Citation: CHEN Meng-wei, GUO Da-liang, WANG Lin-fang, XUE Guo-xin. Depolymerization mechanism of alkali lignin in sub- and supercritical ethanol[J]. Journal of Fuel Chemistry and Technology, ;2016, 44(10): 1203-1210. shu

Depolymerization mechanism of alkali lignin in sub- and supercritical ethanol

1.
College of Materials and Textiles, Zhejiang Sci-Tech University, Hangzhou 310018, China
2.
Key Laboratory of Recycling and Eco-Treatment of Waste Biomass of Zhejiang Province, Zhejiang University of Science and Technology, Hangzhou 310023, China

Corresponding author: XUE Guo-xin, xueguoxin@126.com
Received Date: 5 April 2016
Revised Date: 12 June 2016

Figures(6)

The depolymerization process of wheat straw alkali lignin in sub- and supercritical ethanol was investigated with a micro autoclave reactor. The degraded product properties and the depolymerization mechanism of lignin structure were studied by scanning electron microscopy (SEM), gas chromatography/mass spectrometry (GC/MS) and infrared spectroscopy (FT-IR). The experimental results show that the minimum residual char yield (16.5%) is obtained at the condition of ethanol supercritical point (240℃, 7.2 MPa). Under subcritical ethanol conditions, alkali lignin firstly melts and disperses in ethanol as 1.0-2.0 μm diameter of microspheres, then a small amount of ether linkages and benzene ring side chain C_α are broken to form phenols, esters, ketones and acids products. Under supercritical ethanol conditions, the diameter of molten microsphere is significantly reduced, and plenty of ether linkages and benzene ring side chain C_α are continuously broken, meanwhile, the lipid products are subjected to secondary decomposition reaction. The yield of lipid is decreased (11.94%), while the yield of phenolic products from depolymerization is increased (52.14%).
- alkali lignin,
- sub- and supercritical ethanol,
- depolymerization
1. [1]
  AZADI P, INDERWILDIA O, FARNOOD R, KING D A. Liquid fuels, hydrogen and chemicals from lignin:A critical review[J]. Renewable Sustainable Energy Rev, 2013,21:506-523. doi: 10.1016/j.rser.2012.12.022
2. [2]
  YOSHIKAWA T, YAGI T, SHINOHARA S, FUKUNAGA T, NAKASAKA Y, TAGO T, MASUDA T. Production of phenols from lignin via depolymerization and catalytic cracking[J]. Fuel Process Technol, 2013,108:69-75. doi: 10.1016/j.fuproc.2012.05.003
3. [3]
  PANDEY M P, KIM C S. Lignin depolymerization and conversion:A review of thermochemical methods[J]. Chem Eng Technol, 2011,34(1):29-41. doi: 10.1002/ceat.v34.1
4. [4]
  TOLEDANO A, SERRANO L, LABIDI J. Improving base catalyzed lignin depolymerization by avoiding lignin repolymerization[J]. Fuel, 2014,116:617-624. doi: 10.1016/j.fuel.2013.08.071
5. [5]
  YUAN Z, CHENG S, LEITCH M, XU C C. Hydrolytic degradation of alkaline lignin in hot-compressed water and ethanol[J]. Bioresour Technol, 2010,101(23):9308-9313. doi: 10.1016/j.biortech.2010.06.140
6. [6]
  MAHMOOD N, YUAN Z, SCHMIDT J, XU C C. Hydrolytic depolymerization of hydrolysis lignin:Effects of catalysts and solvents[J]. Bioresour Technol, 2015,190:416-419. doi: 10.1016/j.biortech.2015.04.074
7. [7]
  ZHOU Jing-hui, XIE Zhang-hong, WANG Xing, ZHENG Lai-jiu. Advance in lignin-depolymerization and reaction mechanism by supercritical fluids technique[J]. J Dalian Polytech Univ, 2013,32(6):426-431.
8. [8]
  PIŃKOWSKA H, WOLAK P, ZŁOCIŃSKA A. Hydrothermal decomposition of alkali lignin in sub-and supercritical water[J]. Chem Eng J, 2012,187:410-414. doi: 10.1016/j.cej.2012.01.092
