Study On Synthesis Of Novle Exreactive/oxidative Ionic Liquid And Application In Deep Desulfurization Of Fuel

In this paper, four types of desulfurization systems and a cooperative project with an enterprise have been designed including?1? a deep extractive desulfurization system of simulation gasoline with ionic liquids containing-OH group as the extraction agent,?2? a deep extractive-oxidative desulfurization system of simulation gasoline with ionic liquids extraction agent,?3? a H₂O₂ oxidative desulfurization system of simulation gasoline catalyzed by a variety of metal-doped phosphotungstic acid ionic liquids,?4? a H₂O₂ oxidative desulfurization system of simulation gasoline catalyzed by metal-doped phosphotungstic acid ionic liquids under ultrasonic,?5? a cooperative project to reduce the sulfur content of light hydrocarbon oil under 10 ppm. Four types of desulfurization systems have achieved a better desulfurization effect and the cooperative project has reached the target of the enterprise requirements.A series of extractive ionic liquids have been synthesized by using triethylamine, n-butylimidazole, 8-chloro-octanol, p-toluenesulfonic acid, tetrafluoroboric acid etc. as raw materials. The structures of the ionic liquids are characterized by IR and 1H NMR, and the ionic liquids have been used in the experiment of extracting desulfurition. The best extraction ionic liquid is [BIM?CH2?8OH]BF4. The optimum conditions in extracting desulfurization are as follows: m?IL?=1.0 g, V?oil?=10.0 mL, T=25 oC and t=10 min. Under these conditions, the first stage extraction rate can reach 76.88 %, and the three stage extraction rate can reach 98.15 %. After 6 recycles of the ionic liquid, the desulfurization rate only has a little decrease, and the repeated use of ionic liquid is realized.A series of extractive ionic liquids have been synthesized by using n-octylimidazole, tributylamine, 8-chloro-octanol, p-toluenesulfonic acid etc. as raw materials. The structures of the ionic liquids are characterized by IR and 1H NMR, and the ionic liquids have been used in the experiment of oxidative/extractive desulfurition. The best ionic liquid is [OIM?CH2?8OH]PTSA. The optimum conditions in oxidative/extractive desulfurization are as follows: m?IL?=0.5 g, V?C H3COOH?=0.25 mL, V?H₂O₂?= 0.25 mL, V?oil?=10.0 mL, T=70 oC and t=80 min. Under these conditions, the desulfurization rate for simulate gasoline can be 99.7 %. After 6 recycles of the ionic liquid, the desulfurization rate could still reach 90.0 %, and the repeated use of ionic liquid is realized.A series of Fe-doped, Co-doped, Ti-doped, Ce-doped phosphotungstic acid ionic liquids have been synthesized by using imidazole, propane sultone, n-butyl chloride, chloroacetate, cerous carbonate, phosphotungstic acid as raw materials. The structures of the catalysts are characterized by IR and 1H NMR. The catalysts are used for catalyzing H₂O₂ oxidative desulfurization of simulate gasoline. The best catalyst is Ce0.66[BMIM]PW12O40. The optimum conditions are as follows: n?cat.?=0.014 mmol, V?H₂O₂?=30 ?L, V?oil?=10.0 mL, V?acetonitrile?=1.0 mL, T=55 oC and t=6 min. Under the above conditions, the sulfur removel can reach 98.83 %. However, the repeated use of the catalyst is not very ideal.A series of metal-doped phosphotungstic acid ionic liquids have been synthesized. The structures of the catalysts are characterized by IR and 1H NMR. The catalysts are used for catalyzing H₂O₂ oxidative desulfurization of simulate gasoline under ultrasonic. The best catalyst is Zr0.25[BMIM]HPW12O40. The selected optimal conditions are as follows: n?cat.?=0.008 mmol, V?H₂O₂?=40 mL, V?simulated oil?=10 mL, V?acetonitrile?=1 mL, T=25 oC, t=10 min, the ultrasonic power 300 w, the ultrasonic time 2 s, and the ultrasonic off- time 1.5 s. Under the above conditions, the sulfur removel can reach 97.8 %. After 5 recycles of the ionic liquid, the desulfurization rate could reach 81.9 %. Although with the help of ultrasonic, the desulfurization rate increases, the repeated use of ionic liquid need be improved.A series of ionic liquids including 4 kinds of basic ionic liquids and 3 kinds of phosphate ester ionic liquids have been synthesized by using n-methylimidazole, n-butyl chloride, sodium hydroxide, sodium carbonate, sodium acetate, tributyl phosphate as raw materials, The structures of the ionic liquids are characterized by IR and 1H NMR, and the ionic liquids have been used in the experiment of extracting desulfurition of light hydrocarbon oil. The best ionic liquid is [BMIM]OH. The first stage extraction rate can reach 76.08 %, and the second stage extraction rate can reach 96.18 %. After two stage extraction, the sulfur content of light hydrocarbon oil is reduced to 4.275 ppm and meets the requirements of enterprise, which demands to reduce the sulfur content of the light hydrocarbon oil to 10 ppm.In summary, this paper has successfully established a variety of deep desulfurization systems. The study provides new science basis for the application of ionic liquid in deep desulfurization.