Fuel 217 (2018) 202–210

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Fuel
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Full Length Article

Understanding the relationship between the structure and depolymerization T

behavior of lignin
⁎
Jaeyong Parka, Asim Riaza, Rizki Insyanib, Jaehoon Kima,b,
a
School of Mechanical Engineering, Sungkyunkwan University, 2066 Seobu-Ro, Jangan-Gu, Suwon, Gyeong Gi-Do 16419, Republic of Korea
b
SKKU Advanced Institute of Nanotechnology (SAINT), Sungkyunkwan University, 2066 Seobu-Ro, Jangan-Gu, Suwon, Gyeong Gi-Do 16419, Republic of Korea

G RA P H I C A L AB S T R A C T

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

Keywords: Various lignin depolymerization methods have been proposed. Nevertheless, the relationship between the
Lignin structure of lignin and its depolymerization behavior has not been widely investigated. Herein, six types of lignin
Lignin structure samples were produced from oakwood (OW, hardwood) and pinewood (PW, softwood) using three different
Depolymerization delignification techniques (ethanolsolv, formasolv, and Klason). The content of ether linkages in the OW-derived
Supercritical ethanol
lignins was approximately three times higher than that in the PW-derived lignins because of the presence of the
Formic acid
sinapyl alcohol unit in the former. The contents of ether linkages in the lignin isolated via the different methods
followed the order: formasolv > ethanolsolv > Klason. The lignin samples were depolymerized in a mixture of
supercritical ethanol (scEtOH) and formic acid at temperatures of 250–350 °C. At 350 °C, regardless of the lignin
type, high conversion (> 95%) and a high bio-oil yield (> 81 wt%) could be achieved, demonstrating that the
combined use of scEtOH-HCOOH was very effective for the depolymerization of various types of lignin. At the
low temperatures of 250–300 °C, the lignin conversion and bio-oil yield were highly dependent on the amount of
ether linkages; for example, at 300 °C, the use of OW-derived formasolv lignin resulted in a high bio-oil yield
(86.2 wt%), whereas the use of OW-derived Klason lignin resulted in a very low bio-oil yield (27.9 wt%). The
properties of the bio-oils produced from the different types of lignin were discussed.

⁎
Corresponding author at: School of Mechanical Engineering and SKKU Advanced Institute of Nanotechnology (SAINT), Sungkyunkwan University, 2066 Seobu-Ro, Jangan-Gu,
Suwon, Gyeong Gi-Do 16419, Republic of Korea.
E-mail address: jaehoonkim@skku.edu (J. Kim).

