Chemical Engineering Journal 356 (2019) 461–471

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Chemical Engineering Journal

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Catalytic depolymerization of organosolv lignin from bagasse by T

carbonaceous solid acids derived from hydrothermal of lignocellulosic
compounds
Panuruj Asawaworarita, Pornlada Daorattanachaia, Weerawan Laosiripojanab,
⁎
Chularat Sakdaronnarongc, Artiwan Shotiprukd, Navadol Laosiripojanaa,
a
The Joint Graduate School of Energy and Environment, King Mongkut’s University of Technology Thonburi, Prachauthit Road, Bangmod, Bangkok 10140, Thailand
b
Department of Tool and Materials Engineering, Faculty of Engineering, King Mongkut’s University of Technology Thonburi, Prachauthit Road, Bangmod, Bangkok 10140,
Thailand
c
Department of Chemical Engineering, Faculty of Engineering, Mahidol University, 25/25 Phutthamonthon 4 Road, Salaya, Phutthamonthon, Nakorn Pathom 73170,
Thailand
d
Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Thailand

H I GH L IG H T S

• Catalytic depolymerization of lignin from organosolv fractionation of bagasse was studied.

• Carbonaceous solid acid catalysts were synthesized from hydrothermal of sugar, cellulose, lignin.
• Catalyst from hydrothermal of lignin showed the highest catalytic activity and stability.
• Methyl isobutyl ketone (MIBK) is the best solvent for the reaction.
• 4-ethylphenol and guaiacol were the major phenolic products from the reaction.

A R T I C LE I N FO A B S T R A C T

Keywords: In the present work, depolymerization of isolated lignin from organosolv fractionation of bagasse in the presence
Organosolv lignin of several homogeneous and heterogeneous acid catalysts was studied. The catalysts included homogeneous
Depolymerization acids (i.e. H2SO4, H3PO4 and HCl), and heterogeneous carbonaceous solid acids (CSAs) synthesized from the
Hydrothermal carbon hydrothermal treatment of glucose, cellulose and lignin. It was found that the highest phenolic monomers yield
Phenolic monomers
was achieved from CSA derived from lignin (CSAlignin). In addition, this catalyst showed the highest activity and
stability after 5 consecutive cycles, which was related to its high acidity as well as its low acid leaching compared
to CSACellulose and CSAGlucose. The effects of catalyst loading, reaction temperature, reaction time, and solvent
type (i.e. methanol, ethyl acetate, methyl isobutyl ketone (MIBK), acetone) on the depolymerization perfor-
mance were also performed. It was observed that the reaction at 350 °C for 3 h using MIBK as solvent with
CSAlignin loading of 10 wt% gave the maximum total phenolic yield of 32.8%, from which 4-ethylphenol and
guaiacol were the major phenolic products from the reaction. The results in the work suggest that catalytic
depolymerization of organosolv lignin in the presence of CSA is a promising way for production of high value-
added chemicals.

1. Introduction been widely investigated globally. Generally, lignocellulosic biomass

Nowadays, fossil feedstock (i.e. crude oil and natural gas) con-
sumption has been increasing due to the high demand of petro-based
chemicals, fuels, and energies. Therefore, the concept of replacing these
raw materials with renewable feedstock e.g. lignocellulosic biomass has
consists mainly of three organic compounds including cellulose
(40–50%), hemicellulose (20–30%), and lignin (10–25%) [1]. Among
these compounds, lignin represents the most abundant organic mate-
rial, which could be efficiently converted to a wide range of industrial-
needed chemicals. Typically, lignin from different types of biomass

⁎
Corresponding author.
E-mail address: navadol@jgsee.kmutt.ac.th (N. Laosiripojana).

