energies

Review
A Review of Thermochemical Conversion of Waste Biomass
to Biofuels
Shivangi Jha 1,2 , Sonil Nanda 1 , Bishnu Acharya 1 and Ajay K. Dalai 1, *

1 Department of Chemical and Biological Engineering, University of Saskatchewan,

Saskatoon, SK S7N 5A9, Canada
2 School of Environment and Sustainability, University of Saskatchewan, Saskatoon, SK S7N 5C8, Canada
* Correspondence: [email protected]; Tel.: +1-(306)-966-4771

Abstract: Biofuels are sustainable alternatives to fossil fuels because of their renewable and low-cost
raw materials, environmentally friendly conversion technologies and low emissions upon combus-
tion. In addition, biofuels can also be upgraded to enhance their fuel properties for wide applicability
in power infrastructures. Biofuels can be produced from a wide variety of biomasses through thermo-
chemical and biological conversion processes. This article provides insights into the fundamental and
applied concepts of thermochemical conversion methods such as torrefaction, pyrolysis, liquefaction,
gasification and transesterification. It is important to understand the physicochemical attributes of
biomass resources to ascertain their potential for biofuel production. Hence, the composition and
properties of different biomass resources such as lignocellulosic feedstocks, oilseed crops, municipal
solid waste, food waste and animal manure have been discussed. The properties of different biofuels
such as biochar, bio-oil, bio-crude oil, syngas and biodiesel have been described. The article con-
cludes with an analysis of the strength, weaknesses, opportunities and threats of the thermochemical
conversion technologies to understand their scale-up applications and commercialization.

Keywords: biofuels; pyrolysis; torrefaction; liquefaction; gasification; transesterification

Citation: Jha, S.; Nanda, S.;
Acharya, B.; Dalai, A.K. A Review of
Thermochemical Conversion of
Waste Biomass to Biofuels. Energies 1. Introduction
2022, 15, 6352. https://doi.org/
Renewable resources such as wind, nuclear and solar power are promising alternative
10.3390/en15176352
sources of energy to complement fossil fuel resources. However, they cannot produce
Academic Editors: Federico Galli, liquid or gaseous fuels for transportation as well as combined heat and power generation.
Samira Lotfi and James Butler Furthermore, they are seasonal and largely dependent on the weather, atmospheric, or
Received: 6 August 2022
environmental conditions. It should be noted that some of these renewable resources
Accepted: 30 August 2022
have certain geographical and environmental limitations. For example, wind and tidal
Published: 31 August 2022
energies account for the channeling of wind and water, whereas solar energy is preferred
in regions with adequate hours of sunlight. On the other hand, biomass-derived energy in
Publisher’s Note: MDPI stays neutral
the form of bioenergy is preferable because they are available in most regions of the world.
with regard to jurisdictional claims in
However, biomass can be converted to energy, energy carriers, and value-added chemicals
published maps and institutional affil-
via thermochemical (e.g., gasification and pyrolysis) and biological conversion processes
iations.
(e.g., anaerobic digestion and fermentation) [1]. Renewable energy supply attributed to
nearly 14% of the world’s total primary energy supply in 2018 [2]. It is estimated that the
global demand for biofuels can rise to 41 billion liters by 2026 [3]. Currently, the worldwide
Copyright: © 2022 by the authors.
demands for bioethanol, renewable diesel, biodiesel and bio-jet fuels are 17, 14.5, 7.6 and
Licensee MDPI, Basel, Switzerland. 1.5 billion L/year. In terms of regions, North America (15.9 billion L/year) has the max-
This article is an open access article imum total demand for biofuels followed by Asia (10.8 billion L/year), Latin America
distributed under the terms and (10.4 billion L/year) and Europe (3.4 billion L/year) [3].
conditions of the Creative Commons The rising energy consumption, growing demands for fossil fuels, soaring fuel prices,
Attribution (CC BY) license (https:// and increasing levels of greenhouse gas (GHG) emissions are some of the issues contribut-
creativecommons.org/licenses/by/ ing to the need for a global shift towards renewable energy. Waste biomasses such as oil
4.0/). seed crops, lignocellulosic materials (e.g., agricultural and forest residues), microalgae,

Energies 2022, 15, 6352. https://doi.org/10.3390/en15176352 https://www.mdpi.com/journal/energies

Energies 2022, 15, 6352 2 of 23

energy crops, manure, food waste and organic fraction of municipal solid waste have
a huge potential to provide energy and value-added products via different conversion
technologies. Some examples of thermochemical processes are liquefaction, pyrolysis,
gasification, torrefaction, carbonization, transesterification and catalytic processes, whereas
fermentation, biomethanation and enzymatic processes are widely used biological tech-
nologies for biomass conversion [4]. In biological conversion methods, biomass residue
is hydrolyzed chemically and enzymatically to release the fermentable components after
which responsible microorganisms degrade them to produce high-value products such as
biofuels and biochemicals. In the thermochemical conversion processes, the feedstocks un-
dergo thermal breakdown of the organic components regardless of microbially fermentable
matter (i.e., saccharides) and non-fermentable components (i.e., lignin) to produce biofuels
and biochemical building blocks. Compared to biological conversion processes, thermo-
chemical methods have faster reaction rates due to the involvement of high temperatures,
pressures and catalysts.
The composition and characteristics of biomass largely impact the process parameters,
reaction rate as well as yields and quality of the conversion products. The main properties of
biomass can be determined through proximate and ultimate composition [5]. The proximate
composition is measured through the levels of moisture, ash, fixed carbon and volatile
matter. On the other hand, the ultimate composition includes carbon, hydrogen, nitrogen,
sulfur and oxygen. Ash includes mineral matter that remains as a residue after combustion.
Higher ash content could be a challenge for the formation of agglomeration and cause
sintering and corrosion during thermochemical conversion, especially in combustion,
pyrolysis, gasification and co-firing [6]. In addition, the higher moisture content in biomass
results in greater energy input to dry the feedstock before their thermochemical conversion
and reduced heating value of the biofuel product. The calorific value of the conversion
product can be improved with lower contents of moisture, oxygen and ash [7].
Biomass conversion technologies are variable depending on their processing require-
ments such as feedstock properties, process parameters, and product types and composition.
Hence, it is often difficult to make a comparative assessment of the thermochemical and
biological conversion technologies. In addition, an articulate understanding of the sources,
classification, origin and physicochemical properties of different waste biomass is lacking,
which impacts both upstream and downstream processing of biorefineries. Although the
applications of widely used thermochemical technologies are well documented, insights
into their fundamental concepts are lacking in the existing pool of literature. With this
objective, this article presents an overview of different waste biomass classifications based
on their source, origin, composition and physicochemical properties. Subsequently, dif-
ferent thermochemical biomass conversion technologies such as torrefaction, pyrolysis,
liquefaction, gasification and transesterification are described based on their fundamental
operating principles, parameters, applications and product type and composition. Lastly,
the properties of different products from thermochemical conversion of biomass such as
biochar, bio-crude oil, bio-oil, syngas and biodiesel are described in this review article.

2. Classification of Waste Biomass and Biogenic Materials

2.1. Lignocellulosic Biomass
Lignocellulosic biomass is a sustainable, cost-effective and carbon-neutral feedstock
that characteristically contains cellulose (40–60 wt.%), hemicellulose (20–40 wt.%) and lignin
(10–24 wt.%). Some of the sources of lignocellulosic biomass are agricultural crop residues,
forestry biomass and energy crops. Agricultural wastes are the residues produced by the
harvesting and processing of agricultural vegetative crops. Crop residues are generally
divided into two types such as field residues and agro-food processing residues. Since these
agro-residues are non-edible, they pose no competition to the food supply or fertile arable
lands. Regardless of the environmental, societal, and profitability of woody biomass in
different valuable products for household, industrial, construction and power sectors, most
of the forestry biomass remain underutilized. Some barricades that restrain the utilization
Energies 2022, 15, 6352 3 of 23

of agricultural and forest biomass for the production of bioenergy are associated with their
seasonal, geographical and climatic variations, which determine their availability and cost.
Research interest in energy crops has augmented worldwide due to their diversity,
rapid growth, high production rate, the potential to fix CO2 during photosynthesis, cost-
effectiveness and resilience to grow on marginal quality soils [8]. Therefore, their cultivation
can encompass a substantial probability to biofuel industries to fulfill the clean energy
necessity. Some common energy crops include switchgrass, elephant grass, timothy grass,
Miscanthus and hybrid poplar.

