Dehydroxylation of Glycerol to Propylene Glycol over Cu-ZnO/Al2O3 Catalyst: Effect of Feed Purity

The catalytic dehydroxylation of glycerol to propylene glycol was investigated over Cu-ZnO/Al2O3 prepared by incipient wetness impregnation (IWI) method with different purity feedstocks - refined glycerol and technical grade glycerol. The main purpose is to investigate the effects of feed impurities that cause the catalyst deactivation. The prepared catalyst were tested for its catalytic activity and selectivity in a continuous flow fixed bed reactor at 523 K, 500 psig, H2/feed molar ratio of 4 and WHSV of 3 h-1. The results showed that conversion of refined glycerol and technical grade glycerol at time on stream 6 hour are 99% and 71% and selectivity to propylene glycol are 87% and 56% respectively. The ICP-EOS and TPO results indicated that the cause of catalyst deactivation was the amount of impurities in the feedstock. The higher amount of impurities (especially Na and K) the lower catalytic activity.




References:
[1] M. Pagliaro, M. Rossi, The future of glycerol: new usages for a versatile
raw material, RSC Publishing, Cambridge, 2008.
[2] Dasari, M.A., Kiatsimkul, P., Sutterlin, W.R., and Suppes, G.J. (2005).
Low-pressuse hydrogenolysis of glycerol to propylene glycol. Applied
Catalysis A: Genaral, 281(1-2), 225-231.
[3] Z. Chi, D. Pyle, Z. Wen, C. Frear, S. Chen, A laboratory study of
producing docosahexaenoic acid from biodiesel-waste glycerol by
microalgal fermentation, Process Biochem. 42 (2007) 1537-1545.
[4] T. Miyazawa, Y. Kusunoki, K. Kunimori, K. Tomishige, J. Catal. 240
(2006) 213.
[5] M. Hájek, F. Skopal, Treatment of glycerol phase formed by biodiesel
production, Bioresource Technol 101 (2010) 3242-3245.
[6] I. Gandarias, P.L. Arias, J. Requies, M. El Doukkali, M.B. G├╝emez,
(2011) .Liquid-phase glycerol hydrogenolysis to 1,2-propanediol under
nitrogen pressure using 2-propanol as hydrogen source, J.Cat. 282. 237-
247.
[7] E.P. Maris, W.C. Ketchie, M. Murayama, R.J. Davis, J. Catal. 251
(2007) 281. [9] L. Ma, D. He, Z. Li, Catal. Commun. 9 (2008) 2489.
[8] D.G. Lahr, B.H. Shanks, J. Catal. 232 (2005) 386.
[9] Sitthisa, S. (2007). Dehydroxylation of glycerol for propanediols
production. M.S. Thesis, The Petroleum and Petrochemaical College,
Chulalongkorn University.
[10] Swangkotchakorn, C. (2008). Dehydroxylation of glycerol for
propanediols production: Catalytic activity and stability Testing. M.S.
Thesis, The Petroleum and Petrochemical College, Chulalongkorn
University.
[11] Chirddilok, I. (2009). Dehydroxylation of glycerol to propylene glycol
over copper/zinc oxide-based catalysts: Effect of catalyst preparation.
M.S. Thesis, The Petroleum and Petrochemical College, Chulalongkorn
University.
[12] S. Panyad, S. Jongpatiwut, T. Sreethawong, T.Rirksomboon, S. Osuwan,
(2011). Catalytic dehydroxylation of glycerol to propylene glycol over
Cu-ZnO/Al2O3 catalysts: Effects of catalyst preparation and
deactivation, Catalysis Today. 174. 59-64.
[13] L. Zhang, X. Wang, B. Tan, U.S. Ozkan, J.Mol. Catal. A: Chem. 297
(2009) 26-34.
[14] P. Kurr, I. Kasatkin, F. Girgsdies, A. Trunschk, R. Schlögl, T. Ressle,
Appl. Catal.A: Gen. 348 (2008) 153-164.
[15] J.-P. Shen, C. Song, Catal. Today 77 (2002) 89-98.