Mobile atom insertion reaction, mobile atom transmissive membrane for carrying out the reaction, and reactor incorporating the mobile atom transmissive membrane

• US 4,908,114 A
• Filed: 11/06/1987
• Issued: 03/13/1990
• Est. Priority Date: 09/27/1985
• Status: Expired due to Term

• Current Assignee: William Ayers
• Original Assignee: William Ayers
• Inventors: Ayers, William
• Primary Examiner(s): NOT, DEFINED
• Assistant Examiner(s): Hsing, Ben C.
• Application Number:
  US07/117,298
• Time in Patent Office: 858 Days
• Field of Search: 204/295-296, 204/252, 204/253-254, 204/73 R, 204/74-77, 204/267-268, 429/17, 429/19, 429/21, 429/41
• US Class Current: 204/252
• CPC Class Codes: B01J 19/2475 Membrane reactors
• CPC Class Codes: B01J 2219/00177 controlling the pH
• CPC Class Codes: B01J 2219/00186 controlling the composition of the reactive mixture
• CPC Class Codes: B01J 4/04 using osmotic pressure using membranes, porous plates
• CPC Class Codes: C01B 15/029 Preparation from hydrogen and oxygen
• CPC Class Codes: C01B 21/16 Hydrazine; Salts thereof
• CPC Class Codes: C01C 1/04 Preparation of ammonia by synthesis in the gas phasepreparation or purification of gas mixtures for ammonia synthesis C01B3/025
• CPC Class Codes: C01C 1/0405 from N2 and H2 in presence of a catalyst
• CPC Class Codes: C07C 45/00 Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
• CPC Class Codes: C07C 45/49 by reaction with carbon monoxide
• CPC Class Codes: C25B 13/08 based on organic materials
• CPC Class Codes: C25B 3/25 Reduction
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

Disclosed is a method of carrying out a mobile atom insertion reaction, such as a hydrogen insertion reaction, for the synthesis of reduced, hydrogenated compounds. Such reactions include the production of ammonia and hydrazine from nitrogen, formic acid and methanol from carbon dioxide, and hydrogen peroxide from oxygen. The insertion reactions are carried out at a bipolar mobile atom transmissive membrane comprising a membrane formed of a mobile atom pump material, as a hydrogen pump material, conductive atom transmissive means on one surface of the membrane and conductive atom transmissive means on the opposite surface of the membrane. The mobile atom, such as hydrogen, diffuses across the membrane, to provide a source of hydrogen on the insertion reaction side of the membrane. The insertion reaction side of the membrane is positively biased with respect to a counterelectrode so that a reactant molecule, such as carbon dioxide, is electrosorbed on that surface of the membrane. The electrosorbed reactant molecular chemically reacts with the surface hydrogen by the insertion reaction to form a reduced, hydrogenated product such as formic acid. Also disclosed is a chemical reactor, containing the membrane, and several electrical field assisted chemical reactions utilizing the membrane and reactor.

Claims

1. A bipolar atom transmissive membrane for hydrogen insertion reactions comprising:

(a) a membrane comprising atom permeable, molecular impermeable, atom pump material, said membrane having a hydrogen insertion reaction side and a hydrogen receiving side;

(b) electrically conductive, atom permeable, biasing means on the hydrogen insertion reaction side of said membrane to control the surface potential thereof;

(c) electrically conductive, atom permeable biasing means on the opposite, hydrogen receiving side of said membrane;

(d) a first power source connected to said biasing means on said hydrogen insertion reaction side; and

,

(e) a second power source connected to said biasing means on said hydrogen receiving side.

2. The membrane of claim 1 wherein said membrane is a hydrogen pump material which absorbs hydrogen on one side and desorbs hydrogen on the opposite side.

3. The membrane of claim 2 wherein said hydrogen pump material absorbs hydrogen at a negatively biased surface and desorbs hydrogen at an opposite, positively biased surface.

4. The membrane of claim 2 having an atomic hydrogen flux of at least about 10^-9 moles/square centimeter-second.

5. The membrane of claim 2 wherein said hydrogen pump material is a low temperature hydride having a hydrogen equilibrium pressure of at least 1 standard atmosphere at a temperature of 25 degrees centigrade.

