Process for separating nitrogen from methane using microchannel process technology

• US 7,250,074 B2
• Filed: 08/26/2004
• Issued: 07/31/2007
• Est. Priority Date: 08/29/2003
• Status: Expired due to Fees

• Current Assignee: Velocys Incorporated (Velocys PLC)
• Original Assignee: Velocys Incorporated (Velocys PLC)
• Inventors: Litt, Robert Dwayne, Qiu, Dongming, Tonkovich, Anna Lee, Arora, Ravi, Neagle, Paul, Dritz, Terence Andrew, Pagnotto, Kristina M., Lamont, Michael Jay
• Primary Examiner(s): LAWRENCE JR, FRANK M
• Application Number:
  US10/927,370
• Publication Number:
  US 20050045030A1
• Time in Patent Office: 1,069 Days
• Field of Search: 95/90, 95/96, 951/06, 951/14, 951/15, 951/30, 951/43, 951/48, 959/03, 961/26, 961/31
• US Class Current: 95/130
• CPC Class Codes: B01D 2253/102 Carbon
• CPC Class Codes: B01D 2253/104 Alumina
• CPC Class Codes: B01D 2253/106 Silica or silicates
• CPC Class Codes: B01D 2253/108 Zeolites
• CPC Class Codes: B01D 2253/202 Polymeric adsorbents
• CPC Class Codes: B01D 2253/204 Metal organic frameworks (MOF's)
• CPC Class Codes: B01D 2253/3425 Honeycomb shape
• CPC Class Codes: B01D 2256/10 Nitrogen
• CPC Class Codes: B01D 2256/24 Hydrocarbons
• CPC Class Codes: B01D 2257/102 Nitrogen
• CPC Class Codes: B01D 2257/7022 Aliphatic hydrocarbons
• CPC Class Codes: B01D 2259/40096 by using electrical resistance heating
• CPC Class Codes: B01D 53/0446 Means for feeding or distributing gases
• CPC Class Codes: B01D 53/0462 Temperature swing adsorption
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C07C 7/11 by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
• CPC Class Codes: C07C 9/04 Methane production by treatment of sewage C02F11/04; natural gas, synthetic natural gas C10L3/06
• CPC Class Codes: C10L 3/10 Working-up natural gas or synthetic natural gas
• CPC Class Codes: Y02C 20/20 of methane
• CPC Class Codes: Y02C 20/40 of CO2
• CPC Class Codes: Y10S 95/903 : Carbon

Abstract

The disclosed invention relates to a process for separating methane or nitrogen from a fluid mixture comprising methane and nitrogen, the process comprising: (A) flowing the fluid mixture into a microchannel separator, the microchannel separator comprising a plurality of process microchannels containing a sorption medium, the fluid mixture being maintained in the microchannel separator until at least part of the methane or nitrogen is sorbed by the sorption medium, and removing non-sorbed parts of the fluid mixture from the microchannel separator; and (B) desorbing the methane or nitrogen from the sorption medium and removing the desorbed methane or nitrogen from the microchannel separator. The process is suitable for upgrading methane from coal mines, landfills, and other sub-quality sources.

Claims

1. A process for separating methane or nitrogen from a fluid mixture comprising methane and nitrogen, the process comprising:

(A) flowing the fluid mixture into a microchannel separator, the microchannel separator comprising a plurality of process microchannels containing a sorption medium, the sorption medium having a preferential affinity for sorbing methane over nitrogen, the fluid mixture being maintained in the microchannel separator until at least part of the methane is sorbed by the sorption medium, and removing non-sorbed parts of the fluid mixture from the microchannel separator;

(B) desorbing the methane from the sorption medium and removing the desorbed methane from the microchannel separator; and

wherein tail gas is produced during step (A).

2. The process of claim 1 wherein the temperature during step (A) is in the range from about 0°

C. to about 200°

C.

3. The process of claim 1 wherein the temperature during step (B) is in the range from about 20°

C. to about 400°

C.

