Syntheses of Carboxyl Functionalized Benzotriazol-based Ionic Liquids and Their Application in Extraction-oxidative Desulfurization†

doi:10.7503/cjcu20150192

Abstract

Abstract:

A new class of ionic liquids(ILs) 1-alkyl-3-carboxymethyl double trifluoromethanesulfonimide was synthesized and characterized. Ionic liquids and hydrogen peroxide were tested in extraction-oxidative desulfurization system, and 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([C₂O₂BBTA][NTf₂]) was both extractant and catalyst, n(H₂O₂)∶n(S)=2.5∶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), benzothiophene(BT) and 4,6-dimethyldibenzothiophene(4,6-DMDBT) reached 98.3%, 98.3% and 96.6%. Ionic liquid can be recycled for 10 times with an unnoticeable decrease in desulfurization activity. The method can realize deep desulfurization the depth have the advantages of both simple operation and mild reaction condition.

Key words: Benzotriazole, Ionic liquid, Extraction-oxidative, Desulfurization

CLC Number:

O621.1

TrendMD:

XUE Fei, MA Rong, SUN Yadong, ABDUKADERA Ablimit, ZHANG Yonghong, LIU Chenjiang. Syntheses of Carboxyl Functionalized Benzotriazol-based Ionic Liquids and Their Application in Extraction-oxidative Desulfurization^†[J]. Chem. J. Chinese Universities, 2015, 36(7): 1298.

Figures/Tables 9

Scheme 1 Synthesis route of the carboxyl functionalized ionic liquids

Table 1 Appearance, ESI-MS and IR data for ionic liquids 2a—2d

IL	Appearance	ESI-MS, m/z	IR(KBr), $ν ˙ max$ /cm^-1
2a	Colourless transparency liquid	206.1[M]⁺, 279.9[M]^-	3553, 3111, 3006, 1751, 1611, 1505, 1430, 1351, 1200, 1136, 1056, 753, 616
2b	Colourless transparency liquid	234.1[M]⁺, 279.9[M]^-	3549, 3110, 2967, 2879, 1744, 1610, 1505, 1470, 1351, 1196, 1136, 1057, 753, 616
2c	Colourless transparency liquid	290.2[M]⁺, 279.9[M]^-	3108, 3006, 2929, 2857, 1745, 1504, 1468, 1350, 1195, 1137, 1058, 753, 616, 600
2d	Colourless transparency liquid	346.3[M]⁺, 279.9[M]^-	3108, 3002, 2920, 2851, 1732, 1504, 1467, 1337, 1192, 1137, 1058, 753, 612, 598

Table 1 Appearance, ESI-MS and IR data for ionic liquids 2a—2d

IL	Appearance	ESI-MS, m/z	IR(KBr), $ν ˙ max$ /cm^-1
2a	Colourless transparency liquid	206.1[M]⁺, 279.9[M]^-	3553, 3111, 3006, 1751, 1611, 1505, 1430, 1351, 1200, 1136, 1056, 753, 616
2b	Colourless transparency liquid	234.1[M]⁺, 279.9[M]^-	3549, 3110, 2967, 2879, 1744, 1610, 1505, 1470, 1351, 1196, 1136, 1057, 753, 616
2c	Colourless transparency liquid	290.2[M]⁺, 279.9[M]^-	3108, 3006, 2929, 2857, 1745, 1504, 1468, 1350, 1195, 1137, 1058, 753, 616, 600
2d	Colourless transparency liquid	346.3[M]⁺, 279.9[M]^-	3108, 3002, 2920, 2851, 1732, 1504, 1467, 1337, 1192, 1137, 1058, 753, 612, 598

