Chemosphere 286 (2022) 131824

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Lignocellulosic biomass-based pyrolysis: A comprehensive review

Yogalakshmi K N a, 1, Poornima Devi T b, 1, Sivashanmugam P c, Kavitha S b, Yukesh Kannah R b,
Sunita Varjani d, S. AdishKumar e, Gopalakrishnan Kumar f, Rajesh Banu J g, *
a
Department of Environmental Science and Technology, School of Environment and Earth Sciences, Central University of Punjab, Bathinda, Punjab, 151001, India
b
Department of Civil Engineering, Anna University Regional Campus, Tirunelveli, 627007, Tamilnadu, India
c
Department of Chemical Engineering, National Institute of Technology, Tiruchirappalli, 620015, Tamilnadu, India
d
Gujarat Pollution Control Board, Gandhinagar, Gujarat, 382010, India
e
Department of Civil Engineering, University V.O.C College of Engineering, Anna University Thoothukudi Campus, Tamil Nadu, India
f
School of Civil and Environmental Engineering, Yonsei University, Seoul, 03722, Republic of Korea
g
Department of Life Sciences, Central University of Tamil Nadu, Neelakudy, Tiruvarur, 610005, India

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Pyrolysis efficiently converts lignocel­

lulosic biomass to value added products.
• Temperature, residence time and heat­
ing rate has a great impact on the
pyrolysis.
• Lignocellulose pyrolysis is viable due to
low carbon foot print at commercial
level.
• Factors affecting pyrolysis of lignocel­
lulosic biomass were discussed in detail.
• Environmental and economic aspects of
pyrolysis were extensively reviewed.

A R T I C L E I N F O A B S T R A C T

Handling Editor: Derek Muir The efficacious application of lignocellulosic biomass for the new valuable chemicals generation curbs the
excessive dependency on fossil fuels. Among the various techniques available, pyrolysis has garnered much
Keywords: attention for conversion of lignocellulosic biomass (encompasses cellulose, hemicellulose and lignin components)
Cellulose into product of solid, liquid and gases by thermal decomposition in an efficient manner. Pyrolysis conversion
Hemicellulose
mechanism can be outlined as formation of char, depolymerisation, fragmentation and other secondary re­
Lignin
actions. This paper gives a deep insight about the pyrolytic behavior of the lignocellulosic components accom­
Pyrolysis
Biochar panied by its by-products. Also several parameters such as reaction environment, temperature, residence time
Bio-oil and heating rate which has a great impact on the pyrolysis process are also elucidated in a detailed manner. In
addition the environmental and economical facet of lignocellulosic biomass pyrolysis for commercialization at
industrial scale is critically analyzed. This article also illustrates the prevailing challenges and inhibition in
implementing lignocellulosic biomass based pyrolysis with possible solution.

* Corresponding author.
E-mail address: [email protected] (R.B. J).
1
These two authors are equally contributed.

https://doi.org/10.1016/j.chemosphere.2021.131824
Received 16 June 2021; Received in revised form 27 July 2021; Accepted 4 August 2021
Available online 6 August 2021
0045-6535/© 2021 Elsevier Ltd. All rights reserved.
Y. K N et al. Chemosphere 286 (2022) 131824

1. Introduction of lignocellulosic biomass throughout worldwide in industrial sector

(Toczyłowska-Mamińska, 2017). Table 1 shows the details of pilot scale
The soaring fossil fuel prices and depletion of its resources has led to pyrolysis unit operated throughout worldwide.
the lookout for alternative and sustainable energy resources. Biomass Pyrolysis is the thermal degradation of lignocellulosic biomass ma­
which has gained prominent attention worldwide as a renewable trix at elevated temperature in non-oxidizing conditions. This process
carbonaceous resource is existent in diverse forms and is used to has garnered much attention nowadays for its pliability to engender a
generate heat, electricity, fuels and other value added byproducts. range of solid, liquid and gaseous products from discrete biomass and
Generally biomass is categorized as virgin biomass (comprising ligno­ hence classified as slow pyrolysis, fast pyrolysis and flash pyrolysis
celluloses, crops and vegetables), waste biomass (includes municipal based upon the process parameter like rate of heat, temperature and
solid waste and sewage) and agricultural wastes. Biomass can be solids residence time (Papari and Hawboldt, 2015). Slow pyrolysis oc­
transformed into fuels and other products either via biochemical curs at relatively low temperature (<500 ◦ C) with long residence time
(Kavitha et al, 2014, 2020) or thermo-chemical processes (Dai et al., and usually termed as carbonization and utilized widely for charcoal
2020; Kumar et al., 2020). Amidst the variant thermo-chemical tech­ production. Fast pyrolysis takes place at a higher heating rate
niques accessible, pyrolysis has emanated as a front line research area (10-200 ◦ C/s) and a reduced residence time (<2s) with high bio-oil yield
for the bio-oil, bio-char and other pyrolytic gaseous by-products gen­ (50–70 %). Flash pyrolysis happens at an even more high rate
eration from different biomass available. (103–104 ◦ C/s) with a concise residence time (<0.5s) leading to high
Lignocellulosic biomass derived from agricultural waste and forest bio-oil yield (75–80 %) (Kan et al., 2016). In order to accomplish high
debris is the sole renewable energy source encompassing carbon and energy efficiency through biomass pyrolysis system, multifarious py­
found to be an opportune resource for conversion into bio-fuels and rolysis parameters should be taken into consideration which includes
chemicals. They are classified into three major components as cellulose biomass type, particle size, reaction conditions, reactor type and trans­
(40–45 %), hemicelluloses (25–35 %) and lignin (20–30 %). It also port phenomena within the reactor and also other variables like catalyst
comprises minimal quantity of extractives (such as lipids, essential oils, addition and the mechanism for vapor condensation. The different py­
resins, proteins, simple sugars, starch, water) hydrocarbons, and inor­ rolysis reactors used in studies are fixed bed reactors, batch or
ganic ash. These components are scattered along the cell wall in a semi-batch reactors, rotary kilns, fluidized bed reactors, microwave
haphazard manner as a skeletal structure, combining element and rigid assisted reactors and a few contemporary types such as plasma or solar
solids respectively (Mettler et al., 2012). Conventionally, cellulose reactors (Bridgwater, 2012). Thus this paper gives a comprehensive
clusters into tenacious fibers and forms a skeletal framework along the review about the intricacy in lignocellulosic biomass structure and the
cell wall and the interior spaces are filled with hemicelluloses and lignin associated pyrolysis behavior of its components along with its
which acts as a binding compound. Hemicellulose and lignin element by-products. It also elucidates the various parameters affecting pyrolysis
couples with cellulose through hydrogen bond whilst lignin and hemi­ yield. It also presents the challenges posed while implementing the
cellulose components are both hydrogen and covalently bonded and process and the possible solution that gives an opportunity for the
found to impact the pyrolysis characteristics of biomass (Collard and advancement of the process.
Blin, 2014). Likewise, in the course of pyrolysis, the synergy between the
lignocellulosic biomass components can be analyzed by perusing the 2. Whole lignocellulosic biomass based pyrolysis
aspects of element distribution, tar characteristics and gas content.
Excess amount of lignocellulosic biomass is originated from two major The behavior of lignocellulosic biomass components during pyrolysis
sector for example agriculture and industrial sector (Ahorsu et al., is overseen by parameters like the divergent reaction rate and stability of
2018). In agricultural field, nonedible crop product such as rice straw a particular element, the interconnection between the biomass compo­
(Chen et al., 2017), rice husk (Park and Jang, 2012) wheat straw (Wu nents and the receptivity of the pyrolysis by-products which greatly
et al., 2019) and sugarcane baggase (Duku et al., 2011) etc are consid­ influences the reactor configuration. Numerous reactions occur during
ered as a waste lignocellulosic biomass, which are directly utilized as a lignocellulosic pyrolysis which is conventionally condensed into three
raw material for production of bioenergy, biofuels and value added vital steps as a) evaporation of available moisture b) primary biomass
products etc. Developing country like India, the lignocellusic biomass degradation and c) secondary reactions (inclusive of oil cracking and
from agriculture field is abundantly available throughout the year. repolymerisation). Maximum biomass decomposition takes place at
Paper and pulp manufacturing industries is major source for generation 200-400 ◦ C during the primary stage which results in solid char

Table 1
Pilot scale pyrolysis unit operated throughout worldwide.
S. Type of pyrolysis Pyrolysis Reactor Reactor designed and Location Biomass Product yield References
No type operated feeding rate

1. Non-catalytic fast Conical spouted University of the Basque Spain 25 kg/h Bio-oil (65.8 wt%), bio-char Fernandez-Akarregi et al.
pyrolysis bed Country UPV/EHU (15.4 wt%) and pyro-gas (18.8 wt (2013)
%)
2. Catalytic fast Circulating National Renewable Energy United 30 kg/h Bio-oil, bio-char and pyro-gas Gao et al. (2020)
pyrolysis fluidized bed Laboratory States
3. Non -catalytic Fluidized bed Sardar Patel Renewable India 3 kg/h Bio-oil (~38 wt%), bio-char Karmee et al. (2020)
fast pyrolysis Energy Research Institute (~12 wt%) and pyro-gas (~50 wt
%)
4. Catalytic fast Fluidized bed Sardar Patel Renewable India 3 kg/h Bio-oil (~44 wt%) bio-char (~4 Karmee et al. (2020)
pyrolysis Energy Research Institute wt%) and pyro-gas (~52 wt%)
5. Catalytic fast Circulating Research Institute of Republic of 42 kg/h Bio-oil (60 wt%), Park et al. (2019)
pyrolysis fluidized bed Petroleum Technology Korea
6. Non -catalytic Fixed bed Sardar Patel Renewable India 15 kg/h Bio-oil (34.9 wt%), bio-char Soni and Karmee (2020)
fast pyrolysis Energy Research Institute (38.6 wt%) and pyro-gas (26.5 wt
%)
7. Catalytic fast Fixed bed Sardar Patel Renewable India 15 kg/h Bio-oil (41.05 wt%), bio-char Soni and Karmee (2020)
pyrolysis Energy Research Institute (27.9 wt%) and pyro-gas (31.6 wt
%)

