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Surface-gel-conversion synthesis of submicron-thick MFI zeolite membranes to expedite shape-selective separation of hexane isomers

表面胶转化法合成亚微米厚度MFI型分子筛薄膜应用于快速择形分离己烷异构体

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Abstract

Ultrathin zeolite membranes are of paramount importance in accelerating gas transport during membrane separation, and lowering down their membrane thicknesses to submicron scale is deemed to be very challenging. Herein, we develop an advanced approach of surface gel conversion for synthesis of submicron-thick pure silica MFI (silicalite-1) zeolite membranes. Viscous gel is prepared by finely adjusting the precursor composition, enabling its reduced wettability. The unfavorable wetting of the support surface can effectively prevent gel penetration into alumina support voids. Aided by the seeds, the surface gel is directly and fully crystallized into an MFI zeolite membrane with minimal water steam. A membrane with a thickness of 500 nm is successfully acquired and it is free of visible cracks. Additionally, the as-synthesized membranes exhibit rapid and selective separation of hexane isomers by virtue of unprecedentedly high n-hexane permeance of 24.5×10−7 mol m−2 s−1 Pa−1 and impressive separation factors of 13.3-22.6 for n-hexane over its isomers. This developed approach is of practical interest for sustainable synthesis of high-quality zeolite membranes.

摘要

在膜分离中, 薄膜超薄化对促进气体传输至关重要, 而将膜厚降至亚微米级则极具挑战性. 本文中, 我们提出表面胶转化法来合成亚微米厚度的纯硅MFI分子筛膜. 通过精细调控前驱体化学组成制备了低浸润性的黏性胶, 有效防止凝胶从氧化铝载体表面渗透至空隙中. 在晶种的诱导下, 辅以少量水蒸气, 表面凝胶经历了直接和完全晶化过程, 形成了厚度为~500 nm并且连续致密的MFI分子筛膜. 合成的分子筛膜展示出对正己烷同分异构体的快速选择性分离性能: 超高的正己烷渗透量(24.5×10−7 mol m−2 s−1 Pa−1); 以及可观的分离系数(13.3–22.6, 正己烷对其同分异构体). 此外, 该方法还是一种绿色合成方法, 为可持续性制备高质量分子筛膜奠定了科学基础.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21531003, 21501024 and 21971035), Jilin Scientific and Technological Development Program (20170101198JC and 20190103017JH), Jilin Education Office (JJKH20180015KJ), “111” Program (B18012), and open projects from the State Key Laboratory of Inorganic Synthesis & Preparative Chemistry and State Key Laboratory of Heavy Oil Processing (2018-8, SKLOP201902003).

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Authors and Affiliations

  1. Faculty of Chemistry, Northeast Normal University, Changchun, 130024, China

    Huazhen Rong  (荣华臻), Gaimei Wang  (王改梅), Xiaoqin Zou  (邹小勤) & Guangshan Zhu  (朱广山)

  2. Key Laboratory of UV-Emitting Materials and Technology of Ministry of Education, Northeast Normal University, Changchun, 130024, China

    Jiaxu Yan  (闫佳旭)

Authors
  1. Huazhen Rong  (荣华臻)
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  2. Gaimei Wang  (王改梅)
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  3. Jiaxu Yan  (闫佳旭)
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  4. Xiaoqin Zou  (邹小勤)
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  5. Guangshan Zhu  (朱广山)
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Contributions

Author contributions Zou X conceived the idea, designed and supervised the experiment; Rong H carried out the experiment, analyzed the data and drafted the paper; Wang G and Yan J performed the SEM and Raman measurements; Zhu G helped the data interpretation and commented on the paper. All authors contributed to the paper writing.

Corresponding author

Correspondence to Xiaoqin Zou  (邹小勤).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Huazhen Rong received his BSc degree in 2016 from Shandong Agricultural University, and joined Prof. Guangshan Zhu’s research group in the same year. He is currently pursuing a PhD degree under the supervision of Prof. Xiaoqin Zou and Prof. Guangshan Zhu at Northeast Normal University. His research is centered on the synthesis and characterization of microporous membranes for separations.

Gaimei Wang obtained her BSc degree in 2017 from Taiyuan Normal University. She is currently a master student under the supervision of Prof. Xiaoqin Zou at Northeast Normal University. Her current research interest focuses on the preparation and separation performance of microporous membranes.

Jiaxu Yan received his BSc degree from Changchun University of Science and Technology in 2018. He is studying at Northeast Normal University for his MSc degree. His research interest focuses on the preparation and optical property modulation of 2D materials.

Xiaoqin Zou received his BSc and MSc degrees from Jilin University (2006 and 2009, respectively), and PhD degree (2012) from the University of Caen, France. He worked as a post-doc researcher during 2013–2015 in the University of California at Berkeley (USA). In 2015, he was appointed as a full professor in Northeast Normal University. His current scientific interests include the syntheses, characterizations and advanced applications of novel microporous materials.

Guangshan Zhu studied chemistry in 1993 and earned his PhD degree at Jilin University in 1998. He worked as a post-doc fellow in 1999 at Tohoku University in Japan. He was a full professor since 2001 in Jilin University and moved to Northeast Normal University in 2015. The current research in his group focuses on the design and synthesis of porous materials, in particular, porous aromatic frameworks with applications in adsorption, separation and other areas.

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Surface-gel-conversion synthesis of submicron-thick MFI zeolite membranes to expedite shape-selective separation of hexane isomers

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Rong, H., Wang, G., Yan, J. et al. Surface-gel-conversion synthesis of submicron-thick MFI zeolite membranes to expedite shape-selective separation of hexane isomers. Sci. China Mater. 64, 374–382 (2021). https://doi.org/10.1007/s40843-020-1400-y

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