Bioresource Technology 165 (2014) 319–322

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Hydrothermal conversion of lignin to substituted phenols and aromatic

ethers
Rawel Singh a, Aditya Prakash a, Shashi Kumar Dhiman a, Bhavya Balagurumurthy a, Ajay K. Arora b,
S.K. Puri b, Thallada Bhaskar a,⇑
a
Bio-Fuels Division (BFD), CSIR-Indian Institute of Petroleum (IIP), Dehradun 248005, India
b
Indian Oil Corporation, R&D Centre, Faridabad, Haryana, India

h i g h l i g h t s

 Hydrothermal liquefaction of lignin was performed using ethanol & methanol.

 Maximum liquid yield (85%) was observed at low reaction temperature of 200 °C.
 The major liquid products are substituted phenols and aromatic ethers.
 The maximum organic carbon conversion was found to be 72%.

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

Article history: Hydrothermal liquefaction of lignin was performed using methanol and ethanol at various temperatures
Received 10 January 2014 (200, 250 and 280 °C) and residence times of 15, 30 and 45 min. Maximum liquid product yield (85%) was
Received in revised form 19 February 2014 observed at 200 °C and 15 min residence time using methanol. Increase in temperature was seen to
Accepted 21 February 2014
decrease the liquid products yield. With increase in residence time, liquid yields first increased and then
Available online 1 March 2014
decreased. FTIR and 1H NMR showed the presence of substituted phenols and aromatic ethers in liquid
products and breakage of b-O-4 or/and a-O-4 ether bonds present in lignin during hydrothermal lique-
Keywords:
faction was confirmed through FTIR of bio-residue. In comparison to the existing literature information,
Lignin
Bio-oil
higher lignin conversion to liquid products and maximum carbon conversion (72%) was achieved in this
Hydrothermal liquefaction study.
Thermo-chemical conversion Ó 2014 Elsevier Ltd. All rights reserved.
Substituted phenols

1. Introduction
The growing interest in biofuels from lignocellulosic feedstock
can provide a path towards replacing petroleum-based fuels with
sustainable biofuels which have the potential to lower greenhouse
gas (GHG) emissions. Lignocellulose consists mainly of plant cell
wall materials and is a complicated natural composite with three
main biopolymers, cellulose (40–50%), hemicellulose (15–25%)
and lignin (15–35%).
The lignocellulosics-to-ethanol process makes use of the cellu-
lose and hemicelluloses, leaving behind lignin as waste. In addi-
tion, the pulp and paper industry also generates huge amounts of
lignin. Presently, lignin is being utilised as a low-grade boiler fuel
to provide heat and power to the process. However, the aromatic
structure of lignin suggests that it may be a good source of valuable
⇑ Corresponding author. Tel.: +91 9410151846; fax: +91 1352660202.
E-mail addresses: tbhaskar@iip.res.in, thalladab@yahoo.com (T. Bhaskar).
bulk and specialty chemicals like aromatics (Benzene, Toluene, and
Xylene, etc.), phenols, aromatic ethers, vanillin, etc., if broken into
smaller molecular units by the development of appropriate
thermochemical method/catalytic technology. Lignin-derived
products find application as fuels, solvents, chemical reagents,
and polymers. However, lignin depolymerisation with selective
bond cleavage is the major challenge for converting it into value-
added chemicals.
Superior to pyrolysis technology, high-pressure direct liquefac-
tion technology has the potential to produce liquid oils that is not
miscible in water, with much higher calorific values and a range of
chemicals including vanillin, phenols, aldehydes, and organic acids,
etc. (Huber et al., 2006). The process is best suited for wet materials
as the drying of feedstock is not necessary and water is used as one
of the reactants.
Methanol and ethanol have lower boiling as well as critical
points than water. Due to the lower dielectric constants of these
solvents, high molecular weight products produced as a result of

