Alkylation of benzene with carbon dioxide to low-carbon aromatic hydrocarbons over bifunctional Zn-Ti/HZSM-5 catalyst

Abstract

Alkylation of benzene to value-added, high octane number and low toxic toluene and xylenes provides a way to lower benzene content in gasoline pool, and is hence a method to promote fuel quality. On the other hand, CO₂ accumulation in the atmosphere causes global warming and requires effective route for its valorization. Utilization of CO₂ as a carbon source for benzene alkylation could achieve both goals. Herein, alkylation of benzene with CO₂ and H₂ was realized by a series of low-cost bifunctional catalysts containing zinc/titanium oxides (Zn/Ti oxides) and HZSM-5 molecular sieves in a fixed-bed reactor. By regulating and controlling oxygen vacancies of Zn/Ti oxides and the acidities of HZSM-5, benzene conversion and CO₂ conversion reached 28.7% and 29.9% respectively, along with a total selectivity of toluene and xylene higher than 90%. In this process, more than 25% CO₂ was effectively utilized and incorporated into the target products. Moreover, the mechanism of the reaction was analyzed and the course was simultaneously traced. CO₂ was transformed into methanol firstly, and then methanol reacted with benzene generating toluene and xylene. The innovation provides a new method for upgrading of fuels and upcycling the emissions of CO₂, which is of great environmental and economic benefits.

Graphical abstract

Keywords

carbon dioxide / benzene / alkylation / bifunctional catalyst / mechanism

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Acknowledgements

This project was sponsored financially by Shanghai Postdoctoral Scientific Program (Grant No. 14R21410400) and the National Natural Science Foundation of China (Grant No. 2177061270).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at http://dx.doi.org/10.1007/s11705-021-2045-y and is accessible for authorized users.

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