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Fuel Processing Technology xxx (2012) xxxxxx

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Fuel Processing Technology


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

Production of phenols from lignin via depolymerization and catalytic cracking


Takuya Yoshikawa a, Taichi Yagi a, Satoshi Shinohara a, Tetsuya Fukunaga b, Yuta Nakasaka a,
Teruoki Tago a,, Takao Masuda a
a
b

Research Group of Chemical Engineering, Division of Chemical Process Engineering, Faculty of Engineering, Hokkaido University, N13W8, Kita-ku, Sapporo, Hokkaido 0608628, Japan
Idemitsu Kosan Co., Ltd., Advanced Technology Research Laboratories, 1280 Kami-izumi, Sodegaura, Chiba 2990293, Japan

a r t i c l e

i n f o

Article history:
Received 14 November 2011
Received in revised form 24 April 2012
Accepted 1 May 2012
Available online xxxx
Keywords:
Biomass utilization
Lignin conversion
Phenols
Iron oxide catalyst
Demethoxylation

a b s t r a c t
Production of phenols from lignin was investigated using a new conversion process consisting of two reaction
steps. In the rst step, depolymerization of lignin was carried out in an autoclave reactor using a silicaalumina catalyst in a water/1-butanol solution. The yield of lignin-derived liquid product reached 8588 Cmol% under the appropriate reaction conditions. In the second step, catalytic cracking of the liquid products
from the rst step was carried out using a xedbed ow reactor over an iron oxide catalyst. With this method, total recovered fraction of phenols and the conversion of methoxy phenol reached 6.68.6% and 9294%,
respectively.
2012 Elsevier B.V. All rights reserved.

1. Introduction
From the perspective of fossil fuel depletion and the need for control
of carbon dioxide emissions, the production of fuels and useful chemicals
from lignocellulose, which is the most abundant inedible biomass in nature, is becoming increasingly important [13]. Lignocellulose resources
are composed of cellulose, hemicellulose and lignin. Recently, the production of bio-ethanol from cellulose and hemicellulose has been developed
worldwide [4]. In these production processes, lignin is removed as residue. Lignin is a high molecular weight polymer composed of alkylphenol
units. Therefore, it can be regarded as a rich source of phenols. However, it
is difcult to decompose lignin into phenols because of its complex
structure.
Various methods for the production of phenols from lignocellulose, especially lignin have been reported, such as solvolysis including
hydrolysis, hydrocracking (hydrogenolysis), pyrolysis, and alkaline
oxidation [5,6]. Early studies on lignin hydrolysis using homogeneous
acid catalysts aimed at structural analysis of lignin, resulting in the
formation of carbonaceous residue, whereas it was reported that the
use of base catalysts such as NaOH and KOH [7,8], and RbCO3 and
CsCO3 [9] was effective in the decrease in char formation and the production of phenolic compounds. Famous study on hydrocracking of
lignin was the patented Noguchi process, in which iron (II) sulde
based catalyst was used at 523723 K under 1546 MPa of initial hydrogen pressure [10]. In addition to conventional CoMo and NiMo

Corresponding author. Tel.: +81 11 706 6551; fax: +81 11 706 6552.
E-mail address: tago@eng.hokudai.ac.jp (T. Tago).

based catalysts in petrochemical industry, various kinds of heterogeneous catalysts including V/Al2O3 [11] and MgOAl2O3 [12] were applied to hydrocracking of lignin or its model compounds. Not only
molecular hydrogen but also hydrogen donating solvent such as
tetralin [13] and formic acid [14] was also used as hydrogen source
of hydrocracking. Most of early research on pyrolysis lignin or biomass focused on the production of bio-oil (or bio-fuel), whereas recent studies related to the production of phenols by pyrolysis of
biomass and its model compounds were reviewed [15]. Upgrading
of bio-oil to produce aromatic compounds was also investigated
using zeolite or other solid acid catalysts [16,17]. Alkaline oxidation
of lignin produces aromatic aldehydes, Nitrobenzene, metal oxides
and oxygen are preferable oxidants to preserve aromatic rings in lignin [18]. Because a part of articial vanillin is commercially produced
by alkaline oxidation of lignin sulfonate, which is a by-product of sulte pulping process, the possible application of kraft lignin, which is
produced in plenty from main stream of pulp industry, has been investigated recently [19,20].
We focus on the possibility of production of lignin-derived phenols, and propose a new conversion process that consists of two reaction steps, as shown in Scheme 1. First, lignin is depolymerized into
lower molecular weight liquid products, and partly into lignin constituent monomers, dimers, and oligomers. In this study, the obtained
liquid products are referred to as the lignin-derived slurry liquid. For
this step of the process, hydrolysis of lignin was carried out using a
solid acid catalyst in a water/alcohol mixed solution. Next, the
lignin-derived slurry liquid is converted into phenols. For this catalytic conversion of biomass resources, we have developed an iron oxide
catalyst, and have succeeded in carrying out the selective production

