Lu and Gu 

Biotechnology for Biofuels and Bioproducts (2022) 15:106 Biotechnology for Biofuels
https://doi.org/10.1186/s13068-022-02203-0
and Bioproducts

REVIEW Open Access

A review on lignin pyrolysis: pyrolytic

behavior, mechanism, and relevant upgrading
for improving process efficiency
Xinyu Lu and Xiaoli Gu*

Abstract
Lignin is a promising alternative to traditional fossil resources for producing biofuels due to its aromaticity and renew-
ability. Pyrolysis is an efficient technology to convert lignin to valuable chemicals, which is beneficial for improving
lignin valorization. In this review, pyrolytic behaviors of various lignin were included, as well as the pyrolytic mecha-
nism consisting of initial, primary, and charring stages were also introduced. Several parallel reactions, such as dem-
ethoxylation, demethylation, decarboxylation, and decarbonylation of lignin side chains to form light gases, major
lignin structure decomposition to generate phenolic compounds, and polymerization of active lignin intermediates
to yield char, can be observed through the whole pyrolysis process. Several parameters, such as pyrolytic temperature,
time, lignin type, and functional groups (hydroxyl, methoxy), were also investigated to figure out their effects on lignin
pyrolysis. On the other hand, zeolite-driven lignin catalytic pyrolysis and lignin co-pyrolysis with other hydrogen-rich
co-feedings were also introduced for improving process efficiency to produce more aromatic hydrocarbons (AHs).
During the pyrolysis process, phenolic compounds and/or AHs can be produced, showing promising applications in
biochemical intermediates and biofuel additives. Finally, some challenges and future perspectives for lignin pyrolysis
have been discussed.
Keywords: Lignin, Pyrolysis, Phenolic compounds, Aromatic hydrocarbons

Introduction lignin mainly formed between bulky aromatic rings, mak-

Due to the natural aromatic polystructure, lignin (which ing their cleavage more difficult. Besides, C–O bonds are
can mainly be extracted from softwood, hardwood, and the most abundant linkages in native lignin, accounting
grass, and the model lignin structures is shown in Fig. 1 for two-thirds or more of total linkages [9–12]. There-
[1]) has been regarded as a sustainable alternative to fore, much attention has been paid to the efficient cleav-
fossil-derived resources to provide valuable biochemi- age of C–O and C–C bonds in lignin, especially under
cals [2–7]. Interunits of lignin are connected by C–O mild conditions, such as catalytic [13–18], photocata-
and C–C bonds (such as β-O-4, β–β, and β-5, Fig. 1), lytic [19–21], ionic liquid promoted depolymerization
wherein the later contains higher bond dissociation ener- [22–26], and reductive catalytic fractionation [27–31] to
gies (BDE = 69–123 kcal/mol) than that of the former achieve efficient lignin transformation or selective con-
(BDE = 52–80 kcal/mol) [8]. Furthermore, C–C bonds in version of lignin model compounds to target products.
In these studies, some obvious defects can limit their
wide applications in the industrial scale, such as the com-
*Correspondence: guxiaoli@njfu.edu.cn mon utilization of noble metal (e.g., ruthenium and rho-
Jiangsu Co‑Innovation Center of Efficient Processing and Utilization of Forest dium) supported catalysts and lignin model compounds
Resources, College of Chemical Engineering, Nanjing Forestry University, (e.g., dimers containing C–O bonds or lignin-derived
Nanjing 210037, China

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Fig. 1 Model lignin structures containing 11 units for A a softwood, B hardwood, and C grass [1]

monophenols) with high price, non-noble metal sup- absence of oxygen due to its easier operation and lower
ported catalysts with complex preparation processes cost for lignin conversion to gases (containing H­ 2O, CO,
(such as Ni/Al2O3 prepared from NiAl-LDH (layered ­CO2, ­CH4, and ­H2), liquid biofuels (containing monophe-
double hydroxide), and Co/MoS2−x with defect sites), nols or polyphenols), and solid char with shorter reac-
and low energy conversion efficiency (e.g., photocatalytic tion time, of which the performance mainly depends on
conversion). the reaction temperature, time, heating rate and reactor
Commonly, strategies for lignin conversion to biofuels configuration [35–37]. Massive studies have focused on
or biochemicals can be summarized into pyrolysis (ther- lignin pyrolysis using different techniques such as TGA
mal and catalytic pyrolysis), hydroprocessing (hydrog- (thermogravimetric analysis), Py-GC/MS (pyrolysis-gas
enolysis, hydrodeoxygenation, hydrogenation, and chromatograph/mass spectroscopy) and fixed-/fluidized-
integrated hydrogen processing), oxidation (organome- bed reactors, and the products evolution was investigated
tallic catalysis, metal-free organocatalytic system, base comprehensively [38–41]. For deeply understanding the
and acid catalysts, metal salt catalysis, photocatalytic pyrolysis mechanism, some studies also used lignin-
oxidation, and electrocatalytic oxidation), gasification derived model compounds as pyrolyzed subjects, reveal-
and liquid-phase or steam reforming [9, 32, 33]. Recently, ing that several linkages cleavage (such as C ­ β–O and
catalytic self-transfer hydrogenolysis has been found as a ­Cα–Cβ) occurred simultaneously [42, 43].
sustainable method for lignin hydrogenolysis due to the Although lignin pyrolysis mechanism has been
renewable ­H2 source produced from lignin structure [34]. explored and lignin oils (rich in phenolic compounds)
Among these conversion methods, pyrolysis technology can be produced, due to the high oxygen content,
has been confirmed as a more effective method in the acidity, and corrosiveness, further upgrading of liquid

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Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 3 of 43

oils is necessary [44]. Recently, catalytic pyrolysis has corresponding products yield and selectivity were also
been applied as an efficient method for improving oil obtained.
quality and stability via deoxygenation reactions with
assistance of suitable catalysts [45, 46]. The most used Lignocellulosic biomass pyrolysis
catalysts are zeolites, such as ZSM-5, MCM-41, beta, Background
mordenite, ferrierite, and USY with low cost and vast Lignocellulosic biomass is a narrow concept of bio-
availability, of which the catalytic effect would promote mass materials, broadly including forestry/agricultural
deoxygenation via dehydration, decarbonylation, and residues, industrial waste biomass, and grasses [62, 63],
decarboxylation reactions [47–49]. Furthermore, func- which is the most popular material for preparing biofu-
tionalities of zeolites on acidity, mesoporosity, and large els [64, 65]. Pyrolysis is a kind of thermochemical reac-
external surface area make positive effects on aromat- tion performed in the absence of oxygen with a certain
ics production and char inhibition [50–52]. Aromatic of heating rate [66], which is an efficient method for
hydrocarbons (AHs), such as monocyclic aromatic converting biomass materials into biofuels [67–71].
hydrocarbons (MAHs) and polycyclic aromatic hydro- Typically, lignocellulosic biomass conversion via pyroly-
carbons (PAHs), are the major products from lignin sis technology involves the thermal decomposition of
catalytic pyrolysis using zeolites, wherein naphthalene three main basic components in lignocellulosic biomass
and anthracene obtained from PAHs can be directly (i.e., cellulose, hemicellulose, and lignin) [72], which can
used as fuel additives [53, 54]. On the other hand, for be transformed into valuable products, such as sugars,
improving oil quality, it is feasible to increase the effec- cyclopentenes, furans, phenols, and aliphatics in biofuels
tive hydrogen index (EHI) of pyrolyzed feedstock due [73].
to the uncompetitive content of effective hydrogen
in lignin (only around 0.3) [55]. Therefore, lignin co- Pyrolysis of cellulose, hemicellulose, and lignin
pyrolysis with other hydrogen-rich feedstock has been From Fig. 2A, cellulose is the most abundant polysac-
proposed as a useful method to improve oil quality charide in nature, which is a linear polymer of d-glucosyl
[56]. For example, lignin co-pyrolysis with low-density surrounded by the heterogeneous polysaccharide, hemi-
polyethylene over ZSM-5 [57], with polyethylene tere- cellulose, and lignin, and connected by β-1,4-glycoside
phthalate over calcium oxide and zeolites [58], or with and intra/intermolecular hydrogen bonds [74]. Due to
plastics (such as polyethylene, polypropylene and poly- its relatively simple structure, cellulose has been widely
styrene) over LOSA-1, spent FCC, and Gamma-Al2O3 applied in pyrolysis process, briefly including the starting
[59] showed the enhanced production of AHs owing depolymerization at around 350 °C, and further conver-
to the synergistic effect of deoxygenation (from cata- sion into active cellulosic species, levoglucosan (LGA),
lysts) and hydrogen transferring (from hydrogen-rich levoglucone (LGO), and other monosaccharides via
co-feedstock) [60]. In addition, waste cooking oils have bonds cracking and dehydration. The primary pyrolytic
been used as hydrogen donors during lignin pyrolysis products from cellulose are anhydrosugars, which can be
[61], showing the promising application of co-pyrolysis further converted into some light oxygenates (e.g., furans,
with some hydrogen-rich feedstock in lignin oil upgrad- aldehydes, ketones, acids, etc.) at higher temperatures
ing, which is also feasible for both lignin valorization (Fig. 2B) [75, 76]. In comparison with cellulosic compo-
and other wastes with high value-added recycling. nents, hemicellulose has a more complex structure with
In this review, we comprehensively summarized the abundant branched chains and various substituents,
mechanism of lignin pyrolysis (detailedly divided into which is mainly composed of xylan and glucomannans,
three stages, e.g., initial, primary and charring stages, and where the later contains the similar pyrolytic properties
the characteristic products evolution, and mechanism to anhydrosugars (which leads to the similar pyrolytic
during each stage was introduced, including gas, liquid, characteristics to cellulose). Therefore, the pyrolysis pro-
and solid). On the other hand, the pyrolytic behaviors of cess of xylan can be selected as a modifier to study the
different kinds of lignin (e.g., Kraft lignin, alkali lignin, pyrolytic mechanism of hemicellulose, majorly includ-
organosolv lignin, DES lignin, biological lignin, and ionic ing initial depolymerization, the generation of furan, and
liquid lignin, also including their isolations, pretreat- pyran derivatives via dehydration, and the breakage of
ments, structures, and pyrolytic oil properties) were also furanose and pyranose-derived rings to form some light
introduced in this review. Furthermore, lignin catalytic oxygenates (Fig. 2C) [77]. Lignin, a complex biopolymer
pyrolysis using zeolites as the most used catalysts and co- with aromatic structure, mainly associates with cellulose
pyrolysis with other hydrogen-rich feedstock were also and hemicellulose together to form plants skeleton. In
included in this review for improving lignin oils quality the process of lignin pyrolysis, higher temperatures are
via deoxygenation and increasing AHs content, and the required for linkages cleavage to generate large amounts

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Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 4 of 43

Fig. 2 A Composition and structure of lignocellulosic biomass, and possible pyrolysis mechanism of B cellulose, C hemicellulose, and D lignin
(Reproduced from Refs. [63, 75] with permission from Elsevier)

of phenolic compounds together with small amounts of be significantly influenced by the pyrolytic temperature
acid, alcohols, and light aromatic hydrocarbons (Fig. 2D) [79]. Besides, different types of lignocellulosic biomass
[78]. determine various compositions of cellulose, hemicellu-
lose, and lignin, which also influence the pyrolytic char-
Influencing factors of lignocellulosic pyrolysis acteristics. Typically, cellulosic components can produce
Zhao et al. used commercial cellulose, hemicellu- the higher yield of biofuels (~ 60%) compared to those of
lose, and lignin as raw materials without any pretreat- hemicellulose (~ 40%) and lignin (~ 30%). Other influenc-
ments and found that the pyrolytic characteristics can ing parameters, such as the contents of ash, metal, and

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Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 5 of 43

moisture, also affect the production and properties of (e.g., corn cob, wheat straw, rice straw and rice husk, with
final generated biofuels. Higher contents of moisture in further drying, crushing and sieving) contain their own
lignocellulosic biomass would reduce the calorific value ideal pyrolytic temperatures to generate the highest yield
and deteriorate the quality of biofuels. of biofuels [98, 99].
During pyrolysis, the function of pyrolytic tempera- Except for the pyrolytic temperature, Qiu et al. pointed
ture is to provide heat to decompose the structure of out that the type of biomass feedstock is also an impor-
substrates, and increasing the pyrolytic temperature can tant factor to influence the generation of biofuels due to
enhance the conversion efficiency. At lower pyrolytic the differences of their compositions and structures [72].
temperatures, ash in raw materials would be retained in Oasmaa et al. found that wood biomass can produce
solid products to yield more semi-coke. In addition, met- more biofuels with lower yield of aqueous and gaseous
als existing in the ash, such as kalium and calcium, can products [100]. Among these formed biofuels, different
enhance the pyrolytic heating rate while reduce the yield compositions of raw materials lead to the different prop-
of biofuels due to their catalyzed effect to promote the erties of biofuels. For example, cellulosic-derived biofuels
secondary cracking reactions among products in biofuels are rich in acids, furans, and ketones, which are similar to
[80]. For example, Tsai et al. used rice husk as raw mate- those of hemicellulose-derived ones, while lignin-derived
rial with further grinding and rose the pyrolytic tempera- biofuels reveal a great capacity to produce phenolic com-
ture from 400 to 500 °C, leading to the higher production pounds [101]. There is a positive correlation of ketones
of biofuels from 11.26 to 35.92 wt% and reaching the and cellulose, furans and holocellulose, and phenols and
maximum yield (i.e., 38.8 wt%) at 800 °C [81]. Lazzari lignin, while there is a negative correlation of short-chain
et al. used mango fruit seeds as raw materials (which acids and ash, and hydrocarbons and cellulose. Further-
were separated into tegument and almond) and obtained more, with increasing the pyrolytic temperature, various
the highest yield of biofuels at 38.8 wt% when the pyro- interactions occur to change the composition of biofuels.
lytic temperature increasing to 650 °C [82]. It is suggested For example, Huang et al. found that alkenes, alkanes,
that increasing the pyrolytic temperature makes a posi- long-chain fatty acids/esters, aliphatic nitriles, and
tive effect on the production of biofuels, while the oppo- amides can be obtained at lower pyrolytic temperatures,
site trend would be found at a very high temperature due while higher pyrolytic temperatures favor the cracking
to the occurrence of the secondary cracking reactions reaction among aliphatic species and the formation of
[83]. Jung et al. used rice straw and bamboo sawdust as aromatic compounds [102]. Ly et al. found that a higher
raw materials with further sieving into small particle sizes pyrolytic temperature produces biofuels with more
and pointed out that as the pyrolytic temperature of bam- short aliphatic carbons, low-molecular-weight alcohols,
boo sawdust increases over 500 °C, biofuel yield would ketones, and their derivatives due to the further decom-
gradually decrease, and the optimal pyrolytic tempera- position reaction occurring [103]. Alvarez et al. observed
ture for rice straw is 445 °C to yield more biofuels [84]. that increasing the pyrolytic temperature would reduce
In addition, the optimal pyrolytic temperature ranges for the yield of ketones and acids, while increase the yield
rice husks/sawdust and cotton stalk without ant pretreat- of phenols [88]. In addition, the pyrolytic temperature is
ments are confirmed at 420–540 and 480–530 °C, respec- also an important factor for determining the quality of
tively [85–87], and the maximum yield of biofuels for rice biofuels, such as H/C ratio, which is an essential indica-
husk (with further grinding) (70.0 wt%) [88], palm waste tor for HHV (high heating value, kJ/mol) [104]. Ates and
(with further grinding) (72.4 wt%) [89], neem de-oiled Ly et al. also observed that increasing the pyrolytic tem-
cake (without any pretreatments) (40.2 wt%) [90], Cynara perature is beneficial for reducing oxygen content in bio-
cardunculus (without any pretreatments) (56.2 wt%) [91], fuels, while increasing the content of hydrogen, showing
olive bagasse (without any pretreatments) (46.3 wt%) the higher calorific value of biofuels [105, 106].
[92], sugarcane bagasse (with further drying, grind-
ing, and sieving) (61.4 wt%) [93], cassava rhizome (with The meaning of further investigations on lignin pyrolysis
further drying, grinding and sieving) (63.2 wt%) and Even though massive studies have focused on lignocel-
cassava stalk (with further drying, grinding and siev- lulosic biomass pyrolysis, the biggest challenge is about
ing) (61.4 wt%) [94], Jatropha seed shell cake (without the high-efficiency conversion of lignin. Lignin account-
any pretreatments) (48.0 wt%) [95], pistachio shell (with ing for 40% of energy (higher than that of polysaccha-
further drying and grinding) (20.5 wt%) [96], and polar rides) has been considered as the most promising source
wood (without any pretreatments) (69.0 wt%) [97] can for biochemical platform and bioenergy due to its aro-
be obtained at 450, 500, 400, 400, 600, 475, 472, 469, 470, matic structure [107, 108]. Nowadays, over 90% of lignin
550, and 455 °C, respectively. Biswas and Pattiya et al. is burned with low efficiency, and only 2% of lignin is
also suggested that different kinds of biomass materials utilized efficiently due to its complex structure and low

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Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 6 of 43

reactivity [109, 110]. As the stubbornest component in to determine mass loss, volatiles evolution, and decom-
lignocellulosic biomass, the efficient conversion of lignin posed products distribution, respectively. For example, a
has attracted much attentions from both industry and coupling analysis of TG-FTIR-GC/MS was used by Yang
research community and is still a researching hotspot et al. to investigate the pyrolytic mechanism of lignin-rich
up to now. Pyrolysis technology has been considered as residue obtained from Arundo donax. Pyrolytic results
an effective method for lignin conversion to well-fined including the composition, carbon number and atomic
chemicals due to its low cost, easy operation, high effi- ratio (C/H, C/O) of bio-oils was obtained for propos-
ciency for energy extraction, and fuel production [111– ing pyrolysis mechanism and possible reaction pathway
114]. As the only renewable alternative of non-renewable [128]. Through TG analysis, three main stages of lignin
fossil fuels for producing aromatic compounds, lignin pyrolysis can be obtained, including water evaporation
can be thermally decomposed via pyrolysis technology (< 200 °C), primary decomposition (at 250–500 °C), and
to obtain low-molecular-weight phenolic compounds carbonization (> 500 °C) [129–132]. Through the cou-
(important intermediates in biochemical platform) and pling analysis of TG, FTIR, and GC/MS, lignin pyrolytic
to generate aromatic hydrocarbons (advanced fuel addi- mechanism can be elucidated in Fig. 3, where chemical
tives with sustainable energy density) [115]. On the other linkages, such as C–C and C–O–C bonds, can be cleaved
hand, biorefinery economic can benefit from high-quality to produce phenols and aromatic hydrocarbons, and
recovery of lignin by lowering the manufacturing price of functional groups, such as carboxyl, carbonyl, and meth-
biochemicals and biofuels [116]. oxy, would be escaped from benzene ring to form some
light gases. Finally, lignin biochar with abundant func-
Lignin pyrolysis tional groups (such as –OH and –OCH3) would be gen-
Background erated via carbonization [133]. On one hand, functional
Lignin is one of the three main components in ligno- groups in biochar would be further cracked with the tem-
cellulosic biomass, combined with cellulose and hemi- perature rising to form light gases. On the other hand,
cellulose via hydrogen and ester bonds [117–119]. So active aromatic species in bio-oils would be transformed
far, large quantities of lignin have been produced from into biochar via repolymerization.
industrial and agricultural activities, and pyrolysis tech-
nology has been considered as an effective method for Influencing factors of lignin pyrolysis
its high-efficiency conversion [120–122]. Unfortunately, Yu et al. investigated the importance of pyrolytic tem-
the presence of cellulose and hemicellulose would affect perature on lignin pyrolysis, where monophenols are
the pyrolytic behavior of lignin owing to a series of cou- the main components at the temperature range of 450–
pling interactions occurring [123–125], hence leading to 525 °C, and higher temperatures prefer the generation of
a more intangible pyrolysis process. After delignification, dimers [134]. Through the further cracking reactions of
different kinds of lignin with high purity and homogene- carboxylic acid, ketone, and aldehyde, and the inhibition
ity can be extracted from raw biomass and then pyro- of coupling reactions of free mono radicals, the produc-
lyzed into low-molecular-weight compounds, which are tion of phenols can be enhanced. Besides, some func-
the so-called pyrolytic oils (mainly composed of phenolic tional groups in lignin, such as methoxy and phenolic
compounds, aldehydes, acids, and other aromatic hydro- hydroxyls, significantly change the pyrolytic characteris-
carbons) [126, 127]. tics of lignin [135]. Methoxy is an important functional
group in lignin, which can affect the repolymerization
Lignin pyrolysis mechanism degree of lignin during pyrolysis [136], and also is defined
Typically, the radical reaction of lignin pyrolysis has been as an important factor to promote the formation of char
established and divided into three stages: initial, primary, residues [137–139]. The positive effect of demethyla-
and charring stages (or namely the radical inducing, the tion on repolymerization inhibition can be confirmed by
main reacting and the quenching stages [126]). Prior to the lower char yield of demethylated lignin compared
the detail description of their own pyrolytic characteris- to that of raw lignin. Besides, with the enhancement of
tics and product distributions, we first introduce the gen- demethylation degree, the main components of demeth-
eral pyrolytic mechanisms of lignin pyrolysis. ylated lignin pyrolytic products are adjusted from meth-
oxyphenols to H-type phenols, such as phenols, methyl
General pyrolytic mechanism of lignin phenols, and catechol [140]. On the other hand, the char-
Lignin pyrolytic mechanisms can be researched via sev- ring mechanism of lignin pyrolysis suggests that (1) char
eral techniques, such as thermogravimetric analysis cannot be generated when there is only one phenolic
(TG), Fourier transform infrared spectroscopy (FTIR), hydroxyl; (2) a bromine group as an electron withdrawing
and gas chromatography/mass spectrometry (GC/MS) site can decrease electron cloud density in ortho position,

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Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 7 of 43

Fig. 3 Proposed pyrolytic mechanism of lignin (Reproduced from Ref. [128] with permission from Elsevier)

reduce the bond dissociation energy of phenolic hydroxyl, is directly proportional to the amount of methoxy in the
and promote dehydrogenation, which is conductive for ortho position of phenolic hydroxyl [140].
char formation; (3) methoxy, as an electron-donating
group, does not promote the repolymerization reaction, Initial stage of lignin pyrolysis
while phenolic hydroxyl, as an electron donor group, can Lignin pyrolysis process can be divided into three stages,
promote repolymerization by affecting electron could including initial, primary, and charring stages, and each
density; (4) the intramolecular reaction between methoxy stage has its own characteristic pyrolytic behaviors
and phenolic hydroxyl groups significantly promote the (Fig. 4) and mechanisms (introduced in the following
repolymerization, and the promotion of char formation sections).

