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b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 6 0 7 e1 6 1 1

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Short communication

Decomposition characteristics of softwood lignophenol under


hydrothermal conditions
Hiroshi Nonaka*, Masamitsu Funaoka
Graduate School of Bioresources, Mie University, 1577 Kurimamachiya-cho, Tsu, Mie 514-8507, Japan

article info

abstract

Article history:

Lignophenol is a novel lignin-based functional polymer. Hydrothermal decomposition of

Received 30 October 2009

ligno-p-cresol derived from softwood (Douglas r) was studied from 300 to 400  C as

Received in revised form

a candidate technology for modication of the molecular structure and the recovery of

5 November 2010

monophenols. Ligno-p-cresol was promptly depolymerized probably by hydrolysis of aryl

Accepted 22 December 2010

ether linkages and the half was converted to ether-soluble compounds at 300  C for 10 min.

Available online 22 January 2011

With increasing temperature and reaction time, the yields of char and gas were increased,
indicating the acceleration of carbonization and decomposition of monophenols. The

Keywords:

monophenols obtained were mainly p-cresol and guaiacol. Their yields only exceed 10% at

Lignophenol

365  C and 60 min probably due to the inefcient pyrolysis of 1,1-bis aryl structures.

Phase separation system

2010 Elsevier Ltd. All rights reserved.

Lignin
Softwood
Hydrothermal decomposition
Monophenol

1.

Introduction

Cellulose, hemicellulose and lignin are three major compo


nents of plants. Cellulose and hemicellulose are polymers of
sugars, and lignin is an aromatic polymer produced by dehy
drogenative polymerization of few monomeric precursors.
Lignin forms interpenetrating polymer network structure
with cellulose and hemicellulose in woody tissues, therefore,
it is impossible to extract most lignin simply by organic
solvents. Tremendous efforts have been made to isolate lignin
from plants for the purpose of analyzing the structure of
native lignin or utilizing lignin as an alternative of fossil
resources. However, we have not seen any successful tech
nology to isolate native lignin in a high yield and any

promising lignin-based products on the market. One reason is


that every industrial lignin e.g. kraft lignin on paper making
and hydrolysis lignin on saccharication of woody materials,
suffers structural changes under isolation conditions, result
ing in the formation of lignin with unexpectable and uncon
trollable molecular structure.
Phase separation system [1e3] realized isolation of lignin
from plants as a useful polymer in a high yield. This novel
lignin-based polymer is named lignophenol by Funaoka. In
this system, wood meals are treated with a phenol derivative
and a concentrated acid under atmospheric temperature.
Crystalline cellulose is swollen and hydrolyzed by the
concentrated acid. Non-crystalline cellulose and hemi
cellulose are more easily hydrolyzed and dissolved by acid. In

* Corresponding author. Tel.: 81 59 231 9520; fax: 81 59 231 9591.


E-mail addresses: nonaka@bio.mie-u.ac.jp (H. Nonaka), funaoka@bio.mie-u.ac.jp (M. Funaoka).
0961-9534/$ e see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2010.12.040

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b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 6 0 7 e1 6 1 1

contrast, lignin is phenolated with the surrounding phenol


derivative at the benzyl (Ca) positions under the acidic
condition, thereby making condensation reactions between
lignin molecules avoid. The lignin becomes relatively linear
polymer due to the cleavage of a-aryl-ether bond. Based on the
fact that the rate of hydrolysis of a-aryl-ether bond is much
faster than that of b-aryl-ether bond [4], the reaction
temperature and time is designed so that the hydrolysis of
b-aryl-ether bond could be almost inhibited in the phase
separation system.
Lignin in softwood species consists of guaiacyl propane
units originated from dehydrogenative polymerization of
coniferyl alcohol. Although several kinds of linkages are
known between the monomeric units, the half is b-aryl-ether
bond [5,6], whose formation is typically followed by nucleo
philic attack of water or a phenolic group to Ca position. This
representative structure of softwood lignin is converted
through the phase separation system as demonstrated in
Fig. 1. The major structures of softwood lignophenol are
b-aryl-ether bond and 1,1-bis-aryl structure derived from the
grafted phenol derivative. This strong information enables us
to control and modify its structure and properties, which has
resulted in novel applications as functional polymers for these
several years [7e10].
Since lignin is the only promising renewable source of
aromatic compounds, it is also important to develop a tech
nology to convert lignin-based polymers to simple monophenols for chemical industries after used as a functional
polymer. The purpose of this study is to examine the adapt
ability of hydrothermal decomposition to selective and efcient
conversion of softwood lingophenol into monomeric phenols
and to obtain fundamental information on what are key reac
tions and how to control them. The motive is stimulated by the
possibility of highly selective hydrolysis of b-aryl-ether bond in
concurrence with pyrolytic cleavage of 1,1-bis-aryl structure
into phenolic units.

