CO_(2)加氢制甲醇催化剂与项目进展

Advances in catalysts and project progress for CO_(2)hydrogenation to methanol

甲醇是重要的有机化工原料和优质燃料。在气候危机、能源危机背景下,发展甲醇经济利于实现化工、能源和交通运输行业绿色低碳转型,保障能源供应安全。系统地介绍了两步法、一步法CO_(2)加氢制甲醇工艺路线,分析、归纳和梳理了铜基、铟基、固溶体与贵金属催化剂性能表现。由数据可知4类催化剂反应条件集中分布在200~300℃,1.5~5.0 MPa。铜基催化剂是目前研究和应用最广的催化剂,其CO_(2)转化率和甲醇选择性中位数分别为13.6和69.2。与铜基催化剂相比,铟基催化剂和固溶体催化剂CO_(2)转化率和甲醇选择性与铜基催化相当,但稳定性更优。而贵金属催化剂CO_(2)转化率(最佳值66,最小值0.6)和甲醇选择性(最佳值100,最小值11)极值差别大且少见稳定性相关的数据。固溶体催化剂在工业条件表现出优异的催化性能和稳定性,可能成为未来规模化应用的催化剂种类之一。此外,梳理了国内和国际现有CO_(2)加氢制甲醇的项目与技术路线。目前国内外二氧化碳加氢制甲醇项目数量不断增多,其中部分已建成投产,甲醇生产能力从4000 t/a到200000 t/a不等。目前这些项目甲醇生产碳源主要来自工业排放源CO_(2)捕集装置,而氢气主要通过电解水获取。碳中和目标下,CO_(2)加氢制甲醇技术的重要性愈发显著,建议从CO_(2)加氢制甲醇催化剂技术研发和项目产业化应用方面加大支持力度。

Methanol is a crucial organic raw material and fuel,particularly in the context of the climate and energy crisis.Developing a methanol economy is crucial to promoting a green,low-carbon transformation of the chemical,energy,and transportation sectors while ensuring a secure energy supply.A comprehensive overview of the CO_(2)hydrogenation process routes to methanol was offered,including an analysis and summary of the performance of copper-based,indium-based,solid solution,and noble metal catalysts.The data show that the reaction conditions of all four types of catalysts are concentrated at 200-300℃and 1.5-5.0 MPa.While copper-based catalysts were the most widely studied and applied,with a median CO_(2)conversion and methanol selectivity of 13.6 and 69.2,respectively,indium-based catalysts and solid solution catalysts have comparable CO_(2)conversion and methanol selectivity but exhibit better stability.The extreme values of CO_(2)conversion and methanol selectivity for noble metal catalysts vary significantly,with limited data related to stability.Solid solution catalysts demonstrate exceptional catalytic performance and stability under industrial conditions,making them a promising catalyst type for large-scale application in the future.Furthermore,this paper provides an overview of existing CO_(2)hydrogenation to methanol projects and technical routes both domestically and abroad.The number of carbon dioxide hydrogenation to methanol projects is increasing,with production capacities ranging from 4000 t/a to 200000 t/a.Industrial emission source CO_(2)capture devices as the carbon source and electrolytic water as the primary source of hydrogen were primarily relied on.As the goal of carbon neutralization becomes increasingly critical,the CO_(2)hydrogenation to methanol technology becomes even more vital.Therefore,it is recommended that research and development of CO_(2)hydrogenation to methanol catalyst technology receive greater support,as well as industrial application of the project.