https://doi.org/10.1016/j.fuel.2017.12.079
Received 15 October 2017; Received in revised form 8 December 2017; Accepted 19 December 2017
Available online 02 January 2018
0016-2361/ © 2017 Elsevier Ltd. All rights reserved.
J. Park et al.
1. Introduction
Lignocellulosic biomass is considered one of the most promising
non-edible renewable resources for producing bio-derived fuels and
chemicals because of its natural abundance and global availability
[1–4]. In a typical sugar platform pathway for producing biofuels and
biochemicals (e.g., cellulosic bioethanol and biobutanol), it is necessary
to separate lignin from cellulose using an appropriate pretreatment
method [5–7]. When the current, active commercialization status of
lignocellulosic biofuels worldwide is taken into account, a huge amount
of lignin (which corresponds to 25–35 wt% of lignocellulosic biomass
[8]) is generated from biorefinery plants as a byproduct [3,9]. Ap-
proximately 40% of the lignin produced from cellulosic biofuel plants
would be required as a source of internal energy from combustion [10];
thus, the development of effective techniques for lignin valorization to
produce liquid fuels and value-added chemicals is highly desired. The
production of surplus lignin in the near future and its rich aromatic
structure make it a promising alternative to petroleum-based aromatic
chemicals. Nowadays, however, only a very small fraction (1–2%) of
the lignin produced from pulping liquors is used to produce specialty
chemicals [11]. One reason for the limited use of lignin as a feedstock
for producing liquid fuels and chemicals is the highly recalcitrant and
complex nature of lignin, which makes depolymerization very difficult.
Moreover, the presence of various types of chemical bonds in the lignin
derived from different wood sources and the unpredictable changes in
the chemical bonding during delignification make it difficult to develop
a “generalized” depolymerization technique; a depolymerization
method that is effective for a certain type of lignin is not necessarily
effective for other types of lignin. Therefore, it is crucial to understand
the relationship between the lignin structure and its depolymerization
behavior to develop an efficient valorization technique for ultimate
utilization of various types of lignin.
Various methods of separating lignin from cellulose have been de-
veloped, including the steam explosion, Kraft, alkali, concentrated
strong acid hydrolysis, and organosolv approaches [7]. During the
pretreatment of lignocellulosic biomass, the structure of “native” lignin
is ultimately changed; the degree and extent of the structural change is
highly dependent on the pretreatment method selected for lignin se-
paration. Most of the pretreatment methods proceed at elevated tem-
peratures of 100–200 °C in the presence of acid or base catalysts. Under
these conditions, CeC coupling reactions tend to occur, making the
isolated lignin more recalcitrant to depolymerization [12,13]. There-
fore, the chemical nature of isolated lignin (phenyl propanol mono-
mers, ether and condensed linkages, bonding energies, substituent
groups, etc.) is not only dependent on the lignin source (e.g., hardwood,
softwood), but also on the separation technique. This makes it very
difficult to develop a generalized depolymerization method for the ef-
fective production of value-added aromatic chemicals and fuel ad-
ditives from various types of lignin.
Various lignin depolymerization approaches have been proposed,
including fast pyrolysis [14], the ionic liquid-assisted method [15],
biological degradation [16], and hydrothermal/solvothermal reactions
with or without a catalyst [17,18]. Among these approaches, the hy-
drothermal/solvothermal technique is considered very promising be-
cause of its high liquid yield (up to 95 wt%) with low char formation
(5–20 wt%) [19]. To enhance the conversion of lignin under hydro-
thermal/solvothermal conditions, various types of solvents (e.g., water,
methanol, ethanol, isopropyl alcohol (IPA), acetone [20–22]) and cat-
alysts (e.g., NaOH [23], KOH [24], H-USY (ultra-stable zeolite Y, Si/
Al = 15) [25], CuMgAlOx [22], Pt/Al2O3 [26]) have been evaluated. To
develop a versatile method for the depolymerization of lignin produced
from various lignocellulose sources and using different pretreatment
methods, it is necessary to gain comprehensive understanding of the
relationship between the lignin structure and its depolymerization be-
havior. However, only a few studies have been dedicated to under-
standing the depolymerization behavior using different lignin sources;
203
Fuel 217 (2018) 202–210
for example, Xabier et al. compared the depolymerization behavior of
three types of organosolv lignin (acetosolv, formosolv, and acetosolv/
formosolv) produced from a single wood resource using supercritical
acetone, ethanol, and methanol [27]. In supercritical acetone at 300 °C
and 6.6–6.7 MPa, the use of an acetosolv/formosolv lignin for 40 min
resulted in a higher oil yield (38 wt%) than obtained with individual
acetosolv and formosolv lignin (32–34 wt%). One of the key parameters
determining the oil yield is the molecular weight of lignin; the oil yield
was found to be lower when the molecular weight of lignin was lower.
Jun et al. studied the catalytic solvolysis of organosolv lignins produced
from Chinese fir and maple in a mixture of supercritical ethanol and 1-
