Method of obtaining carbon dioxide from carbon dioxide-containing gas mixture

• US 8,617,292 B2
• Filed: 07/01/2010
• Issued: 12/31/2013
• Est. Priority Date: 12/15/2009
• Status: Active Grant

• Current Assignee: L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Original Assignee: L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Inventors: Kulkarni, Sudhir S., Sanders, Edgar S. Jr., Tranier, Jean-Pierre, Terrien, Paul, Hasse, David J.
• Primary Examiner(s): Greene, Jason M
• Application Number:
  US12/828,293
• Publication Number:
  US 20110247360A1
• Time in Patent Office: 1,279 Days
• Field of Search: 95/39, 95/51, 96/4, 96/14, 626/02, 626/17, 626/21, 626/24, 626/29, 629/28, 626/06, 607/83
• US Class Current: 95/51
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 53/002 by condensation
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 53/229 Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
• CPC Class Codes: B01D 71/50 Polycarbonates
• CPC Class Codes: B01D 71/52 Polyethers
• CPC Class Codes: B01D 71/5223 Polyphenylene oxide, phenyl ether polymers or polyphenylethers
• CPC Class Codes: B01D 71/64 Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: B01D 71/68 Polysulfones; Polyethersulfones
• CPC Class Codes: B01D 71/82 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
• CPC Class Codes: F25J 2205/20 using solidification of components
• CPC Class Codes: F25J 2205/40 using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
• CPC Class Codes: F25J 2205/80 using membrane, i.e. including a permeation step
• CPC Class Codes: F25J 2210/04 Mixing or blending of fluids with the feed stream
• CPC Class Codes: F25J 2210/70 Flue or combustion exhaust gas
• CPC Class Codes: F25J 2215/04 Recovery of liquid products
• CPC Class Codes: F25J 2220/82 Separating low boiling, i.e. more volatile components, e.g. He, H2, CO, Air gases, CH4
• CPC Class Codes: F25J 2230/08 Cold compressor, i.e. suction of the gas at cryogenic temperature and generally without afterstage-cooler
• CPC Class Codes: F25J 2230/30 Compression of the feed stream
• CPC Class Codes: F25J 2230/80 the fluid being carbon dioxide
• CPC Class Codes: F25J 2235/80 : the fluid being carbon dioxide
• CPC Class Codes: F25J 2240/80 : Hot exhaust gas turbine combustion engine
• CPC Class Codes: F25J 2240/90 : Hot gas waste turbine of an indirect heated gas for power generation
• CPC Class Codes: F25J 2245/02 : Recycle of a stream in general, e.g. a by-pass stream
• CPC Class Codes: F25J 2270/02 : Internal refrigeration with liquid vaporising loop
• CPC Class Codes: F25J 2270/06 : with multiple gas expansion loops
• CPC Class Codes: F25J 3/067 : separation of carbon dioxide production of carbon dioxide in general C01B32/00
• CPC Class Codes: Y02C 20/40 : of CO2

Abstract

Disclosed are methods of obtaining carbon dioxide from a CO₂-containing gas mixture. The methods combine the benefits of gas membrane separation with cryogenic temperatures.

Claims

1. A method of obtaining carbon dioxide from a CO₂-containing gas mixture, said method comprising the steps of:

obtaining a CO₂-containing gas mixture;

cooling the gas mixture to a temperature from 5°

C. to about −

60°

C.;

flowing the cooled gas mixture into a gas separation membrane module made of a polymeric material to produce a carbon dioxide-rich stream and a carbon dioxide-lean stream, wherein the polymeric material has a CO₂ solubility at 35°

C. and 10 bar pressure of >

0.03 [(cm³ of CO₂ at STP)/(cm³ of polymeric material)(cmHg)] and a glass transition temperature of >

210°

C.;

compressing the carbon dioxide-rich stream;

at least partially condensing the compressed carbon dioxide-rich stream through cooling;

subjecting the cooled, compressed carbon dioxide-rich stream to cryogenic phase separation to produce a CO₂ rich liquid and a CO₂ lean vapor stream; and

combining the CO₂ lean vapor stream with the CO₂-containing gas mixture.

2. The method of claim 1, wherein the polymeric material is selected from the group consisting of:

polyimides;

fluoropolysulfones;

poly (phenylene oxides);

poly (fluorocarbonates); and

condensation polymers of 2,2,2-trifluoroacetophenone and either biphenyl or terphenyl ether.

3. The method of claim 2 wherein the polymeric material is a polyimide polymer or copolymer having repeating units of formula (I):

4. The method of claim 3, wherein each R₁ is a molecular segment of formula (g) and each R₂ consists of formula (D).

5. The method of claim 3, wherein each R₁ is a molecular segment of formula (e) and each R₂ consists of formula (D).

6. The method of claim 3, wherein each R₁ is a molecular segment of formula (e) and each R₂ consists of formula (C).

7. The method of claim 3, wherein R₁ consists of molecular segments of formulae (a) and (e) in a 1:

1 ratio and each R₂ consists of formula (D).

