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Piperazine as a versatile organic structure-directing agent for zeolite synthesis: effect of SiO2/Al2O3 ratio on phase selectivity

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Abstract

The synthesis of aluminosilicate zeolites by using piperazine as the organic structure-directing agent was studied. Under optimized conditions, zeolites ZSM-4 (MAZ), mordenite (MOR), ZSM-35 (FER), ZSM-5 (MFI) and ZSM-12 (MTW) were obtained in pure phase. The effect of SiO2/Al2O3 ratio in the initial gel on zeolite phase selectivity was systematically investigated. The SiO2/Al2O3 ratio ranges for the formation of each zeolite had been established. At low SiO2/Al2O3 ratios, ZSM-4 (SiO2/Al2O3 = 9) and mordenite (SiO2/Al2O3 = 12.8) could be obtained, while ZSM-35 (14.3 ≤ SiO2/Al2O3 ≤ 29.3), ZSM-5 (SiO2/Al2O3 = 58.7) and ZSM-12 (SiO2/Al2O3 = 117.2) gradually evolved as the SiO2/Al2O3 ratio increased. Piperazine was considered to have a charge-compensatory role when the amine group was protonated; its overall effectiveness depended on the zeolite structure. Piperazine fitted best with the FER structure, and the obtained FER zeolite had a hierarchical house of card texture which was assembled by the primary plate-shaped crystals. The ZSM-4, mordenite and ZSM-35 zeolites (in acidic form) were tested for the dimethyl ether carbonylation reaction; the essential role of 12-member ring (12MR) pore in mordenite for molecule transportation to the 8MR pore was proved by comparing to ZSM-4 that lacks interconnectivity between 12MR and 8MR pores.

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Acknowledgements

This work was supported by the Natural Science Foundation of China (Grant No. 21773229 and 21878244).

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Authors and Affiliations

  1. School of Chemical Engineering, Northwest University, Xi’an, 710069, Shaanxi, China

    Luyi Bai & Shuang Li

  2. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China

    Luyi Bai, Zhiping Xiong, Ensheng Zhan & Wenjie Shen

  3. University of Chinese Academy of Sciences, Beijing, 100049, China

    Zhiping Xiong

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Bai, L., Xiong, Z., Zhan, E. et al. Piperazine as a versatile organic structure-directing agent for zeolite synthesis: effect of SiO2/Al2O3 ratio on phase selectivity. J Mater Sci 54, 7589–7602 (2019). https://doi.org/10.1007/s10853-019-03433-8

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