butanol in the presence of a Ru/C catalyst at 300 °C under a pressure of
40 MPa for a reaction time of 40 min [28]; the lower oil yield from
Chinese fir lignin (32 wt%) than that from maple lignin (41 wt%) was
attributed to the different lignin origins according to the wood types.
Although the previous studies illustrated a plausible relationship be-
tween the lignin sources and bio-oil yields, there is still a lack of un-
derstanding of the fundamental properties of lignins and their depoly-
merization behaviors.
Herein, we investigate the chemical and physical properties of
lignin produced by using two different types of lignocellulosic biomass
(oak (hardwood) and pine (softwood)) and three different lignin se-
paration methods (ethanolsolv, formasolv, Klason). The produced
lignin was depolymerized in a supercritical mixture of ethanol (scEtOH)
and formic acid (HCOOH) to gain fundamental understanding of the
properties of lignin and its depolymerization behavior. The yields and
properties of the lignin-derived oils from the depolymerization of
oakwood-derived and pinewood-derived lignins are discussed in detail.
2. Materials and methods
2.1. Materials
Oakwood (Ouercus, OW, hardwood) and pinewood (Pinus, PW,
softwood) were purchased from a local market in South Korea. The
cellulose, hemicellulose, and lignin content were analyzed by using the
Van Soest method [29], as listed in Table S1. HPLC grade ethanol,
acetone, and dichloromethane (DCM) were purchased from Burdick &
Jackson (USA). Aqueous sulfuric acid (H2SO4, ≥99.5%, ACS reagent
grade) was purchased from Sigma-Aldrich (USA). Formic acid (reagent
grade) and HCl (35%, extra pure grade) were purchased from Daejung
Chemical & Metal (South Korea). Distilled-de-ionized (DDI) water was
prepared by using an AQUAMax™-Basic 360 water purification system
(Younglin Instrument Co., Ltd., South Korea). High-purity N2
(99.999%) for purging the reactor was purchased from JC Gas Company
(South Korea).
2.2. Lignin separation methods
To produce the ethanolsolv lignin, a batch reactor with an inner
volume of 140 mL was filled with 10 g of wood, 80 mL of ethanol/water
mixture (50:30 v/v), and 1 g of sulfuric acid as a catalyst. The reactor
was heated to 190 °C by using cartridge heaters and a heating furnace
and kept for 1 h. After delignification, the solid and black liquid pro-
ducts were collected from the reactor and separated by centrifugation at
4000 rpm for 10 min. The solid products contained cellulose and a small
fraction of unreacted lignin. A 240-mL aliquot of water was then added
to the recovered filtrate to precipitate the fragmented lignin in the black
liquid. This precipitated lignin was then dried in a drying oven over-
night at 80 °C. The ethanolsolv lignin samples produced using oakwood
and pinewood are designated as OW-E and PW-E, respectively. For the
production of formasolv lignin, the batch reactor was filled with 10 g of
wood, 80 mL of a formic acid/water mixture (80:20 w/w), and 0.2 g of
HCl as a catalyst. The reactor was then heated to 120 °C and kept for
1.5 h. After the reaction, the same separation protocol that was em-
ployed to recover the ethanolsolv lignin was used to obtain the
J. Park et al.
formasolv lignin. The formasolv lignin samples produced using oak-
wood and pinewood are designated as OW-F and PW-F, respectively.
Klason lignin was prepared by a two-step acid hydrolysis reaction; first,
the wood sample was hydrolyzed with a concentrated strong acid (72%
H2SO4) for 2 h at room temperature. The reaction mixture was then
diluted to give a 3% H2SO4 aqueous solution by adding DDI water, and
the mixture was reacted at 110 °C under reflux conditions for 4 h for the
subsequent weak acid hydrolysis reaction. After the two-step acid hy-
drolysis reaction, the holocellulose was dissolved in aqueous sulfuric
acid and the lignin precipitated at the bottom of the flask. The pre-
cipitated lignin was separated from the dissolved holocellulose by
centrifugation. The recovered lignin was washed with DDI water sev-
eral times and then dried in a drying oven at 80 °C for 12 h. The Klason
lignin samples produced using oakwood and pinewood are designated
as OW-K and PW-K, respectively. The yields of lignin recovered from
each delignification method followed the order: Klason (100 wt
%) > ethanolsolv (63–71 wt%) > formasolv (53–54 wt%), as listed in
Table S2.
2.3. Lignin depolymerization reaction
The depolymerization experiments were performed by using a
custom-built, batch reactor made of SUS 316 having an inner volume of
140 mL, equipped with a magnetically driven stirrer. The reactor was
rated to rated 500 °C at 50 MPa. In each lignin depolymerization reac-
tion, 3 g of lignin, 60 g of ethanol and 12 g of formic acid were placed
into the reactor. The reactor was closed and purged with N2 gas three
times through a purge line dipped into the solution to remove dissolved
oxygen in the liquid phase and the oxygen in the reactor head, and then
pressurized at 1 MPa with N2. The reactor was heated to the experi-
mentally desired temperatures of 250–350 °C at a heating rate of ap-
proximately 20 °C min−1. After reaching the desired reaction tem-
perature, the reaction was allowed to proceed for 1 h. After the
reaction, the reactor was quickly quenched to 100 °C using a water
basket, in order to prevent further possible reaction during the cooling