0378-3820/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2012.05.003

Please cite this article as: T. Yoshikawa, et al., Production of phenols from lignin via depolymerization and catalytic cracking, Fuel Process.
Technol. (2012), doi:10.1016/j.fuproc.2012.05.003

T. Yoshikawa et al. / Fuel Processing Technology xxx (2012) xxxxxx

Scheme 1. Outline of the process for the production of phenols from lignin.

of phenols and ketones from tar derived from wood biomass [2123].
In addition, this catalyst is active for the decomposition of lignin constituent monomers and dimers [24]. For these reasons, catalytic
cracking of the lignin-derived slurry liquid was carried out using
this catalyst.
In this study, the optimal reaction conditions for the depolymerization of lignin were investigated, and the reaction mechanism is discussed. In addition, the possible application of the iron oxide catalyst
in the second step of the process was examined.

chromatographs with thermal conductivity and ame ionization detectors (GC-8A; Shimadzu Co., Ltd.) with activated charcoal and
Porapak Q columns, respectively. The lignin-derived slurry liquid
was analyzed using a gas chromatograph with a ame ionization detector (GC-2014; Shimadzu Co., Ltd.) and a gas chromatographmass
spectrometer (GC-17A GCMS-QP5050; Shimadzu Co., Ltd.) with a DBWax capillary column. Thermal analysis of the slurry liquid was carried out under a nitrogen atmosphere with a thermal gravimetric analyzer (TGA-50; Shimadzu Co. Ltd.). The temperature program was
set as follows: after holding at 323 K for 1 h to remove solvent in
the slurry liquid, heating was carried out from 323 K to 823 K at a
rate of 5 K/min. The carbon content of the solid product, which consists of a mixture of the coke deposited on the catalyst and the residue, was analyzed using an elemental analyzer (ECS 4010; Costech
Instruments).
Carbon yield of the products was calculated based on carbon content of lignin put into the autoclave reactor. Carbon content of OSLPr
and KL was analyzed using an elemental analyzer, and was found to
be 54.5 wt.% and 51.1 wt.%, respectively.
2.2. Preparation and characterization of the iron oxide catalyst

2. Experimental
2.1. Depolymerization of lignin
Depolymerization of lignin was carried out in an autoclave reactor
made of Hastelloy alloy C-276 (KH-50; Hiro Co., Ltd.) with an inner volume of 36 cm3 at 473623 K for 0.58 h. Organosolv lignin propionate
(Alrdich, abbreviated as OSLPr) or kraft lignin (Tokyo Chemical Industry, abbreviated as KL), silica-alumina with an Si/Al = 2 (N631HN; Nikki
Chemical Co., Ltd.) and a mixed solution of distilled water (H2O) and 1butanol (BuOH) were placed into the reactor. The weight ratio of lignin
to silica-alumina to solvent was xed at 1:1:30. The molar ratio of H2O
to BuOH varied in the range of 110, and only H2O or BuOH was also
used. Other organic solvents such as ethanol (EtOH) and benzene
were used for comparison. The reactor was swung back and forth
about 20 times per minute during the reaction.
Scheme 2 shows the analytical procedure for the depolymerization
reaction of lignin. After termination of the reaction, the gaseous
products were collected with a gas pack, and the remains in the reactor were ltered to obtain the lignin-derived slurry liquid and any
solid products. The gaseous products were analyzed using gas

