Cu/ZnO/Al2O3改性催化剂上CO2加氢制甲醇的本征动力学  

Intrinsic Kinetics of Hydrogenation of CO2 towards Methanol on a Cu/ZnO/Al2O3 Modified Catalyst

作　　者：车轶菲 李涛[1] 张海涛[1] CHE Yifei;LI Tao;ZHANG Haitao(Engineering Research Center of the Large Scale Reactor Engineering and Technology,Ministry of Education,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]华东理工大学大型工业反应器工程教育部工程研究中心,上海200237

出　　处：《华东理工大学学报（自然科学版）》2020年第3期326-333,共8页Journal of East China University of Science and Technology

摘　　要：在等温积分反应器中探讨了操作条件对CO2加氢制甲醇反应的影响。采用80~100目(150~180μm)Cu/ZnO/Al2O3改性催化剂,在温度240.0~280.0℃、压力4.00~8.00 MPa、原料气H2和CO2的物质的量之比为3.0~3.4条件下探讨了CO2加氢制甲醇的本征动力学,并以甲酸盐加氢为反应速率控制步骤推导出了以各组分逸度表示的双速率本征动力学模型,同时用最大继承法对动力学模型参数进行估值。模型检验和残差分析结果表明,两种动力学模型均适用,相比于文献中以CO2直接解离吸附生成CO的模型,双速率本征动力学模型相对误差更小。Since the industrial revolution,the use of fossil fuels has led to a sharp increase in CO2 emissions,which has caused a series of environmental problems.Therefore,the conversion and utilization of CO2 have become one of the most important green chemistry research topics.Among them,the preparation of methanol from CO2 is considered as a promising resource utilization way.The effects of operating conditions on the hydrogenation of CO2 towards methanol were investigated in an isothermal integral reactor.The experimental results show that under the experimental conditions,higher conversion of CO2 and yield of methanol can be obtained at a reaction temperature of 240.0℃,higher reaction pressure and ratio of hydrogen to CO2.Meanwhile,the intrinsic kinetics of hydrogenation of CO2 towards methanol was studied on a Cu/ZnO/Al2O3 modified catalyst with 80-100 meshes(150-180μm)under the condition of 240.0-280.0℃,4.00-8.00 MPa and 3.0-3.4 of feed gas n(H2)/n(CO2).Orthogonal method was used to design experiments and measure the kinetic data.A double-rate intrinsic kinetic model expressed by the fugacity of each component was deduced by taking the hydrogenation of formate as the rate control step,and its kinetic parameters were estimated by the maximum inheritance method.The statistical test,physicochemical meaning analysis and residual analysis results of the models show that both the kinetic models are applicable,and the relative error of the proposed double-rate kinetic model is smaller than that of the model of CO generation by direct dissociation and adsorption of CO2 in the literature.

关 键 词：二氧化碳 加氢 甲醇合成 动力学模拟 参数估值 

分 类 号：TQ013.2[化学工程]