Apparatus and methods for separation/purification utilizing rapidly cycled thermal swing sorption

• US 6,508,862 B1
• Filed: 04/30/2001
• Issued: 01/21/2003
• Est. Priority Date: 04/30/2001
• Status: Expired due to Term

• Current Assignee: Battelle Memorial Institute
• Original Assignee: Battelle Memorial Institute
• Inventors: Monzyk, Bruce F., Wang, Yong, Fitzgerald, Sean P., Perry, Steven T., Simmons, Wayne W., Tonkovich, Anna Lee Y., VanderWiel, David P., McDaniel, Jeffrey S., Weller, Albert E. Jr.
• Primary Examiner(s): Simmons, David A.
• Assistant Examiner(s): LAWRENCE JR, FRANK M
• Application Number:
  US09/845,777
• Time in Patent Office: 631 Days
• Field of Search: 95/90, 95/96, 95/99, 951/06, 951/14, 951/15, 951/16, 961/21, 961/26, 961/46, 210/670, 210/676, 210/660, 210/180, 210/185
• US Class Current: 95/106
• CPC Class Codes: B01D 2253/108 Zeolites
• CPC Class Codes: B01D 2253/1126 Metal hydrides
• CPC Class Codes: B01D 2253/25 Coated, impregnated or composite adsorbents
• CPC Class Codes: B01D 2253/304 Linear dimensions, e.g. particle shape, diameter
• CPC Class Codes: B01D 2253/308 Pore size
• CPC Class Codes: B01D 2256/16 Hydrogen
• CPC Class Codes: B01D 2257/102 Nitrogen
• CPC Class Codes: B01D 2257/104 Oxygen
• CPC Class Codes: B01D 2257/108 Hydrogen
• CPC Class Codes: B01D 2257/11 Noble gases
• CPC Class Codes: B01D 2257/30 Sulfur compounds
• CPC Class Codes: B01D 2257/50 Carbon oxides
• CPC Class Codes: B01D 2257/702 Hydrocarbons
• CPC Class Codes: B01D 2257/80 Water
• CPC Class Codes: B01D 2258/0208 from fuel cells
• CPC Class Codes: B01D 2259/4006 Less than four
• CPC Class Codes: B01D 2259/4009 using hot gas
• CPC Class Codes: B01D 2259/40096 by using electrical resistance heating
• CPC Class Codes: B01D 53/02 by adsorption, e.g. preparative gas chromatography solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01
• CPC Class Codes: B01D 53/0438 Cooling or heating systems
• CPC Class Codes: B01D 53/0462 : Temperature swing adsorption
• CPC Class Codes: B01J 19/0093 : Microreactors, e.g. miniaturised or microfabricated reactors laboratory containers with capillary fluid transport in microfabricated channels or chambers B01L3/5027
• CPC Class Codes: C01B 2203/043 : Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
• CPC Class Codes: C01B 2203/0465 : Composition of the impurity
• CPC Class Codes: C01B 2203/047 : the impurity being carbon monoxide
• CPC Class Codes: C01B 2203/0475 : the impurity being carbon dioxide
• CPC Class Codes: C01B 2203/048 : the impurity being an organic compound
• CPC Class Codes: C01B 2203/0485 : the impurity being a sulfur compound
• CPC Class Codes: C01B 2203/0495 : the impurity being water
• CPC Class Codes: C01B 3/56 : by contacting with solids; Regeneration of used solids C01B3/508 takes precedence
• CPC Class Codes: F28D 9/00 : Heat-exchange apparatus having stationary plate-like or laminated conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall F28F3/083, F28F3/086 take precedence
• CPC Class Codes: F28F 2260/02 : having microchannels

Abstract

The present invention provides apparatus and methods for separating fluid components. In preferred embodiments, the apparatus and methods utilize microchannel devices with small distances for heat and mass transfer to achieve rapid cycle times and surprisingly large volumes of fluid components separated in short times using relatively compact hardware.

