Surface reactions of dimethyl ether on γ-Al2O3

The surface reactions of dimethyl ether (DME) on industrial alumina (gamma-Al2O3) were studied by chromatographic analysis of the products at the outlet of the flow reactor and (independently) by diffuse reflectance IR spectroscopy. The major products of the reactions at 250A degrees D were found to be methanol formed in the reaction of DME with hydroxyl groups (the 3720 and 3674 cm(-1) bands in the diffuse reflectance spectrum) and various methoxy groups (the 1121, 1070, 695, and 670 cm(-1) bands in the differential spectra). The presence of molecularly adsorbed methanol was confirmed by experiments with methanol fed in a high-temperature IR cell. The interaction of the resulting methanol molecule with the hydroxyl group led to the formation of a water molecule in the gas phase and a methoxy group on the oxide surface. Strong adsorption of molecular DME was revealed, which was favored by an increase in the temperature of the preliminary calcination of oxide from 250 to 450-500A degrees D; treatment of alumina with water vapor after its preliminary contact with DME led to a recovery of the hydroxyl coating and a replacement of molecularly adsorbed DME with hydroxyl. The thermal effect recorded in a flow reactor was positive during the adsorption of DME and negative during the desorption of weakly bonded DME. Schemes of formation of methoxy groups in the interaction of DME and methanol with surface hydroxyls were suggested.