http://dx.doi.org/10.1016/j.biortech.2014.02.076
0960-8524/Ó 2014 Elsevier Ltd. All rights reserved.
320 R. Singh et al. / Bioresource Technology 165 (2014) 319–322
reaction of cellulose and hemicellulose readily dissolve in them
(Mazaheri et al., 2010). Liquefaction in organic solvents other than
water produces a higher yield of water insoluble oily products
making methanol and ethanol promising solvents for the liquefac-
tion of biomass to produce valuable hydrocarbons (Zhou et al.,
2012).
Beauchet et al. used aqueous alkaline solution to depolymerise
Kraft lignin, Indulin AT into gas fraction (mainly CO2), methanol,
acetic acid and formic acid, aromatic monomers (19.1 wt.%) and
oligomers (polyaromatic molecules) and modified lignin (45–
70 wt.%) (Beauchet et al., 2012). Gosselink et al. used supercritical
fluid consisting of carbon dioxide/acetone/water (300–370 °C,
100 bar) for converting organosolv hardwood and wheat straw lig-
nins to a phenolic oil and monomeric aromatic compounds (10–
12%) (Gosselink et al., 2012). Yuan et al. used hot-compressed
water–ethanol medium for depolymerisation of alkaline lignin into
oligomers using NaOH as the catalyst and phenol as the capping
agent at 220–300 °C. The optimal process condition as reported
in their study was 260 °C for 3 h (Yuan et al., 2010). Song et al.
studied the conversion of native birch wood lignin into monomeric
phenols like propylguaiacol and propylsyringol with total selectiv-
ity >90% at a lignin conversion of about 50%, over nickel-based cat-
alysts common alcohols as solvents (Song et al., 2013).
In the present investigation, lignin depolymerisation was stud-
ied in organic solvents viz. ethanol and methanol under various
temperatures (200, 250 and 280 °C) and residence times of 15,
30 and 45 min. The lignin and its reaction products were analysed
using various physicochemical characterisation methods such as
TG, Powder X ray Diffraction (XRD), FTIR, NMR, and Total Organic
Carbon (TOC) to understand and confirm the formation of mono-
meric lignophenols from macromolecular lignin.
2. Methods
Lignin was procured from Asian Lignin Manufacturing™ (ALM)
in the form of Protobind™ 1000, a renewable product obtained
from agricultural fibrous feedstocks. The properties of the lignin
are presented as Table S1 in Supplementary materials.
Hydrothermal liquefaction of lignin was carried out in stainless
steel tubular reactor (35 ml). The thermocouples were placed in
the skin and heart of the reactor. In a typical hydrothermal lique-
faction experiment, the reactor was loaded with lignin and etha-
nol/methanol (1:10 by weight). Then the reactor was purged five
times with nitrogen to remove the inside air. The temperature
was then raised to required point at heating rate of 10 °C min 1
and kept for a specific residence time. After the specified reaction
time, the reactor was taken out of the furnace and was immedi-
ately submerged into a water bath to stop the further reaction.
After cooling to room temperature, the reaction contents were fil-
tered and washed with the respective solvent (ethanol/methanol).
Upon removal of the solvent in a rotary evaporator under reduced
pressure, the liquid products were obtained and weighed. The solid
residue was dried in the oven and after drying weight of solid res-
idue was noted. The liquid and solid products obtained were then
analysed.
Lignin and reaction products obtained after the hydrothermal
upgradation (HTU) of lignin were analysed by powder XRD, and
FTIR. The thermogravimetric analysis was carried out in Perkin–
Elmer TG instrument. The gross calorific value of lignin has been
found out using Parr 6300 Bomb Calorimeter. The bio-oil samples
were analysed using FTIR and NMR. Powder XRD pattern of lignin
was collected on a Bruker D8 advance X-ray diffractometer. The 1H
