HIGH CYCLIC CAPACITY AMINES FOR HIGH EFFICIENCY CO2 SCRUBBING PROCESSES

• US 20140030177A1
• Filed: 07/02/2013
• Published: 01/30/2014
• Est. Priority Date: 07/30/2012
• Status: Active Grant

• Current Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Inventors: Kortunov, Pavel, Siskin, Michael, Thomann, Hans
• Granted Patent: US 9,272,242 B2
• Time in Patent Office: Days
• US Class Current: 423/228
• CPC Class Codes: B01D 2252/20405 Monoamines
• CPC Class Codes: B01D 2252/20426 Secondary amines
• CPC Class Codes: B01D 2252/20484 with one hydroxyl group
• CPC Class Codes: B01D 2258/0283 Flue gases
• CPC Class Codes: B01D 53/1475 Removing carbon dioxide
• CPC Class Codes: B01D 53/1493 Selection of liquid materials for use as absorbents
• CPC Class Codes: B01D 53/62 Carbon oxides
• CPC Class Codes: C10L 3/104 Carbon dioxide
• CPC Class Codes: Y02C 20/40 of CO2

Abstract

A high cyclic capacity carbon dioxide scrubbing process contacts a gas stream containing carbon dioxide in a sorption zone with a liquid scrubbing solution of a low molecular weight sterically hindered amine, particularly a secondary alkanolamine or aminoether at a high concentration, typically at least 3.5M and at a temperature of at least 30° C. to sorb the carbon dioxide into the solution and form a rich stream of the sorbed carbon dioxide in the solution in the form of dissolved amine carbamate and/or alkanolamine bicarbonate. The rich stream is then passed from the sorption zone to at least one regeneration zone and the sorbed carbon dioxide is desorbed as gas from the solution to form a lean solution containing a reduced concentration of sorbed carbon dioxide relative to the rich stream; the lean stream is then returned to the sorption zone for a further sorption cycle.

Claims

1. A high cyclic capacity carbon dioxide scrubbing process which comprises:

(i) contacting a gas stream containing carbon dioxide in a sorption zone with an aqueous liquid scrubbing solution of a sterically hindered secondary amine at a total secondary amine concentration of at least 3.5M and at a temperature of at least 10°

C. to sorb the carbon dioxide into the amine solution and form a rich stream of the sorbed carbon dioxide in the amine solution in the form of amine carbamate and/or amine bicarbonate dissolved in the solution;

(ii) passing the rich stream from the sorption zone to at least one regeneration zone and desorbing the sorbed carbon dioxide as gas from the amine solution to form a lean solution containing a reduced concentration of sorbed carbon dioxide relative to the rich stream; and

(iii) returning the lean stream to the sorption zone.

2. The process according to claim 1, wherein the total secondary amine concentration of the secondary amine in the amine solution is at least 4.0M.

3. The process according to claim 1, wherein the total secondary amine concentration of the secondary amine in the amine solution is at least 5.0M.

4. The process according to claim 1, wherein the total secondary amine concentration of the secondary amine in the amine solution is from 5.0M to about 7.0M.

5. The process according to claim 1, wherein the carbon dioxide is contacted with the amine solution in the sorption zone at a temperature of at least 40°

C.

6. The process according to claim 1, wherein the carbon dioxide loading in the rich stream is at least 0.4 mol CO₂ per mol of secondary amine.

7. The process according to claim 1, wherein the carbon dioxide is contacted with the amine solution in the sorption zone at a temperature of at least 30°

C.

8. The process according to claim 7, wherein the carbon dioxide is contacted with the amine solution in the sorption zone at a temperature from 30°

C. to 60°

C.

9. The process according to claim 1, wherein the carbon dioxide is contacted with the amine solution in the sorption zone at a temperature from 60°

C. to 90°

C.

10. The process according to claim 1, wherein the carbon dioxide loading in the rich stream is at least 0.3 mol CO₂ per mol of secondary amine.

11. The process according to claim 1, wherein the carbon dioxide is contacted with the amine solution in the sorption zone at a carbon dioxide partial pressure of at least 0.025 bar.

12. The process according to claim 1, wherein the viscosity of the rich stream is not more than about 10 cPs.

13. The process according to claim 1, wherein a molar ratio of bicarbonate to carbamate in the rich stream is at least 1.0.

14. The process according to claim 1, wherein the sorbed carbon dioxide is desorbed from the rich stream in at least one regeneration zone at a temperature higher than the temperature of the sorption zone.