https://doi.org/10.1016/j.cej.2018.09.048
Received 27 September 2017; Received in revised form 27 August 2018; Accepted 6 September 2018
Available online 07 September 2018
1385-8947/ © 2018 Elsevier B.V. All rights reserved.
P. Asawaworarit et al.
always comprises of three aromatic alcohols, including p-coumaryl al-
cohol, coniferyl alcohol, and sinapyl alcohol, linked together by con-
densed and ether linkages such as β-O-4, β-β, β-5, 4-O-5, and dihy-
drobenzofuran [2]. The proportion of these aromatic alcohols depends
considerably from species to species, particularly with regard to the
type and quantity of linkages in polymer and the number of methoxy
groups present on the aromatic rings.
Prior to the conversion of lignin to value-added products, extraction
or fractionation of lignocellulosic components is an important initial
step where each biopolymers are separated and utilized for maximized
values by conversion to a spectrum of biofuels, commodity and speci-
alty chemicals. Among the biomass fractionation methods, organosolv
process is versatile to types of biomass and offers high selectivity and
purity to lignocellulose components. Several organic solvents including
alcohols (e.g. methanol and ethanol), esters, and ketones have been
studied for organosolv fractionation of different lignocellulosic mate-
rials [3,4]. Recently, the clean fractionation (CF) process using ternary
mixture of solvents including short-chain alcohol, methylisobutylk-
etone (MIBK), and water in the presence of sulfuric acid as promoter
has been reported as an effective approach for separation of lig-
nocellulose components [5,6]. The extracted lignin from this fractio-
nation process is called organosolv lignin, which has been known as a
promising lignin source for depolymerization to bio-based valuable
chemicals because its structure is highly pure, unaltered, and sulfur-free
which is greatly benefit for utilizing in several catalytic applications.
Regarding the current lignin utilization approaches, most lignin has
been used mainly as a low-grade fuel for heat and power generation in
pulp and paper industries. Only a few proportion of lignin has been
employed as binders, dispersant or emulsifier, carbon fiber, phenolic
resins, and bio-fuels [7,8]. Recently, chemical reaction approaches for
lignin conversion to low molecular weight phenolic compounds have
been widely reported including hydrolysis, hydrogenolysis (or hydro-
cracking), pyrolysis, solvolysis, and oxidation [9]. Among these pro-
cesses, lignin depolymerization is mostly dominated by thermochemical
transformation which requires harsh conditions with and/or without
catalysts [10]. Additional of suitable catalyst to promote lignin depo-
lymerization is an attractive strategy to achieve high yields and high
selectivity of desired phenolic products. It is known that strong acids
(i.e. H2SO4) can efficiently catalyze the depolymerization reactions.
Nevertheless, the main concern for the use of strong mineral acids are
the corrosive nature of acids, formation of possible unwanted by-pro-
ducts, and the requirement for an acid-containing waste treatment
[11,12]. Alternatively, the use of heterogeneous acid catalysts would
efficiently eliminate or minimize these drawbacks. Previously, several
solid acid catalysts such as zeolites (H-USY, H-MOR, H-BEA, and H-
ZSM-5) and amorphous silica-alumina (SiO2-Al2O3) and carbonaceous
solid acids (CSA) have been widely reported for upgrading bio-oil via
liquefaction in hydrocracking process [13–16]. Among them, CSA have
several favorable characteristics such as high catalytic activity and se-
lectivity, long catalyst life, and ease in recovery. CSA catalysts with
SO3H, COOH and OH groups were also reported to active for the hy-
drolysis of cellulose and its derived polysaccharides [17–22]. Further-
more, CSA can be easily synthesized by the low temperature hydro-
thermal of renewable hydrocarbon feedstocks e.g. cellulose, lignin,
sugars. The purpose of this study is to examine catalytic performance of
CSA for lignin depolymerization into phenolic monomers. The pre-
paration method of CSA and the precursor type were intensively stu-
died. In details, hydrothermal synthesis was applied while the types of
precursor for CSA included glucose, cellulose and lignin. For the de-
polymerization test, the effects of catalyst loading, solvent system,
temperature and hydrogen donor on the product yield were performed
over lignin isolated from bagasse by organosolv fractionation process.
The liquid and solid products i.e. oil, residual lignin and char/un-
converted lignin were intensively analyzed. In addition, different
characterization techniques including Klason lignin determination,
elemental analysis, FT-IR, and Gel permeation chromatography (GPC)
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Chemical Engineering Journal 356 (2019) 461–471
were also employed for qualitative and quantitative analysis of the
isolated lignin compared to the commercial grade organosolv lignin.
2. Experimental
2.1. Chemicals and raw materials
The standard of aromatic monomers (guaiacol, phenol, 2,6-di-
methoxyphenol, p-cresol, vanillin, 4-ethylphenol, and 4-ethylguaiacol)
were purchased from Sigma-Aldrich and Tokyo chemical industry Co.
Ltd. For catalyst synthesis, D-Glucose anhydrous was of analytical grade
and was purchased from Ajax Finechem Pty Ltd (Thailand). Sulfuric
acid was of analytical grade and was purchased from Fluka (Singapore).
Cellulose was purchased from Wako Pure Chemical Company (Osaka,
Japan), while organosolv lignin was also supplied from Chemical Point
UG (Germany). All chemicals and reagents were used as received.
Sugarcane bagasse was obtained from PTT Global Chemicals PCL,
Rayong, Thailand. It was dried at 70 °C for 24 h and cut by Retsch
ZM200 to be the average particles size of 0.5–0.85 mm in diameter.
According to the standard NREL analysis [23], the biomass contained
38.3 wt% cellulose, 20.7 wt% hemicelluloses, 24.6 wt% lignin, and
4.3 wt% ash.
2.2. Lignin isolation procedure
Isolated lignin was obtained by our developed fractionation proce-
dure. In details, 10 g of bagasse was mixed with 100 mL of the single-
