Brönsted-Lewis有机-无机杂多酸催化模拟催化裂化汽油的烷基化脱硫反应

doi:10.7503/cjcu20160533

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (1): 72.doi: 10.7503/cjcu20160533

Brönsted-Lewis有机-无机杂多酸催化模拟催化裂化汽油的烷基化脱硫反应

于凤丽¹, 王庆玉¹, 李桂晓¹, 袁冰¹, 解从霞¹(), 于世涛²

1. 青岛科技大学生态化工国家重点实验室培育基地
2. 化工学院, 青岛 266042

收稿日期:2016-07-25 出版日期:2017-01-10 发布日期:2016-12-12
作者简介:联系人简介: 解从霞, 女, 博士, 教授, 博士生导师, 主要从事环境友好催化和生物质资源转化利用等方面的研究. E-mail: xiecongxia@126.com
基金资助:
国家自然科学基金(批准号: 21476120)、山东省重点发展计划(批准号: 2015GGX107008)和山东省泰山学者工程专项(批准号: ts201511033)资助.

Alkylation Desulfurization of FCC Gasoline over Brönsted-Lewis Organic-inorganic Heteropoly Acid Catalyst^†

YU Fengli¹, WANG Qingyu¹, LI Guixiao¹, YUAN Bing¹, XIE Congxia^1,^*(), YU Shitao²

1. State Key Laboratory Base of Eco-chemical Engineering
2. College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

Received:2016-07-25 Online:2017-01-10 Published:2016-12-12
Contact: XIE Congxia E-mail:xiecongxia@126.com
Supported by:
† Supported by the National Natural Science Foundation of China(No. 21476120), the Emphasis Development Plan of Shandong Province, China(No. 2015GGX107008) and the Taishan Scholars Projects of Shandong Province, China(No. ts201511033).

摘要/Abstract

摘要：

合成了一系列Brönsted-Lewis双酸性有机-无机杂多酸, 并将其应用于催化模拟催化裂化(FCC)汽油的烷基化脱硫反应中. 筛选出脱硫效果最佳的催化剂为Sm_0.33[MIM-PS]HPW₁₂O₄₀, 考察了该催化剂用量、反应温度及反应时间等因素对模拟油中噻吩类硫化物转化率的影响. 获得的最佳反应条件为剂/油质量比1:50、反应温度125 ℃及反应时间1 h. 在最佳反应条件下, 3种硫化物噻吩(T)、 2-甲基噻吩(2-MT)和3-甲基噻吩(3-MT)均几乎完全转化, 即脱硫率都接近100%. 催化剂Sm_0.33[MIM-PS]HPW₁₂O₄₀具有良好的循环使用性能, 循环使用12次, 其催化活性基本保持不变.

关键词: 烷基化脱硫, 催化裂化汽油, 噻吩类硫化物, Brönsted-Lewis杂多酸

Abstract:

A series of Brönsted-Lewis organic-inorganic heteropoly acids was synthesized and used for catalyzing alkylation desulfurization of model fluid catalytic cracking(FCC) gasoline. Among these prepared Brönsted-Lewis organic-inorganic heteropoly acids, Sm_0.33[MIM-PS]HPW₁₂O₄₀ has the highest acid strength and exhibits the best catalytic activity for the alkylation of three thiophenic sulfides including thiophene(T), 2-methyl thiophene(2-MT) and 3-methyl thiophene(3-MT) in model FCC gasolines. The effects of the dosage of the catalyst, reaction temperature and reaction time on the conversions of three thiophenic sulfides catalyzed by Sm_0.33[MIM-PS]HPW₁₂O₄₀ were investigated. The selected optimal conditions as follows: the mass ratio of the catalyst to model FCC gasoline 1:50, reaction temperature 125 ℃ and reaction time 1 h. Under the optimal conditions, T, 2-MT and 3-MT all can be nearly completely transformed. The recyclability of the catalyst Sm_0.33[ MIM-PS]HPW₁₂O₄₀ was investigated. The results show the catalyst exhibits very excellent recyclability. Under the above selected reaction conditions, the catalytic activity of Sm_0.33[MIM-PS]HPW₁₂O₄₀ for the alkylation of three thiophenic sulfides nearly remains unchanged during 12 recycles.

