咪唑类离子液体的制备、性质及其在燃料油脱硫中的应用
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摘要
离子液体作为一种环境友好、“可设计性”绿色溶剂,能够脱除燃油中的硫、氮化合物,具有潜在的经济价值。本文以N-甲基咪唑为原料,利用微波反应仪合成溴代3-丁基-1-甲基咪唑盐[BMIm]Br,通过考察体系温度的变化及单因素实验确定了最佳制备条件,并通过红外光谱表征了结构和纯度。对合成出的不同烷基取代的咪唑类离子液体[RMIm]Br的熔点、溶解性、黏温性及吸水性等进行了测定和研究,发现了明显的递变规律,这与咪唑阳离子的结构及溶质的结构有密切的关系。进一步用[RMIm]Br分别对模型油品中的噻吩、二苯并噻吩、2-甲基吡啶进行了萃取研究,考察了剂油比、温度、萃取级数、离子液体含水量、再生、离子液体种类等因素对脱硫、脱氮的影响。结果表明,通过增大剂油比,提高萃取级数都能有效降低油品中的硫、氮含量;适宜的温度及降低离子液体的含水量有利于降低油品中的硫含量;选用不同烷基取代的[RMIm]Br萃取,溴代3-乙基-1-甲基咪唑盐[EMIm]Br效果最好;采用水萃取再生方法处理的[RMIm]Br能保持良好、稳定的脱硫、脱氮效果。在硫、氮含量的测定中,建立了紫外可见分光光度法。此法可以迅速、准确的测定模型油品中硫、氮的含量,具有非常实际的应用价值。
As a kind of environment friendly and designable solvents, the ionic liquids behave good abilities in desulfurization and denitrification. The ionic liquid [BMIm]Br was prepared with N-methyl imidazole in microwave radiation instrument. The best preparation conditions were determined through the single-factor experiment and temperature variation. The structure and purity of the ionic liquid were also characterized by IR survey in this article. All the research including melting point, viscosity, hydroscopicity of the ionic liquids and solubility of different organic compounds in it show obvious regularity which is closely related to the structures of the imidazole cation and organics. The extractive experiment of thiophene, dibenzothiophene(DBT), 2-methyl pyridine in modeling oil with [RMIm]Br were carried out. In this research, the effect of volume ratio of ionic liquids to oil, temperature, water content, time of extraction, regeneration and the ionic liquids’patten to the desulfurization and denitrification were investigated. The results indicate that big volume ratio and more times of extraction are favorable for desulfurization and denitrification, low temperature are beneficial to DBT extraction. [EMIm]Br shows the best extractive result in different ionic liquids [RMIm]Br. The regenerated [RMIm]Br by water diluting display good and steady desulfurization ability. Ultraviolet spectrophotometry is very practical in content determine of sulfur and nitrogen in modeling oil.
As a kind of environment friendly and designable solvents, the ionic liquids behave good abilities in desulfurization and denitrification. The ionic liquid [BMIm]Br was prepared with N-methyl imidazole in microwave radiation instrument. The best preparation conditions were determined through the single-factor experiment and temperature variation. The structure and purity of the ionic liquid were also characterized by IR survey in this article. All the research including melting point, viscosity, hydroscopicity of the ionic liquids and solubility of different organic compounds in it show obvious regularity which is closely related to the structures of the imidazole cation and organics. The extractive experiment of thiophene, dibenzothiophene(DBT), 2-methyl pyridine in modeling oil with [RMIm]Br were carried out. In this research, the effect of volume ratio of ionic liquids to oil, temperature, water content, time of extraction, regeneration and the ionic liquids’patten to the desulfurization and denitrification were investigated. The results indicate that big volume ratio and more times of extraction are favorable for desulfurization and denitrification, low temperature are beneficial to DBT extraction. [EMIm]Br shows the best extractive result in different ionic liquids [RMIm]Br. The regenerated [RMIm]Br by water diluting display good and steady desulfurization ability. Ultraviolet spectrophotometry is very practical in content determine of sulfur and nitrogen in modeling oil.
