Composite hydrogen separation element and module

• US 5,645,626 A
• Filed: 01/11/1996
• Issued: 07/08/1997
• Est. Priority Date: 08/10/1990
• Status: Expired due to Term

• Current Assignee: ATI Properties Incorporated (Allegheny Technologies Incorporated)
• Original Assignee: Bend Research Inc. (Lonza Group AG)
• Inventors: Frost, Chester B., Edlund, David J., Newbold, David D.
• Primary Examiner(s): SPITZER, ROBERT H
• Application Number:
  US08/583,969
• Time in Patent Office: 544 Days
• Field of Search: 55/524, 95/55, 95/56, 96/7, 96/11
• US Class Current: 95/56
• CPC Class Codes: B01D 2257/108 Hydrogen
• CPC Class Codes: B01D 2313/14 Specific spacers
• CPC Class Codes: B01D 2313/42 Catalysts within the flow path
• CPC Class Codes: B01D 2323/081 Heating
• CPC Class Codes: B01D 2323/10 Specific pressure applied
• CPC Class Codes: B01D 2323/12 Specific ratios of components used
• CPC Class Codes: B01D 2325/04 Characteristic thickness
• CPC Class Codes: B01D 53/22 by diffusion manufacturing semi-permeable membranes B01D67/00; form, structure or properties of semi-permeable membranes B01D69/00; material for semi-permeable membranes B01D71/00
• CPC Class Codes: B01D 53/226 in serial connexion
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 63/082 comprising a stack of flat membranes
• CPC Class Codes: B01D 67/00411 by sintering
• CPC Class Codes: B01D 67/0046 by slurry techniques, e.g. die or slip-casting
• CPC Class Codes: B01D 67/0065 by anodic oxidation
• CPC Class Codes: B01D 67/0069 by deposition from the liquid phase, e.g. electrochemical deposition B01D67/0046 takes precedence
• CPC Class Codes: B01D 67/0072 by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
• CPC Class Codes: B01D 69/1216 Three or more layers
• CPC Class Codes: B01D 71/02 Inorganic material
• CPC Class Codes: B01D 71/022 Metals
• CPC Class Codes: B01D 71/02231 Palladium
• CPC Class Codes: B01D 71/0227 : comprising an intermediate layer for avoiding intermetallic diffusion
• CPC Class Codes: B01J 19/2475 : Membrane reactors
• CPC Class Codes: B01J 19/249 : Plate-type reactors
• CPC Class Codes: B01J 2219/00108 : involving reactant vapours
• CPC Class Codes: B01J 2219/00159 : controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
• CPC Class Codes: B01J 2219/2453 : Plates arranged in parallel
• CPC Class Codes: B01J 2219/2467 : Additional heat exchange means, e.g. electric resistance heaters, coils
• CPC Class Codes: B01J 2219/2475 : Separation means, e.g. membranes inside the reactor
• CPC Class Codes: B01J 2219/2485 : Metals or alloys
• CPC Class Codes: B01J 2219/2486 : Steel
• CPC Class Codes: B01J 2219/2487 : Ceramics
• CPC Class Codes: B01J 2219/2493 : Means for assembling plates together, e.g. sealing means, screws, bolts
• CPC Class Codes: B01J 2219/2496 : Means for assembling modules together, e.g. casings, holders, fluidic connectors
• CPC Class Codes: B01J 2219/2498 : Additional structures inserted in the channels, e.g. plates, catalyst holding meshes
• CPC Class Codes: C01B 17/0456 : the hydrogen sulfide-containing gas being a Claus process tail gas
• CPC Class Codes: C01B 17/0495 : by dissociation of hydrogen sulfide into the elements
• CPC Class Codes: C01B 2203/0405 : Purification by membrane separation
• 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 3/04 : by decomposition of inorganic compounds, e.g. ammonia C01B3/0005 takes precedence
• CPC Class Codes: C01B 3/12 : by reaction of water vapour with carbon monoxide
• CPC Class Codes: C01B 3/34 : by reaction of hydrocarbons with gasifying agents
• CPC Class Codes: C01B 3/501 : by diffusion
• CPC Class Codes: C01B 3/503 : characterised by the membrane
• CPC Class Codes: C01B 3/505 : Membranes containing palladium
• CPC Class Codes: C01C 1/0405 : from N2 and H2 in presence of a catalyst
• CPC Class Codes: C07C 1/04 : from carbon monoxide with hydrogen
• CPC Class Codes: C07C 5/32 : by dehydrogenation with formation of free hydrogen
• CPC Class Codes: C23C 28/00 : Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
• CPC Class Codes: Y02E 60/36 : Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts

Abstract

There are disclosed improvements in multicomponent composite metal membranes useful for the separation of hydrogen, the improvements comprising the provision of at least one common-axis hole through all components of the composite membrane and the provision of a gas-tight seal around the periphery of the hole or holes through a coating metal layer of the membrane.

