Fe-HZSM-5分子筛催化剂的甲醇制汽油动力学研究  

Study on kinetics of methanol to gasoline over Fe-HZSM-5 catalysts

作　　者：王晓龙[1] 吴成成 肖天存 王琪 王有和 季生福[2] Wang Xiaolong;Wu Chengcheng;Xiao Tiancun;Wang Qi;Wang Youhe;Ji Shengfu(Huaneng Clean Energy Research Institute,Beijing 102209,China;State Key Laboratory of Chemical Resource Engineering,Beijing University of Chemical Technology,Beijing 100029,China;State Key Laboratory of clean coal-based energy,Beijing 102209,China;Beijing Key Laboratory of CO2 capture and utilization,Beijing 102209,China)

机构地区：[1]中国华能集团清洁能源技术研究院有限公司,北京102209 [2]北京化工大学化工资源有效利用国家重点实验室,北京100029 [3]煤基清洁能源国家重点实验室,北京10229 [4]二氧化碳捕集与处理北京市重点实验室,北京102209

出　　处：《工业催化》2018年第5期89-96,共8页Industrial Catalysis

基　　金：中国华能集团有限公司科技项目(TY-15-HJK02)

摘　　要：通过水热晶化法,合成含有骨架杂原子Fe的Fe-HZSM-5分子筛催化剂,采用XRD、BET和NH3-TPD对催化剂进行表征,在微型固定床反应器中测定催化剂的甲醇制汽油的反应性能和反应动力学数据,对Fe-HZSM-5分子筛催化剂的甲醇制汽油本征动力学进行研究。结果表明,ZSM-5分子筛骨架引入杂原子Fe,可以增加对产物汽油选择性有利的弱酸量。采用Chen and Reagan建立的甲醇制汽油三集总动力学模型,通过Runge-Kutta法和最小二乘法对实验数据的回归计算,获得反应速率常数为k1=0.921×1012exp(-108 600/RT)、k2=0.155×1012exp(-116 400/RT)和k3=1.008×107exp(-96 130/RT)。以目标残差函数OF参数值为检验模型的标准,模拟值和实验值的相关系数R2均超过0.99。因此,Chen and Reagan建立的甲醇制汽油三集总动力学模型可以准确描述Fe-HZSM-5分子筛催化剂的甲醇制汽油反应动力学行为。Fe-HZSM-5 zeolite catalysts containing skeleton heteroatom Fe were synthesized by hydrothermal crystallization method and characterized by XRD,BET and NH 3-TPD.Catalytic activity of the catalysts for methanol to gasoline and reaction kinetics data were studied in micro fixed bed reactor to get intrinsic kinetics of methanol to gasoline over Fe-HZSM-5 zeolite.Results showed that amount of weak acid beneficial for gasoline selectivity increased when heteroatom Fe into ZSM-5 zeolite framework.Using three-lumped kinetic model of methanol to gasoline established by Chen and Reagan,k 1=0.921×10 12 exp(-108 600/R T)、k 2=0.155×10 12 exp(-116 400/R T)and k 3=1.008×10 7exp(-96 130/R T).were calculated based on experimental data regression by Runge-Kutta method and the least-squares method.Taking target residual function(OF)parameter value as criterion of test,the correlation coefficient R 2 of simulated value and experimental value was above 0.99.Therefore,the methanol to gasoline three-lumped kinetic model established by Chen and Reagan could accurately describe the kinetics of methanol to gasoline reaction on Fe-HZSM-5 zeolite catalysts.

关 键 词：催化化学 Fe-HZSM-5分子筛催化剂 甲醇制汽油 动力学 三集总模型 

分 类 号：O643.12[理学—物理化学] TE665[理学—化学]