[미국특허]
Method for recovery of CO2 from gas streams
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C01B-017/16
C01B-017/00
출원번호
US-0459519
(2003-06-12)
발명자
/ 주소
Hakka,Leo E.
Ouimet,Michel A.
출원인 / 주소
Cansolv Technologies Inc.
대리인 / 주소
Bereskin &
인용정보
피인용 횟수 :
106인용 특허 :
11
초록▼
A process for recovering CO2 from a feed gas stream comprises treating the feed gas stream with a regenerated absorbent comprising at least one tertiary amine absorbent having a pK a for the amino function of from about 6.5 to about 9 in the presence of an oxidation inhibitor to obtain a CO2 rich st
A process for recovering CO2 from a feed gas stream comprises treating the feed gas stream with a regenerated absorbent comprising at least one tertiary amine absorbent having a pK a for the amino function of from about 6.5 to about 9 in the presence of an oxidation inhibitor to obtain a CO2 rich stream and subsequently treating the CO2 rich stream to obtain the regenerated absorbent and a CO2 rich product stream. The feed gas stream may also include SO2 and/or NOx.
대표청구항▼
What is claimed is: 1. A process for recovering CO2 from a feed gas stream comprising treating the feed gas stream with a regenerated absorbent comprising at least one tertiary amine absorbent having a pK a for the amino function of from about 6.5 to about 9 in the presence of an oxidation inhibito
What is claimed is: 1. A process for recovering CO2 from a feed gas stream comprising treating the feed gas stream with a regenerated absorbent comprising at least one tertiary amine absorbent having a pK a for the amino function of from about 6.5 to about 9 in the presence of an oxidation inhibitor to obtain a CO2 rich stream, maintaining a sufficient oxidation inhibitor concentration in the absorbent to essentially prevent the oxidation of the absorbent by molecular oxygen and subsequently treating the CO2 rich stream to obtain the regenerated absorbent and a CO2 rich product stream. 2. The process as claimed in claim 1 wherein the process further comprises selecting the at least one tertiary amine absorbent from the group consisting of methyldiethanolamine, triethanolamine, N,N'-di-(hydroxyalkyl)piperazine, N,N,N',N'-tetrakis(hydroxyalkyl)-1,6-hexanediamine, tertiary alkylamine sulfonic acids and mixtures thereof. 3. The process as claimed in claim 1 wherein the process further comprises selecting the at least one tertiary amine absorbent from the group consisting of methyldiethanolamine, N,N'-di-(2-hydroxyethyl)piperazine, N,N'-di-(3-hydroxypropyl)piperazine, N,N,N',N'-tetrakis(2-hydroxyethly)-1,6-hexanediamine, N,N,N',N'-tetrakis(2-hydroxypropyl)-1,6-hexanediamine, tertiary alkylamine sulfonic acids, triethanolamine, and mixtures thereof. 4. The process as claimed in claim 3 wherein the tertiary alkylamine sulfonic acid is selected from the group consisting of 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid, 4-(2-hydroxyethyl)-1-piperazinepropanesulfonic acid, 4-(2-hydroxyethyl)-1-piperazinebutanesulfonic acid, 4-(2-hydroxyethyl)piperazine-1-(2-hydroxypropanesulfonic acid), 1,4-piperazinedi(ethanesulfonic acid) and mixtures thereof. 5. The process as claimed in claim 1 wherein the process further comprises selecting the tertiary amine absorbent such that it has a vapour pressure less than about 1 mm Hg at 120째 C. as the pure compound. 6. The process as claimed in claim 1 wherein the absorbent further comprises at least one secondary amine. 7. The process as claimed in claim 6 further comprising selecting at least one piperazine as the secondary amine. 8. The process as claimed in claim 6 wherein the at least one secondary amine is selected from the group consisting of piperazine, N-(2-hydroxyethyl)piperazine and an N-(hydroxypropyl)piperazine and mixtures thereof. 9. The process as claimed in claim 6 wherein the at least one secondary amine is selected from the group consisting of piperazine, N-(2-hydroxyethyl)piperazine and mixtures thereof. 10. The process as claimed in claim 6 wherein the absorbent comprises an aqueous solution comprising 10-50 wt % of the tertiary amine and 1-40 wt % of a secondary amine. 11. The process as claimed in claim 6 wherein the absorbent comprises 10-50 wt % of the tertiary amine, 0-8 wt % of piperazine, 1-30 wt % of N-(2-hydroxyethyl)piperazine with the remainder comprising water. 