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

doi:10.7503/cjcu20160539

Abstract

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

CLC Number:

O643.3
O621

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2016, 37(12): 2184.

Figures/Tables 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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