化工学报 ›› 2005, Vol. 56 ›› Issue (6): 1020-1025.

• 催化、动力学与反应器 • 上一篇    下一篇

超细粒子Fe-Mn工业催化剂F-T合成集总机理动力学(Ⅰ)反应机理与动力学模型描述式

吉媛媛;相宏伟;李永旺;徐元源;钟炳   

  1. 中国科学院山西煤炭化学研究所煤转化国家重点实验室,山西 太原 030001;中国石油化工股份有限公司北京化工研究院,北京 100013
  • 出版日期:2005-06-25 发布日期:2005-06-25

Lumped mechanism kinetics of Fischer-Tropsch synthesis over ultrafine particle Fe-Mn commercial catalyst(Ⅰ) Reaction mechanism and kinetic model description

JI Yuanyuan;XIANG Hongwei;LI Yongwang;XU Yuanyuan;ZHONG Bing   

  • Online:2005-06-25 Published:2005-06-25

摘要: 为获得超细粒子Fe-Mn工业催化剂在F-T合成中CO转化的动力学模型描述式,为其工业放大过程中反应器设计提供依据,将F-T合成这样一个包括数百个反应的体系集总为F-T烃生成反应和水煤气转换(WGS)反应.这样,反应物CO的转化速率可近似地用烃生成速率与CO2生成速率之和来表示.在碳化物机理基础上建立烃生成基元反应步骤,以决定烃“结构单元”CH*2生成的步骤为速控步骤建立动力学模型.同时,在甲酸盐机理基础上建立CO2生成的基元反应步骤,以甲酸盐物种的生成步骤为速控步骤建立动力学模型.将二者组合,获得同时包括F-T烃生成反应和WGS反应的F-T合成集总动力学模型.

关键词: F-T合成, Fe-Mn催化剂, 集总机理动力学, 烃生成, WGS反应

Abstract: The objective of this paper is to establish a kinetic model description of CO conversion over the ultrafine particle Fe-Mn commercial catalyst in the Fischer-Tropsch process to provide the design basis for scaling up commercial reactor.Fischer-Tropsch process, including hundreds of reactions, was lumped into two kinds of reactions.One was Fischer-Tropsch reaction, in which the main product hydrocarbons were formed.The other was Water Gas Shift (WGS)reaction, in which the main by-product CO2 was formed. Thus, the reaction rate of CO was approximately expressed as the sum of hydrocarbon formation rate and CO2 formation rate.The description of the elementary step in the hydrocarbon formation was established based on the carbide mechanism.The rate-controlling step in the hydrocarbon formation model was the one controlling the formation of the structure unit CH*2. Meanwhile, the description of the elementary step in Water Gas Shift reaction was found based on the formate mechanism,and the rate-controlling step in Water Gas Shift reaction model was the formation of formate species.The kinetic model description of the Fischer-Tropsch process, including both Fischer-Tropsch reaction and Water Gas Shift reaction, was acquired by the combination of the above two kinds of kinetic models.

Key words: F-T合成, Fe-Mn催化剂, 集总机理动力学, 烃生成, WGS反应