Fig. 4 Characteristic pyrolytic behaviors of initial, primary, and charring stages

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Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 8 of 43

Li et al. investigate the reaction pathway of initial stage dimers or trimers). The decrease of both H/C and O/C
comprehensively, revealing that a complex initial reac- ratios in THF-soluble fraction with increasing tempera-
tion of lignin pyrolysis mainly occurs at the temperature ture from 100 to 300 °C illustrates that some mono-aro-
range of 160–330 °C (before 160 °C, external and internal matics would be repolymerized into condensed phases
water removing causes a light mass decrease) with mass with fused-ring structures in THF-insoluble fraction.
loss of approximately 20% to form considerable amounts The change of char structure with the increase of tem-
of volatile products [141]. During initial stage, some light perature illustrates that (1) the aliphatic carbon struc-
gaseous products start to release (e.g., H ­ 2O releasing ture decreases due to the escape of alkyl side chains,
at the ranges of 160–330 and 330–400 °C due to dehy- (2) the methoxy carbon structure decreases due to the
droxylation and hydroxyl cracking in lignin hydrogen decomposition of ether bonds (such as α-O-4 and β-O-
bond network; ­CO2 releasing at the ranges of 160–270, 4), (3) the aromatic carbon structure increases due to the
270–330, and 330–400 °C due to fatty ether bonds cleav- enhanced aromaticity, and (4) the carbonyl carbon struc-
age and oxidation, carboxylic acid group cleavage, and ture decreases due to the release of light gases (such as
carbonyl group cleavage and oxidation; CO releasing at ­CO2).
the ranges of 170–330 and 330–400 °C due to the cleav-
age of ether bonds and side chains C–O; ­CH4 releasing Primary stage of lignin pyrolysis
at the range of 330–400 °C due to the methoxy cleavage). Primary stage of lignin pyrolysis containing more intense
The variations of activation energy of these light gases structural decomposition happens at the temperature
are mainly due to their formations from different sources range of 400–600 °C after initial stage, where phenolic
with different bond energies [142]. When the tempera- compounds (which is both temperature induced and
ture increases up to 150 °C, the polymerization reac- time induced) are the major components during this
tion happens to form the condensed lignin phase with stage [146–148]. The pyrolytic temperature and residence
a larger molecular weight, and oil-based components time have significant influences on products generation
(such as lignin monomers, dimers, and trimers) would [149–151]. Lin et al. investigated the effect of tempera-
be orderly generated after the temperature further rising ture and time on the generation of phenolic products,
to 330 °C [141]. On the other hand, lignin surface adhe- illustrating that the maximum yield of phenolic products
sion occurs to transform raw lignin into a bulk, and the can be obtained at 450 °C [152]. With increasing temper-
evolution of functional groups illustrates that hydroxyl ature, the production of phenolic monomers is enhanced
and hydrocarbon groups in bulk lignin are temperature significantly due to the increasing conversion rate of
induced (of which the content decreases as the temper- lignin [153–155]. However, due to the secondary reac-
ature increases to form more light gases). In addition, tion occurring with the extension of reaction time, more
non-conjugated carbonyl, conjugated carbonyl, aromatic, phenolic monomers would be transformed into light
guaiacyl, and syringyl groups in lignin are all tempera- gases (which leads to no further increase of the detecting
ture induced, which can be converted into aromatic com- response of phenolic monomers at 600 °C when the resi-
pounds, together with the escape of side chains to form dence time increases from 1 to 5 s). On the other hand,
light gases with increasing pyrolytic temperature. Finally, the reaction equilibrium would also lead to no obvi-
the structure polymerization of condensed lignin or the ous enhancement of products generation at 600 °C with
repolymerization among aromatic compounds happen to the extension of residence time [127, 155]. Expect for
generate biochar with fused aromatic rings. the temperature and reaction time, lignin structure also
The structural changes of char produced from initial influences the pyrolytic behavior at primary stage [155,
stage was investigated by Chua et al. [143]. With increas- 156]. For example, Marathe et al. investigated the effect
ing temperature (over the softening temperature of lignin of molecular weight on lignin pyrolysis, and the results
at ~ 140 °C [144]), the content of THF-insoluble frac- demonstrate that (1) the increasing molecular weight of
tion of obtained lignin char contains a larger molecular lignin would decrease the oil yield due to higher yields of
weight, indicating the occurrence of repolymerization gases and solids obtained; (2) the molecular weight of liq-
reaction. For THF-soluble fraction, almost the half is uid products is independent to that of lignin but is associ-
transformed into volatile products and the remainder is ated with the reaction pressure; and (3) the yield of liquid
repolymerized into THF-insoluble fraction (of which the products is proportional to the reaction temperature
structure is composed of mono, 2–3 fused, and 3–5 fused [157]. Besides, Yuan et al. investigated the effect of lignin
aromatic rings [145]) when the temperature increases up structure on the formation of phenolic compounds, and
to 300 °C. From RT to 250 °C, the aromatic structure of various lignin extracted from softwood (pine), hard-
char is reduced due to the generation of light gases and wood (eucalyptus), and herbaceous feedstock (corn
oil component compounds (e.g., phenolic monomers, stalk and bamboo) were pyrolyzed, presenting different

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Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 9 of 43

compositions of liquid products, wherein lignin samples primary structure decomposition, and aromatic conden-
from corn stalk and bamboo favor H-type phenols, and sation reactions occurring to cause the aromatic polycon-
that from pine prefers G-type phenols, while that from densation over 400 °C. The pyrolysis mechanism can be
eucalyptus majorly produces polyphenols [158]. summarized as (1) almost no lignin conversion happens
At the temperature range of 400–600 °C, the structure before 200 °C due to its thermal stability, (2) aromatic
decomposition of lignin is driven by the linkage cleavage side chains can be cleaved to form some light gases as
(e.g., ether bonds with bond dissociation energy (BDE) the temperature increasing up to 250 °C [171], (3) from
of ~ 291 kJ/mol, and C–C bonds with BDE of ~ 323 kJ/ 250 to 350 °C, depolymerization and condensation exist
mol), wherein the chemical linkage with lower BDE as competing reactions to generate abundant liquid prod-
would be broken easier with the increase of temperature, ucts (i.e., methoxyphenols) via linkages cleavage [172],
while that with higher BDE would be more temperature (4) from 350 to 450 °C, the condensation reaction is
resistance, which can be presented as functional groups enhanced, including repolymerization and condensation,
in final products [159–161]. In the process of linkages to generate char with 1 × 2 and 2 × 2 fused-ring struc-
cleavage, hydroxyl radicals are produced from scission of tures, (5) at 450–600 °C, demethylation, demethoxyla-
aliphatic side chains, and hydrogen radicals can be gen- tion, and dehydrogenation reactions occur to form C ­ H4
erated from β-scission reactions (from C–OH to C=O), and ­H2, and further convert guaiacyl-type compounds
which might migrate to either aliphatic side chains or into catechol-type ones and alkyl phenols [173], and (6)
aromatic rings with oxygen radicals [162, 163]. Further- at 450–600 °C, the structure of lignin char can be gen-
more, due to the high temperature resistance property of erated consisting of 2 × 2, 3 × 3, 4 × 4, and other fusing
methoxy (i.e., BDE = 481 kJ/mol), large amounts of meth- rings.
oxylated phenols are generated [9, 164]. From Fig. 5, the
obtained products can be mainly categorized as guaiacyl, Charring stage of lignin pyrolysis
cresol, and catechol types, where guaiacyl units are sug- Through the above studies on lignin pyrolysis, it is well
gested to produce G-type phenols via depolymerization known that the structure of lignin char changes obviously
and dehydration (P1) [165]. Cresol and catechol are gen- with increasing temperature. Zheng et al. studied the
erated by the cleavage of interunit linkages and the crack- char structure evolution during lignin fast pyrolysis from
ing of aliphatic side chains (P2, P3, and P6). The higher 200 to 800 °C [40]. Raman spectra in Fig. 6A show that
temperature would lead to more demethylation and dem- the graphitization degree of lignin char is relatively low
ethoxylation reactions of guaiacyl units (P2 and P6) to due to the presence of low-strength G band of graphite
increase the yield of cresol and catechol-type compounds crystals (~ 1585 ­cm−1) [174]. Figure 6A shows the fitting
[160, 166]. In addition, cresol-type compounds can also curves of Raman spectrum of char obtained at 800 °C,
be generated from p-hydroxyphenyl units via depolym- consisting of G ­ L (at 1680 ­cm−1, carbonyl group C=O),
erization (P3 and P4) [167]. Phenol-type compounds are G (at 1585 ­cm−1, graphite E ­ 22g; aromatic ring quadrant
created by demethoxylation (P5) of guaiacyl units [168], breathing; alkene C=C), ­GR (at 1540 ­cm−1, aromatics
and acetaldehyde is suggested to be formed from carbo- with 3–5 rings; amorphous carbon structures), ­VL (at
hydrate fractions and side chains via dehydration (P8) 1465 ­cm−1, methylene or methyl; semi-circle breath-
and fragmentation (P7), respectively [77, 149, 169]. In ing of aromatic rings; amorphous carbon structures),
addition, water can be produced via dehydration reaction ­VR (at 1380 ­ cm−1, methyl group; semicircle breath-
between hydroxyl and hydrogen radicals, and methanol ing of aromatic rings; amorphous carbon structures), D
and methane can be generated from methyl radicals via (at 1320 ­cm−1, D band on highly ordered carbonaceous
demethoxylation promoted by hydrogen or hydroxyl rad- materials; C–C between aromatic rings and aromatics
icals [163]. with not less than 6 rings), ­SL (at 1230 ­cm−1, aryl–alkyl
Yang et al. elucidated lignin pyrolysis at primary stage ether; para-aromatics), S (at 1185 ­cm−1, ­Caromatic–Calkyl;
comprehensively (i.e., from 200 to 600 °C), especially for aromatic (aliphatic) ethers; C–C on hydro-aromatic
the structural evolution of char at this stage [170]. After rings; hexagonal diamond carbon ­sp3; C–H on aromatic
400 °C, ­H2 has been gradually generated and obtains its rings), ­SR (at 1060 ­cm−1, C–H on aromatic rings; benzene
maximum content at 600 °C due to the polymerization of (ortho-di-substituted) ring), and R (at 960–800 ­ cm−1,
aromatic rings [127]. With the increase of temperature C–C on alkanes and cyclic alkanes; C–H on aromatic
(from 350 to 600 °C), the condensation of aromatic rings rings) [174, 175]. Raman bands of inorganic matters are
happens to form char residues with polycondensed aro- mostly below 1100 ­cm−1; therefore, organic components
matic structure. The evolution of char structure includes occupy the main proportion of lignin char. Figure 6B
the conversion of hydroxyl groups to carbonyls and ali- shows the relationship of ring condensation degree ver-
phatic chain C–H to alkene C–C, mainly due to the sus temperature, elucidating that the aromatization starts

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Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 10 of 43

HO HO HO HO HO

HO HO Cresol type
Catechol type
P3
HO P6
P2 Phenol
CH3 HO
HO

P4 P5
O Guaiacyl O
O
•H HO unit Acetaldeh
O
p-Hydroxyphenyl O
HO
unit O
P7 P
O
O
HO
O HO O
HO
O
H
OH
O
O

OH
O Carbohy
O
O •OH OH in lignin
OH
OH
P1 •H O

O
H2 O
Guaiacyl type
O O O O

HO HO HO HO

O O O O
O

HO HO HO HO

O O O O OH
OH
O O
HO HO HO HO

Fig. 5 Proposed reaction pathways for primary stage of lignin pyrolysis (P1: depolymerization and dehydration; P2: side-chain scission and
demethylation; P3, P4: depolymerization; P5: demethoxylation; P6: side-chain scission and demethoxylation; P7: fragmentation of lignin side
chains; P8: dehydration and fragmentation of carbohydrate) [39]

at 350 °C, followed by the evolution of char structure lignin char, indicating that the higher heating rate would
from 2 × 3 fused ring to 4 × 5 fused ring over 700 °C. increase the oxygen content and decrease the HHV value
The behavior of carbon deposit on fusing rings would be of char, and lead to the further structural decomposition
enhanced owing to the recombination and recondensa- [38].
tion of volatile products at higher temperatures [176].
Besides, not only temperature but also heating rate can
affect the formation and structure of char significantly. Li Recent progress of lignin pyrolysis
et al. investigated the effect of heating rate on the evo- According to the pyrolysis mechanism presented above,
lution of functional groups and structural properties of in this section, we mainly introduce the pyrolytic behav-
iors of different types of lignin, including Kraft lignin

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Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 11 of 43

Fig. 6 A Curve fitting for the first-order Raman spectrum of char obtained at 800 °C, and B relationships between ring condensation degree and
pyrolytic temperature (Reproduced from Ref. [40] with permission from Elsevier)

(Table 1), alkali lignin (Table 1), organosolv lignin due to the release of foul-smelling sulfur compounds
(Table 1), DES (deep eutectic solvents) lignin (Table 2), [152, 183]. Furthermore, sulfur contaminations would
biological lignin (Table 3), and ionic liquid lignin also inhibit the depolymerization of Kraft lignin [184].
(Table 4), and their own characteristic reaction pathways. Therefore, before being used in pyrolysis, sulfur remov-
ing would be necessary to improve the oil production.
Kraft lignin For example, many methods, such as adsorption, sodium
Kraft lignin (a kind of technical lignin) is generated from hydroxide treatment, the oxidation of thiols and sulfides
Kraft pulping process in the pulp and paper industries to sulfoxides and sulfones followed by organosolv extrac-
from black liquor, among which sulfide solutions (i.e., tion, direct sulfur extraction by organic solvents, recover-
sulfuric acid) is commonly used [177]. In the delignifica- ing organic sulfur compounds by P(III)-based systems as
tion process, hydrogen sulfide would react with lignin. well as elemental sulfur recovery with heavy metals and
Although these sulfur-containing components would be sodium sulfite, and neutralization of acidic and basic sul-
decomposed at the later stage of cooking process, the fur-containing compounds to form salts, have been cited
formed elemental sulfur can combine with hydrogen for reducing sulfur content [180].
sulfide to produce polysulfide, which still leads to 2–3% The produced Kraft lignin mainly consists of guaia-
sulfur content in the Kraft lignin [178]. For example, cyl- and syringyl-type units, and also contains consider-
organic sulfur-containing species in Kraft lignin are pre- able amounts of phenolic hydroxyl due to the extensive
sented in forms of free sulfur, sulfides, sulfites, sulfones, cleavage of β-O-4 linkage during pulping process [185,
sulfates, disulfides, polysulfides, thiols, etc. [179, 180]. 186]. Therefore, massive studies have used Kraft lignin as
Han et al. investigated the evolution of sulfur-containing pyrolytic subject to produce abundant phenolic products
compounds during Kraft lignin pyrolysis [181]. During in recent years. Zhang et al. investigated the pyrolytic
pyrolysis process, the formed sulfur-containing com- behaviors of synthetic Kraft lignin by TG–FTIR (thermo-
pounds in pyrolytic products can be presented in forms gravimetric–Fourier transform infrared spectrometry)
of ­H2S, ­SO2, ­CH3SH, ­CH3SCH3, and ­CH3SSCH3. On the and Py-GC/MS techniques, and the resulted volatiles
other hand, the role of inorganic sulfur compounds in include ­H2O, ­CO2, CO, alkyls, carbonyls, alkenes, and
the pyrolysis of Kraft lignin was reported by Dondi et al. aromatics (where guaiacol is the main component) [187].
that the presence of sulfates as oxidizers can increase the Fan et al. studied the pyrolysis process of a commercial
amount of ­CO2 formed at high pyrolytic temperatures Kraft lignin, and the maximum oil yield can be obtained
(> 200 °C), higher than the theoretical value of C ­ O2 pro- at 550–600 °C. The further increase of pyrolytic tempera-
duction from carboxyl groups in lignin [182]. However, ture would cause a significant increase in gas produc-
the remaining sulfur content in Kraft lignin is disadvan- tion, while have no obvious effect on char generation.
tageous for its application on pyrolysis due to the acid- Among phenolic products, S-type phenols occupy the
ity of generated oils and air pollution during pyrolysis main proportion (i.e., ~ 70%) from 400 to 700 °C. Besides,

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 Table 1 Structures, isolations, and/or treatments of Kraft lignin, organosolv lignin, and alkali lignin, and their pyrolytic behaviors
Raw material Isolation Treatment Lignin Lignin properties Pyrolysis Pyrolytic property Refs.
temperature
Yield Major compositions
in oils

Commercial Kraft N/A N/A KL G/S-type lignin with C = 62.45%, RT-400–700 °Ca 400 °Ca—gas/oil/ 400–700 °Cb (S-type [188]
lignin (KL) H = 5.28%, N = 0.27%, O = 31.01%, char (10/21/69%); phenols from 58 to 72%,
S = 0.16%, ash = 0.83, H/Ceff = 0.63 500 °Ca—gas/oil/ G-type phenols from 18
char (19/33/48%); to 22%)
600 °Ca—gas/oil/
char (24/34/43%);
700 °Ca—gas/oil/char
(33/29/38%)
Norway spruce LignoBoost process N/A KL (Ligno- G-type lignin with HHV (dry RT-500 °Cc 500 °Cc—char (36%) 500 °Cc (guaiacols, cat- [116]
(Picea abies) boost™ lignin) ash free) = 27.1 MJ/kg, HHV echols, alkylphenols)
(moist) = 18.2 MJ/kg, C = 65.1%,
Lu and Gu Biotechnology for Biofuels and Bioproducts

H = 5.8%, N = 0.1%, O = 26.1%,

S = 2.5%
Black liquor of euca- Acid precipitation Thermal treatment Thermal-treated KL-200 °C (90 s) (exp.): G/H/S- RT-550 °Cc 550 °Cd—char 225 °Cc (methoxycat- [189]
lypt Kraft pulping (175, 200, 225 °C for KL type lignin with C = 66.30%, (~ 10%) echol syringol, 4-methyl-
30, 90, 150 s) H = 5.63%, N = 0.11%, O = 26.07%, syringol)
S = 1.70%, HHV = 26.52 MJ/kg,
(2022) 15:106

soluble lignin = 5.97%, insoluble

lignin = 91.41%, sugars = 0.80%,
ash = 1.56%
Black liquor of pop- Acid precipitation Fractionation by KL and F1 KL/F1/F2/F3/F4: G/H/S-type lignin RT-500, 650, 750 °Cd—char: KL 500 °Cc: KL, F1, F2, F3 [154]
lar Kraft pulping ultrafiltration (54.3%), F2 with Mn = 584/1141/703/484 g/ 800 °Cc (35.1%), F1 (33.8%), F2 (syringol, 4-methylguai-
(25.9%), F3 mol, Mw = 1507/2640/1119/700 g/ (25.3%), F3 (31.8%) acol, guaiacol); 650 °Cc:
(15.4%), F4 mol, Ðe = 2.58/2.31/1.59/1.44, KL (syringol, 4-methyl-
(4.4%) fraction- acid-insoluble lignin (AIL) = 76.6 guaiacol, guaiacol), F1
ated in series 8/78.41/77.62/75.35/76.56%, acid (4-methylguaiacol, guai-
by membranes soluble lignin (ASL) = 5.19/5.31/ acol, 4-vinylguaiacol),
with 10, 5, 1 kDa 7.09/7.13/6.97%, total carbohy- F2 (syringol, guaiacol,
drates = 4.99/8.11/3.69/0.07/0%, phenol), F3 (syringol,
ash = 0.95/1.84/1.19/1.07/1.09% guaiacol, 4-vinylguai-
acol); 800 °Cc: KL (phenol,
syringol, toluene), F1
(phenol, 4-methylphenol,
2,4-dimethylphenol),
F2 (syringol, guaiacol,
4-vinylguaiacol), F3
(phenol, syringol, 4-vinyl-
guaiacol)

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Page 12 of 43
 Table 1 (continued)
Raw material Isolation Treatment Lignin Lignin properties Pyrolysis Pyrolytic property Refs.
temperature
Yield Major compositions
in oils

Black liquor of euca- Acid precipitation Fractionation by KL and F1 KL/F1/F2/F3: G/S-type lignin with RT-400, 500, 600 °Cf 600 °Cd—char: KL 400 °Cb, g: KL, F1, F2, F3 [135]
lypt Kraft pulping organic solvents (59.65%), F2 Mn = 2033/2872/1611/620 g/mol, (40.61%), F1 (38.88%), (G-/S-type phenols);
(28.70%), Mw = 4664/6158/2397/814 g/ F2 (33.32%), F3 500 °Cb, g: KL, F1, F2, F3
F3 (10.93%) mol, Ðe = 2.29/2.14/1.49/1.32, (18.37%) (G-/S-type phenols);
fractionated C = 61.30/61.01/62.26/62.49%, 600 °Cb, g: KL, F1, F2, F3
in series using H = 5.56/5.59/5.80/5.92%; (G-/S-/H-type phenols)
ethyl acetate N = 0.19/0.28/0.01/0.00%,
(F1), acetate/ O = 30.81/30.86/29.92/29.91%,
petroleum ether S = 2.14/2.26/2.01/1.68%, O/C
(F2), petroleum (mol/mol) = 0.38/0.38/0.36/0.36,
ether (F3) H/C (mol/
mol) = 1.09/1.10/1.12/1.14, HHV =
Lu and Gu Biotechnology for Biofuels and Bioproducts

24.86/24.80/25.55/25.73 kJ/kg, S/G

(unit ratio) = 2.44/2.12/2.32/2.49,
β-O-4 = 3.7/12.6/2.8/0%,
β–β = 1.2/2.2/0.9/0.3%,
β-5 = 5.4/5.5/4.8/4.2%, aliphatic
OH = 1.06/1.47/0.84/0.29 mm
(2022) 15:106

ol/g, total phenolic OH = 3.81/

2.51/3.49/4.81 mmol/g, COOH
= 0.54/0.49/0.52/0.73 mmol/g,
condensed phenolic OH = 0.48/
0.35/0.54/0.81 mmol/g, meth-
oxy = 6.86/6.11/6.59/7.19 mmol/g
Black liquor of pop- Acid precipitation Fractionation by KL (extracted KL: G/S/H-type lignin with RT-500, 650, 750 °Cd—char: KL 500 °Cc: KL, ­LpH6, ­LpH4 [190]
lar Kraft pulping gradient acid pre- under pH = 2) Mn = 821/1057/703/462 g/mol, 800 °Cc (35.1%), ­LpH6 (38.4%), (syringol, 4-methylguai-
cipitation and ­LpH6 Mw = 2118/2399/1057/712 g/ ­LpH4 (29.1%), ­LpH2 acol, guaiacol), ­LpH2:
(52.5%), ­LpH4 mol, Ðe = 2.58/2.27/1.73/1.54, (26.8%) (syringol, 4-ethylguaiacol,
(29.7%), ­LpH2 C = 52.89/60.31/60.27/48.42%, guaiacol); 650 °Cc: KL
(17.8%) fraction- H = 4.85/5.28/5.28/3.86%, (syringol, 4-methylguai-
ated in series N = 0.15/0.16/0.30/0.22%, acol, guaiacol), ­LpH6,
under pH = 6, O = 29.51/32.57/32.13/23.61%, ­LpH2 (syringol, 4-ethyl-
4, 2 S = 12.60/1.76/2.02/23.89% guaiacol, guaiacol), ­LpH4
(3-methoxycatechol,
syringol, 4-methylguai-
acol); 800 °Cc: KL (phenol,
syringol, toluene),
­LpH6 (acetosyringone,
3-methoxycatechol,

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phenol), ­LpH4 (syringol,
4-ethylguaiacol, 4-meth-
ylguaiacol), ­LpH2 (syringol,
phenol, guaiacol)
Page 13 of 43
 Table 1 (continued)
Raw material Isolation Treatment Lignin Lignin properties Pyrolysis Pyrolytic property Refs.
temperature
Yield Major compositions
in oils

Commercial alkali N/A N/A AL G/H/S-type lignin with C = 55.3%, RT-400, 450, 500 600 °C–chard (39.0%); 400–800 °Cb (phenol, [221]
lignin (AL) H = 5.3%, N = 0.1%, O = 35.2%, 550, 600, 650, 700, 800 °C—chard 2-methylphenol, 4-meth-
Lu and Gu Biotechnology for Biofuels and Bioproducts

S = 1.3%, HHV = 20.62 MJ/kg, 750, 800 °Ca (40.8%); 400– ylphenol, 4-ethylphenol)
volatiles = 62.3%, fixed car- 800 °Ca—gas/oil/char
bon = 34.9%, ash = 2.8% (15/25/65%)
Commercial alkali N/A N/A AL G/H/S-type lignin with C = 60.00%, RT-300, 350, 400, 300 °Ca—gas/oil/solid 300, 350, 400, 450 °Cb [204]
lignin H = 7.18%, N = 0.00%, O = 29.90%, 450 °Ca (11.8/26.2/62.0%); (guaiacols, alkyl phenols,
S = 2.92%, HHV = 20.62 MJ/kg, 350 °Ca—gas/oil/solid catechols)
(2022) 15:106

moisture = 6.2%, volatiles = 88.0%, (12.7/32.3/55.0%);

fixed carbon = 9.4%, ash = 2.6% 400 °Ca—gas/oil/solid
(16.5/33.5/50.0%);
450 °Ca—gas/oil/solid
(20.9/34.1/45.0%)
Commercial alkali N/A N/A AL G/H/S-type lignin 40–900 °Cc, i 900 °Cd—char 300, 500, 900 °Cc [222]
lignin (~ 50%) (2-methoxy-phenol)
Commercial alkali N/A N/A AL G/H-type lignin with aliphatic OH/ RT-400, 500, N/A 400 °Cb (no obvious [39]
lignin COOH/phenolic OH/total OH/H 600 °Cc response); 500, 600 °Cb
(unit)/G (unit) = 2.36/0.38/3.35/6.0 (2-methoxyl-4-methyl-
9/0.27/3.08 mmol/g phenol, acetaldehyde,
2-methoxyl-4-vinylphe-
nol, 2-methoxyl-phenol)

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Page 14 of 43
 Table 1 (continued)
Raw material Isolation Treatment Lignin Lignin properties Pyrolysis Pyrolytic property Refs.
temperature
Yield Major compositions
in oils

Black liquor (BL) Acid precipitation Fractionation by AL, AL, AL-10/5/1 kDa: RT-400, 600, 1000 °Cd—char: AL 400 °Cb: AL, AL-10 kDa [205]
ultrafiltration AL-10/5/1 kDa G/H-type lignin with 800 °Ch (43.06%), AL-10 kDa (guaiacol, 4-methylguai-
Mn = 3284/6076/4045/2616 g/mol, (38.42%), AL-5 kDa acol, 4-ethylguaiacol),
Mw = 7423/12,060/6752/3864 g/ (39.27%), AL-1 kDa AL-5 kDa, AL-1 kDa
mol, Ðe = 2.260/1.985/1.669/1.478, (36.34%) (guaiacol, phenol,
G-type OH = 0.90/1.07/0.86/0.77 4-methylguaiacol);
mmol/g, H-type OH = 0.22/0.15 600 °Cb: AL, AL-10 kDa,
/0.17/0.30 mmol/g, aliphatic OH AL-5 kDa (guaiacol,
= 1.23/1.47/1.06/1.05 mmol/g, phenol, 4-methyl-
condensed phenolic OH = 1.21/1. guaiacol), AL-1 kDa
Lu and Gu Biotechnology for Biofuels and Bioproducts

74/1.17/1.00 mmol/g, COOH = 1.0 (phenol, 4-methylphenol,

2/1.19/0.74/0.76 mmol/g 3-ethylphenol); 800 °Cb:
AL, AL-10 kDa, AL-5 kDa
(phenol, indene,
naphthalene), AL-1 kDa
(1-ethenyl-2-methyl-ben-
zene, indene, naphtha-
(2022) 15:106

lene), (39.27%)
Corncob residue Organosolv method N/A Organosolv G/S/H-type lignin with RT-800 °Ca 350 °Ca—gas/oil/char 350 °Cb (4-vinylphenol, [223]
(tetrahydrofuran) lignin (OL) Mn = 1238 g/mol, Mw = 3203 g/ (31.5/16.3/52.2%); 4-vinylguaiacol, syringol)
mol, Ðe = 2.59 800 °C—chard
(36.02%)
Pine, poplar, bam- Organosolv method N/A PiL (29.3%), PoL PiL: G/H-type lignin with RT-800 °Ca 800 °Cd—char: 400–600 °Cb: PiL (guai- [110]
boo (dioxane) (35.2%), BaL Mn = 2580 g/mol, Mw = 9940 g/ PiL (39.33%), PoL acol), PoL (phenol), BaL
(48.9%) mol, Ðe = 3.85, β-O-4 (A) = 46.02%, (30.19%), BaL (20.71%) (4-vinylphenol)
phenylcoumarans (B) = 8.63%,
resinol (C) = 5.78%, cinnamyl
alcohol end groups (I) = 6.72%,
S/G/H (unit) = 0/99.35/0.65%;
PoL/BaL: G/S/H-type lignin
with Mn = 3540/3420 g/
mol, Mw = 13,240/8840 g/
mol, Ðe = 3.74/2.58, β-O-4
(A) = 56.31/59.52%, phenylcou-
marans (B) = 7.13/5.68%, resinol
(C) = 13.56/4.16%, cinnamyl

