木质素单体模化物的热解与产物分析

doi:10.3785/j.issn.1008-973X.2021.05.018

浙江大学学报(工学版)

2021, Vol. 55

Issue (5): 976-983 DOI: 10.3785/j.issn.1008-973X.2021.05.018

材料与化学工程

木质素单体模化物的热解与产物分析

杨华美(

),李靖,堵锡华

徐州工程学院材料与化学工程学院，江苏徐州 221018

Pyrolysis and product analysis of lignin monomer model compounds

Hua-mei YANG(

),Jing LI,Xi-hua DU

School of Materials and Chemical Engineering, Xuzhou University of Technology, Xuzhou 221018, China

全文: PDF(1252 KB) HTML

摘要：

采用苯酚、邻苯二酚、愈创木酚和紫丁香酚为木质素单体模化物，利用两段裂解反应器-在线气相色谱仪（GCs）进行热解实验和产物分析，采用多色谱柱对无机气体（IGs）、C₁~C₅烃（C₁~C₅ LHs）、非芳基含氧化合物、酚和芳烃进行定量分析，以确定羟基和甲氧基对木质素热解过程中开环反应及产物分布的影响. 结果显示：羟基和甲氧基可以提高模化物的转化率，且羟基和甲氧基的存在影响芳基开环反应、芳基取代反应和重排反应间的竞争关系，使热解产物分布存在明显差异. 4种模化物热解产物主要是芳环的开环反应产物，包括IGs（质量分数为27.29%~33.56%）和C₁~C₅烃（20.46%~39.51%）. 一氧化碳产率（23.82%~29.18%）随羟基数增加而升高，随甲氧基数增加而降低；二氧化碳产率（0.19%~9.61%）随甲氧基数增加而升高. 羟基和甲氧基的存在降低了C₁~C₅烃的质量选择性，促进了烷基苯、大分子化合物和焦炭的形成.

关键词： 木质素; 单体模化物; 热解; 开环反应; C₁~C₅烃

Abstract:

Phenol, catechol, guaiacol and syringol, as lignin monomer model compounds, were pyrolyzed in a two-stage tubular reactor, and pyrolysis products were quantified by on-line gas chromatography (GCs). Inorganic gases (IGs), C₁~C₅ hydrocarbons (C₁~C₅ LHs), non-aryl oxygen-containing compound, phenols and aromatic hydrocarbon were quantified by GC. The purpose is to determine the effect of hydroxyl and methoxy on the ring-opening reaction of aromatic ring and product distribution during lignin pyrolysis process. Results show that hydroxyl and methoxy can improve the model compound conversion rate, and the existence of hydroxyl and methoxy affects the competition of aryl ring opening reaction, aryl substitution reaction and rearrangement reaction, leading to the obvious products distribution differences in the model compounds pyrolysis. The main products are formed from the ring-opening reaction, including IGs (mass fraction of 27.29%~33.56%) and C₁~C₅ LHs (20.46%~39.51%). The CO yield (23.82%~29.18%) is improved by hydroxyl, and reduced by methoxy. Methoxy enhances the CO₂ formation with its yield in 0.19%~9.61%. Hydroxyl and methoxy reduce the mass selectivity of C₁~ C₅ hydrocarbon, but promote the formation of alkyl benzene, macromolecular compounds and coke.

Key words: lignin monomer model compound pyrolysis ring-opening reaction C₁~C₅ hydrocarbons

收稿日期: 2020-04-29 出版日期: 2021-06-10

CLC:

TK 6

基金资助: 国家自然科学基金青年基金资助项目（21703194）；江苏省自然科学基金资助项目（BK20190156）；江苏省高校自然科学研究基金资助项目（18KJB480008）；徐州市应用基础研究计划资助项目（KC19048）

作者简介: 杨华美（1987—），女，讲师，博士，从事碳质资源的高效转化利用研究. orcid.org/0000-0003-2697-7250. E-mail： yhmcumt@yeah.net

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引用本文:

杨华美,李靖,堵锡华. 木质素单体模化物的热解与产物分析[J]. 浙江大学学报(工学版), 2021, 55(5): 976-983.

Hua-mei YANG,Jing LI,Xi-hua DU. Pyrolysis and product analysis of lignin monomer model compounds. Journal of ZheJiang University (Engineering Science), 2021, 55(5): 976-983.

链接本文:

http://www.zjujournals.com/eng/CN/10.3785/j.issn.1008-973X.2021.05.018 或 http://www.zjujournals.com/eng/CN/Y2021/V55/I5/976

图 1 两段式裂解反应器-在线气相色谱仪示意图

表 1 在线GC条件设置及检测产物

图 2 木质素模化物在750 ℃下热解所得各类产物的质量选择性

图 3 木质素模化物热解所得酚类化合物的质量选择性

图 4 木质素模化物热解所得CO和CO2的质量选择性

图 5 木质素模化物热解所得C1~C5烃的质量选择性

图 6 木质素模化物热解所得非芳基含氧化合物的质量选择性

图 7 木质素模化物热解所得芳烃的质量选择性

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