NMR spectra of the liquid samples have been recorded in the Bru-
ker Ultra shield 500 plus instrument and DMSO-d6 has been used
as solvent. The FTIR spectra were recorded on a Nicolet 8700 FTIR
spectrometer. TOC analysis of lignin and bio-residue was per-
formed using Shimadzu TOC-L unit with solid sample module
SSM-5000A.
3. Results and discussion
The presence of organic solvents is known to improve the solu-
bility of lignin and its decomposition products (Kang et al., 2013).
Moreover, methanol can be used as a hydrogen donor in lignin liq-
uefaction, which is in favour of low oxygen content oil production
(Barta et al., 2010). Maximum liquid product yield was observed at
low temperature and effect of various reaction conditions is ex-
plained below (Fig. 1a and b).
3.1. Effect of temperature
The reaction temperature is an important factor for the product
distribution. The maximum liquid product yield was observed at
200 °C for both ethanol and methanol. Raising the temperature
would promote the decomposition of lignin and repolymerisation
of the intermediates simultaneously. The maximum liquid product
yield was observed at 30 min residence time so this residence time
has been considered to see the effect of temperature on liquid
product yields. With the increase of temperature from 200 to
280 °C the yield of liquid products obtained by hydrothermal liq-
uefaction of lignin using ethanol decreased. At 200 °C the liquid
yield was maximum at 81% and with increase of temperature to
250 °C liquid product yield decreased to 75%. Further decrease of
liquid product yield at 65% was observed at 280 °C. The similar
trend of decrease in liquid product yield with increase in temper-
ature was also observed at residence times of 15 and 45 min
respectively for hydrothermal liquefaction of lignin using ethanol.
Solid bio-residue yield increased with increase in temperature and
similar result was found by Ye et al. where yield of liquid products
decreased with increasing temperature from 225 to 300 °C for lig-
nin depolymerisation in ethanol–water. This was attributed to the
formation of solid residue through side reactions such as repoly-
merisation of lignin decomposition intermediates. This indicates
that lower temperature favoured depolymerisation reaction
whereas with the increase of temperature formation of higher
reactive radicals promoted repolymerisation (Ye et al., 2012). Sim-
ilar phenomenon is observed in coal liquefaction. Similar effect of
temperature on liquid products yield was observed in case of
hydrothermal liquefaction of lignin using methanol. Maximum
liquid products yield (85%) was observed at 200 °C and liquid prod-
ucts yield gradually decreased with the increase of temperature.
3.2. Effect of residence time
The maximum liquid product yield was observed at 200 °C and
30 min residence time for hydrothermal liquefaction of lignin
using ethanol and the effect of residence time at different temper-
atures is discussed below. At 200 °C the effect of residence time on
liquid products yield is negligible and liquid yield was constant at
all residence times of 15, 30 and 45 min respectively. At 250 °C the
liquid product yield first increased with increasing residence time
from 15 to 30 min. With the further increase of residence time to
45 min the liquid product yield decreased. The liquid product yield
was 60%, 75% and 55% at residence time of 15, 30 and 45 min
respectively. Similar trend of decrease in liquid product yield with
increase of residence time was observed at 280 °C. The liquid prod-
uct yield was 42%, 65% and 41% at residence time of 15, 30 and
45 min respectively. During lignin degradation, cracking reactions
and condensation occur simultaneously. After a certain reaction
time when most of the easily cleaved bonds in lignin molecule
 R. Singh et al. / Bioresource Technology 165 (2014) 319–322 321