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Y. K N et al. Chemosphere 286 (2022) 131824

formation whilst the secondary reactions which happens in the interior 2.2. Bio-oil
surface of biomass furthermore accelerates the temperature (Yaashikaa
et al., 2019). Hemicellulose decomposition usually characterized by Bio-oil also known as pyrolysis oil/liquid is a dark brown liquid
xylan occurs between 250 and 350 ◦ C whereas cellulose based pyrolysis encompassing an assorted number of oxygenated elements and exploi­
happens between 325 and 400 ◦ C with levoglucosan as its by-product ted to be utilized as fuels/chemicals. Generally bio-oil is classified under
and lignin the utmost stable product degrades at surpassing tempera­ three categories as small carbonyl compounds (acids, ketones, alde­
ture of 300–550 ◦ C. hydes), sugar based compound (furans and hydrosugars), and lignin
based compounds (phenols, aromatic oligomers). Fast/flash pyrolysis
2.1. Biochar process is typically adopted to augment the bio-oil yield. The lesser
heating value of bio oil is owing to presence of high H2O content (15–30
Biochar, the solid product resulting from lignocellulosic biomass %). Besides high O2 content (35–40 %) and high moisture content, ex­
pyrolysis is a highly carbonaceous material with carbon content be­ istence of carboxylic acids lowers the pH value be to 2–3.7 and act as a
tween 65 and 90 %. The physic-chemical property of the solid biochar is detriment in bio-oil production (Kan et al., 2016). Hence the
largely based on type of feedstock and the process parameters and physic-chemical properties of bio-oil need to be uplifted ahead of its
thereby actuates its usage widely. Biochar yield was found to be replacement with conventional fuel. This can be accomplished by
maximal during slow pyrolysis (<500 ◦ C) by contracting the bio-oil employing techniques such as catalytic cracking technique and high
yield (Li et al., 2020a). Likewise their micro porous nature, cation ex­ pressure hydro processing for transformation of bio-oil into liquid fuel
change capacity and high specific surface area enhance their ability for for transportation. Further they can also be utilized as raw material in
filtration and adsorption of toxic pollutants. Owing to their adsorptive chemical production like phenols (manufacture of resins), add-on in
property they serve as forerunners for mass production of activated fertilizer and pharmaceutical industry, flavor enhancer (like glyco­
carbon by virtue of its physic chemical activation (Czajczyńska et al., laldehyde) in food industry and various other specialty chemicals (Balat,
2017). Further they have found application in catalysis, composting, 2011). Fig. 1 shows schematic diagram of biomass pyrolysis to biochar
fermentation detoxication and electrochemical energy storage. Biochar and bio-oil.
can also be used as an organic fertilizer due its high nutrient retention
ability in soil and provides a symbiotic environment for microorganisms.
Withal, it gives a substantially greater GHG savings as to direct biomass 2.3. Pyrolytic gases
incineration as a result of biochar effect on output and carbon seques­
tration (Lee et al., 2013). Akom et al. (2020) have reported that around Pyrolytic gases are chiefly a blend of H2, hydrocarbon gases (C1–C4),
0.36–0.45 kg of biochar can produce from one kg of lignocellulosic CO2, CO, and H2S. Elevated temperatures, catalysts addition and slow
biomass and the conversion rate is approximately in the range of 36–45 residence time are the most preferred conditions for lignocellulosic
%. Fig. 1 shows schematic diagram of biomass pyrolysis to biochar and biomass pyrolysis for generation of synthetic gas or H2 rich gas (Kan
bio-oil. et al., 2016). Thermal degradation of carbonyl and carboxyl functional
groups results in CO2 formation whereas detachment of C–O–C and
C–
– O bonds led to CO generation. Likewise C–H and aromatics group
rupture causes H2 formation. Nonetheless low temperature produces CO

Fig. 1. Schematic diagram of biomass pyrolysis to biochar and bio-oil.

3
Y. K N et al. Chemosphere 286 (2022) 131824

and CO2 as the principal gaseous products while lignin depolymerisation pyran whereas levoglucosan go through polymerization to yield –COOH,
at accelerated temperatures engenders CH4 as main gaseous products –COO–, –C– – O, –OH, and C–O–C as active functional groups (Stefanidis
(Zhan et al., 2019). In general pyrolytic gases have LHV between 10 and et al., 2014). Furthermore these functional groups left in char products
20 MJ/Nm3 which depends upon product distribution. ZnCl2, dolomite, undergo reactions such as decarboxylation and decarbonylation
K2CO3, Na2CO3, Ni/Al,Ni/Fe, CaO, Fe2O3, Cr2O3 and Rh/CeO2 are used augment the aromatic extent of biochar along with the release of
as catalysts to boost H2 gas generation and conforms the gas content for gaseous products. Table 2 represents the various products obtained from
downstream application (Fischer-Tropsch synthesis) (Qinglan et al., cellulose based pyrolysis of lignocellulosic biomass.
2010; Xu et al., 2011). It is also seen that wet biomass engenders 40%
higher yield of H2 than the dry one. Preclusive to its usage widely certain
3.1. Products obtained from cellulose based pyrolysis
treatment is necessary to curb the unwanted elements present in pyro­
lytic gases such as dust, tar, heavy metals, steam and hydrogen sulphide.
3.1.1. Levoglucosan (LG)
Aside from the above facts, it is widely used for generating heat/elec­
Levoglucosan is a chief product obtained from fast pyrolysis of cel­
tricity, liquid bio fuel or in some cases used as carrier gas in pyrolysis
lulose is a oxygenate C5–6 ring compounds with a yielding capacity of
reactor (Hossain and Davies, 2013).
about 20–60 % (Shen et al., 2015). Besides depolymerisation and rup­
tures the 1, 4-glycosidic bonds during cellulose pyrolysis at elevated
3. Cellulose based pyrolysis
temperature and time resulted in copious amount of levoglucosan. Wei
et al. (2012) confirmed in their study that cellulose base pyrolysis yields
Cellulose is a linear macromolecular polysaccharide comprising of a
51.3 % of levoglucosan of the entire pyrolytic compounds generated at a
lengthened glucose chain linked by β-1, 4-glycosidicbonds and interacts
temperature of 400 ◦ C. Also levoglucosan yield declined at temperature
with each other through intermolecular/intramolecular hydrogen bonds
surpassing 530 ◦ C while large concentration of levoglucosan (>10%
which contributes to its crystalline structure and chemical stability. The
weight) was used as a pointer to analyze the bio-oil quality (Jiang et al.,
glycosidic bond linkages in cellulose are unstable and incline to rupture
2019). It can moreover be used right away to harvest ethanol fuel
under acidic environment or elevated temperature (Dai et al., 2020).
through microbial fermentation and utilized as a carbon source for
The reaction pathway of cellulose based pyrolysis is depicted in Fig. 2.
succinic acid generation (Wang et al., 2020). Conjointly, a counteraction
The fundamental reaction step in cellulose pyrolysis occurs at <300 ◦ C
between levoglucosan-producing reactions and degradation reaction in
that comprises of decomposition and polymerization reactions and leads
cellulose pyrolysis constrained its yielding capacity and secondary re­
to formation of low molecular compounds like glycoaldehyde, furan,
actions engendered light oxygenated compounds and non-condensable
hydroxyl acetaldehyde, formic acid, H2O and CO2 elements etc (Zheng
gases (Lindstrom et al., 2019).
et al., 2016). When the temperature reaches above <800 ◦ C the cellulose
biomass turns to produce bio-oil and biochar. In general, anhydrosugars
3.1.2. Hydroxyacetaldehyde (HAA)
(chiefly levoglucosan) are the principal product formed by pyrolysis
Several literatures have proclaimed that HAA is formed by the sec­
vapor owing to the cleavage of glycosidic bonds and dehydration re­
ondary degradation of LG or intermediate fragmentation during cellu­
actions. Also at proliferating temperatures (>300 ◦ C), levoglucosan goes
lose pyrolysis (Lu et al., 2016). Dong et al. (2012) in their study revealed
through relocation and hydration generating levoglucosenone and
a remarkable increase in HAA production until 550 ◦ C and further rise in
further cyclization reactions occurs which transforms into stable
temperature (600 ◦ C) constricted its yield. This confirms that principal
oxygenated compounds like furfural, 5-hydroxyl methyl furfural, and
cellulose decomposition caused a cleft in glycosidic bond and

Fig. 2. The pathways of cellulose pyrolysis at different temperature.

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Y. K N et al. Chemosphere 286 (2022) 131824

Table 2
Various products obtained from cellulose based pyrolysis of different lignocellulosic biomass.
S. Type of Type of pyrolysis Operational Reactor/ Type of Products Key findings Reference
No lignocellulosic conditions analyzer products yield
biomass employed

1. Rice straw Flash carbonization Temp- 800- Fixed bed Biochar 20.80–61.54 Specific surface area Chen et al.
1200 ◦ C reactor % decreased at elevated (2017)
Residence time- temperature
5s
Heating rate-
1000 ◦ C/min
2. Rice husk Fast Temp-500 ◦ C semi-batch Bio-oil 2.6 % More oxygenated compounds Kusworo et al.
pyrolysis reactor generated (2020)
3. Oil palm empty fruit Fast Temp-500 ◦ C semi-batch Bio-oil 4.3 % More hydrocarbon product Kusworo et al.
bunches (OPEFB) pyrolysis reactor generation (2020)
4. palm kernel shell, Slow Temp- 500 ◦ C FTIR Biochar 35.14–79.16 Char possessed potential for Lee et al.
empty fruit Residence time- spectroscopy % biofuel (2017)
bunch, etc. 60s
Heating rate-
10 ◦ C/min
5. Rice husk Fast Temp-500 ◦ C Fluidized bed Bio-oil 60 % Yield increases with heating Montoya et al.
reactor rate (2015)
6. Coconut shell Flash/fast Temp-600 ◦ C Fixed bed Bio-oil 48.7 % Temperature plays a chief role Sarkar and
reactor in product yield and waste Wang (2020)
characteristics
7. Coconut shell Flash/fast Temp- 400 to Fixed bed Biochar 33.6 to 28.6 Temperature plays a chief role Sarkar and
600 ◦ C reactor % in product yield and waste Wang (2020)
characteristics
8. mahua seed Catalyzed pyrolysis Catalyst ratio Cao -catalyst Bio-oil 40.71 % Catalyst presence increased Shadangi and
2:1 the fuel quality Mohanty
Temp-525 ◦ C (2014)
9. Corncob Fast (with and Temp-550 ◦ C Fluidized bed Bio-oil 56.8 % Zeolite catalyst utilization Zhang et al.
without catalyst) caused a increase in bio-oil (2009)
quality
10. Rice husk Catalytic pyrolysis Temp-550 ◦ C Fixed bed Bio-oil 57.61 % NaCl improved the quality of Zhao and Li
NaCl-3%wt bio-oil (2016)
11. Wood waste Continuous Temp-800 ◦ C Customized Lab Syngas 67 vol% Continuous microwave Zhao et al.
microwave-assisted scale reactor assisted pyrolysis system (2020)
pyrolysis designed to produce syngas.

