Chemical Engineering Journal 309 (2017) 187196

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Production of phenolic hydrocarbons using catalytic depolymerization of

empty fruit bunch (EFB)-derived organosolv lignin on Hb-supported Ru
Minsun Kim a,b, Deokwon Son a,b, Jae-Wook Choi a, Jungho Jae a,c, Dong Jin Suh a,d,e, Jeong-Myeong Ha a,c,e,,
Kwan-Young Lee b,e
a
Clean Energy Research Center, Korea Institute of Science and Technology, Seoul 02792, Republic of Korea
b
Department of Chemical and Biological Engineering, Korea University, Seoul 02841, Republic of Korea
c
Department of Clean Energy and Chemical Engineering, Korea University of Science and Technology, Daejeon 34113, Republic of Korea
d
Department of Green Process and System Engineering, Korea University of Science and Technology, Daejeon 34113, Republic of Korea
e
Green School (Graduate School of Energy and Environment), Korea University, Seoul 02841, Republic of Korea

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Catalytic depolymerization of lignin

to monophenyl hydrocarbons.
 Ru/Hb exhibited the largest yields of
monophenyls and the smallest
molecular weight.
 Acid sites improve the
depolymerization with the help of
hydrogen-adsorbing metals.

a r t i c l e i n f o a b s t r a c t

Article history: Catalytic depolymerization of empty fruit bunch (EFB)-derived organosolv lignin, which is free of ash and
Received 30 May 2016 catalyst-poisoning sulfur, is performed using supported metal catalysts. Without the improved reaction
Received in revised form 1 October 2016 activity in the presence of supercritical solvents, water and ethanol in this study, at the subcritical con-
Accepted 4 October 2016
ditions, Hb-supported Ru catalyst achieved 16.5% yield of small molecule phenolic hydrocarbons, includ-
Available online 4 October 2016
ing guaiacol, 4-methylguaiacol, 4-ethylguaiacol, cerulignol, and iso-eugenol, and produced degraded
lignin polymer with 63% decreased weight-average molecular weight based on polystyrene-calibrated
Keywords:
gel permeation chromatography results. The catalytic depolymerization activity was determined by
Organosolv lignin
Catalyst
the quantity of acid sites on the catalysts; however, the presence of metal nanoparticles is required to
Depolymerization supply hydrogen atoms to the reaction system, which particles improve the catalytic depolymerization
Ru/Hb activity. The structure of organosolv lignin prepared by extraction using a mixture of ethanol and water
Solid acid was also studied using GPC and NMR results, which indicated that a possibly linear polymer composed of
phenolic monomers with two or fewer linking functionalities.
2016 Elsevier B.V. All rights reserved.

1. Introduction

Lignin has been a byproduct of traditional pulping processes

Corresponding author at: Clean Energy Research Center, Korea Institute of
Science and Technology, Seoul 02792, Republic of Korea.
E-mail address: jmha@kist.re.kr (J.-M. Ha).
and recently developed bioalcohol production; it is used as a
low-energy solid fuel for the heating units of pulping plants [1
3] and as an additive for the construction materials [4,5]. With

http://dx.doi.org/10.1016/j.cej.2016.10.011
1385-8947/ 2016 Elsevier B.V. All rights reserved.
188 M. Kim et al. / Chemical Engineering Journal 309 (2017) 187196

