Preparation of methylimidazole hydrochloride/oxalic acid type deep eutectic solvent and its application in oxidative desulfurization of model oil

doi:10.11949/j.issn.0438-1157.20160330

Abstract

Abstract:

Methylimidazole hydrochloride/oxalic acid ([HMIM]Cl/H₂C₂O₄) type deep eutectic solvent was synthesized by a simple heating and stirring mixture of methyl imidazole hydrochloride and oxalic acid. The removal of dibenzothiophene (DBT) in model oil was carried out by using[HMIM]Cl/H₂C₂O₄ as a catalyst and hydrogen peroxide as oxidant. The effect of different reaction parameters such as different desulfurization system, reaction temperature, catalyst amount, molar ratio of hydrogen peroxide to sulfur and the type of sulfur-containing compounds in oil on the desulfurization rate was investigated. The experimental results indicated that the removal rate of DBT can reach 92.2% under the optimum conditions of 5 ml model oil, 1.25 ml of[HMIM]Cl/H₂C₂O₄ and O/S mole ratio of 12 in 140 min and 40℃. The kinetics analysis showed that the oxidative desulfurization system was in accord with the first order reaction kinetics equation. The catalyst was reused for 7 times without significant decrease in activity.

Key words: methylimidazole hydrochloride, [HMIM]Cl/H₂C₂O₄, catalysts, deep eutectic solvent, oxidation, reaction kinetics

摘要：

通过简单加热并搅拌甲基咪唑盐酸盐和草酸的混合物合成了甲基咪唑盐酸盐/草酸（[HMIM]Cl/H₂C₂O₄）型酸性低共熔溶剂，以[HMIM]Cl/H₂C₂O₄为萃取剂和催化剂、H₂O₂为氧化剂催化氧化法脱除模拟油中的二苯并噻吩，考察不同的脱硫体系、反应温度、催化剂加入量、氧硫比、模拟油中含硫化合物类型对脱硫率的影响。实验表明，在反应温度为40℃、模拟油量为5 ml、[HMIM]Cl/H₂C₂O₄加入量为1.25 ml、O/S 12、反应时间为140 min的最佳反应条件下二苯并噻吩的脱除率可以达到92.2%。动力学分析表明，该氧化脱硫体系符合一级反应动力学方程。循环使用7次后催化剂的活性没有明显降低。

关键词: 甲基咪唑盐酸盐, [HMIM]Cl/H₂C₂O₄, 催化剂, 低共熔溶剂, 氧化, 反应动力学

CLC Number:

TE624

HOU Liangpei, ZHAO Rongxiang, LI Xiuping, SHI Weiwei. Preparation of methylimidazole hydrochloride/oxalic acid type deep eutectic solvent and its application in oxidative desulfurization of model oil[J]. CIESC Journal, 2016, 67(9): 3972-3980.

侯良培, 赵荣祥, 李秀萍, 石薇薇. 甲基咪唑盐酸盐/草酸型低共熔溶剂的制备及其在模拟油中氧化脱硫中的应用[J]. 化工学报, 2016, 67(9): 3972-3980.

