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Scientific Journal of Frontier Chemical Development

June 2014, Volume 4, Issue 2, PP.22-28

Study on Degradation of Lignin in Ionic Liquid


Liyuan Xue, Jun Zhu, Man Jiang#, Zuowan Zhou
Key Laboratory of Advanced Technologies of Materials, Ministry of Education, School of Materials Science & Engineering,
Southwest
#Email: jiangman1021@163.com

Abstract
Lignin is proved to be the highest energy component, as well as natural aromatic polymer consisting of phenol units. Degraded
lignin efficiently and environmentally friendly provides an important way to improve its utilization efficiency. Two kinds ionic
liquids were adopted (BnMIMCl and BnMIMTFA) as the mediums for the lignin degradation, and the effects of temperature and
time on the reaction were investigated. The highest liquefaction efficiency of 77.27% was obtained under the optimized conditions.
It was found out through GC-MS analysis that the main components of the low molecular products were phenols in the extracted
liquor from the degraded liquid by ethyl acetate. The study provides a favorable approach to efficient utilization of lignin through
degradation of liquefied.
Keywords: Lignin; Ionic Liquid; Degradation; Liquefaction Ratio; Low Molecular Phenols

610031

1--3-BnMIMCl1--3-
BnMIMTFA
77.27% GC-MS

-
C-C C-O
[1-2] -O-4-O-4-5-O--4-O-55-5 -1
-O-4 -O-4 [3-5]

[6-7]

100 C
[8-9]
*51303151(2011GZX0052)

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[10-11]
[12-14]
[15-16]

Blair

[17-19]

HMIMBrHMIMHSO4HMIMClHMIMBF4

[20]

BMIMHSO4
-O-4 Blair
[21] HMIMCl
-O-4
[22]

1--3-BnMIMCl 1--3BnMIMTFA

1.1
DL (99.9%) (37%)
N-(99.5%)(99.5%)(99.0%)(99.0%)
(99.5%)(99.5%)(96%)(99.7%)
BnMIMCl BnMIMTFA

1.2

1
1
N2 : ILs (g/g) (C)

ILs
(h)
(g)
(%)
1#
BnMIMCl
1:10
120
3
0.257
48.91
2#
BnMIMCl
+
1:10
120
3
0.286
41.87
3#
BnMIMCl
1:10
120
8
0.123
75.45
4#
BnMIMCl
1:10
120
10
0.167
66.26
5#
BnMIMCl
1:10
200
3
0.203
74.13
6#
BnMIMCl
1:10
100
3
0.130
59.54
7#
BnMIMCl
1:5
120
3
0.223
55.58
8#
BnMIMCl
1:3
120
3
0.153
69.88
9#
BnMIMTFA
1:10
120
8
0.115
77.27
-+ 0.5000 g

3 h
HCl (1 ml) 2 h

20 ml

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GC-Mass 1
%=Wt - Wt/ Wt100

(1)

Wt----(g)

1.3
Nicolet-57004000-400cm-1
KBr KBr
KBr
GC-MS GCMS-QP2010 Plus
HP5-MS 80 C 280 C
80 C 2 min 15 C/min 200 C 200 C 25 min 10 C/min
280 C 280 C 2 min

2.1
[23]
1 1#2#

1-5
732
1-4
1-3
1-2
2864

1-1
2962

1100
1262

2941

789
1136

4000

35000

3000

2500
2000
Wave numbers (cm-1)

1500

1000

500

1 FTIR
1-1 1-2 1-3 1-4
1-5

1 1
3435 cm-1
2941cm-1 C-H 2 2962 cm-1 2864 cm-1
C-H 1262 cm-1 789 cm-1 C-O
C-H 1136cm-1
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3435 cm-1 2941cm-1 C-H 600


900cm-1 789 cm-1 732 cm-1

2.2
1 1#3#4# 3 h8 h 10 h
51.09% 24.55% 8 h10 h

2
2 2941cm-1 2 (2973
2852 cm-1)1036 cm-1 2 (1093cm-1 1062cm-1)1262 cm-1 789 cm-1
699 cm-1 726
cm-1
2-5
2-4
726

2-3

699

2-2
2-1

2852
1262

2973

1093
1062

2941

789

1036
3500

3000

2500
2000
1500
Wave numbers (cm-1)

1000

500

2 FTIR
2-1 2-2 3 h 2-3 8 h
2-4 3 h 2-5 8 h

2.3
1 1#5#6#
200 C
3
3 2941cm-1 2 2970 cm-1 2865 cm-1789cm-1
1643 cm-1 705 cm-1
C=C 726cm-1

2.4
1 1#7#8# 3:1
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0.153g 10:1 10 h
3-5

3-4

726

3-2
2865

3-1
3-3

705

1643
2970
2941

789
1092

4000

3500

3000

2500
2000
Wave numbers (cm-1)

1500

1000

500

3 FTIR
3-1 3-2 100 3-3 200
3-4 1003-5 200

0.115g 3:1
ILs
2941cm-1 2 2970cm-1
2856cm-1789cm-1 1643cm-1 697cm-1
718cm-1

2.4
1 3#BnMIMCl9#BnMIMTFA

[23]
2941cm-1 3160cm-1
C-H 1777cm-1 C=O 1262
cm-1 1212 cm-1 C=O C-H 718cm-1
718 cm-1

2.5 GC-MS
GC-MS
5% 2
2 86.93%

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23.67

17.84

14.05

13.64

12.71

6.09

5.59

5.29

BnMIMCl BnMIMTFA

75.45% 77.27% 120 C8 h


3:1

REFERENCES
[1]

S. Sahoo, M. Misra, A. K. Mohanty. Enhanced Properties of Lignin-based Biodegradable Polymer Composites Using Injection
Moulding Process [J]. Composites: Part A, 2011, 42: 17101718.

