Temperature swing adsorption of CO2 from flue gas using a parallel channel contractor

• US 7,947,120 B2
• Filed: 05/16/2008
• Issued: 05/24/2011
• Est. Priority Date: 05/18/2007
• Status: Active Grant

• Current Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Inventors: Hershkowitz, Frank, Deckman, Harry W., Kelley, Bruce T., Chance, Ronald R., Corcoran, Edward W. Jr., Northrop, Paul S.
• Primary Examiner(s): Hill, Jr.; Robert J
• Assistant Examiner(s): Jones; Christopher P
• Application Number:
  US12/152,875
• Publication Number:
  US 20080282888A1
• Time in Patent Office: 1,103 Days
• Field of Search: 95/96, 951/15, 951/39, 961/08, 961/30, 961/34, 961/40, 961/41
• US Class Current: 95/139
• CPC Class Codes: B01D 2253/108 Zeolites
• CPC Class Codes: B01D 2253/311 Porosity, e.g. pore volume
• CPC Class Codes: B01D 2253/342 Monoliths
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2259/4143 arranged as a mixture
• CPC Class Codes: B01D 53/02 by adsorption, e.g. preparative gas chromatography solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01
• CPC Class Codes: B01D 53/0423 Beds in columns
• CPC Class Codes: B01D 53/0462 Temperature swing adsorption
• CPC Class Codes: Y02C 20/40 of CO2

Abstract

The adsorption of CO₂ from flue gas streams using temperature swing adsorption. Adsorbent contactors are used in the temperature swing adsorption unit that contain a plurality of substantially parallel channels comprised of or coated with an adsorbent material that is selective for adsorbing CO₂ from flue gas.

Claims

1. A process for the removing CO₂ from a flue gas stream containing CO₂, which process comprises:

a) conducting said flue gas stream to a temperature swing adsorption gas separation unit wherein the gas separation unit contains at least one adsorbent contactor comprised of;

i) a process gas inlet end; and

ii) a process gas outlet end;

wherein the gas inlet end and the gas outlet end are in fluid connection by a plurality of open flow channels wherein the surfaces of the open flow channels are comprised of an adsorbent material that has an adsorption selectivity for CO₂ over at least one other gaseous component of the flue gas stream of greater than 1, thereby resulting in a substantially CO₂-free flue gas stream and CO₂ adsorbed onto said adsorbent material;

b) venting said substantially CO₂-free flue gas stream into the atmosphere; and

c) heating said adsorbent material having CO₂ adsorbed thereon to an effective temperature that results in the desorption of at least a fraction of CO₂, thereby resulting in a CO₂ rich stream;

wherein the adsorbent contactor has less than about 20% of its open pore volume in pores greater than about 20 angstroms, and wherein the open pore volume (in volume percentage) is defined as the volume of the pores in the adsorbent structure that are greater than about 20 angstroms in diameter that are not occupied by a blocking agent divided by the total volume of the adsorbent contactor that is occupied by the adsorbent material; and

the adsorbent contactor is comprised of substantially parallel channels wherein the geometry of the adsorbent contactor is selected from monoliths, a plurality of tubular members, stacked layers of adsorbent sheets with or without spacers between each sheet, multi-layered spiral rolls, bundles of hollow fibers, and bundles of substantially parallel solid fibers.

2. The process of claim 1 wherein the adsorbent contactor has less than about 15% of its open pore volume in pores greater than about 20 angstroms.

3. The process of claim 1 wherein the temperature swing adsorption gas separation unit process is performed at a cycle time of less than about 2 minutes between successive adsorption steps.

4. The process of claim 1 wherein at least about 75 mol % of the CO₂ in the flue gas stream is removed to produce the substantially CO₂ free flue gas stream.

5. The process of claim 1 wherein the adsorbent material is comprised of a zeolite.

6. The process of claim 5 wherein the zeolite is a cationic zeolite having Si/Al molar ratio of less than about 5.

7. The process of claim 6 wherein the cationic zeolite is selected from the group consisting of a faujasite zeolite, a BETA zeolite, a SAPO zeolite, and a ALPO zeolite.

8. The process of claim 5 wherein the zeolite is a MFI zeolite.

9. The process of claim 1 wherein the adsorbent contactor is comprised of at least two adsorbent materials and the first adsorbent material has a selectively for water over CO₂ of greater than 1 and is located upstream with respect to the flow of flue gas stream to a second adsorbent material that has a selectivity for CO₂ over N₂ of greater than 1.

10. The process of claim 9 wherein water is adsorbed from the flue gas stream onto the first adsorbent material so that less than about 400 ppmv remains in the flue gas stream downstream of the first adsorbent material.

11. The process of claim 10 wherein water is adsorbed from the flue gas stream onto the first adsorbent material so that less than about 50 ppmv remains in the flue gas stream downstream of the first adsorbent material.

12. The process of claim 9 wherein NOx, SOx or both NOx and SOx are adsorbed.

13. The process of claim 9 wherein at least one adsorbent material is comprised a cationic zeolite having a Si/Al molar ratio of less than about 5.

14. The process of claim 1 wherein a first adsorbent material that has a selectivity for water over CO₂ of greater than 1 is part of a contactor that is separate from a second adsorbent contactor containing an adsorbent material that has a selectivity for CO₂ over N₂ of greater than 1.

15. The process of claim 1 wherein the adsorbent contactor is directly heated by passing a heat transfer fluid of an effective temperature through the same open flow channels as the flue gas stream, thereby desorbing CO₂ into the heat transfer fluid.

16. The process of claim 15 wherein the heat transfer fluid is passed co-current or counter-current through the flow channels relative to the direction of flow of the flue gas stream.

17. The process of claim 1 wherein a first fraction of the flow channels of the contactor receive the flow of flue gas stream and a second fraction of flow channels receive the flow of a heat transfer fluid of an effective temperature and wherein at least a portion of the channels of the two fractions are contiguous to each other, but not in fluid communication, so that heat flowing through said second fraction of flow channels is capable of effectively indirectly heating said first fraction of flow channels to provide heat for desorption.

18. The process of claim 17 wherein there are provided multiple adsorbent contactors wherein at least one adsorbent contactor is upstream to at least one other contactor wherein said at least one upstream adsorbent contactor contains an adsorbent material that has a electivity for at least one component selected from the group consisting of water, SO_x, and NO_x over CO₂ of greater than 1.

19. The process of claim 1 comprising at least one upstream contactor that has a selectivity for water over any other component in the flue gas stream of greater than 1.

20. The process of claim 1 wherein said adsorbent contactor contains at least two adsorbent materials and the first adsorbent material has a selectivity for water over CO₂ of greater than 1, and the second adsorbent material has a higher selectivity for CO₂ over water of greater than 1, and wherein the first adsorbent material is located upstream, with respect to the flow of said flue gas stream, of the second adsorbent material.

21. The process of claim 1 wherein all flow channels of said adsorbent contactor containing said flue gas stream have substantially the same channel gap.

22. The process of claim 1 wherein the of the flue gas entering the temperature swing adsorption gas separation unit is at a temperature from about 100°

C. to about 250°

C.

23. The process of claim 1 wherein at least a portion of the CO₂-rich stream is compressed to pressures in excess of about 1,000 psi then injected into a subterranean formation.

24. The process of claim 1 wherein the adsorbent contactor is comprised of a monolith.

25. The process of claim 24 wherein the adsorbent material is coated onto at least a portion of the monolith.

26. The process of claim 24 wherein the monolith is comprised of an adsorbent material formed within the monolith.