2.2. Oilseed Crops

Plant-based oils have traditionally been a significant agrarian commodity. Several
species of plants contain oil in the form of fatty acids, lipids, triglycerides and triacylglycerol.
These components are stored in plant seeds and cells as reserves of carbon and energy
for the improvement of seedlings. The structural similarity of triacylglycerol with long-
chain hydrocarbons forms a foundation for a viable alternative to hydrocarbon-based
products. Moreover, owing to the physicochemical properties of fatty acids, the non-edible
plant-based oils are used to produce biodiesel and components as an integral part of
paints, coatings, lubricants and inks. There is a great demand for plant oils in agricultural,
nutraceuticals, cosmeceutical, pharmaceutical, food and biorefining industries.
Many plant-based oils are consumed as edible oils in cooking and food process-
ing such as canola oil, vegetable oil, mustard oil, olive oil, sunflower oil, soybean oil,
corn oil, almond oil, grapeseed oil and coconut oil. Non-edible plant-based oils are
extracted from microalgae, Ailanthus altissima (heaven tree), Azadirachta indica (Neem),
Jatropha, Linum usitatissimum (flax), Madhuca longifolia (Mahua), Pongamia pinnata (Karanja),
Ricinus communis (Castor), Sapindus mukorossi (Soapnut), Toona sinensis (Juss), Vernicia fordii
(Tung), rubber seed, silk cotton tree, etc. [9]. The fraction of oil fluctuates noticeably in
different oilseed crops. However, it can be inferred that there is scope for genetically
engineering the oilseed plants to generate a greater concentration of oils. Using oil seeds for
biofuels and biodiesel production is an excellent way to replace petroleum-based sources.

2.3. Municipal Solid Waste

The waste materials (e.g., garbage, recyclable and non-recyclable residues) obtained
from municipalities including households are known as municipal solid waste (MSW).
MSW could also include Industrial, Commercial and Institutional (ICI) waste such as
those discarded residues from businesses, large industries, hospitals, institutions, schools,
colleges and universities. It should be mentioned that the composition of MSW and ICI
varies depending on the origin, production patterns, household income and geographical
location [10]. MSW contains items such as kitchen and household materials, plastic and
rubber, metals, paper and cardboards, inert materials, electronic wastes, etc. [11]. MSW also
consists of biodegradable and non-biodegradable fractions. It should be mentioned that
about 15% of the total waste generated in municipalities is recycled while the remaining is
disposed of in landfills or dumped in open sites [12].
The worldwide surge in MSW generation is primarily due to the rise in popula-
tion, urbanization and industrialization. The global production of MSW has surpassed
1.2 billion tonnes per year with a projection to exceed 2 billion tonnes annually by 2025 [13].
It is projected that in some developing countries and other parts of the world, the MSW
generation could reach or exceed that of developed nations without proper regulations
and provisions for landfilling and waste recycling facilities [14]. The growth in the rate
of generation of MSW is also related to the change in food habits, consumption patterns,
consumer behavior and standards of living in rural and urban areas.
MSW generation creates severe environmental pollution when unmanaged. Moreover,
its conversion into value-added products could provide a solution to the challenges of
energy shortage and sustainable waste management. Various ways by which MSW can be
disposed of, recycled or valorized into energy resources are through landfilling, composting,
Energies 2022, 15, 6352 4 of 23

anaerobic digestion, pyrolysis and gasification [11]. The incineration of 1 ton of MSW
could emit 1.3 tons of CO2 equivalent emissions, which is similar to the amount of CO2
emissions from petroleum-based power plants [15]. In addition, incineration of MSW
emits a considerable amount of pollutants such as particulate matter and fly ash into the
atmosphere, making it an unsustainable waste management practice. On the other hand,
the fly and bottom ash produced from the incineration of MSW has been proven to contain
heavy metals posing risks to ecosystems [16].
The disposal of MSW in landfills is preferred by many municipalities globally for
the burial of non-recyclable wastes. Although promising, MSW disposal in landfills faces
challenges such as groundwater pollution from landfill leachate and methane gas emis-
sions. MSW landfill leachate exhibits chronic and acute toxicity and often permeates into
groundwater biomagnification. Moreover, leachate could also contaminate the flow of
water streams [17]. Energy production from MSW helps in minimizing pollution and
could facilitate the economic development of a nation in terms of waste management and
strengthening energy security.

2.4. Food Waste

Food waste, a component of the organic fraction of MSW, refers to the organic and
biodegradable waste produced from various sources including food processing plants,
restaurants, kitchens and households. A large amount of food waste is produced annually
due to food processing and consumption. Food waste could also be generated because of
overproduction, damage to food items including fruits and vegetables by microorganisms,
pests and insects, overwhelming purchases and delayed consumption [18]. Approximately
1.3 billion tonnes of food such as processed meat, dairy products, fruits, and vegetable are
lost along the food supply chain every year [19].
Landfilling and incineration are not feasible waste management practices for food
waste. Landfilling of food waste can lead to the emissions of methane, a more potent
GHG than CO2 . On the other hand, incineration or combustion is suitable for dry biomass.
Hence, high-moisture containing food waste may result in greater energy requirements
for the incinerator leading to high operating costs. In such a scenario, anaerobic digestion
of food waste is a reasonable alternative to producing biogas (or biomethane) through
biomethanation by methanogenic bacteria [20].
Food waste consists of carbohydrates, organic acids, fatty acids, lipids, proteins and
cellulose. Moreover, the carbohydrates present in food waste could undergo hydrolysis
to produce oligosaccharides and monosaccharides suitable for biological conversion [19].
Owing to its organic composition, food waste can also be a crucial resource to produce
bioethanol [21], biobutanol [22] and biohydrogen [23] through fermentation. As biohydro-
gen is gaining popularity, food waste can prove to be an eco-friendly and cost-effective
feedstock for its production through photo/dark fermentation and gasification. Thermo-
chemically, food waste can also be converted to produce bio-oil and biochar by pyrolysis [24]
and hydrogen-rich syngas by hydrothermal gasification [18]. Food waste has also shown
promising results for biochar and activated carbon production [25]. The parameters such as
the composition of food waste, pretreatment methods and processing parameters influence
the production of biofuels.

2.5. Animal Manure

Animal manure refers to the metabolic and waste by-products of livestock and poultry
farming. Manure is a valuable material containing organic matter and nutrients essential
for the cultivation of crops. Moreover, animal manure could also contain different types
of pathogens posing ecological risks. Typically, animal manure contains metabolic waste
or feces, waste feed and waste feedwater. Despite being a major source of agricultural
nutrients, livestock manure can also contribute to the emission of GHGs such as CH4 by
microbial decomposition [26]. It should be mentioned that greenhouse gas emission from
animal manure accounts for 10% of the overall emissions from agricultural production [27].
Energies 2022, 15, 6352 5 of 23

Some other traditional manure treatment includes composting and vermicomposting [27].
These treatments are very common in developing countries because of their simplicity and
cost-effectiveness. Furthermore, composting also ensures the availability of nutrients to
plants. Composting also leads to an increase in the aeration and water infiltration of clay
soils. Animal manure could be valorized by several methods such as anaerobic digestion [28],
dark fermentation [29], fermentation [30], pyrolysis [31], hydrothermal liquefaction [32],
hydrothermal gasification [33] and torrefaction [34] to produce biomethane, biohydrogen,
bioethanol, bio-oil, bio-crude oil, syngas and torrefied biomass, respectively. The digestate left
behind after the anaerobic digestion of manure could be used as feedstock for biochar, bio-oil
and syngas production through pyrolysis, liquefaction and gasification, respectively.
Animal manure has shown significant potential for biofuels and biochemicals produc-
tion via thermochemical and biological conversion processes. Nanda et al. [33] showed
that horse manure is an effective feedstock for hydrogen production via hydrothermal
gasification. In another study, chicken manure was used as feedstock for bioethanol pro-
duction via co-anaerobic digestion with ethanol plant effluent [35]. A mixture of poultry
manure and Eucalyptus wood was used for hydrogen production via catalytic hydrothermal
gasification [36].