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alcohol end groups (I) = 0/0%,
S/G/H (unit) = 69.00/30.62/0.38%
(60.97/35.79/3.24%)
Page 15 of 43
 Table 1 (continued)
Raw material Isolation Treatment Lignin Lignin properties Pyrolysis Pyrolytic property Refs.
temperature
Yield Major compositions
in oils

Sugarcane bagasse Organosolv method N/A BG-Lignin G/S/H-type lignin with G/S/H (unit RT-400, 500, 600, 800 °Cd—char (29%) 400 °Cc (2,6-dimethoxy- [216]
Lu and Gu Biotechnology for Biofuels and Bioproducts

(BG) (ethanol) ratio) = 0.82/0.02/0.16; mois- 700 °Cc phenol); 500 °C–600 °Cc
ture = 3.78%, volatiles = 67.34%, (2,6-dimethoxy-4-(2-
fixed carbon = 28.80%, propenyl)-phenol);
ash = 0.09%, phenolic OH/ali- 700 °Cc (4-ethyl-phenol)
phatic OH = 0.79
Willow biomass Organosolv method N/A L-EAC (83.8%), L-EAC/L-THF/L-GBL: G-type lignin RT-500 °Ca 500 °Ca—gas/ 500 °Cb: L-EAC, L-THF [220]
(2022) 15:106

(ethyl acetate-EAC/ THF (92.3%), with C = 65.00/66.25/66.88%, oil/char: L-EAC (guaiacol, 4-methylguai-
tetrahydrofuran- GBL (72.6%) H = 6.26/6.03/6.32%, (22.15/34.53/43.32%), acol), L-GBL (4-methyl-
THF/γ- N = 0.22/0.30/0.21%, L-THF guaiacol)
butyrolactone-GBL) O = 28.09/27.00/26.61%, (20.97/35.21/43.83%),
ash = 0.44/0.12/0%, mois- L-GBL
ture = 4.5/4.0/4.5% (21.70/33.55/44.75%)
a
A fixed bed
b
GC/MS and/or GC/FID (gas chromatograph/flame ionization detection)
c
Py-GC/MS
d
TG-DTG
e
Dispersity
f
U-type tube pyrolysis device
g
In situ FTIR spectroscopy
h
Tube furnace
i
TG–MS (thermogravimetry–mass spectrometry)

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Page 16 of 43
Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 17 of 43

the proposed radical-mediated reaction processes dur- changes of lignin structure and significant influences on
ing pyrolysis was proposed including lignin homolysis at lignin pyrolysis via reducing activation energy [196].
400–450/450–600 °C (to form active lignin radicals, such For figuring out the influence of ­Na+ species on lignin
as phenolics), and radicals recombination at 600–700 °C pyrolysis, Dalluge et al. investigated the effect of Na treat-
(to generate some low-molecular-weight gases and char/ ment on lignin char and volatiles formations during fast
coke) [188]. Thermal treatment was performed to treat pyrolysis, suggesting that the Na treated lignin exhibits
Kraft lignin before pyrolysis via Demuner et al. to inves- the increasing yields of char (due to the catalytic effect
tigate the pyrolytic behaviors of thermally treated lignin. derived from Na species [197]), the enhanced gasifica-
Results show that the thermal treatment promotes dem- tion of lignin [198] and the highest selectivity to aromatic
ethylation and demethoxylation [189]. On the other volatiles from lignin pyrolysis compared to other alkali
hand, various fractionations (e.g., fractionations via orga- metals (e.g., Li, K, Cs) [199]. According to the above stud-
nosolv method [135], ultrafiltration [154], and gradient ies, Na species bonded with organic phase (e.g., –ONa+
acid precipitation [190]) were used for the treatment of and –COONa+) is a key factor for enhancing the conver-
Kraft lignin. For example, Chen et al. fractionated Kraft sion of alkali lignin. Guo et al. investigated the effect of
lignin into different lignin fractions (F1, F2, and F3) and Na groups on the production of lignin pyrolysis products
further investigated their pyrolysis characteristics [135]. [198]. The effect of different Na chemical forms (includ-
Results show that lignin fractions with different molecu- ing organic/inorganic bonding Na groups, Or-/Inor-Na)
lar weight distributions, linkages type, functional groups on the condensable product composition is obtained
content, and S/G ratio can be obtained, where lignin with that both two chemical forms of Na have the signifi-
more methoxy contains the stronger cracking of β aryl cant catalytic effect on phenolic hydroxyls removing to
ether bonds [191]. Thermal stability of lignin shows that enhance the yield of benzenes (e.g., methoxybenzene,
the smaller molecular weight, the faster maximum deg- 1,2-dimethoxy-benzene, and 1,2,3-trimethoxy-benzene),
radation rate, and the less char residue generated, which and also have a positive effect on cracking alkyl substit-
indicate that lower molecular weight leads to worse ther- uents. The corresponding mechanism can be proposed
mal stability with lower activation energy. Lower tem- that the β-O-4 linkage in lignin can be cleaved easily at
peratures are disadvantageous for monomers production low temperatures to generate alkyl guaiacols, of which
while good for oils generation, and the opposite trend the alkyl groups would be further eliminated by Or-Na,
can be obtained at higher temperatures. Ultrafiltration and Inor-Na is beneficial for removing phenolic hydroxyl
fractionation also influences the distribution of molecu- to generate benzenes. Therefore, the quality of lignin
lar weight of Kraft lignin, where the high-molecular- oils obtained from pyrolysis process can be improved
weight lignin fraction favors the generation of G-type significantly via effective oxygen elimination [200, 201].
compounds, and the low-molecular-weight one prefers For the generation of light gases, both two Na chemi-
S-type compounds. Temperature rising would cause the cal forms reduce the cracking of ether bond and meth-
cleavage of methoxy of G- and S-type compounds to pro- oxy to form CO and ­CH4, respectively. For condensed
duce H-type ones [154]. Similarly, the lignin fractiona- phase, char conversion with temperature indicates that
tion via gradient acid precipitation also affects molecular both two Na chemical forms benefit gasification reaction
weight, which has an obvious effect on relative content of due to their significant catalytic effects [202]. For Or-Na
formed products from lignin pyrolysis [190]. loaded char, char conversion rate is mainly influenced by
the relative distribution of Na on char surface. At lower
Alkali lignin
temperatures, the strong bonding strength of O–Na link-
Alkali lignin is a byproduct obtained from paper indus- ages inhibits the migration of Na element to the porous
try, which is produced by alkaline pulping procedure for surface of char, leading to low catalytic activity. At higher
separating lignin from the alkali lignin waste containing temperatures, O–Na bonding strength becomes weaker,
cellulose and lignin using NaOH and ­Na2S, which con- which is beneficial for Na adsorbing on char surface
tains a large distribution of molecular weight [192, 193]. for enhancing catalytic activity [203]. For Inor-Na (i.e.,
During cooking process, NaOH is commonly used as the NaCl) loaded char, the retention of ­Cl− greatly affects
chemical reagent to separate and degrade lignin frac- the catalytic activity of ­Na+ on char conversion. Besides,
tion, wherein the cleavage of phenolic α-O-4, and non- with increasing temperature, N ­ a+ tends to combine with
phenolic/phenolic β-O-4 linkages, and the combination ­CO2 (which is formed from lignin pyrolysis) to generate
of ­Na+ and phenolic hydroxyl/carboxyl via chemical ­Na2CO3, which significantly deteriorates the catalytic
bonding to form phenolic-Na+ and carboxyl-Na+ groups activity [203].
happen simultaneously [194, 195], leading to obvious Expect for ­Na+ species, other parameters, like tem-
perature, reaction time, and molecular weight, also have

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 Table 2 Structures and isolations of DES lignin, and corresponding pyrolytic behaviors
Raw material DES synthesis Isolation Lignin Lignin properties Pyrolysis Pyrolytic property Refs.
temperature
Yield Major
compositions in
oils

Populus deltoides DESs: ChCl coupled Lignin regener- Lyophilized ChU-115/ChI-115/ChI-150: G/S-type lignin RT-650 °Ca 600 °Cb—char 650 °Ca: ChI-115, [240]
with urea and imi- ated and purified lignin labeled with Mw = 2562–1544 g/mol, Ðe ≤ 1.60, (ChI-115 > ChI- ChI-150, ChU-115
dazole with molar from pretreated as ChU-115 ASL = 7.23/8.18/3.5%, AIL = 19.2/18.9/8.5%, 150 > ChU-115) (phenol)
ratio of 1:2 and 3:7, Populus by DESs (26.4%), ChI- total carbohydrates = 5.26/3.76/1.65%,
followed by heat- (115/150 °C, 15 h) 115 (27.0%), aliphatic OH = 3.61/3.65/3.60 mmol/g, total
ing at 60 °C until via ethanol/water ChI-150 (12.1%) phenolic OH = 1.18/0.94/1.28 mmol/g,
a homogeneous (1:9, v:v) COOH = 1.18/0.94/1.28 mmol/g,
liquid formed β-O-4 = 50.3/48.3/46.9%,
β–β = 10.9/13.7/6.4%, β-5 = 5.5/2.5/2.8%,
S/G = 1.38/1.42/2.27
Lu and Gu Biotechnology for Biofuels and Bioproducts

Oil palm empty fruit DESs: choline chlo- Lignin isolated and DES-extracted LA/CC-LA (1:1)/CC-LA (1:15)/CC-FA- RT-650 °Ca 900 °Cb—char 650 °Ca: LA, CC-LA [241]
bunch (EFB) ride/lactic acid (CC- purified from pre- lignin (DEEL) Lignin: G/S/H-type lignin with lignin (CC-FA > CC-LA (1:1), CC-LA (1:15),
LA) with molar ratio treated EFB using by LA/CC-LA content = 75.15/78.89/80.64.85.84%, 1:15 > CC-LA CC-FA (phenol)
of 1:1 and 1:15, and DESs (120 °C, 8 h) (1:1)/CC-LA glucan = 1.42/1.94/0.00/1.39%, 1:1 > LA)
choline chloride/ via ethanol/water (1:15)/CC-FA xylan = 5.94/0.62/1.02/0.00%,
formic acid (CC-FA) (1:2, v:v) C = 52.87/52.50/53.89/47.86%,
(2022) 15:106

with molar ratio of H = 5.78/5.39/5.17/5.44%,

1:2, heated at 80 °C N = 0.00/1.36/0.77/2.48%,
until homogeneous O = 41.98/40.00/38.80/42.83%,
phase S = 0.49/0.75/1.37/1.40%, G (unit) = 13.97/
29.79/49.91/35.65%, S (unit) = 83.85/64.78/
50.09/62.01%, H (unit) = 2.18/5.43/0/2.34%,
methoxy = 14.16/10.32/29.04/25.95%
Commercial soft- DESs: ChCl/EG (CE), Lignin treated by CEL, ZEL, CAL CAL/CEL/ZEL: G/H-type lignin RT-550 °Ca 900 °Ca-gas/oil/ 550 °Ca: CEL (phe- [229]
wood lignin (SL) ­ZnCl2/EG (ZE), ChCl/ DESs at 120 °C for with C = 63.05/63.11/62.95%, char: CEL, ZEL, CAL nol, p-cresol, guai-
Aa (CA) with the 2 h and collected by H = 5.85/6.15/6.02%, N = 0.13/0.13/0.13%, (15/35/50%) acol, creosol), ZEL
same molar ratio of acid precipitation O = 30.04/29.48/29.93%, (creosol, catechol,
1:2 at 60 °C S = 0.49/0.75/1.37/1.40, guaiacol), CAL
HHV = 25.76/26.22/25.94 MJ/ (guaiacol, creosol,
kg, H/Ceff = 0.38/0.45/0.42, catechol, toluene)
Mw = 2650/2574/2529 g/mol,
Mn = 1233/1238/1204 g/mol,
Ðe = 2.15/2.08/2.10, β-O-4 = 2.9/1.7/0.3,
β–β = 2.3/2.2/2.4, β-5 = 4.0/3.9/4.1, G-type
OH = 2.23/2.16/2.05 mmol/g, C-type
OH = 0.29/0.26/0.40 mmol/g, H-type

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OH = 0.06/0.11/0.05 mmol/g, condensed
G-type OH = 2.15/2.12/2.14 mmol/g,
aliphatic OH = 0.85/1.07/1.10 mmol/g,
COOH = 0.65/0.54/0.46 mmol/g, meth-
oxy = 4.02/3.76/3.45 mmol/g
Page 18 of 43
 Table 2 (continued)
Raw material DES synthesis Isolation Lignin Lignin properties Pyrolysis Pyrolytic property Refs.
Lu and Gu Biotechnology for Biofuels and Bioproducts

temperature
Yield Major
compositions in
oils

Eucalyptus tenui- DESs: choline Raw material A2, A4, A6, F2, A2/A4/A6/F2/F4/F6: G/S-type lignin with RT-800 °Cc 800 °Cb—char: 200–600 °Cc: [236]
folia chloride/formic extracted by F4, F6 F4 > A4 products rich in
(2022) 15:106

glucan = 5.69/3.34/12.17/0/1.12/0.23%, xyl

acid (FDES) and toluene/ethanol an = 9.25/8.86/13.29/8.11/4.96/4.98%, gal aromatic struc-
choline chloride/ (2:1, v:v) for 6–8 h, actan = 1.34/1.33/1.86/3.64/1.64/1.50%, tures, of which the
lactic acid (ADES) followed by DESs C = 58.85/58.24/58.79/60.24/59.86/60.84 functional groups
with the same treatment at 110 °C %, H = 5.72/5.75/5.60/5.70/5.94/5.75%, N = are temperature-
molar ratio of 1:10, for 2, 4, 6 h, and 0.28/0.35/0.21/0.95/1.66/1.02%, O = 34.28 induced to form
heated at 60–80 °C lignin isolated and /35.33/35.18/29.86/29.50/30.59%, meth- light gases, ­H2O,
until homogeneous purified by acetone/ oxy = 23.15/22.86/21.57/23.25/23.50/22.50% ­CO2 CO, and ­CH4
phase water (7:3, v:v)
a
Py-GC/MS
b
TG-DTG
c
TG-FTIR

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Page 19 of 43
 Table 3 Structures and isolations of biological lignin, and corresponding pyrolytic behaviors
Raw material Enzyme Isolation Lignin Lignin properties Pyrolysis Pyrolytic property Refs.
temperature
Yield Major
compositions in
oils

Softwood (Fir), Industrial cellulase Enzymatic treat- Softwood/hard- Softwood EMAL lignin: G/H-type RT-300, 400, 500, 800 °Cb—char: 300 °Cb: softwood [126]
hardwood (Euca- (CMCase) ment (hydrolysis) wood/non-wood lignin with G (unit) = 91.2%, H 600 °Ca ~ 30% EMAL lignin
lyptus), non-wood of biomass using EMAL lignin (> 50%) (unit) = 2.8%, β-O-4 = 56.1%, α-O-4 (coniferyl alcohol,
(moso-bamboo) CMCase at 40 °C and β-5 = 19.0%, β–β = 5.3%, sinapyl alcohol);
for 48 h, followed β-1 = 2.9% 400 °Cb: hard-
by lignin collection Hardwood/non-wood EMAL wood EMAL lignin
via centrifugation lignin: G/S/H-type lignin (coniferyl alcohol,
and purification via with G (unit) = 24.7/36.1%, S sinapyl alcohol);
mild acidolysis in (unit) = 54.6/42.9%, H (unit) 400 °Cb: non-
dioxane/acidified 1.5/21.0%, β-O-4 = 36.3/38.7%, wood EMAL lignin
Lu and Gu Biotechnology for Biofuels and Bioproducts

water (0.01 mol/L α-O-4 and β-5 = 4.4/5.2%, (4-vinylphenol,

HCl, 85:15, v:v) at β–β = 9.6/6.0%, β-1 = 2.0/0% 4-vinylguaiacol,
87 °C 4-vinylsringol)
Ginkgo, poplar White-rot fungus Lignin isolated Ginkgo lignin- Ginkgo lignin-laccase, pop- RT-400, 600, 800 °Cc 600 °C (exp.)c—gas/ 600 °C (exp.)c: [249]
Physisporinus vitreus from biomass using laccase, poplar lar lignin-laccase: G/H-type oil/char: Ginkgo Ginkgo lignin-
Björkman method lignin-laccase lignin with acid soluble lignin lignin-laccase laccase (2-meth-
(2022) 15:106

and modified by (ASL) = 0.32/0.29%, Klason (13.8/14.5/43.3%), oxy-phenol,

white-rot fungus at lignin = 97.26/97.05%, car- poplar lignin- vanillin2-methoxy-
30 °C and 150 rpm bohydrates = 1.18/1.32%, laccase 4-methyl-phenol),
for 48 h ash = 0.38/0.41%, (15.5/11.4/40.7%) poplar lignin-lac-
C = 59.98/58.89%, H = 6.01/5.57%, case (2,6-dimeth-
N = 0.43/0.15%, O = 33.32/35.21%, oxy-phenol,
S = 0.26/0.18%, O/C (molar 2-methoxy-phenol,
ratio) = 0.42/0.45, H/C (molar isoeugenol)
ratio) = 1.20/1.13, meth-
oxy = 11.17/15.68%
Four technical Lignin peroxidase Lignin treated SE-Lignin, SAQ- SE-Lignin, SAQ-Lignin, RT-550 °Cd 550 °Cd—gas/oil/ 550 °Ce: SE-Lignin, [255, 256]
lignin [sugarcane (LiP), quinone by LiP and OR in Lignin, NaE-Lignin, NaE-Lignin, NaPE-Lignin: char: SE-E-Lignin SAQ-Lignin, NaE-
bagasse steam reductase (OR) sodium tartrate NaPE-Lignin G/S/H-type lignin with (8.8/47.4/43.8%), Lignin (phenol),
explosion (SE), buffer (pH 3.0) at Mw = 10,126/6087/10,833/9023 g/ SAQ-E-Lignin NaPE-Lignin
sugarcane bagasse 25 °C for 24 h mol, Mn = 800/1112/3165/4351 g/ (22.0/40.6/37.3%), (guaiacol)
soda-anthraqui- mol, Ðe = 12.7/5.5/3.4/2.1 NaE-E-Lignin
none (SAQ), sodium (21.2/27.5/51.3%),
lignosulfonate NaPE-E-Lignin
from eucalyptus (36.4/19.8/43.8%)
(NaE) and sodium
lignosulfonate from

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a mixture of euca-
lyptus and pine
wood (NaPE)]
Page 20 of 43
 Table 3 (continued)
Raw material Enzyme Isolation Lignin Lignin properties Pyrolysis Pyrolytic property Refs.
Lu and Gu Biotechnology for Biofuels and Bioproducts

temperature
Yield Major
compositions in
oils

Bamboo White-rot fungus Enzymatic hydroly- Lignin from enzy- G/S-type lignin with G/S (unit RT-600 °Ca 1100 ­Kf-char: 31.64, 600 °Ca: 2,3-dihy- [257]
Echinodontium sis performed in matic treated EHRL 32.18, 33.04% at 40, drobenzofuran,
(2022) 15:106

ratio) = 0.49, and with the decreas-

taxodii sodium acetate (86.4%) ing content of β-O-4 structure 20, 10 K/min syringol, vanillic
buffer (pH = 4.8) at acid
48 °C for 3 days, and
lignin isolated by
centrifugation
a
Py-GC/MS
b
GC-FID
c
A fixed bed reactor
d
A stainless steel tubular reactor
e
GC/MS
f
TG/DTG

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Page 21 of 43
 Table 4 Structures and isolations/treatments of ionic liquid lignin, and corresponding pyrolytic behaviors
Raw material Ionic liquid Isolation/ Lignin Lignin properties Pyrolysis Pyrolytic property Refs.
treatments temperature
Yield Major
compositions in
oils

Empty fruit bunches Pyridinium formate Biomass pretreated EFB lignin, PMF EFB lignin, PMF lignin, 50–550 °Ca 800 °C (10 °C/ 550 °Ca: EFB lignin [271, 274]
Lu and Gu Biotechnology for Biofuels and Bioproducts

(EFB), palm meso- [PyFor] by [PyFor], and lignin lignin, PKS lignin PKS lignin: with min)b—char (exp.): (cyclotetradecane,
carp fiber (PMF) and regenerated via dis- C = 42.02/42.95/45.59%, EFB lignin (3.87%), naphthalene,
palm kernel shells solving in acetone/ H = 6.48/5.70/6.21%, PMF lignin (5.79%), 4-t-butylcyclohex-
(PKS) water followed by N = 5.74/6.56/7.02%, PKS lignin (9.25%) anone), PMF lignin
acetone evaporation O = 44.59/44.63/40.90%, (naphthalene,
S = 0.18/0.16/0.28%, 4-t-butylcyclohex-
acid insoluble anone, phenol),
(2022) 15:106

lignin = 17.82/32.23/45.54%, PKS lignin (phenol,

HHV = 27.05/27.40/28.20 MJ/ 2-methoxy-phenol,
kg 2,4-dimethylphenol)
Sugarcane straw 1-Ethyl-3-methylim- SCS pretreated by Recovered lignin N/A 50–700 °Cc 700 °C—chard: 44% 350 °Cc: phenols, [125]
(SCS) idazolium acetate [Emin][OAc] at 90 °C methanol, formal-
[Emin][OAc] for 5 h, and lignin dehyde
recovered via dis-
solving in acetone/
water followed by
acetone evaporation
Industrial lignin 1-Butyl-3-methylim- Lignin pretreated in BMIC-lignin50, BMIC- N/A RT-300, 400, 500, 300–400 °Ce-liquid 300–500 °Cf: BMIC- [280]
idazolium chloride a microwave appa- lignin100, BMIC- 600, 700, 800°Ce (exp.): BMIC-lignin50 lignin50, BMIC-
(BMIC) ratus using BMIC at lignin150 (~ 0.150 g/glignin), lignin100, BMIC-
50, 100, 150 °C for BMIC-lignin100 lignin150 (phenolics,
30 min and precipi- (~ 0.125 g/glignin), arenes, alkanes)
tated using water BMIC-lignin150
(~ 0.125 g/glignin)

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Page 22 of 43
 Table 4 (continued)

Raw material Ionic liquid Isolation/ Lignin Lignin properties Pyrolysis Pyrolytic property Refs.
treatments temperature
Yield Major
compositions in
oils
Lu and Gu Biotechnology for Biofuels and Bioproducts

Industrial lignin 1-Sulfonic acid Lignin pretreated Lignin-50, Industrial lignin: ash = 3.77%, RT-300, 400, 500, 300–400 °Ce—tar 300–500 °Cf: [279]
butyl-3-methylimi- in a microwave lignin-100, volatiles = 56.73%, 600, 800°Ce (exp.): Lignin-50 Lignin-50,
dazolium trifluo- apparatus using lignin-150, C = 66.22%, H = 6.30%, (0.1889 g/ lignin-100,
romethanesulfonate [B(SO3H)min]-OTf at lignin-200 O = 25.58%, N = 1.09%, glignin) lignin-100 lignin-150,
[B(SO3H)min]-OTf 50, 100, 150, 200 °C S = 0.81% (0.1231 g/ lignin-200 (phenol,
for 1 h under N­ 2, glignin) lignin-150 guaiacol, 2-ethyl-
(2022) 15:106

and regenerated by (0.1338 g/ phenol, 4-methox-

washing with water glignin) lignin-200 yguaiacol)
(0.0751 g/glignin)
Industrial lignin 1-Butyl-3-methylimi- Lignin pretreated in Lignin-50, Industrial lignin: mois- RT-300, 400, 500, 300–400 °Ce-liquid 300–500 °Cf: [270]
dazolium dihydro- a microwave reactor lignin-100, ture = 2.6%, ash = 2.5%, 800 °Ce (exp.): Lignin-50 lignin-50, lignin-100,
gen phosphate using ­[Bmin]H2PO4 lignin-150 volatiles = 62.4%, C = 63.9%, (~ 0.15 g/glignin) lignin-150 (pheno-
­[Bmin]H2PO4 at 50, 100, 150 °C for H = 5.6%, O = 28.6%, lignin-100 (~ 0.12 g/ lics, arenes, alkanes)
30 min, and washed N = 1.1%, S = 0.8% glignin) lignin-150
out by water (~ 0.12 g/glignin)
a
Py-GC/MS
b
TG-DTG
c
TG-FTIR
d
TG-DTG
e
A vertical fixed-bed quartz reactor
f
GC/MS