引文
[1]邓友全.离子液体-性质、制备与应用[M].北京:中国石化出版社,2006:3-6
[2]胡德荣,张新位,赵景芝.离子液体简介[J].首都师范大学学报,2005,26(2):40-44
[3]刘维民,牟宗刚,周峰.含膦酸酯官能团的离子液体及其制备方法和用途[P].中国专利:10117751,2003
[4]梅乐和,王永泽,姚善泾.一种水溶性离子液体的合成方法[P].中国专利:1579609,2005
[5]刘庆彬,张占辉,张福军.一种无毒离子液体、制备方法及其应用[P].中国专利:1651089,2005
[6]邵媛,胡杰,邓宇.微波辐射下烷基吡啶季铵盐类离子液体的制备[J].化工中间体,2006,8:20-23
[7]李春蕾,周永昌.卤代二烃基咪唑离子液体合成研究进展[J].安徽工业大学学报,2005,22(1):25-29
[8] Khadilkar B M, Rebeiro G L. Microwave-assisted synthesis of room-temperature ionic liquid precursor in closed vessel [J]. Org Process Res Dev, 2002, 6(6): 826-828
[9] Varma R S, Namboodiri V V. An expeditious solvent-free route to ionic liquids using microwaves[J]. Chemical Communication, 2001: 643-644
[10] Lévêque J M, Luche J L, Rouxa C P R, et al. An improved preparation of ionic liquids by ultrasound [J]. Green Chemistry, 2002, 4: 357-360
[11] Anna S L, John D H, Fook S T, et al. Designing ionic liquids: imidazolium melts with inert carborane anion[J]. Journal of the American Chemical Society, 2000, 122(14): 7264-7272
[12]蒋栋,王媛媛,刘洁,等.咪唑类离子液体结构与熔点的构效关系及其基本规律[J].化学通报,2007,5:371-375
[13]张锁江,吕兴梅.离子液体——从基础研究到工业应用[M].北京:科学出版社,2006:1～681
[14] Holbrey J D, Seddon K R. The phase behaviour of 1- alkyl-3-methylimidazolium tetrafluoroborates: ionic liquids and ionic liquids crystals[J]. Journal of the Chemical Society, 1999, 13: 2133-2139
[15] Wasserscheid P, Keim W. Ionic liquids-New“solution”for transition metal catalysis. Angewandte Chemie International Edition, 2000,39: 3772-3789
[16]高枝荣,刘道胜,廖克俭,等.烷基铵盐-氯铝酸类离子液体的物理性质[J].辽宁石油化工大学学报,2004,24(2):8-11
[17]叶天旭,张予辉,刘金河,等.烷基咪唑氟硼酸盐离子液体的合成与溶剂性质研究[J].石油大学学报(自然科学版),2004,28(4):105-107
[18] Cláudia C. Cassol, Alexandre P,Umpierre, et al. On the Extraction of Aromatic Compounds from Hydrocarbons by Imidazolium Ionic Liquids [J]. Int. J. Mol. Sci. 2007, 8, 593-605
[19]郭文希,高鹏,张姝妍,等.室温离子液体的物化性能[J].辽宁化工,2003,32(6):256-259
[20]张景涛,朴香兰,朱慎林.离子液体及其在萃取中的应用研究进展[J].化工进展,2001,19 (5):29-34
[21]王均凤,张锁江,陈慧萍,等.离子液体的性质及其在催化反应中的应用[J].过程工程学报,2003,3(2):177-l85
[22]黄碧纯,黄仲涛.离子液体的研究开发及其在催化反应中的应用[J].工业催化,2003,14(2):1-5
[23]黄蔚霞,李云龙,汪燮卿.离子液体在催化裂化汽油脱硫中的应用[J].化工进展,2004,23 (3):297-299
[24]张成中,黄崇品,李建伟,等.离子液体的结构及其汽油萃取脱硫性能[J].化学研究,2005,16(1):23-25
[25] Lu Liang, Cheng Shifu, Gao Jinbao, et al. Imidazolium-based alkylphosphate ionic liquids– A potential solvent for extractive desulfurization of fuel [J]. Energy & Fuels, 2007, 21: 383-384
[26] Zhu Wenshuai, Li Huaming, Jiang Xue, et al. Oxidative Desulfurization of Fuels Catalyzed by Peroxotungsten and Peroxomolybdenum Complexes in Ionic Liquids[J]. Energy & Fuels, 2007, 21: 2514-2516
[27]张进,朴香兰,朱慎林.离子液体对燃油含硫化合物的萃取性能研究[J].化学试剂,2006,28 (7):385～387
[28]周瀚成,陈楠,石峰,等.离子液体萃取脱硫新工艺研究[J].分子催化,2005,19(2):94-97
[29]王玉新,李丹东,曹祖宾,等.室温氯铝酸离子液体络合吸附噻吩类硫化物的研究[J].石油化工高等学校学报,2004,17 (4) :42-46
[30] Varma R S, Namboodiri V V. An expeditious solvent-free route to ionic liquids using microwaves [J]. Chem Commun, 2001: 643-644
[31] Spectral Database for Organic Compounds SDBS [DB/OL] http://riodbol.ibase.aist.go.jp/sdbs/cgi_bin/direct_frame_top.cgi