15. The process according to claim 14, wherein the sorbed carbon dioxide is desorbed from the rich amine stream in a regeneration zone(s) at a temperature from 65°

C. to 120°

C.

16. The process according to claim 1, wherein the carbon atom alpha to the nitrogen atom of the sterically hindered secondary amine is a secondary carbon having one proton.

17. The process according to claim 1, wherein the carbon atom alpha to the nitrogen atom of the sterically hindered secondary amine is a tertiary carbon having two C₁-C₂ alkyl substituents.

18. The process according to claim 1, wherein the carbon atom alpha to the nitrogen atom of the sterically hindered secondary amine is a tertiary carbon having two methyl substituents.

19. The process according to claim 1, wherein the secondary amine comprises an alkanolamine.

20. The process according to claim 19, wherein the secondary amine comprises a sterically hindered alkanolamine in which the carbon atom alpha to the nitrogen atom is a secondary carbon having one proton.

21. The process according to claim 20, wherein the secondary alkanolamine comprises 2-N-methylamino-1-propanol.

22. The process according to claim 21, wherein the aqueous liquid alkanolamine scrubbing solution consists essentially of an aqueous solution of 2-N-methylamino-1-propanol.

23. The process according to claim 19, wherein the secondary amine comprises at least one alkanolamine having the general formula R₃HN—

C(R₁R₂)—

(CH₂)_n—

R₄, where R₁ is hydrogen or a C₁-C₄ alkyl or hydroxyalkyl group;

R₂ is a C₁-C₄ alkyl or hydroxyalkyl group;

R₃ is a C₁-C₄ alkyl group; and

R₄ is —

OH or —

OR₅, where R₅ is —

CH₂—

C(R₁R₂)—

NHR₃; and

n is an integer from 1 to 4 (e.g., from 1-3), but substantially no alkanolamines where both R₁ and R₂ are methyl, n is 1, and R₄ is —

OH.

24. The process according to claim 23, wherein the secondary amine comprises 2-N-methylamino-1-propanol but substantially no 2-N-methylamino-2-methyl-1-propanol.

25. The process according to claim 1, wherein the sterically hindered secondary amine comprises an aminoether having a molecular weight of not more than 180.

26. The process according to claim 25, wherein the sterically hindered secondary amine comprises a sterically hindered aminoether in which the carbon atom alpha to the nitrogen atom is a secondary carbon having one proton having a molecular weight of not more than 180.

27. The process according to claim 26, wherein the aminoether comprises N-methylaminoethyl-methyl ether, N-methylaminoethyl-ethyl ether, N-ethylaminoethyl-methyl ether, N-ethylaminoethyl-ethyl ether, N-methylaminoethyl-propyl ether, N-methylaminoethyl-tert-butyl ether, or a combination thereof.

28. The process according to claim 1, wherein the sorbed carbon dioxide is desorbed from the rich stream in at least one regeneration zone at a temperature higher than the temperature of the sorption zone at a temperature from 65°

C. to 100°

C.

29. The process according to claim 1, wherein the gas stream containing carbon dioxide comprises flue gas from a hydrocarbon combustion process and/or natural gas.

30. The process according to claim 1, wherein the desorbing in step (ii) is accomplished by

(a) sending the rich amine solution to a first regeneration zone flash drum, where carbon dioxide is desorbed from the rich amine solution to form a first intermediate desorbed solution;

(b) sending the first intermediate desorbed solution to a stripping zone in which it is contacted, directly or indirectly, with a stripping medium to desorb further carbon dioxide from the first intermediate desorbed solution, thus forming a second intermediate desorbed solution; and

(c) optionally sending the second intermediate desorbed solution to a second regeneration flash drum, where still further carbon dioxide is desorbed from the second intermediate desorbed solution, thus forming a third intermediate desorbed solution,

wherein the second intermediate desorbed solution and/or the optional third intermediate desorbed solution is/are returned to the sorption zone as the lean stream in step (iii).

31. A high cyclic capacity carbon dioxide scrubbing process which comprises:

(i) contacting a flue gas from a hydrocarbon combustion process containing carbon dioxide in an sorption zone with an aqueous liquid alkanolamine scrubbing solution of 2-N-methylamino-1-propanol at a total concentration of 2-N-methylamino-1-propanol of at least 4.0M of the alkanolamine and at a temperature of at least 30°

C. and a pressure of at least 0.025 bar to sorb the carbon dioxide from the flue gas into the amine solution and form a rich stream of the sorbed carbon dioxide in the amine solution in the form of alkanolamine carbamate and/or alkanolamine bicarbonate dissolved in the amine solution;

(ii) passing the rich amine stream from the sorption zone to a regeneration zone and desorbing the sorbed carbon dioxide as gas from the alkanolamine solution to form a lean solution containing a reduced concentration of sorbed carbon dioxide relative to the rich stream and regenerated 2-N-methylamino-1-propanol; and

(iii) returning the lean stream to the sorption zone.

