibiting a relatively good efficiency (about
48%). The concentrated ethanol stream (35 to 50%) is removed from the column
by a side stream. The overhead vapors contain mostly CO2 (approximately 84%),
a significant amount of ethanol (12%), and a small amount of water.
The bottoms of this column, called stillage or vinasses, concentrate the non-
volatile substances and suspended solids that enter along with the culture broth.
CO2 Water
Gases washer
Concentration Rectification
column column
Hydrated
ethanol
Preheater (90–95%% p/p)
Wort
Winne Stillage
Bottom
Fermenter
Figure 8.1 Technological scheme of the concentration and rectification steps during
fuel ethanol production.
Stillage composition depends on the feedstock employed for fuel ethanol produc-
tion. The heat of this bottom’s stream is utilized to preheat the stream feeding the
same distillation column. As an example of the location along this column of these
streams, the design information for a concentration column corresponding to the
biomass-to-ethanol process is provided (Wooley et al., 1999). This column has 32
plates, the feed stream is supplied to the fourth plate from the top, the side ethanol
stream is removed from the eighth plate, and the reflux ratio required is 6.1.
The second column or rectification column is fed with the side ethanol stream
from the concentration column. The operation of this column allows for a distil-
late with 90 to 92% ethanol concentration, which is sent to the dehydration step.
The bottoms of this column have a very low ethanol content (less than 1%), being
mostly water. For illustration purposes, the design data of the rectification col-
umn for the above-mentioned lignocellulosic ethanol process are provided as well
(Wooley et al., 1999). The column has 69 plates and an additional feed stream
corresponding to the recycle stream from the dehydration step, which is fed into
the nineteenth plate from the top. The feed stream from the concentration column
is supplied in the forty-fourth plate; fixed-valve Nutter-type plates are employed
and the reflux ratio required is 3.2.
8.2 Ethanol Dehydration
The distillate product from the rectification column represents the stream enter-
ing the ethanol dehydration scheme, where the fuel ethanol with ethanol content
greater than 99.5% should be produced. To achieve this high purity from streams
containing 90 to 92% ethanol, it is necessary to employ nonconventional separation
CONCENTRATION VACUUM
COLUMN COLUMN
Anhydrous
ethanol
Wine
Stillage Wastewater
8.2.1 Pressure-Swing Distillation
To achieve the separation of an azeotropic mixture by using pressure-swing dis-
tillation, the manipulation of the column pressure is required, e.g., by utilizing a
second distillation column working under vacuum conditions (Figure 8.2). This
type of distillation makes use of the change of the vapor–liquid phase equilibrium
at lower pressures than atmospheric (vacuum) leading to the disappearance of the
azeotrope. The pressure required to eliminate the azeotrope in an ethanol–water
mixtures is less than 6 kPa. But to obtain a high purity product, distillation columns
with a large number of plates (above 40) and a high reflux ratio are needed. These
conditions imply significant capital costs (large column diameters) and increased
energy costs due to the maintenance of vacuum in distillation towers with many
plates. This configuration has no fluxes or refluxes connecting the two columns.
In general, pressure-swing distillation cannot always be employed; its utilization is
limited to mixtures with azeotropes susceptible to be displaced with small changes
of pressure, which is not exactly the case in ethanol–water systems.
8.2.2 Azeotropic Distillation
Most methods involving distillation for ethanol dehydration utilized in the indus-
try comprise at least three steps: (1) distillation of dilute ethanol until it reaches a
concentration near the azeotropic point, (2) distillation using a third component
CO2 Water
A C
B 7
3
4 5 6 8
Wort Wine
1 Stillage Bottom 9 Wastewater
Anhydrous
ethanol
Figure 8.3 Technological scheme for ethanol separation and dehydration by azeotro-
pic distillation using benzene as the entrainer: (1) fermenter, (2) scrubber, (3) preheater,
(4) concentration column, (5) rectification column, (6) azeotropic column, (7) decanter,
(8) column for entrainer recovery, (9) product cooler. A = benzene-enriched stream, B =
benzene make-up stream, C = water-enriched stream.
added that allows the ethanol removal, and (3) distillation to recover the third
component and reutilize it in the process (Montoya et al., 2005). The azeotropic
distillation corresponds to this scheme. This technology consists of the addition
of an entrainer to the ethanol–water mixture to form a new azeotrope. The azeo-
trope formed is ternary (involves three components) and allows a much easier
separation in schemes involving two or three distillation columns. Among the
substances most used as entrainers for separation of ethanol–water mixtures are
benzene, toluene, n-pentane, and cyclohexane.
In the case of benzene, the process comprises one dehydration (azeotropic) col-
umn, which is fed with the mixture containing 90 to 92% ethanol from rectifica-
tion column (Figure 8.3). The benzene is added in the upper plate. From the lower
part of the azeotropic column, ethanol is removed with water content below 1%,
while the overhead vapors in the column top, which correspond to a mixture with
a composition equal or near to the composition of the ethanol–water–benzene
ternary azeotrope, are condensed and sent to a liquid–liquid separator (decanter).
Due to the mixture properties, the ternary azeotrope is located in the immiscibil-
ity zone of the ethanol–water–benzene system (Figure 8.4), so once condensed,
it is separated into two liquid phases: one phase with high benzene content that
is recirculated as a reflux to the azeotropic column, and the another phase with
higher water content that is fed to a smaller column for entrainer recovery (strip-
ping column). The distillate from the stripping column has a significant benzene
concentration and, for this reason, this stream is recycled back to the azeotropic
column or to the decanter. The bottoms of the stripping column contain mostly
water. If these bottoms have an important amount of ethanol, they are recircu-
lated to the concentration column; in this way, the separation of water and ethanol
is attained and the entrainer is recovered. As the process is operated in continuous
0
1.0
0.0
0
G
0.9
0.1
I
0
F
0.8
0.2
0
II
0
0.3
0.7
P
0
0
0.4
0.6
R M
0
0
0.5
C
0.5
0
0
0.4
0.6
0
0
N
0.7
0.3
A S
0
0
0.8
0.2
0
III
0
0.9
0.1
0
0
0.0
W B
1.0
0
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
D
the two distillation boundaries, which coincide in the ternary azeotrope with the
minimum boiling point. The distillation boundaries define the process constraints
because any distillation operation (indicated by straight lines of mass balances)
cannot have distillates and bottoms whose compositions are in different regions.
When drawing a balance line corresponding to the indirect distillation for the
point M (the prolongation of the straight line EM until the distillation boundary
represented by the curve AC), bottoms with a composition corresponding to pure
ethanol E and distillate with a composition near to the ternary azeotrope repre-
sented by the point N are obtained. The composition of this distillate corresponds
to the immiscibility zone of the system so it is separated into two liquid phases
indicated by the points R and S that are determined following the tie lines of the
liquid–liquid equilibrium plot (bimodal plot). The point R represents the liquid
phase with higher water content (the raffinate) and the point S represents the liq-
uid phase with higher benzene content (the extract) that is evidenced by its higher
proximity to the vertex B (pure benzene) compared to point R. The stream with
the composition of the point S is recirculated as the reflux to the azeotropic col-
umn. The raffinate stream, in turn, undergoes distillation in the stripping column,
which is represented by the balance line WRP that is located in the distillation
region II. The composition of point P corresponds to the composition of the distil-
late stream from the stripping column that is recycled back to either the azeotropic
column or the decanter. This type of analysis allows one to predict the behavior of
the system without carrying out a rigorous assessment (short-cut method). These
short-cut methods allow one to obtain valuable information for the subsequent
rigorous modeling of the system. In particular, the application of these methods
facilitates the specification of the operating conditions in the distillation columns
when commercial process simulators employing rigorous methods are used.
The above-described distillation receives the name hetero-azeotropic distillation
considering that the entrainers form azeotropes located within the immiscibility
zone of the system. This implies its separation into two liquid phases. The utiliza-
tion of n-octane as a co-entrainer along with benzene has been proposed in order
to decrease the energy costs of the traditional process (Chianese and Zinnamosca,
1990). The simulation and optimization accomplished based on a mass-transfer
model (nonequilibrium model) for this process show that if the values of operat-
ing parameters of the column are adjusted to minimize the amount of plates in the
azeotropic column, it is possible to reduce the capital costs, but increasing the heat
flow rates required implies an increase of the energy costs. In terms of energy costs,
the most influencing process parameters are the reflux ratio and flow rate of the
stream recirculated from the stripping column to the azeotropic column. For these
parameters, their optimum values have been obtained according to economic con-
siderations (Mortaheb and Kosuge, 2004). However, the utilization of benzene as
an entrainer is not desirable due to its carcinogenic properties. In addition, the azeo-
tropic distillation using this compound leads to the appearance of multiple steady
states and the occurrence of a parametric sensibility related to small changes in col-
umn pressure (Wolf Maciel and Brito, 1995). Taking into account these drawbacks,
the use of less contaminant entrainers has been attempted. In particular, some new
8.2.3 Extractive Distillation
In this type of distillation, a third substance called an extractive agent or solvent
is added to the ethanol–water system. The extractive agent modifies the relative
volatility of the mixture components without forming new azeotropes and allow-
ing, in this manner, the separation.
The solvent added should have a low volatility such that its separation in the
second distillation column where it is recovered would be much easier. In addition,
the solvent should have a high boiling point. It has been suggested that the high
relative viscosity of the solvents employed in extractive distillation could decrease
the mass transfer efficiency of the process (Meirelles and Telis, 1994). Ethylene
glycol has been traditionally used for these purposes, but the energy costs are
higher than in the case of the azeotropic distillation using benzene. Nevertheless,
Meirelles et al. (1992) point out that extractive distillation can become competi-
tive under specific operating conditions. In fact, in a previous work that implied
the simulation of ethanol–water mixtures resulting from fermentation broths by
extractive and azeotropic distillation (Montoya et al., 2005), the possibility of
achieving lower energy costs during the extractive distillation using ethylene gly-
col was demonstrated (see Section 8.3).
The technological scheme for ethanol dehydration by extractive distillation
using ethylene glycol is shown in Figure 8.5. The solvent is fed into a tray located
above the ethanol feed stream coming from the rectification column. Unlike the
azeotropic distillation, anhydrous ethanol is recovered in the distillate stream
of the extractive column, while a stream with a ternary composition containing
almost the total amount of ethylene glycol is removed from the bottoms. This
stream is sent to the column for solvent recovery where the ethylene glycol is col-
lected in the bottoms thanks to its low volatility. These bottoms are recycled back
to the extractive column. Water contained in the starting mixture is recovered in
the distillate of the recovery column. When ethylene glycol is recirculated, the
reduction of stream temperature down to 80°C is required in order to feed it to
the extractive column ensuring, in this way, a better separation. This is achieved
by exchanging heat with the feed stream of this column (Montoya et al., 2005).
CO2 Water
9
2 Anhydrous
ethanol
A
Wastewater
3 6
4 5 7 8
Wort Wine
1 Stillage Bottom
Figure 8.5 Technological scheme for ethanol separation and dehydration by extractive
distillation using ethylene glycol as the solvent: (1) fermenter, (2) scrubber, (3) preheater, (4)
concentration column, (5) rectification column, (6) heat exchanger, (7) extractive column,
(8) column for solvent recovery, (9) product cooler. A = ethylene glycol make-up stream.
To avoid a possible thermal decomposition of ethylene glycol due to its high boil-
ing point, the recovery column operates at 0.2 atm in such a way that the bottoms
temperature does not reach 150°C.
The effect of the solvent can be considered as the breaking of the binary azeo-
trope between the ethanol and water. The ethylene glycol modifies the relative
volatility of ethanol in such a way that it can then be recovered through direct dis-
tillation. The ternary diagram corresponding to the extractive distillation scheme
is illustrated in Figure 8.6. The solvent is added to the starting mixture F. The
straight line FG represents this. The point M indicates the starting state of the
system within the extractive column. The dashed curve AI’ represents those com-
positions with a relative volatility equal unity (iso-volatility curve). As the point
M is located in the region where the relative volatility of the ternary mixtures
are greater than unity, their direct distillation is possible. This is represented by
the balance line EM, which is prolonged until point N in the base of the ternary
diagram. This point corresponds to the binary water–ethylene glycol mixtures. In
this way, pure ethanol distillate (E) and bottoms containing water and ethylene
glycol are obtained. These bottoms are fed to the recovery column. In this col-
umn, the distillation starting from point N implies the production of pure water
distillate (point W) and pure ethylene glycol bottoms (point G), which are recy-
cled back to the extractive column.
For small- and medium-scale ethanol producing facilities, batch extractive
distillation is more suitable than the continuous process due to its higher flex-
ibility to handle the separation of small volumes and feed streams with great vari-
ability in their compositions under limited capital costs conditions. In particular,
the task of finding the best conditions to operate a batch extractive distillation
process that includes a single tank located between two columns (rectification
and stripping columns) using ethylene glycol as the solvent has been undertaken
(Ruiz Ahón and Luiz de Medeiros, 2001). Varying the feed state and the purity
degree and employing ideal thermodynamic models, they defined the best policy
0
1.0
0 .0
A
F
0.9
0.1
0
0
0.8
0.2
0
0
0.7
0.3
0
0.6
0
0.4
0
M
0.5
0
0.5
0
0.4
0
0.6
0
0.3
0
0.7
0
0.2
0
0.8
0
0.1
0
0.9
0
N
0.0
G
1.0
0
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.0
for removing the streams in the top of the rectification column and in the bottoms
of the stripping column in such a way that anhydrous ethanol could be obtained.
In early works, gasoline was proposed as a solvent for ethanol dehydration
by extractive distillation (Chianese and Zinnamosca, 1990). In this case, gaso-
line (C7 and C8 oil fractions) causes the inversion of the water–ethanol volatility
allowing the removal of water with small amounts of residual ethanol and light
hydrocarbon fractions from the column top while ethanol mixed with the solvent
is withdrawn from the bottoms (unlike the ethylene glycol). No water is present
in these bottoms so this stream can be used as a gasohol (a blend of gasoline
and ethanol as the oxygenate). Models contemplating the dynamics of extractive
distillation for ethanol dehydration have been developed (Wolf Maciel and Brito,
1995). These models take into account the simultaneous mass and heat transfer,
hydraulic behavior of the trays, and rigorous representation of the phase equi-
librium. Based on these studies, it is noted that the composition of the distillate
stream that contains the anhydrous ethanol varies slightly with changes in the
solvent flowrate, though it does vary with changes in reflux and feed flowrates.
8.2.5 Adsorption
Adsorption is another unit operation widely employed in the industry for etha-
nol dehydration. In this operation, the ethanol–water mixture passes through an
apparatus (usually cylindrical) that contains a bed with an adsorbent material.
Due to the difference in the affinity of molecules of water and ethanol with
respect to the adsorbent, the water remains entrapped in the bed while the ethyl
alcohol passes though this same bed increasing its concentration in the stream
leaving the apparatus.
In early work carried out in the 1980s, the utilization of different biomaterials
as adsorbents for ethanol dehydration, such as corn, xylan, pure cellulose, corn sto-
ver, corn flour, wheat straw, and sugarcane bagasse, was proposed. Such materials
whose structure is based on polysaccharides demonstrated their ability to separate
water and ethanol (Hong et al., 1982; Ladisch and Dyck, 1979; Ladisch et al., 1984;
Westgate and Ladisch, 1993). In particular, the broken corn grains showed good
properties to absorb water in aqueous solutions of ethanol. In pilot plant stud-
ies, the possibility of concentrating ethanol from 91% to more than 99% using a
bed of broken corn grains was demonstrated. The bed can be used during several
adsorption–regeneration cycles (up to more than 30; Tanaka and Otten, 1987).
The bed can then be utilized as a starch source for ethanol production. In
principle, the energy costs were lower than those of azeotropic distillation. More
recently, some works have shown the great adsorption ability of different starchy
materials that have adsorptive properties similar to those of the inorganic adsor-
bents when the mixture to be separated contains about 10% water. In addition, the
enzymatic modification using α-amylase contributes to enhance the adsorptive
properties of starch (Beery and Ladisch, 2001a, b).
However, the adsorption of water employing the so-called molecular sieves to
dehydrate ethanol has been the technology that has acquired more development in
past years in the fuel ethanol industry. In fact, this technology has been replacing
the azeotropic distillation. The molecular sieves are granular rigid materials with
a spherical or cylindrical shape manufactured from potassium aluminosilicates.
They are classified according to the nominal diameter of the large amount of
internal pores that provide access to the interstitial free volume found in their
microcrystalline structure (Madson and Monceaux, 1995). For ethanol dehydra-
tion, sieves with an average diameter of the interstitial passageways of 3 ang-
stroms (Type 3Å sieves) are commonly used. The water molecule has a diameter
lower than that of the interstitial passageways of this type of sieves, while the
ethanol molecule does not. In addition, the water can be adsorbed onto the inter-
nal surface of the passageways in the molecular sieve structure. Thus, ethanol
molecules pass out of the apparatus without adsorbing onto the bed.
The adsorption operation requires that, once the adsorbent bed is saturated
with the substance to be separated, the desorption of this substance should be
accomplished to make possible the reutilization of the adsorbent material (regen-
eration cycle). For regeneration of the sieves, hot gas is needed that rapidly dete-
riorates them especially if the bed is fed with a liquid stream during the previous
CO2 Water
6 7
3
4 5
Wort Wine 8
1
Stillage 9
Bottom Regenerate 10 Anhydrous
ethanol
Figure 8.7 Technological scheme for ethanol separation and dehydration by adsorp-
tion using molecular sieves: (1), fermenter, (2) scrubber, (3) preheater, (4) concentration
column, (5) rectification column, (6) heat exchanger, (7) molecular sieves, (8) regenerate
tank, (9) head exchanger, (10) product cooler.
8.2.6 Pervaporation
Different applications of the membranes for both concentration of ethanol solu-
tions and ethanol dehydration have been developed recently. Although the reverse
osmosis was first proposed (Leeper and Tsao, 1987), the pervaporation definitively
boosted the introduction of membranes into the fuel ethanol industry (Sánchez
and Cardona, 2005). The pervaporation (evaporation through membranes) is an
operation based on the separation of two components by a selective membrane
under a pressure gradient in which the component passing across the membrane is
removed as a gaseous stream (permeate), while the other component remains in the
liquid phase and is removed as a more concentrated stream (retentate), as shown in
Figure 8.8. This operation began to exhibit industrial feasibility when polyvinyl
alcohol (PVA) composite membranes were developed at the end of 1980s. These
membranes present a high selectivity by favoring the water passing across them
Ethanol-Water
Mixture
Tin
Anhydrous
n ethanol Vacuum Pump
Tout
Condenser
Membrane Unit
Water
Figure 8.8 Schematic diagram of pervaporation for ethanol dehydration. Tin > Tout.
and a high retention of several organic solvents. Just the PVA membranes allow
the change of the phase equilibrium of ethanol–water solutions in such a way that
the mass transfer between the liquid and vapor phases is determined by the semi-
permeable membrane and not by the free interphase (Sander and Soukup, 1988).
Thus, it is possible to obtain a concentrated ethanol stream with a composition
above the azeotropic. The driving force of pervaporation is maintained thanks to
the application of a vacuum in the permeate side of the membrane. This driving
force is evidenced by the difference of partial pressures or activities of the com-
ponent passing across the membrane. This difference of partial pressures can be
increased making the feed temperature as high as possible. The permeate is later
condensed to generate a liquid stream that can be recycled back to the rectification
column. Diverse chemical modifications of PVA membranes have been proposed
to improve the hydrophilic/hydrophobic ratio in order to enhance the selectivity
and flux of these membranes (Chiang and Chen, 1998).
The pervaporation offers a series of advantages compared to azeotropic or
extractive distillations because the product contains no entrainer or solvent traces.
In addition, this technology is easily adjustable and very flexible with respect to
the changes of the feed concentration. The start-up and stop of the process require
minimum labor and supervision. Finally, the pervaporation units are compact and
need no large areas compared to the big towers of azeotropic distillation schemes
(Sánchez and Cardona, 2005; Sander and Soukup, 1988). As this operation con-
sumes less energy than the conventional operations based on distillation, the use
as the costs of pervaporation. Pinto et al. (2000) used Aspen Plus® for simulation
and optimization of the saline extractive distillation for several substances (NaCl,
KCl, KI, and CaCl2). This configuration was compared to the simulated scheme
of conventional extractive distillation with ethylene glycol and to data for azeotro-
pic distillation. Obtained results showed considerably lower energy consumption
for the process with salts. However, for this latter case, the recovery of salts was
not simulated. Thus, if evaporation and recrystallization of salts is contemplated,
energy requirements could significantly increase, taking into account the energy
expenditures. In this way, the utilization of commercial simulators shows the
viability for predicting the behavior of a given process configuration providing
the appropriate thermodynamic models of studied systems, as illustrated in the
following case study.
In contrast, adsorption with molecular sieves showed the best results regard-
ing operation costs, i.e., this technology presents lower energy costs (7.68 MJ/L).
Elevated capital costs for the configuration involving adsorption are related to the
complexity of the automation and control system inherent to the pressure swing
adsorption technology. The higher energy consumption for azeotropic (9.77 MJ/L)
and extractive (8.44 MJ/L) distillation is explained by the presence of two addi-
tional distillation towers that increase the energy costs. The product for these lat-
ter schemes contains traces of the entrainer or the solvent unlike the dehydration
by adsorption where these third components are not utilized. Simulation results
indicate that the extractive distillation can be competitive compared to azeotropic
distillation from an energy point of view, as pointed out by Meirelles et al. (1992).
According to the simulations performed, the amount of ethylene glycol required to
attain the desired dehydration of ethanol was 17,900 kg/h, but it is necessary to cre-
ate only 50 kg/h of this solvent thanks to the recirculation stream from the recovery
column. The amount of benzene required for azeotropic distillation was 19,980
kg/h, but the amount of fresh benzene in the make-up stream was only 17 kg/h. It is
worth noting that the convergence of the simulation of this dehydration scheme was
a difficult task that required numerous successive simulation runs. This behavior
can be explained by the appearance of multiple steady states and the presence of
a parametric sensitivity with small changes in the column pressure when benzene
is the entrainer used, as indicated by Wolf and Brito (1995). The obtained results
represented a suitable approximation of the results published in different sources
(Chianese and Zinnamosca, 1990; Luyben, 2006) as well as the predictions of the
thermodynamic-topological analysis. It should be emphasized that the azeotropic
distillation using benzene is not an environmentally friendly process and the opera-
tion of such dehydration schemes imply the utilization of a carcinogenic substance
that can involve potential risks for the operating staff.
From outcomes achieved, it is evident that process simulation represents a pow-
erful tool to design the downstream processes of such biotechnological processes
as fuel ethanol production. Similarly, the importance of applying a suitable ther-
modynamic approach to study the separation operations is another crucial factor
influencing the success of the simulation procedures.
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steady-states in the system. For this reason, integrated processes require robust
control loops, which are expensive and difficult to design. In addition, the use of
third substances in some integrated schemes, such as extractive reaction where
the addition of an extractive agent is necessary, indicates the need for using recov-
ery units in order to decrease the operating costs of the process (Cardona et al.,
2008). One of the most difficult issues during the design of integrated processes
is related to the lack of appropriate models for describing this type of configura-
tion. Most of the developed models correspond to short-cut methods where main
phenomena taking place in the system are quite simplified. These methods are
mostly based on equilibrium models. However, this kind of method has allowed
the preliminary and conceptual design of many integrated processes as well as
the assessment of the viability of their implementation.
In a previous work (Rivera and Cardona, 2004), the classification of integrated
processes was provided. Such processes can be divided into two main classes
depending on whether unit operation or unit process is being combined. The inte-
grated process is homogenous when two or more unit operations or two or more
reactions (unit processes) are combined and heterogeneous when the combination
is carried out between one unit operation (physical process) and one chemical
reaction. Each case can be accomplished through either simultaneous or conju-
gated configuration. In the first case, the physical and/or chemical processes are
simultaneously carried out in a single unit. In the second case, the processes are
carried out in different apparatuses connecting them by fluxes or refluxes, i.e.,
by coupling two or more units (Cardona et al., 2008). In relation to the process
steps that can be combined, integrated processes can be of the following types:
reaction–reaction, reaction–separation, or separation–separation.
In this context, the design of technologies with improved performance accord-
ing to technical, economic, and environmental criteria for producing fuel ethanol
is required. The reduction of energy consumption along with the decrease in the
capital costs through process integration offers promising opportunities for the
improvement of the overall process for bioethanol production. Thus, this reduc-
tion can contribute to the worldwide development of the biofuels industry with its
inherent economic, social, and environmental benefits. The aim of this chapter is
to study and recognize the vast possibilities of process integration during the con-
ceptual design and development of high-performance technologies for production
of fuel ethanol from different feedstocks.
Process integration, as a mean for process intensification, is a successful
approach for designing improved technological configurations for fuel ethanol
production in which energy consumption, production costs, and negative envi-
ronmental impacts can be reduced. This fact is remarkably important taking into
account that the main objective of using liquid biofuels, like bioethanol, is the
progressive displacement of fossil fuels. This implies the sustainable exploitation
of the huge biomass resources of our planet and the use of clean and renewable
energy sources. Solutions provided by the process integration approach have to be
proved at an industrial level in order to develop energy efficient, environmentally
friendly, and even “politically correct” processes for fuel ethanol production. In
fact, some technologies directly involving the principle of integration for bioetha-
nol production have already been successfully implemented.
