Abstract

The one-step selective oxidation of methanol to dimethoxymethane (DMM) was demonstrated over titania-supported molybdenum oxide catalysts, containing different amounts of molybdenum and prepared using two different impregnation techniques, namely wet impregnation and incipient wetness impregnation. The corresponding catalysts exhibited both acidic and redox properties, which are necessary for the oxidation of methanol to formaldehyde with subsequent condensation of the latter with excess methanol to finally yield DMM. The formation of well-dispersed polyoxomolybdate species on the catalyst surface was evidenced using IR-Raman, X-ray diffraction, and nitrogen physisorption. Varying the amount of these polyoxomolydate species was associated with a modulation of the acidic and redox properties, as shown by NH3-TPD and H2-TPR. With respect to the catalytic performances, the best balance between acid and redox properties was observed over the samples containing 8 wt.% Mo, which corresponds to a theoretical MoO x species coverage close to a monolayer.

Abstract

Investigations into direct methane to methanol conversion are justified based on the avoidance of synthesis gas generation, which accounts for around 60% of the capital cost of synthesis gas to methanol conversion. A significant body of information already exists on the process chemistry, but little has been reported on the engineering of such a process. An engineering evaluation of the process was performed and the potential of this process as a platform technology for small-scale gas-to-liquids (GTL) applications was evaluated. It was found that direct methane to methanol conversion had 35% carbon efficiency and 28% thermal efficiency, which were about half of the process efficiencies of indirect methanol synthesis using synthesis gas. The poor process efficiency was mainly a consequence of the irreversible loss of carbon to CO x during conversion. The direct methane to methanol process also required an air separation unit, which eroded the stated benefit of avoiding a synthesis gas generation step in the process. The utility footprint was typical of GTL processes, with large gas compression duties and cooling duties. Overall, the engineering evaluation indicated there was no benefit to employ direct methane to methanol conversion instead of indirect methanol synthesis (the industry standard), and there was no specific benefit of direct methane to methanol conversion, irrespective of scale, for GTL applications.