US3208815A - Process of preparation of uranium compounds from uranium-molybdenum alloys - Google Patents

Process of preparation of uranium compounds from uranium-molybdenum alloys Download PDF

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Publication number
US3208815A
US3208815A US12290161A US3208815A US 3208815 A US3208815 A US 3208815A US 12290161 A US12290161 A US 12290161A US 3208815 A US3208815 A US 3208815A
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Prior art keywords
uranium
reaction
molybdenum
oxygen
compounds
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Expired - Lifetime
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English (en)
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Bourgeois Michel
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G43/00—Compounds of uranium
    • C01G43/04—Halides of uranium
    • C01G43/06—Fluorides
    • C01G43/063—Hexafluoride (UF6)
    • C01G43/066—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G43/00—Compounds of uranium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02—Obtaining thorium, uranium, or other actinides
    • C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
    • C22B60/0213—Obtaining thorium, uranium, or other actinides obtaining uranium by dry processes
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21C—NUCLEAR REACTORS
    • G21C19/00—Arrangements for treating, for handling, or for facilitating the handling of, fuel or other materials which are used within the reactor, e.g. within its pressure vessel
    • G21C19/42—Reprocessing of irradiated fuel
    • G21C19/44—Reprocessing of irradiated fuel of irradiated solid fuel
    • G21C19/48—Non-aqueous processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/30—Nuclear fission reactors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies

Definitions

  • the present invention relates to a process for preparing compounds (or a compound) of uranium which are practically free from molybdenum, from uranium-molybdenum alloys. This preparation is carried out at moderate temperatures, and enables the molybdenum to be eliminated at the same time as the alloy is attacked.
  • the process according to the invention comprises treating a uranium-molybdenum alloy with a gaseous mixture of a hydrogen halide and an oxygen-containing gas, the alloy at least initially being at a temperature of from 100 to 300 C. in order to initiate the reaction between the gaseous mixture and the alloy and the product of the reaction constituting the desired compounds.
  • the reaction is preferably carried out with gaseous mixtures containing hydrochloric or hydrofluoric acid and oxygen. It may also be carried using hydriodic acid or hydrobromic acid as the hydrogen halide but these acids are less advantageous,-in particular because of their cost, and do not lead to an industrial process as economical as do hydrochloric and hydrofluoric acid.
  • the residue or product of the reaction has the advantage that it can be converted into substantially pure uranium hexafluoride (in particular free from moylbdenum) by fluoridizing and then distilling the product of the reaction.
  • the reaction is carried out with a gaseous mixture containing hydrochloric acid
  • the major part of the molybdenum present in the alloy is sublimated in the form of oxychloride, a little uranium is also carried away with the sublimate as uranium oxychloride is also very volatile.
  • the uranium remains in the residue chiefly in the form of oxide.
  • this oxide may subsequently be fluoridized by any suitable method, such as the action of fluorine or an halogen fluoride.
  • This oxide may also subsequently be subjected to damp treatment in order to extract uranium by any suitable method based, for example, on the use of organic resins or solvents.
  • the molybdenum oxyfluoride formed is eliminated by vaporization, while the uranium remains in the residue in the form of a mixture of oxyfluoride and tetrafluoride.
  • This residue is particularly suitable for the production of uranium hexafluoride by fluoridation, since it already contains, in the combined state, about a third of the total quantity of fluorine present in the desired hexafluoride.
  • the additional quantity of fluorine required can be introduced by using hydrofluoric acid, which is a much more economical reagent than fluorine.
  • the fluoridation reaction starting from this intermediate mixture of uranium oxyfluoride and tetrafluoride is less exothermic and easier to control than the reaction starting from a uranium oxide and this also has the advantage of reducing corrosion of the equipment used.
  • FIGURES 1, 2, .3 and 4 diagrammatically illustrate the treatment of uraniummolybdenum alloys containing 0.5%, 1%, 2% and 10% of molybdenum respectively.
  • the reactions were carried out in a horizontal stainless steel or Monel tube according to whether hydrochloric acid or hydrofluoric acid was used; the alloy to be treated was preferably in a subdivided state, for example in the form of granules.
  • the reaction tube was placed inside an oven which was adjusted to give a temperature rise of C. per hour and the gaseous mixture used in the reaction was passed at a low rate from one end of the oven to the other, the gaseous mixture could instead have been introduced all at once for the whole duration of the reaction.
  • Each figure shows the curve a of temperature rise T of the alloy as a function of time'in the absence of the gaseous mixture, and the three curves b, c and d of temperature rise of the alloy as a function of time t expressed in hours, obtained respectively with a mixture of hydrochloric acid and oxygen, with a mixture of hydrofluoric acid and oxygen, with oxygen alone.
  • the process can also be carried out with the oxidizing reaction starting only after the oven has been thermally balanced.
  • the rate of reaction always increases with temperature; thus, if the temperature is increased at the beginning'of the reaction by thermally balancing the oven at a higher temperature and if the foregoing ratio is allowed to remain constant, the rate of reaction is increased.
  • the rate of reaction is practically unaffected by variation in the HF/O ratio, at least when the latter is between 0.5 and 10.
  • the molecular ratio of hydrogen halide/oxygen should preferably be between 0.5 and 10, the optimum value being in the region of 2; with mixtures richer in oxygen, the reaction tends to start only at a high temperature (above 300 C.); with mixtures richer in hydrogen halide, more particularly in the case of the hydrochloric acidoxygen mixtures, the rate of reaction becomes too low.
  • one or more gaseous diluents may be present in the gaseous mixture containing hydrofluoric or hydrochloric acid and oxygen and the reaction with the alloy may thus be carried out with the oxygen replaced by air which may or may not be enriched in oxygen, the nitrogen enabling some'of the reaction heat to be removed.
  • the maximum permissible quantity of nitrogen is of the order of 73% by volume: the introduction of nitrogen does not upset the limits of the hydrogen halide/oxygen ratio mentioned above.
  • a process for preparing from uranium-molybdenum alloys a substantially molybdenum free residue of uranium compounds selected from the group consisting of uranium-oxyfluoride, uranium-tetrafluoride and uranium oxides comprising the steps of initiating a reaction between said uranium-molybdenum alloy and a gaseous mixture comprising hydrofluoric acid and an oxygen-containing gas at a temperature of at least 100 C. but below 200 C. to eliminate said molybdenum as a volatile oxyhalide and recover a non-volatile uranium residue containing at least one of said uranium compounds and continuing said reaction until substantially all of said molybdenum has been eliminated.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • High Energy & Nuclear Physics (AREA)
  • General Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Environmental & Geological Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
US12290161 1960-08-03 1961-07-10 Process of preparation of uranium compounds from uranium-molybdenum alloys Expired - Lifetime US3208815A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR834863A FR1272542A (fr) 1960-08-03 1960-08-03 Procédé de récupération de l'uranium, notamment sous forme d'hexafluorure d'uranium, à partir d'alliages uranium-molybdène

Publications (1)

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US3208815A true US3208815A (en) 1965-09-28

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US12290161 Expired - Lifetime US3208815A (en) 1960-08-03 1961-07-10 Process of preparation of uranium compounds from uranium-molybdenum alloys

Country Status (8)

Country Link
US (1) US3208815A (de)
BE (1) BE606034A (de)
CH (1) CH435227A (de)
DE (1) DE1141628B (de)
FR (1) FR1272542A (de)
GB (1) GB927735A (de)
LU (1) LU40388A1 (de)
NL (1) NL267653A (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4017583A (en) * 1974-02-07 1977-04-12 Japan Atomic Energy Research Institute Volitilization process for separation of molybdenum-99 from irradiated uranium
WO2011156446A3 (en) * 2010-06-09 2012-05-31 General Atomics Methods and apparatus for selective gaseous extraction of molybdenum-99 and other fission product radioisotopes
CN104870370A (zh) * 2012-11-16 2015-08-26 霍尼韦尔国际公司 钼值从铀过程馏出物的分离和回收
RU2713745C1 (ru) * 2019-06-25 2020-02-07 Федеральное государственное унитарное предприятие "Научно-исследовательский институт Научно-производственное объединение "ЛУЧ" (ФГУП "НИИ НПО "ЛУЧ") Способ переработки уран-молибденовой композиции