Claims

1. A method of separating a fluid component from a mixture comprising:

a first step comprising sorbing a fluid component, this first step comprising passing a fluid mixture into a flow channel at a first temperature;

wherein the flow channel comprises a porous sorbent within the channel and wherein substantially all the fluid mixture flowing through the flow channel flows through the porous sorbent,

wherein the sorbent is cooled by fluid flowing through a heat exchanger; and

wherein flow through the channel is constrained such that in at least one cross-sectional area of the channel that comprises the sorbent, the height of the flow channel is 1 cm or less;

a second step comprising increasing the temperature of the sorbent, this second step comprising adding energy from an energy source; and

desorbing a fluid component at a second temperature and obtaining a fluid component that was sorbed in the first step, wherein the second temperature is higher than the first temperature; and

wherein the first and second steps, combined,

for a non-condensed fluid mixture take 10 seconds or less and wherein at least 20% of the gaseous component sorbed in the first step is desorbed from the sorbent;

or

for a liquid mixture take 1000 seconds or less and wherein at least 20% of the fluid component sorbed in the first step is desorbed from the sorbent.

2. The method of claim 1 wherein the sorbent is a porous sorbent having a pore volume of 5 to 95% wherein at least 20% of the sorbent'"'"'s pore volume is composed of pores in the size range of 0.1 to 300 microns.

3. The method of claim 2 wherein the heat exchanger comprises an array of heat exchanger microchannels.

4. The method of claim 1 wherein the flow channel is disposed in a planar array of flow channels.

5. The method of claim 3 wherein the flow channel is disposed in a planar array of flow channels that is disposed between planar arrays of heat exchanger microchannels.

6. The method of claim 1 wherein the sorbent is disposed on a thermally-conductive felt or continuously porous foam.

7. The method of claim 2 wherein the flow of the fluid through the heat exchanger is cross-flow or counter-flow in relation to gas flow through the flow channel.

8. The method of claim 2 wherein the fluid flowing through the heat exchanger comprises a heat transfer liquid.

9. The method of claim 1 wherein the fluid flowing through the heat exchanger comprises water.

10. The method of claim 1 wherein conditions for sorption or desorption are selected to coincide with a phase change of heat transfer fluid.

11. The method of claim 2 wherein sorption is conducted at 1 to 1000 psig.

12. The method of claim 2 wherein a feed stream is distributed among multiple flow channels each of which is sandwiched between heat exchangers.

13. The method of claim 2 wherein the flow channel has a height of 2 mm or less.

14. The method of claim 2 wherein the porous sorbent has a thickness of between 100 and 500 microns.

15. The method of claim 13 wherein at least 50% of the sorbent'"'"'s pore volume is composed of pores in the size range of 0.3 to 200 microns.

16. The method of claim 1 wherein sorbent comprises sorbent fibers.

17. The method of claim 2 wherein heat from the sorbent is transferred through a metal channel wall to the fluid in the heat exchanger.

18. The method of claim 2 wherein the flow channel comprises a bulk flow path and a porous sorbent plug.

19. The method of claim 18 comprising laminar flow through the flow channel.

20. The method of claim 2 comprising flowing a gas through at least two flow channels and further comprising mixing gases from the at least two flow channels in a mixing chamber.

21. The method of claim 18 wherein bulk flow from at least two flow channels flows into a porous sorbent.

22. The method of claim 2 comprising adding heat from an electically resistive heating element to desorb the fluid component.

23. The method of claim 2 wherein desorption is conducted by heating the length of a flow channel to drive off sorbed fluid while introducing feed to the beginning of the flow channel.

24. The method of claim 2 further comprising a step of pretreating the gas mixture to remove constituents.

25. The method of claim 2 wherein the desorbed fluid component is recycled back to the flow channel.

26. The method of claim 1 wherein the gas mixture comprises sulfurous gases.

27. The method of claim 2 wherein the gas mixture comprises a gas selected from the group consisting of:

H₂, CO, CO₂, H₂O, CH₄, C₂H₆, C₃H₈, N₂, O₂, Ar, NH₃, CH₃OH and C₂H₅OH.

28. The method of claim 2 wherein the gas mixture flows into the flow channel at a partial pressure of 1×

10<sup>−

3</sup> to 20 bar.