process, and was then further cooled to room temperature using an
electric fan. The reactor pressure was recorded after complete cooling
to calculate amount of gas produced. The produced gas was collected in
a 0.5-L Tedlar bag for compositional analysis. The reaction mixture in
the reactor was then collected in a beaker by washing with acetone. The
liquid and solid products were separated using a Whatman filter paper.
The solid residue was dried in a drying oven at 70 °C for 6 h. The liquid
product, which contained solvent, bio-oil, and byproduct, was evapo-
rated at 50 °C and 0.02 MPa using a rotary evaporator. After the eva-
poration process, the bio-oil was further dried in a vacuum oven at
60 °C at ∼0 MPa for 6 h to remove the residual solvent. All the ex-
periments were performed in triplicate and the average values are re-
ported.
The conversion and the yields of bio-oil, solid residue, and gas
product were calculated using the following equations:
Conversion
Weight of dry ash free lignin-Weight of organics in solid residue
= The lignin samples were characterized by proximate and ultimate
Weight of dry ash free lignin
× 100 (1)
Weight of bio oil
Yield of bio oil (wt%) = × 100
Weight of dry ash free lignin (2)
Weight of solid residue
Yield of solid residue (wt%) = × 100
Weight of dry lignin (3)
Weight of produced gas
Yield of gas (wt%) = × 100
Weight of dry ash free lignin (4)
204
Fuel 217 (2018) 202–210
2.4. Analysis and characterization
To quantify the ether linkages in the lignin samples (e.g., β-O-4, α-
O-4, 4-O-5), the vanillin and syringaldehyde contents were analyzed
using nitrobenzene oxidation, as proposed by Chen [30]. Prior to ni-
trobenzene oxidation, the wood samples were ground and extracted
using a Soxhlet apparatus with a toluene/ethanol mixture (2:1) at
120 °C for 6 h. Fifty milligrams of dried lignin or 200 mg of dried wood,
7 mL of 2 M NaOH, and 0.48 g of nitrobenzene were placed into a
stainless-steel bomb reactor with an inner volume of 11 mL. The reactor
was then heated to 170 °C and the oxidation was allowed to proceed for
2.5 h. After the reaction, the liquid mixture was collected from the re-
actor and water and DCM were added to the reaction mixture. The
whole solution was kept in a separating funnel for 4 h to separate the
oxidized products in the aqueous phase from nitrobenzene in the DCM
phase. The aqueous phase was collected from the funnel and then
acidified to pH 2–3 using aqueous HCl. The acidified species in the
aqueous phase were then extracted using DCM in three liquid-liquid
extraction cycles. The DCM phase was evaporated using a rotary eva-
porator at 40 °C and 0.04 MPa to recover the products for further
analysis. Thermogravimetric analysis (TGA) was conducted over the
temperature range of 30–800 °C using a TA Instruments Q50 TGA in-
strument at a heating rate of 10 °C min−1. The gas flow rate was fixed at
60 mL min−1. Elemental analysis (EA) of the samples was conducted
with a Vario EL cube elemental analyzer equipped with a TCD detector
(Elementar Analysensysteme GmbH, Germany). The combustion tube
and the reduction tube temperature were maintained at 1150 °C and
850 °C, respectively. The oxygen content was analyzed using a TCD
detector in O-mode with a pyrolysis tube at 1170 °C. The higher heating
value (HHV) of the raw lignin samples and bio-oil was calculated using
the DIN 51900 standard:
HHV (MJ. kg−1) = (34 C+ 124.3 H+ 6.3 N+ 19.3S−9.8O)/100 (5)
where C, H, N, S, and O are the weight percentages of carbon, hy-
drogen, nitrogen, sulfur, and oxygen, which were obtained by EA.
The molecular weight distribution of bio-oil was characterized by
using a Bruker UltrafleXtreme™ matrix-assisted laser desorption ioni-
zation time-of-flight mass spectrometer (MALDI-TOF/MS, USA). The
composition of the produced gases was analyzed by using a
PerkinElmer Clarus 600 GC-Model Arnel 1115PPC Refinery Gas
Analyzer (RGA, PerkinElmer, CT, USA). The detailed specifications of
the RGA-GC have been reported previously [31]. The bio-oil was
characterized using an Agilent Technologies 7890A GC with a time-of-
flight mass spectrometer (TOF/MS) detector for both qualitative and
quantitative analysis. A detailed description of the GC-TOF/MS equip-
ment is given elsewhere [32]. The functional groups on the sample
surface were characterized by using a NICOLET iS10 Fourier-transform
infrared (FT-IR) spectrometer (Thermo Electron Co., USA).
3. Results and discussion
3.1. Characterization of lignin
analyses, as listed in Table 1. All the lignin samples produced from the
different types of wood and by the different delignification methods had
similar contents of volatile matter (49–55 wt%) and fixed carbon
(45–49 wt%). The ash content of the Klason lignin was slightly higher
than that of the ethanolsolv and formasolv lignin samples. During the
ethanolsolv and formasolv processes, the lignin was dissolved in the
organic solvents and recovered by precipitation in water. On the other
hand, during the Klason process, the lignin remained in the solid form
and holocellulose was dissolved in the acidic aqueous solvent, and thus
some fraction of ash present in the wood sample could be trapped in the
solid lignin phase. The sulfur contents of the ethanolsolv and formasolv
lignin samples were under the detection limit of EA (< 0.01 wt%), but
J. Park et al. Fuel 217 (2018) 202–210

