逆水煤气变换反应研究进展

doi:10.16085/j.issn.1000-6613.2022-0816

摘要/Abstract

摘要：

逆水煤气变换（RWGS）反应是将二氧化碳（CO₂）加氢转化为甲醇、低碳烯烃、芳烃以及汽油等高附加值化学品和燃料的关键步骤，对于实现CO₂资源化利用具有重要意义。本文综述了近年来RWGS反应的研究进展，包括RWGS反应热力学分析、催化机理、可选择的催化剂种类以及提升催化剂性能策略等方面。文章从热力学角度分析，RWGS反应在高温下有利，而低温下存在甲烷化竞争反应。RWGS反应机理主要包括氧化还原机理以及缔合机理，其中缔合机理包括甲酸盐路径和羧酸盐路径等。相比于其他催化体系，负载型金属催化剂展现出较优异的RWGS反应性能。另外，通过添加碱金属助剂、形成双金属合金以及选择合适载体和减小金属颗粒尺寸以优化金属-载体相互作用等手段可实现低温高效稳定的RWGS反应催化剂的设计开发。

关键词: 逆水煤气变换反应, 二氧化碳, 一氧化碳, 热力学, 催化剂

Abstract:

Reverse water gas conversion (RWGS) reaction is a key step in the catalytic hydrogenation of carbon dioxide (CO₂) to high value-added chemicals and fuels such as methanol, light olefins, aromatics and gasoline, which is of great significance for the utilization of CO₂. This review summarizes the research progress of RWGS reaction in recent years, including thermodynamic analysis of RWGS reaction, catalytic mechanisms, selective catalysts and strategies to improve the performance of catalysts. From the perspective of thermodynamics, RWGS reaction is favorable at high temperature, as methanation reaction emerges at low temperature. The mechanisms of RWGS reaction mainly consist of redox mechanism and association mechanism, and the latter further contains a formate route and/or carboxylate route. Compared with other catalyst system, supported metal catalysts commonly exhibit a superior RWGS reaction performance. In addition, the rational design of RWGS reaction catalysts with high reactivity and durability could be realized by adding alkali metal additives, forming bimetallic alloy as well as modulating the metal-support interaction via selecting a good support or reducing the metal particle size.

Key words: reverse water gas shift reaction, carbon dioxide, carbon monoxide, thermodynamics, catalyst

中图分类号:

TQ073

王晓月, 张伟敏, 姚正阳, 郭晓宏, 李聪明. 逆水煤气变换反应研究进展[J]. 化工进展, 2023, 42(3): 1583-1594.

WANG Xiaoyue, ZHANG Weimin, YAO Zhengyang, GUO Xiaohong, LI Congming. Research progress of reverse water gas shift reaction[J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1583-1594.

图/表 17

图1 在压力为0.1MPa、H2/CO2摩尔比为3/1时，温度对RWGS反应热力学平衡的影响[15]

图2 钾在Pt/莫来石催化剂上逆水煤气反应中的促进作用[26]

图3 Pt/CeO2催化剂上逆水煤气变换反应活性位点的鉴定及机理研究[29]

图4 Pt/TiO2催化剂上RWGS反应路径[30]

图5 Pt/CeO2催化剂上逆水煤气反应活性位点证明及机理研究[31]

图6 Pd/Al2O3催化剂上CO2加氢反应机理：动力学和瞬态漂移-质谱研究[33]

图7 单个金属活性位点浓度及稳定性控制催化CO2的还原选择性[34]

图8 负载型金属催化剂关于CO2向CO高选择性转化的理论见解和相应结构[35]

图9 不同载体负载的Cu基催化剂的产物选择性[37]

图10 Ni/CeO2、Fe/CeO2和Fe-掺杂Ni/CeO2催化剂CO2转化的相对活性[44]

图11 In2O 3 -CeO 2 催化剂上的逆水煤气变换[46]

图12 在钙钛矿型氧化物上CO2的逆水煤气化学循环转化[51]

图13 质量分数1% Cu/β-Mo2C催化剂和36% Cu/ZnO/Al2O3催化剂在RWGS反应中的稳定性性能[53]

图14 在钙钛矿型氧化物上CO2的逆水煤气化学循环转化[54]

图15 低温重构CeO2负载Ru纳米颗粒决定CO2催化还原的选择性[55]

图16 Cu促进的C2O3-Fe3O4氧化物催化剂上CO2活化期间活性氧中间体的性质[23]

图17 在RWGS反应转化率为10%时，d带中心对CO/CH4产率的影响[60]

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