Removal of CO 2 , N 2 , and H 2 S from gas mixtures containing same

• US 8,545,602 B2
• Filed: 04/04/2008
• Issued: 10/01/2013
• 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: Chance, Ronald R., Reyes, Sebastian C., Deckman, Harry W., DeMartin, Gregory J., Kelley, Bruce T., Northrop, Paul S., Thomas, Eugene R.
• Primary Examiner(s): Hopkins, Robert A
• Application Number:
  US12/080,783
• Publication Number:
  US 20080282887A1
• Time in Patent Office: 2,006 Days
• Field of Search: 95/96, 951/48, 961/30
• US Class Current: 95/96
• CPC Class Codes: B01D 2253/108 Zeolites
• CPC Class Codes: B01D 2253/308 Pore size
• CPC Class Codes: B01D 2253/342 Monoliths
• CPC Class Codes: B01D 2257/102 Nitrogen
• CPC Class Codes: B01D 2257/304 Hydrogen sulfide
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• 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 53/047 Pressure swing adsorption
• CPC Class Codes: C10L 3/10 Working-up natural gas or synthetic natural gas
• CPC Class Codes: C10L 3/102 of acid contaminants
• CPC Class Codes: Y02C 20/40 of CO2

Abstract

The removal of one or more of the gases CO₂, N₂ and H₂S from gas mixtures containing at least one of said gases with use of an 8-ring zeolite having a Si:Al ratio from about 1:1 to about 1000:1. The preferred gas mixture is a natural gas feedstream and the preferred 8-ring zeolite is DDR.

Claims

1. A process for the removing a first gas component selected from the group consisting of CO₂, N₂, and H₂S from a gas mixture containing said first gas component and a second gas component, which process comprises:

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

i) a gas inlet end; and

ii) a gas outlet end;

wherein the gas mixture is introduced into said gas inlet end and a product stream exits the gas outlet end, which is in fluid communication with said gas inlet end, by a plurality of flow channels, wherein the adsorbent contactor is comprised of an adsorbent material comprised of an 8-ring zeolite, wherein the adsorbent material has a selectivity for said first gas component over said second gas component greater than 5, and the 8-ring zeolite has a Si to Al ratio of about 1;

1 to about 1000;

1, and wherein at least a portion of said first gas component is adsorbed into said adsorbent material, thereby resulting in said product stream which is depleted of said first gas component;

b) collecting said product stream;

c) desorbing the adsorbed gases from said adsorbent material, thereby resulting in a waste gas stream rich in said first gas component; and

d) collecting said waste gas stream;

wherein the second gas component is CH₄ and the gas mixture is comprised of natural gas.

2. The process of claim 1 wherein greater than about 90% of the CH₄ in the gas mixture is recovered in the product stream.

3. The process of claim 1 wherein the 8-ring zeolite is a DDR framework zeolite.

4. The process of claim 1 wherein the 8-ring zeolite is selected from Sigma-1 and ZSM-58.

5. The process of claim 1 wherein the adsorbent contactor contains an effective amount of a thermal mass material capable of adsorbing heat.

6. The process of claim 1 wherein the adsorbent contactor is a parallel channel contactor.

7. The process of claim 6 wherein greater than about 90% of the CH₄ in the gas mixture is recovered in the product stream.

8. The process of claim 6 wherein the 8-ring zeolite is a DDR framework zeolite.

9. The process of claim 6 wherein the 8-ring zeolite is selected from Sigma-1 and ZSM-58.

10. A process for the removing a first gas component selected from the group consisting of CO₂, N₂, and H₂S from a gas mixture containing said first gas component and a second gas component, which process comprises:

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

i) a gas inlet end; and

ii) a gas outlet end;

wherein the gas mixture is introduced into said gas inlet end and a product stream exits the gas outlet end, which is in fluid communication with said gas inlet end, by a plurality of flow channels, wherein the adsorbent contactor is comprised of an adsorbent material comprised of an 8-ring zeolite, wherein the adsorbent material has a selectivity for said first gas component over said second gas component greater than 5, and the 8-ring zeolite has a Si to Al ratio of about 1;

1 to about 1000;

1, and wherein at least a portion of said first gas component is adsorbed into said adsorbent material, thereby resulting in said product stream which is depleted of said first gas component;

b) collecting said product stream;

c) desorbing the adsorbed gases from said adsorbent material, thereby resulting in a waste gas stream rich in said first gas component; and

d) collecting said waste gas stream;

wherein the adsorbent contactor is comprised of a first adsorption zone comprising a first adsorbent material which is in fluid contact with a second adsorption zone comprising a second adsorbent material, wherein the composition of the first adsorbent material is different from the composition of a second adsorbent material.

