木质素类生物质催化热解制备精细化学品研究进展

doi:10.16085/j.issn.1000-6613.2018-1065

摘要/Abstract

摘要：

能源和环境是当今世界的两大挑战，将生物质转化为燃料和化学品是应对该挑战的低碳方案。其中，催化热解木质素获得燃料和化学品是低碳方案的重要部分。本文以能源和环境问题为出发点，阐述了木质素催化热解制备燃料和化学品的可行性和必要性，并对催化裂解行为、催化裂解过程和催化产物等方面的国内外研究现状进行了系统介绍。文章首先对木质素的结构和转化过程进行了概述；然后从催化热解行为、催化热解产物以及催化剂的研究现状等方面进行了系统阐述，并对现有的催化木质素热解过程的机理研究进行了讨论。通过对木质素催化热解制备燃料和化学品的发展前景、技术瓶颈以及逻辑方面进行评估表明，木质素转化为燃料和化学品过程中提高产品的产率和能量效率是今后的总体目标，而原料供给和生产、催化剂开发、产品分离纯化、反应机理和动力学以及计算模拟等方面将是深入研究木质素高效利用的重要研究内容。

关键词: 木质素, 生物质, 精细化学品, 催化裂解, 多级孔分子筛

Abstract:

Energy and environment had been become the two major global challenges in the present world. The production fuels and chemicals from lignin may be an important part of the low-carbon solution to both issues. This paper took the energy and environmental problems as the starting point, the feasibility and necessity of the production of fuel and chemicals via catalytic pyrolysis lignin were described, and then the status of the research on the catalytic pyrolysis behavior, catalytic pyrolysis process and catalytic products at home and abroad were systematically introduced. A brief introduction of the structure and transformation process of lignin was presented. Then the catalytic pyrolysis behavior, catalytic pyrolysis products, and the research status of the used catalysts were systematically elaborated, and the existing mechanism of catalytic pyrolysis lignin was discussed. The assessment of the challenges and opportunities, mitigating technical, environmental, and logistical issues in the process of catalytic pyrolysis lignin for the fuel and chemicals production showed that improving product productivity and energy efficiency in the conversion of lignin into fuel and chemicals will be the overall goal in the future, and the raw material supply and production, catalyst development, product separation and purification, reaction mechanism and kinetics, and computational simulation will be important research fields for further study on effective utilization of lignin.

Key words: lignin, biomass, fine chemicals, catalytic pyrolysis, hierarchical molecular sieves

中图分类号:

陈宇, 纪红兵. 木质素类生物质催化热解制备精细化学品研究进展[J]. 化工进展, 2019, 38(01): 626-638.

Yu CHEN, Hongbing JI. Catalytic pyrolysis of lignin biomass for the production of fine chemicals[J]. Chemical Industry and Engineering Progress, 2019, 38(01): 626-638.

