ADSORBENTS AND METHODS OF USE

• US 20160281003A1
• Filed: 03/25/2016
• Published: 09/29/2016
• Est. Priority Date: 03/26/2015
• Status: Active Grant

• Current Assignee: Auterra, Inc., Cenovus Energy Incorporated
• Original Assignee: Auterra, Inc., Cenovus Energy Incorporated
• Inventors: Shipley, Erica H., Scudder, Michael, Litz, Kyle E., Rankin, Jonathan P., McCaskill, Trent A.
• Granted Patent: US 10,246,647 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: B01J 20/0211 Compounds of Ti, Zr, Hf
• CPC Class Codes: C10G 25/003 Specific sorbent material, not covered by C10G25/02 or C10G25/03
• CPC Class Codes: C10G 25/12 Recovery of used adsorbent

Abstract

Systems, methods and compositions for reducing the heteroatom content of hydrocarbon feed using transition metal complexes and adsorption techniques. The transition metal complexes include titanyl, hafnyl and zirconyl complexes activated using one or more hydroperoxides or peracids. The activated adsorbents are incorporated into one or more vessels as an adsorption bed for adsorbing the heteroatoms present in hydrocarbon feeds. The systems, methods and compositions separate the heteroatoms passed through the system by contacting the adsorption compositions with the heteroatoms of the hydrocarbon feed, adsorbing the heteroatom to the adsorption material, further allowing for the retrieval of a hydrocarbon product having a reduced heteroatom content.

Claims

1. An adsorbent composition comprising:

a metal complex including a titanyl, wherein a titanium molecule of the titanyl is covalently bound to an alcohol or a polyol; and

an inorganic oxide support of the metal complex bound to the titanium molecule of the titanyl.

2. The adsorbent composition of claim 1, further comprising a hydroperoxide or peracid bound to the titanyl of the metal complex, wherein the hydroperoxide or peracid covalently is bound to an oxygen molecule double bound to the titanium molecule.

3. The adsorbent composition of claim 1, wherein the alcohol or the polyol are selected from the group consisting of glycerol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, dithioerythritol, axomadol, azidamfenicol, alfatradiol, bronopol, 1,4-butynediol, capsidiol, chloramphenicol, cyclohexane-1,2-diol, cyclohexanedimethanol, estradiol, ethambutol, methane diol, triethylene glycol, methanol, ethanol, propanol, butanol, pentanol, hexanol, hetpanol, oxanol, polypropylene glycol, 1,2-propylene glycol, glycerine, trimethylolpropane, pentaerythritol, sorbitol, sucrose and combinations thereof.

4. The adsorbent composition of claim 1, wherein the inorganic oxide support is an oxide having a metal from groups I-A, I-B, II-A, II-B, III-A, III-B, IV-A, IV-B, V-B, VI-B, VII-B, and VIII-B of the Periodic Table of Elements.

5. The adsorbent composition of claim 4, wherein the inorganic oxide support is selected from the group consisting of Li₂O, Na₂O, K₂O, Rb₂O, Cs₂O, Fr₂O, BeO MgO, CaO, SrO, BaO, ZnO, ZrO₂, TiO₂ and talc.

6. The adsorbent composition of claim 2 wherein the hydroperoxide or peracid is selected from the group consisting of hydrogen peroxide, tert-butyl hydroperoxide, ethylbenzene hydroperoxide, cumyl hydroperoxide, tetrahydronaphthalene hydroperoxide, performic acid, peracetic acid and combinations thereof.

7. The adsorbent composition of claim 1, wherein the metal complex is selected from the group consisting of bis(glycerolato)oxotitanium(IV), bis(sorbitolato)oxotitanium(iv), bis(erythritolato)oxotitanium (IV), bis(mannitolato)oxotitanium(IV) and combinations thereof.

8. The adsorbent composition of claim 2, wherein the metal complex is selected from the group consisting of bis(polyol)(hydroperoxo)oxotitanium(IV), wherein the polyol is glycerol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, dithioerythritol, triethylene glycol, ethanol, propanol, butanol, sorbitol or a combination thereof and the hydroperoxide is tert-butyl hydroperoxide, ethylbenzene hydroperoxide, cumyl hydroperoxide, tetrahydronaphthalene hydroperoxide or a combination thereof.

9. The adsorbent composition of claim 8, wherein the metal complex of bis(polyol)(hydroperoxo)oxotitanium(IV) is bis(polyol)(tert-butyl hydroperoxo)oxotitanium(IV).

10. The adsorbent composition of claim 2, wherein the metal complex comprises a general chemical structure:

11. The adsorbent composition of claim 2, wherein the metal complex has a chemical structure:

12. A method for reducing a heteroatom content of a hydrocarbon feed comprising the steps of:

providing an adsorbent having a metal complex bound to an inorganic oxide support, wherein the metal complex is a titanyl having a titanium molecule covalently bonded to an alcohol or polyol;

contacting the adsorbent with a hydroperoxide or a peracid, forming an activated adsorbent;

contacting the activated adsorbent with the hydrocarbon feed;

binding a heteroatom present in the hydrocarbon feed to the activated adsorbent, forming a heteroatom-bound adsorbent, leaving behind a hydrocarbon feed having a reduced heteroatom content; and

separating the hydrocarbon feed having the reduced heteroatom content from the heteroatom-bound adsorbent.

13. The method of claim 12, further comprising the step:

contacting the heteroatom bound adsorbent with a solvent, the solvent removing the heteroatom from the heteroatom-bound adsorbent, forming a regenerated activated adsorbent.

14. The method of claim 13, wherein the solvent is a hydroperoxide or peracid.

15. The method of claim 13, further comprising the step of:

separating the heteroatom dissolved in the solvent from the regenerated activated adsorbent.

16. The method of claim 13, further comprising the steps of:

contacting the regenerated activated adsorbent with a second hydrocarbon feed; and

binding a heteroatom of the second hydrocarbon feed to the regenerated activated adsorbent.

17. The method of claim 12, wherein the metal complex is selected from the group consisting of bis(glycerolato)oxotitanium(IV), bis(sorbitolato)oxotitanium(iv), bis(erythritolato)oxotitanium (IV), bis(mannitolato)oxotitanium(IV) and combinations thereof.

18. The method of claim 12, wherein hydroperoxide or peracid is selected from the group consisting of hydrogen peroxide, tert-butyl hydroperoxide, ethylbenzene hydroperoxide, cumyl hydroperoxide, tetrahydronaphthalene hydroperoxide, performic acid, peracetic acid and combinations thereof.

19. The method of claim 12, wherein the metal complex of the activated adsorbent is bis(polyol)(tert-butyl hydroperoxo)oxotitanium(IV), bis(polyol)(ethylbenzene hydroperoxo)oxotitanium(IV), bis(polyol)(cumyl hydroperoxo)oxotitanium(IV) or bis(polyol)(tetrahydronaphthalene hydroperoxo)oxotitanium(IV).

20. The method of claim 12, wherein heteroatom content of the hydrocarbon feed is reduced by at least 85%.