晶种导向蒸汽辅助晶化法全硅BETA沸石的合成研究

doi:10.15541/jim20170554

摘要/Abstract

摘要：

全硅BETA沸石在卷烟烟气减害和石油化工领域有较好的应用前景。利用单模板剂合成方法——晶种导向蒸汽辅助晶化法(SAC)合成了全硅的BETA沸石。利用X射线衍射(XRD)、扫描电镜(SEM)、红外(FT-IR)和氮吸附对样品进行了分析。结果表明, 晶种量、模板剂四乙基氢氧化铵(TEAOH)和碱度对全硅BETA沸石的合成有着重要的影响。同时还发现, 利用SAC法合成的全硅BETA沸石晶体中, 四方晶系(A晶型)占有58%~68%, 并且原料的配比不影响A晶型的丰富程度。全硅BETA沸石具有一定疏水性, 有望用于有机物/水分离体系。

关键词: 晶种导向, 蒸汽辅助晶化法, SAC, 全硅, BETA沸石

Abstract:

The pure-silica zeolite BETA has a promising prospect in the field of cigarette harm reduction and petrochemical industry. In present work, the single-template method, named as the seed-direct steam-assisted crystallization (SAC), was used to synthesize the pure-silica zeolite BETA. And then the samples were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption, and Fourier Transform infrared spectroscopy (FT-IR). The results revealed that BETA seeds, template (TEAOH) and alkalinity exert great effects on the synthesis of pure-silica zeolite BETA. The BETA zeolite with polymorph A enrichments (58%-68%) is synthesized by SAC method, which can not be affected by the change of molar ratio of the raw materials. The pure-silica zeolite BETA possesses the hydrophobic properties, which can be used in the separation of organic/H₂O, and the removal of harmful organic materials in cigarette smoke.

Key words: seed-directed, steam-assisted-crystallization, SAC, pure-silica, zeolite BETA

中图分类号:

TQ174

冯守爱, 周俊, 杨玄宇, 刘鸿, 黄江锋, 白家峰, 程晓维, 邓勇辉. 晶种导向蒸汽辅助晶化法全硅BETA沸石的合成研究[J]. 无机材料学报, 2018, 33(9): 963-968.

FENG Shou-Ai, ZHOU Jun, YANG Xuan-Yu, LIU Hong, HUANG Jiang-Feng, BAI Jia-Feng, CHENG Xiao-Wei, DENG Yong-Hui. Synthesis of Pure-silica BETA Zeolite by the Method of Seed-direct Steam-assisted Crystallization[J]. Journal of Inorganic Materials, 2018, 33(9): 963-968.

图/表 11

参考文献 22

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Code	Sample	Molar composition	(Seed/SiO₂)/wt%	Temp.(℃)/Time (h)	Product
1	BETA-0T10S150/48	1SiO₂:0TEAOH : 0.4NaOH : 9.4H₂O	10	150/48	Amorphous
2	BETA-0.1T10S140/48	1SiO₂ : 0.1TEAOH : 0.3NaOH : 9.4H₂O	10	150/48	Amorphous
3	BETA-0.1T2S150/48	1SiO₂ : 0.1TEAOH : 0.3NaOH : 9.4H₂O	2	150/48	Amorphous
4	BETA-0.1T5S150/48	1SiO₂ : 0.1TEAOH : 0.3NaOH : 9.4H₂O	5	150/48	BETA
5	BETA-0.1T8S150/48	1SiO₂ : 0.1TEAOH : 0.3NaOH : 9.4H₂O	8	150/48	BETA
6	BETA-0.1T10S150/48	1SiO₂ : 0.1TEAOH : 0.3NaOH : 9.4H₂O	10	150/48	BETA
7	BETA-0.2T2S150/48	1SiO₂ : 0.2TEAOH : 0.2NaOH : 9.4H₂O	2	150/48	Amorphous
8	BETA-0.2T5S150/48	1SiO₂ : 0.2TEAOH : 0.2NaOH : 9.4H₂O	5	150/48	BETA
9	BETA-0.2T8S150/48	1SiO₂ : 0.2TEAOH : 0.2NaOH : 9.4H₂O	8	150/48	BETA
10	BETA-0.2T10S150/48	1SiO₂ : 0.2TEAOH : 0.2NaOH : 9.4H₂O	10	150/48	BETA
11	BETA-0.3T2S150/48	1SiO₂ : 0.3TEAOH : 0.1NaOH : 9.4H₂O	2	150/48	Amorphous
12	BETA-0.3T5S150/48	1SiO₂ : 0.3TEAOH : 0.1NaOH : 9.4H₂O	5	150/48	BETA
13	BETA-0.3T8S150/48	1SiO₂ : 0.3TEAOH : 0.1NaOH : 9.4H₂O	8	150/48	BETA
14	BETA-0.3T10S150/48	1SiO₂ : 0.3TEAOH : 0.1NaOH : 9.4H₂O	10	150/48	BETA
15	BETA-0.3T10S150/48Ⅰ	1SiO₂ : 0.3TEAOH : 0NaOH : 9.4H₂O	10	150/48	Amorphous
16	BETA-0.3T10S150/48Ⅱ	1SiO₂ : 0.3TEAOH : 0NaOH : 9.4H₂O : 0.1NaCl	10	150/48	Amorphous
17	BETA-0.3T10S150/48Ⅲ	1SiO₂ : 0.3TEAOH : 0.2NaOH : 9.4H₂O	10	150/48	BETA