increasing efforts to improve the economic feasibility of biofuels combined investigation o small-molecule aromatic hydrocarbon
and develop more valuable chemicals from biomass, aromatic products and lignin residue, the depolymerization of lignin on
monomeric units of lignin have attracted significant interest the catalysts can be explained in detail.
because they can be converted to valuable aromatic fine chemicals
that are not easy to obtain from other carbon sources including
2. Experimental
recently booming natural or shale gas and biomass-derived
carbohydrates.
2.1. Materials
Lignocellulose consists of cellulose, hemicellulose, and lignin.
Lignin is composed of 1530% by weight and 40% by energy of
Ruthenium (III) chloride hydrate (RuCl3
xH2O), tetraamine plat-
the lignocellulosic biomass; it is the only sustainable resource in
inum(II) chloride hydrate (Pt(NH3)4Cl2
xH2O), carbon-supported
nature that is composed of aromatics [2,68]. While cellulose
5 wt% Ru/C (5 wt% Ru/C), toluene (99%), 4-ethylguaiacol (98%),
and hemicellulose, which are important in fermentation and other
cerulignol (2-methoxy-4-propenylphenol, 99%), eugenol (2-
chemical processes to produce fuels and fine chemicals, are natural
methoxy-4-(2-propenyl)phenol, 99%), ethanol (anhydrous, 99.5%),
polymers made of well-defined sugars, lignin is a natural amor-
methyl homovanillate (methyl 4-hydroxy-3-methoxyphenylace
phous and three-dimensional complex branched polymer com-
tate, 97%), 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane
posed of phenolic monomers, including p-coumaryl, coniferyl,
(95% TMDP), chromium (III) acetyl acetonate (99.9%), deuterated
and synapyl alcohol subunits [1]. These subunits are mainly
chloroform (99.96% CDCl3), deuterated dimethyl sulfoxide (DMSO,
cross-linked by COC ether bonds and CC bonds, while cellulose
99.9%), cyclohexanol (99%), pyridine (anhydrous, 99.8%), acetic
and hemicellulose are made of glucosidic bonds between sugars.
anhydride (99%), magnesium oxide (light), and silica-alumina
Because of its unique structure, lignin is highly touted as a poten-
powder (SiO2-Al2O3, grade 135) were purchased from Aldrich (Mil-
tial renewable resource for producing both aromatic fuels and
waukee, WI, USA). Sulfuric acid and tetrahydrofuran (HPLC grade,
chemicals; the depolymerization of lignin into its monophenyl
stabilized with butylated hydroxytoluene) were purchased from
units is required to use lignin as a feedstock for further processes.
J.T. Baker (Phillipsburg, NJ, USA). Zeolite b (ammonium form, BET
Several methods have been suggested to depolymerize lignin
surface area = 680 m2/g and Si/Al = 25 (atom/atom)) and zeolite Y
for value added products. Thermochemical methods, including
(hydrogen form, BET surface area = 760 m2/g and Si/Al = 60
pyrolysis and hydrothermal/solvothermal liquefaction, have been
(atom/atom)) were purchased from Zeolyst (Conshohocken, PA,
developed to degrade lignin [916]; however, these methods are
USA). Alumina (Al2O3, c-phase, 99.97%), silica gel (SiO2, 60325
difficult to control and have been found to lead to the formation
mesh), and ZSM-5 (ammonium form, BET surface area = 420 m2/g
of large amounts of gases, tar, and char. The significant carboniza-
and Si/Al = 50(atom/atom)) were purchased from Alfa Aesar (Ward
tion of lignin melt at high temperature has also been found to be a
Hill, MA, USA). Nickel (II) nitrate hexahydrate (Ni(NO3)2
6H2O) was
critical issue making the thermochemical methods difficult to scale
purchased from Junsei (Tokyo, Japan). Copper (II) nitrate trihydrate
up and commercialize. Compared to the thermochemical methods,
(Cu(NO3)3
H2O) was purchased from Daejung (Seoul, Korea).
the chemical depolymerization of lignin to distillable small mole-
Hydrogen gas (H2, 99.999%), helium gas (He, 99.999%), 5% (v/v)
cules is less active for the conversion of biomass but possibly more
H2/Ar gas, 0.5% (v/v) O2/N2 gas, and 1% CO gas were purchased from
selective for valuable aromatic monomers [2].
Shinyang Sanso (Seoul, Korea). Deionized water was prepared
Because lignin can be obtained as a byproduct of pulping pro-
using the aquaMAX Ultra 370 water purification system from
cesses, a lot of lignin products have been suggested and their
YoungLin Instrument (Anyang, Korea).
chemical properties will certainly affect the operation of catalytic
depolymerization [17]. Kraft lignin, mass-produced by the Kraft
pulping process [5] and containing sulfur atoms in its structure, 2.2. Isolation of organosolv lignin from empty fruit bunch
has a complex structure and is frequently used for the depolymer-
ization research [1,4,1820]. Organosolv lignin, free of sulfur and Lignin was extracted from oil palm empty fruit bunch (EFB from
ash [21], has also been depolymerized [2224]. Ethanol and Malaysia) using the modified organosolv process [28,30,35]. The
methanol can be used for extracting lignin from lignocellulose reaction was performed in a 10 L stainless autoclave type batch
under relatively mild conditions [2527]. reactor. A mixture of biomass (1000 g), ethanol/water (5000 mL,
The objectives of this study are to produce lignin-derived small 66 wt% ethanol), and aqueous sulfuric acid solution (15 mM) was
molecule aromatic hydrocarbons and more processible lower stirred at 170 C for 1 h. The mixture was cooled to 40 C or lower.
molecular weight lignin. Organosolv lignin is selected as a feed- The obtained suspension was filtered using a Whatman type 3
stock because its sulfur-free structure cannot poison the metal cat- paper filter. The filtrate (organosolv liquor) was stored in a refrig-
alysts and because the less complex structure, compared to that of erator for lignin recovery. Organosolv lignin was precipitated in the
Kraft lignin, makes it easier for researchers to understand the organosolv liquor and washed using refrigerated water (water/so-
depolymerization behavior of lignin [2830]. Noble or transition lution = 3 (w/w)). The particles were further centrifuged and
metal catalysts, including Pt, Ru, Ni, and Cu, supported on solid freeze-dried to obtain the lignin.
acids, including metal oxides and zeolites, are studied to depoly-
merize organosolv lignin. Supercritical reaction conditions of tem- 2.3. Compositional analysis of empty fruit bunch-derived organosolv
perature above 374 C and pressure of 221 bar for water and lignin
temperature of 241 C and pressure of 63 bar for ethanol were
avoided in order to focus on the screening of optimum catalysts. The fractions of cellulose, hemicellulose, and lignin were mea-
Both lignin-derived small molecule aromatic hydrocarbon prod- sured using a method reported in the literature [3638]. The sam-
ucts and remaining lignin polymer are analyzed. The analysis of ple (0.3 g, dry basis) was treated with sulfuric acid (72 wt%) at
small-molecule aromatic hydrocarbon products determines the 30 C for 1 h and stirred every 15 min. Deionized water
most active catalysts; lignin residue was found to provide a win- (18.2 MX
cm, 84 mL) was added to the mixture to obtain 4 wt%
dow into how catalytic depolymerization occurs, which knowledge sulfuric acid solution. The mixture was then heated to 121 C in
may improve understanding of the catalytic depolymerization pro- a pressure tube glass (8648-30 ACE glass) with screw-on Teflon
cess. To understand the depolymerization pathway, nuclear mag- caps and o-ring seals (5845-47 plug) and left for 1 h at 100 C.
netic resonance (NMR) spectroscopy is used [3134]. With the The mixture was cooled to room temperature and further filtered.
 M. Kim et al. / Chemical Engineering Journal 309 (2017) 187196
Quantities of acid-insoluble-lignin (AIL), acids, water-free solid
residue, and ash were measured based on the methods of NREL/
TP-510-42621 and 42622 [3638].
2.4. Preparation of catalysts
Commercially available supports of Al2O3, SiO2, silica-alumina
(SiAl), MgO, and HY were directly used without any further treat-
ment. Hb and HZSM-5 were prepared by calcining NH3-zeolite b
and NH3-ZSM-5 at 550 C for 3 h. The support powder was sieved
to obtain particles smaller than 150 lm prior to impregnation.
5 wt% Ru was impregnated onto each support using an incipient-
wetness method. All impregnated catalysts were calcined in air
at 400 C for 2 h. The calcined catalysts were reduced in a 5%
(v/v) H2/Ar flow at 400 C for 4 h and passivated in a 0.5% (v/v)
O2/N2 flow at room temperature for 30 min. The prepared catalysts
were stored under ambient conditions prior to use.
2.5. Characterizations of catalysts
The acidity of the catalysts was measured using ammonia-
temperature programmed desorption (NH3-TPD) using BELCAT-B
(Bel Japan, Osaka, Japan) equipped with a thermal conductivity
detector (TCD) and a quadrupole mass spectrometer BELMass
(Bel Japan, Osaka, Japan). The catalyst powder (3050 mg) was out-
gassed in a He flow (50 mL/min) at 400 C for 60 min and passi-
vated in a 7.5% NH3/He at 100 C for 30 min. After stabilizing TCD
at 100 C for 60 min in a He environment (30 mL/min), desorbed
NH3 was measured using a TCD and a mass spectrometer at 100
900 C at a ramping rate of 10 C/min in a He flow (30 mL/min).
The quantity of desorbed NH3 was measured in a range of
100500 C. CO-chemisorption was performed using a BELCAT-B
catalyst analyzer (BEL Japan, Inc.) equipped with a thermal conduc-
tivity detector (TCD). The catalyst powder (50 mg), placed in a
U-shaped quartz reactor, were heated to 300 C with 10 C/min
of heating rate in a He flow (50 mL/min), and reduced in a H2 flow
(50 mL/min) at 300 C for 1 h. The treated catalyst powder was
cooled to 50 C in a He flow (50 mL/min). After treating the catalyst
powder using a He flow (50 mL/min) at 50 C for 30 min, the pulses
of 1% CO in He were injected to measure the active metal surface
area. H2-chemisorption was performed using a Autochem 2920
(Micromeritics) equipped with a thermal conductivity detector
(TCD). The catalyst powder (50 mg), placed in a quartz reactor,
were heated to 300 C with 10 C/min of heating rate in an Ar flow
(50 mL/min), and reduced in a H2 flow (50 mL/min) at 300 C for
1 h. The treated catalyst powder was cooled to 30 C in an Ar flow
(50 mL/min). After treating the catalyst powder using an Ar flow
(50 mL/min) at 30 C for 30 min, the pulses of 1% H2 in Ar were
injected to measure the active metal surface area.
2.6. Catalytic depolymerization of empty fruit bunch-derived
organosolv lignin
The catalytic depolymerization of lignin was performed in a
100-mL stainless steel batch autoclave reactor [20,39]. Organosolv
lignin prepared in this study was dried in a vacuum at 35 C for
16 h prior to use. In a typical process, dry organosolv lignin
(0.3 g) was dissolved in a mixture of ethanol and water (30 mL,
65% (v/v)) at 50 C for 60 min. The catalyst powder (0.1 g) was
added to the reactor along with the lignin solution. The reactor
was purged three times using H2 and pressurized to 40 bar. The
reaction mixture was heated to 225 C and agitated at 500 rpm.
After 6 h, the reaction mixture was slowly cooled to room temper-
ature. The mixture was extracted with toluene (10 mL) and frac-
tionated into two products [20,39]. First, the toluene layer
containing lignin monomers was collected and observed using
189
GC/MS and GC-FID equipment to identify and quantify the prod-
ucts dissolved in toluene. Second, the ethanol-water layer, remain-
ing after removing the toluene layer, was dried at 50 C using a
rotavapor; this was followed by further drying in a vacuum at
50 C for 16 h. The remaining solid was assigned as lignin residue
in this study. The collected dry lignin residue was weighed and fur-
ther characterized.
2.7. GC/MS and GC-FID for aromatic monomer products
Aromatic monomer products dissolved in toluene were identi-
fied using a GC/MS (Agilent 5975C inert XL MSD with a triple-
axis detector) equipped with a HP-5ms capillary column
(60 m  0.25 mm  0.25 lm) and quantified using a GC-FID
(YoungLin 6500 series gas chromatograph system) equipped with
a HP-5 capillary column (60 m  0.25 mm  0.25 lm) and a flame
ionization detector (FID).
2.8. Gel-permeation chromatography for polymer products
The number-average molecular weight (Mn), weight-average
molecular weight (Mw), and polydispersity index (PDI) of lignin resi-
due were determined by GPC after acetylation. In brief, a lignin resi-
due sample (0.050 g) was dissolved in an acetic anhydride/pyridine
(5 mL, 1:1 v/v) mixture and stirred for 24 h at room temperature.
Ethanol was added to the mixture, which was rotoevaporated and
further dried in a vacuum at 50 C for 16 h to obtain the acetylated
lignin. The acetylated lignin residue was dissolved in tetrahydrofu-
ran (THF) (1.0 g/L). The GPC analysis was performed at 30 C using
a THF eluent at a flow rate of 1.00 mL/min with an Agilent HPLC
gel-permeation chromatography (GPC) system equipped with two
columns (Shodex LF-804) and UV detector (observed at 270 nm).
The calibration for the GPC was performed using the plystyrene
standard ReadyCal set (Aldrich, 2502,000,000 g/mol) [4042].
31
2.9. P, 1H, 13
C, and HSQC-NMR
31
P NMR was performed using an Agilent spectrometer at
600 MHz with a 90 pulse angle, a 25-s pulse delay, an inverse gated
proton decoupling pulse, a temperature of 298 K, and 256 scans, as
described in the literature [31]. For 31P NMR, lignin powder (60 mg)
containing a relaxation agent (2.5 mg of chromium(III) acetylaceto-
nate) was dried in a vacuum at 35 C for 16 h, after which N,N-
dimethylformamide (150 lL), anhydrous pyridine (150 lL), and
cyclohexanol (20 lL, internal standard) were added. The
suspension was stirred for 12 h at room temperature to obtain a
homogenous solution. 2-Chloro-4,4,5,5-tetramethyl-1,3,2-dioxa
phospholane (TMDP) (200 lL) mixed with CDCl3 (400 lL) was
added to the lignin mixture and stirred for 23 min at room tem-
perature. The mixture was transferred to a 5 mm NMR tube for a
31
P NMR analysis. 1H and 13C NMR were performed using an Agilent
spectrometer at 600 MHz. HSQC analysis was performed using a
Bruker Avance 600 MHz equipped with cryoporbe installed at the
National Center for Inter-university Research Facilities (NCIRF) at
Seoul National University (Seoul, Korea). The lignin was dried at
80 C in vacuum for 16 h and dissolved (100 g/L) in deuterated
dimethyl sulfoxide (DMSO) prior to the 1H, 13C, and HSQC-NMR
analyses.
3. Results and discussion
3.1. Composition of empty fruit bunch-derived organosolv lignin
The composition of organosolv lignin prepared in our lab was
measured using a method reported in the literature [37], which
190 M. Kim et al. / Chemical Engineering Journal 309 (2017) 187196