3. Thermochemical Conversion Technologies

3.1. Torrefaction
Torrefaction is a clean and promising thermochemical technology that is often used as a
thermal pretreatment of biomass resources [37]. It has been evident that torrefaction enhances
the performance of thermochemical conversion processes such as pyrolysis, liquefaction and
gasification by removing moisture and partially degrading the biomass [38]. Torrefaction has
received substantial attention not only because torrefied and densified biomass encompasses
better properties, but the technologies linked with torrefaction are close to being marketable.
Some of the superior properties of torrefied biomass as compared to raw biomass are hy-
drophobicity, grindability, higher heating value and low-moisture content and pelletizable
nature [37]. Torrefaction accounts for increasing the percentage of carbon and reducing the
oxygen content consequently enhancing the heating value of biomass.
Figure 1 illustrates a typical torrefaction process flow diagram. Torrefaction refers
to the drying of feedstock typically at a temperature range of 200–300 ◦ C under an inert
atmosphere. The temperature range determines the type of torrefaction, which can be
classified as light (200–235 ◦ C), mild (235–275 ◦ C) and severe (275–300 ◦ C) [39]. It can also
be regarded as the slow heating of biomass under oxygen-free conditions. The volatile
matters that are emitted during the torrefaction process move to the condenser in the form
of hot vapors for condensation. The condensed liquid product of torrefaction contains
water and carboxylic acids along with traces of aldehydes, ketones, ethers, esters and
alcohols [40]. The non-condensable gases contain CO2 , CO, CH4 and traces of H2 . The
torrefied solids that are left behind have properties similar to coal and hence can be used
as their green alternatives. The advantage of using torrefaction is that it does not emit
any GHGs. Instead, it fixed the carbon in the form of densified and dehydrated biomass
for further thermochemical processing. Table 1 summarizes some notable studies on the
torrefaction of waste biomass to solid fuels.
 Energies 2022, 15, x FOR PEER REVIEW 6 of 24

Energies 2022, 15, 6352 Instead, it fixed the carbon in the form of densified and dehydrated biomass for further 6 of 23
thermochemical processing. Table 1 summarizes some notable studies on the torrefaction
of waste biomass to solid fuels.

Figure 1. Typical process representation of torrefaction of biomass.

Figure 1. Typical process representation of torrefaction of biomass.
Table 1. Summary of notable works on torrefaction of waste biomass.
Table 1. Summary of notable works on torrefaction of waste biomass.
Residence
Feedstock Temperature (°C) Observations Reference
Feedstock Time
Temperature (min) Residence Time (min)
(◦ C) Observations Reference
• Oxygen removal efficiency and carbon densification
were amplified by •40% and Oxygen
52%,removal efficiency
respectively at 300and
°C carbon
densification were amplified by 40% and
in 30 min.
52%, respectively at 300 ◦ C in 30 min.
• An increase of 42%• of higher heatingofvalue
An increase 42% when com-
of higher heating
Acacia nilotica pared to biomass in its raw form
value when wascompared
observed.to biomassSinghin its et al. [41]
225–300 15–60
(Babul)(Babul)
Acacia nilotica 225–300 • 15–60
There was an improvement rawinform
the was observed.
physical property of Singh et al. [41]
water. • There was an improvement in the physical
property of water.
• During the process, • the overall
Duringaromatic carbon
the process, and ar-aromatic
the overall
omaticity of the liquid condensate
carbon andwere augmented.
aromaticity of the liquid
condensate were augmented.
• Microwave drying cracked the surface of biomass,
which consequently • released additional
Microwave volatiles
drying cracked with
the surface
lower crystallinity. of biomass, which consequently
Cotton stalk, • released
Torrefied rice husk, sugarcane additional
bagasse and volatiles with
cotton stalk
sugarcane ba- lower crystallinity.
250–300 30 demonstrated higher
• elemental carbon and heating
Torrefied rice husk, sugarcane bagasse Amer et al. [42]
gasse, rice straw value similar to that of bituminous
Cotton stalk, sugarcane bagasse, and cotton coal.
stalk demonstrated higher
and rice husk 250–300 30 Amer et al. [42]
rice straw and rice husk • elemental
Carbon in torrefied rice straw carbonhigh
presented and crystal-
heating value
similar to that of bituminous
linity (around 50%), whereas that in rice husk and sug- coal.
• Carbon in torrefied rice straw presented
arcane bagasse was amorphous.
high crystallinity (around 50%), whereas
• The torrefied products had thatup
in to
rice husk
42% andheating
more sugarcane bagasse
was amorphous.
Oats, willow and value as compared to the untreated biomass. Acharya and
200–300 15–45
poultry litter • The mass and energy • yields
The by oat residues
torrefied productswere
hadthe
up to 42% Dutta [43]
fastest, whereas it was themore
leastheating valuelitter.
in poultry as compared to the
untreated biomass.
• The mass and energy yields by oat
residues were the fastest, whereas it was
Oats, willow and poultry litter 200–300 15–45 the least in poultry litter. Acharya and Dutta [43]
• Mass yield varied from 42% to 91%,
whereas the yield of energy varied
by 49%.
• All products displayed hydrophobic
characteristics.
Energies 2022, 15, 6352 7 of 23

Table 1. Cont.

Feedstock Temperature (◦ C) Residence Time (min) Observations Reference

• Mass balance ranged from 96 wt.%
to 103 wt.%.
• Several condensable species were
Pinewood, Miscanthus, and identified including anhydrous sugars,
250–300 45 Lê Thành et al. [44]
wheat straw terpenes and terpenoids.
• The type of biomass along with
temperature affected the yields of
condensable species.

• The flowability of ground biomass was

Soybean straw, corn straw, rice enhanced by torrefaction.
300 - Xu et al. [45]
straw and rice husk • Rice husk had the highest flowability,
whereas rice straw had the least.

• The volatile content reduced while the

fixed carbon content upsurged.
Switchgrass 200–400 - Nhuchhen et al. [46]
• Severe torrefaction conditions resulted in
a higher mass loss.

3.2. Pyrolysis
In pyrolysis, the organic material present in the biomass undergoes an irreversible
thermochemical decomposition reaction to produce biofuels. Pyrolysis technologies can
be classified as slow, intermediate and fast (Table 2). The fast heating rate and short vapor
residence times result in rapid condensation of the volatile hydrocarbon vapors into bio-oil,
whereas slow pyrolysis results in greater biochar production due to slower carbonization
of biomass due to slow heating rate and longer vapor residence time [47].

Table 2. Typical operating conditions for slow, intermediate and fast pyrolysis.

Heating Rate Vapor Bio-Oil Biochar Gas

Process Temperature (◦ C)
(◦ C/min) Residence Time (wt.%) (wt.%) (wt.%)
Slow pyrolysis 300–500 <50 >30 min 20–50 25–35 20–50
Intermediate pyrolysis 400–600 200–300 10 min 35–50 25–40 20–30
Fast/Flash pyrolysis 400–900 10–1000 <2 s 60–75 10–25 10–30

Figure 2 displays a typical process flow diagram for pyrolysis. Pyrolysis is a thermal
cracking method for biomass at higher temperatures of 300–700 ◦ C in absence of oxygen to
obtain bio-oil, biochar and non-condensable gases (H2 , CH4 , CO and CO2 ). Bio-oil contains
an organic phase and a watery phase. The organic phase of bio-oil consists of tar and
hydrocarbon-rich heavier compounds that can be upgraded to obtain clean transportation
fuels. Bio-oil requires upgrading through catalytic and non-catalytic processes to remove
oxygen, nitrogen and sulfur compounds, which lower the heating value of the fuel and
could lead to NOx and SOx emissions upon combustion [48]. The watery phase of the
bio-oil contains water, esters, ethers, aldehydes, ketones, phenols, alcohols, acids and
other biochemicals [8]. The gas phase especially H2 and CO can be converted to liquid
hydrocarbons through catalytic Fischer-Tropsch synthesis.
A variety of lignocellulosic biomass is utilized by the technology of pyrolysis for
attaining sustainable energy. Characteristics of the products of pyrolysis vary consider-
ably depending upon the process temperature, heating rate, composition of biomass and
residence time. Microwave heating has been established as a fast and energy-efficient
means of heating. The heating caused by microwaves takes place via direct absorption of
microwave energy by components of the material. Microwave radiation can be defined as
an electromagnetic wave having a wavelength in the range of 300 MHz to 300 GHz. The
introduction of microwave heating into the pyrolysis process has been recognized as a
capable solution [49]. There are various advantages of using microwave-assisted pyrolysis
over traditional pyrolysis such as faster heating rate, quicker and consistent heating of
voluminous feedstocks, increased energy efficiency, bio-oil with low aqueous content and
Energies 2022, 15, 6352 8 of 23

prompt
Energies 2022, 15, x FOR PEER REVIEW response of pyrolyzer for start-up and shut down. Table 3 summarizes
8 of 24 some recent
studies on the pyrolysis of biomass.