rearrangement reaction occurs concurrently with LG and was greatly usually encompass glucose, mannose, galactose, xylose, uronic acids,
influenced by acceleration in temperature and residence time. Lu et al. acetyl products etc. In comparison with cellulose thermal decomposition
(2011a) examined the kinetic association between hydroxyacetaldehyde of hemicellulose is easily done which takes place at temperature of
and levoglucosan and found an increase in HAA yield with temperature 220–315 ◦ C. The reaction pathway of hemicellulose based pyrolysis is
rise. Also HAA product formation is generally preferred by alkali addi­ depicted in Fig. 3. The fundamental reaction step in hemicellulose py­
tion but subdued by acid addition like sulphuric acid (Shen et al., 2011). rolysis occurs at <300 ◦ C that comprises of decomposition and poly­
merization reactions and leads to formation of low molecular
3.1.3. Other products compounds like glycoaldehyde, furan, hydroxyl acetaldehyde, formic
Cellulose based pyrolysis is also results in production of mono­ acid, H2O and CO2 elements etc (Zheng et al., 2016). In addition to this it
phenols (Chang et al., 2018). The lignocellulosic biomass contains causes cleavage of glycosidic bond resulting in oligosaccharides for­
phenol compounds coupled with cellulose and hemicellulase. When the mation and further breaks down into xylose liberating water and CO2.
biomass is subjected to microwave pyrolysis at temperature of 480 ◦ C When the temperature reaches above <800 ◦ C the cellulose biomass
and heating rate of 10–200 ◦ C/s to produce activated carbon. Zhang turns to produce bio-oil and biochar. Further proliferation of pyrolysis
et al. (2018) have obtained 99.02 % of monophenol production with temperature of xylose generated light weight oxygenated compounds
maximum mass concentration of 9.3 mg/mL. They have reported the like formic acid, acetic acid, furfural, and furan through cracking and
catalytic mass is positively enhancement the production of selective rearrangement of depolymerized molecule. Also the char produced en­
phenol compounds and accelerate the active reaction of phenol groups compasses C– – O, COOH, –OH, and C–O as active functional groups and
like -O-P, O–– P, and -O-P-O- AC. Acetol (1-hydroxy-2-propanone) is O-containing ring structures which gets formed by polymerization re­
another major product found during cellulose fast pyrolysis. It is formed actions of the pyrolysis intermediates produced during the reaction
by the relocation of C-4 from the pyran ring cleft owing to the levo­ sequence with liberation of water, CO2 and CO (Yang et al., 2020; Zhou
glucosan degradation whereas the other two carbon molecule acts as a et al., 2017). Table 3 Various products obtained from hemicellulose
forerunner for HAA. Shen and Gu (2009) found higher acetol yield when based pyrolysis of different lignocellulosic biomass.
fast pyrolysis of cellulose was performed in fixed bed reactor. A higher
production of acetol and HAA was obtained when the temperature was 4.1. Products obtained from hemicellulose based pyrolysis
increased from 400 to 600 ◦ C at 5s of treatment period (Usino et al.,
2020). 4.1.1. Furfural (FF)
It is a characteristic dehydrated material got from xylose and has the
4. Hemicellulose based pyrolysis ability to produce furfuryl alcohol, γ-valerolactone (GVL), tetrahydro­
furan (THF), and resin and generally utilized additives of fuel and in­
Hemicellulose comprises short chain heterogeneous polysaccharide dustrial constituents. It is formed by the depolymerisation of xylan in the
structure and contributes to 10–35% of lignocellulosic biomass. They course of splitting of hemi-acetal bond or decomposition of 5-HMF (Li

5
Y. K N et al. Chemosphere 286 (2022) 131824

Fig. 3. The pathways of hemicellulose pyrolysis at different temperature.

et al., 2020b). Furfural can be produced by both cellulose and xylose production of 39 % of guaiacol. Guaiacol is unanimously considered a
pyrolysis while their reception was found to be superior in xylan py­ representative prototype of lignin derived bio-oil as it contains two
rolysis as to cellulose based one. Hemicellulose pyrolysis carried out by different forms of carbon-oxygen bonds which characterize majority of
addition of ZnCl2 as a catalyst boosted furfural production in compari­ the lignin and products derived from derivative of lignin. Reactions
son to cellulose pyrolysis thereby recommending pyrolysis of hemicel­ occurring in guaiacol have been studied to determine the function of
lulose biomass for furfural generation (Lu et al., 2011b). Wang et al. catalyst. When the OH group of phenol is converted, it follows either
(2020) observed maximum furfural content of 82.82 % at 200 ◦ C which hydrogenolysis pathway of the aromatic hydroxyl bond or the process of
is attributed to its high selectivity which further generates water soluble hydrogenation of the same bond. The pathways of the reaction rely
oligosaccharides and mono-saccharides superseded by dehydration. largely on the composition of the catalyst. The process of hydro­
deoxygenation catalyzed with demethylation/demethoxylation and
4.1.2. Acids (acetic acid) dehydroxylation remains to be the prime significant reaction (kineti­
Acetic acid is generally produced by the rupture of acetyl groups of cally) during guaiacol catalysis (Yang et al., 2006). Subsequent of
the hemicellulose structure at elevated temperature and liberates CO2 in dehydroxylation, hydrogenation of benzene molecule occurs (Saidi
a parallel manner. At temperature in the range of 425–690 ◦ C hemi­ et al., 2014).
cellulose pyrolysis (xylan based) attained 4.4–2.45 % of acetic acid and
1.9–3.1 % furfural authenticating the dominance of these products in 5.1. Products obtained from lignin based pyrolysis
bio-oil production (Shen et al., 2010). Also decarboxylation of –COOH
functional group are associated with the formation of acetic acid at low 5.1.1. 2- Methoxyphenols
temperature (Collard and Blin, 2014). The compound 2- methoxyphenols or Guaiacol is natural organic
compound which occurs as aromatic oil. It is derived from wood cre­
4.1.3. Other products osole or guaiacum and present in variety of essential oils. It is also
5-Hydroxymethylfurfural (HMF) is one of the major potential prod­ synthesized by several organisms (Duffey et al., 1977). Guaiacol is one of
uct that obtained from hemicellulose-based pyrolysis (Yang et al., 2020). the products produced upon pyrolysis of lignocellulosic biomass. In
The 5-HMF belongs to furanic organic compounds and it is synthesized, addition to being a precursor of man flavoring agents such as eugenol, it
due to dehydration of reducing sugars (Zhou et al., 2017). During py­ is an important precursor for number of useful chemical compound. It is
rolysis, the hexose (mannose and galactose) contains in hemicellulose estimated that around 85 % of global supply of vanillin is derived from
undergoes dehydration reaction to produce 5-HMF. Wang et al. (2014) guaiacol. As guaiacol is derived from the biomass, it is a promising
have documented that the hemicellulose compounds subjected to component and useful precursor for green fuels (Saidi et al., 2014).
thermo-gravimetric pyrolysis to obtain the yield of 5-HMF and H2O from The phenolic monomers such as guaiacol, 4-ethyl phenol, syringol,
transformation of D-mannose as to D-galactose. In addition to this phenol, p-cresol and 2-methoxy-4-vinylphenol are generally profiled
Furfural compounds can be generated from 5-HMF via cracking during lignin pyrolysis. These phenolic monomers were pyrolyzed at
reactions. temperature ranging from 300 ◦ C o 500 ◦ C in the micropyrolyzer. The
pyrolysis-oil and pyrolysis vapor were analyzed and it was found that
5. Lignin based pyrolysis the OH aromatic group and methyl moiety in phenol and cresol,
respectively were found to be thermostable at given temperatures. It
Lignin belongs to group of aromatic compound account in the revealed absolute disappearance of p-cresol and phenol with no yield of
lignocellulosic biomass. It is considered as a renewable and sustainable any derivatives. The pyrolysis facilitated guaiacol to form numerous
aromatic substrate for carbon economy (Cui et al., 2019). A better un­ monomers of phenolic compounds. The most important derived product
derstanding of the lignin pyrolysis at different temperature range is included dimethoxybenzene, phenol, 2-ethyl phenol hydroxy benzal­
shown in Fig. 4. Pyrolysis of lignin converts into anisole, phenol, cresol, dehyde etc, which indicated that the OH aromatic moiety became more
guaiacol, syringol etc., as main products. The pyrolysis of softwood susceptible to reaction in the presence of methoxy group. The methoxy
lignin results in production of primarily guaiacol. Similarly, the pyrol­ and hydroxyl moieties present in guaiacol/2-Methoxyphenol were
ysis of hardwood lignin yields derivatives of guaiacol and syringol. Zhao reorganized by means of most likely splitting of phenolic and aliphatic
et al. (2009) have reported that the fast pyrolysis of lignin will results in group, methylation and different other reaction pathways. The syringol

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Y. K N et al. Chemosphere 286 (2022) 131824

