Environmental Technology & Innovation: Shubhi Gupta, Prasenjit Mondal, Venu Babu Borugadda, Ajay K. Dalai

Environmental Technology & Innovation 21 (2021) 101276
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Environmental Technology & Innovation

journal homepage: www.elsevier.com/locate/eti
Advances in upgradation of pyrolysis bio-oil and biochar

towards improvement in bio-refinery economics: A
comprehensive review
∗
Shubhi Gupta a , Prasenjit Mondal a , , Venu Babu Borugadda b , Ajay K. Dalai b
a
Department of Chemical Engineering, Indian Institute of Technology Roorkee, Roorkee, Uttarakhand 247667, India
b
Department of Chemical and Biological Engineering, University of Saskatchewan, 57 Campus Drive, Saskatoon S7N 5A9, Canada
article info a b s t r a c t
Article history: Depletion of fossil fuel reserves and ever-increasing energy demands necessitates ex-
Received 31 May 2020 ploring green and renewable biofuels. Though biomass-based fuels have the potential to
Received in revised form 28 September 2020 replace fossil fuels but the low quality of fuels along with high process economics limits
Accepted 26 November 2020
direct application. Concept of integrated bio-refinery is the unparalleled solution to this
Available online 13 December 2020
problem which involves the production of hydrocarbon grade fuels along with valuable
Keywords: chemicals from the pyrolysis derived bio-oil. This paper reviews recent advances in
Biomass upgradation techniques of bio-oil along with moisture removal techniques and recovery
Bio-oil upgradation of valuable chemicals from bio-oil. It also reviews current advances in the utilization
Chemical extraction of co-product such as biochar to increase the overall economics of the process. It also
Deoxygenation
elucidates the challenges encountered as well as scope for future work. The current
Biochar
review is peculiarly based on pyrolysis based bio-refinery with detailed literature on
the techniques of conversion of pyrolysis derived bio-oil into valuable biofuels and
industrial grade chemicals with a view to improve the overall economics of the process
through biochar utilization, which is not covered in other reviews. As compared to other
published studies, this work provides more comprehensive information on the topic,
which will give better understanding to a new researcher as well as help to plan and
develop new techniques on bio-refinery for attaining the aim of cleaner and sustainable
future.
© 2020 Elsevier B.V. All rights reserved.
Contents
1. Introduction............................................................................................................................................................................................... 2
2. Pyrolysis products properties and composition ................................................................................................................................... 4
3. Scope of value additions through oil and char upgradation............................................................................................................... 12
4. Advances in moisture removal techniques ........................................................................................................................................... 13
5. Chemical recovery from aqueous phase as well as organic phase .................................................................................................... 15
6. Advances in upgradation techniques of residual organic phase ........................................................................................................ 15
6.1. Emulsification of bio-oil with hydrocarbon fuels .................................................................................................................... 15
6.2. Blending the bio-oil with heavy gas oil and co-refining ........................................................................................................ 17
6.3. Upgradation through deoxygenation ....................................................................................................................................... 17
6.4. Other miscellaneous techniques ................................................................................................................................................ 22
∗ Corresponding author.
E-mail address: mondal2001@gmail.com (P. Mondal).
https://doi.org/10.1016/j.eti.2020.101276
2352-1864/© 2020 Elsevier B.V. All rights reserved.
S. Gupta, P. Mondal, V.B. Borugadda et al. Environmental Technology & Innovation 21 (2021) 101276
7. Advances in biochar utilization .............................................................................................................................................................. 22

7.1. Biochar as a soil amendment ..................................................................................................................................................... 22
7.2. Biochar as a support material and precursor for catalyst synthesis ..................................................................................... 22
7.3. Biochar for gas adsorption and as a sorbent for contaminant reduction, heavy metal removal in soil and water ....... 23
7.4. Biochar in fuel cells, as electrodes in fuel cell systems and supercapacitors ...................................................................... 23
7.5. Biochar application in bioprocessing: Anaerobic digestion, composting and fermentation............................................... 23
8. Techno-economic evaluation of the integrated bio-refinery concept ................................................................................................ 27
9. Challenges and future scope for development ..................................................................................................................................... 28
10. Summary ................................................................................................................................................................................................... 29
Declaration of competing interest.......................................................................................................................................................... 30
Acknowledgments .................................................................................................................................................................................... 30
References ................................................................................................................................................................................................. 30
1. Introduction
With the increase in technological advancement and industrialization, demand for energy is increasing worldwide
leading to the problem of energy crisis. As stated by International Energy Agency (IEA), around 82% of the global energy
requirements are fulfilled through fossil fuel reserves of which are depleting day by day (International Energy Agency (IEA),
2018). According to the world energy resources survey 2016, about 63% requirement of transportation fuels is attained
only through conventional hydrocarbon fuels (World Energy Resources Survey, 2016). Moreover, fossil fuel produces CO2
emissions and other emissions like NOX , SOX, etc. to the atmosphere leading to the pollution problem. In 2015, the United
Nations General Assembly (UNGA) adopted Sustainable Development Goals (SDG) to provide a framework for international
collaboration to achieve a sustainable future for the earth. ‘Agenda 2030’ has 17 SDG with 169 targets to fight injustice and
inequality, end poverty and protecting the earth’s environment. Among all, sustainable energy or SDG 7 is the central goal
for ‘Agenda 2030’ to increase renewable energy share in the global energy mix, improve energy efficiency, and achieve
affordable, reliable, and universal access to new energy services (Gielen et al., 2019). In 2015, about 194 countries signed
the Paris Climate Agreement to reduce global temperature rise by 2 ◦ C by cutting down the harmful greenhouse gas
emissions and exploring new alternative energy resources (Saravanan et al., 2018). Thus, there is an urgent need to search
for an alternative renewable and clean energy source that can reduce fossil fuel consumption. Among all other renewable
sources of energy, biomass seems to be an effective and emerging alternative, which grows continuously on earth and
accounts for 40% of the primary energy needs (British Petroleum Report, 2018). It is one of the most renewable energy
sources which have great potential for solving energy-related problems such as the ‘‘greenhouse’’ effect and the depletion
of non-renewable energy resources. Combustion of biomass emits roughly the same amount of CO2 as taken up during
plant growth; therefore, it does not contribute to a buildup of CO2 in the atmosphere (Cherubini et al., 2011). National
Policy on Biofuels was approved in India in 2018 to increase the replacement of fossil fuels by clean and renewable
biomass-based fuels, aiming to achieve 20% blending of biofuels with fossil-based fuels by the year 2030 (Saravanan
et al., 2018). Among all other thermochemical methods of extracting energy from biomass such as combustion, pyrolysis,
and gasification; pyrolysis is the most suitable pathway to drive a wide variety of energy-rich products from biomass at
a comparatively lower temperature.
Pyrolysis is the process of thermochemical conversion of biomass in which biomass is heated in inert atmosphere
leading to the production of liquid (bio-oil), solid (biochar) and gaseous (non-condensable gases) products (Cherubini et al.,
2011; Açıkalın and Karaca, 2017). Pyrolysis has been utilized from ancient times to produce charcoal, but the production of
transportation fuels is a recent development. All three products have their own commercial applications, making it more
effective for converting biomass. Bio-oil is the main product of pyrolysis that can potentially be utilized as a transportation
fuel in place of hydrocarbon fuels like diesel and other heavy fuels (Onay, 2007). Temperature, heating rate, residence time,
N2 flow rate, etc. are important process variables affecting yield and properties of products obtained through pyrolysis
(Park et al., 2008; Salehi et al., 2011). Gasification is another thermochemical conversion process, which drives energy from
biomass in the form of gaseous fuel. Pyrolysis has distinct advantages over gasification. Pyrolysis products are much easier
to transport and store as compared to syngas produced via gasification. Pyrolysis produces wide range of products such as
bio-oil, biochar and gases, having range of applications in various fields. Pyrolysis is quite flexible in terms of its operating
conditions. It can be easily optimized depending on the desired product, while gasification is a rigid process that requires
a detailed adjustment of process conditions. Also, lower temperature during pyrolysis as compared to gasification makes
it a bit cheaper process (Tripathi et al., 2016). Additionally, lesser emission during pyrolysis compared to gasification,
too makes it superior to gasification (Tripathi et al., 2016). Depending on the operating parameters, pyrolysis can be of
different types, as shown in Table 1, with different distributions of product. Thus, the pyrolysis process can be selected
based on the main product requirement. Pyrolysis of biomass produces fuels containing a lower amount of sulfur and
nitrogen than fossil fuels (Miao and Wu, 2004).
Fast pyrolysis is the most appropriate and widely used process among all the processes for the production of bio-oil
from biomass. It can give the highest yield of bio-oil, about 65%–70%, through high heat and mass transfer rates and rapid
removal and quenching of volatile vapors (Xianwen et al., 2000; Arni, 2018). Although the higher yield of oil is obtained
2
Table 1
Comparison of different pyrolysis processes on the basis of operating conditions (Park et al., 2008; Salehi et al., 2011).
Pyrolysis types Temperature (◦ C) Heating rate (◦ C/s) Residence time Major products
Torrefaction 200–300 – Days Charcoal
Slow pyrolysis 400–600 0.1–0.3 30-60 min Biochar, bio-oil, gas
Fast pyrolysis 700–1200 10–100 10 s Bio-oil
Flash pyrolysis 800–1150 >1000 1 s Bio-oil
through flash pyrolysis, studies showed that low-quality bio-oil is obtained through flash pyrolysis with low thermal
stability, high solid content, high water content and high corrosivity. Its viscosity and corrosive property increases during
storage (Kumar and Nanda, 2016).
Key problems associated with direct use of bio-oil in combustion engines are low energy density, high viscosity,
corrosiveness, high solid content and high thermal instability compared to hydrocarbon fuels (Zheng et al., 2008; Gupta
et al., 2019). Thus, it requires significant upgradation so that its properties reach up to that of hydrocarbon fuels. Further,
bio-oil contains large number of undesirable oxygenated compounds such as aldehydes (like acetaldehyde, formaldehyde),
acids (such as acetic and propanoic acid), ketones (including acetone, cyclopentanone), alcohols (like methanol and
ethanol), phenols (including phenol, methyl phenol, dimethyl phenol), furans (such as furfurol, furfural), sugars (1,6-
anhydroglucose), miscellaneous oxygenates (glycolaldehyde, acetol) and many more (Gupta and Mondal, 2020; Lu et al.,
2008). It also contains a high amount of water around 30%–40% (m/m or v/v) and many of these chemicals are present in
the aqueous phase of the bio-oil.
Thus, there is an urgent need to improve the properties of pyrolysis oil before its commercial utilization. There are
many methods available for upgrading bio-oil, but the process of evolving maximum high-value products with minimum
waste is desirable. To achieve this target, an integrated bio-refinery concept is being investigated. Firstly, in this process,
moisture is separated from the bio-oil as aqueous phase using different available methods and then valuable chemicals are
extracted from the aqueous phase to improve process economics. Some chemicals may also be recovered from the organic
phase. The residual organic part of bio-oil is then upgraded to transport fuel using several methods such as deoxygenation,
catalytic cracking, hydrocracking, emulsification as well as blending with heavy fuel oils followed by refining. This leads
to the way towards the improvement of overall process economics by extracting highly valuable chemicals from bio-oil
and upgrading the residual oil into transport fuel.
Numerous review articles have been published on the concept of integrated bio-refinery aiming to produce fuels and
valuable chemicals with zero-waste production. Most of the reviews on this subject give general overview of the concept
describing different type of bio-refineries (such as pyrolysis based bio-refinery, biosyngas based bio-refinery, hydrothermal
based bio-refinery and fermentation based bio-refinery) highlighting their importance and barriers associated with them
but very few are based on any single type of bio-refinery process providing more exhaustive review (Demirbas, 2009;
Banu et al., 2020; Neves et al., 2020). Several reviews on the conversion of different industrial wastes such as food
processing wastes, winery waste and eucalyptus wood waste based on the concept on integrated bio-refinery through
thermochemical and biochemical conversion into several high-value bioproducts, fuels, organic acids, organic fertilizers,
etc. have been published (Teigiserova et al., 2019; Ahmad et al., 2020; Penín et al., 2020). Most of the studies have
discussed on the recent developments and challenges in microalgal based hydrolysis, fermentation as well as combined
thermochemical processes for the conversion of microalgae into energy rich biofuels (ethanol, butanol) and valuable
bioproducts (biogas, biofertilizers, bio-oil, biochar) based on zero waste bio-refinery concept (Cuevas-Castillo et al., 2020;
Fan et al., 2020; Rajak et al., 2020). A recent review by Hassan et al. (2019) provides critical update on future of bio-
refinery industries along with technical challenges. It provides emphasis on its role in bioeconomy. Among most of the
recently published reviews, a review based explicitly on the bio-refinery model of algal biomass to produce biofuels and
bio-products discussed in detail different processes such as transesterification, oil extraction, fermentation, anaerobic
digestion, hydrothermal liquefaction, pyrolysis and gasification (Kumar et al., 2020b). A recent review on activation
and functionalization of biochar to produce biochar supported catalysts for numerous applications such as pollutants
degradation, bio-syngas reforming, tar removal, biodiesel and value-added chemicals production has been published
(Kumar et al., 2020c). Kumar et al. (2020a) also presented an innovative approach to produce bio-diesel from fatty acids
and triacylglycerol (TAG) produced from bacterial metabolism using waste materials as carbon source. Another review
of Nie et al. (2020) on microalgal technology discussed the bioremediation of pesticides containing water. Briefly, it
introduced waste microalgae recycling by converting biodiesel and biochar through the bio-refinery approach. But it
involves very little discussion on the bio-refinery model of microalgae oil conversion to biodiesel by focusing only on
transesterification. Thus, a lot of work has been done in the field of integrated bio-refinery conversion but till date, there
has been no study that is individually based on pyrolysis based bio-refinery with an exhaustive review on the different
available technologies for conversion of pyrolysis derived bio-oil into valuable biofuels and chemicals. The present study
is different from most of these recently published reviews. The current review involves detailed, exhaustive discussion
on bio-refinery model of specifically pyrolysis process with different biomass feedstocks. It discussed the conversion and
utilization of pyrolysis derived bio-oil into biofuels and industrial grade chemicals along with advanced biochar utilization
pathways in a view to present a more complete model of bio-refinery which will help to improve the overall process
economics.
3
Table 2
Comparison between properties of bio-oil and hydrocarbon fuels (Ikura et al., 2003; Miao and Wu, 2004; González
et al., 2005; Yin et al., 2010).
Properties Bio-oil Diesel Gasoline
Ultimate analysis (wt. %)
C 54–58 86 87
H 5–8 11 13
O 34–40 0.02 Negligible
N 0-0.3 0.06 –
pH 2–3 7 7
Water content (wt. %) 20–40 Negligible 0–0.01
Viscosity (Cst) at 50 ◦ C 26–1000 <2.30 0.77
Density (kg/m3 ) 1200–1300 854 746
Pour point (◦ C) −10 to −20 −23 −40 to −50
Flash point (◦ C) 60–80 85 −45
Heating value (MJ/kg) 16–20 44.5 46
This current study reviews detailed literature and recent advances on each of the different techniques involved for
product utilization and concepts of moisture removal, valuable chemical extraction, emulsification, bio-oil co-processing
in FCC refinery and bio-oil deoxygenation techniques. It also discusses in detail the advancements in biochar utilization
in different fields, including in catalysis and bioprocessing. Also, this review explored the possibility of utilizing biochar
in the process of upgrading bio-oil to make the process more integrated and economically feasible. A critical analysis
of different methods has been discussed in detail. Challenges and scope for further development to make the process
technically and economically viable have also been identified and discussed. Thus, as compared to published literatures
including latest ones (Ahmad et al., 2020; Fan et al., 2020; Neves et al., 2020), this work will aid to the knowledge of the
readers working in the area of pyrolysis and its utility, further this review will help to plan their future research more
effectively, towards the aim of achieving cleaner and sustainable future.
2. Pyrolysis products properties and composition
In physical appearance, bio-oil is a dark brown color containing some solid particles, highly viscous liquid with a
pungent smell. Water is present as principal constituent occupying about 30%–40% of bio-oil. Presence of water is mainly
due to the internal moisture content of biomass or dehydration reaction occurring during pyrolysis. Water has both
positive as well as negative effects on the utilization of bio-oil as fuel. Presence of water reduces the viscosity of bio-
oil and improves its flow properties. However, it increases the oxygen content in bio-oil and lowers its heating value
and increases ignition delay in bio-oil combustion. Table 2 compares the properties of bio-oil and that of petroleum fuels
such as diesel and gasoline (Ikura et al., 2003; Miao and Wu, 2004; González et al., 2005; Yin et al., 2010). From Table 2,
it seems that bio-oil contains a high amount of oxygen than diesel and petrol. Bio-oil viscosity is also very high. More
than 300 oxygenated organic compounds are formed through condensation of pyrolytic vapors, which are responsible for
the high viscosity and low heating value (Lu et al., 2008). Thus, significant upgradation of bio-oil is required so that its
properties reach up to that of hydrocarbon fuels.
Properties and composition of bio-oil highly depend on feedstock composition and process conditions like temperature,
heating rate, etc. Generally, high temperature favors bio-oil formation with an increase in its carbon, reduction in oxygen
and water content. Table 3 summarizes the properties and compositions of bio-oil obtained from various feedstocks under
different process conditions and reactor systems.
Biochar is the carbonaceous solid residue and an important co-product of the pyrolysis process, which is produced
due to the partial degradation of biomass. Slow pyrolysis conditions favor the production of biochar. Different physical,
chemical, morphological properties of biochar produced from a range of biomass feedstock and various process conditions
are summarized in Table 4. Literature shows that biochar properties are the function of feedstock type and pyrolysis
conditions employed during their preparation. High heating value of biochar as equivalent to coal makes it an attractive
alternative in place of coal. Morphological analysis of biochar reveals its microscopic structure and high surface area, which
shows its potential applications such as adsorption of organic or inorganic contaminants, catalysts support material and
fuel cell applications. Morphological properties of biochar further improve after applying different physical or chemical
activation processes (Kan et al., 2016). A range of inorganic mineral nutrients present in the biochar makes it an effective
soil amendment and carbon sequestration agent. Concentration of nutrient elements increases with the increase in
pyrolysis temperature due to the removal of volatile matter and accumulation of these mineral nutrients at higher
temperature (Li et al., 2019). Mostly biochar has alkaline pH and can be applied in the soil for pH mediation. Cation
exchange capacity (CEC) influences the nutrient retaining ability of soil. Generally, higher CEC is desirable for better soil
pH mediation and nutrient retention (Li et al., 2019). Also, pH buffering, higher CEC and nutrient-rich composition helps
to provide a favorable environment for bioprocessing such as anaerobic digestion, composting and fermentation.
4
S. Gupta, P. Mondal, V.B. Borugadda et al.
Table 3
Summary of bio-oil properties and composition obtained through different biomass feed and varying process conditions.
Feedstock Process condition Reactor Bio-oil yield Properties of bio-oil Elemental Major Ref.
(wt. %) composition compounds
(wt. %)
Density Viscosity HHV pH Flash Pour Water
(kg/m3 ) (Cst) (MJ/kg) point point content
(◦ C) (◦ C) (wt. %)
Safflower T: 600 ◦ C Fixed bed 53 1020.8 33.7 41 – 77 −16 – C: 77 Ethyl Onay (2007)
HR: 300 ◦ C/min reactor H: 12.2 linoleate,
FR: 100 cm3 /min O: 8.4 octadecanoic
N: 2.5 acid linoleic
acid, hex-
adecanoic
acid, phenol
Rice husk T: 475 ◦ C Fluidized – 1139.9 13.4 16.58 3.1 68.1 – 28.2 C: 40 Ketones, Lu et al.
RT: 1.5–2 s bed reactor H: 8.2 aldehydes, (2008)
N: 0.6 phenols,
guaiacols
Oil palm T: 500 ◦ C Fixed bed 40.9 1052 2 24.32 3.2 – – 53 C: 50.6 – Abnisa et al.
residue HR: 10 ◦ C/min reactor H: 10 (2013)
FR: 2 L/min O: 38.9
RT: 60 min N: 1.071
Almond T: 400 ◦ C Fluidized 51.5 1106 1.68 12.4 5.5 110 −15 22.3 C: 48.8 Benzene, González
5
shell HR: 5 ◦ C/min bed reactor H: 6.2 toluene, et al. (2005)