29. The method of claim 28 wherein no pumping is utilized.

30. The method of claim 29 wherein at least 85% of equilibrium is reached during sorption.

31. The method of claim 30 wherein the step of sorbing a fluid component occurs for 0.1 to 10 seconds.

32. The method of claim 31 wherein the sorption/desorption cycle time is 100 to 1000 Hz.

33. The method of claim 2 wherein, prior to the step of desorbing a fluid component, the flow channel is at least partially evacuated for a time of less than 2 seconds.

34. A method for separating a fluid component from a fluid mixture, comprising:

passing a fluid mixture into a first sorption region at a first temperature and first pressure, wherein the first sorption region comprises a first sorbent and wherein the temperature and pressure in the first sorption region are selected to favor sorption of the fluid component into the first sorbent in the first sorption region;

transferring heat from the first sorption region into a microchannel heat exchanger and selectively removing the fluid component from said fluid mixture thus resulting in a sorbed component in the first sorbent and a fluid mixture that is relatively depleted in said component;

passing the relatively component-depleted fluid mixture into a second sorption region at a second temperature and second pressure, wherein the second sorption region comprises a second sorbent and wherein the temperature and pressure in the second sorption region are selected to favor sorption of the fluid component into the sorbent in the second sorption region;

transferring heat from the second sorption region into a microchannel heat exchanger and selectively removing the fluid component from said relatively component-depleted fluid mixture thus resulting in sorbed component in the second sorbent and a relatively more component-depleted gas mixture;

wherein the second temperature is different than the first temperature;

adding heat to the first sorbent, through a distance of about 1 cm or less to substantially the entire first sorbent, to raise the first sorbent to a third temperature and desorbing said component from the first sorbent;

adding heat to the second sorbent, through a distance of about 1 cm or less to substantially the entire second sorbent, to raise the second sorbent to a fourth temperature and desorbing said component from the second sorbent; and

obtaining the component desorbed from the first and second sorbents.

35. The method of claim 34 wherein the second pressure is different from the first pressure.

36. The method of claim 34 wherein the first sorbent is a porous sorbent.

37. The method of claim 34 wherein the component desorbed from the first and second sorbents is recycled back into the first sorption region.

38. The method of claim 34 wherein the first temperature and the second temperature are controlled by heated or cooled heat transfer fluid, water, or gas.

39. The method of claim 34 further comprising a step of precooling the first sorption region.

40. The method of claim 34 wherein the second temperature is lower than the first temperature.

41. The method of claim 40 wherein the fluid mixture comprises a mixture of liquids.

42. The method of claim 40 wherein the fluid mixture comprises an alkane.

43. The method of claim 34 wherein the fluid mixture comprises a gas selected from the group consisting of:

H₂, CO, CO₂, H₂O, CH₄, C₂H₆, C₃H₈, N₂, O₂, Ar, and NH₃.

44. The method of claim 40 wherein the component desorbed from the second sorbent is recycled back into the first sorption region.

45. The method of claim 34 further comprising the step of pretreating the fluid mixture to remove constituents that could poison the sorbent surface.

46. The method of claim 34 wherein the fluid mixture passes into a first header and is distributed into multiple flow channels with intervening heat exchangers and wherein the fluid component is sorbed into sorbent that is disposed in the flow channels.

47. The method of claim 46 wherein a component-depleted fluid from the multiple flow channels is collected in a header and passed into a second unit where more fluid component is sorbed.

48. The method of claim 34 wherein the step of adding heat to the first sorbent comprises electrical resistance heating.

49. The method of claim 34 wherein, in the first sorbent region, the fluid mixture flows along one side of a porous sorbent, makes at least one bend, and then travels along the other side of the porous sorbent in the opposite direction.

50. The method of claim 34 wherein the fluid mixture is a gas mixture;

wherein the first sorption region comprises a first compartment having a dimension of 2 mm or less, and wherein the first sorption region comprises a porous sorbent.

51. The method of claim 34 wherein the first sorption region comprises at least two sorption chambers and wherein flow from the at least two sorption chambers flows into a porous material.