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Page 23 of 43
Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 24 of 43

significant effects on alkali lignin pyrolysis. For example, (hardwood), and corn stalk (herbaceous feedstock), and
the effect of temperature and residence time on thermal bamboo (herbaceous feedstock) via organosolv fractiona-
decomposition reactions during fast pyrolysis of a soft- tion using 96% dioxane as organic solvent, and investi-
wood alkali lignin was investigated by Supriyanto et al. gated the structural effect on phenolic production [158].
and the results show that there is a general increase in Herbaceous-derived lignin shows higher molecular
the yield of organic volatiles (of which the majority is weight and dispersity compared to other lignin obtained
G-type phenols) with the increase of temperature from from softwood and hardwood, suggesting the generation
400 to 600 °C, wherein the cleavage of the lignin poly- of heterogeneous lignin structure [213]. Thermal stability
meric structure to form linear carbonyl (acetaldehyde) is directly related to lignin structure (e.g., the content of
and G-type aromatic compounds is enhanced by increas- methoxy [191]), which indicates that the higher disper-
ing temperature [39]. On the other hand, the promoted sity, the lower yield of char residue, suggesting the worse
effect of residence time (from 0.5 to 5 s) on lignin pyrol- thermal stability [214]. For deeply understanding the cor-
ysis is significant at a lower temperature (i.e., 500 °C), relation between lignin structure and phenolic produc-
while the extension of residence time at a higher temper- tion, lignin pyrolysis was conducted at 500 °C, and the
ature (i.e., 600 °C) would lead to more secondary crack- results show that lignin can be mainly decomposed into
ing reactions to inhibit the further increase of aromatic phenolic compounds, of which the distribution is sig-
volatile compounds generation. Biswas et al. demon- nificantly influenced by different lignin types. The major-
strated that increasing temperature benefits oil produc- ity of 4-vinylphenol (H-type phenol) can be obtained
tion, and the higher temperature prefers to alkyl phenols from the pyrolysis of herbaceous lignin (i.e., from corn
and catechols via demethylation, demethoxylation, and stalk and bamboo) due to the dominant H-type struc-
deoxygenation [204]. Guo et al. investigated the effects ture and abundant β-O-4 linkage in herbaceous lignin
of molecular weight on the pyrolysis products properties after organosolv fractionation, and demethylation and
of alkali lignin, and the results show that the molecular demethoxylation reactions during pyrolysis (to con-
weight of alkali lignin is not significantly influenced on vert G-/S-type phenolic hydroxyls into H-type one via
the temperature and species of products evolution, while reducing the content of methoxy) [110, 215]. Soongpra-
is positively affected on the yields of C­ H4, CO, phenols, sit et al. used sugarcane bagasse (BG) as raw material
aromatic products. The lower molecular weight benefits for lignin separation (i.e., BG-lignin) using organosolv
the cracking of methoxy of lignin to generate C ­ H4, CO, method (95% ethanol) and investigated its phenolic pro-
­CO2, phenol, and alkyl phenol, but the higher molecular duction from fast pyrolysis using Py-GC/MS technique
weight favors the generation of guaiacol and alkyl guai- [216]. With the temperature rising, several interconver-
acol. Besides, the molecular weight of formed aromatic sion reactions are all enhanced, such as (1) S-/G-type
compounds is influenced by both lignin molecular weight phenols converted to H-type ones via demethoxylation
and pyrolysis temperature [205]. reaction of methoxy; (2) H-type phenols converted to
aromatic hydrocarbons via dehydroxylation reaction
Organosolv lignin [217, 218]; (3) monolignol compounds converted to
Due to the low requirement for strong acids or bases, sul- hydrocarbons via dealkylation [127]. On the other hand,
fur absence, simple downstream separation, and solvent temperature rising also makes a significant influence on
recycling, organosolv fractionation using ethanol (the phenolic selectivity via enhancing the cleavage of meth-
most commonly used) [206–209], ethyl acetate [210], oxy and other functional aromatic substituent groups
acetone [211], etc., can be used as an efficient and eco- [219], leading to the generation of oxygenated-alkyl
nomical method to separate lignin from lignocellulosic methoxy phenols (OR-Ph-OCH3), alkyl methoxy phe-
biomass. In organosolv fractionation, cellulose fraction nols (R-Ph-OCH3), methoxy phenols (Ph-OCH3), alkyl
can be remained in solid phase, and removed via filtra- phenols (R-Ph), and phenols (Ph), where (1) the oxygen
tion. Lignin fraction can be separated via precipitation elimination from OR-Ph-OCH3 at ­C4 positon via deoxy-
(e.g., by adding excessive water in the obtained previous genation would form R-Ph-OCH3 and Ph-OCH3; (2) the
liquid containing hemicellulose and lignin fractions) and cleavage of methoxy from Ph-OCH3 via demethoxylation
collected by centrifugation/filtration, which contains bet- would generate Ph and/or R-Ph (especially at high tem-
ter solubility (in many organic solvents) and higher purity peratures due to the high BDE of methoxy); and (3) the
with lower structural modification compared to those of gasification of Ph via secondary cracking would produce
lignin obtained Kraft and soda processes [212]. hydrocarbons or other oxygenated volatiles [163]. Wang
Yuan et al. obtained lignin from different lignocellu- et al. investigated the influence of solvent fractionation
losic biomass materials, like pine (softwood), eucalyptus (including ethyl acetate-EAC, tetrahydrofuran-THF, and

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Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 25 of 43

γ-butyrolactone-GBL fractionations) on lignin pyrolysis to untreated lignin, DES-treated samples can produce
[220], finding that different structures of lignin separated more MAHs due to their improved hydrogen to carbon
using different organic solvents via organosolv fractiona- efficient ratio (i.e., H/Ceff) [235]. Furthermore, more phe-
tion (i.e., EAC lignin contains the most oxygen-contain- nolic products containing carbon number between C6
ing functional groups, GBL-lignin has the highest content and C9 can be produced from DES-treated lignin pyroly-
of large-molecule fragments, and THF-lignin possesses sis, suggesting the positive effect of DES treatment on the
the highest Tmax at 398 °C) result in the different pyrolytic generation of monophenols.
behaviors. For example, during pyrolysis, more intense Li et al. extracted lignin with ChCl-formic acid/lactic
cleavage of ­Cα–Cβ linkage can be obtained in GBL-lignin, acid systems (FDES/AEDS) for the comparative investi-
while the ­C1–Cα linkage of in EAC- and THF-lignin is gation of lignin structure, thermal stability, and pyrolytic
more fragile to be broken. After pyrolysis, (1) EAC-lignin products distribution [236]. The results show that lignin
mainly yields more guaiacol and 4-methylguaiacol via the molecular weight can be reduced through DES treatment
cleavage of C ­ 1–Cα and ­Cα–Cβ linkages, (2) THF-lignin via initial lignin depolymerization [237], such as β-O-4
produces more guaiacol, 4-ethylguaiacol, and 4-methyl- dissociation. On the other hand, DES treatment can also
guaiacol via cleaving ­C1–Cα, ­Cβ–Cγ, and ­Cα–Cβ linkages, dissociate lignin–carbohydrate complex (LCC) and lignin
and (3) GBL-lignin generated the dominant 4-methyl- substructures (e.g., aryl ether and carbon–carbon bonds)
guaiacol via breaking the ­Cα–Cβ linkage. to purify lignin and make structural degradation. During
pyrolysis, different stages can be observed, including dry-
DES (deep eutectic solvents) lignin ing stage (from 25 to 150 °C, including moisture remov-
Deep eutectic solvents (DES), composed of hydrogen ing) and pyrolysis stage (from 200 to 350 °C, mainly
bond donor and acceptor, is an eco-friendly, economi- involving β-O-4 degradation; from 350 to 400 °C, mainly
cal and non-toxic method used for lignin extraction involving lignin side-chain oxidation; > 400 °C, mainly
[224–227]. DES can reduce lignin molecular weight via involving aromatic rings saturation and carbon–carbon
cleaving weak bonding linkages, like β-O-4, which is bonds breaking; 400–600 °C, mainly involving the cleav-
conductive to improve the subsequent lignin pyrolysis age of methoxy group) [238], and lignin extracted from
efficiency [135, 228]. Three different DESs [i.e., choline ADES contains more side chains and lower thermal
chloride/acetic acid (CA), choline chloride/ethylene gly- stability compared to those of FDES extracting lignin.
col (CE), and zinc chloride/ethylene glycol (ZE)] were Volatiles releasing during pyrolysis shows that some
used by Li et al. to modify softwood Kraft lignin (SKL) for low-molecular-weight gaseous products (e.g., CO, C ­ O2,
improving the pyrolytic products distribution [229]. TG- ­CH4, and H ­ 2O) are formed from the escape of functional
DTG analysis shows significant difference of lignin pyro- groups outside the aromatic rings of lignin, where meth-
lytic behaviors during the temperature of 250–600 °C, oxy, methyl, and methylene are the main sources of ­CH4,
where the maximum degradation temperature (Tmax) of ­CO2 is formed by decarboxylation and/or decarbonyla-
DES treated lignin increases, indicating the higher ther- tion, CO is formed by the cleavage of ether bonds, and
mal stability caused by the removal of unstable chemical ­H2O mainly comes from dehydroxylation [239]. Further-
linkages, such as β-O-4. The decreasing content of lignin more, the yield of aromatic products of lignin increases
char after pyrolysis (especially for lignin treated by CE) with richer contents of non-condensable gaseous prod-
indicates that DES treatment is beneficial for char inhibi- ucts after DES treatment, indicating that DES treatment
tion. The volatile products distribution shows that G-type is beneficial for thermal decomposition of lignin during
phenols are the major compounds due to the nature pyrolysis.
of Kraft lignin extracted from black liquor [230, 231].
Among all phenolic compounds, G- and H-type phenols Biological lignin
are generated by lignin side-chain fragmentation and free Biological treatment (an environmentally friendly
radical polymerization, while C-type phenols are mainly method with low energy consumption) of lignin with
derived from side-chain fracture and thermal demethyla- assistance of fungus or bacterium has been recently
tion of other types of monophenols [232, 233]. During reported as an effective pathway to facilitate lignin
pyrolysis, G-type phenols can be gradually transformed pyrolysis, including increasing thermal conversion rate
into H-type ones due to the enhanced cleavage of methyl and pyrolytic selectivity of lignin to specific products,
aryl ether bond caused by DES treatment. On the other decreasing pyrolytic temperature and activation energy
hand, a small amount of mono aromatic hydrocarbons [242–244]. For example, bio-treated bamboo lignin using
(MAHs) can also be observed, formed via secondary white-rot fungi contained lower thermal stability, which
reactions, such as dehydroxylation and demethoxyla- can be decomposed into more G-type phenols through
tion at high temperatures [234]. In addition, compared fast pyrolysis [245]. Lignin generated from bio-treatments

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Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 26 of 43

(e.g., using cellular ligninolytic enzymes like laccase and Some ILs have been used as solvents for lignocellulosic
peroxidases) can obtain certain structural modifications, biomass pretreatment, such as 1-butyl-3-methylimidazo-
of which the mechanism is based on the lignin structure lium chloride ([Bmin][Cl]), 1-hexyl-3-methylimidazolium
oxidation and degradation (e.g., lignin side chains oxida- chloride [Hmin][Cl], 1-octyl-3-methylimidazolium chlo-
tion, demethoxylation, demethylation, and some linkages ride ([Omin][Cl]) [262], 1-ethyl-3-methylimidazolium
cleavage) [246–248]. For deeply understanding the effect acetate [Emin][OAc] [263, 264], and 1-butyl-3-meth-
of biological treatment on lignin pyrolysis, Wang et al. ylimidazolium acetate [Bmin][OAc] [265]. Due to the
used a white-rot fungi in the bio-treatment of softwood high solubility of lignin (of which the mechanism is pro-
ginkgo and hardwood poplar, where ligninolytic enzymes posed to be realized by breaking H-bonds in lignin and
modified lignin structure and enhanced pyrolytic effi- combining the aromatic nucleus and aliphatic chain of
ciency [249]. For example, oil production can be signifi- lignin [266]), low energy consumption, environmentally
cantly improved after lignin enzymatic modification at friendly, solvent recycling, and low cost for synthesis
all reaction temperatures, which is due to the decreasing [267, 268], many ILs have been used for lignin extrac-
content of C–C bonds in treated lignin samples [250], tion from biomass, such as [Bmin][Cl], [Bmin][OAc],
leading to the enhanced depolymerization of lignin struc- 1-ethyl-3-methylimidazolium lysinate [Emin][Lys], tri-
ture, especially at higher temperatures. Besides, ether ethylammonium hydrogen sulfate ­ [TEA][HSO4], and
bonds (which can be cleaved at lower temperatures) are N,N-dimethylethanolammonium succinate ([DMEAS])
dominant in lignin interunit linkages, which are much [269]. On the other hand, IL-treated lignin sample can
easier to be decomposed compared to C–C bonds [251, exhibit the improved yields of pyrolytic oils and phenolic
252], resulting in the significant increase of bio-oil from compounds during lignin pyrolysis due to the cleavage
lignin (e.g., at 400 °C, Ginkgo lignin treated by Laccase of hydrogen, ester, and ether bonds in lignin through IL
yielding 52.2% oils, higher than 49.8% oils obtained from treatment [270]. Rashid et al. used a protic ionic liquid
untreated Ginkgo lignin; at 400 °C, Poplar lignin treated pyridinium formate [PyFor] to extract lignin from vari-
by Laccase producing 51.9% oils, higher than 46.5% oils ous palm biomass, such as empty fruit bunches (EFB),
obtained from untreated Poplar lignin [249]). Besides, palm mesocarp fiber (PMF), and palm kernel shell (PKS)
bio-treatment can also reduce the content of methoxy [271], and three kinetic models (i.e., Flynn–Wall–Ozawa
via enzymatic oxidation [253] and demethylation [254], (FWO), Kissinger–Akahira–Sunose (KAS), and Starink)
thus decreasing char yield at high temperatures (e.g., at were used to investigate the activation energy of [PyFor]
800 °C, Poplar lignin treated by Laccase generating 21.2% extracted lignin. Thermal stability of different lignin sam-
char, lower than 23.2% char obtained from untreated ples depends on their functional groups, intermolecular
Poplar lignin [249]). The selectivity of specific products of bonds, extraction methods, and condensation degree
lignin can be improved significantly after bio-treatment, [272]. For example, due to the presence of increased
where G-/S-type phenols obtained from treated Pop- branching/condensed structures and higher lignin con-
lar lignin can be effectively transformed into phenol at tent with higher molecular weight, higher thermal stabil-
800 °C due to the further temperature-induced cracking, ity can be obtained [273–275]. Furthermore, heating rate
including demethylation, demethoxylation, decarbonyla- is another important factor for lignin pyrolysis, indicat-
tion, and dealkylation in side chains [168]. ing that the increasing heating rate would increase the
reaction temperature and reduce the reaction period
Ionic liquid lignin by accelerating pyrolysis [265, 276, 277]. Except for the
The strong electrostatic interactions between ions endow nature of IL-extracted lignin, the secondary intra-particle
ionic liquid (ILs) with negligible vapor pressure and low reactions are also important factors in exothermic behav-
flammability, which is beneficial for their applications iors and thermal runway, thus having a significant effect
under high-vacuum conditions without contamina- on the kinetic mechanism and the magnitude of activa-
tion problems. Also, their nature and properties can be tion energy during pyrolysis [274, 278]. Halder et al. con-
adjusted by changing the chemical structures of both cat- firmed that the IL treatment would lead to the cleavage
ions and anions according to specific applications [258, of β-O-4 bond in lignin and then cause the improved
259]. On the other hand, ILs can be recovered from the generation of phenolic compounds from lignin pyrolysis
pretreated mixture by adding anti-solvents (e.g., ethanol [125]. Lei et al. also found that the tar obtained from the
or ­H2O, which would cause the generation of impurities pyrolysis of 1-sulfonic acid butyl-3-methylimidazolium
in recovered ILs) [260], reverse micelle method (which trifluoromethanesulfonate [B(SO3H)min][OTf ]-treated
can extract almost pure [Mmim] and [DMP] from pre- lignin (of which the content of aryl ether increases and
treated mixture), or membrane distillation (separating that of fatty ether decreases) is mainly phenols and phe-
ILs and water) [261]. nol derivatives, accounting for > 90% of all compounds,

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Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 27 of 43

wherein the improved yields can be obtained for phe- 80% and naphthalene at ~ 50% [289]. ­ZrO2/ZSM-5 real-
nol, cresol, guaiacol, 2-ethylphenol, 4-ethyl-2-methoxy- ized the significant reduction of oxygen content from 30
phenol, and 4-methoxyguaiacol in light tar (of which the to 10 wt% (with a higher share of aromatics and lower
yield increases by 1.5 times compared to that of untreated heavy components) [290], Zn-HZSM-5 improved total
lignin) [279]. aromatics from 31.1 to 46.1 mg/g [291], and double-layer
metal supported core–shell (ZSM-5@MCM-41, Z@M)
Catalytic pyrolysis using zeolites catalysts ­(Me1Z@Me2M) showed synergistic effect on the
Zeolite‑driven lignin catalytic pyrolysis with high MAHs promotion of MAHs selectivity via phenols, immoder-
selectivity ate aromatization, and polymerization inhibitions [292].
Table 5 shows the recent progress of some effective cata- Mixed zeolite, like HZSM-5@Al-SBA-15, was confirmed
lysts used in lignin catalytic pyrolysis for producing aro- with both pre-cracking and enhanced diffusion (Al-
matic hydrocarbons (AHs), mainly including zeolites, SBA-15), and shape AHs selectivity (HZSM-5), which
carbon-based, and some metal-based catalysts. During can improve MAHs production while inhibit PAHs gen-
catalytic pyrolysis, the main reaction pathway is divided eration [284, 293].
into two parts, including in situ and ex situ catalytic Carbon-based materials, such as activated carbon (AC),
pyrolysis. The feature of in situ catalytic pyrolysis is that has also been confirmed as effective catalysts in upgrad-
the catalyst is mixed with lignin and then put into reac- ing pyrolysis of lignin, due to their well-developed pore
tor together for pyrolysis, while ex situ one refers to the structures and abundant acidic surface groups. Further-
process of direct pyrolysis of lignin to form pyrolytic more, AC has been investigated as an effective catalyst
volatiles and then contact with the catalyst to obtain sec- for the selective generation of phenols (the heavy com-
ondary catalytic pyrolysis [72]. ponents in bio-oils) [294, 295]. Yang et al. also confirmed
Among all catalysts, zeolites have been widely used that AC (produced from steam activation of lignin char)
in lignin catalytic pyrolysis due to their availability, low has the great potential to be used as upgrading catalyst
cost, thermal stability, acidity, porosity, and excellent for lignin catalytic pyrolysis. The catalytic effect of AC
catalytic selectivity and charring inhibition capacity [44, derived from surface sodium and alkali metals, and the
281–284]. Huang et al. [48] used five types of parent zeo- enhanced diffusion efficiency for reactive intermediates
lites [HZSM-5 (25), HZSM-5 (85), Al-MCM-41, HY, and attributed to its inside mesopores were believed to be the
USY] in lignin pyrolysis, among which HZSM-5 (25) is important determinant of high activity and selectivity of
the most effective one to produce AHs (BTX), showing AC to produce guaiacol-rich oils. Another important fac-
the highest selectivity of 56.56%. Kumar et al. found that tor is its efficient inhibition to tar production and char
Y-zeolite is the most effective one for demethoxylation agglomeration [296]. Therefore, many studies focused on
and dehydroxylation of both small and bulky oxygenates the combination of carbon-based materials and zeolites,
in lignin catalytic pyrolysis as compared to mordenite on one hand, to increase intermediates yield via cleav-
and ZSM-5 [285]. Some modifications further enhance ing C–O bonds on carbon-based materials, on the other
the catalytic activity and selectivity to AHs, such as alkali hand, to generate more AHs via sharp selectivity of zeo-
treatment and metal incorporation. After alkali treat- lites. For example, HZSM-5/lignin char catalyst prepared
ment (i.e., NaOH), the pore properties and acidic sites by Zhang et al. both showed high depolyermization of
density of zeolites are all changed, with the enhanced lignin (to generate more small-molecular-weight inter-
performance on cracking bulky oxygenates (such as phe- mediates) and created the increased yield of total aromat-
nols) to produce AHs with sharper selectivity [47, 286, ics (from 29.5 to 50.1 mg/g). Besides, the addition of char
287]. After metal incorporation (Fe, Co, Ni, Cu, Zn, Ga) can also alleviate the deactivation of HZSM-5 caused by
to form bi-functional zeolite catalyst, deoxygenation and coke deposition [297].
aromatization reactions are enhanced to sharply increase
the selectivity to AHs (or MAHs), due to the increased Other catalysts‑driven lignin catalytic pyrolysis
mesoporous surface area, average size of parent zeo- Other types of catalyst were also used in lignin pyrolysis
lites, and enhanced lignin mass-transfer efficiency. The (shown in Table 5), such as ­Mo2C, ­Nb2O5, and perovs-
modification of zeolites conducted by Jin et al. obtained kites. Due to the similar properties to noble metal cata-
the highest MAHs content of 29.3% over Co-HZSM-5, lysts, transition metal carbides, which have good catalytic
which is also attributed to its better inhibition of carbon performance (such as C–O cleavage and deoxygenation
deposition [288]. In addition, Ni-ZSM-5 obtained the abilities for ­Mo2C under H ­ 2 condition), were used in
maximum selectivity of hydrocarbons at 72% [47] and lignin catalytic pyrolysis. In situ pyrolysis products of
Fe-ZSM-5 obtained the maximum selectivity to ­C2H4 at biomass can be used as carbon source and supporter for

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Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 28 of 43

carburizing Mo precursor to produce biomass-Mo2C, and plastic wastes (e.g., polyethylene, polypropylene,
which would contain more activity to realize carboniza- polystyrene, polyvinylchloride, and polyethylene tereph-
tion and metal reduction in one step [298]. On the other thalate [318–320]) have been remained with a huge pro-
hand, lignin bonds breaking and deoxygenation can be duction annually, which significantly requires us to take
achieved under normal pressure via biomass-Mo2C to actions for their highly effective utilizations. Co-pyroly-
obtain high yield of MAHs (13.26 wt%) with high selec- sis is a feasible and simple thermochemical technology
tivity to toluene (> 98%) and high deoxygenation ratio of for achieving the goal of high-efficiency utilization of
> 95% [298]. Some metal oxides were also introduced in these common wastes in our life due to the same heat-
lignin catalytic pyrolysis, such as ­Fe2O3, CuO, ZnO, and ing system with pyrolysis technology without any signifi-
CaO, which can also increase AHs yield and reduce heavy cant adjustment [321]. Furthermore, blended substrates
components in oils [299, 300]. Among these catalysts, placed in the co-pyrolysis technique would produce more
niobium pentoxide ­(Nb2O5) has gained much attention yields and wider distributions (i.e., MAHs, PAHs, and
in lignin catalytic pyrolysis both in batch- and fixed-bed other long-chain hydrocarbons) of pyrolytic products as
reactions [301–303]. Lewis acid sites endow niobium compared to those of single lignin used due to the syner-
pentoxide with high catalytic activity in hydrodeoxy- gistic effect (Table 6) [64, 322]. The quality of formed oils
genation of lignin or its derivatives [304], exhibiting high can be improved via co-feeding with plastics to increase
AHs yield at 11.2 wt% with extremely high selectivity of the C/H content [323], and the heating value of conden-
MAHs at 94% due to its efficient inhibition of PAHs and sable products obtained from co-pyrolysis would also be
coke/char formation and effective deoxygenation abil- enhanced obviously [324]. Esso et al. summarized some
ity [303]. Finally, perovskite-type oxides, due to their important parameters, such as blending ratio, heating
high activity, high stability, strong resistance to poison- system (including heating rate and reaction temperature),
ing, low cost, and excellent properties of transporting and catalyst used on the synergy effect between biomass
oxygen ions and electrons, have played an important role and co-feedings [316]. Lignin is hydrogen-deficient com-
in catalytic reactions [305]. They have also been selected ponent in lignocellulosic biomass only with H/Ceffective
as effective catalysts in lignin catalytic pyrolysis, such as range of 0–0.3; hence, the hydrogen donors (such as low-
­Ca0.5Pr0.5FeO3 [306], ­La0.8M0.2FeO3 (M = La, Ca, Sr, Ba) density polyethylene, high-density polyethylene, phenol–
[307], ­LaTixFe1−xO3 [308], and ­LaTi0.2Fe0.8O3 [309, 310]. formaldehyde resins, polyolefins, and spent bleaching
The main component in bio-oils obtained after catalytic clay) can be used for promoting hydroprocessing (such as
pyrolysis over perovskite-type oxides is aryl oxygen-con- hydrogenolysis and/or hydrogenation) of lignin oxygen-
taining compounds with high selectivity (from 60 to 80%, ates species to increase the yield of AHs [55, 325–330].
such as phenolics, guaiacols, syringols and phenylates) Typically, hydrogen radicals produced from the thermal
instead of MAHs, while the inhibition of decarboxylation degradation of hydrogen donors were beneficial for lignin
and decarbonylation can reduce the generation of CO/ oils and char upgrading via hydrocracking, hydrogen-
CO2 and increase aliphatic hydrocarbons fracture on aro- olysis, dehydration, oligomerization, and polymerization
matic rings [307]. [64]. On the other hand, some studies also focused on the
enhancement of oil production and char evolution via
Co‑pyrolysis with other hydrogen‑rich feedstock co-pyrolysis, such as lignin–collagen [331], lignin–cel-
According to the description above (“Catalytic pyroly- lulose [123, 124], lignin–waste oil [61], lignin–oil shale
sis using zeolites” section), zeolite catalysts are applied [332], lignin/cellulose/sawdust-coke bottle [333], and
widely for improving the quality of lignin-based oils lignin–coal [334, 335], of which the detailed information
via deoxygenation to increase the production of AHs, is listed in Table 6. Through co-pyrolysis, not only lignin
although their yields are relatively low owing to the but also other kinds of wastes with low-efficient utiliza-
low H/Ceffective ratio (or the low key hydrogen index) of tion can achieve their valorizations.
mere lignin used [315]. On the other hand, the addition
of catalysts would lead to the formation of coke which Condensing and separating processes of pyrolytic
decreases the production of oils and affect the pyroly- oils
sis efficiency. The co-pyrolysis is a popular method to The determination of oil compositions can be achieved
improve the oil quality via combination of lignin with by Py-GC/MS [222], and volatile evolutions can be
other hydrogen-rich feedstock, such as the co-pyrolysis detected by TG-FTIR [205] during the pyrolysis reac-
of lignin with plastics (a common hydrogen-rich sub- tion. In addition, through dissolving oils in some spe-
strate) [316, 317]. On the other hand, due to the massive cific solvents (e.g., isopropanol), GC/MS/FID, 2D-GC/
agricultural, industrial and human activities, biomass FID, or NMR techniques can be used to obtain their