Figure 2. Typical process representation of pyrolysis of biomass.

Figure 2. Typical process representation of pyrolysis of biomass.
A variety of lignocellulosic biomass is utilized by the technology of pyrolysis for at-
Table 3. Summary of notable works on pyrolysis of waste biomass.
taining sustainable energy. Characteristics of the products of pyrolysis vary considerably
depending upon the process temperature, heating rate, composition of biomass and resi-
Feedstock Catalyst Reactor Temperature (◦ C) Observations Reference
dence time. Microwave heating has been established as a fast and energy-efficient means
of heating. The heating caused by microwaves takes•placeThe viayield
directand characteristics
absorption of
of micro-
wave energy by components of the material. Microwave biochar fromcan
radiation bothbebiomasses
defined were
as an
significantly influenced by the
Bamboo and pigeon pea electromagnetic wave having a wavelength in the range of 300 MHz
biomass to 300 GHz. The in-
composition.
No catalyst
stalk biomass troduction Muffle furnace
of microwave 400–600
heating into the pyrolysis •process
Duehas been recognized
to higher lignin contentasina ca-
Sahoo et al. [50]

pable solution [49]. There are various advantages of usingbamboo biomass, more biochar
microwave-assisted pyrolysis
was produced compared to that
over traditional pyrolysis such as faster heating rate, quicker and consistent heating of
from pigeon pea stalk.
voluminous feedstocks, increased energy efficiency, bio-oil with low aqueous content and
Coconut shell, palm prompt response of pyrolyzer for start-up and shut •down. The existence
Table of steam andsome re-
3 summarizes
kernel shell, rice husk, catalyst notably elevated the
cotton stalk, wheat
cent studies on the pyrolysis of biomass. percentage of gas production
straw, sugarcane Two-stage fixed bed (specifically H2 ).
10 wt.% NiAl2 O3 550 Akubo et al. [51]
bagasse and biomass reactor • Lignin was responsible to
model compounds generate maximum H2 when
(hemicellulose, cellulose compared to hemicellulose
and lignin) and cellulose.

• The highest yield of biochar was

obtained from oat hull (29.1 wt.%)
followed by canola hull
(28.8 wt.%) and food waste
(28.4 wt.%).
Food waste, canola hull
No catalyst Tubular reactor 300–600 • High-temperature biochar also Patra et al. [24]
and oat hull
demonstrated increased carbon
aromaticity and thermal stability.
• The phenolic and aromatic
chemicals were found in bio-oil
produced at higher temperatures.
Energies 2022, 15, 6352 9 of 23

Table 3. Cont.

Feedstock Catalyst Reactor Temperature (◦ C) Observations Reference

• Biochar yield decreased from
33 wt.% at 350 ◦ C to 20 wt.%
Hinoki cypress No catalyst Fixed bed reactor 350–600 at 600 ◦ C. Yu et al. [52]
• Biochar attained a microporous
structure at 500 ◦ C.

• Oxygen and sulfur contents in the

bio-oil reduced significantly while
the heating value augmented.
• A maximum degree of
Fluidized bed and fixed
Miscanthus 5 wt.% Pd/C 350–550 deoxygenation of bio-oil was Wang and Lee [53]
bed reactor
noticed with improved viscosity.
• The bio-oil revealed the potential
to replace traditional
combustion fuels.

• The percentage of aromatics in the

pyrolysis liquid product from
Jatropha cake (after removal of oil)
with Org-CaO/NZSM-5
augments to 93%.
• The yield of benzene, toluene and
xylene (BTX) along with
Peanut shell, corncob A dual-catalyst naphthalene (70%) nearly doubled
Org-CaO/Nano-
Jatropha seeds de-oiled fixed-bed reactor 50–320 than that obtained with the Yi et al. [54]
ZSM-5
cake and bagasse system traditional CaO/ZSM-5.
• The thermal cracking ability of
biomass was better with Org-CaO.
• When compared with the
pyrolysis of corncob, peanut shell
and bagasse, de-oiled Jatropha
cake generated more aromatics
with Org-CaO/NZSM-5.

• The fraction of liquids in

pinewood and peanut shells
drastically decreased, whereas
Pinewood, peanut shell that of rice straw showed the least
K2 CO3 Fixed bed reactor 300–700 Fan et al. [55]
and rice straw decline.
• Pinewood had the highest
catalytic effect followed by peanut
shell and rice straw.

• Sugarcane bagasse produced

more biochar (50 wt.%) and
bio-oil (26 wt.%) at 450 ◦ C.
Sugarcane bagasse, • The elemental analysis of biochar
de Almeida
straw and acid-treated No catalyst Fixed bed reactor 450–650 produced from various feedstocks
et al. [56]
biomass revealed a higher carbon content
(65–81 wt.%) and a lower oxygen
content (23–31%) than
sugarcane bagasse.

• The fraction of product varied

Switchgrass and from 12–18 wt.% for biochar and
Trace minerals Fast pyrolysis reactor 500 Zaimes et al. [47]
Miscanthus ash, 45–53 wt.% for bio-oil and
24–27 wt.% for gases.

• With the increase in fly ash

content (1–10 wt.%) in wheat
straw, the alteration of biomass
augmented.
• Methylene blue was removed by
the use of heterogeneous wheat
1–10 wt.% coal
Wheat straw 450–750 straw fly ash biochar. Gao et al. [57]
fly ash
• Fly ash could be a cost-effective
catalyst for biomass pyrolysis
concurrently fabricating
heterogeneous sorbents with
improved adsorption capacities
for organic pollutants.
Energies 2022, 15, 6352 10 of 23

Table 3. Cont.

Feedstock Catalyst Reactor Temperature (◦ C) Observations Reference

• CH4 yield was augmented with
the use of catalysts.
Willow, sugarcane Two-stage
10 wt.% • CH4 yield produced from
bagasse, Ugu plant and pyrolysis-catalytic 500 Jaffar et al. [58]
Ni/Al2 O3 hemicellulose and cellulose was
rice straw hydrogenation reactor
higher than that obtained
from lignin.

3.3. Liquefaction
Liquefaction is another thermochemical process for biomass conversion that predom-
inantly produces bio-crude oil. Bio-crude oil is formed because of hydrogenation and
high-pressure thermal disintegration of biomass. Hydrothermal liquefaction (HTL) re-
quires the usage of water and catalysts to transform high-moisture containing solid waste
into bio-crude oil. Figure 3 shows the process flow diagram for liquefaction. Liquefaction
generally operates at a temperature range of 240–380 ◦ C and pressures of 5–30 MPa. The
reaction mechanism of liquefaction can be summarized by the following basic routes [59]:
(i) Hydrolysis of biomass → smaller monomer
(ii) Smaller monomer → smaller compounds (by cleavage and decarboxylation)
Energies 2022, 15, x FOR PEER REVIEW 11 of 24
(iii) Recombination of the smaller fragments → new compounds (by condensation, poly-
merization)

Figure 3. Typical process representation of liquefaction of biomass.

