Oxidative desulfurization using a titanium(IV) catalyst and organohydroperoxides

• US 8,283,498 B2
• Filed: 07/19/2011
• Issued: 10/09/2012
• Est. Priority Date: 07/20/2010
• Status: Active Grant

• Current Assignee: Auterra, Inc.
• Original Assignee: Auterra, Inc.
• Inventors: Litz, Kyle E., Vreeland, Jennifer L.
• Primary Examiner(s): Solola, Taofiq A
• Application Number:
  US13/185,552
• Publication Number:
  US 20120022272A1
• Time in Patent Office: 448 Days
• Field of Search: 568/27
• US Class Current: 568/27
• CPC Class Codes: B01J 2231/70 Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
• CPC Class Codes: B01J 2531/46 Titanium
• CPC Class Codes: B01J 31/1691 Coordination polymers, e.g. metal-organic frameworks [MOF] preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F
• CPC Class Codes: B01J 31/2226 Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
• CPC Class Codes: B01J 31/2239 Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
• CPC Class Codes: C07D 333/76 Dibenzothiophenes
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 27/12 with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates plumbites or plumbates C10G19/06

Abstract

Oxidative desulfurization (ODS) is an attractive alternative to hydrodesulfurization (HDS) technology due to its lower energy requirement for the removal of refractory sulfur species, such as dibenzothiophene (DBT), from heavier petroleum streams. Diesel containing DBT may be oxidized using a heterogeneous titanium(IV) catalyst and organohydroperoxide oxidant, such as tert-butyl hydroperoxide (TBHP), cumyl hydroperoxide (CHP) and/or ethylbenzene hydroperoxide (EBHP), which proves effective for the selective oxidation and removal of refractory sulfur compounds from diesel fuel.

Claims

1. A sulfoxidation method comprising:

providing a hydrocarbon stream comprising at least one sulfur compound;

providing an oxidant comprising organohydroperoxide;

providing a catalyst that selectively oxidizes sulfides, is substantially non-leaching, and is generated in situ, the catalyst comprising a metal compound represented by the general formula M(OOR)(OH)(OR′

)₂ wherein M is a metal;

R is selected from the group consisting of hydride, alkyl groups, aryl groups, and/or alkylaryl groups; and

wherein R′

is selected from the group consisting of ethylene glycol, glycerol, sorbitol, xylitol and/or mixtures thereof

contacting the hydrocarbon stream with the oxidant in the presence of the catalyst, resulting in the oxidation of at least one sulfur compound.

2. The method of claim 1 wherein M is titanium.

3. The method of claim 1 wherein R′

is polymerized by reaction with a compound Q-R-Q′

wherein Q and Q′

each independently is selected from the group consisting of isocyanate, anhydride, sulfonyl halide, benzyl halide, carboxylic acid halide, phosphoryl acid halide, silyl chloride and/or mixtures thereof and R is a linking group.

4. The method of claim 1 wherein the catalyst is prepared by the reaction of bis(glycerolato)oxotitanium(IV) with 4,4′

bisphenol A dianhydride followed by reaction with hydroperoxide.

5. The method of claim 4 wherein the hydroperoxide is of the general formula HOOR wherein R is selected from the group consisting of hydride, alkyl groups, aryl groups, alkylaryl groups, and/or mixtures thereof.

6. The method of claim 5 wherein the catalyst comprises a polymeric (hydroxy)bis(polyol)(hydroperoxo)titanium(IV).

7. The method of claim 5 wherein the catalyst comprises a polymeric (hydroxy)bis(polyol)(organoperoxo)titanium(IV).

8. The method of claim 7 wherein the polyol is selected from the group consisting of ethylene glycol, glycerol, sorbitol, xylitol and/or mixtures thereof.

9. The method of claim 7 wherein a pendant —

OH group of the polyol selectively detaches from a titanium center to allow a sulfide or sulfoxide to attach to the titanium center and thereby become oxidized, and wherein the pendant —

OH group of the polyol selectively blocks the oxidation of non-sulfur containing compounds by remaining attached to the titanium center.

10. The method of claim 7 wherein an intermediate free complex of the catalyst is formed with specific coordination of an organoperoxo group.

11. The method of claim 1 wherein the organohydroperoxide is of the general formula HOOR, wherein R is selected from the group consisting of alkyl groups, aryl, alkylaryl groups and/or mixtures thereof.

12. The method of claim 11 wherein the organohydroperoxide is selected from the group consisting of ethylbenzene hydroperoxide, tert-butyl hydroperoxide, cumyl hydroperoxide and/or mixtures thereof.

13. The method of claim 1 wherein the method is carried out at a pressure in the range of from about 0.5 atmospheres to about 10 atmospheres and at a temperature in the range of from about 50°

C. to about 90°

C., with a reaction time in the range of from about 30 minutes to about 120 minutes.

14. The method of claim 1 wherein the catalyst is in pellet or powder form.

15. The method of claim 1 wherein the catalyst is supported on an inorganic or organic support material.

16. The method of claim 1 wherein the catalyst is poly[bis(glycerolato)(hydroxo)(ethylbenzylperoxo)titanium(IV) bisphenol A ester].

17. The method of claim 1 wherein the catalyst is poly[bis(glycerolato)(hydroxo)(cumylperoxo)titanium(IV) bisphenol A ester].

18. The method of claim 1 wherein the catalyst is poly[bis(glycerolato)(hydroxo)(tert-butylperoxo)titanium(IV) bisphenol A ester].