均相催化CO2加氢制备MeOH的研究进展

doi:10.3969/j.issn.1006-396X.2022.05.003

摘要/Abstract

摘要：

大气中CO₂质量分数于2021年创下历史新高（414.7 $μ g / g$ ），由此引发的一系列生态环境问题已成为不争的事实。为解决全球变暖的问题，CO₂资源化利用势在必行。从CO₂利用和甲醇（MeOH）经济性角度看，CO₂加氢制备MeOH是一个非常具有发展潜力的能源路线，可作为实现碳中和的关键路径之一。总结了均相体系中以H₂作为还原剂，还原CO₂制备MeOH的最新进展；围绕CO₂直接加氢制备MeOH、经CO₂衍生物加氢制备MeOH以及经HCOOH歧化制备MeOH等3条路径，介绍了每条路径中涉及的催化剂体系设计、构?效关系以及反应机理；概述了每条加氢路径存在的不足，并提出了实现工业化CO₂加氢制备MeOH需解决的问题。

关键词: 碳中和, CO₂, 加氢, 均相催化, 甲醇

Abstract:

The concentration of CO₂ in the atmosphere reached an all?time high in the 2021(414.7 μg/g), which has caused a series of ecological and environmental problems. In order to solve the problem of global warming, CO₂ resource utilization is imperative. From the view of CO₂ utilization and methanol (MeOH) economy, the preparation of MeOH by CO₂ hydrogenation is a potential energy route, which can be used as one of the key paths to achieve carbon neutrality. The recent progress in preparation of MeOH by reduction of CO₂ with H₂ as reductant in homogeneous system was summarized.According to the three routes of preparing MeOH by direct hydrogenation of CO₂,preparing MeOH by hydrogenation of CO₂ derivatives,and preparing MeOH by dissimilation of HCOOH,the catalyst system design,structure?activity relationship and reaction mechanism involved in each route were introduced,and the shortcomings of each hydrogenation route were summarized,the problems needed to be solved in the industrial production of MeOH by CO₂ hydrogenation were put forward.

Key words: Carbon neutrality, Carbon dioxide, Hydrogenation, Homogeneous catalysis, Methanol

中图分类号:

TQ032.4

康杏思, 陈琼遥, 何林. 均相催化CO₂加氢制备MeOH的研究进展[J]. 石油化工高等学校学报, 2022, 35(5): 25-35.

Xingsi Kang, Qiongyao Chen, Lin He. Recent Advances on MeOH Production via Homogeneous Catalytic CO₂ Hydrogenation[J]. Journal of Petrochemical Universities, 2022, 35(5): 25-35.

图/表 17

图1 一步法实现CO2制备MeOH的Ru基催化体系

Fig.1 Ru?based catalytic system for the preparation of MeOH by CO2 was realized in one step

图2 催化剂5用于CO2还原制备MeOH[27]

Fig.2 Catalyst 5 tested in CO2 hydrogenation to MeOH

图3 三催化剂体系用于CO2还原制备MeOH

Fig.3 Three?catalysts system for the synthesis of MeOH from CO2

图4 三催化剂体系实现一锅法从CO2制备MeOH

Fig.4 Cascade catalysis through one?pot method for CO2 reduction to MeOH

图5 Ru、Rh络合物体系用于温和条件下CO2加氢制备MeOH

Fig.5 Ru and Rh complexes examined for CO2 hydrogenation to MeOH under mild conditions

图6 催化剂12在二甲胺辅助下经甲酰胺中间体还原制备MeOH

Fig.6 Amine assisted sequential methanol synthesis from CO2 via N?formylation in the presence of catalyst 12

图7 乙醇胺衍生物捕捉CO2经氨基甲酸酯制MeOH

Fig.7 Synthesis of methanol via carbamate using aminoethanol derivatives to capture CO2

图8 催化剂12/PEHA双相体系一锅法实现CO2捕集和还原制备MeOH

Fig.8 One?pot two?step CO2 capture and hydrogenation to methanol by catalyst 12/PEHA catalysis using a biphasic setup

图9 催化剂配体结构和胺种类对MeOH产率的影响（a）催化剂配体结构（b）胺的种类

Fig.9 Effect of catalyst molecular structures and types of amine

图10 SSAs捕捉CO2再经催化剂12还原为MeOH

Fig.10 SSAs used in catalyzed 12 CO2 capture and hydrogenation

图11 利用碱金属氢氧化物的乙二醇溶液吸收CO2实现催化剂12催化CO2制备MeOH

Fig.11 Integrated CO2 scavenging using alkali hydroxide with ethylene glycol and subsequent catalyst 12 catalyzed CO2 to MeOH

图12 催化剂16用于CO2加氢制备MeOH

Fig.12 The catalyst 16 used in CO2 hydrogenation to MeOH

图13 Fe催化剂17用于CO2加氢MeOH

Fig.13 Fe?based catalyst 17 tested in CO2 hydrogenation to MeOH

图14 催化剂18用于HCOOH歧化制备MeOH

Fig.14 The catalyst 18 used in disproportionation of HCOOH to MeOH

图15 HCOOH歧化制备MeOH的路径

Fig.15 Proposed pathways for the disproportionation of formic acid to MeOH

图16 Ir催化剂19用于HCOOH加氢制备MeOH

Fig.16 Disproportionation HCOOH to MeOH by Ir complex catalyst 19

图17 多核Ir体系用于CO2加氢制备MeOH（a） Himeda等开发的多核Ir催化剂用于（b）催化剂20?m在气固相体系（Cycle 1）和液相体系（Cycle 2）中的反应机理CO2加氢制MeOH X=H or H2O，n=1 or 2

Fig.17 Multinuclear Ir complex catalyst for CO2 hydrogenation to MeOH

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均相催化CO₂加氢制备MeOH的研究进展

Recent Advances on MeOH Production via Homogeneous Catalytic CO₂ Hydrogenation

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