Synthesis of methanol by hydrogenolysis of biobased methyl formate using highly stable and active Cu-spinel catalysts in slurry and gas phase reactions

Haagen V, Iser J, Schörner M, Weber D, Franken T, Wasserscheid P, Schühle P (2023)

Publication Type: Journal article

Publication year: 2023

Journal

Green Chemistry Royal Society of Chemistry

Original Authors: Vera Haagen, Jakob Iser, Markus Schörner, Dennis Weber, Tanja Franken, Peter Wasserscheid, Patrick Schühle

DOI: 10.1039/D2GC04420J

Abstract

This contribution deals with a new atom efficient two-stage production route for green methanol (MeOH) from biomass that includes biomass conversion to methyl formate (MF)/formic acid (FA) mixtures followed by hydrogenolysis to MeOH. Herein, we focus on the hydrogenolysis step and propose a materials solution to the problem of catalyst corrosion by the acidic MF/FA mixture formed in the previous biomass oxidation step. We show that Cu0.9Al2O4 spinel materials are very effective hydrogenolysis catalysts for the conversion of MA/FA mixtures to MeOH. Compared to commercial catalysts such as CuO/Cr2O3, the spinel material does not contain hazardous chromium compounds or require them during synthesis. Furthermore, this spinel catalyst shows much lower corrosion than known commercial hydrogenolysis catalysts. By using reactive frontal chromatography, nitrogen sorption, IR-ATR and XRD measurements we show, that CuO/MgO/ZnO/Al2O3 and CuO/Cr2O3 suffer from leaching of copper and chromium in the presence of FA due to the formation of mobile metal formate species. In contrast, the strongly fixed nature of copper in the highly ordered crystal structure of our Cu0.9Al2O4 spinel type catalyst leads to exceptional stability in the presence of FA and in continuous hydrogenolysis experiments for more than 110 h time-on-stream.

Authors with CRIS profile

Jakob Iser Lehrstuhl für Partikelsynthese (LFG) Dennis Weber Juniorprofessur für katalytische und elektrokatalytische Systeme und Verfahren Tanja Franken Juniorprofessur für katalytische und elektrokatalytische Systeme und Verfahren Peter Wasserscheid Lehrstuhl für Chemische Reaktionstechnik (CRT) Patrick Schühle Lehrstuhl für Chemische Reaktionstechnik (CRT)

Involved external institutions

Helmholtz-Institut Erlangen-Nürnberg für Erneuerbare Energien (HI-ERN) DE Germany (DE)

How to cite

APA:

Haagen, V., Iser, J., Schörner, M., Weber, D., Franken, T., Wasserscheid, P., & Schühle, P. (2023). Synthesis of methanol by hydrogenolysis of biobased methyl formate using highly stable and active Cu-spinel catalysts in slurry and gas phase reactions. Green Chemistry. https://doi.org/10.1039/D2GC04420J

MLA:

Haagen, Vera, et al. "Synthesis of methanol by hydrogenolysis of biobased methyl formate using highly stable and active Cu-spinel catalysts in slurry and gas phase reactions." Green Chemistry (2023).

BibTeX: Download