离子液体1-烷基-3-羧甲基苯并咪唑双三氟甲磺酰亚胺盐的合成及在油品中的脱硫应用

doi:10.7503/cjcu20160124

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (5): 886.doi: 10.7503/cjcu20160124

离子液体1-烷基-3-羧甲基苯并咪唑双三氟甲磺酰亚胺盐的合成及在油品中的脱硫应用

刘治庆, 薛飞, 雷振凯, 刘晨江()

石油天然气精细化工教育部 & 自治区重点实验室, 乌鲁木齐绿色催化与合成技术重点实验室,新疆大学理化测试中心, 乌鲁木齐 830046

收稿日期:2016-03-01 出版日期:2016-05-10 发布日期:2016-04-20
作者简介:联系人简介: 刘晨江, 男, 博士, 教授, 主要从事有机合成方法学、绿色化学和功能杂环化合物的合成研究.E-mail: pxylcj@126.com
基金资助:
新疆维吾尔自治区重点实验室开放课题(批准号: 2015KL014)、国家自然科学基金(批准号: 21572195, 21262035, 21162025)、新疆维吾尔自治区青年科技创新人才培养工程(批准号: 2014721004)和新疆大学自然科学基金(批准号: BS110133)资助

Synthesis of ILs 1-Alkyl-3-carboxymethyl Benzimidazole Double Trifluoromethanesulfonimide and Application in Desulfurization of Fuels^†

LIU Zhiqing, XUE Fei, LEI Zhenkai, LIU Chenjiang^*()

Key Laboratory of Oil and Gas Fine Chemicals, Ministry of Education & Xinjiang Uygur Autonomous Region,Urumqi Key Laboratory of Green Catalysis and Synthesis Technology, Physics and Chemistry Detecting Center,Xinjiang University, Urumqi 830046, China

Received:2016-03-01 Online:2016-05-10 Published:2016-04-20
Contact: LIU Chenjiang E-mail:pxylcj@126.com
Supported by:
† Supported by the Open Issue of the Xinjiang Uygur Autonomous Region Key Laboratory, China(No.2015KL014), the National Natural Science Foundation of China(Nos.21572195, 21262035, 21162025), the Program for Outstanding Youth Science and Technology Innovation Talents Training in Xinjiang Uygur Autonomous Region, China(No.2014721004) and the Natural Science Foundation of Xinjiang University, China(No.BS110133)

摘要/Abstract

摘要：

合成并表征了一类新型离子液体1-烷基-3-羧甲基苯并咪唑双三氟甲磺酰亚胺盐, 将其与双氧水组合用于脱除模型油中的硫化物. 结果表明, 当模型油与萃取/催化剂1-辛基-3-羧甲基苯并咪唑双三氟甲磺酰亚胺盐([C₂O₂OBIM][Tf₂N])的质量比为5∶1, H₂O₂/S摩尔比为5∶1, 于75 ℃反应1 h后, 模型油中二苯并噻吩(DBT)脱硫率为98.8%; 脱硫过程符合一级动力学方程, 5种硫化物的脱硫速率大小顺序为二苯并噻吩(DBT)> 4,6-二甲基二苯并噻吩(4,6-DMDBT)> 苯并噻吩(BT)> 2,5-二甲基噻吩(2,5-DMT)> 噻吩(T), 其中脱除DBT和BT的反应表观活化能分别为44.16和52.10 kJ/mol. 该离子液体循环再生使用14次, 脱硫率无明显下降. 该深度脱硫方法具有操作简便及条件温和的特点.

关键词: 苯并咪唑, 离子液体, 萃取-氧化脱硫, 动力学

Abstract:

A new class of ionic liquids(ILs) 1-alkyl-3-carboxymethyl benzimidazole double trifluoromethanesulfonimide was synthesized and characterized. Ionic liquids and hydrogen peroxide were tested in extraction-oxidative desulfurization system, the sulphur removal efficiency of S-compounds in the model oil was investigated. The results showed that the 1-butyl-3-carboxymethyl double trifluoromethanesulfonimide salt([C₂O₂OBIM][Tf₂N]) was both extractant and catalyst, n(H₂O₂)∶n(DBT)=5∶1, m(Model oil)∶m(Ionic liquid)=5∶1, at 75 ℃ for 1 h. The ratios of desulfurization to the model oil of dibenzothiophene(DBT) reached 98.8%. All oxidation desulfurization processes conformed to the pseudo first-order kinetics equation. The sulfide removal rate of the order of five sulfide is dibenzothiophene(DBT)>4,6-dimethyldibenzothiophene(4,6-DMDBT)>thianaphthene(BT)>2,5-dimethylthiophene(2,5-DMT)>thiophene(T). The apparent activation energy of removal of DBT and BT is 44.16 and 52.10 kJ/mol, respectively. Ionic liquid can be recycled for 14 times with an unnoticeable decrease in desulfurization activity. The method can realize deep desulfurization the depth and have the advantages of both simple operation and mild reaction condition.