4. The process of claim 1 wherein the microchannel separator further comprises a header, the header being a multiple entry header which comprises a fluid mixture section, a purging fluid section, and a flush fluid section;

the fluid mixture flows from the fluid mixture section into the process microchannels;

a purging fluid flows from the purging fluid section into the process microchannels; and

the flush fluid flows from the flush fluid section into the process microchannels.

5. The process of claim 1 wherein the process further comprises the step of regenerating the sorption medium subsequent to step (B).

6. The process of claim 1 wherein the process microchannels are at a first average sorbent temperature during step (A) and a second average sorbent temperature during step (B), the first temperature being lower than the second temperature.

7. The process of claim 1 wherein the process microchannels are at a first average sorbent temperature at the beginning of step (A) and a second average sorbent temperature at the end of step (A), the first temperature being higher than the second temperature.

8. The process of claim 1 wherein the process microchannels are heated using a resistance heater.

9. The process of claim 1 wherein the sorption medium comprises a metal structure that functions as a resistance heater.

10. The process of claim 1 wherein the process microchannels exchange heat with heat exchange channels.

11. The process of claim 10 wherein the heat exchange channels comprise microchannels.

12. The process of claim 10 wherein fluid flowing through the process microchannels flows in a first direction, and a heat exchange fluid flows through the heat exchange channels in a second direction, the second direction being cross current relative to the first direction.

13. The process of claim 1 wherein the process microchannels are made of a material comprising:

steel;

aluminum;

titanium;

nickel;

platinum;

rhodium;

copper;

chromium;

brass;

an alloy of any of the foregoing metals;

a polymer;

ceramics;

glass;

a composite comprising a polymer and fiberglass;

quartz;

silicon;

or a combination of two or more thereof.

14. The process of claim 10 wherein the heat exchange channels are made of a material comprising:

steel;

aluminum;

titanium;

nickel;

platinum;

rhodium;

copper;

chromium;

brass;

an alloy of any of the foregoing metals;

a polymer;

ceramics;

glass;

a composite comprising polymer and fiberglass;

quartz;

silicon;

or a combination of two or more thereof.

15. The process of claim 1 wherein the sorption medium is in the form of a flow-by sorption medium.

16. The process of claim 1 wherein the sorption medium is in the form of a flow-through sorption medium.

17. The process of claim 1 wherein the process microchannels have interior surfaces and the sorption medium is coated on the interior surfaces of the process microchannels.

18. The process of claim 1 wherein the sorption medium is in the form of particulate solids.

19. The process of claim 1 wherein the sorption medium is in the form of a foam, felt, wad, gauze, honeycomb, fin assembly, or a combination of two or more thereof.

20. The process of claim 19 wherein the foam, felt, wad, gauze or fin assembly functions as a resistance heater.

21. The process of claim 1 wherein the sorption medium has a serpentine configuration.

22. The process of claim 1 wherein the sorption medium occupies about 1 to about 99 percent of the cross sectional area of at least one cross section of the process microchannel.

23. The process of claim 1 wherein the sorption medium comprises metal-organic complex, copper metal complex, zeolite, activated carbon, microporous carbon powder, porous carbon foam, carbon nanotubes, or a combination of two or more thereof.

24. The process of claim 1 wherein at least about 5% by volume of the methane sorbed during step (A) is desorbed during step (B), the time to complete steps (A) and (B) being up to about 10 seconds.

25. The process of claim 1 wherein the sorption medium is at a first average sorbent temperature during step (A) and a second average sorbent temperature during step (B), the difference between the first temperature and the second temperature being about 1°

C. to about 200°

C.

26. The process of claim 1 wherein the fluid mixture prior to step (A) comprises methane, nitrogen and carbon dioxide.

27. The process of claim 1 wherein the fluid mixture prior to step (A) comprises methane, nitrogen, carbon dioxide, oxygen and water vapor.

28. The process of claim 1 wherein the concentration of methane in the fluid mixture prior to step (A) is from about 1% to about 98% by volume.

29. The process of claim 1 wherein the fluid mixture comprises a methane containing composition derived from a coal mine or landfill, the process microchannels being at a first average sorbent temperature during step (A) and a second average sorbent temperature during step (B), the first average sorbent temperature being lower than the second average sorbent temperature.