RT: 30 min O: 44.7 styrene,
N: 0.3 naphtha-
lene,
pyrene
Grape T: 550 ◦ C Fixed bed 27 992 32 32.95 2 61 – – C: 71.7 n-pentane Demiral and

bagasse HR: 50 ◦ C/min reactor H: 8.69 soluble Ayan (2011)
FR: 100 mL/min O: 16.9 fractions,
RT: 30 min N: 2.7 asphaltenes
Eucalyptus T: 450 ◦ C Batch 55.5 1300 16.09 13 1.8 68 −12 – – 2-Furan Kumar et al.
reactor carboxalde- (2010)
hyde,
2,6-
dimethoxy
phenol,
2-methoxy
phenol,
3-furan
carboxylic
acid,
3-hydroxy-
4-methoxy
benzoic acid
(continued on next page)

Table 3 (continued).
Feedstock Process Reactor Bio-oil yield Properties of bio-oil Elemental Major compounds Ref.
condition (wt. %) composi-
tion (wt.
%)
(◦ C) (◦ C) (wt. %)
Wood T: 500 ◦ C Fluidized 62.1 – – 13.33 3.3 – – 37.62 C: 33.84 Phenols, acetic acids Salehi
sawdust FR: 15 bed reactor H: 7.34 and their derivatives et al.
L/min O: 55 (2011)
Cherry seed T: 400 ◦ C Fluidized 50 – – 24.2 – – – 14.27 C: 44.23 Furfural, glycuronic Duman
FR: 0.66 bed reactor H: 7.42 acid, formaldehyde, et al.
m3 /h O: 45.05 acetaldehyde, (2011)
RT: 1–2 s N: 3.26 phenols
Cherry seed T: 400 ◦ C Fixed bed 30 – – 32.46 – – – 5.6 C: 67.18 Glycuronic acid, Duman
HR: reactor H: 8.48 acetic acid, et al.
5 ◦ C/min O: 21.86 hydroxymethylfural, (2011)
FR: 25 N: 2.45 furfural, phenols
6
mL/min
Rapeseed T: 500 ◦ C Fixed bed 45.6 918 43 38.4 – 83 – – C: 74.04 Phenols, ketones, Şensöz
HR: reactor H: 10.3 quinones, aldehydes, et al.
40 ◦ C/min O: 11.7 alkanes, aromatics (2000)
RT: 30 min N: 3.97
Hornbeam T: 550 ◦ C Fixed bed 24.67 1056 1.4 30 – – – – C: 66.42 P-creosol, Morali

shell HR: reactor H: 6.9 o-methoxyphenol, and
50 ◦ C/min O: 25.11 1,2-benzenediol, 2- Şensöz
FR: N: 1.54 furancarboxaldehyde, (2015)
100 cm3 /min benzene ethanol
Switchgrass T: 600 ◦ C – 28 920 10 36.3 – – – 13 C: 50 Methyl, methoxy Imam
HR: H: 9.3 and propenyl and
6 ◦ C/min O: 37 attached phenols, Capareda
RT: 20 min N: 1.6 indene, (2012)
methyl-indene,
benzene, toluene,
methyl ester fatty
acids

tion (wt.
%)
(◦ C) (◦ C) (wt. %)
Soyabean T: 400 ◦ C Fixed bed 25.81 1107 72.38 33.6 – 63 – – C: 67.9 Polar, aromatic and Şensöz
cake HR: reactor H: 7.77 aliphatic fractions and
50 ◦ C/min O: 13.5 Kaynar
N: 10.84 (2006)
Corncob T: 500 ◦ C Fluidized 61 1177 36.9 26.2 – – – 25.3 C: 55.14 Levoglucosan, hy- Mullen
bed reactor H: 7.56 droxyacetaldehyde, et al.
O: 37 acetol, acetic acid, (2010)
N: 0.56 phenols
Corn stover T: 500 ◦ C Fluidized 61.6 1245.1 24.3 – – – 9.2 C: 53.9 Levoglucosan, hy- Mullen
bed reactor H: 6.92 droxyacetaldehyde, et al.
O: 37.9 acetol, acetic acid, (2010)
7
N: 1.18 phenols
Cotton stalk T: 510 ◦ C Fluidized 55 1160 125 17.77 3.3 – – 24.4 C: 42.33 Toluene, formic Zheng
bed reactor H: 7.9 acid, et al.
O: 49.4 b-hydroxybutyric (2008)
N: 0.3 acid, ethyl hydrogen
fumarate, 1,2-

cyclobutanedione
Pine T: 520 ◦ C Fluidized 74 1200 27.5 18.7 2.4 56 −36 17 C: 45.7 Aldehydes, ketones, Oasmaa
sawdust RT: 0.6–0.7 bed reactor H: 7 furans, pyrans, et al.
s N: <0.1 sugars (2009)
Sugarcane T: 500 ◦ C Fixed bed 42 1048 7.36 19.1 3.02 <30 – – C: 52.83 2-Methylphenol, Ahmed
bagasse HR: reactor H: 7.74 3,4-dimethyl-1,5- et al.
20 ◦ C/min O: 38.9 hexadiene, (2018)
FR: 50 N: 0.5 4-ethoxyphenol,
mL/min 2,5-dimethyl-2,4-
hexadienedioic
acid

tion (wt.
%)
(◦ C) (◦ C) (wt. %)
Sugarcane T: 500 ◦ C Fixed bed 50 916 3.63 41 3.5 <30 – – C: 85.35 1,2,3-trimethyl- Ahmed
bagasse + HR: reactor H: 9.98 benzene, et al.
scrap tire 20 ◦ C/min O: 4.13 1,4- (2018)
(1:3) FR: 50 N: 0.54 dimethylbenzene,
mL/min D-limonene, 2,3,6-
8
trimethylnaphthalene,
ethylbenzene
Palm kernel T: 490 ◦ C Fluidized 48.7 – – 18 3.3 – – 30 C: 47.6 Acetic acid, phenol, Kim
shell FR: 63 bed reactor H: 8.1 furfural, o-guaiacol, et al.
mL/min, O: 43.7 catechol, syringol (2010)
N: 0.6

