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Promoting Mechanism of MCAR/MDA Coupling Reaction Under Oxygen-Rich Condition to Avoid Rapid Deactivation of MDA Reaction

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UV Raman, TG-MS (TPO) and nitrogen physisorption characterization were used to characterize deactivated Mo/HZSM-5 catalysts from coupling reaction of methane CO2 autothermal reforming (MCAR) and methane dehydroaromatization (MDA). The results show that MCAR/MDA maintains the Mo-oxo species throughout the process, reducing the maximum C6H6 yield, but extending the reaction life by at least 4 time. As O/CH4 increases, MCAR/MDA changes from oxygen-deficient to oxygen-rich state. For MCAR/MDA under oxygen-deficient condition, O2 can only delay the accumulation of aromatics. Grown of coke on Brӧnsted acid eventually leads to complete blockage of the micropores of the catalyst. Slowly deposited graphite coke in MCAR/MDA extended the critical time by nearly 4 times. For MCAR/MDA under oxygen-rich condition, a 70% C6H6 selectivity was maintained throughout the process. After 3700 min of operation, the remaining micropore volume and micropore surface of the deactivated catalyst remained above 1/3. The timely removal of graphite coke at the pore mouth by the MCAR/MDA reaction under oxygen-rich conditions can eliminate the limitation of C6H6 diffusion, thereby effectively preventing the acceleration of the coke deposit micropores which cause the MDA reaction to be rapidly deactivated.

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Acknowledgements

This work was supported by the key project of Liaoning Province Natural Science Fund Project (20170540459), the open objects of the major science and technology platform, Liaoning University of Science and Technology (USTLKFZD 201632) and the 47th batch Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry of China.

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Authors and Affiliations

  1. Provincial Major Science and Technology Platform, University of Science and Technology Liaoning, Anshan, 114051, Liaoning, China

    Xilong Chen, Shuangxi Lin, Haowen Zhang & Songdong Yao

  2. Graduate School, University of Science and Technology Liaoning, Anshan, 114051, Liaoning, China

    Xilong Chen, Yanzeng Dong, Xiaohang Yu, Zhiheng Wang & Yanyan Liu

  3. Liaoning Institute of Energy Research Co., Ltd, Yingkou, 115000, Liaoning, China

    Jiankun Liu

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  1. Xilong Chen
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Chen, X., Dong, Y., Lin, S. et al. Promoting Mechanism of MCAR/MDA Coupling Reaction Under Oxygen-Rich Condition to Avoid Rapid Deactivation of MDA Reaction. Catal Lett 150, 2115–2131 (2020). https://doi.org/10.1007/s10562-020-03114-1

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