References 51

[1]	张存, 王峰, 潘小玉, 等. 酸性离子液体萃取-氧化模拟油品脱硫研究[J]. 燃料化学学报, 2011, 39(9):689-693. ZHANG C, WANG F, PAN X Y, et al. Study on extraction-oxidation desulfurization of model oil by acidic ionic liquid[J]. Journal of Fuel Chemistry and Technology, 2011, 39(9):689-693.
[2]	DAI B, WU P, ZHU W, et al. Heterogenization of homogenous oxidative desulfurization reaction on graphene-like boron nitride with a peroxomolybdate ionic liquid[J]. RSC Advances, 2016, 6(1):140-147.
[3]	范珍龙, 俞星明, 吕效平, 等. 钨酸盐/H2O2/[HNMP] [HSO4]体系的催化氧化脱硫性能[J]. 南京工业大学学报(自然科学版), 2015, 37(1):44-48. FAN Z L, YU X M, LÜ X P, et al. Desulfurization by catalytic oxidation with tungstate/H2O2/[HNMP] [HSO4] [J]. Journal of Nanjing Technology University (Natural Science Edition), 2015, 37(1):44-48.
[4]	WANG C, ZHU W, CHEN Z, et al. Light irradiation induced aerobic oxidative deep desulfurization of fuel in ionic liquid[J]. RSC Advances, 2015, 5(121):99927-99934.
[5]	ASUMANA C, YU G, LU X, et al. Extractive desulfurization of fuel oils with low-viscosity dicyanamide-based ionic liquids[J]. Green Chemistry, 2010, 12(11):2030-2037.
[6]	ABRO R, ABDELTAWAB A A, AL-DEYAB S S, et al. A review of extractive desulfurization of fuel oils using ionic liquids[J]. RSC Advances, 2014, 4(67):35302-35317.
[7]	YU F L, LIU C Y, XIE P H, et al. Oxidative-extractive deep desulfurization of gasoline by functionalized heteropoly acid catalysts[J]. RSC Advances, 2015, 5(104):85540-85546.
[8]	LU L, CHENG S F, GAO J B, et al. Deep oxidative desulfurization of fuels catalyzed by ionic liquid in the presence of H2O2[J]. Energy Fuels, 2007, 21:383-384.
[9]	VALIGI M, GAZZOLI D, PETTITI I, et al. WOx/ZrO2 catalysts (Ⅰ):Preparation, bulk and surface characterization[J]. Applied Catalysis A:General, 2002, 231(1):159-172.
[10]	赵地顺, 孙智敏, 李发堂, 等. 酸性离子液体萃取/催化二苯并噻吩氧化脱硫反应的优化[J]. 燃料化学学报, 2009, 37(2):194-198. ZHAO D S, SUN Z M, LI F T, et al. Optimization of oxidative desulfrization of dibenzothiophen using acidic ionic liquid as catalytic solvent[J]. Journal of Fuel Chemistry and Technology, 2009, 37(2):194-198.
[11]	李佳慧, 胡嘉, 赵荣祥, 等. 氯化胆碱/草酸型低共熔溶剂氧化脱除模拟油硫化物[J]. 燃料化学学报, 2014, 42(7):870-876. LI J H, HU J, ZHAO R X, et al. Oxidative desulfurization of model oil with choline chloride/oxalic acid as a eutectic solvent[J]. Journal of Fuel Chemistry and Technology, 2014, 42(7):870-876.
[12]	LI F, WU B, LIU R, et al. An inexpensive N-methyl-2-pyrrolidone-based ionic liquid as efficient extractant and catalyst for desulfurization of dibenzothiophene[J]. Chemical Engineering Journal, 2015, 274:192-199.
[13]	LI X, LIU L, WANG A, et al. Creation of oxygen vacancies in MoO3/SiO2 by thermal decomposition of pre-impregnated citric acid under N2 and their positive role in oxidative desulfurization of dibenzothiophene[J]. Catal. Lett., 2014, 144:531-537.
[14]	YAN X M, MEI Z, MEI P, et al. Self-assembled HPW/silica-alumina mesoporous nanocomposite as catalysts for oxidative desulfurization of fuel oil[J]. Journal of Porous Materials, 2014, 21(5):729-737.
[15]	BAKAR W A W A, ALI R, KADIR A A A, et al. Effect of transition metal oxides catalysts on oxidative desulfurization of model diesel[J]. Fuel Processing Technology, 2012, 101:78-84.
[16]	LIU B S, XU D F, CHU J X, et al. Deep desulfurization by the adsorption process of fluidized catalytic cracking (FCC) diesel over mesoporous Al-MCM-41 materials[J]. Energy Fuels, 2007, 21(1):250-255.
[17]	许本静, 孙新, 田辉平, 等. 负载氧化钼催化剂催化氧化脱硫研究[J]. 工业催化, 2009, 17(6):30-34. XU B J, SUN X, TIAN H P, et al. Oxidative desulfurization catalyzed by supported MoO3 catalysts[J]. Industrial Catalysis, 2009, 17(6):30-34.