9.2 Reaction–Reaction Integration
for Bioethanol Production
Process integration is gaining more and more interest due to the advantages
related to its application in the case of bioethanol production: reduction of energy
costs, decrease in the size and number of process units, and intensification of the
biological and downstream processes, among others. For instance, the combina-
tion in a same unit of the enzymatic hydrolysis and the microbial transformation
leads to the reduction of the negative effect due to the inhibition of the enzymes
by the product of the reaction catalyzed by them. This corresponds to an integra-
tion of the reaction–reaction type.
In general, reaction–reaction integration has been proposed for the integra-
tion of different biological transformations taking place during ethanol produc-
tion (Cardona and Sánchez, 2007). This type of integration mainly includes the
combination of the enzymatic reactions for hydrolysis of starch or cellulose with
the microbial conversion of formed sugars into ethyl alcohol. There exist different
possibilities for reaction–reaction integration during production of ethanol from
starch (Figure 9.1) and lignocellulosic biomass (Figure 9.2).
Considering as the starting point the nonintegrated separate hydrolysis and fer-
mentation (SHF) process, several cases of reaction–reaction integration may be
analyzed for ethanol production from both starchy and lignocellulosic materials.
Starch
Gelatinization
SSF SSYPF
Production of (Am) Starch
Amylases Hydrolysis
(G)
CBP (EtOH)
Anhydrous
Conventional Ethanol Ethanol
Distillation Dehydration
Figure 9.1 Possibilities for reaction–reaction integration during fuel ethanol pro-
duction from starchy materials: SSF = simultaneous saccharification and fermentation;
SSYPF = simultaneous saccharification, yeast propagation and fermentation; CBP =
consolidated bioprocessing. Main streams components: Am = amylases, G = glucose, Y
= yeasts, EtOH = ethanol. (From Cardona, C.A., and Ó.J. Sánchez. 2007. Bioresource
Technology 98:2415–2457. Elsevier Ltd. With permission.)
Nevertheless, the process itself corresponds to an SHF scheme because the cel-
lulose has to be hydrolyzed in a previous bioreactor using cellulases.
9.2.2.1 SSF of Starch
SSF technology born in the 1970s was assimilated by the starch-processing
industry for ethanol production obtaining high and sustainable yields on the
Biomass Pretreatment
(C+H+L)
Solid fraction Liquid fraction
(C+L) (P+I)
Detoxification
SSF SSCF
Production of (Cel) Cellulose
Cellulases Hydrolysis
(G) (P+I)
Hexose Pentose
Fermentation Fermentation
CF
Figure 9.2 Possibilities for reaction–reaction integration during fuel ethanol produc-
tion from lignocellulosic biomass: CF = co-fermentation; SSF = simultaneous saccharifi-
cation and fermentation; SSCF = simultaneous saccharification and co-fermentation; CBP
= consolidated bioprocessing. Main stream components: C = cellulose, H = hemicellulose,
L = lignin, Cel = cellulases, G = glucose, P = pentoses, I = inhibitors, EtOH = ethanol.
(From Cardona, C.A., and Ó.J. Sánchez. 2007. Bioresource Technology 98:2415–2457.
Elsevier Ltd. With permission.)
Enzymatic Co-fermentation
Pretreatment of hexoses and Product Ethanol
hydrolysis recovery
pentoses
Solid residues
(co-products)
Figure 9.3 Block diagram of fuel ethanol production from lignocellulosic biomass
involving the co-fermentation of hexoses and pentoses.
order of 0.410 L/kg of corn (Madson and Monceaux, 1995). In the case of the
saccharification step when starch is used as feedstock, glucoamylase experiences
the inhibitory effect caused by glucose released as the hydrolysis of this bio-
polymer advancement. This effect is more pronounced at high conversions of
starch into ethanol. In contrast, integration by SSF makes it possible for yeasts
to consume the glucose immediately as it forms under the action of the amylases
on starch. In addition, the risk of bacterial contamination of the wort is dras-
tically reduced because of the low level of glucose in the medium during the
SSF process. The elimination of the external step of saccharification, the major
source of infection by bacteria, also contributes to the reduction of contamination
(Madson and Monceaux, 1995). In the same way, capital costs are reduced as a
consequence of the increase in the compactness of the system (fewer numbers of
units). Moreover, low glucose concentrations in the medium decrease the osmotic
pressure over the yeasts because the use of concentrated solutions is avoided
(Bothast and Schlicher, 2005). Energy costs can also be reduced considering that
the SSF process is operated at temperatures less than those of the separate sac-
charification process; this implies the reduction in the steam consumption. All
these synergic features have allowed gains of ethanol yields higher than those of
the SHF process.
The main disadvantage of the SSF process is that the optimum temperature
of glucoamylase (65ºC) does not coincide with the optimum temperature for
yeast growth (30ºC). Fortunately, starch saccharification can be carried out at
30 to 35ºC although at a slower rate. For this reason, higher enzyme dosages are
required. Finally, processing times for batch SSF are longer than the correspond-
ing times for batch SHF.
Most ethanol production facilities utilizing the corn dry-milling technology
employ batch SSF processes. The duration of this process is 48 to 72 h achiev-
ing final ethanol concentrations in the medium of 10 to 12% by volume (Bothast
and Schlicher, 2005). A number of modifications of the SSF of starchy materials
have been proposed in order to decrease the production costs. Some of them are
included in Table 9.1. Montesinos and Navarro (2000) have studied the possibility
of utilizing raw wheat flour during the batch SSF process with the aim of reducing
costs attaining a decrease in the process time. On the other hand, the SSF per-
formed at a temperature above 34ºC using a thermotolerant yeast, which enabled
the reduction of cooling requirements and the improvement of the conversion
process, as claimed in the patent of Otto and Escovar-Kousen (2004).
Source: Adapted from Cardona, C.A., and Ó.J. Sánchez. 2007. Bioresource Technology 98:2415–2457. Elsevier Ltd.
229
© 2010 by Taylor & Francis Group, LLC
230 Process Synthesis for Fuel Ethanol Production
Table 9.2
Energy Comparison of Two Processes for Fuel Ethanol
Production from Corn Grains by Dry-Milling
Integrated Process Non-Integrated Process
Item (SSF) (SHF)
Ethanol produced (kg EtOH/h) 17,837 17,838
Energy consumption (MJ/h) 270,487 290,856
Energy consumption (MJ/L EtOH) 11.67 12.55
The objective of this configuration is to increase the contact time between the
mash and yeasts in order to reduce the bacterial growth. This allows reaching
higher yields, an earlier ethanol production (that also reduces the contamination),
and reducing the need of handling large amounts of yeasts (Novozymes & BBI
International, 2005). At the beginning of an SSYPF process, pH is adjusted to 5.2
for favoring the growth of microorganisms and, as the cultivation goes forward, pH
is diminished to 4.5 at the end of fermentation (Madson and Monceaux, 1995).
Production Cellulases
Lignocellulosic of Cellulases
biomass
Product
Pretreatment SSF Ethanol
Recovery
Process steam
Electricity for
Sale of electricity to the process
the grid
Figure 9.4 Simplified diagram of the integrated process for fuel ethanol production
from lignocellulosic biomass by simultaneous saccharification and fermentation (SSF).
centrifugation from the liquid fraction of stillage and burnt in order to extract
its high energy content. The obtained thermal energy is converted into process
steam, which is employed within the same process. If co-generation is considered,
part of the released energy is transformed into electricity that can supply all the
needs of the plant, with a remaining surplus that can be sold to the grid. These
energy recovery possibilities are an important feature of ethanol production pro-
cesses when lignocellulosic biomass is utilized, and they allow the compensation
of energy demands represented mostly by the steam requirements for the pretreat-
ment reactor, distillation columns, and dehydration scheme.
Intensive research to carry out the SSF of lignocellulosic biomass has been car-
ried out. Some examples of these efforts are presented in Table 9.1. Considering
that enzymes account for an important part of production costs, it is necessary
to find methods reducing the cellulases doses to be used. Thus, the integration
of the cellulase production process using Trichoderma reesei with ethanolic fer-
mentation has been proposed. As a small amount of enzymes remains entrapped
in fungal cells producing cellulases, the addition of the whole culture broth of
this process to the SSF reactor was proposed. Besides the fungal biomass and
obtained cellulases, this broth contains residual cellulose and lignin. This allows
the increase of the β-glucosidase activity, essential for the reduction of cellobiose
levels, and a more complete utilization of sugars employed during the production
of cellulases (Wyman, 1994). The addition of surfactants has been proposed for
these purposes as well. Alkasrawi et al. (2003) showed that the addition of the
nonionic surfactant Tween-20 to the steam exploded wood during the batch SSF
using Saccharomyces cerevisiae has some effects: 8% increase in ethanol yield,
50% reduction in cellulases dosage (from 44 FPU/g cellulose to 22 FPU/g cellu-
lose), an increase of enzyme activity at the end of the process, and a decrease in
the time required for reaching the highest ethanol concentration. It is postulated
that the contamination was higher when washed substrate was used, in com-
parison with the utilization of the whole suspension resulting from pretreat-
ment. This indicates that acidolactic bacteria are more sensitive to inhibitors’
presence than yeasts.
As mentioned above, one of the main disadvantages of SSF processes using
lignocellulosic biomass lies in the different optimum conditions of enzymatic
hydrolysis of cellulose and fermentation. Cellulases work in an optimal way
at 40° to 50ºC and pH of 4 to 5, whereas the fermentation of hexoses with S.
cerevisiae is carried out at 30ºC and pH of 4 to 5, and fermentation of pentoses is
optimally performed at 30° to 70ºC and pH of 5 to 7 (Olsson and Hahn-Hägerdal,
1996; Sánchez and Cardona, 2008). Varga et al. (2004) proposed a nonisothermal
regime for batch SSF process applied to wet oxidized corn stover. In the first
step of SSF, small amounts of cellulases were added at 50ºC in order to obtain
better mixing conditions. In the second step, more cellulases were added along
with the yeast S. cerevisiae at 30ºC. In this way, the final solid concentration in
the hydrolyzate could be increased up to 17% dry matter concentration achieving
78% ethanol yield.
In general, increased cultivation temperature accelerates metabolic processes
and lowers the refrigeration requirements (Sánchez and Cardona, 2008). Yeasts
such as Kluyveromyces marxianus have been tested as potential ethanol produc-
ers at temperatures higher than 40°C (Ballesteros et al., 2004; Hari Krishna et al.,
2001). Kádár et al. (2004) compared the performance of thermotolerant K. marx-
ianus and S. cerevisiae during batch SSF of waste cardboard and paper sludge
not finding great differences between both microorganisms at 40ºC, although
cellulose conversions (55 to 60%) and ethanol yields (0.30 to 0.34 g/g cellulose)
were relatively low. Ballesteros et al. (2001) carried out several fed-batch SSF
tests at 42ºC during 72 h using K. marxianus in the case of by-products of olive
oil extraction (olive pulp and fragmented olive stones). Their results showed
76% ethanol yields of theoretical for olive pulp and 59% yield for acid-catalyzed
steam-exploded olive stones. With the aim of increasing ethanol yields from
olive pulp, Ballesteros et al. (2002) employed liquid hot water (LHW) pretreat-
ment reaching an 80% yield of the theoretical value and recovering potentially
valuable phenolic compounds.
If, when thermotolerant yeasts are used, the microbial cells can also assimilate
pentoses, the SSF process can become more perspective (Cardona and Sánchez,
2007). Yeasts such as Candida acidothermophilum, C. brassicae, S. uvarum, and
Hansenula polymorpha can be used for these purposes. In this case, the addition
of a larger amount of nutrients to the medium is required. Alternatively, the uti-
lization of higher cell concentrations could be implemented for obtaining better
results (Olsson and Hahn-Hägerdal, 1996; Ryabova et al., 2003). The difficulty
lies in the fact that higher temperatures enhance the inhibitory effect of ethanol.
Therefore, the isolation and selection of microorganisms that could be adapted
in a better way to these hard conditions should be continued. Kádár et al. (2004)
make reference to several reports about the utilization of thermotolerant microor-
ganisms for ethanol production.
One approach to accomplish the SSF of biomass without the addition of cel-
lulases consists in the utilization of mixed cultures in such a way that the hydro-
lysis and fermentation of lignocellulosic biomass be carried out simultaneously
(Cardona and Sánchez, 2007). This procedure was applied to sweet sorghum stalks
employing cellulase- and hemicellulase-producing fungus Fusarium oxysporum
along with S. cerevisiae (Mamma et al., 1995). Considering that sweet sorghum
stalks contain several carbohydrates, such as sucrose, glucose, hemicellulose, and
cellulose, the obtained yields in this process were higher than the theoretical yield
from only glucose (0.51 g EtOH/g glucose); this is explained by the additional
bioconversion of cellulose and hemicellulose into ethanol (Mamma et al., 1996).
However, the final ethanol concentrations in this type of SSF process were quite
low considering the separation process. Logically, the mixed culture presents
a high complexity during its implementation at the industrial level and has the
additional disadvantage that optimal growth conditions for two or more different
microorganisms are not the same. Besides, part of the substrate is deviated for
the growth of the enzyme-synthesizing microorganism. Panagiotou et al. (2005a)
carried out the SSF of cellulose with F. oxysporum demonstrating the produc-
tion of ethanol under anaerobic conditions. In addition, the metabolite profiling
of the microorganisms cultivated in different media was achieved through the
measurement of the intracellular concentration of key metabolites (Panagiotou et
al., 2005a, 2005b, 2005c).
The SSF process also can be done in continuous regime. In the same work of
South et al. (1993) cited above, the behavior of a continuous-stirred tank reactor
(CSTR) for continuous SSF of hardwood using the same microorganism and
the same enzymes was investigated. For a residence time of 3 d, 83% conver-
sion was achieved, i.e., less than in the case of batch SSF, which is explained
by the decrease in the reactivity when conversion in the biomass hydrolysis is
increased. Ethanol concentration reached 20.6 g/L for a residence time of about
2 d. Obtained results showed that enzyme and substrate concentrations in the
feed within studied ranges did not influence cellulose conversion. This indicates
the existence of mass transfer restrictions related to cellulose, besides inhibi-
tory effects caused by the substrate and products. The fact that the enzymatic
hydrolysis rate decreases with the course of hydrolysis has often been reported
in the literature. According to Zhang and Lynd (2004), this decreased reactiv-
ity of residual cellulose can be due to less surface area, fewer accessible chain
ends, and/or adsorption of inactive cellulase on the surface of lignocellulosic
particles. The addition of fresh substrate can stimulate the release of more sol-
uble sugars indicating the loss of cellulose reactivity at the end of hydrolysis or
the increase of reactivity for the “new” encounters enzyme-substrate compared
with the “old” ones.
to the several factors affecting the kinetics of cellulose hydrolysis were also high-
lighted in that section. Evidently, these difficulties are also present when model-
ing of cellulose SSF is performed. One of the most comprehensive mathematical
models for this process in both batch and continuous regimes corresponds to
the description provided by South et al. (1995). As mentioned in Section 5.2.3.2,
these authors developed a model based on experimental data obtained in their
previous work using commercial fungal cellulase (South et al., 1993) employing
pretreated wood as the feedstock. The kinetic model includes the cellulose con-
version, the formation and disappearance of cellobiose and glucose, the forma-
tion of cells, and the biosynthesis of ethanol structure, i.e., the main enzymatic
and microbial phenomena taking place during the SSF process. In addition, a
Langmuir-type model taking into account the adsorption of cellulases on the
solid particles of cellulose and lignin is also considered. Moreover, this math-
ematical description contemplates a population model for the residence time of
solid particles entering the bioreactor in the case of the continuous regime. Thus,
expressions describing the dependence of cellulose conversion on the residence
time of nonsoluble, solid particles of biomass were derived. This last description
confers great validity to the model because it provides a better approximation to
real processes, which cannot be suitably explained by the traditional models for
CSTR with soluble substances.
ES kS /G kS / P
rs = −( k ⋅ (1 − x )n + c) ⋅ ⋅ ⋅ (9.1)
ς S C + kS /G P + kS / P
k ⋅ C ⋅ Bg
rc = −1.056 ⋅ rs − c (9.2)
G
K ⋅
m 1 + + C
kC / G
( Xc ⋅ µ maxG ) P
rx = ⋅ 1 − (9.3)
G + kG kC / P
rx
rG = (−1.056 ⋅ rs − rc ) ⋅ 1.053 − (9.4)
Yx / G
YP /G
rP = rx ⋅ (9.5)
Y X /G
The nomenclature of all the variables and kinetic parameters involved in the
above equations are presented in Table 9.3. In Equation (9.1), the last two terms
represent the inhibition by cellobiose and ethanol. These terms influence all
the rate equation directly or indirectly. Similar expressions can be observed in
Equation (9.2) for the inhibitory effect of glucose on the β-glucosidase activity.
In Equation (9.3), the expression for biomass formation rate has a lowering term
due to high ethanol concentrations present in the broth. For this case, a cellulose
conversion (x) of 0.70 was preset. The general mass balance expression for each
one of i components (cellulose S, cellobiuse C, cell biomass X, glucose G, and
ethanol P) is:
d (Ci )
= ri (9.6)
dt
Table 9.3
Nomenclature of the Variables and Kinetic Parameters Involved in
Equations Derived from the Model of South et al. (1995)
Symbol Remark Symbol Remark
B Input stream to the pervaporator, l/h n Exponent of the declining substrate
reactivity, dimensionless
Bg β-glucosidase concentration in P Ethanol concentration, g/L
solution, U/L
c Conversion independent component Po Initial ethanol concentration, g/L
in rate function, 1/h
C Cellobiose concentration, g/L Q Output stream for pervaporation
(permeate), L/h
Ci Concentration of the i-th R Recirculation (retentate) stream from
component pervaporation unit to reactor, L/h
Co Initial cellobiose concentration, g/L ri Rate of formation of compound i,
g/(L × h)
ES Concentration of cellulose-cellulase S Cellulose component of the biomass
complex, U/L substrate remaining, g/L
F Feed reactor stream, L/h So Initial cellulose component of the
biomass substrate, g/L
G Glucose concentration, g/L V Reaction volume, L
Go Initial glucose concentration, g/L W Residual flow, L/h
k Hydrolysis rate constant, g/L x Fractional reactor cellulose
conversion, dimensionless
kc Rate constant for hydrolysis of X Cell concentration, g/L
cellobiose to glucose, g/(U×h)
kG Monod constant, g/L Xo Initial cell concentration, g/L
kC/G Inhibition of cellobiose hydrolysis YX/G Cell yield per substrate consumed,
by glucose, g/L dimensionless
kS/C Inhibition of cellulose hydrolysis YP/G Ethanol yield per substrate
by cellobiose, g/L consumed, dimensionless
kS/P Inhibition of cellulose hydrolysis α Separation factor in pervaporation
by ethanol, g/L
KS Adsorption constant for cellulosic Specific capacity of cellulosic
ςS
fraction of biomass, L/U component for cellulose, U/g
Km Adsorption constant for µmax Maximum cell growth rate, 1/h
β-glucosidase for cellobiose, g/L
Subindex
i Any of the substances involved in the fermentation
0 Initial concentration in batch processes or feed concentration in continuous processes
P Product (ethanol)
Source: Adapted from South, C.R., D.A.L. Hogsett, and L.R. Lynd. 1995. Enzyme and Microbial
Technology 17:797–803.
9
60
8
50 7
6
40
C, X, G[g/L]
S, P [g/L]
30 4
3
20
2
10
1
0 0
0 10 20 30 40 50 60 70
Time [h]
Cellulose (S) Ethanol (P) Cellobiose (C) Biomass (X) Glucose (G)
Figure 9.5 Behavior of batch SSF process for ethanol production from cellulose.
The results for batch SSF process can be seen in Figure 9.5. The final cellu-
lose concentration was 28.6 g/L and the ethanol concentration reached at the end
of fermentation was 17.5 g/L. The amounts of cellobiose and glucose when the
cultivation was finished were near zero, which shows the efficiency of the com-
bined process and the neutralization of the inhibitory effects of glucose on cel-
lulases. In the case of the SHF process, the accumulating glucose in the medium
during cellulose saccharification leads to reduced conversion of cellulose and
hydrolyzates with lower concentrations of fermentable sugars. In contrast, dur-
ing the SSF process, the accumulation of ethanol in the medium can inhibit the
growth rate and, therefore, the ethanol production rate according to the kinetic
expressions on which the model was based. The productivity attained by the
batch SSF process was 0.292 g/(L × h) and the ethanol yield was 0.454 g/g, cal-
culated at 48 h of cultivation.
For solving the model of an SSF process in a CSTR, the mass balance for each
of the i substances involved in the process (cellulose, cellobiose, biomass, glucose,
and ethanol) was considered according to following equation:
Taking into consideration that Equations (9.1) through (9.5) describe the forma-
tion or consumption rate of each component, a system of five nonlinear algebraic
equations with five unknowns was obtained by applying equation (9.7). For solving
this system, the Newton–Raphson algorithm was used with the same initial con-
centrations used for the SSF process in batch regime. Equation (9.1) includes a term
for cellulose conversion (x) that in the original paper of South et al. (1995) is a func-
tion of mean residence time of particulate matter of cellulose. In this case study,
the conversion was set to a value of 0.70 with the use of a CSTR for carrying out
both transformations (cellulose hydrolysis and ethanol fermentation) and, therefore,
assuming an intensive mixing of the reaction volume.
The results obtained for continuous SSF process with a mean residence time of
72 h showed that the cellulose had a more complete conversion and that the ethanol
was produced in higher amounts. The concentrations of cellulose and ethanol in the
outlet stream were 10.7 and 24.9 g/L, respectively. The biomass concentration in
the exiting stream was 5.6 g/L, which is comparable with that of the corresponding
batch process. The concentrations of the other involved components in the effluent
of the fermenter were near zero, demonstrating the good performance of the SSF
process. In this case, the concentration of cellulose in the feed stream was 60 g/L.
The productivity attained by the continuous SSF process was 0.345 g/(L × h) and
the ethanol yield was 0.506 g/g showing favorable performance indexes related to
the batch SSF process.
Cellulases
Production of
Lignocellulosic Cellulases
biomass
Product Ethanol
Pretreatment SSCF
Recovery
Lignin
Co-generation
Process steam
Electricity for
Sale of electricity to the process
the grid
Figure 9.6 Simplified diagram of the integrated process for fuel ethanol produc-
tion from lignocellulosic biomass by simultaneous saccharification and co-fermentation
(SSCF).
Source: Modified from Cardona, C.A., and Ó.J. Sánchez. 2007. Bioresource Technology 98:2415–2457. Elsevier Ltd.
Note: SHCF = separate hydrolysis and co-fermentation.
Lignocellulosic
biomass
Product Ethanol
Pretreatment SSCF
Recovery
Lignin
CBP Cogeneration
Process steam
Electricity for
Sale of electricity the process
to the grid
Figure 9.7 Simplified diagram of the integrated process for fuel ethanol production
from lignocellulosic biomass by consolidated bioprocessing (CBP).
the enzymatic and fermentation systems are entirely compatible (Cardona and
Sánchez, 2007).
The extended concept of CBP involves four biologically mediated transforma-
tions: (1) the production of saccharolytic enzymes (cellulases and hemicellulases);
(2) the hydrolysis of carbohydrate components present in pretreated biomass to
form sugars; (3) the fermentation of hexose sugars (glucose, mannose, and galac-
tose); and (4) the fermentation of pentose sugars (xylose and arabinose). These
four transformations occur in a single step. In this case, a dedicated process for
production of cellulases is not required to make CBP a highly integrated configu-
ration (Cardona and Sánchez, 2007; Lynd et al., 2005). This process is conceptu-
ally depicted in Chapter 6, Figure 6.5 for the case of ethanol production from
lignocellulosic biomass.
Process integration through CBP represents a considerable improvement of
technologies for conversion of lignocellulosic biomass into ethanol. The enhance-
ment of the conversion technology contributes by far the most reduction of etha-
nol production costs (Cardona and Sánchez, 2007). According to projections of
Lynd (1996), the reduction of production costs due to an advanced configuration
involving the CBP is three times greater than the reduction related to the scale
economy of the process and 10 times greater than the reduction associated with a
lower cost of the feedstock. This diminish would be accomplished thanks to the
reduction of more than eight times in the costs of biological conversion (Lynd et
al., 1996). Lynd et al. (2005) reported the comparative simulation of SSCF and
CBP processes assuming aggressive performance parameters intended to be rep-
resentative of mature technology. Their results indicate that production costs of
ethanol for SSCF reach US4.99 cents/L including the costs of dedicated cellulase
production, whereas CBP gives total costs of only US1.11 cents/L demonstrating
the potential effectiveness of this process configuration.
Most studies on CBP of biomass contemplate the use of the thermophilic
bacterium Clostridium thermocellum, which is employed for cellulase produc-
tion, cellulose hydrolysis, and glucose fermentation. In addition, the bacterium
Thermoanaerobacter thermosaccharolyticum can be co-cultured along with C.
thermocellum to allow the simultaneous conversion of pentoses obtained from
hemicellulose hydrolysis into ethanol (Cardona and Sánchez, 2007; Wyman,
1994). In particular, the CBP using C. thermocellum showed a substrate conversion
31% higher than a system using T. reesei and S. cerevisiae. South et al. (1993)
tested the continuous CBP of cellulose into ethanol using C. thermocellum and
showed, under very specific conditions with a residence time of 0.5 d, higher con-
versions than a continuous SSF process. Some filamentous fungi such as Monilia
sp., Neurospora crassa, and Paecilomyces sp. are also able to transform cellulose
into ethanol (Szczodrak and Fiedurek, 1996). Nevertheless, this technique faces
the problem of the low tolerance of clostridia to ethanol and the reduction in the
ethanol yield due to the formation of acetic acid and salts of other organic acids
like lactates (Baskaran et al., 1995; Cardona and Sánchez, 2007; McMillan, 1997;
Wyman, 1994). This means that the final ethanol concentration is low in compari-
son with the traditionally used yeasts (0.8 to 60 g/L) with very large cultivation
times of 3 to 12 d (Szczodrak and Fiedurek, 1996).