Rapeseed T: 500 ◦ C Fixed bed 59.7 993 38 36.4 62 6 0.001 C: 73.74 – Özçimen
HR: reactor H: 10.7 and
7 ◦ C/min O: 10.5 Karaos-
FR: N: 4.65 manoǧlu
150 cm3 /min (2004)
T: Temperature; HR: Heating rate; FR: Flow rate; RT: Retention time.
Table 4
Summary of the variation of biochar properties with the variation in feedstock type and process conditions.
Feedstock Process Biochar properties Ref.
conditions
Proximate Ultimate Specific Heating Mineral pH Electrical Cation
properties properties surface area value composition conductivity exchange
(wt. %) (wt. %) (m2 /g) (MJ/kg) (mg/kg) (EC) (mS/m) capacity
(CEC)
(Cmol/kg)
Cork T: 550 ◦ C; – C: 87.51 245.2 – – – – – Wang et al.
RT: 1 h H: 3.23 (2020)
N: 1.52
O: 5.09
Rice husk T: 500 ◦ C; FC: 20.9 C: 77.30 – – – 10.5 – – Campos
RT: 1 h VM: 46.0 H: 3.30 et al. (2020)
AC: 33.1 N: 0.90
O: 18.30
Malt T: 600 ◦ C; FC: 61.61 – 2.67 – – – – – Machado
bagasse HR: VM: 26.21 et al. (2020)
5 ◦ C/min; AC: 12.19
FR: 150 MC: 7.58
mL/min;
RT: 30 min
9
Softwood T: 525 ◦ C; FC: 68.7 C: 75.8 10.6 28.4 – 7.5 – – Krutof et al.
FR: 300 VM: 24.1 H: 3.0 (2020)
mL/min; AC: 2.2 N: 0.1
MC: 5.0 O: 21.2
Co-pyrolysis T: 525 ◦ C; FC: 53.1 C: 73.5 20.1 28.2 – 8.1 – – Krutof et al.
of softwood FR: 300 VM: 36.8 H: 2.5 (2020)

and Mussel mL/min; AC: 5.2 N: 0.1
shell (1:1) MC: 4.8 O: 23.8
Sawdust T: 550 ◦ C FC: 58.33 C: 59.19 431.91 – Cd: 0.03 6.66 1.50 47.3 Pariyar et al.
VM: 29.77 H: 3.97 Co: 2.04 (2020)
AC: 11.90 N: 0.51 Cu: 23.24
MC: 7.24 O 20.73 Fe: 4893.04
Mg: 101.71
Ni: 1.91
Zn: 90.9
Rice husk T: 550 ◦ C FC: 44.51 C: 48.20 248.99 – Cd: 0.22 7.89 0.99 29.59 Pariyar et al.
VM: 18.09 H: 2.61 Co: 1.7 (2020)
AC: 37.40 N: 0.73 Cu: 23.32
MC: 4.78 S: 0.08 Fe: 854.29
O: 10.98 Mg: 297.06
Ni: 2.41
Zn: 87.9

conditions
(CEC)
(Cmol/kg)
Food waste T: 550 ◦ C FC: 58.85 C: 63.13 2.07 – Cd: 0.08 9.92 20.06 17.35 Pariyar et al.
VM: 26.05 H: 2.92 Co: 0.89 (2020)
AC: 15.10 N: 2.77 Cu: 16.25
MC: 4.00 S: 0.08 Fe: 1042.41
O: 16.0 Mg: 72.09
Ni: 1.60
Zn: 65.76
Poultry T: 550 ◦ C FC: 40.74 C: 28.91 18.12 – Cd: 0.07 9.99 12.62 51.45 Pariyar et al.
litter VM: 16.06 H: 1.75 Co: 4.37 (2020)
AC: 43.20 N: 0.23 Cu: 64.98
MC: 2.74 S: 0.05 Fe:
O: 12.87 10 876.45
Mg: 435.56
Paper sludge T: 550 ◦ C FC: 22.84 C: 40.77 61.52 – Cd: 0.39 8.70 1.26 48.43 Pariyar et al.
VM: 20.96 H: 2.61 Co: 2.00 (2020)
AC: 56.20 N: 4.28 Cu: 45.28
MC: 1.17 S: 0.09 Fe: 3460.67
10
O: 9.05 Mg: 97.63

Ni: 1.94
Zn: 92.14
Swine T: 600 ◦ C FC: 57.5 C: 39.4 – – Ca: 15.1 9.59 0.08 47.8 Rodriguez
manure VM: 11.2 H: 0.54 K: 17.3 et al. (2020)
AC: 42.8 N: 1.49 P: 121
O: 15.8 Mg: 9.24

S: 3.83
Na: 3.73
Fe: 1760
Construction T: 600 ◦ C FC: 43.0 C: 93.6 – – Ca: 134 9.51 0.009 30.0 Rodriguez
wood VM: 11.8 H: 1.98 K: 1.14 et al. (2020)
AC: 4.22 N: 1.49 P: 1.25
O: 15.8 Mg: 0.23
S: 1.09
Na: 0.58
Fe: 490
Tire waste T: 600 ◦ C FC: 78.2 C: 66.6 – – Ca: 29.4 8.55 0.044 21.0 Rodriguez
VM: 7.9 H: 0.21 K: 0.44 et al. (2020)
AC: 12.0 N: 0.09 P: 2.27
O: 21.1 Mg: 0.16
S: 3.70
Na: 0.09
Fe: 400

conditions
(CEC)
(Cmol/kg)
PVC plastic T: 600 ◦ C FC: 77.6 C: 24.3 – – Ca: 74.5 11.8 14.6 31.9 Rodriguez
VM: 1.2 H: 4.86 K: 0.05 et al. (2020)
AC: 49.5 N: 0.00 P: 0.00
O: 21.3 Mg: 8.62
11
S: 2.15
Na: 0.06
Fe: 340
Rice straw T: 400 ◦ C FC: 6.27 C: 31.02 – – Na: 420 8.4 412 41.15 Chandra and
RT: 90 min VM: 49.69 H: 1.87 K: 6060 Bhat-
AC: 35.64 N: 5.63 Ca: 890 tacharya
MC: 8.4 O: 25.84 Mg: 1720 (2019)