Code	Sample	Molar composition	(Seed/SiO₂)/wt%	Temp.(℃)/Time (h)	Product
1	BETA-0T10S150/48	1SiO₂:0TEAOH : 0.4NaOH : 9.4H₂O	10	150/48	Amorphous
2	BETA-0.1T10S140/48	1SiO₂ : 0.1TEAOH : 0.3NaOH : 9.4H₂O	10	150/48	Amorphous
3	BETA-0.1T2S150/48	1SiO₂ : 0.1TEAOH : 0.3NaOH : 9.4H₂O	2	150/48	Amorphous
4	BETA-0.1T5S150/48	1SiO₂ : 0.1TEAOH : 0.3NaOH : 9.4H₂O	5	150/48	BETA
5	BETA-0.1T8S150/48	1SiO₂ : 0.1TEAOH : 0.3NaOH : 9.4H₂O	8	150/48	BETA
6	BETA-0.1T10S150/48	1SiO₂ : 0.1TEAOH : 0.3NaOH : 9.4H₂O	10	150/48	BETA
7	BETA-0.2T2S150/48	1SiO₂ : 0.2TEAOH : 0.2NaOH : 9.4H₂O	2	150/48	Amorphous
8	BETA-0.2T5S150/48	1SiO₂ : 0.2TEAOH : 0.2NaOH : 9.4H₂O	5	150/48	BETA
9	BETA-0.2T8S150/48	1SiO₂ : 0.2TEAOH : 0.2NaOH : 9.4H₂O	8	150/48	BETA
10	BETA-0.2T10S150/48	1SiO₂ : 0.2TEAOH : 0.2NaOH : 9.4H₂O	10	150/48	BETA
11	BETA-0.3T2S150/48	1SiO₂ : 0.3TEAOH : 0.1NaOH : 9.4H₂O	2	150/48	Amorphous
12	BETA-0.3T5S150/48	1SiO₂ : 0.3TEAOH : 0.1NaOH : 9.4H₂O	5	150/48	BETA
13	BETA-0.3T8S150/48	1SiO₂ : 0.3TEAOH : 0.1NaOH : 9.4H₂O	8	150/48	BETA
14	BETA-0.3T10S150/48	1SiO₂ : 0.3TEAOH : 0.1NaOH : 9.4H₂O	10	150/48	BETA
15	BETA-0.3T10S150/48Ⅰ	1SiO₂ : 0.3TEAOH : 0NaOH : 9.4H₂O	10	150/48	Amorphous
16	BETA-0.3T10S150/48Ⅱ	1SiO₂ : 0.3TEAOH : 0NaOH : 9.4H₂O : 0.1NaCl	10	150/48	Amorphous
17	BETA-0.3T10S150/48Ⅲ	1SiO₂ : 0.3TEAOH : 0.2NaOH : 9.4H₂O	10	150/48	BETA

Code	Sample	Height[cts] lower angle peak	Height[cts] higher angle peak	A/(A+B) peak ratio
1	BETA-0.3T 5S150/48	1000	1673	62.6%
2	BETA-0.3T 8S150/48	1102	1738	61.2%
3	BETA-0.3T 10S150/48	982	2073	67.9%
4	BETA-0.2T 5S150/48	1414	2235	61.2%
5	BETA-0.2T 8S150/48	945	2061	68.6%
6	BETA-0.2T 10S150/48	1139	2036	64.1%
7	BETA-0.1T 5S150/48	1358	1940	58.8%
8	BETA-0.1T 8S150/48	1211	2061	63.0%
9	BETA-0.1T 10S150/48	1252	2121	62.9%

Code	Sample	Height[cts] lower angle peak	Height[cts] higher angle peak	A/(A+B) peak ratio
1	BETA-0.3T 5S150/48	1000	1673	62.6%
2	BETA-0.3T 8S150/48	1102	1738	61.2%
3	BETA-0.3T 10S150/48	982	2073	67.9%
4	BETA-0.2T 5S150/48	1414	2235	61.2%
5	BETA-0.2T 8S150/48	945	2061	68.6%
6	BETA-0.2T 10S150/48	1139	2036	64.1%
7	BETA-0.1T 5S150/48	1358	1940	58.8%
8	BETA-0.1T 8S150/48	1211	2061	63.0%
9	BETA-0.1T 10S150/48	1252	2121	62.9%

Code	Sample	Average size/nm
1	BETA-0.3T5S150/48	310
2	BETA-0.3T8S150/48	280
3	BETA-0.3T10S150/48	200
4	BETA-0.2T5S150/48	630
5	BETA-0.2T8S150/48	420
6	BETA-0.2T10S150/48	150
7	BETA-0.1T5S150/48	300
8	BETA-0.1T8S150/48	315
9	BETA-0.1T10S150/48	190