多级孔无铝Beta分子筛的合成与表征

doi:10.7503/cjcu20130931

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (2): 215.doi: 10.7503/cjcu20130931

• 研究论文: 无机化学 • 上一篇下一篇

多级孔无铝Beta分子筛的合成与表征

翁强¹, 陈沛¹(), 赵凤起², 高红旭², 陈新兵¹, 安忠维^1,²

1. 陕西师范大学材料科学与工程学院, 应用表面与胶体化学教育部重点实验室, 西安 710062
2. 西安近代化学研究所燃烧与爆炸技术重点实验室, 西安 710065

收稿日期:2013-09-22 出版日期:2014-02-10 发布日期:2013-12-30
作者简介:联系人简介: 陈沛, 女, 博士, 副教授, 主要从事无机功能材料制备及应用研究. E-mail:chenpei@snnu.edu.cn
基金资助:
教育部长江学者和创新团队发展计划(批准号: IRT1070)、陕西省重点科技创新团队(批准号: 2012KCT-21)、陕西省自然科学基金(批准号: 2012JM2002)、陕西省科技攻关项目(批准号: 2012K08-09)、中央高校团队项目(批准号: GK261001108, GK261001009)和中央高校基本科研业务费专项资金(批准号: GK201101003, GK201302036, GK201302037)资助

Synthesis and Characterization of Hierarchical Aluminum Free Beta Zeolite^†

WENG Qiang¹, CHEN Pei^1,^*(), ZHAO Fengqi², GAO Hongxu², CHEN Xinbing¹, AN Zhongwei^1,²

1. Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710062, China
2. Science and Technology on Combustion and Explosion Laboratory, Xi’an Modern Chemistry Research Institute, Xi’an 710065, China

Received:2013-09-22 Online:2014-02-10 Published:2013-12-30
Contact: CHEN Pei E-mail:chenpei@snnu.edu.cn
Supported by:
† Supported by the Changjiang Scholars and Innovative Research Team in University, China(No.IRT1070), the Key Science & Technology Innovation Team of Shaanxi Province, China(No.2012KCT-21), the Natural Science Foundation of Shaanxi Province, China(No.2012JM2002), the Key Science and Technology Program of Shaanxi Province, China(No.2012K08-09), the State Education Ministry for the Research Team of Central Universities, China(Nos.GK261001108, GK261001009), and the State Education Ministry Fundamental Research Funds for the Central Universities, China(Nos.GK201101003, GK201302036, GK201302037)

摘要/Abstract

摘要：

研究了氟介质条件下, 合成参数对前驱体黏度和无铝Beta分子筛晶化过程的影响. X射线衍射结果表明, 高水硅比可降低前驱体的黏度, 但抑制分子筛的晶化. 当合成体系中加入成核促进剂(二氧化锗)和晶化促进剂(高氯酸根或磷酸根)后, 即使水硅摩尔比高达20~30, 在150 ℃水热合成4 d, 仍可获得高结晶性、微米级球形或多面体形无铝Beta分子筛. 热重和能谱分析结果表明, 极少量高氯酸根和磷酸根可进入分子筛孔道, 并影响模板剂四乙基铵根离子的热分解过程. 氮气吸附-脱附、扫描电子显微镜、透射电子显微镜和选区电子衍射分析结果表明, 所得无铝Beta分子筛具有多级孔结构, 介孔尺寸在3.4~3.8 nm之间, 由纳米晶体或纳米棒堆积而成.

关键词: 高水硅比, 晶化条件, 多级孔结构, 无铝Beta分子筛

Abstract:

The influence of various parameters upon the physical state of precursor and crystallization of aluminum-free Beta zeolite were investigated in fluoride media. X-Ray diffraction(XRD) analysis showed that H₂O/SiO₂ molar ratio in the precursor played an important role in the viscosity of precursor and the crystallization of aluminum-free Beta zeolite. High H₂O/SiO₂ molar ratio(>10) was benefited to the precursor’s viscosity but inhibited the crystallization process of aluminum-free Beta zeolite. While, high crystalline aluminum-free Beta zeolite with polyhedron or sphere morphology in micrometer scale could be obtained in the presence of nucleation promoter(GeO₂) and crystallization promoter such as Cl $O 4 -$ and P $O 4 3 -$ at 150 ℃ for 4 d, even though H₂O/SiO₂ molar ratio was high to 20—30. The analysis of thermogravimetry and energy dispersive spectrometry proved that small amount of Cl $O 4 -$ and P $O 4 3 -$ maybe incorporated into the channel of Beta zeolite and influenced the thermal decomposition process of template(tetraethyl ammonium cation). Further characterization for the morphology, crystalline and pore structure of the resultant aluminu-free Beta zeolite were carried out by environmental scanning electron microscope(SEM), transmission electron microscope(TEM), selected-area electron diffraction(SAED) and nitrogen adsorption-desorption isotherm. The results indicate that the obtained aluminum-free Beta zeolite is hierarchical structure, which constructed by nanoparticles or nanosheets. The mesoporous pore size is in the range of 3.4—3.8 nm.