52. The method of claim 34 wherein the first sorption region comprises a chamber comprising a bulk flow path and a porous sorbent.

53. The method of claim 52 wherein the fluid mixture comprises a gas, and wherein the first sorption region further comprises a porous plug that serves to provide sorbent contact to any gaseous species that remain unsorbed after passage through the bulk flow path.

54. The method of claim 34 wherein the first sorption region comprises a chamber comprising a chamber wall that separates the sorbent from the microchannel heat exchanger;

and wherein the chamber wall is made of plastic or metal.

55. The method of claim 36 wherein the porous sorbent has a pore volume of 5 to 98% wherein at least 20% of the sorbent'"'"'s pore volume is composed of pores in the size range of 1 to 100 microns.

56. The method of claim 34 carried out at a pressure of 1 to 300 psig.

57. The method of claim 34 wherein conditions for sorption in the second sorption region are selected to coincide with a phase change of a heat transport fluid.

58. The method of claim 34 wherein, in the first sorption region, a feed stream is distributed among multiple flow channels each of which is sandwiched between microchannel heat exchangers.

59. The method of claim 34 wherein the flow of the fluid through the microchannel heat exchanger is cross-flow or counter-flow in relation to flow through the first sorption region.

60. The method of claim 54 wherein the first sorption region comprises an open channel having a height of less than 2 mm.

61. A fluid separation apparatus comprising:

a flow channel comprising a porous sorbent, the flow channel having at least one dimension of 1 cm or less, wherein, in at least one cross-section of the flow channel the porous sorbent occupies at least 90% of the cross-sectional area; and

a microchannel heat exchanger in thermal contact with the flow channel.

62. The apparatus of claim 61 wherein the flow channel comprises an inlet and there is no contactor disposed between the inlet and the sorbent.

63. The apparatus of claim 61 wherein the porous sorbent comprises a thermally-conductive felt or thermally-conductive continuously porous foam.

64. The apparatus of claim 61 comprising:

at least 4 layers, each of said at least 4 layers comprising a microchannel heat exchanger;

alternating with at least 3 layers comprising at least one flow channel in each of said at least 3 layers.

65. The apparatus of claim 63 wherein the sorbent comprises a promoter on the surface of the sorbent.

66. The apparatus of claim 64 comprising at least one first gas inlet to a first at least 3 layers, wherein each layer comprises at least one flow channel;

at least one first gas outlet from said first at least 3 layers comprising at least one flow channel;

said at least one first gas outlet connected to at least one second gas inlet to a second at least 3 layers comprising at least one flow channel;

at least one second gas outlet from said second at least 3 layers, wherein each layer comprises at least one flow channel; and

further comprising

a first at least 4 layers alternating with said first at least 3 layers, each of said first at least 4 layers comprising a microchannel heat exchanger; and

a second at least 4 layers alternating with said second at least 3 layers, each of said second at least 4 layers comprising a microchannel heat exchanger.

67. A use of the apparatus of claim 61 to purify a fluid component from a fluid mixture.

68. The apparatus of claim 61 wherein the flow channel has at least one internal surface and wherein the distance from any point in the flow channel is 0.1 mm or less.

69. The apparatus of claim 61 wherein the flow channel has a height of 0.5 to 2 mm.

70. The apparatus of claim 61 wherein the flow channel has a width of 2 to 25 cm.

71. The apparatus of claim 61 wherein the flow channel has a length of 2 to 25 cm.

72. The apparatus of claim 65 wherein the promoter comprises Ru.

73. The apparatus of claim 61 wherein the microchannel heat exchanger and the flow channel are adjacent and substantially coextensive thin layers with width and length substanially larger than height.

74. The apparatus of claim 61 wherein the porous sorbent has a thickness of between 100 and 500 microns.

75. The apparatus of claim 61 wherein the porous sorbent has a pore volume of 5 to 8% wherein at least 50% of the sorbent'"'"'s pore volume is composed of pores in the size range of 0.3 to 200 microns.

76. The apparatus of claim 61 wherein the porous sorbent comprises sorbent fibers.

77. The apparatus of claim 61 wherein the flow channel is defined by channel walls that are metal.

78. The apparatus of claim 61 wherein the porous sorbent comprises a core of a large pore structure and a small pore structure on the outer sides.