[2]

Yamin Li, Dongxu Cui, Yuanjian Tong, et al. Study on Structure and Thermal Stability Properties of Lignin during Thermo
stabilization and Carbonization [J]. International Journal of Biological Macromolecules, 2013, 62: 663- 669.

[3]

Mengmeng Zhao. Explorations of Condition and Mechanism of Degradation of Lignin in Subcritical Water [D]. Southwest Jiao
Tong University, 2013.

[4]

Songyan Jia, Blair J. Cox, Xinwen Guo, et al. Hydrolytic Cleavage of -O-4 Ether Bonds of Lignin Model Compounds in an Ionic
Liquid with Metal Chlorides [J]. Ind. Eng. Chem. Res., 2011, 50: 849- 855.

[5]

Huaming Yu, Jia Hu, Juan Fan, et al. One-Pot Conversion of Sugars and Lignin in Ionic Liquid and Recycling of Ionic Liquid[J].
Industrial & Engineering Chemistry Research, 2012, 51: 34523457.

[6]

Minghui Fan, Peiwen Jiang, Peiyan Bi, et al. Directional Synthesis of Ethyl benzene through Catalytic Transformation of Lignin
[J]. Bioresource Technology, 2013, 143: 5967.

[7]

Ning Yan, Yuan Yuan, Ryan Dykeman, et al. Hydrodeoxygenation of Lignin-Derived Phenols into Alkanes by Using
Nanoparticle Catalysts Combined with Bronsted Acidic Ionic Liquids [J]. Angewandte Chemie-international Edition, 2010, 49:
5549 5553.

[8]

G Laus, G Bentivoglio, H Schottenberger. Ionic Liquids: Current Developments, Potential and Drawbacks for Industrial
Applications [J]. Lenzinger Berichte, 2005, 84: 71-85.

[9]

Ruxiong Li. Green SolventsSynthesis and Application of Ionic Liquids [M]. Beijing: Chemical Industry Press, 2004, 19-21.

[10] R Liu, J Liu, Y Yin. Ionic Liquids in Sample Preparation [J]. Analytical and Bioanalytical Chemistry, 2009, 393: 871-883.
- 27 www.sjfcd.org

[11] C. L Hussey, L. A King, R. A Carpio. The Electrochemistry of Copper in a Room Temperature Acidic Chloroaluminate Melt ()
[J]. Electrochem. Soc., 1979, 126:1029-1034.
[12] Sumit Bali, Marcus A. Tofanelli, Richard D. Ernst, et al. Chromium (III) Catalysts in Ionic Liquids for the Conversion of Glucose
to 5-(hydroxymethyl)furfural (HMF): Insight into Metal Catalyst: Ionic Liquid Mediated Conversion of Cellulosic Biomass to
Biofuels and Chemicals [J]. Biomass and Bioenergy, 2012, 42: 224-227.
[13] Dongbao Fu, Giuseppe Mazza, Yukihiro Tamaki. Lignin Extraction from Straw by Ionic Liquids and Enzymatic Hydrolysis of the
Cellulosic Residues [J]. Journal of Agricultural and Food Chemistry, 2010, 58: 29152922.
[14] Tony Vancov, Amy-Sue Alston, Trevor Brown, et al. Use of Ionic Liquids in Converting Lignocellulosic Material to Biofuels [J].
Renewable Energy, 2012, 45: 1-6.
[15] Bin Li, Ilari Filpponen, Dimitris S. Argyropoulos. Acidolysis of Wood in Ionic Liquids [J]. Industrial & Engineering Chemistry
Research, 2010, 49: 31263136.
[16] Carsten Sievers, Mariefel B. Valenzuela-Olarte, Teresita Marzialetti, et al. Ionic-Liquid-Phase Hydrolysis of Pine Wood [J].
Industrial & Engineering Chemistry Research, 2009, 48: 12771286.
[17] Y Pu, N Jiang, A J Ragauskas. Ionic Liquid as a Green Solvent for Lignin [J]. J. Wood Chem. Technol., 2007, 27: 23- 33.
[18] N Sun, M Rahman, Y Qin, et al. Complete Dissolution and Partial Delignification of Wood in the Ionic Liquid
1-ethyl-3-methylimidazolium Acetate [J]. Green Chem., 2009, 11: 646-655,
[19] M Zavrel, D Bross, M Funke. High-throughput Screening for Ionic Liquids Dissolving (Ligno-) cellulose [J]. Bioresour. Technol.,
2009, 100: 2580-2587.
[20] Blair J. Cox, Songyan Jia, Z. Conrad Zhang, et al. Catalytic Degradation of Lignin Model Compounds in Acidic Imidazolium
Based Ionic Liquids: Hammett Acidity and Anion Effects [J]. Polymer Degradation and Stability, 2011, 96: 426-431.
[21] Blair J. Cox, John G. Ekerdt. Depolymerization of Oak Wood Lignin under Mild Conditions using the Acidic Ionic Liquid
1-H-3-methylimidazolium Chloride as both Solvent and Catalyst [J]. Bioresource Technology, 2012, 118: 584588.
[22] Amadou Diop, Amel Hadj Bouazza, Claude Daneault, et al. New Ionic Liquid for the Dissolution of Lignin [J]. Bioresources,
2013, 8:4270-4282.
[23] Man Jiang, Mengmeng Zhao, Zuowan Zhou, et al. Isolation of Cellulose with Ionic Liquid from Steam Exploded Rice Straw [J].
Industrial Crops and Products, 2011, 33: 734738.

1990-
Email: xueliyuan0412@163.com

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