IP Library Granted Patent US 8,187,366
Granted Patent B2
US 8,187,366 · App. 12/263,844 · Granted May 29, 2012

Natural gas desulfurization

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Quick Facts
Patent No.
US 8,187,366
App. No.
12/263,844
Granted
May 29, 2012
Kind
B2
Abstract

A method for desulfurizing natural gas includes contacting the natural gas with an adsorbent which preferentially adsorbs at least one of hydrogen sulfide, COS, sulfur odorants, or combinations thereof, at a selected temperature and pressure, thereby producing desulfurized natural gas and an at least one of hydrogen sulfide/COS/sulfur odorant/combinations thereof-rich adsorbed component. The adsorbent includes a copper species adapted to form π-complexation bonds and direct metal-sulfur bonds with the at least one of hydrogen sulfide, COS, sulfur odorants, or combinations thereof, and wherein the preferential adsorption occurs by π-complexation and direct metal-sulfur bonding.

Claims (27)

1. A method for desulfurizing natural gas hydrocarbons, the method comprising:

contacting the natural gas with an adsorbent which preferentially adsorbs at least one of hydrogen sulfide, COS, sulfur odorants, or combinations thereof, at a selected temperature and pressure, thereby producing desulfurized natural gas and a hydrogen sulfide, COS, sulfur odorant, or combinations thereof-rich adsorbed component, wherein the adsorbent comprises a Cu + species adapted to form π-complexation and direct metal-sulfur bonds with the at least one of hydrogen sulfide, COS, sulfur odorants, or combinations thereof, and wherein the preferential adsorption occurs by π-complexation and direct metal-sulfur bonding.

2. The method of claim 1 , wherein the natural gas is pipeline natural gas, and wherein the sorbent adsorbs hydrogen sulfide and sulfur odorants.

3. The method of claim 2 , wherein the sulfur odorants are dimethyl sulfide.

4. The method of claim 1 , wherein the adsorbent is activated by pretreatment at a temperature ranging between about 250° C. and about 600° C. and for a time ranging between about one hour and about 20 hours, followed by cooling.

5. The method of claim 4 , wherein the adsorbent is activated in a reductive atmosphere.

6. The method of claim 1 , further comprising pretreating the natural gas using a desiccant.

7. The method of claim 6 , wherein the desiccant is selected from activated alumina, silica gel, activated carbon and combinations thereof.

8. The method of claim 1 , further comprising pretreating the natural gas using a non-sulfur selective sorbent that removes hydrocarbons heavier than methane.

9. The method of claim 1 , wherein the adsorbent further includes a zeolite or a mesoporous support.

10. The method of claim 1 , wherein prior to contacting the natural gas with the adsorbent, the method further comprises pretreating the adsorbent, the pretreatment process comprising the steps of:

activating the adsorbent at a temperature ranging from about 250° C. to about 600° C. in an inert or reducing atmosphere for an amount of time ranging between about one hour and about 20 hours; and

then cooling the adsorbent in an inert atmosphere.

11. The method of claim 1 , wherein the selected temperature is ambient temperature and the selected pressure is ambient pressure.

12. The method of claim 1 , wherein the adsorbed component comprises compounds of the formula:

R—S—H; R—S—R; or Ar—S—Ar,

wherein R represents an aliphatic ligand and Ar represents an aromatic ligand, and wherein the ligands are capable of not interfering with the formation of p-complexation by steric hinderance.

13. An intermediate complex of the formula:

R—S(Cu)—H; R—S(Cu)—R; or Ar—S(Cu)—Ar,

produced by the process of claim 1 , wherein R represents an aliphatic ligand and Ar represents an aromatic ligand, wherein the ligands are capable of not interfering with the formation of p-complexation by steric hinderance, and wherein Cu + is π-bonded to the sulfur containing compound.

14. The method of claim 1 , further comprising regenerating the adsorbent by calcining the adsorbent.

15. The method of claim 1 , wherein the adsorbent comprises Cu(I)Y or supported Cu+ compounds on high area surface substrates.

16. The method of claim 1 , wherein the adsorbent comprises an ion-exchanged zeolite or mesoporous support.

17. The method of claim 1 , wherein the natural gas is present in ambient air.

18. The method of claim 1 , wherein the adsorbed component comprises compounds of the formula:

R—S(Cu)—H; R—S(Cu)—R; or Ar—S(Cu)—Ar,

wherein R represents an aliphatic ligand and Ar represents an aromatic ligand, wherein the ligands are capable of not interfering with the formation of p-complexation by steric hinderance, and wherein Cu + is π-bonded to the sulfur containing compound.

Assignments (4)
CONFIRMATORY LICENSE Recorded Dec 23, 2011
From: UNIVERSITY OF MICHIGAN
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 027440/0216 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 23, 2009
From: YANG, RALPH T.; WANG, YUHE; AMESTICA, LUIS
To: REGENTS OF THE UNIVERSITY OF MICHIGAN
Reel/Frame 022996/0211 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 23, 2009
From: REGENTS OF THE UNIVERSITY OF MICHIGAN
To: AMESTICA, LUIS
Reel/Frame 022996/0466 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 23, 2009
From: AMESTICA, LUIS
To: INTERNATIONAL COPPER ASSOCIATION LTD
Reel/Frame 022996/0536 →
Continuity (2)
Provisional Application 60984602 · Nov 1, 2007
Related Publication 20090118528A1 · May 7, 2009