EMIES/nC_9H_(10)O_2基低共熔溶剂的制备及其氧化脱硫活性的研究
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摘要
通过简单加热1-乙基-3-甲基咪唑硫酸乙酯(EMIES)离子液体和3-苯丙酸(C_9H_(10)O_2)的混合物,制备了一系列酸性低共熔溶剂EMIES/nC_9H_(10)O_2(n=0.25,0.5,1,2,4)。通过FTIR,~1H NMR和TGA的表征,确定EMIES/nC_9H_(10)O_2的结构。以该低共熔溶剂为催化剂和萃取剂,H_2O_2为氧化剂,组成氧化-萃取脱硫体系,用于脱除模拟油中的硫化物。考察了原料配比、反应温度、氧硫比(O/S)、低共熔溶剂加入量和不同硫化物对脱硫性能的影响。结果表明,在EMIES和C_9H_(10)O_2摩尔比为1∶1,反应温度为50℃,O/S比为8,低共熔溶剂加入量为1.5 g和模拟油5 ml的反应条件下,二苯并噻吩、4,6-二甲基二苯并噻吩和苯并噻吩的脱除率分别为94.8%、91.6%和46.4%。低共熔溶剂可循环使用6次,活性无明显下降。此外,对该氧化-萃取脱硫体系的脱硫机理进行了探讨。
A series of acidic deep eutectic solvents(DESs) EMIES/nC_9H_(10)O_2(n=0.25, 0.5, 1, 2, 4) were synthesized by simply heating the mixture of 1-ethyl-3-methylimidazolium ethylsulfate(EMIES) and 3-phenylpropionic acid(C_9H_(10)O_2). The structure of EMIES/nC_9H_(10)O_2 was determined by FTIR,1 H NMR and TGA characterization. The extraction-oxidation desulfurization system was developed to remove sulfides from model oil using EMIES/nC_9H_(10)O_2 as the extractant and catalyst, H_2O_2 as the oxidation. The influences of raw material ratio, reaction temperature, O/S ratio, amount of DESs and different sulfide on the desulfurization performance were investigated. The experimental results demonstrated the optimal reaction conditions were molar ratio of EMIES to C_9H_(10)O_2 of 1∶1, temperature of50℃, O/S ratio of 8, the amount of DESs of 1.5 g and 5 ml model oil. Removal rate of DBT, 4, 6-DMDBT and BT reached 94.8%, 91.6% and 46.4%, respectively, under the optimal condition. The DESs can be reused for 6 times without significant decrease in activity. In addition, the desulfurization mechanism of the oxidation-extraction desulfurization system was discussed.
A series of acidic deep eutectic solvents(DESs) EMIES/nC_9H_(10)O_2(n=0.25, 0.5, 1, 2, 4) were synthesized by simply heating the mixture of 1-ethyl-3-methylimidazolium ethylsulfate(EMIES) and 3-phenylpropionic acid(C_9H_(10)O_2). The structure of EMIES/nC_9H_(10)O_2 was determined by FTIR,1 H NMR and TGA characterization. The extraction-oxidation desulfurization system was developed to remove sulfides from model oil using EMIES/nC_9H_(10)O_2 as the extractant and catalyst, H_2O_2 as the oxidation. The influences of raw material ratio, reaction temperature, O/S ratio, amount of DESs and different sulfide on the desulfurization performance were investigated. The experimental results demonstrated the optimal reaction conditions were molar ratio of EMIES to C_9H_(10)O_2 of 1∶1, temperature of50℃, O/S ratio of 8, the amount of DESs of 1.5 g and 5 ml model oil. Removal rate of DBT, 4, 6-DMDBT and BT reached 94.8%, 91.6% and 46.4%, respectively, under the optimal condition. The DESs can be reused for 6 times without significant decrease in activity. In addition, the desulfurization mechanism of the oxidation-extraction desulfurization system was discussed.
引文
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[23] Stack R J, Cotta M A. Effect of 3-phenylpropanoic acid on growthof and cellulose utilization by cellulolytic ruminal bacteria[J].Applied and Environmental Microbiology, 1986, 52(1):209-210.
[24] Wilkes J S, Zaworotko M J. Air and water stable 1-ethyl-3-methylimidazolium based ionic liquids[J]. Journal of theChemical Society, Chemical Communications, 1992,(13):965-967
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[26] Jiang Y, Zhu W, Li H, et al. Oxidative desulfurization of fuelscatalyzed by Fenton-like ionic liquids at room temperature[J].ChemSusChem, 2011, 4(3):399-403.