Claims

1. A process for the separation of hydrogen from other gases comprising:

(a) providing a feed gas comprising a mixture of gases containing hydrogen;

(b) providing a hydrogen separation element which, after fabrication, comprises a nonporous hydrogen-permeable coating metal layer supported by a rigid ceramic, carbon, or metal support matrix, and a porous intermediate layer between said coating metal layer and said support matrix, wherein, at a temperature of from about 200°

C. to about 1000°

C.,

said intermediate layer does not chemically react with hydrogen or with said coating metal layer or with said support matrix to form a hydrogen-impermeable layer, and said support matrix does not react with hydrogen or with said intermeiate layer to substantially reduce the tensile strength of said support matrix,

and wherein each of said coating metal layer, said support matrix and said inter mediate layer are planar and have at least one common axis hole therethrough in alignment along a common axis and having a gas-tight gasket about the periphery of said at least one hole of said coating metal layer;

(c) contacting said feed gas with said hydrogen separation element to form a hydrogen permeate stream; and

(d) collecting said hydrogen permeate stream.

2. The process of claim 1 conducted at a temperature in the range of about 200°

C. to about 700°

C.

3. The process of claim 2 wherein the hydrogen partial pressure of said feed gas is at least one atmosphere.

4. The process of claim 3 wherein said feed gas includes at least one sulfur compound in a concentration of at least 10 ppmv, and said coating metal layer of said hydrogen separation element comprises a Pd-Cu alloy.

5. The process of claim 4 wherein said Pd-Cu alloy is 50-55 atom % Cu, balance Pd.

6. The process of claim 5 conducted at a temperature in the range from about 500°

C. to about 800°

C.

7. A hydrogen separation module comprising a housing that has at least one feed inlet, at least one permeate outlet, at least one raffinate outlet and at least one hydrogen separation element which, after fabrication, comprises a nonporous hydrogen-permeable coating metal layer supported by a rigid ceramic, carbon, or metal support matrix, and a porous intermediate layer between said coating metal layer and said support matrix, wherein, at a temperature of from about 200°

C. to about 1000°

C.,

said intermediate layer does not chemically react with hydrogen or with said coating metal layer or with said support matrix to form a hydrogen-impermeable layer, and

said support matrix does not react with hydrogen or with said intermediate layer to substantially reduce the tensile strength of said support matrix,

and wherein each of said coating metal layer, said support matrix and said intermediate layer are planar and have at least one common axis hole therethrough in alignment along a common axis and having a gas-tight gasket about the periphery of said at least one hole of said coating metal layer.

8. The module of claim 7 wherein said coating metal layer, said support matrix and said intermediate layer have a common regular geometric shape.

9. The module of claim 8 wherein said coating metal layer, said support matrix, and said intermediate layer are annular in shape.

10. The module of claim 8 or 9, including a first hydrogen-impermeable spacer about the periphery of said intermediate layer and between said coating metal layer and said support matrix, and a second hydrogen-impermeable spacer associated with said at least one hole and located between said coating metal layer and said support matrix.

11. The module of claim 10 wherein said first and second spacers are integral with said support matrix.

12. The module of claim 10 wherein said first and second spacers are separate elements bonded to said support matrix.

13. The module of claim 10 wherein said first and second spacers are formed of a metal selected from Cu, Ni, Fe, A1 and alloys thereof.

14. The module of claims 7 or 8 or 9 wherein said coating metal layer is textured.

15. The module of claims 7 or 8 or 9 wherein said coating metal layer is a hydrogen-permeable metal selected from a transition metal, alloys and composites thereof, said coating metal layer being chemically and physically stable at temperatures of at least 200°

C.

16. The module of claim 15 wherein said coating metal layer is selected from the group consisting of the transition metals from Groups VIIB and VIIIB of the Periodic Table, and alloys containing ≧

20 wt % of said metals.

17. The module of claim 16 wherein said coating metal layer is selected from the group consisting of Fe, Mn, Ni, Pd, Pt and Ru.

18. The module of claim 16 wherein said coating metal layer is an alloy selected from the group consisting of Pd-Ag, Pd-Cu and Pd-Ag-Cu.