Table 3
Various products obtained from hemicellulose based pyrolysis of different lignocellulosic biomass.
S. Type of Type of Operational Reactor/analyzer Type of products Products yield Key findings References
No lignocellulosic pyrolysis conditions employed
biomass

1. Hemicellulose Fast 500 ◦ C Micro-pyrolyzer Main product: Char 7.14 wt% of Hot water Patwardhan
from corn pyrolysis coupled to a GC-MS/ Other products: anhydroxylopyranose, treatment was et al. (2011)
stover FID system anhydroxylopyranose, 17.76 wt% of provided to extract
dianhydroxylopyranose, dianhydroxylopyranose, hemicellulose from
glycolaldehyde, methyl 12.85 wt% of corn stover. Yield of
glyoxal, acetaldehyde, glycolaldehyde, acetic acid was very
furaldehyde, acetol, H2O, 3.31 wt% of methyl low due to removal
CO2, char and acetic acid. glyoxal, of acetyl groups
1.15 wt% of from hemicellulose
acetaldehyde, by hot water
2.20 wt% of 2- treatment
furaldehyde,
1.20 wt% of acetol,
14.98 wt% of H2O,
6.02 wt% of CO2,
1.72 wt% of CO,
09.44 wt% of char and
0.18 wt % of acetic acid
2. Wheat straw Fast – 700 ◦ C Main product: Char 24 wt% char Other products Peng and
pyrolysis Other products: Acetic yields were greatly Wu (2010)
acid, char, carbon oxides, affected by
2-furaldehyde, temperature
cyclopenten-1-one and
some aromatic
compounds
3. Sugar cane Fast Tubular reactor- 550–850 ◦ C, Major product: Acetic 41.2 % acetic acid Product yield as a Peng and
bagasse pyrolysis Gas N2, 300 mL/min acid function of Wu (2011)
chromatograph . temperature
mass
spectrometry
4. Xylan from – 25–700 ◦ C, Thermogravimetric Main product: Char 24 % char Rate of loss Peng and
wheat straw 5–30 ◦ C/min, analyzer Other products: acetic happened at 315 ◦ C Wu (2011)
N2, 60 mL/min acid, carbon oxide, 2-fur­
aldehyde, cyclopenten-1-
one and some aromatic
compounds
5. Douglas fir Fast Batch-operated 400–690 1C, 0.5s Major product: Pyrolytic 31–42 wt % gases and Energy Shen et al.
pyrolysis updraft gases and bio oil 35–45 wt % bio oil consumption is (2010)
entrained flow medium and it
reactor includes both
heating power and
mechanical power
consumed
6. Hemicellulose Fast 550 ◦ C Thermogravimetric Main product: Char Acetic acid with yields of A neutral solvent, Wang et al.
from pyrolysis analyzer/pyrolyzer Other product: Acetic 11.49 wt%, dimethylsulfoxide (2015)
agricultural gas chromotograph/ acid 17.82 wt%, 11.50 wt%, (DMSO), was able
residues corn Mass spectrometry 7.15 wt%, 16.15 wt%, to retain the acetyl
stalk, rice straw, and 10.74 wt% was groups and other
softwood obtained 30 wt% of char side or branching
and hardwood groups
7. Rice straw Fast 500 ◦ C Fixed bed reactor Main product: Furfural Furfural yield of 4.2 % Hydrothermal Wang et al.
(Hemicellulose) pyrolysis and levoglucosan and Levoglucosan yield treatment and (2020)
of 7.3 % subsequent
pyrolysis simulate
the product yield
8. Xylan from – 25–900 ◦ C, Thermogravimetric Char 20 % char Xylan undergoes Yang et al.
birch wood 10 ◦ C/min, analyzer thermal (2006)
120 mL/min degradation at
315 ◦ C and
maximal rate of loss
happened at 260 ◦ C
9. Corn stover Fast Pyrolyzer-Gas 500 ◦ C, Main product: Acetic acid 52.56 % acetic acid [75 Interaction among Zhang et al.
pyrolysis chromatograph/ 5 ◦ C/min, and Furfural g] and 37.5 wt% furfural cellulose, (2015)
Mass N2, 103 L/min Other products: hemicellulose and
spectrometry glycolaldehyde, lignin
anhydroxylopyranose,
dianhydroxylopyranose,
furfural, methyl glyoxal,
and acetaldehyde

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Y. K N et al. Chemosphere 286 (2022) 131824

Fig. 4. The pathways of lignin pyrolysis at different temperature.

pyrolysis resulted in several products such as 3-methoxy guaiacol, methoxyphenol are the significant lignin determined essential items.
Methyl 3,4,5-trimethoxybenzoate, 2 methoxy-3-methylphenol, 3- During the pyrolysis of the lignin, different radicals were shaped by
methoxy-1, 2-benzenediol etc. However, the derivatives of syringol is homolysis responses. As per the structure of lignin, β-O-4 is the domi­
slightly lesser when compared to guaiacol. The 2 methoxy 4 vinyl phenol nating coupling link and represents 50 % of the linkages in lignin. Ho­
showed to be more reactive as compared to other monomers examined. molytic splitting of O–CH3 in methoxyl faction generates S1 and G1
During slow pyrolysis of syringol, catechols and pyrogallols were pro­ radicals which indicates gathering in S and G-type structures of lignin.
duced in secondary reactions but were absent in the process of fast py­ The H radical present on the phenolic hydroxyl group and methoxyl
rolysis. Alternatively numerous derived products of methoxy group is donated to S1 and G1 radicals which through transition ab­
compounds were found. So it can be inferred that the secondary reaction stracts the H radical to form hydrogenated product, catechol sur­
system is diverse for fast pyrolysis and slow pyrolysis. mounting energy obstruction of 112.3 and 67.3 kJ/mol. Past
The bio-oil obtained from different materials such as pine sawdust, investigations have demonstrated that during pyrolysis Cβ-O and O–CH3
palm kernel shell and wheat straw were examined in one of the studies bonds break easily and are reported to be abundantly present in lignin.
and it was found that G-type phenolic products such as 2-methoxy-4-(1- Further, new radicals G-2 and G-3 radicals are produced during the
propenyl) phenol, guaiacol and 4-methyl-2-methoxyphenol) were in transformation of 2-methoxyphenol (G). Henceforth, to summarize a
higher amount in the wheat straw and pine sawdust when compared to strong interaction exists between 2-methoxyphenol (G) and radicals.
the other feedstock (Chang et al., 2016). In one of the previous studies Abstraction of H radicals from 2-methoxyphenol forms phenol (PH), 3-
relating to the bio-oil analysis, acetic acid was found to be the key methoxycatechol, ethylbenzene (EB) and catechol (G-4) with low en­
product in wheat straw (6.89 %) and pine sawdust (14.34 %) which ergy barriers while loss of H radicals resulted in results in G2 and G3
resulted from considerable cracking of O-acetyl moeties in the cellulose radicals, subsequently rearranged to 2- hydroxy-benzaldehyde (Xu et al.,
and hemicellulose components of the feedstock (Shen et al., 2010). The 2016).
higher level of 2-methoxy-phenol, 2-methoxy-4-(1-propenyl) phenol
and 4-methyl-2-methoxyphenol in wheat straw and pine sawdust can be 5.1.2. Catechols
attributed to huge number of structural units of guaiacyl alcohol. Catechols are generally found in plant leafy materials as chlorogenic
The formation of methoxyaromatics rich bio-oil during synergistic acid and it is a structural unit of quercetin and rutin, a kind of flavo­
pyrolysis of Eucalyptus pulverulenta was observed in fixed bed reactor noids. Moreover, it represents the structures found in lignin and coal.
operated at 300–500 ◦ C. The outcomes demonstrated that the around The reactions occurring in pyrolysis are categorized into primary re­
38.45 wt% of bio-oil was produced at 400 ◦ C within the sight of sodium actions and secondary reactions. During primary pyrolysis, the aromatic
carbonate. Likewise, grouping of methoxyaromatics were achieved in compounds produced are (methoxy groups) predominantly stable and
bio-oil at 400 ◦ C. 4-Ethyl-2-methoxy phenol, syringol, guaiacol, and constitute 2,6-dimethoxyphenols (4-substituted syringols) and 2-
1,2,4-trimethoxybenzene were the dominating methoxyaromatic com­ methoxyphenols (4- substituted guaiacols) obtained from S and G-lig­
pounds of bio-oil. Pyrolytic product, gas examination evidenced the nins, respectively. In secondary pyrolysis, the temperature increases to
presence of carbon dioxide as a major gas at lower temperatures. 400 ◦ C–450 ◦ C, where rapid conversion of syringols and guaiacols into
Methane and hydrogen formation were observed at expanding pyrolytic catechols or pyrogallols and o-cresols or xylenols occurs in addition to
temperature. Sodium bicarbonate contributed to the arrangement of phenolic compounds (Kawamoto, 2017). At 550 ◦ C, the concentration of
methoxyaromatics unlike sodium hydroxide that enhanced the devel­ catechols and pyrogallols fades away and the concentration of
opment of phenolic substance. non-condensable gas such as carbon monoxide drastically increases.
Intermolecular interaction during lignin pyrolysis performed Therefore methyl and methoxy groups are central structural elements
through analytical pyrolysis gas chromatography/mass spectrometry for the production of coke. The kinetic mechanism of catechol is chiefly
experiments and density functional theory indicated the existence of a derived from the gas phase reaction of aromatic and phenolic com­
robust interaction amid lignin and radicals. Subsequently, intermolec­ pounds and they serve as basis for further kinetic mechanism for py­
ular interaction system, as opposed to unimolecular disintegration rolysis and oxidation of more substituted aromatic compounds such as
component, ruled the lignin pyrolysis. 2,6-dimethoxyphenol and 2- 4-hydroxy-3-methoxy-benzaldehyde. The pyrolysis bio-oil obtained

