Oxidative desulfurization of sulfur-containing hydrocarbons

• US 7,374,666 B2
• Filed: 12/11/2002
• Issued: 05/20/2008
• Est. Priority Date: 12/13/2001
• Status: Expired due to Fees

• Current Assignee: Lehigh University
• Original Assignee: Lehigh University
• Inventors: Wachs, Israel E
• Primary Examiner(s): Langel; Wayne A.
• Application Number:
  US10/498,362
• Publication Number:
  US 20050150819A1
• Time in Patent Office: 1,987 Days
• Field of Search: 423/244.01, 423/244.02, 423/244.03, 423/244.04, 208/208.R, 208/226, 208/230, 208/243, 208/244, 208/247, 208/248, 208/249
• US Class Current: 208/208.00R
• CPC Class Codes: C07C 7/14816 oxygen; ozone
• CPC Class Codes: C10G 27/04 with oxygen or compounds generating oxygen
• CPC Class Codes: C10G 29/16 Metal oxides

Abstract

A method for desulfurizing a hydrocarbon stream (10) containing heterocyclic sulfur compounds, which process comprises contacting the heterocyclic sulfur compounds in the gas phase (60) in the presence of oxygen (70) with a supported metal oxide catalyst, or with a bulk metal oxide catalyst (600) to convert at least a portion of the heterocyclic sulfur compounds to oxygenated products as well as sulfur-deficient hydrocarbons and separately recovering the oxygenated products separately from a hydrocarbon stream with substantially reduced sulfur.

Claims

1. A process for desulfurizing a hydrocarbon stream containing heterocyclic sulfur compounds, which process comprises contacting a gaseous hydrocarbon feed stream containing said heterocyclic sulfur compounds, or sulfinyl (═

SO) or sulfonyl (═

SO₂) derivatives thereof, in the gas phase and in the presence of oxygen with a supported metal oxide catalyst, or with a bulk metal oxide catalyst.

2. The process of claim 1 wherein the contacting converts at least a portion of the heterocyclic sulfur compounds, or the sulfinyl (═

SO) or sulfonyl (═

SO₂) derivatives thereof, to oxygenated products.

3. The process of claim 1 wherein the contacting converts at least a portion of the heterocyclic sulfur compounds, or the sulfinyl (═

SO) or sulfonyl (═

SO₂) derivatives thereof, to oxygenated products and then recovering a hydrocarbon stream with substantially reduced sulfur separately from the oxygenated products.

4. The process of claim 1 wherein the contacting converts at least a portion of the heterocyclic sulfur compounds, or the sulfinyl (═

SO) or sulfonyl (═

SO₂) derivatives thereof, to sulfur-deficient hydrocarbons.

5. The process of claim 1 wherein the contacting converts at least a portion of the heterocyclic sulfur compounds, or the sulfinyl (═

SO) or sulfonyl (═

SO₂) derivatives thereof, to oxygenated products and sulfur-deficient hydrocarbons.

6. The process of claim 1 wherein the contacting converts at least a portion of the heterocyclic sulfur compounds, or the sulfinyl (═

SO) or sulfonyl (═

SO₂) derivatives thereof, to oxygenated products and sulfur-deficient hydrocarbons and then recovering a hydrocarbon stream with substantially reduced sulfur separately from the oxygenated products.

7. The process of claim 1, 2, 3, 4, 5 or 6 wherein the supported metal oxide catalyst comprises a metal oxide substrate, or support selected from the group consiting of titania, silica, zirconia, alumina, niobia, tantala, ceria, magnesia, manganates, lanthanum oxide, tin oxide and mixtures thereof, whose surface has been modified with a monolayer of an oxide of a catalytic metal selected from the group consisting of titanium (Ti), zirconium (Zr), molybdenum (Mo), rhenium (Re), vanadium (V), chromium (Cr), tungsten (W), manganese (Mn), niobium (Nb), tantalum (Ta) and mixtures thereof.

8. The process of claim 7 wherein the catalytic metal is either vanadium alone or is a mixture containing vanadium.

9. The process of claim 1, 2, 3, 4, 5 or 6 wherein the bulk metal oxide catalyst comprises a compound selected from the group consisting of molybdates (Mo), chromates (Cr), vanadates (V), rhenates (Re), titanates (Ti), niobates (Nb), tantalates (Ta), tungstates (W), manganates (Mn) and mixtures thereof.

10. The process of claim 9 wherein the bulk metal oxide catalyst is selected from the group consisting of PbV₂O₆, NaVO₃, Na₃VO₄, BiVO₄AlVO₄, FeVO₄, Mg₃(VO₄)₂, Mg₂V₂O₇, CeVO₄, Zn₃(VO₄)₂, CdV₂O₇, Zn₂V₂O₇, VOPO₄, KVO₃, Pb₂V₂O₇, TlVO₄, PbMoO₄, CaMoO₄, Bi₂Mo₂O₉, Bi₃(FeO₄)(MoO₄)₃, Na₂MoO₄, MnMoO₄, Gd₂(MoO₄)₃, MgMoO₄, CuMoO₄, CoMoO₄, Fe₂(MoO₄)₃, Te₂MoO₇, NiMoO₄, Al₂(MoO₄)₃, Cr₂(MoO₄)₃, Na₂Mo₂O₇, YNbO₄, YbNbO₄, LiNbO₃, NaNbO₃, KNbO₃, AlNbO₄, K₈Nb₆O₁₉, BiNbO₄, SbNbO₄, NbOPO₄, CaNb₂O₆, K₄Nb₆O₁₇, KCa₂Nb₃O₁₀, Li₆WO₆, FeWO₄, CoWO₄, MnWO₄, NiWO₄, CuWO₄, CaWO₄, Cs₂WO₄, Na₂WO₄, B_aWO₄, Fe₂(WO₄)₃, Al₂(WO₄)₃, SrWO₄, K₂WO₄, Na₂W₂O₇, Li₂WO₄, CsLuW₂O₈, BiWO₄, Na₂CrO₄, Na₂Cr₂O₇, Na₂Cr₃O₁₀, Na₂Cr₄O₁₃, K₂CrO₄, K₂Cr₂O₇, K₂Cr₃O₁₀, K₂Cr₄O₁₃, Fe₂(CrO₄)₃, CaCrO₄, Cs₂CrO₄, BiCrO₄, NaReO₄, Li₆ReO₄, Mg(ReO₄)₂, Na₂TiO₄, NaTiO₃, BaTiO₄, BaTiO₃, Mn₃(VO₄)₂, MnAl₂O₄, KMnO₄, MnO, MnO₂, Mn₂O₃and Mn₃O₄.