Key words: High H2O/SiO2 molar ratio, Crystallization parameter, Hierarchical structure, Aluminum free Beta zeolite

中图分类号:

O613.7

TrendMD:

翁强, 陈沛, 赵凤起, 高红旭, 陈新兵, 安忠维. 多级孔无铝Beta分子筛的合成与表征. 高等学校化学学报, 2014, 35(2): 215.

WENG Qiang, CHEN Pei, ZHAO Fengqi, GAO Hongxu, CHEN Xinbing, AN Zhongwei. Synthesis and Characterization of Hierarchical Aluminum Free Beta Zeolite^†. Chem. J. Chinese Universities, 2014, 35(2): 215.

图/表 14

参考文献 21

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Sample	Molar composition^a				State^b	Seed^c	T^d/℃	t^e/d	Heat source^f
Sample	x				State^b	Seed^c	y	z	m
H7.5-150/11	0	0	0	7.5	S	N	150	11	H
H7.5-150/8	0	0	0	7.5	S	N	150	8	H
C9H7.5-150/4	0	0.09	0	7.5	S	N	150	4	H
C9H10-150/4	0	0.09	0	10	S	N	150	4	H
C9H10-150/4-s	0	0.09	0	10	S	Y	150	4	H
C9H20-150/4	0	0.09	0	20	S	N	150	4	H
C9H20-150/4-s	0	0.09	0	20	S	Y	150	4	H
C9H30-150/4	0	0.09	0	30	G	N	150	4	H
C9H30-150/4-s	0	0.09	0	30	G	Y	150	4	H
G1C9H30-150/4	0.1	0.09	0	30	G	N	150	4	H
G1C9H30-150/4-s	0.1	0.09	0	30	G	Y	150	4	H
G2C9H30-150/4	0.2	0.09	0	30	L	N	150	4	H
G2C9H30-150/4-s	0.2	0.09	0	30	L	Y	150	4	H
G3C9H30-150/4	0.3	0.09	0	30	L	N	150	4	H
G3C9H30-150/4-s	0.3	0.09	0	30	L	Y	150	4	H
G3C9H20-150/4	0.3	0.09	0	20	L	N	150	4	H
G3C9H20-150/4-s	0.3	0.09	0	20	L	Y	150	4	H
G3C9H10-150/4	0.3	0.09	0	10	G	N	150	4	H
G3C9H10-150/4-s	0.3	0.09	0	10	G	Y	150	4	H
G3C9H30-150/0.5-m	0.3	0.09	0	30	L	N	150	0.5	M
G3C9H30-150/0.5-m-s	0.3	0.09	0	30	L	Y	150	0.5	M
G3C9H30-160/0.5-m	0.3	0.09	0	30	L	N	160	0.5	M
G3C9H30-160/0.5-m-s	0.3	0.09	0	30	L	Y	160	0.5	M
G3C9H30-170/0.5-m	0.3	0.09	0	30	L	N	170	0.5	M
G3C9H30-170/0.5-m-s	0.3	0.09	0	30	L	Y	170	0.5	M
P3H10-150/4	0	0	0.03	10	S	N	150	4	H
P9H10-150/4	0	0	0.09	10	S	N	150	4	H
P23H10-150/4	0	0	0.23	10	S	N	150	4	H
P28H10-150/4	0	0	0.28	10	S	N	150	4	H
P33H10-150/4	0	0	0.33	10	G	N	150	4	H
P48H10-150/4	0	0	0.48	10	L	N	150	4	H
G3P23H10-150/4	0.3	0	0.23	10	G	N	150	4	H
G3P28H10-150/4	0.3	0	0.28	10	L	N	150	4	H
G3P33H10-150/4	0.3	0	0.33	10	L	N	150	4	H
G3P48H10-150/4	0.3	0	0.48	10	L	N	150	4	H
G3P48H20-150/4	0.3	0	0.48	20	L	N	150	4	H
G3P48H30-150/4	0.3	0	0.48	30	L	N	150	4	H

