Apparatus and method for extracting hydrogen

• US 5,205,841 A
• Filed: 04/03/1992
• Issued: 04/27/1993
• Est. Priority Date: 04/03/1992
• Status: Expired due to Fees

• Current Assignee: Versum Materials US, LLC (Merck & Co., Inc.)
• Original Assignee: TPC Technologies, Inc.
• Inventors: Vaiman, Lev A.
• Primary Examiner(s): SPITZER, ROBERT H
• Application Number:
  US07/862,802
• Time in Patent Office: 389 Days
• Field of Search: 55/16, 55/68, 55/158, 55/524, 427/38, 427/39, 427/245, 427/328, 427/405, 428/380, 428/381, 428/606, 428/607, 428/615
• US Class Current: 95/46
• CPC Class Codes: B01D 2313/42 Catalysts within the flow path
• CPC Class Codes: B01D 2323/12 Specific ratios of components used
• 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 63/06 Tubular membrane modules
• CPC Class Codes: B01D 67/0069 by deposition from the liquid phase, e.g. electrochemical deposition B01D67/0046 takes precedence
• CPC Class Codes: B01D 71/022 Metals
• CPC Class Codes: B01D 71/02231 Palladium
• CPC Class Codes: C01B 2203/0405 Purification by membrane separation
• 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 3/505 Membranes containing palladium

Abstract

A membrane for extracting hydrogen from gaseous and gaseous-liquid mixtures at low temperature makes use of a palladium or palladium alloy substrate and permits reduction of the surface resistance of the substrate. The membrane includes combined coatings including vacuum-deposited palladium ions driven into the substrate with inert gas ions and an electrochemically applied catalyst coating in the form of palladium or palladium/platinum black. A method for fabricating the membrane and a method for using the membrane to separate ultra-pure hydrogen are also disclosed.

Claims

1. A membrane comprising:

A. a substrate consisting essentially of palladium metal and having opposed first and second sides;

B. a first film consisting essentially of palladium metal applied in overlying relation to the first side of said substrate;

C. a second film consisting essentially of a metal black selected from the group consisting of palladium black and palladium/platinum black overlying said first film; and

D. a third film consisting essentially of a metal black selected from the group consisting of palladium black and palladium/platinum black overlying the second side of said substrate.

2. The membrane of claim 1, wherein said substrate is tubular.

3. The membrane of claim 1, which is selectively permeable to hydrogen gas at a temperature less than 250°

C.

4. A method of extracting essentially pure hydrogen from a fluid mixture including free molecular hydrogen, comprising the steps of:

A. providing the membrane of claim 1;

B. exposing the second film of said membrane to a fluid mixture including free hydrogen at a partial pressure of hydrogen, pressure drop across said membrane, and a temperature, and for a time sufficient to selectively pass hydrogen from said mixture through said membrane; and

C. collecting the hydrogen passed through said membrane.

5. The hydrogen extraction method of claim 4, wherein said temperature is from about 20°

C. to about 300°

C.

6. A method of fabricating a membrane, comprising the steps of:

A. providing a substrate consisting essentially of palladium and having first and second sides;

B. applying a first film of a material consisting essentially of palladium overlying the first side of said substrate;

C. applying a second film consisting essentially of a metal black selected from the group consisting of palladium black and palladium/platinum black overlying the second side of said substrate; and

D. applying a third film consisting essentially of a metal black selected from the group consisting of palladium black and palladium/platinum black overlying said first film.

7. The fabricating method of claim 6, wherein said first film is from about 1 μ

m to about 3 μ

m thick.

8. The fabricating method of claim 6, comprising the further step, after said first film applying step, of bombarding said first film with ions of an inert gas having an energy of from about 30 to about 60 kev under conditions effective to improve the adhesion of said first film.

9. The fabricating method of claim 6, wherein said palladium and palladium/platinum black applying steps are carried out by galvanic plating.

10. The fabricating method of claim 9, wherein said palladium and palladium/platinum black applying steps are carried out at a current density of from about 3 to about 12 ma/cm².

11. The fabricating method of claim 10, wherein said current density is increased during said palladium and palladium/platinum black applying steps from an initial value of about 3 to a final value of about 12 ma/cm².

12. The fabricating method of claim 10, wherein said current density is increased at the rate of about 0.5 ma/min.

13. The fabricating method of claim 9, wherein said palladium and palladium/platinum black are applied at a coating weight of from about 1 mg/cm² to about 10 mg/cm².

14. The fabricating method of claim 9, wherein said palladium is applied by providing a platinum anode, using said substrate as a cathode, and using a solution consisting essentially of an aqueous palladium salt as the electrolyte.

15. The fabricating method of claim 14, wherein said aqueous palladium salt consists essentially of:

A. about 4.5% by weight PtHCl₂ ;

B. about 2% by weight PdCl₂ ;

C. about 2% Hcl; and

D. water in an amount effective to disperse the other ingredients.

16. The fabricating method of claim 6, comprising the subsequent step of heating said membrane in a hydrogen environment at about 200°

C. for about two hours.