水煤气变换反应作用下的CO和CO_(2)混合物加氢转化制烃和醇--热力学平衡研究  

Conversion of the CO and CO_(2)mixture to alcohols and hydrocarbons by hydrogenation under the influence of the water-gas shift reaction,a thermodynamic consideration

作　　者：郭淑佳 王晗 秦张峰[1] 李志凯[1] 王国富[1] 董梅[1] 樊卫斌[1] 王建国[1,2] GUO Shu-jia;WANG Han;QIN Zhang-feng;LI Zhi-kai;WANG Guo-fu;DONG Mei;FAN Wei-bin;WANG Jian-guo(State Key Laboratory of Coal Conversion,Institute of Coal Chemistry,Chinese Academy of Sciences,Taiyuan 030001,China;University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]中国科学院山西煤炭化学研究所、煤转化国家重点实验室,山西太原030001 [2]中国科学院大学,北京100049

出　　处：《燃料化学学报（中英文）》2023年第4期482-491,共10页Journal of Fuel Chemistry and Technology

基　　金：supported by the National Key Research and Development Program of China(2020YFB0606404);National Natural Science Foundation of China(21991092,22272195,U2003123,U1910203).

摘　　要：受水煤气变换反应(或其逆反应)的干预,CO(或CO_(2))加氢反应制烃类或醇类化合物经常会遭遇较高的CO_(2)(或CO)选择性,而目标产物烃和醇的选择性往往较低,这使得对相关反应过程的评估显得非常混乱。为此,本工作对水煤气变换反应作用下的CO、CO_(2)及其混合物的加氢转化制烃(以乙烯为例)和醇(以甲醇为例)反应进行了详细的热力学研究。结果表明,对于CO(或CO_(2))加氢反应,水煤气变换(或逆水煤气变换)反应作为连接CO和CO_(2)的连通器,虽然会给CO(或CO_(2))的平衡转化率带来很大的改变并生成大量的CO_(2)(或CO),但其对目标醇和烃产物的碳基平衡收率影响相对较小。CO加氢反应的烃醇产物的碳基平衡收率比CO_(2)加氢反应的高,而CO和CO_(2)混合物加氢的烃醇产物的总碳基平衡收率位于两者之间。对于CO和CO_(2)混合物加氢,尽管CO或CO_(2)的平衡转化率随原料组成的不同有较大幅度的变化,但烃醇产物的总碳基平衡收率变化较为简单,即随着CO_(2)/(CO+CO_(2))摩尔比的增大而线形降低。鉴于CO或CO_(2)加氢过程的尾气均为CO和CO_(2)混合物,用CO和CO_(2)混合物加氢制烃醇或许更为有利;无论CO、CO_(2)还是其混合物的加氢过程,都应以目标产物的碳基总收率作为评估指标。Due to the intervention from the water-gas shift(WGS)reaction(or the reverse one(RWGS)),the hydrogenation of CO(or CO_(2))into alcohols and hydrocarbons often displays rather high selectivity to CO_(2)(or CO),which makes it rather puzzling to evaluate such conversion processes by using the relatively low selectivity to the target products.Herein,a thermodynamic consideration is made to elaborately evaluate the effect of the WGS/RWGS reaction on the hydrogenation of CO,CO_(2),and their mixture to typical alcohols(e.g.methanol)and hydrocarbons(e.g.ethene).The results indicate that for the hydrogenation of CO(or CO_(2)),although the WGS(or RWGS)reaction,acting as a communicating vessel connecting CO and CO_(2),may have a severe influence on the equilibrium conversion of CO(or CO_(2)),forming a large amount of CO_(2)(or CO),it only has a relatively minor impact on the C-based equilibrium yield of the target alcohol/hydrocarbon product.The hydrogenation of CO shows a higher C-based equilibrium yield for the target product than the hydrogenation of CO_(2),while the overall C-based equilibrium yield of target product for the hydrogenation of the CO and CO_(2)mixture just lies in between.For the hydrogenation of the CO and CO_(2)mixture,although the equilibrium conversion of CO and CO_(2)may vary greatly with the change in the feed composition,the relation between the overall C-based equilibrium yield of the target product and the feed composition is rather simple;that is,the overall C-based equilibrium yield of alcohol/hydrocarbon product decreases almost lineally with the increase of the CO_(2)/(CO+CO_(2))molar ratio in the feed.These results strongly suggest that the mixture of CO and CO_(2)is credible in practice for the production of alcohols and hydrocarbons through hydrogenation,where the overall C-based yield should be used as the major index for the hydrogenation of CO,CO_(2),and their mixture.

关 键 词：热力学平衡 CO_(2)加氢 CO加氢 水煤气变换 总碳基收率 甲醇 乙烯 CO和CO_(2)混合物 

分 类 号：O643.36[理学—物理化学]