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Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 29 of 43

chemical compositions/structures [116, 204]. Gooty and charring stages), where light gases (­H2O, ­CO2, CO,
et al. proposed a condensing system consisting of two ­CH4), phenolic compounds (G-/S-/H-/C-type phenols),
cyclonic condensers (i.e., condensers 1 and 3), an elec- and char with aromatic fused-ring structures can be
trostatic precipitator-cum-condenser (i.e., C-ESP), and obtained. In addition, zeolites and other catalysts (acti-
a cotton wool filter for pyrolytic oils collection [336]. vated carbon, M­ o2C, metal oxides, and perovskites) were
The generated vapor/gas flows through condenser 1, used for lignin oils upgrading to generate AHs via deoxy-
C-ESP, condenser 3, and the cotton wood filter in series, genation. Finally, hydrogen-rich co-feedings were applied
wherein the liquid yield can be obtained by measuring to form more AHs (MAHs, PAHs) via increasing H/Ceff
the weight of cyclonic condensers and C-ESP before and ratio of blending substrates and generating hydrogen rad-
after each run, and oil deposit can be recovered with icals from hydrogen donors during co-pyrolysis.
a specially designed scraper [337]. However, the com- In spite of huge effort put on lignin pyrolysis, there still
plexity of oil composition makes the subsequent sepa- some challenges. Some suggestions are made below for
ration difficult. So far, solvent extraction is an efficient the future perspective.
method for products separation. For example, Deng
et al. performed the extraction of phenols from bio- 1. Lignin is a natural source of phenolic compounds, of
oil aqueous fraction using hydrophobic ionic liquids which the production of G-/S-/H-/C-type phenolic
(i.e., ­[Bmin][NTf2]), where the extraction efficiencies compounds are majorly determined by the compo-
of acetic acid, phenol, guaiacol, and 2-methylguaiacol sition and content of corresponding phenolic units
in aqueous fraction were 2.71, 95.41, 92.04, and 97.98% in lignin. For example, G-type phenolic compounds
[338]. Yao et al. extracted and recovered phenolic com- (e.g., guaiacol) can be significantly produced from
pounds from aqueous solution by thermo-separating G-type lignin. However, the complexity of lignin
magnetic ionic liquid aqueous two-phase system (two structure always leads to the complexity of formed
polypropylene glycol, PPG600-based thermo-separat- phenolic products (mainly including G-/S-/H-type
ing magnetic ionic liquid aqueous), where the extrac- phenolic compounds). The efficient removal of
tion efficiencies of phenol, o-cresol, and m-cresol were methoxy from lignin can adjust and regularize lignin
higher than 95% [339]. A hydroxyl-functionalized ionic structure to improve the selectivity of generated phe-
liquid (i.e., [­C2OH-4-pic][NO3]) was used by Xu et al. nolic compounds (which is beneficial for the forma-
to extract phenolic compounds from model coal tar, tion of H-type phenolic compounds). On the other
which obtained the extraction efficiency of 98.99, 98.39, hand, the removal of methoxy can reduce the forma-
98.65, and 99.99% for m-cresol, o-cresol, p-cresol, and tion of light gases, which is beneficial for lignin con-
phenol, respectively [340]. A binary petroleum ether/ version to liquid products.
dichloromethane solvent (PE/DCM) was used by Yang 2. Holocellulose can also be converted into phenolic
et al. to extract aromatic monomers from lignin oils, compounds via the promotion of specific catalysts.
of which the extraction efficiency was 80% [341]. In Furthermore, electronegative products and radicals
addition, PAHs can be efficiently extracted by various generated from lignin pyrolysis can be involved in the
techniques, such as supercritical and subcritical fluid secondary reaction of polyhydroxy volatiles from hol-
extraction, microwave-assisted solvent extraction, plant ocellulose. Therefore, further investigations should
oil-assisted extraction, and some microextraction tech- be made on concerning the interactions between vol-
niques using less organic solvents [342]. atiles of lignin and holocellulose, which can be solved
by isotope-labeled model compounds with typical
functional groups together with the control of pyrol-
Summary and future perspective ysis conditions.
In this review, we introduced pyrolysis technology for 3. For lignin catalytic pyrolysis, other capacities (except
lignin conversion and further lignin oils upgrading via for deoxygenation) of catalysts used should be
catalytic pyrolysis using zeolites and co-pyrolysis with obtained, such as hydrogenation, alkylation, decar-
other hydrogen-rich feedstock. Different lignin samples, bonylation, and demethylation, to avoid the gen-
such as Kraft lignin, alkali lignin, organosolv lignin, DES eration of phenolic compounds with distinct sub-
lignin, biological lignin, and ionic liquid lignin, and their stituents. The development of promising catalysts
corresponding pyrolytic behaviors were presented, which used for lignin upgrading will never be an outdated
indicated the effect of lignin type, reaction temperature, researching topic for a long time.
and time on lignin pyrolytic properties. Lignin pyrolysis 4. Co-pyrolysis is an efficient method, and will be
can be mainly divided into three stages (initial, primary a main direction of lignin pyrolysis in the future.

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 Table 5 Recent progresses of catalysts used in lignin catalytic pyrolysis, and their selectivity
Lignin Catalyst Catalytic pyrolysis Reaction conditions Products yield Important findings Product selectivity Ref.

Kraft lignin Aluminosilicate In situ 450, 550, and 650 °C, N/A HZSM5-30 showed the Hydrocarbons selectivity: HZSM5- [311]
12,500–40,625 °C/s, 6 s, most promising anti- 30 > HY > HZSM5-300/MCM41-40/
He coking performance and MCM41-Si
the highest selectivity
to desired products,
HZSM5-500 showed
good diffusion and high
reaction rate, and the
anti-coking performance
of HY/MCM41 was
weaker than HZSM5
Beech wood lignin Micro/meso porous In/Ex situ 400, 500, and 600 °C, Organic phase: Both two catalysts exhib- MAHs selectivity: meso- [312]
ZSM-5 20 min, N
­ 2 15–35 wt%; char: ited excellent dealkoxy- ZSM-5 > ZSM-5
~ 40 wt%; gas: < 20 wt% lation/aromatization
Lu and Gu Biotechnology for Biofuels and Bioproducts

reactivity to yield more

aromatics. Meso-ZSM-5
induces higher dealkoxy-
lation reactivity, leading
to higher selectivity to
BTX aromatics without
(2022) 15:106

the increase of PAHs

Cellulolytic enzyme Micro-meso ZSM-5 In-situ 873 K, 30 s Char: ~ 30 wt% > coke: Mesoporous structure AHs selectivity: C6 > C8 > C10+ ≈ [281]
lignin ~ 15 wt% > aromatics: was beneficial for the C7 > C9+ > C14+
~ 8 wt% > phenolics: diffusion of heavy phe-
~ 3 wt% > catechols: nols and modulation of
~ 2 wt% pyrolysis products
Rice straw lignin Modified ZSM-5 In situ 450, 500, 550, and 600 °C N/A These ZSM-5 catalysts Hydrocarbons selectivity: (with- [47]
showed shape selectivity out catalyst) oxygenates > phe-
and acidity, beneficial for nols > PAHs > MAHs; (with
pyrolytic products distri- ZSM-5) PAHs > MAHs ≈ oxygen-
bution, and demethoxy- ates ≈ phenols; (with alkali ZSM-5)
lation and dehydroxyla- PAHs > MAHs > phenols > oxy-
tion of oxygenates genates; (with Ni-ZSM-5)
MAHs ≈ PAHs > oxygenates > phe-
nols. MAHs: naphthalenes with
40–60%
Commercial lignin Modified HZSM-5 Ex situ 500 °C (I) and 450–600 °C Organic liquid: HZSM-5 treated by Alkali treated HZSM-5 preferred [313]
(II), 20 °C/min, N
­ 2 17.5–22.7 wt%; solid: organic alkali exhibited phenols, while Co-alkali-HZSM-5
42.7–43.2 wt%; gas: a coordinated micro/ exhibited much higher selectivity
19.2–19.8 wt% meso-proportion with to MAHs (38%) than phenols

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proper size and acidity, (23%)
of which the acid-
ity would be further
enhanced after cobalt
incorporation, exhibiting
better MAHs selectivity
Page 30 of 43
 Table 5 (continued)
Lignin Catalyst Catalytic pyrolysis Reaction conditions Products yield Important findings Product selectivity Ref.

Commercial lignin HZSM-5/biochar Ex situ 500 °C, 10 min, N

­ 2 Oil: 35 wt%; total AHs: LC (lignin carbon) incor- The production of AHs from [297]
50 mg/g (maximum) porating lignin depolym- lignin/LC/HZSM-5 was almost two
erization produced more times higher than lignin/HZSM-5
phenols, which can be (from 30 to 50 mg/g)
further transformed into
aromatic hydrocarbons
through HZSM-5
Alkali lignin ZSM-5/biochar In situ 500 °C, 10 min, N
­ 2 Oil: ~ 20 wt%; char: The addition of biochar Total aromatics (12.32%) > meth- [314]
~ 40 wt%; gas: < 20 wt%; enhanced bond breaking oxyphenols (5.17%) > alkylphenols
aromatics: > 30 mg/g of lignin to yield more (4.4%) > phenols (2.42%) > acid
oils, and ZSM-5 acted as (0.85%)
a selective aromatization
to obtain higher content
Lu and Gu Biotechnology for Biofuels and Bioproducts

of aromatics
Corn cob lignin HZSM-5@Al-SBA-15 In situ 550 °C, 10 °C/min, ­N2 Gas: ~ 35 wt%, water: Mixed zeolite with AHs selectivity: MAHs [293]
< 10 wt%; organic liquid: tailored properties of (~ 40%) > PAHs (~ 25%) > phenols
< 15 wt% acidity and porosity reg- (~ 13%) > aliphatics (~ 8%) > meth-
ulated the composition oxyphenols (~ 0%)
of AHs by pre-cracking
(2022) 15:106

and enhanced diffusion

Commercial lignin Pine-Mo2C In situ 300, 400, and 500 °C, Total AHs: 12.36 wt%; Pine carbon supported Deoxygenation rate: pine-Mo2C [298]
WHSV = 1 ­h−1, ­H2(N2) light gases: 29.68 wt% ­Mo2C catalyst showed (100%); MAHs selectivity: toluene
(maximum) good selective deoxy- (98%) > others (benzene and
genation targeting C-O xylenes, < 2%)
cracking to produce
more monocyclic aro-
matic hydrocarbons
Enzymatic hydrolysis Nb2O5 In situ 500–650 °C, 0.5 min Phenols: ~ 4 wt%; MAHs: Nb2O5 exhibited excel- AHs selectivity: [303]
lignin ~ 6 wt% lent deoxygenation C6+C7+C8+C9+C9+ (MAHs, up
ability to convert lignin to 90%) > C10+C11+C12+C12+
into AHs, especially for (PAHs, up to 8%)
MAHs
Kraft lignin Biochar, activated carbon In situ 550 °C, 5 min, N
­ 2 Oil: 13.15 wt%; char: The catalytic effect of Products selectivity: phe- [296]
58.76 wt%; gas: 39.74 biochar was derived nols > PAHs > oxygenates
wt% (maximum) from surface sodium and
alkali metals. The addi-
tion of AC resulted in the
high-phenol-concentra-
tion oils production

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Page 31 of 43
 Table 5 (continued)
Lu and Gu Biotechnology for Biofuels and Bioproducts

Lignin Catalyst Catalytic pyrolysis Reaction conditions Products yield Important findings Product selectivity Ref.

Bagasse lignin Ca0.5Pr0.5FeO3 In situ 20 °C/min, 2 h, N

­ 2 Oil: ~ 25 wt%; char: Guaiacols, syringols, and Products selectivity: Guai- [306]
> 50 wt%; gas: > 40 wt% phenols were the main acols > syringols > phenyl
(maximum) component in pyrolytic ethers > phenolics > phenyl
oils, and the content of ketones
(2022) 15:106

light aliphatic hydro-

carbons increased after
catalysts addition
Bagasse lignin La0.8M0.2FeO3 (M = La, Ca, In situ 600 °C, 10 °C/min, 2 h, N
­ 2 Oil: ~ 25.73 wt%; char: Perovskites improved the LaFeO3, ­La0.8Ca0.2FeO3, [307]
Sr, Ba) > 40.65 wt%; gas: generation of aliphatic L­ a0.8Sr0.2FeO3, and ­La0.8Ba0.2FeO3
> 42.89 wt% (maximum) hydrocarbons via inhibit- produced the maximum selectiv-
ing decarboxylation and ity of phenolics (24.59%), syrin-
decarbonylation, and gols (25.78%), guaiacols (23.79%),
increased aryl oxygen- syringols (22.47%), respectively
containing compound
yield

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Page 32 of 43
 Table 6 Detailed information of lignin co-pyrolysis
Blending mixture Catalyst Reactor Synergistic effect Yield Selectivity Ref.

Lignin/low-density polyethylene HZSM-5 A thermogravimetric analyzer 1. The synergistic effect decreased 800 °C—char: lignin > lignin + LDP Lignin + LDPE + HZSM-5: aromat- [325]
(LDPE) the starting temperature of pyroly- E > lignin + LDPE + HZSM-5 > LDPE ics, ­alkanea
sis and accelerated the decompo-
sition rate
2. The composition of pyrolysis
products contained more alkane
and aromatic hydrocarbons
Lignin/plastics (PS) Red clay (RC) A micro reactor The synergistic effect increased the 900 °Cb—char: lignin (14.9%), Lignin (guaiacol, 60.41%), lignin/ [317]
yield of guaiacol lignin/PS (6.04%), lignin/PS/RC RC (guaiacol, 67.37%), lignin/PS
(33.54%); 500 °Cc—lignin-/PS-/ (styrene-C8, 70.22%), lignin/PS/RC
lignin + PS-/lignin + PS + RC- (styrene-C8, 86.86%)
derived compounds:
0.81/6.03/4.67/14.67%
Lu and Gu Biotechnology for Biofuels and Bioproducts

Lignin/phenol–formaldehyde HZSM-5 A vertical pyrolysis reactor The synergistic effect improved 650 °Cc—total compounds/ 650 °Cc: lignin (simple phenols, [326]
resins (PF) the yield of aromatic amines aromatic amines: PF (24.5/14.2%), 75.62%, catechols, 14.49%,
lignin (7.2/3.7%), lignin/PF = 1/5 aromatic hydrocarbon, 9.89%)
(22.0/13.3%) lignin/PF (simple phenols, 84.16%,
dimers, 6.30%, aromatic hydrocar-
bons, 4.23%), PF (simple phenols,
83.2%, aromatic hydrocarbons,
(2022) 15:106

8.6%, dimers, 6.80%)

Lignin/spent bleaching clay (BC) N/A A fixed-bed reactor system 1. The synergistic effect promoted 550 °C—gas/oil/char: BC 550 °Cc: BC (aliphatic hydrocar- [329]
the production of P-type phenols (~ 9/25/66%), lignin (~ 34/24/42%), bons), lignin (phenols), lignin/
and aromatic hydrocarbons, and lignin/BC = 1/1 (~ 19/25/57%) BC = 1/1 (H-type phenols)
the inhibition of oxygenates
species
2. The addition of spent bleaching
clay reduced the activation energy
and improve the oil quality
Lignin/polyolefins N/A A fixed-bed reactor 1. Liquid yield was improved by 650 °C—gas/liquid/Wax/char: Lignin + PE: hydrocarbons [327]
adding polyolefins due to the lignin/PE (~ 10/40/25/20%), lignin/ like > C26 and C19-C25, ad diesel
formation of lower poly-hydrocar- PP (~ 10/50/15/20%) (C14–C18)c; Lignin + PP: hydrocar-
bons derived from polyolefins bons like > C26 and C11–C13, and
2. The yield of gasoline and kero- gasoline (C5–C10)c
sene was climbed, revealing that
lignin pyrolytic products enhanced
the cracking of polyethylene (PE)
intermediates
3. The rearrangement reactions of
polypropylene (PP) intermediates

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enhanced liquid production via
inhibiting the formation of solid
Page 33 of 43
 Table 6 (continued)
Blending mixture Catalyst Reactor Synergistic effect Yield Selectivity Ref.

Lignin/waste cooking oil (WCO) HZSM-5 A Py-GCMS system The addition of waste cooking oil 823 ­Kc—feedstock conversion rate: 823 ­Kc: lignin (phenolics, MAHs, [61]
in lignin with appropriate catalyst- lignin (~ 65%, phenolics, MAHs), ~ 65%), lignin/WCO = 1/1 (MAHs,
to-feedstock ratio contributed to WCO (~ 100%, MAHs, PAHs), lignin/ ~ 75%), WCO (MAHs, ~ 60%)
high selectivity to aromatics via WCO = 1/1 (~ 85%, MAHs, PAHs)
enhancing alkylation and demeth-
oxylation
Lignin/collagen N/A An applied test system, Inc. 1. Collagen addition benefited the 600 °C—char: lignin (45.1%), 600 °Cd—C:O/C:H/C:N (aromatic [331]
Lu and Gu Biotechnology for Biofuels and Bioproducts

series 3210 vertical tube formation and evolution of char lignin/collagen (45.4–48.4%), ratio of char): lignin (3.21/0.90/0),
furnace with abundant oxygenated poly- collagen (24.9%); 1000 °C—char: lignin/collagen (3.17/0.84/32.26),
aromatic structures lignin (41.8%), lignin/collagen collagen (2.32/0.54/3.18)
2. Collagen addition improved the (42.2–43.6%), collagen (22.6%)
hydrogen aromaticity index via
reducing aromatic substitution
and/or facilitating the removal of
(2022) 15:106

functional groups
3. Collagen acted as a binder
for lignin to form stronger fused
framework
Cellulose/lignin/sawdust N/A A self-made fixed-bed reactor 1. Interactions between the vola- 500 °C—gas/oil/char: cellulose 500 °Cc: lignin (phenols), cellulose [123]
tiles generated from cellulose and (28.1/55.6/16.3%), sawdust/ (sugars, aldehydes, ketones),
sawdust promoted oil production cellulose (11.5/71.0/17.5%), sawdust (sugars), sawdust/lignin
2. Repolymerization happened sawdust (25.2/50.0/24.8%), lignin (phenols, aldehydes, ketones),
between light species from cellu- (8.5/39.6/51.9%), sawdust/lignin cellulose/sawdust (aldehydes,
lose and heavy species from lignin (17.5/41.5/41%) ketones), cellulose/lignin (sugars)
to generate more condensable
liquids
3. Interaction between heavy
species from lignin and sawdust
created more carbonaceous char
a
TG-FTIR
b
TG-DTG
c
GC/MS, GC/FID
d
Elemental analysis

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Page 34 of 43
Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 35 of 43

Hydrogen donors provided from other co-feedings Competing interests

The authors declare that they have no competing interests.
are significantly beneficial for oil hydroprocessing to
generate high yield of AHs. On the other hand, these Received: 2 August 2022 Accepted: 28 September 2022
co-feedings used in co-pyrolysis can be produced
from agricultural, industrial, and human activities in
large quantities annually. Therefore, lignin co-pyrol-
ysis with other new co-feedings and their pyroly- References
sis mechanisms should be investigated in the near 1. Abu-Omar MM, Barta K, Beckham GT, Luterbacher JS, Ralph J, Rinaldi R,
et al. Guidelines for performing lignin-first biorefining. Energy Environ
future. Sci. 2021;14(1):262–92.
5. Hydrogen provided by lignin itself (self-hydrogen 2. Sethupathy S, Murillo Morales G, Gao L, Wang H, Yang B, Jiang J, et al.
transfer) used for lignin hydrogenolysis has been a Lignin valorization: status, challenges and opportunities. Bioresour
Technol. 2022;347: 126696.
popular researching topic in recent years, which can 3. Radhika NL, Sachdeva S, Kumar M. Lignin depolymerization and
also be applied in lignin pyrolysis with certainly con- biotransformation to industrially important chemicals/biofuels. Fuel.
trolling pyrolysis conditions, reactor designed, and/ 2022;312: 122935.
4. Kim HU, Kim JW, Tran NT, Limarta SO, Ha J-M, Park Y-K, et al. Direct
or catalysts used. conversion of lignin to high-quality biofuels by carbon dioxide-assisted
hydrolysis combined with transfer hydrogenolysis over supported
ruthenium catalysts. Energy Convers Manag. 2022;261: 115607.
5. Yang L, Zheng T, Huang C, Yao J. Using deep eutectic solvent
pretreatment for enhanced enzymatic saccharification and lignin
utilization of masson pine. Renew Energy. 2022;195:681–7.
Abbreviations 6. Roberto Paz Cedeno F, Belon de Siqueira B, Gabriel Solorzano Chavez
BDE: Bond dissociation energy; LDH: Layered double hydroxide; TGA​ E, Ulises Miranda Roldán I, Moreira Ropelato L, Paul Martínez Galán
: Thermogravimetric analysis; DTG: Derivative thermogravimetric analysis; J, et al. Recovery of cellulose and lignin from Eucalyptus by-product
Py-GC/MS: Pyrolysis-gas chromatograph/mass spectroscopy; AHs: Aromatic and assessment of cellulose enzymatic hydrolysis. Renew Energy.
hydrocarbons; MAHs: Monocyclic aromatic hydrocarbons; PAHs: Polycyclic 2022;193:807–20.
aromatic hydrocarbons; EHI: Effective hydrogen index; LGA: Levoglucosan; 7. Yuan Y, Jiang B, Chen H, Wu W, Wu S, Jin Y, et al. Recent advances
LGO: Levoglucone; HHV: High heating value; FTIR: Fourier transform infrared in understanding the effects of lignin structural characteristics on
spectroscopy; GC/MS: Gas chromatography/mass spectrometry; TG-IR-GC/ enzymatic hydrolysis. Biotechnol Biofuels. 2021;14(1):205.
MS: Fourier transform infrared spectroscopy and gas chromatography–mass 8. Mahdavi M, Mirmohammadi M, Baghdadi M, Mahpishanian S. Visible
spectrometry; THF: Tetrahydrofuran; KL: Kraft lignin; TG–FTIR: Thermogravimet- light photocatalytic degradation and pretreatment of lignin using
ric–Fourier transform infrared spectrometry; AL: Alkali lignin; OL: Organosolv magnetic graphitic carbon nitride for enhancing methane produc-
lignin; EAC: Ethyl acetate; GBL: γ-Butyrolactone; GC/FID: Gas chromatograph/ tion in anaerobic digestion. Fuel. 2022;318: 123600.
flame ionization detection; TG–MS: Thermogravimetry–mass spectrometry; 9. Li C, Zhao X, Wang A, Huber GW, Zhang T. Catalytic transforma-
DES: Deep eutectic solvent; CA: Choline chloride/acetic acid; CE: Choline chlo- tion of lignin for the production of chemicals and fuels. Chem Rev.
ride/ethylene glycol; ZE: Zinc chloride/ethylene glycol; FDES: Choline chloride/ 2015;115(21):11559–624.
formic acid; ADES: Chloride/lactic acid; LCC: Lignin–carbohydrate complex; ILs: 10. Chakar FS, Ragauskas AJ. Review of current and future softwood kraft
Ionic liquids; FWO: Flynn–Wall–Ozawa; KAS: Kissinger–Akahira–Sunose; EFB: lignin process chemistry. Ind Crop Prod. 2004;20(2):131–41.
Empty fruit bunches; PMF: Palm mesocarp fiber; PKS: Palm kernel shell; SCS: 11. Lin F, Ma Y, Sun Y, Song Z, Men X, Wu Y, et al. Selective hydrodeoxy-
Sugarcane straw; Ð: Dispersity; Tmax: The temperature with maximum deg- genation of lignin model compound to renewable fuel precursors
radation rate; G-/S-/H-: Guaiacyl-/syringyl-/p-hydroxyphenyl-; UV: Ultraviolet; using two-dimensional nanosheet Ni/HZ5-NS catalyst. Renew
2D-GC/FID: 2D-gas chromatograph/flame ionization detection; NMR: Nuclear Energy. 2022;189:1278–91.
magnetic resonance spectroscopy. 12. Umar Y, Velasco O, Abdelaziz OY, Aboelazayem O, Gadalla MA, Hulte-
berg CP, et al. A renewable lignin-derived bio-oil for boosting the
Acknowledgements oxidation stability of biodiesel. Renew Energy. 2022;182:867–78.
This research was financially supported by the National Natural Science 13. vom Stein T, den Hartog T, Buendia J, Stoychev S, Mottweiler J, Bolm
Foundation of China (No. 21774059), China Scholarship Council (CSC, No. C, et al. Ruthenium-catalyzed C–C bond cleavage in lignin model
202108320294), and the Priority Academic Program Development (PAPD) of substrates. Angew Chem Int Ed. 2015;54(20):5859–63.
Jiangsu Higher Education Institutions. 14. Nichols JM, Bishop LM, Bergman RG, Ellman JA. Catalytic C–O
bond cleavage of 2-aryloxy-1-arylethanols and its application to
Author contributions the depolymerization of lignin-related polymers. J Am Chem Soc.
XL conceived the idea for the review. XL performed the literature research and 2010;132(36):12554–5.
writing; XL and XG revised the manuscript. Both authors read and approved 15. Liu Y, Li C, Miao W, Tang W, Xue D, Li C, et al. Mild redox-neutral
the final manuscript. depolymerization of lignin with a binuclear Rh complex in water. ACS
Catal. 2019;9(5):4441–7.
16. Liu YX, Li CZ, Miao W, Tang WJ, Xue D, Xiao JL, et al. Rhodium–terpy-
Declarations ridine catalyzed redox-neutral depolymerization of lignin in water.
Green Chem. 2020;22(1):33–8.
Ethics approval and consent to participate
17. Jiang L, Guo HW, Li CZ, Zhou P, Zhang ZH. Selective cleavage of lignin
Ethical approval and consent to participate are not required.
and lignin model compounds without external hydrogen, catalyzed
by heterogeneous nickel catalysts. Chem Sci. 2019;10(16):4458–68.
Consent for publication
18. Wu K, Wang W, Guo H, Yang Y, Huang Y, Li W, et al. Engineering co
All authors agree to the submission and publication of the manuscript in the
nanoparticles supported on defect ­MoS2–x for mild deoxygenation of
journal Biotechnology for Biofuel.
lignin-derived phenols to arenes. ACS Energy Lett. 2020;5(4):1330–6.