The iron oxide catalyst was prepared via co-precipitation method. 1.9 g of ZrO(NO3)22H2O, 7.2 g of Al(NO3)39H2O, and 40 g of
Fe(NO3)39H2O was dissolved in 750 cm3 of distilled water. 10 wt.%
of ammonia solution was added to the solution with micro pump,
adjusting the pH to 7. All reagents were purchased from Wako Pure
Chemical Industries (Japan) and were used without further purication.
The precipitate was ltered, and oven-dried at 383 K overnight to get
the catalyst precursor, which was subsequently calcined at 773 K for
2 h in an air atmosphere. The obtained catalyst are denoted as ZrO2
Al2O3FeOX hereafter. The ZrO2 and Al2O3 content in the catalyst was
analyzed by X-ray uorescence analysis (XRF Supermini; Rigaku Co.,
Ltd.) and was found to be 9 wt.% ZrO2 and 6 wt.% Al2O3.
2.3. Catalytic cracking of the lignin-derived slurry liquid over
ZrO2Al2O3FeOX
The lignin-derived slurry liquid consisted of two phases, a water
and a BuOH phase. Because the targeted chemicals were mainly
found in the BuOH phase (see Section 3.2), and the process of solvent
removal from BuOH phase possibly led to the loss of phenols in the
slurry liquid, catalytic cracking of the BuOH phase containing the solvent was carried out using a xed-bed ow reactor at 673 K for 2 h
under atmospheric pressure. N2 gas was introduced as a carrier gas
at a ow rate of 10 cm 3/min. The time factor W/F was 0 (without catalyst) or 1 h, where W is the amount of catalyst and F is the ow rate
of feedstock. FH2O/F was 1, where FH2O was the ow rate of steam. The
liquid and gaseous products were collected with an ice trap and a gas
pack, respectively. The liquid products were analyzed using a gas
chromatograph with a ame ionization detector (GC-2014; Shimadzu
Co., Ltd.) and a gas chromatographmass spectrometer (GC-17A GCMSQP5050; Shimadzu Co., Ltd.) with a DB-Wax capillary column. The gaseous products were analyzed using gas chromatographs with thermal
conductivity and ame ionization detectors (GC-8A; Shimadzu Co.,
Ltd.) with activated charcoal and Porapak Q columns, respectively.
3. Results and discussion
3.1. Effect of solvent composition on the yield of lignin-derived slurry liquid

Scheme 2. Analytical procedure of depolymerization reaction of lignin.

Depolymerization of OSLPr was carried out in different compositions of H2O/BuOH solutions at 473 K for 3 h. Fig. 1 shows the effect of
the molar ratio of H2O to BuOH in the solvent on the yield of ligninderived slurry liquid. The yields of slurry liquid were higher when
H2O/BuOH solutions were used than those obtained in water or

Please cite this article as: T. Yoshikawa, et al., Production of phenols from lignin via depolymerization and catalytic cracking, Fuel Process.
Technol. (2012), doi:10.1016/j.fuproc.2012.05.003

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Liquid product

H2O/BuOH
(molar ratio)

Solid product
Identified by GC
(Water phase)

0 (BuOH)

Identified by GC
(BuOH phase)

Unidentified
+ undetectable by GC

Coke + Residue

10
(H2O)
0

20

40

60

80

100

Carbon yield based on lignin /C-mol%


Fig. 1. Effect of the molar ratio of H2O to BuOH solutions on the yield of lignin-derived slurry liquid. Reaction conditions: OSLPr, reaction temperature and time = 473 K, 3 h.