Rice straw T: 500 ◦ C FC: 7.45 C: 32.23 – – Na: 130 8.38 688 33.21 Chandra and
RT: 60 min VM: 50.98 H: 2.13 K: 3300 Bhat-
AC: 31.15 N: 3.07 Ca: 910 tacharya
MC: 10.42 O: 31.42 Mg: 630 (2019)
T: Temperature; RT: Retention time; FR: Flow rate; FC: Fixed carbon content; VM: Volatile matter content; AC: Ash content; MC: Moisture content.
Fig. 1. Different routes for bio-oil upgradation.
3. Scope of value additions through oil and char upgradation
Application of bio-oil directly in place of diesel and gasoline fuel causes the following operational challenges (Oasmaa
and Czernik, 1999):
• Does not produce sufficient heat due to very low calorific value, large number of oxygenated compounds and high
water content.
• Provides flow barrier during its flow through injectors and engines due to high viscosity.
• Results in corrosion and damage to engines due to the presence of acidic compounds in bio-oil.
• Creates problem for starting of the engine.
• Creates problem of coking during combustion due to the presence of a significant amount of solid particles in it.
• Contains high molecular weight compounds and pungent smell, which make it unsuitable for handling.
• Creates corrosion in diesel and gasoline engines.
Thus, to overcome these difficulties with direct bio-oil usage, extensive research is being carried around the world to
enhance the quality of the bio-oil via various upgradation techniques. Further, it contains many valuable chemicals,
recovery of which can improve the economy of the process. Fig. 1 shows different routes investigated for the upgradation
of bio-oil, including moisture removal and chemical recovery, which are described in subsequent sections.
Pyrolysis bio-oil contains a considerable amount of moisture (30%–40%) depending upon the type of biomass and
operating conditions (González et al., 2005). It also contains different polar and nonpolar organic compounds. Polar
compounds such as acids, ketones, alcohols, esters, and ethers present in pyrolysis oil are soluble in water. They can
be transferred into the aqueous phase, whereas phenolic and other lignin-rich nonpolar compounds get into the viscous
organic phase. Removal of moisture and recovery of valuable platform chemicals is imperative to increase the bio-refinery
process economics. To achieve this target, moisture of bio-oil is usually transferred in aqueous phase by addition of water,
followed by the recovery of platform chemicals from the aqueous phase and the organic phase through solvent extraction.
Recovery of chemicals such as various acids (acetic acid, formic acid, etc.), hydroxyacetaldehyde, hydroxyacetone,
furfural, levoglucosan through solvent extraction with various solvents makes the overall process economically viable.
However, the selection of a low-cost solvent and an efficient method requires more investigation. Water extraction process
extracts most of the polar compounds (about 80%–90%) from bio-oil and thus reduces oil complexity prior to additional
isolation steps (Vitasari et al., 2011). To utilize organic phase of bio-oil (the residual part after water separation and
chemical recovery) in place of hydrocarbon fuels, it needs to be deoxygenated to reduce its oxygen content and raise its
heating value. Furthermore, bio-oil quality can also be upgraded through emulsification with hydrocarbon fuels (such as
diesel) with suitable emulsifying agents. Bio-oil can also be blended with heavy gas oil and refined further to produce
different refinery products. Biochar, produced as a co-product from pyrolysis process, also has various applications in
12
Fig. 2. Schematic representation of utilization of bio-oil and biochar on the basis of integrated bio-refinery concept.
the field of fuels, soil amendment, catalysis, contaminant removal through adsorption, fuel cells and gas storage due
to its various physiochemical properties. In recent years, much attention has been given towards utilization of biochar
as catalysts in bio-oil upgradation processes such as hydrotreating, hydrodeoxygenation, esterification, etc. (Ren et al.,
2014a). Development of biochar, which is a by-product of biomass pyrolysis, as a catalyst in bio-oil upgradation in
place of expensive metal-based catalysts, helps to make the process more integrated, economic, and environmentally
friendly. Also, biochar has potential to be utilized in the production of several chemicals and biofuels such as methane,
butanol, bio-ethanol, bio-diesel, hydrogen, hydrocarbons, etc. In addition, pH buffering, cation exchange capability, supply
of macronutrients and micronutrients help to provide relevant and supportive habitant for microbial activity. These
characteristics of biochar lead to its recent utilization in the field of composting, anaerobic digestion and microbial
fermentation (Sun et al., 2020). Fig. 2 gives a schematic representation of utilization techniques of pyrolysis products
(bio-oil and biochar), based on integrated bio-refinery concept.
4. Advances in moisture removal techniques
As discussed in the earlier sections, the presence of water content in bio-oil decreases its heating value and consumes
a large amount of latent heat of vaporization. It also influences the performance of the bio-oil upgradation to liquid
transportation fuels. To solve the water issue in bio-oil, different approaches have been tested in recent years, including
pretreatment of raw material and modification in the process.
Hussain et al. (2018) adopted three strategies to reduce the content of water and oxygenated compounds and increase
the hydrocarbon content in bio-oil derived from water hyacinth. The adopted strategies include the use of cement
catalysts, biomass pretreatment and additional pyrolysis. Utilization of cement catalysts was to retain and split the
water molecules formed during pyrolysis with the organic moieties and hydrogen-rich molecules while reducing the
water content. The elemental composition of the cement catalyst showed a maximum affinity for water to stabilize
the unstabilized molecules. Biomass pretreatment intends to destroy the biopolymers into condensed form and water
molecules through enzyme activity during microbial treatment. Likewise, fractional distillation eliminated water, while
additional pyrolysis process enhanced the hydrogen content by oxygen removal.
Wigley et al. (2016) revealed the mutual use of torrefaction and demineralization of biomass pretreatment to reduce
the moisture content of bio-oil via pyrolysis. Demineralization and torrefaction aimed to minimize the inorganics and
water present in the raw biomass. Their study showed that moisture contained in biomass acted as an autocatalyst for
the production of pyrolytic water due to scission of glycosidic bonds and consequently reduced the degree of cellulose
polymerization during pyrolysis process. Pretreatment improved the properties of bio-oil by reduction in water, pyrolytic
lignin and organic acids along with an increase in its aromatic and levoglucosan content. Further, Lin and Bartek (2012)
patented an azeotropic distillation technology to remove bound water from pyrolysis bio-oil. The mentioned technology
comprises of combining the water bound bio-oil with an azeotropic agent mainly water insoluble C6 -C10 hydrocarbons
such as toluene, benzene, naphthalene or their combinations and thereby subjecting the resulting bio-oil to azeotropic
distillation at reduced pressure conditions. The process of azeotropic distillation separates a significant portion of bound
water from bio-oil by producing a water depleted bio-oil phase, which is more stable, less corrosive and highly soluble
with hydrocarbons. Ghodke et al. (2015) reported the azeotropic removal of water by reactive distillation of bio-oil
via esterification using 1-butanol in presence of solid acid catalyst (Amberlyst-15). The process of reactive distillation
combined both chemical reaction and distillation in one unit to produce stabilized bio-oil with lower moisture and acidic
content. The water present in the bio-oil, along with that produced as a result of esterification reaction, was removed
by simultaneous distillation in one step. Although both heterogeneous and homogeneous catalysts can be applied for
the esterification process, but the use of heterogeneous catalysts is preferred due to easier separation of catalysts from
products. Electrodialysis (ED) techniques have also been investigated for the removal of moisture from bio-oil (Lister
13
Table 5
Summary of different chemicals recovery techniques using a variety of feedstocks and solvents.
Feedstock Separation techniques Solvents used Applications Ref.
Switchgrass (Panicum Pyrolysis water extraction, Deionized water Neutralized bio-oil organic phase Park et al.
virgatum L.) capacitive deionization for fuel production and (2018)
neutralized bio-oil aqueous phase
fed to microbial electrolysis cells
for hydrogen production using
carbon aerogel electrodes
Nannochloropsis sp. Gravity separation/decantation, Ultrapure water, acetone Production of struvite and Shanmugam
vacuum filtration methane et al. (2017a)
Switchgrass (Panicum Water extraction, sequential Hexane, petroleum ether, Furans and phenolic hydrocarbons Ren et al.
virgatum L.) solvent extraction chloroform, ethyl acetate act as feedstock for catalytic (2017)
upgrading, levoglucosan fermented
to produce alcohols and diols,
hydrogen production from organic
acids via microbial electrolysis
Nannochloropsis Gravity separation/decantation – Bio-gas, CH4 production via Shanmugam
by separatory funnel catalytic gasification et al. (2017b)
Green pine wood Fractionation, extraction 2-butanone, Amberlyst Furfural and HMF production by Abou-Yousef
16 wet cation exchange dehydration of sugars and Hassan
resin (2014)
Horse manure and Bio-oil distillation, solvent NaOH, conc. HCl Hydrocarbons upgraded to fuels Elkasabi et al.
litter extraction, re-acidification via hydrogenation while phenols (2015)
and acids used as pure products
Oak wood Water extraction, Water Hydrogenation of unstable Vispute and
centrifugation, decantation aqueous phase compounds Huber (2009)
hydroxyacetaldehyde,
hydroxyacetone, furfural,
2-furanone, guaiacol, levoglucosan,
glucose, sorbitol to corresponding
alcohols. Later on, Production of
hydrogen and alkanes via
aqueous-phase processing
Barley straw Extraction Water Recirculation of aqueous phase to Zhu et al.
increase bio-oil yield (2015a)
Pine, aspen wood Distillation – Hydrothermal carbonization of the Fu et al. (2016)
meal, rice husk aqueous phase was carried out to
produce stable oxygen-containing
liquid fuels and biochar
Microalgae Solvent extraction Chloroform The aqueous phase was recycled Yang et al.
Tetraselmis to increase the bio-oil and solid (2017)
sp. Species residue yield with decrease in gas
yield
Pine wood sawdust Wet oxidation of bio-oil Butyl acetate Hydrogen production from formic Müller et al.
aqueous phase in acidic acid for catalytic (2016)
medium liquid–liquid hydrodeoxygenation of organic
extraction phase
Bio-oil procured from Centrifugation, decantation Water Catalytic steam reforming of Seyedeyn-Azad
biomass technology aqueous phase for hydrogen et al. (2014)
group, Netherlands production
Palm shell Solvent extraction Diethyl ether Catalytic conversion of aqueous Abnisa et al.
phase over HZSM-5 catalyst to (2014)
produce liquid fuel with 38.44
MJ/kg calorific value
Chlorella vulgaris Gravity separation/decantation Water Recycling aqueous phase to HTL Hu et al. (2017)
process to raise bio-oil yield
Penicillin mycelial Vacuum filtration, Solvent CH2 Cl2 Aqueous phase recycling for algae Zhuang et al.
waste extraction cultivation, fermentation and (2018)
anaerobic digestion
et al., 2018). Electrodialysis technique electrochemically treats bio-oil through electrolysis scheme by employing both
AEM (anion exchange membrane) and CEM (cation exchange membrane). The process removes organic acids and water,
along with partial hydrogenation of organic functionalities to produce stable bio-oil.
14
In summary, directly water can be removed from bio-oil by biomass pretreatment prior to pyrolysis, esterification,
distillation and electrodialysis. On the other hand, upon addition of the water to bio-oil after a certain value, the
moisture of bio-oil comes into aqueous phase along with polar compounds due to their solubility in water. The non-polar
compounds stay in the organic phase (Vitasari et al., 2011).
5. Chemical recovery from aqueous phase as well as organic phase
Upon separation of the water-soluble and insoluble fractions, various techniques including chromatography, solvent
extraction, and distillation have been developed for the separation and recovery of aqueous and organic phase chemical
compounds. Among these methods, solvent extraction is found to be more effective as it can be carried out at ambient
temperature and pressure. Earlier studies also revealed that solvent extraction with one solvent is not enough to remove
all the value-added chemicals from bio-oil (Garcia-Perez et al., 2007b). Therefore, a series of solvent extraction steps have
been used to recover the chemical compounds as per their chemical groups. Different solvents such as ethyl acetate,
petroleum ether, methanol, ethanol, diethyl ether, hexane, chloroform etc. have been used to recover the chemical
compounds with varying polarity and solubility for various applications such as producing resins, deicers, levoglucosan,
hydroxyacetaldehyde, pharmaceuticals, synthetic fibers, fertilizers, fuels, lubricants, and flavoring agents (Elliott et al.,
2004; Abou-Yousef and Hassan, 2014; Park et al., 2018). During the extraction and recovery of value-added chemicals,
certain processes are affected negatively due to the presence of undesirable chemical compounds. Thus, the maximum
removal of undesirable compounds from the bio-oil is needed to increase the product yield and conversion. Different
feedstocks, separation techniques and chemicals used for solvent recovery along with the application of recovered
chemicals are summarized in Table 5.
