Claims
- 1. In a desulfurization process for producing a hydrocarbon product of reduced sulfur content from a sulfur-containing hydrocarbon feedstock a major portion of which boils above about 550.degree.F., wherein a portion of said contained sulfur is preferentially oxidized and said oxidized sulfur-containing hydrocarbon feedstock is treated to remove at least a portion of the oxidized sulfur and wherein said hydrocarbon product of reduced sulfur content is recovered, the improvement which comprises heating said sulfur-containing hydrocarbon feedstock prior to the oxidation step with at least one liquid hydrocarbon compound capable of transferring hydrogen to said sulfur-containing hydrocarbon feedstock without the presence of a catalyst under conditions such that hydrogen which is transferred from at least a portion of said liquid hydrocarbon compound is reacted with said sulfur-containing hydrocarbon feedstock to form hydrogen sulfide, said heating being conducted at a ratio of 100 parts by weight of said sulfur-containing hydrocarbon feedstock to from about 5 parts to about 2000 parts by weight of said hydrocarbon compound, and said heating being conducted at a temperature in the range from about 500.degree.F. to about 1350.degree.F.
- 2. The process of claim 1 wherein said hydrocarbon compound is selected from the group consisting of mixed napthenic-aromatic condensed ring compounds having up to about 40 carbon atoms per molecule, aromatic compounds containing from about 9 to about 26 carbon atoms per mole and having at least one alkyl substituent having from about 3 to about 20 carbon atoms, cyclo-paraffins containing from about 3 to about 15 carbon atoms per molecule, alkyl derivatives of said cyclo-paraffins containing at least one alkyl group having from 1 to about 15 carbon atoms, and mixtures thereof.
- 3. The process of claim 2 wherein said hydrocarbon compound is selected from the group consisting of indane, C.sub.10 to C.sub.12 tetralins, decalin, di-, tetra-, and octahydroanthracene, C.sub.12 and C.sub.13 acenaphthenes, tetrahydroacenaphthene, partially hydrogenated anthracene, partially hydrogenated phenanthrene, partially hydrogenated pyrene and mixtures thereof.
- 4. The process of claim 3 wherein said heating is being conducted at a ratio of 100 parts of said sulfur-containing hydrocarbon feedstock to from about 100 parts to about 1000 parts by weight of said hydrocarbon compound, said heating being conducted at a temperature in the range from about 650.degree.F. to about 1000.degree.F. at a pressure in the range from about atmospheric pressure to about 2000 psig. and for a period of time in the range from about 10 minutes to about 8 hours.
- 5. The process of claim 4 wherein said compound is selected from the group consisting of C.sub.10 to C.sub.12 tetralins and mixtures thereof.
- 6. A desulfurization process for producing a hydrocarbon product of reduced sulfur content which comprises:
- a. heating a sulfur-containing hydrocarbon feedstock a major portion of which boils above about 550.degree.F., with at least one liquid hydrocarbon compound capable of transferring hydrogen to said sulfur-containing hydrocarbon feedstock without the presence of a catalyst under conditions such that hydrogen which is transferred from at least a portion of said liquid hydrocarbon compound is reacted with said sulfur-containing hydrocarbon feedstock to form hydrogen sulfide, said heating being conducted at a ratio of 100 parts by weight of said sulfur-containing hydrocarbon feedstock to from about 5 parts to about 2000 parts by weight of said hydrocarbon component is present, and said heating being conducted at a temperature in the range from about 500.degree.F to about 1350.degree.F.
- b. oxidizing at least a portion of the remaining sulfur contained in said heated hydrocarbon feedstock;
- c. treating said oxidized sulfur-containing hydrocarbon feedstock to remove at least a portion of said remaining sulfur from said oxidized sulfur-containing hydrocarbon feedstock; and
- d. recovering a hydrocarbon product having reduced sulfur content.