BuOH alone, and the yield of liquid product reached 96 C-mol% at


H2O/BuOH = 4. Fig. 2 shows the yields of identied products in the
slurry liquids depicted in Fig. 1, as determined by gas chromatography. The phenols mainly consisted of methoxyphenol, and its yield
was about 0.60.8 C-mol% when the mixture of H2O/BuOH was
used. The carboxylic acids consisted mainly of propionic acid. It was
reported that lignin esters were produced in the reaction of raw lignin
with acid anhydride, resulting in the esterication of OH groups in
raw lignin [25,26]. Because esterication reaction is generally reverse
reaction, propionic acid was considered to be formed by hydrolysis of
the substituent groups of OSLPr. The carboxylate esters consisted
mainly of butyl propionate. It was reported that esterication of carboxylic acid and alcohol proceeded over various kinds of solid acid
catalysts [27]. Therefore, carboxylate esters were assumed to be
mainly produced by the reaction of the carboxylic acids and BuOH
over the silica-alumina.
3.2. Investigation of the reaction route for depolymerization of lignin
To clarify the function of H2O/BuOH solution during the depolymerization of lignin, the distribution of each component identied
by gas chromatography in each phase was investigated, and the results are summarized in Table 1. The distribution was calculated as
the proportion of the carbon amount in the water (or BuOH) phase
to the total carbon amount in both the water and BuOH phases. The
phenols and carboxylate esters mainly existed in the BuOH phase. It
is believed that hydrolysis of lignin over silica-alumina mainly occurred in the water phase to produce phenolic compounds, and thus
the extraction of the phenolic compounds from the H2O phase into
the BuOH phase promoted the reaction, leading to the improvement
of the yield of the lignin-derived slurry liquid. When the carboxylic

H2O/BuOH
(molar ratio)
0 (BuOH)

acids were esteried with BuOH over silica-alumina, the ester compounds were then extracted to the BuOH phase as well. Some of the
carboxylic acids would, however, be recombined with other products,
resulting in the formation of the carbonaceous residue. Accordingly,
an additional function of the H2O/BuOH solution was assumed to be
suppression of the recombination reactions of the carboxylic acids
with the degraded lignin compounds. Based on the above discussion,
the expected reaction routes are shown in Fig. 3: one is the extraction
of the degraded aromatic compounds from the water phase to the
BuOH phase, and the other is esterication of the carboxylic acids
with BuOH followed by extraction of the produced carboxylate esters
from the water phase to the BuOH phase. Considering depolymerization of lignin using H2O/BuOH solution was caused by hydrolysis in
water phase, the expected reaction formula was shown in Fig. 4, referring to the reaction mechanism of lignin depolymerization using
acid catalysts [28]. The reaction mechanism of Because lignin has a
complex structure, and lignin-derived slurry liquid contained the unidentied and undetectable products by gas chromatography, the
structure of OSLPr in Fig. 4 was simplied using the basic unit described in the Section 3.4.
Depolymerization of lignin using other organic solvents was carried
out for comparison with the reaction using the H2O/BuOH solution.
Fig. 5 shows the results of depolymerization of lignin using H2O/EtOH
and H2O/benzene as a solvent at 573 K for 2 h. The yields of ligninderived slurry liquid using the H2O/EtOH and H2O/benzene solutions
were lower than that obtained with H2O/BuOH. While EtOH does undergo the esterication reaction with carboxylic acids, it is completely
miscible in water, and thus the extraction of degraded aromatic compounds did not occur in the H2O/EtOH solution. On the other hand, in
the H2O/benzene solution, the degraded aromatic compounds were
extracted from the water phase into the benzene phase, while esterication of benzene with the carboxylic acids did not proceed. These
properties were assumed to cause the low yields of lignin-derived slurry liquid using H2O/EtOH and H2O/benzene. Therefore, the ability to

Phenols
Carboxylate acids

Carboxylic esters
Alcohol

4
10
(H2O)
0

10

15

20

25

30

35

Carbon yield based on lignin /C-mol%


Fig. 2. Yields of identied products by GC in the slurry liquids in Fig. 2. Reaction conditions: OSLPr, reaction temperature and time = 473 K, 3 h.