Key words: Benzimidazole, Ionic liquid, Extraction-oxidative desulfurization, Kinetics

中图分类号:

TrendMD:

刘治庆, 薛飞, 雷振凯, 刘晨江. 离子液体1-烷基-3-羧甲基苯并咪唑双三氟甲磺酰亚胺盐的合成及在油品中的脱硫应用. 高等学校化学学报, 2016, 37(5): 886.

LIU Zhiqing, XUE Fei, LEI Zhenkai, LIU Chenjiang. Synthesis of ILs 1-Alkyl-3-carboxymethyl Benzimidazole Double Trifluoromethanesulfonimide and Application in Desulfurization of Fuels^†. Chem. J. Chinese Universities, 2016, 37(5): 886.

图/表 13

参考文献 22

[1]	Zhang C., Pan X. Y., Wang F., Liu X. Q., Fuel,2012, 102, 580—584
[2]	Zhang H. X., Gao J. J., Meng H., Li C. X., Ind. Eng. Chem.Res., 2012, 51, 6658—6665
[3]	Wan M. W., Yen T. F., Appl. Catal.A-Gen., 2007, 319, 237—245
[4]	Dharaskar S. A., Wasewar K. L., Varma M. N., Shende D. Z., Yoo C. K., Ind. Eng. Chem.Res., 2014, 53, 19845—19854
[5]	Carnaroglio D., Gaudino E. C., Mantegna S., Moreira E. M., Castro A. V., Flores E. M. M., Cravotto G., EnergyFuels, 2014, 28, 1854—1859
[6]	Subhan F., Aslam S., Yan Z. F., Ikram M., Rehman S., Microporous MesoporousMater., 2014, 199, 108—116
[7]	Jiang W., Zhu W. S., Li H. P., Wang X., Yin S., Chang Y. H., Li H. M., Fuel,2015, 140, 590—596
[8]	Wang A. J., Ruan L. F., Teng Y., Li X., Lu M. H., Ren J., Wang Y., Hu Y. K., J. Catal., 2005, 229, 314—321
[9]	Yu F. L., Wang Y. Y., Liu C. Y., Xie C. X., Yu S. T., Chem. Eng.J., 2014, 255, 372—376
[10]	Bhatia S., Sharma D. K., Pet. Sci.Technol., 2006, 24, 1125—1159
[11]	Dinamarca M. A., Rojas A., Baeza P., Espinoza G., Ibacache-Quiroga C., Ojeda J., Fuel,2014, 116, 237—241
[12]	Kulkarni P. S., Afonso C. A. M., GreenChem., 2010, 12, 1139—1149
[13]	Rodríguez-Cabo B., Arce A., Soto A., Fluid PhaseEquilib., 2013, 356, 126—135
[14]	Dharaskar S. A., Wasewar K. L., Varma M. N., Shende D. Z., Yoo C. K., Ind. Eng. Chem.Res., 2014, 53, 19845—19854
[15]	Wang F., Zhang Z. Q., Yang J., Wang L. P., Lin Y., Wei Y., Fuel,2013, 107, 394—399
[16]	Khan N. A., Hasan Z., Jhung S. H., Chem. Eur.J., 2014, 20, 376—380
[17]	Ma C. H., Dai B., Liu P., Zhou N., Shi A. J., Ban L. L., Chen H. W., J. Ind. Eng.Chem., 2014, 20, 2769—2774
[18]	Xiao J., Wu L. M., Wu Y., Liu B., Dai L., Li Z., Xia Q. B., Xi H. X., Appl.Energ., 2014, 113, 78—85
[19]	Xu P. P., Wang C. F., Sun D., Chen Y. J., Zhun K. L., Chem. Res. ChineseUniversities, 2015, 31, 730—735
[20]	Ma Y. Q., Wang R., Chem. J. Chinese Universities,2014, 35(7), 1515—1522
	(马云倩, 王睿. 高等学校化学学报, 2014, 35(7), 1515—1522)
[21]	Xue F., Ma R., Sun Y. D., Abdukadera A., Zhang Y. H., Liu C. J., Chem. J. Chinese Universities,2015, 36(7), 1298—1303
	(薛飞, 麻荣, 孙亚栋, 阿布力米提·阿布都卡德, 张永红, 刘晨江. 高等学校化学学报, 2015, 36(7), 1298—1303)
[22]	Otsuki S., Nonaka T., Takashima N., Qian W. H., Ishihara A., Imai T., Kabe T., EnergyFuels, 2000, 14, 1232—1239