11. The process of claim 10 wherein the first adsorbent material has a selectivity for the first gas component of the gas mixture over the second gas component greater than 5;

the second adsorbent material has a selectivity for a third gas component over the second gas component greater than 5; and

the second adsorbent material has a greater adsorption uptake for the third gas component than the first adsorbent material.

12. The process of claim 11 wherein the first gas component is CO₂, the second gas component is CH₄ and the third gas component is H₂S.

13. The process of claim 11 wherein the first gas component is N₂, the second gas component is CH₄ and the third gas component is H₂S.

14. The process of claim 11 wherein the first adsorbent material is comprised of an 8-ring zeolite that has a Si to Al ratio of about 1:

1 to about 1000;

1.

15. The process of claim 14 wherein the second adsorbent material is comprised of a stannosilicate.

16. The process of claim 15 wherein the 8-ring zeolite is a DDR framework zeolite.

17. The process of claim 15 wherein the 8-ring zeolite is selected from Sigma-1 and ZSM-58.

18. A process for the removing a first gas component selected from the group consisting of CO₂, N₂, and H₂S from a gas mixture containing said first gas component and a second gas component, which process comprises:

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

i) a gas inlet end; and

ii) a gas outlet end;

wherein the gas mixture is introduced into said gas inlet end and a product stream exits the gas outlet end, which is in fluid communication with said gas inlet end, by a plurality of flow channels, wherein the adsorbent contactor is comprised of an adsorbent material comprised of an 8-ring zeolite, wherein the adsorbent material has a selectivity for said first gas component over said second gas component greater than 5, and the 8-ring zeolite has a Si to Al ratio of about 1;

1 to about 1000;

1, and wherein at least a portion of said first gas component is adsorbed into said adsorbent material, thereby resulting in said product stream which is depleted of said first gas component;

b) collecting said product stream;

c) desorbing the adsorbed gases from said adsorbent material, thereby resulting in a waste gas stream rich in said first gas component; and

d) collecting said waste gas stream;

wherein the gas mixture is comprised of a natural gas stream containing CH₄ and the adsorbent material has a selectivity for said first gas component over CH₄ greater than 5;

the adsorbent contactor is a parallel channel contactor; and

wherein the adsorbent contactor is comprised of a first adsorption zone comprising a first adsorbent material which is in fluid contact with a second adsorption zone comprising a second adsorbent material, wherein the composition of the first adsorbent material is different from the composition of a second adsorbent material.

19. The process of claim 18 wherein the first adsorbent material has a selectivity for the first gas component of the gas mixture over CH₄ greater than 5;

the second adsorbent material has a selectivity for a third gas component over CH₄ greater than 5; and

the second adsorbent material has a greater adsorption uptake for the third gas component than the first adsorbent material.

20. The process of claim 19 wherein the first gas component is CO₂ and the third gas component is H₂S.

21. The process of claim 19 wherein the first gas component is N₂ and the third gas component is H₂S.

22. The process of claim 19 wherein the first adsorbent material is comprised of an 8-ring zeolite that has a Si to Al ratio of about 1:

1 to about 1000;

1.

23. The process of claim 19 wherein the second adsorbent material is comprised of a stannosilicate.

24. The process of claim 19 wherein the parallel channel contactor contains an effective amount of a thermal mass material capable of adsorbing heat.

25. The process of claim 19 wherein the swing adsorption gas separation unit is a rapid cycle pressure swing adsorption unit operating at cycle times of less than about 1 minute.

26. The process of claim 19 wherein the parallel channel contactor is in the form selected from:

a) monolith comprised of a the 8-ring zeolite and a binder;

b) a monolith formed from a non-adsorbent material but whose channels are lined with an 8-ring zeolite;

c) an array of hollow fibers comprised of an 8-ring zeolite; and

d) laminated sheets having an upper and lower face both of which are comprised of an 8-ring zeolite.

27. The process of claim 19 wherein the channel gap of the flow channels is from about 5 to about 1000 microns.

28. The process of claim 19 wherein the ratio of adsorbent volume to open flow channel volume is from about 0.5:

1 to about 100;

1.

29. The process of claim 19 wherein the pressure of the natural gas stream is from about 1000 to about 5000 psig.

30. The process of claim 19 wherein the swing adsorption gas separation unit contains more than one type of adsorbent material each having a different selectivity for each of CO₂, N₂ and H₂S over CH₄.