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

›› 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. 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. 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

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

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.

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]. CIESC Journal, 2010, 18(3): 384-390.

References

1 Feng, J., Yuan, M.L., Chen, H., Li, X.J., “Studies and applications of catalytic hydrogenolysis of glycerol”, Prog. Chem., 19, 651-658(2007).
2 Behr, A., Eilting, J., Irawadi, K., Leschinski, J., Lindner, F., “Improved utilisation of renewable resources:New important derivatives of glycerol”, Green Chem., 10, 13-30(2008).
3 Zhou, C.H., Beltramini, J.N., Fan, Y.X., Lu, G.Q., “Chemoselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals”, Chem. Soc. Rev., 37, 527-549(2008).
4 Zheng, Y.G., Chen, X.L., Shen, Y.C., “Commodity chemicals derived from glycerol, an important biorefinery feedstock”, Chem. Rev., 108, 5253-5277(2008).
5 Speight, J.G., Chemical and Process Design Handbook, McGraw-Hill, New York(2002).
6 Dasari, M.A., Kiatsimkul, P.P., Sutterlin, W.R., Suppes, G.J., “Low-pressure hydrogenolysis of glycerol to propylene glycol”, Appl. Catal. A:Gen., 281, 225-231(2005).
7 Chiu, C.W., Dasari, M.A., Suppes, G.J., “Dehydration of glycerol to acetol via catalytic reactive distillation”, AIChE J., 52, 3543-3548(2006).
8 Suppes, G.J., Sutterlin, W.R., “Method of producing lower alcohols from glycerol”, WO Pat., 053705(2007).
9 Chiu, C.W., Tekeei, A., Sutterlin, W.R., Ronco, J.M., Suppes, G.J., “Low-pressure packed-bed gas phase conversion of glycerol to acetol”, AIChE J., 54, 2456-2463(2008).
10 Miyazawa, T., Kusunoki, Y., Kunimori, K., Tomishige, K., “Glycerol conversion in the aqueous solution under hydrogen over Ru/C + an ion-exchange resin and its reaction mechanism”, J. Catal., 240, 213-221(2006).
11 Miyazawa, T., Koso, S., Kunimori, K., Tomishige, K., “Development of a Ru/C catalyst for glycerol hydrogenolysis in combination with an ion-exchange resin”, Appl. Catal. A:Gen., 318, 244-251(2007).
12 Miyazawa, T., Koso, S., Kunimori, K., Tomishige, K., “Glycerol hydrogenolysis to 1,2-propanediol catalyzed by a heat-resistant ion-exchange resin combined with Ru/C”, Appl. Catal. A:Gen., 329, 30-35(2007).
13 Wang, S., Liu, H.C., “Selective hydrogenolysis of glycerol to propylene glycol on Cu-ZnO catalysts”, Catal. Lett., 117, 62-67(2007).
14 Balaraju, M., Rekha, V., Sai Prasad, P.S., Prasad, R.B.N., Lingaiah, N., “Selective hydrogenolysis of glycerol to 1,2 propanediol over Cu-ZnO catalysts”, Catal. Lett., 126, 119-124(2008).
15 Huang, L., Zhu, Y.L., Zheng, H.Y., Li, Y.W., Zeng, Z.Y., “Continuous production of 1,2-propanediol by the selective hydrogenolysis of solvent-free glycerol under mild conditions”, J. Chem. Technol. Biotechnol., 83, 1670-1675(2008).
16 Meher, L.C., Gopinath, R., Naik, S.N., Dalai, A.K., “Catalytic hydrogenolysis of glycerol to propylene glycol over mixed oxides derived from a hydrotalcite-type precursor”, Ind. Eng. Chem. Res., 48, 1840-1846(2009).
17 Montassier, C., Ménézo, J.C., Hoang, L.C., Renaud, C., Barbier, J., “Aqueous polyol conversions on ruthenium and on sulfur-modified ruthenium”, J. Mol. Catal., 70, 99-110(1991).
18 Maris, E.P., Davis, R.J., “Hydrogenolysis of glycerol over carbon-supported Ru and Pt catalysts”, J. Catal., 249, 328-337(2007).
19 Lahr, D.G., Shanks, B.H., “Kinetic analysis of the hydrogenolysis of lower polyhydric alcohols:Glycerol to glycols”, Ind. Eng. Chem. Res., 42, 5467-5472(2003).
20 Lahr, D.G., Shanks, B.H., “Effect of sulfur and temperature on ruthenium-catalyzed glycerol hydrogenolysis to glycols”, J. Catal., 232, 386-394(2005).
21 Xi, Y.Y., Holladay, J.E., Frye, J.G., Oberg, A.A., Jackson, J.E., Miller, D.J., “A kinetic and mass transfer model for glycerol hydrogenation in a trickle-bed reactor”, In:2007 AIChE Annual Meeting Conference Proceedings, Salt Lake City, USA(2007).
22 Feng, J., Wang, J.B., Zhou, Y.F., Fu, H.Y., Chen, H., Li, X.J., “Effect of base additives on the selective hydrogenolysis of glycerol over Ru/TiO₂ catalyst”, Chem. Lett., 36, 1274-1275(2007).
23 Singh, U.K., Vannice, M.A., “Kinetics of liquid phase hydrogenation reactions over supported metal catalysts—A review”, Appl. Catal. A:Gen., 213, 1-24(2001).
24 Chen, Y.Q., Miller, D.J., Jackson, J.E., “Kinetics of aqueous-phase hydrogenation of organic acids and their mixtures over carbon supported ruthenium catalyst”, Ind. Eng. Chem. Res., 46, 3334-3340(2007).
25 Zhou, Z.M., Cheng, Z.M., Cao, Y.N., Zhang, J.C., Yang, D., Yuan, W.K., “Kinetics of the selective hydrogenation of pyrolysis gasoline”, Chem. Eng. Technol., 30, 105-111(2007).
26 Rosenbrock, H.H., Storey, C., Computational Techniques for Chemical Engineers, Pergamon, New York(1966).
27 Yaws, C.L., Chemical Properties Handbook, McGraw-Hill, New York(1999).
28 Reid, R.C., Prausnitz, J.M., Poling, B.E., The Properties of Gases and Liquids, 4th edition, McGraw-Hill, New York(1987).
29 Nimlos, M.R., Blanksby, S.J., Qian, X.H., Himmel, M.E., Johnson, D.K., “Mechanism of glycerol dehydration”, J. Phys. Chem. A, 110, 6145-6156(2006).

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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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