文献类型：期刊文献

中文题名：ZrO_2改性Co-Ru/γ-Al_2O_3催化剂F-T合成的本征动力学

英文题名：Intrinsic Kinetics of ZrO_2 Modified Co-Ru/γ-Al_2O_3 Catalyst for F-T Synthesis

作者：李晨[1];曹发海[1];应卫勇[1];房鼎业[1]

机构：[1]华东理工大学化工学院,上海200237

年份：2006

卷号：32

期号：11

起止页码：1253

中文期刊名：华东理工大学学报（自然科学版）

外文期刊名：Journal of East China University of Science and Technology

收录：CSTPCD;;EI(收录号：20070310373192);Scopus;北大核心:【北大核心2004】；CSCD:【CSCD2011_2012】；

基金：博士学科点专项科研基金(20050251006)

语种：中文

中文关键词：费-托合成;钴钌双金属催化剂;动力学模型

外文关键词：Fischer-Tropsch synthesis; Co-Ru bimetal catalyst; kinetics model

摘要：根据费-托（F—T）合成的表面碳化物机理；推导出合成气反应的8个动力学模型。利用固定床微分反应器对ZrO2改性Co—Ru／γ-Al2O3催化剂在473K和458～498K下的F—T合成动力学进行了研究。结果表明：473K时，H2完全解离，吸附态CO加氢生成甲酰（HCO），HCO加氢生成表面C，同时氧以水的形式脱除（模型6），实验结果最吻合。在473K时，反应速率表达式为：-dNco／dw=kpcopH2^1/2（1＋1.499PH2^1/2＋1．609Pco＋2．541pH2^1/2）。k为99．83mmol／（h·g·MPa^1.5）。通过实验数据对模型6的非线性回归，对反应活化能、吸附活化能等进行了估算，活化能为68．34kJ／mol。
Fischer-Tropsch （F-T） synthesis is a complex heterogeneous surlace catalytic reacion, ana hydrocarbon products is formed by surface polymerization reaction of monomer CH2. Based on the carbide mechanism of F-T synthesis, 8 models of the CO consumption rate expressions were derived. Using differential fixed bed reactor, reaction rate data were determined for CO hydrogenation on ZrO2 modified Co-Ru/γ-Al2O3 catalyst at 458-498 K, 0. 50-2.00 MPa, 3 000-5 000 h^-1, nH2^ ：nco=2.0, fitting the kinetic models by using experimental data at 473 K. The results indicate that the model 6, i.e. H2 completely dissociation, formation of HCO species by adsorbed CO hydrogenation, then formation surface C and simultaneously O removal by H2O through HCO species hydrogenation, is in good agreement with the kPcoPH2^1/2 experimental results. The rate is expressed by-dNco/dw= PcoPH2^1/2（1＋ 1. 499PH2^1/2＋1.609PH2^Pco ＋ 2. 541PH2^1/2Pco）^2, where k=99.83 mmol/（h· g· MPa^1.5） at 473 K. Nonlinear-regression is carried out for the model 6 with the experimental results at 458-478 K, 1.00 MPa and 5 000 h^-1 for F-T synthesis of ZrO2 modified Co-Ru/γ-Al2O3 catalyst, the activation energy, adsorption activity energy and pre-exponential factor of the model are obtained, which the activity energy is 68.34 kJ/mol.