Method for the purification of a gas containing CO 2

• US 8,465,570 B2
• Filed: 07/08/2008
• Issued: 06/18/2013
• Est. Priority Date: 07/13/2007
• 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: Alban, Bruno, Claeys, Christophe, Court, Philippe, Darde, Arthur, De Smedt, Guillaume, Ha, Bao, Hasanov, Vladimir, Jallais, Simon, Monereau, Christian, Moreau, Serge, Renou, Elise, Sanchez-Molinero, Ivan, Tranier, Jean-Pierre
• Primary Examiner(s): Hopkins, Robert A
• Application Number:
  US12/668,536
• Publication Number:
  US 20100263529A1
• Time in Patent Office: 1,806 Days
• Field of Search: 95/39, 95/41, 95/96, 951/48, 961/30
• US Class Current: 95/39
• CPC Class Codes: B01D 2253/102 Carbon
• CPC Class Codes: B01D 2256/22 Carbon dioxide
• CPC Class Codes: B01D 2257/102 Nitrogen
• CPC Class Codes: B01D 2257/104 Oxygen
• CPC Class Codes: B01D 2257/11 Noble gases
• CPC Class Codes: B01D 2257/2045 Hydrochloric acid
• CPC Class Codes: B01D 2257/2047 Hydrofluoric acid
• CPC Class Codes: B01D 2257/2064 Chlorine
• CPC Class Codes: B01D 2257/302 Sulfur oxides
• CPC Class Codes: B01D 2257/304 Hydrogen sulfide
• CPC Class Codes: B01D 2257/404 Nitrogen oxides other than dinitrogen oxide
• CPC Class Codes: B01D 2257/408 Cyanides, e.g. hydrogen cyanide (HCH)
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2257/60 Heavy metals or heavy metal compounds
• CPC Class Codes: B01D 2257/708 Volatile organic compounds V.O.C.'s
• CPC Class Codes: B01D 2257/80 Water
• CPC Class Codes: B01D 53/002 by condensation
• CPC Class Codes: B01D 53/0462 Temperature swing adsorption
• CPC Class Codes: B01D 53/047 Pressure swing adsorption
• CPC Class Codes: B01D 53/12 according to the "fluidised technique"
• CPC Class Codes: C01B 32/50 : Carbon dioxide
• CPC Class Codes: F25J 2205/40 : using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
• CPC Class Codes: F25J 2205/60 : using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
• CPC Class Codes: F25J 2210/70 : Flue or combustion exhaust gas
• 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 2230/30 : Compression of the feed stream
• CPC Class Codes: F25J 2230/80 : the fluid being carbon dioxide
• 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
• CPC Class Codes: Y02P 20/129 : Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
• CPC Class Codes: Y02P 20/151 : Reduction of greenhouse gas [GHG] emissions, e.g. CO2
• CPC Class Codes: Y02P 20/54 : using solvents, e.g. supercritical solvents or ionic liquids

Abstract

A method for the purification of a feed gas stream containing at least CO₂ and at least one impurity with by the incorporation of a purification step, enabling water to be at least partially removed is provided.

Claims

1. A method for the purification of a feed gas stream, comprising;

introducing a feed gas stream comprising CO₂, water and at least one impurity chosen from the group consisting of nitrogen, oxygen, argon, rare gases, SOx, CS₂, H₂S, NOx, HCN, HCl, CHCl₃, HF, volatile organic compounds, and the following metals;

mercury, arsenic, iron, nickel, tin, lead, cadmium, vanadium, molybdenum and selenium and compounds derived from these metals,

a) pretreating the feed gas stream, thereby eliminating, at least partially, at least one of the impurities;

b) compressing the pretreated gas stream to a pressure of between 10 and 50 bar;

reducing the temperature of the compressed, pretreated gas steam to a temperature of <

5°

C.;

c) eliminating at least one impurity present in the compressed gas stream with the aid of exchangers combined with separators, the impurity selected from the group consisting of nitrogen, oxygen, argon and the rare gases;

d) recovering a purified gas stream enriched in CO₂ in the liquid, gaseous or supercritical state;

wherein, between steps a) and c), a purification step is carried out enabling water contained in the gas stream to be at least partially eliminated, and at least partially eliminating at least one other impurity chosen from the group consisting of nitrogen, oxygen, argon, the rare gases, SO_x, CS₂, H₂S, NOx, HCN, HCl, CHCl₃, HF, volatile organic compounds, the following metals, mercury, arsenic, selenium, cadmium, iron, and nickel, and compounds derived from these metals, wherein between steps a) and c), a purification step is carried out enabling water contained in the gas stream to be at least partially eliminated, and at least partially eliminating at least partially SOx_x and wherein the compression step b comprises successive compression phases and in that the purification step is carried out between two successive compression phases of said compression step b).

