SCI和EI收录∣中国化工学会会刊

›› 2010, Vol. 18 ›› Issue (3): 384-390.

• CATALYSIS, KINETICS AND REACTORS • Previous Articles     Next Articles

Kinetics of Hydrogenolysis of Glycerol to Propylene Glycol over Cu-ZnO-Al2O3 Catalysts

ZHOU Zhiming1, LI Xun2, ZENG Tianying1, HONG Wenbin1, CHENG Zhenmin1, YUAN Weikang1   

  1. 1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China;
    2. School of Chemistry and Biological Engineering, Changsha University of Science and Technology, Changsha 410077, China
  • Received:2009-12-09 Revised:2010-04-07 Online:2010-06-28 Published:2010-06-28
  • Supported by:
    Supported by the National High Technology Research and Development Program of China(2008AA05Z405);the National Natural Science Foundation of China(20706018);the Program for Changjiang Scholars and Innovative Research Team in University(IRT0721)

Kinetics of Hydrogenolysis of Glycerol to Propylene Glycol over Cu-ZnO-Al2O3 Catalysts

周志明1, 李浔2, 曾天鹰1, 洪闻彬1, 程振民1, 袁渭康1   

  1. 1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China;
    2. School of Chemistry and Biological Engineering, Changsha University of Science and Technology, Changsha 410077, China
  • 通讯作者: ZHOU Zhiming,E-mail:zmzhou@ecust.edu.cn
  • 基金资助:
    Supported by the National High Technology Research and Development Program of China(2008AA05Z405);the National Natural Science Foundation of China(20706018);the Program for Changjiang Scholars and Innovative Research Team in University(IRT0721)

Abstract: A series of Cu-ZnO-Al2O3 catalysts with various metal compositions of Cu/Zn/Al were prepared by the co-precipitation method,and screened for glycerol hydrogenolysis to propylene glycol.The catalyst with a Cu/Zn/Al molar ratio of 1:1:0.5 exhibited the best performance for glycerol hydrogenolysis,and thus selected for kinetic investigation.Under elimination of external and internal diffusion limitation,kinetic experiments were performed in an isothermal fixed-bed reactor at a hydrogen pressure range of 3.0-5.0 MPa and a temperature range of 493-513 K. Based on a dehydration-hydrogenation two-step hydrogenolysis mechanism,a two-site Langmuir-Hinshelwood kinetic model taking into account competitive adsorption of glycerol,acetol and propylene glycol was proposed and successfully fitted to the experimental data.The average relative errors between observed and predicted outlet concentrations of glycerol and propylene glycol were 6.3% and 7.6%,respectively.The kinetic and adsorption parameters were estimated by using the fourth-order Runge-Kutta method together with the Rosenbrock algorithm.The activation energies for dehydration and hydrogenation reactions were 86.56 and 57.80 kJ·mol-1,respectively.

Key words: kinetics, hydrogenolysis, glycerol, propylene glycol, catalyst

摘要: A series of Cu-ZnO-Al2O3 catalysts with various metal compositions of Cu/Zn/Al were prepared by the co-precipitation method,and screened for glycerol hydrogenolysis to propylene glycol.The catalyst with a Cu/Zn/Al molar ratio of 1:1:0.5 exhibited the best performance for glycerol hydrogenolysis,and thus selected for kinetic investigation.Under elimination of external and internal diffusion limitation,kinetic experiments were performed in an isothermal fixed-bed reactor at a hydrogen pressure range of 3.0-5.0 MPa and a temperature range of 493-513 K. Based on a dehydration-hydrogenation two-step hydrogenolysis mechanism,a two-site Langmuir-Hinshelwood kinetic model taking into account competitive adsorption of glycerol,acetol and propylene glycol was proposed and successfully fitted to the experimental data.The average relative errors between observed and predicted outlet concentrations of glycerol and propylene glycol were 6.3% and 7.6%,respectively.The kinetic and adsorption parameters were estimated by using the fourth-order Runge-Kutta method together with the Rosenbrock algorithm.The activation energies for dehydration and hydrogenation reactions were 86.56 and 57.80 kJ·mol-1,respectively.

关键词: kinetics, hydrogenolysis, glycerol, propylene glycol, catalyst