12. The process as claimed in claim 1 wherein the CO2 rich stream is treated with steam to regenerate the absorbent. 13. The process as claimed in claim 1 further comprising removing only a portion of the heat stable salts from the absorbent. 14. The process as claimed in claim 1 in which the oxidation inhibitor comprises a free radical scavenger. 15. The process as claimed in claim 14 wherein the process further comprises selecting an alcohol, alkanolamine, thiosulfate and mixtures thereof as the free radical scavenger. 16. The process as claimed in claim 14 wherein the process further comprises selecting thiosulfate as the free radical scavenger. 17. The process as claimed in claim 1 wherein the process further comprises selecting at least one phenolic amine antioxidant or aromatic amine antioxidant as the free radical scavenger. 18. The process as claimed in claim 1 in which the oxidation inhibitor comprises an oxygen scavenger. 19. The process as claimed in claim 18 wherein the process further comprises selecting sulfite or bisulfite as the oxygen scavenger. 20. The process as claimed in claim 1 in which the oxidation inhibitor comprises a mixture of at least one oxygen scavenger and at least one free radical scavenger. 21. The process as claimed in claim 1 further comprising treating the regenerated absorbent to comprise greater than 0.05 wt. % thiosulfate. 22. The process as claimed in claim 1 further comprising adding a chelating agent to reduce metal ion catalyzed oxidation of the absorbent. 23. The process as claimed in claim 1 further comprising subjecting the absorbent to an ion exchange step to remove multivalent metal ions to reduce metal ion catalyzed oxidation of the absorbent. 24. The process as claimed in claim 1 wherein the absorbent is in solution and the process further comprises increasing the concentration of absorbent or salts in the solution to reduce the solubility of O2 in the solution. 25. The process as claimed in claim 1 wherein the feed gas stream further comprises NOx and the process further comprises treating the feed gas stream to remove at least a portion of the NO x. 26. The process as claimed in claim 1 wherein the feed gas stream further comprises NOx and the process further comprises providing a reagent to react with the NOx to produce reaction products comprising molecular nitrogen, sulfonated ammonia chemicals, and sulfate and/or dithionate ions, treating the CO2 rich stream to remove sulfate andlor dithionate ions and regenerate the reagent and adjusting the pH of the regenerated absorbent from about 7 to about 9.5. 27. The process as claimed in claim 26 further comprising selecting the reagents from the group consisting of a metal chelate, sulfite and mixtures thereof. 28. The process as claimed in claim 27 further comprising selecting the metal chelate from the group consisting of iron nitrilotriacetic acid, iron ethylenediaminetetraacetic acid, iron diethylenetriaminepentaacetic acid and mixtures thereof. 29. A process for recovering SO2 and CO2 from a feed gas stream comprising: (a) treating the feed gas stream in an SO2 scrubbing loop with a first absorbent stream to obtain a SO2 rich stream and a SO2 lean stream and subsequently treating the SO2 rich stream to obtain a first regenerated absorbent stream which is used in the SO2 scrubbing loop; (b) treating the SO2 lean stream in a CO2 scrubbing loop with a second absorbent stream to obtain a CO2 rich stream and subsequently treating the CO2 rich stream to obtain a second regenerated absorbent stream which is used in the CO2 scrubbing loop; and, (c) treating at least a potion of one or both of the first and second regenerated absorbent streams to remove heat stable salts wherein the absorbent used in each of the scrubbing loops comprises at least one tertiary amine and at least one secondary amine as an activator. 30. The process as claimed in claim 29 further comprising selecting the tertiary amine from N,N'-di-(2-hydroxyethyl)piperazine, N, N'-di-(3-hydroxypropyl)piperazine, N,N,N',N'-tetrakis(2-hydroxypropyl)-1, 6-hexanediamine or mixtures thereof, and selecting the secondary amine from N-2-hydroxyethylpiperazine, piperazine, a N-(hydroxypropyl) piperazine or mixtures thereof as an activator. 