有机-无机杂多酸类离子液体催化汽油超声氧化脱硫

doi:10.7503/cjcu20160539

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (12): 2184.doi: 10.7503/cjcu20160539

有机-无机杂多酸类离子液体催化汽油超声氧化脱硫

于凤丽¹, 谢盼辉¹, 朱国强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:2016-12-10 发布日期:2016-11-18
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转化利用方面的研究. 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项目(批准号: 2015GGX107008)和山东省泰山学者工程专项经费(批准号: ts201511033)资助

Oxidative Desulfurization of Gasoline Catalyzed by Organic-inorganic Heteropoly Acid Ionic Liquids Under Ultrasound^†

YU Fengli¹, XIE Panhui¹, ZHU Guoqiang¹, 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:2016-12-10 Published:2016-11-18
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 Engineering Special Funding of Shandong Taishan Scholar, China(No.ts201511033)

摘要/Abstract

摘要：

合成了一系列有机-无机杂多酸类离子液体, 并将其应用于超声作用下的催化模拟汽油氧化脱硫反应. 结果表明, 在超声波辅助下, 不仅反应时间大大缩短, 而且脱硫效率也大幅提高. 在合成的一系列催化剂中, Zr_0.25[BMIM]HPW₁₂O₄₀表现出最佳的催化活性. 考察了超声波功率、超声/间隙时间、催化剂用量、 H₂O₂用量、反应温度及反应时间等因素对脱硫效果的影响. 以Zr_0.25[BMIM]HPW₁₂O₄₀为催化剂, 在优化的条件下[n(Cat.)=0.008 mmol, V(H₂O₂)=40 μL, V(模拟油)=10 mL, V(乙腈)=1 mL, 温度25 ℃, 时间10 min, 超声功率300 W, 超声时间2 s, 间隙时间1.5 s], 二苯并噻吩(DBT)的脱硫率达到97.8%; 该催化剂循环使用5次后, 脱硫率仍为81.9%; 其对不同硫化物的催化活性顺序为DBT>4,6-二甲基苯并噻吩(4,6-DMDBT)>乙硫醚>苯硫醚>正丁硫醇>甲基苯基硫醚>苯并噻吩(BT)>噻吩.

关键词: 杂多酸离子液体, 氧化脱硫, 萃取脱硫, 超声, 二苯并噻吩

Abstract:

A series of Organic-inorganic heteropoly acid ionic liquids was synthesized and used for catalyzing oxidative desulfurization of simulated gasoline under ultrasound. With the help of ultrasonic wave, the reaction time was largely reduced, and the desulfurization efficiency was also raised. The results showed that Zr_0.25[BMIM]HPW₁₂O₄₀ exhibits the best catalytic activity. The effects of ultrasonic power, ultrasonic/clearance time, the amount of catalyst, reaction temperature, reaction time, and the amount of H₂O₂ on the desulfurization rate were fully investigated. The selected optimal conditions were as follows: n(Cat.)=0.008 mmol, V(H₂O₂)=40 μL, V(simulated oil)=10 mL, V(acetonitrile)=1 mL, reaction temperature 25 ℃, reaction time 10 min, the ultrasonic power 300 W, the ultrasonic time 2 s, and the ultrasonic off-time 1.5 s. Under the optimal conditions, the sulfur removal of DBT could reach 97.8%. The solid catalyst Zr_0.25[BMIM]HPW₁₂O₄₀ could be directly separated out after the reaction, and could be reused after the vacuum drying. The results showed that Zr_0.25[BMIM]HPW₁₂O₄₀ also exhibited good recyclability. After 5 recycles, the desulfurization rate still could reach 81.9%. By using Zr_0.25[BMIM]HPW₁₂O₄₀ as catalyst, the reaction activity decreased in the order of DBT>4,6-DMDBT>ethyl thioether>phenyl thioether>n-butyl mercaptan>methyl phenyl thioether>BT>thiophene.

Key words: Heteropoly acid ionic liquid, Oxidative desulfurization, Extractive desulfurization, Ultrasound, Dibenzothiophene

中图分类号:

O643.3
O621

TrendMD:

于凤丽, 谢盼辉, 朱国强, 袁冰, 解从霞, 于世涛. 有机-无机杂多酸类离子液体催化汽油超声氧化脱硫. 高等学校化学学报, 2016, 37(12): 2184.

YU Fengli, XIE Panhui, ZHU Guoqiang, YUAN Bing, XIE Congxia, YU Shitao. Oxidative Desulfurization of Gasoline Catalyzed by Organic-inorganic Heteropoly Acid Ionic Liquids Under Ultrasound^†. Chem. J. Chinese Universities, 2016, 37(12): 2184.

图/表 10

Table 1 Influence of different heteropolyacid catalysts on the desulfurization rate*

Entry	Catalyst	Desulfurization rate(%)
1	H₃PW₁₂O₄₀	26.5
2	Zr_0.25H₂PW₁₂O₄₀	75.9
3	Zr_0.5HPW₁₂O₄₀	89.1
4	Zr_0.75PW₁₂O₄₀	79.9
5	Zr_0.25[BMIM]₂PW₁₂O₄₀	58.8
6	Zr_0.25[BMIM]HPW₁₂O₄₀	94.2
7	Ce_0.33[BMIM]HPW₁₂O₄₀	80.6
8	Ti_0.25[BMIM]HPW₁₂O₄₀	41.4
9	Fe_0.33[BMIM]HPW₁₂O₄₀	14.4
10	Co_0.5[BMIM]HPW₁₂O₄₀	5.0

Fig.1 Influence of the ultrasonic power on the desulfurization rate

Fig.2 Influence of the ultrasonic time on the desulfurization rate

Fig.3 Influence of the ultrasonic off-time on the desulfurization rate

Fig.4 Influence of the amount of catalyst on the desulfurization rate

Fig.5 Influence of the reaction temperature on the desulfurization rate

Fig.6 Influence of the reaction time on the desulfurization rate

Fig.7 Influence of the amount of H2O2 on the desulfurization rate

Fig.8 Influence of the recycle numbers of catalyst on the desulfurization rate

Table 2 Desulfurization efficiencies of different sulfides

Sulfide	Desulfurization rate(%)	Sulfide	Desulfurization rate(%)
n-Butyl mercaptan	84.2	4,6-DMDBT	89.6
Ethyl thioether	88.3	DBT	97.8
Phenyl thioether	86.3	BT	40.8
Methyl phenyl thioether	76.4	Thiophene	28.1

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有机-无机杂多酸类离子液体催化汽油超声氧化脱硫

Oxidative Desulfurization of Gasoline Catalyzed by Organic-inorganic Heteropoly Acid Ionic Liquids Under Ultrasound^†

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有机-无机杂多酸类离子液体催化汽油超声氧化脱硫

Oxidative Desulfurization of Gasoline Catalyzed by Organic-inorganic Heteropoly Acid Ionic Liquids Under Ultrasound†

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Oxidative Desulfurization of Gasoline Catalyzed by Organic-inorganic Heteropoly Acid Ionic Liquids Under Ultrasound^†