ILs	Appearance	m. p. /℃	ESI-MS, m/z	IR(KBr), ν_max/cm^-1
2a	White solid	66—69	205.1[M]⁺, 279.9[M]^-	3159, 3098, 2999, 2956, 1747, 1575, 1428, 1354, 1193, 1135, 1054, 757, 617, 570
2b	White solid	76—79	233.1[M]⁺, 279.8[M]^-	3540, 3150, 3084, 2967, 2880, 1729, 1569, 1463, 1355, 1195, 1135, 1053, 754, 614, 571
2c	White solid	67—69	247.1[M]⁺, 279.9[M]^-	3149, 3084, 2963, 2875, 1735, 1570, 1463, 1355, 1196, 1135, 1054, 754, 614, 570
2d	Red liquid		289.2[M]⁺, 279.9[M]^-	3155, 3088, 2933, 2862, 1746, 1572, 1464, 1352, 1195, 1135, 1057, 750, 616, 571

ILs	Appearance	m. p. /℃	ESI-MS, m/z	IR(KBr), ν_max/cm^-1
2a	White solid	66—69	205.1[M]⁺, 279.9[M]^-	3159, 3098, 2999, 2956, 1747, 1575, 1428, 1354, 1193, 1135, 1054, 757, 617, 570
2b	White solid	76—79	233.1[M]⁺, 279.8[M]^-	3540, 3150, 3084, 2967, 2880, 1729, 1569, 1463, 1355, 1195, 1135, 1053, 754, 614, 571
2c	White solid	67—69	247.1[M]⁺, 279.9[M]^-	3149, 3084, 2963, 2875, 1735, 1570, 1463, 1355, 1196, 1135, 1054, 754, 614, 570
2d	Red liquid		289.2[M]⁺, 279.9[M]^-	3155, 3088, 2933, 2862, 1746, 1572, 1464, 1352, 1195, 1135, 1057, 750, 616, 571

ILs	¹H NMR(400 MHz, DMSO), δ	¹³C NMR(100 MHz, DMSO), δ
2a	1.55(t, J=7.2 Hz, 3H, CH₃), 4.58(q, 2H, CH₂), 5.40(s, 2H, CH₂), 7.68—8.11(m, 4H, ArH), 9.76(s, 1 H, CH)	14.0, 42.1, 47.8, 113.4, 113.7, 119.4(q, ¹J_CF=320 Hz, 2C, CF₃SO₃), 126.4, 126.6, 130.4, 131.6, 142.7, 167.8
2b	0.93(t, J=7.2 Hz, 3H, CH₃), 1.29—1.38(m, 2H, CH₂), 1.85—1.93(m, 2H, CH₂), 4.56(t, J=7.2 Hz, 2H, CH₂), 5.35(s, 2H, CH₂), 7.67—8.13(m, 4H, ArH), 9.75(s, 1H, CH)	13.1, 18.9, 30.4, 46.4, 47.9, 113.5, 113.7, 119.4(q, ¹J_CF=320 Hz, 2C, CF₃SO₃), 126.4, 126.6, 130.5, 131.5, 143.0, 167.7
2c	0.86(t, J=6.4 Hz, 3H, CH₃), 1.28—1.35(m, 4H, 2×CH₂), 1.90—1.93(m, 2H, CH₂), 4.56(t, J=7.2 Hz, 2H, CH₂), 5.41(s, 2H, CH₂), 7.68—8.12(m, 4H, ArH), 9.77(s, 1H, CH)	13.5, 21.4, 27.7, 28.1, 46.6, 47.8, 113.5, 113.7, 119.4(q, ¹J_CF=320 Hz, 2C, CF₃SO₃), 126.4, 126.6, 130.5, 131.5, 143.0, 167.8
2d	0.85(t, J=6.4 Hz, 3H, CH₃), 1.18—1.31(m, 10H, 5×CH₂), 1.91(t, J=6.8 Hz, 2H, CH₂), 4.57(t, J=7.2 Hz, 2H, CH₂), 5.45(s, 2H, CH₂), 7.69—8.13(m, 4H, ArH), 9.76(s, 1H, CH)	13.7, 21.9, 25.5, 28.2, 28.4, 31.0, 46.7, 47.6, 113.5, 113.7, 119.4(q, ¹J_CF=320 Hz, 2C, CF₃SO₃), 126.4, 126.6, 130.5, 131.1, 131.5, 143.0, 167.9