[27] Mokhtar W N A W, Bakar W A W A, Ali R, et al. Deepdesulfurization of model diesel by extraction with N, N-dimethylformamide:optimization by Box–Behnken design[J].Journal of the Taiwan Institute of Chemical Engineers, 2014, 45(4):1542-1548.
[28] Li F, Liu R, Wen J, et al. Desulfurization of dibenzothiophene bychemical oxidation and solvent extraction with Me3NCH2C6H5Cl·2ZnCl2ionic liquid[J]. Green Chemistry, 2009, 11(6):883-888.
[29] Qiu L, Cheng Y, Yang C, et al. Oxidative desulfurization ofdibenzothiophene using a catalyst of molybdenum supported onmodified medicinal stone[J]. RSC Advances, 2016, 6(21):17036-17045.
[30] Ede S R, Kundu S. Microwave synthesis of SnWO4nanoassemblies on DNA scaffold:a novel material for highperformance supercapacitor and as catalyst for butanol oxidation[J]. ACS Sustainable Chemistry&Engineering, 2015, 3(9):2321-2336.
[31] Dong Y, Nie Y, Zhou Q. Highly efficient oxidative desulfurizationof fuels by Lewis acidic ionic liquids based on iron chloride[J].Chemical Engineering&Technology, 2013, 36(3):435-442.
[32] Chen J, Chen C, Zhang R, et al. Deep oxidative desulfurizationcatalyzed by an ionic liquid-type peroxotungsten catalyst[J]. RSCAdvances, 2015, 5(33):25904-25910.
[33] Chen X, Song D, Asumana C, et al. Deep oxidative desulfurization of diesel fuels by Lewis acidic ionic liquids based on 1-n-butyl-3-methylimidazolium metal chloride[J]. Journal of MolecularCatalysis A:Chemical, 2012, 359:8-13.
[34] Zhu W S, Li H, Gu Q Q, et al. Kinetics and mechanism foroxidative desulfurization of fuels catalyzed by peroxo-molybdenum amino acid complexes in water-immiscible ionicliquids[J]. Journal of Molecular Catalysis A:Chemical, 2011, 336(1/2):16-22.
[35] Komintarachat C, Trakarnpruk W. Oxidative desulfurization usingpolyoxometalates[J]. Industrial&Engineering ChemistryResearch, 2006, 45(6):1853-1856.
[36] Wei L, Zhou Z Y, Chen S P, et al. Electrochemically shape-controlled synthesis in deep eutectic solvents:triambicicosahedral platinum nanocrystals with high-index facets andtheir enhanced catalytic activity[J]. Chemical Communications,2013, 49(95):11152-11154.
[37] Gao H, Guo C, Xing J, et al. Deep desulfurization of diesel oil withextraction using pyridinium-based ionic liquids[J]. SeparationScience and Technology, 2012, 47(2):325-330.
[38] Mao C, Zhao R, Li X. Phenylpropanoic acid-based DESs asefficient extractants and catalysts for the removal of sulfurcompounds from oil[J]. Fuel, 2017, 189:400-407.
[39] Zaid H F M, Chong F K, Mutalib M I A. Extractive deepdesulfurization of diesel using choline chloride-glycerol eutectic-based ionic liquid as a green solvent[J]. Fuel, 2017, 192:10-17.
[40] Maggi R, Piscopo C G, Sartori G, et al. Supported sulfonic acids:metal-free catalysts for the oxidation of hydroquinones tobenzoquinones with hydrogen peroxide[J]. Applied Catalysis A:General, 2012, 411:146-152.
[2] Stanislaus A, Marafi A, Rana M S. Recent advances in the science and technology of ultra low sulfur diesel(ULSD)production[J].Catalysis Today, 2010, 153(1/2):1-68.
[3] Soleimani M, Bassi A, Margaritis A. Biodesulfurization of refractory organic sulfur compounds in fossil fuels[J].Biotechnology Advances, 2007, 25(6):570-596.
[4] Ma X, Zhou A, Song C. A novel method for oxidative desulfurization of liquid hydrocarbon fuels based on catalytic oxidation using molecular oxygen coupled with selective adsorption[J]. Catalysis Today, 2007, 123(1/2/3/4):276-284.