8
Y. K N et al. Chemosphere 286 (2022) 131824

from pine bark (raw) possess high heating values of around 25 MJ/kg lignocellulosic biomass yields phenolic compounds. According to Chen
and dominated with hydroxyl groups such as catechol, aliphatic hy­ et al. (2019), phenol and aldehydes are the major products of lignin
droxyl faction, p-hydroxy-phenyl OH groups and guaiacol. Catechol, pyrolysis. At temperature of 400–500 ◦ C, cracking of the
p-hydroxy-phenyl OH groups and guaiacol are predominantly derived phenyl-propane units of the macromolecule lattice of lignin occurs and
from the splitting of the lignin O-4 bond while the aliphatic hydroxyl results in phenol as the prime product. Subsequent increase in temper­
faction are attributed to the splitting of cellulose glycosidic bonds. When ature degrades vanillin, acetovanillone, and homovanillic acid. Vanillin
aromatic rings such as catechol decompose into gaseous compounds and degrades to 2-methoxyphenol (guaiacol) via the transfer of hydrogen
other products at temperature of more than 550 ◦ C, it leads into the atom of the formyl group to the substituted aromatic. The study also
formation of coke (Asmadi et al., 2011). As the number of methyl group evidenced that temperatures above 600 ◦ C leads to a drop in phenols in
increases, the productivity of coke also increases. Therefore methoxy the pyrolysis product. It was observed in the study that above the
and methyl groups are central structural elements for coke production. phenolic content decreases gradually. Duan et al. (2019) reported
Fast pyrolysis of bark of Pinus radiata especially the tannins produce phenol generation of 85.5 % (0.6 mg/mL) at 550 ◦ C. Pretreatment of
compounds of highly valuable renewable source such as catechol (Pinto lignin with acids increased the production of phenol up to 98.2 % (7.0
et al., 2018). When pyrolysis products were compared in one of the mg/mL). Free radicals and intermediates of carbenium ion released
bench scale assay amongst renewable sources of phenol, it was reported during the partial cleavage of β-O-4 bond indicating the polymerization
that tannins produced higher amount of catechols whereas carbohy­ of lignin might be the reason for enhanced phenol production (Jensen
drates derived compounds and guaiacols were found in bark products et al., 2017; Wang et al., 2012). It was as well reported that acid pre­
and lignin respectively. In this bench scale assay, apart from 37 wt% of treatment of lignin suppresses the production of 2-methyoxyphenol by
oil yield from pyrolysis at 550 ◦ C, the maximum production of catechol demethoxylation reaction and promote production of monophenol
and 4- methyl catechol was 4.4 wt% and 2.3 wt% respectively at same (Duan et al., 2019; Wang et al., 2012).
temperature. The process of methanol water extraction yields two main Catalytic pyrolysis is used to enhance the production of phenol.
fractions (viz.) water-soluble and insoluble tannins. The condensed Catalysts such as CaO, HZSM-5, Ca(OH)2, Na2CO3; K2CO3; Al2O3, ZnO,
tannins procured from the bark of Pinus radiata are commonly oligo­ KOH, NaOH and PKS biochar are used in pyrolysis of lignocellulosic
meric/polymeric flavanols. They are produced by coupling of C-4 of one biomass to produce phenol from lignin (Auta et al., 2014; Peng et al.,
monomer to C-8 or C-6 of the other monomeric entity in the presence of 2014; Wang et al., 2010; Wu et al., 2019). It was observed that alkaline
prodelphinidins. Epicatechin (− ) and catechin (+) possessing similar additives facilitate the thermal cracking of lignin resulting in the pro­
ring with a catechol structure are identified as the principal monomers duction of monophenolics. During lignin pyrolysis, deoxygenation of
of condensed tannins of bark Pinus radiata. A bench scale (32.5 cm methoxyl was effectively promoted by strong basic solids like KOH and
length and 4.8 cm of inner diameter) system to perform fast pyrolysis of NaOH (Wang et al., 2010; Wu et al., 2019). Potassium phosphates also
tannins (water insoluble) was studied to establish the consequence of possessed brilliant competence for enriching phenolic compounds dur­
changing temperature on the yield of catechols. It was found that at ing pyrolysis of biomass (Lu et al., 2013; Zhang et al., 2014). Studies also
400 ◦ C, catechol constituted the major portion of the bio-oil. PAHs, shows that phenolics positively corelated with K3PO4 and followed the
terpenes, alkyl compounds, long-chain esters and fatty compounds were basicity order of K3PO4, K2HPO4 and KH2PO4 (Zhang et al., 2014). When
the other associated chemical groups present in the bio-oil. The chemical compared with K2HPO4 and KH2PO4, 50 wt% of K3PO4 enhanced the
constituents of the aqueous portion showed the presence of catechols, selectivity of phenolic compounds up to 64 % (Lu et al., 2013). Chang
methoxyphenols and phenols along with few carbohydrate derivatives et al. (2018) used palm kernel shell (PKS) for phenol production through
(levoglucosan). catalytic pyrolysis at a temperature of 265–320 ◦ C and
The plausible pyrolysis pathway which includes unimolecular and biomass-to-catalyst ratio of 5:1. PKS bio-oils yielded phenol as high as
bimolecular decomposition were studied for kinetic analysis and it was 0.0075 g/g with CaO as catalyst at 275 ◦ C. It was reported that the
found that catechol followed the unimolecular decomposition pathways catalysts augmented the cracking of aldehydes and ketones to form
as it dominated the most. Unimolecular decomposition pathway was non-condensable gases. Naron et al. (2019) used catalysts such as Al2O3,
based on the theory of transition state where isomerization of catechol ZnO, NaOH and KOH on 1 % lignin mass feedstock namely eucalyptus,
occurs and converts it into 2-hydroxycyclohexa-2,4-dien-1-one by the pine and sugar cane at pyrolysis temperature up to 600 ◦ C and heating
relocation of the hydroxyl H atoms. It is further decomposed into carbon rate of 10 ◦ C/min for phenol extraction. It was observed that KOH
monoxide, acetylene and 1,3-butadiene. In the bimolecular pathway of yielded phenol of 26 % in sugarcane bagasse in comparison to the py­
catechol decomposition, coupling of an H2 radical to the C- atom in the rolysis performed under non-catalytic conditions, while NaOH yielded
benzene ring occurs and results in the formation of phenol and a hy­ phenol of 40 % from eucalyptus (E-K) lignin. Moreover, the major S-type
droxyl radical via the process of dehydroxylation. In case of coupling of phenolic compound, syringol yield increased in the presence of NaOH
H2 radical to the C- atom with the methoxyl group, phenol is most likely from E-K lignin showing around 1.86 wt% net productivity. Depoly­
to form while homolysis of O–CH3 leads to the formation of catechol merisation in the first decomposition stages could be the primary reason
(Furutani et al., 2017). It has also been revealed that calcium pretreat­ for the enhanced yield of phenol by hydroxide catalysts. On other hand
ment followed by pyrolysis also improves the quality of end products oxide, catalysts (Al2O3 and ZnO) showed inadequate effects on the
(Cui et al., 2019). manufacture of S-type and G-type phenols unlike P-type phenol.
Sawdust pellets subjected to microwave pyrolysis with activated carbon,
5.1.3. Phenols MRX and DARCO 830 as catalyst at 400 ◦ C and heating value of
Phenol is widely used in different industries for production of fine 40–60 ◦ C/min yielded phenol of 74.8 %. Reuse potential of these cata­
chemicals, energies, food additives and phenolic resins (Kim, 2015). lysts were 3–4 times with an average bio-oil yield of 55 % (Bu et al.,
Since the last decade the production of phenol has aroused by a rate of 2013).
1.8 % per annum (Zhang et al., 2018). Around 90 % of the phenol
worldwide is produced from petrochemical sources that results in huge 5.1.4. Methanols
carbon footprints, ultimately triggering the environmental pollution. Methanol is gaining attention globally due to multiple advantages
Alternate sources especially the lignocellulosic biomass appears to be a viz. Less carbon footprint in comparison to ethanol at the similar extent
promising source for phenol production. Scientific community and re­ of heat; elevated octane number than gasoline, efficient usage in devices
searchers across the globe are exploring the various options to increase (fuel cells), high energy density, efficient fuel for gas turbines, simple
the production of phenol from lignocellulosic biomass with minimum structure and ease of conversion to CO2 and water. At present, more than
environmental footprint. Thermal degradation of lignin in 0.2 million tons of biomethanol is produced every year across the world