30. The process of claim 1 wherein at least about 50% by volume of the methane in the fluid mixture entering the microchannel separator is recovered.

31. The process of claim 1 wherein the microchannel separator further comprises a microchannel separator core for housing the process microchannels, the flow of the fluid mixture through the process microchannels being at least about 20 standard cubic meters per hour per cubic meter of volume of the microchannel separator core, the recovery of methane or nitrogen from the fluid mixture being at least about 50% by volume of the methane or nitrogen in the fluid mixture entering the microchannel separator.

32. The process of claim 1 wherein the tail gas is used as a source of energy.

33. The process of claim 32 wherein at least a portion of the tail gas is combusted within a microchannel.

34. The process of claim 1 wherein the process microchannels are heated during steps (A) and/or (B) by a heat exchange fluid flowing through heat exchange channels, the heat exchange fluid being heated at least in part by combustion of the tail gas.

35. The process of claim 1 wherein during step (A) a purging fluid flows through the process microchannels to remove non-sorbed parts of the fluid mixture from the microchannel separator.

36. The process of claim 1 wherein during step (A) the temperature and/or pressure within the process microchannels is increased to remove non-sorbed parts of the fluid mixture from the microchannel separator.

37. The process of claim 1 wherein during step (B) a flush fluid flows through the process microchannel to remove desorbed methane or nitrogen from the microchannel separator.

38. The process of claim 1 wherein during step (B) the temperature and/or pressure within the process microchannels is increased to remove desorbed methane from the microchannel separator.

39. A process for separating methane or nitrogen from a fluid mixture comprising methane and nitrogen, the process comprising:

(A) flowing the fluid mixture into a microchannel separator, the microchannel separator comprising a plurality of process microchannels containing a sorption medium, the sorption medium comprising microporous carbon powder, the fluid mixture being maintained in the microchannel separator until at least part of the methane is sorbed by the sorption medium, the time for sorbing methane being in the range from about 0.1 to about 10 seconds, and removing non-sorbed parts of the fluid mixture from the microchannel separator; and

(B) desorbing the methane from the sorption medium and removing the desorbed methane from the microchannel separator, the average sorbent temperature in the process microchannels during step (B) being in the range from about 5000 to about 70°

C., the average sorbent temperature in the process microchannels during step (A) being in the range from about 30°

C. to about 50°

C.

40. The process of claim 39 wherein the temperature in the process microchannels during step (A) is about 40°

C.

41. The process of claim 39 wherein the temperature in the process microchannels during step (B) is about 60°

C.

42. The process of claim 39 wherein tail gas is produced during step (A).

43. The process of claim 42 wherein the tail gas is used as a source of energy.

44. The process of claim 42 wherein the process microchannels are heated during steps (A) and/or (B) by a heat exchange fluid flowing through heat exchange channels, the heat exchange fluid being heated at least in part by combustion of the tail gas.

45. The process of claim 39 wherein the pressure within the process microchannels is in the range from about 6 to about 8 atmospheres gauge pressure.

46. The process of claim 39 wherein the process microchannels are heated during steps (A) and/or (B) and a compressor is used to increase the pressure of the fluid mixture, the compressor producing heat, the heat from the compressor being used as an energy source to provide at least part of the heat for heating the process microchannels.

47. A process for separating methane or nitrogen from a fluid mixture comprising methane and nitrogen, the process comprising:

(A) flowing the fluid mixture into a microchannel separator, the microchannel separator comprising a plurality of process microchannels containing a sorption medium, the fluid mixture being maintained in the microchannel separator until at least part of the methane or nitrogen is sorbed by the sorption medium, and removing non-sorbed parts of the fluid mixture from the microchannel separator; and

(B) desorbing the methane or nitrogen from the sorption medium and removing the desorbed methane or nitrogen from the microchannel separator;

wherein the process microchannels are at a first average sorbent temperature during step (A) and a second average sorbent temperature during step (B), the first temperature being higher than the second temperature.

