Process for the in situ recovery of chemical values from UF 6 gaseous diffusion process equipment

• US 5,787,353 A
• Filed: 03/26/1996
• Issued: 07/28/1998
• Est. Priority Date: 03/26/1996
• Status: Expired due to Term

• Current Assignee: Southeastern Technologies, Inc.
• Original Assignee: Southeastern Technologies, Inc.
• Inventors: Kibbe, Keith, Kephart, Wilbur L., Visnapuu, Aarne
• Primary Examiner(s): MAI, NGOCLAN THI
• Application Number:
  US08/622,261
• Time in Patent Office: 854 Days
• Field of Search: 423/19, 423/149, 423/258, 376/309, 976/DIG. 376, 134/30, 134/2
• US Class Current: 423/19
• CPC Class Codes: C01G 43/066 Preparation
• CPC Class Codes: C01G 53/02 Carbonyls
• CPC Class Codes: C22B 23/065 carbonyl methods
• CPC Class Codes: C22B 60/0213 by dry processes
• CPC Class Codes: C22B 7/002 by treating with halogens, sulfur or compounds thereof; by carburising, by treating with hydrogen (hydriding)
• CPC Class Codes: G21F 9/002 Decontamination of the surface of objects with chemical or electrochemical processes
• CPC Class Codes: G21F 9/30 Processing separating different isotopes of the same chemical element B01D59/00

Abstract

A process for the recovery of chemical values, particularly uranium, nickel and/or radionuclides from process equipment theretofore employed in a uranium hexafluoride isotope enrichment cascade. Preferably, the process is carried out, in situ, at subatmospheric pressure employing the existing process equipment from which the chemical values are to be recovered. In one aspect, the process includes recovery of uranium values employing a gaseous fluorinating agent at subatmospheric pressure, followed by recovery of nickel values employing a gaseous reactant comprising a mixture of carbon monoxide and a promoter, preferably hydrogen sulfide and at subatmospheric pressure.

Claims

1. A process for the recovery of uranium and nickel values from one or more items of process equipment theretofore employed in a uranium hexafluoride isotope enrichment gaseous diffusion plant employing the steps of

conditioning an item of process equipment to ensure its freedom from undesirable chemical values,

subjecting said conditioned item of process equipment to a quantity of a gaseous fluorinating agent that is capable of converting at least uranium oxide and/or uranyl fluoride to gaseous uranium hexafluoride at a temperature not greater than about 65°

C., and at subatmospheric pressure, for a time sufficient to convert at least uranium compounds disposed on the surfaces of the item of process equipment to gaseous uranium hexafluoride,

withdrawing and capturing said uranium hexafluoride,

thereafter, subjecting said item of process equipment to a mixture of gaseous carbon monoxide and a gaseous promoter, at subatmospheric pressure and at a temperature less than the temperature at which nickel carbonyl decomposes when at a subatmospheric pressure, for a time sufficient to convert metallic nickel exposed on the surfaces of the item of process equipment to gaseous nickel carbonyl,

withdrawing said gaseous nickel carbonyl, and

converting said gaseous nickel carbonyl to metallic nickel.

2. The process of claim 1 wherein the gaseous fluorinating agent comprises gaseous chlorine trifluoride.

3. The process of claim 1 wherein the gaseous promoter comprises gaseous hydrogen sulfide.

4. The process of claim 1 wherein the items of process equipment comprise the process equipment included in a preexisting cell of a cascade for the isotope enrichment of uranium hexafluoride.

5. The process of claim 1 and including the step of maintaining the temperature of the gaseous fluorinating agent at a temperature not greater than about 65°

C.

6. The process of claim 1 and including the step of maintaining the temperature of the mixture of carbon monoxide and gaseous promoter, during the time in which the mixture of gas is in position to convert metallic nickel exposed on the surfaces of the item of process equipment to gaseous nickel carbonyl, at a temperature less than the temperature at which the pressure developed by the gaseous mixture of carbon monoxide, gaseous promoter and nickel carbonyl is no longer subatmospheric.

7. The process of claim 1 and including the step of circulating the mixture of carbon monoxide and gaseous promoter past metallic nickel exposed on the surfaces of the item of process equipment to develop a flowing gas stream containing a mixture of gaseous carbon monoxide, gaseous promoter and gaseous nickel carbonyl.

8. The process of claim 7 and including the steps of circulating the flowing gas stream through a treatment loop disposed remote from the item of process equipment, and within the treatment loop, converting nickel carbonyl in the flowing gas stream to metallic nickel.

9. The process of claim 1 and including the step of selecting the gaseous fluorinating agent from the group of gases comprising chlorine trifluoride, bromine trifluoride, iodine heptafluoride, and dioxygen difluoride.

10. The process of claim 1 and including the step of selecting the gaseous promoter from the group of gases comprising hydrogen sulfide, ammonia, ammonium polysulfide, and a mixture of hydrogen sulfide and water vapor.

11. The process of claim 1 wherein the gaseous fluorinating agent comprises gaseous fluorine or a halofluoride gas.

12. The process of claim 1 and including the step of collecting gaseous chemical values other than uranium or nickel values separately from the uranium and nickel values.

13. The process of claim 1 and including the step of repeating the steps of claim 1 following the withdrawal of nickel values.