32. The process according to claim 31, wherein the sorbed carbon dioxide is desorbed from the rich stream in at least one regeneration zone at a temperature higher than the temperature of the sorption zone below 100°

C.

33. The process according to claim 31, wherein the sorbed carbon dioxide is desorbed from the rich stream in at least one regeneration zone at a temperature higher than the temperature of the sorption zone at a temperature from 90°

C. to 100°

C.

34. The process according to claim 31, wherein the sorbed carbon dioxide is desorbed from the rich stream in at least one regeneration zone at a temperature higher than the temperature of the sorption zone at a temperature from 100°

C. to 120°

C.

35. The process according to claim 31, wherein the sorbed carbon dioxide is desorbed from the rich stream by stripping the rich stream with gas in at least one regeneration zone.

36. The process according to claim 31, wherein the sorbed carbon dioxide is desorbed from the rich stream by stripping with CO₂ in at least one regeneration zone.

37. The process according to claim 31, wherein the sorbed carbon dioxide is desorbed from the rich stream in at least one regeneration zone and the desorbed CO₂ is recycled to the regeneration zone to strip the rich stream.

38. The process according to claim 31, wherein the aqueous liquid alkanolamine scrubbing solution consists essentially of an aqueous solution of 2-N-methylamino-1-propanol.

39. The process according to claim 31, wherein the aqueous liquid alkanolamine scrubbing solution comprises substantially no alkanolamines where both R₁ and R₂ are methyl, n is 1, and R₄ is —

OH.

40. The process according to claim 31, wherein the desorbing in step (ii) is accomplished by

(a) sending the rich amine solution to a first regeneration zone flash drum, where carbon dioxide is desorbed from the rich amine solution to form a first intermediate desorbed solution;

(b) sending the first intermediate desorbed solution to a stripping zone in which it is contacted, directly or indirectly, with a stripping medium to desorb further carbon dioxide from the first intermediate desorbed solution, thus forming a second intermediate desorbed solution; and

(c) optionally sending the second intermediate desorbed solution to a second regeneration flash drum, where still further carbon dioxide is desorbed from the second intermediate desorbed solution, thus forming a third intermediate desorbed solution,

wherein the second intermediate desorbed solution and/or the optional third intermediate desorbed solution is/are returned to the sorption zone as the lean stream in step (iii).

41. A high cyclic capacity carbon dioxide scrubbing process which comprises:

(i) contacting a natural gas stream containing carbon dioxide in an sorption zone with an aqueous liquid alkanolamine scrubbing solution of 2-N-methylamino-1-propanol at a total concentration of 2-N-methylamino-1-propanol of at least 4.0M of the alkanolamine and at a temperature of at least 30°

C. and a pressure of at least 0.025 bar to sorb the carbon dioxide from the natural gas stream into the amine solution and form a rich stream of the sorbed carbon dioxide in the amine solution in the form of alkanolamine carbamate and/or alkanolamine bicarbonate dissolved in the amine solution;

(ii) passing the rich amine stream from the sorption zone to a regeneration zone and desorbing the sorbed carbon dioxide as gas from the alkanolamine solution to form a lean solution containing a reduced concentration of sorbed carbon dioxide relative to the rich stream and regenerated 2-N-methylamino-1-propanol, which comprises

(a) sending the rich amine solution to a first regeneration zone flash drum, where carbon dioxide is desorbed from the rich amine solution to form a first intermediate desorbed solution;

(b) sending the first intermediate desorbed solution to a stripping zone in which it is contacted, directly or indirectly, with a stripping medium to desorb further carbon dioxide from the first intermediate desorbed solution, thus forming a second intermediate desorbed solution; and

(c) optionally sending the second intermediate desorbed solution to a second regeneration flash drum, where still further carbon dioxide is desorbed from the second intermediate desorbed solution, thus forming a third intermediate desorbed solution,

wherein the lean stream is comprised of the second intermediate desorbed solution and/or the optional third intermediate desorbed solution; and

(iii) returning the lean stream to the sorption zone.