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Risultati sfruttabili
The present research programme involves development of inert and catalytic membrane reactors for oxidation of light alkanes mainly focused on propane oxidative dehydrogenation to propene and oxidation of propane to acrylic acid and based on catalytic formulations which consist in a magnesium vanadate oxide (V/VMgO) and vanadium phosphorus oxide VPO.
For the oxidative dehydrogenation of propane to propene, the composition of the surrounding atmosphere does not seem to determine the state of oxidation of the V/VMgO catalyst. However, under HC rich atmosphere (low oxygen concentration), the catalyst is less active but more selective towards propene. An advanced description of the working surface and of the ODHP mechanism has been provided, which ascertains a Mars-van Krevelen mechanism.
In view of their application in membrane reactors, a special method of preparation for a V-Mg-O catalyst was developed. Starting from a mixture of magnesium and vanadium alkoxides, synthesis of a series of V-Mg-O catalyst samples exhibiting relatively high surface areas was developed.
The sol-gel derived infiltrated VPO membranes showed an original gas permeance behavior due to their reversible redox (V4+/V5+) properties. The permeance drastically changes with the oxidative/reducing nature of the permeating gas. Such VPO membranes are potentially attractive to regulate O2 transport in oxidative reactions. The powder catalysts xV/VMgO derived from metallo-organic precursors revealed original attractive properties (texture, structure and performance) in comparison with those of the "classical" VMgO catalysts derived from salts. These studies help in understanding the VMgO catalyst function in ODHP reaction.
A ceramic membrane reactor has been used as an efficient contactor in the oxidative dehydrogenation of propane (ODH). The composite silica membrane used as a reactant distributor provided an adequate permeation flux and performance. The best configuration involves the feeding of propane and inert gas to the tube side and oxygen to the shell side. The best improvement achieved in the Inert Membrane Reactor (IMR) relative to the Fixed Bed Reactor is around 10 percentage points in selectivity for a given propane conversion. The best propene yield achieved is c.a. 18%. Experiments designed to demonstrate the applicability of the IMR concept to the production of oxygenates from propane have shown that the predominant oxygenated products formed are mixtures of alcohols and aldehydes. Cofeeding of a proportion of the oxygen on the tube side gave an increase in the production of propanol and also more propene.
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