phase solvent mixture containing 70–90% by volume of solvent mixture
[water/ethanol/ethyl acetate (50%:25%:25% as the starting ratio)]
with 10–30% by volume of formic acid. Nitrogen was purged into the
reactor and adjusted the initial pressure to 20 bar. The system was
heated to the desirable temperature (160 °C) for a specified residence
time (30 min). Then, the reactor was quenched in a water bath to stop
the reaction. The solid cellulose-enriched fraction was separated by
filtration and washed with the ethyl acetate and water (1:2 v/v) mix-
ture. The liquid fraction was combined with the rinsate and placed into
a separatory funnel. Water was added to the aqueous-organic fraction
until phase separation was obtained. The mixture was stirred and then
placed at room temperature for 20 min for complete phase separation.
The aqueous phase containing hemicelluloses and soluble products was
recovered. The separated organic phase was dried at 105 °C to obtain
isolated lignin.
The sample was characterized by several techniques. Fourier
transform infrared spectroscopy (FT-IR) analysis was performed using
Perkin-Elmer System 2000 and the samples were prepared by using KBr
pellet method. The measurement resolution was set at 4 cm−1 with 64
scans in the range from 4000 to 400 cm−1. The purity of lignin was
determined by Klason lignin technique, from which 0.3 of lignin sample
was added with 3 mL of 72% H2SO4 in pressure tubes. The tubes were
then immersed in a water bath at 30 °C for 1–2 h. The hydrolyzed lignin
samples were then diluted to 4% through the addition of water and
autoclaved at 121 °C for 1 h. The samples were filtered with porcelain
crucibles to remove any solids and the liquid fraction was analyzed by
high performance liquid chromatography (HPLC) for glucose, xylose
and arabinose. The solid fraction comprised of acid-insoluble lignin and
the acid-insoluble ash was placed in a muffle furnace at 575 °C for 3 h.
After cooling, the remaining acid-insoluble ash was weighted and cal-
culated as a percentage of the original dry weight of sample [24]. The
elemental composition of organosolv lignin was estimated by an Ele-
mental Analyzer CHN-S 628 (LECO Corp.). Lignin samples were dried at
60 °C in vacuum evaporator with 20 mbar to remove moisture. Then,
0.1 g of lignin sample was encapsulated in the container to determine
carbon, hydrogen, and nitrogen in sample. For sulfur analysis, 0.2 g of
lignin sample was placed into ceramic boat furnace. This was in-
cineration at 1350 °C using sulfur IR cells detect the amount of sulfur.
Lastly, the molecular weight of isolated lignin was determined by GPC,
P. Asawaworarit et al.
from which the sample was prepared in eluent of Tetrahydrofuran
(THF) at a concentration of 0.2 mg/ml. Prior to analysis, the slurry was
filtered through a 0.45 µm syringe filter to remove any solid residues.
HPLC was used with a Shodex Asahipak GS-320 HQ column and a
Water 2487 UV detector (280 nm). The mobile phase was THF with the
flow rate of 0.5 mL/min. The temperature of column was maintained at
30 °C. Sodium polystyrene sulphonate standards with molecular
weights 1530, 4950, 16600, and 34700 g/mol were used to prepare a
standard calibration curve. Lignin weight average molecular weight
(Mw) and number average molecular weight (Mn) were calculated after
comparison with standards.
2.3. Catalyst preparation and characterization
CSA was initially prepared in stainless steel closed batch reactor by
hydrothermally carbonizing of 1 g carbon precursor (i.e. glucose, cel-
lulose and lignin) in 5 mL of deionized water. The closed batch reactor
containing the mixture was heated with an electric heater to the desired
temperature, 220 °C. After a holding period of 3 h, the reactor was
cooled to room temperature by submerging it into a water bath. The
solid product was separated from the liquid carbonization portion by
filtering and then washed with deionized water until the pH of washed
water was neutral. After drying overnight at 110 °C, the CSA was pre-
pared by heating 5 g of the hydrothermal solid in 50 mL of concentrated
H2SO4 (> 96%) using a 3-neck round bottom flask at 150 °C for 15 h.
The obtained CSA was washed with deionized water (1000 mL) before
being separated with a vacuum filter. The solid was repeatedly washed
with boiling distilled water until no change in water pH was observed
and eventually dried at 110 °C. It is noted that the glucose, cellulose and
lignin derived CSAs are called CSAglucose, CSAcellulose and CSAlignin, re-
spectively. The elemental compositions (C, H, and N) of CSAs were
determined by a CHN analyzer (LECO CHN628 elemental analyzer).
The oxygen (O) was calculated by sub-traction of C, H, and N content
from 100%. The specific area, pore volume and pore size diameter of
samples were determined by N2 physisorption technique using the
Brunauer-Emmet-Teller (BET) method with a Belsorp-mini (BEL Japan,
Tokyo, Japan); the samples were pre-treated to remove moisture at
150 °C for 3 h prior to measurement. The total acidity of the samples
was analyzed by temperature-programmed desorption (TPD) with am-
monia.
2.4. Lignin depolymerization test
The mixture of 1.75% (w/v) lignin in selected solvents with and
without the presence of catalyst was filled in a stainless steel tubular
reactor (1/2 in. O.D. and 10 cm, length) before heating to the desired
temperatures. Various acid catalysts used in this study were loaded at
1% (w/w) into the reactor. Initially, the reactor was purged with ni-
trogen and shake in vertical dimension at 40 rpm. After the reaction,
the reactor was quenched in a water bath to stop the reaction im-
mediately. The liquid fraction was separated from solid fraction (in-
clude char, unconverted lignin, and catalyst) by centrifugation at
5000 rpm for 10–15 min described in Fig. 1. Subsequently, the liquid
fraction was acidified to a pH of 2.0 with sulfuric acid (1 M). In this
step, residual lignin (RL) fraction was precipitated out as a solid form
and was dried overnight at 60 °C. Apart from that, the liquid fraction
(containing phenolic monomers) was filtered through a 0.45 μm syringe
filter and further characterized by GC-MS and GC-FID, respectively. The