2.

Materials and methods

2.1.

Synthesis of ligno-p-cresol

sulfuric acid was added to wood meals sorbing p-cresol. The


mixture was stirred vigorously for 1 h at room temperature,
and then poured into excess water with vigorous stirring. The
precipitate was washed and extracted with acetone. The
acetone solution was added drop-wise to an excess amount
of cold diethyl ether with vigorous stirring. Ligno-p-cresol is
collected by centrifugation and dried.

2.2.

Hydrothermal decomposition of ligno-p-cresol

Small stainless steel batch-type reactors with a volume of


8.5 mL were used for hydrothermal reactions. After 0.1 g of
ligno-p-cresol and 3.4 g of distilled water are added to
a reactor, the reactor was immersed in a molten salt bath for
heating to desired temperature. For experiments at 400  C,
a mufe furnace was used for heating. The reactor was
transferred to a water bath to stop the reaction. The product
was washed with acetone, and then ltrated. The acetoneinsoluble residue was weighed after oven drying. The ltrate
was subjected to evaporation of acetone, and then was
extracted by diethyl ether using a separating funnel with
salting-out technique. Ether-insoluble compounds were
collected by deionized water and weighed after oven drying.
The ether solution was partly oven-dried to obtain the yield of
ether-soluble products.

2.3.

Analyses of the products

Acetone and n-butyl phenol were added to the remaining


ether solution, and then was subjected to GC-FID analysis
(Shimadzu GC-17A) to determine monophenols. A non-polar
capillary column (Quadrex crosslinked methyl silicone
column, Length: 50 m, Id: 0.25 mm, Thickness: 0.25 mm) was
used with helium as a carrier gas. The column temperature
was increased from 100  C to 270  C at a rate of 4  C/min. The
injector and the detector were maintained at 250  C. The
added n-butyl phenol was used as an internal standard to
calculate the yields of monophenols. The molecular weight
distributions of the ether-insoluble and ether-soluble prod
ucts after the decomposition at 300  C and 10 min were
measured by GPC (Shimadzu Class LC-10 system) equipped
with four columns (Shodex KF804, KF803, KF802 and KF801 in
series) using THF as an eluent. FT-IR spectra of some samples
were obtained by KBr method. The KBr disks were prepared by
a mini-hand press kit (Shimadzu MHP-1).

Ligno-p-cresol was isolated from extractive-free wood meals


of Douglas r (Psedotsuga menziesii) through the two step
process II of the phase separation system [3,8] as a repre
sentative of softwood lignophenol. Seventy two percent of

1,1-bis aryl structure

RO

1
6
5
4-O-5
-5
5-5

OH OH

OH

R = H, Aryl

2
3
4 OMe
O(H)

Representative structure
of native lignin

H3C

H+

OMe

O
OMe

OH

OMe
H3C

p-cresol
as a phenol
derivative

-aryl ether bond

O(H)

Representative structure
of ligno-p-cresol

Fig. 1 e Change of the major structure of softwood lignin using concentrated acid and p-cresol through the phase separation
system.

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b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 6 0 7 e1 6 1 1

Ligno-p -cresol
300 , 10 min

365 , 10 min
365 , 60 min

4400

3400

2400

1400

400

-1

Wave number (cm )

Fig. 2 e Yield of each fraction after the treatment of


softwood ligno-p-cresol under hydrothermal conditions.

3.

Results and discussion

3.1.

Characterization of the products

Fig. 4 e Comparison of FT-IR spectra between ligno-p


cresol and ether-insoluble products obtained at each
experimental condition.