Table 1
Proximate and ultimate analysis of the lignin feedstocks used in this study.

Proximate analysis (wt%, d.b.)a Ultimate analysis (wt%, d.a.f)b

VMc FCd Ashe Moisture C H O N S O/C H/C

OW-E 50.6 48.2 0.1 1.1 69.2 5.13 23.9 N.D.f N.D. 0.26 0.92
OW-F 54.4 44.5 N.D. 1.1 63.6 5.15 28.2 N.D. N.D. 0.33 0.97
OW-K 54.2 44.0 0.6 1.2 60.9 4.84 30.1 N.D. 5.85 0.37 0.95
PW-E 52.5 45.7 N.D. 1.8 68.0 5.02 24.7 N.D. N.D. 0.27 0.89
PW-F 53.5 46.2 0.2 0.3 66.4 5.08 26.4 N.D. N.D. 0.30 0.92
PW-K 49.0 49.1 0.6 1.3 60.6 4.57 26.3 N.D. 5.92 0.33 0.90

c,d
VM and FC were determined using TGA in N2.
a
On a dry basis.
b
On a dry, ash-free basis.
c
VM: volatile matter.
d
FC: fixed carbon.
e
Ash content was determined using TGA in air.
f
Not detectable: under the detection limit of EA (0.01 wt%).

