Research progress in preparation of fuel chemicals by dual catalytic pyrolysis of biomass

doi:10.16085/j.issn.1000-6613.2020-1149

Abstract

Abstract:

The target product bio-oil from biomass pyrolysis is difficult to be directly applied due to its high oxygen content and complex components. Deoxidization and upgrading of bio-oil can be realized by upgrading pyrolysis steam with suitable catalyst. Based on the previous studies, this paper firstly summarized the structural characteristics, catalytic principle and catalytic effect of metal oxides as well as zeolite catalysts in catalytic pyrolysis of biomass. Then, the construction principle and catalytic mode of micro-mesoporous composite together with metal oxide/ZSM-5 composite dual catalytic system were introduced in detail, as well as their influence on the product distribution of biomass catalytic pyrolysis, and the feasibility and practicability of dual catalytic system were also illustrated. At the same time, other factors including raw material characteristics, process parameters and operation working mode which affected biomass catalytic pyrolysis were summarized. Finally, in view of the existing problems in research and development of dual catalytic pyrolysis, the prospect of the comparative study of different dual catalytic modes, improvement of dual catalytic system to reduce production costs, and exploration of the multiple use values of dual catalyst were put forward.

Key words: biomass, pyrolysis, catalyst, dual catalysis, bio-oil, deoxidation

摘要：

生物质热解所得目标产物生物油因高含氧量、组分复杂等问题难以直接应用，通过使用适宜的催化剂升级热解蒸气可实现生物油的脱氧提质。本文基于前人研究，首先总结了生物质催化热解中金属氧化物和分子筛催化剂的结构特点、催化原理与催化效果。然后详细介绍了微介孔复合型、金属氧化物/ZSM-5复合型双级催化体系的构建原理、催化模式及其对于生物质催化热解产物分布规律产生的影响，并说明了双级催化体系的可行性与实用性；同时概述了影响生物质催化热解的其他因素，包括原料特性、工艺参数、操作模式等。最后针对目前双级催化热解研究与发展中存在的问题，对进行双级催化模式的比较研究、改进催化体系以降低生产成本、发掘双级催化剂的多种使用价值等方向提出了展望。

关键词: 生物质, 热解, 催化剂, 双级催化, 生物油, 脱氧

CLC Number:

ZHANG Shumei, WANG Yunpu, XIA Meiling, ZENG Yuan, LIU Yuhuan, JIANG Lin, TIAN Xiaojie, ZENG Zihong, WU Qiuhao, RUAN Roger. Research progress in preparation of fuel chemicals by dual catalytic pyrolysis of biomass[J]. Chemical Industry and Engineering Progress, 2021, 40(5): 2496-2508.

张淑梅, 王允圃, 夏美玲, 曾媛, 刘玉环, 姜林, 田晓洁, 曾子鸿, 吴秋浩, RUAN Roger. 生物质双级催化热解制备燃料化学品的研究进展[J]. 化工进展, 2021, 40(5): 2496-2508.

Figures/Tables 4

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催化类型	催化剂	原料	催化剂作用	参考文献
核壳型	ZSM-5、SBA-15、核壳ZSM-5@SBA-15	玉米秸秆	ZSM-5@SBA-15催化剂改善了传质扩散问题；使用ZSM-5@SBA-15比仅使用ZSM-5、SBA-15催化剂得到了更多的酚类、烃类化合物	[31]
	MCM-41、HY、核壳HY/MCM-41	废轮胎	HY/MCM-41在降低轮胎热解油中硫和多环芳烃含量、提高石油化工产量等方面应用前景广阔；HY/MCM-41的裂化活性、石化选择性高于纯HY和MCM-41	[40]
	HZSM-5/MCM-41	稻壳、温室塑料薄膜	有助于芳烃的生成	[49]
	ZSM-5/MCM-41	废弃农用地膜、含可溶物的干酒糟	ZSM-5/MCM-41催化比仅ZSM-5、MCM-41催化脱氧效果更好；利用核壳ZSM-5/MCM-41催化剂可显著提高生物油中的烃类得率	[52]
	核壳ZSM-5@SBA-15	玉米秸秆	介孔壳部SBA-15促进了生物质热解蒸气传质，核部ZSM-5的酸性促进芳烃形成；适宜的SBA-15介孔壳层孔扩散长度利于大分子裂解成含氧中间体；介孔壳SBA-15的孔通道内酸性若过强，会促进焦炭生成并有不利影响	[57]
连续型	MCM-41、HZSM-5	秸秆、皂角	添加MCM-41促使大分子化合物发生裂解并抑制焦炭生成，有利于延长HZSM-5的寿命	[53]
连续型核壳型	HZSM-5/MCM-41	竹子	连续型催化在适宜条件下能促进烃类生成；核壳型催化灵活性高于连续型催化	[50]
连续型混合型	Al-MCM-41、HZSM-5	山毛榉木质生物质	连续型催化可促进烃类、酚类、呋喃类、醇类等有利化合物的生成；HZSM-5与Al-MCM-41在连续催化和混合催化体系中可能存在协同效应；连续型催化对含氧化合物的裂化效果强于混合型催化	[54]