Table 1
The distribution of each component identied by GC in the water and BuOH phases in
Fig. 2.
Component

Phenols

H2O/BuOH (molar ratio)


BuOH phase/C-mol%
Water phase/C-mol%

1
99
1.0

Carboxylate ester

Component

Carboxylic acid

H2O/BuOH (molar ratio)


BuOH phase/C-mol%
Water phase/C-mol%

1
99
1.0

4
93
7.0

4
74
26

10
73
27

1
100
0.0

4
99
1.0

10
96
4.0

4
46
54

10
21
79

Alcohol
10
31
69

1
95
5.0

Please cite this article as: T. Yoshikawa, et al., Production of phenols from lignin via depolymerization and catalytic cracking, Fuel Process.
Technol. (2012), doi:10.1016/j.fuproc.2012.05.003

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BuOH Phase

OH
O

OH

BuOH
Esterification

OH
O

OH

O
OH

Hydrolysis
Recombination

Water
Phase
Lignin(OSL Pr)

Silica-alumina

Fig. 3. Expected reaction routes in the depolymerization of lignin (OSLPr) using H2O/
BuOH solution over silica-alumina.

both undergo esterication reactions with the carboxylic acids and to


extract the phenolic compounds is required for an organic solvent,
and it is concluded that mixed solutions of water and a relatively hydrophobic alcohol such as BuOH are suitable as solvents for the depolymerization of lignin.

3.3. Effect of reaction conditions


Table 2 (a) and (b) shows the effects of reaction temperature and
time, respectively, on the yield of lignin-derived slurry liquid and
phenols using H2O/BuOH at the molar ratio of 4. As shown in
Table 2 (a), the yield of phenols increased as the temperature increased from 473 K to 573 K, whereas the yield of phenols and
lignin-derived slurry liquid decreased at 623 K. Because the BuOH
phase of the slurry liquid was dark brown in contrast to the water
phase, which was a nearly colorless and transparent solution, it was
determined that the lignin-derived products were mainly contained
in the BuOH phase. For this reason, TGA analyses were conducted
using the BuOH phase. Fig. 6 (a) shows the results of the TGA analyses
of the BuOH phases of the slurry liquids obtained under the conditions shown in Table 2 (a). The weight loss curves of the ligninderived products in the BuOH phase shifted to the lower temperature
region as the depolymerization temperature increased from 473 K to

623 K. Weight loss of a sample in the lower temperature region of a


TGA analysis indicates that the sample consists of chemicals with
lower molecular weights. Accordingly, this shift indicated that the
lignin-derived products became lighter and depolymerization of lignin proceeded further with increasing reaction temperature. With respect to the effect of reaction time (Table 2 (b)), the yield of phenols
increased as the reaction time increased from 0.5 h to 2 h, whereas
the yield of lignin-derived slurry liquid slightly decreased at 8 h.
TGA analyses of the BuOH phases of the slurry liquids obtained
under the conditions shown in Table 2 (b) were also conducted.
There were no signicant differences of the weight loss curves of
lignin-derived products in the BuOH phases between 0.5 and 8 h of
reaction time. From these results, it was concluded that recombination reactions as well as depolymerization of lignin proceeded
under excessive conditions, resulting in a decrease in the yield of phenols and/or lignin-derived slurry liquid, and that the appropriate reaction temperature and time were 573623 K and 24 h for this
study.
The depolymerization reaction was then applied to KL, another
type of lignin that is a by-product obtained from a mainstream process of the chemical pulp industry. Fig. 7 shows the results of depolymerization of KL at 573 K for 2 h. The yield of KL-derived slurry liquid
reached a maximum at H2O/BuOH = 4. In addition, the KLderived
products in the BuOH phase obtained at H2O/BuOH = 4 were analyzed by TGA, and the change in weight loss of the products with temperature was compared with raw KL, as shown in Fig. 6 (b). The curve
of the product shifted to the lower temperature region as compared
with KL, indicating that KL was also effectively depolymerized by
this method. Therefore, the rst step of the process was applicable
to KL as well as OSLPr.