Table 1
Composition and elemental analysis results of organosolv lignin.

Composition analysis (wt%) Elemental analysis (atom%)

Cellulose Hemicellulose Lignin C H N S O
2.53.5 3.14.4 92.094.1 39.4 43.1 0 0 13.2

revealed that the fraction of lignin including acid insoluble and sol-
uble lignin components was in the range of 92.094.1 wt%
(Table 1). The amount of sugar impurities derived from cellulose
and hemicellulose was in the range of 5.67.9 wt%; these seem
to have been obtained from organosolv liquor [35]. Atomic compo-
sition measurement indicated that the organosolv lignin prepared
in this study was composed of 42.3% (atom/atom) C, 45.5% (atom/
atom) H, and 13.8% (atom/atom) O, with no detectable N or S
(Table 1). Sulfur-free organosolv lignin, compared to sulfur-
containing ligninsulfonates and Kraft lignin, is a suitable feedstock
for a reaction using metal catalysts because sulfur-free reactants
do not poison the metal catalyst surface [43].
3.2. Catalytic depolymerization of empty fruit bunch-derived
organosolv lignin
Two isolated products, including aromatic monomers extracted
in the toluene phase and polymeric lignin residue dissolved in the
aqueous (ethanol-water) phase after the toluene-extraction, were
analyzed; this analysis measured the quantity of depolymerized
lignin and the degree of depolymerization, respectively. It should
be noted that the lignin reactant can be converted into (i) aromatic
small molecules dissolved in toluene (measurements depicted in
Table 2), (ii) aromatic small molecules dissolved in ethanol/water
mixture (not measured), (iii) lignin residue precipitated in the mix-
ture of toluene, ethanol, and water (not measured), (iv) lignin resi-
due dissolved in the toluene layer (not measured), (v) lignin
residue dissolved in the ethanol/water mixture (measured), and
(vi) light hydrocarbons vaporized to hydrogen-rich gas phase
(not measured). Among these, (i) was analyzed to measure yields
of aromatic small molecules, (v) was analyzed to measure the
quantity of lignin residue, (ii) was not measured because the solu-
bility of aromatic compounds is low in aqueous solvents, (iii) was
not measured because the isolation of lignin residue from catalyst
powder was difficult, (iv) was not measured because we assumed
that only small aromatic molecules could be extracted in toluene,
and (vi) was difficult to quantify because of the dilution by large
amount of H2 gas. In this study, the small molecule products
extracted in the toluene layer (i) were used to measure the yield
of reaction products and the efficiency of the catalytic reaction.
The lignin residue dissolved in the ethanol/water mixture (v) was
also analyzed to measure the degree of depolymerization. The
complete mass balance was not measured because some fractions
of products were difficult to quantify.

Table 2
Concentrations and yields of major aromatic monomer products.a

Catalyst Concentration (mM in 10 mL toluene)