yields of the all dried fractions (liquid acid soluble fraction, residual
lignin fraction, and char/unconverted lignin fraction) were measured
gravimetrically and the yields were calculated in comparison to initial
weight of lignin.
Phenolic products were identified by GC-MS. The GC-MS system
was equipped with an Agilent CP-Sil 5 CB capillary column
(60 m × 0.32 mm × 1.00 μm; Agilent, USA). The temperature program
started at 50 °C to 120 °C for 5 min. Then, the reaction was heated up to
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Chemical Engineering Journal 356 (2019) 461–471
280 °C and kept at this temperature for 10 min. The final temperature
was held at 300 °C for 10 min at the same heating rate. The main
phenolic monomers showing a relatively high concentration in the li-
quid product were further quantitated by using external standard
method on GC-FID (Shimadzu GC-2014, Japan). The quantitative ana-
lysis was carried out by a GC-FID (Shimadzu GC-2014, Japan) equipped
with a PetrocolTM DH 50.2 fused silica capillary column
(50 m × 0.2 mm × 0.5 μm; Supelco, USA) with flame ionization de-
tector (FID). The column was initially kept at 50 °C for 5 min, then was
heated at a rate of 10 °C·min−1 to 120 °C, and maintained for 5 min.
Then, it was heated up to 280 °C at 10 °C·min−1 and kept at this tem-
perature for 15 min. The phenolic products were quantified using the
calibration curves of a number of lignin depolymerization products (i.e.
guaiacol, phenol, 2,6-dimethoxyphenol, p-cresol, vanillin, 4-ethyl-
phenol, and 4-ethylguaiacol).
The yields of phenolic monomers, residual lignin (RL), liquid acid
soluble, and char/unconverted lignin, and lignin conversion were cal-
culated using the following equations:
Phenolic monomers yield (\%)
weight of phenolic monomers (g) ⎞
= 100 ⎜⎛ ⎟
⎝ weight of initial lignin (g) ⎠
weight of RL in acid insoluble (g) ⎞
Residual lignin yield (\%) = 100 ⎛⎜ ⎟
⎝ weight of initial lignin (g) ⎠
Liquid acid soluble yield (\%)
weight of liquid fraction (g) − weight of RL (g) ⎞
= 100 ⎛⎜ ⎟
⎝ weight of initial lignin (g) ⎠
Char/unconverted lignin yield (\%)
weight of solid fraction (g)− weight of catalyst (g) ⎞
= 100 ⎜⎛ ⎟
⎝ weight of initial lignin (g) ⎠
Lignin converion (\%)
weight of initial lignin (g)− weight of solid fraction (g)− weight of RL (g) ⎞
= 100 ⎜⎛ ⎟
⎝ weight of initial lignin (g) ⎠
3. Results
3.1. Isolated lignin characterizations
Prior to the conversion test, the characteristics of isolated lignin in
the present work were examined and compared to commercial orga-
nosolv lignin by several techniques including FT-IR, Klason lignin,
CHNS and GPC analyses. FT-IR of lignin was employed in order to
identify the presence of chemical functional groups. As presented in
Fig. 2, it can be seen that isolated lignin and commercial organosolv
lignin samples contain a broad band at 3437 cm−1, attributed to the
hydroxyl (OeH) groups in phenolic and aliphatic structures, and the
bands centered around 2934 and 2839 cm−1 predominantly arising
from C-H stretching in aromatic methoxyl groups and in methyl and
methylene groups of side chains. The bands at 1609, 1511, and
1422 cm−1 were absorbed due to aromatic skeleton vibrations. The
characteristics of adsorption of lignin at 834 cm−1 were related to the
out of plane CeH vibration in guaiacyl (G) units. In addition, the band
at 1115 cm−1 assigned to the characteristic absorption of p-hydro-
xypheny (H) units. The peak at 1710 cm−1 assigned to C]O stretching
vibration.
To determine the chemical compositions as well as impurities in-
cluding insoluble lignin (AIL), acid soluble lignin (ASL), sugars, and ash
content, the samples was analyzed by Klason lignin technique. As
shown in Table 1, the AIL proportion of isolated lignin in the present
study (92.3%) was relatively in the same range as that of commercial
organosolv lignin (91.7%). In addition, the compositions of C6 sugars
P. Asawaworarit et al.
Fig. 1. Diagram of product separation after depolymerization reactions.
Fig. 2. FT-IR spectra of commercial organosolv lignin and bagasse lignin
samples.
and ash contents of isolated lignin were much lower than that of
commercial organosolv lignin, whereas the content of C5 sugars espe-
cially arabinose was relatively higher. The organic and inorganic ele-
ments (C, H, N, and S) as well as the molecular weight of C9-formulae in
isolated lignin were given in Table 2. CHNS elemental analysis revealed
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Chemical Engineering Journal 356 (2019) 461–471
that the isolated lignin composes of 61–63% C and 5–6% H with sig-
nificantly low sulphur content (< 0.4%). The general formula is CxHyOz
with x of 7.9–9.0; y of 10–10.62; and z of 2.89–4.5, which correlates
well those reported in the literature [10].
GPC analysis was also applied to identify the molecular weight of
isolated lignin. As shown in Fig. 3 and Table 3, the isolated lignin
contained Mn of 1719 gmol−1, Mw of 3144 gmol−1 with D (Mw/Mn) of
1.8, while the commercial organosolv lignin exhibited Mn of
1133 gmol−1, Mw of 1424 gmol−1 with D (Mw/Mn) of 1.3. These
characterization results implied that the isolated lignin in this study has
higher heterogeneous distribution of fractions with different chain
lengths than the commercial organosolv lignin.
3.2. Catalytic activities toward lignin depolymerization
Lignin depolymerization reaction was initially carried out at 300 °C
for 1 h under atmospheric pressure in MIBK with and without the
presence of catalysts. The phenolic yields from the reaction are illu-
strated in Fig. 4. Although the conversion of lignin was always higher
than 90%, it was found that without the presence of catalyst only 11.6%
of total phenolic yield was observed. Importantly, the additional of
catalyst clearly promote the phenolic yield production, from which the
reaction with H2SO4 gained higher activity than that with H3PO4 and
HCl. Interestingly, the reaction with CSAs can produce higher phenolic
yield than that with homogeneous acids. Among the CSA catalysts,
CSAlignin provided the highest yield of phenolic monomers of 17.5%
with high selective productions of guaiacol and 4-ethylphenol. This
P. Asawaworarit et al. Chemical Engineering Journal 356 (2019) 461–471

