Method for desulfurizing thiophene derivatives contained in fuels
First Claim
1. Method of selective desulfurizing of thiophene compounds contained in refined or unrefined hydrocarbons derived from the distillation of crude oil, comprising:
- oxidizing thiophene sulfur atoms into sulfone in the presence of an oxidizing agent; and
separating the sulfone compounds from said hydrocarbons,characterized in that the thiophene compounds are oxidized in a two-phase turbulent phase consisting of a hydrocarbon phase and an aqueous phase, in the presence of at least one oxidizing agent soluble in at least one of the two phases, the oxidizing agent being selected from the group consisting of organic peroxides, hydrogen peroxide, organic hydroperoxides, peracids, alkaline persulfates, and alkaline earth persulfates, and in the presence of at least one metal catalyst selected from the group consisting of (1) metal phthalocyanines and (2) catalysts comprising (i) a support selected from the group consisting of silicas, aluminas, zirconias, amorphous or crystalline aluminosilicates, aluminophosphates, mesoporous solids, and mixtures thereof, and (ii) at least one metal selected from the group consisting of titanium, zirconium, vanadium, chromium, molybdenum, iron, manganese and tungsten, where said metal (ii) can be introduced into the support network or impregnated in complex or non complex form,wherein the separation and the oxidation occur simultaneously, and wherein the aqueous solution pH is kept under 12.
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Abstract
The invention concerns a method for selectively desulphurizing thiopene compounds contained in hydrocarbons derived from crude oil distillation, whether refined or not, which consists in oxidising the thiophene sulphur atoms into sulphone in the presence of an oxidising agent and in separating said sulphonated compounds from said hydrocarbons. The invention is characterised in that it consists in oxidising the thiophene compounds in a two-phase turbulent medium comprising a hydrocarbon phase and an aqueous phase, in the presence of at least an oxidising agent soluble in at least one of the two phases and of at least a metal catalyst in soluble or dispersed form in a liquid of in solid form, separation and oxidation occurring simultaneously.
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Citations
23 Claims
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1. Method of selective desulfurizing of thiophene compounds contained in refined or unrefined hydrocarbons derived from the distillation of crude oil, comprising:
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oxidizing thiophene sulfur atoms into sulfone in the presence of an oxidizing agent; and separating the sulfone compounds from said hydrocarbons, characterized in that the thiophene compounds are oxidized in a two-phase turbulent phase consisting of a hydrocarbon phase and an aqueous phase, in the presence of at least one oxidizing agent soluble in at least one of the two phases, the oxidizing agent being selected from the group consisting of organic peroxides, hydrogen peroxide, organic hydroperoxides, peracids, alkaline persulfates, and alkaline earth persulfates, and in the presence of at least one metal catalyst selected from the group consisting of (1) metal phthalocyanines and (2) catalysts comprising (i) a support selected from the group consisting of silicas, aluminas, zirconias, amorphous or crystalline aluminosilicates, aluminophosphates, mesoporous solids, and mixtures thereof, and (ii) at least one metal selected from the group consisting of titanium, zirconium, vanadium, chromium, molybdenum, iron, manganese and tungsten, where said metal (ii) can be introduced into the support network or impregnated in complex or non complex form, wherein the separation and the oxidation occur simultaneously, and wherein the aqueous solution pH is kept under 12. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19)
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20. Method of selective desulfurizing of thiophene compounds contained in refined or unrefined hydrocarbons derived from the distillation of crude oil, comprising:
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oxidizing thiophene sulfur atoms into sulfone in the presence of an oxidizing agent; and separating the sulfone compounds from said hydrocarbons, characterized in that the thiophene compounds are oxidized in a two-phase turbulent phase consisting of a hydrocarbon phase and an aqueous phase, in the presence of at least one oxidizing agent soluble in at least one of the two phases, the oxidizing agent being selected from the group consisting of organic peroxides, hydrogen peroxide, organic hydroperoxides, peracids, alkaline persulfates, and alkaline earth persulfates, and in the presence of at least one metal catalyst selected from the group consisting of (1) metal phthalocyanines and (2) catalysts comprising (i) a support selected from the group consisting of silicas, aluminas, zirconias, amorphous or crystalline aluminosilicates, aluminophosphates, mesoporous solids, and mixtures thereof, and (ii) at least one metal selected from the group consisting of titanium, zirconium, vanadium, chromium, molybdenum, iron, manganese and tungsten, where said metal (ii) can be introduced into the support network or impregnated in complex or non complex form, characterized in that the metal catalyst is a titanium catalyst selected from the group consisting of titanium zeolite without extra-network titanium, with a pore diameter greater than or equal to 0.65 nm and titanium mesoporous composites, and wherein the separation and the oxidation occur simultaneously. - View Dependent Claims (21, 22)
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23. Method of selective desulfurizing of thiophene compounds contained in refined or unrefined hydrocarbons derived from the distillation of crude oil, comprising:
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oxidizing thiophene sulfur atoms into sulfone in the presence of an oxidizing agent; and separating the sulfone compounds from said hydrocarbons, characterized in that the thiophene compounds are oxidized in a two-phase turbulent phase consisting of a hydrocarbon phase and an aqueous phase, in the presence of at least one oxidizing agent soluble in at least one of the two phases, the oxidizing agent being selected from the group consisting of organic peroxides, hydrogen peroxide, organic hydroperoxides, peracids, alkaline persulfates, and alkaline earth persulfates, and in the presence of at least one metal catalyst selected from the group consisting of (1) metal phthalocyanines and (2) catalysts comprising (i) a support selected from the group consisting of silicas, aluminas, zirconias, amorphous or crystalline aluminosilicates, aluminophosophates, mesoporous solids, and mixtures thereof, and (ii) at least one metal selected from the group consisting of titanium, zirconium, vanadium, chromium, molybdenum, iron, manganese and tungsten, where said metal (ii) can be introduced into the support network or impregnated in complex or non complex form, wherein the separation and the oxidation occur simultaneously, and wherein the metal catalyst is a non-oxidized titanium catalyst.
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Specification