[18]	赵地顺, 李发堂, 刘文丽. 催化裂化汽油光化学氧化脱硫[J]. 石油化工, 2006, 35(10):963-966. ZHAO D S, LI F T, LIU W L. Photochemical oxidative desulfrization of fluidized catalytic cracking gasoline[J]. Petrochemical Technology, 2006, 35(10):963-966.
[19]	唐克, 宋丽娟, 段林海, 等. 杂原子Y分子筛的二次合成及其吸附脱硫性能[J]. 燃料化学学报, 2007, 35(5):1116-1120. TANG K, SONG L J, DUAN L H, et al. Deep desulfurization by selective adsorption on heteroatom zeolite prepared by secondary synthesis[J]. Journal of Fuel Chemistry and Technology, 2007, 35(5):1116-1120.
[20]	ABBOTT A P, CAPPER G, DAVIES D L, et al. Novel solvent properties of choline chloride/urea mixtures[J]. Chem. Commun., 2003, 1:70-71.
[21]	ABBOTT A P, CAPPER G, MCKENZIE K J, et al. Electrodeposition of zinc-tin alloys from deep eutectic solvents based on choline chloride[J]. Journal of Electroanalytical Chemistry, 2007, 599(2):288-294.
[22]	ABBOTT A P, CAPPER G, DAVIES D L, et al. Electrodeposition of chromium black from ionic liquids[J]. Transactions of the Institute of Metal Finishing, 2004, 82:14-17.
[23]	LIU W, YU Y, CAO L, et al. Synthesis of monoclinic structured BiVO4 spindly microtubes in deep eutectic solvent and their application for dye degradation[J]. Journal of Hazardous Materials, 2010, 181(1):1102-1108.
[24]	ZHANG J, CHEN J, LI Q. Microwave heating synthesis and formation mechanism of chalcopyrite structured CuInS2 nanorods in deep eutectic solvent[J]. Materials Research Bulletin, 2015, 63:88-92.
[25]	ABBOTT A P, CAPPER G, DAVIES D L, et al. Selective extraction of metals from mixed oxide matrixes using choline-based ionic liquids[J]. Inorganic Chemistry, 2005, 44(19):6497-6499.
[26]	ABBOTT A P, CULLIS P M, GIBSON M J, et al. Extraction of glycerol from biodiesel into a eutectic based ionic liquid[J]. Green Chemistry, 2007, 9(8):868-872.
[27]	GANO Z S, MJALLI F S, AL-WAHAIBI T, et al. Solubility of thiophene and dibenzothiophene in anhydrous FeCl3- and ZnCl2-based deep eutectic solvents[J]. Industrial & Engineering Chemistry Research, 2014, 53(16):6815-6823.
[28]	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 central-composite design[J]. Chemical Engineering and Processing:Process Intensification, 2015, 93:10-20.
[29]	GANO Z S, MJALLI F S, AL-WAHAIBI T, et al. The novel application of hydrated metal halide (SnCl2·2H2O)-based deep eutectic solvent for the extractive desulfurization of liquid fuels[J]. International Journal of Chemical Engineering and Applications, 2015, 6(5):367-371.
[30]	ZHU W, WANG C, LI H, et al. One-pot extraction combined with metal-free photochemical aerobic oxidative desulfurization in deep eutectic solvent[J]. Green Chemistry, 2015, 17(4):2464-2472.
[31]	LÜ H, LI P, DENG C, et al. Deep catalytic oxidative desulfurization (ODS) of dibenzothiophene (DBT) with oxalate-based deep eutectic solvents (DESs)[J]. Chemical Communications, 2015, 51(53):10703-10706.
[32]	DAI D, WANG L, CHEN Q, et al. Selective oxidation of sulfides to sulfoxides catalysed by deep eutectic solvent with H2O2[J]. Journal of Chemical Research, 2014, 38(3):183-185.
[33]	YIN J, WANG J, LI Z, et al. Deep desulfurization of fuels based on an oxidation/extraction process with acidic deep eutectic solvents[J]. Green Chemistry, 2015, 17(9):4552-4559.
[34]	李大勇, 魏莉, 蒋景阳. 离子液体在两相催化中的研究进展和应用前景[J]. 化工进展, 2004, 23(6):605-608. LI D Y, WEI L, JIANG J Y. Development and perspective of ionic liquids in biphasic catalysis[J]. Chemical Industry and Engineering Progress, 2004, 23(6):605-608.
[35]	李学玲, 顾烁玥, 杨项军. 草酸-硝酸盐低热固相反应法制备(Ni0.58Cu0.2Zn0.22)Fe0.96O4铁氧体[J]. 材料导报, 2009, 23(18):103-106. LI X L, GU S Y, YANG X J. Synthesis of nanocrystalline (Ni0.58Cu0.2Zn0.22)Fe0.96O4 by low-heating solid-state reaction[J]. Materials Review, 2009, 23(18):103-106.