6. Advances in upgradation techniques of residual organic phase
Bio-oil can be upgraded via emulsification with hydrocarbon fuels such as diesel and surfactants as well as co-
processing with heavy gas oils in FCC units. Both raw bio-oil and aqueous phase separated bio-oil can be used for this
process. However, bio-oil used after aqueous phase separation gives better results in terms of the properties of the final
product and the percentage of bio-oil blended. The organic phase is more miscible with hydrocarbon fuels due to the
presence of a relatively smaller fraction of polar oxygenated compounds (which gets separated in aqueous phase). The
maximum percentage of raw bio-oil blended with hydrocarbon fuels varies in the range of 10%–18% while it even reaches
to 38%–40% in case of aqueous phase separated bio-oil (Alcala and Bridgwater, 2013; Botella et al., 2018). Moreover,
aqueous phase separated from the bio-oil can be utilized in the production of value-added chemicals, thereby improving
process economics.
6.1. Emulsification of bio-oil with hydrocarbon fuels
Different blends in a range of 10 to 40% of bio-oil in hydrocarbon fuels such as diesel have been prepared and tested by
many researchers for assessing their suitability as a transportation fuel. It was significantly found that an increase in bio-oil
percentage in blend with diesel fuel leads to degradation in its properties such as heating value, viscosity, corrosiveness,
cetane number, etc. Blend with 10% of bio-oil has properties similar to conventional diesel fuel (Ikura et al., 2003).
In this process, bio-oil and diesel are mixed in a blender/mixture to form an emulsion with intermediate properties.
It was reported that high-speed blender gives much better performance than the vortex mixer (de Luna et al., 2017).
New technologies such as microemulsification, ultrasonic emulsification, ultrasonic mechanical based emulsification,
pressurized emulsification etc. are more effective for producing superior quality emulsion fuel and are fascinating
number of researchers. Few studies show that ultrasonic mechanical based emulsification is much better than ultrasonic
emulsification process in terms of stability, but it results in reducing middle and heavier fractions from the product (Guo
et al., 2014).
Stability and viscosity of emulsions are very important parameters for their application as a transportation fuel, which
are highly dependent on the bio-oil feedstock, emulsifying reagent and emulsification process. Since bio-oil continues
to undergo various polymerization reactions resulting in solid products, pulverizing these solid products or using freshly
produced bio-oil results in increasing stability and viscosity of bio-oil (Chiaramonti et al., 2003). Centrifugation can also be
used as a pre-mixing step to remove such solids in bio-oil. Several polymeric and non-polymeric surfactants such as Span
80, Span 85, Emarol 85, Tween 80 have been used by the researchers as emulsifying agents (Guo et al., 2014; Liang et al.,
2018). Addition of co-surfactants improves the stability of resulting emulsion by reducing density difference between two
phases due to micelles formation. A number of co-surfactants such as methanol, ethanol, butanol, octanol, etc. are being
analyzed and used in the emulsification process (Wang et al., 2014; de Luna et al., 2017). Table 6 summarizes some critical
work done in emulsification with the type of fuel used, surfactants utilized, process conditions along with main technique
involved.
15
Table 6
Summary of the work done on the emulsification of bio-oil.
Pyrolysis oil Blending Process requirements Technology utilized Main findings Ref.
type fuel
Rubber- Diesel Surfactants: Atlox 4914 Centrifugation prior to • Co-surfactants addition de Luna
wood Co-surfactants: Ethanol, premixing followed by improves stability of emulsions et al. (2017)
oil Methanol, n-Butane high speed mixing at even containing a higher bio-oil
3000, 13 000 and 17 000 percentage
rpm • Of the three surfactants used,
methanol showed the best
performance
• Stability improves at higher
speed
Synthetic Diesel Surfactant: Span 80 Microemulsification • 5:5 was optimum bio-oil to Wang et al.
bio-oil Co-surfactants: technology diesel fuel ratio (2014)
n-Alcohols (C4–C8) • n-octanol being best
co-surfactant
• Increase in co-surfactant
percentage increases the capacity
blend to take bio-oil
• Properties improve after
blending compared to raw bio-oil
Sewage Diesel Surfactants: Span 80, Microemulsification • Best ratio to span 80 to tween Liang et al.
sludge Tween 80 technology 80 is 7/3 with 2% n-hexanol (2018)
bio-oil Co-surfactants: Alcohols • Comparative reduction in CO2 ,
CO and NOX emissions
• Mixed surfactant and
co-surfactant addition have a
positive effect on smoke intensity
reduction
Pineapple Diesel fuel Surfactants: Span 80, Ultrasonic emulsification, • Higher stability blends obtained Guo et al.
bio-oil Span 85, Tween 80 ultrasonic mechanical with ultrasonic emulsification (2014)
based emulsification (about 30 days)
• Ultrasonic mechanical based
emulsification further improves
stability over ultrasonic method
but it reduces for middle and
heavier fractions
Pinewood Crude Surfactants: Span 80, Sequential addition of • Surfactants and temperature Zhang and
bio-oil glycerol Tween 80 bio-oil, glycerol, and are more important parameter Wu (2017)
Co-surfactants: Sodium surfactants with varying affecting stability then time and
oleate, Sodium chloride, ratios of span 80 to stirring speed
Sodium hydroxide, tween 80 followed by • Presence of soap shortens the
Methanol high-speed stable time for emulsions due to
homogenization micelles formation
• Aging of bio-oil–glycerol
mixture prior emulsification
improves stability
• Stirring at high speed not
important for producing high
stability blends
Pine chip Biodiesel Methanol Heating of bio-oil and • Easy to extract fuels of interest Garcia-Perez
bio-oil biodiesel with at 60 ◦ C from the emulsion et al.
and 30 min, then • Viscosity and density increased (2007a)
shaking in a water bath with a small change in heating
for 10 min value and solid content
• Requires neutralization with a
weak base like NaHCO3 to remove
organic acids being soluble in the
biodiesel
• Phase separation results on
cooling blends
Switch grass Biodiesel – Highly pressurized • Improve storage stability and He et al.
homogenization physiochemical properties of (2009)
bio-oil
• Compared with conventional
methods, this method gives more
improvement in viscosity, heating
value, ash content, water content,
ash, etc.
16
6.2. Blending the bio-oil with heavy gas oil and co-refining
Through this process, bio-oil can be blended with heavy gas oil and be converted into refinery grade products like
gasoline, diesel, LPG, etc. Investigations are ongoing to increase the proportion of bio-oil in such mixed refinery feed with
heavy gas oils by developing low cost and technically effective catalyst with more stability against corrosion.
During the refining process, cracking of oxygenated compounds such as phenols, acetic acid and hydroxyacetone with
gas oils in presence of a commercial catalyst (E-CAT) results in the production of gasoline and LPG with relatively small
coke yield. However, much better results in terms of lighter products yield and combustion properties can be obtained by
mixing commercial catalyst with ZSM 5 catalyst due to less reduction in hydrogen content during cracking (Graça et al.,
2009). Many studies confirmed the technical feasibility of the process. Removal of oxygenated compounds occurs through
conversion into CO, CO2 , and H2 O, while rest converts into valuable carbon in gasoline and diesel products (Thegarid et al.,
2014; Pinho et al., 2017). Though co-processing of bio-oil with heavy gas oils is highly advantageous, but certain issues
are associated with it. One such issue is the corrosion problem created by oxygenated compounds in bio-oil. Brady and
co-workers tested on different range alloys and found that proper selection of alloy material is also necessary along with
other parameters (Brady et al., 2017). Catalytic cracking of gas oil mixed with bio-oil generated from catalytic pyrolysis
produces gasoline with properties similar to that produced through hydrodeoxygenation (HDO) (Thegarid et al., 2014).
Thus, it seems that by developing an appropriate catalytic process, the need for high-cost hydrodeoxygenation process
(HDO) can be eliminated. Table 7 shows the effects of refinery process conditions, catalysts, and conversion on product
yield of different bio-oil feedstocks.
6.3. Upgradation through deoxygenation
Deoxygenation of bio-oil is normally accomplished through catalytic cracking and hydroprocessing routes such as
hydrotreatment, hydrodeoxygenation, and hydrocracking. Catalytic cracking is the process of thermal breakdown of larger
complex compounds into simpler ones at high temperature (350–600 ◦ C) and atmospheric pressure in the presence of
catalysts (such as zeolites). The process is accompanied by deoxygenation via the production of gases such as CO, CO2 ,
etc. along with lighter hydrocarbons and coke. Hydroprocessing involves the use of high-pressure hydrogen (up to about
7 MPa) and temperature (350-500 ◦ C) which converts oxygenated heavier bio-oil into oxygen-free simpler compounds
in presence of catalysts (Ni, NiMo, Pt, Ru supported on Al2 O3 , SiO2 , ZrO2 , etc.). Use of hydrogen improves product quality
and yield. Hydrogen removes O, N as well as S present in bio-oil in the form of H2 O, NH3 and H2 S respectively (Saber
et al., 2016). Several reactions involving hydrogenation, hydrocracking, hydrodeoxygenation occur during the process. In
hydrotreatment, breaking of C–O, C–N, C–S bonds are the main reactions compared to C–C bond while in hydrocracking
breakage of C–C bond occurs mainly (Saber et al., 2016).
Upgrading methods such as hydrotreatment, hydrocracking, catalytic cracking, etc. are superior compared to direct
blending with hydrocarbon fuel. These processes produce fuel having properties similar to that of petroleum fuels. But
the only disadvantages with these are their high operating cost due to the utilization of high-cost catalyst, the problem
of coke formation and rapid catalyst deactivation, costly reactors and high-pressure requirement which limits their
commercial application. Significant studies have been carried out to make the process technically as well as economically
feasible. Catalysts such as Pd, Pt, Ru, PtCo, PtNi, NiMoCx , Mo2 C, CoMo, Mo2 N, HZSM-5, modernite zeolite, Y-zeolite, etc.
are emerging as most effective catalysts for deoxygenation and cracking, further developments are going on in this field
of heterogeneous catalysts (Ruddy et al., 2014). Recently, low-cost waste material based catalysts are also being targeted
for these reactions (Bennett et al., 2016). Red mud, which is a waste material of Bayer’s process of bauxite ore refining
into alumina, can also be utilized for upgradation of pyrolysis derived bio-oil. It is a mixture of metal oxides (like Al2 O3,
SiO2 , Fe2 O3 , alkali, and alkaline earth metal oxides like CaO and Na2 O). A study by Karimi et al. (2010) revealed that
upgradation of hemp seed-derived bio-oil using 25 wt% red mud as catalyst resulted in the production of less viscous and
chemically more stable bio-oil. Further, solid acid catalyst is another group of catalysts reported by Zhang et al. (2006).
Simple oxides (Al2 O3 , SiO2 , ZrO2 ), mixed oxides (SiO2 -Al2 O3 , ZrO2 -Al2 O3 , ZrO2 -SiO2 , MgO-Al2 O3 ), zeolites (HZSM-5, HY, HB,
mordernite), activated carbons and carbon supported materials (mesoporous carbon, activated carbon, carbon nanotubes)
are the most common solid acid catalysts utilized in hydrodeoxygenation of bio-oil. Presence of Lewis and Bronsted acidic
sites acts as an active catalytic site for deoxygenation of oxygen-containing compounds present in bio-oil. Degree of
deoxygenation depends on the availability as well as the strength of the acidic sites. In addition, vast research has been
going on to develop new bi-functional and multifunctional catalysts having the capability to produce bio-oil similar in
properties to that of hydrocarbon fuels (Tang et al., 2008, 2009). This class of catalysts includes transition or noble metal
catalysts supported on the acidic base. These catalysts include both acidic as well as metallic functionality with high
activity for HDO reactions. The oxygen from oxygen-containing compounds gets adsorbed onto Lewis or Bronsted acid
sites of acidic support while metallic sites are responsible for activation or dissociation of hydrogen molecule to participate
in deoxygenation reaction. Biochar-based catalysts produced after certain physical and chemical modifications, which is a
byproduct of pyrolysis process, also exhibit high activity in bio-oil deoxygenation and are of great interest for researchers
in order to make the whole process more economical and integrated. A more detailed explanation of low-cost biochar
based catalysts has been presented in Section 7.2.
17
Table 7
Effects of refinery process conditions, catalysts on conversion and product yield of different bio-oil feedstocks.
Feedstock Process Catalyst Catalyst to Conversion Gasoline Coke LPG Yield H2 yield LCO Carbon yield Ref.
conditions feed ratio yield yield
CO CO2
50% Glycerol 500 ◦ C ZSM-5 3 70 16 17 37 2 – 14 4 Corma et al.
30 s (2007)
Pine bio-oil (5%) 540 ◦ C CATa 62 39.8 6.5 13 0.061 20.4 0 0 Pinho et al.
+ vacuum gas oil 2.7 bar (2017)
Phenol + acetic 535 ◦ C E-CATb 6 65 37 11 15 0.14 20 0.08 0.4 Graça et al.
acid + (2009)
hydroxyacetone +
gas oil
Phenol + gas oil 535 ◦ C E-CAT + 5 63 33.3 9.5 16.7 0.18 17.6 0.06 0.34 Graça et al.
ZSM-5c (2009)
Catalytically 500 ◦ C FCC catalyst 3 75 55 4 14 0.05 19.5 – 0.1 Thegarid
pyrolyzed pine 1.2 bar (15% et al. (2014)
bio-oil (10%) + 1 min Y-zeolite)d
vacuum gas oil
Hydrodeoxy- 500 ◦ C FCC catalyst 3 70 45 4.2 20 0.25 24 – 0.09 Thegarid
genated pine 1.2 bar (15% et al. (2014)
Y-zeolite)d
18
bio-oil (10%) + 1 min