ILs	¹H NMR(400 MHz, DMSO), δ	¹³C NMR(100 MHz, DMSO), δ
2a	1.55(t, J=7.2 Hz, 3H, CH₃), 4.58(q, 2H, CH₂), 5.40(s, 2H, CH₂), 7.68—8.11(m, 4H, ArH), 9.76(s, 1 H, CH)	14.0, 42.1, 47.8, 113.4, 113.7, 119.4(q, ¹J_CF=320 Hz, 2C, CF₃SO₃), 126.4, 126.6, 130.4, 131.6, 142.7, 167.8
2b	0.93(t, J=7.2 Hz, 3H, CH₃), 1.29—1.38(m, 2H, CH₂), 1.85—1.93(m, 2H, CH₂), 4.56(t, J=7.2 Hz, 2H, CH₂), 5.35(s, 2H, CH₂), 7.67—8.13(m, 4H, ArH), 9.75(s, 1H, CH)	13.1, 18.9, 30.4, 46.4, 47.9, 113.5, 113.7, 119.4(q, ¹J_CF=320 Hz, 2C, CF₃SO₃), 126.4, 126.6, 130.5, 131.5, 143.0, 167.7
2c	0.86(t, J=6.4 Hz, 3H, CH₃), 1.28—1.35(m, 4H, 2×CH₂), 1.90—1.93(m, 2H, CH₂), 4.56(t, J=7.2 Hz, 2H, CH₂), 5.41(s, 2H, CH₂), 7.68—8.12(m, 4H, ArH), 9.77(s, 1H, CH)	13.5, 21.4, 27.7, 28.1, 46.6, 47.8, 113.5, 113.7, 119.4(q, ¹J_CF=320 Hz, 2C, CF₃SO₃), 126.4, 126.6, 130.5, 131.5, 143.0, 167.8
2d	0.85(t, J=6.4 Hz, 3H, CH₃), 1.18—1.31(m, 10H, 5×CH₂), 1.91(t, J=6.8 Hz, 2H, CH₂), 4.57(t, J=7.2 Hz, 2H, CH₂), 5.45(s, 2H, CH₂), 7.69—8.13(m, 4H, ArH), 9.76(s, 1H, CH)	13.7, 21.9, 25.5, 28.2, 28.4, 31.0, 46.7, 47.6, 113.5, 113.7, 119.4(q, ¹J_CF=320 Hz, 2C, CF₃SO₃), 126.4, 126.6, 130.5, 131.1, 131.5, 143.0, 167.9

ILs System	Sulfur-removal ratio(%)
ILs System	Extraction	Extraction and oxidation^b
[C₂O₂EBIM][Tf₂N]	10.9	96.4
[C₂O₂BBIM][Tf₂N]	13.6	96.7
[C₂O₂PBIM][Tf₂N]	14.8	96.8
[C₂O₂OBIM][Tf₂N]	22.1	98.8/82.5^c

离子液体1-烷基-3-羧甲基苯并咪唑双三氟甲磺酰亚胺盐的合成及在油品中的脱硫应用

Synthesis of ILs 1-Alkyl-3-carboxymethyl Benzimidazole Double Trifluoromethanesulfonimide and Application in Desulfurization of Fuels^†

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 22

相关文章 15

编辑推荐

Metrics

本文评价

Substrate	DBT	4,6-DMDBT	BT	2,5-DMT	T
k₁/min^-1	0.065	0.060	0.034	0.019	0.009
t_1/2/min	10.66	11.55	20.39	36.48	77.02