[5] Ko N H, Lee J S, Huh E S, et al. Extractive desulfurization using Fe-containing ionic liquids[J]. Energy&Fuels, 2008, 22(3):1687-1690.
[6] Park J G, Ko C H, Yi K B, et al. Reactive adsorption of sulfur compounds in diesel on nickel supported on mesoporous silica[J].Applied Catalysis B:Environmental, 2008, 81(3/4):244-250.
[7] Zhang S, Zhang Q, Zhang Z C. Extractive desulfurization and denitrogenation of fuels using ionic liquids[J]. Industrial&Engineering Chemistry Research, 2004, 43(2):614-622.
[8] Wu Z, Xue Y, Zhang Y, et al. SnS2nanosheet-based microstructures with high adsorption capabilities and visible light photocatalytic activities[J]. RSC Advances, 2015, 5(31):24640-24648.
[9] Abbott A P, Capper G, Davies D L, et al. Novel solvent properties of choline chloride/urea mixtures[J]. Chemical Communications,2003,(1):70-71.
[10] Li C, Li D, Zou S, et al. Extraction desulfurization process of fuels with ammonium-based deep eutectic solvents[J]. Green Chemistry, 2013, 15(10):2793-2799.
[11] Li J, Xiao H, Tang X, et al. Green carboxylic acid-based deep eutectic solvents as solvents for extractive desulfurization[J].Energy&Fuels, 2016, 30(7):5411-5418.
[12] Gano Z S, Mjalli F S, Al-Wahaibi T, et al. Extractive desulfurization of liquid fuel with FeCl3-based deep eutectic solvents:experimental design and optimization by centralcomposite design[J]. Chemical Engineering and Processing:Process Intensification, 2015, 93:10-20.
[13] Li C, Zhang J, Li Z, et al. Extraction desulfurization of fuels with‘metal ions.based deep eutectic solvents(MDESs)[J]. GreenChemistry, 2016, 18(13):3789-3795.
[14] Ekezie F G C, Sun D W, Cheng J H. Acceleration of microwave-assisted extraction processes of food components by integratingtechnologies and applying emerging solvents:a review of latestdevelopments[J]. Trends in Food Science&Technology, 2017,67:160-172.
[15] Dai D, Wang L, Chen Q, et al. Selective oxidation of sulfides tosulfoxides catalysed by deep eutectic solvent with H2O2[J].Journal of Chemical Research, 2014, 38(3):183-185.
[16] Yin J, Wang J, Li Z, et al. Deep desulfurization of fuels based onan oxidation-extraction process with acidic deep eutectic solvents[J].Green Chemistry, 2015, 17(9):4552-4559.
[17] Kudtak B, Owczarek K, Namie?nik J. Selected issues related tothe toxicity of ionic liquids and deep eutectic solvents—a review[J]. Environmental Science and Pollution Research, 2015, 22(16):11975-11992.
[18] Leclercq L, Suisse I, Nowogrocki G, et al. Halide-free highly-pure imidazolium triflate ionic liquids:preparation and use inpalladium-catalysed allylic alkylation[J]. Green Chemistry, 2007,9(10):1097-1103.
[19] Jiang X, Nie Y, Li C, et al. Imidazolium-based alkylphosphateionic liquids—a potential solvent for extractive desulfurization offuel[J]. Fuel, 2008, 87(1):79-84.
[20]邢鹏飞,赵荣祥,李秀萍,等. Bi2WO6的制备及其在离子液体中的超深度氧化脱硫[J].中国炼油与石油化工, 2017, 19(1):99-105.Xing P F, Zhao R X, Li X P, et al. Preparation of Bi2WO6and itsultra-deep oxidative desulfurization performance in ionic liquids[J]. China Petroleum Processing and Petrochemical Technology,2017, 19(1):99-105.
[21] Wheeler J L, Pugh M K, Atkins S J, et al. Thermal breakdownkinetics of 1-ethyl-3-methylimidazolium ethylsulfate measuredusing quantitative infrared spectroscopy[J]. AppliedSpectroscopy, 2017, 71(12):2626-2631.
[22] Dubey S, Bharmoria P, Gehlot P S, et al. 1-Ethyl-3-methylimidazolium diethylphosphate based extraction ofbioplastic “polyhydroxyalkanoates” from bacteria:green andsustainable approach[J]. ACS Sustainable Chemistry&Engineering, 2017, 6(1):766-773.
