Method for the purification of noble gases, nitrogen and hydrogen

• US 5,669,961 A
• Filed: 11/10/1994
• Issued: 09/23/1997
• Est. Priority Date: 07/12/1993
• Status: Expired due to Fees

• Current Assignee: Battelle Energy Alliance LLC (Battelle Memorial Institute)
• Original Assignee: Lockheed Martin Idaho Technologies Co (Martin Marietta Corporation)
• Inventors: Baker, John D., Tuggle, Dale G., Meikrantz, David H.
• Primary Examiner(s): SPITZER, ROBERT H
• Application Number:
  US08/337,574
• Time in Patent Office: 1,048 Days
• Field of Search: 95/115, 95/117, 95/121, 95/127, 95/128, 95/138-140, 95/143, 95/146, 95/900, 96/109, 96/112, 96/121, 96/126, 96/127, 96/133, 96/143, 156/DIG. 66, 252/181.1, 252/181.4, 252/181.6, 252/181.7, 445/55
• US Class Current: 95/115
• CPC Class Codes: B01D 2253/10 Inorganic adsorbents
• CPC Class Codes: B01D 2256/10 Nitrogen
• CPC Class Codes: B01D 2256/16 Hydrogen
• CPC Class Codes: B01D 2256/18 Noble gases
• CPC Class Codes: B01D 2257/102 Nitrogen
• CPC Class Codes: B01D 2257/104 Oxygen
• CPC Class Codes: B01D 2257/406 Ammonia
• CPC Class Codes: B01D 2257/502 Carbon monoxide
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2257/80 Water
• CPC Class Codes: B01D 53/02 by adsorption, e.g. preparative gas chromatography solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01
• CPC Class Codes: B01D 53/04 with stationary adsorbents B01D53/025 takes precedence
• CPC Class Codes: Y02C 20/40 of CO2
• CPC Class Codes: Y10S 95/90 Solid sorbent

Abstract

A method and apparatus for the purification and collection of hydrogen isotopes in a flowing inert gaseous mixture containing impurities, wherein metal alloy getters having the capability of sorbing non-hydrogen impurities such as oxygen, carbon dioxide, carbon monoxide, methane, ammonia, nitrogen and water vapor are utilized to purify the gaseous mixture of impurities. After purification hydrogen isotopes may be more efficiently collected. A plurality of parallel process lines utilizing metal getter alloys can be used to provide for the continuous purification and collection of the hydrogen isotopes.

Claims

1. A method for the purification of a gaseous mixture containing reactive impurities, comprising the steps of:

(a) providing a bulk purifying getter in a casing, said purifying getter being comprised of a zirconium-manganese-iron-aluminum alloy having the capability of sorbing non-hydrogen reactive impurities and the capability of not sorbing hydrogen isotopes;

(b) heating the bulk purifying getter;

(c) introducing the gaseous mixture into the purifying getter casing for a sufficient residence time and at an effective temperature to cause the cracking and sorption of the non-hydrogen reactive impurities from the gaseous mixture by the purifying getter; and

(d) removing the remaining non-sorbed gaseous mixture from the purifying getter casing.

2. The method of claim 1 wherein the amount of non-hydrogen reactive impurities contained within the gaseous mixture is in excess of 100 parts per million.

3. The method of claim 1 wherein the reactive impurities comprise between 0.01% to 1.1% of the gaseous mixture.

4. The method of claim 1 further comprising the step of collecting hydrogen isotopes from the remaining non-sorbed gaseous mixture.

5. The method of claim 4 wherein the hydrogen isotopes are collected from the remaining gaseous mixture by introducing at an effective getter temperature and residence time the remaining gaseous mixture into a second casing containing a collecting getter, said collecting getter having the capability of sorbing hydrogen isotopes.

6. The method of claim 5 wherein the collecting getter comprises a zirconium alloy.

7. The method of claim 5 wherein the collecting getter comprises a lanthanide-nickel alloy.

8. The method of claim 5 wherein the collecting getter is comprised of uranium.

9. The method of claim 1 wherein the purifying getter alloy contains in percent by weight approximately, 40% zirconium, 25% manganese, 25% iron, and 10% aluminum.

10. The method of claim 1 wherein the gaseous mixture to be purified is substantially hydrogen isotopes.

11. The method of claim 1 wherein the gaseous mixture to be purified is substantially a noble gas.

12. The method of claim 1 wherein the gaseous mixture to be purified is substantially nitrogen.

13. The method of claim 1 wherein the reactive impurities are selected from the group comprised of C_x Q_y, CQ₄, CO, CO₂, N₂, O₂, or NQ₃, where x and y are integers, and Q is a hydrogen isotope.

14. The method of claim 1 wherein the temperature of the purifying getter is in the range of between 400°

C. and 1000°

C.