To date, there is no microorganism known that can exhibit the whole com-
bination of features required for the development of a CBP, as the one shown
in Figure 6.5 (Chapter 6). However, there are realistic expectations about the
possibility of overcoming the limitations of current CBP organisms. In Section
6.3.2.2, the main strategies for developing engineered microorganisms that can
be used in technological configurations involving CBP were disclosed. In this
way, the huge possibilities of CBP are based on the development of genetically
modified microorganisms allowing such a high degree of reaction–reaction inte-
gration that can make possible the direct conversion of pretreated lignocellu-
losic biomass into ethanol at elevated yields under industrial conditions. Some
examples of CBP, not only of lignocellulosic materials but also of starch, are
presented in Table 9.5.
9.3 Reaction–Separation Integration
for Bioethanol Production
Reaction–reaction integration allows for the increase of process efficiency through
the improvement of reaction processes. However, separation is the step where
major costs are generated in the process industry. Therefore, reaction–separation
integration could have the highest impact on the overall process in comparison
with homogeneous integration of processes (reaction–reaction, separation–sep-
aration; Cardona and Sánchez, 2007). The reaction–separation integration is a
Source: Modified from Cardona, C.A., and Ó.J. Sánchez. 2007. Bioresource Technology 98:2415–2457. Elsevier Ltd.
245
© 2010 by Taylor & Francis Group, LLC
246 Process Synthesis for Fuel Ethanol Production
Concentrated
ethanol
Vacuum
Chamber
Fermenter
Feed
To distillation
step
Cells
Centrifuge
Broth
from the condensation of ethanol. The model proposed by these authors showed
that ethanol inhibition influences especially the cell yield reaching a value of 60
g/L of ethanol in the broth above which the inhibition is very strong. The authors
point out that the values of kinetic parameters depend in a high degree on the
type of fermentation: batch or continuous. Later, Taylor et al. (2000) employed a
saccharified corn mash containing high levels of suspended solids as a feed and
compared the results obtained with a state-of-the-art dry-milling process using
Aspen Plus. Savings of US0.8 cents/L of ethanol can be attained in comparison
with the state-of-the-art process for which saccharification and fermentation are
carried out separately (Cardona and Sánchez, 2007).
Other variants of this type of integrated configuration have been proposed as
evidenced in Table 9.7. Gong et al. (1999) report the simultaneous variant of the
fermentation-stripping process using an air-lift reactor with a side arm (external
loop) that improves liquid circulation and mass transfer. A more complex configu-
ration integrating the fermentation and stripping was developed by Bio-Process
Innovation, Inc. (West Lafayette, IN, USA). A pilot plant was designed and built
for ethanol production from lignocellulosic biomass using a 130 L multistage, con-
tinuous-stirred, reactor separator (MSCRS) for the SSF of cellulose and hemicel-
lulose (Dale and Moelhman, 2001). The MSCRS consists of a series of six stirred
Source: Modified from Cardona, C.A., and Ó.J. Sánchez. 2007. Bioresource Technology 98:2415–2457. Elsevier Ltd.
EtOH+CO2
Broth+CO2
3
2 B 4
Feed 1 A
Concentrated
To distillation ethanol
step
Figure 9.9 Simplified diagram of the fermentation process with ethanol removal by
using CO2 as a stripping gas: (A) liquid circulation loop, (B) gas circulation loop, (1)
fermenter, (2) stripping column, (3) condenser, (4) refrigerator. (Adapted from Cardona,
C.A., and Ó.J. Sánchez. 2007. Bioresource Technology 98:2415–2457. Elsevier Ltd.)
stages in which the SSF of biomass is carried out. Each stage has a stirred tank for
the reaction and a gas–liquid separation contactor. In the three upper stages, SSF
of cellulose is carried out at 42ºC using a thermotolerant K. marxianus, while in
three lower stages, the fermentation of xylose is achieved using the yeast P. stipi-
tis at 30ºC. In addition, part of the broth containing enzymes is recirculated from
the last stage to the first upper stage in order to favor the reaction with the fresh
pretreated biomass. Reaction–reaction integration is implemented because com-
mercial cellulases were added for the saccharification of pretreated biomass. This
defines the process temperature helping the generation of ethanol vapors. The
broth overflowing from one stage into the next stage is contacted with a stripping
stream of CO2 that entraps the ethanol. A gas stream passes across the reactor
and then through an absorption tower where water is used for removing ethanol
vapors. CO2 is again recirculated to the reactor. In this way, reaction–separation
integration is verified through the in situ removal of ethanol produced in each
stage. The same company has installed a pilot plant reactor using MSCRS tech-
nology (Dale, 1992) in the plant of Permeate Refining, Inc., located in Hopkinton,
IA (USA), that produces 11.36 million liters per year of ethanol from starch. This
unit has been in operation since September 1995 and employs starch dextrins,
thought its use for lignocellulosic biomass has been proposed. Unfortunately, no
reports are available describing the modeling and performance of this type of
configuration (Cardona and Sánchez, 2007).
Source: Modified from Cardona, C.A., and Ó.J. Sánchez. 2007. Bioresource Technology 98:2415–2457. Elsevier Ltd.
Note: ALSA = Airlift reactor with a side arm, MSCRS = Multistage continuous reactor–separator.
membrane modules coupled to fermenters) or water from ethanol (as in the opera-
tion of pervaporation during ethanol dehydration). Membranes make possible the
removal of ethanol from a culture broth, which neutralizes the inhibitory effect of
ethanol on microorganisms. Most of integrated schemes of this kind correspond to
membrane modules coupled to fermenters. The use of ceramic membranes located
inside the fermenter has been proposed, although most of these systems have been
studied only on a laboratory scale. These laboratory configurations have shown
interesting results, but their implementation at an industrial scale can be very dif-
ficult. The utilization of ceramic membranes has been proposed for the filtration
of cell biomass and the removal of ethanol during the fermentation (Ohashi et al.,
1998). The removed ethanol is distilled and the obtained bottoms are recycled
back to the culture broth resulting in a drastic reduction of generated wastewater.
This configuration uses a stirred ceramic membrane reactor (SCMR). In the same
way, immobilized cells can be used in order to allow an easier separation of etha-
nol and the recirculation of distillation bottoms to the reactor (Kishimoto et al.,
1997). Kobayashi et al. (1995) developed a mathematical model for optimization
of temperature profiling during the batch operation of a fermenter coupled with a
hollow-fiber module. The temperature was kept initially at 30ºC descending later
to 20ºC and attaining higher ethanol concentration and productivity. However, it is
necessary to analyze the scalability of these configurations due to their complexi-
ties (immobilization, presence of membranes, recirculation, repeated batches) and
taking into account that no mathematical description has been presented (Cardona
and Sánchez, 2007). The utilization of liquid membranes (porous material with an
organic liquid) in schemes involving the extraction of ethanol by the organic phase
and the reextraction with a liquid stripping phase used as an extractant (perstrac-
tion or membrane-aided solvent extraction) or gaseous stripping phase have been
also coupled to the fermentation process showing the increased effectiveness of
the latter configuration (Cardona and Sánchez, 2007; Christen et al., 1990). Some
of these configurations are summarized in Table 9.8.
Pervaporation has offered new possibilities for integration, as evidenced in
Table 9.8. The coupling of fermentation with the pervaporation allows the remov-
ing of produced ethanol (Figure 9.10), reducing the natural inhibition of the cell
growth caused by high concentrations of ethyl alcohol (Cardona and Sánchez,
2007). Nomura et al. (2002) observed that the separation factor of silicalite zeolite
membranes used for continuous pervaporation of fermentation broth was higher
than the corresponding value for ethanol–water mixtures due to the presence of
salts that enhance the ethanol selectivity. Ikegami et al. (2003, 2004) employed
this same kind of membrane coated with two types of silicone rubber or covered
with a silicone rubber sheet as a hydrophobic material for obtaining concentrated
solutions of ethanol. The coupling of T. thermohydrosulfuricum that directly
converts uncooked starch into ethanol with pervaporation has also been tested
obtaining ethanol concentrations in the permeate of 27 to 32% w/w (Mori and
Inaba, 1990).
O’Brien et al. (2000) employed process simulation tools (Aspen Plus) for
evaluating the costs of the global process involving fermentation–pervaporation
253
© 2010 by Taylor & Francis Group, LLC
254
Table 9.8 (Continued)
Reaction–Separation Integration for Alcoholic Fermentation Processes through Ethanol Removal by Using Membranes
Technology BioagentUunit Operation Feedstock/Medium Remarks References
Source: Modified from Cardona, C.A., and Ó.J. Sánchez. 2007. Bioresource Technology 98:2415–2457. Elsevier Ltd.
Note: CMFS = continuous membrane fermentor–separator, HFMEF = hollow-fiber membrane extractive fermentor, PAAH = polyacrylamide hydrazide, SCMR = stirred
ceramic membrane reactor.
255
© 2010 by Taylor & Francis Group, LLC
256 Process Synthesis for Fuel Ethanol Production
Liquid
retentate PERVAPORATION
UNIT
Conc.
Gaseous EtOH
permeate
FERMENTER
Feed
To distillation
step
Figure 9.10 Simplified diagram of fermentation process with ethanol removal using
a pervaporation unit coupled to the fermenter. (Adapted from Cardona, C.A., and Ó.J.
Sánchez. 2007. Bioresource Technology 98:2415–2457. Elsevier Ltd.)
module leading to the ethanol removal from culture broth diminishing the inhibi-
tion effect and obtaining an increase in ethanol yield and productivities. Gryta
(2001) points out that when a tubular fermenter working in a continuous regime
is coupled with the membrane distillation module, higher increases in ethanol
productivity can be achieved (up to 5.5 g/(L × h)). This author determined that the
number of yeast cells that are deposited on the membrane is practically zero dur-
ing the operation of these modules (Gryta, 2002). Calibo et al. (1989) also dem-
onstrated the possibility of coupling the continuous fermentation with membrane
distillation. They used a column fermenter, a cell settler, and a membrane mod-
ule. This system operated during almost 700 h with a feed of molasses. García-
Payo et al. (2000) studied the influence of different parameters for the case of
air gap membrane distillation based on the model of temperature polarization. It
was observed that permeate flux increases in a quadratic way when ethanol con-
centration increases in the membrane distillation module. Similarly, Banat and
Simandl (1999) indicate that the effects of concentration and temperature polar-
ization should be accounted for during the modeling of this process and highlight
the need for optimizing it with respect to feed stream temperature. Banat et al.
(1999) also analyzed different models based on Fick’s law and on the solution of
Maxwell–Stefan equations for this type of distillation. Likewise, the characteris-
tics of the vacuum membrane distillation (Izquierdo-Gil and Jonsson, 2003) and
direct contact membrane distillation have been studied for the concentration of
aqueous solutions of ethanol (Fujii et al., 1992a, 1992b). Without a doubt, these
studies are of great interest considering the simulation of these integrated con-
figurations (Cardona and Sánchez, 2007).
In the case of the bioethanol production from sugarcane, the integration of
fermentation with pervaporation or vacuum membrane distillation can allow the
recovery of a valuable product: the fructose. For this, mutant strains of yeasts
without the capacity of assimilating this monosaccharide should be used. Thus,
continuous ethanol removal through the membranes coupled to the fermenter
makes possible the accumulation of fructose in the culture medium that can be
recovered in an extraction column (Cardona and Sánchez, 2007). According to Di
Luccio et al. (2002), the simulation of this process based on experimental data and
semiempiric models for the evaluation of the required membranes area allowed
performing of a preliminary economic analysis. This analysis showed that vari-
able costs involving membrane area influence in a higher degree the viability of
the process. The process is viable only if the cost of membranes is not greater
than US$550/m2 for a new plant or US$800/m2 for an adapted plant considering
an internal return rate of 17%.
Cellulases Retentate
R
Cells
Feed Permeate
F Q
Microfiltration Pervaporation
Reactor unit
W
modeling of processes involved during the SSF of cellulose was presented. In this
case study, the SSF model presented, which was based on the mathematical descrip-
tion of South et al. (1995), was applied to a reaction–separation integrated process
in which the SSF bioreactor was coupled with a pervaporation module.
The schema used to simulate the SSF process coupled with pervaporation
appears in Figure 9.11. The CSTR has two outlet streams, one of which is directed
to a microfiltration unit where biomass and other nonsoluble components are
removed and recycled back to the reactor. The soluble components (mainly glucose,
cellobiose, and ethanol) are sent to the pervaporation unit where the main part of
the ethanol is selectively removed through a silicate membrane and the retentate is
recirculated to the reactor. A cell-separating device was included in order to avoid
the cell biomass and other related solids to enter the pervaporation unit. In the
stream W all of the components of the culture medium are present, including the
cell biomass. Unlike the membranes employed for ethanol dehydration, the silicate
membranes have a higher selectivity for the ethanol, causing the concentration of
this alcohol in the retentate to be reduced, which allows the recirculation of this
stream to the reactor where the biological transformation takes place. It should
be noted that this process implies the application of the integration principle in
two ways: reaction–reaction integration through the SSF of cellulose and reaction–
separation integration through the coupling of a membrane device (the pervapora-
tion unit). The objective of this case study, presented in a previous work (Sánchez et
al., 2005), was to assess the effect of ethanol removal from culture broth by using
membranes. Both semicontinuous and continuous regimes were considered.
In the case of the SSF coupled with pervaporation in semicontinuous regime,
the permeate stream Q is continuously removed from the system causing a decrease
in the total liquid volume in the reactor. This situation can be described by the fol-
lowing mass balance equations for all i components:
d (VCi )
= Vri (9.8)
dt
d (VP )
= −QPP + VrP (9.9)
dt
dV
= −Q (9.10)
dt
where Ethanol is the concentration of ethanol and Water the concentration of water
(in g/L) and the subindices Perm and Feed correspond to the permeate and feed,
respectively. The formulation of α was taken from Nomura et al. (2002) for a sili-
cate membrane. These authors reported also different values of this separation fac-
tor for water–ethanol mixtures (α = 41), solutions containing yeast (α = 38), salts (α
= 62), and fermentation broth (α = 88). The last value was used in this case study.
The simulation of the batch SSF process coupled with pervaporation for the
same initial concentrations and a residence time identical to those of the batch
process presented in Case Study 9.2 gave a final ethanol concentration in the fer-
mentation broth of 0.04 g/L as a consequence of the product removal in the per-
vaporation module. The concentration of ethanol in the permeate varied with the
time due to the changes in the broth volume and reached relatively high values of
92 g/L (Figure 9.12). The cellulose consumption was 45.3% higher (considering
the volume change) than in the case of batch SSF without pervaporation indicating
the favorable effect of product removal on the diminishing of inhibition effect of
ethanol on cellulose uptake rate, growth rate, and product biosynthesis rate. The
cell biomass had a similar profile in the batch SSF process with and without per-
vaporation, but had a better growth in the former case because of the minor ethanol
concentration in the broth.
In the case of continuous SSF of cellulose coupled with a pervaporation unit and
taking into account the scheme shown in Figure 9.11, the mass balance equations
were formulated assuming that the stream of permeate Q only contains ethanol and
water. Therefore, the global material balances are the same as those used for the
SSF process in a CSTR (see Case Study 9.2), except for ethanol balance that now
includes a term considering the separation achieved in the pervaporation unit:
Ethanol and biomass productivities and product yield were evaluated consider-
ing the variation in the mean residence time (or dilution rate) and in the fraction of
100 9
90 8
80 7
70
6
60
C, X, G, P [g]
5
S [g] , Pp [g/L]
50
4
40
3
30
2
20
10 1
0 0
0 10 20 30 40 50 60 70
Time [h]
Cellulose (S) Ethanol in permeate (Pp)
Cellobiose (C) Biomass (X)
Glucose (G) Ethanol in broth (P)
outlet stream that is sent to the pervaporation unit. For the base case, the value of
the feed stream was 100 L/h and the mean residence time was 72 h.
When the analysis of the continuous SSF process coupled with pervaporation
was performed, the concentration of ethanol in the permeate increased significantly
reaching 248.3 g/L, whereas the ethanol concentration in the fermentation broth
was 4.1 g/L. This low concentration has no inhibition effects on the bioprocess for
this fermentation regime. In addition, the cellulose concentration in the broth was
3.9 g/L revealing an important increase in the substrate conversion. The biomass
concentration was higher than in all the other cases (7.2 g/L). The concentration of
cellobiose and glucose in the broth were negligible. In this case, a flow rate of per-
meate of 12 L/h and a separation factor of 88 were considered and the concentration
of cellulose in the feed stream was 60 g/L. The results were obtained for a mean
residence time of 72 h and a feed flow rate of 120 L/h. Comparing the obtained
data with those of the previous configuration, it can be observed a better produc-
tion of ethanol, a greater consumption of cellulose, an improved production of cell
biomass, and similar results for cellobiose and glucose.
If the permeate flowrate is changed, an increase of the productivity can be
observed due to the higher removed amounts of ethanol and to the corresponding
reduced end product inhibition. On the other hand, productivity decreases with
the increase of residence time and the subsequent rise in the reactor volumes. The
cellulose conversion was highly affected by the residence time as expected, but a
100
0.5 90
80
0.4
Productivity [g/(L×h)]
70
Conversion [%]
60
0.3
50
40
0.2
30
0.1 20
10
0 0
15 20 25 30 35 40 45 50 55 60
Mean Residence Time [h–1]
Figure 9.13 Productivity and cellulose conversion for SSF process with and without
pervaporation (PV) for various values of permeate flow rates (Q) expressed as a fraction
of feed flow rate (F).
reduce conversion was observed for the case when pervaporation was not included
in the configuration. These results are shown in Figure 9.13.
Four models for comparing the consumption of cellulosic biomass and the pro-
duction of ethanol were solved (considering the two models of Case Study 9.2) and
analyzed considering configurations with and without pervaporation and for batch
and continuous regimes. From the results, it can be observed that better conversion
to ethanol of cellulose is obtained when the pervaporation is included in the SSF
process. This can be explained by a lower ethanol concentration in the fermentation
broth. This reduced ethanol concentration implies that the value of the inhibition
terms in the rates equations be lesser leading to the increase of the cellulose and
cellobiose hydrolysis, the growth of biomass, the consumption of glucose, and con-
sequently, the production of ethanol. For the two configurations involving pervapo-
ration, the selective separation effect of the membrane module allowed the effective
removal of the product from the reaction–fermentation zone.
Although the pervaporation model employed is a simple representation, it is
a good estimation for analyzing the behavior of a simultaneous saccharification
and fermentation process along with this separation method. The proposed models
allowed observing how the inhibition effects by ethanol influence its production,
and how its continuous removal causes a considerable increase of cellulose con-
version and, for this reason, an extra production of ethanol. The productivities for
the evaluated configurations are presented in Table 9.9. The ethanol produced per
Table 9.9
Productivities and Ethanol Yields for Different
Configurations of Alcoholic Fermentation Using
Cellulose as Feedstock
Productivity/ Ethanol Yield/
Configuration g/(L × h) g/g
Batch SSF 0.2916 0.454a
Batch SSF+ PV 0.3645 0.493
Continuous SSF 0.3451 0.506
Continuous SSF + PV 0.4791 0.525
hour, considering, in batch cases, a break of 12 h to discharge, clean, and charge the
equipment was considered. The better configuration is SSF + PV in a CSTR. The
calculated ethanol yields evaluated as the grams of produced ethanol from 1 g of
consumed cellulose showed better results again for the simultaneous saccharifica-
tion and fermentation process coupled with pervaporation in a CSTR. In contrast,
the minimum yield corresponded to the batch SSF.
The ethanol in the permeate must be passed through separation equipment
(i.e., distillation) to get rid of the excess water to obtain an appropriate ethanol
for fuel use. At this point, it is important to remark that the increased concentra-
tion of ethanol allows the reduction of energy costs during the distillation of
permeate in comparison with those corresponding to the distillation of fermenta-
tion broth where the ethanol concentration is very low (approximately 25 g/L for
a continuous SSF process, according to the performed simulations). This case
study allows comparing these four systems and obtaining results that can be used
for future studies involving more meticulous models of pervaporation developed
from rigorous mass, momentum, and energy balances and disregards many com-
mon assumptions, such as constant pressure, constant temperature, binary mix-
ture, steady-state conditions, and constant physical properties. In addition, the
proposed approach for modeling of this process can be used for the design of
laboratory and pilot plant experiments. The proposed configuration of simultane-
ous saccharification and fermentation coupled with pervaporation in a CSTR has
advantages over other batch and continuous systems in terms of productivities and
product yield. Therefore, this process becomes attractive considering that the use
of biomass to produce ethanol is not economically feasible on a large commercial
scale yet, and should be taken into consideration due to the significant qualitative
and quantitative improvements demonstrated through modeling of this complex
bioprocess. However, the limitations inherent in membrane technologies in real
practice should be thoroughly assessed.
Concentrated
ethanol
Flash Unit
Solvent
Bioreactor
Solvent phase
Feed
Decanter
Top distillation
Aqueous step
phase
Figure 9.14 Simplified diagram of fermentation process with ethanol removal by liq-
uid extraction (extractive fermentation). (Adapted from Cardona, C.A., and Ó.J. Sánchez.
2007. Bioresource Technology 98:2415–2457. Elsevier Ltd.)
265
© 2010 by Taylor & Francis Group, LLC
266
Table 9.10 (Continued)
Reaction–Separation Integration for Alcoholic Fermentation Processes through Ethanol Removal by
Liquid–Liquid Extraction
Technology Bioagent/Unit Operation Feedstock/Medium Remarks References
Fed-batch SSEF S. cerevisiae/commercial Primary clarifier sludge Reactor with up to 2.5% aqueous phase; 50% Moritz and Duff (1996)
Source: Modified from Cardona, C.A., and Ó.J. Sánchez. 2007. Bioresource Technology 98:2415–2457. Elsevier Ltd.
Note: HFMEF = hollow-fiber membrane extractive fermenter, SSEF = simultaneous saccharification and extractive fermentation.
The selection of the solvent is a crucial factor for extractive fermentation tech-
nology. Bruce and Daugulis (1991) developed a solvent screening program for
evaluating possible extracting agents to be used in extractive fermentation con-
figurations. This program considered the biocompatibility of the solvent and uti-
lized the UNIFAC activity model for predicting liquid–liquid equilibrium data.
Using this program, these authors (Bruce and Daugulis, 1992) identified the sol-
vent mixture of oleyl alcohol with 5% (v/v) 4-heptanone as a promising extract-
ant due to its reduced inhibitory effect and increased distribution coefficient.
A large amount of alcohols have been tested in order to examine their ethanol
extracting properties in water–ethanol–solvent systems (Offeman et al., 2005a,
2005b). The collected data have allowed insight into the relationship between
the structure of the solvent and its extracting characteristics. For this type of
work, molecular simulation can provide a deeper understanding on solvent con-
formation and associations among water, ethanol, and solvent. Although these
works are intended to the selection of proper solvent for ethanol dehydration, the
obtained results are of great value for extractive fermentation studies, provided
the needed biocompatibility tests are done (Cardona and Sánchez, 2007).
Another approach for extractive fermentation that has been used is the appli-
cation of aqueous two-phase fermentation where two phases are formed in the
bioreactor as a result of adding two or more incompatible polymers (Banik
et al., 2003). In this way, ethanol can be partitioned between both phases
accumulating in the upper layer, whereas cell biomass is accumulated in the
lower phase. This allows the separation of the ethanol-rich phase and the dis-
tillation of this alcohol reducing its inhibition effect. Nevertheless, the com-
plexity of the process in the case of continuous regime and the high cost of
polymers have delayed further development in this ethanol production technol-
ogy (Cardona and Sánchez 2007).
down into elementary sugars like hexoses (glucose) and pentoses (mainly xylose).
Formed sugars are converted into ethanol in the reactor. Ethanol is distributed
between aqueous and organic (solvent) phases, diminishing its concentration in the
culture aqueous broth and allowing reduction of the product inhibition effect on the
microorganisms. The ethanol-enriched solvent phase is continuously removed from
the reactor through a decanting unit. This stream is sent to a flash unit in order to
recover the obtained ethanol and to regenerate the solvent, which can be recycled
to the CSTR.
With the aim of developing a rigorous model that describes both the fermen-
tation and liquid–liquid extraction processes, the kinetics cultivation is coupled
with an extraction model. The liquid–liquid equilibrium was described through
an algorithm based on the mass balance equations developed for the isothermal
flash in the case of two liquid immiscible phases. Activities of components in
each phase were calculated by means of the UNIFAC model, since this model
has demonstrated to be the most appropriate for description of equilibrium
when two or more liquid phases are present for this case. This algorithm was
integrated into the ModELL-R software, which was especially designed by the
research group to which the authors of this book belong. The software couples
two convergence algorithms (Newton–Raphson and False Position Method) in
order to calculate the liquid fraction of each phase. ModELL-R was developed
in Delphi package v7.0 (Borland Software Corp., Austin, TX, USA).