9. [9]
  KIM J Y, OH S, WANG H H, CHO T S, CHOI I G, CHOI J W. Effects of various reaction parameters on solvolytical depolymerization of lignin in sub-and supercritical ethanol[J]. Chemosphere, 2013,93(9):1755-1764. doi: 10.1016/j.chemosphere.2013.06.003
10. [10]
  TAN S S, MACFARLANE D R, UPFAL J, EDYE L A, DOHERTY W O, PATTI A F, SCOTT J L. Extraction of lignin from lignocellulose at atmospheric pressure using alkylbenzenesulfonate ionic liquid[J]. Green Chem, 2009,11(3):339-345. doi: 10.1039/b815310h
11. [11]
  CHENG S, WIKS C, YUAN Z, LEITCH M, XU C C. Hydrothermal degradation of alkali lignin to bio-phenolic compounds in sub/supercritical ethanol and water-ethanol co-solvent[J]. Polym Degrad Stab, 2012,97(6):839-848. doi: 10.1016/j.polymdegradstab.2012.03.044
12. [12]
  HU J, SHEN D, WU S, ZHANG H, XIAO R. Effect of temperature on structure evolution in char from hydrothermal degradation of lignin[J]. J Anal Appl Pyrolysis, 2014,106:118-124. doi: 10.1016/j.jaap.2014.01.008
13. [13]
  SHARMA R K, WOOTEN J B, BALIGA V L, LIN X, CHAN W G, HAJALIGOL M R. Characterization of chars from pyrolysis of lignin[J]. Fuel, 2004,83(11):1469-1482.
14. [14]
  LORA J H, GLASSER W G. Recent industrial applications of lignin:A sustainable alternative to nonrenewable materials[J]. J Polym Environ, 2002,10(1/2):39-48. doi: 10.1023/A:1021070006895
1. [1]
  Chunyang Bao , Ruoxuan Miao , Yuhan Ding , Qingfu Ban , Yusheng Qin , Jie Liu , Zhirong Xin . The Comprehensive Experiment Design of Preparation of Depolymerizable Thermosetting Polymers. University Chemistry, 2025, 40(4): 59-65. doi: 10.12461/PKU.DXHX202405087
2. [2]
  Qishen Wang , Changzhao Chen , Mengqing Li , Lingmin Wu , Kai Dai . Lignin derived carbon quantum dots and oxygen vacancies coregulated S-scheme LCQDs/Bi₂WO₆ heterojunction for photocatalytic H₂O₂ production. Acta Physico-Chimica Sinica, 2025, 41(11): 100147-0. doi: 10.1016/j.actphy.2025.100147
3. [3]
  Dongdong Yao , JunweiGu , Yi Yan , Junliang Zhang , Yaping Zheng . Teaching Phase Separation Mechanism in Polymer Blends Using Process Representation Teaching Method: A Teaching Design for Challenging Theoretical Concepts in “Polymer Structure and Properties” Course. University Chemistry, 2025, 40(4): 131-137. doi: 10.12461/PKU.DXHX202408125
4. [4]
  Shiyi Chen , Jialong Fu , Jianping Qiu , Guoju Chang , Shiyou Hao . Waste medical mask-derived carbon quantum dots enhance the photocatalytic degradation of polyethylene terephthalate (PET) over BiOBr/g-C₃N₄ S-scheme heterojunction. Acta Physico-Chimica Sinica, 2026, 42(1): 100135-0. doi: 10.1016/j.actphy.2025.100135
5. [5]
  Zunxiang Zeng , Yuling Hu , Yufei Hu , Hua Xiao . Analysis of Plant Essential Oils by Supercritical CO₂Extraction with Gas Chromatography-Mass Spectrometry: An Instrumental Analysis Comprehensive Experiment Teaching Reform. University Chemistry, 2024, 39(3): 274-282. doi: 10.3866/PKU.DXHX202309069
6. [6]
  Chi Li , Jichao Wan , Qiyu Long , Hui Lv , Ying Xiong . N-Heterocyclic Carbene (NHC)-Catalyzed Amidation of Aldehydes with Nitroso Compounds. University Chemistry, 2024, 39(5): 388-395. doi: 10.3866/PKU.DXHX202312016
7. [7]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
8. [8]
  Yiping HUANG , Liqin TANG , Yufan JI , Cheng CHEN , Shuangtao LI , Jingjing HUANG , Xuechao GAO , Xuehong GU . Hollow fiber NaA zeolite membrane for deep dehydration of ethanol solvent by vapor permeation. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 225-234. doi: 10.11862/CJIC.20240224