the Klason lignin contained approximately 5 wt% sulfur, which may formasolv method was used as compared to the ethanolsolv and Klason
have originated from the sulfuric acid treatment. methods. During the lignin separation reaction, the α-aryl ether and β-
To quantify the ether linkages (e.g., β-O-4, α-O-4, 4-O-5) in the aryl ether bonds of lignin in the wood undergo hydrolysis to produce
lignin samples, nitrobenzene oxidation was employed; during the ni- small soluble fractions, which are detached from the cellulose. Proto-
trobenzene oxidation, vanillin (V) and syringaldehyde (S) were formed nation of the hydroxyl group in the α or β position with acid catalysts
by cleavage of the ether linkages [30], which are the major chemical can convert the α or β carbon into a carbocation, which can break the
bonds in lignin. As listed in Table 2, the amount of V and S produced ether bond. On the other hand, the formed carbocation may be re-
during the nitrobenzene oxidation was highly dependent on the wood condensed in an intramolecular manner to produce cyclic species or
source as well as the type of lignin produced using the various isolation may react with other fragmented lignins [35,36]. The extent of the
methods. When the wood samples were oxidized, the total V + S yield recondensation reaction may depend on the relative amount of guaiacyl
from OW was approximately three times higher than that produced alcohol and sinapyl alcohol units in a given lignin species because the
from PW because of the presence of syringaldehyde in the oxidized sinapyl alcohol, in which the ortho position of the aromatic ring is
mixture. Lignin from hardwood contains both guaiacyl alcohol (G) and occupied by methoxy groups, can effectively suppress self-re-
sinapyl alcohol (S) units with G/S ratios in the range of 1–4, which condensation [36]. Therefore, the OW-derived lignin samples gave rise
leads to a high ether linkage content in the range of 64–86%. On the to higher V + S yields than the PW-derived lignin samples. In addition
other hand, softwood lignin consists of almost 95% guaiacyl alcohol to the wood source, the degree of recondensation is also known to be
units, and thus the amount of ether linkages (59–74%) in softwood is dependent on the delignification method and conditions [12]. As listed
lower than that in hardwood [33,34]. The V + S content of the lignin in Table 2, the formasolv method resulted in consistently higher V + S
samples was an order of magnitude smaller than that of the “intact” yields than achieved with the ethanolsolv method, regardless of the
lignin present in the corresponding woods. This indicates that the wood type. The lower reaction temperature (120 °C) of the formasolv
structure of lignin changed significantly to form CeC condensed lin- method than that of the ethanolsolv method (190 °C) may account for
kages at the expense of the ether linkages during the lignin separation the lower degree of condensation in the former case. In addition, when
process. Notably, the V + S yields from the lignin samples were highly the Klason method was used, much lower V + S yields were obtained
dependent on the delignification methods. For example, when OW was than achieved with the formasolv and ethanolsolv methods because of
used, the V+S yield followed the order: OW-F the use of a large quantity of strong acid [35]. Because the CeC bond
(129.3 µmol g−1) > OW-E > (116.4 µmol g−1) > OW-K dissociation energy (BDE) (234.9–483.4 kJ mol−1) is larger than the
(83.4 µmol g−1). A similar trend in the V yield was observed for the PW- CeO BDE (182.7–311.6 kJ mol−1) [37], the high degree of re-
derived lignin samples. This indicates that less condensation to form condensation can make lignin depolymerization more difficult.
condensed linkages at the expense of ether linkages occurred when the The functional groups in the lignin samples were analyzed using FT-
IR, and the results are shown in Fig. 1. Signals of hydroxyl (νeCeOH at
∼3430 cm−1, including vibrations from COOH and H2O), carbonyl (ν-
Table 2 C]O at 1710 cm−1), skeletal aromatic ring vibrations (νeC]C at 1605
Nitrobenzene oxidation data.
and 1510 cm−1), and CeH (νeCeH at 1460 and 1365 cm−1) groups
Feedstock Vanillin (V) Syringaldehyde (S) (µmol Total (V + S) were clearly detectable in the profile of the lignin samples, which
(µmol g−1) g−1) (µmol g−1) agrees well with previous observations [28,38]. The signals of the CeO
groups at 1320 and 1120 cm−1 only appeared in the profile of the OW-
OWa 520.1 788.2 1308.3
derived lignin samples, indicating that the corresponding ether bonds
OW-Eb 49.8 66.6 116.4
OW-Fc 35.6 93.7 129.3 originated from the syringol group. On the other hand, the signals of the
OW-Kd 40.6 42.8 83.4 CeO groups at 1270 and 1030 cm−1 (which correspond to the guaiacol
PWe 459.3 0 459.3 group) in the profile of the PW-derived lignin samples had a stronger
PW-E 35.4 0 35.4 transmittance than observed for the OW-derived counterparts. Com-
PW-F 68.9 0 68.9
PW-K 23.0 0 23.0
pared to the ethanolsolv and formasolv lignin samples, the Klason
lignin exhibited weak peaks at 1320 and 1270 cm−1, indicating that
a
Oakwood. fewer CeO bonds of the guaiacol and syringol groups were present.
b
Ethanolsolv lignin from oakwood. This agrees well with the nitrobenzene oxidation results.
c
Formasolv lignin from oakwood. The lignin samples were not completely soluble in acetone or formic
d
Klason lignin from oakwood.
e acid, and thus only the molecular weights of the soluble fraction were
Pinewood.