Table 1
Comparison of lignin composition in this work and other recent publications.
Lignin samplea Klason lignin (%) Sugar (%) Ash (%) Moisture (%) Ref.

Glucose Xylose Arabinose

COL 91.7 0.92 0.12 0.12 0.86 < 0.1 This study
IL 92.3 0.16 0.52 0.27 0.22 < 0.1 This study
FL 79.0 1.00 0.75 0.14 2.71 N/A Ercodia et al. [44]
AL 69.1 2.61 2.26 0.14 2.57 N/A Ercodia et al. [44]
ACL ∼90 ————————Sugars: 0.50———————— < 0.1 <4 Bozell et al. [5]

a
COL: commercial organosolv lignin, IL: isolated lignin, FL: formasolv lignin, AL: acetosolv lignin, ACL: alcell lignin.

Table 2 higher porosity than CSAGlucose. The trends of these physical and che-
Elemental composition of lignin samples. mical characteristics are in good agreement with the catalytic perfor-
Lignin sample Elemental analysis (wt%) mance toward lignin depolymerization reaction.
It should be noted that the depolymerization reaction over CSA
C H O N S synthesized from commercial grade organosolv lignin (CSACOL) was
also tested for comparison. As shown in Fig. 4, the reaction perfor-
COL 61.43 5.61 30.99 0.81 0.30
IL 62.41 5.91 30.67 0.56 0.19
mance catalyzed by CSACOL was slightly less than that catalyzed by
CSAlignin. This could be due to the higher molecular weight of sugarcane
bagasse lignin compared to commercial grade organosolv lignin, which
leads to the better catalyst surface properties and acidity value (as also
presented in Table 4). The catalyst reusability was then carried out as
shown in Fig. 6(a)–(c). The post-reaction solid sample was rinsed with
acetone for several times to remove lignin fraction. The spent catalyst
and char were then tested without separation. After 5 consecutive cy-
cles, the reaction with CSAlignin also provided the lowest deactivation
percentage compared to CSACellulose and CSAGlucose. From the post-re-
action TPD, the acidity of CSAlignin decreased by 8.14%, whereas that of
CSAGlucose and CSACellulose decreased by 15.7% and 21.5%, respectively.
These results indicated the relatively lower acid leaching from CSAlignin,
which would be greatly benefited for the long-term reaction operation.
The elemental analysis of CSAlignin after 5 consecutive cycles was also
analyzed. It was found that the carbon content increased from C:H:O of
75.39:7.48:16.89 to 79.28:7.35:13.19, which could be due to the char
deposition on the surface of the spent catalyst.
The effect of catalyst loading was also studied as shown in Fig. 7.
Increasing CSAlignin loading up to 10 wt% at temperature of 300 °C for
1 h resulted in a maximum increase in the yield of phenolic monomers.
By loading more than 10%, the liquid yield in acid soluble fraction
Fig. 3. GPC curves of commercial organosolv lignin and bagasse lignin.
trends to decrease while residual lignin and solid char proportions
oppositely increased significantly. This result corresponded with Klein
Table 3 et al. [26] who reported that 10 wt% catalyst loading for depolymer-
Molecular weight of lignin samples. ization of lignin from woody biomass gave the highest yield of lignin-
Molecular weight (g/mol) derived products. It is noted that the increases of guaiacol and 4-
ethylphenol in the acid soluble fraction was accompanied by the de-
Lignin sample Mw Mn D (Mw/Mn) creases of phenol and p-cresol. This implied that an increased catalyst
loading efficiently depolymerized and suppressed recondensation be-
COL 1424 1133 1.257
IL 3144 1719 1.828 tween lignin fragments, but overwhelming catalyst amount led to fur-
ther decomposition to the side reactions.