[1]	崔伟, 赵德银, 白文轩, 张晓东, 余江. CO₂在非质子溶剂与铁基离子液体复合体系中的吸收[J]. 高等学校化学学报, 2022, 43(8): 20220120.
[2]	彭奎霖, 李桂林, 江重阳, 曾少娟, 张香平. 电解液调控CO₂电催化还原性能微观机制的研究进展[J]. 高等学校化学学报, 2022, 43(7): 20220238.
[3]	高志伟, 李军委, 史赛, 付强, 贾钧儒, 安海龙. 基于分子动力学模拟的TRPM8通道门控特性分析[J]. 高等学校化学学报, 2022, 43(6): 20220080.
[4]	季双琦, 靳钊, 观文娜, 潘翔宇, 关彤. 双阳离子型离子液体和十八烷基修饰的混合模式硅胶固定相的制备及色谱性能[J]. 高等学校化学学报, 2022, 43(6): 20220008.
[5]	曾晛阳, 赵熹, 黄旭日. 细胞松弛素B对葡萄糖/质子共转运蛋白GlcPSe的抑制机理[J]. 高等学校化学学报, 2022, 43(4): 20210822.
[6]	刘嘉欣, 闵杰, 许华杰, 任海生, 谈宁馨. 基于反应力场分子模拟的乙烯燃烧自由基与氮气相互作用研究[J]. 高等学校化学学报, 2022, 43(4): 20210834.
[7]	陈瀚翔, 边绍菊, 胡斌, 李武. LiCl-NaCl-KCl-H₂O溶液体系渗透压的分子动力学模拟[J]. 高等学校化学学报, 2022, 43(3): 20210727.
[8]	孙翠红, 吕立强, 刘迎, 王妍, 杨静, 张绍文. 硝酸异丙酯与Cl原子、 OH和NO₃自由基反应的机理及动力学[J]. 高等学校化学学报, 2022, 43(2): 20210591.
[9]	胡波, 朱昊辰. 双层氧化石墨烯纳米体系中受限水的介电常数[J]. 高等学校化学学报, 2022, 43(2): 20210614.
[10]	常斯惠, 陈涛, 赵黎明, 邱勇隽. 离子液体增塑生物基聚丁内酰胺的热分解机理[J]. 高等学校化学学报, 2022, 43(11): 20220353.
[11]	张伶育, 张继龙, 曲泽星. RDX分子内振动能量重分配的动力学研究[J]. 高等学校化学学报, 2022, 43(10): 20220393.
[12]	唐元晖, 李春玉, 林亚凯, 张春晖, 刘泽, 余立新, 王海辉, 王晓琳. 链段刚性对非溶剂致相分离成膜过程影响的耗散粒子动力学模拟[J]. 高等学校化学学报, 2022, 43(10): 20220169.
[13]	张想, 谢旭岚, 熊力堃, 彭扬. 海胆针状金纳米颗粒用于电催化二氧化碳还原[J]. 高等学校化学学报, 2021, 42(9): 2824.
[14]	雷晓彤, 金怡卿, 孟烜宇. 基于分子模拟方法预测PIP₂在双孔钾通道TREK-1上结合位点的研究[J]. 高等学校化学学报, 2021, 42(8): 2550.
[15]	李聪聪, 刘明皓, 韩佳睿, 朱镜璇, 韩葳葳, 李婉南. 基于分子动力学模拟的VmoLac非特异性底物催化活性的理论研究[J]. 高等学校化学学报, 2021, 42(8): 2518.

Temperature/℃	k/min^-1
Temperature/℃	DBT	BT
55	0.025	0.011
65	0.037	0.019
75	0.065	0.034

Temperature/℃	k/min^-1
Temperature/℃	DBT	BT
55	0.025	0.011
65	0.037	0.019
75	0.065	0.034

离子液体1-烷基-3-羧甲基苯并咪唑双三氟甲磺酰亚胺盐的合成及在油品中的脱硫应用

Synthesis of ILs 1-Alkyl-3-carboxymethyl Benzimidazole Double Trifluoromethanesulfonimide and Application in Desulfurization of Fuels†

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 22

相关文章 15

编辑推荐

Metrics

本文评价

Synthesis of ILs 1-Alkyl-3-carboxymethyl Benzimidazole Double Trifluoromethanesulfonimide and Application in Desulfurization of Fuels^†