Fig. 2 shows the proportions of acetone-insoluble, ether-insol


uble and ether-soluble products for each experimental condi
tion. Ligno-p-cresol is originally acetone-soluble and etherinsoluble compounds because it is puried as such using acetone
and ether in the phase separation system. After the treatment at
300  C for 10 min, the half changed to ether-soluble compounds.
By GPC analyses, we conrmed that the molecular weights of
ether-insoluble and ether-soluble products are transformed to
higher and signicantly lower than that of the raw ligno-p
cresol, respectively (Fig. 3). First, a little amount of a-aryl-ether
linkage remaining in ligno-p-cresol must be cleaved. Moreover,
to account for the low molecular weight of ether-soluble prod
ucts it is natural to consider that b-aryl-ether bonds were partly
cleaved in this condition. Since p-cresol is not introduced at all
benzyl positions, typically about 25wt% (0.65 mol/C9) for soft
wood ligno-p-cresol [3], simultaneous polymerization could be
due to condensation reaction at the most reactive benzyl posi
tions even at low temperature such as 300  C.
With increasing temperature and prolonging reaction time,
acetone-insoluble and undetected fractions increased. Such
conditions promote pyrolysis, resulting in polymerization via
radical coupling of pyrolyzed products and further carbon
ization. In reality, the colors of the ether-insoluble products
obtained at 365  C were nearly black. FT-IR analyses demon
strate that ether-insoluble products at 300  C almost maintain
the original structure of ligno-p-cresol, whereas those at
Mw

8000

2000

228

108
Ligno-p-cresol

Response

Ether-insoluble
Ether-soluble

20

25

30

35

40

45

Time (min)

Fig. 3 e Gel permeation chromatograms of each fraction for


softwood ligno-p-cresol treated at 300  C for 10 min.

Fig. 5 e GC chromatograms of ether-soluble products after


hydrothermal treatments at (a) 300  C, 10 min, (b) 365  C,
10 min, (a) 365  C, 60 min.

Yield (g/g-dry ligno-p -cresol)

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b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 6 0 7 e1 6 1 1

0.09
0.08
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0.00

This is because guaiacol is easily converted to catechol under


hydrothermal conditions [11]. At 400  C and 60 min, we could
not get the higher yield of p-cresol and guaiacol than 365  C.
Since it is reported that supercritical water treatment of
guaiacol at 673 K and 30 MPa gives 25% unknown derivatives
and a small amount of solid residue [11], this result is similarly
suggesting the promotion of the decomposition of monophenols and the participation of monophenols in char
formation [11e13] at higher temperature. The yield of p-cresol
was always larger than that of guaiacol. It is because about
half of the guaiacyl units are originally connected to another
monomeric unit via 4-O-5, b-5 and b-b bonds.

p-cresol
guaiacol
p-cresol, 365
guaiacol, 365

400 C

300 C

60

120

Reaction time (min)

Fig. 6 e Change of the yields of p-cresol and guaiacol from


softwood ligno-p-cresol at 365  C with reaction time and
the yields at other temperatures (300 and 400  C).

3.3.

365  C only show broad adsorption suggesting they are char


red (Fig. 4). The increase of the undetected fraction, probably
gas such as CO2 or volatile organic matters, could be explained
by the acceleration of carbonization and further decomposi
tion of the produced monophenols.

3.2.

Production of monophenols

Fig. 5 shows GC chromatograms of ether-soluble products


after hydrothermal treatments. The monophenols obtained
were mainly p-cresol and guaiacol (2-methoxyphenol). Fig. 6
shows the yields of p-cresol and guaiacol with reaction time.
Their total yield only exceeds 10% at 365  C and 60 min.
Therefore, it is likely that the pyrolysis of 1,1-bis-aryl structure
is a rate-limiting step. At 365  C, the yield of p-cresol seems to
reach the equilibrium yield around 8%, while the yield of
guaiacol gradually decreases after 10 min with reaction time.

Decomposition mechanism

Decomposition mechanism under hydrothermal conditions is


tentatively proposed for softwood ligno-p-cresol as shown in
Fig. 7. Softwood ligno-p-cresol has two pathways: hydrolysis
or polymerization. At lower hydrothermal temperature like
300  C, hydrolysis mainly takes place to give low molecular
weight products. A part of lignophenol could be probably
polymerized via reactive benzyl positions without p-cresol
because every benzyl position in lignin can not be phenolated
by p-cresol. With increasing temperature and reaction time,
pyrolysis would be promoted to give many radical species,
resulting in further polymerization and the following
carbonization. From a view point of low yields of p-cresol, the
pyrolysis of 1,1-bis-aryl structure is a rate-limiting step.
Therefore, it would be the most important to nd a reaction
condition and catalysts for accelerating the cleavage of 1,1
bis-aryl structure. Continuous extraction of producing
monophenols from the reactor would also be effective if the
formation of monophenols is achieving equilibrium.