Figure 3. Typical process representation of liquefaction of biomass.
Ethanol and subcritical water are some commonly used solvents in liquefaction. The
Ethanol and subcritical
role of solvents water areinsome
is critical commonly
the dissolution usedbysolvents
of biomass in liquefaction.
breaking hemicellulose, cellu- The
role of solvents is critical
lose, and in theinto
lignin dissolution
the volatile of biomass
matter by breaking
[59]. Thereafter, hemicellulose,
two phases cellulose,
are formed, i.e., the
tar phase and the watery phase similar to pyrolysis. The watery phase containing water
and lignin into the volatile matter [59]. Thereafter, two phases are formed, i.e., the tar
and biochemicals (as discussed earlier) can be recycled back and utilized as a solvent in
phase and the watery phase
the process [60]. similar to pyrolysis.
Bio-crude obtained The watery
from liquefaction phase upgrading
requires minimal containing water
by hy-
and biochemicalsdrotreating
(as discussed earlier) can be
unlike pyrolysis-derived recycled
bio-oil because ofback and utilized
low oxygen as hydro-
content, more a solvent
in the process [60].carbon yields, better
Bio-crude energy density
obtained from and flowability. Table
liquefaction 4 shows some
requires promising
minimal stud-
upgrading
ies on the liquefaction of biomass to bio-crude oil.
by hydrotreating unlike pyrolysis-derived bio-oil because of low oxygen content, more
hydrocarbon yields, better
Table energy
4. Summary density
of notable works and flowability.
on liquefaction of wasteTable
biomass.4 shows some promising
studies on the liquefaction Temperature
of biomass to bio-crude oil.
Feedstock Catalyst Reactor Observations Reference
(°C)
• The yield of bio-crude oil and cellulose con-
version was affected by an alkaline catalyst.
Cellulose High pressure Singh et al.
KOH 280 • Low molecular weight compounds were
and lignin autoclave [61]
found in the liquid products due to the hy-
drolysis of cellulose and lignin.
• The yield of hydrocarbons was highest at 350
°C.
• The rise in pressure negatively affected hy-
Autoclave re- drochar yield while retention time has negli- Mathanker et
Corn stover - 250–375
actor gible effects. al. [62]
• The formation of agglomerates at higher
temperatures was due to repolymerization
reactions.
Loblolly • Wet feedstocks have the potential to be uti-
pine, sewage Bench-top re- lized to generate bio-crude which can further Saba et al.
- 250–300
sludge and actor be utilized as liquid fuels and other value- [63]
cow manure added products.
• Effective conversion of wastewater sludge,
Microbial bi- fast-growing algae and bacteria having a low Goswami et
- - 200–300
omass fraction of lipids into biofuels was demon- al. [64]
Energies 2022, 15, 6352 11 of 23

Table 4. Summary of notable works on liquefaction of waste biomass.

Feedstock Catalyst Reactor Temperature (◦ C) Observations Reference

• The yield of bio-crude oil and cellulose
conversion was affected by an alkaline catalyst.
Cellulose High pressure
KOH 280 • Low molecular weight compounds were found Singh et al. [61]
and lignin autoclave
in the liquid products due to the hydrolysis of
cellulose and lignin.

• The yield of hydrocarbons was highest

at 350 ◦ C.
• The rise in pressure negatively affected
Autoclave hydrochar yield while retention time has Mathanker
Corn stover - 250–375
reactor negligible effects. et al. [62]
• The formation of agglomerates at
higher temperatures was due to
repolymerization reactions.

• Wet feedstocks have the potential to be utilized

Loblolly pine,
Bench-top to generate bio-crude which can further be
sewage sludge and - 250–300 Saba et al. [63]
reactor utilized as liquid fuels and other
cow manure
value-added products.

• Effective conversion of wastewater sludge,

fast-growing algae and bacteria having a Goswami
Microbial biomass - - 200–300
low fraction of lipids into biofuels et al. [64]
was demonstrated.

• Energy content and nutrients in food waste can

Potato starch, be recovered via HTL.
Stainless-steel Gollakota and
Casein and - 350–600 • HTL proved to be an efficient method to
batch reactors Savage [65]
sunflower oil turn food waste into bio-crude which is dense
in energy.

• Homogeneous alkali catalysts proved suitable

Potassium for biofuel production and impede the
Bench-top
Spruce wood fluoride doped 250–350 formation of char. Alper et al. [66]
reactor
alumina catalyst • Heterogeneous catalysts were preferred for HTL
of lignocellulosic biomass.

• Wet food waste demonstrated potential as

Autoclave
Tomato plant waste H2 SO4 and KOH 220–280 a bioresource to produce liquid fuels Zhang et al. [67]
reactor
through HTL.

• The quantity of hydrochar obtained was highest

Wood biomass
when no catalyst was used.
(larch and K2 CO3 Batch reactor 300 Hwang et al. [68]
• With the addition of catalysts, the conversion of
Mongolian oak)
biomass to bio-crude oil notably increased.

3.4. Gasification
Gasification is termed a thermochemical process that has the potential to transform
any carbonaceous material into syngas [69]. Gasification provides flexibility for using a
variety of feedstocks to generate gaseous products (e.g., H2 , CO, CO2 and CH4 ) and char.
Using syngas, several different forms of energy such as heat, power, biofuel, biomethane,
chemicals and hydrogen can be generated [70]. Figure 4 illustrates a simplistic process flow
diagram for gasification. While thermal gasification of coal and complex biomass uses high
temperatures (800–1200 ◦ C), hydrothermal gasification can operate at relatively moderate
temperatures (400–700 ◦ C). Apart from the main gaseous products, gasification also results
in condensable liquids rich in water and biochemicals. Due to higher temperature, there
is restricted tar formation, making cleaning and recovery of the gas fairly simple [69].
Moreover, high temperatures in gasification contribute to a faster reaction rate favored by
endothermic reactions such as water-gas shift, methanation and steam reforming leading
to near-complete decomposition of biomass to gases. The syngas can be converted to clean
fuels and value-added products by Fischer-Tropsch catalysis [71].
 chemicals and hydrogen can be generated [70]. Figure 4 illustrates a simplistic process
flow diagram for gasification. While thermal gasification of coal and complex biomass
uses high temperatures (800–1200 °C), hydrothermal gasification can operate at relatively
moderate temperatures (400–700 °C). Apart from the main gaseous products, gasification
also results in condensable liquids rich in water and biochemicals. Due to higher temper-
ature, there is restricted tar formation, making cleaning and recovery of the gas fairly sim-
ple [69]. Moreover, high temperatures in gasification contribute to a faster reaction rate
Energies 2022, 15, 6352 12 of 23
favored by endothermic reactions such as water-gas shift, methanation and steam reform-
ing leading to near-complete decomposition of biomass to gases. The syngas can be con-
verted to clean fuels and value-added products by Fischer-Tropsch catalysis [71].

Figure 4. Typical process representation of gasification of biomass.

Figure 4. Typical process representation of gasification of biomass.

Hydrothermal gasification (HTG) utilizes subcritical or supercritical water as a reaction

media to produce syngas. Subcritical and supercritical water occur below and beyond the
critical temperature (374 ◦ C) and critical pressure (22.1 MPa) of water, respectively. The chief
benefit of using HTG is that it can efficiently transform biomass comprising high moisture,
which would otherwise involve cost-intensive and energy-intensive drying steps before
gasification [72]. In contrast, converting wet biomass through pyrolysis, liquefaction and
gasification tends to be inefficient as the heat of moisture evaporation generally surpasses
the heat of combustion of biomass. The product of HTG has several different applications
such as chemical synthesis, power generation and fuel cells related to hydrogen production.
It is a challenge to enhance the levels of H2 and CO in the syngas. However, several
strategies that can address this issue are the application of catalysts that can promote water-
gas shift, steam reforming, tar reforming and syngas redox reactions [73,74]. In addition,
optimizing the gasification process conditions such as temperature, pressure, reaction time,
reaction medium, feedstock concentration, equivalence ratio and catalyst loading can result
to improve gasification efficiency, carbon conversion efficiency, hydrogen selectivity and
calorific value of syngas [75]. Table 5 summarizes some recent studies on the gasification of
waste biomass to syngas.
Table 5. Summary of notable works on gasification of waste biomass.

Feedstock Catalyst Reactor Temperature (◦ C) Observations Reference

• Ca(OH)2 and cement kiln dust
were effective in increasing the
yield of gas and decreasing tar
Cotton stalks, corn Marly clay, calcium
Bench-scale and char yields.
stalks and hydroxide, dolomite, 700–850 Hamad et al. [76]
fixed-bed reactor • Cotton stalks contributed a
rice straw and cement kiln dust
greater percentage of gases
compared to rice straw and
corn stalks.

K2 CO3 , Li2 CO3 , • Catalytic activity was enhanced

Rb2 CO3 , CaCO3 , by using CaCO3 , Li2 CO3 and
MSW and
CsCO3 , - 800–950 Na2 CO3 for the gasification of Vamvuka et al. [77]
wastepaper
CaSO4 and sewage sludge, wastepaper and
Na2 CO3 MSW, respectively.