The kinetic model of alcoholic fermentation was taken from Leksawasdi et
al. (2001; see Chapter 7, Case Study 7.1). This model describes the simultane-
ous consumption by a recombinant strain of Z. mobilis of two main substrates
contained in the lignocellulosic hydrolyzates: glucose and xylose. The following
assumptions were considered for the development of the overall model of extractive
fermentation:
• The substrate uptake, biomass formation, and product biosynthesis are car-
ried out only in the aqueous phase; hence, no reactions occur in the organic
(solvent) phase.
• Ethanol is the main component migrating to the solvent phase; small
amounts of water can migrate to the organic phase depending on the
solvent.
• No migration of substrates and biomass to the solvent phase takes place.
• Solvent is biocompatible with the microorganisms and does not have effect
on the fermentation process.
• Stirring of bioreactor ensures total mixing between liquid phases and does
not produce damage to the growing cells.
−QA X + VA rX = 0 (9.13)
FA S20 − QA S2 − VA rS 2 = 0 (9.15)
FE P0* − QA P − QE P * + VA rP = 0 (9.16)
P * = kEtOH P (9.18)
where r X is the cell growth rate (in g/(L × h)), r S1 and r S2 are the glucose and xylose
consumption rates, respectively (in g/(L × h)), and r P is the ethanol formation rate
(in g/(L × h)); X, S1, S2 , and P are the concentrations of cell biomass, glucose,
xylose, and ethanol in the aqueous effluent from the bioreactor (in g/L), and X0,
S10, S20, and P0 are the corresponding concentrations in the aqueous feed stream
(in g/L); P* and P0* are the ethanol concentrations in the solvent effluent and in
the solvent feed streams, respectively (in g/L). The balance can be applied for the
case when the solvent contains small amounts of ethanol as a result of noncomplete
regeneration of the extracting agent. This system of equations is nonlinear due to
the equations describing the process kinetics and is solved through multivariate
Newton–Raphson algorithm. For this, a constant solvent volume/aqueous volume
ratio is assumed. The relationship between both effluent flow rates is fixed. The
ethanol concentration in the solvent phase (P*) that is in equilibrium with ethanol
concentration in the aqueous phase is determined using the distribution coefficient
k EtOH as shown by equation (9.18), which is calculated by the algorithm for liquid–
liquid equilibrium. The determination of all variables involved in the model is per-
formed using the algorithm shown in Figure 9.15 incorporated into the software
ModELL-R. For specified inlet aqueous dilution rate (DAi = FA /VA) and solvent feed
flow rate/aqueous feed flow rate ratio (R = FE/FA), the program requires concentra-
tions of cell biomass, substrates, and ethanol in feed streams.
The simulation of alcoholic extractive fermentation from biomass was performed
with a glucose concentration of 100 g/L and an xylose concentration of 50 g/L in
the feed aqueous stream. These concentrations correspond to those of lignocel-
lulosic hydrolyzates. The behavior of this process for R = 2 in dependence of inlet
dilution rate (DAi) is shown in Figure 9.16. The cell washout occurs at dilution rates
near 0.33 h-1. These results were obtained for a solvent volume/aqueous volume
ratio (VE/VA) of 2. Higher ethanol productivities are found in the range 0.25 to 0.30
h-1. In order to elucidate the best operating value of DAi, GAMS software (General
Algebraic Modeling System, GAMS Development Corp., Washington, DC, USA)
was used for maximizing total ethanol productivity. For this, a simple linear rela-
tionship for Equation (9.18) was considered. The optimal DAi was 0.265 h–1.
The coupled algorithm was used for process simulation varying the solvent feed
flow rate/aqueous feed flow rate ratio (R) for an inlet dilution rate of 0.265 h-1. Best
results were obtained for values greater than 4 that correspond to an increased
F, Zi, T, P
S10 S20 X0 P0 R, P* = 0
Initial Guess
Multivariate Newton- Raphson Algorithm: Xa, Xb, Q.
- Kinetic Model
- Mass Balance Eq. S1, S2 X, P
K = f (UNIFAC Model)
Liquid- Liquid Equilibrium K = iXa/Xb
Algorithm P, P*
Univariate Newton–Raphson
q = FE/FA
Yes No
PELL, PELL* Xo,E+1 –Xa,E <1e–5
No PNR–PLLE< Yes
1.10–5 P, P , X S1;
S2 Pr, Pr T
amount of consumed substrates. Both total productivity and productivity for etha-
nol recovered from solvent phase are approaching constant values. For R higher
than 8, the model predicts the formation of homogeneous mixture without extrac-
tion. The simulation of this process modifying both R and DAi shows that the zone
of manipulating variables with higher productivities (inlet concentrations of glu-
cose and xylose in the aqueous stream of 100 g/L and 50 g/L, respectively) corre-
sponded to dilution rates near washout conditions, and to higher values of R within
the range 1.29 to 7.9. If the concentration of both substrates in the feed stream is
varied, the problem becomes more complex. Physically, the increase in substrate
can be achieved as a result of evaporation of initial hydrolyzate obtained from bio-
mass pretreatment. For this reason, the proportion of glucose and xylose in the inlet
aqueous stream should be constant and equal to 2:1. Best values of total productiv-
ity and ethanol productivity recovered from solvent phase correspond to an inlet
concentration of total sugars of about 600 g/L. The simulation was carried out until
the concentration of sugars was less than or equal to 600 g/L, which corresponds to
maximum solubility of these sugars in water.
In this way, a model describing extractive co-fermentation was developed. This
model allows for doing the analysis of this reaction–separation integration process
in order to consider it in subsequent process synthesis methodologies. This is espe-
cially valuable for such process synthesis approaches as the hierarchical decompo-
sition (see Chapter 2) that requires the development of proper models for simulation
of alternative configurations during each hierarchical level of analysis.
S1 S2
P P*
35
100
30
80 25
S1, S2 [g/L]
P, P* [g/L]
60 20
15
40
10
20
5
0 0
0.0 5 0.1 5 0.2 5 0.3 5
DA(i) [1/h]
(a)
8 16
7 14
6 12
Productivity [g/(L.h)]
5 10
X [g/L]
4 8
3 6
2 4
1 2
0 0
0.05 0.15 0.25 0.35
DA(i) [1'/h]
(b)
C6 H12O 6 Z
. mobilis
→ 2C2 H 5OH + 2CO 2
Glucose Ethanol
3C5 H10O 5 Z
. mobilis
→ 5C2 H 5OH + 5CO 2
Xylose Ethanol
Substrate Ethanol
Solubility
Boundary
A Ethanol
Ethanol inhibition
B boundary
W D E
C B
C
B n-dodecanol Water R1 R2 R3
n-dodecanol
Water
(a) (b)
Ethanol
Ethanol inhibition
G boundary
H
Substrate solubility
B" boundary
I D"
D´
E
C n-dodecanol
Water R1 R2 R3 K
Table 9.11
Preliminary Optimum Results for Manipulating Variables
Calculated by GAMS and Corresponding Values Calculated by
ModELL-R Software
Variable DAi S10 S20 PrT P P* S1 S2
Units R 1/h g/L g/L g/(L×h) g/L g/L g/L g/L
ModELL-R 3.038 0.185 400 200 54.79 40.31 73.88 5.33 16.77
GAMS 3.038 0.185 400 200 51.46 40.52 73.55 5.39 19.95
with the maximum concentrations of sugars in the culture broth. For a given inlet
dilution rate of 0.1 h-1, an R ratio of 3.6 (line R2), and a working volume of 1 L, the
location of the point D′ and the corresponding composition of the extract, can be
found. In this case, the ethanol mass content of the extract and raffinate is of 7.5%
and 9.0%, respectively, resulting in a total ethanol productivity of 26.4 g/(L × h).
The productivity calculated by the rigorous model using ModELL-R is 28.86 g/(L
× h). Hence, the developed short-cut method allows one to determine the feasibility
of operating parameters and an estimation of the productivities.
The delimited zones can be taken into account for the development of a pre-
liminary strategy of optimization. Since the region of feasible steady-states was
determined in the ternary diagram (see Figure 9.18), the values range of such
manipulating variables as inlet dilution rate, the R ratio, and the concentration of
the sugars in the inlet aqueous stream is known and can be bounded for solving
an optimization algorithm. The GAMS system was employed to find the optimal
value of above-mentioned variables that maximize the total ethanol productivity
using the nonlinear programming (NLP) solver CONOPT3. With this aim, liquid–
liquid equilibrium relationships were simplified for generating a way to evaluate
the ethanol concentration in both phases during extractive fermentation. For this,
the distribution coefficient k EtOH was assumed to be linearly dependent of the total
concentration of substrates. A good concordance with the data obtained from the
ModELL-R was achieved, especially for high values of substrates concentration.
The results of this optimization are presented in Table 9.11. From this table, it is evi-
dent that calculated optimal variables are indeed in the zone predicted by the short-
cut method, and the predicted increase in total productivity is effectively attained,
as is shown by the rigorous model.
For a more accurate solution of the optimization problem, the rigorous descrip-
tion of the equilibrium model should be coupled or embedded into the GAMS code.
Further analysis of this extractive fermentation process could include the formula-
tion of an objective function that considers, besides ethanol productivity, other per-
formance indexes like the conversion of sugars (better utilization of the feedstock),
or the amount of generated wastewater (evaluation of environmental impact). These
issues are very significant considering process synthesis procedures. After obtain-
ing a global picture of the space of operating conditions and their optimal values
for the studied process, experimental runs should be performed in order to confirm
the validity of the given theoretical approach. In this manner, the acquired insight
of the process will make possible the reduction of expensive experimental work in
the search of the optimal operation.
9.4 Separation–Separation Integration
for Bioethanol Production
The development of technologies for separation–separation integration has been
linked to the development of the different unit operations involved during down-
stream processes and to new approaches for process intensification. The examples
of separation–separation integration in the case of ethanol production mostly cor-
respond to integration of the conjugated type, i.e., when integrated processes are
carried out in different equipments closing the flowsheet by fluxes or refluxes.
Integration possibilities are particularly important for ethanol dehydration.
In Chapter 8, the features and advantages of the integrated process of extractive
distillation were emphasized. In the specific case of fuel ethanol production, the
utilization of salts as extractive agents (saline extractive distillation) has dem-
onstrated certain energetic advantages compared to other dehydration schemes
according to some reports (Barba, et al. 1985; Llano-Restrepo and Aguilar-Arias,
2003). Cited results indicate that energy costs of saline distillation were lower
than is the case of azeotropic distillation (using benzene, pentane, or diethyl
ether), extractive distillation (using ethylene glycol or gasoline), or solvent extrac-
tion, being almost the same as the costs of pervaporation. Pinto et al. (2000)
employed Aspen Plus for the simulation and optimization of the saline extractive
distillation for several substances (NaCl, KCl, KI, and CaCl2). This configura-
tion was compared to the simulated scheme of conventional extractive distil-
lation with ethylene glycol and with data for azeotropic distillation. Obtained
results showed considerably lower energy consumption for the process with salts.
However, for this latter case, the recovery of salts was not simulated. Thus, if
evaporation and recrystallization of salts is contemplated, energy requirements
could significantly increase, taking into account the energetic expenditures. In
this way, the utilization of commercial simulators shows the viability for pre-
dicting the behavior of a given process configuration provided the appropriate
thermodynamic models of studied systems has been completed.
Gros et al. (1998) describe the process synthesis for ethanol dehydration using
near critical propane. To this end, these authors combined thermodynamic mod-
els for the description of ethanol recovery under supercritical conditions based
on Group Contribution Associating Equation of State (GCA-EOS) with robust
methods of simulation and optimization (integrating the SQP with MINLP).
Considering the energy consumption as the objective function, the developed
software analyzed the main units required by the configuration: high-pressure
multistage extractors, distillation columns, and multiphase flash separators.
Obtained results showed that configurations involving vapor recompression and
feed preconcentration are competitive alternatives in comparison to azeotropic
distillation (Cardona and Sánchez, 2007).
The utilization of pervaporation for the production of absolute (anhydrous)
ethanol through its coupling with the previous distillation step has been reported
(Cardona and Sánchez, 2007). The modeling and optimization of the process using
MINLP tools showed 12% savings in the production costs with a 32% increase
in membrane area and a reduction in both reflux ratio and ethanol concentration
in the distillate of the column (Lelkes et al., 2000; Szitkai et al., 2002). Through
pilot plant studies, the integration of distillation process with the pervaporation
has been attained resulting in good indexes in terms of energy savings. These sav-
ings are due to the low operation costs of pervaporation and to the high yield of
dehydrated ethanol, typical of pervaporation processes (Tsuyomoto et al., 1997).
The comparison between azeotropic distillation using benzene and the pervapo-
ration system using multiple membrane modules showed that, at same ethanol
production rate and quality (99.8 %), operation costs, including the membrane
replacement every two to four years, for the pervaporation system are approxi-
mately one-third to one-quarter those of azeotropic distillation.
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285
corn process shows intermediate indicators for BOD and COD (37,000 mg/L
and 56,000 mg/L, respectively) but a higher stillage yield (6.20 L/kg). Finally, in
the case of lignocellulosic ethanol produced from hardwood, the values of BOD,
COD, and yield are 13,200 mg/L, 25,500 mg/L, and 20.4 L/kg, respectively
(Wilkie et al., 2000).
If stillage is directly discharged into natural water streams, the microorgan-
isms present in them will degrade the organic matter discharged, which uses the
oxygen dissolved in the water. This leads to a critical diminution of dissolved
oxygen provoking the death of most aquatic organisms. In addition, the utilization
of nutrients contained in molasses can lead to the massive propagation of algae on
the surface of ponds and lakes causing the blocking of solar light leading to the
death of fish and other living organisms. This phenomenon is known as eutrophi-
cation. Thus, the stillage discharge can seriously alter the ecological equilibrium
of the aquatic ecosystems affected. Residual sugars from fermentation cause still-
age COD to reach high values. For every 1% of residual sugar, a stillage COD
increment of 16,000 mg/L can be expected (Wilkie et al., 2000). For this reason,
full completion of fermentation is desirable in order to reduce stillage volume
(greater ethanol concentrations) and minimize the concentration of remaining
sugars. For each 1% ethanol left in the stillage (in the case of nonefficient distilla-
tion), the stillage COD is incremented by more than 20,000 mg/L.
Due to its elevated organic matter content of stillage, methods for its treatment
and economic utilization should be implemented in the industry. Among the most
used methods for stillage treatment, irrigation, recycling, evaporation, incinera-
tion, and composting should be highlighted. Some of the new treatment methods
produce value-added substances. The most important stillage treatment methods
are presented in the next sections.
10.1.2.1 Stillage Recycling
Usually, in ethanol producing plants, the stillage obtained from the distillation
step (whole stillage) undergoes centrifugation in order to recover organic solids,
especially yeast debris. The liquid fraction is known as thin stillage. In a typi-
cal distillery, more than 20 liters of thin stillage can be generated per each liter
of ethanol produced. To minimize the effluent treatment costs, a portion of thin
stillage (from 25 to 75%) is recycled in different process steps as fermentation
or saccharification (in the case of conversion of starchy materials). In a simi-
lar way, the whole stillage can be recycled back to the fermentation step when
cane molasses is used. Although this procedure decreases the volume of fresh
water employed, it decreases, in turn, the volume of stillage generated; the total
amount of organic matter in the stillage (measured as COD) does not change
because its concentration increases with the amount of recycled stillage (Wilkie
et al., 2000).
The North American ethanol industry that uses corn as feedstock makes use
of a fraction of thin stillage to replace a percentage of water required during
the mashing process (saccharification step). The thin stillage stream recycle is
called backset. The drawback to this practice is that there is an accumulation of
10.1.2.2 Stillage Evaporation
The evaporation represents an intermediate step during the stillage treatment.
The evaporated stillage is the starting point for solids recovery, fertilization,
and incineration of stillage. Thus, during ethanol production from corn by the
dry-milling technology, the thin stillage obtained can be evaporated in order to
produce syrup (also called distiller’s solubles). This syrup is combined with the
solids from corn to produce a co-product used for animal feed (DDGS). The con-
densed water generated in the multiple-effect evaporators contains small amounts
of volatile organic compounds and can be employed during cooking and liquefac-
tion steps of the corn suspension, but the accumulation of inhibitors impedes the
100% recycling of these condensates. The condensates from evaporators can also
undergo aerobic or anaerobic treatment, thus providing all the nutrients required
(Wilkie et al., 2000). Palmqvist et al. (1996) proposed, from bench-scale data, to
fraction the stillage by evaporation and recirculate only those fractions that have
demonstrated having no inhibitory effects on fermentation using Saccharomyces
cerevisiae in the case of willow wood hydrolyzates pretreated by steam explo-
sion. The nonvolatile fraction has high inhibitory effects presumably caused by
the presence of lignin degradation products. Other fractions have low levels of
BOD and COD so they can be directly discharged without any treatment. Similar
studies were carried out for pine and spruce (softwood) performing the simula-
tion of evaporation step using a six-effect evaporation train to optimize the energy
consumption (Larsson et al., 1997).
10.1.2.3 Solids Recovery
The stillage obtained from the process employing sugarcane molasses can be
centrifuged to collect the yeast debris, which has a significant nutritive value,
remaining the thin stillage. This stillage is later evaporated leaving up to 50 to
65% solids to increase its stability against the microbial action. In this way, it can
be commercialized for animal feed. However, its high salts content, especially
potassium, has limited its use to only up to 10% of the ruminant diet (less than 2%
in swine diet) to avoid laxative effects (Nguyen, 2003). The stillage derived from
other types of sucrose-containing feedstocks, such as cane juice or beet molasses,
can be used in the same way.
10.1.2.4 Stillage Incineration
The stillage obtained in processes employing sugarcane, acid hydrolyzates of
wood, or spent sulfite liquors as feedstocks can be incinerated, which offers a posi-
tive energy return as well as the recovery of minerals. Before its incineration, the
stillage should be concentrated up to 50 to 60% solids in 4- or 5-effect evapora-
tors. Just the combustion of stillage offers the energy needed for this concentration
process. The incineration ash has about 30 to 40% K2O and 2 to 3% P2O5, which
converts it into a fertilizer after its dilution in water and neutralization with sulfu-
ric acid (Nguyen, 2003; Olguín et al., 1995; Sheehan and Greenfield, 1980). The
burners of stillage require special designs in order to support its high ash content.
10.1.2.5 Fertilization
The stillage from sugarcane molasses retains potassium and the ash contained
in the original raw materials. Where economically viable, this stillage is trans-
ported by trucks to irrigate the surrounding sugarcane plantations. One option to
directly apply the stillage is to combine this effluent with 10% total solids, as done
in Colombia (Gnecco, 2003). To reduce the transport costs during the fertiliza-
tion of cane fields, evaporated stillage (up to 60° Brix) is employed allowing the
reincorporation of potassium into the soil, though this process means high energy
consumption (Goyes and Bolaños, 2005). Thus, the evaporation of stillage up to
55% solids and its mixing with a nitrogen source allows the production of a liquid
fertilizer that is quite appropriate for cane plantations (Gnecco, 2003). In particu-
lar, the fertilization experiences using this evaporate stillage in Colombia have
shown signs of productivity increases of both sugarcane and cane sugar of nearly
6%, and reductions in fertilization of 2%. In addition, this evaporated stillage can
undergo drying in order to produce a solid stillage that is also commercialized as
a fertilizer (Gnecco, 2006).
The stillage aids in the formation of an initial buffer in the soil with calcium
and magnesium elevating its pH. In addition, it improves the physical proper-
ties of the soil and increases the retention of water and salts, as well as the soil
microflora, increasing the land yield. Among the drawbacks of using stillage as
a fertilizer are the strong odors, insect invasion, increase of the soil acidity, salts
lixiviation, putrescibility, manganese deficiency, and inhibition of seed germina-
tion. In addition, the accumulation of sulfates reduces them to hydrogen sulfide,
which is, in turn, transformed by soil bacteria into sulfuric acid (Navarro et al.,
2000; Nguyen, 2003; Olguín et al., 1995). Furthermore, inadequate handling of
irrigation techniques can increase the pollution of groundwater. The use of deni-
trifying bacteria for detoxification of the distillery effluents through the removal
of potassium, chlorides, and sulfates has been referenced (Olguín et al., 1995).
In Australia, the wheat-milling residue is washed with water to obtain an efflu-
ent containing starch (starch waste) that is employed as a feedstock for fuel etha-
nol production. The stillage generated in this process is centrifuged to recover
yeast fragments and then neutralized with lime and used for irrigating planta-
tions. In a preliminary analysis of different treatment alternatives, Nguyen (2003)
shows that the irrigation is a valid option, but with the augment of the capacities
of ethanol production facilities, the soil can reach its maximum nutrients load,
thus other options have to be considered. In principle, the stillage from the pro-
cess directly employing starch and the stillage derived from starch waste have the
same advantages and drawbacks.
10.1.2.6 Anaerobic Digestion
The stillage that cannot be used as animal feed and that has high BOD and COD
values can be treated by anaerobic digestion. During this process, the transforma-
tion of the organic matter by a mixed bacterial culture is carried out in such a way
that the BOD is reduced and the resulting sludge can be more easily disposed of,
i.e., it is stabilized. Wilkie et al. (2000) have reviewed the conditions for accom-
plishing the anaerobic digestion of different stillage types under both mesophilic
and thermophilic conditions and have reported the main configurations of the
equipment required by this process. COD reductions of 97% for corn stillage in
an up-flow anaerobic sludge blanket (UASB) reactor, as well as 94% reduction of
the soluble COD of sugarcane stillage, have been achieved. For stillage derived
from wheat starch, some studies at pilot plant scale have shown 89 to 92% reduc-
tions of COD (Nguyen, 2003).
The production of sludge by anaerobic digestion is about 10% lower than the
sludge produced by aerobic digestion. This anaerobic sludge can be used as a feed-
stock for producing components for balanced animal feed (Wilkie et al., 2000).
The effluents from anaerobic digestion contain plant macronutrients (nitrogen,
phosphorous, and potassium), as well as micronutrients (iron, zinc, manganese,
copper, and magnesium), so they could be applied to plantations ensuring an
appropriate dosage. These nutrients should be removed when the liquid efflu-
ents are to be directly discharged into the natural water streams. If they are not
removed, eutrophication problems can arise. These nutrients can be removed
through the cultivation of algae in special ponds containing these effluents. In
general, the stillage treated by anaerobic digestion should undergo color removal
through different methods, including flocculation and coagulation, photovoltaic
removal, or microbial removal (Wilkie et al., 2000). One alternative for degrada-
tion of the organic matter contained in the stillage is the use of aerobic processes
like high-rate oxidation ponds for those cases when low cost lands are available
(Olguín et al., 1995).
10.1.2.7 Composting
The stillage can be employed in composting processes as well. In particular, a
mixture containing the organic fraction of the municipal solid waste (MSW) and
stillage with a 3:1 ratio has been proposed to produce compost. In this case, the
stillage supplies the nutrients needed for the process. The aerobic fermentation
process inherent to the composting can be carried out during 30 to 50 days. Good
results have been reported for this type of stillage treatment (Vaccari et al., 2005).
In a similar way, the by-product from sugarcane cropping can be mixed with the
stillage for their composting with a residence time of 35 days (Goyes and Bolaños,
2005). In Colombia, most of the sugar mills with co-located distilleries use the
stillage, evaporated up to 30% solids, in mixtures with press mud for producing a
solid fertilizer through composting for cane plantations (Gnecco, 2003). The use
of concentrated stillage with 55% solids is also possible for its direct utilization
as a fertilizer or for composting processes. The compost produced from the press
mud, ash from boilers using cane bagasse, and concentrated stillage with 30%
solids can supply a third of the nitrogen and much more phosphorous and potas-
sium required by the sugarcane. In addition, the composting reduces by 50% the
volume of the used materials since the oxidation reactions occurring during the
aerobic solid-state fermentation are exothermal and, therefore, contribute to the
vaporization of moisture contained in the stillage (Gnecco, 2003).
10.1.2.9 Stillage Oxidation
The oxidation of stillage from sugarcane in supercritical water (temperatures
higher than 550°C and pressures above 25 MPa) is chemically equivalent to incin-
eration. When the organic compounds make contact with the supercritical water
in the presence of excess oxygen, the total oxidation reaction prevails allowing
the degradation of the organic matter, which is converted into CO2, water, and
nitrogen. When the oxygen is not in excess, the pyrolysis and hydrolysis reactions
prevail, which can generate some value-added products. The main drawbacks of
this technology are related to the corrosion and presence of insoluble inorganic
salts that generate incrustations in the equipment. Goyes and Bolaños (2005) have
carried out tests for total oxidation of cane stillage using hydrogen peroxide in a
batch reactor achieving a 97% conversion of the organic matter with residence
times lower than 3.5 min. Moreover, a carbonaceous material with an elevated
surface area under partial oxidation conditions of stillage was obtained.
It is estimated that in the fuel ethanol production process from lignocellu-
losic biomass, 15 liters of wastewater from each liter of ethanol produced are
generated. Besides the conventional options for treating this liquid effluent by
concentration–incineration and anaerobic digestion, catalytic oxidation has been
proposed. The feasibility of oxidizing the generated stillage through heteroge-
neous catalysts based on mixed metallic oxides (MnO2/CeO2) within a process
for producing ethanol from timothy grass pretreated by steam explosion has been
demonstrated (Belkacemi et al., 2000).
Effluents
Digestion
Combination Cogeneration
(Power and Steam)
Figure 10.1 Option for effluent treatment analyzed in Case Study 10.1.
pretreatment and detoxification). In addition, the solid residues generated during the
centrifugation of the whole stillage were also studied. These residues are mainly
represented by the lignin nontransformed during the process, residual cellulose and
hemicellulose, and the cell biomass (in this case Zymomonas mobilis fragments).