48. A process for separating methane or nitrogen from a fluid mixture comprising methane and nitrogen, the process comprising:

(A) flowing the fluid mixture into a microchannel separator, the microchannel separator comprising a plurality of process microchannels containing a sorption medium, the fluid mixture being maintained in the microchannel separator until at least part of the methane or nitrogen is sorbed by the sorption medium, and removing non-sorbed parts of the fluid mixture from the microchannel separator; and

(B) desorbing the methane or nitrogen from the sorption medium and removing the desorbed methane or nitrogen from the microchannel separator;

wherein the process microchannels exchange heat with heat exchange channels, fluid flowing through the process microchannels flows in a first direction, and a heat exchange fluid flows through the heat exchange channels in a second direction, the second direction being cocurrent relative to the first direction.

49. A process for separating methane or nitrogen from a fluid mixture comprising methane and nitrogen, the process comprising:

(A) flowing the fluid mixture into a microchannel separator, the microchannel separator comprising a plurality of process microchannels containing a sorption medium, the fluid mixture being maintained in the microchannel separator until at least part of the methane or nitrogen is sorbed by the sorption medium, and removing non-sorbed parts of the fluid mixture from the microchannel separator; and

(B) desorbing the methane or nitrogen from the sorption medium and removing the desorbed methane or nitrogen from the microchannel separator;

wherein the sorption medium is in the form of a flow-by structure with an adjacent gap, a foam with an adjacent gap, a fin assembly with gaps, a washcoat on an inserted substrate, or a gauze that is parallel to the flow direction with a corresponding gap for flow.

50. A process for separating methane or nitrogen from a fluid mixture comprising methane and nitrogen, the process comprising:

(A) flowing the fluid mixture into a microchannel separator, the microchannel separator comprising a plurality of process microchannels containing a sorption medium, wherein the sorption medium comprises microporous carbon powder, the fluid mixture being maintained in the microchannel separator until at least part of the methane or nitrogen is sorbed by the sorption medium, and removing non-sorbed parts of the fluid mixture from the microchannel separator; and

(B) desorbing the methane or nitrogen from the sorption medium and removing the desorbed methane or nitrogen from the microchannel separator.

51. A process for separating methane or nitrogen from a fluid mixture comprising methane and nitrogen, the process comprising:

(A) flowing the fluid mixture into a microchannel separator, the microchannel separator comprising a plurality of process microchannels containing a sorption medium, the fluid mixture being maintained in the microchannel separator until at least part of the methane or nitrogen is sorbed by the sorption medium, and removing non-sorbed parts of the fluid mixture from the microchannel separator; and

(B) desorbing the methane or nitrogen from the sorption medium and removing the desorbed methane or nitrogen from the microchannel separator;

wherein the sorption medium is derived from Fe(II), Co(II), Cu(I), V(II), Mn(II), Mn(III), Cr(II), Ag(I), Rh(I), Rh(II), Rh(III), U(IV), V(IV), Ru(II), Ru(IV), Ti(III), Cr(IV), Bi(III), Ni(II), W(V), W(IV), Mo(II), Mo(III), Mo(IV), Mo(V), Mo(VI), or a combination of two or more thereof.

52. A process for separating methane or nitrogen from a fluid mixture comprising methane and nitrogen, the process comprising:

(A) flowing the fluid mixture into a microchannel separator, the microchannel separator comprising a plurality of process microchannels containing a sorption medium, the fluid mixture being maintained in the microchannel separator until at least part of the methane or nitrogen is sorbed by the sorption medium, and removing non-sorbed parts of the fluid mixture from the microchannel separator; and

(B) desorbing the methane or nitrogen from the sorption medium and removing the desorbed methane or nitrogen from the microchannel separator;

wherein the sorption medium is derived from;

dipyridyl;

2,6-[1-(2-imidazol-4-ylethylimino) ethyl pyridine];

cyclen;

cyclam;

a Schiff base ligand;

acetyl acetonate or an oligomer or polymer thereof;

a carboxylate;

bipyridyl or an oligomer or polymer thereof;

a porphyrin or an oligomer or polymer thereof;

a corin or an oligomer or polymer thereof;

a polyamide;

a protein;

8-hydroxy quinoline or an oligomer or polymer thereof;

ethyl cysteinate or an oligomer or polymer thereof;

an N-alkyl alkanohydroxamic acid;

dimethyiglyoxime;

sym-diethylethylenediamine;

or a combination of two or more thereof.

