화학공학소재연구정보센터
Journal of Catalysis, Vol.158, No.2, 452-476, 1996
Catalytic Synergy in the Oxidative Dehydrogenation of Propane over Mgvo Catalysts
Synergetic effects in the oxidative dehydrogenation of propane have been studied over magnesium vanadate catalysts containing three different Mg/V ratios : 1/2, 2/2, and 3/2, denoted as MgV(1/2), MgV(2/2), and MgV(3/2). Four types of catalysts were analysed : (a) pure magnesium vanadate oxides, (b) mechanical mixtures of the pure magnesium vanadate oxides, (c) mechanical mixtures of the magnesium vanadate oxides with alpha-Sb2O4, and (d) impregnated MgV(2/2) and MgV(3/2) with Sb ions. Synergetic effects are observed in MgV(3/2) and in MgV(2/2) oxides when they are in presence of (alpha-Sb2O4. In the mixtures of MgV(3/2) with alpha-Sb2O4, the principal effect is an increase in the selectivity with a corresponding decrease in propane conversion, whereas in the mixtures of MgV(2/2) with alpha-Sb2O4, there is a strong increase in propane conversion with a moderate increase in propene yield. Concerning the mixtures of MgV(3/2) and MgV(2/2), synergetic effects in the conversion, in the yield, and in the selectivity are observed. However, no synergetic effects in selectivity or conversion are exhibited by MgV(2/2) and MgV(3/2) when they are mixed with MgV(1/2). Highly dispersed (SbxOy), formed on impregnated MgV(2/2) and MgV(3/2), sinters and detaches from MgV(2/2) and MgV(3/2) surfaces. No formation of a new phase or contamination in the presence of alpha-Sb2O4 takes place when MgV(3/2) is used. Thus, these catalysts contain two separate phases in contact. In MgV(2/2) + alpha-Sb2O4 mechanical mixtures a new phase, MgSb2O6, (formed during the test) is also present in small quantities. The mixtures of MgV(3/2) with MgV(2/2) reveal neither formation of a new phase nor contamination. The synergetic effects in the selectivity exhibited by MgV(3/2) mixed with MgV(2/2) and with alpha-Sb2O4 is explained by a remote control mechanism. MgSb2O6, formed in MgV(2/2)-containing catalysts, is responsible for the increase in complete oxidation and the strong decrease in selectivity.