[36]	卢泽湘, 袁霞, 吴剑, 等. 咪唑类离子液体的合成和光谱表征[J]. 化学世界, 2005, 46(3):148-150. LU Z X, YUAN X, WU J, et al. Synthesis and spectroscopic characterization of N,N-dialkylimidazolium-based ionic liquids[J]. Chemical World, 2005, 46(3):148-150.
[37]	何志强, 鄢浩, 王骑虎, 等. 温度对氯化胆碱/多元醇型低共熔溶剂物性的影响[J]. 上海大学学报(自然科学版), 2015, 21(3):384-392. HE Z Q, YAN H, WANG Q H, et al. Effect of temperature on physic-chemical properties of deep eutectic solvent based on chloride and polyols[J]. Journal of Shanghai University (Natural Science), 2015, 21(3):384-392.
[38]	LÜ H, WANG S, DENG C, et al. Oxidative desulfurization of model diesel via dual activation by a protic ionic liquid[J]. Journal of Hazardous Materials, 2014, 279:220-225.
[39]	乔焜, 邓友全. 氯铝酸室温离子液体中缩醛和缩酮反应[J]. 化学学报, 2002, 60(3):528-531. QIAO K, DENG Y Q. Acetalization and ketalization reactions in chloroaluminate room temperature ionic liquids[J]. Acta Chimica Sinica, 2002, 60(3):528-531.
[40]	王利, 吴晓军, 桂建舟, 等. 酸性离子液体[(CH2)4SO3HMIm]TSO在噻吩类氧化脱硫中的应用[J]. 石油化工高等学校学报, 2008, 21(3):29-31. WANG L, WU X J, GUI J Z, et al. The application of the acidic ionic liquid of[(CH2)4SO3HMIm]TSO in thiophene-based oxidative desulfurization[J]. Journal of Petrochemical Universities, 2008, 21(3):29-31.
[41]	李宇慧, 冯丽娟, 王景刚, 等. MoO3/Al2O3介孔催化剂在柴油氧化脱硫中的应用[J]. 石油学报(石油加工), 2011, 27(6):878-883. LI Y H, FENG L J, WANG J G, et al. Oxidative desulfurization of diesel oil by mesoporous catalyst MoO3/Al2O3[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2011, 27(6):878-883.
[42]	苏建勋, 艾东, 赵荣祥, 等. CuWO4/C复合物的制备和其在模拟油氧化脱硫中的应用[J]. 燃料化学学报, 2015, 43(12):1476-1481. SU J X, AI D, ZHAO R X, et al. Study of the preparation of CuWO4/C composite and its application in oxidative desulfurization of model oil[J]. Journal of Fuel Chemistry and Technology, 2015, 43(12):1476-1481.
[43]	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 Molecular Catalysis A:Chemical, 2012, 359:8-13.
[44]	张存, 马春艳, 刘晓勤. 超声强化过氧化氢/三氯乙酸催化氧化柴油深度脱硫研究[J]. 燃料化学学报, 2009, 37(3):324-329. ZHANG C, MA C Y, LIU X Q. Ultrasound enhanced catalytic oxidative deep desulfurization of diesel with H2O2-trichloroacetic acid[J]. Journal of Fuel Chemistry and Technology, 2009, 37(3):324-329.
[45]	LÜ H, ZHANG Y, JIANNG Z, et al. Aerobic oxidative desulfurization of benzothiophene, dibenzothiophene and 4,6-dimethyl, dibenzothiophene using an Anderson-type catalyst[(C18 H37)2N(CH3)2]5[IMo6O24] [J]. Green Chemistry, 2010, 12(11):1954-1958.
[46]	CEDEÑO-CAERO L, GOMEZ-BERNAL H, FRAUSTRO-CUEVAS A, et al. Oxidative desulfurization of synthetic diesel using supported catalysts (Ⅲ):Support effect on vanadium-based catalysts[J]. Catalysis Today, 2008, 133:244-254.
[47]	SHI Z, SHANGL, ZHAO S, et al. Oxidative desulfurization in diese1 via microwave irradiation under H2O2-CH3COOH-DMF system[J]. Journal of Petrochemical Universities, 2008, 21(4):41-44.
[48]	ZHU W, WANG C, LI H, et al. One-pot extraction combined with metal-free photochemical aerobic oxidative desulfurization in deep eutectic solvent[J]. Green Chemistry, 2015, 17(4):2464-2472.
[49]	LIANG W, ZHANG S, LI H, et al. Oxidative desulfurization of simulated gasoline catalyzed by acetic acid-based ionic liquids at room temperature[J]. Fuel Processing Technology, 2013, 109:27-31.
[50]	SHIRAISHI Y, TACHIBANA K, HIRAI T, et al. Desulfurization and denitrogenation process for light oils based on chemical oxidation followed by liquid-liquid extraction[J]. Industrial & Engineering Chemistry Research, 2002, 41(17):4362-4375.
[51]	DONG Y, NIE Y, ZHOU Q. Highly efficient oxidative desulfurization of fuels by Lewis acidic ionic liquids based on iron chloride[J]. Chemical Engineering & Technology, 2013, 36(3):435-442.