C306催化剂上甲醇合成宏观动力学研究  

Macro-Kinetics of Methanol Synthesis over C306 Catalyst

作　　者：陈鹏[1] 唐黎华[1] 张琪[1] 吴勇强[1] 倪燕慧[1] 朱子彬[1] 

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中心,上海200237

出　　处：《高校化学工程学报》2010年第4期602-607,共6页Journal of Chemical Engineering of Chinese Universities

摘　　要：在内循环无梯度反应器中对C306铜基催化剂甲醇合成反应宏观动力学进行了研究。实验压力为5MPa,反应温度为483.15～523.15K,原料气气体组成与工业生产条件类似,内循环无梯度反应器满足宏观动力学实验要求。实验采用工业原粒度ф5mm×5mm圆柱状催化剂,选取各组成以逸度表示的CO、CO2加氢合成甲醇的Langmuir-Hinshelwood-Hougen-Watson型宏观动力学模型,即:rco=-dNCOdw=k1fCOfH22(1-β1)(1+KCOfCO+KCO2fCO2+KH2fH2)3、rCO2=-dNCO2dw=k2fCO2fH32(1-β2)(1+KCOfCO+KCO2fCO2+KH2fH2)4,其中k1=k01exp(-E1/RT)、k2=k02exp(-E2/RT)。根据测定的20套动力学实验数据,运用改进的遗传算法和马夸特算法相结合的方法,通过计算机数值模拟确定动力学参数,其中CO和CO2的指前因子k01、k02分别为379.9和5405.2,活化能E1、E2分别为40605.75J·mol-1和60435.19J·mol-1。残差分析和统计检验表明,动力学模型是适定的。与同等条件下的其它国产催化剂比较表明,催化剂C306低温段的甲醇生成反应速率最高。In an internal recycle gradientless reactor,the experiments of methanol synthesis by hydrogenating CO and CO2 over C306 Cu-based catalyst with various mole compositions of syngas and under the pressure of 5 MPa,temperature of 483.15～523.15 K were conducted.The used C360 catalyst is cylindrical particles with the size of Φ5 mm×5 mm.The Langmuir-Hinshelwood-Hougen-Watson type macro-kinetic models were used to express the macro-kinetics of the above synthesis process,and in the proposed models,the reactant components were expressed by their fugacity.The factors of the proposed double rate macro-kinetic models were determined by fitting 20 sets of experimentally obtained mole fractions of all reactants;and in order to estimate the kinetic parameters of the proposed models,the method of improved Genetic Algorithm integrated with Marquardt method was used.The calculations show that the pre-exponential factors of CO and CO2 are 379.9 and 5405.2,respectively,and the activation energies of them are 40605.75 J·mol-1 and 60435.19 J·mol-1,respectively.The residual error distributions and the statistic tests show that the proposed macro-kinetic models are reliable and adequate.Compared with other conventional used methanol synthesis catalysts,the C306 catalyst used in this study shows the highest methanol formation rate at the lower temperature stage.

关 键 词：甲醇合成 宏观动力学 C306催化剂 模型参数估计 

分 类 号：TQ316.333[化学工程—高聚物工业]