Mechanism and Kinetics of Propane Dehydrogenation and Cracking over Ga/H-MFI Prepared via Vapor-Phase Exchange of H-MFI with GaCI3

In this study, the mechanism and kinetics of C3H8 dehydrogenation and cracking are examined over Ga/H-MFI catalysts prepared via vapor-phase exchange of H-MFI with GaCl3. The present study demonstrates that [GaH](2+) cations are the active centers for C3H8 dehydrogenation and cracking, independent of the Ga/A1 ratio. For identical reaction conditions, [GaH](2+) cations in Ga/H-MFI exhibit a turnover frequency for C3H8 dehydrogenation that is 2 orders of magnitude higher and for C3H8 cracking, that is 1 order of magnitude higher than the corresponding turnover frequencies over H-MFI. C3H8 dehydrogenation and cracking exhibit first-order kinetics with respect to C3H8 over H-MFI, but both reactions exhibit first-order kinetics over Ga/H-MFI only at very low C3H8 partial pressures and zero-order kinetics at higher C3H8 partial pressures. H-2 inhibits both reactions over Ga/H-MFI. It is also found that the ratio of the rate of dehydrogenation to the rate of cracking over Ga/H-MFI is independent of C3H8 and H-2 partial pressures but weakly dependent on temperature. Measured activation enthalpies together with theoretical analysis are consistent with a mechanism in which both the dehydrogenation and cracking of C3H8 proceed over Ga/H-MFI via reversible, heterolytic dissociation of C3H8 at [GaH](2+) sites to form [C3H7-GaH](+)-H+ cation pairs. The rate-determining step for dehydrogenation is the beta-hydride elimination of C3H6 and H-2 from the C3H7 fragment. The rate-determining step for cracking is C-C bond attack of the same propyl fragment by the proximal Bronsted acid O-H group. H-2 inhibits both dehydrogenation and cracking over Ga/H-MFI via reaction with [GaH](2+) cations to form [GaH2](+)-H+ cation pairs.


Published in:
Journal Of The American Chemical Society, 141, 4, 1614-1627
Year:
Jan 30 2019
ISSN:
0002-7863
Keywords:
Laboratories:




 Record created 2019-06-18, last modified 2019-06-27


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