205
J. Park et al.
Fig. 1. FT-IR spectra of the lignin samples (a) wavenumber range from 4000 to 800 cm−1,
(b) wavenumber range from 1400 to 1100 cm−1.
analyzed using MALDI-TOF/MS, as shown in Fig. S1. The Klason lignin
was not soluble any solvents, and thus its molecular weight could not be
analyzed. The most intense peak of the lignin samples produced from
the ethanolsolv method was observed at 900 m/z, whereas that pro-
duced from the formasolv method had a maximum peak at 1200 m/z. In
addition, the formasolv lignin samples contained a large amount of
high-molecular-weight species with signals in the range of
2000–3500 m/z. This indicates that the lignin structure underwent less
fragmentation during the formasolv process than in the ethanolsolv
process. The low delignification temperature of the formasolv method
may be responsible for the high-molecular-weight fraction in the for-
masolv lignin samples.
3.2. Depolymerization of lignin produced from OW
To investigate the lignin depolymerization behavior and the prop-
erties of the bio-oils from the lignin samples produced by the different
separation methods, OW-E, OW-F, and OW-K were reacted with formic
acid (5:1 w/w ratio) in scEtOH at different reaction temperatures of
250–350 °C. At the end of the 1 h reaction, the pressure increased to
∼10 MPa at 250 °C and to ∼46 MPa at 350 °C. As listed in Table S3,
almost complete conversion of lignin with a high bio-oil yield of > 90
wt% and a low solid-residue yield (< 2.5 wt%) could be achieved at
the high reaction temperature of 350 °C, regardless of the lignin sam-
ples used. This indicates that the combined use of scEtOH and formic
acid at 350 °C is very effective for the conversion of various types of
lignin into bio-oils. This may be because ethanol in its supercritical
206
Fuel 217 (2018) 202–210
Fig. 2. (a) Yields of bio-oil and solid reside produced from the depolymerization of OW-E,
OW-F, and OW-K at temperatures of 250–350 °C. Reaction conditions: 9–10 MPa (250 °C),
19–23 MPa (300 °C), 30–46 MPa (350 °C), 3 g lignin, 60 g ethanol, 12 g formic acid,
60 min. (b) Correlation between the amount of ether linkages and bio-oil yield.
state can donate hydrogen [39–44] and the addition of formic acid to
the reaction mixture enhanced the hydrogen generation [45,46] which
effectively quenches the radicals and suppresses repolymerization
during the cracking reaction [47–51]. In addition, formation of ether
bonding followed by elimination-hydrogenolysis could help depoly-
merize lignin [52–54]. As shown in Fig. S2, H2 comprised approxi-
mately 30 mol% of the gases produced during the depolymerization. In
addition to its role as a hydrogen donor, supercritical ethanol can
participate in the reaction by ring alkylation [55–57] and esterification
[58,59]. Self-decomposition of ethanol to produce low-molecular-
weight oxygenated hydrocarbons [39] may also occur during the de-
polymerization in scEtOH. These factors may result in the yield of bio-
oil produced from OW-F being over 100%.
Although the yields of bio-oil produced from the different types of
OW-derived lignins were quite similar at the high reaction temperature
of 350 °C, the conversion and bio-oil yields were significantly depen-
dent on the types of lignin at lower reaction temperatures of
250–300 °C, as shown in Fig. 2a. When the reaction temperature de-
creased from 350 to 250 °C, the conversion of OW-K and the bio-oil
yield decreased significantly from 97.7% to 19.3% and 89.9 to 18.7 wt
%, respectively. In contrast, when OW-E and OW-F were used, the
conversion and bio-oil yield decreased to a lower extent as compared to
OW-K; for example, at the low reaction temperature of 250 °C, the
yields of bio-oil from OW-E and OW-F were still as high as 68.0 wt%
and 77.5 wt%, respectively. In the case of OW-K, the significant drop in
the conversion and bio-oil yield at low temperature may be attributable
to the high content of recalcitrant CeC linkages formed during the
J. Park et al. Fuel 217 (2018) 202–210

Fig. 3. GC-TOF/MS chromatograms of bio-oils

produced from OW-derived lignin. Reaction
conditions: 350 °C, 30–46 MPa, 3 g lignin, 60 g
ethanol, 12 g formic acid, 60 min.

