杏壳木质素的结构表征及其热解特性研究

doi:10.3969/j.issn.1673-5854.2019.06.005

生物质化学工程 ›› 2019, Vol. 53 ›› Issue (6): 27-32.doi: 10.3969/j.issn.1673-5854.2019.06.005

杏壳木质素的结构表征及其热解特性研究

马欢欢^1,²(),万意凌¹,谢凌翔¹,孟凡蕊¹,周建斌^1,^2,*()

1. 南京林业大学材料科学与工程学院, 江苏南京 210037
2. 江苏省生物质气化多联产工程研究中心, 江苏南京 210037

收稿日期:2019-01-15 出版日期:2019-11-30 发布日期:2019-12-10
通讯作者: 周建斌 E-mail:mahuanhuan@njfu.edu.cn;zhoujianbin@njfu.com.cn
作者简介:马欢欢(1989—),男,安徽宿州人，实验师,博士生,从事生物质热解与炭材料研究; E-mail: mahuanhuan@njfu.edu.cn
基金资助:
国家重点研发计划资助项目(2016YFE0201800);江苏高校优势学科建设工程资助项目(无编号)

Structural Characterization and Pyrolysis Characteristics of Apricot Shell Lignin

Huanhuan MA^1,²(),Yiling WAN¹,Lingxiang XIE¹,Fanrui MENG¹,Jianbin ZHOU^1,^2,*()

1. College of Materials Science and Engineering, Nanjing Forestry University, Nanjing 210037, China
2. Research Center of Biomass Gasification and Liquidation Engineering, Nanjing Forestry University, Nanjing 210037, China

Received:2019-01-15 Online:2019-11-30 Published:2019-12-10
Contact: Jianbin ZHOU E-mail:mahuanhuan@njfu.edu.cn;zhoujianbin@njfu.com.cn
Supported by:
国家重点研发计划资助项目(2016YFE0201800);江苏高校优势学科建设工程资助项目(无编号)

摘要/Abstract

摘要：

为研究杏壳木质素的结构、热解特性及其产物的生成规律，通过硫酸脱除法从杏壳中分离出杏壳木质素，并通过红外光谱(FT-IR)和核磁共振(NMR)对其结构组成进行表征，利用热重及热重-红外联用分析研究其热解产物生成特性。研究结果表明：硫酸脱除法得到的杏壳木质素得率为30.42%，红外光谱图显示有较强的紫丁香基峰，还有一定量的愈创木基，二维核磁共振图谱表明杏壳木质素中有紫丁香基(S)、愈创木基(G)和对羟基苯基(H)3种木质素结构单元，属于SGH型木质素。热重及热重-红外联用分析表明杏壳木质素热解过程主要分为3个阶段，主要热解阶段发生在150~650 ℃之间的较宽温度范围内，360 ℃时热失重速率最大，热解产物主要为H₂O、CO、CO₂、CH₄以及醇、醛、酚、酸等。杏壳木质素中苯丙烷侧链上醚键和苯环间醚键断裂及挥发分二次裂解使CO的析出温度范围较宽，在200~700 ℃之间；羧基和羰基等官能团不稳定易断裂和重整，使CO₂的析出温度范围较窄，在250~650 ℃之间；苯丙烷侧链的断裂和苯环上甲氧基官能团的去甲基化反应，以及芳香环的深度断裂，使CH₄的析出在400和600 ℃时呈现2个峰值。

关键词: 杏壳木质素, 酸溶解法, 结构组成, 热重红外联用

Abstract:

The lignin of apricot shell was separated from apricot shell by sulfuric acid removal method to study the structure, pyrolysis characteristics and product formation of apricot shell lignin, and its structure and composition were confirmed by Fourier transform infrared spectroscopy(FT-IR) and nuclear magnetic resonance(NMR). The formation characteristics of pyrolysis products was studied by thermogravimetric and thermogravimetric-infrared spectroscopy. The results showed that the yield of apricot shell lignin was 30.42% by sulfate removal method. The FT-IR showed that the apricot shell lignin could be qualitatively determined guaiacyl unit and syringyl unit. The 2D heteronuclear single quantum correlation nuclear magnetic resonance (2D HSQC NMR) of apricot shell lignin indicated which contained syringyl(S), guaiacyl(G) and p-hydroxyphenyl proane(H). Apricot shell lignin pyrolysised in a wide temperature range between 150 and 650 ℃, and the pyrolysis process was mainly divided into three stages analyzied by thermogravimetric and thermogravimetric-infrared spectroscopy. The maximum thermal decomposition weightlessness temperature was 360 ℃, and H₂O, CO, CO₂, CH₄, alcohols, aldehydes, phenols and acids were generated. The precipitation temperature range of CO occured in a wide temperature range between 200-700 ℃, that mainly created by the dissociation of the ether bond on the side chain of phenylpropane at the low temperature, and created by the dissociation of the ether bond between benzene rings and the volatile decomposed secondary. The precipitation temperature range of CO₂ was narrow between 250-650 ℃, which mainly created by the fracture and rearrangement of the carbonyl and carboxyl on the side chain of phenylpropane. The precipitation of CH₄ had two peaks, the one 400 ℃ was the dissociation of the side chain of phenylpropane and the demethylation of the methoxy on the benzene, and the other one 600 ℃ was rupturing deeply of the aromatic ring.

Key words: apricot shell lignin, acid dissolution method, structure compositions, TG-FTIR

中图分类号:

TQ35
TK6

马欢欢,万意凌,谢凌翔,孟凡蕊,周建斌. 杏壳木质素的结构表征及其热解特性研究[J]. 生物质化学工程, 2019, 53(6): 27-32.

Huanhuan MA,Yiling WAN,Lingxiang XIE,Fanrui MENG,Jianbin ZHOU. Structural Characterization and Pyrolysis Characteristics of Apricot Shell Lignin[J]. Biomass Chemical Engineering, 2019, 53(6): 27-32.

图/表 6

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杏壳木质素的结构表征及其热解特性研究

Structural Characterization and Pyrolysis Characteristics of Apricot Shell Lignin

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