Guaiacol 4-methylguaiacol 4-ethylguaiacol Cerulignol Iso-eugenol Combined concentration (mM)b Yield (%)c
No catalyst 0 0 1.18 1.83 0 3.01 (0.48) 1.6
5 wt% Ru/MgO 0 0.10 1.11 2.72 0 3.93 (0.64) 2.1
5 wt% Ru/SiO2 0 0.06 0.53 2.51 0.21 3.31 (0.54) 1.7
5 wt% Ru/SiO2 (with aqueous HNO3)d 0 0 0.90 5.58 2.52 8.99 (1.48) 4.9
5 wt% Ru/Al2O3 0 0.08 1.00 4.82 0.42 6.31 (1.03) 3.4
5 wt% Ru/SiAl 0 0.15 1.24 4.28 2.92 8.60 (1.40) 4.6
5 wt% Ru/HY 0.43 0.33 2.01 11.09 1.57 15.42 (2.50) 8.2
5 wt% Ru/HZSM-5 0.56 0.67 2.94 12.21 1.08 17.45 (2.81) 9.3
5 wt% Ru/Hb 0.62 0.51 2.29 18.99 7.44 29.85 (5.02) 16.5
5 wt% Ru/Hb (spent) 0 0 0.84 6.91 0 7.75 (1.28) 4.2
5 wt% Pt/MgO 0 0.19 1.07 1.80 0.36 3.42 (0.55) 1.7
5 wt% Pt/SiO2 0 0.08 0.85 5.76 0.25 6.95 (1.14) 3.7
5 wt% Pt/Al2O3 0 0.06 1.53 3.53 0.74 5.87 (0.95) 3.2
5 wt% Pt/SiAl 0 0.12 1.04 5.90 1.36 8.43 (1.38) 4.5
5 wt% Pt/HY 0.17 0.67 1.68 15.47 1.57 19.56 (3.20) 10.6
5 wt% Pt/HZSM-5 0.46 0.43 2.05 20.76 0.27 23.98 (3.92) 13.0
5 wt% Pt/Hb 0.36 0.71 1.46 18.65 2.15 23.33 (3.82) 12.5
20 wt% Cu/MgO 0 0.06 1.10 1.22 0.26 2.63 (0.42) 1.4
20 wt% Cu/SiO2 0 0.03 0.83 1.60 0.37 2.83 (0.46) 1.5
20 wt% Cu/Al2O3 0 0.08 0.85 2.30 0.11 3.34 (0.54) 1.8
20 wt% Cu/SiAl 0 0.08 0.82 2.26 0.09 3.25 (0.53) 1.7
20 wt% Cu/HY 0 0.15 1.19 8.24 0.20 9.79 (1.61) 5.2
20 wt% Cu/HZSM-5 0.58 0.41 1.90 9.41 1.21 13.51 (2.18) 7.1
20 wt% Cu/Hb 0.29 0.17 1.09 13.78 1.96 17.30 (2.84) 9.4
20 wt% Ni/MgO 0 0.08 1.06 1.40 0.27 2.81 (0.45) 1.5
20 wt% Ni/SiO2 0 0.12 0.40 1.64 0.53 2.69 (0.44) 1.4
20 wt% Ni/Al2O3 0 0.09 0.99 4.00 2.04 7.11 (1.16) 3.8
20 wt% Ni/SiAl 0 0.18 0.84 1.92 1.21 4.16 (0.67) 2.2
20 wt% Ni/HY 0 0.10 0.37 8.95 0.05 9.46 (1.56) 5.0
20 wt% Ni/HZSM-5 0.17 0.25 1.01 9.28 3.75 14.47(2.37) 7.7
20 wt% Ni/Hb 0.13 0.31 0.95 13.17 1.13 15.88(2.61) 8.4
a
Reaction conditions: 0.1 g catalysts, 0.3 g organosolv lignin dissolved in a mixture of ethanol/water (30 mL, 65% (v/v)), 6 h reaction time, 40 bar H2, 225 C, and agitation
rate of 500 rpm.
b
Numbers in parentheses are concentrations in g/L.
c
Yield (%) = (Weight of produced guaiacol, 4-methylguaiacol, 4-ethylguaiacol, cerulignol, and iso-eugenol)/(Weight of dry lignin reactant)  100.
d
Aqueous nitric acid (66 wt%, 0.03 mL, approximately 3 equivalent of acidity of Hb) was added to the reaction mixture.
 M. Kim et al. / Chemical Engineering Journal 309 (2017) 187196 191

Table 3 The small molecule aromatic hydrocarbon products (i)

Molecular weights (Mw and Mn), and polydispersity index (PDI = Mw/Mn) of lignin and extracted with toluene were identified and quantified using GC/
lignin residue.a
MS and GC-FID to calculate the aromatic monomer yields and
Catalysts Mn (g/mol) Mw (g/mol) PDI determine the most active catalysts. The GC/MS results for the aro-
Lignin, no reaction 1333 3899 2.92 matic monomers exhibited that there were five major phenolic
No catalyst 1097 2787 2.54 compounds: guaiacol, 4-methylguaiacol, 4-ethylguaiacol, cerulig-
5 wt% Ru/MgO 1044 2465 2.36 nol (2-methoxy-4-propylphenol), and iso-eugenol (Table 2,
5 wt% Ru/SiO2 1007 2230 2.31
5 wt% Ru/Al2O3 942 2052 2.18
Figs. S1, and S2); these results are similar to results obtained using
5 wt% Ru/SiAl 980 1995 2.04 transition metals [44], Pt/C with formic acid [24], and supported
5 wt% Ru/HY 877 1662 1.90 noble metals [45,46]. Other products were ignored in this study
5 wt% Ru/HZSM-5 883 1610 1.87 because of their negligible quantities; no production of phenol or
5 wt% Ru/Hb 698 1431 2.05
catechol was observed as their formation has been reported for
5 wt% Pt/MgO 1239 2797 2.26
5 wt% Pt/SiO2 1161 2674 2.30 reactions using metal oxides [19]. Hydrodeoxygenated products
5 wt% Pt/Al2O3 1119 2551 2.28 of deoxygenated aromatic or cycloalyl molecules were not
5 wt% Pt/SiAl 1018 2303 2.26 observed although solid-acid-supported metals are known to be
5 wt% Pt/HY 1039 2247 2.16 good hydrodeoxygenation catalysts [4751]. Phenol and catechol
5 wt% Pt/HZSM-5 1120 2199 1.96
were the major products of the noncatalytic supercritical-phase
5 wt% Pt/Hb 961 1474 1.53
20 wt% Cu/MgO 1105 2775 2.51 reaction of Kraft lignin [15], but only guaiacol and alkyl guaiacol
20 wt% Cu/SiO2 1041 2709 2.60 derivatives were observed in this study. The major products of gua-
20 wt% Cu/Al2O3 859 2670 3.11 iacol and 4-alykyl-substituted guaiacols were derived from the
20 wt% Cu/SiAl 1090 2623 2.41
coniferyl alcohol units, which are the major monomeric compo-
20 wt% Cu/HY 978 2098 2.41
20 wt% Cu/HZSM-5 863 1687 1.95 nent of softwood lignin [52]. Syringol derivatives and vanillin,
20 wt% Cu/Hb 757 1536 2.03 which were observed as the products of the depolymerization of
20 wt% Ni/MgO 1186 2709 2.28 Miscanthus giganteus-derived lignin, were not observed [53].
20 wt% Ni/SiO2 1100 2698 2.45 Among the four metal particle catalysts, 5 wt% Ru and Pt exhib-
20 wt% Ni/Al2O3 1125 2605 2.31
ited better activity than 20 wt% Cu and Ni. For the Ru catalysts,
20 wt% Ni/SiAl 1118 2486 2.22
20 wt% Ni/HY 1003 2266 2.26 5 wt% Ru/Hb exhibited the largest yield of aromatic monomers,
20 wt% Ni/HZSM-5 995 2162 2.17 producing 0.62 mM guaiacol, 0.51 mM 4-methylguaiacol,
20 wt% Ni/Hb 989 2032 2.05 2.29 mM 4-ethylguaiacol, 18.99 mM cerulignol, and 7.44 mM iso-
a
Reaction conditions: 0.1 g catalyst, 0.3 g organosolv lignin dissolved in a mix- eugenol; these results demonstrated a value of 29.85 mM of com-
ture of ethanol/water (30 mL, 65% (v/v)), 6 h reaction time, 40 bar H2, 225 C, and bined concentration of five major products dissolved in 10 mL
agitation rate of 500 rpm.

