C306催化剂上甲醇合成宏观动力学研究_陈鹏.docxVIP

第 24 卷第 4 期高 校化 学工 程 学 报No.4Vol.242010 年 8 月Journal of Chemical Engineering of Chinese UniversitiesAug.2010文章编号：1003-9015(2010)04-0602-06C306 催化剂上甲醇合成宏观动力学研究陈鹏, 唐黎华, 张琪,吴勇强, 倪燕慧, 朱子彬(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)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 5 MPa，反应温度为 483.15~523.15 K，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 ф5 mm×5 mm 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 = k1 fCO fH22 (1 ? β1)(1 + KCO fCO + KCO2 fCO2 + KH2 fH2)3 、rCO= ? dNCOdw = k2 fCOf 3(1 ? β2) (1 + KCO fCO + KCO2fCO2+ KHfH)4 ，其中 k = k01exp(?E / RT ) 、 k2= k02exp(?E2/ RT) 。根222H22211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 40605.75 J?mol?1 和 60435.19 J?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。关键词：甲醇合成；宏观动力学；C306 催化剂；模型参数估计中图分类号：文献标识码：AMacro-Kinetics of Methanol Synthesis over C306 CatalystCHEN Peng, TANG Li-hua, ZHANG Qi, WU Yong-qiang, NI Yan-hui, ZHU Zi-bing (Engineering Research Center of Large Scale Reactor Engineering and Technology, Ministry of Education, EastChina University of Science and Technology, Shanghai 200237, China)Abstract: 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,