• All the catalysts irrespective

of their type improved
Ru/activated carbon, gasification yields.
Ni/activated carbon, • KOH resulted in a high gas
Poplar wood chips Batch reactor 300–600 Gökkaya et al. [78]
KOH, Dolomite, Trona yield and low residue yield.
and Borax • Ru/activated carbon had the
best activity for increasing
H2 yields.

• High thermal stability and high

Bubbling fluidized
Willow wood chips - 600–850 carbon conversion efficiency of Hai et al. [79]
bed reactor
willow chips were observed.

3.5. Transesterification
Transesterification is the process by which non-edible oils react with alcohols (methanol
and ethanol) to produce biodiesel. These alcohols are widely used since they are easily
Energies 2022, 15, 6352 13 of 23

available and inexpensive. Transesterification is known to decrease the viscosity of non-

edible oils and facilitate the formation of triglycerides into esters with easy miscibility in
diesel [80]. Figure 5 represents the process flow diagram for biodiesel production through
Energies 2022, 15, x FOR PEER REVIEW 14 of 24
transesterification. The waste fat and oil are mixed with alcohol to produce methyl esters
and methanol. The methyl esters can be catalytically converted into glycerol and biodiesel.
The biodiesel methanol mixture can be further separated and re-used, whereas methyl ester
and biodiesel. The biodiesel methanol mixture can be further separated and re-used,
can be catalyticallywhereas converted
methyltoester
glycerol
can beand biodiesel
catalytically [81]. to glycerol and biodiesel [81].
converted

Figure 5. Typical process representation of transesterification of waste fats and oil.

Figure 5. Typical process representation of transesterification of waste fats and oil.
Biodiesel can be produced using homogeneous and heterogeneous acid and alkaline
Biodiesel can catalysts.
be produced Due tousing homogeneous
their high and heterogeneous
activity, homogeneous acid used
catalysts are typically andinalkaline
chemical
catalysts. Due to their high activity, homogeneous catalysts are typically
reactions. However, due to the difficulty in recovering the spent homogeneous used in chemical
catalysts,
reactions. However, thedue to thecost
operating difficulty in recovering
of the process could increase.the Heterogeneous
spent homogeneous catalysts arecatalysts,
relatively
easier for recovery and subsequent recyclability [82].
the operating cost of the process could increase. Heterogeneous catalysts are relatively Additionally, mineral acids and het-
erogeneous base catalysts are combined in solid acids catalysts of Brønsted type (e.g., ma-
easier for recoveryterials
andcontaining
subsequent recyclability [82]. Additionally, mineral acids and
sulfonic acid) and Lewis type (e.g., mixed sulfated oxides). However,
heterogeneous base catalysts are combined in solid acids using
the production of soap during transesterification catalysts of Brønsted
heterogeneous type
catalysts is a(e.g.,
draw-
materials containing backsulfonic
leading toacid) andinLewis
challenges producttype (e.g., mixed
purification sulfated
and separation [83].oxides). How-
ever, the production ofThe soap application
duringoftransesterification
alkali catalysts can make the transesterification
using heterogeneousprocess faster is
catalysts witha
drawback leading better yields and product selectivity. Catalytic conversion of oil to biodiesel consists of
to challenges in product purification and separation [83].
acid-catalyzed esterification and base-catalyzed transesterification. Acid catalysts are uti-
The application offor
lized alkali catalysts
esterification or can make
free fatty the(FFA).
acids transesterification
Some examples ofprocess faster
acid catalysts arewith
phos-
better yields and product
phoric acid,selectivity. Catalytic
sulfuric acid, organicconversion
sulfonic acidsof andoilhydrochloric
to biodiesel consists
acid [84]. Evenofthough
acid-
the useand
catalyzed esterification of acid catalysts for transesterification
base-catalyzed makes it slower
transesterification. in comparison
Acid catalysts aretoutilized
alkali ca-
for esterification ortalysis, they are
free fatty appropriate
acids (FFA). for Someglycerides that contain
examples more
of acid water and
catalysts FFAs.
are Some of the
phosphoric
alkali catalysts used for transesterification are NaOH, KOH, carbonates and alkoxides
acid, sulfuric acid, such
organic sulfonic acids and hydrochloric acid [84]. Even though the use
as sodium methoxide (CH3NaO) and sodium ethoxide (C2H5ONa) [85]. The alkali-
of acid catalysts for transesterification
catalyzed transesterification makes
is rapiditasslower
compared in to
comparison
acid catalysts.to alkali catalysis,
Regardless of catalytic
they are appropriate for glycerides
or non-catalytic that
routes, contain morerequires
transesterification waterthe and FFAs. Some
separation of the
of alcohol, oil, alkali
applied
catalyst and other impurities from the liquid products.
catalysts used for transesterification are NaOH, KOH, carbonates and alkoxides such as
sodium methoxide (CHSome NaO) of the benefits of using solid acid catalysts include recyclability, product selec-
and sodium ethoxide (C2 H5 ONa) [85]. The alkali-catalyzed
tivity, 3regeneration and minimization of reactor corrosion [86]. Nevertheless, heterogene-
transesterification ous
is rapid as compared
catalytic processes can produce to acidhigh-quality
catalysts. oils Regardless
due to theirof catalytic
sensitivity or non-
toward high
catalytic routes, transesterification
FFAs. Heteropoly acids requires
(HPAs)the areseparation of alcohol,
among the several oil,catalysts
solid acid appliedeffective
catalyst for
and other impurities biodiesel
from production
the liquiddue to their strong acidity and elevated tolerance to high FFA levels
products.
and water
Some of the benefits of content
using [87].
solidSome
acidother advantages
catalysts includeof HPAs are their elastic
recyclability, structure,
product excep-
selectiv-
tional dispersion and appropriate interaction with support materials. The surface area and
ity, regeneration and minimization of reactor corrosion [86]. Nevertheless, heterogeneous
thermal stability of the catalyst are increased when HPAs are immobilized on a suitable
catalytic processes support
can produce materialhigh-quality oils due toshould
[88]. Careful consideration theirbe sensitivity
given to thetoward high FFAs.
support material’s sur-
Heteropoly acids (HPAs)
face area areand among
porosity, thewhichseveral solidthe
can increase acid catalysts
catalyst’s effective
effectiveness andfor biodiesel
activity.
production due to theirInstrongenzyme-catalyzed
acidity and transesterification,
elevated tolerance lipase enzyme
to high acts as a levels
FFA bio-catalyst
andfor trans-
water
esterification reactions [89]. Enzymes have a huge possibility for dropping the necessity
content [87]. Some other advantages of HPAs are their elastic structure, exceptional dis-
persion and appropriate interaction with support materials. The surface area and thermal
stability of the catalyst are increased when HPAs are immobilized on a suitable support
material [88]. Careful consideration should be given to the support material’s surface area
and porosity, which can increase the catalyst’s effectiveness and activity.
Energies 2022, 15, 6352 14 of 23

In enzyme-catalyzed transesterification, lipase enzyme acts as a bio-catalyst for trans-

esterification reactions [89]. Enzymes have a huge possibility for dropping the necessity
of high energy requirements and reducing the environmental complications in biodiesel
refineries. Enzymatic transesterification takes place at a comparatively lower temperature
as compared to other acid and base-catalyzed transesterification reactions to avoid the
loss of lipase activity. Since the lipase-catalyzed reactions require moderate temperature,
enzymatic transesterification is less energy-intensive. There are several benefits of enzy-
matic transesterification such as high selectivity, mild reaction conditions and availability
of a wide range of substrates. Nevertheless, the cost, stability and low recyclability of
enzymes are some of the limitations that require more research [90]. Table 6 summarizes
some notable work on the conversion of waste oils to biodiesel via transesterification.

Table 6. Summary of notable works on transesterification of waste oil and biomass to biodiesel.

Feedstock Catalyst Reactor Temperature (◦ C) Observations Reference

• The optimized conditions for
Biomass from the
transesterification involved the
oleaginous yeast
temperature of 50 ◦ C, reaction time of
Yarrowia lipolytica H2 SO4 - 65–110 Katre et al. [91]
8 h, sonication time of 5 min, 100 mL
cultivated on waste
methanol, 10 mL chloroform, 1 mL/g
cooking oil
catalyst and 4 g biomass.