Sample	Molar composition^a				State^b	Seed^c	T^d/℃	t^e/d	Heat source^f
Sample	x				State^b	Seed^c	y	z	m
H7.5-150/11	0	0	0	7.5	S	N	150	11	H
H7.5-150/8	0	0	0	7.5	S	N	150	8	H
C9H7.5-150/4	0	0.09	0	7.5	S	N	150	4	H
C9H10-150/4	0	0.09	0	10	S	N	150	4	H
C9H10-150/4-s	0	0.09	0	10	S	Y	150	4	H
C9H20-150/4	0	0.09	0	20	S	N	150	4	H
C9H20-150/4-s	0	0.09	0	20	S	Y	150	4	H
C9H30-150/4	0	0.09	0	30	G	N	150	4	H
C9H30-150/4-s	0	0.09	0	30	G	Y	150	4	H
G1C9H30-150/4	0.1	0.09	0	30	G	N	150	4	H
G1C9H30-150/4-s	0.1	0.09	0	30	G	Y	150	4	H
G2C9H30-150/4	0.2	0.09	0	30	L	N	150	4	H
G2C9H30-150/4-s	0.2	0.09	0	30	L	Y	150	4	H
G3C9H30-150/4	0.3	0.09	0	30	L	N	150	4	H
G3C9H30-150/4-s	0.3	0.09	0	30	L	Y	150	4	H
G3C9H20-150/4	0.3	0.09	0	20	L	N	150	4	H
G3C9H20-150/4-s	0.3	0.09	0	20	L	Y	150	4	H
G3C9H10-150/4	0.3	0.09	0	10	G	N	150	4	H
G3C9H10-150/4-s	0.3	0.09	0	10	G	Y	150	4	H
G3C9H30-150/0.5-m	0.3	0.09	0	30	L	N	150	0.5	M
G3C9H30-150/0.5-m-s	0.3	0.09	0	30	L	Y	150	0.5	M
G3C9H30-160/0.5-m	0.3	0.09	0	30	L	N	160	0.5	M
G3C9H30-160/0.5-m-s	0.3	0.09	0	30	L	Y	160	0.5	M
G3C9H30-170/0.5-m	0.3	0.09	0	30	L	N	170	0.5	M
G3C9H30-170/0.5-m-s	0.3	0.09	0	30	L	Y	170	0.5	M
P3H10-150/4	0	0	0.03	10	S	N	150	4	H
P9H10-150/4	0	0	0.09	10	S	N	150	4	H
P23H10-150/4	0	0	0.23	10	S	N	150	4	H
P28H10-150/4	0	0	0.28	10	S	N	150	4	H
P33H10-150/4	0	0	0.33	10	G	N	150	4	H
P48H10-150/4	0	0	0.48	10	L	N	150	4	H
G3P23H10-150/4	0.3	0	0.23	10	G	N	150	4	H
G3P28H10-150/4	0.3	0	0.28	10	L	N	150	4	H
G3P33H10-150/4	0.3	0	0.33	10	L	N	150	4	H
G3P48H10-150/4	0.3	0	0.48	10	L	N	150	4	H
G3P48H20-150/4	0.3	0	0.48	20	L	N	150	4	H
G3P48H30-150/4	0.3	0	0.48	30	L	N	150	4	H

Sample	N/Si	O/Si	F/Si	Al/Si	Cl/Si	P/Si	Ge/Si
C9H7.5-150/4	0.14	2.06	0.07	0	0.001	0	0
G3C9H30-150/4-s	0.14	2.30	0.02	0.07	0.003	0	0.19
G3P48H20-150/4	0.14	2.03	0.03	0	0	0.001	0.13
G3P48H30-150/4	0.19	2.04	0.01	0	0	0.001	0.12

Sample	N/Si	O/Si	F/Si	Al/Si	Cl/Si	P/Si	Ge/Si
C9H7.5-150/4	0.14	2.06	0.07	0	0.001	0	0
G3C9H30-150/4-s	0.14	2.30	0.02	0.07	0.003	0	0.19
G3P48H20-150/4	0.14	2.03	0.03	0	0	0.001	0.13
G3P48H30-150/4	0.19	2.04	0.01	0	0	0.001	0.12

Sample	S_a/(m²·g^-1)	S_mic/(m²·g^-1)	S_ext/(m²·g^-1)	V_p/(cm³·g^-1)	V_mic/(cm³·g^-1)
C9H7.5-150/4	373	350	23	0.135	0.198
G3C9H30-150/4-s	356	338	18	0.132	0.181
G3P48H20-150/4	490	435	54	0.172	0.259
G3P48H30-150/4	511	458	53	0.179	0.267

多级孔无铝Beta分子筛的合成与表征

Synthesis and Characterization of Hierarchical Aluminum Free Beta Zeolite^†

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多级孔无铝Beta分子筛的合成与表征

Synthesis and Characterization of Hierarchical Aluminum Free Beta Zeolite†

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Synthesis and Characterization of Hierarchical Aluminum Free Beta Zeolite^†