Method and apparatus for anhydrous ammonia production

• US 7,811,442 B2
• Filed: 02/10/2007
• Issued: 10/12/2010
• Est. Priority Date: 02/10/2007
• Status: Expired due to Fees

• Current Assignee: Nhthree LLC
• Original Assignee: N H Three LLC
• Inventors: Holbrook, John H., Ganley, Jason C.
• Primary Examiner(s): Langel; Wayne
• Assistant Examiner(s): Martinez; Brittany M
• Application Number:
  US11/705,177
• Publication Number:
  US 20080193360A1
• Time in Patent Office: 1,340 Days
• Field of Search: 423/352, 423/359, 423/362, 423/363, 422/148, 205/552
• US Class Current: 205/552
• CPC Class Codes: C25B 1/00 Electrolytic production of inorganic compounds or non-metals
• CPC Class Codes: C25B 13/04 characterised by the material
• CPC Class Codes: C25B 9/23 comprising ion-exchange membranes in or on which electrode material is embedded

Abstract

A method and apparatus for synthesizing anhydrous ammonia utilizing proton conducting electrolyte having a water vapor dissociating electrocatalyst on one side and a nitrogen dissociating electrocatalyst on the other side. A voltage is provided across the proton conducting electrolyte, protons are separated from the water vapor and transferred through the middle of the proton conducting electrolyte to the second side of the proton conducting electrolyte. Nitride ions are formed from nitrogen and the electrons provided by the voltage on the second side of the proton conducting electrolyte. The protons are then reacted with the nitride ions on the second side of the proton conducting electrolyte to produce anhydrous ammonia. A preferred proton conducting electrolyte is barium cerium oxide doped with about 10% ytterbium with a water vapor dissociating electrocatalyst of Ni and Pd, and a nitrogen dissociating electrocatalyst of Co and Ru.

Claims

1. A method for synthesizing anhydrous ammonia comprising the steps of:

a. providing a proton conducting electrolyte having a first side and a second side, wherein at least a portion of the first side of the proton conducting electrolyte is provided in contact with a water vapor dissociating electrocatalyst and at least a portion of the second side of the proton conducting electrolyte is provided in contact with a nitrogen dissociating electrocatalyst,

b. providing a voltage across the proton conducting electrolyte,

c. exposing the first side of the proton conducting electrolyte to water vapor, and

d. exposing the second side of the proton conducting electrolyte to nitrogen at a pressure of between about 10 atm and about 300 atm.

2. The method of claim 1 wherein the step of exposing the first side of the proton conducting electrolyte to water vapor is performed at a pressure and temperature sufficient to substantially prevent condensation of water.

3. The method of claim 1 wherein the step of exposing the first side of the proton conducting electrolyte to water vapor is performed at a temperature of between about 400°

C. and about 800°

C.

4. The method of claim 1 wherein the step of exposing the first side of the proton conducting electrolyte to water vapor is performed at substantially the same pressure as the step of exposing the second side of the proton conducting electrolyte to nitrogen.

5. The method of claim 1 wherein the proton conducting electrolyte is a perovskite having a dopant.

6. The method of claim 5 wherein the perovskite having a dopant is in the form ABO₃ where A is an element that forms a divalent cation, B is an element that forms a quadravalent cation, and a portion of B is replaced with a dopant.

7. The method of claim 6 wherein A is selected from the group consisting of alkaline earth elements, other elements that form divalent cations, and combinations thereof, and B is selected from the group consisting of IVB transition metals, the group IVA metals, other elements that form quadravalent cations, and combinations thereof.

8. The method of claim 7 wherein the dopant is selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu, B, Al, Ga, In, Sb, Bi, Cr, Fe, Ru, Os, Co, Rh, Ir, and combinations thereof.

9. The method of claim 1 wherein the water vapor dissociating electrocatalyst preferentially decomposes water vapor in favor of adsorbing oxygen.

10. The method of claim 9 wherein the water vapor dissociating electrocatalyst is selected from the group consisting of Pt, Pd, Ni, Co, Cu, Ag, W, Os, Ru, Rh, Ir, Cr, Fe, Mo, V, Re, Mn, Nb, Ta, oxides and sulfides of the forgoing, and alloys of combinations thereof.

11. The method of claim 1 wherein said nitrogen dissociating electrocatalyst is selected as an electrocatalyst that preferentially dissociates diatomic nitrogen in favor of dissociating ammonia.

12. The method of claim 1 wherein the nitrogen dissociating electrocatalyst is selected from the group consisting of Pt, Pd, Ni, Co, Cu, Ag, W, Os, Ru, Rh, Ir, Cr, Fe, Mo, V, Re, Mn, Nb, Ta, oxides and sulfides of the forgoing, and alloys of combinations thereof.

13. The method of claim 1 wherein the voltage is applied across the proton conducting electrolyte by using the water vapor dissociating electrocatalyst and the nitrogen dissociating electrocatalyst as electrodes.

14. The method of claim 1 wherein at least one proton conducting electrolyte is provided in a tubular geometry.

15. The method of claim 1 wherein at least one proton conducting electrolyte is provided in a planar geometry.

16. The method of claim 1 further comprising the steps of

e. decomposing the water vapor to produce protons and oxygen after the step of exposing the first side of the proton conducting electrolyte to water vapor,

f. transferring the protons from the first side of the proton conducting electrolyte to the second side of the proton conducting electrolyte, and

g. forming ammonia after the step of exposing the second side of the proton conducting electrolyte to nitrogen.

17. The method of claim 16 wherein the water vapor is provided in a first loop.

18. The method of claim 17 wherein oxygen formed by decomposing water vapor is removed from the water vapor present in the first loop.

19. The method of claim 16 wherein the nitrogen is provided in a second loop.

20. The method of claim 19 wherein ammonia is separated from the nitrogen present in the second loop.

21. A method for synthesizing anhydrous ammonia comprising the steps of:

p1 a. providing a proton conducting electrolyte of barium cerium oxide doped with about 10% ytterbium having a first side and a second side,

b. providing the first side of the proton conducting electrolyte in contact with a water vapor dissociating electrocatalyst selected from the group consisting of Ni, Pd,and combinations thereof,

c. providing the second side of the proton conducting electrolyte in contact with a nitrogen dissociating electrocatalyst selected from the group consisting of Co, Ru, and combinations thereof,

d. providing a voltage across the proton conducting electrolyte,

e. exposing the first side of the proton conducting electrolyte to water vapor, and

f. exposing the second side of the proton conducting electrolyte to nitrogen at a pressure of between about 10 atm and about 300 atm.