Method for producing halogenated products from metal halide feeds

• US 5,717,149 A
• Filed: 06/05/1995
• Issued: 02/10/1998
• Est. Priority Date: 06/05/1995
• Status: Expired due to Term

• Current Assignee: Quantum Catalytics LLC
• Original Assignee: Molten Metal Technology Incorporated
• Inventors: Bach, Robert D., Johnston, James E., Nagel, Christopher J., Stephenson, Michael J.
• Primary Examiner(s): Mai, Ngoclan
• Application Number:
  US08/460,887
• Time in Patent Office: 981 Days
• Field of Search: 588/201, 75/398, 75/399, 75/437, 75/500
• US Class Current: 75/398
• CPC Class Codes: G21F 9/32 by incineration

Abstract

A method and apparatus producing halogenated products from metal halide feeds. In one embodiment, uranium hexafluoride is treated by separating fluorine from the metal of the uranium hexafluoride. Uranium hexafluoride is introduced into a molten metal bath under conditions whereby the uranium hexafluoride in the presence of hydrogen and oxygen can react to form a uranium dioxide and anhydrous hydrogen fluoride. The anhydrous hydrogen fluoride is removed from the molten metal bath as a gas stream and the uranium dioxide is discharged as a ceramic phase.

Claims

1. A method for processing uranium hexafluoride, comprising the steps of:

a) providing an aluminum-based refractory lined reactor;

b) providing a nickel metal bath in said reactor;

c) directing said uranium hexafluoride into the molten metal bath at a rate and condition which causes the uranium hexafluoride to interact with at least one reactant;

d) directing said reactant into the reactor;

e) maintaining a carbon concentration in the molten metal bath of less than about 0.1 weight percent; and

f) establishing and maintaining conditions in said reactor to cause said uranium hexafluoride to react to produce recoverable uranium and fluorinated products, whereby the products are discharged from the molten metal bath for subsequent recovery.

2. A method for producing a halogenated product from a metal halide feed comprising the steps of:

a) providing a reactor containing a molten metal bath, said molten metal bath having a free energy of halogenation, under the temperature and halide partial pressure conditions of the reactor, greater than that of the metal halide feed;

b) directing said metal halide feed into the molten metal bath at a rate and condition which causes the metal halide to interact with a halogenated product-forming reactant;

c) directing said halogenated product-forming reactant into the reactor; and

d) establishing and maintaining conditions in said reactor to cause said metal halide feed to react with the reactant, thereby forming a halogenated product, whereby the halogenated product is discharged from the molten metal bath for subsequent recovery.

3. A method of claim 2 wherein the bath metal includes nickel.

4. A method of claim 2 wherein the bath metal includes copper.

5. A method of claim 2 wherein the bath metal is an alloy.

6. A method of claim 2 wherein the halogenated product forming reactant includes a Group 1A element.

7. A method of claim 2 wherein the halogenated product forming reactant includes hydrogen.

8. A method of claim 2 wherein the halogenated product forming reactant includes magnesium.

9. A method of claim 2 wherein the halogenated product includes an anhydrous haloacid.

10. A method of claim 2 wherein the halogenated product includes HF.

11. A method of claim 2 wherein the halogenated product includes CaCl₂.

12. A method of claim 2 wherein the halogenated product includes CaF₂.

13. A method of claim 2 wherein the halogenated product includes MgF₂.

14. A method of claim 2 wherein an oxidizing reactant is fed to the reactor, under the operating conditions of the reactor, in about a 1:

1 stoichiometric ratio of oxygen to oxidizable portion of the metal halide feed.

15. A method of claim 2 wherein the process is operated continuously.

16. A method of claim 2 wherein the process is operated in a batch mode.

89. A method of claim 2 wherein the reactant includes an oxidizing agent.

90. A method of claim 2 wherein the reactant includes a reducing agent.

91. A method of claim 2 wherein the reactant includes a reducible metal oxide.

92. A method of claim 2 wherein the reactant includes steam.

93. A method of claim 2 wherein the reactant includes an organic.

94. A method of claim 2 wherein the reactant includes a hydrocarbon.

95. A method of claim 2 wherein the reactant includes carbon.

96. A method of claim 2 wherein the reactant includes inorganically bound oxygen.

97. A method of claim 2 wherein the product includes an iron alloy.

17. A method for producing a non-halogenated product from a metal halide feed, comprising the steps of:

a) providing a reactor containing a molten metal bath, said molten metal bath having a free energy of halogenation, under the temperature and halide partial pressure conditions of the reactor, greater than that of the metal halide feed;

b) directing said metal halide feed into the molten metal bath at a rate and condition which causes the metal halide to interact with a non-halogenated product-forming reactant;

c) directing said non-halogenated product-forming reactant into the reactor; and

d) establishing and maintaining conditions in said reactor to cause said metal halide feed to react with reactant, thereby forming a non-halogenated product, whereby the non-halogenated product is discharged from the molten metal bath for subsequent recovery.

