Effects of oxide carriers on surface functionality and process performance of the Cu–ZnO system in thesynthesis of methanol via CO2 hydrogenation

Journal of Catalysis, Volume 300, April 2013, Pages 141-151.
Francesco Arena, Giovanni Mezzatesta, Giovanni Zafarana, Giuseppe Trunfio, Francesco Frusteri, Lorenzo Spadaro

Dipartimento di Chimica Industriale e Ingegneria dei Materiali, Università degli Studi di Messina, Viale F. Stagno D’Alcontres 31 c.p. 29, I-98166 S. Agata (Messina), Italy

Istituto CNR-ITAE “Nicola Giordano”, Salita S. Lucia 5, I-98126 S. Lucia (Messina), Italy

 

 

Abstract

Physico-chemical properties and CO2-to-methanol hydrogenation functionality (TR, 453-513K; PR, 0.1-5.0 MPa) of Al2O3, ZrO2 and CeO2 supported Cu-ZnO catalysts were systematically addressed. Carriers control texture and metal surface exposure (MSA), while characterization of “steady-state” catalysts shows extensive CO2 and H2 coverage regardless of MSA, proving a crucial influence of oxide carrier on the adsorption properties of Cu-ZnO system. The kinetic dependence on pCO2 and pH2 confirms that dioxo-methylene intermediate hydrogenation is the rate limiting step (r.d.s.) at P<0.1 MPa, while a low kinetic dependence on pressure (0.3-0.5) signals that product desorption is r.d.s. at P>0.1 MPa. The influence of flow rate on selectivity pattern discloses that CH3OH is the primary reaction product at T<473K, while at higher temperature CO forms by consecutive decomposition of methanol (MD) and parallel reverse water gas shift (RWGS). Textural and chemical effects of zirconia carrier confer a superior performance to Cu-ZnO/ZrO2 system, attaining space time yield (STY) of 1.2 kgCH3OH×kgcat-1×h-1 at 10% conversion per pass.

 

 

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Additional Information

Nowadays the CO2 hydrogenation to methanol and dimethylether represents a very promising prospective for a valuable carbon dioxide recycling from stationary emission sources. In fact, as effective substitutes of oil-derived fuels, methanol-dimethylether would attain the strategic environmental goals of cutting greenhouse gas emissions and reducing air pollution levels in big metropolitan areas. CO2 hydrogenation processes feasibility, yet, relies on the availability of hydrogen produced by zero-emissions sources (for instance, renewable and/or nuclear energy). Hence, the fundamental research in catalysis is destined to play a pivotal role in providing effective systems operating at lower temperature and pressure. Coupled with novel engineering approaches, it is expected that improved catalysts will increase the technical and economical feasibility of the methanol-dimethylether synthesis technology.

 

Effects of oxide carriers on surface functionality

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