Integrating hydroformylations into a methanol economy

Abstract

In almost all man-made chemical products, the carbon skeletons originate from unsustainable fossil resources¹. As the green transition gains traction, introducing CO₂ as a feedstock for organic synthesis will be one of the keys to a carbon-neutral chemical industry^2-4. However, redesigning large scale processes for alternative feedstocks is challenging. Methanol sourced from CO₂ is presently becoming available, linked to the emergence of a methanol economy utilising it as circular fuel^5,6. This presents an ideal entry point to rethink the highly interconnected chemical production chains. Here, we report that interlocking a ruthenium-catalysed methanol-to-syngas reforming with a low-pressure rhodium-catalysed hydroformylation in a two-reactor setup affords oxo-products in high yields and selectivity. This study elucidates the kinetics and selectivity of gas formation and their key role in matching both catalytic cycles. Finally, the utilisation of fuel-grade green methanol as a syngas source is demonstrated. If combined with methanol-to-olefin processes and green methanol production, oxo-products could thus be generated using solely CO₂ as the carbon feedstock through a methanol platform. The here developed dual catalysis can be considered a blueprint for remodelling industrial processes.