Table 2 1H NMR and 13C NMR data for ionic liquids 2a—2d

IL	¹H NMR(400 MHz, DMSO), δ		¹³C NMR(100 MHz, DMSO), δ
2a	1.67(t, J=4.0 Hz, 3H, CH₃), 5.08(q, J=7.2 Hz, 2H, CH₂), 5.99(s, 2H, CH₂), 7.99—8.44(m, 4H, ArH)		13.55, 47.05, 52.37, 113.94, 114.14, 119.37(q, ¹J_CF=320 Hz, 2C, CF₃SO₃), 130.73, 131.21, 134.07, 135.05, 166.41
2b	0.94(t, J=7.2 Hz, 3H, CH₃), 1.30—1.40(m, 2H, CH₂), 1.99—2.06(m, 2H, CH₂), 5.09(t, J=7.2 Hz, 2H, CH₂), 5.93(s, 2H, CH₂), 7.99—8.47(m, 4H, ArH)		13.08, 18.80, 30.27, 51.09, 52.66, 113.86, 114.22, 119.37(q, ¹J_CF=320 Hz, 2C, CF₃SO₃), 130.82, 131.14, 134.23, 135.00, 166.28
2c	0.84(t, J=7.2 Hz, 3H, CH₃), 1.23—1.32(m, 10H, 5×CH₂), 2.05(t, J=7.2 Hz, 2H, CH₂), 5.07(t, J=7.2 Hz, 2H, CH₂), 5.92(s, 2H, CH₂), 7.99—8.45(m, 4H, ArH)	13.70, 21.88, 25.43, 28.12, 28.28, 30.98, 51.32, 52.72, 113.83, 114.23, 119.38(q, ¹J_CF=320 Hz, 2C, CF₃SO₃), 130.78, 131.10, 134.22, 135.00, 166.29
2d	0.85(t,J=6.8 Hz, 3H, CH₃), 1.22—1.31(m, 18H, 9×CH₂), 2.03(t, J=6.8 Hz, 2H, CH₂), 5.06(t, J=6.8 Hz, 2H, CH₂), 5.92(s, 2H, CH₂), 8.02—8.45(m, 4H, ArH)	13.82, 21.98, 25.44, 28.17, 28.29, 28.59, 28.65, 28.77, 28.87, 31.18, 51.31, 52.64, 113.88, 114.24, 119.37(q,¹J_CF=320 Hz, 2C, CF₃SO₃), 130.81, 131.14, 134.22, 134.99, 166.16

Table 3 Effect of different desulfurization systems on DBT removal

Entry	Desulfurization system	Sulfur-removal ratio(%)	Entry	Desulfurization system	Sulfur-removal ratio(%)
1	[C₂O₂BBTA][Cl]	0.2	7	[C₂O₂BBTA][Cl] + H₂O₂	4.9
2	[C₂O₂EBTA][NTf₂]	8.5	8	[C₂O₂EBTA][NTf₂] + H₂O₂	96.7
3	[C₂O₂BBTA][NTf₂]	12.4	9	[C₂O₂BBTA][NTf₂] + H₂O₂	98.3
4	[C₂O₂OBTA][NTf₂]	16.8	10	[C₂O₂OBTA][NTf₂] + H₂O₂	97.5
5	[C₂O₂DBTA][NTf₂]	17.2	11	[C₂O₂DBTA][NTf₂] + H₂O₂	98.4
6	H₂O₂	0.1

Fig.1 Effect of H2O2/DBT molar ratio on DBT removalReaction conditions: 75 ℃, m(Model oil)∶m(Ionic liquid)=5∶1, 1 h, IL: [C2O2BBTA][NTf2], DBT(S: 500 mg/L) in n-octane.

Fig.2 Effect of reaction temperature and time on DBT removalReaction conditions: n(H2O2)∶n(DBT)=2.5∶1, m(Model oil)∶m(Ionic liquid)=5∶1, IL: [C2O2BBTA][NTf2], DBT(S: 500 mg/L) in n-octane. a. 55 ℃ ; b. 65 ℃ ; c. 75 ℃.

Fig.3 Effect of mass ratio of model oil to ionic li-quid on DBT removalReaction conditions: 75 ℃, n(H2O2)∶n(DBT)=2.5∶1, 1 h, IL: [C2O2BBTA][NTf2], DBT(S: 500 mg/L) in n-octane.

