Selective hydrogenolysis of glycerol to propylene glycol by using Cu:Zn:Cr:Zr mixed metal oxides catalyst

被引:86
作者
Sharma, Rajesh V. [1 ]
Kumar, Pardeep [1 ]
Dalai, Ajay K. [1 ]
机构
[1] Univ Saskatchewan, Dept Chem & Biol Engn, Catalysis & Chem React Engn Labs, Saskatoon, SK S7N 5A9, Canada
关键词
Glycerol; Propylene glycol; Heterogeneous catalyst; Hydrogenolysis reaction; GAS-PHASE DEHYDRATION; PRODUCT SELECTIVITY; ZINC-OXIDE; COPPER; ACID; TEMPERATURE; ZIRCONIA; HYDROGENATION; CONVERSION; SURFACE;
D O I
10.1016/j.apcata.2014.03.007
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Hydrogeneolysis of glycerol to propylene glycol has high interest due to cost and ease of availability of glycerol. In this study, Cu:Zn:Cr:Zr based catalyst was used for selective hydrogeneolysis of glycerol to propylene glycol. It was observed that incorporation of zinc and zirconium in Cu:Cr catalyst matrix improved glycerol conversion and propylene glycol selectivity. This improvement is due to increases in acidity which is confirmed by NH3-TPD and Cu dispersion in the catalyst matrix which is measured by CO-chemisorption. XRD results confirmed the presence of active metallic Cu in the reduced catalyst. The liquid phase reaction was carried out with 80 wt% of glycerol solution at 240 degrees C, with 4 MPa of hydrogen pressure and 3 wt% catalyst loading. The novel catalyst Cu:Zn:Cr:Zr with the elemental molar ratio of 3:2:1:3 gave 100% of pure glycerol conversion and 97% of propylene glycol selectivity. The effects of temperature, hydrogen pressure, glycerol concentration and speed of agitation were studied for reaction optimization. A hydrogenolysis of crude glycerol obtained from biodiesel process, was also carried out under similar reaction condition to yield 90% of propylene glycol. Kinetic study was delineated and reaction followed the pseudo first order with respect to glycerol. The apparent activation energy was found to be 31.7 kcal/mol. The catalyst has good reusability up to four runs. Crown Copyright (C) 2014 Published by Elsevier B.V. All rights reserved.
引用
收藏
页码:147 / 156
页数:10
相关论文
共 37 条
[1]   Dehydration-hydrogenation of glycerol into 1,2-propanediol at ambient hydrogen pressure [J].
Akiyama, Masaki ;
Sato, Satoshi ;
Takahashi, Ryoji ;
Inui, Kanichiro ;
Yokota, Masahiro .
APPLIED CATALYSIS A-GENERAL, 2009, 371 (1-2) :60-66
[2]   Palladium catalysts supported on sulfated ceria-zirconia for the selective catalytic reduction of NOx by methane: Catalytic performances and nature of active Pd species [J].
Azambre, B. ;
Zenboury, L. ;
Da Costa, P. ;
Capela, S. ;
Carpentier, S. ;
Westermann, A. .
CATALYSIS TODAY, 2011, 176 (01) :242-249
[3]   Surface and structural properties of titania-supported Ru catalysts for hydrogenolysis of glycerol [J].
Balaraju, M. ;
Rekha, V. ;
Devi, B. L. A. Prabhavathi ;
Prasad, R. B. N. ;
Prasad, P. S. Sai ;
Lingaiah, N. .
APPLIED CATALYSIS A-GENERAL, 2010, 384 (1-2) :107-114
[4]   THE ROLE OF COPPER AND ZINC-OXIDE IN METHANOL SYNTHESIS CATALYSTS [J].
BURCH, R ;
GOLUNSKI, SE ;
SPENCER, MS .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1990, 86 (15) :2683-2691
[5]   Glycerol hydrogenolysis on heterogeneous catalysts [J].
Chaminand, J ;
Djakovitch, L ;
Gallezot, P ;
Marion, P ;
Pinel, C ;
Rosier, C .
GREEN CHEMISTRY, 2004, 6 (08) :359-361
[6]  
Che T. M., 1987, US Patent, Patent No. 4642394
[7]   Low-pressure hydrogenolysis of glycerol to propylene glycol [J].
Dasari, MA ;
Kiatsimkul, PP ;
Sutterlin, WR ;
Suppes, GJ .
APPLIED CATALYSIS A-GENERAL, 2005, 281 (1-2) :225-231
[8]   Hydrogenolysis of glycerol to propanediols over a Pt/ASA catalyst: The role of acid and metal sites on product selectivity and the reaction mechanism [J].
Gandarias, I. ;
Arias, P. L. ;
Requies, J. ;
Guemez, M. B. ;
Fierro, J. L. G. .
APPLIED CATALYSIS B-ENVIRONMENTAL, 2010, 97 (1-2) :248-256
[9]   Hydrogenolysis of glycerol to 1,2-propanediol catalyzed by Cu-H4SiW12O40/Al2O3 in liquid phase [J].
Hao, Shun-Li ;
Peng, Wei-Cai ;
Zhao, Ning ;
Xiao, Fu-Kui ;
Wei, Wei ;
Sun, Yu-Han .
JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY, 2010, 85 (11) :1499-1503
[10]   Highly dispersed silica-supported copper nanoparticles prepared by precipitation-gel method: A simple but efficient and stable catalyst for glycerol hydrogenolysis [J].
Huang, Zhiwei ;
Cui, Fang ;
Kang, Haixiao ;
Chen, Jing ;
Zhang, Xinzhi ;
Xia, Chungu .
CHEMISTRY OF MATERIALS, 2008, 20 (15) :5090-5099