DMO经两种反应路径加氢制乙醇催化剂研究进展

Research progress on catalysts for dimethyl oxalate hydrogenation to ethanol via two reaction pathways

煤基合成气经草酸二甲酯(DMO)加氢制乙醇(EtOH)是合成气间接制EtOH的一条重要路径。在DMO加氢反应过程中,同时存在经乙二醇(EG)中间体加氢制EtOH和经乙酸甲酯(MA)中间体加氢制EtOH两种不同的反应路径。分析了两种不同反应路径的特点,并总结了DMO加氢制EtOH两种不同反应路径所用催化剂及其影响EtOH选择性的关键因素。DMO经EG中间体加氢制EtOH的反应路径通常需要较高的反应温度和多活性位点协同催化,可从载体结构、制备方法以及添加助剂3个方面对常用的Cu基催化剂的催化活性进行调控。DMO经MA中间体加氢制EtOH的反应温度相对较低,常用催化剂以过渡金属碳化物(Mo基和Fe基)为主,但仍存在催化剂加氢能力不足的问题。所总结内容有助于加深对DMO加氢制EtOH两条路径的系统认识,并为未来合理设计和制备高稳定、低成本的DMO加氢制EtOH的催化剂提供参考。

One significant route for producing ethanol(EtOH)indirectly from syngas is the hydrogenation of coal-based syngas to EtOH via dimethyl oxalate(DMO)intermediates.There are two reaction pathways for DMO hydrogenation to EtOH:hydrogenation to EtOH via ethylene glycol(EG)intermediates and hydrogenation to EtOH via methyl acetate(MA)intermediates.The characteristics of two reaction pathways for DMO hydrogenation to EtOH were analyzed,and the catalysts commonly utilized in these pathways and the key factors affecting selectivity of EtOH were summarized.DMO hydrogenation to EtOH via EG intermediates typically requires high reaction temperature and synergistic catalysis of multiple active sites.The catalytic activity of commonly used Cu-based catalysts can be regulated from three aspects:support structure,preparation method and additive addition.The reaction temperature of DMO hydrogenation to EtOH via MA intermediates is relatively low,and commonly used catalysts are mainly transition metal carbides(Mobase and Fe-base),but the hydrogenation capacity of catalysts is still insufficient.It helps to deepen the systematic understanding of the two pathways for DMO hydrogenation to EtOH and provides reference for the rational design and preparation of highly stable and lowcost catalysts for DMO hydrogenation to EtOH in the future.