14. The process of claim 1 wherein the gaseous fluorinating agent is adjusted to a temperature of between about 15°

C. and about 65°

C. when the gaseous fluorinating agent is presented to a uranium value.

15. The process of claim 1 and including the step of continuously circulating the gaseous fluorinating agent past uranium-containing deposits exposed on the surfaces of the item of process equipment to develop a flowing gas stream containing the mixture of the gaseous fluorinating agent and uranium hexafluoride gas.

16. The process of claim 15 and including the steps of circulating the flowing gas stream through a treatment loop disposed remote from the item of process equipment, and within the treatment loop, and extracting at least a portion of the uranium hexafluoride from the flowing gas stream.

17. The process of claim 15 wherein the temperature of the flowing gas stream when the gas stream is disposed within the item of process equipment is maintained at a level which assures that the partial pressure of any uranium hexafluoride contained within the flowing gas stream is below that partial pressure at which the uranium hexafluoride will desubliminate within the item of process equipment.

35. The process of claim 23 and including the step of repeating the steps of claim 1 following the withdrawal of nickel values.

18. A process for the recovery of metallic nickel from an item having metallic nickel exposed on the surface thereof comprising

disposing the item having metallic nickel exposed on the surface thereof in a closed reaction vessel,

circulating through the reaction vessel a mixture of gaseous carbon monoxide and a gaseous promoter, at subatmospheric pressure and at a temperature less than the temperature at which nickel carbonyl decomposes, to convert the nickel exposed on the surface of the item to gaseous nickel carbonyl to develop a flowing gas stream containing carbon monoxide, gaseous promoter and nickel carbonyl,

continuously withdrawing at least a portion of the flowing gas stream from the reaction vessel, and

continuously converting at least a portion of the nickel carbonyl in the flowing gas stream which is withdrawn from the vessel to metallic nickel.

19. The process of claim 18 and including the step of returning the flowing gas stream to the reaction vessel following the conversion of at least a portion of the nickel carbonyl in the flowing gas stream to metallic nickel.

20. The process of claim 18 and including the step of adding to the flowing gas stream additional gaseous carbon monoxide.

21. The process of claim 18 and including the step of adding to the flowing gas steam an additional gaseous promoter.

22. The process of claim 18 and including the step of selecting the gaseous promoter from the group of gases including hydrogen sulfide, carbonyl sulfide, ammonia, ammonium polysulfide and a mixture of hydrogen sulfide and water vapor.

23. A process for the in situ recovery of uranium and nickel values from one or more items of process equipment theretofore employed in a uranium hexafluoride isotope enrichment gaseous diffusion plant employing the steps of

conditioning an item of process equipment in situ to ensure its freedom from undesirable chemical values,

subjecting said conditioned item of process equipment to a quantity of a gaseous fluorinating agent that is capable of converting uranium oxide and/or uranyl fluoride to gaseous uranium hexafluoride at a temperature not greater than about 65°

C., and at subatmospheric pressure, for a time sufficient to convert uranium compounds disposed on the surfaces of the item of process equipment to gaseous uranium hexafluoride,

withdrawing and capturing said uranium hexafluoride,

thereafter, subjecting said item of process equipment to a quantity of a mixture of gaseous carbon monoxide and a gaseous promoter, at subatmospheric pressure, and a temperature less than the temperature at which nickel carbonyl decomposes, for a time sufficient to convert metallic nickel exposed on the outer surfaces of the item of process equipment to gaseous nickel carbonyl,

withdrawing said gaseous nickel carbonyl, and

converting said gaseous nickel carbonyl to metallic nickel.

24. The process of claim 23 wherein the gaseous fluorinating agent comprises gaseous fluorine or a halo-fluoride gas.

25. The process of claim 23 wherein the gaseous fluorinating agent comprises gaseous chlorine trifluoride.

26. The process of claim 23 wherein the gaseous promoter comprises gaseous hydrogen sulfide.

27. The process of claim 23 wherein the items of process equipment comprise the process equipment included in a preexisting cell of a cascade for the isotope enrichment of uranium hexafluoride.

28. The process of claim 23 and including the step of maintaining the temperature of the gaseous fluorinating agent at a temperature between about 15°

C. and about 65°

C.

29. The process of claim 23 and including the step of maintaining the temperature of the mixture of carbon monoxide and gaseous promoter, during the time in which the mixture of gas is in position to convert metallic nickel exposed on the surfaces of the item of process equipment to gaseous nickel carbonyl, at a temperature less than the temperature at which the pressure developed by the mixture of gaseous carbon monoxide, gaseous promoter and gaseous nickel carbonyl is no longer subatmospheric.

30. The process of claim 23 and including the step of continuously circulating the mixture of carbon monoxide and gaseous promoter past metallic nickel exposed on the surfaces of the item of process equipment to develop a flowing gas stream containing the mixture of carbon monoxide and gaseous promoter and gaseous nickel carbonyl.

31. The process of claim 30 and including the steps of circulating the flowing gas stream through a treatment loop disposed remote from the item of process equipment, and within the treatment loop, converting nickel carbonyl in the flowing gas stream to metallic nickel.

32. The process of claim 23 and including the step of selecting the gaseous fluorinating agent from the group of gases comprising chlorine trifluoride, bromine trifluoride, iodine heptafluoride, and dioxygen difluoride.

33. The process of claim 23 and including the step of selecting the gaseous promoter from the group of gases comprising hydrogen sulfide, ammonia, ammonium polysulfide, and a mixture of hydrogen sulfide and water vapor.

34. The process of claim 23 and including the step of collecting gaseous chemical values other than uranium or nickel values separately from the uranium and nickel values.