90 bio-residue yield increased beyond 30 min. Therefore, 30 min

(a) Ethanol
would be a desirable reaction time for hydrothermal liquefaction
80 of lignin using methanol and ethanol. The gas yield was less in
all cases and was vented after the completion of the reaction.
70
TOC analysis of the lignin and bio-residue obtained by hydro-
% Yield Liquid

30 min thermal liquefaction of lignin using ethanol was studied. TOC re-
60
sults are in good agreement with the above results of effect of
temperature and residence times on liquid product yield. Carbon
50
conversion decreased with the increase of temperature. Maximum
15 min
45 min
carbon conversion was observed at 200 °C and 30 min which is also
40
optimum condition for production of higher liquid yields (Supple-
30
mentary Table S2).

20 3.3. Analysis of lignin

200 220 240 260 280

Temperature, ºC XRD spectra of lignin showed its amorphous nature. The

TG–DTG of lignin feed is seen to have a single significant decompo-
sition temperature though a slightly complex behaviour is also ob-
(b) 90
Methanol served due to overlapping decomposition temperatures (Fig. S1).
80 FTIR spectra of pure lignin shows absorbance peak at 1035 cm 1
which is due to the CAO, C@C and CACAO stretching vibrations.
70 The peak at 1217 cm 1 is due to the CAC and CAO stretching vibra-
tions. The peak at 1268 cm 1 corresponds to the aromatic ring
% Yield Liquid

60 vibration. The peak at 1330 cm 1 corresponds to the CAO of

syringyl ring present in lignin. The peak at 1425 cm 1 is due to
50 the CAH in plane deformation. CAH stretching vibrations in lignin
15 min are observed at 2805 and 2922 cm 1. Peak at 3427 cm 1 is due to
40 OAH stretching vibrations and shows the presence of phenolic hy-
droxyl groups. The peak at 1704 shows presence of C@O groups in
45 min
30 lignin. Aromatic ring vibrations are observed at 1514 cm 1 (Xu
30 min et al., 2013).
20
200 220 240 260 280 3.4. Analysis of liquid products
Temperature, ºC
The FTIR spectrum of liquid products (Fig. S2) showed absor-
(c) 60 bance at 1120, 1222, 1460, 1514, 1604, 1700, and 2934 cm 1.
ETH200
ETH250 The absorbances at 2934 and 1460 cm 1 are attributed to CAH
ETH280 stretching vibrations of methyl and methylene and absorbance of
50 METH200 these peaks increased in liquid samples and indicates the presence
METH250
METH280 of alkane groups in liquid products. The increased absorption peak
40
at 1700 cm 1 suggests the presence of conjugated aromatic ke-
tones or esters. The absorbances at 1514 and 1604 cm 1 corre-
% Proton

