二氧化碳加氢制甲醇本征反应动力学研究

Study on intrinsic reaction kinetics of carbon dioxide hydrogenation to methanol

为实现“双碳”目标,针对燃煤电厂二氧化碳(CO_(2))制大宗化学品甲醇(CH3OH),在温度为200~280℃、压力为3.0~6.0 MPa、原料气中氢气(H_(2))与CO_(2)物质的量之比为3~9、空速为9600 mL/(g·h)的条件下,研究了二氧化碳加氢制甲醇本征反应动力学,建立了幂函数动力学模型,并回归拟合得到了模型参数;经残差分析及统计校验,表明模型是适当的,可为工业反应器设计提供依据。通过动力学模型模拟,研究了工艺条件对二氧化碳加氢制甲醇反应的影响,并对比分析了实验值与模型计算值,进一步验证了动力学模型的适用性,并得到最优工艺条件,其中温度为260℃、压力为4.5 MPa、原料气中H_(2)与CO_(2)物质的量之比为4。

In order to achieve the“two-carbon”goal,for the production of bulk chemical methanol(CH3OH)from carbon dioxide(CO_(2))in coal-fired power plants,the intrinsic reaction kinetics of carbon dioxide hydrogenation to methanol was studied under the experimental conditions of temperature range from 200℃ to 280℃,pressure range from 3.0 MPa to 6.0 MPa,the molar ratio of hydrogen(H_(2))to CO_(2) in the feed gas range from 3 to 9,and space velocity of 9600 mL/(g·h),the power function kinetics model was established,and the model parameters were gained by regression fitting.The model is appropriate through residual analysis and statistical verification,which can provide a basis for industrial reactor design.The effects of process condition on carbon dioxide hydrogenation to methanol were investigated by kinetic model simulation,the applicability of the kinetic model was further verified by comparing experimental values with model calculated values,and the optimal process condition was gained,where the temperature is 260℃,the pressure is 4.5 MPa,the molar ratio of H_(2) to CO_(2) in the feed gas is 4.