Fig. 1. Representative molecular weight distributions of lignin and lignin residue after the reaction on (a) 5 wt% Ru, (b) 5 wt% Pt, (c) 20 wt% Cu, and (d) 20 wt% Ni depending
on supports.
192 M. Kim et al. / Chemical Engineering Journal 309 (2017) 187196

Table 4 a value of Mw = 2465 g/mol. 5 wt% Ru/Hb also exhibited a sharp

NH3-TPD and CO-chemisorption results of catalysts. peak at 300 g/mol indicating the formation of lignin oligomer
Catalyst NH3-TPD CO-chemisorption H2-chemisorption (Fig. 1).
Quantity of acid sites [CO]/[Ru] [H]/[Ru] The most active catalyst, Ru/Hb, was recycled after the reaction,
(lmol/g) (mol/mol) (mol/mol) and the spent Ru/Hb, when calcined and reduced, exhibited
5 wt% Ru/MgO 0 0.0364 0.00123
decreased activity with a combined yield of 4.2%, which is only
5 wt% Ru/SiO2 0 0.0505 0.00332 25% of the yield observed for the fresh Ru/Hb (Table 2). The
5 wt% Ru/Al2O3 60 0.1251 0.00509 decreasing activity can be attributed to the loss of active sites on
5 wt% Ru/SiAl 636 0.0778 0.0118 metals and to the loss of solid acid support during the reaction
5 wt% Ru/HY 827 0.00650 0.00243
as the BET surface area of Ru/Hb decreased from 575 to 401 m2/g.
5 wt% Ru/HZSM-5 1113 0.0182 0.00133
5 wt% Ru/Hb 1375 0.0264 0.0746
3.3. Characterization of catalysts

NH3-temperature programmed desorption (NH3-TPD) and CO/

Fig. 2. Correlation of quantities of acid sites of Ru-based catalysts with (a) yield of
small molecule hydrocarbons and (b) weight-average molecular weight (Mw).
toluene from the 30 mL reaction mixture, indicating that 16.5% of
the initial lignin reactants were converted to phenolic monomers.
In comparison, the least active catalysts among Ru and Pt catalysts,
Ru/SiO2, produced a combined concentration of 3.31 mM or 1.7%
yield. GPC measurements of acetylated lignin and lignin residue
were used to determine the molecular weight distribution along
with the number-average molecular weight (Mn), weight-average
molecular weight (Mw), and polydispersity index (PDI = Mw/Mn),
which depicts the depolymerization activity (Table 3, Figs. 1, and
S3). With the initial value of Mw = 3899 g/mol of the lignin reac-
tant, 5 wt% Ru/Hb, which exhibited the lowest amount of lignin
residue and the highest concentration of aromatic monomer
products, produced lignin residue with a value of Mw = 1431 g/mol,
exhibiting a 63% decrease of Mw. In contrast, 5 wt% Ru/MgO, which
exhibited the largest amount of lignin residue and the lowest
concentration of aromatic monomers, produced lignin residue with
H2-chemisorption of catalysts were performed to understand the
observed catalytic activity based on acidity and metal dispersion
(Table 4, Figs. S4, and S5). Supported 5 wt% Ru catalysts were
selected for these measurements. For the acidity, zeolite-
supported Ru exhibited large quantities of acid sites. The acidity
was not well correlated with the BET surface area (Fig. S6). For
the dispersion of Ru, Ru/Al2O3 and Ru/SiAl exhibited the large ratio
of [CO]/[Ru], but zeolite (HY, HZSM-5, and Hb)-supported Ru cata-
lysts were poorly dispersed, exhibiting a ratio of [CO]/[Ru] < 0.03.
Ru/Hb exhibited the largest [H]/[Ru] ratio based on the H2-
chemisorption results. It should be noted that the catalysts with
low dispersions exhibited significantly different dispersions in
CO- and H2-chemisorption methods because of the high uncer-
tainty. Based on the results depicted in Table 4, we attempted to
correlate the dispersions of Ru and the acidities of the catalysts
with the catalytic activities, as represented by the yields of small
molecule hydrocarbons, weight-averaged molecular weights of lig-
nin residue, and quantities of remaining lignin residue. We were
not able to observe any reliable correlation between the dispersion
of Ru and the catalytic activity. In comparison, the acidity exhibited
good correlation with the catalytic activity (Fig. 2). These results
indicate that the catalytic depolymerization activity is determined
by the surface acidity of the catalysts. 5 wt% Ru/Hb, which pro-
duced the highest yield of major aromatic products and the lowest
value of Mw of the lignin residues exhibited the highest total acid-
ity (1375 lmol/g). With increasing acidity of the catalysts, the
yield of the major aromatic monomer products increased, while
the quantity of small molecule hydrocarbons and the weight-
average molecular weight (Mw) decreased; these results indicate
better depolymerization activity on more acidic catalysts. The con-
trol experiment using Ru/SiO2 with an addition of aqueous nitric
acid (approximately 3 equivalents of acidity of Hb) increased the
formation of small molecule products 2.7 times, indicating that
the acidity improved the depolymerization of lignin (Table 2).
We also note that, according to our previous observations, the Hb
used in this study is a nanostructured material with a particle size
smaller than 50 nm [54].
Although the depolymerization activity is better correlated with
the quantity of acids, the presence of metal particles on the solid

Table 5
Effects of metals and H2 on the catalysis results.a

Catalyst Concentration (mM in 10 mL toluene)

Guaiacol 4-methylguaiacol 4-ethylguaiacol Cerulignol Iso-eugenol Combined concentration (mM)b Yield (%)c
Hb 0 0.93 2.11 1.77 2.64 7.45 (1.29) 4.25
5 wt% Ru/Hb 0 0 3.15 20.30 4.42 27.87 (4.82) 15.89
5 wt% Ru/Hb (No H2, in 40 bar He) 0 2.49 2.25 2.75 4.18 11.67 (2.02) 6.65
a
Reaction conditions: 0.1 g catalyst, 0.3 g organosolv lignin dissolved in a mixture of ethanol/water (30 mL, 65% (v/v)), 6 h reaction time, 40 bar H2, 250 C, and agitation
rate of 500 rpm.
b
Numbers in parentheses are concentrations in g/L.
c
Yield (%) = (Weight of produced guaiacol, 4-methylguaiacol, 4-ethylguaiacol, cerulignol, and iso-eugenol)/(Weight of dry lignin reactant)  100.
 M. Kim et al. / Chemical Engineering Journal 309 (2017) 187196 193

Table 6
1
H NMR results of lignin and lignin residue.

Catalyst Aromatic H Hc of b-O-4 Methoxy H Aliphatic H

(6.17.9 ppm) (4.24.8 ppm) (3.44.0 ppm) (0.62.9 ppm)
No reaction 1 0.23 0.74 0.60
No catalyst 1 0.06 1.61 0.55
5 wt% Ru/SiO2 1 0.06 1.89 0.58
5 wt% Ru/Hb 1 0.06 1.65 0.53

Table 7
31
P NMR results of lignin and lignin residue.

Catalyst Aliphatic C5-substituted Guaiacyl OH p-

used OH (144.5 guaiacyl OH (137.5.0 Hydroxyphenyl
148.0 ppm) (140.0 140.0 ppm) OH
143.5 ppm) (137.0 ppm)
No reaction 0.68 (1)a 0.03 (0.06) 1.86 (2.74) 0.02 (0.03)
No catalyst 1.79 (1) 0.03 (0.02) 1.91 (1.07) 0.03 (0.02)
5 wt% Ru/SiO2 1.91 (1) 0.08 (0.04) 1.98 (1.04) 0.07 (0.04)
5 wt% Ru/Hb 1.90 (1) 0.12 (0.06) 2.85 (1.50) 0.05 (0.03)
Fig. 3. 1H NMR results of (a) lignin, (b) lignin with no catalyst, 5 wt% Ru supported
a
on (c) SiO2, and (d) Hb. (1: Aromatic H, 2: Hc of b-O-4, 3: methoxy H, 4: ethoxy H. 5: Numbers in parentheses are relative areas of peaks regarding that of aliphatic
aliphatic H.). OH.