vacuum gas oil
Hydrotreated 550 ◦ C Commercial 4 68 25 6 – – – - – Samolada
eucalyptus bio-oil catalyst et al. (1998)
(15%) + light ReUSYe
cycle oil
Pine sawdust 550 ◦ C HZSM-5 – – – 9.07 25 – – 25.55 10.37 Ma et al.

bio-oil (50%) + (Si/Al = 50) (2018)
waste kitchen oil
Poplar bio-oil 560 ◦ C FCC catalyst – 72 35 6 20 – 19 0.5 1.5 Ibarra et al.
(20%) + vacuum 6 s (15% HY (2016)
gas oil zeolite)f
Beech wood 525 ◦ C FCC 10 68.9 40.18 7.5 12.5 0.04 17.7 0.7 0.25 Wang et al.
bio-oil (10%) + catalystg (2016)
vacuum gas oil
a
Commercial fluid catalytic cracking (FCC) equilibrium catalyst with 44.9% Al2 O3 , 0.33% Na2 O, 1.9% Re2 O3 by weight along with 1047 ppm V and 1560 ppm Ni.
b
FCC equilibrium catalyst (E-CAT) containing 41.2 wt. % Al2 O3 , 0.49 wt. % Na2 O, 2.35 wt%, 1559 ppm Ni and 1820 ppm V.
c
Mixture of 90% FCC equilibrium catalyst (E-CAT) (containing 41.2 wt. % Al2 O3 , 0.49 wt. % Na2 O, 2.35 wt%, 1559 ppm Ni and 1820 ppm V) and 10% ZSM-5 additive.
d
Equilibrium FCC catalyst containing 15% Y-zeolite, 2.5% rare earth oxides by weight along with 240 ppm Ni and 870 ppm V.
e
Commercial equilibrium FCC catalyst with 0.6 weight % Re2 O3 content.
f
Commercial FCC equilibrium catalyst containing 15% HY zeolite by weight.
g
Commercial FCC equilibrium catalyst containing 45% Al2 O3 and 1.8% Re2 O3 by weight with 1000 ppm V and 2200 ppm Ni.
Table 8
Brief summary of properties of bio-oil obtained through different upgrading methods along with the process conditions and catalyst utilized.
Process Feedstock Catalyst Process Oil yield Water HHV Elemental analysis Major finding Ref.
conditions (%) (wt. %) (MJ/kg)
C (%) H (%) O (%) N (%)
Hydrotreating Mixed Pd/C 340 ◦ C, 62 2.7 – 75.5 9.4 12 0.6 • Coke deposition: Elliott
wood 75–150 atm, major limitation et al.
1–10 m3 • Minimization in gas (2009)
H2 /L bio-oil production
Pine Ni/HZSM-5 240 ◦ C, – 52.01 14.32 54.3 7.0 38 – • Cracking as well as Zhang
sawdust (10% nickel 4 MPa, hydrogenation occurs et al.
loading, 200 mL simultaneously during (2013)
Si/Al = 38) H2 /min, hydrotreating
3 h • Product composition
effected with
temperature
Microalga Pd/C 400 ◦ C, 81 – 43.02 81.2 11.7 4.85 3.1 • Coke and gas Duan
(Nan- (40% 3.4 MPa H2 , formation increases with and
nochlorop- catalyst 4 h increase in reaction time Savage
sis) loading) and catalyst loading (2011)
after certain limit
• Higher alkane and
aromatic content in
bio-oil
19
Microalgae NiMo/Al2 O3 380 ◦ C, 96.6 – 38.36 72.5 11.5 13.9 2.1 • O/C and heating value Patel
(3% Ni & 5 min similar to crude oil with et al.
14% Mo low coke formation (2017)
loading) • Problem of high N
content thus needs
proper catalyst or
pre-denitrification before

hydrotreatng
Sawdust Co–Mo–P/γ - 360 ◦ C, 52 – 41.4 87.7 8.9 3 0.4 • Upgradation makes Zhang
Al2 O3 2 MPa H2 , bio-oil soluble in oil et al.
30 min while raw bio-oil was (2005)
soluble in methanol
Hydrocracking Mixed Pd/C 400 ◦ C, 61 2.5 – 86.6 12.9 0.4 <0.06 • Quality of bio-oil Elliott
wood 1500 psig raises up to diesel fuel et al.
(2009)
Kraft Rh/C (5% 330 ◦ C, 80 – 37 80.78 8.18 10.9 0.1 • Use of isopropanol as Yang
lignin catalyst 4 h, during hydrocracking et al.
loading) 12 mL solvent raises the quality (2016)
Isopropanol of bio-oil
solvent • Rh/C catalyst produces
the product with HHV
and high phenolic
conversion
C (%) H (%) O (%) N (%)
Kraft Pd/C (5% 350 ◦ C, 70.5 – 36.38 79.47 8.2 12.1 0.2 • Use of isopropanol as Yang
lignin catalyst 4 h, during hydrocracking et al.
loading) 12 mL solvent raises the quality (2016)
Isopropanol of bio-oil
solvent
Hydrodeoxy- Pinyon Ni/ 450 ◦ C, 44.8 0 45.44 83.47 16.4 0 0.1 • High temperature Jahromi
genation juniper SiO2 -Al2 O3 7 MPa H2 , increases catalytic and
60 min activity Agblevor
• Hydration occurs at (2017)
low temperature while
deoxygenation and
cracking favored at high
temperature
• High hydrogen
consumption and high
coke formation is a
major challenge
20
Poplar Pd/C (4% 350 ◦ C, 22.5 0.6 34.5 73.8 8 17.5 0.7 • Low temperature Kim
wood catalyst 60 min favors hydration while et al.
loading) high temperature favors (2014)
cracking and
deoxygenation
• Formation of gaseous
products and char

increases with time
Poplar Pd/C (4% 350 ◦ C, 23.6 0.6 33.9 72.5 8.5 18.3 0.7 • Temperature, time Kim
wood catalyst 90 min and catalyst loading are et al.
loading) important parameters (2014)
affecting product
distribution
• Low temperature
favors hydration while
high temperature favors
cracking and
deoxygenation
• Formation of gaseous
products and char
increases with time
C (%) H (%) O (%) N (%)
Switch Pt/C (5% 320 ◦ C, 3.45 2.1 – 75.4 8.48 15.1 1.1 • Total degree of Elkasabi
grass catalyst 2100 psig, hydrodeoxygenation et al.
loading) 4 h does not depend on (2014)
feedstock type and
catalyst utilized
Pine Fe-Co/SiO2 300 ◦ C, 28 2.68 30.78 63.5 6.76 28.9 0.8 • Bimetallic catalyst Cheng
sawdust 3.45 MPa produce better results in et al.
H2 , terms of yield, properties (2017)
5 h and hydrocarbon
composition compared
to monometallic catalyst
Catalytic Empty ZSM-5 400 ◦ C, 80.3 – – 60–75 18–23 0 – • Combination of Hew
cracking fruit 1 L/h N2 , catalytic cracking with et al.
bunch 15 min distillation produces (2010)
gasoline with RON-95
Swine Modified 400 ◦ C, 45 3.6 41.4 70.6 11.2 15.0 1.6 • Parameters like Cheng
manure zeolite (5% 0.69 MPa catalyst loading, reaction et al.
catalyst N2 , time and temperature (2014)
loading) 30 min are important
parameters affecting
21
yield and properties of

oil
• High catalyst loading
and temperature
increases the formation
of alkanes, alkenes in
the upgraded product