may be due to unique characteristics of catalysts (shape selectivity,

3.3. Effect of solvent type
acidity and strength of the acid sites, surface area, pore diameter, pore
volume) as well as the complexity of the reactions in terms of which
As the next step, the reactions using different types of organic sol-
bonds in lignin were interacting with catalytically active sites under the
vents including methanol, acetone and ethyl acetate were tested and
reaction conditions [25]. According to the TPD and BET measurements
compared to the use of MIBK. It is noted that the reaction was carried
(Table 4), among all CSAs, CSAlignin showed the highest acidity
out at 300 °C for 1 h in the presence of 10 wt% CSAlignin. As shown in
(14.13 mmol g−1 compared to 12.57 mmol g−1, and 10.69 mmol g−1
Fig. 8, the reaction with acetone provided the highest lignin conversion
for CSAGlucose and CSACellulose respectively) as well as specific surface
with relatively low proportions of solid char and residual lignin gen-
area (14.7 m2 g−1 compared to 4.2 m2 g−1 and 8.8 m2 g−1 for
erated from the reactions, whereas the use of ethyl acetate gained the
CSAGlucose and CSACellulose respectively). In addition, a scanning elec-
lowest lignin conversion. These results implied that acetone can effi-
tron microscope (SEM, JEOL, JSM-6610 LV) connected with an Energy
ciently break the functional linkages in lignin compounds, whereas
Dispersive X-Ray Spectrometer (EDS) analyzer was also used for the
ethyl acetate shows limit ability for breaking down lignin to monomeric
morphology observation. As shown in Fig. 5, SEM micrograph of
phenols. Nevertheless, in term of total phenolic production yield, MIBK
CSAlignin revealed a homogeneous surface characteristic with relatively
can comparatively gain the highest yield of total phenolic products.

465
P. Asawaworarit et al. Chemical Engineering Journal 356 (2019) 461–471

Fig. 4. Effect of catalyst type on lignin conversion and products yield from depolymerization of bagasse lignin at 300 °C in MIBK for 1 h.

Table 4
Surface area and acid properties of CSA catalysts.
Catalysts BET Surface Pore volume Pore size Total acidity
Areaa (m2 g−1) (cm3 g−1) (nm) (mmol g−1)

CSAGlucose 4.2 0.005 10.39 12.57

CSACellulose 8.8 0.006 7.92 10.69
CSALignin 14.7 0.011 4.28 14.13
CSACOL 11.3 0.009 5.73 13.06

This could be due to the fact that MIBK solvent is not inert under the
depolymerization; it undergoes condensation reactions. Therefore, it
can be clarified from this study that acetone is appropriate for lignin
decomposition, whereas the most suitable solvent for maximizing the
phenolic compound production from lignin depolymerization is MIBK.
In addition, it is clear that the reaction medium strongly affects the
degree of lignin conversion as well as the distribution of each phenolic
compound in lignin depolymerization reactions.

3.4. Effects of reaction temperature and time

Lastly, the effects of reaction temperature and time on product yield

of phenolic monomers in the presence of CSAlignin using MIBK as solvent
was investigated in order to determine the conditions where the yield of
phenolic monomers can be maximized. As illustrated in Fig. 9, the re-
action temperature showed strong impact on lignin conversion and
product yield. It was found that the lignin conversion considerably in-
creased at higher temperature, while the proportions of char and re-
sidual lignin contents significantly decreased; nevertheless, above
350 °C, the char contents oppositely increased, which could be due to
the formation of organic acids in the side chains of phenolic propanoid
units [27–29]. In term of liquid product, the amount of liquid acid
soluble greatly increased from 9.1 to 24.0% with increasing the tem-
perature from 250 to 350 °C, which could be due to the fact that in-
creasing the reaction temperature likely promotes the rates of depoly-
merization reaction especially the cleavage of β-O-4 ether bonds in
lignin to monomeric phenols as well as the increased lignin solubility.
This result is consistent with Ren et al. [30], in which the yield of
phenol and alkyl phenols elevated with increasing temperature at Fig. 5. Surface morphologies of CSAGlucose (a) and CSAlignin (b) analyzed by
SEM.
350 °C due to occurred secondary reactions via demethylation and de-
methoxylation. Above 350 °C, the yield of phenolic monomers tended to