18. A method of claim 17 wherein the non-halogenated product forming reactant includes an oxidizing agent.

19. A method of claim 17 wherein the non-halogenated product forming reactant includes a reducible metal oxide.

20. A method of claim 17 wherein the non-halogenated product forming reactant includes steam.

21. A method of claim 17 wherein the non-halogenated product forming reactant includes inorganically bound oxygen.

22. A method for processing at least one uranium fluoride, comprising the steps of:

a) providing a reactor containing a molten metal bath, said molten metal bath having a free energy of fluorination, under the temperature and fluorine partial pressure conditions of the reactor, greater than that of the uranium fluoride;

b) directing said uranium fluoride into the molten metal bath at a rate and condition which causes the uranium fluorides to interact with at least one product-forming reactant;

c) directing said product-forming reactant into the reactor; and

d) establishing and maintaining conditions in said reactor to cause said uranium fluorides to react with the product-forming reactant to produce recoverable uranium and fluorinated products, whereby the products are discharged from the molten metal bath for subsequent recovery.

23. A method for processing uranium hexafluoride, comprising the steps of:

a) providing a graphite-lined reactor;

b) providing a molten metal bath in said reactor, said molten metal bath having a free energy of fluorination, under the temperature and fluorine partial pressure conditions of the reactor, greater than that of the uranium hexafluoride;

c) directing said uranium hexafluoride into the molten metal bath at a rate and condition which causes the uranium hexafluoride to interact with at least one product-forming reactant;

d) directing said product-forming reactant into the reactor; and

e) establishing and maintaining conditions in said reactor to cause said uranium hexafluoride to react to produce recoverable uranium and fluorinated products, whereby the products are discharged from the molten metal bath for subsequent recovery.

24. A method for processing uranium hexafluoride, comprising the steps of:

a) providing a graphite-lined reactor;

b) providing a molten metal bath in said reactor, said molten metal bath having a free energy of fluorination, under the temperature and fluorine partial pressure conditions of the reactor, greater than that of the uranium hexafluoride;

c) directing said uranium hexafluoride into the molten metal bath at a rate and condition which causes the uranium hexafluoride to interact with at least one product-forming reactant;

d) directing said product-forming reactant into the reactor;

e) maintaining a carbon concentration at about the equilibrium solubility of carbon in the bath metal; and

f) establishing and maintaining conditions in said reactor to cause said uranium hexafluoride to react to produce recoverable uranium and fluorinated products, whereby the products are discharged from the molten metal bath for subsequent recovery.

25. A method for processing uranium hexafluoride, comprising the steps of:

a) providing a lanthanum boride-lined reactor;

b) providing a molten metal bath in said reactor, said molten metal bath having a free energy of fluorination, under the temperature and fluorine partial pressure conditions of the reactor, greater than that of the uranium hexafluoride;

c) directing said uranium hexafluoride into the molten metal bath at a rate and condition which causes the uranium hexafluoride to interact with at least one product-forming reactant;

d) directing said product-forming reactant into the reactor; and

e) establishing and maintaining conditions in said reactor to cause said uranium hexafluoride to react to produce recoverable uranium and fluorinated products, whereby the products are discharged from the molten metal bath for subsequent recovery.

26. A method for processing uranium hexafluoride, comprising the steps of:

a) providing a graphite-lined reactor;

b) providing a molten metal bath in said reactor, said molten metal bath having a free energy of fluorination, under the temperature and fluorine partial pressure conditions of the reactor, greater than that of the uranium hexafluoride;

c) directing said uranium hexafluoride into the molten metal bath at a rate and condition which causes the uranium hexafluoride to interact with at least one product-forming reactant;

d) directing said product-forming reactant into the reactor; and

e) establishing and maintaining conditions in said reactor to cause said uranium hexafluoride to react to produce recoverable uranium and anhydrous hydrogen fluoride products, whereby the products are discharged from the molten metal bath for subsequent recovery.

27. A method for processing uranium hexafluoride, comprising the steps of:

a) providing a graphite-lined reactor;

b) providing a molten metal bath in said reactor, said molten metal bath having a free energy of fluorination, under the temperature and fluorine partial pressure conditions of the reactor, greater than that of the uranium hexafluoride;

c) directing said uranium hexafluoride into the molten metal bath at a rate and condition which causes the uranium hexafluoride to interact with at least one product-forming reactant;

d) directing said product-forming reactant into the reactor; and

e) establishing and maintaining conditions in said reactor to cause said uranium hexafluoride to react to produce recoverable uranium oxide and calcium fluoride products, whereby the products are discharged from the molten metal bath for subsequent recovery.