Klason process. Overall, as shown in Fig. 2b, there is a strong correla- achieved with the scEtOH + HCOOH mixture above 350 °C, regardless
tion between the amount of ether linkages (determined by nitrobenzene of the type of lignin used.
oxidation) and the bio-oil yield at the low-to-medium temperature The molecular weights of the bio-oil produced from the OW-derived
range of 250–300 °C, whereas a high-yield bio-oil (> 81 wt%) was lignin samples are shown in Fig. S3a. After depolymerization, the peak

207
J. Park et al.
of the bio-oil produced from OW-E shifted from 900 m/z (Fig. S1) to
500 m/z. A similar peak shift to the low-molecular-weight range was
observed for the bio-oil produced from OW-F. In addition, the signals of
the high-molecular-weight species (> 2000 m/z) observed in the profile
of the OW-F sample (Fig. S1) disappeared in the profile of the bio-oil.
The molecular weight of the bio-oil produced from OW-K was similar to
that from OW-E. This indicates that scEtOH + HCOOH is a highly
versatile medium for the effective depolymerization of various types of
lignins with different chemical bonds.
The chemical species in the bio-oils produced from OW-E, OW-F,
and OW-K at 350 °C were analyzed using GC-TOF/MS and the chro-
matograms are shown in Fig. 3. The chemical species in the bio-oils
were categorized into three groups: linear and branched short-chain
oxygenated species in the short retention times (< 10 min), mono-
aromatic species in the middle retention time (10–20 min), and long-
chain fatty acid alkyl esters in the long retention time (> 20 min) zone.
The linear and branched short-chain oxygenated species (see Table S4
for detailed information) may have originated from the decomposition
of ethanol and formic acid at 350 °C [39]. To confirm the decomposi-
tion of ethanol and formic acid, a mixture of 60 g of ethanol and 12 g of
formic acid (without lignin) was treated at 350 °C and 29–35 MPa for
30 min and the product was analyzed using GC-TOF/MS, as shown in
Fig. S4. Similar types of oxygenated species were formed during the
blank reaction. At 250–300 °C, relatively less of the short-chain oxy-
genated species was observed (Fig. S5), indicating less ethanol de-
composition at the low liquefaction temperatures. Among the mono-
aromatic species, the most abundant compounds were guaiacol, syr-
ingol, and their alkylation compounds (e.g., creosol and 3,5-dimethoxy-
4-hydroxy toluene). The long-chain fatty acid ethyl esters (e.g., octa-
decanedioic acid and E-11-hexadecenoic acid ethyl ester) in the bio-oil
produced from the OW-derived lignins may have originated from the
esterification of woody fat with ethanol [60]. To confirm this, Soxhlet
extraction of OW in hexane for 6 h was conducted and the recovered
liquid extract is shown in Fig. S6; a substantial amount of woody fat
could be extracted. Similarly, long-chain fatty acids and their ester
species were detected in the OW-derived lignins (Fig. S7).
As shown in Fig. S5, the low-temperature liquefaction resulted in a
relatively large amount of carbonyl-containing or double bond-con-
taining branched mono-aromatics such as 1-(4-hydroxy-3-methox-
yphenyl)-2-propanone (8, Fig. S5a), 2,6-dimethoxy-4-(2-propenyl)-
phenol (10, Fig. S5a), and 3,5-dimethoxy-4-hydroxyphenylacetic acid
(15, Fig. S5a). This suggests that the deoxygenation and hydrogenation
ability associated with scEtOH may be lower at the lower reaction
temperatures. This agrees well with the EA results, as listed in Table S5.
As the reaction temperature increased, the O/C ratios of the bio-oil
produced from the OW-derived lignins decreased and the HHV of the
bio-oil increased. For example, when the reaction temperature in-
creased from 250 to 350 °C, the O/C ratio of the bio-oil produced from
OW-K decreased from 0.31 to 0.25 and the HHV increased from 25.8 to
30.4 MJ kg−1.
3.3. Comparison of the reactivity of the lignin samples derived from OW and
PW
As discussed in Section 3.1, the lignin samples produced from PW
had lower V + S contents than those produced from OW, suggesting
that the PW-derived lignin samples may have lower depolymerization
activity. To examine the difference in the depolymerization behavior
depending on the wood sources, the PW-derived lignin samples were
depolymerized in a mixture of scEtOH and formic acid at 350 °C for 1 h.
During the course of liquefaction, the pressure in the reactor increased
from 30 to 46 MPa. As listed in Table S3, when PW-F was used, a high
conversion of 99.4% with a high bio-oil yield of 90.7 wt% and a low
solid residue yield of 0.6 wt% were achieved. The use of PW-E resulted
in a slightly lower conversion (97.1%) and a lower bio-oil yield (88.1 wt
%) as compared to those of PW-F. This depolymerization behavior is
208
Fuel 217 (2018) 202–210
comparable to that observed in the depolymerization of OW-F and OW-
E. Therefore, despite the low content of labile ether linkages in the PW-
derived lignins produced by the formasolv and ethanolsolv methods,
the high depolymerization activity associated with scEtOH + formic
acid is not significantly affected by the structure of lignin derived from
different wood sources. The lowest conversion (95.1%) and bio-oil yield
(81.7 wt%) were achieved with PW-K because of the high content of
CeC linkages. However, even when the highly recalcitrant PW-K was
used as the feedstock, the bio-oil yield was higher than that achieved
via the acid-catalyzed depolymerization of dealkaline lignin at 250 °C
for 30 min (60 wt% THF soluble) [25], base-catalyzed depolymerization
of organosolv lignin at 300 °C (52 wt%) for 40 min [23], and metal-
catalyzed depolymerization of alkali lignin at 265 °C (45.8 wt%) for 1 h
[61] (see Table S6 for a comparison of the bio-oil yield). This indicates
that scEtOH + formic acid is a highly versatile and effective medium
for the depolymerization of various types of lignin.
The molecular weight distributions of the bio-oils produced from
the PW-derived lignins are shown in Fig. S3b. As in the case of the OW-
derived lignins and their corresponding bio-oils, the peaks were shifted
to the low-molecular-weight direction for the bio-oils produced from
PW-derived lignin. The bio-oils produced from the different lignin
samples had similar molecular weight distributions. Again, this clearly
indicates the effective depolymerization of the various types of lignin in
the scEtOH + formic acid medium.
The GC-TOF/MS chromatograms of the bio-oils produced from the
PW-derived lignins are shown in Fig. 4. Again, the main chemicals were
mono-aromatic species in the middle retention time and short-chain
oxygenated species were also present in the short reaction time zone, as
in the case of the bio-oils produced from the OW-derived lignins. The
absence of syringol in the bio-oil produced from the PW-derived lignin
samples is quite straightforward because the lignins were derived from
softwood. However, the bio-oil produced from PW-derived lignin did
not contain long-chain fatty acid esters and acid. This could be because
of the absence of fatty acid species in the PW.
4. Conclusion
Six different types of lignin samples were depolymerized in a mix-
ture of supercritical ethanol (scEtOH) and formic acid at temperatures
of 250–350 °C. The content of ether linkages in the samples was highly
dependent on the wood source (i.e., whether it was derived from oak-
wood, OW or pinewood, PW) and the lignin isolation method (etha-
nolsolv, E; formasolv, F; Klason, K). This may be because the formation
of condensed linkages at the expense of ether linkages is dependent on
the presence of the sinapyl alcohol unit and the isolation conditions.
The amount of ether linkages in the lignin samples played an important
role in determining the bio-oil yield in the low-to-medium temperature
range; for example, the content of ether linkages followed the order:
OW-F (129.3 µmol g−1) > OW-E (116.4 µmol g−1) > OW-K
−1
(83.4 µmol g ), and the bio-oil yield followed the order: OW-F
(77.5 wt%) > OW-E (68.0 wt%) > OW-K (18.7 wt%) at 250 °C. On
the other hand, at the high temperature of 350 °C, all the lignin sam-
ples, even PW-K with an extremely low amount of ether linkages
(23.0 µmol g−1), could be converted effectively into high-yield bio-oil
(> 81 wt%). The compositional analysis suggested that during the de-
polymerization, hydrodeoxygenation and hydrogenation occurred to
some degree.
Acknowledgements
This work was supported by the New and Renewable Energy Core
Technology Program (No. 20143030090940) of the Korea Institute of
Energy Technology Evaluation and Planning (KETEP) financed by the
Ministry of Trade, Industry and Energy, Republic of Korea. Additional
support from the Technology Development Program to Solve Climate
Changes of the National Research Foundation (NRF) funded by the
J. Park et al. Fuel 217 (2018) 202–210

Fig. 4. GC-TOF/MS chromatograms of bio-oils pro-

duced from PW-derived lignin. Reaction conditions:
350 °C, 30–46 MPa, 3 g lignin, 60 g ethanol, 12 g formic
acid, 60 min.

209
J. Park et al.
Ministry of Science, ICT & Future Planning (No. 2017M1A2A2087635)
was appreciated.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.fuel.2017.12.079.
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