Fe-HZSM-5分子筛催化剂的甲醇制汽油动力学研究
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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 NH3-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,k1= 0. 921 × 1012 exp(-108 600/RT) 、k2= 0. 155 × 1012 exp(-116 400/RT) and k3= 1. 008 × 107 exp(-96 130/RT).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 coeffi-cient R2 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.
Fe-HZSM-5 zeolite catalysts containing skeleton heteroatom Fe were synthesized by hydrothermal crystallization method and characterized by XRD,BET and NH3-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,k1= 0. 921 × 1012 exp(-108 600/RT) 、k2= 0. 155 × 1012 exp(-116 400/RT) and k3= 1. 008 × 107 exp(-96 130/RT).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 coeffi-cient R2 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.
引文
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[18]甄开吉,王国甲,毕颖丽,等.催化作用基础[M].2005.
[19]Haw J F,Song W,Marcus D M,et al.The mechanism of methanol to hydrocarbon catalysis[J].Accounts of Chemical Research,2003,36(5):317-326.
[20]Epelde E,Aguayo A T,Olazar M,et al.Kinetic model for the transformation of 1-butene on a K-modified HZSM-5catalyst[J].Industrial&Engineering Chemistry Research,2014,53(26):10599-10607.
[2]Olah G A.Beyond oil and gas:the methanol economy[J].Angewandte Chemie International Edition,2005,44(18):2636-2639.
[3]陈佩文.甲醇制汽油技术进展及其经济性[J].煤炭加工与综合利用,2014,(8):11-13.Chen Peiwen.Progress of methanol to gasoline technology and economy[J].Coal Processing and Comprehensive Utilization,2014,(8):11-13.
[4]Wan Z,Wu W,Chen W,et al.Direct synthesis of hierarchical ZSM-5 zeolite and its performance in catalyzing methanol to gasoline conversion[J].Industrial&Engineering Chemistry Research,2014,53(50):19471-19478.
[5]Rojo-Gama D,Nielsen M,Wrag D S,et al.A straightforward descriptor for the deactivation of zeolite catalyst HZSM-5[J].Acs Catalysis,2017,7(12):8235-8246.
[6]刘斌,宋宝东,曹刚.改性HZSM-5分子筛在甲醇制汽油中的研究进展[J].化学工程,2014,42(6):9-14.Liu Bin,Song Baodong,Cao Gang.Advances in modified HZSM-5 molecular sieve catalysts for methanol-to-gasoline reaction[J].Chemical Engineering,2014,42(6):9-14.
[7]Ni Y,Sun A,Wu X,et al.Preparation of hierarchical mesoporous Zn/HZSM-5 catalyst and its application in MTG reaction[J].Journal of Natural Gas Chemistry,2011,20(3):237-242.
[8]蒋忠祥,王海彦,张玲,等.Zn、Ga改性多级孔ZSM-5分子筛的原位合成及甲醇芳构化催化性能[J].天然气化工,2016,41(4):10-14.Jiang Zhongxiang,Wang Haiyan,Zhang Ling,et al.In-situ synthesis of Ga and Zn modified hierarchical ZSM-5 zeolites and their catalytic performances in methanol aromatization[J].Natural Gas Chemical(C1 Chemistry and Chemical Engineering),2016,41(4):10-14.
[9]Li J,Miao P,Li Z,et al.Hydrothermal synthesis of nanocrystalline H[Fe,Al]ZSM-5 zeolites for conversion of methanol to gasoline[J].Energy Conversion and Management,2015,93:259-266.
[10]Park T Y,Froment G F.Kinetic modeling of the methanol to olefins process.Ⅰ.Model formulation[J].Industrial&Engineering Chemistry Research,2001,40(20):4172-4186.
[11]Olsbye U,Bjrgen M,Svelle S,et al.Mechanistic insight into the methanol-to-hydrocarbons reaction[J].Catalysis Today,2005,106(1):108-111.
[12]杜明仙,郝栩.甲醇制汽油(MTG)集总动力学模型[J].煤炭转化,1994,17(2):14-19.Du Mingxian,Hao Yu.Lumping kinetic modelfor methanol conversion to gasoline[J].Coal Conversion,1994,17(2):14-19.
[13]Olsbye U,Bjrgen M,Svelle S,et al.Mechanistic insight into the methanol-to-hydrocarbons reaction[J].Catalysis Today,2005,106(1):108-111.
[14]Soltanali S,Halladj R,Rashidi A,et al.The effect of HZSM-5catalyst particle size on kinetic models of methanol to gasoline conversion[J].Chemical Engineering Research and Design,2016,106:33-42.
[15]Chang C D,Lang W H,Smith R L.The conversion of methanol and other o-compounds to hydrocarbons over zeolite catalysts:Ⅱ.Pressure effects[J].Journal of Catalysis,1979,56(2):169-173.
[16]孙长勇,宋一兵,叶飞,等.Fe-ZSM-5杂原子分子筛的合成与表征[J].光谱实验室,2003,20(3):448-451Sun Changyong,Song Yibing,Ye Fei,et al.Synthesis and characterization of heteroatom-containing zeolite FeZSM-5[J].Chinese Journal of Spectroscopy Laboratory,2003,20(3):448-451.
[17]王志彦,李金来.Fe改性HZSM-5分子筛催化剂的表征及其MTP(甲醇制丙烯)反应活性研究[J].世界科技研究与发展,2008,30(2):135-137.Wang Zhi yan,Li Jinlai.Characterization and the MTP(methanol to propylene)reaction activity of fe modified HZSM-5 zeolite catalyst[J].World Sci-Tech R&D,2008,30(2):135-137.
[18]甄开吉,王国甲,毕颖丽,等.催化作用基础[M].2005.
[19]Haw J F,Song W,Marcus D M,et al.The mechanism of methanol to hydrocarbon catalysis[J].Accounts of Chemical Research,2003,36(5):317-326.
[20]Epelde E,Aguayo A T,Olazar M,et al.Kinetic model for the transformation of 1-butene on a K-modified HZSM-5catalyst[J].Industrial&Engineering Chemistry Research,2014,53(26):10599-10607.