Sulfoxidation catalysts and methods and systems of using same

• US 8,394,261 B2
• Filed: 10/31/2008
• Issued: 03/12/2013
• Est. Priority Date: 03/26/2008
• Status: Active Grant

• Current Assignee: Auterra, Inc.
• Original Assignee: Auterra, Inc.
• Inventors: Litz, Kyle E., Jordan, Tracey M., Rossetti, Mark N., Loughran, Anthony J., Vreeland, Jennifer L.
• Primary Examiner(s): Singh, Prem C
• Assistant Examiner(s): Stein, Michelle
• Application Number:
  US12/933,898
• Publication Number:
  US 20110011771A1
• Time in Patent Office: 1,593 Days
• Field of Search: 208/208.R, 208/213, 208/240
• US Class Current: 208/189
• CPC Class Codes: B01J 2531/46 Titanium
• CPC Class Codes: B01J 31/165 Polymer immobilised coordination complexes, e.g. organometallic complexes
• CPC Class Codes: B01J 31/2226 Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
• CPC Class Codes: B01J 31/223 At least two oxygen atoms present in one at least bidentate or bridging ligand
• CPC Class Codes: C07F 7/28 Titanium compounds
• CPC Class Codes: C10G 2300/104 Light gasoline having a boiling range of about 20 - 100 °C
• CPC Class Codes: C10G 2300/1044 Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
• CPC Class Codes: C10G 2300/1051 Kerosene having a boiling range of about 180 - 230 °C
• CPC Class Codes: C10G 2300/1055 Diesel having a boiling range of about 230 - 330 °C
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/44 Solvents
• CPC Class Codes: C10G 27/10 in the presence of metal-containing organic complexes, e.g. chelates, or cationic ion-exchange resins

Abstract

Catalysts amenable to oxidizing sulfur compounds and systems and methods of using these catalysts to effect the removal of sulfur from crude oil and crude oil distillates are disclosed. The catalyst is disposed with a titanyl moiety which serves to selectively coordinate sulfur compounds and affect their oxidation. The titanyl may be bound within a polymer or on the surface of a polymer or on the surface or in the pores of an inorganic support. The resulting oxidized sulfur compounds are readily separated from the initial crude oil or crude oil distillate streams by traditional separation techniques arrayed as described in the systems and methods disclosed.

Claims

1. A sulfoxidation method comprising:

providing a hydrocarbon stream including at least one sulfur compound;

providing an oxidant;

providing a catalyst comprising a metal compound represented by the general formula M_mO_m(OR)_n, wherein M is a metal complex;

R is carbon group having at least 3 carbon atoms, where at each occurrence R is individually a substituted alkyl group containing at least one OH group, a substituted cycloalkyl group containing at least one OH group, a substituted cycloalkylalkyl group containing at least one OH group, a substituted heterocyclyl group containing at least one OH group, or a heterocyclylalkyl containing at least one OH group; and

the subscripts m and n are each independently integers between about 1 and about 8; and

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

2. The method of claim 1 further comprising:

providing a phase transfer agent/solvent.

3. The method of claim 2 wherein the phase transfer agent/solvent is selected from the group consisting of acetic acid, formic acid, propanoic acid, octenoic acid, butenoic acid, long chain aliphatic acids, alkyl substituted aromatic acids, other polar protic liquids, and mixtures thereof.

4. The method of claim 1 wherein the catalyst comprises:

bis(polyol)oxotitanium(IV).

5. The method of claim 4 wherein the polyol further comprises:

ethylene glycol, glycerol, erythritol, sorbitol, xylitol, pentaerythritol, a sugar, a carbohydrate, and/or mixtures thereof.

6. The method of claim 1 wherein the method is carried out between 20 degrees Celsius and 90 degrees Celsius.

7. The method of claim 1 wherein the concentration of the catalyst is between 100.00% and 0.00004% by weight with respect to elemental sulfur.

8. The method of claim 1 wherein the catalyst is at least one of incorporated within a polymer and bound to a support surface, wherein the support surface comprises an organic polymer, an inorganic oxide, or mixtures thereof.

9. The method of claim 8 wherein the inorganic oxide is selected from the group consisting of:

silicates, aluminates, titanates, independently and/or mixtures thereof, and

wherein the organic polymer is selected from the group consisting of;

polystyrene-co-divinylbenzene, containing reactive chemical functionalities comprising, isocyanates, anhydrides, sulfonyl halides, benzyl halides, carboxylic acid halides, phosphoryl acid halides, silyl chlorides, or any chemical functionality capable of reacting with the —

OH pendant group of the catalyst.

10. The method of claim 1 wherein the catalyst is a solid in a form selected from the group consisting of a polymer, a complex, a cluster complex, a mixture of isomers, a nano-dimensional material, and mixtures thereof;

wherein the hydrocarbon stream including at least one sulfur compound is selected from a group consisting of gasoline, diesel fuel, jet oil, heavy oil, heavy sour crude oil, other refinery products and intermediates, and mixtures thereof, and

wherein the oxidant is selected from the group consisting of hydrogen peroxide, sodium hypochlorite, oxygen, trioxygen, air, permanganate compounds, nitrous oxide, and mixtures thereof and different forms thereof.