• The rate of reaction was strongly

influenced by catalyst loading, Bashiri and
Soyabean oil NaOH Stirred tank reactor 50
reaction rate, oil-to-methanol ratio Pourbeiram [92]
and temperature.

• The conversion rate of 97% was

obtained under optimal conditions
such as a temperature of 55 ◦ C, the
oil-to-methanol ratio of 1.94, catalyst
Heater equipped with
Waste cooking oil CaO and Clay 45–55 loading of 9.6 wt.%, toluene Mohadesi et al. [93]
a magnetic agitator
concentration of 16.1 wt.% and
reaction time of 74 min.
• The catalyst was reusable up to
5 times.

• The blending of biodiesel with

commercial diesel was an effective
Waste frying oil NaOH Shake flask 55 Duti et al. [94]
method to reduce its viscosity for
direct use in diesel engines.

• A high percentage of biodiesel was

obtained implying that the
Wet sewage sludge H2 SO4 Hydrothermal reactor 70–160 hydrothermal process can stimulate Hu et al. [95]
the transfer of lipids from feedstock to
the separating solvent.

4. Major Biofuel Products

4.1. Biochar
Biochar, a solid co-product of pyrolysis and high-temperature torrefaction, is rich in
carbon and can be prepared from several kinds of raw materials such as crop residues,
woody biomass and other solid wastes. Biochar is primarily composed of carbon and
smaller fractions of minerals based on the precursor or feedstock. It has been revealed that
the higher yields of biochar are inversely proportional to the pyrolysis temperatures. Hence,
the low pyrolysis temperature contributes to high yields of biochar, electrical conductivity
and cation-exchange capacity in addition to high levels of volatiles [96]. In contrast, biochar
obtained at higher temperatures has a greater surface area as well as carbon content.
Biochar is gaining popularity owing to its exclusive features such as a high percent-
age of carbon and cation exchange capacity, greater surface area and thermally stable
structure [96,97]. Similarly, due to the presence of a high percentage of carbon, the char
encompasses high energy content that in turn can be utilized to produce heat to prepare
activated carbon. Other applications of biochar are as a nutrient for soil remediation and
as a filtrate for pollutants. Biochar is also used as an adsorbent to sequester heavy metals
and organic micro-pollutants. Its ability to be used as an adsorbent results from its physico-
chemical properties such as distribution of pore size, surface area, functional groups and
Energies 2022, 15, 6352 15 of 23

cation exchange capacity [98]. Recently, the utilization of biochar as a catalyst supports
particularly for the processes of upgrading bio-oil such as esterification, hydrotreating,
and hydrodeoxygenation is gaining a lot of attention [99]. Biochar is recently being recog-
nized as a promising bioresource as a fuel and reducing agent to replace coal and coke in
metallurgical processes [100].
Hydrochar is a carbon-rich product of hydrothermal conversion processes such as
hydrothermal gasification, hydrothermal liquefaction and hydrothermal carbonization.
They exhibit dissimilar physicochemical properties when compared with biochar due to
different operating conditions involved in their production. The atomic ratios of H/C and
O/C of hydrochar are relatively higher when compared to that of biochar [96]. Moreover,
hydrochar contains more oxygenated functional groups and is slightly acidic compared to
biochar [101]. On the other hand, biochar tends to display alkaline characteristics due to
the presence of alkali and alkaline earth metals [102]. This property of biochar is beneficial
for application to acidic soils for neutralization of the soil pH levels. Hydrochar also
exhibits a relatively low specific surface area and porosity when compared to biochar.
However, the properties of hydrochar could be tailored for various industrial applications
including catalysts support, activated carbon production, wastewater treatment, and soil
remediation [103].

4.2. Bio-Crude Oil

Bio-crude oil is an energy-rich liquid product that can be produced via thermochemical
routes such as hydrothermal liquefaction. Nevertheless, bio-crude oil obtained from both
the above-mentioned routes has some unwanted properties including a high amount of
moisture, high acidity, high tendency to corrode. These undesirable properties should be
eliminated before utilizing the bio-crude oil in refineries for co-processing or to be used as
a commercial fuel in transportation [104].
Algae are considered suitable as a feedstock for bio-crude oil production via HTL ow-
ing to their higher efficiency for photosynthesis, fast growth, no requirement of agricultural
lands, cultivation in wastewater, less dependency on nutrients, CO2 capture and fixation
and higher production of lipids [105]. Nowadays, bio-raw oil production from microalgae
is gaining popularity. The nitrogen recovery from unrefined oil is lower than that from
pure algae [106].
Bio-crude oil and bio-oil have a few unsought characteristics such as a high percentage
of moisture, high viscosity, greater ash content, a high fraction of oxygen, and a tendency to
corrode the reactors due to high acidity. These undesirable properties need remedy before
utilizing the bio-oil in the refineries and the power sectors. This is achieved by catalytic and
non-catalytic upgrading technologies (discussed earlier) that reduce the contents of oxygen,
nitrogen and sulfur from bio-crude and bio-oil along with enhancing their fuel properties
such as heating value, viscosity, reduced corrosivity, reduced polymerization and lower
emissions [107]. Therefore, it is imperative to enhance the bio-crude oil properties to make
it commercially viable via catalytic upgrading or any other economically viable upgrading
technologies. Specifically, a catalyst with high product selectivity, reactive performance,
low cost, durability, reusability and resistance to high temperatures and coking is mostly
preferred for upgrading bio-crude oil and bio-oil.

4.3. Bio-Oil
Bio-oil is defined as the key product derived from the pyrolysis of biomass. The
feature and yield of bio-oil are dependent on the residence time, temperature, heating
rate and biomass composition [108]. The major constituent of bio-oil is water which
generally comprises 30–40 wt.% of bio-oil [109]. The reason for the presence of water
could be attributed to the amount of moisture in the biomass as well as dehydration and
decarboxylation reactions taking place during pyrolysis [110]. Bio-oil also contains phenols,
hydrocarbon derivates and esters, concentrations of which depend on biomass properties
and process parameters. Bio-oil particularly obtained from the lignocellulosic biomass is a
Energies 2022, 15, 6352 16 of 23

combination of the degraded product obtained from the hemicellulose, cellulose and lignin.
The specific degraded product from the cellulose and hemicellulose that are present in
bio-oil are acids, furans, sugars, aldehydes, esters and oxygenates [111].
The chemical composition of the biomass feedstock also performs a key role in the
characteristic and yield of bio-oil during thermochemical conversion processes. The major
issues related to the utilization of bio-oil are its low energy density, tendency to corrode the
reactor, high viscosity, thermal instability, polymerization and presence of a high percentage
of heteroatoms (e.g., oxygen, nitrogen and sulfur) [110]. In addition, bio-oil is known to be
chemically unstable and highly oxygenated in its raw form, thus requiring upgrading as
discussed earlier.

4.4. Syngas
Syngas is a major product of biomass to gas technologies such as gasification. It
comprises gaseous mixtures such as H2 , CO2 , CO and CH4 as the key components. Syngas
is an important intermediate in the chemical industry that can be used for the manufacture
of transportation fuels and green chemicals [70]. Another application of syngas is its direct
use as a fuel for generating electricity [112]. Hydrogen is an important constituent of
syngas. Owing to its exceptional properties has appeared as an ideal renewable future
energy carrier. Hydrogen is used in a variety of industrial applications including fuel cells,
synthesis of platform chemicals, medicines, aerospace, maritime purposes, metallurgy and
electrical devices.
The hydrogen economy is an anticipated system where hydrogen produced is widely
utilized as an energy carrier. The effective deployment of hydrogen economy will result in
several benefits concerning profitability, energy security, environment and end-users [113].
Although hydrogen energy is considered substitute energy, currently, its usage is restricted
only to small-scale operations. The major challenge associated with the large-scale pro-
duction of hydrogen energy is difficulty in the distribution and commercial application
of hydrogen energy [114]. As competition is absent in, hydrogen energy currently, the
governments are recommended to execute policies to promote the portable, stationary and
transportation applications of hydrogen energy.