79. The apparatus of claim 61 comprising at least two flow channels and a mixing chamber connected to both of said at least two flow channels.

80. The apparatus of claim 61 further comprising an electrical resistance heater in thermal contact with the flow channel.

81. The apparatus of claim 62 comprising multiple alternating layers of heat exchangers and flow channels.

82. The apparatus of 61 wherein the apparatus is constructed of materials comprising plastics.

83. The apparatus of claim 82 comprising polyimide.

84. A fluid separation apparatus comprising:

a first array of flow channels;

the first array of flow channels comprising;

at least two flow channels;

each of the at least two flow channels comprising an inlet, an outlet and a sorbent disposed between the inlet and the outlet;

each of the at least two flow channels in thermal contact with a microchannel heat exchanger;

each of the at least two flow channels having at least one dimension of 1 cm or less, wherein the at least one dimension is in a direction toward a microchannel heat exchanger; and

at least one array inlet and at least one array outlet; and

a second array of flow channels;

the second array of flow channels comprising;

at least two flow channels;

each of the at least two flow channels comprising an inlet, an outlet and a sorbent disposed between the inlet and the outlet;

each of the at least two flow channels in thermal contact with a microchannel heat exchanger;

each of the at least two flow channels having at least one dimension of 1 cm or less, wherein the at least one dimension is in a direction toward a microchannel heat exchanger; and

at least one array inlet and at least one array outlet;

at least one fluid conduit connecting the outlet of the first array to the inlet of the second array; and

a valve capable of controlling the flow through the conduit.

85. The apparatus of claim 84 wherein the at least one array inlet in the first array is the same inlet as a flow channel inlet in the first array.

86. A method of using the apparatus of claim 84 comprising:

sorbing a fluid compenent in the first array, and, simultaneously,

desorbing a fluid component in the second array.

87. The apparatus of claim 85 comprising alternating layers of heat exchangers and flow channels.

88. The apparatus of claim 85 further comprising an electrical resistance heater in thermal contact with the flow channels in the first array.

89. The apparatus of claim 84 wherein the sorbent in the first array comprises a porous sorbent.

90. The apparatus of claim 89 wherein the porous sorbent comprises a core of a large pore structure and a small pore structure on the outer sides.

91. The apparatus of claim 89 wherein the porous sorbent comprises a porous sorbent matrix material within which there are contiguous bulk flow channels.

92. The apparatus of claim 89 wherein the at least two flow channels in the first array comprise baffles and the baffles comprise a porous sorbent.

93. The apparatus of claim 89 wherein the at least two flow channels are defined by channel walls that are metal.

94. The apparatus of claim 84 wherein the sorbent disposed in the second array comprises a corrugated insert.

95. The apparatus of claim 89 wherein the porous sorbent has a thickness between 100 and 500 microns.

96. The apparatus of claim 84 wherein less structural support is provided in regions that will operate at relatively lower pressure.

97. The apparatus of claim 84 wherein, in the first array, the at least two flow channels and the microchannel heat exchanger are substantially coextensive thin layers with width and length substantially larger than height.

98. The apparatus of claim 84 wherein, in the first array, a layer comprising the at least two flow channels is adjacent to a layer comprising the microchannel heat exchanger;

and

wherein, in the second array, a layer comprising the at least two flow channels is adjacent to a layer comprising the microchannel heat exchanger.

101. The apparatus of claim 98 wherein, in the first array, the at least two flow channels are straight and comprise an obstructed open channel.

102. The apparatus of claim 101 wherein, in the first array, a distance from any point in the open channels to an internal surface of the flow channels is 0.1 mm or less.

103. The apparatus of claim 101 wherein, in the first array, wherein the open channels have a height of less than 2 mm.

104. The apparatus of claim 103 wherein, in the first array, wherein the open channels have a width of 2 to 25 cm.

99. The apparatus of 98 wherein the apparatus is constructed of materials comprising plastics.

100. The apparatus of claim 99 comprising polyimide.