[2]胡德荣,张新位,赵景芝.离子液体简介[J].首都师范大学学报,2005,26(2):40-44
[3]刘维民,牟宗刚,周峰.含膦酸酯官能团的离子液体及其制备方法和用途[P].中国专利:10117751,2003
[4]梅乐和,王永泽,姚善泾.一种水溶性离子液体的合成方法[P].中国专利:1579609,2005
[5]刘庆彬,张占辉,张福军.一种无毒离子液体、制备方法及其应用[P].中国专利:1651089,2005
[6]邵媛,胡杰,邓宇.微波辐射下烷基吡啶季铵盐类离子液体的制备[J].化工中间体,2006,8:20-23
[7]李春蕾,周永昌.卤代二烃基咪唑离子液体合成研究进展[J].安徽工业大学学报,2005,22(1):25-29
[8] Khadilkar B M, Rebeiro G L. Microwave-assisted synthesis of room-temperature ionic liquid precursor in closed vessel [J]. Org Process Res Dev, 2002, 6(6): 826-828
[9] Varma R S, Namboodiri V V. An expeditious solvent-free route to ionic liquids using microwaves[J]. Chemical Communication, 2001: 643-644
[10] Lévêque J M, Luche J L, Rouxa C P R, et al. An improved preparation of ionic liquids by ultrasound [J]. Green Chemistry, 2002, 4: 357-360
[11] Anna S L, John D H, Fook S T, et al. Designing ionic liquids: imidazolium melts with inert carborane anion[J]. Journal of the American Chemical Society, 2000, 122(14): 7264-7272
[12]蒋栋,王媛媛,刘洁,等.咪唑类离子液体结构与熔点的构效关系及其基本规律[J].化学通报,2007,5:371-375
[13]张锁江,吕兴梅.离子液体——从基础研究到工业应用[M].北京:科学出版社,2006:1～681
[14] Holbrey J D, Seddon K R. The phase behaviour of 1- alkyl-3-methylimidazolium tetrafluoroborates: ionic liquids and ionic liquids crystals[J]. Journal of the Chemical Society, 1999, 13: 2133-2139
[15] Wasserscheid P, Keim W. Ionic liquids-New“solution”for transition metal catalysis. Angewandte Chemie International Edition, 2000,39: 3772-3789
[16]高枝荣,刘道胜,廖克俭,等.烷基铵盐-氯铝酸类离子液体的物理性质[J].辽宁石油化工大学学报,2004,24(2):8-11
[17]叶天旭,张予辉,刘金河,等.烷基咪唑氟硼酸盐离子液体的合成与溶剂性质研究[J].石油大学学报(自然科学版),2004,28(4):105-107
[18] Cláudia C. Cassol, Alexandre P,Umpierre, et al. On the Extraction of Aromatic Compounds from Hydrocarbons by Imidazolium Ionic Liquids [J]. Int. J. Mol. Sci. 2007, 8, 593-605
[19]郭文希,高鹏,张姝妍,等.室温离子液体的物化性能[J].辽宁化工,2003,32(6):256-259
[20]张景涛,朴香兰,朱慎林.离子液体及其在萃取中的应用研究进展[J].化工进展,2001,19 (5):29-34
[21]王均凤,张锁江,陈慧萍,等.离子液体的性质及其在催化反应中的应用[J].过程工程学报,2003,3(2):177-l85
[22]黄碧纯,黄仲涛.离子液体的研究开发及其在催化反应中的应用[J].工业催化,2003,14(2):1-5
[23]黄蔚霞,李云龙,汪燮卿.离子液体在催化裂化汽油脱硫中的应用[J].化工进展,2004,23 (3):297-299
[24]张成中,黄崇品,李建伟,等.离子液体的结构及其汽油萃取脱硫性能[J].化学研究,2005,16(1):23-25
[25] Lu Liang, Cheng Shifu, Gao Jinbao, et al. Imidazolium-based alkylphosphate ionic liquids– A potential solvent for extractive desulfurization of fuel [J]. Energy & Fuels, 2007, 21: 383-384
[26] Zhu Wenshuai, Li Huaming, Jiang Xue, et al. Oxidative Desulfurization of Fuels Catalyzed by Peroxotungsten and Peroxomolybdenum Complexes in Ionic Liquids[J]. Energy & Fuels, 2007, 21: 2514-2516
[27]张进,朴香兰,朱慎林.离子液体对燃油含硫化合物的萃取性能研究[J].化学试剂,2006,28 (7):385～387
[28]周瀚成,陈楠,石峰,等.离子液体萃取脱硫新工艺研究[J].分子催化,2005,19(2):94-97
[29]王玉新,李丹东,曹祖宾,等.室温氯铝酸离子液体络合吸附噻吩类硫化物的研究[J].石油化工高等学校学报,2004,17 (4) :42-46
[30] Varma R S, Namboodiri V V. An expeditious solvent-free route to ionic liquids using microwaves [J]. Chem Commun, 2001: 643-644
[31] Spectral Database for Organic Compounds SDBS [DB/OL] http://riodbol.ibase.aist.go.jp/sdbs/cgi_bin/direct_frame_top.cgi