19. The module of claim 18 wherein said alloy is a Pd-Ag alloy containing about 25 wt % Ag.

20. The module of claim 18 wherein said alloy is a Pd-Cu alloy containing about 40 wt % Cu.

21. The module of claims 7 or 8 or 9 wherein said intermediate layer is flexible.

22. The module of claim 21 wherein said intermediate layer is non-sintered.

23. The module of claims 7 or 8 or 9 wherein said intermediate layer is non-metallic.

24. The module of claims 7 or 8 or 9 wherein said intermediate layer is a fabric.

25. The module of claim 24 wherein said fabric is selected from woven and non-woven.

26. The module of claim 25 wherein said fabric is selected from a paper and a felt.

27. The module of claim 26 wherein said paper or felt is predominantly composed of fibers of a material selected from silicon dioxide, aluminum oxide, zirconium oxide, titanium oxide, yttrium oxide, hafnium oxide, vanadium oxide, niobium oxide, tantalum oxide, silicate glasses, borate glasses, carbon, and mixtures thereof.

28. The module of claim 25 wherein said intermediate layer is a woven fabric comprising woven fibers of a material selected from aluminum oxide, silicon oxide, mixtures containing ≧

50% aluminum oxide and silicon oxide, zirconium oxide, titanium oxide, yttrium oxide, hafnium oxide, vanadium oxide, niobium oxide, tantalum oxide, silicate glasses, borate glasses, carbon, and mixtures thereof.

29. The module of claim 25 wherein said intermediate layer is a non-woven fabric comprising non-woven fibers of a material selected from aluminum oxide, silicon oxide, mixtures containing ≧

50% aluminum oxide and silicon oxide, zirconium oxide, titanium oxide, yttrium oxide, hafnium oxide, vanadium oxide, niobium oxide, tantalum oxide, silicate glasses, borate glasses, carbon, and mixtures thereof.

30. The module of claims 7 or 8 or 9 wherein said intermediate layer comprises a material selected from aluminum oxide, silicon oxide, mixtures containing ≧

50% aluminum oxide and silicon oxide, zirconium oxide, titanium oxide, yttrium oxide, hafnium oxide, vanadium oxide, niobium oxide, tantalum oxide, silicate glasses, borate glasses, carbon, and mixtures thereof.

31. The module of claims 7 or 8 or 9 wherein said intermediate layer comprises a material selected from a metal oxide, a metal carbide, a metal nitride, a metal sulfide, and mixtures thereof.

32. The module of claims 7 or 8 or 9 wherein said support matrix is a material selected from ceramic, metal, carbon and mixtures thereof.

33. The module of claims 7 or 8 or 9 wherein said support matrix is metal and is in a form selected from a perforated sheet, a non-perforated sheet, a slotted sheet, a mesh, a porous sheet and a nonporous sheet.

34. The module of claims 7 or 8 of 9 wherein said intermediate layer is woven or textured and said coating metal is textured by pressing said coating metal in the form of a foil onto said intermediate layer.

35. The module of claim 7 or 8 or 9 wherein said housing comprises a multiplicity of said hydrogen separation elements.

36. The module of claim 7 wherein said at least one common axis hole of each of said coating metal layer, said support matrix, and said intermediate layer comprise a gas flow channel.

37. The module of claim 36 wherein said gas flow channel is a feed channel.

38. The module of claim 7 wherein said gas flow channel is a permeate channel.

39. The module of claim 7 wherein said coating metal layer and said support matrix have at least one common peripheral hollow on their respective peripheries, said at least one common hollow comprising a feed gas flow channel.

40. The module of claim 39 comprising more than one hydrogen separation element, each having at least one of said common peripheral hollows, wherein said common peripheral hollows on adjacent hydrogen separation elements are not in radial alignment.

41. The module of claim 40 wherein said common peripheral hollows on said adjacent hydrogen separation elements are at least 5°

out of radial alignment.

42. The module of claim 7 wherein said hydrogen separation element comprises two coating metal layers and two intermediate layers oriented on opposite sides of said support matrix.

43. A hydrogen separation element which, after fabrication, comprises a nonporous hydrogen-permeable coating metal layer supported by a rigid ceramic, carbon, or metal support matrix, and a porous intermediate layer between said coating metal layer and said support matrix, wherein, at a temperature of from about 200°

C. to about 1000°

C.

said intermediate layer does not chemically react with hydrogen or with said coating metal layer or with said support matrix to form a hydrogen-impermeable layer, and

said support matrix does not react with hydrogen or with said intermediate layer to substantially reduce the tensile strength of said support matrix,

and wherein each of said coating metal layer, said support matrix and said intermediate layer are planar and have at least one common axis hole therethrough in alignment along a common axis and having a gas-tight seal about the periphery of said at least one hole of said coating metal layer.