Methanol synthesis, in the context of catalytic organic transformations of C1 feedstocks, is the catalytic hydrogenation of carbon monoxide or carbon dioxide to methanol at a metal surface that activates both hydrogen and the carbon oxide. The concept is bounded by a net reduction in which the carbon atom of CO or CO2 is converted to the methyl carbon of CH3OH without further chain growth to higher alcohols or hydrocarbons. Essential components are a hydrogenating metal, most commonly copper in a Cu/ZnO/Al2O3 formulation, a support or promoter that stabilizes the active copper–zinc interface, and reaction conditions that favor methanol over the reverse water–gas shift or methanation [1][2]. The industrial Cu/ZnO/Al2O3 system presents a dynamic copper surface whose activity is promoted by ZnO, which modifies the copper particles and participates in the active ensemble [1][3]. Alternative formulations employ copper–ceria contacts or indium oxide to hydrogenate CO2 with high methanol selectivity [2][4]. The process is distinguished from Fischer–Tropsch chemistry by the absence of C–C coupling and from methanol steam reforming by the opposite direction of the same formal equilibrium.
- methanol
- CO2 hydrogenation
- copper–zinc catalyst
- C1 catalysis
Carbon dioxide utilization in catalysis • Process Chemistry and Technology • Chemical Engineering • Physical Sciences
References
- Malte Behrens; Felix Studt; Igor Kasatkin; Stefanie Kühl; Michael Hävecker; Frank Abild-Pedersen; Stefan Zander; Frank Girgsdies; Patrick Kurr; Benjamin-Louis Kniep; et al. The Active Site of Methanol Synthesis over Cu/ZnO/Al 2 O 3 Industrial Catalysts. Science 2012, 336, 893-897, 10.1126/science.1219831.
- Jesús Graciani; Kumudu Mudiyanselage; Fang Xu; Ashleigh E. Baber; Jaime Evans; Sanjaya D. Senanayake; Darío J. Stacchiola; Ping Liu; Jan Hrbek; Javier Fernández Sanz; et al. Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO 2. Science 2014, 345, 546-550, 10.1126/science.1253057.
- Sebastian Kuld; Max Thorhauge; Hanne Falsig; Christian F. Elkjær; Stig Helveg; Ib Chorkendorff; Jens Sehested; Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis. Science 2016, 352, 969-974, 10.1126/science.aaf0718.
- Oliver Martin; Antonio J. Martín; Cecilia Mondelli; Sharon Mitchell; Takuya F. Segawa; Roland Hauert; Charlotte Drouilly; Daniel Curulla‐Ferré; Javier Pérez‐Ramírez; Indium Oxide as a Superior Catalyst for Methanol Synthesis by CO2 Hydrogenation. Angew. Chem. Int. Ed. 2016, 55, 6261-6265, 10.1002/anie.201600943.