sponds to aryl groups. The peaks at around 1220 and 3420 cm 1

30
20
10
0 mation to FTIR spectra and the ability to quantify and compare
0.5-1.5 1.5-3.0 3.0-4.5 4.5-6.0 6.0-8.5
Chemical Shift (ppm)
Fig. 1. (a) Effect of residence time and temperature on liquid products yield using
ethanol. (b) Effect of residence time and temperature on liquid products yield using
methanol. (c) NMR of liquid products obtained from lignin using ethanol and
methanol. ETH200: 200 °C, 30 min, ethanol; ETH250: 250 °C, 30 min, ethanol;
ETH280: 280 °C, 30 min, ethanol; METH200: 200 °C, 30 min, methanol; METH250:
250 °C, 30 min, methanol; METH280: 280 °C, 30 min, methanol.
such as ether bonds and carbonyl groups were cracked, lignin
depolymerisation was essentially complete. Further increasing
the residence time would favour the condensation of the degraded
lignin intermediates, which should be the reason that solid
indicate the presence of phenols. The peak at 1120 cm 1 belongs
to methoxy groups and is present in all the liquid products. The
peak at 834 cm 1 indicates the presence of para-substituted aro-
matic groups (Ye et al., 2012). The FTIR spectra of liquid products
obtained from the hydrothermal liquefaction of lignin using etha-
nol and methanol indicates the presence of phenols and aromatic
ethers.
NMR spectra provided complementary functional group infor-
8.5-10.0 integration areas between spectra. A summary of integrated peak
area regions assigned to different functional group classes present
in the liquid products obtained from hydrothermal liquefaction of
lignin using methanol and ethanol at 30 min residence time are
shown in Fig. 1c. The region from 0.5 to 3.0 ppm is composed of
protons on aliphatic carbon. The region from 0.5 to 1.5 ppm corre-
sponds to protons on aliphatic carbon atoms at least two bonds
away from C@C or heteroatom and the region from 1.5 to
3.0 ppm corresponds to the protons on aliphatic carbon atoms that
may be bonded to a C@C double bond or heteroatom. Liquid prod-
ucts obtained from hydrothermal liquefaction of lignin showed
high proton percentage in this region. With the increase in temper-
ature proton percentage increased in this region. The next portion
of the 1H NMR spectrum at 3.0–4.5 ppm represents methoxyl
322 R. Singh et al. / Bioresource Technology 165 (2014) 319–322
protons (Kosa et al., 2011) or methylene group that joins two aro-
matic rings. The latter moiety would exist in a partially decom-
posed lignin oligomer present in the bio-oil (Mullen et al., 2009).
All the liquid products show high proton percentage in this region.
The region between 4.5 and 6.6 ppm represents aromatic ether
protons i.e. lignin derived methoxy phenols. The region of the spec-
trum between 6.0 and 8.5 ppm corresponds to the aromatic region
of spectrum. The liquid products showed significant proton
percentage in this region. The liquid products obtained using
methanol as solvent showed higher percentage in this region.
Maximum proton percentage (17%) was observed in this region
using methanol at 200 °C. The downfield spectrum regions (8.5–
10 ppm) of the bio-oils arise from the aldehydes and the proton
percentage was very low in this region at around 1%. The FTIR
and 1H NMR of the liquid products indicate the presence of substi-
tuted phenols and aromatic ethers present in the liquid product
obtained. In a study by Ye et al. liquid products obtained were
mainly composed of phenolics (4-ethylphenol, 4-vinylphenol,
guaiacol, 4-ethylguaiacol, and 4-vinylguaiacol) which constitute
almost 85% of the identified compounds (Ye et al., 2012). The for-
mation of substituted phenols and aromatic ethers may be due
to the breakage of various CAC and CAOAC ether bonds (b-O-4
or/and a-O-4) present in lignin. The ethanol and methanol may
further react with the OAH groups to give corresponding methyl
and ethyl ethers. During lignin hydrothermal liquefaction, various
reactions like hydrolysis and cleavage of the ether and CAC bond,
demethoxylation, alkylation and condensation, etc. occur. Various
linkages like b-O-4 and Ca–Cb were easier to break whereas the
aromatic rings were not affected during hydrothermal liquefaction.
This indicates that at milder conditions of relatively low tempera-
ture and short residence time, phenolic monomers and dimers may
be formed and as temperature is increased demethoxylation and
alkylation of lignin derived phenolic compounds are enhanced
and various alkyl phenols may be formed (Kang et al., 2011, 2013).
