Abstract
[Display omitted]
•Core@shell and hybrid pellets were synthetized for direct synthesis of DME.•A crystallite pore network model was adapted to the two bifunctional systems.•Transport limitations over the zeolite shell are observed by modelling.•Core changes during the shell synthesis are observed via characterization.•Hybrid pellet system shows more feasible preparation and better performance.
The direct synthesis of dimethyl ether (DME) from synthesis gas via methanol as an intermediate is a promising process for realizing a decentralized, small-scale Power-to-X concept. The efficient realization of this coupled process depends to a large extent on the appropriate catalyst configuration, i.e. the combination of the catalyst for methanol formation with the one for the subsequent dehydration step. In this work, two catalyst configurations were compared in terms of CO-conversion and DME-selectivity using modelling and experiments. Catalysts for methanol formation (Cu/ZnO/Al2O3, CZA) and dehydration (Zeolite H-ZSM-5, Z) prepared via flame spray pyrolysis and hydrothermal synthesis, respectively, were combined in the form of hybrid pellets (CZA&Z) and CZA-core@zeolite-shell (CZA@Z) particles. During the synthesis of the CZA@Z system, alteration of the CZA core in terms of CuO-reducibility and activity in methanol synthesis were found after individual steps of calcination and hydrothermal shell synthesis. In contrast, the preparation of the CZA&Z system presents an easy and tunable method with promising catalytic properties in terms of CO-conversion and DME-selectivity, once the proper mass ratio of the two catalysts was set. From modelling, for the same CZA/Z ratio in general higher CO-conversion was found for the CZA&Z system as compared to the CZA@Z, while the latter system shows higher DME-selectivity.