1. National Engineering Research Center of Lower-Carbon Catalysis Technology, Dalian National Laboratory for Clean Energy, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China 2. School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China 3. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
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.
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