amount of Hc of b-O-4 decreased significantly on the lignin residue,

Fig. 4. 31P NMR results of (a) lignin, (b) lignin with no catalyst, 5 wt% Ru supported
on (c) SiO2, and (d) Hb. (1: aliphatic OH. 2: C5 substituted guaiacyl OH. 3: guaiacyl
OH. 4: p-hydroxyphenyl OH.)
acids is required for depolymerization, which was confirmed dur-
ing H2-free and metal-free control experiments (Table 5). When
Hb without deposited metal catalysts was used, the yield of small
molecule hydrocarbons was smaller than 1/3 of that of the Ru-
deposited catalyst, indicating that the presence of metal on the
solid acid supports improves the reaction. When H2 was replaced
with He, the catalytic activity was also poor, indicating that the
supply of hydrogen is important to initiate the reaction. From these
observations, we suggest that the depolymerization occurred on
the acid sites of solid acid support: the metal particles allow hydro-
gen atoms to adsorb to the metal catalyst surface and react with
lignins ether bonds to produce cleaved hydrocarbons. Thus, H2
seems to improve the hydrogenolysis of the ether bonds by supply-
ing hydrogen atoms to the reactants, lignin in this study, and
improving the cleavage of ether bonds.
3.4. NMR results for empty fruit bunch-derived organosolv lignin and
lignin residue
1
H NMR was performed to identify and quantify the functional-
ities of lignin and lignin residue (Fig. 3 and Table 6) [55]. The
indicating a cleavage of b-O-4 during the catalytic depolymeriza-
tion of lignin. The formation of ethoxy H was observed because
of possible etherification between ethanol solvent and hydroxyls
of lignin.
31
P NMR was performed to observe the hydroxyl groups in lig-
nin and lignin residue; these groups may be produced by ether
cleavage during the depolymerization of lignin (Fig. 4 and Table 7)
[31]. Observed 31P NMR results indicate that organosolv lignin in
this study contained aliphatic OH, C5-substituted guaiacyl OH,
guaiacyl OH, and p-hydroxyphenyl OH. Syringyl OH at 142
144 ppm was not observed, but guaiacyl OH at 137.5140.0 ppm
was clearly observed, indicating that the organosolv lignin used
in this study was produced from softwood, actually palm empty
fruit bunch (EFB) [52]. Carboxylic groups were also observed but
ignored in this study because of their negligible amount. The
amounts of C5-substituted guaiacyl OH and guaiacyl OH of lignin
residue increased after the catalytic depolymerization of lignin,
which indicates ether cleavage to produce a polymeric lignin resi-
due with a lower molecular weight. For lignin and lignin residue,
the amount of p-hydroxyphenyl OH was negligible compared with
other hydroxyl functionalities, but its amount slightly increased
after the depolymerization of lignin, indicating the cleavage of
the corresponding ether bonds. For the most active catalyst, Ru/
Hb, the combined amounts of C5-substituted guaiacyl OH and gua-
iacyl OH significantly increased indicating the greater cleavage of
the guaiacyl ether linkages.
2D HSQC NMR results of lignin and lignin residue. We per-
formed two-dimensional HSQC NMR analysis to characterize the
changes of lignin and lignin residue structures during reactions,
thus clarifying the depolymerization pathway (Figs. 5 and 6)
[29,56,57]. In the aliphatic side-chain region, methoxy, b-O-4 link-
age, b-5 linkage, and a-O-4 linkage can be observed clearly in
organosolv lignin. The presence of b-O-4 linkage was observed by
CH correlation for the a, b, and c positions. The CH correlation
in phenylcoumaran was shown for the a-O-4 and b-5 positions.
In the aromatic region of the spectrum, only the guaiacyl unit
was found for the C2/H2, C5/H5, and C6/H6 correlations. These
results confirm that the reactant used in this study was softwood
lignin (from EFB in this study) [52]. After the reaction, cross peaks
for the b-O-4, b-5, and a-O-4 linkages decreased or even disap-
peared in the lignin residue with 5 wt% Ru/Hb. In addition, cross
peaks for guaiacyl units decreased significantly in the lignin
194 M. Kim et al. / Chemical Engineering Journal 309 (2017) 187196

Fig. 5. HSQC NMR results of organosolv lignin (A and B) and lignin residue (C and D, after the reaction using 5 wt% Ru/Hb).

Fig. 6. Major units in organosolv lignin. (A, b-O-4 linkage; B, b-5/a-O-4 phenyl-
coumaran, G, guaiacyl).
residue with 5 wt% Ru/Hb. These results indicate that the cleavage
of the b-O-4, b-5, and a-O-4 linkages in the guaiacyl unit is the
main path to produce small-molecule hydrocarbons during
depolymerization of lignin.
Based on the above observations, we propose the model struc-
ture of organosolv lignin from EFB used in this study (Fig. 7); this
structure may consist of coniferyl alcohols, which are guaiacyl
units linked with b-O-4, a-O-4, and b-5 bonds. Instead of a
complex networked structure [52,58], a linear polymer composed
of guaiacols and 4-alkyl-substituted guaiacols is suggested [59]
based on the following reasons: (i) Monomeric units obtained
after the depolymerization exhibited only two possible cleaved

Fig. 7. Schematic structure of organosolv lignin extracted from EFB.

