Coupling of Methanol and Carbon Monoxide over H-ZSM-5 to Form Aromatics

Angew Chem Int Ed Engl. 2018 Sep 17;57(38):12549-12553. doi: 10.1002/anie.201807814. Epub 2018 Aug 28.

Abstract

The conversion of methanol into aromatics over unmodified H-ZSM-5 zeolite is generally not high because the hydrogen transfer reaction results in alkane formation. Now circa 80 % aromatics selectivity for the coupling reaction of methanol and carbon monoxide over H-ZSM-5 is reported. Carbonyl compounds and methyl-2-cyclopenten-1-ones (MCPOs), which were detected in the products and catalysts, respectively, are considered as intermediates. The latter species can be synthesized from the former species and olefins. 13 C isotope tracing and 13 C liquid-state NMR results confirmed that the carbon atoms of CO molecules were incorporated into MCPOs and aromatic rings. A new aromatization mechanism that involves the formation of the above intermediates and co-occurs with a dramatically decreased hydrogen transfer reaction is proposed. A portion of the carbons in CO molecules are incorporated into aromatic, which is of great significance for industrial applications.

Keywords: H-ZSM-5; aromatics; carbon monoxide; heterogeneous catalysis; methanol.