9
Y. K N et al. Chemosphere 286 (2022) 131824

to meet the increasing demand and is expected to project to 1 million 6. Factors affecting product yield of pyrolysis
tons per annum. Biomethanol is produced from various processes such
as pyrolysis of wood and corncobs, gasification of woodchips and 6.1. Reaction environment
biomass char, bio-oil and sewage sludge in addition to recently devel­
oped methods such as electrolysis and photo-electrochemical. Yield of Reaction environment plays a significant role as pyrolysis process is
products on larger scale and ease of manipulating the control parameters done under inert atmosphere to remove the influence of oxygen. Other
favours pyrolysis among other technologies. gases like carbon dioxide, steam, hydrogen, helium, carbon monoxide,
Lignin and cellulose were popularly investigated for the production methane are also explored as reaction environment. According to Kan
of methanol. Jegers and Klein (1985) evidenced methanol production of et al. (2016), the gases in the reaction environment can influence the
around 0.65 from kraft lignin pyrolyzed at 300 ◦ C and 50 min of reaction pyrolysis process and distribution of products. Organic oxygenated
time. Increase in temperature (400 ◦ C) and decrease in reaction time (15 compounds are produced when steam is used as inert environment.
min) yielded maximum phenol of 2.7. Presence of aliphatic methyl Steam also prevents secondary cracking reactions (Pütün et al., 2008).
moieties favoured higher methanol yield during wood lignin pyrolysis as Methane gas reaction environment yields highest bio-oil of 58.7 %.
compared to kraft lignin. The mechanism of lignin degradation in Fir Likewise CO, yields low levels of bio-oil (49.6 %) enriched with lower
and Birch by pyrolysis was framed by Wang et al. (2009). According to methoxy-containing compound larger than monofunctional phenols.
the study, pyrolysis process occurs in two stages: Stage 1 where small Carbon dioxide when used as sweeping gas also results in the generation
molecules of the gases like CO2, CO and phenol and other volatiles like of methoxy-containing monofunctional phenols in addition to char of
methanol are generated at the lower temperature range of 423–600 ◦ C. varying chemical composition and increased surface area (Guizani et al.,
Methanol formation occurs at low temperatures where free OH groups 2014). Also they increase the yield of permanent gases as they facilitate
along with C–O linkage facilitate methanol formation. In the second increased thermal cracking of volatiles and formation of secondary char.
major pyrolysis stage temperature range above 600 ◦ C resulted in the It is also reported that CO2 environment favours better thermal
discharge of gases such as carbon monoxide, carbon dioxide and decomposition of lignocellulosic feedstock. Formation of harmful com­
methane and high molecular weight volatiles due to the breaking of pounds such as benzene and its derivatives and polycyclic aromatic
methyl group –CH2- possessing high bond energy. Significant amount of hydrocarbons are suppressed under carbon dioxide reaction environ­
methanol was also generated from secondary reactions during cracking ment. Mo et al. (2020) used catalysts such as ZSM-5, ZSM-5-MgO and
of additional compounds and also observed maximum production level MgO for the pyrolysis of microalgae Spirulina Platensis at 300–500 ◦ C and
at 700 K. Fir lignin pyrolysis produced more methanol as compared to inert atmosphere of N2 and CO2. MgO catalyst under N2 atmosphere
birch. Zhang et al. (2020) produced methanol from cellulosic insulating yielded C7 to C18 hydrocarbon rich bio-oil with high heating value of
paper and applied molecular dynamics technique which is based on 36.8 MJ/kg. The catalysts inhibited the oxygenated compounds and the
reactive force field (ReaxFF) to create cellobiose pyrolysis at 500–3000 stability of the oil was improved due to reduction of C–– O. High heating
K. It was reported that methanol generation was stable at temperature value bio-oils are produced when hydrogen is used as inert gas (Zhang
range of 1600–2200 K. A subsequent increase in temperature resulted in et al., 2009). Moreover, the hydrogen radicals generated during
drop in stability of methanol production. Breakage of cellobiose methane environment reacts with olefins and oxygenates to form furans.
occurred in C–O followed by C–C chemical bond (Shi et al., 2016).
Further β-1,4-glycosidic bond of cellobiose also undergoes fracture 6.2. Temperature
(Wang et al., 2017).
Im-orb and Arpornwichanop (2020) IBPGM, integrated biomass Temperature: Pyrolysis is an advanced thermal treatment process
pyrolysis, methanol synthesis with the CO2 recycle fraction for rice straw and hence temperature significantly influences the process. Tempera­
feedstock. Pyrolysis temperature of 400–700 ◦ C yielded bio-oil and tures above 300 ◦ C are used for thermal conversion of lignocellulosic
methanol at the rate of 0.09 and 0.23 kmol h− 1 respectively. A biomass wastes and depending upon the temperature and heating rate the py­
feed rate of 1 kmol h− 1 resulted in 60.7 % energy efficiency. Sugar cane rolysis is categorized as fast (800–1300 ◦ C with a heating rate of
bagasse yielded methanol of 3.11 (wt%) at 500 ◦ C temperature, reaction 10–200 ◦ C) and slow pyrolysis (400–500 ◦ C with a heating rate of
time of 120 min and 2 L/min of nitrogen flow (Yousef et al., 2020). 0.1–1 ◦ C/s) (Azargohar et al., 2013; Tripathi et al., 2016). Moreover, the
Fuzzy logic technique with PSO (Particle Swarm Optimization) algo­ quality and domination of the end products yield (biochar, bio-oil and
rithm to optimize the operating parameters to maximize the gas) depends on the temperature. Fast pyrolysis yields more bio-oil as
bio-methanol yield. Hazel nut pyrolysis performed at variations of 100 k compared to char and gas showing a yield distribution of 60–75 %,
from 295 K to 1275 K at the heating value of 2–4 K/s for solid residence 15–20 % and 10–20 % of bio-oil, char and gaseous products, respectively
time of 300–500 s yielded high quantity of methanol in 72 % of aqueous (Bridgwater, 2003). Contrary, slow pyrolysis performed at 400–500 ◦ C
distillate consisting of other compounds such as acetaldehyde, acrolein, resulted in production of biochar and trace levels of liquid fuel and gas
furan, acetone etc. (Demirbas and Arin, 2002). Bio-oil yields reach to a peak at a temper­
ature range of 400–550 ◦ C. Subsequent heating results in decline in
5.1.5. Other products bio-oil distribution and at temperatures above 600 ◦ C, the char and
Lignocellulosic biomass happens to be enormous resource that yields bio-oil are converted to gaseous products via secondary decomposition
bio-oil as one of the main end products via pyrolysis (Kim, 2015). The reactions. Temperature also influences the composition of bio-oil. When
bio-oils produced from lignin are unstable and considered poor quality temperature is increased from 300-500 ◦ C to 600–800 ◦ C, decarboxyl­
fuel and so need an upgrading. Upgrading bio-oil entails converting high ation and dehydrations occur resulting in increased carbon content and
molecular weight lignin, which is oxygen rich into hydrocarbons that polar, aliphatic, oxygenated hydrocarbons and aromatic compounds in
are equivalent to existing petroleum fuels (Montoya et al., 2015). The bio-oil (Ateş and Işıkdağ, 2008; Worasuwannarak et al., 2007). Benzene
bio-oils are then subjected to hydrodeoxygenation where O2 gets elim­ and naphthalene dominated the tar produced from green waste heated
inated as water molecules via chemical conversion at high hydrogen at 700–900 ◦ C. Increasing temperatures always resulted in increased
partial pressure and high temperature of around 570 K–670 K. The ratio of large to small aromatic rings and loss of O-containing functional
chemical reaction that occur during hydrodeoxygenation include rings. Hydrogen evolution also occurs at increasing temperature. Zhang
decarboxylation, hydrogenation followed by hydrogenolysis, hydro­ et al. (2017) worked with peanut shell, oak and sugarcane at varying
cracking and then dehydration to produce hydrocarbons and organic temperature range from 350 to 900 ◦ C. Peanut shell yielded highest
compounds containing oxygen along with water (Chen et al., 2019). biochar (43 %) with highest carbon and all essential minerals at a
temperature of 350 ◦ C. Subsequent increase in temperature resulted in

10
Y. K N et al. Chemosphere 286 (2022) 131824

decreased yield. The results of Opatokun et al. (2016), too supported decrease with increasing temperature and heating rates. Low tempera­
increased biochar yield in tomato seeds at 300 ◦ C. The characteristics of ture 400 ◦ C and heating rates of 10 ◦ C, 30 ◦ C, and 50 ◦ C per min resulted
the biochar viz carbon content, organic and inorganic constituents, in 2.88 wt% decrease in char yield (Chen et al., 2017). Unlike bio-oil and
surface area, pore size, crystallinity, electrical conductivity, water char, heating rates does not influence gas generation.
holding capacity, adsorption capacity and nutritional status are greatly
influenced by pyrolysis temperature (Burhenne et al., 2013; Park and
Jang, 2012). Increasing pyrolysis temperature, increased the micro and 6.3. Residence time
macronutrient in the biochar. However, the nitrogen levels in the bio­
char decreased at increased temperature Opatokun et al. (2016). A study Residence time is considered as one of the important operating
conducted by Johari et al. (2016) with coconut pith reported that the condition that determines the formation and distribution of products
yield, nitrogen and oxygen content, volatile matter and moisture levels during the process of pyrolysis. Short residence time favours bio-oil
decreased with increase in temperature from 300 ◦ C to 900 ◦ C. Contrary, production by limiting the secondary reactions. Increase in residence
high carbon and adsorption capacity was observed at 900 ◦ C. Temper­ time converts the organic vapours generated from the lignocellulosic
ature can be used to manipulate phosphorous levels in biochars (Zwet­ biomass to char and total gases. At temperatures below 800 ◦ C and
sloot et al., 2015). 750 ◦ C, increasing residence time yields higher tar and gases, respec­
Pyrolytic gases include permanent (H2, CO, CO2) and light aliphatic tively. Sweet gum hard wood and raw sorghum pyrolysis at 700 and 525
hydrocarbons (CH4, C2H4, C2H6) gases. Around 86 % of the gases and residence time in the range of 0.7–1.7 s and 0.2–0.9 s showed a
released during pyrolysis process are light aliphatic hydrocarbons. Gases decrease in bio-oil production by 24 % and 31.8 %, respectively. Ningbo
are formed due to secondary reactions that occur between solid and et al. (2015) evidenced the production of phenol in bio-oils at higher
vapor phase; vapor phase and among volatile species. At high temper­ temperature and longer residence time. A residence time of 6 min can
atures, secondary gas phase reactions occur among volatile species yield an energy profit of 6.5 % at 900 ◦ C.
thereby determining the properties and composition of gases. According
to Uddin et al. (2013), hydrogen generation increases with increase in
6.4. Biomass particle size
pyrolytic temperature unlike other gases which changes according to the
feed stock composition. Mallee wood pyrolysis a temperature 450 to
The selection of biomass particle size is considered as an important
550 ◦ C resulted in increased concentration of other gases such as CO,
parameter for effective pyrolysis and its product yield (Soria-Verdugo,
CO2, CH4, C2H6, and C2H4 unlike birch wood pyrolysis that showed
2020). The low thermal conductivity of biomass has greater influence on
decrease in other gases production. Similar observations (i.e) decrease in
the reaction rate and heat transfer effect of biomass. Generally small size
other gases were recorded in pine saw dust too at 700–900 ◦ C. Though
biomass is most commonly suggested by many researcher to achieve
chemical composition of feedstock determines the nature of gases, it’s
rapid and uniform heating of the biomass (Guedes et al., 2018). If the
the thermal severity or the temperature that determines the increase or
biomass particle size is very fine which leads to faster thermal destruc­
decrease of gases (Uddin et al., 2013).
tion and convert the biomass into permanent gases (pyrolysis vapor).
Metal behavior during the pyrolysis process was also influenced by
This could affect the production of bio-oil during biomass pyrolysis
pyrolytic temperature. Bert et al. (2017) reported that metal behavior is
(Islam et al., 2010). In fast pyrolysis, very fine biomass particle size
governed by temperature ranging from 450 ◦ C to 800 ◦ C. Chlorine in
directly converted into inert gas and it removes from the reactor (Sor­
association with temperature increased the metal volatilization. Metals
ia-Verdugo, 2020).
like zinc and lead form metal chlorides and hence volatilized and ended
in biochar followed by bio-oil at 450 ◦ C. Copper formed metal chlorides
at 900 ◦ C. Moreover, metal volatilization depends on chlorine mass in 6.5. Biomass moisture content
the lignocellulosic biomass. The oxidizable, exchangeable and reducible
fraction of Cd, Pb and Zn varied with temperature (Bert et al., 2017). Most commonly, the biomass is connected with considerable amount
Cadmium decreased in the products of pyrolysis when an increase in of water in it, which is referred as moisture content. During pyrolysis,
temperature from 350 to 450 ◦ C was observed. The mobility of trace the water account in the biomass gets vapor and the biomass gets liquid
metals in biochar is also influenced by temperature. Avicennia marina free. Many researchers have reported that the biomass with low mois­
biomass pyrolysis at temperature 300–800 ◦ C evidenced Cd to be more ture content is more preferable to achieve cost effective product yield
volatile as compared to Cu and Fe. Pyrolysis was effective in reducing (Johari et al., 2016; Tripathi et al., 2016). Because if the water content in
the bioavailability and mobility of metals in biochar. the biomass is too high then it may, leads to formation of tar. Subse­
quently it reduce the quality and quantity of pyrolytic product yield. On
6.2.1. Rate of heating economic point of view, high water content in the biomass demands
Pyrolysis is classified into fast and slow pyrolysis depending on the excess heat energy for drying and it raise the biomass temperature.
heating rate. Slow pyrolysis done at low heating rate and long residence However, the moisture content in the biomass is major drawback in
time maximizes char formation due to availability of increased duration pyrolysis. Therefore, the selection of biomass with less than 30 % of
for conversion. Contrary, fast heating rates results in rapid fragmenta­ moisture content is more preferable (Lee et al., 2017).
tion of lignocellulosic biomass due to reduced limitations in mass and
heat transfer. Availability of less time for the occurrence of secondary
reactions also favours faster fragmentation. Bio-oil production is fav­ 6.6. Impurities
oured during higher heating rates due to quick fragmentation of the
lignocellulosic biomass. Impurities in the biomass slightly affects the quality of pyrolytic
The yield and distribution of the pyrolysis products are greatly product yield (Li et al., 2021). Typically, the following impurities are
determined by the heating rate. Chen et al. (2017) reported that pyro­ frequently found in the pyrolytic biomass such as carbonates, phos­
lytic temperature has more influence on the product distribution than phates, sulphates, and chlorides (Neupane et al., 2015). Similarly, the
heating rates. Pyrolysis of poplar wood at pyrolysis temperature and occurrence of certain metals such as potassium, sodium, calcium, and
heating rates of 400, 450, 500, 550, and 600 ◦ C and 10, 30, and magnesium in pyrolytic biomass deteriorate the quality of product yield
50 ◦ C/min resulted in 2–3 wt% increase in bio-oil yield when temper­ during pyrolysis (Jönsson and Martín, 2016). In addition to this, the
ature was shifted from 400 to 500 ◦ C. A further increase in temperature occurrence of metal in biomass leads to pyrolysis rector corrosion and
resulted in decline of bio-oil yield. Contrary, char yields showed a improves the ash production (Giudicianni et al., 2018).

