Enhancing the aromatic selectivity of cyclohexane aromatization by CO₂ coupling

Abstract

Improving the aromatic selectivity in the alkane aromatization process is of great importance for its practical utilization but challenge to make because the high H/C ratio of alkanes would lead to a serious hydrogen transfer process and a large amount of light alkanes. Herein, CO₂ is introduced into the cyclohexane conversion process on the HZSM-5 zeolite, which can improve the aromatic selectivity. By optimizing the reaction conditions, an improved aromatic (benzene, toluene, xylene, and C₉₊) selectivity of 48.2% can be obtained at the conditions of 2.7 MPa (CO₂), 450 °C, and 1.7 h⁻¹, which is better than that without CO₂ (aromatic selectivity = 43.2%). In situ transmission Fourier transform infrared spectroscopy spectra illustrate that many oxygenated chemical intermediates (e.g., carboxylic acid, anhydride, unsaturated aldehydes/ketones or ketene) would be formed during the cyclohexane conversion process in the presence of CO₂. ¹³C isotope labeling experimental results demonstrate that CO₂ can enter into the aromatics through the formation of oxygenated chemical intermediates and thereby improve the aromatic selectivity. This study may open a green, economic, and promising way to improve the aromatic selectivity for alkane aromatization process.

Graphical abstract

Keywords

aromatics / carbon dioxide / aromatization / coupling reaction / ZSM-5 zeolite

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Conflicts of interest

There are no conflicts to declare.

Acknowledgements

This work was supported by the National Key Research and Development Program of China (Grant No. 2022YFE0116000), the National Natural Science Foundation of China (Grant Nos. 22202193, 21991092, 21991090, 22172166 and 22288101), the China Postdoctoral Science Foundation (Grant No. 2019M661147), the Excellent Postdoctoral Support Program of Dalian Institute of Chemical Physics, CAS, the Excellent Research Assistant Funding Project of CAS, the Youth Innovation Promotion Association CAS (Grant No. 2021182), the Innovation Research Foundation of Dalian Institute of Chemical Physics, Chinese Academy of Sciences (Grant No. DICP I202217)

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