3.4. Catalytic cracking of lignin-derived slurry liquid over ZrO2Al2O3FeOX


For the above-mentioned reasons (see Section 2.3 and Table 1),
catalytic cracking of BuOH phase containing the solvent was carried
out over ZrO2Al2O3FeOX. It was reported that the partial oxidation
of alcohol to produce carboxylic acid occurred, followed by the
ketonization of carboxylic acid over iron oxide catalyst [23,29]. In addition, it was conrmed that catalytic reaction of BuOH alone over
ZrO2Al2O3FeOX didn't produce any phenols. Therefore, this study
focused on phenols among whole products after the reaction. Fig. 8
(a) shows the typical recovered fraction of phenols after the reaction
of the OSL-Pr slurry liquid. The recovered fraction was calculated
based on the assumption that the constituent monomer of OSLPr is
2,6-dimethoxy-4-(1,2-dihydroxy-3-propionyloxy)-propylphenol,

+ C4H9OH
C2H5COOC4H9 + H2O

O
H2C
Lignin

C2H5

C2H5COOH

O CH
HC OH

+ H 2O

Further
depolymerization

OH

Lignin
H2C OH

O CH3

H3C O

C
CH2

OH

OCH3

H3C O

OH
Fig. 4. Expected reaction formula of the depolymerization of lignin (OSLPr) using H2O/BuOH solution over silica-alumina.

Please cite this article as: T. Yoshikawa, et al., Production of phenols from lignin via depolymerization and catalytic cracking, Fuel Process.
Technol. (2012), doi:10.1016/j.fuproc.2012.05.003

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Solvent
species
H2O
/EtOH

Identified by GC

H2O
/Benzene

Identified by GC
(Organic phase)

Identified by GC
(Water phase)

Unidentified
+ undetectable by GC

H2O
/BuOH

Coke + Residue

20

40

60

80

100

Carbon yield based on lignin /C-mol%


Fig. 5. Effect of solvent on the yield of lignin-derived slurry liquid. Reaction conditions: OSLPr, H2O/organic solvent = 4, reaction temperature and time = 573 K, 2 h.

and the recovered fraction was obtained using the following equations:

Catalytic cracking of the KL-derived slurry liquid was also carried


out. Fig. 8 (b) shows a typical recovered fraction of phenols after
the reaction. The recovered fraction was calculated with the assumption that the constituent monomer of KL is 2-methoxy-4-(2,3-

mols of aromatic ring in lignin


weight of lignin used for the depolymerization reaction

molecular weight of constituent monomer

mols of aromatic ring in phenols after the catalytic cracking


carbon mols of the obtained phenols

carbon numbers in one molecular of the phenols

1.0

From Eq. (1), mols of aromatic ring in lignin put into the autoclave
reactor was calculated using the basic unit of lignin, and from Eq. (2),
mols of aromatic ring in phenols were calculated based on the GC
analysis of products obtained after the catalytic reaction over ZrO2
Al2O3FeOX. From (1) and (2),

0.8

473 K

Weight Change (W/W0) /

recovered fraction of phenols=%


mols of aromatic ring in phenols

 100
mols of aromatic ring in lignin

(a) OSL Pr

523 K
raw
OSL Pr

0.6

573 K
0.4

623 K
0.2

Table 2
Effects of (a) reaction temperature and (b) reaction time on the yield of lignin-derived
slurry liquid and phenols. Reaction conditions: OSLPr, H2O/BuOH = 4, (a) reaction
time = 2 h, (b) reaction temperature = 573 K.
(a) Effect of reaction temperature
Temperature/K
(Pressure/MPa)
Phenols/C-mol%
Lignin-derived slurry liquid/C-mol%
Reaction time = 2 h
(b) Effect of reaction time
Time/h
Phenols/C-mol%
Lignin-derived slurry liquid/C-mol%
Reaction temperature = 573 K

473
(1.1)
0.44
88

523
(4.1)
1.3
91

573
(9.7)
3.0
88

623
(23)
2.0
86

0
273

473

673

873

Temperature /K

(b) KL
1.0

0.8

Weight Change (W/W0) /

Without any catalyst, the recovered fraction slightly increased and its
composition was almost the same as that in the lignin-derived slurry liquid. On the other hand, the recovered fraction of phenols increased after
reaction over ZrO2Al2O3FeOX. This result indicated that lignin-derived
compounds in the slurry liquid were converted into phenols over ZrO2
Al2O3FeOX. In addition, methoxyphenol drastically decreased, and
phenol and cresol increased. This result is in good agreement with that
of a reaction using a lignin constituent-related aromatic as a model
compound. Specically, guaiacol (2-methoxyphenol) was selectively
converted into phenol over ZrO2Al2O3FeOX [10]. Therefore, it is
considered that methoxyphenol in the slurry liquid was selectively
decomposed via a reaction path similar to that involved in the reaction
of guaiacol.

