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ORIGINAL RESEARCH ARTICLE

Kinetic analysis and process optimization of carbon dioxide hydrogenation to methanol over copper/zinc oxide/self-pillared pentasil-zeolite catalyst

Xiaolong Liu1 ,  Guangying Fu1 ,  Ruiqin Ding1 ,  Ke Liang2 ,  Qiaolin Lang1* ,  Xiaobo Yang3*
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1 Key Laboratory of Photoelectrochemical Conversions, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, Shandong, China
2 Tianjin Passion Advanced Material Technology LLC., Binhai, Tianjin, China
3 R&D Division, Vitalite ApS, Allerød, Hovedstaden, Denmark
JES, 025310015 https://doi.org/10.36922/JES025310015
Received: 31 July 2025 | Revised: 12 September 2025 | Accepted: 12 September 2025 | Published online: 7 October 2025
© 2025 by the Author(s). This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution 4.0 International License ( https://creativecommons.org/licenses/by/4.0/ )
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Abstract

Hydrogenation of carbon dioxide (CO2) using hydrogen generated by renewable electricity-powered water electrolysis is a key technology for producing e-fuels and supporting other carbon capture, utilization, and storage applications. Studies on reaction kinetics, reactors, and process engineering have predominantly focused on copper (Cu)/zinc oxide (ZnO)/aluminum oxide catalysts. This study analyzes the reaction kinetics of CO2 hydrogenation into methanol and carbon oxide using a novel catalyst composed of Cu, ZnO, and self-pillared pentasil (SPP) zeolite. The one-site microkinetic model developed by Vanden Bussche and Froment was applied to fit initial laboratory-scale test data. The Cu/ZnO/SPP-zeolite catalyst demonstrates rapid kinetics and low apparent activation energy for methanol synthesis and the reversed water–gas shift reaction. As a result, it achieved an enhanced space-time yield of methanol at 1.75 kg⋅kgcat−1/h at 230°C and 50 bar in a single path simulation with a CO2/3H2 feed stream. Furthermore, a corresponding process optimization aiming at maximizing methanol yield was conducted, incorporating one recycling loop of the vapor products. The process simulation successfully converged with a 90% recycling rate, enabling the conversion of 2,000 NT of CO2 per year, resulting in 1,836 NT of crude methanol at a concentration of 62.5 wt%. These findings provide a valuable addition to the existing literature.

Graphical abstract
Keywords
Carbon dioxide fixation
Carbon dioxide hydrogenation
Copper/zinc oxide/self-pillared pentasil-zeolite catalyst
Reaction kinetics
Process optimization
Funding
This work was funded by the Natural Science Foundation of Shandong Province, China (ZR2022MB053 and ZR2022QB216).
Conflict of interest
The authors declare that they have no competing interests.
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