图/表 6

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催化剂	原料	反应器	结论	参考文献
Ga/ZSM-5	木质纤维素生物质	固定床和流化床	Ga/ZSM-5催化剂能够提高芳香烃的产率；金属Ga能够提高脱羰和烯烃芳构化速率	[24]
M/ZSM-5（M= Fe、Co、Mn、Cu、Zr、Ce和Zn）	木屑	固定床	负载Zn获得最高的液体产率，同时具有较高的H/C和较低的 O/C；Zn/ZSM-5 改善液体品质、获得更多液体产物	[25]
Co/ZSM-5、Ni-ZSM-5	山毛榉	原位小型反应器和中试循环流化床	液体产率降低但质量提高； Co/ZSM-5催化剂增加CO₂的形成； Co/ZSM-5催化剂能够提高芳香烃含量	[26]
Ru/C	松木乙醇有机溶剂木质素	两步水相加氢	芳香烃的产生通过重油中醚键和甲氧基的水解断裂；第一、二步加氢反应中碳转化率分别为35%和33%	[27]
ZSM-5、Fe/ZSM-5	木屑	Py-GC/MS	Fe/ZSM-5比ZSM-5催化剂具有更高的脱氧反应和产生更多环芳香烃；	[28]
Fe/ZSM-5	山毛榉	固定床	Fe/ZSM-5催化剂降低液体产物含量；提高热解产物的质量；提高液体有机相中氧原子的除去；产物主要为酚类和芳香烃化合物	[29]
6%La-HZSM-5	丙烷	固定床石英反应器	随着温度升高强酸酸性位减少；催化剂提高轻质烯烃含量	[30]
ZSM-5、丝光沸石、 β-沸石和 Y 沸石	木质素	Py-GC-MS	加入ZSM-5催化剂得到最高的芳香烃；Beta和Y 沸石有利于木质素衍生物的脱氧反应	[31]
HZSM-5(25)、HZSM-5(50)、HZSM-5(210)、H-β和H-USY	纸浆黑液木质素	Py-GC-MS	低于650℃时，HZSM-5(25)催化剂促进单环芳香烃形成；H-USY 催化剂促进苯、甲苯和二甲苯芳香烃的生成	[32]
NiO/H-ZSM-5, NiO/H-BETA, NiO/H-Y	硬木木质素	中试固定床反应器	提高芳香烃的产率，降低含氧物质的产率；加入NiO/H-Y 催化剂时获得最高的液体和气体产率而焦炭产率最低；加入NiO/H-ZSM-5催化剂获得最高的芳香烃产率以及最低的含氧化合物	[33]

催化剂	原料	反应器	结论	参考文献
Ga/ZSM-5	木质纤维素生物质	固定床和流化床	Ga/ZSM-5催化剂能够提高芳香烃的产率；金属Ga能够提高脱羰和烯烃芳构化速率	[24]
M/ZSM-5（M= Fe、Co、Mn、Cu、Zr、Ce和Zn）	木屑	固定床	负载Zn获得最高的液体产率，同时具有较高的H/C和较低的 O/C；Zn/ZSM-5 改善液体品质、获得更多液体产物	[25]
Co/ZSM-5、Ni-ZSM-5	山毛榉	原位小型反应器和中试循环流化床	液体产率降低但质量提高； Co/ZSM-5催化剂增加CO₂的形成； Co/ZSM-5催化剂能够提高芳香烃含量	[26]
Ru/C	松木乙醇有机溶剂木质素	两步水相加氢	芳香烃的产生通过重油中醚键和甲氧基的水解断裂；第一、二步加氢反应中碳转化率分别为35%和33%	[27]
ZSM-5、Fe/ZSM-5	木屑	Py-GC/MS	Fe/ZSM-5比ZSM-5催化剂具有更高的脱氧反应和产生更多环芳香烃；	[28]
Fe/ZSM-5	山毛榉	固定床	Fe/ZSM-5催化剂降低液体产物含量；提高热解产物的质量；提高液体有机相中氧原子的除去；产物主要为酚类和芳香烃化合物	[29]
6%La-HZSM-5	丙烷	固定床石英反应器	随着温度升高强酸酸性位减少；催化剂提高轻质烯烃含量	[30]
ZSM-5、丝光沸石、 β-沸石和 Y 沸石	木质素	Py-GC-MS	加入ZSM-5催化剂得到最高的芳香烃；Beta和Y 沸石有利于木质素衍生物的脱氧反应	[31]
HZSM-5(25)、HZSM-5(50)、HZSM-5(210)、H-β和H-USY	纸浆黑液木质素	Py-GC-MS	低于650℃时，HZSM-5(25)催化剂促进单环芳香烃形成；H-USY 催化剂促进苯、甲苯和二甲苯芳香烃的生成	[32]
NiO/H-ZSM-5, NiO/H-BETA, NiO/H-Y	硬木木质素	中试固定床反应器	提高芳香烃的产率，降低含氧物质的产率；加入NiO/H-Y 催化剂时获得最高的液体和气体产率而焦炭产率最低；加入NiO/H-ZSM-5催化剂获得最高的芳香烃产率以及最低的含氧化合物	[33]

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