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Y. K N et al. Chemosphere 286 (2022) 131824

7. Environmental and economic aspects of lignocellulosic kg), it might be compensated by the substantial cost related to the supply
pyrolysis of feedstock and logistics of pyrolysis process. It was estimated the po­
tential size of pyrolysis biorefineries in the study conducted by the PNNL
7.1. Potential benefits towards commercialization (Pacific Northwest National Laboratory) was 2000 DMTPD having Nth
plant assumptions has capacity to produce biofuels with expected value
Lignocellulosic biomass is considered to be long term promising of $2.04/gal. Economically, the fast pyrolysis of lignocellulosic biomass
alternative source of energy through the process of pyrolysis in a sce­ is extra favourable because of the formation of high rate products such
nario of population explosion, increased energy demand, global warm­ as bio-oil in comparison to biochar a major slow pyrolysis product.
ing and depleting fossil fuels. Therefore, in order to increase the
commercialization of the pyrolysis products, a further extensive 7.2. Environmental implications and industrial applications
research is needed. Improving the quality of pyrolysis bio-oil is foremost
important. Lignocellulosic biomass along with other biomass are chief renew­
Commercialized pyrolysis bio-oil ought to keep up its actual prop­ able energy resource existing on this plane and are deemed to be reliable
erties and consistency. It is possible in case the oil displays elevated non- option for the supply of renewable gaseous solid, and liquid fuel.
homogeneity and low sub-atomic mass monomers (Fahmi et al., 2007). Lignocellulosic biomass is a traditional source of energy and since age
High atomic weight determined combinations found in pyrolysis oil old times humans have derived raw materials, chemicals and fuel from it
appear from the monomers of lignin found in the biomass. Henceforth, which are now obtained from petroleum and natural gas. However as
biomass having less amount of lignin is attractive because it would the existing petroleum, coal and natural gas are limited, they will get
decrease the heavier atomic weight and intensify the pyrolysis oil pro­ eventually depleted in near future, therefore energy derived from
ducing a more homogenous fluid (Bridgwater, 2003). In spite of the fact lignocellulosic biomass is highlighted, focused and promoted. This has
that the presence of water (hydrophilic) brings down NOx, while led to extensive research and studies to improve the energy yield from
improving stream attributes of bio-oil, it likewise implies that bio-oil is lignocellulosic biomass. Several large-scale lignocellulosic biomass-
non soluble in water showing hydrophobic nature, and brings down the based pyrolysis units are in operation. The process of pyrolysis has
warming estimation of biofuel. The thickness of bio-oil may increase due several environmental implications.
to increase in viscosity when retained for longer period of time. This A large number of investigations related to fast pyrolysis process and
might create a negative effect on the oil when planned to be used as a supply series exists but there is lack of systematic evaluation of various
viable fuel. Henceforth, to tackle the problem, the bio-oil needs value series configurations about their environmental performance and
adjustment to improve the quality of bio-oil. economy while considering numerous end products and various inte­
Economic feasibility is the critical factor in the advancement of gration opportunities. Throughout the globe 150 billion tonnes of lignin
commercial pyrolysis measures. Presently, pyrolysis items cannot is produced annually out of which less than 5 % is utilized for
contend monetarily with non-renewable energy sources because of manufacturing products derived from lignin and rest ~95 % is either
soaring costs of manufacture. The pyrolysis innovation needs to prevail burned for energy production or disposed off in landfills (Demirbaş,
over a variety of specialized and non-specialized hindrances prior to 2001). The direct burning of lignin can cause serious hazard to the
commercialization and utilization of industry. The cost of manufacture environment. The process of conversion of lignocellulosic biomass into
of pyrolysis product is highly contrasted with the creation of petroleum bioethanol if integrated with the biorefinery technology, especially
product. The primary part of pyrolysis plants is the reactor, in spite of lignin biorefinery, then it can effectively help in cutting off GHG emis­
the fact that it happens to be just 10 %–15 % of complete resources sions along with being significantly economical. The lignin waste con­
expense. The remaining cost is incurred for sorting of biomass, stock­ version into diverse useful products efficiently can be promising in
piling and cutting of biomass, kicking the bucket and pounding, item comparison to conventional petrochemical based refinery because lignin
assortment and capacity, and so forth. The expense creation of a py­ is biodegradable in nature. Moreover, it possesses a reinforcing capa­
rolysis plant will possibly be arranged in two principle classifications: bility and the presence of hydroxyl, aromatic groups and lipohydrophilic
capital speculation, and working or other expenses. Capital or fixed arrangement makes it a powerful source for the manufacture of
expense incorporates: pyrolysis unit, fundamental hardware, feedstock bio-based carbon fibers, polymers and other useful compounds (Cule­
supply and capacity, and advancement of offices (land, street, transport, bras et al., 2018). However, lignin valorization is restricted because of
building etc.) The fixed expense basically relies upon the innovation, its complex nature and moreover when it undergoes degradation, the
size of plant and type biomass feedstock. The erratic expenses incorpo­ lignin fraction become highly reactive in nature and susceptible to the
rate harvesting of biomass or maintenance of feedstock, utility and process of condensation reactions (Banu et al., 2019). In Joensuu,
product transfer (Jahirul et al., 2012). Finland, a unit of circulating fluidized bed reactor was incorporated with
Continuous efforts has been taken by the global community to combined heat and power plan. It proved to be advantageous in logis­
renovate petroleum-based market to bio-based market. Bio-based tics, heat integration and other benefits related to increased productiv­
economy, as the name indicates is giving more attention to use ity. Heat integration can help eliminating emissions. Numerous studies
biomass and technology to derive goods, energy and services. In the past suggest the process of hydroprocessing after fast pyrolysis because of its
two decades, development of the new methods and techniques for fuel environmental and economic benefits. In his process, the source of
and chemicals generation from biomass (lignocellulosic feedstock) hydrogen plays significant role in greenhouse gas emissions (GHG),
attracted the attentions of government agencies and private stake­ where hydrogen derived from the natural gas contribute to almost 50 %
holders across the globe. The industrial application of second-generation of the total GHG emissions (Han et al., 2013).
technology in commercial application could boost the sustainability of The worldwide accessibility of horticultural buildups, for example,
production of biofuel as compared to its predecessor (i.e) first generation rice, wheat, corn straw and sugarcane bagasse in 2012 was 1394.39 Mt.
fuel. The commercialization of lignocellulosic based industries possesses In 2010, 88.74 Mt of new void organic product bundles from palm oil
huge potential for sustainable development due to their low carbon plants is delivered and squandered due to wasteful usage of the acces­
footprint or higher reduction in GHG and ILUC, low Indirect Land Use sible biomass. With each palm oil company created in Malaysia, dry
Change impact. biomass of around 4 kg buildup was generated. In view of the 2008
The monetary prospective of pyrolysis biorefineries are measured on gauge in Ghana, energy of nearly 72.20 TJ was created by lignocellulosic
the basis of their annual productivity and amount of biomass processed. biomass (Duku et al., 2011). Taken cognizance to natural and farming
Although the lignocellulosic biomass’s energy density (18 MJ/kg) is limitations, biomass assets can give power somewhere in the range of
comparatively lower in contrast to petroleum derived fuels (42.8 MJ/ 130 and 270 EJ/year in 2050. The force can fulfill 15–25 % of things to

