石油炼制与化工 ›› 2023, Vol. 54 ›› Issue (6): 55-63.

• 基础研究 • 上一篇    下一篇

可控b轴长度的MFI纳米分子筛膜的原位定向构筑及其在正/异丁烷分离上的应用

张永汾,李金芝,刘洪全,于中伟,周勇   

  1. 中石化石油化工科学研究院有限公司
  • 收稿日期:2022-10-21 修回日期:2023-01-09 出版日期:2023-06-12 发布日期:2023-05-29
  • 通讯作者: 李金芝 E-mail:lijinzhi.ripp@sinopec.com

IN-SITU ORIENTED CONSTRUCTION OF MFI NANO-ZEOLITE MEMBRANES WITH CONTROLLABLE b-ORIENTED LENGTH AND ITS SEPARATION PERFORMANCE FOR n-BUTANE/i-BUTANE

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  • Received:2022-10-21 Revised:2023-01-09 Online:2023-06-12 Published:2023-05-29

摘要: 通过向合成液引入晶化调节剂尿素,分别采用一步恒温晶化和两步变温晶化法在氧化铝支撑体上原位制备了定向生长的MFI纳米分子筛膜。采用X射线衍射、冷场扫描电子显微镜表征技术分别对制备的MFI分子筛及其MFI分子筛膜的结构、形貌进行表征。通过调节合成液中尿素配比和两步变温原位水热晶化时间,得到系列高横径比和高纵径比的分子筛晶种,在合成液中尿素添加量(以尿素与硅的物质的量比计)为基准、先120 ℃晶化6 h、后180 ℃晶化8 h时,得到的分子筛尺寸最小,b轴最短,仅为60 nm,同样条件下在氧化铝支撑体上制备得到b轴取向生长性高的纳米MFI分子筛膜。延长高温段晶化时间至14 h,得到对正/异丁烷混合液化气(正丁烷质量分数40%,异丁烷质量分数60%)有良好的渗透性能和分离能力的b轴定向生长分子筛膜,在25 ℃条件下,正丁烷渗透通量为2.2×10-7 mol/(m2·s·Pa),分离因子为23.9,连续评价100 h后分离效果无明显降低。

关键词: MFI纳米分子筛膜, 短b轴, 原位定向生长, 正丁烷, 异丁烷

Abstract: MFI nano-zeolite membranes were prepared in-situ on alumina supports by one-step constant temperature and two-step varying-temperature crystallization with urea as crystallization regulator. The structure and morphology of MFI zeolite and MFI zeolite membranes were characterized by XRD and SEM. A series of zeolite seeds with high transverse diameter ratio and longitudinal diameter ratio were obtained by adjusting the ratio of urea in the synthetic solution and the two-step in-situ hydrothermal crystallization time at variable temperature. When the amount of urea added in the synthetic solution (based on the mass ratio of urea to silicon) and the crystallization time of 120 ℃ for 6 h and then 180 ℃ for 8 h, the size of the zeolite was the smallest, and the b-axis was the shortest, only 60 nm. Under the same conditions, nano-MFI zeolite membranes with high b-axis orientation were prepared on alumina supports. Extending the crystallization time of the high temperature section to 14 h to obtain a b-axis oriented zeolite membrane with good permeability and separation ability for n-butane/i-butane liquefaction (40% of n-butane and 60% of i-butane), the osmoticflux of n-butane was 2.2×10-7 mol/(m2·s·Pa),and the separation factor was 23.9 under the condition of 25 ℃. The effect of 100 h continuous evaluation was not significantly decreased.

Key words: MFI nano-zeolite membrane, short b-axis, in situ directional growth, n-butane, i-butane