Two-stage conversion of CO2 to methanol and dimethyl ether using CuO–ZnO–Al2O3/protonated Y-type zeolite catalysts

Abstract

The CuO-ZnO-Al2O3/protonated Y-type zeolite (CZA/HYZ) catalysts were prepared via co-precipitation method and employed in a two-stage CO2 conversion process using a dual fixed–bed column at different temperatures and 50 bar. Catalytic components of CZA/HYZ were copper species that have been identified with XPS. Remarkably, the fine structures of CZA/HYZ catalysts metal atoms were confirmed with XANES and EXAFS spectra. Molecular configurations of catalytic species in CZA/HYZ catalyst simulated from the XANES/EXAFS spectra-analyzed fine structural parameters were schematically displayed. The optimal catalytic performances of CZA/HYZ (CH3OH conversion=78.0%, CH3OCH3/HCOOH selectivity=91.7%/8.3%, CH3OCH3/HCOOH yield=71.5%/6.5%) were achieved at 250 ºC. The Arrhenius equation and a pseudo-first-order/second-order model were used to evaluate the activation energies and rate constants of CH3OH and CH3OCH3 formations at various catalytic temperatures. The low activation energies (2.720 and 1.160 kJ mol−1) and Gibbs energies (3.26 and −40.00 kJ mol−1) of CH3OH and CH3OCH3 formations at 250 ºC, demonstrated that their spontaneities were remarkably improved via CZA/HYZ, respectively. The total income from a 10–ton per day (10–TPD) for a petrochemical refinery plant waste gas utility process was USD $43,557d−1, as well a payback of 3.23 years, based on cost evaluation. The proposed process provides a continuous two-step process for manufacturing high–value-added chemicals using industrial CO2 emitted and syngas.