通过产物转化分离推动CO2加氢制甲醇过程的研究进展

doi:10.16085/j.issn.1000-6613.2024-0341

摘要/Abstract

摘要：

将过量排放的CO₂加氢合成高附加值甲醇的过程因受热力学限制使其原料转化利用率较低，通过产物转化分离的方式能够打破热力学平衡，从而推动反应正向进行，提高CO₂转化率。本文以将甲醇作为中间体耦合其他反应继续转化成低碳烯烃、芳烃等化工原料，以及利用膜反应器将副产水原位脱除等两种典型的产物转化分离方式为中心，分别展开论述其在促进CO₂加氢反应过程中，耦合反应条件优化、催化剂筛选制备以及分子筛膜反应器设计与改性等方面的研究现状。重点讨论了耦合反应的双功能型催化剂中分子筛载体的酸性与孔道结构对反应性能的影响，并分析了膜反应器未来的研发重点与难点在于进一步提高其制备可重复性。

关键词: CO₂加氢, 甲醇, 热力学, 低碳烯烃, 芳烃, 膜反应器

Abstract:

The synthesis of high value-added methanol by hydrogenation of excess CO₂ is limited by thermodynamics equilibrium, resulting in lower conversion and utilization efficiency of raw materials. Product transformation and separation can promote the forward progress of CO₂ hydrogenation reaction. This article centers around two most typical methods, namely using methanol as an intermediate to further produce low-carbon olefins and aromatics, and utilizing membrane reactors to remove by-product water in situ. The research progress in promoting CO₂ hydrogenation process through the above two means is specifically discussed from the aspects of condition optimization of coupled reaction, catalysts preparation, and membrane reactors design and modification. The influence of acidity and pore structure of molecular sieve supports on coupled reaction performance is also analyzed. Moreover, the key and challenge for further research of membrane reactors is to improve the preparation repeatability.

Key words: CO₂ hydrogenation, methanol, thermodynamics, low-carbon olefins, aromatics, membrane reactors

中图分类号:

O643.3

周秋明, 牛丛丛, 吕帅帅, 李红伟, 文富利, 徐润, 李明丰. 通过产物转化分离推动CO₂加氢制甲醇过程的研究进展[J]. 化工进展, 2024, 43(5): 2776-2785.

ZHOU Qiuming, NIU Congcong, LYU Shuaishuai, LI Hongwei, WEN Fuli, XU Run, LI Mingfeng. Promoting CO₂ hydrogenation to methanol through product transformation and separation[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2776-2785.

图/表 13

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催化剂	温度/℃	压力/MPa	CO₂转化率/%	低碳烯烃选择性/%	参考文献
In₂O₃-ZrO₂/SAPO-34	400	3.0	35.0	80.0	[2]
ZnO-ZrO₂/SAPO-34	380	2.0	12.6	80.0	[5]
ZnGa₂O₄/SAPO-34	370	3.0	13.0	86.0	[6]
ZnAl₂O₄/SAPO-34	370	3.0	15.0	87.0	[6]
In₂O₃/SAPO-34	360	2.5	34.6	70.0	[8]
CZZ@SAPO-34	400	2.0	19.6	60.5	[9]
CuO-ZnO/SAPO-34	400	3.0	43.5	63.9	[10]
ZnZrO _x /bio-SAPO-34	380	3.0	13.8	83.0	[11]
ZZ/4%MnSAPO-34	380	2.0	17.3	83.2	[12]

催化剂	温度/℃	压力/MPa	CO₂转化率/%	低碳烯烃选择性/%	参考文献
In₂O₃-ZrO₂/SAPO-34	400	3.0	35.0	80.0	[2]
ZnO-ZrO₂/SAPO-34	380	2.0	12.6	80.0	[5]
ZnGa₂O₄/SAPO-34	370	3.0	13.0	86.0	[6]
ZnAl₂O₄/SAPO-34	370	3.0	15.0	87.0	[6]
In₂O₃/SAPO-34	360	2.5	34.6	70.0	[8]
CZZ@SAPO-34	400	2.0	19.6	60.5	[9]
CuO-ZnO/SAPO-34	400	3.0	43.5	63.9	[10]
ZnZrO _x /bio-SAPO-34	380	3.0	13.8	83.0	[11]
ZZ/4%MnSAPO-34	380	2.0	17.3	83.2	[12]

催化剂	温度/℃	压力/MPa	CO₂转化率/%	C₅₊中芳烃选择性/%	参考文献
ZnZrO/ZSM-5	320	4.0	14.1	73.0	[30]
ZnZrO _x /HZSM-5	315	3.0	17.5	60.3	[31]
ZnO-ZrO₂/ZSM-5	340	4.0	14.0	74.0	[32]
ZnO/ZrO₂-Z5-300	340	3.0	9.0	70.0	[33]
ZnCrO _x -ZnZSM-5	320	5.0	19.9	81.1	[34]
ZnCr₂O₄-ZSM-5	350	4.0	23.4	66.1	[35]
ZnAlO _x /HZSM-5	320	3.0	5.8	73.9	[36]
Cr₂O₃/H-ZSM-5	350	3.0	34.5	76.0	[37]
Cr₂O₃/Zn-ZSM-5@SiO₂	350	3.0	22.1	58.4	[38]
In₂O₃/HZSM-5	320	3.0	23.2	34.1	[39]
ZnFeO _x -4.25Na/S-HZSM-5	320	3.0	41.2	75.6	[40]

催化剂	温度/℃	压力/MPa	CO₂转化率/%	C₅₊中芳烃选择性/%	参考文献
ZnZrO/ZSM-5	320	4.0	14.1	73.0	[30]
ZnZrO _x /HZSM-5	315	3.0	17.5	60.3	[31]
ZnO-ZrO₂/ZSM-5	340	4.0	14.0	74.0	[32]
ZnO/ZrO₂-Z5-300	340	3.0	9.0	70.0	[33]
ZnCrO _x -ZnZSM-5	320	5.0	19.9	81.1	[34]
ZnCr₂O₄-ZSM-5	350	4.0	23.4	66.1	[35]
ZnAlO _x /HZSM-5	320	3.0	5.8	73.9	[36]
Cr₂O₃/H-ZSM-5	350	3.0	34.5	76.0	[37]
Cr₂O₃/Zn-ZSM-5@SiO₂	350	3.0	22.1	58.4	[38]
In₂O₃/HZSM-5	320	3.0	23.2	34.1	[39]
ZnFeO _x -4.25Na/S-HZSM-5	320	3.0	41.2	75.6	[40]

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通过产物转化分离推动CO₂加氢制甲醇过程的研究进展

Promoting CO₂ hydrogenation to methanol through product transformation and separation

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