31. The process as claimed in claim 29 wherein only the first regenerated absorbent stream is treated to remove heat stable salts and a bleed stream of the treated amine is bled into the CO2 removal loop and a bleed steam from the CO2 scrubbing loop is provided to the SO2 scrubbing loop. 32. The process as claimed in claim 29 further comprising adjusting the treatment of the feed gas stream in the SO2 scrubbing loop such that the SO2 lean gas stream has a concentration of SO2 so as to maintain a concentration of sulfite in the CO2 scrubbing loop sufficient to essentially prevent the oxidation of the absorbent by molecular oxygen. 33. The process as claimed in claim 29 wherein the feed gas stream further comprises NOx and the process further comprises providing a metal chelate to react with the NOx to produce sulfate and/or dithionate ions, treating the CO2 rich stream to remove sulfate and/or dithionate ions and regenerate the reagent and adjusting the pH of the second regenerated absorbent from about 7 to about 9.5. 34. The process as claimed in claim 33 further comprising selecting the metal chelate from the group consisting of iron nitrilotriacetic acid, iron ethylenediaminetetraacetic acid, iron diethylenetriaminepentaacetic acid and mixtures thereof. 35. The process as claimed in claim 29 further comprising conducting steps (a) and (b) in a single adsorption column. 36. The process as claimed in claim 29 further comprising selecting the same amines for each loop. 37. The process as claimed in claim 29 further comprising conducting step (a) at a pH in the range of about 3-6 and step (b) at a pH in the range of about 6-9. 38. A process for removal of CO2 and NOx from a gas stream containing SO2 at a mole ratio <5 times the NOx content, comprising treating the feed gas stream to obtain a CO2 rich stream by exposing the feed gas stream to a regenerated absorbent comprising at least one tertiary amine absorbent having a pK a for the amino function of from about 6.5 to about 9, an oxidation inhibitor, a metal chelate and sulfite and or other reactants and reducing agents to react with the NOx to produce reaction products comprising molecular nitrogen, sulfonated ammonia chemicals, and sulfate and/or dithionate ions, treating the CO2 rich stream to remove heat stable salts including sulfate and/or dithionate ions and adjusting the pH of the regenerated absorbent from about 7 to about 9.5 and subsequently treating the CO2 rich stream to obtain the regenerated absorbent. 39. The process as claimed in claim 38 wherein the regenerated absorbent comprises greater than 0.5 wt. % sulfite, greater than 0.05 wt. % thiosulfate and greater than 0.005 molar FeEDTA. 40. The process as claimed in claim 39 wherein the regenerated absorbent has a pH in the range 6-9.5. 41. The process as claimed in claim 40 wherein the regenerated absorbent has a pH in the range 7-9.5 and the maximum concentrations of the metal chelate and sulfite and/or other reactants and reducing agents are each equal to their solubility limit at 20째 C. 42. A process for recovering SO2 and CO2 from a feed gas stream comprising: (a) subjecting the feed gas stream to a SO2 removal step using a SO2 absorbent and recovering a SO2 lean stream and a SO2 rich absorbent stream; (b) regenerating the SO2 absorbent at a first temperature to obtain a regenerated SO2 absorbent stream and a first vapour stream; (c) subjecting the SO2 lean stream to a CO2 removal step using a CO2 absorbent and recovering a CO2 lean stream and a CO2 rich absorbent stream; (d) regenerating the CO2 absorbent at a second temperature to obtain a regenerated CO2 absorbent stream and a second vapour stream wherein the first temperature is lower than the second temperature so that at least a portion of the second vapour stream is used to regenerate the SO2 absorbent. 43. The process as claimed in claim 42 wherein the SO2 absorbent is regenerated by steam produced in a reboiler and at least a portion of the second vapour stream is used to provide heat to the reboiler. 44. The process as claimed in claim 43 wherein the second vapour stream is used to indirectly heat to the reboiler and is subsequently returned to be used in the regeneration of the CO2 absorbent.
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