Key words: Alkylation desulfurization, FCC gasoline, Thiophenic sulfide, Brönsted-Lewis heteropoly acid

中图分类号:

O643
O621

TrendMD:

于凤丽, 王庆玉, 李桂晓, 袁冰, 解从霞, 于世涛. Brönsted-Lewis有机-无机杂多酸催化模拟催化裂化汽油的烷基化脱硫反应. 高等学校化学学报, 2017, 38(1): 72.

YU Fengli, WANG Qingyu, LI Guixiao, YUAN Bing, XIE Congxia, YU Shitao. Alkylation Desulfurization of FCC Gasoline over Brönsted-Lewis Organic-inorganic Heteropoly Acid Catalyst^†. Chem. J. Chinese Universities, 2017, 38(1): 72.

图/表 6

参考文献 34

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Catalyst	Acid strength/ mV	Conversion(%)
Catalyst	Acid strength/ mV	T	2-MT	3-MT
[MIM-PS]H₂PW₁₂O₄₀	715	100	100	100
Al_0.33[MIM-PS]HPW₁₂O₄₀	584	93.4	97.6	95.1
Fe_0.33[MIM-PS]HPW₁₂O₄₀	551	87.8	95.8	93.3
Zn_0.5[MIM-PS]HPW₁₂O₄₀	522	89.8	95.6	92.4
Sm_0.33[MIM-PS]HPW₁₂O₄₀	605	99.7	99.9	99.7
Sm_0.66[MIM-PS]PW₁₂O₄₀	452	48.5	51.8	48.4
Cu_0.5[MIM-PS]HPW₁₂O₄₀	504	86.3	92.6	90.8
Cr_0.33[MIM-PS]HPW₁₂O₄₀	510	81.4	88.2	85.5
Zr_0.5[MIM-PS]HPW₁₂O₄₀	514	93.6	96.4	94.2

Catalyst	Acid strength/ mV	Conversion(%)
Catalyst	Acid strength/ mV	T	2-MT	3-MT
[MIM-PS]H₂PW₁₂O₄₀	715	100	100	100
Al_0.33[MIM-PS]HPW₁₂O₄₀	584	93.4	97.6	95.1
Fe_0.33[MIM-PS]HPW₁₂O₄₀	551	87.8	95.8	93.3
Zn_0.5[MIM-PS]HPW₁₂O₄₀	522	89.8	95.6	92.4
Sm_0.33[MIM-PS]HPW₁₂O₄₀	605	99.7	99.9	99.7
Sm_0.66[MIM-PS]PW₁₂O₄₀	452	48.5	51.8	48.4
Cu_0.5[MIM-PS]HPW₁₂O₄₀	504	86.3	92.6	90.8
Cr_0.33[MIM-PS]HPW₁₂O₄₀	510	81.4	88.2	85.5
Zr_0.5[MIM-PS]HPW₁₂O₄₀	514	93.6	96.4	94.2

Brönsted-Lewis有机-无机杂多酸催化模拟催化裂化汽油的烷基化脱硫反应

Alkylation Desulfurization of FCC Gasoline over Brönsted-Lewis Organic-inorganic Heteropoly Acid Catalyst^†

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Brönsted-Lewis有机-无机杂多酸催化模拟催化裂化汽油的烷基化脱硫反应

Alkylation Desulfurization of FCC Gasoline over Brönsted-Lewis Organic-inorganic Heteropoly Acid Catalyst†

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Alkylation Desulfurization of FCC Gasoline over Brönsted-Lewis Organic-inorganic Heteropoly Acid Catalyst^†