Content courtesy of Springer Nature, terms of use apply. Rights reserved.

Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 36 of 43

19. Liu H, Li H, Lu J, Zeng S, Wang M, Luo N, et al. Photocatalytic cleavage 41. Tran QK, Le ML, Ly HV, Woo HC, Kim J, Kim S-S. Fast pyrolysis of pitch
of C–C bond in lignin models under visible light on mesoporous pine biomass in a bubbling fluidized-bed reactor for bio-oil production.
graphitic carbon nitride through π–π stacking interaction. ACS Catal. J Ind Eng Chem. 2021;98:168–79.
2018;8(6):4761–71. 42. Yu H, Wang S, Sun Y, Zhang W, Li R, Kang X. Pyrolysis mechanism law
20. Liu H, Li H, Luo N, Wang F. Visible-light-induced oxidative lignin C–C of β-O-4 lignin dimer model compounds: a density functional theory
bond cleavage to aldehydes using vanadium catalysts. ACS Catal. study. Ind Crop Prod. 2022;180: 114746.
2020;10(1):632–43. 43. Wang L, Yin J, Jiang J, Zhang Y, Song M, Zhang R, et al. Revealing
21. Nguyen JD, Matsuura BS, Stephenson CRJ. A photochemical strategy G-lignin model compounds pyrolysis behavior: β-O-4 and 5–5′ dimer
for lignin degradation at room temperature. J Am Chem Soc. and trimer. Fuel. 2022;317: 123531.
2014;136(4):1218–21. 44. Paysepar H, Venkateswara Rao KT, Yuan Z, Shui H, Xu C. Production of
22. Liu E, Segato F, Prade RA, Wilkins MR. Exploring lignin depolymeriza- phenolic chemicals from hydrolysis lignin via catalytic fast pyrolysis. J
tion by a bi-enzyme system containing aryl alcohol oxidase and Anal Appl Pyrol. 2020;149: 104842.
lignin peroxidase in aqueous biocompatible ionic liquids. Bioresour 45. Ryu HW, Lee HW, Jae J, Park Y-K. Catalytic pyrolysis of lignin for the pro-
Technol. 2021;338: 125564. duction of aromatic hydrocarbons: effect of magnesium oxide catalyst.
23. Li Y, Cai Z, Liao M, Long J, Zhao W, Chen Y, et al. Catalytic depolymeri- Energy. 2019;179:669–75.
zation of organosolv sugarcane bagasse lignin in cooperative ionic 46. Zheng A, Huang Z, Wei G, Zhao K, Jiang L, Zhao Z, et al. Controlling
liquid pairs. Catal Today. 2017;298:168–74. deoxygenation pathways in catalytic fast pyrolysis of biomass and
24. Mehta MJ, Kulshrestha A, Sharma S, Kumar A. Room temperature its components by using metal-oxide nanocomposites. iScience.
depolymerization of lignin using a protic and metal based ionic 2020;23(1):100814.
liquid system: an efficient method of catalytic conversion and value 47. Nishu, Li Y, Liu R. Catalytic pyrolysis of lignin over ZSM-5, alkali, and
addition. Green Chem. 2021;23(3):1240–7. metal modified ZSM-5 at different temperatures to produce hydrocar-
25. Prado R, Brandt A, Erdocia X, Hallet J, Welton T, Labidi J. Lignin bons. J Energy Inst. 2022;101:111–21.
oxidation and depolymerisation in ionic liquids. Green Chem. 48. Huang M, Xu J, Ma Z, Yang Y, Zhou B, Wu C, et al. Bio-BTX production
2016;18(3):834–41. from the shape selective catalytic fast pyrolysis of lignin using differ-
26. Dier TKF, Rauber D, Durneata D, Hempelmann R, Volmer DA. Sustainable ent zeolite catalysts: relevance between the chemical structure and
electrochemical depolymerization of lignin in reusable ionic liquids. Sci the yield of bio-BTX. Fuel Process Technol. 2021;216: 106792.
Rep. 2017;7:1–12. 49. Rahman MM, Liu R, Cai J. Catalytic fast pyrolysis of biomass over
27. Liu X, Bouxin FP, Fan J, Budarin VL, Hu C, Clark JH. Recent advances in zeolites for high quality bio-oil—a review. Fuel Process Technol.
the catalytic depolymerization of lignin towards phenolic chemicals: a 2018;180:32–46.
review. ChemSusChem. 2020;13(17):4296–317. 50. Lee HW, Kim TH, Park SH, Jeon J-K, Suh DJ, Park Y-K. Catalytic fast
28. Schutyser W, Renders T, Van den Bosch S, Koelewijn SF, Beckham pyrolysis of lignin over mesoporous Y zeolite using Py-GC/MS. J
GT, Sels BF. Chemicals from lignin: an interplay of lignocellulose Nanosci Nanotechnol. 2013;13(4):2640–6.
fractionation, depolymerisation, and upgrading. Chem Soc Rev. 51. Kim S-S, Lee HW, Ryoo R, Kim W, Park SH, Jeon J-K, et al. Conversion
2018;47(3):852–908. of kraft lignin over hierarchical MFI zeolite. J Nanosci Nanotechnol.
29. Questell-Santiago YM, Galkin MV, Barta K, Luterbacher JS. Stabilization 2014;14(3):2414–8.
strategies in biomass depolymerization using chemical functionaliza- 52. Custodis VBF, Karakoulia SA, Triantafyllidis KS, van Bokhoven JA.
tion. Nat Rev Chem. 2020;4(6):311–30. Catalytic fast pyrolysis of lignin over high-surface-area mesoporous
30. Rinaldi R, Jastrzebski R, Clough MT, Ralph J, Kennema M, Bruijnincx aluminosilicates: effect of porosity and acidity. ChemSusChem.
PCA, et al. Paving the way for lignin valorisation: recent advances 2016;9(10):1134–45.
in bioengineering, biorefining and catalysis. Angew Chem Int Ed. 53. Serrano L, Cecilia JA, García-Sancho C, García A. Lignin depolymeriza-
2016;55(29):8164–215. tion to BTXs. Topics Curr Chem. 2019;377(5):26.
31. Liao Y, Koelewijn S-F, Van den Bossche G, Van Aelst J, Van den Bosch S, 54. Luo Z, Lu K, Yang Y, Li S, Li G. Catalytic fast pyrolysis of lignin to
Renders T, et al. A sustainable wood biorefinery for low-carbon foot- produce aromatic hydrocarbons: optimal conditions and reaction
print chemicals production. Science. 2020;367(6484):1385–90. mechanism. RSC Adv. 2019;9(55):31960–8.
32. Zhou C-H, Xia X, Lin C-X, Tong D-S, Beltramini J. Catalytic conversion 55. Fan L, Chen P, Zhang Y, Liu S, Liu Y, Wang Y, et al. Fast microwave-
of lignocellulosic biomass to fine chemicals and fuels. Chem Soc Rev. assisted catalytic co-pyrolysis of lignin and low-density polyethylene
2011;40(11):5588–617. with HZSM-5 and MgO for improved bio-oil yield and quality. Biore-
33. Xu C, Arancon RAD, Labidi J, Luque R. Lignin depolymerisation sour Technol. 2017;225:199–205.
strategies: towards valuable chemicals and fuels. Chem Soc Rev. 56. Xie Q, Addy M, Liu S, Zhang B, Cheng Y, Wan Y, et al. Fast microwave-
2014;43(22):7485–500. assisted catalytic co-pyrolysis of microalgae and scum for bio-oil
34. Shen X, Zhang C, Han B, Wang F. Catalytic self-transfer hydrogenolysis production. Fuel. 2015;160:577–82.
of lignin with endogenous hydrogen: road to the carbon-neutral future. 57. Zhang X, Lei H, Zhu L, Qian M, Zhu X, Wu J, et al. Enhancement of
Chem Soc Rev. 2022;51(5):1608–28. jet fuel range alkanes from co-feeding of lignocellulosic biomass
35. Yu J, Sun L, Berrueco C, Fidalgo B, Paterson N, Millan M. Influence of with plastics via tandem catalytic conversions. Appl Energy.
temperature and particle size on structural characteristics of chars from 2016;173:418–30.
Beechwood pyrolysis. J Anal Appl Pyrol. 2018;130:127–34. 58. Park Y-K, Jung J, Ryu S, Lee HW, Siddiqui MZ, Jae J, et al. Catalytic co-
36. Asmadi M, Kawamoto H, Saka S. Gas- and solid/liquid-phase reactions pyrolysis of yellow poplar wood and polyethylene terephthalate over
during pyrolysis of softwood and hardwood lignins. J Anal Appl Pyrol. two stage calcium oxide-ZSM-5. Appl Energy. 2019;250:1706–18.
2011;92(2):417–25. 59. Zhang H, Xiao R, Nie J, Jin B, Shao S, Xiao G. Catalytic pyrolysis of black-
37. Figueiredo MB, Hita I, Deuss PJ, Venderbosch R, Heeres H. Pyrolytic liquor lignin by co-feeding with different plastics in a fluidized bed
lignin: a promising biorefinery feedstock for the production of fuels and reactor. Bioresour Technol. 2015;192:68–74.
valuable chemicals. Green Chem. 2022;24:4680–702. 60. Sophonrat N, Sandström L, Zaini IN, Yang W. Stepwise pyrolysis of mixed
38. Li C, Hayashi J-I, Sun Y, Zhang L, Zhang S, Wang S, et al. Impact of heat- plastics and paper for separation of oxygenated and hydrocarbon
ing rates on the evolution of function groups of the biochar from lignin condensates. Appl Energy. 2018;229:314–25.
pyrolysis. J Anal Appl Pyrol. 2021;155:105031. 61. Fan L, Ruan R, Li J, Ma L, Wang C, Zhou W. Aromatics production from
39. Supriyanto, Usino DO, Ylitervo P, Dou J, Sipponen MH, Richards T. Identi- fast co-pyrolysis of lignin and waste cooking oil catalyzed by HZSM-5
fying the primary reactions and products of fast pyrolysis of alkali lignin. zeolite. Appl Energy. 2020;263: 114629.
J Anal Appl Pyrol. 2020;151: 104917. 62. Wang Y, Akbarzadeh A, Chong L, Du J, Tahir N, Awasthi MK. Catalytic
40. Zheng Q, Zhang D, Fu P, Wang A, Sun Y, Li Z, et al. Insight into the fast pyrolysis of lignocellulosic biomass for bio-oil production: a review.
pyrolysis of lignin: unraveling the role of volatile evolving and char Chemosphere. 2022;297: 134181.
structural evolution. Chem Eng J. 2022;437: 135316.

Content courtesy of Springer Nature, terms of use apply. Rights reserved.

Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 37 of 43

63. Zhong S, Zhang B, Liu C, Shujaa Aldeen A, Mwenya S, Zhang H. A 88. Alvarez J, Lopez G, Amutio M, Bilbao J, Olazar M. Bio-oil production
minireview on catalytic fast co-pyrolysis of lignocellulosic biomass for from rice husk fast pyrolysis in a conical spouted bed reactor. Fuel.
bio-oil upgrading via enhancing monocyclic aromatics. J Anal Appl 2014;128:162–9.
Pyrol. 2022;164: 105544. 89. Abdullah N, Gerhauser H. Bio-oil derived from empty fruit bunches.
64. Zhang X, Lei H, Chen S, Wu J. Catalytic co-pyrolysis of lignocel- Fuel. 2008;87(12):2606–13.
lulosic biomass with polymers: a critical review. Green Chem. 90. Volli V, Singh RK. Production of bio-oil from de-oiled cakes by thermal
2016;18(15):4145–69. pyrolysis. Fuel. 2012;96:579–85.
65. Kan T, Strezov V, Evans TJ. Lignocellulosic biomass pyrolysis: a review of 91. Encinar JM, González JF, González J. Fixed-bed pyrolysis of Cynara car-
product properties and effects of pyrolysis parameters. Renew Sustain dunculus L. product yields and compositions. Fuel Process Technol.
Energy Rev. 2016;57:1126–40. 2000;68(3):209–22.
66. Balagurumurthy B, Bhaskar T. Hydropyrolysis of lignocellulosic biomass: 92. Encinar JM, Beltrán FJ, Ramiro A, González JF. Pyrolysis/gasifica-
state of the art review. Biomass Convers Biorefin. 2014;4(1):67–75. tion of agricultural residues by carbon dioxide in the presence of
67. Patel M, Kumar A. Production of renewable diesel through the hydro- different additives: influence of variables. Fuel Process Technol.
processing of lignocellulosic biomass-derived bio-oil: a review. Renew 1998;55(3):219–33.
Sustain Energy Rev. 2016;58:1293–307. 93. Islam MR, Parveen M, Haniu H. Properties of sugarcane waste-derived
68. Acharya B, Sule I, Dutta A. A review on advances of torrefaction bio-oils obtained by fixed-bed fire-tube heating pyrolysis. Bioresour
technologies for biomass processing. Biomass Convers Biorefin. Technol. 2010;101(11):4162–8.
2012;2(4):349–69. 94. Pattiya A, Suttibak S. Production of bio-oil via fast pyrolysis of agricul-
69. Homagain K, Shahi C, Luckai N, Sharma M. Biochar-based bioenergy tural residues from cassava plantations in a fluidised-bed reactor with
and its environmental impact in Northwestern Ontario Canada: a a hot vapour filtration unit. J Anal Appl Pyrol. 2012;95:227–35.
review. J Forestry Res. 2014;25(4):737–48. 95. Kim SW, Koo BS, Ryu JW, Lee JS, Kim CJ, Lee DH, et al. Bio-oil from the
70. Bridgwater AV. Review of fast pyrolysis of biomass and product upgrad- pyrolysis of palm and Jatropha wastes in a fluidized bed. Fuel Process
ing. Biomass Bioenergy. 2012;38:68–94. Technol. 2013;108:118–24.
71. Mohan D, Pittman CU, Steele PH. Pyrolysis of wood/biomass for bio-oil: 96. Apaydin-Varol E, Pütün E, Pütün AE. Slow pyrolysis of pistachio shell.
a critical review. Energy Fuel. 2006;20(3):848–89. Fuel. 2007;86(12–13):1892–9.
72. Qiu B, Tao X, Wang J, Liu Y, Li S, Chu H. Research progress in the 97. Makibar J, Fernandez-Akarregi AR, Amutio M, Lopez G, Olazar M. Perfor-
preparation of high-quality liquid fuels and chemicals by catalytic mance of a conical spouted bed pilot plant for bio-oil production by
pyrolysis of biomass: a review. Energy Convers Manag. 2022;261: poplar flash pyrolysis. Fuel Process Technol. 2015;137:283–9.
115647. 98. Biswas B, Pandey N, Bisht Y, Singh R, Kumar J, Bhaskar T. Pyrolysis of
73. Chen Y, Fang Y, Yang H, Xin S, Zhang X, Wang X, et al. Effect of agricultural biomass residues: comparative study of corn cob, wheat
volatiles interaction during pyrolysis of cellulose, hemicellulose, and straw, rice straw and rice husk. Bioresour Technol. 2017;237:57–63.
lignin at different temperatures. Fuel. 2019;248:1–7. 99. Pattiya A. Bio-oil production via fast pyrolysis of biomass residues
74. Jiang L, Luo J, Xu F, Qian L, Wang Y, Li H, et al. High yield production from cassava plants in a fluidised-bed reactor. Bioresour Technol.
of levoglucosan via catalytic pyrolysis of cellulose at low tempera- 2011;102(2):1959–67.
ture. Fuel. 2022;323: 124369. 100. Oasmaa A, Solantausta Y, Arpiainen V, Kuoppala E, Sipila K. Fast
75. Gu X, Ma X, Li L, Liu C, Cheng K, Li Z. Pyrolysis of poplar wood saw- pyrolysis bio-oils from wood and agricultural residues. Energy Fuel.
dust by TG-FTIR and Py–GC/MS. J Anal Appl Pyrol. 2013;102:16–23. 2010;24(2):1380–8.
76. Lin Y-C, Cho J, Tompsett GA, Westmoreland PR, Huber GW. 101. Li J, Chen Y, Yang H, Zhu D, Chen X, Wang X, et al. Correlation
Kinetics and mechanism of cellulose pyrolysis. J Phys Chem C. of feedstock and bio-oil compound distribution. Energy Fuel.
2009;113(46):20097–107. 2017;31(7):7093–100.
77. Patwardhan PR, Brown RC, Shanks BH. Product distribution from the 102. Huang X, Cao J-P, Shi P, Zhao X-Y, Feng X-B, Zhao Y-P, et al. Influences
fast pyrolysis of hemicellulose. ChemSusChem. 2011;4(5):636–43. of pyrolysis conditions in the production and chemical composition
78. Leng E, Guo Y, Chen J, Liu S, Jiaqiang E, Xue Y. A comprehensive of the bio-oils from fast pyrolysis of sewage sludge. J Anal Appl Pyrol.
review on lignin pyrolysis: mechanism, modeling and the effects of 2014;110:353–62.
inherent metals in biomass. Fuel. 2022;309: 122102. 103. Ly HV, Kim S-S, Woo HC, Choi JH, Suh DJ, Kim J. Fast pyrolysis of
79. Zhao C, Jiang E, Chen A. Volatile production from pyrolysis of cel- macroalga Saccharina japonica in a bubbling fluidized-bed reactor for
lulose, hemicellulose and lignin. J Energy Inst. 2017;90(6):902–13. bio-oil production. Energy. 2015;93:1436–46.
80. Zhang Y, Chen P, Liu S, Peng P, Min M, Cheng Y, et al. Effects of 104. Pütün E, Ateş F, Pütün AE. Catalytic pyrolysis of biomass in inert and
feedstock characteristics on microwave-assisted pyrolysis—a review. steam atmospheres. Fuel. 2008;87(6):815–24.
Bioresour Technol. 2017;230:143–51. 105. Ates F, Işıkdağ MA. Evaluation of the role of the pyrolysis temperature
81. Tsai W, Lee M, Chang Y. Fast pyrolysis of rice husk: product yields and in straw biomass samples and characterization of the oils by GC/MS.
compositions. Bioresour Technol. 2007;98(1):22–8. Energy Fuel. 2008;22(3):1936–43.
82. Lazzari E, Schena T, Primaz CT, da Silva Maciel GP, Machado ME, 106. Ly HV, Kim S-S, Choi JH, Woo HC, Kim J. Fast pyrolysis of Saccharina
Cardoso CAL, et al. Production and chromatographic characterization japonica alga in a fixed-bed reactor for bio-oil production. Energy
of bio-oil from the pyrolysis of mango seed waste. Ind Crop Prod. Convers Manag. 2016;122:526–34.
2016;83:529–36. 107. Wang J, Liu Z, Li J, Yan B, Tao J, Cheng Z, et al. In-situ hydrodeoxygena-
83. Isahak WNRW, Hisham MW, Yarmo MA, Hin T-YY. A review on bio-oil tion of lignin via hydrothermal liquefaction with water splitting metals:
production from biomass by using pyrolysis method. Renew Sustain comparison between autocatalytic and non-autocatalytic processes. Int
Energy Rev. 2012;16(8):5910–23. J Hydrog Energy. 2022;47(11):7252–62.
84. Jung S-H, Kang B-S, Kim J-S. Production of bio-oil from rice straw and 108. Zhang L, Zhang S, Hu X, Gholizadeh M. Progress in application of
bamboo sawdust under various reaction conditions in a fast pyrolysis the pyrolytic lignin from pyrolysis of biomass. Chem Eng J. 2021;419:
plant equipped with a fluidized bed and a char separation system. J 129560.
Anal Appl Pyrol. 2008;82(2):240–7. 109. Du X, Wu S, Li T, Yin Y, Zhou J. Ozone oxidation pretreatment of soft-
85. Zheng J-l, Zhu X-f, Guo Q-x, Zhu Q-s. Thermal conversion of rice wood kraft lignin: an effective and environmentally friendly approach
husks and sawdust to liquid fuel. Waste Manag. 2006;26(12):1430–5. to enhance fast pyrolysis product selectivity. Fuel Process Technol.
86. Ji-lu Z. Bio-oil from fast pyrolysis of rice husk: yields and related prop- 2022;231: 107232.
erties and improvement of the pyrolysis system. J Anal Appl Pyrol. 110. Wang T-P, Li H, Yuan J-M, Li W-X, Li K, Huang Y-B, et al. Structures and
2007;80(1):30–5. pyrolytic characteristics of organosolv lignins from typical softwood,
87. Zheng J-L, Yi W-M, Wang N-N. Bio-oil production from cotton stalk. hardwood and herbaceous biomass. Ind Crop Prod. 2021;171: 113912.
Energy Convers Manag. 2008;49(6):1724–30. 111. Demirbaş A. Analysis of liquid products from biomass via flash pyrolysis.
Energy Sources. 2002;24(4):337–45.

Content courtesy of Springer Nature, terms of use apply. Rights reserved.

Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 38 of 43

112. Luo Z, Wang S, Guo X. Selective pyrolysis of Organosolv lignin over zeo- 135. Chen S, Cheng H, Wu S. Pyrolysis characteristics and volatiles formation
lites with product analysis by TG-FTIR. J Anal Appl Pyrol. 2012;95:112–7. rule of organic solvent fractionized kraft lignin. Fuel. 2020;270: 117520.
113. Hu C, Liu C, Liu Q, Zhang H, Wu S, Xiao R. Effects of steam to enhance 136. Lyu G, Wu Q, Li T, Jiang W, Ji X, Yang G. Thermochemical properties of
the production of light olefins from ex-situ catalytic fast pyrolysis of lignin extracted from willow by deep eutectic solvents (DES). Cellulose.
biomass. Fuel Process Technol. 2020;210: 106562. 2019;26(15):8501–11.
114. Chen W-H, Wang C-W, Ong HC, Show PL, Hsieh T-H. Torrefaction, pyroly- 137. Akazawa M, Kato Y, Kojima Y. Application of two resinols as lignin dimer
sis and two-stage thermodegradation of hemicellulose, cellulose and models to characterize reaction mechanisms during pyrolysis. J Anal
lignin. Fuel. 2019;258: 116168. Appl Pyrol. 2016;122:355–64.
115. Sharma A, Kaur P, Singh G, Arya SK. Economical concerns of lignin in the 138. Hosoya T, Kawamoto H, Saka S. Role of methoxyl group in char
energy sector. Clean Eng Technol. 2021;4: 100258. formation from lignin-related compounds. J Anal Appl Pyrol.
116. Ghalibaf M, Alén R, Hita I, Deuss PJ, Jan Heeres H, de Wild P. Valoriza- 2009;84(1):79–83.
tion potential of technical lignins from Norway spruce (Picea abies) via 139. Pu L, Wang X, Cao Q, Liu B, Liu H, Han Y, et al. Novel nonprecious metal
pyrolysis. J Anal Appl Pyrol. 2022;165: 105549. loading multi-metal oxide catalysts for lignin depolymerization. Energy
117. Mahmood N, Yuan Z, Schmidt J, Xu C. Depolymerization of lignins and Fuel. 2019;33(7):6491–500.
their applications for the preparation of polyols and rigid polyurethane 140. Ma H, Li T, Wu S, Zhang X. Demethylation of a methoxy group to inhibit
foams: a review. Renew Sustain Energy Rev. 2016;60:317–29. repolymerization during alkaline lignin pyrolysis. Fuel. 2021;286: 119394.
118. Lee HV, Hamid SBA, Zain SK. Conversion of lignocellulosic biomass to 141. Li J, Bai X, Fang Y, Chen Y, Wang X, Chen H, et al. Comprehensive mecha-
nanocellulose: structure and chemical process. Sci World J. 2014;2014: nism of initial stage for lignin pyrolysis. Combust Flame. 2020;215:1–9.
631013. 142. Faravelli T, Frassoldati A, Migliavacca G, Ranzi E. Detailed kinetic
119. Raveendran K, Ganesh A, Khilar KC. Pyrolysis characteristics of biomass modeling of the thermal degradation of lignins. Biomass Bioenergy.
and biomass components. Fuel. 1996;75(8):987–98. 2010;34(3):290–301.
120. Deng W, Xu K, Xiong Z, Chaiwat W, Wang X, Su S, et al. Evolution of 143. Chua YW, Yu Y, Wu H. Structural changes of chars produced from fast
aromatic structures during the low-temperature electrochemical pyrolysis of lignin at 100–300 °C. Fuel. 2019;255: 115754.
upgrading of bio-oil. Energy Fuel. 2019;33(11):11292–301. 144. Shrestha B, le Brech Y, Ghislain T, Leclerc S, Carré V, Aubriet F, et al. A
121. Xiong Z, Guo J, Chaiwat W, Deng W, Hu X, Han H, et al. Assessing the multitechnique characterization of lignin softening and pyrolysis. ACS
chemical composition of heavy components in bio-oils from the Sustain Chem Eng. 2017;5(8):6940–9.
pyrolysis of cellulose, hemicellulose and lignin at slow and fast heating 145. Wang Y, Li X, Mourant D, Gunawan R, Zhang S, Li C-Z. Formation
rates. Fuel Process Technol. 2020;199: 106299. of aromatic structures during the pyrolysis of bio-oil. Energy Fuel.
122. Lu X, Zhu X, Guo H, Que H, Wang D, Liang D, et al. Investigation on 2012;26(1):241–7.
the thermal degradation behavior of enzymatic hydrolysis lignin with 146. Thangalazhy-Gopakumar S, Adhikari S, Gupta RB, Fernando SD.
or without steam explosion treatment characterized by TG-FTIR and Influence of pyrolysis operating conditions on bio-oil components: a
Py-GC/MS. Biomass Convers Biorefin. 2020. https://​doi.​org/​10.​1007/​ microscale study in a pyroprobe. Energy Fuel. 2011;25(3):1191–9.
s13399-​020-​00987-5. 147. Jiang G, Nowakowski DJ, Bridgwater AV. Effect of the tempera-
123. Li C, Sun Y, Dong D, Gao G, Zhang S, Wang Y, et al. Co-pyrolysis of cel- ture on the composition of lignin pyrolysis products. Energy Fuel.
lulose/lignin and sawdust: Influence of secondary condensation of the 2010;24(8):4470–5.
volatiles on characteristics of biochar. Energy. 2021;226: 120442. 148. Klemetsrud B, Eatherton D, Shonnard D. Effects of lignin content and
124. Chua YW, Wu H, Yu Y. Effect of cellulose–lignin interactions on char temperature on the properties of hybrid poplar bio-oil, char, and gas
structural changes during fast pyrolysis at 100–350 °C. Proc Combust obtained by fast pyrolysis. Energy Fuel. 2017;31(3):2879–86.
Inst. 2021;38(3):3977–86. 149. Ma Z, Sun Q, Ye J, Yao Q, Zhao C. Study on the thermal degradation
125. Halder P, Kundu S, Patel S, Parthasarathy R, Pramanik B, Paz-Ferreiro J, behaviors and kinetics of alkali lignin for production of phenolic-
et al. TGA-FTIR study on the slow pyrolysis of lignin and cellulose-rich rich bio-oil using TGA–FTIR and Py–GC/MS. J Anal Appl Pyrol.
fractions derived from imidazolium-based ionic liquid pre-treatment of 2016;117:116–24.
sugarcane straw. Energy Convers Manag. 2019;200: 112067. 150. Mei Y, Zhang S, Wang H, Jing S, Hou T, Pang S. Low-temperature
126. Lei M, Wu S, Liang J, Liu C. Comprehensive understanding the chemical deoxidization of lignin and its impact on liquid products from pyrolysis.
structure evolution and crucial intermediate radical in situ observation Energy Fuel. 2020;34(3):3422–8.
in enzymatic hydrolysis/mild acidolysis lignin pyrolysis. J Anal Appl 151. Zhao S, Liu M, Zhao L, Zhu L. Influence of interactions among three
Pyrol. 2019;138:249–60. biomass components on the pyrolysis behavior. Ind Eng Chem Res.
127. Liu C, Hu J, Zhang H, Xiao R. Thermal conversion of lignin to phenols: 2018;57(15):5241–9.
relevance between chemical structure and pyrolysis behaviors. Fuel. 152. Lin X, Sui S, Tan S, Pittman CU, Sun J, Zhang Z. Fast pyrolysis of four
2016;182:864–70. lignins from different isolation processes using Py-GC/MS. Energies.
128. Yang J, Wang X, Shen B, Hu Z, Xu L, Yang S. Lignin from energy plant 2015;8(6):5107–21.
(Arundo donax): pyrolysis kinetics, mechanism and pathway evaluation. 153. Jegers HE, Klein MT. Primary and secondary lignin pyrolysis reaction
Renew Energy. 2020;161:963–71. pathways. Ind Eng Chem Process Des Dev. 1985;24(1):173–83.
129. Qiao Y, Wang B, Ji Y, Xu F, Zong P, Zhang J, et al. Thermal decomposition 154. Shao L, Zhang X, Chen F, Xu F. Fast pyrolysis of Kraft lignins fractionated
of castor oil, corn starch, soy protein, lignin, xylan, and cellulose during by ultrafiltration. J Anal Appl Pyrol. 2017;128:27–34.
fast pyrolysis. Bioresour Technol. 2019;278:287–95. 155. Akhtar J, Amin NS. A review on operating parameters for optimum
130. Wu Z, Zhu X, Guo H, Jiang Y, Gu X. A kinetic study of lignin pyrolysis liquid oil yield in biomass pyrolysis. Renew Sustain Energy Rev.
over base catalyst during steam exploded depolymerization. Catal 2012;16(7):5101–9.
Today. 2019;327:226–34. 156. Ansari KB, Arora JS, Chew JW, Dauenhauer PJ, Mushrif SH. Fast pyrolysis
131. Yeo JY, Chin BLF, Tan JK, Loh YS. Comparative studies on the pyrolysis of cellulose, hemicellulose, and lignin: effect of operating temperature
of cellulose, hemicellulose, and lignin based on combined kinetics. J on bio-oil yield and composition and insights into the intrinsic pyrolysis
Energy Inst. 2019;92(1):27–37. chemistry. Ind Eng Chem Res. 2019;58(35):15838–52.
132. Ding Y, Zhang W, Yu L, Lu K. The accuracy and efficiency of GA and PSO 157. Marathe PS, Westerhof RJM, Kersten SRA. Fast pyrolysis of lignins with
optimization schemes on estimating reaction kinetic parameters of different molecular weight: experiments and modelling. Appl Energy.
biomass pyrolysis. Energy. 2019;176:582–8. 2019;236:1125–37.
133. Hung C-M, Chen C-W, Huang C-P, Yang Y-Y, Dong C-D. Suppression of 158. Yuan J-M, Li H, Xiao L-P, Wang T-P, Ren W-F, Lu Q, et al. Valorization of
polycyclic aromatic hydrocarbon formation during pyrolytic production lignin into phenolic compounds via fast pyrolysis: impact of lignin
of lignin-based biochar via nitrogen and boron co-doping. Bioresour structure. Fuel. 2022;319: 123758.
Technol. 2022;355: 127246. 159. Beste A, Buchanan AC. Computational study of bond dissociation
134. Yu J, Wang D, Sun L. The pyrolysis of lignin: Pathway and interaction enthalpies for lignin model compounds. Substituent effects in phene-
studies. Fuel. 2021;290: 120078. thyl phenyl ethers. J Org Chem. 2009;74(7):2837–41.

Content courtesy of Springer Nature, terms of use apply. Rights reserved.

Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 39 of 43

160. Hu J, Shen D, Xiao R, Wu S, Zhang H. Free-radical analysis on thermo- 182. Dondi D, Zeffiro A, Speltini A, Tomasi C, Vadivel D, Buttafava A. The role
chemical transformation of lignin to phenolic compounds. Energy Fuel. of inorganic sulfur compounds in the pyrolysis of Kraft lignin. J Anal
2013;27(1):285–93. Appl Pyrol. 2014;107:53–8.
161. Younker JM, Beste A, Buchanan Iii AC. Computational study of bond 183. Beis SH, Mukkamala S, Hill N, Joseph J, Baker C, Jensen B, et al. Fast
dissociation enthalpies for substituted β-O-4 lignin model compounds. pyrolysis of lignins. BioResources. 2010;5(3):1408–24.
ChemPhysChem. 2011;12(18):3556–65. 184. Daniel D, Khachatryan L, Astete C, Asatryan R, Marculescu C, Boldor D.
162. McMillen DF, Malhotra R, Chang S-J, Ogier WC, Nigenda SE, Flem- Sulfur contaminations inhibit depolymerization of Kraft lignin. Bioresour
ing RH. Mechanisms of hydrogen transfer and bond scission of Technol Rep. 2019;8: 100341.
strongly bonded coal structures in donor-solvent systems. Fuel. 185. Ibarra D, Chávez MI, Rencoret J, Del Río JC, Gutiérrez A, Romero J, et al.
1987;66(12):1611–20. Lignin modification during Eucalyptus globulus Kraft pulping followed
163. Kawamoto H. Lignin pyrolysis reactions. J Wood Sci. 2017;63(2):117–32. by totally chlorine-free bleaching: a two-dimensional nuclear magnetic
164. Feng Y, Wang JT, Liu L, Guo QX. C–H and N–H bond dissociation ener- resonance, Fourier transform infrared, and pyrolysis-gas chromatogra-
gies of five-and six-membered ring aromatic compounds. J Phys Org phy/mass spectrometry study. J Agric Food Chem. 2007;55(9):3477–90.
Chem. 2003;16(12):883–90. 186. Wen J-L, Sun S-L, Yuan T-Q, Sun R-C. Structural elucidation of whole
165. Garcia-Perez M, Wang S, Shen J, Rhodes M, Lee WJ, Li C-Z. Effects lignin from Eucalyptus based on preswelling and enzymatic hydrolysis.
of temperature on the formation of lignin-derived oligomers Green Chem. 2015;17(3):1589–96.
during the fast pyrolysis of Mallee woody biomass. Energy Fuel. 187. Zhang M, Resende FLP, Moutsoglou A, Raynie DE. Pyrolysis of lignin
2008;22(3):2022–32. extracted from prairie cordgrass, aspen, and Kraft lignin by Py-GC/MS
166. Ojha DK, Viju D, Vinu R. Fast pyrolysis kinetics of alkali lignin: evaluation and TGA/FTIR. J Anal Appl Pyrol. 2012;98:65–71.
of apparent rate parameters and product time evolution. Bioresour 188. Fan Y, Zhang Z, Wang Z, Yu H, Kong X, Li P, et al. Radical footprinting and
Technol. 2017;241:142–51. regularity revealing during the pyrolysis of technical lignins. Bioresour
167. Asatryan R, Bennadji H, Bozzelli JW, Ruckenstein E, Khachatryan L. Technol. 2022;360: 127648.
Molecular products and fundamentally based reaction pathways in the 189. Demuner IF, Gomes FJB, Coura MR, Gomes JS, Demuner AJ, Carvalho
gas-phase pyrolysis of the lignin model compound p-coumaryl alcohol. AMML, et al. Determination of chemical modification of eucalypt
J Phys Chem A. 2017;121(18):3352–71. kraft lignin after thermal treatment by Py-GC-MS. J Anal Appl Pyrol.
168. Dong C-Q, Zhang Z-F, Lu Q, Yang Y-P. Characteristics and mechanism 2021;156: 105158.
study of analytical fast pyrolysis of poplar wood. Energy Convers 190. Cao X, Shao L, Huang W, Wang C, Mao J, Xu F, et al. Thermal degrada-
Manag. 2012;57:49–59. tion of lignins fractionated by gradient acid precipitation. J Anal Appl
169. Patwardhan PR, Dalluge DL, Shanks BH, Brown RC. Distinguishing pri- Pyrol. 2021;157: 105200.
mary and secondary reactions of cellulose pyrolysis. Bioresour Technol. 191. Shimizu S, Posoknistakul P, Akiyama T, Yokoyama T, Matsumoto Y.
2011;102(8):5265–9. Effects of aromatic ring type on reactions subsequent to the β-O-4
170. Yang H, Dong Z, Liu B, Chen Y, Gong M, Li S, et al. A new insight of lignin bond cleavage of non-phenolic lignin model compounds under
pyrolysis mechanism based on functional group evolutions of solid alkaline pulping conditions. J Wood Sci. 2018;64(5):664–74.
char. Fuel. 2021;288: 119719. 192. Yu Q, Wang Y, Chen X, Wang F, Tian X, Gao Y, et al. Deep eutectic
171. Jiang W, Wu S, Lucia LA, Chu J. A comparison of the pyrolysis behavior solvent assists Bacillus australimaris to transform alkali lignin waste
of selected β-O-4 type lignin model compounds. J Anal Appl Pyrol. into small aromatic compounds. J Clean Prod. 2021;320: 128719.
2017;125:185–92. 193. Chandra R, Singh S, Krishna Reddy MM, Purohit HJ, Kapley A. Isolation
172. Jiang X-Y, Lu Q, Dong X-C, Hu B, Dong C-Q. Theoretical study on and characterization of bacterial strains Paenibacillus sp. and Bacillus
the effect of the substituent groups on the homolysis of the ether sp. for kraft lignin decolorization from pulp paper mill waste. J Gen
bond in lignin trimer model compounds. J Fuel Chem Technol. Appl Microbiol. 2008;54(6):399–407.
2016;44(3):335–41. 194. Guo D-L, Wu S-B, Liu B, Yin X-L, Yang Q. Catalytic effects of NaOH
173. Dong Z, Yang H, Chen P, Liu Z, Chen Y, Wang L, et al. Lignin characteriza- and ­Na2CO3 additives on alkali lignin pyrolysis and gasification. Appl
tion and catalytic pyrolysis for phenol-rich oil with ­TiO2-based catalysts. Energy. 2012;95:22–30.
Energy Fuel. 2019;33(10):9934–41. 195. Sun R, Tomkinson J, Bolton J. Effects of precipitation pH on the
174. Xu J, Tang H, Su S, Liu J, Xu K, Qian K, et al. A study of the relationships physico-chemical properties of the lignins isolated from the black
between coal structures and combustion characteristics: the insights liquor of oil palm empty fruit bunch fibre pulping. Polym Degrad
from micro-Raman spectroscopy based on 32 kinds of Chinese coals. Stabil. 1999;63(2):195–200.
Appl Energy. 2018;212:46–56. 196. Khanh Tran Q, Vu Ly H, Tae Hwang H, Kim J, Kim S-S. Study on pyroly-
175. Li X, Hayashi J-I, Li C-Z. Volatilisation and catalytic effects of alkali and sis of Organosolv lignin impregnated with alkali and alkaline earth
alkaline earth metallic species during the pyrolysis and gasification metals: kinetics, thermodynamics, and product characterization. Fuel.
of Victorian brown coal. Part VII. Raman spectroscopic study on the 2022;329: 125472.
changes in char structure during the catalytic gasification in air. Fuel. 197. Quyn DM, Wu H, Bhattacharya SP, Li C-Z. Volatilisation and catalytic
2006;85(10):1509–17. effects of alkali and alkaline earth metallic species during the pyroly-
176. Custodis VBF, Bährle C, Vogel F, van Bokhoven JA. Phenols and aromat- sis and gasification of Victorian brown coal. Part II. Effects of chemical
ics from fast pyrolysis of variously prepared lignins from hard- and form and valence. Fuel. 2002;81(2):151–8.
softwoods. J Anal Appl Pyrol. 2015;115:214–23. 198. Guo D-L, Yuan H-Y, Yin X-L, Wu C-Z, Wu S-B, Zhou Z-Q. Effects of
177. Vishtal AG, Kraslawski A. Challenges in industrial applications of techni- chemical form of sodium on the product characteristics of alkali
cal lignins. BioResources. 2011;6(3):3547–68. lignin pyrolysis. Bioresour Technol. 2014;152:147–53.
178. Gierer J. Chemical aspects of kraft pulping. Wood Sci Technol. 199. Dalluge DL, Kim KH, Brown RC. The influence of alkali and alkaline
1980;14(4):241–66. earth metals on char and volatile aromatics from fast pyrolysis of
179. Fenner RA, Lephardt JO. Examination of the thermal decomposition lignin. J Anal Appl Pyrol. 2017;127:385–93.
of kraft pine lignin by Fourier transform infrared evolved gas analysis. J 200. Zabeti M, Nguyen TS, Lefferts L, Heeres HJ, Seshan K. In situ catalytic
Agric Food Chem. 1981;29(4):846–9. pyrolysis of lignocellulose using alkali-modified amorphous silica
180. Evdokimov AN, Kurzin AV, Fedorova OV, Lukanin PV, Kazakov VG, alumina. Bioresour Technol. 2012;118:374–81.
Trifonova AD. Desulfurization of kraft lignin. Wood Sci Technol. 201. Nguyen TS, Zabeti M, Lefferts L, Brem G, Seshan K. Conversion of
2018;52(4):1165–74. lignocellulosic biomass to green fuel oil over sodium based catalysts.
181. Han T, Sophonrat N, Evangelopoulos P, Persson H, Yang W, Jönsson P. Bioresour Technol. 2013;142:353–60.
Evolution of sulfur during fast pyrolysis of sulfonated Kraft lignin. J Anal 202. Lv D, Xu M, Liu X, Zhan Z, Li Z, Yao H. Effect of cellulose, lignin, alkali
Appl Pyrol. 2018;133:162–8. and alkaline earth metallic species on biomass pyrolysis and gasifica-
tion. Fuel Process Technol. 2010;91(8):903–9.

Content courtesy of Springer Nature, terms of use apply. Rights reserved.

Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 40 of 43

203. Quyn DM, Wu H, Hayashi J-I, Li C-Z. Volatilisation and catalytic effects 225. Li T, Lyu G, Liu Y, Lou R, Lucia LA, Yang G, et al. Deep eutectic solvents
of alkali and alkaline earth metallic species during the pyrolysis (DESs) for the isolation of willow lignin (Salix matsudana cv. Zhuliu). Int J
and gasification of Victorian brown coal. Part IV. Catalytic effects Mol Sci. 2017;18(11):2266.
of NaCl and ion-exchangeable Na in coal on char reactivity. Fuel. 226. Liu X, Li T, Wu S, Ma H, Yin Y. Structural characterization and compari-
2003;82(5):587–93. son of enzymatic and deep eutectic solvents isolated lignin from
204. Biswas B, Singh R, Kumar J, Khan AA, Krishna BB, Bhaskar T. Slow various green processes: toward lignin valorization. Bioresour Technol.
pyrolysis of prot, alkali and dealkaline lignins for production of 2020;310: 123460.
chemicals. Bioresour Technol. 2016;213:319–26. 227. Xu H, Kong Y, Peng J, Song X, Liu Y, Su Z, et al. Comprehensive analysis
205. Guo D, Wu S, Lyu G, Guo H. Effect of molecular weight on the pyroly- of important parameters of choline chloride-based deep eutectic
sis characteristics of alkali lignin. Fuel. 2017;193:45–53. solvent pretreatment of lignocellulosic biomass. Bioresour Technol.
206. Pongchaiphol S, Suriyachai N, Hararak B, Raita M, Laosiripojana N, 2021;319: 124209.
Champreda V. Physicochemical characteristics of organosolv lignins 228. Kim J-Y, Choi JW. Effect of molecular size of lignin on the formation
from different lignocellulosic agricultural wastes. Int J Biol Macromol. of aromatic hydrocarbon during zeolite catalyzed pyrolysis. Fuel.
2022;216:710–27. 2019;240:92–100.
207. Cheng X-C, Guo X-R, Qin Z, Wang X-D, Liu H-M, Liu Y-L. Structural 229. Li T, Yin Y, Wu S, Du X. Effect of deep eutectic solvents-regulated lignin
features and antioxidant activities of Chinese quince (Chaenomeles structure on subsequent pyrolysis products selectivity. Bioresour Tech-
sinensis) fruits lignin during auto-catalyzed ethanol organosolv nol. 2022;343: 126120.
pretreatment. Int J Biol Macromol. 2020;164:4348–58. 230. Jampa S, Puente-Urbina A, Ma Z, Wongkasemjit S, Luterbacher JS, Van
208. Sheng Y, Ma Z, Wang X, Han Y. Ethanol organosolv lignin from differ- Bokhoven JA. Optimization of lignin extraction from pine wood for fast
ent agricultural residues: toward basic structural units and antioxi- pyrolysis by using a γ-valerolactone-based binary solvent system. ACS
dant activity. Food Chem. 2022;376: 131895. Sustain Chem Eng. 2019;7(4):4058–68.
209. Parchami M, Agnihotri S, Taherzadeh MJ. Aqueous ethanol orga- 231. Wang S, Ru B, Lin H, Sun W, Luo Z. Pyrolysis behaviors of four lignin
nosolv process for the valorization of Brewer’s spent grain (BSG). polymers isolated from the same pine wood. Bioresour Technol.
Bioresour Technol. 2022;362: 127764. 2015;182:120–7.
210. Warner G, Hansen TS, Riisager A, Beach ES, Barta K, Anastas PT. Depo- 232. Li S, Luo Z, Wang W, Lu K, Yang Y, Liang X. Characterization of pyrolytic
lymerization of organosolv lignin using doped porous metal oxides in lignin and insight into its formation mechanisms using novel tech-
supercritical methanol. Bioresour Technol. 2014;161:78–83. niques and DFT method. Fuel. 2020;262: 116516.
211. Ramakoti B, Dhanagopal H, Deepa K, Rajesh M, Ramaswamy S, 233. Wang S, Ru B, Dai G, Shi Z, Zhou J, Luo Z, et al. Mechanism study on the
Tamilarasan K. Solvent fractionation of organosolv lignin to improve pyrolysis of a synthetic β-O-4 dimer as lignin model compound. Proc
lignin homogeneity: structural characterization. Bioresour Technol Rep. Combust Inst. 2017;36(2):2225–33.
2019;7: 100293. 234. Li TF, Lyu G, Saeed HAM, Liu Y, Wu YL, Yang GH, et al. Analytical pyrolysis
212. Laurichesse S, Avérous L. Chemical modification of lignins: towards characteristics of enzymatic/mild acidolysis lignin (EMAL). BioResources.
biobased polymers. Prog Polym Sci. 2014;39(7):1266–90. 2018;13(2):4484–96.
213. Tolbert A, Akinosho H, Khunsupat R, Naskar AK, Ragauskas AJ. Charac- 235. Dai L, Wang Y, Liu Y, Ruan R, He C, Duan D, et al. Bridging the relation-
terization and analysis of the molecular weight of lignin for biorefining ship between hydrothermal pretreatment and co-pyrolysis: effect of
studies. Biofuel Bioprod Biorefin. 2014;8(6):836–56. hydrothermal pretreatment on aromatic production. Energy Convers
214. Hong S, Shen XJ, Pang B, Xue Z, Cao XF, Wen JL, et al. In-depth interpre- Manag. 2019;180:36–43.
tation of the structural changes of lignin and formation of diketones 236. Li X-Y, Guo T-S, Li M-F, Peng F. Comparison of structure, thermal stability,
during acidic deep eutectic solvent pretreatment. Green Chem. and pyrolysis products of lignin extracted with ChCl-formic acid/lactic
2020;22(6):1851–8. acid systems. J Mater Res Technol. 2021;14:841–50.
215. Hu B, Zhang B, Xie W-L, Jiang X-Y, Liu J, Lu Q. Recent progress in quan- 237. Shen X-J, Chen T, Wang H-M, Mei Q, Yue F, Sun S, et al. Structural and
tum chemistry modeling on the pyrolysis mechanisms of lignocellu- morphological transformations of lignin macromolecules during bio-
losic biomass. Energy Fuel. 2020;34(9):10384–440. based deep eutectic solvent (DES) pretreatment. ACS Sustain Chem
216. Soongprasit K, Sricharoenchaikul V, Atong D. Phenol-derived products Eng. 2020;8(5):2130–7.
from fast pyrolysis of organosolv lignin. Energy Rep. 2020;6:151–67. 238. Wen JL, Xue BL, Sun SL, Sun RC. Quantitative structural characterization
217. Harman-Ware AE, Crocker M, Kaur AP, Meier MS, Kato D, Lynn B. and thermal properties of birch lignins after auto-catalyzed organosolv
Pyrolysis-GC/MS of sinapyl and coniferyl alcohol. J Anal Appl Pyrol. pretreatment and enzymatic hydrolysis. J Chem Technol Biotechnol.
2013;99:161–9. 2013;88(9):1663–71.
218. Asmadi M, Kawamoto H, Saka S. Thermal reactions of guaiacol 239. Ma Z, Sun Q, Ye J, Yao Q, Zhao C. Study on the thermal degradation
and syringol as lignin model aromatic nuclei. J Anal Appl Pyrol. behaviors and kinetics of alkali lignin for production of phenolic-
2011;92(1):88–98. rich bio-oil using TGA-FTIR and Py-GC/MS. J Anal Appl Pyrol.
219. Dorrestijn E, Mulder P. The radical-induced decomposition of 2-meth- 2016;117:116–24.
oxyphenol. J Chem Soc Perkin Trans 2. 1999;4:777–80. 240. Li H, Li X, You T, Li D, Nawaz H, Zhang X, et al. Insights into alkaline
220. Wang W, Liu Y, Wang Y, Liu L, Hu C. The influence of solvent on the choline chloride-based deep eutectic solvents pretreatment for Populus
pyrolysis of organosolv lignins extracted from willow. Energy Convers deltoides: lignin structural features and modification mechanism. Int J
Manag X. 2022;13: 100139. Biol Macromol. 2021;193:319–27.
221. Chen D, Cen K, Zhuang X, Gan Z, Zhou J, Zhang Y, et al. Insight into 241. Tan YT, Chua ASM, Ngoh GC. Evaluation on the properties of deep
biomass pyrolysis mechanism based on cellulose, hemicellulose, and eutectic solvent-extracted lignin for potential aromatic bio-products
lignin: evolution of volatiles and kinetics, elucidation of reaction path- conversion. Ind Crop Prod. 2020;154: 112729.
ways, and characterization of gas, biochar and bio-oil. Combust Flame. 242. Wang T, Ye X, Yin J, Jin Z, Lu Q, Zheng Z, et al. Fast pyrolysis product
2022;242: 112142. distribution of biopretreated corn stalk by methanogen. Bioresour
222. Wang C, Xia S, Cui C, Kang S, Zheng A, Yu Z, et al. Investigation into the Technol. 2014;169:812–5.
correlation between the chemical structure of lignin and its tempera- 243. Yu H, Liu F, Ke M, Zhang X. Thermogravimetric analysis and kinetic study
ture-dependent pyrolytic product evolution. Fuel. 2022;329: 125215. of bamboo waste treated by Echinodontium taxodii using a modified
223. Lv X, Li Q, Jiang Z, Wang Y, Li J, Hu C. Structure characterization and three-parallel-reactions model. Bioresour Technol. 2015;185:324–30.
pyrolysis behavior of organosolv lignin isolated from corncob residue. J 244. Ke J, Singh D, Yang X, Chen S. Thermal characterization of softwood
Anal Appl Pyrol. 2018;136:115–24. lignin modification by termite Coptotermes formosanus (Shiraki). Bio-
224. Chen Z, Bai X, Lusi A, Wan C. High-solid lignocellulose processing mass Bioenergy. 2011;35(8):3617–26.
enabled by natural deep eutectic solvent for lignin extraction and 245. Yan K, Liu F, Chen Q, Ke M, Huang X, Hu W, et al. Pyrolysis characteris-
industrially relevant production of renewable chemicals. ACS Sustain tics and kinetics of lignin derived from enzymatic hydrolysis residue
Chem Eng. 2018;6(9):12205–16.