6. The membrane of claim 2 wherein said hydrogen pump material has a hydrogen content of at least 10²² hydrogen atoms per cubic centimeter at a temperature of 25 degrees centigrade.

7. The membrane of claim 2 wherein said hydrogen pump material forms a hydride having a heat of formation less negative than minus 15 kilocalories per mole at 25 degrees centigrade.

8. The membrane of claim 2 wherein said hydrogen pump material is chosen from the group consisting of palladium, titanium, nickel and alloys and hydrides thereof.

9. The membrane of claim 1 wherein the bipolar membrane is mechanically supported by support means allowing molecular and atomic transport to and from said sides of said membrane.

10. The membrane of claim 1 wherein said biasing means on the hydrogen insertion reaction side comprises a mobile atom transmissive, reactant dissociation catalyst.

11. The membrane of claim 1 wherein said biasing means on the hydrogen insertion reaction side of the membrane comprises a hydrogen insertion catalyst.

12. The membrane of claim 11 wherein said hydrogen insertion catalyst is chosen from the group consisting of cobalt, ruthenium, osmium, nickel, palladium, platinum, and alloys, compounds and mixtures thereof.

13. The membrane of claim 1 wherein said biasing means on the hydrogen receiving side comprises a hydrogen atom transmissive hydrogen formation catalyst.

14. The membrane of claim 13 wherein said hydrogen formation catalyst is chosen from the group consisting of platinum, palladium, gold, iron, chromium, silver, tantalum, tungsten, and alloys, compounds and mixtures thereof.

15. The membrane of claim 13 wherein said biasing means includes a catalyst that enhances formation of atomic hydrogen while substantially inhibiting evolution of molecular hydrogen.

16. The membrane of claim 15 wherein said hydrogen formation catalyst is chosen from the group consisting of cadmium, lead, indium, and mixtures thereof.

17. The membrane of claim 1 wherein said biasing means on the hydrogen receiving side comprises a hydride formation catalyst.

18. The membrane of claim 17 wherein said hydride formation catalyst is chosen from the group consisting of palladium, titanium, vanadium, nickel, lanthanum, and alloys, compounds and mixtures thereof.

19. A chemical reactor comprising:

(a) an insertion reaction compartment;

(b) a mobile atom generation compartment; and

,

(c) a bipolar membrane therebetween having;

(i) a membrane formed of a mobile atom permeable, molecule impermeable atom pump material;

(ii) conductive, a first mobile atom transmissive biasing means on one side of said membrane, facing the insertion reaction compartment so as to affect the potential on said surface and thereby affect the formation of a mobile atom insertion reaction product; and

,

(iii) a second and separate conductive mobile atom transmissive biasing means on the opposite side of the membrane, facing the mobile atom generation compartment.

20. The chemical reactor of claim 19 wherein said atom transmissive membrane absorbs the mobile atom on the mobile atom generation compartment side of said membrane and desorbs the mobile atom on the insertion reaction compartment side of the membrane.

21. The chemical reactor of claim 20 comprising means for controlling mobile atoms on the insertion reaction compartment side of the membrane.

22. The chemical reactor of claim 21 wherein said means for controlling the mobile atoms on the insertion reaction compartment side of the membrane comprises control of the mobile atom flux by a concentration gradient of mobile atoms across the membrane.

23. The chemical reactor of claim 19 comprising means for controlling the insertion reaction compartment side potential with respect to a reference or counter electrode.

24. The chemical reactor of claim 19 comprising means for controlling the pH and composition of fluid in contact with the insertion reaction compartment side of the membrane whereby to control potential of the insertion surface of the membrane with respect to a reference electrode.

25. The chemical reactor of claim 19 comprising means for controlling an electrical bias between the insertion reaction compartment side and a counter electrode whereby to control potential of the insertion reaction compartment side of the membrane.

