THE UPGRADING OF METHANE TO AROMATICS OVER TRANSITION METAL LOADED HIERARCHICAL ZEOLITES

Abstract

With the boom of shale gas production, the conversion of methane to higher hydrocarbons (MTH) promises a great future as the substituent for hydrocarbon production from crude oil based processes. Among various MTH processes, direct methane aromatization (DMA) is promising since it can achieve one-step methane valorization to aromatics. The molybdenum/zeolite (Mo/MFI or Mo/MWW) has been the most active catalyst for the DMA reaction, which, however, is impeded from industrial practice due to the rapid deactivation by coke deposition. To address this challenge, in this work, transition metal loaded hierarchical 2 dimensional (2D) lamellar MFI and MWW zeolites have been studied as catalysts for the DMA reaction. The effects of micro- and mesoporosity, external and internal Brønsted acid sites, as well as particle size of 2D lamellar zeolites on the DMA reaction have been investigated. Firstly, the spatial distribution of Brønsted acid sites in 2D lamellar MFI and MWW zeolites has been quantified by a combination of organic base titration and methanol dehydration reaction. The unit-cell thick 2D zeolites after Mo loading showed mitigation on deactivation, increase in activity, and comparable aromatics selectivity to the Mo loaded 3D zeolite analogues. A detailed analysis of the DMA reaction over Mo/hierarchical MFI zeolites with variable micro- and mesoporosity (equivalent to variation in particle sizes) showed a balance between dual porosity was essential to modulate the distribution of active sites (Mo and Brønsted acid sites) in the catalysts as well as the consequent reaction and transport events to optimize performance in the DMA reaction. External Brønsted acid sites have been proposed to be the cause of coke deposition on Mo/zeolite catalysts. Deactivation of the external acid sites have been practiced to improve the catalyst performances in the DMA reaction in this work. Atomic layer deposition (ALD) of silica species was conducted on the external surface of 2D lamellar MFI and MWW zeolites to deactivate the external acid sites in Mo/2D lamellar zeolites for the DMA reaction. Another strategy to deactivate external acid sites in Mo/zeolite catalysts was the overgrowth of 2D lamellar silicalite-1 on the microporous zeolites. The as-prepared catalysts showed higher methane conversion and aromatics formation as well as higher selectivity to naphthalene and coke in comparison with Mo loaded microporous analogues.