Content courtesy of Springer Nature, terms of use apply. Rights reserved.

Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 41 of 43

of bamboo pretreated with white-rot fungus. Biotechnol Biofuel. 268. Usmani Z, Sharma M, Gupta P, Karpichev Y, Gathergood N, Bhat R,
2016;9(1):1–11. et al. Ionic liquid based pretreatment of lignocellulosic biomass for
246. Kong W, Fu X, Wang L, Alhujaily A, Zhang JL, Ma FY, et al. A novel and enhanced bioconversion. Bioresour Technol. 2020;304: 123003.
efficient fungal delignification strategy based on versatile peroxidase 269. Muhammad N, Man Z, Mutalib MA, Bustam MA, Wilfred CD, Khan AS,
for lignocellulose bioconversion. Biotechnol Biofuel. 2017;10:1–15. et al. Dissolution and separation of wood biopolymers using ionic
247. Shi L, Yu H, Dong T, Kong W, Ke M, Ma F, et al. Biochemical and molecu- liquids. ChemBioEng Rev. 2015;2(4):257–78.
lar characterization of a novel laccase from selective lignin-degrading 270. Yu W, Lei Z, Shui H, Ren S, Wang Z, Kang S, et al. Effect of ionic liquid
white-rot fungus Echinodontium taxodii 2538. Process Biochem. 1-butyl-3-methyl-imidazolium dihydrogen phosphate pretreatment on
2014;49(7):1097–106. pyrolysis of lignin. Coke Chem. 2017;60(11):439–44.
248. Xu Z, Peng L, Zhai R, Wen Z, Jin M. Recent advances in lignin valoriza- 271. Rashid T, Sher F, Khan AS, Khalid U, Rasheed T, Iqbal HMN, et al. Effect
tion with bacterial cultures: microorganisms, metabolic pathways, and of protic ionic liquid treatment on the pyrolysis products of lignin
bio-products. Biotechnol Biofuel. 2019;12:1–19. extracted from oil palm biomass. Fuel. 2021;291: 120133.
249. Wang L, Ni H, Zhang J, Shi Q, Zhang R, Yu H, et al. Enzymatic treatment 272. Sher F, Pans MA, Sun C, Snape C, Liu H. Oxy-fuel combustion
improves fast pyrolysis product selectivity of softwood and hardwood study of biomass fuels in a 20 kWth fluidized bed combustor. Fuel.
lignin. Sci Total Environ. 2020;717: 137241. 2018;215:778–86.
250. Ma F, Huang X, Ke M, Shi Q, Chen Q, Shi C, et al. Role of selective fungal 273. Guida M, Bouaik H, Tabal A, Hannioui A, Solhy A, Barakat A, et al.
delignification in overcoming the saccharification recalcitrance of Thermochemical treatment of olive mill solid waste and olive mill
bamboo culms. ACS Sustain Chem Eng. 2017;5(10):8884–94. wastewater. J Therm Anal Calorim. 2016;123(2):1657–66.
251. Kozliak EI, Kubatova A, Artemyeva AA, Nagel E, Zhang C, Rajappagowda 274. Rashid T, Gnanasundaram N, Appusamy A, Kait CF, Thanabalan M.
RB, et al. Thermal liquefaction of lignin to aromatics: efficiency, selectiv- Enhanced lignin extraction from different species of oil palm biomass:
ity, and product analysis. ACS Sustain Chem Eng. 2016;4(10):5106–22. kinetics and optimization of extraction conditions. Ind Crop Prod.
252. Wang C, Ouyang XH, Su SS, Liang X, Zhang C, Wang WY, et al. Effect of 2018;116:122–36.
sulfonated lignin on enzymatic activity of the ligninolytic enzymes C 275. Mohtar S, Busu TTM, Noor AM, Shaari N, Yusoff N, Bustam M, et al.
alpha-dehydrogenase LigD and beta-etherase LigF. Enzyme Microb Extraction and characterization of lignin from oil palm biomass via ionic
Technol. 2016;93–94:59–69. liquid dissolution and non-toxic aluminium potassium sulfate dodec-
253. Brebu M, Vasile C. Thermal degradation of lignin—a review. Cell Chem ahydrate precipitation processes. Bioresour Technol. 2015;192:212–8.
Technol. 2010;44(9):353–63. 276. Hu Y, Wang Z, Cheng X, Ma C. Non-isothermal TGA study on the com-
254. Venkatesagowda B, Dekker RFH. Enzymatic demethylation of Kraft bustion reaction kinetics and mechanism of low-rank coal char. RSC
lignin for lignin-based phenol-formaldehyde resin applications. Biomass Adv. 2018;8(41):22909–16.
Convers Biorefin. 2020;10(2):203–25. 277. Mabuda A, Mamphweli N, Meyer E. Model free kinetic analysis of bio-
255. Majeke BM, Collard FX, Tyhoda L, Görgens JF. The application of mass/sorbent blends for gasification purposes. Renew Sustain Energy
enzymatic pretreatment with subsequent pyrolysis to improve the pro- Rev. 2016;53:1656–64.
duction of phenols from selected industrial (technical) lignins. Waste 278. Muhammad N, Omar WN, Man Z, Bustam MA, Rafiq S, Uemura Y. Effect
Biomass Valoriz. 2022;13(4):2009–15. of ionic liquid treatment on pyrolysis products from bamboo. Ind Eng
256. Majeke BM, Collard FX, Tyhoda L, Görgens JF. The synergistic application Chem Res. 2012;51(5):2280–9.
of quinone reductase and lignin peroxidase for the deconstruction of 279. Lei Z, Dong L, Hu Z, Li Z, Yan J, Shui H, et al. Pyrolysis of acidic ionic
industrial (technical) lignins and analysis of the degraded lignin prod- liquid 1-sulfonic acid butyl-3-methylimidazolium trifluorometh-
ucts. Bioresour Technol. 2021;319: 124152. anesulfonate-treated lignin for phenolics production. Energy Fuel.
257. Yan K, Liu F, Chen Q, Ke M, Huang X, Hu W, et al. Pyrolysis characteris- 2019;33(6):4767–74.
tics and kinetics of lignin derived from enzymatic hydrolysis residue 280. Lei Z-P, Hu Z-Q, Shui H-F, Ren S-B, Wang Z-C, Kang S-G, et al. Pyrolysis
of bamboo pretreated with white-rot fungus. Biotechnol Biofuel. of lignin following ionic liquid pretreatment at low temperature. Fuel
2016;9(1):76. Process Technol. 2015;138:612–5.
258. Chiappe C, Pieraccini D. Ionic liquids: solvent properties and organic 281. Sun H, Luo Z, Wang W, Li S, Xue S. Porosity roles of micro-mesostruc-
reactivity. J Phys Org Chem. 2005;18(4):275–97. tured ZSM-5 in catalytic fast pyrolysis of cellulolytic enzyme lignin for
259. Zhang Q, Hu J, Lee D-J. Pretreatment of biomass using ionic liquids: aromatics. Energy Convers Manag. 2021;247: 114753.
research updates. Renew Energy. 2017;111:77–84. 282. Soongprasit K, Sricharoenchaikul V, Atong D. Selective aromatic produc-
260. Feng Y, Li Q, Kang G, Ji G, Tang Y, Tu J. Aqueous two-phase/reverse tion from fast pyrolysis of sugarcane bagasse lignin over ZSM-5 catalyst.
micelle continuous process for recycling and simultaneous purifica- Energy Rep. 2021;7:830–43.
tion of polar ionic liquid from enzymatic hydrolysate. J Chem Technol 283. Zhang H, Xiao R, Wang D, Zhong Z, Song M, Pan Q, et al. Catalytic fast
Biotech. 2016;91(2):394–9. pyrolysis of biomass in a fluidized bed with fresh and spent fluidized
261. Lynam JG, Chow GI, Coronella CJ, Hiibel SR. Ionic liquid and water catalytic cracking (FCC) catalysts. Energy Fuel. 2009;23(12):6199–206.
separation by membrane distillation. Chem Eng J. 2016;288:557–61. 284. Wang S, Li Z, Yi W, Fu P, Zhang A, Bai X. Renewable aromatic hydro-
262. Swatloski RP, Spear SK, Holbrey JD, Rogers RD. Dissolution of cellose carbons production from catalytic pyrolysis of lignin with Al-SBA-15
with ionic liquids. J Am Chem Soc. 2002;124(18):4974–5. and HZSM-5: synergistic effect and coke behaviour. Renew Energy.
263. Carneiro AP, Rodriguez O, Macedo EA. Dissolution and fractionation of 2021;163:1673–81.
nut shells in ionic liquids. Bioresour Technol. 2017;227:188–96. 285. Kumar A, Kumar A, Kumar J, Bhaskar T. Catalytic pyrolysis of soda lignin
264. da Costa Lopes AM, João KG, Rubik DF, Bogel-Łukasik E, Duarte LC, over zeolites using pyrolysis gas chromatography–mass spectrometry.
Andreaus J, et al. Pre-treatment of lignocellulosic biomass using ionic Bioresour Technol. 2019;291: 121822.
liquids: wheat straw fractionation. Bioresour Technol. 2013;142:198–208. 286. Tang S, Zhang C, Xue X, Pan Z, Wang D, Zhang R. Catalytic pyrolysis of
265. Khan AS, Man Z, Bustam MA, Kait CF, Ullah Z, Nasrullah A, et al. Kinetics lignin over hierarchical HZSM-5 zeolites prepared by post-treatment
and thermodynamic parameters of ionic liquid pretreated rubber wood with alkaline solutions. J Anal Appl Pyrol. 2019;137:86–95.
biomass. J Mol Liq. 2016;223:754–62. 287. Balasundram V, Ibrahim N, Kasmani RM, Hamid MKA, Isha R, Hasbul-
266. Xue Z, Zhao X, Sun R-C, Mu T. Biomass-derived γ-valerolactone-based lah H, et al. Thermogravimetric catalytic pyrolysis and kinetic studies
solvent systems for highly efficient dissolution of various lignins: of coconut copra and rice husk for possible maximum production of
dissolution behavior and mechanism study. ACS Sustain Chem Eng. pyrolysis oil. J Clean Prod. 2017;167:218–28.
2016;4(7):3864–70. 288. Jin T, Wang H, Peng J, Wu Y, Huang Z, Tian X, et al. Catalytic pyrolysis
267. Pin TC, Nascimento VM, Costa AC, Pu Y, Ragauskas AJ, Rabelo SC. of lignin with metal-modified HZSM-5 as catalysts for monocyclic
Structural characterization of sugarcane lignins extracted from different aromatic hydrocarbons production. Fuel Process Technol. 2022;230:
protic ionic liquid pretreatments. Renew Energy. 2020;161:579–92. 107201.
289. Yang M, Shao J, Yang Z, Yang H, Wang X, Wu Z, et al. Conversion of
lignin into light olefins and aromatics over Fe/ZSM-5 catalytic fast

Content courtesy of Springer Nature, terms of use apply. Rights reserved.

Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 42 of 43

pyrolysis: significance of Fe contents and temperature. J Anal Appl 311. Yang H, Han T, Yang W, Sandström L, Jönsson PG. Influence of the
Pyrol. 2019;137:259–65. porosity and acidic properties of aluminosilicate catalysts on coke
290. Lago A, Hernando H, Moreno JM, Serrano DP, Fermoso J. Valorisation of formation during the catalytic pyrolysis of lignin. J Anal Appl Pyrol.
a lignin-rich residue via catalytic pyrolysis over ­ZrO2/ZSM-5 technical 2022;165: 105536.
catalyst. Fuel Process Technol. 2021;215: 106746. 312. Margellou AG, Lazaridis PA, Charisteidis ID, Nitsos CK, Pappa CP, Foto-
291. Zhang H, Luo B, Wu K, Wu H, Yu J, Wang S. Enhancing aromatic yield poulos AP, et al. Catalytic fast pyrolysis of beech wood lignin isolated by
from catalytic pyrolysis of C­ a2+-loaded lignin coupled with metal- different biomass (pre)treatment processes: organosolv, hydrothermal
modified HZSM-5. Appl Energy Combust Sci. 2022;9: 100049. and enzymatic hydrolysis. Appl Catal A-Gen. 2021;623: 118298.
292. Xue S, Luo Z, Wang W, Li S, Sun H, Zhou Q, et al. Preparation of aromat- 313. Jin T, Zhang D, Peng J, Wu Y, Ma J, Zhang J, et al. Pretreatment of
ics from catalytic pyrolysis of enzymatic lignin over double-layer metal HZSM-5 with organic alkali and cobalt: application in catalytic pyrolysis
supported core–shell catalyst. J Anal Appl Pyrol. 2020;150: 104884. of lignin to produce monocyclic aromatic hydrocarbons. Fuel Process
293. Wang S, Li Z, Yi W, Fu P, Bai X. Regulating aromatic hydrocarbon Technol. 2022;233: 107308.
components from catalytic pyrolysis of corn cob lignin with a tailored 314. Zhao B, Wu K, Zhong L-P, Wei G, Hu Z-H, Zheng W-G, et al. Experimental
HZSM-5@Al-SBA-15 hierarchical zeolite. Ind Crop Prod. 2022;181: study on catalytic pyrolysis of lignin under char and ZSM-5 for prepara-
114813. tion of aromatics. J Fuel Chem Technol. 2021;49(3):304–11.
294. Li W, Wang D, Zhu Y, Chen J, Lu Y, Li S, et al. Efficient ex-situ catalytic 315. Fan L, Zhang Y, Liu S, Zhou N, Chen P, Cheng Y, et al. Bio-oil from fast
upgrading of biomass pyrolysis vapors to produce methylfurans and pyrolysis of lignin: effects of process and upgrading parameters. Biore-
phenol over bio-based activated carbon. Biomass Bioenergy. 2020;142: sour Technol. 2017;241:1118–26.
105794. 316. Engamba Esso SB, Xiong Z, Chaiwat W, Kamara MF, Longfei X, Xu J, et al.
295. Yang H, Chen Z, Chen W, Chen Y, Wang X, Chen H. Role of porous Review on synergistic effects during co-pyrolysis of biomass and plastic
structure and active O-containing groups of activated biochar catalyst waste: significance of operating conditions and interaction mechanism.
during biomass catalytic pyrolysis. Energy. 2020;210: 118646. Biomass Bioenergy. 2022;159: 106415.
296. Yang H, Han T, Shi Z, Sun Y, Jiang J, Sandström L, et al. In situ catalytic 317. Patil V, Adhikari S, Cross P. Co-pyrolysis of lignin and plastics using red
fast pyrolysis of lignin over biochar and activated carbon derived from clay as catalyst in a micro-pyrolyzer. Bioresour Technol. 2018;270:311–9.
the identical process. Fuel Process Technol. 2022;227: 107103. 318. Kunwar B, Cheng HN, Chandrashekaran SR, Sharma BK. Plastics to fuel: a
297. Zhang H, Luo B, Wu K, Zhao B, Yu J, Wang S, et al. Ex-situ catalytic review. Renew Sustain Energy Rev. 2016;54:421–8.
pyrolysis of lignin using lignin-carbon catalyst combined with HZSM-5 319. Xiong S, Zhuo J, Zhou H, Pang R, Yao Q. Study on the co-pyrolysis of
to improve the yield of high-quality liquid fuels. Fuel. 2022;318: 123635. high density polyethylene and potato blends using thermogravimetric
298. Yu J, Luo B, Wang Y, Wang S, Wu K, Liu C, et al. An efficient way to analyzer and tubular furnace. J Anal Appl Pyrol. 2015;112:66–73.
synthesize biomass-based molybdenum carbide catalyst via pyrolysis 320. Sophonrat N, Sandström L, Johansson A-C, Yang W. Co-pyrolysis of
carbonization and its application for lignin catalytic pyrolysis. Bioresour mixed plastics and cellulose: an interaction study by Py-GC×GC/MS.
Technol. 2022;346: 126640. Energy Fuel. 2017;31(10):11078–90.
299. Torri C, Reinikainen M, Lindfors C, Fabbri D, Oasmaa A, Kuoppala E. 321. Yuan C, Wang S, Cao B, Hu Y, Abomohra AE-F, Wang Q, et al. Optimiza-
Investigation on catalytic pyrolysis of pine sawdust: catalyst screening tion of hydrothermal co-liquefaction of seaweeds with lignocellulosic
by Py-GC-MIP-AED. J Anal Appl Pyrol. 2010;88(1):7–13. biomass: merging 2nd and 3rd generation feedstocks for enhanced
300. Zhang X, Sun L, Chen L, Xie X, Zhao B, Si H, et al. Comparison of catalytic bio-oil production. Energy. 2019;173:413–22.
upgrading of biomass fast pyrolysis vapors over CaO and Fe(III)/CaO 322. Önal E, Uzun BB, Pütün AE. Bio-oil production via co-pyrolysis of
catalysts. J Anal Appl Pyrol. 2014;108:35–40. almond shell as biomass and high density polyethylene. Energy Con-
301. Guan W, Chen X, Jin S, Li C, Tsang C-W, Liang C. Highly stable N ­ b2O5– vers Manag. 2014;78:704–10.
Al2O3 composites supported Pt catalysts for hydrodeoxygenation of 323. Zhong S, Zhang B, Liu C, Shujaa AA. Mechanism of synergistic effects
diphenyl ether. Ind Eng Chem Res. 2017;56(47):14034–42. and kinetics analysis in catalytic co-pyrolysis of water hyacinth and
302. Kong L, Zhang L, Gu J, Gou L, Xie L, Wang Y, et al. Catalytic hydrotreat- HDPE. Energy Convers Manag. 2021;228: 113717.
ment of kraft lignin into aromatic alcohols over nickel-rhenium sup- 324. Stančin H, Šafář M, Růžičková J, Mikulčić H, Raclavská H, Wang X, et al.
ported on niobium oxide catalyst. Bioresour Technol. 2020;299: 122582. Co-pyrolysis and synergistic effect analysis of biomass sawdust and
303. Li S, Luo Z, Wang W, Sun H, Xie J, Liang X. Catalytic fast pyrolysis of polystyrene mixtures for production of high-quality bio-oils. Process Saf
enzymatic hydrolysis lignin over Lewis-acid catalyst niobium pentoxide Environ. 2021;145:1–11.
and mechanism study. Bioresour Technol. 2020;316: 123853. 325. Tao L, Ma X, Ye L, Jia J, Wang L, Ma P, et al. Interactions of lignin and
304. Xin Y, Dong L, Guo Y, Liu X, Hu Y, Wang Y. Correlation of the catalytic LDPE during catalytic co-pyrolysis: thermal behavior and kinetics study
performance with ­Nb2O5 surface properties in the hydrodeoxygenation by TG-FTIR. J Anal Appl Pyrol. 2021;158: 105267.
of lignin model compound. J Catal. 2019;375:202–12. 326. Xu L, He Z, Zhang H, Wu S, Dong C, Fang Z. Production of aromatic
305. Ding Y, Wang S, Zhang L, Chen Z, Wang M, Wang S. A facile method to amines via catalytic co-pyrolysis of lignin and phenol-formaldehyde res-
promote ­LaMnO3 perovskite catalyst for combustion of methane. Catal ins with ammonia over commercial HZSM-5 zeolites. Bioresour Technol.
Commun. 2017;97:88–92. 2021;320: 124252.
306. Han H, Ge Q, Zhang M, Chen Y, Wang H, Zhang Y, et al. Production of 327. Ma C, Xie S, Kumagai S, Takahashi Y, Saito Y, Kameda T, et al. Synergistic
phenolic compounds in catalytic pyrolysis of bagasse lignin in the pres- effects during co-pyrolysis of milled wood lignin and polyolefins at
ence of ­Ca0.5Pr0.5FeO3. J Rare Earth. 2022;40(2):279–88. the gas phase and liquid/solid phase contacting modes. Chem Eng J.
307. Wang H, Han H, Sun E, Zhang Y, Li J, Chen Y, et al. Production of aryl 2022;431: 134030.
oxygen-containing compounds via catalytic pyrolysis of bagasse 328. Ke L, Wang Y, Wu Q, Zhou N, Dai L, Tian X, et al. Pressurized ex-situ cata-
lignin over ­La0.8M0.2FeO3 (M=La, Ca, Sr, Ba). J Anal Appl Pyrol. 2019;142: lytic co-pyrolysis of polyethylene and lignin: efficient BTEX production
104624. and process mechanism analysis. Chem Eng J. 2022;431: 134122.
308. Wang H, Han H, Sun E, Zhang Y, Li J, Chen Y, et al. Production of aryl 329. Wan Z, Wang S, Li Z, Yi W, Zhang A, Li Y, et al. Co-pyrolysis of lignin and
oxygen-containing compounds from catalytic pyrolysis of bagasse spent bleaching clay: insight into the catalytic characteristic and hydro-
lignin over ­LaTixFe1−xO3. Chin J Chem Eng. 2019;27(8):1939–44. gen supply of spent bleaching clay. J Anal Appl Pyrol. 2022;163: 105491.
309. Wang H, Han H, Sun E, Zhang Y, Li J, Chen Y, et al. Production of aryl 330. Anuar Sharuddin SD, Abnisa F, Wan Daud WMA, Aroua MK. A review on
oxygen-containing compounds by catalytic pyrolysis of bagasse pyrolysis of plastic wastes. Energy Convers Manag. 2016;115:308–26.
lignin over ­LaTi0.2Fe0.8O3 prepared by different methods. J Rare Earth. 331. Zhao Z, Cannon FS, Nieto-Delgado C. Synergistic interaction between
2020;38(1):76–83. lignin and collagen during co-pyrolysis. Carbon. 2019;154:254–65.
310. Wang H, Han H, Zhang Y, Li J, Chen Y, Song H, et al. Influence of calcina- 332. Bai J, Chen X, Shao J, Jia C, Wang Q. Study of breakage of main covalent
tion temperature for ­LaTi0.2Fe0.8O3 on catalytic pyrolysis of bagasse bonds during co-pyrolysis of oil shale and alkaline lignin by TG-FTIR
lignin. J Rare Earth. 2019;37(8):837–44. integrated analysis. J Energy Inst. 2019;92(3):512–22.

Content courtesy of Springer Nature, terms of use apply. Rights reserved.

Lu and Gu Biotechnology for Biofuels and Bioproducts (2022) 15:106 Page 43 of 43

333. Li C, Sun Y, Yi Z, Zhang L, Zhang S, Hu X. Co-pyrolysis of coke bottle

wastes with cellulose, lignin and sawdust: impacts of the mixed feed-
stock on char properties. Renew Energy. 2022;181:1126–39.
334. Fan Y, Yang B, Zhang B, Wu Z, Sun Z, Shang J. Synergistic effects from
fast co-pyrolysis of lignin with low-rank coal: on-line analysis of prod-
ucts distribution and fractal analysis on co-pyrolysis char. J Energy Inst.
2021;97:152–60.
335. Bi H, Ni Z, Tian J, Jiang C, Sun H, Lin Q. Influence of lignin on coal
gangue pyrolysis and gas emission based on multi-lump parallel
reaction model and principal component analysis. Sci Total Environ.
2022;820: 153083.
336. Tumbalam Gooty A, Li D, Berruti F, Briens C. Kraft-lignin pyrolysis
and fractional condensation of its bio-oil vapors. J Anal Appl Pyrol.
2014;106:33–40.
337. Xu R, Ferrante L, Briens C, Berruti F. Flash pyrolysis of grape residues into
biofuel in a bubbling fluid bed. J Anal Appl Pyrol. 2009;86(1):58–65.
338. Deng J-J, Luo Z-J, Wang C, Zhu X-F. Extraction of phenols from bio-oil
aqueous fraction by hydrophobic ionic liquids. J Fuel Chem Technol.
2021;49(12):1832–9.
339. Yao T, Li H, Ren Y, Feng M, Hu Y, Yan H, et al. Extraction and recovery of
phenolic compounds from aqueous solution by thermo-separating
magnetic ionic liquid aqueous two-phase system. Sep Purif Technol.
2022;282: 120034.
340. Xu D, Wang S, Zhang T, Peng L, Bing X, Zhang L, et al. Extraction and
interaction insights for enhanced separation of phenolic compounds
from model coal tar using a hydroxyl-functionalized ionic liquid. Chem
Eng Res Des. 2022;178:567–74.
341. Yang W, Wang X, Ni S, Liu X, Liu R, Hu C, et al. Effective extraction of
aromatic monomers from lignin oil using a binary petroleum ether/
dichloromethane solvent. Sep Purif Technol. 2021;267: 118599.
342. Kariyawasam T, Doran GS, Howitt JA, Prenzler PD. Polycyclic aromatic
hydrocarbon contamination in soils and sediments: sustainable
approaches for extraction and remediation. Chemosphere. 2022;291:
132981.

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