有机-无机杂多酸类离子液体催化汽油超声氧化脱硫

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]HPW_(12)O_40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、H_2O_2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]HPW_(12)O_40为催化剂,在优化的条件下n(Cat.)=0.008 mmol,V(H_2O_2)=40μL,V(模拟油)=10 m L,V(乙腈)=1 m L,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DBT4,6-二甲基苯并噻吩(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.

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

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 Zr0?25BMIM]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 H2 O2 on the desulfurization rate were fully investigated. The selected optimal conditions were as follows: n(Cat.)=0?008 mmol, V( H2 O2 )=40μL, 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 Zr0?25BMIM]HPW12O40 could be directly separated out after the reaction, and could be reused after the vacuum drying. The results showed that Zr0?25 BMIM ] HPW12 O40 also exhibited good recyclability. After 5 recycles, the desulfurization rate still could reach 81.9%. By using Zr0?25BMIM]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.