The configurations were simulated using Aspen Plus® v11.1 applying the general
guideline for simulations described in Chapter 8, Case Study 8.1. To analyze the
biological transformations taking place during the degradation of the organic mat-
ter contained in the stillage, the stoichiometric approach was employed in the
framework of the process simulator. The percentage of organic matter removal
(degradation) was evaluated based on the mass balance results calculated. In addi-
tion, preliminary data on generation of electricity was also taken into account. The
aim of this case study was to investigate different flowsheet configurations and their
combinations for the treatment of the liquid and solid effluents obtained during fuel
ethanol production from lignocellulosic biomass.
The treatment procedures analyzed consider the anaerobic digestion of the
thin stillage, the aerobic digestion of this same stream, the combination of these
two treatments, and the incineration of solid residues in order to obtain electricity.
These options are depicted in Figure 10.1. The anaerobic digestion was analyzed
through the following chemical reactions mediated by a consortium (mixed culture)
of anaerobic bacteria in the corresponding reactor:
C6H12O6 + O2 → 6 CO2 + 6 H 2O
Glucose Oxygen Carbon dioxide Water
Flue gas
Water Pump
HP-water
Boiler Boiler water
Solids
Dryer Burner
Mixer
HP-steam
Methane Turbogenerator
Cyclone
Liquid Decanter w
Power
Anaerobic Ash
Sludge
Anaerobic LP-steam
Digester Clarified
water
Figure 10.2 Effluent treatment for liquid and solid wastes from biomass-to-ethanol
process by anaerobic digestion and co-generation.
system consists of a burner where the combustion reaction is carried out, a cyclone
for removing the ash, a heat exchanger representing the boiler, and a turbogenera-
tor where the electricity is produced employing the high-pressure (HP) steam from
the boiler. The low-pressure (LP) steam can be used to cover the thermal energy
required in the overall ethanol production process. This configuration is schemati-
cally depicted in Figure 10.2.
The second configuration is based on the aerobic digestion of the wastewater.
As in the previous case, the aerobic sludge generated and the solids residue are sent
to the cogeneration system (Figure 10.3). Finally, the third configuration comprises
the combination of anaerobic and aerobic digestion as well as the delivery of the
generated sludge and solids residue to the cogeneration unit, as can be observed in
Figure 10.4.
Flue gas
Water Pump
HP-water
Boiler
Solids
Dryer Burner
Mixer
HP-steam
CO2 Turbogenerator
Liquid Decanter
Cyclone Power
Anaerobic Ash
Sludge
Aerobic LP-steam
Reactor Clarified
Air water
Figure 10.3 Effluent treatment for liquid and solid wastes from biomass-to-ethanol
process by aerobic digestion and co-generation.
Flue gas
Water Pump
HP-water
Boiler
Solids Burner
Mixer
Methane
Liquid HP-steam
CO2
Turbogenerator
Anaerobic w
Sludge Cyclone Power
Anaerobic
Digester Ash
Clarified
water LP-steam
Air Aerobic
Reactor
Figure 10.4 Effluent treatment for liquid and solid wastes from biomass-to-ethanol
process by co-generation and anaerobic digestion followed by aerobic digestion.
The preliminary results obtained are presented in Table 10.1. The scheme involv-
ing the anaerobic digestion of the liquid effluents followed by the aerobic digestion
of the liquid stream exiting the anaerobic digester represents higher removal of the
organic matter contained in these effluents, as suggested in the work of Merrick &
Company (1998). If only one type of digestion is considered, the anaerobic diges-
tion gives better results. In the Table 10.1, the sole incineration of the two types
of effluent streams (solid and liquid) is also considered as a fourth configuration.
In this case, the power regenerated was considered as the comparison standard
Table 10.1
Reduction of Organic Load for Different Effluent Treatment
Configurations
Configuration Configuration Configuration Configuration
Compound Ia IIb IIIc IVd
Glucose/% 40.55 51.89 100.00 N/A
Cellulose/% 100.00 60.00 100.00 N/A
Hemicellulose/% 100.00 70.00 100.00 N/A
Xylose/% 100.00 55.00 100.00 N/A
Ammonia/% 100.00 100.00 100.00 N/A
Acetic acid/% 91.13 100.00 100.00 N/A
Ethanol/% 100.00 50.00 100.00 N/A
Furfural/% 100.00 49.81 100.00 N/A
Power generated/% 94.30 92.02 90.68 100.00
10.2 Environmental Performance of
Fuel Ethanol Production
The assessment of fuel ethanol production processes from an environmental point
of view implies not only the quantification and analysis of the polluting burdens
generated by the conversion technologies, but also the evaluation of the environ-
mental performance of such processes considering their influence on the planet in
terms of the depletion of natural resources, contamination of the ecosystems, and
global environmental impacts generated.
The starting point to satisfy the standard of clean production is the environmen-
tal diagnosis in order to determine the opportunities for preventing or reducing
the contamination sources and the viable alternatives to carry out such reduction.
In the last four decades, the design of processes and the production of chemicals
have experienced a great evolution (Montoya et al., 2006). Initially, reaction and
separation systems were designed and optimized according to only one economic
objective. In the 1970s and 1980s due to the global energy crisis, the utility sys-
tem (thermal energy, power, cooling water) was included in the process design
and optimization procedures. Nowadays, under the clean production scheme, the
environmental objective should be taken into account along with the economic
objective. In this sense, the environmental objective should be to consider not
only the specific environmental impact of the process, but also its impacts in
other steps of its life cycle.
The waste minimization as a means to attain the clean production and con-
tribute to the sustainable development has been extensively studied in the process
industry and in academic circles. The waste minimization incorporates both the
waste reduction in the source and the use of recycling to reduce the amount and
risk of the residues. Nevertheless, the difference between hazardous and nonhaz-
ardous wastes is not considered. In this connection, the minimization of the envi-
ronmental impact is a much stricter norm and, although its scope is similar to the
waste minimization, emphasizes in a higher degree the different impacts of the
chemical species on the environment (Yang and Shi, 2000). The measurement of
the environmental performance of a process can be viewed as a decision problem
involving two levels: screening indices on the process level and environmental
performance indicators on the chemical species level. The latter indicators are
the base of the screening indexes and offer enough flexibility to consider the fate
of all the components involved and their subsequent impacts. Such impacts are
in the framework of a group of categories, i.e., environmental performance indi-
cators show the impact with which the process contributes to a given category.
Among these categories, the following should be highlighted, as reported by Yang
and Shi (2000): energy consumption, resource consumption, greenhouse effect,
ozone depletion, acidification, eutrophication, photochemical smog, human toxic-
ity, ecotoxicity, area used and species diversity, odor, and noise. To consider the
environmental impact of a process, several methodologies have been developed,
such as the life cycle assessment (LCA) and the waste reduction (WAR) algo-
rithm, among others.
10.2.1 WAR Algorithm
In Chapter 2, Table 2.1, the different steps involved in the development of an
industrial process during its life cycle were highlighted. During the conceptual
process design step, the information available is quite limited and uncertain. In
this case, the screening indexes and environmental performance indicators should
be based on simple mass and energy balances. Thus, the environmental indicators
developed by Heinzie et al. (1998) that take into account the different decision
levels during the conceptual design are based on mass losses. In a similar way, the
ecotoxicological models developed by Elliot et al. (1996) are also based in mass
units instead of concentration units (Yang and Shi, 2000).
The waste reduction algorithm originally proposed by Hilaly and Sikdar (1994)
was based on the concept of pollution balance. Currently, the WAR algorithm is
one of the most practical methodologies for assessing the environmental impact
of a process, especially at the conceptual design step. It allows assessing and com-
paring the environmental friendliness of many different industrial processes. The
methodology of the WAR algorithm developed by the National Risk Management
Research Laboratory of the U.S. Environmental Protection Agency (EPA) uses
the concept of potential environmental impact (PEI) and proposes to add a con-
servation relationship over the PEI based on the input and output impact flows
of the process. In this context, the PEI of a given quantity of mass and energy is
understood as the effect that this mass and energy would have on average on the
environment if they were to be discharged into the environment from this process
(Cardona et al., 2004; Young and Cabezas, 1999). This definition implies that the
impact is a quantity still not realized and the PEI has a probabilistic nature. Thus,
the PEI of a chemical process is usually caused by the mass and energy that this
process acquires or emits into the environment. In this way, the WAR algorithm
is a tool to perform the evaluation of the PEI of a process based on the product
streams, outlet wastes, and the feed to the process.
ψk = ∑α ψ
l
l kl (10.1)
where ψkl represents every impact category and αl is the weighting factor, which is
used to emphasize the particular areas of concern. These categories fall into two
general areas of concern— global atmospheric and local toxicological—with four
categories in each area. The four global atmospheric impact categories include
This algorithm was modified in a previous work (Cardona et al., 2004) and
the changes incorporated into the new versions of WARGUI (WAste Reduction
algorithm—Graphical User Interface) software released by the EPA.
The WAR algorithm handles two classes of indexes to assess the environmen-
tal impact of a chemical process. The first class measures the PEI emitted by
the process while the other one measures the PEI generated within the process.
Each class has two main indexes: total output rate of PEI (expressed as PEI per
time unit) and PEI leaving the system per mass of product streams. The first class
characterizes the PEI emitted by the system and is used to answer questions about
the external environmental efficiency of the process, i.e., the ability of the plant
to produce the desired products at a minimum discharge PEI. The second class
of indexes characterizes the PEI generated by the system and its importance lies
in the determination of the internal environmental efficiency of the process, i.e.,
how much PEI is being generated or consumed inside the process. The lower
the values of these indexes, the more environmentally efficient the process is.
Considering the variation of the plant capacities, the index per mass of products
should be employed if the goal is to assess the environmental impact of a process
independent of its production rate, especially if different alternative processes are
to be evaluated (process synthesis).
0.4
0.3
0.2
0.1
0.0
HTPI HTPE TTP ATP GWP ODP PCOP AP TOTAL**
Impact Categories
Corn ethanol/MS Biomass ethanol/AD Biomass ethanol/MS
Figure 10.5 Potential environmental impact (PEI) per mass of product streams for
different ethanol production flowsheets according to the eight impact categories addressed
by the WAR algorithm: HTPI = human toxicity potential by ingestion, HTPE = human
toxicity potential by either inhalation or dermal exposure, TTP = terrestrial toxicity poten-
tial, ATP = aquatic toxicity potential, GWP = global warming potential, ODP = ozone
depletion potential, PCOP = photochemical oxidation or smog formation potential, AP =
acidification or acid-rain potential. Dehydration technologies: AD = azeotropic distilla-
tion, MS = molecular sieves.
kinds of separation technologies for the same feedstock (wood biomass), the utili-
zation of molecular sieves for recovery of the product has slightly lower PEI than
the process involving azeotropic distillation due to the release of relatively small
amounts of the entrainer (in this case, the toxic benzene) into the output streams. In
this sense, the adsorption with molecular sieves is a cleaner separation technology
and it is currently being used in the bioethanol industry.
The two remaining impact categories in the WAR algorithm methodology were
assigned the following weights: TTP 2.5 and ODP 2.5.
The results obtained indicate that the use of sugarcane presents a higher envi-
ronmental friendliness than the use of lignocellulosic biomass. This is explained
by the complexity of the conversion process from biomass to ethanol. For such
conversion, a pretreatment step involving the use of inorganic acids and high pres-
sure is required. In addition, the hydrolysis of cellulose and fermentation of formed
3.00 Cane A
Cane B
PEI/kg Products
2.00
Cane C
1.00 Biomass A
Biomass B
0.00
Process
Figure 10.6 Total output rate of potential environmental impact (PEI) per mass of
products for five process configurations for fuel ethanol production: Cane A = production
of ethanol and fertilizer (concentrated stillage) from sugarcane employing bagasse for
co-generation, Cane B = production of ethanol and fertilizer (concentrated stillage) from
sugarcane without co-generation, Cane C = production of ethanol from sugarcane without
co-generation, Biomass A = production of ethanol from lignocellulosic biomass without
co-generation, Biomass B = production of ethanol from lignocellulosic biomass employ-
ing the recovered lignin for co-generation.
0.25
0.20
Cane A
PEI/kg Products
0.15 Cane B
Cane C
0.10 Biomass A
Biomass B
0.05
0.00
HTPI HTPE TTP ATP GWP ODP PCOP AP
Impact Categories
Figure 10.7 Potential environmental impact (PEI) per mass of product streams for
different ethanol production configurations according to the eight impact categories
considered by the WAR algorithm (the denominations of the categories are presented in
Figure 10.5): Cane A = production of ethanol and fertilizer (concentrated stillage) from
sugarcane employing bagasse for co-generation, Cane B = production of ethanol and fer-
tilizer (concentrated stillage) from sugarcane without co-generation, Cane C = production
of ethanol from sugarcane without co-generation, Biomass A = production of ethanol from
lignocellulosic biomass without co-generation, Biomass B = production of ethanol from
lignocellulosic biomass employing the recovered lignin for cogeneration.
studies using the cereal straw or corn stover as feedstocks for biomass ethanol
have also indicated the environmental benefits, but show problems related to soil
acidification and eutrophication (Gabrielle and Gagnaire, 2008; Kim and Dale,
2005b).
In a similar way, the LCA performed in France by comparing the ethyl tert-
butyl ether (ETBE) obtained from beet ethanol (a partial renewable product) to
the methyl tert-butyl ether (MTBE) from fossil origin showed that the energy
yield of ethanol (1.18) and ETBE (0.93) are higher than the yields of gasoline
(0.74 to 0.80) and MTBE (0.73). Moreover, the ETBE has a lower contribution to
the greenhouse gas effect due to its renewable character, and its use as a gasoline
oxygenate provokes fewer emissions of nonburnt hydrocarbons than in the case of
MTBE. Nevertheless, the ethanol cost for ETBE production in France has been
higher than the cost of gasoline and methanol (a feedstock for MTBE production;
Poitrat, 1999).
under the same physical condition, the equivalent solar energy (emergy) concen-
trated to supply the given input. In this regard, the emergy is a measure of the
global convergence of energy, time, and space needed to make available a given
resource. Bastanioni and Marchettini (1996) analyzed four systems for bioethanol
production and concluded that mankind is far from a sustainable production of
biofuels because it appears that the biomass energy cannot be the basic energy
source in countries having a high level of energy consumption, with arable land
being the major constraint. Other methodologies for environmental assessment of
fuel ethanol production from lignocellulosic biomass have been reported as the
application of the sustainable process index (SPI), a highly aggregated indicator
of the environmental pressure of a process, to the bioenergy assessment model
(BEAM), which have allowed showing that the bioenergy integrated systems are
superior to the fossil fuel systems in terms of their environmental compatibility
(Krotscheck et al., 2000).
Berthiaume et al. (2001) propose a method to quantify the renewability of a
biofuel taking as an example the ethanol production from corn. This method con-
siders the exergy (useful or available energy) as the quantitative measure of the
maximum amount of work that can be obtained from an imbalance between the
physical system and the environment surrounding it. The exergy was accounted
for evaluating the departure from ideal behavior of a system caused by a con-
sumption of nonrenewable resources through the so-called restoration work.
These authors point out that ethanol production is not renewable, though they
emphasize that this evaluation was performed employing many simplifications.
Thus, further research is needed to improve the accurateness of the results and
the validity of the conclusions.
Undoubtedly, the unification of the environmental assessment criteria is
required in such a way that the main aspects of fuel production and utilization,
including both fossil fuels and biofuels, are taken into account. The large number
of consideration, supposition, assumption, approximation, and methodological
approaches limit the use and comparison of the environmental indicators that
have been applied to fuel ethanol production. An example is the contradictory
results about the environmental and energy performance of corn ethanol that
have been published (Patzek et al., 2005; Pimentel, 2003; Shapouri et al., 2003;
Wang et al., 1999). This difficulty imposes some constraints when different pro-
cess alternatives for bioethanol production are being evaluated, especially if the
optimization of an objective function considering not only the technoeconomic
indicators but also the environmental performance indexes of the different tech-
nological configurations proposed is performed.
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311
fermentation. From the resulting culture broth, cell biomass is separated and then
the concentration of ethanol and its dehydration are carried out employing differ-
ent unit operations. The product is the anhydrous ethanol that is the trade form
in which fuel ethanol is utilized as a gasoline oxygenate. This process can utilize
not only the crushed cane but also cane molasses as a feedstock as well as other
streams with high content of fermentable sugars derived from the process for
cane sugar production in sugar mills, as mentioned in Chapter 3, Section 3.1.5 (for
example, a fraction of the clarified syrup). In the latter case, ethanol production
facilities are located next to sugar mills, as in the case of Colombian distilleries.
In the former case, distilleries can operate in an independent way as in Brazil,
where an important number of autonomous (stand-alone) distilleries employing
cane juice are currently in operation.
The overall process for fuel ethanol production from sugarcane in autonomous
distilleries is shown in Figure 11.1. Production process in a distillery co-located
at a sugar mill differs from the autonomous distilleries in the first steps (cleaning,
milling, clarification). After these steps, the process is almost the same, although
it is necessary to condition the molasses before fermentation. Fuel ethanol pro-
duction process from sugar beet is similar to the process from sugarcane. Culture
broth (fermented wort) is extracted from fermenters and sent to centrifuges for
cell biomass separation. The removed microorganisms can be reutilized in the
fermentation step. The obtained wine is directed to the first distillation column
(concentration column) where the ethanol concentration of the wine is increased.
Exhaust gas from fermenters having a fraction of volatilized ethanol is collected
and sent to the scrubber. In this unit, ethanol is dissolved in a water stream, where
a dilute alcoholic solution is obtained that is also sent to the first distillation col-
umn. The resulting ethanol-enriched stream is fed to the second distillation col-
umn (rectification column) whose distillate has a high ethanol concentration (near
Purge Water
Cane
Feedstock Preparation in a molasses
Scrubber
Co-Located Distillery
Conditioning
of molasses
Adsorption
Column I
Cane juice
Cleaning Milling Clarification Fermentation
Bagasse
Wastewater
Rotary wine
Centrifugue
filter Anhydrous
ethanol
Evaporation Concentrate
FEED STOCK PREPARATION INAN Condensates Train
AUTONOMOUS DISTILLERY stillage
Press mud
Figure 11.1 Simplified diagram of fuel ethanol production from sugarcane. The dotted
box represents process steps carried out in an autonomous distillery.
96% by weight). This stream is sent through the dehydration step that can be car-
ried out using different technologies. In the flowsheet depicted in Figure 11.1, it
is indicated that the ethanol dehydration is performed by adsorption with molec-
ular sieves. The bottoms of the concentration column or stillage (vinasses) are
directed to the effluent treatment step where they are generally evaporated for
their concentration.
The fermentation step is central to the overall process for fuel ethanol produc-
tion because it represents the transformation of sugar-containing raw materials
into ethyl alcohol employing yeasts or other ethanol-producing microorganisms.
Ethanolic fermentation technologies of sucrose-based media, mainly cane juice
and cane or beet molasses, can be considered relatively mature, especially if
they are operated batchwise. However, many research efforts are being made
worldwide in order to improve the efficiency of the process. In particular, these
efforts are aimed at increasing conversion of the feedstock and ethanol produc-
tivity, and at reducing production costs, especially energy costs. The features of
ethanolic fermentation of sucrose-containing materials are discussed in Chapter
7, Section 7.1.2.
Process simulation plays a crucial role during the analysis of the technical,
economic, and environmental performance of fuel ethanol production from
sucrose-containing materials. In addition, simulation tools are very significant
when process synthesis procedures are being applied, particularly when the
knowledge-based process synthesis approach is employed (see Chapter 2). Thus,
if the hierarchical decomposition procedure is applied, process simulation can
provide the necessary data on the process behavior in order to select or discard
the different alternatives proposed during each hierarchical level of analysis (see,
for example, the work of Sánchez, 2008).
Sugarcane
Purge Water
7
1
Yeast 8 9 10
2
Sulfuric acid
3 5 Fermentation
gases
Sugar cane
juice
Yeast
recycle
Bagasse
4
Press Culture
6
mud broth
Regenerate
11
Condensated
13
water Wastewater
Flue gases
Ethanol
Water Stillage
Steam
Concentrated stillage
12 Very low (Fertilizer)
Low pressure
steam
High pressure
pressure steam
steam
Figure 11.2 Simplified flowsheet of fuel ethanol production from sugarcane: (1) wash-
ing tank, (2) mill, (3) clarifier, (4) rotary drum, (5) fermenter, (6) centrifuge, (7) ethanol
absorber, (8) concentration column, (9) rectification column, (10) molecular sieves. (11)
evaporator train, (12) combustor, (13) turbogenerator. (From Quintero, J.A., M.I. Montoya,
Ó.J. Sánchez, O.H. Giraldo, and C.A. Cardona. 2008. Energy 33 (3):385–399. Elsevier
Ltd. With permission.)
and sent to the first distillation column. The culture broth containing 8 to 11%
(by weight) ethanol is recovered in a separation step consisting of two distillation
columns. In the first (concentration) column, aqueous solutions of ethanol are con-
centrated up to 63%. In the second (rectification) column, the concentration of the
ethanolic stream reaches a composition near the azeotrope (95.6%). The dehydra-
tion of this ethanol is achieved through adsorption in vapor phase with molecular
sieves by the PSA technology (see Chapter 8, Section 8.2.5). The stream obtained
during the regeneration of molecular sieves containing 70% ethanol is recycled to
the rectification column.
The stillage treatment consists of an evaporation step allowing the generation of
a marketable by-product employed as a fertilizer of cane plantations. If the stillage
is not concentrated or evaporated at a low degree, it can be used for both irriga-
tion and fertilization of sugarcane plantations surrounding the ethanol production
facility. Hence, the environmental impact of the whole process is reduced since the
most important liquid effluent is converted into a value-added product. Condensed
water from evaporators and bottoms from the rectification column are collected and
sent to the wastewater treatment step. Part of this water can be used as feed water
for the co-generation system. Currently, the bagasse obtained is employed in sugar
mills and cane-based distilleries for combined generation of the steam and power
required by the process. For this, co-generation units have to be installed. These
units basically comprise a burner (combustor) for combustion of solid bagasse, a
boiler where the feed water is converted into steam, and a turbogenerator (steam
turbine), where exhausted steam for the process is obtained along with power. The
electricity surplus not consumed by the plant can be sold to the energy network.
The simulation of this process was carried out employing Aspen Plus®. Main
input data employed for process simulation are shown in Table 11.1. The simula-
tion considered a production capacity of about 17,830 kg/h anhydrous ethanol. The
simulation approach described in Chapter 8, Case Study 8.1 and others, was also
applied for this case study. The economic analysis was performed using the Aspen
Icarus Process Evaluator® (Aspen Technology, Inc., Burlington, MA, USA) pack-
age. This analysis was estimated in US dollars for a 10-year period at an annual
interest rate of 16.02% (typical for the Colombian economy), using the straight-
line depreciation method and a 33% income tax. The above mentioned software
estimates the capital costs of process units as well as the operating costs, among
other valuable data, employing the mass and energy balance information provided
by Aspen Plus. In addition, specific information regarding the local conditions was
used for the economic analysis in the framework of the package utilized. In this
way, the net present value (NPV) of the process was determined.
Some simulation results of main streams for the process studied are shown in
Table 11.2. The compositions of the streams calculated by simulation, agree very
well with those reported for commercial processes. The moisture and fiber con-
tents of bagasse and press mud are close to the contents of moisture (bagasse: 50%,
press mud: 75%) and fiber (bagasse: 46%, press mud: 13%) previously reported for
these co-products (ETPI, 2003; Moreira, 2000). The value of generated cane stillage
per liter of ethanol obtained from simulation (11.01 L/L EtOH) is within the range
reported by Wilkie et al. (2000) from experimental data (10 to 20 L/L EtOH). The
stillage composition calculated by simulation is close to the stillage composition
of Brazilian distilleries, as cited by Sheehan and Greenfield (1980). For instance,
the content of organic matter in nonconcentrated stillage is calculated at 26 g/L,
while the corresponding average values in Brazilian distilleries using cane juice
and cane molasses are 19.5 g/L and 63.4 g/L, respectively. In general, streams data
determined through simulation for this processes were compared to available data
of existing production facilities taken from literature and personal communications.
Hence, the simulation results were satisfactorily validated.
