Synthesis and Characterization of Hierarchical Aluminum Free Beta Zeolite†

doi:10.7503/cjcu20130931

Abstract

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

CLC Number:

O613.7

TrendMD:

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

Figures/Tables 14

References 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