不同硅铝比ZSM-5分子筛的合成及其性能研究

doi:10.3969/j.issn.1001-1803.2021.01.008

日用化学工业 ›› 2021, Vol. 51 ›› Issue (1): 44-49.doi: 10.3969/j.issn.1001-1803.2021.01.008

不同硅铝比ZSM-5分子筛的合成及其性能研究

宋凯雲¹(),李国栋¹,李宁¹,梁亚凝²,李晓峰¹(),窦涛^1,²

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:2020-04-16 修回日期:2021-01-04 出版日期:2021-01-22 发布日期:2021-01-20
通讯作者: 李晓峰
作者简介:宋凯雲（1993-）,男,研究硕士生,E-mail: 1825178960@qq.com。
基金资助:
国家科技型中小企业创新项目资助(14C26211400552)

Research on the synthesis and performance of ZSM-5 zeolite withdifferent SiO₂/Al₂O₃ ratios

SONG Kai-yun¹(),LI Guo-dong¹,LI Ning¹,LIANG Ya-ning²,LI Xiao-feng¹(),DOU Tao^1,²

1. Insititute of Fine Chemical Engineering, Taiyuan University of Technology, Taiyuan, Shanxi 030024, China
2. Taiyuan Dacheng Huanneng Chemical Co., Ltd., Taiyuan, Shanxi 030024, China

Received:2020-04-16 Revised:2021-01-04 Online:2021-01-22 Published:2021-01-20
Contact: Xiao-feng LI

摘要/Abstract

摘要：

以廉价的四乙基溴化铵为表面活性剂,水玻璃、硫酸铝为基础原料,在2 L高压磁力搅拌反应釜中水热合成了5种投料硅铝比分别为100,110,120,160和200的ZSM-5分子筛,并制备成催化剂,用XRD,SEM和NH₃-TPD等手段对样品进行表征。结果表明：随着投料硅铝比的增大,产物的硅铝比和平均粒径逐渐增大,总孔和微孔的数量减小,介孔数量则先增大后减小,强、弱酸量均逐渐降低。在温度370 ℃、氢气压力0.8 MPa、质量空速8 h^-1、氢烃摩尔比值2.0的条件下,对乙苯脱乙基型二甲苯异构化反应进行样品催化性能评价。结果表明,随着分子筛投料硅铝比的增大,乙苯转化率逐渐降低,二甲苯异构化活性先升高后降低。当投料硅铝比为120时,相应样品具有较佳的综合性能,其乙苯转化率为57.60%,二甲苯异构化活性达到热力学平衡值24.04%。

关键词: ZSM-5分子筛, 硅铝比, 乙苯脱乙基, 二甲苯异构化

Abstract:

Five kinds of ZSM-5 with SiO₂/Al₂O₃ratios of 100, 110, 120, 160 and 200 were synthesized using the low-cost tetraethlammonium bromide （TEABr） as surfactant, sodium silicate and aluminium sulfateunder as raw materials under hydrothermal condition in a 2 L high pressure magnetic stirred reactor, and were prepared as catalysts. The samples were characterized by XRD, SEM and NH₃-TPD. The results showed that with the increase of SiO₂/Al₂O₃ratio, the SiO₂/Al₂O₃ ratio and the average particle size of the product increase, the number of the total pores and micropores decreases, the number of mesoporous increases at first then decreases, and the strong and weak acidity decrease gradually. The ethylbenzene dealkylation/xylene isomerization reaction was carried out over these samples to evaluate the catalytic performance under the following conditions: temperature of 370 ℃, hydrogen pressure of 0.8 MPa, mass space velocity of 8 h^-1 and hydrogen-hydrocarbon molar ratio of 2.0. It was found that with the increase of SiO₂/Al₂O₃ratio, the conversion of ethylbenzene decreases, and the isomerization activity of xylene increases at first then decreases. The corresponding sample with SiO₂/Al₂O₃ ratio of 120 has the optimum comprehensive performance, the conversion of ethylbenzene is 57.60%, and the isomerization activity of xylene reaches the thermodynamic equilibrium value of 24.04%.

Key words: ZSM-5 zeolite, SiO₂/Al₂O₃ ratio, ethylbenzene dealkylation, xylene isomerization

中图分类号:

TQ423

宋凯雲,李国栋,李宁,梁亚凝,李晓峰,窦涛. 不同硅铝比ZSM-5分子筛的合成及其性能研究[J]. 日用化学工业, 2021, 51(1): 44-49.

SONG Kai-yun,LI Guo-dong,LI Ning,LIANG Ya-ning,LI Xiao-feng,DOU Tao. Research on the synthesis and performance of ZSM-5 zeolite withdifferent SiO₂/Al₂O₃ ratios[J]. China Surfactant Detergent & Cosmetics, 2021, 51(1): 44-49.

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样品	产物硅铝比	相对结晶度/%
S-100	42.88	110.53
S-110	44.51	110.75
S-120	46.22	108.79
S-160	57.14	110.01
S-200	65.18	108.37

样品	S_BET/（m²·g^-1）	S_mic/（m²·g^-1）	S_ex/（m²·g^-1）	V_tota/（cm³·g^-1）	V_mic/（cm³·g^-1）	V_meso/（cm³·g^-1）
S-100	412.21	370.21	42.00	0.16	0.15	0.01
S-110	402.87	357.06	45.81	0.18	0.14	0.04
S-120	376.25	292.52	83.73	0.19	0.12	0.07
S-160	361.76	282.39	79.37	0.17	0.11	0.06
S-200	329.68	264.56	65.12	0.15	0.10	0.05

样品	弱酸		强酸		总量/（mmol·g^-1）
样品	温度/℃	数量/（mmol·g^-1）	温度/℃	数量/（mmol·g^-1）	总量/（mmol·g^-1）
S-100	231	1.04	451	0.70	1.74
S-110	240	1.03	454	0.66	1.69
S-120	240	0.96	440	0.65	1.61
S-160	232	0.91	451	0.39	1.30
S-200	243	0.87	452	0.36	1.23

不同硅铝比ZSM-5分子筛的合成及其性能研究

Research on the synthesis and performance of ZSM-5 zeolite withdifferent SiO₂/Al₂O₃ ratios

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Research on the synthesis and performance of ZSM-5 zeolite withdifferent SiO₂/Al₂O₃ ratios