The results obtained for ethanol yield in the process analyzed, along with total
operating and capital costs are shown in Table 11.3. For sugarcane in the case of the
most productive zone in Colombia (the Cauca River valley), this value is 123 ton/ha
for a harvesting time of 13 months (CENICAÑA, 2003). The average yield for all
the country, including nontechnified cane crops, reaches 92.7 ton/ha which can be
compared to the average yield of sugarcane in Brazil (73.91 ton/ha) and India (59.05
ton/ha; FAO, 2007), the major sugar producers in the world. The calculated ethanol
production cost (Table 11.4) is higher than the average production cost of Brazilian
ethanol (US$0.198/L in 2007; Xavier, 2007). The price of Brazilian hydrous etha-
nol could be even lower—about US$0.150/L (Macedo and Nogueira, 2005). This
could be explained by the lower cost of the sugarcane in Brazil (about US$0.010/kg
in some producing states). As with Brazil, the high productivity of sugarcane, the
advantageous output/input energy ratio of the cane-to-ethanol process compared to
Table 11.1
Main Process Data for Simulation of Fuel Ethanol Production
from Sugarcane
Feature Value Feature Value
Feedstock Sugarcane Product Fuel ethanol
Composition Sugars 14%a, fiber Composition Ethanol 99.5%, water
13.5%, protein Flow rate 0.5%
0.4%, ash 1.5%, 17,822 kg/h
acids and fats 0.6%,
moisture 70%
Feed flow rate 292,619 kg/h
Co-product 1 Cachaza Co-product 2 Concentrated stillage
Pretreatment Ethanol dehydration
Milling Technology PSA with molecular
sieves
Number of mills 2 Number of units 2
Water flow rate 75,640 kg/h Temperature 116ºC
pH conditioning and Pressure 1.7 atm (adsorption)
sucrose hydrolysis 0.14 atm (desorption)
Agent Dilute H2SO4 Cycle time 10 min
Temperature 65ºC Co-generation
system
Residence time 5 min Solid fuel Cane bagasse
Number of units 1 Solid fuel flow rate 77,623 kg/h
Sucrose conversion 90% Flue gases 176ºC
temperature
Fermentation Temperature of 510ºC
steam from boiler
Bioagent Saccharomyces Pressure of the
cerevisiae exhausted steam
from turbines
Temperature 31ºC High 13 atm
Residence time 48 h Low 4.42 atm
Number of units 16 Very low 1.68 atm
Ethanol content 6% Stillage
concentration
Conventional Number of 5
distillation evaporators
Number of columns 2 Average area of each 2458 m2
evaporation unit
Pressure of columns 1 atm Involved components 21
Ethanol content at 58% Blocks 34
distillate (1st column)
Table 11.1 (Continued)
Main Process Data for Simulation of Fuel Ethanol Production
from Sugarcane
Feature Value Feature Value
Ethanol content at 90% Streams 137
distillate (2nd Substreams in 3
column) streams
Source: Quintero, J.A., M.I. Montoya, Ó.J. Sánchez, O.H. Giraldo, and C.A. Cardona. 2008. Energy
33 (3):385–399. Elsevier Ltd. With permission.
a All the percentages are expressed by weight.
Table 11.2
Flow Rates and Composition of Some Streams for Sugarcane-Based
Ethanol Process
Streams
Press Concentrated
Sugarcane Bagasse mud Purge Ethanol stillage
Compounds wt.% wt.% wt.% wt.% wt.% wt.%
Ethanol — — — 0.02 99.62 —
Sugars 14.00 1.02 — — — 28.84
Fiber 13.50 47.33 16.28 — — —
CO2 — — — 98.25 — —
Protein 0.40 0.12 1.94 — — —
Water 70.00 49.90 67.80 1.67 0.38 44.93
Ash 1.50 1.53 7.30 — — 10.38
Others 0.60 0.10 6.68 0.06 — 15.85
Total flow 292,618.77 77,623.30 20,369.78 17,143.62 17,821.67 24,702.60
rate (kg/h)
Source: Quintero, J.A., M.I. Montoya, Ó.J. Sánchez, O.H. Giraldo, and C.A. Cardona. 2008.
Energy 33 (3):385–399. Elsevier Ltd. With permission.
Table 11.3
Ethanol Yields and Total Capital and Operating Costs
for Fuel Ethanol Production from Two Feedstocks
Item Sugarcane Corn
Ethanol yield (L/ton of feedstock) 77.19 446.51
Ethanol yield (L/[ha*year]) 8,764.00 6,698.00
Total capital costs (thous. US$) 75,613.00a 36,447.50
Total operating costs (thous. US$/year) 36,255.20 70,670.30
Source: Quintero, J.A., M.I. Montoya, Ó.J. Sánchez, O.H. Giraldo, and
C.A. Cardona. 2008. Energy 33 (3):385–399. Elsevier Ltd. With
permission.
a Includes the cost of the co-generation unit.
Table 11.4
Unit Costs of Fuel Ethanol (US$/L of Anhydrous Ethanol)
Corn-Based Cane-Based
Item Process Share/% Process Share/%
Raw materials 0.2911 70.84 0.1611 66.45
Utilities 0.0604 14.70 0.0033 1.35
Operating labor 0.0017 0.41 0.0028 1.14
Maintenance and operating charges 0.0053 1.30 0.0117 4.83
Plant overhead and general and 0.0322 7.84 0.0218 8.97
administrative costs
Depreciation of capital a 0.0202 4.91 0.0418 17.26
Co-products credit –0.0728 — 0.0272 —
Total 0.3381 100.00 0.2153 100.00
Source: Quintero, J.A., M.I. Montoya, Ó.J. Sánchez, O.H. Giraldo, and C.A. Cardona. 2008.
Energy 33 (3):385–399. Elsevier Ltd. With permission.
a Calculated by straight line method.
corn or lignocellulosic biomass, and the low cost of labor force, among other fac-
tors, makes this feedstock the more viable option for new ethanol production facili-
ties. The commercialization of the co-products (e.g., press mud and concentrated
stillage) allows a substantial economic balance improvement. The data presented in
Table 11.5 shows a confirmation of the economic viability of this process.
One of the features of the simulation presented above is the inclusion of the co-
generation unit. The simulation of this unit allows performing a more complete envi-
ronmental evaluation of the overall technological configuration. The co-generation
step employs the combustion of cane bagasse to cover the needs of both thermal and
electric energy required by the whole ethanol production facility. In the following
case study, the specific aspects of the co-generation simulation are presented.
Table 11.5
Some Economic Indicators of Two Processes for Fuel Ethanol
Production Using Different Feedstocks
Economic Indicator Ethanol from Sugarcane Ethanol from Corn
Payout period (years) 4.13 3.85
Net present value (thous. US$) 174,453.00 130,251.00
Internal rate of return (%) 59.48 66.75
Source: Quintero, J.A., M.I. Montoya, Ó.J. Sánchez, O.H. Giraldo, and C.A.
Cardona. 2008. Energy 33 (3):385–399. Elsevier Ltd. With permission.
Table 11.6
Main Atmospheric Emissions from the Co-Generation
System Using Sugarcane Bagasse
Emission
Pollutant kg/ton bagasse kg/ton steam mg/m3 Source
CO2 840.6511 335.5544 159,388 This case study
706.6800 390.0000 — EPA (1993, 1996)
CO 8.1478 3.2523 1,544 This case study
— — 1,526 Gheewala (2005)
NOx 0.7592 0.3031 144 This case study
0.5436 0.3000 — EPA (1993, 1996)
— — 92 Gheewala (2005)
Source: Quintero, J.A., M.I. Montoya, Ó.J. Sánchez, O.H. Giraldo, and C.A.
Cardona. 2008. Energy 33 (3):385–399. Elsevier Ltd. With permission.
kWh/ton cane of electricity surplus (Macedo and Nogueira, 2005). This type of
co-generation unit has been proposed for new Brazilian sugar mills and distilleries,
being an excellent option for new ethanol production facilities in Colombia.
The environmental performance of the technological configuration for fuel
ethanol production from sugarcane was carried out applying the WAR (WAste
Reduction) algorithm by using the software WAR GUI (WAR graphical user inter-
face). For this, the data on mass and energy balances obtained from the simulation
with Aspen Plus were employed. As discussed in Chapter 10, Case Study 10.3,
highest weightings (10.0) were assigned to the four local toxicological categories in
comparison to the weightings of the four global environmental physical categories
(2.5). These assignments were done to give higher importance to the local condi-
tions taking into account that Colombia is an agricultural country with vast hydric
resources and rich biodiversity that should be protected. Results using equally
weighted categories can be found in a previous work (Montoya et al., 2006).
The total output rate of environmental impact for cane ethanol process is shown
in Figure 11.3 and the potential environmental impact generated within the system
is shown in Figure 11.4. The improved environmental performance (in the terms of
potential environmental impact (PEI) leaving the system per mass of products) of
the sugarcane-based process can be explained by the operation of the co-generation
unit. In this unit, one of the process by-products, the bagasse, is employed as renew-
able fuel in order to generate all thermal and mechanical energy required by the
process as well as the power needed. When bagasse is burned, the negative effect of
CO2 released into the atmosphere during its combustion is compensated positively
by the CO2 fixed from the atmosphere during the sugarcane growth. Therefore, the
utilization of bagasse as a solid biofuel does not necessarily imply a net increase of
0.30
Sugarcane Corn
0.25
0.20
PEI/kg Product
0.15
0.10
0.05
0.00
HTPI HTPE TTP ATP GWP ODP PCOP AP TOTAL
Impact Categories
Figure 11.3 Total output rate of environmental impact for the studied processes. The
impact is expressed as the PEI leaving the system per mass of product streams. (From
Quintero, J.A., M.I. Montoya, Ó.J. Sánchez, O.H. Giraldo, and C.A. Cardona. 2008.
Energy 33 (3):385–399. Elsevier Ltd. With permission.)
0.50
Sugarcane Corn
0.00
–0.50
PEI/kg Product
–1.00
–1.50
–2.00
–2.50
–3.00
HTPI HTPE TTP ATP GWP ODP PCOP AP TOTAL
Impact Categories
Figure 11.4 Potential environmental impact generated within the studied processes.
The impact is expressed as the PEI generated within the process per mass of product
streams. (From Quintero, J.A., M.I. Montoya, Ó.J. Sánchez, O.H. Giraldo, and C.A.
Cardona. 2008. Energy 33 (3):385–399. Elsevier Ltd. With permission.)
CO2 in the atmosphere. However, the environmental impact of the involved mass
and energy flows in the whole life cycle is not assessed by the WAR GUI software.
It only performs the evaluation of the potential environmental impact of the streams
leaving or generated during the conversion process. To overcome the problem of
CO2 emissions, the flue gases stream leaving the co-generation unit was analyzed
as if it were free of carbon dioxide. Thus, zero CO2 net emissions were considered
on a life cycle basis.
The commercial utilization of press mud and concentrated stillage indicates the
drastic reduction of two polluting streams generated during the cane-to-ethanol
process. Stillage is a highly contaminating liquid stream due to its high biologi-
cal oxygen demand (BOD; 30,000 to 60,000 mg/L). Several methods have been
proposed for its treatment, but few have been employed. The evaporation of stillage
to obtain a co-product used as a fertilizer for cane plantations is one of the most
popular applications, along with its use for irrigation. However, the properties of
the soil may be affected by the utilization of huge volumes of concentrated stillage.
These effects have not been properly studied within the framework of the life cycle
assessment methodology and further studies are required.
Starch is a high yield feedstock for ethanol production. Glucose is obtained by the
hydrolysis of starch. Then, the glucose solution undergoes fermentation toward
ethanol. From each 100 g of starch, 111 g of glucose theoretically can be obtained,
which implies a stoichiometric ratio of 9:10. The output/input ratio of energy for
Purge
Water
Scrubber
α amylase Glucoamylase Yeast Exhaust
gases
Column II
Adsorption
Column I
Grains Cleaning Saccharifi-
and Cooking Liquefac- Ferment-
grinding tion cation ation
Centrifuge
Wine
Anhydrous
ethanol
Evaporation Concentrated
Condensates
train stillage
Figure 11.5 Simplified diagram for production of fuel ethanol from cereal grains by
dry-milling technology.
corn ethanol is in the range of 1.1 to 1.2 (Prakash et al., 1998; Sánchez and Cardona,
2005). Fuel ethanol production from materials with a high content of starch needs
some additional process steps compared to the process that employs sucrose-based
materials as the feedstock. The process flowsheet comprises a pretreatment step of
the starchy materials to make starch more susceptible to enzymatic hydrolysis. In
this step, known as liquefaction, starch is partially hydrolyzed at a high tempera-
ture. In the following step of saccharification, liquefied starch undergoes a deeper
hydrolysis where fermentable sugars (glucose) are obtained (Figure 11.5). After
glucose fermentation, the process does not significantly differ from that one that
employs materials with a high content of sucrose. Nevertheless, depending on the
specific type of employed starchy feedstock, certain co-products used for animal
feed can be produced during the evaporation of stillage.
When cereals are used as the feedstock for producing fuel ethanol, the raw
material enters the process as grains, which should undergo cleaning and milling.
Either wet-milling or dry-milling processes can carry out grain milling of such
cereals as corn, wheat, and barley. The wet-milling process implies that only the
starch enters fuel ethanol production process, as discussed in Chapter 4, Section
4.2. In this process, all the components of the kernel should be separated prior to
the cooking step. These components represent value-added products that are used
for food and feed. Moreover, part of the produced starch can be deviated to the
production of sweeteners, such as the high fructose corn syrup (HFCS). During
the dry milling of grains, the whole kernel enters the ethanol production line,
which means that all its components are processed along with starch. Nonutilized
components of the kernel are built up in the bottoms of the first distillation col-
umn and are concentrated to form a product utilized as animal feed. In general,
the liquefaction, saccharification, and fermentation steps are the same for both
types of technologies.
The overall production process of bioethanol from corn by the dry-milling
technology includes the breakdown of this polysaccharide to obtain an appropriate
Purge
Water
Scrubber
Corn
Cleaning and
Grinding
α-amylase Glucoamylase Yeasts Exhaust
gas
Column II
Adsorption
Column I
Cooking Liquefaction Saccharification Fermentation
Backset
Wine
Condensates
Centrifuge
Anhydrous
ethanol
Syrup Solids
Drying DDGS
Purge
Water
Corn
Scrubber
Cleaning and
Grinding
Adsorption
Column II
Column I
Cooking Liquefaction SSF
Backset
Condensates Wine
Centrifuge
Anhydrous
ethanol
Syrup Solids
Drying DDGS
thus, the acquisition and utilization of fossil fuels to supply the steam for the pro-
cess are required.
The simulation of this process was carried out using Aspen Plus as well. Main
input data employed for process simulation are shown in Table 11.7. As in the case
of cane ethanol, the simulation used a production capacity of about 17,830 kg/h
anhydrous ethanol. The simulation approach described in Chapter 8, Case Study
8.1 and others was also applied for this case study. Enzymatic hydrolysis and con-
tinuous fermentation processes were simulated based on a stoichiometric approach
that considered the conversion of starch into glucose as well as the transformation
of glucose into cell biomass, ethyl alcohol, and other fermentation by-products. The
economic analysis was performed by using the Aspen Icarus Process Evaluator
package and the same local conditions of Case Study 11.1.
Some simulation results of main streams for this process are shown in Table 11.8.
The compositions of the streams calculated by simulation agree very well with those
reported for commercial processes. The DDGS generally contains 9% moisture and
27 to 32% protein (McAloon et al., 2000). Results of many analyses done during
a five-year period (1997 to 2001) to determine the composition of DDGS obtained
in corn dry-milling ethanol production facilities in the United States (Belyea et al.,
2004) revealed good agreement with the simulation data obtained (see Table 11.8).
The results obtained for ethanol yield in the process analyzed, along with total
operating and capital costs, are shown in Table 11.3. In this regard, the average
5
Glucoamylase 6 7 8
α-amylase Yeast
2 Fermentation
gases
3 4
Condensate Culture broth
Regenerate
Thin stillage
9
11 10 Ethanol
Stillage
Solids
DDGS
12
Figure 11.8 Simplified flowsheet of fuel ethanol production from corn: (1) wash-
ing tank, (2) crusher, (3) liquefaction reactor, (4) SSF reactor, (5) ethanol absorber, (6)
concentration column, (7) rectification column, (8) molecular sieves, (9) first evaporator
train, (10) centrifuge, (11) second evaporator train, (12) dryer. (From Quintero, J.A., M.I.
Montoya, Ó.J. Sánchez, O.H. Giraldo, and C.A. Cardona. 2008. Energy 33 (3):385–399.
Elsevier Ltd. With permission.)
yield of technified corn crop in Colombia is about 5 ton/ha for a harvesting time
of four months (Quintero et al., 2004). This yield is lower than the corn yield in
the United States, the major corn producer in the world. Note from Table 11.3 that
the calculated ethanol yield from corn (in terms of produced ethanol per tonne of
feedstock entering the plant) is greater than that from sugarcane because of the
higher amount of fermentable sugars (glucose) that may be released from the origi-
nal starchy material. However, the annual ethanol yield from each hectare of cul-
tivated corn is 23.6% lower than that for sugarcane. This preliminary fact shows
the comparative advantage of using sugarcane as feedstock for ethanol production
under high-productivity conditions for cane cropping in Colombia.
Total operating costs are significantly higher for ethanol production from corn
than from sugarcane under Colombian conditions (Table 11.3). This is mostly
explained by the feedstock cost, as shown in Table 11.4, where operating costs were
Table 11.7
Main Process Data for Simulation of Fuel Ethanol Production from Corn
Feature Value Feature Value
Feedstock Corn Product Fuel Ethanol
Composition Starch 60.6%a, Composition Ethanol 99.5%, water
cellulose 3.46%, Flow rate 0.5%
hemicellulose 4.6%, 17,837 kg/h
lignin 0.4%,
glucose 8.7%,
protein 2.2%, fatty
acids 3.64%, ash
1.17, moisture
15.5%
Feed flow rate 50,630 kg/h
Co-product DDGS
Pretreatment Ethanol dehydration
Milling Technology PSA with molecular
sieves
Number of mills 2 Number of units 2
Hydrolysis Temperature 116 ºC
(liquefaction)
Bioagent α-amylase Pressure 1.7 atm (adsorption)
0.14 atm (desorption)
Temperature 88ºC Cycle time 10 min
Residence time 5 min DDGS processing
Number of units 6 Number of 2
evaporator trains
Starch conversion 99% Number of 2
evaporators (1st
train)
Simultaneous Number of 2
saccharif. and evaporators (2nd
fermentation train)
Bioagent Glucoamylase and Average area of each 1,186 m2
Saccharomyces evaporation unit
cerevisiae (1st train)
Temperature 33ºC Average area of each 42 m2
evaporation unit
(2nd train)
Residence time 48 h Type of dryer Indirect contact rotary
dryer
Number of units 10
Ethanol percentage 11%
Table 11.7 (Continued)
Main Process Data for Simulation of Fuel Ethanol Production from Corn
Feature Value Feature Value
Feedstock Corn Product Fuel Ethanol
Conventional
distillation
Number of columns 2
Pressure of columns 1 atm Involved components 19
Ethanol content at 63% Blocks 23
distillate (1st column)
Ethanol content at 90% Streams 83
distillate (2nd column) Substreams in 3
streams
Source: Quintero, J.A., M.I. Montoya, Ó.J. Sánchez, O.H. Giraldo, and C.A. Cardona. 2008. Energy
33 (3):385–399. Elsevier Ltd. With permission.
a All the percentages are expressed by weight.
Table 11.8
Flow Rates and Composition of Some Streams for Corn-Based
Ethanol Process
Streams
Compounds Corn (wt.%) Purge (wt.%) Ethanol (wt.%) DDGS (wt.%)
Ethanol — 0.05 99.50 —
Sugars 2.19 — — 1.96
Starch 60.59 — — 0.17
Fiber 8.21 — — 33.21
CO2 — 98.13 — —
Fats 3.64 — — 14.70
Protein 8.69 — — 35.15
Water 15.50 1.81 0.50 9.82
Ash 1.18 — — 4.76
Others — 0.01 — 0.23
Total flow rate (kg/h) 50,629.99 17,247.83 17,836.83 12,483.97
Source: Quintero, J.A., M.I. Montoya, Ó.J. Sánchez, O.H. Giraldo, and C.A. Cardona. 2008.
Energy 33 (3):385–399. Elsevier Ltd. With permission.
disaggregated. In comparison to corn, the greater cane demand for producing the
same amount of ethanol (about six times the grain requirements) is compensated
for by the lower cost of this raw material. In fact, the main part of fuel ethanol
costs corresponds to the feedstock: 66.45% and 70.84% using sugarcane and corn,
respectively. Usually the feedstock cost for Brazilian cane ethanol is about 60% of
the production costs (Xavier, 2007), whereas for corn (mostly transgenic) the cost
is about 63% in the United States (McAloon et al., 2000). These results confirm the
validity of the data obtained by simulation, as well as the assumptions considered
during the economic analysis. Steam and power generation through the combustion
of cane bagasse reduces the utilities cost considerably. This makes a big differ-
ence in cane-to-ethanol processes and justifies the installation and operation of
bagasse combustion systems. On the contrary, a corn-based process requires the
consumption of fossil fuels that negatively affects its operating costs and environ-
mental performance. Total capital costs are lower for the corn process (Table 11.3),
even though it has a more complex configuration involving an additional enzymatic
hydrolysis step. For the cane-based process and due to the higher amount of feed-
stock to be handled, a greater capacity of equipment is required. In addition, the
co-generation system increases the required investment for such types of configura-
tions. Nevertheless, the possibility of selling electricity contributes to offset these
additional expenses.
The production costs structure of one liter of ethanol produced from corn (as
shown in Table 11.4) is comparable to the costs structure estimated by the NREL
for the mature process of ethanol production from corn via dry-milling technology
in the United States. In the latter case, ethanol production costs reach US$0.232
per liter of anhydrous ethanol (McAloon et al., 2000). The main difference in
the production costs are mostly explained by the higher corn prices in Colombia
related to cheaper U.S. corn (0.076 US$/kg). In fact, the utilization of imported
corn from the United States as feedstock for new ethanol production facilities
located on the Colombian Caribbean coast has been proposed by different orga-
nizations including the Colombian government. In any case, the volatility of corn
prices is a crucial factor to be accounted for. Production costs obtained in this case
study are very close to those reported by Macedo and Nogueira (2005) for ethanol
production from milo (a kind of sorghum) in the United States. It should be noted
that co-product (DDGS) sales in corn ethanol production play a significant role in
process sustainability.
The confirmation of the economic viability of the two analyzed processes is
presented in Table 11.5. In relation to their profitability indicators, both processes
are comparable although the production costs for sugarcane are clearly smaller.
Moreover, ethanol from cane offers a higher NPV with a lower internal rate of
return (IRR). Different evaluations simulating changes in the price of the main
feedstock show that the process employing sugarcane is much more stable to
these kinds of variations. Thus, a 71% increase in the price of corn (likely to
occur under Colombian conditions) leads to negative NPV during the lifetime
of the project. In contrast, this same increase in the price of sugarcane (whose
price is much more stable in Colombia) only leads to a 38.7% reduction in NPV
and 28.4% decrease in IRR. These results allow the conclusion that ethanol pro-
duction process from sugarcane represents the best investment possibility under
Colombian conditions.
The four case studies presented above demonstrate the power of the simula-
tion approach employed. In order to obtain a general framework for comparing
different technological configurations for ethanol production from diverse feed-
stocks according to technoeconomic and environmental criteria, the formulation
of an overall comparison criterion is required. This is shown in the following
case study.
AHP Ranking
Qualitative weightings
Normalization Normalization
NPV PEI
Aspen Icarus Environmental
Economic evaluation WAR Algorithm
Process Evaluator Evaluation
Figure 11.9 Analytical hierarchy structure (AHP) employed for the analysis of two
processes for fuel ethanol production.
evaluation software and WAR algorithm, respectively). The indexes (NPV and PEI)
for each process are determined from these evaluations. Alternatively, other eco-
nomic indexes, such as IRR, can be used. The indexes are normalized, so that
they do not exceed a normalization value, and converted to quantitative scores. The
normalization value for each index was calculated as the sum of the index values in
both processes. The economic score of a given process was determined as the ratio
between the NPV of the process and the corresponding normalization value, i.e.,
the sum of the two calculated NPVs. The environmental score was calculated tak-
ing the difference between the corresponding normalization value and the PEI of
the process and dividing the result obtained by the normalization value. The AHP
score of a process design represents the sum of the products of the average process
score for a given attribute and the weighting for that attribute, that is:
where P Ecn is the normalized economic score calculated from the NPV of the two
analyzed processes, and P Env is the normalized environmental score resulting from
the PEI values of the two processes. The qualitative weightings of economic and
environmental attributes were taken as 0.82 and 0.18, respectively. These values are
suggested by Chen et al. (2002) who applied them to several chemical processes
based on the survey carried out by Dechanpanya (1998) on the comparison of eco-
nomic and environmental attributes for a chemical process from several faculty
members and graduate students at Michigan Technological University using the
AHP approach (Hussain et al. 2006).
The results obtained from the integration of the economic and environmental
assessments following the proposed methodological approach are presented in
Table 11.9. From these results, the sugarcane-based process exhibits a higher AHP
score, indicating that it has better performance than the corn-based process when
both economic and environmental criteria are analyzed in a combined manner.
Changes in the evaluation of the AHP when different weightings are selected for
both processes show that the sugarcane-based process will always have a better
Table 11.9
Results of Environmental and Economic Integration of
the Fuel Ethanol Production Process Using Two
Feedstocks
Feedstock NPV/thous. US$ PEcn PEI PEnv AHP
Sugarcane 174,453.00 0.573 0.224 0.567 0.571
Corn 130,251.00 0.427 0.293 0.433 0.429
Source: Quintero, J.A., M.I. Montoya, Ó.J. Sánchez, O.H. Giraldo, and
C.A. Cardona. 2008. Energy 33 (3):385–399. Elsevier Ltd. With
permission.
performance with any value of the economic weighting. When this weighting is
increased (this is equivalent to the reduction of the environmental weighting), the
AHP score will also increase. In contrast, the corn-based process shows slightly
worse performance when the economic attribute has a higher weight. This means
that the economic advantages for the sugarcane process are actually better than
those displayed for the corn scenario. Therefore, assigning weightings for this case
study does not affect the final qualitative result of the combined evaluation within
the AHP framework. Thus, the process that employs sugarcane for producing fuel
ethanol shows better performance.
