Effect of operating parameters on H-2/CO2 conversion to methanol over Cu-Zn oxide supported on ZrO2 polymorph catalysts: Characterization and kinetics

Author(s)

Marcos, Francielle C. F. ^[1] ; Cavalcanti, Fabio M. ^[1] ; Petrolini, Davi D. ^[2] ; Lin, Lili ^[3] ; Betancourt, Luis E. ^[3] ; Senanayake, Sanjaya D. ^[3] ; Rodriguez, Jose A. ^[3] ; Assaf, Jose M. ^[4] ; Giudici, Reinaldo ^[1] ; Assaf, Elisabete M. ^[2]

Affiliation

^[1] Univ Sao Paulo, Dept Chem Engn, Escola Politecn, Av Prof Luciano Gualberto, T 3, 380, BR-05508010 Sao Paulo, SP - Brazil

^[2] Univ Sao Paulo, Sao Carlos Inst Chem, Av Trabalhador Sao Carlense 400, BR-13560970 Sao Carlos, SP - Brazil

^[3] Brookhaven Natl Lab, Chem Dept, Upton, NY 11973 - USA

^[4] Univ Fed Sao Carlos, Rod W Luiz Km 235, BR-13565905 Sao Carlos, SP - Brazil

• Document type: Journal article
• Source: CHEMICAL ENGINEERING JOURNAL; v. 427, JAN 1 2022.
• Web of Science Citations: 1

Abstract

Kinetic aspects of the operating parameters for the catalytic conversion of H-2/CO2 to methanol over two novel catalysts were evaluated to understand the effect of the polymorphic ZrO2 phase composed of Cu0/+-ZnO sites at the atomic level and its impact on the reaction mechanism. The catalysts were characterized by in situ and ex-situ XRD, N-2 adsorption/desorption isotherms, FRX, TPR, TPD-N2O, in situ XANES, TPD-CO2, and in situ DRIFTS techniques. The influence of different reaction variables such as the GHSV, temperature, pressure, and H-2/CO2 ratio were studied using a fixed bed continuous plug flow reactor. The Cu-ZnO catalyst supported on the tetragonal zirconia polymorph exhibited the highest methanol yield due to the lower activation energy when compared to the catalyst with a greater amount of the monoclinic phase. In addition, the catalysts were reused for 8 cycles of 6 h to evaluate their stability, which can translate into lower costs for large-scale methanol production. The estimation of the kinetic parameters for the Cu-Zn oxide catalysts supported on ZrO2 polymorphs was important to understand the reaction mechanism, as well as to provide useful information for scaling up the process. (AU)

• FAPESP's process: 19/10980-9 - Oxidative Coupling of Methane using A2B2O7 catalysts
• Grantee: Davi Domingos Petrolini
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 17/08293-8 - Project 14: direct synthesis of methanol from CO2
• Grantee: Francielle Candian Firmino Marcos
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 17/11940-5 - Evaluation of catalysts supported on carbon nanotubes and kinetic modeling of the process for the Water-Gas-Shift reaction (WGS)
• Grantee: Fábio Machado Cavalcanti
• Support Opportunities: Scholarships in Brazil - Doctorate
• FAPESP's process: 14/50279-4 - Brasil Research Centre for Gas Innovation
• Grantee: Julio Romano Meneghini
• Support Opportunities: Research Grants - Applied Research Centers Program
• FAPESP's process: 18/05799-0 - A surface science investigation of methanol synthesis on Cu-Ga/ZrO2 catalysts
• Grantee: Francielle Candian Firmino Marcos
• Support Opportunities: Scholarships abroad - Research Internship - Post-doctor