53. A process for separating methane or nitrogen from a fluid mixture comprising methane and nitrogen, the process comprising:

(A) flowing the fluid mixture into a microchannel separator, the microchannel separator comprising a plurality of process microchannels containing a sorption medium, the fluid mixture being maintained in the microchannel separator until at least part of the methane or nitrogen is sorbed by the sorption medium, and removing non-sorbed parts of the fluid mixture from the microchannel separator; and

(B) desorbing the methane or nitrogen from the sorption medium and removing the desorbed methane or nitrogen from the microchannel separator;

wherein the sorption medium comprises silica gel, foamed copper, sintered stainless steel fiber, alumina, poly(methyl methacrylate), polysulfonate, poly(tetrafluoroethylene), iron, nickel sponge, nylon, polyvinylidene difluoride, polypropylene, polyethylene, polyethylene ethylketone, polyvinyl alcohol, polyvinyl acetate, polyacrylate, polymethylmethacrylate, polystyrene, polyphenylene sulfide, polysulfone, polybutylene, or a combination of two or more thereof.

54. A process for upgrading sub-quality methane gas wherein the sub-quality methane gas comprises methane and nitrogen, the process comprising:

(A) flowing the sub-quality methane gas into a microchannel separator, the microchannel separator comprising a plurality of process microchannels containing a sorption medium, the sub-quality methane gas being maintained in the microchannel separator until at least part of the methane is sorbed by the sorption medium, and removing non-sorbed parts of the sub-quality methane gas from the microchannel separator; and

(B) desorbing the methane from the sorption medium and removing the desorbed methane from the microchannel separator;

wherein the sub-quality methane gas further comprises water vapor and the water vapor is separated from the sub-quality methane gas prior to step (A).

55. A process for upgrading sub-quality methane gas wherein the sub-quality methane gas comprises methane and nitrogen, the process comprising:

(A) flowing the sub-quality methane gas into a microchannel separator, the microchannel separator comprising a plurality of process microchannels containing a sorption medium, the sub-quality methane gas being maintained in the microchannel separator until at least part of the methane is sorbed by the sorption medium, and removing non-sorbed parts of the sub-quality methane gas from the microchannel separator; and

(B) desorbing the methane from the sorption medium and removing the desorbed methane from the microchannel separator;

wherein the sub-quality methane gas further comprises oxygen and/or carbon dioxide and the oxygen and/or carbon dioxide is separated from the sub-quality methane gas subsequent to step (B).

56. A process for separating methane or nitrogen from a fluid mixture comprising methane and nitrogen, the process comprising:

(A) flowing the fluid mixture into a microchannel separator, the microchannel separator comprising a plurality of process microchannels containing a sorption medium, the sorption medium having a preferential affinity for sorbing methane over nitrogen, the fluid mixture being maintained in the microchannel separator until at least part of the methane is sorbed by the sorption medium, and removing non-sorbed parts of the fluid mixture from the microchannel separator;

(B) desorbing the methane from the sorption medium and removing the desorbed methane from the microchannel separator;

wherein the process microchannels exchange heat with heat exchange channels and wherein fluid flowing through the process microchannels flows in a first direction, and a heat exchange fluid flows through the heat exchange channels in a second direction, the second direction being counter current relative to the first direction.

57. A process for separating methane or nitrogen from a fluid mixture comprising methane and nitrogen, the process comprising:

(A) flowing the fluid mixture into a microchannel separator, the microchannel separator comprising a plurality of process microchannels containing a sorption medium, the sorption medium having a preferential affinity for sorbing methane over nitrogen, the fluid mixture being maintained in the microchannel separator until at least part of the methane is sorbed by the sorption medium, and removing non-sorbed parts of the fluid mixture from the microchannel separator;

(B) desorbing the methane from the sorption medium and removing the desorbed methane from the microchannel separator; and

wherein the sorption medium is in the form of particulate solids which are mixed with heat conductive particulate solids to increase the thermal conductivity of the sorption medium.