2. The method of claim 1, wherein after step d), the gas stream is in either the liquid state or the supercritical state, and stored.

3. The method of claim 1, wherein after step d), the gas stream is in either the supercritical state or the gaseous state, and transported.

4. The method of claim 1, wherein the purification step is carried out between step a) and step b).

5. The method of claim 1, wherein the purification step is carried out between step b) and step c).

6. The method as of claim 1, wherein the purification step is carried out at a pressure of between 2 bar absolute and 25 bar absolute.

7. The method of claim 6, wherein the purification step is carried out at a pressure of between 3 and 9 bar absolute.

8. The method of claim 7, wherein the purification step is carried out at a pressure of between 3.5 and 6 bar absolute.

9. The method of claim 1, wherein during the purification step, one or more organic materials are employed for at least partially eliminating water contained in the gas stream.

10. The method of claim 1, wherein during the purification step, one or more inorganic materials are employed for at least partially eliminating water contained in the gas stream.

11. The method of claim 9, wherein during the purification step, one or more organic materials are also employed that are identical to or different from those for eliminating water, for at least partially eliminating at least one impurity chosen from the group consisting of nitrogen, oxygen, argon, the rare gases, SOx, CS₂, H₂S, NOx, HCN, HCl, CHCl₃, HF, volatile organic compounds, the following metals:

mercury, arsenic, selenium, cadmium, iron, and nickel carbonyl, and compounds derived from these metals.

12. The method of claim 9, wherein during the purification step, one or more organic materials are also employed that are identical to or different from those for eliminating water, for at least partially eliminating SO_x.

13. The method of claim 10, wherein during the purification step, one or more inorganic materials are also employed that are identical to or different from those for eliminating water, for at least partially eliminating at least one impurity chosen from the group consisting of nitrogen, oxygen, argon, the rare gases, SOx, CS₂, H₂S, NOx, HCN, HCl, CHCl₃, HF, volatile organic compounds, the following metals:

mercury, arsenic, selenium, cadmium, iron, and nickel carbonyl, and compounds derived from these metals.

14. The method of claim 10, wherein during the purification step, one or more inorganic materials are also employed that are identical to or different from those for eliminating water, for at least partially eliminating SO_x.

15. The method of claim 9, wherein the organic materials are adsorbent materials.

16. The method of claim 10, wherein the inorganic materials are adsorbent materials.

17. The method of claim 15, wherein the adsorbent materials are employed in at least one fluidized bed reactor.

18. The method of claim 15, characterized in that the adsorbent materials are employed in at least one fixed bed reactor.

19. The method of claim 17, wherein at least one fluidized bed or falling bed reactor in the regeneration phase corresponds to each fluidized bed reactor in the adsorption phase.

20. The method of claim 17, wherein all the reactors are subjected to the same cycle of the PSA, VSA or TSA type.

21. The method of claim 20, wherein at least one of the reactors is subjected to a TSA cycle and at least one of the reactors is subjected to a PSA cycle.

22. The method of claim 20, wherein at least one reactor is subjected to a TSA cycle and a PSA cycle at the same time.

23. The method of claim 1, wherein at least one residual gas is recovered during the purification step.

24. The method of claim 23, wherein during the purification step, a first residual gas is recovered having an NOx content T1 and a second residual gas having an NOx content T2, such that T2<

T1.

25. The method of claim 24, wherein the first residual gas is recycled in an oxy-furnace.

26. The method of claim 23, wherein at least one residual gas is recycled upstream of the purification step in the main stream.

27. The method of claim 23, wherein the first residual gas is recycled upstream of the purification step in the main stream.

28. The method of claim 24, wherein the second residual gas is either discharged directly to atmosphere or treated and then discharged to atmosphere.

29. The method of claim 24, wherein the second residual gas is treated by washing and/or refrigeration followed by gas-liquid separation.

30. The method of claim 15, characterized in that at least one portion of the CO₂-rich gas stream coming from the purification step enables at least part of the adsorbent materials of the purification unit to be regenerated.

31. The method of claim 15, wherein a carbon bed is employed in the purification step and said spent carbon is then mixed with fuel in an oxycombustion furnace.

32. The method of claim 1, wherein the feed gas stream is an oxycombustion fume.

33. The method of claim 1, wherein the volatile organic compounds are chosen from the group consisting of formaldehyde, acetaldehyde, formic acid, acrolein and acetic acid.

34. The method of claim 1, wherein the pre-treatment a) comprises at least one of the following treatments:

catalysis, filtration, washing and desulfuration, it being possible for washing to be coupled with cooling of the feed gas stream.