 M. Kim et al. / Chemical Engineering Journal 309 (2017) 187196
functionalities, hydroxyl and alkyl, while the networked polymer
can be obtained in the presence of monomers containing three or
more functionalities. (ii) The networked polymer can be obtained
by the condensation of monomers at the condensation centers of
ternary or quaternary carbons, which may produce branched-
alkyl-substituted phenolic monomers by depolymerization;
however, branched-alkyl-substituted phenolic monomers, for
example iso-propyl- or iso-butyl-substituted phenolic monomers,
were not observed among the final small molecule hydrocarbon
products. It should be noted that the suggested structure of
organosolv lignin in this study appears to be limited to the
organosolv lignin extracted by the mixed solvent of ethanol and
water mixture. The large fraction of lignin, not extracted by the
ethanol/water mixture, may be different from the schematic
structure suggested in Fig. 7.
4. Conclusions
The catalytic depolymerization of organosolv lignin was per-
formed using supported metal catalysts. The small molecule aro-
matic hydrocarbon products extracted with toluene were
identified and quantified using GC/MS and GC-FID to calculate
the aromatic monomer yields and to determine the most active
catalysts. Compared to the literature on the use of supported metal
catalysts, the use of acidic zeolites as supports of the metal cata-
lysts in this study improved the production of small aromatic
molecules from lignin. The solid acid-supported metal catalysts
work as bifunctional catalysts to depolymerize lignin by the syner-
gic effect of the solid acid and metal. Ru/Hb, exhibiting the largest
quantity of acid sites, produced the largest yield (16.5%) of small
molecule monophenyl hydrocarbons and the polymeric lignin resi-
due with the smallest weight-average molecular weight. Com-
pared with previous works [15,16], in this study supercritical
conditions for water or alcohol were not used and the activity of
the supported metal catalysts determined the catalytic activity; it
was found that Ru/Hb exhibited good depolymerization activity
without the support of supercritical conditions. The depolymeriza-
tion activity of the catalysts was best described by the quantity of
surface acid sites, but the presence of deposited metals along with
an H2 environment also improved the activity. The NMR results
indicate that the cleavage of b-O-4, a-O-4, and b-5 ether linkages
in the guaiacyl units occurred; this was the major pathway of the
depolymerization of organosolv lignin. The NMR results along with
the catalysis results suggest that the organosolv lignin prepared in
our lab may be a linear polymer with one or two linking function-
alities in its monomer units, supporting the suggestion in one
recent report [59], and not a networked complex polymer with
three or more linking functionalities in its monomer units [52,58].
Acknowledgements
This work was supported by the National Research Council of
Science & Technology (NST) grant by the Korea government (MSIP)
(No. CAP-11-04-KIST). This work was also supported by the New &
Renewable Energy Core Technology Program of the Korea Institute
of Energy Technology Evaluation and Planning (KETEP) granted
financial resource from the Ministry of Trade, Industry & Energy,
Republic of Korea (No. 20143010091790).
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.cej.2016.10.011.
195
References
[1] C.R. Kumar, N. Anand, A. Kloekhorst, C. Cannilla, G. Bonura, F. Frusteri, K. Barta,
H.J. Heeres, Solvent free depolymerization of Kraft lignin to alkyl-phenolics
using supported NiMo and CoMo catalysts, Green Chem. 17 (2015) 49214930.
[2] H. Wang, M. Tucker, Y. Ji, Recent development in chemical depolymerization of
lignin: a review, J. Appl. Chem. 2013 (2013) 838645.
[3] X. Huang, T.I. Kornyi, M.D. Boot, E.J. Hensen, Catalytic depolymerization of
lignin in supercritical ethanol, ChemSusChem 7 (2014) 22762288.
[4] J. Zakzeski, A.L. Jongerius, P.C.A. Bruijnincx, B.M. Weckhuysen, Catalytic lignin
valorization process for the production of aromatic chemicals and hydrogen,
ChemSusChem 5 (2012) 16021609.
[5] M.P. Pandey, C.S. Kim, Lignin depolymerization and conversion: a review of
thermochemical methods, Chem. Eng. Technol. 34 (2011) 2941.
[6] J. Long, Y. Xu, T. Wang, Z. Yuan, R. Shu, Q. Zhang, L. Ma, Efficient base-catalyzed
decomposition and in situ hydrogenolysis process for lignin depolymerization
and char elimination, Appl. Energy 141 (2015) 7079.
[7] J. Zhang, J. Teo, X. Chen, H. Asakura, T. Tanaka, K. Teramura, N. Yan, A series of
NiM (M = Ru, Rh, and Pd) bimetallic catalysts for effective lignin
hydrogenolysis in water, ACS Catal. 4 (2014) 15741583.
[8] A.J. Ragauskas, G.T. Beckham, M.J. Biddy, R. Chandra, F. Chen, M.F. Davis, B.H.
Davison, R.A. Dixon, P. Gilna, M. Keller, Lignin valorization: improving lignin
processing in the biorefinery, Science 344 (2014) 1246843.
[9] D.J. Nowakowski, A.V. Bridgwater, D.C. Elliott, D. Meier, P. de Wild, Lignin fast
pyrolysis: results from an international collaboration, J. Anal. Appl. Pyrolysis
88 (2010) 5372.
[10] A.A. Peterson, F. Abild-Pedersen, F. Studt, J. Rossmeisl, J.K. Nrskov, How
copper catalyzes the electroreduction of carbon dioxide into hydrocarbon
fuels, Energy Environ. Sci. 3 (2010) 13111315.
[11] Y. Muranaka, R. Murata, I. Hasegawa, K. Mae, Production of depolymerized
lignin resin material from lignocellulosic biomass using acetonewater binary
solution, Chem. Eng. J. 274 (2015) 265273.
[12] K. Kang, R. Azargohar, A.K. Dalai, H. Wang, Systematic screening and
modification of Ni based catalysts for hydrogen generation from
supercritical water gasification of lignin, Chem. Eng. J. 283 (2016) 10191032.
[13] D. Shen, N. Liu, C. Dong, R. Xiao, S. Gu, Catalytic solvolysis of lignin with the
modified HUSYs in formic acid assisted by microwave heating, Chem. Eng. J.
270 (2015) 641647.
[14] S. Brand, R.F. Susanti, S.K. Kim, H.-S. Lee, J. Kim, B.-I. Sang, Supercritical ethanol
as an enhanced medium for lignocellulosic biomass liquefaction: influence of
physical process parameters, Energy 59 (2013) 173182.
[15] H.-S. Lee, J. Jae, J.-M. Ha, D.J. Suh, Hydro- and solvothermolysis of kraft lignin
for maximizing production of monomeric aromatic chemicals, Bioresour.
Technol. 203 (2016) 142149.
[16] H.S. Lee, H. Lee, J.M. Ha, J. Kim, D.J. Suh, Production of aromatic compounds
from oil palm empty fruit bunches by hydro- and solvothermolysis, Ind. Crops
Prod. 76 (2015) 104111.
[17] J. Lora, W. Glasser, Recent industrial applications of lignin: a sustainable
alternative to nonrenewable materials, J. Polym. Environ. 10 (2002) 3948.
[18] H.X. Ben, A.J. Ragauskas, One step thermal conversion of lignin to the gasoline
range liquid products by using zeolites as additives, RSC Adv. 2 (2012) 12892
12898.
[19] T. Yoshikawa, T. Yagi, S. Shinohara, T. Fukunaga, Y. Nakasaka, T. Tago, T.
Masuda, Production of phenols from lignin via depolymerization and catalytic
cracking, Fuel Process. Technol. 108 (2013) 6975.
[20] B. Sanyoto, A.A. Dwiatmoko, J.-W. Choi, J.-M. Ha, D.J. Suh, C.S. Kim, J.-C. Lim,
Catalytic depolymerization of alkali lignin using supported Pt nanoparticle
catalysts, J. Nanosci. Nanotechnol. 16 (2016) 45704575.
[21] J. Quesada-Medina, F.J. Lpez-Cremades, P. Olivares-Carrillo, Organosolv
extraction of lignin from hydrolyzed almond shells and application of the d-
