二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展

doi:10.16085/j.issn.1000-6613.2023-0837

摘要/Abstract

摘要：

二氧化碳加氢制甲醇反应研究对解决能源紧缺和环境问题具有重要意义。以Cu/ZnO/Al₂O₃为代表的铜基催化剂因其反应活性高、成本低廉而备受关注，受限于催化剂中Cu物种的电子结构多样性与表征技术的发展水平，铜基催化剂的真实活性位点、反应机理尚不清楚。本文综述了二氧化碳加氢制甲醇过程中铜基催化剂活性位点的研究进展，并结合原位表征技术的研究进展对其反应机理进行综述。研究人员结合多种先进表征手段确定了活性位点的结构和组成，同时揭示了不同催化剂结构对反应性能的影响。通过原位表征技术的应用，可以实时观察反应过程中催化剂的结构变化，揭示了反应关键步骤和催化剂的作用方式。未来可以结合更多原位表征技术和计算模拟方法，探索催化剂微观结构和反应机理，以更高的反应性能制备绿色甲醇。

关键词: 二氧化碳加氢, 甲醇合成, 铜基催化剂, 活性位点, 原位表征技术

Abstract:

The study of carbon dioxide hydrogenation to methanol reaction holds significant importance in addressing energy shortages and environmental issues. Copper-based catalysts, such as Cu/ZnO/Al₂O₃, have attracted great attention due to their high reactivity and low cost. However, limited by the electronic structure diversity of the Cu species in the catalysts and insufficient characterization techniques, the true active sites and reaction mechanisms of the Cu-based catalysts are still unclear. This paper reviews the research progress on the active sites of copper-based catalysts for the hydrogenation of carbon dioxide to methanol, and the reaction mechanism in conjunction with the research progress of in-situ characterization techniques. By combining various advanced characterization techniques, researchers determined the structure and composition of the active sites, as well as reveals the effects of different catalyst structures on the reaction performance. Through the application of in-situ characterization techniques, the structural changes of catalysts during the reaction process can be observed in real-time, revealing the key steps of the reaction and the action mode of catalysts. In the future, more in-situ characterization techniques and computational simulation methods can be combined to explore the catalyst microstructure and reaction mechanism to prepare green methanol with better reaction performance.

Key words: CO₂ hydrogenation, methanol synthesis, Cu-based catalysts, active site, in-situ characterization technique

中图分类号:

TQ426

时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.

SHI Yongxing, LIN Gang, SUN Xiaohang, JIANG Weigeng, QIAO Dawei, YAN Binhang. Research progress on active sites in Cu-based catalysts for CO₂ hydrogenation to methanol[J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 287-298.

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时间	单位/机构	规模	技术特点
2009年	三井化学公司	—
2009年	日本三菱重工	100t/a	Cu/ZnO/Al₂O₃，9MPa，247℃
2010年	德国鲁齐	—	Cu/ZnO/Al₂O₃，5~8MPa，220~270℃
2013年	冰岛碳循环公司	中试及示范，1000~4000t/a	地热CO₂-发电，托普索技术
2016年	中国科学院山西煤炭化学研究所	单管试验	Cu/ZnO/Al₂O₃
2016年	中国科学院上海高等研究院/上海华谊集团	—	工业单管试验成功
2018年	德国克莱恩	—	Cu/ZnO/Al₂O₃，MegaMax
2019年	中国石油大庆油田	实验室放大	Cu/ZnO/Al₂O₃，大连瑞克技术
2020年	中国科学院大连化学物理研究所	中试及示范，1200t/a	光伏-电解水制氢，ZnZrO _x
2020年	中国科学院上海高等研究院	工业侧线，5000t/a	富碳天然气，Cu/ZnO/Al₂O₃

时间	单位/机构	规模	技术特点
2009年	三井化学公司	—
2009年	日本三菱重工	100t/a	Cu/ZnO/Al₂O₃，9MPa，247℃
2010年	德国鲁齐	—	Cu/ZnO/Al₂O₃，5~8MPa，220~270℃
2013年	冰岛碳循环公司	中试及示范，1000~4000t/a	地热CO₂-发电，托普索技术
2016年	中国科学院山西煤炭化学研究所	单管试验	Cu/ZnO/Al₂O₃
2016年	中国科学院上海高等研究院/上海华谊集团	—	工业单管试验成功
2018年	德国克莱恩	—	Cu/ZnO/Al₂O₃，MegaMax
2019年	中国石油大庆油田	实验室放大	Cu/ZnO/Al₂O₃，大连瑞克技术
2020年	中国科学院大连化学物理研究所	中试及示范，1200t/a	光伏-电解水制氢，ZnZrO _x
2020年	中国科学院上海高等研究院	工业侧线，5000t/a	富碳天然气，Cu/ZnO/Al₂O₃

