Polymer formulations for gettering hydrogen

• US 5,837,158 A
• Filed: 09/23/1996
• Issued: 11/17/1998
• Est. Priority Date: 09/23/1996
• Status: Expired due to Term

• Current Assignee: Sandia Corporation (Martin Marietta Corporation)
• Original Assignee: Sandia Corporation (Martin Marietta Corporation)
• Inventors: Shepodd, Timothy Jon, Whinnery, LeRoy L.
• Primary Examiner(s): ANTHONY, JOSEPH DAVID
• Application Number:
  US08/716,752
• Time in Patent Office: 785 Days
• Field of Search: 252/181.1, 252/181.6, 252/188.28, 252/181.7, 252/184, 252/181.2, 423/226, 423/230, 423/245.1, 423/248
• US Class Current: 252/181.6
• CPC Class Codes: B01J 21/18 Carbon
• CPC Class Codes: B01J 23/42 Platinum
• CPC Class Codes: B01J 23/44 Palladium
• CPC Class Codes: B01J 31/06 containing polymers organometallic polymers B01J31/123; polymer-bound organometallic complexes B01J31/165; coordination polymers B01J31/1691
• CPC Class Codes: C01B 13/0281 in getters
• CPC Class Codes: C01B 21/0483 in getters
• CPC Class Codes: C01B 2210/0053 Hydrogen
• CPC Class Codes: C01B 23/0084 in getters
• CPC Class Codes: C01B 3/001 characterised by the uptaking medium; Treatment thereof
• CPC Class Codes: C01B 3/0015 Organic compounds; Solutions thereof
• CPC Class Codes: C01B 3/508 by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions the appropriate mediums per se C01B3/0005
• CPC Class Codes: C01C 1/024 Purification
• CPC Class Codes: C08C 19/02 Hydrogenation
• CPC Class Codes: C08L 21/00 Compositions of unspecified rubbers
• CPC Class Codes: H01J 7/183 Composition or manufacture of getters
• CPC Class Codes: H01M 10/52 Removing gases inside the secondary cell, e.g. by absorption vent plugs or other mechanical arrangements for facilitating escape of gases H01M50/30
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/32 Hydrogen storage
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

A novel composition comprising organic polymer molecules having carbon-carbon double bonds, for removing hydrogen from the atmosphere within enclosed spaces.

Organic polymers molecules containing carbon-carbon double bonds throughout their structures, preferably polybutadiene, polyisoprene and derivatives thereof, intimately mixed with an insoluble catalyst composition, comprising a hydrogenation catalyst and a catalyst support, preferably Pd supported on carbon, provide a hydrogen getter composition useful for removing hydrogen from enclosed spaces even in the presence of contaminants such as common atmospheric gases, water vapor, carbon dioxide, ammonia, oil mists, and water. The hydrogen getter composition disclosed herein is particularly useful for removing hydrogen from enclosed spaces containing potentially explosive mixtures of hydrogen and oxygen.

Claims

1. A hydrogen getter composition for removing hydrogen and its isotopes from within an enclosed space, comprising:

an organic polymer, said organic polymer further comprising a plurality of repeating monomer units, said units having up to six side branches, said side branches further comprising C₁ -C₈ alkyl that contain or are substituted with one or more functionalities selected from the group consisting of C₂ -C₈ alkene, C₂ -C₈ alkyne, C₁ -C₈ ether, C₁ -C₈ alcohol, C₁ -C₈ ester, phenyl, C₁ -C₁₀ anhydride, C₁ -C₈ isocyanate, C₁ -C₈ ketone, C₁ -C₈ epoxide, and C₁ -C₈ carboxylic acid such that each said unit contains at least one carbon-carbon double bond;

a hydrogenation cataylst consisting essentially of a noble metal catalyst and an inert catalyst support material, said hydrogenation catalyst distributed throughout said getter composition wherein said double bonds and said noble metal catalyst are in reactive association; and

an inert diluent, said diluent selected from the list consisting of carbon black powders, mineral powders, salts, thixotropic agents and combinations thereof.