28. A method for processing uranium hexafluoride, comprising the steps of:

a) providing a graphite-lined reactor;

b) providing a copper metal bath in said reactor;

c) directing said uranium hexafluoride into the molten metal bath at a rate and condition which causes the uranium hexafluoride to interact with at least one reactant;

d) directing said reactant into the reactor; and

e) establishing and maintaining conditions in said reactor to cause said uranium hexafluoride to react to produce recoverable uranium and fluorinated products, whereby the products are discharged from the molten metal bath for subsequent recovery.

29. A method for processing uranium hexafluoride comprising the step of:

a) providing a reactor containing a molten metal bath, said molten metal bath having a free energy of fluorination, under the temperature and fluorine partial pressure condition of the reactor, greater than that of said uranium hexafluoride;

b) directing said uranium hexafluoride into the molten metal bath at a rate and condition which causes the uranium hexafluoride to interact with at least one reactant;

c) directing said reactant into the reactor; and

e) establishing and maintaining conditions in said reactor to cause said uranium hexafluoride to react to produce recoverable uranium metal and fluorinated products, whereby the products are discharged from the molten metal bath for subsequent recovery.

30. A method of claim 29 wherein the products are recovered sequentially.

31. A method of claim 29 wherein the process is operated continuously.

32. A method of claim 29 wherein the process is operated in a batch mode.

33. A method for proceeding iron chlorides, comprising the steps of:

a) providing a reactor containing a molten metal bath, said molten metal bath having a free energy of chlorination, under the temperature and chlorine partial pressure conditions of the reactor, greater than that of the iron chlorides;

b) directing said iron chlorides into the molten metal bath at a rate and condition which causes the iron chlorides to interact with a reactant;

c) directing said reactant into the reactor; and

d) establishing and maintaining conditions in said reactor to cause said iron chlorides to react to product recoverable iron and chlorinated products, whereby the products are discharged from the molten metal bath for subsequent recovery.

34. A method of claim 33 wherein the reactant includes an oxidizing agent.

35. A method of claim 33 wherein the reactant includes a reducing agent.

36. A method of claim 33 wherein the reactant includes a reducible metal oxide.

37. A method of claim 33 wherein the reactant includes steam.

38. A method of claim 33 wherein the reactant includes an organic.

39. A method of claim 33 wherein the reactant includes a hydrocarbon.

40. A method of claim 33 wherein the reactant includes carbon.

41. A method of claim 33 wherein the reactant includes inorganically bound oxygen.

42. A method of claim 33 wherein the product includes an iron alloy.

43. A method for treating uranium hexafluoride, comprising the steps of:

a) directing the uranium hexafluoride into a molten metal bath; and

b) directing a chemical reactant into the molten metal bath, whereby said chemical reactant reacts with the uranium hexafluoride to form a uranium product.

44. The method of claim 43 wherein the chemical reactant is an oxidizing agent.

45. The method of claim 44 wherein the oxidizing reactant includes steam.

46. The method of claim 44 wherein the oxidizing reactant includes a metal oxide.

47. The method of claim 46 wherein the metal oxide includes a calcium oxide.

48. The method of claim 46 wherein the metal oxide includes an aluminum oxide.

49. The method of claim 48 wherein the metal oxide is alumina.

50. The method of claim 46 wherein the metal oxide includes silicon dioxide.

51. The method of claim 43 wherein the uranium hexafluoride is directed into a molten iron bath.

52. The method of claim 43 wherein the uranium hexafluoride is directed into a molten nickel bath.

53. The method of claim 43 wherein the uranium hexafluoride is directed into a molten copper bath.

54. The method of claim 43 wherein the chemical reactant is a reducing reactant.

55. The method of claim 54 wherein the reducing agent includes magnesium.

56. The method of claim 54 wherein the reducing reactant includes hydrogen gas, whereby said uranium product is uranium tetrafluoride.

57. The method of claim 56, further including the step of directing an oxidizing reactant into said bath, whereby said oxidizing reactant reacts with at least a portion of said uranium tetrafluoride to form an oxidized uranium product.

58. The method of claim 57 wherein said oxidizing reactant includes steam, whereby the oxidized uranium product includes uranium dioxide.

59. The method of claim 58, further including the step of directing a carbon-containing material into the molten metal bath, whereby at least a portion of oxygen in said molten metal bath reacts with carbon of said carbon-containing material to form a carbon oxide gas that is discharged from the molten metal bath.