raw KL
0.6

0.4

KL derived
slurry liquid
(BuOH phase)

0.2

0
273

473

673

873

Temperature /K
0.5
2.3
88

2
3.0
87

4
2.9
81

8
2.7

Fig. 6. Results of TGA analysis of lignin-derived slurry liquid (BuOH phase). W0: The
weight after holding at 323 K for 1 h under N2 atmosphere. Reaction conditions: (a)
OSLPr, H2O/BuOH = 4, reaction temperature and time = 473623 K, 2 h (b) KL, H2O/
BuOH = 4, reaction temperature and time = 573 K, 2 h.

Please cite this article as: T. Yoshikawa, et al., Production of phenols from lignin via depolymerization and catalytic cracking, Fuel Process.
Technol. (2012), doi:10.1016/j.fuproc.2012.05.003

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H2O/BuOH
(molar ratio)
Identified by GC
(Water phase)

0 (BuOH)

Identified by GC
(BuOH phase)
Unidentified
+ undetectable by GC

Coke + Residue
(H2O)
0

20

40

60

80

100

Carbon yield based on lignin /C-mol%


Fig. 7. Product yields after the depolymerization of KL. Reaction conditions: KL, reaction temperature and time = 573 K, 2 h.

dihydroxy-1-mercapt)-propylphenol. Demethoxylation of the phenols proceeded similarly, and the total recovered fraction of phenols
increased over ZrO2Al2O3FeOX. From these results, it can be concluded that this catalyst is effective for the decomposition of ligninderived slurry liquids.

to be H2O/BuOH = 4, 573623 K and 24 h, respectively. This reaction


was also applicable to KL. For the second step, the BuOH phase of the
lignin-derived slurry liquid obtained in the rst step was used as the
feedstock. After the reaction over ZrO2Al2O3FeOX, the total recovered fraction of phenols increased, and the substituted phenols
were simplied into phenol and cresol. These results therefore indicate that this process provides a method for producing phenols
from lignin.

4. Conclusions
To produce phenols from lignin, a two-step process consisting of
depolymerization and catalytic cracking was carried out. In the rst
step, depolymerization of OSLPr over silica-alumina was promoted
using a H2O/BuOH solution. The function of H2O/BuOH was assumed
to be the extraction of the degraded compounds such as phenolic
compounds and carboxylic acids from the water phase into BuOH
phase. The most appropriate reaction conditions including solvent
composition, depolymerization temperature, and time were found

Acknowledgments
This work was supported by the Global COE Program (Project No.
B01: Catalysis as the Basis for Innovation in Materials Science) from
the Ministry of Education, Culture, Sports, Science and Technology,
Japan.

(a) Catalytic cracking of OSL Pr derived slurry liquid


After depolymerization
of OSL Pr
(BuOH phase)

Phenol + Cresol
Methoxy phenol
Alkyl phenol

Without catalyst

ZrO2 Al2O3 FeOX


0

10

Recovery fraction of phenols /%

(b) Catalytic cracking of KL derived slurry liquid


After depolymerization
of KL
(BuOH phase)

Phenol + Cresol
Methoxy phenol
Alkyl phenol

Without catalyst

ZrO2 Al2O3 FeOX


0

10

Recovery fraction of phenols /%


Fig. 8. Recovery fraction of phenols after the reaction of (a) OSLPr derived slurry liquid, (b) KLderived slurry liquid. Reaction conditions: reaction temperature and time = 673 K, 2 h.

Please cite this article as: T. Yoshikawa, et al., Production of phenols from lignin via depolymerization and catalytic cracking, Fuel Process.
Technol. (2012), doi:10.1016/j.fuproc.2012.05.003

T. Yoshikawa et al. / Fuel Processing Technology xxx (2012) xxxxxx

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Please cite this article as: T. Yoshikawa, et al., Production of phenols from lignin via depolymerization and catalytic cracking, Fuel Process.
Technol. (2012), doi:10.1016/j.fuproc.2012.05.003

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