Ligno-p-cresol
OMe
OH

OH OH
H3C

O
OMe

+H2O

OMe

4-O-5
-5
5-5

HO

Hydrolysis of
-aryl-ether

OMe
OH OH
H3C

Inefficient pyrolysis of
1,1-bis aryl structure

OMe
OH

Participation of
small molecules

OMe

O(H)

guaiacol

HO
OMe

OH

OMe

p-cresol

H3C

OH

O(H)

RO

OH

-ROH

Fast hydrolysis
of -aryl-ether

catechol
HO

+H+

OH

OH

O
OMe
OMe

Polymerized residue
via radical coupling

O(H)

Polymerized residue
at lower temperature
through condensation

Char

Undetected
products

Fig. 7 e Proposed mechanism on the decomposition of softwood ligno-p-cresol under hydrothermal conditions.

b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 6 0 7 e1 6 1 1

4.

Conclusions

Softwood lignophenol was depolymerized probably by hydro


lysis under hydrothermal conditions. However, the maximum
yield of monophenols only reaches 10% due to the slow pyrol
ysis of 1,1-bis-aryl structure. Higher temperature and reaction
time simultaneously leads to polymerization, carbonization
and decomposition of monophenols. To maximize the yield of
monophenols from lignophenol, it would be the most impor
tant to nd a reaction condition and catalysts for accelerating
the cleavage of 1,1-bis-aryl structure. Since softwood ligno
phenol almost keeps the structure of native softwood lignin
with the exception of the grafted phenol, our data should be
informative to hydrothermal decomposition of softwood.

Acknowledgments
This work was supported by SORST (Solution Oriented
Research for Science and Technology) grant from Japan
Science and Technology Corporation (JST).

references

[1] Funaoka M, Abe I. Rapid separation of wood into


carbohydrate and lignin with concentrated acid-phenol
system. Tappi J 1989;72:145e9.

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[2] Funaoka M, Matsubara M, Seki N, Fukatsu S. Conversion of


native lignin to a highly phenolic functional polymer and its
separation from lignocellulosics. Biotechnol Bioeng 1995;46:
545e52.
[3] Funaoka M. A new type of phenolic lignin-based network
polymer with the structure-variable function composed of
1,1-diarylpropane units. Polym Int 1998;47:277e90.
[4] Johansson B, Miksche G. Benzyl aryl ether formation in
lignin. II. Model studies. Acta Chem Scand 1972;26:289e308.
[5] Adler E. Lignin chemistry e past, present and future. Wood
Sci Technol 1977;11:169e218.
[6] Erickson M, Larsson S, Miksche GM. Gas-chromatographic
analysis of lignin oxidation products. Structure of the spruce
lignins. Acta Chem Scand 1973;27:903e14.
[7] Kita H, Nanbu K, Hamano T, Yoshino M, Okamoto K,
Funaoka M. Carbon molecular sieving membranes derived
from lignin-based materials. J Polym Environ 2002;10:69e75.
[8] Nagamatsu Y, Funaoka M. Design of recyclable matrixes

from lignin-based polymers. Green Chem 2003;5:595e601.

[9] Parajuli D, Adhikari CR, Kuriyama M, Kawakita H, Ohto K,


Inoue K, et al. Selective recovery of gold by novel ligninbased adsorption gels. Ind Eng Chem Res 2006;45:8e14.
[10] Aoyagi M, Funaoka M. A photochemical cell with nano-porous
TiO2 electrode sensitized by lignophenol under visible light
irradiation. J Photochem Photobiol A Chem 2006;181:114e9.
[11] Wahyudiono, Kanetake T, Sasaki M, Goto M. Decomposition
of a lignin model compound under hydrothermal conditions.
Chem Eng Technol 2007;30:1113e22.
[12] Wahyudiono, Sasaki M, Goto M. Recovery of phenolic
compounds through the decomposition of lignin in near and
supercritical water. Chem Eng Processing 2008;47:1609e19.
[13] Wahyudiono, Sasaki M, Goto M. Conversion of biomass
model compound under hydrothermal conditions using
batch reactor. Fuel 2009;88:1656e64.

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