8. The method of claim 3, wherein each R₁ is a molecular segment of formula (a) and each R₂ consists of formula (C).

9. The method of claim 3, wherein each R₁ is a molecular segment of formula (a) and each R₂ consists of formula (D).

10. The method of claim 3, wherein each R₁ is a molecular segment of formula (e) and each R₂ consists of formula (C).

11. The method of claim 3, wherein each R₁ is a molecular segment of formula ( ) and each R₂ consists of formula ( ).

12. The method of claim 3, wherein R₁ consists of molecular segments of formulae (a) and (c) in a 4:

1 ratio and each R₂ consists of formula (C).

13. The method of claim 3, wherein:

R₁ is of formula (a);

X, X₁, X₂, and X₃ are hydrogen; and

R₂ is of formula (D).

14. The method of claim 3, wherein:

R₁ is of formula (r);

X, X₁, and X₂ are methyl groups;

R₂ is of formula (C); and

Z is of formula (L).

15. The method of claim 3, wherein:

R₁ consists of molecular segments of formulae (a) and (c) in a 4;

1 ratio;

R₂ is of formula (C); and

Z is of formula (L).

16. The method of claim 3, wherein the polymeric material is BPDA-ppODA polymerized from 3,3′

,4,4′

-Biphenyltetracarboxylic dianhydride and 4,4′

oxydianiline.

17. The method of claim 3, wherein the polymeric material is BTDA-ppODA polymerized from 3,3′

,4,4′

-Benzophenone tetracarboxylic dianhydride and 4,4′

oxydianiline.

18. The method of claim 3, wherein the polymeric material is PMDA-MDA polymerized from pyromellitic dianhydride and methylene dianiline.

19. The method of claim 3, wherein the polymeric material is a polyimide polymerized from pyromellitic dianhydride and 4,4′

-oxydianiline.

20. The method of claim 3, wherein the polymeric material is 6FDA/BPDA-FDAM polymerized from hexafluorobisphenol dianhydride/3,3′

,4,4′

-Biphenyltetracarboxylic dianhydride and diamino mesitylene.

21. The method of claim 3, wherein the polymeric material is 6FDA-mpODA polymerized from hexafluorobisphenol dianhydride and 3,4′

oxydianiline.

22. The method of claim 3, wherein the polymeric material is 6FDA-ppODA polymerized from hexafluorobisphenol dianhydride and 4,4′

oxydianiline.

23. The method of claim 3, wherein the polymeric material is 6FDA-PDA polymerized from hexafluorobisphenol dianhydride and phenylene diamine.

24. The method of claim 3, wherein the polymeric material is 6FDA-IPDA polymerized from hexafluorobisphenol dianhydride and isophorone diamine.

29. The method of claim 2, wherein the polymeric material is a poly (phenylene oxide) selected from the group consisting of polyphenylene oxide (PPO) of formula (III);

NO₂-substituted PPO, and NH₂-substituted PPO

32. The method of claim 1, wherein the CO₂-containing gas mixture is compressed to a pressure from about 3 bar to about 60 bar prior to the cooling step.

34. The method of claim 1, wherein at least 90% of the CO₂ in the CO₂-containing gas mixture is recovered in the CO₂ rich liquid.

35. The method of claim 1, further comprising the step of expanding the carbon dioxide lean stream to yield a pressure-reduced carbon dioxide lean stream having a temperature of from about −

30°

C. to about −

60°

C.

36. The method of claim 1, wherein the CO₂-containing gas mixture is obtained from the flue gas of a combustion process, from a natural gas stream, or from a CO₂ exhaust of an fermentative ethanol production plant.

37. The method of claim 36, the CO₂-containing gas mixture is obtained from the flue gas of a combustion process and the combustion process is selected from the group consisting of a steam methane reforming (SMR) process, a blast furnace, and air-fired or oxygen-enhanced fossil fuel combustion processes.

38. The method of claim 37, wherein the combustion process is an oxygen-enhanced fossil fuel combustion process operated in full oxycombustion or partial oxycombustion mode.

39. The method of claim 38, wherein the oxygen-enhanced fossil fuel combustion process is operated in full oxycombustion mode, primary and secondary oxidants thereof being pure oxygen or synthetic air comprising oxygen and recycled flue gas.

40. The method of claim 38, wherein the oxygen-enhanced fossil fuel combustion process is operated in partial oxycombustion mode, a primary oxidant thereof being air and a secondary oxidant thereof being synthetic air comprising oxygen and recycled flue gas.

41. The method of claim 37, wherein the combustion process is an air-fired fossil fuel combustion process, the fossil fuel is coal, and the CO₂-containing gas mixture comprising about 8% v/v to about 16% v/v CO₂.

42. The method of claim 37, wherein the combustion process is an air-fired fossil fuel combustion process, the fossil fuel is natural gas, and the CO₂-containing gas mixture comprising about 3% v/v to about 10% v/v CO₂.

