SULFUR-RESISTANT COMPOSITE METAL MEMBRANES

• US 20120128999A1
• Filed: 01/23/2012
• Published: 05/24/2012
• Est. Priority Date: 04/03/2002
• Status: Abandoned Application

• Current Assignee: Colorado School of Mines
• Original Assignee: Colorado School of Mines
• Inventors: Lusk, Mark, Thoen, Paul, WAY, J. DOUGLAS
• Application Number:
  US13/356,410
• Publication Number:
  US 20120128999A1
• Time in Patent Office: Days
• US Class Current: 428/621
• CPC Class Codes: B01D 2323/14 Ageing features
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 67/0051 by controlled crystallisation, e,.g. hydrothermal growth
• CPC Class Codes: B01D 67/0069 by deposition from the liquid phase, e.g. electrochemical deposition B01D67/0046 takes precedence
• CPC Class Codes: B01D 67/0083 Thermal after-treatment
• CPC Class Codes: B01D 69/12 Composite membranes; Ultra-thin membranes
• 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
• CPC Class Codes: C22C 1/00 Making non-ferrous alloys by electrothermic methods C22B4/00; by electrolysis C25C1/24, C25C3/36
• CPC Class Codes: C23C 18/1601 Process or apparatus
• CPC Class Codes: C23C 18/1639 Substrates other than metallic, e.g. inorganic or organic or non-conductive
• CPC Class Codes: C23C 18/1644 porous substrates
• CPC Class Codes: C23C 18/1651 Two or more layers only obtained by electroless plating
• CPC Class Codes: C23C 18/1658 with two steps starting with metal deposition followed by addition of reducing agent
• CPC Class Codes: C23C 18/1692 Heat-treatment
• CPC Class Codes: C23C 18/1879 Use of metal, e.g. activation, sensitisation with noble metals
• CPC Class Codes: C23C 18/44 using reducing agents
• CPC Class Codes: C23C 18/54 : Contact plating, i.e. electroless electrochemical plating
• CPC Class Codes: H01M 4/94 : Non-porous diffusion electrodes, e.g. palladium membranes, ion exchange membranes
• CPC Class Codes: H01M 8/0668 : Removal of carbon monoxide or carbon dioxide
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10T 428/12535 : with additional, spatially distinct nonmetal component
• CPC Class Codes: Y10T 428/12611 : Oxide-containing component
• CPC Class Codes: Y10T 428/12778 : Alternative base metals from diverse categories
• CPC Class Codes: Y10T 428/31678 : Of metal

Abstract

The invention provides thin, hydrogen-permeable, sulfur-resistant membranes formed from palladium or palladium-alloy coatings on porous, ceramic or metal supports. Also disclosed are methods of making these membranes via sequential electroless plating techniques.

Claims

1. A sulfur-resistant palladium alloy composite membrane comprising:

a palladium layer that makes contact with a surface of a porous substrate;

a second layer comprising a second layer material that makes contact with the palladium layer, wherein the second layer material is selected from the group consisting of copper, silver and gold; and

a third layer comprising a third layer material that makes contact with the second layer, wherein the third layer material is selected from the group consisting of copper, gold and silver and wherein the second layer material and the third layer material are different.

2. The membrane of claim 1, wherein the second layer material is copper and the third layer material is selected from the group consisting of gold and silver.

3. The membrane of claim 1, wherein the second layer material is gold and the third layer material is selected from the group consisting of silver and copper.

4. The membrane of claim 1, wherein the second layer material is silver and the third layer material is selected from the group consisting of gold and copper.

5. The membrane of claim 1, wherein the porous substrate is selected from the group consisting of an oxide ceramics, alumina, titania, zirconia, non-oxide ceramics, SiC, SiN, sintered metal, porous metal, stainless steel, nickel, sintered metals with ceramic surfaces, porous metals with ceramic surfaces, and porous vycor glass.

6. The membrane of claim 1, wherein the porous substrate is tubular.

7. The membrane of claim 1, wherein the porous substrate is planar.

8. The membrane of claim 1, wherein the porous substrate is a stainless steel support.

9. The membrane of claim 8 further comprising a porous ZrO₂ coating on the stainless steel support.

10. The membrane of claim 1, further comprising a sealant.

11. The membrane of claim 1, wherein a thickness of the palladium first layer is between about 1 μ

m and about 7 μ

m.

12. The membrane of claim 1, wherein the second material layer is gold and a thickness of the second layer is between about 1 μ

m and about 7 μ

m.

13. The membrane of claim 1, wherein a pore size of the porous substrate is between 20-80 nm.

14. A sulfur-resistant palladium-gold alloy composite membrane comprising:

a palladium first layer that makes contact with a surface of a porous substrate, wherein the palladium-gold alloy, wherein a thickness of the palladium first layer is between about 1 μ

m and about 7 μ

m; and

a gold second layer that makes contact with the palladium first layer, wherein a thickness of the gold second layer is between about 1 μ

m and about 7 μ

m.

15. The membrane of claim 14, wherein a thickness of the palladium-gold alloy is between about 2 μ

m and about 10 μ

m.

16. The membrane of claim 14, wherein a thickness of the palladium-gold alloy is between about 2 μ

m and about 5 μ

m.

17. The membrane of claim 14, further comprising:

a third layer that makes contact with the second layer, wherein the third layer comprising a third layer material selected from the group consisting of copper and silver.

18. The membrane of claim 14, wherein mass percent of the gold in the palladium-gold alloy is between 5 and 50 mass percent.

19. The membrane of claim 14, wherein the porous substrate is tubular.

20. The membrane of claim 14, wherein the porous substrate is planar.

21. A sulfur-resistant a palladium alloy composite membrane comprising:

a porous substrate; and

a palladium alloy in contact with at least one surface of the porous substrate, comprising palladium;

a second material selected from the group consisting of copper, silver and gold; and

a third material, selected from the group consisting of copper, gold and silver;

wherein the second material and the third material are different from each other, and wherein a thickness of the palladium alloy is between about 2 μ

m and about 10 μ

m.