Due to the surge of natural gas production, feedstocks for chemicals shift towards lighter hydrocarbons, particularly methane. The success of a Gas-to-Chemicals process via synthesis gas (CO and H₂) depends on the ability of catalysts to suppress methane and carbon dioxide formation. We designed a Co/Mn/Na/S catalyst, which gives rise to negligible Water-Gas-Shift activity and a hydrocarbon product spectrum deviating from the Anderson–Schulz–Flory distribution. At 240 °C and 1 bar, it shows a C₂-C₄olefins selectivity of 54%. At 10 bar, it displays 30% and 59% selectivities towards lower olefins and fuels, respectively. The spent catalyst consists of 10 nm Co nanoparticles with hcp Co metal phase. We propose a synergistic effect of Na plus S, which act as electronic promoters on the Co surface, thus improving selectivities towards lower olefins and fuels while largely reducing methane and carbon dioxide formation.

Decentralized chemical plants close to circular carbon sources will play an important role in shaping the postfossil society. This scenario calls for carbon technologies which valorize CO₂ and CO with renewable H₂ and utilize process intensification approaches. The single-reactor tandem reaction approach to convert CO_x to hydrocarbons via oxygenate intermediates offers clear benefits in terms of improved thermodynamics and energy efficiency. Simultaneously, challenges and complexity in terms of catalyst material and mechanism, reactor, and process gaps have to be addressed. While the separate processes, namely methanol synthesis and methanol to hydrocarbons, are commercialized and extensively discussed, this review focuses on the zeolite/zeotype function in the oxygenate-mediated conversion of CO_x to hydrocarbons. Use of shape-selective zeolite/zeotype catalysts enables the selective production of fuel components as well as key intermediates for the chemical industry, such as BTX, gasoline, light olefins, and C₃₊ alkanes. In contrast to the separate processes which use methanol as a platform, this review examines the potential of methanol, dimethyl ether, and ketene as possible oxygenate intermediates in separate chapters. We explore the connection between literature on the individual reactions for converting oxygenates and the tandem reaction, so as to identify transferable knowledge from the individual processes which could drive progress in the intensification of the tandem process. This encompasses a multiscale approach, from molecule (mechanism, oxygenate molecule), to catalyst, to reactor configuration, and finally to process level. Finally, we present our perspectives on related emerging technologies, outstanding challenges, and potential directions for future research.

Reaction-time resolved IR spectroscopy highlights the role of CO and surface –OCH ₃ in the MTO conversion catalysed by CoAPO-18 with maximised concentration of acidic sites.