Pinewood Hydrotreat- 560 ◦ C, 0.1 – – – – – • Coke formation Gueudré
ment: Ni 50 ml reduces with an increase et al.
based N2 /min, in severity of the process (2017)
catalyst 15 min • Naphtha product
Catalytic (blended obtained contain some
cracking: with phenolic compounds
Co–Mo vacuum gas with a reduction in acids
based oil) aliphatic alcohols
catalyst
Pine FCC catalyst 540 ◦ C, 39–41 – – 85.6 12.7 0.2 • Most of the oxygen Graça
(CAT1 and 2.7 bar goes to CO, CO2 , and et al.
CAT2) (blended H2 O, rest to increase the (2009)
with gas oil carbon content of
in 5 and 10 gasoline and diesel
wt. %) products obtained
• Bio-oil only up to
certain wt. % can be
mixed feasibly with gas
oils
Gong et al. (2011) reported that, increase in a number of medium acidic sites while subsequently decrease in the strong
and weak acidic sites or total acidity of the zeolite catalyst due to the incorporation of La, has been found responsible
for enhancing the selectivity for olefins by suppressing coke formation and improving catalyst stability. This can be an
effective way to produce petrochemical industry feedstock through a renewable source. Distillation of oil produced from
catalytic cracking produces gasoline-type fuel with research octane number 95 while that of commercial gasoline is
97 (Hew et al., 2010). Some important investigations on the upgradation of pyrolysis oil through catalytic as well as
hydroprocessing routes are summarized in Table 8.
6.4. Other miscellaneous techniques
Two-step upgradation processes are attracting more attention as compared to single-step process to get higher yield
and quality of transportation fuels. Combination of low-temperature hydrotreating with high-temperature hydrocracking
produces finished product with a large number of polycyclic hydrocarbons and significant reduction in carbon loss (Elliott
et al., 2009). Similarly, catalytic pyrolysis prior to hydrodeoxygenation (HDO) reduces oxygen content and produces bio-
oil with comparatively better properties. Platinum supported mesoporous zeolite catalyst (Pt/MZ-5) shows better activity
compared to old Pt/Al2 O3 catalyst (Wang et al., 2012). Aqueous phase reforming (APR) method has a high potential of
converting oxygenated organic compounds present in bio-oil to hydrogen and a small amount of lighter alkanes (methane)
using platinum and nickel catalyst (Davda et al., 2005; Wen et al., 2008; Fisk et al., 2009). Properties of bio-oil can be highly
improved with an increase in pH and calorific value along with reduction in density and viscosity through a combination
of esterification, hydrotreating and cracking in one step (Tang et al., 2008, 2009).
7. Advances in biochar utilization
During the thermochemical or hydrothermal conversion of lignocellulosic biomass, char is a common byproduct,
which is also called as ‘‘Biochar’’. Biochar is a carbon-rich, fine-grained, highly porous solid material obtained from the
thermochemical or hydrothermal conversion of biomass in an oxygen-limited atmosphere (Qian et al., 2015). In recent
times, biochar utilization has received considerable attention due to its physicochemical, biological properties, low-cost,
and sustainable nature. Effective usage of biochar is vital for enhancing economic feasibility and eco-friendliness. An
overview of recent advancement in biochar utilization pathways in various fields, such as for soil amendment, catalysis,
gas adsorption, sorbent for contamination reduction, fuel cell, gas storage, activated carbon, and mercury removal are
described below.
7.1. Biochar as a soil amendment
In recent days, several studies have been reported on the various benefits of using biochar as a soil amendment, which
includes increasing soil health and mitigation of global warming by carbon sequestration. Improvement in farming has
been attributed to an increase of pH in acidic soils, cation exchange capacity of the soil, higher nutrient retention and
soil microbial activity as well as soil fertility. Likewise, utilization of biochar as a soil amendment leads to mitigation of
greenhouse gas emissions via sequestering carbon in the ground for several years, and indirectly by mending soil health
and fertility (Cole et al., 2019).
7.2. Biochar as a support material and precursor for catalyst synthesis
In recent years, several studies have been reported in the domestic and industrial applications of biochar as a
heterogeneous catalyst without active metal loading or as a support material with active metal loading. In addition to the
effective morphological properties (pore size, pore volume and surface area), acid density (-SO3 H in particular), surface
oxygen functional groups, speciation, metal dispersion and mineral content, biochar has an ability to convert metal oxides
into metallic states, which enhances the catalytic performance of the biochar (Qian et al., 2015; Xiong et al., 2017). Due to
the desired physicochemical properties for catalyst/catalyst support, researchers have been trying to modify the biochar
via acid/base treatments (activation and functionalization) to make it suitable for specific applications. Therefore, biochar
has gained a huge interest to use it as a catalyst for syngas production and cleaning i.e. removal of condensable aromatic
hydrocarbons (naphthalene, phenol, toluene, styrene and other polycyclic aromatic hydrocarbons), conversion of syngas
into hydrocarbons via Fischer–Tropsch synthesis, tar reforming, hydrogen production, methanol electro-oxidation, oxygen
reduction reaction, ammonia ozonation and NOx reduction, photocatalytic degradation of organics, bio-diesel production
(via esterification/transesterification), bio-oil upgradation (via hydrogenation), isomerization, hydrolysis and dehydration
of biomass, biomass pyrolysis as well as gasification (Cao et al., 2017; Lee et al., 2017; Xiong et al., 2017). Some recent
studies reveal that use of biochar as a catalyst in bio-oil upgradation processes is gaining huge attention. Utilization of
one of the co-product of biomass pyrolysis as a catalyst in the upgradation of pyrolysis-derived bio-oil will improve the
economics of the whole process and open pathways towards large-scale applications of the process. Yue et al. (2020)
utilized solid acid catalyst derived from reed biochar in catalytic esterification of reed pyrolysis bio-oil. Upgraded bio-oil
using sulfonated biochar catalyst showed a significant increase in its ester content, calorific value and pH value along with
22
reduction in viscosity. Their study revealed that the activity of the biochar based catalyst was comparable with that of
commercial catalysts. Another study by Dawodu et al. (2019) also demonstrates the esterification of bio-oil through the
use of biochar obtained from the process. Bio-oil undergoes simultaneous esterification and olefination reaction during
bio-oil upgradation process in the presence of sulfonated biochar derived catalyst. Several characterization techniques
disclosed that bio-oil obtained after upgradation process showed remarkable reduction in its oxygen and water content
along with improvement in flammability and calorific value as compared to raw bio-oil. Due to its unique properties,
biochar can also be utilized as a catalyst support in hydrotreatment of bio-oil. Nguyen et al. (2016) utilized nickel doped
biochar catalysts in hydrotreatment of microbial bio-oil. Nickel-based biochar catalyst showed excellent textural and
morphological properties with high mesoporous structure and co-existence of carbon nanotubes. Upgradation process
produced hydrocarbon-rich bio-oil with n-heptadecane as its main component making it suitable for blending with diesel
fuel. Ren et al. (2014b) upgraded pine derived bio-oil by using cost-competitive biochar catalyst. Upgraded bio-oil showed
significant content of phenols (37.2 area %) and hydrocarbons (42.6 area %). Ido et al. (2019) also utilized biochar based
catalysts impregnated with nickel active sites in upgradation process of Scenedesmus obliquus microalgae bio-oil. Biofuel
obtained after upgradation consisted of 100% hydrocarbons with 94% alkanes and 6% aromatics along with improvement in
its properties such as density, heating value (43.7 MJ/kg), viscosity and elemental composition, which became comparable
to that of petroleum-derived diesel fuel. Literature shows that very little work has been done on hydrotreatment of bio-oil
using biochar based catalysts and some more work needs to be done to confirm the feasibility and effectiveness of the
catalyst for the process. Table 9 gives a brief view of feedstocks and preparation methods for different biochar based
catalysts along with their application, process yield, and conversion.
7.3. Biochar for gas adsorption and as a sorbent for contaminant reduction, heavy metal removal in soil and water
Carbon dioxide (CO2 ) and hydrogen sulfide (H2 S) are considered as default contaminants from the combustion of
fossil fuels, wastewater treatment plants, landfill gases, oil and gas processing refineries. Effective capture and storage
technologies are promising to reduce these emissions (Mohan et al., 2014). Upon activation (activated carbon), biochar
is extensively used as an adsorbent in treatment of gases, soil and water purification. Process of activation modifies the
morphological and physicochemical properties of biochar in terms of surface area, micropores, mesopores, total volume,
surface functionalities, etc. There are two processes for activation of biochar: physical activation and chemical activation.
Physical activation enhances the biochar surface area by exposing it to steam, CO2 , air, ozone, etc. at high temperature
(600–1000 ◦ C). While chemical activation involves impregnation of chemical agents such as H2 SO4 , H3 PO4 , ZnCl2 , KOH,
etc. onto biochar surface, leading to high surface area and introduction of active functional groups into the biochar
surface. Chemical activation generally occurs at a temperature lower than physical activation (Dalai and Azargohar, 2009).
Activated biochar enhances the textural properties and makes it suitable for adsorption of CO2 at low temperatures;
likewise, activated carbon with the lower surface area can adsorb H2 S due to its high storage capacity, adsorption rate,
and reversibility (Lee et al., 2000).
Further, biochar can also help to maintain a clean environment by eliminating contaminants and heavy metals from
soil and water. Currently, biochar has been proven to be a promising sorbent for contaminants in soil (Inyang et al., 2016;
Komkiene and Baltrenaite, 2016). Even though the surface area of the biochar is less compared to activated carbon but
the presence of a high number of oxygen-containing groups such as phenolic, carboxyl and hydroxyl surface functional
groups provides binding sites for soil and water contaminants (Uchimiya et al., 2011).
7.4. Biochar in fuel cells, as electrodes in fuel cell systems and supercapacitors
Direct carbon fuel cells (DCFCs) have gained user attention owing to low greenhouse gas emissions and high efficiencies
with respect to the traditional power generation facilities and other gas/liquid fuel cells. In DCFC, chemical energy in
carbon fuel converts directly into electricity without the need for gasification. Based on the type of electrolytes used,
DCFCs are categorized into molten hydroxide, molten carbonate, and solid electrolyte. Further, solid electrolyte DCFCs are
sub-categorized based on media, oxidizing/reducing agent, and type of gasification (Giddey et al., 2012).
The supercapacitor is an energy storage device which can be used as a continuous power source in electrical vehicles
and digital communication systems. Carbon material with high surface area and porous structure are the requirements
for manufacturing supercapacitors. Biochar has gained attention to harvest energy due to its long life cycle, low cost,
readily available, easy processability, versatile existing forms, and low environmental impact. Due to the various forms
of carbon materials, supercapacitors have diverse designs; among them, thin-film electrodes are the most common (Xiao
et al., 2012; Zhang et al., 2014). Table 10 discussed biochar sources, applications, produced power density, and a summary
of the study to aid biochar in electrodes, supercapacitors, and fuel cell systems.
7.5. Biochar application in bioprocessing: Anaerobic digestion, composting and fermentation
Physiochemical properties of activated carbon produced from biochar, obtained from pyrolysis process, indicate its
high surface area, porous structure, cation exchange capacity, pH buffering and electron acceptor and donor capability
(Sun et al., 2018b). Due to the above mentioned physiochemical characteristics, biochar and its derivatives have been
23
Table 9
Summary of biochar based catalyst utilized in different process reactions.
Feedstock Catalyst Application Reaction condition Yield/Conversion Ref.
synthesis
process
Irul wood sawdust Sulfonation Esterification and 85 ◦ C, oil to methanol 64.5% FFA conversion, Chellappan
10 ◦ C/min; 1, 2, 4 h; transesterification of ratio 9:1, catalyst 95.6% yield et al. (2018)
400, 600 ◦ C Pongamia pinnatta oil loading 2 wt. %, 2 h
reaction time
Co-pyrolysis of Bamboo – Deoxygenation 1 g each bamboo and 90 wt. % of oxygen was Chen et al.
wastes and microalgae algae, 200 ml/min Ar, 1 removed (2018a)
g catalyst, 600 ◦ C, 30
min
Walnut shells TiO2 Degradation of methyl 10 g of catalyst mixed 96.88% decolorization Lu et al.
10 ◦ C/min; 2 h; /Biochar by orange (MO) with 40 ml of methyl efficiency, 83.23% (2019)
500–800 ◦ C hydrolysis orange. The mineralization efficiency
photocatalytic activity
was evaluated by the
decolorization efficiency
and mineralization
efficiency of MO
Rice husk Ni/biochar by Upgradation of 3.72 (w/w) dodecane to 69.4% biofuel yield (94% Ido et al.
wet Scenedesmus obliquus oil mass ratio, 5 wt. % alkanes and 6% alkenes) (2019)
impregnation microalgae oil by Ni/C Cat; 500 rpm;
hydrotreating 246.89 ◦ C
Wood waste Sulfonated Sugar hydrolysis and 140–180 ◦ C for 5–60 42.3% yield, 58.7% Xiong et al.
biochar 30% dehydration min selectivity for HMF from (2018)
w/v H2 SO4 fructose,
Maltose hydrolysis to
glucose: 85.4% yield,
88.2% selectivity
Raw sawdust Carbothermal Cr(VI) reduction 50 mg cat, 100 ml Cr(VI) 94% removal Chen et al.
reduction route solution (0.25 ×10−3 ), 1 (2017)
for mL of N2 H4 · H2 O, at
Ru–Cu/biochar room temperature
Rice husk Ru/Activated Syngas methanation 613 K, 2 MPa, H2 /CO = CH4 selectivity 98% and Zhu et al.
biochar by wet 3, GHSV = 1200 h−1 100% CO conversion (2015b)
impregnation
Spent coffee grounds spent coffee Glucose isomerization to 5 min, 120 ◦ C 95% selectivity for Chen et al.
grounds doped fructose fructose (2018b)
with melamine
for N-enriched
biochar
Palm kernel shell Wet Biomass to aromatic 1:1 biomass to catalyst 33.82–49.1% aromatics Wang et al.
impregnation 1, hydrocarbons ratio, 50 ml/min N2 , yield (2019)
3, 5, 10 wt. % 600 ◦ C
metals on
biochar
Wood Tin (Sn) Glucose isomerization 160 ◦ C, 20 min CO2 biochar supported Yang et al.
functionalized catalyst showed 50% (2019)
wood waste yield and 100%
selectivity
Mixed plastics KOH and ZnCl2 Production of aromatic 2 g catalyst, 8 g plastics, 54.9% increment of Sun et al.
catalysts with rich oil from waste up to 500 ◦ C, 20 ◦ C/min, alkanes and 66% (2018)
biochar plastics 1 h, 0.3 L/min N2 flow enrichment of aromatics
activation by in oil
wet
impregnation
recently gaining attention in biological processing for increased production of chemicals and biofuels. Biochar application
can modify microbial processes’ conditions, thereby affecting the metabolism and growth of microorganisms, leading to
the production of products with improved properties (Sun et al., 2020). Different biological or microbial processes include
anaerobic digestion, fermentation and composting.
Anaerobic digestion is the economic and environmentally friendly method of generating energy from organic waste in
the form of biogas. Biogas mainly comprises of CH4 (60%–70%), CO2 (30%–50%) with traces of NH3 and H2 S. Application
24
Feedstock Catalyst Application Reaction condition Yield/Conversion Ref.
synthesis
process
Corn stover Microwave Biomass catalytic 25 g of biomass, 480 ◦ C Torrified biomass Ren et al.
pyrolysis pyrolysis via microwave for 10 min with 700 W catalytic pyrolysis had (2014b)
to enrich syngas and 20.43 vol.% of H2 , 38.34
higher bio-oil quality, vol.% CO in syngas
bio-oil upgrading Upgraded bio-oil showed
37.23 area % of phenols
and 42.56 area % of
hydrocarbons
Corn stover In situ catalytic Bio-oil production from 480 ◦ C for a duration of 52.77% of bio-oil Zhu et al.
pyrolysis microwave-assisted 15 min, microwave obtained from catalytic (2018)
catalytic pyrolysis and frequency of 2450 MHz, pyrolysis over biochar
biochar catalyst 20 g biomass loading catalyst
Karanja seed shells Carbonization Esterification of glycerol 1:5 glycerol to acetic 88.5% conversion Rafi et al.
with acetic acid acid molar ratio, 0.2 g (2015)
catalyst, 120 ◦ C, 4 h
Waste wood Pyrolysis The isomerization of 5 ◦ C/min heating at 73.8 mol.% selectivity Yu et al.
glucose to fructose 160 ◦ C (2019)
Lignocellulose residues Sulfonation Production of furfural by 180 ◦ C for the duration Furfural yield 37.75%, Liu et al.
and concentrated hydrothermal of 170 min conversion rate 62% (2017).
saccharide degradation
Microalgae Ni/biochar Bio-oil hydrotreating Temperature of 300 ◦ C, 71.1% yield Nguyen
catalyst by wet time of 2 h, catalyst et al. (2016)
impregnation content of 5 wt. % and
stirring speed of 400
rmp
Bamboo powder Ionic exchange Cellulose hydrolysis into 80 ◦ C, 3 h via hydrolysis 12.7 to 27.94% HMF Zhang et al.
method reducing sugars and yield (2017)
5-hydroxymethyl furfural
Peanut shell Cu- Activating persulfate for 120 min, 20 mM 98% removal Xu et al.
FeOOH/biochar the tetracycline persulfate, pH 7.0, 25 ◦ C (2019)
degradation
of biochar to anaerobic digestion improves microbial activity and process stability, leading to enhanced substrate
consumption and biogas production. Nutrients released from biochar enhance the nutrient content of the digester sludge
to be utilized as fertilizer (Shen et al., 2017). Literature depicts that anaerobic digestion amended with biochar shows an
increase in CH4 production along with a reduction in CO2 , NH3 and H2 S (Shen et al., 2017). Alkalinity of biochar favors CO2
production during anaerobic digestion into HCO3 − /CO3 2− , which can then be converted into methane by hydrogenotropic
methanogens (Jang et al., 2018). Removal of H2 S produced during the process occurs due to its absorption and oxidation on
the biochar surface. Acidification stage of anaerobic digestion leads to the reduction in pH due to formation of volatile fatty
acids such as propionic, acetic and butyric acids, which are detrimental for the activity of methanogenic bacteria. Biochar
addition to the process inhibits such drastic pH reduction due to its pH buffering capacity, leading to enhanced methane
formation (Wang et al., 2017). Also, the pH buffering capacity of biochar limits the increase in pH due to accumulation of
ammonia in the digester at the later stage of the process, leading to improved methane yield (Pan et al., 2019).
Composting is a process of conversion of organic waste materials into valuable biofertilizers for improving fertility
of soil and agricultural lands. Application of biochar in composting process enhances the compost properties along with
lesser production of toxic compounds and emissions due to improved microbial activity as well as abiotic interactions
(Godlewska et al., 2017). Composting involves degradation of organic matter as a result of microbial activity. Addition
of biochar improves the properties (such as porosity, bulk density, etc.) of the compost pile and enhances the microbial
metabolism by providing better environment for their activity. Biochar amendments helps to reduce heat loss from the
compost pile by acting as a barrier to heat loss and thus biochar amended composting can reach to higher temperature
much faster and maintain that temperature for much longer period of time as compared to that without biochar (Chen
et al., 2010; Zhang et al., 2016). Studies show that higher temperature results in high microbial activity, leading to higher
degradation of organic matter along with elimination of pathogens at higher temperature and forming pathogen-free and
healthier compost or biofertilizer (Zhang et al., 2016). Biochar also helps to maintain high microbial activity by regulating
the moisture content during composting process to the required level (between 50%–60%) due to its water holding capacity
(Li et al., 2015b). Process of decomposition of organic matter also releases certain emissions such as NH3 , H2 S, N2 O, CH4 ,