The procedure proposed to analyze different flowsheet configurations proved to
be a useful methodology for process synthesis and can support the decision making
for further experimental studies at pilot scale and industrial levels. This is a key
issue considering the limited resources for extensive and long-term research in such
countries as Colombia.
conversion (López-Ulibarri and Hall, 1997), considering that cassava flour pro-
duction is simpler and more economic than cassava starch production. However,
it is considered that cassava ethanol would have better economic indicators if
the whole tuber were used as feedstock, especially when small producers are
involved (Sánchez and Cardona, 2008). Fuel ethanol production from whole cas-
sava is equivalent to ethanol production from corn by dry-milling technology.
For this, cassava should be transported as soon as possible from cropping areas
because of its rapid deterioration due to its high moisture content (about 70%).
Hence, this feedstock should be processed within three to four days after its har-
vest. One of the solutions to this problem consists in the use of sun-dried cassava
chips (Sriroth et al., 2007). The farmers send the cassava roots to small chipping
factories where they are peeled and chopped into small pieces. The chips are
sun-dried for two to three days. The final moisture content is about 14% and the
starch content reaches 65%.
The first step of the process in the distillery is the grinding of the dried cas-
sava chips or fresh roots (if a permanent supply is ensured; Sánchez and Cardona,
2008). Milled cassava is mixed with water and undergoes cooking followed by
the liquefaction process (Nguyen et al., 2008). Liquefied slurry is saccharified to
obtain the glucose, which will be assimilated by the yeast during the next fer-
mentation step. The process can be intensified through the SSF as in the case of
corn (Figure 11.10). If fresh roots are employed, a fibrous material is obtained in
the stillage after distillation. This material can be used as an animal feed similar
to the DDGS produced in the corn-based process. The wastewater can be treated
by anaerobic digestion to produce biogas, which can be used to produce steam
and power for the process. Nevertheless, the amount of steam generated is not
enough to cover the needs of the process. Hence, natural gas or other fossil fuel is
required (Dai et al., 2006).
Liquefaction Milling
Distillation Anhydrous
SSF and rectification Dehydration ethanol
CO2 Clarified
Anaerobic liquid
Sedimentation
Sedimentation
digestion
Sludge
Biogas
Thickening
Steam
production
Drying
Dry Sludge
Figure 11.10 Simplified diagram for fuel ethanol production from cassava.
Table 11.10
Comparison of Two Starch-Containing Feedstocks for Fuel Ethanol
Production in a Process Involving the SSF
Mass Flow DDGS
of Produced Ethanol Produced Yield/kg/ Protein
Feedstock/ EtOH/ Yield/L/ton DDGS/ ton Content in
Feedstock kg/h kg/h feedstock kg/h feedstock DDGS/%
Corn 50,630 13,589.76 350.85 12,023.38 237.48 36.59
Cassava 115,755 14,771.96 166.80 4,084.91 35.29* 22.66a
Biomass
P+I HHz Detoxif. P Pentose Ferm. EtOH (a)
LF (Overliming) (Rec. E. coli)
Dilute-acid Hydrous EtOH
Pretreatment Distillation
SF
SSF
C+L EtOH+L
(Rec. K. oxytoce)
Cel (b)
Biomass EtOH
P+I HHz Detoxif. P Dehydration
LF (IE + Overliming) (Mol. Sieves)
Dilute-acid Distillation
Pretreatment
SF C+L SSF Effl. Treatm./ Steam, power
(Rec. Z. mobilus) EtOH+L Cogeneration
Cellulate Prdn.
C+L (T. reesel) Cel+L
(c)
Biomass
L Steam, power
Cogeneration
(d)
Biomass
C+L Cellulase Dehydration EtOH
SF Hydrolysis (Mol. Sieves)
Alkaline Hydr. EtOH
(Ca(OH)2) G Co-Ferm. Distillation
Sol (e)
Sol Sol+L Solvent L L
Recovery Drying
LF
Solvent Hydrous EtOH
Pretreatment Distillation
(Sol: EtOH)
SF C Vacuum SSF
(Candida acido-
Steam thermophilum) EtOH
Explosion
P Pentose Ferm. SCP
(C. utilis)
Figure 11.11 Some proposed flowsheet configurations for ethanol production from
lignocellulosic biomass. (a) Process based on utilization of enteric bacteria (Ingram et al.,
1999). (b) NREL model process (Wooley et al., 1999). (c) Iogen’s process (Tolan, 2002). (d)
Process proposed by Reith et al., (2002). (e) IIT Delhi process (Ghosh and Ghose, 2003).
Main stream components: C = cellulose, L = lignin, G = glucose, P = pentoses, I = inhibi-
tors, Cel = cellulases, EtOH = ethanol, Sol = solvent, SCP = single cell protein. LF = liquid
fraction, SF - solid fraction, HHZ = hemicellulose hydrolyzate, Rec = recombinant, IE
= ion exchange. (From Cardona, C.A., and Ó.J. Sánchez. 2007. Bioresource Technology
98:2415–2457. Elsevier Ltd. With permission.)
for the utilization of lignocellulosic residues of low cost and great availability,
such as corn fiber, were carried out (Schell et al., 2004). The objective of these
tests was the assessment of the operation of the integrated equipments and the
generation of data concerning the process performance. This type of plant allows
the acquisition of valuable experience considering the future implementation of
the industrial process, the same as the feedback of the models utilized during the
design step. In addition, feasibility studies carried out by NREL help industrial
partners make decisions about the potential implementation of these technologies
for fuel ethanol production (Kadam et al., 2000; Mielenz, 1997). Future trends for
costs reduction in the case of the NREL process include more efficient pretreat-
ment of biomass, improvement of specific activity and productivity of cellulases,
the possibility of carrying out the SSCF process at higher temperatures, improve-
ment of recombinant microorganisms for a greater assimilation of all the sugars
released during the pretreatment and hydrolysis processes, and further develop-
ment of co-generation system (Cardona and Sánchez, 2007). Nagle et al. (1999)
proposed an alternative configuration involving a total hydrolysis of yellow poplar
using a three-stage countercurrent dilute-acid process validated at experimental
level. The obtained hydrolyzate is co-fermented by the recombinant strain of Z.
mobilis. In this case, the lignin is recovered prior to the fermentation. Aspen
Plus was utilized for generating the needed information to evaluate the economic
performance of the whole flowsheet configuration through a spreadsheet model.
Optimized values of the key process variables obtained from the simulation are
utilized as target values for bench-scale research to design an advanced two-stage
engineering-scale reactor for a dilute-acid hydrolysis process.
Some commercial firms have also invested funds in the development of an etha-
nol production process employing the lignocellulosic biomass. Iogen Corporation
(Ottawa, Canada) developed an SHF process comprising a dilute-acid-catalyzed
steam explosion and the removal of the major part of the acetic acid released
during the pretreatment, the use of S. cerevisiae as a fermenting organism, distil-
lation of broth, ethanol dehydration, and disposal of stillage in landfill (Tolan,
2002). Later modifications involve the co-fermentation of both hexoses and pen-
toses using genetically modified strains of microorganisms, such as yeasts or bac-
teria (Figure 11.11c). Using the recombinant Z. mobilis strain patented by NREL,
Lawford and Rousseau (2003) tested two configurations for ethanol production
using the conceptual design based on SHF developed by Iogen. These authors
demonstrated that a configuration involving the continuous pentose fermentation
using the recombinant Z. mobilis strain, and the separate enzymatic hydrolysis
followed by continuous glucose fermentation using a wild-type strain of Z. mobi-
lis is the most appropriate in comparison to the use of the co-fermentation process
after the enzymatic hydrolysis or the use of an industrial yeast strain during the
glucose fermentation (Cardona and Sánchez, 2007).
Reith et al. (2002) have reviewed different processes for production of biomass
ethanol and concluded that verge grass, willow tops, and wheat milling residues
could be potential feedstock for fuel ethanol production under the regulations of
the Netherlands. These authors constructed a model using Microsoft™ Excel™
pyrolysis, levoglucosan hydrolysis, and the use of two cultures, S. cerevisiae and P.
stipitis, to ferment hexoses and pentoses, respectively. These authors also analyzed
the SSF process of dilute-acid pretreated feedstock that comprises the pentose fer-
mentation by recombinant E. coli for xylose fermentation, and the SHF process
of dilute-acid pretreated feedstock using a strain of C. shehatae for hexose and
pentose fermentation. The evaluation indicates that the cost of the fast pyrolysis
process is comparable to the other two processes in terms of capital costs, operat-
ing costs, and overall ethanol production costs (Cardona and Sánchez, 2007).
Due to the high costs of the feedstocks accounting for more than 20% in the
case of the lignocellulosic biomass (Kaylen et al., 2000), the optimization of cel-
lulose conversion is of great importance, especially if it is accompanied with the
appropriate handling and utilization of all process streams. Although many related
works can be found, the tendency is the optimization of separate process units. This
implies that the integration of such separately studied units optimized at different
scales does not always provide the correct information on the global process. This
situation is particularly important in the case of the integration of the pretreatment
step with the biological transformations. De Bari et al. (2002) undertook this prob-
lem emphasizing the scale-up features and the potential of produced by-products in
the case of steam-exploded aspen wood chips. The pretreatment step was carried
out in a continuous steam explosion pilot plant fed with 0.15 ton/h of dry matter that
was coupled with the extraction step in order to separate the lignin and the hemicel-
lulose and carry out the detoxification. The subsequent conversion to ethanol was
made by SSF. The process was completed with a packed distillation column with
a maximum reboiler capacity of 150 L working batch-wise. The experimentation
allowed the definition of the best combinations of operation parameters, the selec-
tion of the best detoxification procedure, the determination of yields and operation
conditions of SSF, the analysis of the distillation for its conversion to hydrogen or
ethanol, and the determination of the chemical oxygen demand (COD) of the liquid
stream from the distillation step. However, this work does not report if any analysis
of the process was carried out from the viewpoint of thermodynamic and kinetics
fundamentals of the studied system, or if process synthesis procedures were used
for the definition of the selected configuration of the process. These tools may help
predict the behavior of experimental systems. Similarly, pilot-plant data can pro-
vide feedback to the mathematical models used for the analysis of the system, the
same as for the study of its stability and operability. For this point, the complemen-
tation with simulation tools is invaluable (Cardona and Sánchez, 2007).
In general, it is thought that reductions in processing or conversion costs of
lignocellulosic biomass offer the greatest potential for making biobased products
like ethanol competitive in the market place in comparison to oil-based products
for which high raw material costs are characteristic (Dale, 1999). Therefore, the
fundamental research on the development of cost effective processes for biomass
processing represents the key for attaining the mentioned competitiveness. Lynd
et al. (1999) argue that oil refineries are unlikely to have significant economies
of scale advantages in comparison with the expected mature biomass refineries.
In this way, the challenges associated with the biomass conversion are related to
the recalcitrance of cellulosic biomass (conversion into reactive products like fer-
mentable sugars) and to the product diversification (conversion of reactive inter-
mediates into valuable products; Cardona and Sánchez, 2007).
In general, process synthesis procedures can be significantly enhanced using
process simulation packages. These simulators have allowed the analyzing of sev-
eral technological options and the gaining of insight about the process improve-
ments (Cardona and Sánchez, 2007). Almost all the approaches for carrying out
process synthesis can rely on simulation tools to evaluate different process alter-
natives. This is illustrated in the following case study.
Steam CO2
NH3
Biomass
H2SO4 C. shehatae
4
Water
1 3
2 Liquid
Cellulases fraction
Solid 7
fraction
5
6 8
Steam
Cond.
S. cerevisiae Cond.
9 Cond.
Syrup
Lignin
Figure 11.12 Simplified flowsheet for fuel ethanol production from lignocellulosic
biomass (base case): (1) pretreatment reactor, (2) rotary filter, (3) ionic exchange, (4)
pentose fermentation, (5) enzymatic hydrolysis, (6) hexose fermentation, (7) separation
and dehydration of ethanol by azeotropic distillation, (8) evaporation train for effluent
treatment, (9) centrifuge. S.S. = secondary steam, Cond. = condensate. (Adapted from
Cardona, C.A., and Ó.J. Sánchez. 2006. Energy 31:2447–2459.)
Source: Cardona, C.A., and Ó.J. Sánchez. 2006. Energy 31:2447–2459. Elsevier Ltd. With permission.
Note: DA = dilute acid pretreatment; DLF = deviation of liquid fraction of hemicellulose hydrolyzate for pentose fermentation;
Det = ion exchange detoxification; EH = enzymatic hydrolysis; HF = hexose fermentation; PF = pentose fermentation;
SSF = simultaneous saccharification and fermentation; SSCF = simultaneous saccharification and co-fermentation; Dist =
conventional distillation; Az = azeotropic distillation; Perv =- pervaporation; Ev = stillage evaporation; RW1 = recycling
of water for washing hemicellulose hydrolyzate; RW2 = recycling of water for washing hemicellulose hydrolyzate and for
pretreatment reactor. The symbol “√” indicates that a given step is included in the configuration.
Table 11.12
Comparison of Simulated Configurations according to Their
Energy Consumption
Ethanol Yield Unit Energy Costs Energy Costs
Flowsheet Variant (L/dry wood ton) (MJ/L EtOH) (% of the base case)
Base Case 246.67 34.84 100.00
Configuration 1 262.68 33.12 95.06
Configuration 2 297.70 28.56 81.98
Configuration 3 300.18 27.83 79.87
Configuration 4 302.14 28.37 81.43
Configuration 5 305.34 27.84 79.92
Configuration 6 308.03 26.84 77.05
Source: Modified from Cardona, C.A., and Ó.J. Sánchez. 2006. Energy 31:2447–2459.
Elsevier Ltd.
Recycled Water
for washing
Steam
NH3
Biomass
H2SO4
1 3
2 Liquid
5
Cellulases CO2 fraction
Solid
fraction
Stillage Bottoms Anhydrous Waste-
4 ethanol water
Z. mobilis 6
Steam
Cond.
7 Cond.
Syrup
Figure 11.13 Simplified flowsheet for fuel ethanol production from lignocellulosic
biomass (configuration 5): (1) pretreatment reactor, (2) rotary filter, (3) ionic exchange,
(4) SSCF bioreactor, (5) separation and dehydration of ethanol by azeotropic distilla-
tion, (6) evaporation train for effluent treatment, (7) centrifuge. S.S. = secondary steam,
Cond. = condensate. (Adapted from Cardona, C.A., and Ó.J. Sánchez. 2006. Energy
31:2447–2459.)
preliminary estimation of the energy balance for the ethanol production process
from lignocellulosic biomass was carried out. To this end, the information obtained
during the simulation of the best flowsheet configurations was used (see previous
case study), as well as literature data on biomass handling and transportation costs,
in order to take into account the whole life cycle of the fuel.
The simulation results for the configurations with the best energy perfor-
mance were utilized. In particular, configuration 5 of the previous case study
(see Figure 11.13) was assessed from the point of view of its energy balance. The
production of bioethanol according to the simulation of given configuration was
about 615,000 L EtOH/d. For this analysis, the energy gain in the effluent treatment
step was estimated. The nonfermentable component of biomass, the lignin that is
recovered from centrifuge and sent to the boiler, has an average energy value of
25.4 MJ/kg. The different liquid effluents contain water, minerals, and residual
materials. These liquid streams have a high biological oxygen demand and must be
treated before discharge. Anaerobic digestion is generally carried out for reducing
the organic matter content of the wastewater and releasing biogas. It is estimated
that from 1 L of wastewater can be generated approximately 35 L of biogas. The
biogas, containing about 60% methane and having an approximate calorific value
of 20 to 24 MJ/m3, is fed directly into the boilers for co-generation of both thermal
and electric energy (Prakash et al., 1998). The collected wastewater corresponded
to the effluent streams from the ion exchange used for inhibitor removal during the
detoxification step, the aqueous stream from the bottoms of the fourth distillation
column during the dehydration step (for the case of azeotropic distillation), the
concentrated stream from the evaporators with a high solid content (syrup), and part
of the condensates from evaporation step that was not recycled to the pretreatment
reactor. The simulation provided the amount of produced lignin and wastewater
mass flow rates (28,969 kg/h and 207.7 m3/h, respectively). In this way, the thermal
energy released during the burning of lignin and biogas covers all the requirements
of steam for the process leading to a net thermal energy consumption equal to zero,
as shown in Table 11.13. The amount of electricity co-generated by the process in
the boiler can be estimated from published data (Wang et al., 1999; Wooley et al.,
1999). According to Wang et al., a conservative value of electricity credit should
be 50% of the data reported. Thus, these considerations indicate that 0.225 kWh/L
EtOH of surplus power are produced in the process from biomass. This surplus can
be sold to the grid for balancing the energy costs. The values of recovered energy
in the effluent treatment step are given in Table 11.13.
The presented results demonstrated that the thermal energy required for the
production of biomass ethanol could be offset by the energy carriers generated or
released in the same process (lignin, biogas). Because the combustion of ethanol
releases 21.2 MJ/L EtOH, a NEV for ethanol produced from lignocellulosic bio-
mass of 19.83 to 21.11 MJ/L EtOH was calculated. For the estimation of energy
input needed for ethanol production from lignocellulosic biomass, literature data on
biomass handling and transportation costs were included for considering the entire
life cycle of this biofuel (California Energy Commission, 2001; Wang et al., 1999).
These costs are low compared with corn ethanol because of the nature of waste with
biomass that does not require high energy inputs on fertilizer production, among
other factors. The calculated NEV can be compared with those for corn and sug-
arcane ethanol (see Table 11.13), and for cellulosic ethanol from woody biomass
estimated by Wang et al. (1999) at about 20.9 MJ/L EtOH. Consequently, the use
Table 11.13
Energy Allocation for the Production of Biomass Ethanol and Comparison
with Other Feedstocks according to Their Net Energy Values (NEV)
Energy Energy
Consumption Recovery
Step (MJ/L EtOH) (MJ/L EtOH) Reference
Conversion to ethanol in plant 24.30
Pretreatment and SSCF 4.23
Distillation and dehydration 9.77
Evaporation 7.58
Effluent treatment 2.72
Released biogas 6.36
Burned lignin 28.05
Electricity credit 0.82 Wang et al. (1999)
Net thermal energy consumption in 0.00
plant
Feedstock handling 0.86– 1.06 California Energy
Commission (2006)
Wang et al. (1999)
Transportation 0.05– 1.13 California Energy
Commission (2006)
Wang et al. (1999)
Total 0.91– 2.19 0.82
Energy use for ethanol production 0.09– 1.37
from biomass, MJ/L
Energy value of ethanol, MJ/L 21.20 Prakash et al. (1998)
NEV of biomass ethanol, MJ/L 19.83– 21.11 This case study
NEV of corn ethanol, MJ/L 5.57–6.99 Wang et al. (1999)
NEV of sugarcane ethanol, MJ/L 11.39 Prakash et al. (1998)
Source: Modified from Cardona, C.A., and Ó.J. Sánchez. 2006. Energy 31:2447–2459. Elsevier Ltd.
of biomass ethanol could improve the energy balance of the process and even have
environmental benefits because of the reduction in the process requirements of a
nonrenewable sources of energy, such as oil and natural gas.
production of fuel ethanol has mostly been undertaken using the approach based
on the present knowledge. The other main approach is the optimization-based
process synthesis that relies on the use of optimization for identifying the best
configuration. For this, the definition of a superstructure, which considers a sig-
nificant amount of variations in the topology of technological configurations of a
given process, is required. The evaluation and definition of the best technological
flowsheet are carried out through tools such as mixed-integer nonlinear program-
ming (MINLP). The advantages and drawbacks of this strategy were disclosed in
Chapter 2, Section 2.3.
Several cost-effective flowsheet configurations for the production of fuel etha-
nol from renewable resources like biomass have been reported in the literature.
Most of the proposed flowsheets have been defined using different heuristic rules
and knowledge-based rules, and have involved the use of such tools as commercial
process simulators. However, a cost-effective flowsheet for bioethanol production
utilizing an optimization-based approach has not been found in the literature.
In the following case study, an optimization-based strategy was implemented
in order to preliminarily synthesize several technological schemas for ethanol
production from lignocellulosic biomass employing a net revenue function as a
comparison criterion.
SSCF
Solvent
Pretreated SSF
Anhydrous
Biomass Wine Ethanol
Water
SHF
Wastewater
taken into account, the model reported by Leksawasdi et al. (2001) was used (see
Section 7.2.2). For the calculation of distillation units, the Fenske–Underwood–
Gilliland (FUG) method was utilized considering the presence of binary azeo-
tropes in the system ethanol–water. The separation section of the process, used to
generate 99.5% pure ethanol, consisted of distillation units alone. As there was an
azeotrope formed by water and ethanol, an extractive distillation step was used with
ethylene glycol as the solvent.
The objective function used, in this case, is net revenue defined as the value of
the ethanol produced minus the annualized cost of the process, which is a function
of both capital and operating costs. For the continuous bioreactors, operating and
capital costs are directly related to the residence time. The capital costs of distilla-
tion units are related to the vapor velocity inside the columns and to the number of
stages, and the operating costs are linked to the energy consumption (mainly heat
duty). The problem posed to Jacaranda consists of a superstructure, which is shown
in Figure 11.14. The reaction section has a choice of three paths, the SSF reactor,
the SSCF reactor, and the combination of cellulose hydrolysis followed by hexose
fermentation (SHF). The separation section consists of three distillation steps: con-
centration column, extractive column, and recovery column with a recycle of the
solvent to the extractive column. The superstructure is the basis for an MINLP
model. This model has some characteristics that make it difficult to solve, such as
the physical properties models used (NRTL [nonrandom two-liquid model] in this
case) and the equations for the concentrations in the reactors as a function of resi-
dence time. These are present in the optimization problem as equality constraints
and are difficult to satisfy. Furthermore, the use of different hot and cold utilities
was allowed to meet the heating and cooling demands of any process alternative.
Using discrete utilities means that the objective function is discontinuous even as a
function of only the real valued variables. Furthermore, the capital cost function for
the distillation units uses integer values for the number of stages determined by the
FUG procedure, also leading to discontinuities in the objective function. The result
is that the overall optimization problem is not solvable using standard mathematical
programming approaches.
Jacaranda provides access to a number of optimization procedures including
direct search methods (Kelley, 1999) and stochastic methods, such as genetic algo-
rithms (Goldberg, 1989) and simulated annealing (van Laarhoven and Aarts, 1987).
In this case study, it was decided to use the genetic algorithm (GA) approach. The
GA uses a replacement policy for the population at each generation, with an elite
size of 1, a mutation rate of 10%, a crossover rate of 70%, and a roulette wheel
selection procedure. The fitness function is based on the objective function value
directly with infeasible solutions discarded if they arise (which they do with a fre-
quency of approximately 5 to 6%).
For this first attempt at automated design for the production of ethanol from
biomass, the number of degrees of freedom was limited. Specifically, the residence
times of each reactor and the top and bottom key component recoveries in each
distillation column were selected as the manipulating variables. Therefore, four
residence time variables and six recovery variables were manipulated. The super-
structure makes use of two binary variables for identifying the path taken through
the reaction section of the process.
The results obtained identify the SSCF configuration as the best performing for
the given process. This is reasonable given the high degree of integration achieved
with this configuration, which makes possible the immediate consumption of
the glucose formed during the cellulose hydrolysis. In this way, the inhibition of
cellulose-degrading enzymes (cellulases) is avoided. In addition, the utilization of
xylose allows an increase in the content of fermentation sugars and, therefore, in
the overall amount of produced ethanol. This enhanced utilization of the feedstock
is not characteristic for the SSF process. The SHF option implies the utilization of
an additional bioreactor (the enzymatic hydrolysis and the fermentation are car-
ried out in different units), which involves the increase in the capital costs for this
configuration. Jacaranda allowed the determination of the values of the operating
parameters corresponding to the separation section. In particular, the make-up of
ethylene glycol and the recycle stream flow rate are determined automatically.
Early results demonstrate that the genetic algorithm used by Jacaranda handles
the complexity of the problem design robustly with respect to the numerical diffi-
culties that may arise. The solutions obtained show variability in the technological
option. From 10 different runs, three of the solutions corresponded to SSCF con-
figurations (two of them with the best values of the objective function), six solutions
to the SSF process, and one solution to the SHF configuration.
Undoubtedly, the development of this approach will make possible the synthesis
of technological flowsheets considering the structure of the system on a mathemati-
cal programming basis. The complementation with tools of a knowledge-based
approach will allow gaining a deeper insight of the overall process needed for the
synthesis of technological configurations with increased performance.
generation, and cooling water. Pinch technology is one of the most widely applied
approaches for heat integration in the process industry, especially in the petro-
chemical industry. This technology provides the necessary tools for design of the
heat exchanger networks including plant utilities. During preliminary design of
the heat exchange network, pinch technology allows one to obtain the best values
of many process parameters as the type of utilities and their specifications.
Pinch technology has been utilized for the design of heat exchanger networks
(HEN) during ethanol production. For the case of ethyl alcohol production from
molasses, a process flowsheet was simulated and optimized by heat integration
emphasizing the separation step by distillation (Sobočan and Glavič, 2000). The
simulation was made by shortcut and rigorous methods in order to perform the
heat integration. For ethanol concentrations up to 95.7% by weight, the optimal
configuration corresponded to one single column and not two, as had been pro-
posed. This work demonstrates the usefulness of heat integration since the optimal
design showed a 27% reduction in the total costs (Cardona and Sánchez, 2007).
