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abstract
Article history:
ligno-p-cresol derived from softwood (Douglas r) was studied from 300 to 400 C as
a candidate technology for modication of the molecular structure and the recovery of
5 November 2010
ether linkages and the half was converted to ether-soluble compounds at 300 C for 10 min.
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.
Lignin
Softwood
Hydrothermal decomposition
Monophenol
1.
Introduction
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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
2.
2.1.
Synthesis of ligno-p-cresol
2.2.
2.3.
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
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
3.
3.1.
8000
2000
228
108
Ligno-p-cresol
Response
Ether-insoluble
Ether-soluble
20
25
30
35
40
45
Time (min)
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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
p-cresol
guaiacol
p-cresol, 365
guaiacol, 365
400 C
300 C
60
120
3.3.
3.2.
Production of monophenols
Decomposition mechanism
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
Acknowledgments
This work was supported by SORST (Solution Oriented
Research for Science and Technology) grant from Japan
Science and Technology Corporation (JST).
references
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