Efficient and sustainable V-catalyzed oxidative desulfurization of fuels assisted by ionic liquids
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Abstract: Fuel desulfurization is an appealing topic for the chemical industry since severe environmental regulations regarding SO2 emissions have been legislated in many countries. In order to reduce the amount of sulfur-containing compounds in fuels, responsible for high SOx emission levels, a green chemistry approach is compulsory. In this paper, vanadium salen and salophen complexes were used in the oxidation of a model aromatic sulfide, such as dibenzothiophene (DBT), in the presence of H2O2 as green oxidant. The oxidative process was successfully coupled with the extraction of the oxidized compounds by ionic liquids. The system resulted highly selective for sulfide oxidation, showing poor reactivity toward the oxidation of alkenes and allowing a significant reduction of S content in a model benzine. To note, the use of microwave in place of standard heating allowed to obtain 98% of DBT oxidation and almost complete sulfur extraction in the model fuel in 1000 s. For these reasons, this system was considered an easy, rapid and clean process to achieve fuel desulfurization.
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Key words:
- fuel desulfurization /
- V-catalysis /
- sustainability /
- ionic liquids /
- microwaves
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Table 1 Oxidation reactions of DBT in acetonitrile with 2 equivalents of H2O2
Temperature t/℃ Catalyst Time t/h Conversiona x/% Selectivitya s/% type wmol/% DBTO DBTO2 25 [salenVⅤO]CF3SO3 10 20 44 45 55 [salenVⅤO]CF3SO3 5 20 62 50 50 [salenVⅤO]CF3SO3 1 20 8 85 15 60 [salenVⅤO]CF3SO3 5 2 57 55 45 [salenVⅤO]CF3SO3 1 2 74 64 36 [5, 5'-(t-Bu)2salenVⅤO]CF3SO3 1 10 76 47 53 [salophenVⅤO]CF3SO3 1 0.25 92 54 46 VO(acac)2 1 0.25 90 57 43 reaction conditions: DBT 0.16 mol/L; a: referred to the converted substrate 
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Table 2 V-catalysed oxidation of DBT in acetonitrile
Entry Temperature t/℃ H2O2 (eq) Catalyst Time t/h Conversion x/% Selectivity* s/% DBTO DBTO2 1 50 4 [salenVⅤO]CF3SO3 7 97 37 63 2 4 [salophenVⅤO]CF3SO3 2.5 99 14 86 3 4 VO(acac)2 4 99 14 86 4 60 4 [salenVⅤO]CF3SO3 2.25 96 40 60 5 4 [salophenVⅤO]CF3SO3 1.5 98 23 77 6 4 VO(acac)2 1 98 22 78 7a 4 [salenVⅤO]CF3SO3 2 98 37 63 8a 6 [salenVⅤO]CF3SO3 3.5 99 13 87 9a 6 [salenVⅤO]CF3SO3b 3 86 8 92 10a, c 6 [salenVⅤO]CF3SO3 4.5 86 16 84 11a 70 6 [salenVⅤO]CF3SO3 3 86 8 92 12a, c 6 [salenVⅤO]CF3SO3 2, 5 86 19 81 reaction conditions: DBT 0.16 mol/L, catalyst 1%; a: DBT 0.05 mol/L; b: catalyst 0.5%; c: addition of cyclooctene 0.05 mol/L as competitive substrate; *: referred to the converted substrate
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Table 3 V-catalysed oxidation of DBT in ionic liquids
Ionic liquid H2O2 (eq) Time t/h Conversion x/% Selectivity* s/% DBTO DBTO2 [BMIm]CF3SO3 5 3.5 0 0 0 [BMIm]PF6 4 2 96 2 98 [BMIm]PF6 6 12 100 0 100 [BMIm]PF6a 4 2 94 40 60 [BMIm]PF6b 4 - 97 9 91 reaction conditions: DBT 0.16 mol/L, cat 0.5%, t=60 ℃, H2O2 4 eq.; a: addition of COT 0.16 mol/L; b: addition of cyclohexane 0.16 mol/L; *: referred to the converted substrate
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Table 4 Tri-phase system for desulfurization of a model fuel
Ionic liquid Catalyst Time t/h Conversion x/% Selectivitya s/% DBTO DBTO2 [BMIm]PF6 [salenVⅤO]CF3SO3 24 62 30 70 [BMIm]PF6 [salophenVⅤO]CF3SO3 24 98 - 100 [BMIm]BF4 [salophenVⅤO]CF3SO3 5 a - - [BMIm]Tf2N [salophenVⅤO]CF3SO3 16 98 45 55 reaction conditions: DBT 0.16 mol/L, COT 0.16 mol/L, H2O2 4 equivalents, catalyst 0.5%, t=60 ℃; a: 60% of DBT extracted by IL; *: referred to the converted substrate
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Table 5 Oxidation reaction with and without MW treatment
Ionic liquid Temperature t/℃ MW Time t/s Conversion x/% Extraction of DBT-ox /% [BMIm]PF6 60 no 86400 98 >90 [BMIm]Tf2N 60 no 57600 98 >98 [BMIm]PF6 120 yes 860 97 >93 [BMIm]Tf2N 120 yes 780 96 >98 [PMIm]Tf2N 100 yes 820+820 98 >98 reaction conditions: DBT 0.16 mol/L, COT 0.16 mol/L, H2O2 4 equivalents, [salophenVⅤO]CF3SO3 0.5%, fuel:IL=1:1
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Table 6 Oxidation reaction with and without MW treatment
Temperature t/℃ Heating source Power/W Conversion x/% 50 MW 21 49 50 std - 6 70 MW 27 69 70 std - 9 90 MW 32 88 90 std - 15 100 MW 35 98 100 std - 18 reaction conditions: DBT 0.16 mol/L, COT 0.16 mol/L, H2O2 4 equivalents, [salophenVⅤO]CF3SO3 0.5%, fuel:IL=1:1
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