4.5. Biodiesel
Biodiesel is one of the extensively recognized sustainable biofuels. The crucial fact for
the industrial manufacturing of biodiesel is the low cost of its feedstock, i.e., non-edible oils
as well as waste fats and oils. Biodiesel is preferred over traditional petrol and diesel due to
its characteristics such as non-toxicity, biodegradability and negligible levels of aromatics
and sulfur. With these properties, biodiesel or its blended counterparts can also perform
better than ultra-low sulfur fuel [115]. In most countries, B20 biodiesel blended fuel is
used, which is made of 6–20 vol.% biodiesel in fossil-based diesel fuel. The low biodiesel
fraction in B20 blended fuel makes it suitable for direct use in many diesel-fueled vehicles
worldwide without engine modification.
The commonly used precursors for generating biodiesel are triglyceride-based ma-
terials such as animal fat, vegetable oil (edible and non-edible), waste cooking oil, waste
industrial oil and algal oil. A variety of oilseed crops contribute to biodiesel production
such as mustard, soybean, camelina, cottonseed, canola, sunflower seed, peanuts and
rapeseeds as discussed earlier. Oilseeds have adequate quantities of fat that make their
extraction easy.
Biodiesel can be produced via transesterification using homogeneous and hetero-
geneous catalysts. Potassium methoxide (KOCH3 ), sodium hydroxide (NaOH), sodium
methoxide (NaOCH3 ), hydrochloric acid (HCl), sulfonic acid, organic sulfonic acid, sulfuric
acid (H2 SO4 ) and iron sulfate are some common homogeneous alkali catalysts used for
biodiesel production. Some of the heterogeneous catalysts used are CaO, Ca(OH)2 and
CaCO3 . Heterogeneous catalysts are recyclable, non-corrosive and more effective as com-
pared to homogenous catalysts [116]. It has been observed that biodiesel contributes to
Energies 2022, 15, 6352 17 of 23

fewer emissions in comparison to diesel fuel. There are several reasons for biodiesel being
used as a substitute fuel such as sustainable and renewable energy solution, lesser influence
on climate, decrease in GHG emissions and feasible drop-in substitute to petro-diesel. By
replacing traditional fuels with biodiesel, emissions of particulate matter, CO2 , CO and
unburned hydrocarbons can also be lessened.

5. Strengths, Weaknesses, Opportunities and Threats Analysis

As discussed in this review, some promising thermochemical technologies for bio-
fuel production from biomass are torrefaction, pyrolysis, liquefaction, gasification and
transesterification. Each of these technologies has advantages and limitations that are criti-
cal to understanding to determine their performance, commercialization aspects, techno-
economics and marketability of the products. The key summary of this review in the form of
strengths, weaknesses, opportunities and threats of these thermochemical waste-to-energy
technologies are shown in Table 7.
Table 7. Summary of strengths, weaknesses, opportunities and threats of thermochemical biomass
conversion technologies.

Technology Strengths Weaknesses Opportunities Threats

• It can be used both as a
pretreatment and biomass
conversion technology.
• High energy content per • Lower overall efficiency.
unit volume. • Optimization of • Torrefaction improves the
• Volatilization of phenol,
• Improves the calorific value torrefaction reactors is characteristics of
acetone, and other
of biomass. essential to meet the feedstock in numerous
Torrefaction contaminants, makes
• Pelletizing torrefied end-use necessities ways and can be used as a
flue gas cleaning
biomass makes its financially and reach direct fuel.
more challenging.
transportation easy for product standardization • No catalyst is required.
long-distance. for the market.
• Reduces moisture content.
• Low energy input.
• Reduced operating costs.

• High efficiency.
• Probable applications of
• Complex product stream
produced compounds (e.g.,
• Difficulty in venting out
tar, bio-oil, and char). • Feasibility is established
product gases without • Extensive expertise
• Reduces greenhouse gases only in large-scale plants
treatment owing to high • Development of the
Pyrolysis and wastes going to • Not much efficient for
concentrations of CO. market for pyrolysis
landfills. sewage sludge.
• Issues with recyclability liquid and char products.
• Requires lower energy • High cost.
of homogeneous and
input for slow pyrolysis.
carbon-based catalysts.
• Requires higher energy
input for fast pyrolysis.

• A promising method for

wet biomass. • The feedstock and the
• Drying is not necessary. • Possibility of corrosion. conditions of the
• Easy recovery of inorganics. • Salt deposition in production frequently
• Lower critical point. the reactor. influence the chemical
• High energy efficiency.
• High-energy bio-crude is • No harmful solvents and physical attributes of
Liquefaction • Apt for generating biofuels.
obtained via hydrothermal are involved. bio-oil.
liquefaction and the product • Issues with recyclability • Difficulty in eluting
is low in oxygen and of homogeneous and heavy compounds that
moisture content as carbon-based catalysts. remains uncharacterized
compared to pyrolysis in the column.
bio-crude.
Energies 2022, 15, 6352 18 of 23

Table 7. Cont.

Technology Strengths Weaknesses Opportunities Threats

• Syngas can be directly
• High operating cost.
utilized as a fuel or for • Largescale operations
• High maintenance cost. • Lack of subsidies
value-added products such are possible.
Gasification • Issues with recyclability to farmers.
as synthetic natural gas, • High unexploited potential.
of homogeneous and • High cost.
chemicals, hydrogen,
carbon-based catalysts.
kerosene, naphtha, etc.

• Incidence of unsought
reactions
• Short reaction times.
• Sensitivity of the catalysts
• The cost of the production
towards the existence of • Large-scale production
process is relatively lower. • High biodiesel
water in the feedstock. is possible.
Transesterification • The reaction condition can blending requires
• High concentrations of • High conversion of
be regulated. engine modification.
glycerol and methanol are the feedstocks.
• The methanol generated in
obtained as wastes.
the process can be recycled.
• Issues with recyclability of
homogeneous catalysts.

6. Conclusions
Waste biomass is an exceptional bioresource for valorization to usable forms of energy
carriers such as bio-oil, bio-crude oil, biodiesel, syngas, hydrogen and biochar. As reviewed in
this article, biomass can be categorized into agricultural and forestry biomass, energy crops,
oilseed crops, food waste, municipal solid waste and animal manure. These waste resources
can be converted to biofuel products through thermochemical technologies such as torrefaction,
pyrolysis, gasification, liquefaction and transesterification. Torrefaction results in the production
of torrefied biomass with reduced moisture content and increased heating value in a densified
form factor. Pyrolysis and liquefaction lead to the production of bio-oil and bio-crude oil because
of the thermal cracking of cellulose, hemicellulose, lignin and other organic matter present
in biomass under inert atmospheres and process conditions optimal to produce bio-oil and
bio-crude oil, respectively. Gasification results in the production of syngas, a mixture of H2 and
CO along with CO2 and CH4 under inert, air or hydrothermal conditions (i.e., steam and/or
supercritical water). Biochar is a co-product of pyrolysis and gasification that has a higher
content of fixed carbon. The aromaticity, thermal stability, calorific value, surface area and
porosity of biochar can be improved at higher temperatures. Biodiesel is generated through
transesterification of fatty acids and lipids in waste vegetable oil and/or animal fat mostly in the
presence of chemical or biocatalysts. Nonetheless, the yield and quality of the biofuel products
as well as the process efficiency depend on factors including biomass composition and process
conditions (i.e., temperature, pressure, reaction time, reactor type, applied catalyst, etc.). The
biofuel products can be used as drop-in alternatives to fossil fuels or as blends to reduce GHG
emissions, pollution, global warming and dependency on fossil fuels.

Author Contributions: Conceptualization, S.J., S.N., B.A. and A.K.D.; investigation, S.J., S.N. and
B.A.; resources, B.A. and A.K.D.; data curation, S.J., S.N. and B.A.; writing—original draft preparation,
S.J., S.N. and B.A.; writing—review and editing, S.N., B.A. and A.K.D.; supervision, B.A. and A.K.D.;
project administration, B.A. and A.K.D.; funding acquisition, A.K.D. All authors have read and agreed
to the published version of the manuscript.
Funding: The authors would like to thank the funding received from the Natural Sciences and
Engineering Research Council of Canada (NSERC), the Canada Research Chairs (CRC) program,
Agriculture and Agri-Food Canada (AAFC) and BioFuelNet Canada to support this research.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.
Energies 2022, 15, 6352 19 of 23

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