60. A method for treating uranium hexafluoride, comprising the steps of:

a) directing the uranium hexafluoride into a molten metal bath;

b) directing hydrogen gas into said molten metal bath, whereby hydrogen of said hydrogen gas reduces a portion of the uranium hexafluoride to form uranium tetrafluoride and anhydrous hydrogen fluoride, said anhydrous hydrogen fluoride being discharged from the molten metal bath; and

c) directing a steam into said molten metal bath, whereby at least a portion of said uranium tetrafluoride reacts to form uranium dioxide and anhydrous hydrogen fluoride, said uranium dioxide separating from the molten metal bath, and said anhydrous hydrogen fluoride being discharged from the molten metal bath.

61. The method of claim 60 wherein said molten metal bath includes iron.

62. The method of claim 60 wherein said molten metal bath includes nickel.

63. The method of claim 60 wherein said molten metal bath includes copper.

64. The method of claim 60, further including the step of directing a carbon-containing material into the molten metal bath.

65. The method of claim 60 wherein the hydrogen gas and the steam are directed into the molten metal bath conjointly with the uranium hexafluoride.

66. The method of claim 65 wherein the hydrogen gas, steam and uranium hexafluoride are directed into the molten metal bath continuously.

67. The method of claim 60 wherein the steam directed into the molten metal bath causes formation of uranium dioxide which migrates from the molten metal bath to a ceramic phase of said molten metal bath.

68. The method of claim 67 further including the step of directing an oxygen-containing gas into said ceramic phase.

69. The method of claim 68 wherein said oxygen-containing gas is air.

70. The method of claim 60 further including the step of directing at least one vitreous phase former into the reaction zone.

71. The method of claim 70 wherein the vitreous phase former includes calcium fluoride.

72. The method of claim 70 wherein the vitreous phase former includes cryolite.

73. The method of claim 69 wherein the vitreous phase former is selected from the group consisting of calcium fluoride, sodium fluoride, aluminum fluoride, and aluminum oxide.

74. The method of claim 60, further including the steps of:

a) forming a gaseous discharge stream that includes said anhydrous hydrogen fluoride;

b) cooling said discharge stream;

c) filtering said discharge stream, whereby at least a portion of any entrained uranium oxide is separated from said anhydrous fluoride; and

d) condensing at least a portion of the anhydrous fluoride to form a condensed anhydrous fluoride stream and a residual gas stream.

75. The method of claim 74 further including the step of combining the residual gas stream with a metal oxide to form a metal fluoride precipitate that separates from the residual gas stream.

76. The method of claim 74 further including the step of scrubbing the residual gas stream to form a liquid stream that includes residual fluoride separated from the residual gas stream.

77. The method of claim 76 further including the steps of volatilizing the liquid stream and then directing the volatilized stream into the molten metal bath.

78. The method of claim 67 further including forming a ceramic discharge stream from said ceramic phase, whereby ceramic material is discharged from said reaction zone.

79. The method of claim 78 wherein said ceramic material is discharged continuously from said reaction zone.

80. The method of claim 79 further including the steps of cooling the ceramic material of said ceramic discharge stream and then combining said cooled ceramic material with an oxygen-containing gas, whereby at least a portion of said uranium dioxide component of said ceramic material is converted to U₃ O₈, and whereby entrained anhydrous hydrogen fluoride is separated from the ceramic material to form an entrained hydrogen fluoride gas stream.

81. The method of claim 80 further including the step of separating the anhydrous hydrogen fluoride component from said entrained hydrogen fluoride gas stream.

82. The method of claim 80 wherein said oxygen-containing gas is air.

83. The method of claim 79 further including the steps of cooling the ceramic material of said ceramic discharge stream and combining said cooled ceramic material with carbon monoxide gas and chlorine gas, whereby at least a portion of said uranium dioxide component reacts to form uranium tetrachloride.

84. The method of claim 83 further including the step of reacting said uranium tetrachloride with magnesium to thereby form elemental uranium metal and magnesium chloride.

85. The method of claim 84 further including the step of electrochemically reducing the magnesium chloride to form an elemental magnesium metal stream and a chlorine gas stream.

86. A method for treating uranium hexafluoride, comprising the steps of:

a) directing the uranium hexafluoride into a molten metal bath; and

b) directing a metal reactant into the molten metal bath, whereby said metal reactant reacts with the uranium hexafluoride to form elemental uranium metal or a uranium metal alloy, and a metal fluoride.

87. The method of claim 86 wherein said metal reactant includes magnesium.

88. The method of claim 87 wherein said metal reactant includes calcium.