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P. Asawaworarit et al. Chemical Engineering Journal 356 (2019) 461–471

Fig. 6. Catalyst reusability test for (a) CSALignin, (b) CSACellulose, and (c) CSAGlucose.

decrease, which could be due to the decomposition of these compounds
to several smaller molecule and gaseous compounds.
The reaction time also affected the lignin conversion and product
yield (Fig. 10), from which the conversion and phenolic yield increased
with increasing the reaction time from 0.5 h to 3 h. At longer reaction
time, the positive effect became less pronounce. Therefore, it can be
revealed from this study that the optimizing conditions for depoly-
merizing isolated lignin from organosolv fractionation of bagasse were
using MIBK as solvent in the presence of CSAlignin as catalyst at 350 °C
for 3 h, from which as high as 32.8% phenolic monomers can be gained.

467
P. Asawaworarit et al.
Fig. 7. Effect of catalyst loading on lignin conversion and product distribution from depolymerization of bagasse lignin at 300 °C in MIBK for 1 h in the presence of
CSAlignin.
4. Discussion
The selective depolymerization of lignin to phenolics is one of the
current challenging research areas. Due to the heterogeneity of lignin
structures and the diversity of ether and condensed linkages, the major
difficulties of this reaction include char formation, repolymerization of
products, low product yield and selectivity [31]. It is generally known
that the depolymerization and repolymerization reactions compete
with each other during the lignin conversion [32–34]. To maximize the
lignin depolymerization while restrain lignin repolymerization, the
operating conditions need to be optimized. Recently, several studies
have been attempting to investigate the selections of catalyst, solvent,
and reaction condition where lignin can be effectively cleaved to reduce
the multitude of products and increase product yield as well as se-
lectivity. Carbon-based acid catalysts have been reported to possess
acid sites that can efficiently catalyze several reactions including the
upgrading bio-oil via liquefaction in hydrocracking process and hy-
drolysis of cellulose and its derived polysaccharides. The sources of
carbon can come from the carbonization and/or hydrothermal of hy-
drocarbon compounds. In the present work, we decided to use the CSA
Fig. 8. Effect of solvent system on lignin conversion and product distribution from depolymerization of bagasse lignin at 300 °C for 1 h in the presence of CSAlignin.
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Chemical Engineering Journal 356 (2019) 461–471
from the hydrothermal process as carbon-based acid catalyst since it
has several favorable characteristics compared to activated carbon
when functionalized with acid promoters (e.g. SO3H) such as longer
catalyst life, lower deactivation after recycling and ease in recovery.
Furthermore, CSA can be easily synthesized at moderate temperature
(180–250 °C) under self-generated pressure. The major bottleneck of
activated carbon is the use of high carbonization/pyrolysis tempera-
tures (400–800 °C). The energy requirement becomes even more con-
suming, particularly when additional heat is needed to remove water
from biomass with high moisture content. It is noted that, for com-
parison, the reaction tests over acid-functionalized activated carbon
using commercial grade activated carbon (total surface area of
1343 m2 g−1 and average pore size of 0.67 nm) supplied from Carbo-
karn (Thailand) was also performed. It found that although the con-
version of lignin was slightly higher than the use of CSA, the total
phenolic yield from the reaction is relatively lower (15.6% compared to
17.5%). This could be due to the too high acidity of acid-functionalized
activated carbon, which leads to the unwanted side reactions of phe-
nolic compounds. Moreover, after 5 consecutive cycles, the reaction
with acid-functionalized activated carbon provided relatively higher
P. Asawaworarit et al.
Fig. 9. Effect of reaction temperature on product distribution and lignin conversion from depolymerization of bagasse lignin in MIBK for 1 h in the presence of
CSAlignin.
Fig. 10. Effect of reaction time on product distribution and lignin conversion from depolymerization of bagasse lignin in MIBK at 350 °C in the presence of CSAlignin.
deactivation percentage compared to CSA (15.2% compared to 8.1%
deactivation) due to the high acid leaching percentage.
For the novelty of this study, we found that physical and chemical
characteristics of CSA strongly depends on the source of carbon pre-
cursors, from which CSA synthesized from lignin contained sig-
nificantly higher acidity and porosity compared to that synthesized
from sugar and cellulose. In term of reaction, CSAlignin also showed the
best performance in terms of phenolic monomer yield and potential
reusability. In addition, the characteristics of lignin (i.e. molecular
weight, purity) also affects the properties of CSA. Our study also in-
dicated that the presence of CSAlignin led to a significant formation of
aromatic compounds e.g. guaiacol, which is due to the increase in de-
gree of acid-catalyzed cleavage of ether linkages. Similar result was
reported by Shao et al. [35], who studied the lignin depolymerization
using formic acid as catalyst. They found that bio-oil yield increased
dramatically, accompanied by a decrease in residue with increasing