[23] Stack R J, Cotta M A. Effect of 3-phenylpropanoic acid on growthof and cellulose utilization by cellulolytic ruminal bacteria[J].Applied and Environmental Microbiology, 1986, 52(1):209-210.
[24] Wilkes J S, Zaworotko M J. Air and water stable 1-ethyl-3-methylimidazolium based ionic liquids[J]. Journal of theChemical Society, Chemical Communications, 1992,(13):965-967
[25] Yuan B, Li Y, Yu F, et al. Benzylation with benzyl alcoholcatalyzed by[ChCl][TfOH]2, a Br?nsted acidic DES with reactioncontrol self-separation performance[J]. Catalysis Letters, 2018,148(7):2133-2138.
[26] Jiang Y, Zhu W, Li H, et al. Oxidative desulfurization of fuelscatalyzed by Fenton-like ionic liquids at room temperature[J].ChemSusChem, 2011, 4(3):399-403.
[27] Mokhtar W N A W, Bakar W A W A, Ali R, et al. Deepdesulfurization of model diesel by extraction with N, N-dimethylformamide:optimization by Box–Behnken design[J].Journal of the Taiwan Institute of Chemical Engineers, 2014, 45(4):1542-1548.
[28] Li F, Liu R, Wen J, et al. Desulfurization of dibenzothiophene bychemical oxidation and solvent extraction with Me3NCH2C6H5Cl·2ZnCl2ionic liquid[J]. Green Chemistry, 2009, 11(6):883-888.
[29] Qiu L, Cheng Y, Yang C, et al. Oxidative desulfurization ofdibenzothiophene using a catalyst of molybdenum supported onmodified medicinal stone[J]. RSC Advances, 2016, 6(21):17036-17045.
[30] Ede S R, Kundu S. Microwave synthesis of SnWO4nanoassemblies on DNA scaffold:a novel material for highperformance supercapacitor and as catalyst for butanol oxidation[J]. ACS Sustainable Chemistry&Engineering, 2015, 3(9):2321-2336.
[31] Dong Y, Nie Y, Zhou Q. Highly efficient oxidative desulfurizationof fuels by Lewis acidic ionic liquids based on iron chloride[J].Chemical Engineering&Technology, 2013, 36(3):435-442.
[32] Chen J, Chen C, Zhang R, et al. Deep oxidative desulfurizationcatalyzed by an ionic liquid-type peroxotungsten catalyst[J]. RSCAdvances, 2015, 5(33):25904-25910.
[33] Chen X, Song D, Asumana C, et al. Deep oxidative desulfurization of diesel fuels by Lewis acidic ionic liquids based on 1-n-butyl-3-methylimidazolium metal chloride[J]. Journal of MolecularCatalysis A:Chemical, 2012, 359:8-13.
[34] Zhu W S, Li H, Gu Q Q, et al. Kinetics and mechanism foroxidative desulfurization of fuels catalyzed by peroxo-molybdenum amino acid complexes in water-immiscible ionicliquids[J]. Journal of Molecular Catalysis A:Chemical, 2011, 336(1/2):16-22.
[35] Komintarachat C, Trakarnpruk W. Oxidative desulfurization usingpolyoxometalates[J]. Industrial&Engineering ChemistryResearch, 2006, 45(6):1853-1856.
[36] Wei L, Zhou Z Y, Chen S P, et al. Electrochemically shape-controlled synthesis in deep eutectic solvents:triambicicosahedral platinum nanocrystals with high-index facets andtheir enhanced catalytic activity[J]. Chemical Communications,2013, 49(95):11152-11154.
[37] Gao H, Guo C, Xing J, et al. Deep desulfurization of diesel oil withextraction using pyridinium-based ionic liquids[J]. SeparationScience and Technology, 2012, 47(2):325-330.
[38] Mao C, Zhao R, Li X. Phenylpropanoic acid-based DESs asefficient extractants and catalysts for the removal of sulfurcompounds from oil[J]. Fuel, 2017, 189:400-407.
[39] Zaid H F M, Chong F K, Mutalib M I A. Extractive deepdesulfurization of diesel using choline chloride-glycerol eutectic-based ionic liquid as a green solvent[J]. Fuel, 2017, 192:10-17.
[40] Maggi R, Piscopo C G, Sartori G, et al. Supported sulfonic acids:metal-free catalysts for the oxidation of hydroquinones tobenzoquinones with hydrogen peroxide[J]. Applied Catalysis A:General, 2012, 411:146-152.
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