43. The method of claim 39, wherein the CO₂-containing gas mixture comprising about 60% v/v to about 90% v/v CO₂.

44. The method of claim 37, wherein the combustion process is a steam methane reforming (SMR) process, and the CO₂-containing gas mixture comprises about 15% v/v to about 90% v/v CO₂.

45. The method of claim 37, wherein the combustion process is a blast furnace, and the CO₂-containing gas mixture comprises about 20% v/v to about 90% v/v CO₂.

25. A method of obtaining carbon dioxide from a CO₂-containing gas mixture, said method comprising the steps of:

obtaining a CO₂-containing gas mixture;

cooling the gas mixture;

flowing the cooled gas mixture into a gas separation membrane module made of a polymeric material to produce a carbon dioxide-rich stream and a carbon dioxide-lean stream, wherein the polymeric material has a CO₂ solubility at 35°

C. and 10 bar pressure of >

0.03 [(cm³ of CO₂ at STP)/(cm³ of polymeric material)(cmHg)] and a glass transition temperature of >

210°

C.;

compressing the carbon dioxide-rich stream;

at least partially condensing the compressed carbon dioxide-rich stream through cooling; and

subjecting the cooled, compressed carbon dioxide-rich stream to cryogenic phase separation to produce a CO₂ rich liquid and a CO₂ lean vapor stream, wherein the polymeric material is a polysulfone having repeating units of formula (II)

26. The method of claim 25 wherein the polysulfone has an R₃ of formula (t) and is polymerized from 2,6-dihydroxynaphthalene, tetramethyl bisphenol-A, and bis(4-fluorophenyl)sulfone.

27. The method of claim 25, wherein the polysulfone has an R₃ of formula (u) and is polymerized from 2,6-dihydroxynaphthalene, hexafluoro bisphenol, and bis(4-fluorophenyl)sulfone.

28. The method of claim 25, wherein the polysulfone has an R₃ of formula (v) and is polymerized from 2,6-dihydroxynaphthalene, tetramethyl hexafluorobisphenol, and bis(4-fluorophenyl)sulfone.

30. A method of obtaining carbon dioxide from a CO₂-containing gas mixture, said method comprising the steps of:

obtaining a CO₂-containing gas mixture;

cooling the gas mixture;

flowing the cooled gas mixture into a gas separation membrane module made of a polymeric material to produce a carbon dioxide-rich stream and a carbon dioxide-lean stream, wherein the polymeric material has a CO₂ solubility at 35°

C. and 10 bar pressure of >

0.03 [(cm³ of CO₂ at STP)/(cm³ of polymeric material)(cmHg)] and a glass transition temperature of >

210°

C.;

compressing the carbon dioxide-rich stream;

at least partially condensing the compressed carbon dioxide-rich stream through cooling; and

subjecting the cooled, compressed carbon dioxide-rich stream to cryogenic phase separation to produce a CO₂ rich liquid and a CO₂ lean vapor stream, wherein the polymeric material is a poly (fluorocarbonate) selected from the group consisting of poly (tetrachlorohexafluorocarbonate) and poly (tetrabromohexafluorocarbonate).

31. A method of obtaining carbon dioxide from a CO₂-containing gas mixture, said method comprising the steps of:

obtaining a CO₂-containing gas mixture;

cooling the gas mixture;

flowing the cooled gas mixture into a gas separation membrane module made of a polymeric material to produce a carbon dioxide-rich stream and a carbon dioxide-lean stream, wherein the polymeric material has a CO₂ solubility at 35°

C. and 10 bar pressure of >

0.03 [(cm³ of CO₂ at STP)/(cm³ of polymeric material)(cmHg)] and a glass transition temperature of >

210°

C.;

compressing the carbon dioxide-rich stream;

at least partially condensing the compressed carbon dioxide-rich stream through cooling; and

subjecting the cooled, compressed carbon dioxide-rich stream to cryogenic phase separation to produce a CO₂ rich liquid and a CO₂ lean vapor stream, wherein the polymeric material is a condensation polymer of 2,2,2-trifluoroacetophenone with biphenyl ether, terphenyl ether or both biphenyl ether and terphenyl ether.

33. A method of obtaining carbon dioxide from a CO₂-containing gas mixture, said method comprising the steps of:

obtaining a CO₂-containing gas mixture;

cooling the gas mixture;

flowing the cooled gas mixture into a gas separation membrane module made of a polymeric material to produce a carbon dioxide-rich stream and a carbon dioxide-lean stream, wherein the polymeric material has a CO₂ solubility at 35°

C. and 10 bar pressure of >

0.03 [(cm³ of CO₂ at STP)/(cm³ of polymeric material)(cmHg)] and a glass transition temperature of >

210°

C.;

compressing the carbon dioxide-rich stream;

at least partially condensing the compressed carbon dioxide-rich stream through cooling; and

subjecting the cooled, compressed carbon dioxide-rich stream to cryogenic phase separation to produce a CO₂ rich liquid and a CO₂ lean vapor stream, wherein the gas mixture is cooled to a temperature from about −

20°

C. to about −

50°

C.