Fig.4 Oxidation of different sulfur-containing compoundsReaction conditions: 75 ℃, n(H2O2)∶n(S)=2.5∶1, m(Model oil)∶m(Ionic liquid)=5∶1, 1 h, IL: [C2O2BBTA][NTf2].

Fig.5 Recycling of IL on removal of DBT in model oilReaction conditions: 75 ℃, n(H2O2)∶n(DBT)=2.5∶1, m(Model oil)∶m(Ionic liquid)=5∶1, 1 h, IL: [C2O2BBTA][NTf2], DBT(S: 500 mg/L) in n-octane.

References 20

[1]	Sydbom A., Blomberg A., Pamia S., Stenfors S., Sandström T., Dahlén S. E., Eur. Respir. J., 2001, 17, 733—746
[2]	Stanislaus A., Marafl A., Rana M. S., Catal. Today, 2010, 153, 1—68
[3]	Gao H. S., Li Y. G., Wu Y., Luo M. F., Li Q., Xing J. M., Liu H. Z., Energy Fuels, 2009, 23, 2690—2694
[4]	Li C. Y., Tan R., Zhao J. F., Yin D. H., Chem. J. Chinese Universities, 2014, 35(2), 297—302
	(黎成勇, 谭蓉, 赵江峰, 银董红. 高等学校化学学报,2014, 35(2), 297—302)
[5]	Jia X. D., Han S. Y., Duan H. F., Lin Y. J., Cao J. G., Liang D. P., Wu M. C., Chem. Res. Chinese Universities, 2013, 29(1), 82—86
[6]	Hallett J. P., Welton T., Chem. Rev., 2011, 111, 3508—3576
[7]	Wang Y. L., Luo J., Zhi H. Z., Chem. Res. Chinese Universities, 2013, 29(5), 879—883
[8]	Zhang Q. H., Shreeve J. M., Chem. Rev., 2014, 114, 10527—10574
[9]	Lo W. H., Yang H. Y., Wei G. T., Green Chem., 2003, 5, 639—642
[10]	Chen X. C., Yuan S., Abdeltawab A. A., Al-Deyab S. S., Zhang J. W., Yu L., Yu G. R., Sep. Purif. Technol., 2014, 133, 187—193
[11]	Rodríguez-Cabo B., Rodríguez H., Rodil E., Arce A., Soto A., Fuel, 2014, 117, 882—889
[12]	Zhang H., He J. X., Yang C. R., Chen Z. W., J. Northwest Univ., (Nat. Sci. Edn.), 2013, 43(1), 60—63
	(张航, 贺建勋, 杨彩茸, 陈志伟.西北大学学报(自然科学版), 2013, 43(1), 60—63)
[13]	Dharaskar S. A., Wasewar K. L., Varma M. N., Shende D. Z., Yoo C. K., Ind. Eng. Chem. Res., 2014, 53, 19845—19854
[14]	Liang W. D., Zhang S., Li H. F., Zhang G. D., Fuel Process Technol., 2013, 109, 27—31
[15]	Nie Y., Dong Y. X., Bai L., Dong H. F., Zhang X. P., Fuel, 2013, 103, 997—1002
[16]	Jiang W., Zhu W. S., Chang Y. H., Chao Y. H., Yin S., Liu H., Zhu F. X., Li H. M., Chem. Eng. J., 2014, 250, 48—54
[17]	Wang B., Liu C. J., Wang J. D., Lei Z. K., Hu D. L., Chem. J. Chinese Universities, 2012, 33(1), 76—81
	(王斌, 刘晨江, 王吉德, 雷振凯, 胡东林. 高等学校化学学报,2012, 33(1), 76—81)
[18]	Li H., Liu C. J., Zhang Y. H., Sun Y. D., Wang B., Liu W. B., Org. Lett., 2015, 17, 932—935
[19]	Zhang S. M., Hou Y. W., Huang W. G., Shan Y. K., Electrochim. Acta, 2005, 50, 4097—4103
[20]	Otsuki S., Nonaka T., Takashima N., Qian W. H., Ishihara A., Imai T., Kabe T., Energy Fuels, 2000, 14, 1232—1239