催化类型	催化剂	原料	催化剂作用	参考文献
核壳型	ZSM-5、SBA-15、核壳ZSM-5@SBA-15	玉米秸秆	ZSM-5@SBA-15催化剂改善了传质扩散问题；使用ZSM-5@SBA-15比仅使用ZSM-5、SBA-15催化剂得到了更多的酚类、烃类化合物	[31]
	MCM-41、HY、核壳HY/MCM-41	废轮胎	HY/MCM-41在降低轮胎热解油中硫和多环芳烃含量、提高石油化工产量等方面应用前景广阔；HY/MCM-41的裂化活性、石化选择性高于纯HY和MCM-41	[40]
	HZSM-5/MCM-41	稻壳、温室塑料薄膜	有助于芳烃的生成	[49]
	ZSM-5/MCM-41	废弃农用地膜、含可溶物的干酒糟	ZSM-5/MCM-41催化比仅ZSM-5、MCM-41催化脱氧效果更好；利用核壳ZSM-5/MCM-41催化剂可显著提高生物油中的烃类得率	[52]
	核壳ZSM-5@SBA-15	玉米秸秆	介孔壳部SBA-15促进了生物质热解蒸气传质，核部ZSM-5的酸性促进芳烃形成；适宜的SBA-15介孔壳层孔扩散长度利于大分子裂解成含氧中间体；介孔壳SBA-15的孔通道内酸性若过强，会促进焦炭生成并有不利影响	[57]
连续型	MCM-41、HZSM-5	秸秆、皂角	添加MCM-41促使大分子化合物发生裂解并抑制焦炭生成，有利于延长HZSM-5的寿命	[53]
连续型核壳型	HZSM-5/MCM-41	竹子	连续型催化在适宜条件下能促进烃类生成；核壳型催化灵活性高于连续型催化	[50]
连续型混合型	Al-MCM-41、HZSM-5	山毛榉木质生物质	连续型催化可促进烃类、酚类、呋喃类、醇类等有利化合物的生成；HZSM-5与Al-MCM-41在连续催化和混合催化体系中可能存在协同效应；连续型催化对含氧化合物的裂化效果强于混合型催化	[54]

催化模式	催化剂	原料	催化剂作用	参考文献
模式Ⅰ、模式Ⅱ、模式Ⅲ	CaO、Al₂O₃、 ZnO、ZSM-5	木屑	CaO降低了羧酸有机物和甲氧基苯酚得率；Al₂O₃促进了含氧化合物（分子量>109g·mol^-1）的裂解；在模式Ⅱ催化下芳烃得率较高	[13]
模式Ⅰ	CaO、HZSM-5	木聚糖、LLDPE	双催化剂的使用显著提高了芳烃的得率；酸在热解过程中先被CaO还原成酮，然后在HZSM-5上进行芳构化反应	[63]
模式Ⅰ	MgO、HZSM-5	竹渣、废润滑油	双催化体系具有显著的脱氧和芳构化作用；MgO通过酮化和醛缩合反应表现出明显的脱酸作用	[68]
模式Ⅰ、模式Ⅲ	MgO、CaO、 SrO、HZSM-5	竹屑	模式Ⅲ比模式Ⅰ具有更显著的芳构化和脱氧活性；揭示了碱性催化剂与HZSM-5的协同作用；与模式Ⅰ相比，模式Ⅲ提高了苯酚的相对选择性	[66]
模式Ⅰ、模式Ⅲ	MgO、HZSM-5	废轮胎、竹屑	在较高的HZSM-5比例下，模式Ⅰ能有效产生芳烃；不同HZSM-5/MgO质量比下，模式Ⅰ对烷基苯类物质有积极的累加效应	[70]

催化模式	催化剂	原料	催化剂作用	参考文献
模式Ⅰ、模式Ⅱ、模式Ⅲ	CaO、Al₂O₃、 ZnO、ZSM-5	木屑	CaO降低了羧酸有机物和甲氧基苯酚得率；Al₂O₃促进了含氧化合物（分子量>109g·mol^-1）的裂解；在模式Ⅱ催化下芳烃得率较高	[13]
模式Ⅰ	CaO、HZSM-5	木聚糖、LLDPE	双催化剂的使用显著提高了芳烃的得率；酸在热解过程中先被CaO还原成酮，然后在HZSM-5上进行芳构化反应	[63]
模式Ⅰ	MgO、HZSM-5	竹渣、废润滑油	双催化体系具有显著的脱氧和芳构化作用；MgO通过酮化和醛缩合反应表现出明显的脱酸作用	[68]
模式Ⅰ、模式Ⅲ	MgO、CaO、 SrO、HZSM-5	竹屑	模式Ⅲ比模式Ⅰ具有更显著的芳构化和脱氧活性；揭示了碱性催化剂与HZSM-5的协同作用；与模式Ⅰ相比，模式Ⅲ提高了苯酚的相对选择性	[66]
模式Ⅰ、模式Ⅲ	MgO、HZSM-5	废轮胎、竹屑	在较高的HZSM-5比例下，模式Ⅰ能有效产生芳烃；不同HZSM-5/MgO质量比下，模式Ⅰ对烷基苯类物质有积极的累加效应	[70]

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