【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/-γA l2O3催化剂在473 K和458~498 K下的F-T合成动力学进行了研究。结果表明:473 K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=kpCOp1H/22/(1+1.499p1H/22+1.609pCO+2.541p-H2 1/2pCO)2,k为99.83 mm o l/(h.g.M Pa1.5)。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68.34 kJ/m o l。更多还原

【Abstract】 Fischer-Tropsch（F-T） synthesis is a complex heterogeneous surface catalytic reaction,and 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,n_<sub>H₂∶n_<sub>CO=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（experimental） results.The rate is expressed by -dN_<sub>CO/dw=kp_<sub><sub>COp^<sup>1/2_<sub>H₂/(1+1.499p^<sup>1/2_<sub>H₂+1.609p_<sub><sub>CO+(2.541p^<sup>-1/2_<sub>H₂p_<sub><sub>CO)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.更多还原