活性位点	催化剂	温度 /℃	压力 /MPa	转化率/%	甲醇选择性/%
Cu⁰	Cu/ZnO/ZrO₂^[40]	200	—	15.5	42.1
	Cu/ZnO/Al₂O₃^[40]	200	—	15.27	40.47
	Cu/ZnO/TiO₂^[40]	200	—	10.57	53.89
	Cu/ZnO/Y₂O₃^[40]	200	—	10.46	49.21
	Cu/t-ZrO₂^[41]	300	8	13.96	92.62
	Cu/m-ZrO₂^[41]	300	8	9.28	79.87
	Cu/am-ZrO₂^[41]	300	8	11.3	74.69
	Cu/ZnO/Al₂O₃/SiO₂^[63]	210	3.4	11.7	48.0
	Cu/ZnO-In₂O₃^[64]	280	2	6.3	84.5
Cu⁺	K-Cu _x O/ Cu (111)^[43]	220	5	—	64.14
	Cu/ZnO/Al₂O₃^[44]	200	2	5.19	67.5
	Cu/SiO₂^[45]	320	3	28.0	21.3
	YBa₂Cu₃O₇^[46]	240	3	3.4	34.8
	Cu/SiO₂^[47]	190	3	5.0	79.3
Cu ^δ⁺	CuO/ZrO₂^[52]	240	2	2.4	49.4
	Cu/ZrO₂^[53]	240	1.5	0.36	43.08
	Pd-Cu/ZrO₂^[53]	240	1.5	1.72	53.83
	Cu/ZrO₂^[54]	220	3	6.8	64.4
	Cu-ZnO/ Al₂O₃-ZrO₂^[55]	240	5	14.8	75.8
Cu/ZnO 界面	CuZnAuAl^[58]	270	5	30.0	98.8

活性位点	催化剂	温度 /℃	压力 /MPa	转化率/%	甲醇选择性/%
Cu⁰	Cu/ZnO/ZrO₂^[40]	200	—	15.5	42.1
	Cu/ZnO/Al₂O₃^[40]	200	—	15.27	40.47
	Cu/ZnO/TiO₂^[40]	200	—	10.57	53.89
	Cu/ZnO/Y₂O₃^[40]	200	—	10.46	49.21
	Cu/t-ZrO₂^[41]	300	8	13.96	92.62
	Cu/m-ZrO₂^[41]	300	8	9.28	79.87
	Cu/am-ZrO₂^[41]	300	8	11.3	74.69
	Cu/ZnO/Al₂O₃/SiO₂^[63]	210	3.4	11.7	48.0
	Cu/ZnO-In₂O₃^[64]	280	2	6.3	84.5
Cu⁺	K-Cu _x O/ Cu (111)^[43]	220	5	—	64.14
	Cu/ZnO/Al₂O₃^[44]	200	2	5.19	67.5
	Cu/SiO₂^[45]	320	3	28.0	21.3
	YBa₂Cu₃O₇^[46]	240	3	3.4	34.8
	Cu/SiO₂^[47]	190	3	5.0	79.3
Cu ^δ⁺	CuO/ZrO₂^[52]	240	2	2.4	49.4
	Cu/ZrO₂^[53]	240	1.5	0.36	43.08
	Pd-Cu/ZrO₂^[53]	240	1.5	1.72	53.83
	Cu/ZrO₂^[54]	220	3	6.8	64.4
	Cu-ZnO/ Al₂O₃-ZrO₂^[55]	240	5	14.8	75.8
Cu/ZnO 界面	CuZnAuAl^[58]	270	5	30.0	98.8

原位表征技术	类型	原理	工作条件	探测深度	用于识别活性位点的结构信息	局限性
扫描隧道显微镜	—	隧道效应	大气、真空	1~2原子层	结构和缺陷	（1）表面微粒之间的沟槽不能准确探测（2）受限于材料的导电性
X射线衍射	散射光谱	Bragg衍射	超高真空至30MPa 77~2273K	体相	相结构和缺陷位置	不适用于结晶度低的催化剂
拉曼光谱	散射光谱	Raman散射	超高真空至50MPa 77~1237K	约10nm	相结构	（1）拉曼散射效应的低频导致的微弱信号强度（2）激光可能会加热样品并扰动分析区域
红外光谱	吸收光谱	共振吸收	超高真空至3MPa 77~1237K	表面	吸附中间体 /化学结构	（1）不适用于水溶液（2）由于高温下红外区域中的样品发射，无法在高温下用傅里叶变换红外光谱进行原位研究
X射线光电子能谱	激发光谱	光电效应	超高真空至3kPa 80~1200K	<2nm	电子结构	不适用于具有压敏表面结构的催化剂
X射线吸收光谱	吸收光谱	共振吸收	超高真空至30MPa 80~1773K	体相	电子结构和局部协调环境	（1）相对不适用于含有有机分子的轻元素（2）内部工作通常成本高昂，需要基础设施和辐射源