Copper Phosphinate Complexes as Molecular Precursors for Ethanol Dehydrogenation Catalysts

Abstract

Nowadays, the production of acetaldehyde heavily relies on the petroleum industry. Developing new catalysts for the ethanol dehydrogenation process, which could sustainably substitute current acetaldehyde production methods, is highly desired. Among ethanol dehydrogenation catalysts, copper-based materials have been intensively studied. Unfortunately, the Cu-based catalysts suffer from sintering and coking, which lead to rapid deactivation with time-on-stream (TOS). Phosphorus doping has been demonstrated to diminish coking in methanol dehydrogenation, fluid catalytic cracking, and ethanol-to-olefin reactions. This work reports a pioneering application of the well-characterized copper phosphinate complexes as molecular precursors for copper-based ethanol dehydrogenation catalysts enriched with phosphate groups (Cu-phosphate/SiO2). Three new catalysts (CuP-1, CuP-2, CuP-3), prepared by the deposition of complexes {Cu(SAAP)}n (1), [Cu6(BSAAP)6] (2), and [Cu3(NAAP)3] (3) on the surface of commercial SiO2, calcination at 500 °C, and reduction in the stream of the forming gas 5% H2/N2 at 400 °C exhibited unusual properties. First, the catalysts showed a rapid increase in catalytic activity. After reaching a maximum conversion, the catalyst started to deactivate. The unusual behavior could be explained by the presence of the phosphate phase, which prevented the Cu2+ reduction. The phosphorus content gradually decreased during time-on-stream, copper was reduced, and the activity increased. The deactivation of the catalyst could be related to the copper diffusion processes. The most active CuP-1 catalyst reaches a maximum of 74 % ethanol conversion and over 98 % acetaldehyde selectivity at 325 °C and WHSV = 2.37 h−1.