以两种季铵碱为模板剂合成A形体富集Beta沸石及其晶化过程

doi:10.7503/cjcu20140340

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (7): 1363.doi: 10.7503/cjcu20140340

• 研究论文: 无机化学 • 上一篇下一篇

以两种季铵碱为模板剂合成A形体富集Beta沸石及其晶化过程

郭文¹, 闫文付¹(), 徐如人¹, 王永睿², 慕旭宏²

1. 吉林大学无机合成与制备化学国家重点实验室, 化学学院, 长春 130012;
2. 石油化工催化材料与反应工程国家重点实验室, 中国石化石油化工科学研究院, 北京 100083

收稿日期:2014-04-10 出版日期:2014-07-10 发布日期:2014-06-09
作者简介:联系人简介: 闫文付, 男, 博士, 教授, 博士生导师, 主要从事无机微孔晶体的晶化机理和手性分子筛合成方面的研究.E-mail: yanw@jlu.edu.cn
基金资助:
国家自然科学基金(批准号: 21171063)、优秀青年科学基金(批准号: 21222103)、国家重点基础研究发展规划项目(批准号: 2011CB808703)和石油化工催化材料与反应工程国家重点实验室(中国石油化工股份有限公司石油化工科学研究院)开放课题基金资助

Synthesis and Crystallization Process of Polymorph A Enriched Beta Zeolite in the Presence of Two New Quaternary Ammonium Bases^†

GUO Wen¹, YAN Wenfu^1,^*(), XU Ruren¹, WANG Yongrui², MU Xuhong²

1.State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China;
2. State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China

Received:2014-04-10 Online:2014-07-10 Published:2014-06-09
Contact: YAN Wenfu E-mail:yanw@jlu.edu.cn
Supported by:
Supported by the National Natural Science Foundation of China(No.21171063), the Excellent Young Scientists Fund, China(No.21222103), the State Basic Research Projects of China(No.2011CB808703), and the State Key Laboratory of Catalytic Materials and Reaction Engineering(RIPP, SINOPEC)

摘要/Abstract

摘要：

以三甲基环己基氢氧化铵和二甲基乙基环己基氢氧化铵为模板剂或结构导向剂(SDA), 采用超浓水热方法合成了A形体富集的Beta沸石, 用粉末X射线衍射(XRD)、扫描电子显微镜(SEM)、 ²⁹Si固体魔角自旋核磁共振(²⁹Si MAS NMR)以及氮气吸附等表征手段对其进行了详细表征, 探索了最优合成条件, 研究了其晶化过程. 结果表明, 在晶化初期产物中己出现A形体过量特征, 随着晶化的进行, A形体的过量程度无显著变化.

关键词: β沸石, A形体, 手性分子筛

Abstract:

In the presence of trimethyl-cyclohexyl ammonium hydroxide or ethyl-dimethyl-cyclohexyl ammo-nium hydroxide, chiral polymorph A enriched Beta zeolites were synthesized. The products were further cha-racterized by X-ray powder diffraction(XRD), scanning electron microscope(SEM), ²⁹Si magic-angle spinning nuclear magnetic resonance(²⁹Si MAS NMR) and nitrogen adsorption-desorption analyses. The crystallization process of the polymorph A enriched Beta zeolite in the presence of trimethyl-cyclohexyl ammonium hydroxide and the influence of the water content in the initial mixture on the enrichment of the polymorph A were investigated. The results showed that the appropriate water content in the initial mixture was critical for the formation of polymorph A enriched Beta zeolite, the enrichment of chiral polymorph A occurred in the early stage of crystallization and the degree of the enrichment of polymorph A did not change during the crystallization.

Key words: Beta zeolite, Polymorph A, Chiral zeolite

中图分类号:

O611.4

TrendMD:

郭文, 闫文付, 徐如人, 王永睿, 慕旭宏. 以两种季铵碱为模板剂合成A形体富集Beta沸石及其晶化过程. 高等学校化学学报, 2014, 35(7): 1363.

GUO Wen, YAN Wenfu, XU Ruren, WANG Yongrui, MU Xuhong. Synthesis and Crystallization Process of Polymorph A Enriched Beta Zeolite in the Presence of Two New Quaternary Ammonium Bases^†. Chem. J. Chinese Universities, 2014, 35(7): 1363.

图/表 7

Fig.1 Powder XRD patterns of polymorph A enriched Beta zeolites a. SDA=ethyl-dimethyl-cyclohexyl ammonium hydroxide; b. SDA=trimethyl-cyclohexyl ammonium hydroxide. * Denotes the characteristic diffraction peaks of polymorph A.

Fig.2 Simulated powder XRD patterns of the Beta zeolite with different polymorph ratios of A/B and the experimental powder XRD patterns of the polymorph A enriched Beta zeolite and the normal Beta zeolite a. SDA=ethyl-dimethyl-cyclohexyl ammonium hydroxide; b. SDA=trimethyl-cyclohexyl ammonium hydroxide.

Fig.3 As-synthesized polymorph A enriched Beta zeolite with truncated bipyramidal morphology(A, B) and cubic morphology(C, D) SDA=trimethyl-cyclohexyl ammonium hydroxide.

Fig.4 29Si MAS NMR spectra of polymorph A enriched Beta zeolite SDA=trimethyl-cyclohexyl ammonium hydroxide.

Fig.5 Nitrogen adsorption-desorption isotherms of calcined polymorph A enriched Beta zeolite SDA=trimethyl-cyclohexyl ammonium hydroxide.

Fig.6 XRD patterns of the samples from the gels dried for different time at 80 ℃ SDA=trimethyl-cyclohexyl ammonium hydroxide. Drying treatment time/h: a. 120; b. 168; c. 216; d. 288.

Fig.7 XRD patterns of the samples isolated throughout the hydrothermal treatment period for polymorph A enriched Beta zeolite Hydrothermal treatment time/h: a. 24; b. 48; c. 72; d. 96; e. 120; f. 168; g. 216.

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以两种季铵碱为模板剂合成A形体富集Beta沸石及其晶化过程

Synthesis and Crystallization Process of Polymorph A Enriched Beta Zeolite in the Presence of Two New Quaternary Ammonium Bases^†

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[2]	童明全, 闫文付, 于吉红, 徐如人. A形体过量β沸石的晶化过程[J]. 高等学校化学学报, 2013, 34(3): 494.

以两种季铵碱为模板剂合成A形体富集Beta沸石及其晶化过程

Synthesis and Crystallization Process of Polymorph A Enriched Beta Zeolite in the Presence of Two New Quaternary Ammonium Bases†

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Synthesis and Crystallization Process of Polymorph A Enriched Beta Zeolite in the Presence of Two New Quaternary Ammonium Bases^†