catalyst loading. However, further increase of catalyst loading resulted
in a decrease of bio-oil yield and led to an increase in residue yield since
the recondensation reaction was preferred at a higher acid loading.
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Chemical Engineering Journal 356 (2019) 461–471
Therefore, the suitable amount of acid catalyst loading needs to be
optimized to suppress or prevent recondensation reaction. From our
experiment results, we found that at 10 wt% acid loading gave the
highest yield of aromatic products. It should also be noted that the
presence of phenol as product from the reaction could also suppress
char formation as reported by Toledano et al. [36].
Apart from the study of catalyst, the type of solvent also strongly
affects the performance of lignin depolymerization. The use of good
solvent could reduce char formation, and minimize repolymerization
reactions. According to our previous studies [37,38], lignin solubility
was tested in a wide range of organic solvents including acetone, me-
thanol, ethanol, THF, DMSO, MIBK, ethyl acetate, methanol, and
acetone. We found that the degree of lignin solubility in solvent
strongly affects the lignin depolymerization performance. Among these
solvents, MIBK, ethyl acetate, methanol, and acetone are the promising
solvents in terms of lignin solubility and depolymerization. Further-
more, these solvents can be easily reused because they are stable under
the reaction conditions in this study. Importantly, in term of the prac-
tical application, these solvents are cost effective and commonly used in
P. Asawaworarit et al.
the industries. From the literature, the depolymerization of lignin in the
presence of several solvents i.e. water, methanol, dioxane, tetra-
hydrofuran, ethanol was also compared [39]. It was found that the use
of 1:1 (v/v) of methanol–water shows the best performance among the
uses of water, methanol, dioxane, tetrahydrofuran, ethanol, from which
17.9% yield of monomeric compounds was achieved at 150 °C with
60 min of reaction time. Commonly, alcohols are good choice for lignin
depolymerization since they act as hydrogen-donor solvents [34,40].
Wu et al. [41] reported the depolymerization of lignin catalyzed by
SiO2-Al2O3 using methanol, ethanol, isopropanol, and THF as solvent.
Among these solvents, ethanol was the best solvent in terms of phenolic
yield achievement and char suppression. Chen et al. [42] also reported
that the use of ethanol can reduce char formation and provided high
yield of monomers from the lignin depolymerization reaction. In con-
trast, Wang and Rinaldi [43] indicated that the reaction using methanol
as solvent showed better performance in term of phenol production
than the uses of ethanol and butanol. Furthermore, Ercodia et al. [44]
reported that acetone is the better solvent (compared to methanol and
ethanol) for depolymerizing lignin to phenolic compounds. Sameni
et al. [45] and Gosselink et al. [33] revealed that organosolv lignin
effectively dissolve in acetone compared to alcohols and could lead to
the good depolymerization performance. For the role of acetone in the
depolymerization of lignin, Hwang et al. [46] studied the degradation
of polystyrene in supercritical acetone. They proposed that polystyrene
can be degraded to monomer and dimers by partial cleavage of ether
linkage and carbon-carbon linkage under acetone media. For MIBK, this
solvent is one of the well-known organic solvents for biomass pre-
treatment and fractionation. Until now, the role of MIBK for the de-
polymerization of lignin to low molecular weight products is not clearly
understood. Teng et al. [47] reported that MIBK is one of the preferred
candidates for the biomass conversion process due to its stability to-
ward acid, medium polarity, low toxicity, medium boiling point, poor
miscibility with water, and good extraction ability for polar products.
From these observations, it can be revealed that the effectiveness of
solvent to breakdown lignin depends on several parameters e.g. oper-
ating conditions, source and type of lignin, and lignin solubility.
5. Conclusions
The catalytic activities of several homogeneous and heterogeneous
acid catalysts toward the depolymerization of organosolv lignin to
phenolic monomers were comparatively studied under several oper-
ating conditions. Among all catalysts studied, CSAlignin showed the best
performance in terms of phenolic monomer yield and potential reusa-
bility. Increasing the catalyst dosage to 10 wt% positively promoted the
lignin conversion and the total phenolic monomers (mainly 4-ethyl-
phenol and guaiacol) yield. Furthermore, the study revealed that sol-
vent system, reaction temperature and time also play an important role
on the lignin conversion and the total phenolic monomer production,
from which the reaction using MIBK as solvent at 350 °C for 3 h can gain
the highest phenolic monomers of 32.8%.
Acknowledgements
The author (NL) was supported by the Thailand Research Fund
(Grant number RTA5980006) and National Science and Technology
Development Agency (Grant number P-15-50457). The author (PD) was
supported by the Thailand Research Fund (Grant number
TRG6080013). The author (AS) thank the Thailand Research Fund
(Grant numbers RSA5880047 and IRG5780014) and e-ASIA JRP project
for financial support.
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