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Title: Effect of operating parameters on H2/CO2 conversion to methanol over Cu-Zn oxide supported on ZrO2 polymorph catalysts: Characterization and kinetics

Abstract

Kinetic aspects of the operating parameters for the catalytic conversion of H2/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, N2 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 H2/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 hours to evaluate their stability, which can translate into lower costs for large-scale methanol production. As a result, the estimation of the kinetic parameters over Cu-Zn oxide supported on ZrO2 polymorphs was significant for understanding the reaction mechanism, as well as to provide a pathway for scaling-up of the process.

Authors:
 [1]; ORCiD logo [1];  [2];  [3];  [3];  [3]; ORCiD logo [3];  [4]; ORCiD logo [1];  [2]
+ Show Author Affiliations
  1. Univ. de São Paulo (Brazil)
  2. Univ. de São Paulo, Sao Carlos (Brazil)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Univ. Federal de São Carlos (Brazil)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1805235
Report Number(s):
BNL-221755-2021-JAAM
Journal ID: ISSN 1385-8947
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Engineering Journal
Additional Journal Information:
Journal Volume: 427; Journal ID: ISSN 1385-8947
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; carbon dioxide; methanol; hydrogen; copper; zinc oxide; zirconium oxide; CO2 hydrogenation; zirconia-supported catalysts; zirconia polymorphs; reaction mechanism; kinetics

Citation Formats

Marcos, Francielle C. F., Cavalcanti, Fabio M., Petrolini, Davi D., Lin, Lili, Betancourt, Luis E., Senanayake, Sanjaya D., Rodriguez, José A., Assaf, José M., Giudici, Reinaldo, and Assaf, Elisabete M. Effect of operating parameters on H2/CO2 conversion to methanol over Cu-Zn oxide supported on ZrO2 polymorph catalysts: Characterization and kinetics. United States: N. p., 2021. Web. doi:10.1016/j.cej.2021.130947.
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Marcos, Francielle C. F., Cavalcanti, Fabio M., Petrolini, Davi D., Lin, Lili, Betancourt, Luis E., Senanayake, Sanjaya D., Rodriguez, José A., Assaf, José M., Giudici, Reinaldo, & Assaf, Elisabete M. Effect of operating parameters on H2/CO2 conversion to methanol over Cu-Zn oxide supported on ZrO2 polymorph catalysts: Characterization and kinetics. United States. https://doi.org/10.1016/j.cej.2021.130947
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Marcos, Francielle C. F., Cavalcanti, Fabio M., Petrolini, Davi D., Lin, Lili, Betancourt, Luis E., Senanayake, Sanjaya D., Rodriguez, José A., Assaf, José M., Giudici, Reinaldo, and Assaf, Elisabete M. Wed . "Effect of operating parameters on H2/CO2 conversion to methanol over Cu-Zn oxide supported on ZrO2 polymorph catalysts: Characterization and kinetics". United States. https://doi.org/10.1016/j.cej.2021.130947. https://www.osti.gov/servlets/purl/1805235.
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@article{osti_1805235,
title = {Effect of operating parameters on H2/CO2 conversion to methanol over Cu-Zn oxide supported on ZrO2 polymorph catalysts: Characterization and kinetics},
author = {Marcos, Francielle C. F. and Cavalcanti, Fabio M. and Petrolini, Davi D. and Lin, Lili and Betancourt, Luis E. and Senanayake, Sanjaya D. and Rodriguez, José A. and Assaf, José M. and Giudici, Reinaldo and Assaf, Elisabete M.},
abstractNote = {Kinetic aspects of the operating parameters for the catalytic conversion of H2/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, N2 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 H2/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 hours to evaluate their stability, which can translate into lower costs for large-scale methanol production. As a result, the estimation of the kinetic parameters over Cu-Zn oxide supported on ZrO2 polymorphs was significant for understanding the reaction mechanism, as well as to provide a pathway for scaling-up of the process.},
doi = {10.1016/j.cej.2021.130947},
journal = {Chemical Engineering Journal},
number = ,
volume = 427,
place = {United States},
year = {Wed Jun 23 00:00:00 EDT 2021},
month = {Wed Jun 23 00:00:00 EDT 2021}
}
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