140.0
Hot utilities = 200.7 mill kcal/h
120.0
93.4°C
100.0
Temperature, °C
80.0
88.4°C
60.0
40.0
20.0
Cold utilities = 89.1 mill kcal/h
0.0
0.0 100.0 200.0 300.0 400.0
Enthalpy, mill kcal/h
Figure 11.15 Representation of the heat balance of the process through hot and cold
composite curves for a minimum temperature difference of 5ºC. Minimum approxima-
tion of the curves corresponds to the pinch. Upper curve represents the hot streams; lower
curve represents the cold streams.
into two substreams. These two substreams are organized in such a way that they
transfer heat to the second effect of evaporation and to the heat exchanger utilized
for preheating the evaporated liquid exiting this second effect which is sent to the
third effect of evaporation. This configuration contrasts with the base case configu-
ration where this stream is condensed and sent as a distillate to the second distilla-
tion column (rectification column) without taking advantage of its caloric energy.
Applying the described procedure, the energy saving of the new HEN was
determined compared to the original network for the studied process steps. This
information allowed quantifying the economic benefits that could be obtained if
the defined HENs by means of pinch analysis were implemented. For instance, the
external energy supplied to the process by the hot utilities was reduced by 22.8%
for a minimum temperature difference of 5ºC. The achieved energy recovery is
75.5% of the maximum possible energy recovery calculated in the targeting step
(Grisales et al., 2005).
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and Bioenergy 19:63–102.
Wooley, R., M. Ruth, J. Sheehan, K. Ibsen, H. Majdeski, and A. Galvez. 1999. Lignocellulosic
biomass to ethanol process design and economics utilizing co-current dilute acid pre-
hydrolysis and enzymatic hydrolysis. Current and futuristic scenarios. Technical Report
NREL/TP-580-26157, National Renewable Energy Laboratory, Washington, D.C.
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biofuels is not often regulated by the government, being considered the market
law as the natural judge for this kind of competition. Different scenarios must be
analyzed depending on the type of feedstock and participation of the country in
the supply chain (producer or consumer)
Table 12.1
Use of Corn Produced in the United States from
September 2007 to August 2008
Description Tonnes of Corn *1000 Share/%
High fructose corn syrup (HFCS) 17.278 3.76
Glucose syrup and dextrose 8.302 1.81
Corn starch 9.225 2.01
Fuel ethanol 106.639 23.21
Beverage ethanol 4.771 1.04
Total other food uses and export 313.242 68.17
Total corn production 459.459 100
as livestock feed. DDGs are the high protein feed produced through distilling,
vaporizing, and drying after fermentation in alcohol production from corn. DDGs
contain abundant amino acid, citrine, and diversiform minerals, which are ben-
eficial to the growth of the animals. Countries in Europe (especially Ireland),
Mexico, Taiwan, Indonesia, Venezuela, Malaysia, and Israel are today importers
of DDGs for animal feeding. Therefore, any change in the actual protectionist
policies of the United States for corn and ethanol production could drastically
affect the price of different food products inside and outside this country.
Table 12.2
Use of Sugarcane Produced in Colombia 2006
Cropped land with cane for sugar-cakes or loaves/ha 340,000
Cropped land with cane for sugar or ethanol/ha 200,218
For sugar production/ha 170,218
For ethanol production/ha 30,000
Sugar production/ton 2,356,617
Sugar consumption/ton 1,503,561
Sugar exports/ton 841,237
Fuel ethanol production/L 268,456,000
Fuel ethanol production in Colombia in 2008 rose 400 million liters, but the
country expects to produce 1 billion liters of ethanol per year by 2010, more than
doubling the current output, and the country plans to have enough production by
the end of the year for export. It is believed that the U.S. Congress will approve
the proposed U.S.–Colombia Free Trade Agreement, which will allow Colombia
to permanently ship its ethanol surplus to the United States duty free and not be
subjected to any quotas. The Colombian government believes that agricultural
exports and food security would not be affected by expanding ethanol output
because the cane and other ethanol feedstock for future production will come
from new crops and unused land.
In Colombia today, the food and bioethanol competition based on cane use is
not an important issue; however, in the near future, it could be an important topic
of discussion. The country uses 340,000 hectares (Table 12.2) with low produc-
tivity (30 to 80 ton/ha). The sugar is handcrafted and prepared as brown blocks
rather than as a crystalline powder, by pouring sugar and molasses together into
molds and allowing the mixture to dry. This results in sugar cakes or loaves called
in Colombia panela (jaggery or gur in India). This product is not important on the
international market, but has a very important internal market, as high nutritional
raw material for national beverages. The possibility of using part of the existing
cane hectares for ethanol instead of panela could be a catastrophic scenario for
the food security in Colombia.
Table 12.3
Use of Sugar Cane Produced in Brazil 2007
Cropped land with cane for sugar and other products/ha 7,680,000
Cropped land with cane for ethanol/ha 3,240,000
Sugar production/ton 33,400,000
Sugar consumption/ton 11,950,000
Sugar exports/ton 21,450,000
Fuel ethanol production/L 26,236,000,000
Fuel ethanol export/L 5,320,000,000
from burning the sugarcane trash and bagasse. Today, in Latin America, Brazil is
a major producer (Table 12.3) extending its expertise to other countries, includ-
ing technology and investments. Sugarcane in Brazil has a life cycle of 12 to 18
months and yields a range of 50 to 130 ton/ha.
Brazil is also the world’s largest consumer of sugar, with per capita consump-
tion around 55 kg/year, just beating out Mexico and the United States. But, the
reality today in Brazil is that sugarcane bioethanol production, as in other coun-
tries with available land, has little effect on food production. This is explained
by the fact that there is enough capacity for supporting new requirements in tool
or expanded agricultural activities during the coming years. Another important
fact to be considered is that today Brazil is the second largest producer of fuel
ethanol in the world and simultaneously one of the largest food suppliers in the
international market.
country can expect 90% probability of receiving slightly higher than 750 mm of
rainfall and only about 3% can expect more than 1,250 mm.
The yields and technology for sugarcane growing are very low. Consequently,
the feedstock prices are very high. The production of ethanol in Tanzania from
sugarcane juice or molasses can be economically competitive with global produc-
tion once the costs of feedstock, namely, sugarcane, are reduced by 70 to 80% of
the current cost (Cardona et al., 2009).
Actually, this country is under very serious analysis by FAO (a BEFS project
with the participation of the authors of this book) regarding the biofuels potential
and food security risks. Some considerations about this country will be discussed
in detail later in this chapter.
of ethanol, followed by wheat straw. In general, the total volume of energy from
agricultural residues is estimated at 12 EJ (ExaJoule = 1018 J), as shown in Hall
et al. (1993).
for human consumption” materials into highly valued food protein contained in
meat, milk, and eggs. From this point of view, agricultural residues do not repre-
sent a waste stream, but an important source for the food production chain. In the
case of using lignocellulosic residues (actually used as livestock food) for non-
feed purposes, adaptations must be developed in the food system to compensate
for protein losses, e.g., by growing beans or supplementary livestock feed crops
(Nonhebel, 2007). The author of this work concluded that land requirements for
such adaptations are substantial and larger than the area needed for energy crops
that produce equivalent amounts of energy. Thus, from a land-use perspective,
using the suitable residues for livestock feed while generating bioenergy from
dedicated energy crops is the most preferable option. This result, however, is a
contradiction for those who consider total biomass availability as the way of solv-
ing competition between food and biofuels.
Table 12.4
Some Biotechnology Improvements in Bioethanol Production
Contributing to Food Security
Case Improvement Effect on Food Security
Bioethanol production from Genetic modified plants could Land is used more efficiently
cereals, lignocellulosics, and reach higher productivities for bioethanol crops; food
sugarcane is limited by the per hectare including the crops are then less affected.
maximal weight yield per raising of starch, celluloses
hectare. or sugars content.
Second generation bioethanol Lignin could be partially More economic technology
from cultivated lignocellulosic replaced by transgenically could be increased use of
crops or residues requires reducing or modifying lignin residues instead of food crops.
pretreatment that uses heat content and upregulating
and acid to remove lignin. cellulose biosynthesis.
prices between 2000 and 2007 (Rosegrant, 2008). The impact was 39% of the
real increase in maize prices.
However, these estimations can not be very accurate if the complexity of the
markets and the different interactions between parameters affecting the price of
crops are not scientifically studied in detail. The key question to answer is: Why
small or large farmers can choose to grow crops for biofuels instead of food?
Many challengers would say that it is not a business for farmers, and only govern-
ment subsidies are the reason these projects can exist.
The choice now faced by farmers is between two alternatives. They can choose
either to produce energy crops or to do nothing at all if the actual crop they have is
profitable. However, profits in biofuels depend on how many hectares will be used
for bioethanol feedstock. Usually sugarcane in South America and wheat and
sugar beet in Europe require more than 10 hectares to be profitable depending on
the prices in their annual contracts. Small-scale producers below 10 hectares can
make a profit only when they belong to strong cooperatives or associations. On
the set-aside land, farmers can grow bioethanol crops for a supplementary income
in small-size plantations.
In the case of Africa where food security plays a key role, increased demand
for biofuels is a positive development for African farmers. They have been getting
paid less and less for their products, but now prices for farm products are on the
rise, and farmers’ incomes are rising. After years of suffering from falling sugar
prices, African farmers are finally seeing prices on the upswing due to increased
demand for sugarcane ethanol, which in turn makes it more profitable to grow
the crop. Countries, such as India, Mexico, and the Sudan, are world produc-
ers of sweet sorghum and they see the opportunity for farmers in biofuels. This
crop provides food, livestock feed, and biofuel. It grows in dry conditions; toler-
ates heat, salt, and waterlogging; and provides a steady income for poor farmers.
To produce ethanol, the sorghum stalks are crushed to yield sweet juice that is
fermented. But that grain can also be used for food or for chicken and cattle feed.
The grain, just in case of market fluctuations, is a source of starch that can be used
for bioethanol. This integral use of the crop gives stability to the farmers, which
makes the business more attractive for combined production of raw materials for
food and ethanol.
But one of the more important driving forces in farmer incomes from bioetha-
nol crops is the price of oil. Farmers will rejoice when seeing fuel ethanol prices
rise. Lastly, fuel ethanol prices simultaneously increase as oil prices increase.
Most of the countries producing fuel ethanol define the prices of this product
based on subsidies, raw material price in the market, and oil prices (Bernardi,
2001; Cohen et al., 2008).
1. Availability (production)
2. Access (income and prices)
3. Utilization (nutrition)
4. Stability (price volatility)
But in the context of the bioenergy and food security program (BEFS), the
focus consists on availability and access (FAO, 2008). The BEFS project is
designed in the framework of FAO and the German Gesellschaft für Technische
Zusammenarbeit (GTZ) collaboration to mainstream food security concerns into
national and subnational assessments of bioenergy potential. As reported by the
FAO, the key questions the project will address are:
• What are the best types of bioenergy systems to help diversify agricul-
tural output (energy feedstock), contribute to rural development, and
increase rural employment and incomes?
• How could bioenergy production benefit the environment and increase
energy and food security for producers farming biomass as a source of
energy for themselves, on-farm use, local communities, or commercial
markets?
• How could diversification of domestic energy supply provide increased
energy access to rural enterprises and reduce the household energy bur-
dens of rural women?
• Is there anything different about bioenergy that could mitigate or over-
come factors of exclusion that contribute to food insecurity and rural
poverty?
• How can low-income, food deficit countries ensure that food security
concerns are addressed, given the complex linkages between agricul-
ture, energy, environment, and trade?
• What are the implications on available food supplies and food prices in
terms of competition for natural or human resources?
• How will bioenergy affect agricultural systems, particularly for poorer
households dependent on their own food production?
• Who (public, private, or civil society) is best placed to deal with potential
conflicts arising from competition for food, feed, or fuel use of biomass?
FAO considers that increased competition for land and water resources may
result, and higher and less stable food prices may be one of many possible con-
sequences. Bioenergy may also provide ways to support rural development and
raise farm incomes.
Resuming, the BEFS project will analyze the risks and opportunities of bioen-
ergy and how it could affect food security in partner countries.
BEFS partners include Cambodia, Peru, Tanzania, and Thailand. The project
has already begun in Tanzania. The project provides to these countries a science-
based quantitative methodology to minimize food security risks. This approach
helps to build their own capacity and management, at the same time, appreciat-
ing food security concerns. The project itself is not just an assessment. BEFS
produces a permanent economic forecast and food security monitoring, which
emphasizes deepening insights for developing countries’ bioenergy potentials
Figure 12.1 shows the analytical framework of the BEFS project. Every mod-
ule is linearly connected, but entirely independent in relation to other modules.
One axis is the basis of all the modules: consideration of food security as primary.
The purposes and activities of the modules are discussed below.
• The extent and location of areas suitable for the relevant bioenergy
crops.
1.Biomass
potential Agriculture and
environmental impact
5.Household- 2. Biomass
level food supply chain-
security production
Bioenergy costs
Food Security
4. Economy- 3. Agriculture
wide effects markets
outlook
Figure 12.1 The bioenergy and food security (BEFS) analytical framework. (Based
on FAO, 2008; Cardona Alzate et al., 2009)
12.5.2.2 Module 2
Biomass supply chain and production costs assess the agro-industry development
and biofuel production chains by looking at
12.5.2.3 Module 3
Agricultural market outlook projects the impacts of biofuel production and bio-
fuel policies on agricultural markets in the context of the analyzed country over a
10-year outlook period solving the following questions:
12.5.2.4 Module 4
Economy-wide effects uses innovative tools including:
12.5.2.5 Module 5
Household-level food security assesses how price increases will affect differ-
ent groups:
12.5.2.6 Module 6
Household welfare impacts are based on the net welfare impact calculated from
the difference between production and consumption.
Suitability classes
Figure 12.2 Suitability index for cassava under tillage-based production system at low
level of input (area available) in Tanzania.
373
© 2010 by Taylor & Francis Group, LLC
374 Process Synthesis for Fuel Ethanol Production
Table 12.6
Bioethanol Production Scenarios for Tanzania
Raw Material Scenario Parameter Description
Cassava 7 Stand alone Fresh cassava (single plant), increased cassava yield
Cassava 8 Stand alone Dried cassava (single plant), increased cassava yield
Table 12.7
Cassava Ethanol Production Cost
Depending on Scenario and Level of
Technology
Level of Technology
Low Medium Advanced
Scenario US$/L US$/L US$/L
Scenario 7 Fresh 0.67 0.616 0.559
Scenario 8 Dry 0.695 0.6832 0.592
and the fact that cassava roots perish quickly after harvesting, this production
route may not be the most appropriate. Thus, scenario 8 provides a more viable
alternative whereby fresh cassava roots are first dried to extend the shelf life,
then are transported to an ethanol processing plant. Scenario 8 facilitates greater
opportunity for small farmers in isolated rural areas to participate. The costs pre-
sented in Table 12.7 do not include co-generation or use of by-products.
Ruvuma is a representative region in Tanzania located at the southern bound-
ary with Mozambique. The welfare effects in this region were analyzed based
on a 10% of producer price increase for different crops including cassava. They
found positive welfares in specific cases for cassava. For bean and sugarcane, the
welfare effects were always negative.
Concluding partial results showed that in order to be able to reap the benefits
of bioenergy investments, Tanzania has to consider strengthening and developing
local markets, local production capacity, and its infrastructure. Analysis so far
does not include all crops and full integration across modules. The results are
under discussion in the country.
The preliminary conclusions drawn by the BEFS project indicate that bioen-
ergy development, which safeguards food security, is only sustainable in Tanzania
when a bioenergy project:
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13.1 Feedstocks
The three kinds of feedstocks used for fuel ethanol production correspond to
resources that are present in almost all the countries. In particular, all populated
regions in the world account for vast amounts of lignocellulosic waste materials
that eventually can be converted into ethanol. Tropical countries exhibit compara-
tive advantages in the availability of sucrose- and starch-containing feedstocks
for ethanol production in comparison to European or North American countries.
In fact, the dynamics of the global ethanol market could require these countries
to supply the growing demand of those countries that have implemented or will
implement ambitious programs for the partial substitution of fossil fuels with
renewable liquid fuels. These programs may have dissimilar motivations other
than environmental concerns, but humankind and global climate will be ben-
efited in any case.
For the three main types of feedstocks, the development of effective, continu-
ous fermentation technologies with near 100% yields and elevated volumetric
productivities is one of the main research subjects in the ethanol industry. To
this end, many of newly proposed technologies for reducing the product inhibi-
tion effect on the cell growth rate should be scaled up at the industrial level.
Additionally, past research tendencies for cell-free ethanol production, using
379
only the enzymes involved in the conversion of glucose to ethanol, may offer a
practical and beneficial alternative. This progress should complement the intense
efforts oriented to the selection and development of microbial strains with par-
ticular traits, such as specific flocculating properties or increased tolerance to
ethanol, inhibitors, and salts.
Consequently, an important part of the research trends on fuel ethanol produc-
tion is geared to the reduction of feedstock costs, especially through the utiliza-
tion of less expensive lignocellulosic biomass. In general, most of the research
efforts are oriented to the conversion of lignocellulosics into fermentable sugars
and then to ethanol. One of the key factors for enhancing the competitiveness of
the biomass-to-ethanol process is the economic and concentrated access to large
quantities of biomass distributed in rural areas of the world. Another important
issue in transformation technologies for lignocellulosic feedstocks is the design
of low-cost methods for its delignification. After that, the increase in the specific
activity of cellulases and the decrease in their production costs play a crucial role
in the process costs. The technology of recombinant DNA will provide impor-
tant advances for the development of the fuel ethanol industry. The development
of genetically modified microorganisms capable of converting starch or biomass
directly into ethanol and with a proven stability under industrial conditions will
allow the implementation of the consolidated bioprocessing of the feedstocks.
The massive utilization of fuel ethanol in the world requires that its production
technology must be cost effective and environmentally sustainable. In particular,
ethanol production costs should be lowered. For current technologies employed at
the commercial level, the main share in the cost structure corresponds to the feed-
stocks (above 60%) followed by the processing expenditures. In general, the use
of sucrose-containing materials such as cane molasses allows producing ethanol
with the lowest costs compared to using the starchy materials (mostly grains).
Although the ethanol yield from corn is higher than that from sugarcane, the
lower annual yield of corn per cultivated hectare makes it necessary to use larger
cropping areas. On the other hand, the lignocellulosic biomass represents the
most promising feedstock for ethanol production. The availability and low cost of
a wide range of lignocellulosic materials offer many possibilities for the develop-
ment of bioindustries that could support the growth of the international biofuel
market and contribute to the reduction of greenhouse gas emissions worldwide.
A summary about research perspectives of feedstocks for ethanol production is
presented in Table 13.1.
381
© 2010 by Taylor & Francis Group, LLC
382
Table 13.1 (Continued)
Research Trends and Priorities for Improving Fuel Ethanol Production from Different Feedstocks
Issue All Feedstocks a Sucrose-Containing Materials Starchy Materials Lignocellulosic Biomass
Hydrolysis Low temperature digestion of starch Increase in specific activity, thermal
stability and cellulose-specific
binding of cellulases (e.g., by protein
engineering)
Reduction of costs of cellulases
production (10-fold reduction)
Cellulases production by solid-state
fermentation
a Refers to the three analyzed groups of feedstock: sucrose-containing materials, starchy materials, and lignocellulosic biomass.
in gas stations. This “subsidy” is intended to compensate the inversions made for
maintaining the status quo of international relationships. Logically, we also pay
the consequences of the measures taken to “offset” this state of affairs: social
instability and, unfortunately, to a certain degree, terrorism.
Therefore, the relatively higher production cost of ethanol is the main obstacle
to be overcome. To undertake this, process engineering plays a central role for
the generation, design, analysis, and implementation of technologies improving
the indexes of the global process, or for the retrofitting of employed bioprocesses.
Undoubtedly, process intensification through integration of different phenomena
and unit operations, as well as the implementation of consolidated bioprocess-
ing of different feedstocks into ethanol (that requires the development of tailored
recombinant microorganisms), will offer the most significant outcomes during the
search for efficiency in fuel ethanol production. Great efforts should be focused
on the development of consolidated bioprocessing (CBP) of biomass, as ligno-
cellulosics is the most promising feedstock for ethanol production. Additionally,
the intensification of biological processes indicates a better utilization of the
feedstocks and the reduction of process effluents improving the environmental
performance of the proposed configurations. Attaining this set of goals is a colos-
sal challenge to be faced through the fruitful interaction between biotechnology
and chemical engineering. The most important and promising research priorities
linked to process engineering for improving the global process are briefly sum-
marized in Table 13.2.
Finally, regarding process engineering, this approach has more importance
today when oil prices can change drastically depending on not-easy-to-predict
factors. Then bioethanol “fashion” should be supported by numbers and projec-
tions based on serious studies.
385
© 2010 by Taylor & Francis Group, LLC
386
Table 13.2 (Continued)
Research Trends and Priorities for Improving Fuel Ethanol Production by Means of Process Engineering
Issue All Feedstocks Sugarcane Starchy Materials Lignocellulosic Biomass
Process Integration of fermentation and Development of efficient Development of consolidated Increase of effectiveness of SSF
integration separation processes for co-generation technologies bioprocessing (CBP) and SSCF processes (e.g., by
reduction of product inhibition using cane bagasse Recombinant microorganisms improvement of cellulase
Application of membrane for conversion of starch into activity)
technology (e.g., for ethanol ethanol Development of CBP
removal or dehydration) Increase of ethanol tolerance in
Energy integration (e.g., by microorganisms converting
pinch technology) cellulose into ethanol
this, new problems related to food security will appear. In order to avoid a non-
equilibrium development of a fuel ethanol market based on energy crops, drastic
but fair regulations from governments must be instituted.
Each country has to create appropriate rules and laws for developing fuel
ethanol programs based on its specific supply and demand characteristics.
Additionally, the overall energy policies that include bioenergy should be care-
fully designed to include all possible energy sources in harmonized and balanced
form. It is not logical, for example, that renewable energies coming from the sun
and wind are more developed in countries having limited access to these sources
than in tropical countries.
With purposes of an open discussion about the future of food security concerns
on fuel ethanol production, Table 13.3 presents an overview of the perspectives,
challenges, and risks of different topics involved in this issue.
13.4 Environmental Impacts
It is expected that the newer forms of biofuels, including ethanol, could really be
cleaner and more efficient than traditional forms of biofuels. Favorable CO2 bal-
ance and other emissions reduction when bioethanol is burned in engines could
help mitigate global climate change. Even if aldehyde emissions slowly increase,
the use of catalysts normally destroys this contaminant easily.
Biofuel production may introduce new environmental risks and new chal-
lenges for the producing countries. This will particularly be the case when natural
resource constraints cause greater trade-offs between food production and biofuel
production. Respect for the rainforests and all protected areas should be the core
of any regulations and policies. There are serious concerns in Latin America and
Africa for the deforestation activities.
Fuel ethanol production includes the generation of a large quantity of residues.
Effluent treatment will always be an important topic of research. Reduction of
air pollution must not cause the increase of soil or water contamination. There
are cases of noncompatibility of stillages in Colombia with the soil quality in the
sugarcane plantations.
Using ethanol as a vehicle fuel has the potential to reduce nonrenewable energy
consumption and greenhouse gas (GHG) emissions. However, acidification,
eutrophication, and photochemical smog could increase when compared to using
gasoline as liquid fuel. This information should be analyzed for every feedstock,
location, and blending to avoid confusion about the environmental performance
of fuel ethanol projects.
Life cycle analysis (LCA) enables one to investigate environmental perfor-
mance of fuel ethanol used in different concentrations in gasoline. This analysis
can include a serious waste reduction (WAR) algorithm for numerical calculation
of potential environmental impacts. This type of strategy is an important compo-
nent for identifying practices that will help to ensure that a renewable fuel, such
as ethanol, may be produced in a sustainable manner.
Table 13.3
Perspectives, Challenges, and Risks of Food Security on Different Topics
Involved in Fuel Ethanol Production
Perspectives of
Research and Type of
Topic Development Challenges Risks Solution
Feedstocks New crops for Practical use of Use of cassava for Policies
Amylaceous rural integration ethanol instead of Technology
development technology food in African
countries
Sugar based Limited increase Increase of Sugar prices could Policies
due to land use productivity per increase
competition ha in African and dramatically
central American
countries
Lignocellulosics Tools for assessing Quantitative and Reductions in soil Technology,
availability and qualitative productivity and policies
access analysis possible
High quality increases in
delignification prices for
technologies livestock food
Overall low cost
processing
Overall food Market price Definition of fair Best prices of Policies,
security in the structure and prices for rural crops for energy technology
world international producers than for food use
trade agreements Lignocelluloses
in fuel ethanol biomass as a
import and export profitable
alternative
Energy security Integral Strategically Countries can find Policies
development of integrated use of economically
bioenergy all energy more attractive to
policies resources in produce
Other renewable every country bioenergy instead
energies (solar, of food
geothermal,
wind, etc.)
Other fuels
development
(natural gas,
carbon
derivatives, etc.)
Table 13.4
Perspectives, Challenges, and Risks Related to the Environment on
Different Topics Involved in Fuel Ethanol Production
Type of
Topic Perspectives Challenges Risks Solution
Environmental Precise CO2 New tools for Negative overall Policies,
concerns balance environmental impacts to air, technology
calculations impacts soil, and water
Emissions analysis assessment
for different
blending
strategies
Stillages disposal
Land use Environmental New in situ Use of rainforest Policies
policies for technologies for by poor countries
protecting using residues Negative balance in
rainforest and Use of water cycle use
water nonproductive
Deforestation lands
analysis Strategies for
Afforestation and stopping
reforestation deforestation
strategies