3.5. Analysis of bio-residue
The absorbance from the ether bond CAOAC at 1120 and
1034 cm 1 weaken in intensity for the solid residue in all samples,
which is possible due to the breakage of b-O-4 or/and a-O-4 ether
bonds to form hydroxyl groups and alkyl groups. The weakening of
these absorbance peaks in bio-residue samples indicate that the
breakage of b-O-4 or/and a-O-4 ether bonds to form hydroxyl
groups and alkyl groups started at very low temperature around
200 °C. Solid residue obtained from depolymerisation of lignin
using methanol and ethanol showed similar behaviour. The absor-
bances at 1604, 1514, and 1425 cm 1 that are attributed to aro-
matic nuclei decreased in the bio-residue samples. The weakened
absorbance at 1700 cm 1 implies that decarbonylation occurred
even at very mild condition (Ye et al., 2012).
4. Conclusion
Maximum liquid products yield (85%) was observed at 200 °C
with 30 min residence time using methanol. With increase in
temperature, liquid product yield decreased. FTIR and 1H NMR of
liquid products confirmed the presence of substituted phenols
and aromatic ethers. FTIR of bio-residue samples indicate that
the breakage of b-O-4 or/and a-O-4 ether bonds to form hydroxyl
groups and alkyl groups started at very low temperature (200 °C).
Acknowledgements
The authors thank The Director, CSIR-Indian Institute of Petro-
leum, Dehradun, for his constant encouragement and support.
R.S. and A.P. thank Council of Scientific and Industrial Research
(CSIR), New Delhi, India, for providing Senior Research Fellowship
(SRF) and Junior Research Fellowship (JRF) respectively. The
authors thank CSIR, Government of India for providing financial
support in the form of XII Five Year Plan project (CSC0116/BioEn).
The authors thank the FTIR, NMR and XRD groups at CSIR-Indian
Institute of Petroleum (IIP) for providing analytical support.
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.biortech.2014.
02.076.
References
Barta, K., Matson, T.D., Fetting, M.L., Scott, S.L., Iretskii, A.V., Ford, P.C., 2010.
Catalytic disassembly of an organosolv lignin via hydrogen transfer from
supercritical methanol. Green Chem. 12, 1640–1647.
Beauchet, R., Monteil-Rivera, F., Lavoie, J.M., 2012. Conversion of lignin to aromatic-
based chemicals (L-chems) and biofuels (L-fuels). Bioresour. Technol. 121, 328–
334.
Gosselink, R.J.A., Teunissen, W., van Dam, J.E.G., de Jong, E., Gellerstedt, G., Scott, E.L.,
et al., 2012. Lignin depolymerisation in supercritical carbon dioxide/acetone/
water fluid for the production of aromatic chemicals. Bioresour. Technol. 106,
173–177.
Huber, G.W., Iborra, S., Corma, A., 2006. Synthesis of transportation fuels from
biomass: chemistry, catalysts and engineering. Chem. Rev. 106, 4044–4098.
Kang, S., Li, X., Fan, J., Chang, J., 2011. Classified separation of lignin hydrothermal
liquefied products. Ind. Eng. Chem. Res. 50, 11288–11296.
Kang, S., Li, X., Fan, J., Chang, J., 2013. Hydrothermal conversion of lignin: a review.
Renew. Sust. Energy Rev. 27, 546–558.
Kosa, M., Ben, H., Theliander, H., Ragauskas, A.J., 2011. Pyrolysis oils from CO2
precipitated Kraft lignin. Green Chem. 13, 3196–3202.
Mazaheri, H., Lee, K.T., Bhatia, S., Mohamed, A.R., 2010. Sub/supercritical
liquefaction of oil palm fruit press fiber for the production of bio oil: effect of
solvents. Bioresour. Technol. 101, 7641–7647.
Mullen, C.A., Strahan, G.D., Boateng, A.A., 2009. Characterization of various fast-
pyrolysis bio-oils by NMR spectroscopy. Energy Fuels 23, 2707–2718.
Song, Q., Wang, F., Cai, J., Wang, Y., Zhang, J., Yua, W., et al., 2013. Lignin
depolymerization (LDP) in alcohol over nickel based catalysts via a
fragmentation–hydrogenolysis process. Energy Environ. Sci. 6, 994–1007.
Xu, F., Yu, J., Tesso, T., Dowell, F., Wang, D., 2013. Qualitative and quantitative
analysis of lignocellulosic biomass using infrared techniques: a mini-review.
Appl. Energy 104, 801–809.
Ye, Y., Zhang, Y., Fan, J., Chang, J., 2012. Novel method for production of phenolics by
combining lignin extraction with lignin depolymerization in aqueous ethanol.
Ind. Eng. Chem. Res. 51, 103–110.
Yuan, Z., Cheng, S., Leitch, M., Xu, C., 2010. Hydrolytic degradation of alkaline lignin
in hot-compressed water and ethanol. Bioresour. Technol. 101, 9308–9313.
Zhou, D., Zhang, S., Fu, H., Chen, J., 2012. Liquefaction of macro algae enteromorpha
prolifera in sub-/supercritical alcohols: direct production of ester compounds.
Energy Fuels 26, 2342–2351.