- 7. The process of claim 6 wherein step (2) comprises treating said heated sulfur-containing hydrocarbon feedstock with from about 0.5 atoms to about 10 atoms of active oxygen per atom of sulfur present in said feedstock to preferentially oxidize at least a portion of the sulfur contained in said hydrocarbon feedstock, said active oxygen being in the form of an oxidant selected from the group consisting of oxygen, ozone, hydrogen peroxide, organic peracids, organic hydroperoxides, organic peroxides and mixtures thereof.
- 8. The process of claim 7 wherein said oxidant is selected from the group consisting of organic peroxides, organic hydroperoxides, organic peracids and mixtures thereof containing from 1 to about 30 carbon atoms per active oxygen atom and said oxidizing step (b) is being conducted in the presence of a catalyst comprising a metal in an amount effective to promote the oxidation of sulfur, said metal being selected from the group consisting of Group IV-B metals, Group V-B metals, Group VI-B metals and mixtures thereof.
- 9. The process of claim 8 wherein said hydrocarbon compound is selected from the group consisting of mixed napthenic aromatic condensed ring compounds having up to about 40 carbon atoms per molecule, aromatic compounds containing from about 9 to about 26 carbon atoms per mole and having at least one alkyl substituent having from about 3 to about 20 carbon atoms, cyclo-paraffins containing from about 3 to about 15 carbon atoms per molecule, alkyl derivatives of said cycloparaffins containing at least one alkyl group having from 1 to about 15 carbon atoms and mixtures thereof.
- 10. The process of claim 8 wherein said metal is selected from the group consisting of titanium, zirconium, vanadium, tantalum, chromium, molybdenum, tungsten and mixtures thereof and is present in an amount from about 5 ppm. to about 10% by weight of said heated sulfur-containing hydrocarbon feedstock.
- 11. The process of claim 10 wherein said hydrocarbon compound is selected from the group consisting of indane, C.sub.10 to C.sub.12 tetralins, decalin, di-, tetra-, and octahydroanthracenes, C.sub.12 and C.sub.13 acenaphthenes, tetrahydroacenaphthene, partially hydrogenated anthracene, partially hydrogenated phenanthrene, partially hydrogenated pyrene and mixtures thereof.
- 12. The process of claim 11 wherein said metal is molybdenum.
- 13. The method of claim 12 wherein said compound is selected from the group consisting of C.sub.10 to C.sub.12 tetralins and mixtures thereof.
- 14. The process of claim 11 wherein said catalyst is prepared by a method which comprises interacting molybdenum metal with a compound selected from the group consisting of organic hydroperoxide, organic peroxide, hydrogen peroxide and mixtures thereof in the presence of at least one saturated alcohol having from one to four carbon atoms per molecule at conditions such that at least a portion of said molybdenum is solubilized.
- 15. The process of claim 14 wherein said heating is being conducted at a ratio 100 parts of sulfur-containing hydrocarbon feedstock to from about 50 parts to about 1000 parts by weight of said hydrocarbon compound, said heating is being conducted at a temperature in the range from about 650.degree.F. to about 1000.degree.F. at a pressure in the range from about atmospheric pressure to about 2000 psig. and for a period of time within the range from about 10 minutes to 8 hours, and said interacting of said molybdenum metal with said compound to form said catalyst is being conducted at a temperature in the range from about 25.degree.C. to about 100.degree.C.
- 16. The process of claim 14 wherein said catalyst is prepared by a method which comprises interacting molybdenum metal with tertiary butyl hydroperoxide in the presence of tertiary butyl alcohol and at least one mono- or poly- hydroxy alcohol having from 1 to about 16 carbon atoms per molecule, said mono- or poly- hydroxy alcohol having at least one primary hydroxy group present in an amount sufficient to enhance molybdenum solubility.
Parent Case Info
This application is a continuation-in-part of application Ser. No. 305,595, filed Nov. 10, 1972, now abandoned.
US Referenced Citations (9)
Foreign Referenced Citations (1)
Number |
Date |
Country |
482,796 |
Apr 1952 |
CA |
Continuation in Parts (1)
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Number |
Date |
Country |
Parent |
305595 |
Nov 1972 |
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