二氧化碳加氢制低碳烯烃技术进展
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摘要
以二氧化碳为原料加氢制备低碳烯烃,不但能够缓解二氧化碳排放带来的环保压力,更能实现二氧化碳资源的有效利用。从热力学方面考虑,低温、高压有利于低碳烯烃的生成,适宜的反应条件应该是温度573～673K、压力2.0～3.0MPa、H_2/CO_2=3,在该条件下二氧化碳的平衡转化率为72.8%～74.5%。二氧化碳直接加氢制低碳烯烃可分为两个步骤:逆水气转换反应和连续的费托合成。目前在二氧化碳制备低碳烯烃过程中,降低烷烃特别是甲烷的生成以及提高某一烯烃的选择性是研究的重点。关于反应机理的研究非常多,但结论并不完全一致,这是因为催化剂不同,对二氧化碳的吸附形式就可能不同,产生的中间体就不同,反应机理也就不同。单金属Fe基催化剂在二氧化碳加氢反应中表现出良好的催化性能,一直是首选的催化剂,通过引入其他组分形成双金属或多金属催化剂,其催化性能比单金属催化剂进一步提高。对于二氧化碳加氢制低碳烯烃反应,载体的作用同样不可忽视,甚至是非常重要的。通过电催化方法也可以将二氧化碳转化为低碳烯烃,由于电催化还原二氧化碳可在常温常压下进行,且使用廉价的Cu催化剂就可以将二氧化碳转化为碳氢化合物,因此其在二氧化碳利用方面表现出良好的前景。
The hydrogenation of carbon dioxide for preparing low carbon olefins can not only relieve the environmental pressure caused by carbon dioxide emissions,but also effectively utilize carbon dioxide resources.From the thermodynamic point of view,low temperature and high pressure are beneficial to the formation of low carbon olefins.Suitable reaction temperature should be 573 ～673K,reaction pressure should be 2.0-3.0MPa,and the H_2/CO_2 should be 3.Under these conditions,the equilibrium conversion of carbon dioxide is72.8% ～74.5%.The direct hydrogenation of carbon dioxide to low carbon olefins can be divided into two steps,i.e.reverse water gas shift reaction and continuous Fischer-Tropsch synthesis.At present,during the preparation of low carbon olefins from carbon dioxide,reducing the formation of paraffin,especially methane,and improving the selectivity of a certain olefin are the focus of research.There are many studies on the re-action mechanism,but the conclusions are not exactly the same,because the catalysts are different,the carbon dioxide adsorption form may be different,the intermediates produced are different,and the reaction mechanisms are different.With good catalytic performance,single metal Fe-based catalyst has been the preferred catalyst in carbon dioxide hydrogenation reaction.By introducing other components to form bimetallic or polymetallic catalyst,its catalytic performance can be further improved.For the hydrogenation reaction of carbon dioxide to low carbon olefins,the role of the carrier cannot be ignored,and even it is very important.Carbon dioxide can also be converted into low carbon olefins by electrocatalysis.Since electrocatalytic reduction of carbon dioxide can be carried out at normal temperature and pressure,and carbon dioxide can be converted into hydrocarbons using an inexpensive Cu catalyst,it has good prospects in the utilization of carbon dioxide.
The hydrogenation of carbon dioxide for preparing low carbon olefins can not only relieve the environmental pressure caused by carbon dioxide emissions,but also effectively utilize carbon dioxide resources.From the thermodynamic point of view,low temperature and high pressure are beneficial to the formation of low carbon olefins.Suitable reaction temperature should be 573 ～673K,reaction pressure should be 2.0-3.0MPa,and the H_2/CO_2 should be 3.Under these conditions,the equilibrium conversion of carbon dioxide is72.8% ～74.5%.The direct hydrogenation of carbon dioxide to low carbon olefins can be divided into two steps,i.e.reverse water gas shift reaction and continuous Fischer-Tropsch synthesis.At present,during the preparation of low carbon olefins from carbon dioxide,reducing the formation of paraffin,especially methane,and improving the selectivity of a certain olefin are the focus of research.There are many studies on the re-action mechanism,but the conclusions are not exactly the same,because the catalysts are different,the carbon dioxide adsorption form may be different,the intermediates produced are different,and the reaction mechanisms are different.With good catalytic performance,single metal Fe-based catalyst has been the preferred catalyst in carbon dioxide hydrogenation reaction.By introducing other components to form bimetallic or polymetallic catalyst,its catalytic performance can be further improved.For the hydrogenation reaction of carbon dioxide to low carbon olefins,the role of the carrier cannot be ignored,and even it is very important.Carbon dioxide can also be converted into low carbon olefins by electrocatalysis.Since electrocatalytic reduction of carbon dioxide can be carried out at normal temperature and pressure,and carbon dioxide can be converted into hydrocarbons using an inexpensive Cu catalyst,it has good prospects in the utilization of carbon dioxide.
引文
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