浆态床甲醇合成催化剂的研制及反应宏观动力学研究

Study on preparation and macrokinetics of catalyst for methanol synthesis in slurry bed

针对CuO-ZnO-Al2O3(CZA)催化剂在浆态床热介质中Al2O3易流失的问题,制备了CuO-ZnO(CZ)浆态床甲醇合成催化剂。考察了CZA和CZ两种催化剂在200~230℃温度下的浆态床甲醇合成催化性能,并研究了浆态床甲醇合成反应宏观动力学。结果表明:在浆态床甲醇合成反应中,CZ催化剂性能优于CZA催化剂;在5 MPa、220℃反应条件下,CZ催化剂上CH3OH物质的量分数达到17.04%,接近热力学平衡物质的量分数17.58%。选取双曲型动力学方程的形式建立了以各组分逸度表示的CO,CO2加氢合成甲醇的双速率宏观动力学模型,用参数估值方法获得了动力学模型参数,残差分析和统计检验表明动力学模型是适合的。

The CuO-ZnO(CZ)catalyst is prepared to overcome the defect of Al2O3 in CuO-ZnO-Al2O3(CZA) catalyst easily losing in heat medium of slurry bed reactor.The catalytic performance of CZA and CZ catalysts for methanol synthesis in slurry bed at 200-230 ℃ is investigated,and the macrokinetics of methanol synthesis in slurry bed is also studied.The results show that the performance of CZ catalyst is better than that of CZA catalyst in slurry bed methanol synthesis reaction.The molar fraction of CH3OH on CZ catalyst reaches 17.04% under the reaction conditions of 5 MPa and 220 ℃,which is close to the molar fraction of thermodynamic equilibrium 17.58%.The dual-rate macrokinetics model for methanol synthesis from the hydrogenation of CO and CO2 is proposed using the Langmuir-Hinshelwood type kinetics expressions in the form of reactant fugacity, and the kinetic model parameters are obtained by the parameter estimation. The residual error distribution and statistic test show that the macrokinetics model is suitable.