化工学报 ›› 2017, Vol. 68 ›› Issue (3): 1231-1238.DOI: 10.11949/j.issn.0438-1157.20161381

• 材料化学工程与纳米技术 • 上一篇    下一篇

干胶转化法合成整体式SSZ-13分子筛

冯晴1, 裴仁彦2, 刘红光1,2, 于海斌1,2, 张丽娟2, 张耀日2   

  1. 1 河北工业大学化工学院, 天津 300130;
    2 中海油天津化工设计研究院有限公司, 天津 300130
  • 收稿日期:2016-09-30 修回日期:2016-10-18 出版日期:2017-03-05 发布日期:2017-03-05
  • 通讯作者: 裴仁彦,peirenyan@163.com

Synthesis of monolithic SSZ-13 zeolite by dry-gel conversion method

FENG Qing1, PEI Renyan2, LIU Hongguang1,2, YU Haibin1,2, ZHANG Lijuan2, ZHANG Yaori2   

  1. 1 College of Chemical Engineering, Hebei University of Technology, Tianjin 300130, China;
    2 CNOOC Tianjin Chemical Research & Design Institute, Tianjin 300130, China
  • Received:2016-09-30 Revised:2016-10-18 Online:2017-03-05 Published:2017-03-05
  • Contact: 10.11949/j.issn.0438-1157.20161381

摘要:

采用干胶转化法合成了整体式SSZ-13分子筛,先成型后晶化,系统地考察了物料配比及晶化条件对合成结果的影响,通过X射线衍射(XRD)、X射线荧光(XRF)、热重-差热分析仪(TG-DTA)、扫描电子显微镜(SEM)、氨气的程序升温吸附-脱附(NH3-TPD)、傅里叶红外光谱仪(FI-IR)、液体核磁共振谱(NMR)对产物进行表征分析,并讨论了混合模板剂N,N,N-三甲基-1-金刚烷氢氧化铵和氯化胆碱在晶化过程中起的作用。结果表明,合成的整体式SSZ-13分子筛具有典型的介孔堆积孔、较大的比表面积,在空气中热稳定性良好。氯化胆碱加速了分子筛晶化,缩短了晶化时间,提高产物的结晶度,明显降低了N,N,N-三甲基-1-金刚烷氢氧化铵的使用量,起到了辅助结构导向的作用,且混合模板剂均填充产物孔道。

关键词: 干胶转化, 整体式, SSZ-13, 分子筛, 结晶, 氯化胆碱, 结构导向, 成核

Abstract:

In this work, monolithic SSZ-13 zeolite was synthesized using dry-gel conversion method. The influences of the gel composition and crystallization conditions on the crystallization of SSZ-13 zeolite were investigated. The as-synthesized product was characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF),thermo gravimetric-differential thermal analysis (TG-DTA, scanning electron microscope(SEM), NH3 temperature-programmed desorption(NH3-TPD, Nuclear Magnetic Resonance (NMR). The roles of N,N,N-trimethyl-1-adamantanammonium (TMADa+) and choline chloridein crystallization reaction were discussed. According to the result, the monolithic SSZ-13 zeolite has typical accumulated mesopores, larger surface area and better thermal stability in air. The results in FT-IR and NMR spectra show that choline chloride could act as a secondary structure-directing agent and fill in the pores of zeolite, which significantly reduced the amount of TMADa+. It was confirmed that Choline Chloride favors accelerating zeolite nucleation, shortening the crystallization time, and improving crystallinity of the as-synthesized product.

Key words: dry-gel conversion, monolithic, SSZ-13, zeolite, crystallization, choline chloride, structural-directing, nucleation

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