2. The hydrogen getter composition of claim 1 wherein the noble metal catalyst is palladium or platinum.

3. The hydrogen getter composition of claim 1 wherein the concentration of said hydrogenation catalyst in said getter composition is from about 5 to about 75 weight percent hydrogenation catalyst, and wherein the hydrogenation catalyst contains about 0.1 to about 10 weight percent of the noble metal catalyst, based on the weight of the hydrogenation catalyst.

4. The hydrogen getter composition of claim 1, wherein the concentration of said inert diluent is less than about 95 weight percent of said getter composition.

5. The hydrogen getter of claim 1 wherein the catalyst support material comprises a porous, inert solid.

6. The hydrogen getter of claim 5 wherein the porous, inert solid is activated carbon, aluminum oxide or barium carbonate and combinations thereof.

7. A system for removing hydrogen and its isotopes from an enclosed space, comprising:

a) an enclosed space having an atmosphere contained therein; and

b) the hydrogen getter composition of claim 1 contained within said enclosed space.

8. The system of claim 7, wherein the atmosphere comprises hydrogen and a gas selected from the group consisting of air, water vapor, carbon dioxide, ammonia and oxygen and combinations thereof.

9. The system of claim 7, wherein the atmosphere comprises a mixture of hydrogen and oxygen and wherein the concentration of hydrogen is from about 6 to about 70 vol %.

10. The system of claim 7, wherein the atmosphere is a vacuum.

11. A hydrogen getter composition, comprising:

at least one of a polymeric compound consisting of units described as;

##STR1## wherein;

R₁, --R₆ may be the same or different and comprise hydrogen, or C₁ -C₈ alkyl that contain or are substituted with one or more functionalities selected from the group consisting of hydrogen, C₂ -C₈ alkene, C₂ -C₈ alkyne, C₁ -C₈ ether, C₁ -C₈ alcohol, C₁ -C₈ ester, phenyl, C₁ -C₁₀ anhydride, C₁ -C₈ isocyanate, C₁ -C₈ ketone, C₁ -C₈ epoxide, and C₁ -C₈ carboxylic acid, wherein at least one of R₁ -R₄ contain at least one carbon-carbon double bond, and wherein the functionalities may be partially reacted together, thereby crosslinking some or all of the polymer compound of formula (I) or formula (II);

P₁ -P₄ are terminal groups selected from the group consisting of hydrogen or C₁ -C₈ alkyl that contain or are substituted with one or more functionalities selected from the group consisting of hydrogen, C₂ -C₈ alkene, C₂ -C₈ alkyne, C₁ -C₈ ether, C₁ -C₈ alcohol, C₁ -C₈ ester, phenyl, C₁ -C₁₀ anhydride, C₁ -C₈ isocyanate, C₁ -C₈ ketone, C₁ -C₈ epoxide, and C₁ -C₈ carboxylic acid; and

n is from 5-10000;

a hydrogenation catalyst consisting essentially of a noble metal catalyst and an inert catalyst support material, said hydrogenation catalyst distributed throughout said getter composition wherein said double bonds and said noble metal catalyst are in reactive association; and

an inert diluent, said diluent selected from the list consisting of carbon black powders, mineral powders salts, thixotropic agents and combinations thereof.

12. The hydrogen getter composition of claim 11 comprising both said polymeric compounds described by said formula (I) and said formula (II).

13. The hydrogen getter composition of claim 12 wherein the noble metal catalyst is palladium or platinum.

14. The hydrogen getter composition of claim 12 wherein the concentration of said hydrogenation catalyst in said getter composition is from about 5 to about 75 weight percent hydrogenation catalyst, and wherein the hydrogenation catalyst contains about 0.1 to about 10 weight percent of the noble metal catalyst, based on the weight of the hydrogenation catalyst.

15. The hydrogen getter composition of claim 12, wherein the concentration of said inert diluent is less than about 95 weight percent of said getter composition.