etc. which are harmful to the environment. Biochar addition can reduce these emissions by absorption on its surface
and it also absorbs certain poly-aromatic hydrocarbons often present in sewage sludge (Stefaniuk and Oleszczuk, 2016;
25
Table 10
Summary on biochar utilization as electrode for microbial fuel cell.
Biochar source Objective Temperature/power density (mW Summary Ref.
cm−2 ) /potential (V)
Maple wood, To investigate the potential The power density of carbon felt 15–27% less electricity was MdKhudzari
yellow birch wood benefits of using biochar anode in plant-based MFCs 22.54, generated with microbial fuel et al. (2019)
granules as an alternative to the power density of biochar cells with biochar than MFCs with
the standard carbon felt anode anode in plant-based MFCs 3.66, carbon felt. Methane emission
in microbial fuel cells (MFCs). the power density of carbon felt a was reduced by 39% with MFCs
node in soil-based MFCs 12.47, using biochar anodes.
the power density of biochar
anode in soil-based MFCs 3.38
Corn cob Fuel in direct carbon fuel cell Power density 185 mW/cm2 , Cell resistance and power output Yu et al.
current density 340 mA/cm2 at were dependent on the cell (2014)
750 ◦ C operating temperature.
Olive wood Investigation of chemical and 105 mW/cm2 power density Cell performance was essentially Elleuch
electrochemical reactions related to anodic CO/H2 /CH4 fuel et al. (2015)
mechanisms in direct carbon gases produced from the relatively
fuel cells complex chain gasification
reactions through the olive wood
charcoal lignocellulosic structure.
Wheat straw, Direct carbon solid oxide fuel Power density: 187 (wheat straw), Cell performances completely Qiu et al.
corncob, and cells operated with fuels of 204 (corn cob), 260 (bagasse) depended on the biochar (2019)
bagasse biochar mW/cm2 at 800 ◦ C, 0.5 g of chars physicochemical properties. More
discharged constant current work needs to be carried out for
density 140 mA/cm2 lasted for 15 commercial use.
h (wheat straw), 24 h (corn cob),
and 22 h (bagasse)
Almond shell Biochar as a fuel in V cell potential at 700 ◦ C, power Biochar from almond shell Elleuch
ceria-carbonate based direct density 127 mW/cm2 (almond showed higher performance than et al. (2013)
carbon fuel cell shell biochar fuel), power density activated carbon.
100 mW/cm2 (activated carbon
fuel)
Castor oil cake Utilization of biochar used in Limit of detection 7.5 nmol/L, Biochar with high surface Kalinke
electrode construction for linear dynamic range promoted the sensor performance. et al. (2016)
electrochemical determination 0.03–1 µmol/L
of paraquat
Babassu petiole Biochar application as Electrochemical reversibility ∆Ep Addition of biochar increased Ferreira
electrode modifier to detect < 0.08 V. Peak currents increased peak-to-peak separation, et al. (2018)
organic compounds by as a function of pyrolysis sensitivity, and electrocatalytic
electroanalytical methods temperature activity. Therefore biochar was
considered as a promising
modifier to be used in
simultaneous determinations of
organic compounds with similar
peak potentials.
Pistachio nutshells Pistachio nutshells biochar was Electrodes show 100% columbic Activated biochar can be used as Goldfarb
utilized as activated carbon in efficiency over 4000 electrode materials for energy et al. (2017)
electrochemical cells charge–discharge cycles, specific storage devices by eliminating the
capacitance 45 F/g, scan rate 1 need for fossil fuel originated
mV/s activated carbons.
Vandecasteele et al., 2016). Biochar also increases the nutrient concentration of the formed compost by providing several
macro and micronutrients (such as Na, Mg, Ca, P, K, P, S, Fe, Mn, etc.) that are already being present in the biochar and
thus enhancing the value of compost as organic fertilizer (Zhang et al., 2016).
Fermentation process converts carbon rich organic substrate into valuable biofuels and chemicals such as ethanol,
butanol, acetone, etc. as a result of microbial metabolism. Process of fermentation requires expensive chemicals as
nutrients and buffers that are required for maintaining microbial activity and often makes the overall process costly.
Presence of macro and micronutrients in biochar and its pH buffering capacity can eliminate the use of expensive
buffers and nutrients during fermentation thereby making the process cost-effective (Sun et al., 2018a). Several studies
demonstrate that using biochar as a medium supplement results in significant improvement in the yield of fermented
products compared to medium containing expensive buffers and mineral stock solution (Sun et al., 2018a,b). Moreover,
fermentation of lignocellulosic biomass requires removal of several inhibitory compounds such as vanillin, furfural,
syringic acid, formic acid, acetic acid, hydroxymethylfurfural (HMF), etc. for enhancing the rate of enzymatic hydrolysis
and thus the rate fermentation. Use of biochar can results in absorption of these compounds due to its excellent absorption
26
Biochar source Objective Temperature/power density (mW Summary Ref.
cm−2 ) /potential (V)
Soybean roots Soybean roots biochar was High capacitance 276 F/g at 0.5 Soybean roots were found to be a Guo et al.
used as an electrode material A/g; cycle stability 98% promising precursor to obtain (2016)
for supercapacitors capacitance retention after 10,000 three-dimensional hierarchical
cycles at 5 A/g; ultrahigh power porous carbons by chemical
density 63 000 W/kg activation for supercapacitors.
Sunflower stalk Sunflower stalk biochar Retention rate 15 000 cycles with Biomass derived biochar have the Wang et al.
electrode material in making 81%–95% stability; current density potential for high electrochemical (2018b)
supercapacitors 20 A/g; energy density 35.7 performance in energy storage.
Wh/kg
Sawdust Sawdust biochar as an Durability: 98% capacitance Magnetic nanofibers/mesoporous Liu et al.
electrochemical storage device retention after 10 000 cycles carbon composites show higher (2014)
with high durability catalytic action enhancing
retention capability, stability, and
durability.
Corn cob Preparation of Capacitance 221 F/g; 78% Exfoliation was found to be a Genovese
high-performance corn-cob capability; 3% reduction in novel economic route for high et al. (2015)
biochar based nanosheets for capacitance after 5000 cycles performance energy storage
supercapacitors materials.
Peanut shells Utilization of biochar from Capacitance 315 mAh/g; 0.1 V; Peanut shell nanosheet carbon Ding et al.
peanut shells for ion capacitor stable for 10,000 cycles at 3.2 A/g showed hierarchical porous (2015)
as an active material for anode architecture and high levels of
and cathode doping.
Sterculia Sterculia lychnophora based Capacitor voltage 1.7 V; Desirable electrochemical Zhang et al.
lychnophora biochar applied as a carbon capacitance 47.8 F/g; energy properties and porous structure of (2015)
source for preparing high density 18.5 W h/kg Sterculia lychnophora derived
performance supercapacitors biochar material show high
performance for electrical energy
storage devices.
Pinecone Pinecone biochar as a Capacitance 1.19 F/cm2 for The study concluded that high Genovese
polyoxometalate hybrid activated carbon originated from performance, low-cost electrodes and Lian
material for supercapacitor pine cone biochar can be prepared by using (2017)
electrodes polyoxometalate clusters to
modify the biochar activated
carbon substrates.
Maple wood Maple wood-derived biochar as Capacitance 32 F/g, stability 2600 Mini chuck electrodes exhibited Zhang et al.
supercapacitor electrode potential cycles fast and simple technique to use (2014)
materials (mini-chunk, maple wood-based biochars as an
thin-film, large disk chunk) eco-friendly and high-performance
supercapacitor electrodes without
the need for binder.
Cladophora Anode electrode for Li-ion Capacitance 700 mAh/g; current HCl treatment biochar show high Salimi et al.
glomerata (green batteries density 0.1 A/g performance due to the large (2017)
microalgae) surface area, micropore formation
and nature of functional groups
after HCl treatment.
Algal biomass Use of algal biomass derived 9.1 µA/cm2 electricity was Algal biochar anode density was Wang et al.
biochar as an anode material generated from algal biochar 1.4 times higher than (2018a)
for electricity generation in anode; 8.5 µA/cm2 electricity was graphite-based anodes in
bioelectrochemical systems generated from carbon paper bioelectrical systems.
anode
Rice straw Application of rice straw based 250 mA/g of capacitance Anode electrodes prepared from Ryu et al.
biochar material in preparation rice straw-based biochar is (2015)
of anode material for promising even though it had
lithium-ion batteries inferior properties than graphite.
capability (Lee et al., 2011). Biochar supplemented medium enhances the microbial growth rate and the yield of fermented
products to much higher value than the medium without biochar (Lee et al., 2011; Sun et al., 2018a).
8. Techno-economic evaluation of the integrated bio-refinery concept
Techno-economic analysis (TEA) evaluates both the technical as well as economic aspects of the product with the
quantification of all involved costs and technologies involved in the process. Evaluation of technical as well as economic
prospects of the bio-refinery concept is an important study for checking its viability for commercialization. Minimum fuel
27
selling price (MFSP) is an indicator used to test the economic feasibility of fuel towards commercialization. As shown
in many studies, the price of renewable fuels derived from biomass is higher than that of fossil-derived gasoline and
diesel fuel (Sorunmu et al., 2020). Techno-economic factors that affect the cost of biomass-derived fuel are feedstock
cost, energy cost, operational and capital cost, product yield and utilization as well as market availability. Fuels produced
from waste-derived biomass generally achieve comparatively lower MFSP. Also, variations in the operational and design
parameters can result in variations in the quality and quantity of the products, which can change the revenue generated
from their sale. Several techno-economic analysis (TEA) studies have been done to evaluate the cost competitiveness of
bio-oil conversion technologies compared to fossil derived fuels. A TEA study by Wang and Jan (2018), determined cost
of crude bio-oil production at 10% internal rate of return (IRR) as $2.08 per gallon. However, the cost of bio-oil increases
with the application of different upgradation techniques for improvement in the quality of the product due to additional
costs of equipment, catalyst, hydrogen gas, etc. Wu et al. (2019) conducted an economic analysis of co-processing of raw
pyrolysis oil and catalytic pyrolysis oil with vacuum gas oil (VGO) in fluid catalytic cracker (FCC) and determined their
MFSP as $2.63 and $2.60 per gallon respectively. The price is competitive with that of gasoline derived from petroleum
and can be utilized as a replacement for petroleum-based fuels. Bio-refinery based on in situ and ex situ modes of catalytic
pyrolysis have almost similar MFSP, but ex situ catalytic pyrolysis has comparatively lower techno-economic uncertainty,
which indicates lower risk during commercialization (Li et al., 2015a). TEA study of hydroprocessing pathway of mild
catalytic pyrolysis bio-oil to produce hydrocarbon derived biofuel determined MFSP of biofuel as $3.69 per gallon. This
is significantly higher than that of petroleum-derived fuel, which probably costs $2.92 per gallon, thus possessing a
challenge for biofuels to potentially replace petroleum fuels (Thilakaratne et al., 2014). However, biochar, a co-product of
pyrolysis, can be used as a revenue-generating product to make the process more economical. Studies performed on the
integrated bio-refinery concept show that the utilization of biochar in the field of solid fuel, adsorbent, catalysis, etc. will
significantly improve the process’s economic performance. Application of biochar as solid fuel with selling price of $50 per
MT contributes to about 2.8% of the total revenue generated from the process (Winjobi et al., 2016). Conversion of biochar
into activated carbon can significantly improve its selling price as $1188 per MT, thereby increasing its contribution to
51.11% to total revenue (Kuppens et al., 2015). Co-processing of 5% raw bio-oil and 10% catalytically upgraded bio-oil
with vacuum gas oil (VGO) resulted in a MFSP of $2.83 and $5.10 per gallon, respectively. These values often reduce
to $2.68 and $4.73 per gallon for raw and upgraded bio-oil, respectively, after application of produced biochar in the
soil as soil amendment or carbon sequestrate (Van Schalkwyk et al., 2020). Co-production of platform chemicals with
fuels in biomass driven industry further reduces the economic barrier and eases the commercialization of the process.
This will result in the more economical production of biofuels by increasing the overall revenue of the bio-refinery.
Production of platform chemical furfural and activated carbon from biochar with renewable fuel reduces the MFSP of
the fuel to $2.78 per gallon (Gunukula et al., 2018). In another study by Li et al. (2017), production of mixed alcohols
as a co-product with hydrocarbon fuels lowered the fuel MFSP from $2.85 to $2.77 per gallon, thus increasing the cost-
effectiveness of the process. Hydrogen required in upgradation through hydroprocessing technique significantly enhances
the fuel cost. On-site generation of hydrogen from low-cost natural gas can help in reducing the cost of upgraded oil. Yang
et al. (2018) co-produced hydrogen with cycloalkane range fuel and biochar in an integrated microwave-assisted catalytic
pyrolysis and hydrogenation process, which resulted in a sufficient reduction in MFSP of fuel as $3.78 per gallon. In situ
generated hydrogen was utilized in the hydrotreatment process and remaining was sold in the market. This improved
the economics of the process due to the additional revenue generated from the sale of hydrogen and biochar as coal
substitute. Table 11 shows a brief summary of the techno-economic evaluation of different types of integrated pyrolysis
based bio-refineries. The biomass driven fuel technology is currently less competitive with that fossil driven fuels. Thus,
to fully replace conventional petroleum-derived fuels by renewable biomass-derived fuels, there is a need to make the
process more cost-effective. This can be achieved with improvement in process technologies to produce better yields and
high-value co-products together with utilization of low cost or waste biomass, low-cost hydrogen gas and longer catalysts
life.
9. Challenges and future scope for development
Bio-oil seems to be a viable option for boilers and engines in place of hydrocarbon fuels for energy production and often
acts as a resource for extracting value-rich chemicals. But the use of bio-oil is not an easy task and commercialization of
bio-oil as fuel and chemical source possess the following challenges:
• Bio-oil with low heating value, high viscosity, instability and corrosivity is produced through pyrolysis, which is quite
inferior to gasoline and diesel fuels.
• Upgrading processes such as hydrotreating, hydrodeoxygenation (HDO), and catalytic cracking produces high-grade
fuel but are still not commercialized due to the high cost of catalyst, frequent catalyst deactivation, need for
specialized reactors and high-pressure requirements.
• Extraction of chemicals from bio-oil is a very good option for improving the economics of the whole process, but it
is quite challenging as these chemicals are present in relatively small amount along with the high cost of extraction.
Thus, to make the concept of bio-refinery operational from commercial view, a large amount of research and development
activities are needed. Some critical areas, which require intensive investigation are:
28
Table 11
Brief summary of the techno-economic evaluation of various pyrolysis based bio-refineries.
Feedstock Plant capacity Conversion technology Main product Co-products MFSP ($ per gallon) References
(MT/day)
Wood 2000 Thermal deoxygenation Biofuel Furfural, 2.78 Gunukula
(biofuel), Activated carbon et al. (2018)
Hydrolysis (furfural),
Steam activation
(activated carbon)
Forest 2549 Fluid catalytic cracking Upgraded oil Biochar as soil 2.83 (without (Van
residues (FCC) of raw bio-oil (5%) amending agent co-products), Schalkwyk
with vacuum gas oil 2.68 (with et al., 2020)
(VGO) co-products)
Forest 2549 Catalytic pyrolysis Upgraded oil Biochar as soil 5.10 (without (Van
residues followed by its (10%) amending agent co-products), Schalkwyk
FCC cracking with 4.73 (with et al., 2020)
vacuum gas oil (VGO) co-products)
Hybrid 1000 Microwave assisted Jet fuel ranged Biochar as coal 3.78 Yang et al.
poplar catalytic pyrolysis cycloalkanes alternative (2018)
followed with catalytic
hydrogenation
Guayule 2000 Pyrolysis followed by Gasoline ranked fuel Residual 3.63 Sabaini
bagasse hydrodeoxygenation bio-refinery coke et al. (2018)
(HDO)
Red oak 2000 Hydroprocessing Transportation fuel – 3.09 (transportation Hu et al.
(transportation fuels), (gasoline and fuel fuels), (2016)
Hydrolysis and ranged), 433.7/MT
extraction (biochemical), Biochemicals (dextrose, (biochemical),
2-stage hydrotreating calcium acetate and 773.5 /MT
followed by FCC cracking bioasphalt), (hydrocarbon
(hydrocarbon chemicals) Hydrocarbon chemicals chemicals)
(aromatics and olefins)
Red oak 2000 Hydroprocessing (fuel) Fuel (gasoline and diesel Mixed alcohols 2.85 (without Li et al.
Ketonization and ranged) co-product) (2017)
alkylation (mixed 2.75 (with
alcohols) co-product)
Woody 2000 Deoxygenation through Hydrocarbon ranked – 3.69 Thilakaratne
biomass hydroprocessing biofuels et al. (2014)
Pine wood 1000 Torrefaction followed by Bio-oil Biochar as coal 1.04 Winjobi
pyrolysis substitute et al. (2016)
• Research on improving the yield and properties of pyrolysis bio-oil by employing prominent feedstock and operating
conditions.
• Development of new catalyst formulation mainly in the field of bi-functional, multifunctional and biochar based
catalysts which can be effective along with the low cost of fabrication.
• More understanding of the mechanism involved in carbon formation
• Development of catalyst with low deactivation, high renewability, and high selectivity.
• More understanding of the kinetics and mechanism of the processes involved, such as hydrotreating, hydrodeoxy-
genation (HDO) and catalytic cracking.
• Design of steady as well as fully developed reactors.
• Development of effective and low-cost surfactants for emulsifying bio-oil with hydrocarbon fuels.
• Development of economically feasible technologies in the field of extracting a relatively small amount of valuable
chemicals from bio-oil.
• Development of biochar based catalysts for different applications and electrodes for fuel cells.
• Development of an integrated process that develops transportation fuels from bio-oil along with the extraction of
valuable chemicals from it and finding a proper market for other co-products such as biochar to make the overall
process economically viable.
10. Summary
Biomass seems to be a viable option to combat environmental problems and increasing energy demands across the
globe. Raw bio-oil obtained through pyrolysis cannot be used directly for energy production in engines and boilers due
to the low calorific value, high viscosity, corrosiveness and tendency to form gummy compounds on storage.
29
Integrated refinery technique is the most suitable technique for upgrading bio-oil which produces a large number of
valuable chemicals, gasoline grade fuel along with char utilization. Production of fuel equivalent to hydrocarbon grade fuel
with high cetane number, high heating value, low viscosity, and acidity as well as renewable chemicals has great industrial
importance. But the high cost of catalysts, solvents and process complexity limits their application. Co-products such as
biochar also has immense application in fields of contaminant removal from wastewater, precursor material for several
catalysts, an electrode for microbial fuel cell (MFC), biological processing, etc. The overall bio-refinery concept can be
economically feasible by utilizing all these products effectively and will lead towards the way of achieving a cleaner and
sustainable environment.
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
The authors are likely to express their gratitude towards Ministry of Human Resource Department, Government of
India, Department of Chemical Engineering, Indian Institute of Technology, Roorkee, India and Department of Chemical
and Biological Engineering, University of Saskatchewan, Canada for providing assistance during the research study.
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