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Ionothermal synthesis, physicochemical characterization and catalytic performance of extra-large-pore silicoaluminophosphate zeotype with -CLO structure

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Abstract

Silicoaluminophosphate zeotypes with -CLO structure (SAPO-CLO) were ionothermally synthesized in 1-ethyl-3-methyl imidazolium ([emim]+) ionic liquid in the presence of tetrapropylammonium hydroxide. The physicochemical properties of SAPO-CLO with different silicon content were comparatively studied using several characterization techniques including XRD, SEM, XRF, NMR, BET, NH3-TPD, in situ DRIFTS etc. Notably, 29Si MAS NMR results revealed the incorporation of Si in the structure that was mainly in the form of SMII and SMIII combination. NH3-TPD and in situ DRIFTS results demonstrated that SAPO-CLO exhibited higher acid amount than AlPO-CLO as a result of the formation of new Brönsted acid sites Si–OH–Al in addition to structural P–OH in the framework. N2 physisorption results showed SAPO-CLO compared with AlPO-CLO exhibited higher BET surface area and microporous volume with the presence of extra-large-pore of about 1.2 nm. Finally, the catalytic performance of SAPO-CLO was evaluated in both methanol-to-olefin and propene oligomerization reactions to elucidate its activity, shape-selectivity and hydrothermal stability. SAPO-CLO showed improved catalytic activity in comparison to AlPO-CLO in both reactions, and lower selectivity of light olefins in the former reaction and higher selectivity of C3n oligomers in the latter reaction in comparison to small-pore SAPO-LTA. The deactivated catalyst was unrecoverable in MTO reaction due to structure degradation by water produced during the reaction, whereas recoverable in oligomerization reaction after the removal of coke by high temperature calcination.

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Acknowledgements

The authors thank the financial support from Beijing Natural Science Foundation (No. 2182048) and Fundamental Research Funds for the Central Universities (Nos. XK1802-1 and JD2016).

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Authors and Affiliations

  1. State Key Laboratory of Organic-Inorganic Composites, Beijing Key Laboratory of Energy Environmental Catalysis, Beijing University of Chemical Technology, Beijing, 100029, China

    Xiangzhi Meng, Ke Guo, Yutong Lin, Hao Wang, Hongxia Chen, Pengfei Huang, Ying Wei & Runduo Zhang

  2. Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, 252059, Shandong, China

    Shuo Tao

  3. National Energy Research Center for Coal to Clean Fuels, Synfuels China Co., Ltd, Beijing, 101407, China

    Ling Zhang

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  1. Xiangzhi Meng
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Meng, X., Guo, K., Lin, Y. et al. Ionothermal synthesis, physicochemical characterization and catalytic performance of extra-large-pore silicoaluminophosphate zeotype with -CLO structure. J Porous Mater 28, 1585–1594 (2021). https://doi.org/10.1007/s10934-021-01106-z

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