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Y. K N et al. Chemosphere 286 (2022) 131824

overcome worldwide energy interest. Haberl and his co-workers technologies for bio-oil have been reported so far which includes solvent
revealed that the worldwide potential for bio-energy crop is roughly extraction, hydrodeoxygenation, emulsification, catalytical approaches
30 to 120 EJ/yr (Haberl et al., 2010). In another investigation an and steam reforming. However the yield of the bio-oil in these processes
elevated reach to 148 from 65 EJ/yr with limitations of water shortage is highly erratic, making it another limiting factor for bio-oil production.
and soil corruption was recommended. In this way, biomass buildups The bio-oil products need to be improved while maintaining high yield.
and additional biofuels present an elective substitute to supplant pe­ The relationship between the preliminary precursors (raw material) and
troleum derivatives without extra use of land. The Energy and synthetics the inclusive working of the pyrolysis plant is not understood well which
procured from the lignocellulosic biomass buildups decrease carbon happens to be another challenge.
dioxide emanation, the reliance on woods, backwoods and petroleum In the process of pyrolysis, reactors play crucial role which help in
products in an earth benign way. The lignocellulosic biomass buildups major transformation of the lignocellulosic biomass. Therefore, the
can bring in green innovation in alleviating worldwide environmental configuration of the reactors, heat transfer and temperature control is
transformation and assume a focal part in the foreseen advancement of very important for the performance of the pyrolysis. The different
the globe’s maintainable wellspring of sustainable power. reactor configurations for pyrolysis includes fluidized beds, circulating
It is obvious that pyrolysis is arising as a powerful biomass change fluid beds, rotating cone reactors, ablative reactors, vacuum reactors
innovation, yet to date, most investigations reflect lab or pilot scale and twin screw reactors. Every reactor configuration is associated with
offices where conditions are profoundly modified. Right now, financial certain limitations. Some of the prominent challenges faced in fixed fluid
feasibility of pyrolysis innovations is minor. Late mechanical enhance­ bed include the requirement of size reduced biomass (shredded or pul­
ments to address calculated and innovative difficulties are causing it verized) as a prerequisite before subjecting to thermal degradation.
almost certain that this will to turn into a financially suitable innovation. Particles of size as low as 2–3 mm are generally preferred. Although
Continuous endeavors are centered around improving efficiencies, fixed fluid bed is simple reactor and temperature control is optimum, its
expanding item yields, and expanding co-product usage and valoriza­ requirement for rapid char separation to eliminate vapor cracking is a
tion. Co-pyrolysis of various feedstocks improves bio-oil quality and big challenge. The major challenge in the circulating fluid bed is that the
yield. Reactant change of biomass, just as synergist overhauling or hydrodynamics is very much multifaceted and needs to be explored.
transforming of bio-oil into more important items, are different zones Similarly, the char combustion in the second compartment of the reactor
that are accepting consideration for improving cycle proficiency and strictly requires cautious control. Lack of detailed study on heat transfer
item quality. Incorporated pathways are promising for enhancing the in large scale systems is another limitation of the process. Pilot scale
size of biorefineries to create bio-oil from crop deposits and may like­ rotating cone reactor of capacity 250 kg/h based on wood residue is
wise be suitable for different feedstocks. These advancements will operational. However the main challenge faced with rotating cone
guarantee that pyrolysis frameworks are both proficient at creating reactor include: particle size of less than 6 mm and biomass with
important items and have improved ecological execution. There are moisture content of less than 10 wt%. In case of ablative reactors, the
likewise a few endeavors pointed toward scaling up and commercial­ reactors are very complex and it can be expensive because of its large
izing pyrolysis advances utilizing versatile pyrolysis to address change at surface requirement during scaling up. The other limitation of this
the wellspring of biomass for energy thick items. While there are various reactor is that the reaction rates are restricted by the heat transfer to the
endeavors to improve pyrolysis advancements, creation expenses and reactor.
absence of business sectors for pyrolysis items restrict them as inde­ The consistency of the pyrolysis process has to be ensured by
pendent innovations (Roy and Dias, 2017). On the off chance that py­ upgrading overall energy and material balances for sustainable and
rolysis advances are to turn into a suitable sustainable power source, profitable applications. The process needs to be economically optimized
strategy and monetary help are expected to drive this innovation to to produce high grade bio-oil with high yield. Alternative catalysts such
business scales, for example, motivators and making markets for py­ as magnesium oxide and calcium oxides for zeolites should be studied
rolysis items. and explored for deoxygenation of bio-oil. More studies are required to
produce phenolic rich bio-oil and enhancing the process by addressing
8. Challenges and limitations addition of inorganic salts and carbon based catalysts in the cellulosic
biomass.
The process of pyrolysis is viewed as a striking substitute for con­
verting lignocellulosic biomass into useful products including renewable 9. Conclusions
liquid fuel. Several studies have been done which meticulously details
its kinetics, simulations of the process; extensive characterization of the Rapid demand in production of renewable fuels and biochemicals
biofuels to understand its precise mechanism. Conversely in spite of from waste biomass have triggered the deep investigation of biomass-
clear understanding of the mechanism of pyrolysis process and recent based pyrolysis. There are several studies to report variety of biomass
advancements in this technology, numerous aspects right from the employed for pyrolysis and its impact on pyrolytic product yield.
teething sage needs to be worked out to address those challenges. One of However, this review mainly focus on lignocellulosic biomass and a
the primary challenges associated with the initial biomass pretreatment detailed discussion about its biochemical composition (lignin, cellulose
process is a lack of methodical and uniform approach for the biomass and hemicellulose) based pyrolysis. The complexity of lignocellulosic
pretreatment. Physical pretreatment methods such as reduction of size, biomass and its impact on process for transformation into chemicals and
densification, torrefaction and the chemical pretreatment processes such fuels were discussed. In addition to this factor affecting biomass pyrol­
as alkaline, acid, steam explosion, hydrothermal and wet torrefaction ysis, economic feasibility and environmental implications towards
have been studied and reported but there is no study relating to the commercialization of the pyrolysis process were reviewed. Mainly the
application of ionic liquids pretreated lignocellulosic biomass in pyrol­ three state of fuels are generated in pyrolysis process such as i) liquid
ysis. Ionic liquids may positively impact the process of pyrolysis and (bio-oils), ii) pyro-gas (hydrogen and syngas), and solid (bio-char). The
facilitate improved efficiency. Another major challenge faced by the bio-oils produced during pyrolysis process has potential to replace the
process is the quality of value added products. The produced bio-oil is use of traditional fossil fuels. In addition to this, hundreds of bio­
not appropriate for the direct application as combustion fuel in auto­ chemicals can be synthesized during of biomass pyrolysis. It is practi­
mobile engines due to the existence of higher concentration of oxygen cally viable to enhance the quality and yield of pyrolytic product. To
and moisture. Therefore a suitable method has to be developed to make the pyrolysis process is economically feasible the integration of
eliminate the water content and oxygen in order to yield high grade bio- fuel and chemical production is recommended by upgrading the process
oil equivalent to the existing petroleum fuels. Several upgraded system.

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CRediT author contribution statement Chen, W.-H., Wang, C.-W., Ong, H.C., Show, P.L., Hsieh, T.-H., 2019. Torrefaction,
pyrolysis and two-stage thermodegradation of hemicellulose, cellulose and lignin.
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Yogalakshmi KN: Writing - original draft, Poornima Devi T: Writing - Collard, F.-X., Blin, J., 2014. A review on pyrolysis of biomass constituents: mechanisms
original draft; Sivashanmugam P: Resources, Kavitha S: Conceptualiza­ and composition of the products obtained from the conversion of cellulose,
tion, Writing - review & editing, Data curation. Yukesh Kannah R: hemicelluloses and lignin. Renew. Sustain. Energy Rev. 38, 594–608. https://doi.
org/10.1016/j.rser.2014.06.013.
Software, Writing - review & editing, Sunita Varjani: Resources, Adish Cui, Y., Wang, W., Chang, J., 2019. Study on the product characteristics of pyrolysis
Kumar S: Resources, Gopalakrishana Kumar: Resources, Rajesh Banu J: lignin with calcium salt additives. Mater. (Basel, Switzerland) 12, 1609. https://doi.
Supervision, Methodology. org/10.3390/ma12101609.
Culebras, M., Beaucamp, A., Wang, Y., Clauss, M.M., Frank, E., Collins, M.N., 2018.
Biobased structurally compatible polymer blends based on lignin and thermoplastic
elastomer polyurethane as carbon fiber precursors. ACS Sustain. Chem. Eng. 6,
Declaration of competing interest 8816–8825. https://doi.org/10.1021/acssuschemeng.8b01170.
Czajczyńska, D., Anguilano, L., Ghazal, H., Krzyżyńska, R., Reynolds, A.J., Spencer, N.,
The authors declare that they have no known competing financial Jouhara, H., 2017. Potential of pyrolysis processes in the waste management sector.
Therm. Sci. Eng. Prog. 3, 171–197. https://doi.org/10.1016/j.tsep.2017.06.003.
interests or personal relationships that could have appeared to influence
Dai, L., Wang, Y., Liu, Y., He, C., Ruan, R., Yu, Z., Jiang, L., Zeng, Z., Wu, Q., 2020.
the work reported in this paper. A review on selective production of value-added chemicals via catalytic pyrolysis of
lignocellulosic biomass. Sci. Total Environ. 749, 142386. https://doi.org/10.1016/j.
scitotenv.2020.142386.
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