9. [9]
  Lele Feng , Xueying Bai , Jifeng Pang , Hongchen Cao , Xiaoyan Liu , Wenhao Luo , Xiaofeng Yang , Pengfei Wu , Mingyuan Zheng . Single-atom Pd boosted Cu catalysts for ethanol dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(9): 100100-0. doi: 10.1016/j.actphy.2025.100100
10. [10]
  Xincan Zhou , Xueyao Wang , Xiaokang Chen , Di Lan , Yuting Gao , Xiaoxia Wang , Daohao Li , Shuchao Zhang , Lijie Zhang , Guanglei Wu . Charge redistribution on Pd mediated by electronically asymmetric carbon for boosting ethanol oxidation. Acta Physico-Chimica Sinica, 2026, 42(7): 100287-. doi: 10.1016/j.actphy.2026.100287
11. [11]
  Peipei DING , Jingying DUAN , Haoran XU , Xinru FANG , Xingyu LIU , Juntao YAN , Chunlei WANG . Preparation and adsorption properties of poplar catkin-derived porous carbon by ethanol solvothermal method. Chinese Journal of Inorganic Chemistry, 2026, 42(6): 1203-1214. doi: 10.11862/CJIC.20250370
12. [12]
  Xinhao Yan , Guoliang Hu , Ruixi Chen , Hongyu Liu , Qizhi Yao , Jiao Li , Lingling Li . Polyethylene Glycol-Ammonium Sulfate-Nitroso R Salt System for the Separation of Cobalt (II). University Chemistry, 2024, 39(6): 287-294. doi: 10.3866/PKU.DXHX202310073
13. [13]
  Bing LIU , Huang ZHANG , Hongliang HAN , Changwen HU , Yinglei ZHANG . Visible light degradation of methylene blue from water by triangle Au@TiO₂ mesoporous catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 941-952. doi: 10.11862/CJIC.20230398
14. [14]
  Fen Wang , Qi Yang , Qianfei Ye , Jichao Xiao . Synthesis of Sulfinamidines via the Oxidative Sulfonamination of Sulfenamides: A Recommended Comprehensive Organic Chemistry Experiment. University Chemistry, 2025, 40(11): 354-361. doi: 10.12461/PKU.DXHX202506059
15. [15]
  Chenxu Gong , Weizhen Wang , Ruiying Zhang , Wenfeng Wang , Yuanming Li , Yaofeng Yuan , Keyin Ye . Computational Chemistry-Assisted Organic Structure Analysis (CCAOSA): A Case Study of Propeller-Shaped Hexabenzotriphenylene. University Chemistry, 2026, 41(4): 438-446. doi: 10.12461/PKU.DXHX202503076
16. [16]
  Xiyuan Su , Zhenlin Hu , Ye Fan , Xianyuan Liu , Xianyong Lu . Change as You Want: Multi-Responsive Superhydrophobic Intelligent Actuation Material. University Chemistry, 2024, 39(5): 228-237. doi: 10.3866/PKU.DXHX202311059
17. [17]
  Cen Zhou , Biqiong Hong , Yiting Chen . Application of Electrochemical Techniques in Supramolecular Chemistry. University Chemistry, 2025, 40(3): 308-317. doi: 10.12461/PKU.DXHX202406086
18. [18]
  Fan Yang , Zheng Liu , Da Wang , KwunNam Hui , Yelong Zhang , Zhangquan Peng . Preparation and Properties of P-Bi₂Te₃/MXene Superstructure-based Anode for Potassium-Ion Battery. Acta Physico-Chimica Sinica, 2024, 40(2): 2303006-0. doi: 10.3866/PKU.WHXB202303006
19. [19]
  Lu Zheng , Yueying Sun , Xin Ding , Jitao Liu . Preparation of 3D Printed Metamaterials Based on Molecular Design. University Chemistry, 2026, 41(1): 253-263. doi: 10.12461/PKU.DXHX202506019
20. [20]
  Zhao Gao , Jianxiang Sun , Bin Mu , Yi Yan , Wei Tian . Exploration of Supramolecular Polymer “Chameleons” in Innovative Chemistry Experiments. University Chemistry, 2026, 41(4): 349-355. doi: 10.12461/PKU.DXHX202504044

Get Citation

PDF

XML

Metrics

PDF Downloads(9)
Abstract views(2386)
HTML views(744)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142