SSZ-13分子筛无钠合成工艺与产物物性表征

doi:10.3969/j.issn.1001-1803.2019.04.005

日用化学工业 ›› 2019, Vol. 49 ›› Issue (4): 229-233.doi: 10.3969/j.issn.1001-1803.2019.04.005

SSZ-13分子筛无钠合成工艺与产物物性表征

闵令飞¹,梁亚凝²,李宁²,李晓峰¹(),窦涛¹

^1. 太原理工大学精细化工研究所,山西太原 030024
^2. 太原大成环能化工技术有限公司,山西太原 030024

收稿日期:2018-09-04 修回日期:2019-04-02 出版日期:2019-04-22 发布日期:2019-04-24
通讯作者: 李晓峰
作者简介:闵令飞（1993-）,男,硕士研究生,E-mail：Lingfeimin123@163.com。
基金资助:
国家科技型中小企业技术创新项目(14C26211400552)

Sodium-free synthetic process and characterization of SSZ-13molecular sieves

MIN Ling-fei¹,LIANG Ya-ning²,LI Ning²,LI Xiao-feng¹(),DOU Tao¹

^1. Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan,Shanxi 030024, China
^2. Taiyuan Dacheng Environment & Energy Chemical Technology Co., Ltd, Taiyuan, Shanxi 030024, China;

Received:2018-09-04 Revised:2019-04-02 Online:2019-04-22 Published:2019-04-24
Contact: Xiao-feng LI

摘要/Abstract

摘要：

以氨水弱碱代替NaOH作为碱源,铵型硅溶胶与硫酸铝作为不含钠的硅铝源,N,N,N-三甲基-1-金刚烷基氢氧化铵作为有机模板剂,一步水热法无钠途径合成了不同硅铝比的SSZ-13分子筛。采用X射线衍射仪（XRD）、扫描电子显微镜（SEM）、傅里叶红外光谱（FT-IR）、氨气程序升温脱附（NH₃-TPD）、元素分析、热重分析（TG-DTG）和N₂等温吸附-脱附（BET）等手段表征产物,并以甲醇制烯烃反应（MTO）评价其催化性能。结果表明,采用氨水合成的不同硅铝比的铵型 SSZ-13分子筛,粒径随着硅铝比增加而减小;合成产物直接焙烧后可用于催化反应,硅铝比为75 较25的样品在甲醇制烯烃催化反应中寿命延长了2.6倍。

关键词: 氨水, 铵型SSZ-13分子筛, 无钠合成, 甲醇制烯烃

Abstract:

SSZ-13 molecular sieves with different silica-alumina ratios were synthesized by sodium-free one-step hydrothermal method in which ammonia water was used to replace NaOH as alkaline source, ammonium-type silica sol and aluminum sulfate were used as silicon and aluminum sources, and N,N,N-trimethyl-1-adamantyl ammonium hydroxide was used as the organic template agent. The products were characterized by X-ray diffraction（XRD）, scanning electron microscopy（SEM）, FT-IR, temperature-programmed desorption of ammonia（NH₃-TPD）, elemental analysis, thermogravimetric analysis（TG-DTG） and isothermal N₂ adsorption and desorption（BET）. The catalytic performance of the products was evaluated by Methanol-to-Olefins（MTO） reaction. The results show that the particle size of SSZ-13 molecular sieves with different silica-alumina ratios synthesized by ammonia is decreased with the increase of silica-alumina ratio; the products synthesized can be directly used after calcination for catalytic reaction; in the catalytic reaction of MTO, the catalyst with silica-alumina ratio of 75 exhibits a life span nearly 2.6 times longer than the one with silica-alumina ratio of 25.

Key words: ammonia liquor, ammonium-type SSZ-13 molecular sieve, sodium-free method, Methanol-to-Olefins

中图分类号:

TQ424.25

闵令飞,梁亚凝,李宁,李晓峰,窦涛. SSZ-13分子筛无钠合成工艺与产物物性表征[J]. 日用化学工业, 2019, 49(4): 229-233.

MIN Ling-fei,LIANG Ya-ning,LI Ning,LI Xiao-feng,DOU Tao. Sodium-free synthetic process and characterization of SSZ-13molecular sieves[J]. China Surfactant Detergent & Cosmetics, 2019, 49(4): 229-233.

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Si/Al		t（脱附峰）/℃		总酸量/ （mmol·g^-1）
初始凝胶	元素分析	左峰	右峰	总酸量/ （mmol·g^-1）
25	25.36	233	541	0.963
50	48.33	221	512	0.907
75	74.25	224	494	0.671

样品	总比表面积/	微孔比表面积/	外比表面积/	总孔体积/	微孔体积/	介孔体积/	孔径/
样品	（m²·g^-1）	（m²·g^-1）	（m²·g^-1）	（cm³·g^-1）	（cm³·g^-1）	（cm³·g^-1）	nm
Si/Al=25	593.36	561.18	32.18	0.25	0.22	0.03	1.69
Si/Al=50	666.42	625.42	41.00	0.29	0.24	0.05	1.74
Si/Al=75	664.53	609.88	54.65	0.30	0.24	0.06	1.79

SSZ-13分子筛无钠合成工艺与产物物性表征

Sodium-free synthetic process and characterization of SSZ-13molecular sieves

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