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

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

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. 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

收稿日期:2009-12-09 修回日期:2010-04-07 出版日期:2010-06-28 发布日期:2010-06-28
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)

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. 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)

摘要/Abstract

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

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

周志明, 李浔, 曾天鹰, 洪闻彬, 程振民, 袁渭康. Kinetics of Hydrogenolysis of Glycerol to Propylene Glycol over Cu-ZnO-Al₂O₃ Catalysts[J]. , 2010, 18(3): 384-390.

ZHOU Zhiming, LI Xun, ZENG Tianying, HONG Wenbin, CHENG Zhenmin, YUAN Weikang. Kinetics of Hydrogenolysis of Glycerol to Propylene Glycol over Cu-ZnO-Al₂O₃ Catalysts[J]. , 2010, 18(3): 384-390.

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

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

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