value theory, Bioresour. Technol. 101 (2010) 82528260.
[22] Y. Ye, Y. Zhang, J. Fan, J. Chang, Novel method for production of phenolics by
combining lignin extraction with lignin depolymerization in aqueous ethanol,
Ind. Eng. Chem. Res. 51 (2011) 103110.
[23] A.K. Deepa, P.L. Dhepe, Lignin depolymerization into aromatic monomers over
solid acid catalysts, ACS Catal. 5 (2014) 365379.
[24] W. Xu, S.J. Miller, P.K. Agrawal, C.W. Jones, Depolymerization and
hydrodeoxygenation of switchgrass lignin with formic acid, ChemSusChem 5
(2012) 667675.
[25] Z. Yuan, S. Cheng, M. Leitch, C. Xu, Hydrolytic degradation of alkaline lignin in
hot-compressed water and ethanol, Bioresour. Technol. 101 (2010) 93089313.
[26] R. Thring, Alkaline degradation of ALCELL lignin, Biomass Bioenergy 7 (1994)
125130.
[27] Z. Liu, F.-S. Zhang, Effects of various solvents on the liquefaction of biomass to
produce fuels and chemical feedstocks, Energy Convers. Manage. 49 (2008)
34983504.
[28] M.J. Diaz, W.J.J. Huijgen, R.R. van der Laan, J.H. Reith, C. Cara, E. Castro,
Organosolv pretreatment of olive tree biomass for fermentable sugars,
Holzforschung 65 (2011) 177183.
[29] G. Hu, C. Cateto, Y. Pu, R. Samuel, A.J. Ragauskas, Structural characterization of
switchgrass lignin after ethanol organosolv pretreatment, Energy Fuels 26
(2011) 740745.
[30] W.J.J. Huijgen, J.H. Reith, H. den Uil, Pretreatment and fractionation of wheat
straw by an acetone-based organosolv process, Ind. Eng. Chem. Res. 49 (2010)
1013210140.
196 M. Kim et al. / Chemical Engineering Journal 309 (2017) 187196
[31] Y. Pu, S. Cao, A.J. Ragauskas, Application of quantitative 31P NMR in biomass
lignin and biofuel precursors characterization, Energy Environ. Sci. 4 (2011)
31543166.
[32] Z.C. Xia, L.G. Akim, D.S. Argyropoulos, Quantitative 13C NMR analysis of lignins
with internal standards, J. Agric. Food Chem. 49 (2001) 35733578.
[33] D.S. Argyropoulos, 31P NMR in wood chemistry: a review of recent progress,
Res. Chem. Intermed. 21 (1995) 373395.
[34] L.G. Akim, D.S. Argyropoulos, L. Jouanin, J.C. Leple, G. Pilate, B. Pollet, C.
Lapierre, Quantitative 31P NMR spectroscopy of lignins from transgenic
poplars, Holzforschung 55 (2001) 386390.
[35] W.J.J. Huijgen, G. Telysheva, A. Arshanitsa, R.J.A. Gosselink, P.J. de Wild,
Characteristics of wheat straw lignins from ethanol-based organosolv
treatment, Ind. Crops Prod. 59 (2014) 8595.
[36] A. Sluiter, National Renewable Energy Laboratory (U.S.), Determination of
structural carbohydrates and lignin in biomass laboratory analytical procedure
(LAP): issue date, 4/25/2008, Technical report NREL/TP-510-42618, National
Renewable Energy Laboratory, Golden, Colo., 2008, pp. 16 p. digital, PDF file.
[37] J.B. Sluiter, R.O. Ruiz, C.J. Scarlata, A.D. Sluiter, D.W. Templeton, Compositional
analysis of lignocellulosic feedstocks. 1. Review and description of methods, J.
Agric. Food Chem. 58 (2010) 90439053.
[38] D.W. Templeton, C.J. Scarlata, J.B. Sluiter, E.J. Wolfrum, Compositional analysis
of lignocellulosic feedstocks. 2. Method uncertainties, J. Agric. Food Chem. 58
(2010) 90549062.
[39] B. Sanyoto, A.A. Dwiatmoko, J.-W. Choi, J.-M. Ha, D.J. Suh, C.S. Kim, J.-C. Lim,
Highly dispersed Pt nanoparticles for the production of aromatic hydrocarbons
by the catalytic degrading of alkali lignin, J. Nanosci. Nanotechnol. 16 (2016)
45654569.
[40] R.J. Stoklosa, J. Velez, S. Kelkar, C.M. Saffron, M.C. Thies, D.B. Hodge, Correlating
lignin structural features to phase partitioning behavior in a novel aqueous
fractionation of softwood Kraft black liquor, Green Chem. 15 (2013) 2904
2912.
[41] M. Helander, H. Theliander, M. Lawoko, G. Henriksson, L. Zhang, M.E.
Lindstrm, Fractionation of technical lignin: molecular mass and pH effects,
BioResources 8 (2013) 22702282.
[42] S. Baumberger, A. Abaecherli, M. Fasching, G. Gellerstedt, R. Gosselink, B.
Hortling, J. Li, B. Saake, E. de Jong, Molar mass determination of lignins by size-
exclusion chromatography: towards standardisation of the method,
Holzforschung 61 (2007) 459468.
[43] F.G. Calvo-Flores, J.A. Dobado, Lignin as renewable raw material,
ChemSusChem 3 (2010) 12271235.
[44] Q. Song, F. Wang, J. Cai, Y. Wang, J. Zhang, W. Yu, J. Xu, Lignin depolymerization
(LDP) in alcohol over nickel-based catalysts via a fragmentation-
hydrogenolysis process, Energy Environ. Sci. 6 (2013) 9941007.
[45] Y. Ye, Y. Zhang, J. Fan, J. Chang, Novel method for production of phenolics by
combining lignin extraction with lignin depolymerization in aqueous ethanol,
Ind. Eng. Chem. Res. 51 (2012) 103110.
[46] A. Toledano, L. Serrano, J. Labidi, Organosolv lignin depolymerization with
different base catalysts, J. Chem. Technol. Biotechnol. 87 (2012) 15931599.
[47] A.A. Dwiatmoko, L. Zhou, I. Kim, J.-W. Choi, D.J. Suh, J.-M. Ha,
Hydrodeoxygenation of lignin-derived monomers and lignocellulose
pyrolysis oil on the carbon-supported Ru catalysts, Catal. Today 265 (2016)
192198.
[48] A.A. Dwiatmoko, S. Lee, H.C. Ham, J.-W. Choi, D.J. Suh, J.-M. Ha, Effects of
carbohydrates on the hydrodeoxygenation of lignin-derived phenolic
compounds, ACS Catal. 5 (2015) 433437.
[49] J.S. Yoon, J.-W. Choi, D.J. Suh, K. Lee, H. Lee, J.-M. Ha, Water-assisted selective
hydrodeoxygenation of lignin-derived guaiacol to monooxygenates,
ChemCatChem 7 (2015) 26692674.
[50] J.S. Yoon, Y. Lee, J. Ryu, Y.-A. Kim, E.D. Park, J.-W. Choi, J.-M. Ha, D.J. Suh, H. Lee,
Production of high carbon number hydrocarbon fuels from a lignin-derived a-
O-4 phenolic dimer, benzyl phenyl ether, via isomerization of ether to alcohols
on high-surface-area silica-alumina aerogel catalysts, Appl. Catal. B 142143
(2013) 668676.
[51] C.R. Lee, J.S. Yoon, Y.-W. Suh, J.-W. Choi, J.-M. Ha, D.J. Suh, Y.-K. Park, Catalytic
roles of metals and supports on hydrodeoxygenation of lignin monomer
guaiacol, Catal. Commun. 17 (2012) 5458.
[52] E. Adler, Lignin chemistrypast, present and future, Wood Sci. Technol. 11
(1977) 169218.
[53] J.M.W. Chan, S. Bauer, H. Sorek, S. Sreekumar, K. Wang, F.D. Toste, Studies on
the vanadium-catalyzed nonoxidative depolymerization of Miscanthus
giganteus-derived lignin, ACS Catal. 3 (2013) 13691377.
[54] J.K. Jung, Y. Lee, J.-W. Choi, J. Jae, J.-M. Ha, D.J. Suh, J. Choi, K.-Y. Lee, Production
of high-energy-density fuels by catalytic b-pinene dimerization: effects of the
catalyst surface acidity and pore width on selective dimer production, Energy
Convers. Manage. 116 (2016) 7279.
[55] J.-Y. Kim, E.-J. Shin, I.-Y. Eom, K. Won, Y.H. Kim, D. Choi, I.-G. Choi, J.W. Choi,
Structural features of lignin macromolecules extracted with ionic liquid from
poplar wood, Bioresour. Technol. 102 (2011) 90209025.
[56] J. Rencoret, G. Marques, A. Gutirrez, L. Nieto, J.I. Santos, J. Jimnez-Barbero, .
T. Martnez, J.C. del Ro, HSQC-NMR analysis of lignin in woody (Eucalyptus
globulus and Picea abies) and non-woody (Agave sisalana) ball-milled plant
materials at the gel state, Holzforschung 63 (2009) 691698.
[57] A. Ragauskas, Y. Pu, R. Samuel, N. Jiang, C. Fu, Z.-Y. Wang, Structural
characterization of lignin in wild-type versus COMT down-regulated
switchgrass, Front. Energy Res. 1 (2014) 14.
[58] W.G. Glasser, Potential role of lignin in tomorrows wood utilization
technologies, Forest Prod. J. 31 (1981) 2429.
[59] C. Crestini, F. Melone, M. Sette, R. Saladino, Milled wood lignin: a linear
oligomer, Biomacromolecules 12 (2011) 39283935.