Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia

OP-3-10CATALYTIC GAS PHASE CONVERSION OF GLYCERINSuprun W., Gläser R., Papp H.Institut für Technische Chemie, Universität Leipzig, Germany,Fax: + 49 341 97 36349; e-mail: suprun@chemie.uni-leipzig.deAs a sustainable alternative, acrolein can be synthesized by the doubledehydration of glycerol. Therefore, during the last decade, the catalytic dehydrationof glycerol to acrolein and hydroxyacetone has gained big scientific and industrialinterest. Different solid acid catalysts including zeolites (H-form) and Al 2 O 3 , TiO 2 ,ZrO 2 and SiO 2 impregnated with phosphates and heteropoly acids have beenproposed for glycerol dehydration in gaseous or liquid phases.The aim of the present work is to get more insight into the effect of differenttransition metal oxides supported on acidic Al 2 O 3 -PO 4 on the performance of catalyticgas phase conversion of aqueous solution of glycerine. In particular Cr, Cu, Ce, Fe,Mn, Mo, V and W oxides were investigated to elucidate their role in differentmechanism pathways and thus, formation of main and by-products. This will thenhave repercussions for the deactivation and long-term stability in the selectiveconversion of glycerol to C 2 - C 3 products. Bifunctional catalysts Al 2 O 3 -PO 4 modifiedby Cu-, Cr-, Fe-, V,-, Mo-, W-oxides and SAPO (11, 34) were synthesized undcharacterized by N 2 pysisorption, XRD, NH 3 - and H 2 -TPD analysis. Catalyticconversion of glycerol was investigated at the constant reactions conditions inpresence of water. Glycerol conversion and summary selectivity to acrolien andhydroxyacetone depended strongly on the total acidity and redox properties. Theinfluence of temperature and GHSV on the selectivity of dehydrations products wasalso evaluated. In comparison to acidic catalysts, the Al 2 O 3 -PO 4 donated with W-,Mo-, Cr- and Cu -oxide showed complete glycerol conversion and excellent long timestability. The SAPO samples showed high acrolein selectivity only at the shot time ofstream. The properties of the used catalysts were studied by TPD-NH 3 and DTA-TG,TPO, DRIFT and XPS analysis. Relatively low deactivation rate of MeOx-Al 2 O 3 -PO 4catalyst could be due to oxidative cleavage of carbonaceous deposits. Moreover, themechanism of products formation and catalyst deactivation by glycerol dehydrationwas proposed [1].[1]. W. Suprun, M. Lutecki, T. Haber, H. Papp, J. Molec. Cat. A. 309 (2009) 71.78