15. A method for the purification of a gaseous stream of non-hydrogen reactive impurities and collection of hydrogen isotopes from the purified gaseous stream comprising the steps of:

(a) providing a bulk purifying getter in a casing, said purifying getter being comprised of a zirconium-manganese-iron-aluminum alloy having the capability of sorbing non-hydrogen reactive impurities and the capability of not sorbing hydrogen isotopes;

(b) introducing the gaseous mixture into the purifying getter casing for a sufficient residence time and at an effective temperature to cause the cracking and sorption of the non-hydrogen reactive impurities from the gaseous mixture by the purifying getter;

(c) removing the remaining non-sorbed gaseous mixture from the purifying getter casing;

(d) providing a bulk collection getter in a casing, said collection getter being comprised of an alloy having the capability of sorbing hydrogen isotopes;

(e) introducing the non-sorbed gaseous mixture removed from the purifying getter casing into the collection getter casing for a sufficient residence time and at an effective getter temperature to cause the bulk collection getter to sorb hydrogen isotopes from the gaseous mixture;

(f) removing the non-sorbed gaseous mixture from the collection getter casing.

16. The method of claim 15 wherein the purifying getter alloy contains in percent by weight approximately, 40% zirconium, 25% manganese, 25% iron, and 10% aluminum.

17. The method of claim 16 wherein the reactive impurities comprise between 0.01% to 1.1% of the gaseous mixture.

18. The method of claim 15 wherein the reactive impurities are selected from the group comprised of C_x Q_y, CQ₄, CO, CO₂, N₂, O₂, or NQ₃, where x and y are integers, and Q is a hydrogen isotope.

19. The method of claim 18 wherein the temperature of the purifying getter is in the range of between 400°

C. and 1000°

C.

20. The method of claim 15 wherein the amount of non-hydrogen reactive impurities contained within the gaseous mixture is in excess of 100 parts per million.

21. An apparatus for the purification of hydrogen isotopes from a gaseous mixture containing reactive impurities, comprising:

(a) control means for controlling the flow of the gaseous mixture, said mixture being directed through a housing;

(b) purification getter means within the housing for removing through cracking and sorption substantially all non-hydrogen reactive impurities from the gaseous mixture, the purification getter means being comprised of a zirconium-manganese-iron-aluminum alloy, the remaining gaseous mixture then exiting the housing and being comprised substantially of hydrogen isotopes and other non-sorbed gases; and

(c) temperature control means for controlling the purification getter temperature.

22. The apparatus of claim 21 further comprising primary collection means for collecting hydrogen isotopes from the remaining gaseous mixture exiting the housing.

23. The apparatus of claim 22 further comprising secondary collection means for collecting hydrogen isotopes not previously collected by the primary collection means.

24. The apparatus of claim 23 wherein the primary collection and secondary collection means are zirconium alloys.

25. The apparatus of claim 23 wherein the primary collection and secondary collection means are lanthanide-nickel alloys.

26. The apparatus of claim 23 wherein the primary collection and secondary collection means is uranium.

27. The apparatus of claim 21 wherein the purification getter means is a zirconium-manganese-iron-aluminum alloy having the capability of sorbing non-hydrogen reactive impurities and the capability of not sorbing hydrogen isotopic impurities.

28. The apparatus of claim 22 wherein the reactive impurities cracked and sorbed by the purification getter means are selected from the group comprised of C_x Q_y, CQ₄, CO, CO₂, N₂, O₂, NQ₃, or Q₂ O, where x and y are integers, and Q is a hydrogen isotope.

29. A system for the continuous purification and collection of hydrogen isotopes from a gaseous mixture containing reactive impurities, comprising

(a) valve means for controlling the flow of the gaseous mixture between a plurality of parallel process lines;

(b) a purification getter material within each process line, said getter material being comprised of a zirconium-manganese-iron-aluminum alloy having the capability, when contacted with the gaseous material for a sufficient residence time and at an effective temperature, of sorbing non-hydrogen reactive impurities from the gaseous mixture and having the further capability of not sorbing hydrogen isotopes; and

(c) primary collection getter means, within each process line in downstream communication with said purification getter material, for collecting hydrogen isotopes from the gaseous mixture.

30. The apparatus of claim 29 wherein the purification getter material is a zirconium-manganese-iron-aluminum alloy comprising, in percent by weight, approximately 40% zirconium, 25% manganese, 25% iron and 10% aluminum.

31. The apparatus of claim 29 further comprising secondary collection means, in downstream communication with said primary collection means, for collecting hydrogen isotopes not previously collected by the primary collection means.

32. The apparatus of claim 31 wherein the primary collection and secondary collection means are zirconium alloys.

33. The apparatus of claim 29 wherein the reactive impurities sorbed by the purification getter material are selected from the group comprised of C_x Q_y, CQ₄, CO, CO₂, N₂, O₂, NQ₃, or Q₂ O, where x and y are integers, and Q is a hydrogen isotope.

34. The apparatus of claim 29 wherein the gaseous mixture contains a concentration of the reactive impurities in excess of 100 parts per million.

35. The apparatus of claim 29 wherein the reactive impurities comprise between 0.01% to 1.1% of the gaseous mixture.