木质素及其模型化合物热解研究进展

doi:10.16085/j.issn.1000-6613.2018-1983

化工进展 ›› 2019, Vol. 38 ›› Issue (07): 3088-3096.DOI: 10.16085/j.issn.1000-6613.2018-1983

木质素及其模型化合物热解研究进展

王海英^1,²(),韩洪晶^1,²,宋华^1,²,孙恩浩³,张亚男^1,²,陈彦广^1,²(),赵宏志^1,²,李金鑫^1,²,康越^1,²

1. 东北石油大学化学化工学院，黑龙江大庆 163318
2. 黑龙江省石油与天然气化工省重点实验室，黑龙江大庆 163318
3. 中国石油大庆化工研究中心，黑龙江大庆 163714

收稿日期:2018-10-08 出版日期:2019-07-05 发布日期:2019-07-05
通讯作者: 陈彦广
作者简介:王海英（1990—），女，博士研究生，研究方向为催化材料合成及生物质资源化利用。E-mail：<email>wanghaiying1990@126.com</email>。
基金资助:
国家自然科学基金(51674089);黑龙江省杰出青年科学基金(JC2018002);黑龙江省博士后科研启动基金（LBH-Q16037）：东北石油大学研究生创新科研项目(YJSCX2017-014NEPU)

Progress in pyrolysis of lignin and its model compounds

Haiying WANG^1,²(),Hongjing HAN^1,²,Hua SONG^1,²,Enhao SUN³,Yanan ZHANG^1,²,Yanguang CHEN^1,²(),Hongzhi ZHAO^1,²,Jinxin LI^1,²,Yue KANG^1,²

1. College of Chemistry & Chemical Engineering，Northeast Petroleum University，Daqing 163318，Heilongjiang，China
2. Heilongjiang Provincial Key Laboratory of Oil and Gas Chemical Technology，Daqing 163318，Heilongjiang，China
3. Daqing Petrochemical Research Center, PetroChina, Daqing 163714，Heilongjiang，China

Received:2018-10-08 Online:2019-07-05 Published:2019-07-05
Contact: Yanguang CHEN

摘要/Abstract

摘要：

木质素是世界第二大可再生生物质资源，实现木质素的资源化、高值化利用对国民经济发展具有重要意义。木质素热解因具有成本低廉、操作简单、可获得高附加值产品等优点受到了学者的广泛关注。本文综述了β-O-4、α-O-4、β-5等木质素模型化合物的热解机理，比较了模型化合物中不同种类连接键断裂的难易程度及生成产物的区别；概述了木质素热解过程的特性、影响因素及产物分布规律，阐述了催化剂对热解过程的影响，尤其是金属盐类和分子筛对热解产物组成的影响规律和催化作用机制，详细介绍了木质素热解制备酚类化学品和生物油的关键控制因素及产品特点；针对现有木质素热解技术存在的机理不明确、目标产物选择性低、产物提纯困难等问题，对探索热解机理、开发新型催化剂及生产工艺、提高经济效益等发展方向进行了展望，为木质素资源化利用提供了理论基础。

关键词: 木质素, 热解, 模型化合物, 酚, 生物油

Abstract:

Lignin is the second largest renewable biomass resource in the world, thus making full use of lignin is of great significance to the development of our national economy. The lignin pyrolysis has attracted wide attention of scholars due to its advantages, low cost, simple operation and the production of high value-added products. The pyrolysis mechanisms of lignin model compounds (including β-O-4, α-O-4, β-5, etc.) were reviewed, the degree of difficulty of bonds breaking and the difference of products were compared. The characteristics, influence factors and the products distribution of lignin pyrolysis were summarized, the catalytic pyrolysis mechanisms of lignin especially under the action of metal salts and zeolites were expounded. The key control factors and product characteristics of lignin pyrolysis to produce phenolic chemicals and bio-oil were introduced in detail. In view of the problems existing in the technology of lignin pyrolysis, including unclear mechanism, low selectivities of target products and difficulty in product purification, exploring pyrolysis mechanism, developing new catalysts and production processes, and improving economic efficiency were prospected. It provides a theoretical basis for the resource utilization of lignin.

Key words: lignin, pyrolysis, model compounds, phenolics, bio-oil

中图分类号:

TQ35

王海英, 韩洪晶, 宋华, 孙恩浩, 张亚男, 陈彦广, 赵宏志, 李金鑫, 康越. 木质素及其模型化合物热解研究进展[J]. 化工进展, 2019, 38(07): 3088-3096.

Haiying WANG, Hongjing HAN, Hua SONG, Enhao SUN, Yanan ZHANG, Yanguang CHEN, Hongzhi ZHAO, Jinxin LI, Yue KANG. Progress in pyrolysis of lignin and its model compounds[J]. Chemical Industry and Engineering Progress, 2019, 38(07): 3088-3096.

图/表 5

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化学键变化	ΔE /kJ·mol^-1	主要产物	参考文献
C_β―O 均裂	221.4	，	[11]
C_α―C_β 均裂	259.3	，，含羰基类物质
C_β―O 协同反应	264.4	，，小分子产物
C_β―O 均裂	245.3	，，，，	[12]
C_α―C_β 均裂	259.2	，，，，，
协同反应	>300	，，，CH₂O，CH₄
C_β―O 裂解	228.0	，，，CH₃CH₂OH	[17]
C_α―C_β 裂解	241.1	，，CH₃CH₂OH	[17]
C_β―O 均裂	230.6	，，，，，C₂H₂	[18]
C_α―C_β 均裂	292.5	—
协同反应 1	247.6	，，
协同反应 2	274.8	，，，，H₂C=CHOH

化学键变化	ΔE /kJ·mol^-1	主要产物	参考文献
C_β―O 均裂	221.4	，	[11]
C_α―C_β 均裂	259.3	，，含羰基类物质
C_β―O 协同反应	264.4	，，小分子产物
C_β―O 均裂	245.3	，，，，	[12]
C_α―C_β 均裂	259.2	，，，，，
协同反应	>300	，，，CH₂O，CH₄
C_β―O 裂解	228.0	，，，CH₃CH₂OH	[17]
C_α―C_β 裂解	241.1	，，CH₃CH₂OH	[17]
C_β―O 均裂	230.6	，，，，，C₂H₂	[18]
C_α―C_β 均裂	292.5	—
协同反应 1	247.6	，，
协同反应 2	274.8	，，，，H₂C=CHOH

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木质素及其模型化合物热解研究进展

Progress in pyrolysis of lignin and its model compounds

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