26. The chemical reactor of claim 19 comprising means for controlling potential of the insertion reaction compartment side to facilitate the insertion reaction while substantially avoiding destruction of product.

27. The chemical reactor of claim 19 comprising means for controlling the dielectric constant and conductivity of fluid in contact with the insertion reaction compartment side of the membrane whereby to control potential at the insertion reaction compartment side of the membrane.

28. The chemical reactor of claim 19 comprising means for pulsing or oscillating potential at the insertion reaction compartment side.

29. The chemical reactor of claim 19 comprising means for controlling an electrochemical reaction to generate mobile atoms on the mobile atom generation compartment side of the membrane.

30. The chemical reactor of claim 19 comprising means for controlling an electrochemical reaction on the mobile atom generation side so as to maintain a flux of mobile atoms through the membrane.

31. The chemical reactor of claim 19 comprising means for supplying mobile atom precursors to the mobile atom generation side of the membrane.

32. The chemical reactor of claim 19 comprising means for generating atomic hydrogen at the mobile atom generation compartment side of the membrane by reduction of water, protons, hydrogen or hydrogen atom precursors.

33. The chemical reactor of claim 19 wherein the atom pump material is a hydrogen atom pump material that absorbs hydrogen at the mobile atom generation compartment side and desorbs hydrogen at the insertion reaction compartment side.

34. The chemical reactor of claim 33 having an atomic hydrogen flux of at least 10^-9 moles/square centimetersecond.

35. The chemical reactor of claim 33 comprising means for controlling potential of the insertion reaction compartment side to neutral or positive bias potentials to facilitate the mobile atom insertion reaction at potentials to substantially avoid oxidation of the insertion reaction product.

36. The chemical reactor of claim 33 wherein the hydrogen pump material is a low temperature hydride having a hydrogen equilibrium pressure of at least 1 standard atmosphere at a temperature of 25 degrees centigrade.

37. The chemical reactor of claim 33 wherein the hydrogen pump material has a hydrogen content of at least 10²² hydrogen atoms per cubic centimeter at a temperature of 25 degrees centigrade.

38. The chemical reactor of claim 33 wherein the hydrogen pump material forms a hydride having a heat of formation less negative than minus 15 kilocalories per mole at 25 degrees centigrade.

39. The chemical reactor of claim 33 wherein the hydrogen pump material is chosen from the group consisting of palladium, titanium, and alloys and hydrides thereof.

40. The chemical reactor of claim 19 wherein the insertion reaction compartment side of the membrane comprises a reactant dissociation catalyst.

41. The chemical reactor of claim 40 wherein the dissociation catalyst is chosen from the group consisting of molybdenum, tungsten, iron, chromium, tantalum, and alloys, compounds and mixtures thereof.

42. The chemical reactor of claim 19 wherein the insertion reaction compartment side of the membrane comprises a hydrogen insertion catalyst.

43. The chemical reactor of claim 42 wherein the hydrogen insertion catalyst is chosen from the group consisting of cobalt, ruthenium, osmium, nickel, palladium, platinum, and alloys, compounds and mixtures thereof.

44. The chemical reactor of claim 19 wherein the mobile atom generation compartment side of the membrane comprises a hydrogen formation catalyst.

45. The chemical reactor of claim 44 wherein the hydrogen formation catalyst is chosen from the group consisting of platinum, palladium, gold, iron, chromium, silver, tantalum, tungsten, and alloys, compounds, and mixtures thereof.

46. The chemical reactor of claim 19 wherein the mobile atom generating compartment side of the membrane comprises a catalyst that enhances formation of atomic hydrogen while substantially inhibiting evolution of molecular hydrogen.

47. The chemical reactor of claim 46 wherein the hydrogen formation catalyst is chosen from the group consisting of cadmium, lead, indium and mixtures thereof.

48. The chemical reactor of claim 19 wherein the mobile atom generation compartment side of the membrane comprises a hydride formation catalyst.

49. The chemical reactor of claim 48 wherein the hydride formation catalyst is chosen from the group consisting of palladium, titanium, vanadium, nickel, lanthanum and alloys, compounds and mixtures thereof.