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

doi:10.7503/cjcu20160124

Abstract

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

CLC Number:

TrendMD:

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

Figures/Tables 13

References 22

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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