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2004967A1 (de) * 1969-03-14 1970-09-24 The Babcock & Wilcox Company, New York, N.Y. (V.St.A.) Verfahren zur Rückgewinnung von Bestandteilen aus Kernbrennstoff-Schrott
FR2687140B1 (fr) * 1992-02-11 1994-05-13 Pechiney Uranium Procede de recuperation et d'epuration d'alliage metallique a base d'uranium tres enrichi.
FR2692880B1 (fr) * 1992-06-29 1994-09-02 Pechiney Uranium Procédé d'électro-fluoration sélective d'alliages ou de mélanges métalliques à base d'uranium.
US5698173A (en) * 1996-06-21 1997-12-16 The United States Of America As Represented By The United States Department Of Energy Purification of uranium alloys by differential solubility of oxides and production of purified fuel precursors

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2582941A (en) * 1944-10-12 1952-01-15 Coleman D Wilder Processes of producing uranium chlorides
US2859096A (en) * 1947-02-24 1958-11-04 Fowler Robert Dudley Process for production of uranium hexafluoride
US2865704A (en) * 1947-01-08 1958-12-23 Arthur H Jaffey Method of separating uranium, plutonium, and fission products by bromination and distillation
US2869982A (en) * 1945-04-12 1959-01-20 Harrison S Brown Recovery of pu values by fluorination and fractionation
US2887356A (en) * 1955-09-21 1959-05-19 Horizons Titanium Corp Production of oxygen-free and anhydrous fused salt electrolyte from oxygen containing compounds of uranium
US2907630A (en) * 1958-02-06 1959-10-06 Lawroski Stephen Preparation of uranium hexafluoride
US2910344A (en) * 1948-04-09 1959-10-27 Norman R Davidson Method of preparing uf
US3148941A (en) * 1961-03-30 1964-09-15 Theodore A Gens Dissolution of uranium-molybdenum reactor fuel elements

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2582941A (en) * 1944-10-12 1952-01-15 Coleman D Wilder Processes of producing uranium chlorides
US2869982A (en) * 1945-04-12 1959-01-20 Harrison S Brown Recovery of pu values by fluorination and fractionation
US2865704A (en) * 1947-01-08 1958-12-23 Arthur H Jaffey Method of separating uranium, plutonium, and fission products by bromination and distillation
US2859096A (en) * 1947-02-24 1958-11-04 Fowler Robert Dudley Process for production of uranium hexafluoride
US2910344A (en) * 1948-04-09 1959-10-27 Norman R Davidson Method of preparing uf
US2887356A (en) * 1955-09-21 1959-05-19 Horizons Titanium Corp Production of oxygen-free and anhydrous fused salt electrolyte from oxygen containing compounds of uranium
US2907630A (en) * 1958-02-06 1959-10-06 Lawroski Stephen Preparation of uranium hexafluoride
US3148941A (en) * 1961-03-30 1964-09-15 Theodore A Gens Dissolution of uranium-molybdenum reactor fuel elements

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4017583A (en) * 1974-02-07 1977-04-12 Japan Atomic Energy Research Institute Volitilization process for separation of molybdenum-99 from irradiated uranium
WO2011156446A3 (en) * 2010-06-09 2012-05-31 General Atomics Methods and apparatus for selective gaseous extraction of molybdenum-99 and other fission product radioisotopes
AU2011264982B2 (en) * 2010-06-09 2015-03-26 General Atomics Methods and apparatus for selective gaseous extraction of Molybdenum-99 and other fission product radioisotopes
US9076561B2 (en) 2010-06-09 2015-07-07 General Atomics Methods and apparatus for selective gaseous extraction of molybdenum-99 and other fission product radioisotopes
AU2015203131A1 (en) * 2010-06-09 2015-07-09 General Atomics Methods and apparatus for selective gaseous extraction of molybdenum-99 and other fission product radioisotopes
AU2015203131B2 (en) * 2010-06-09 2015-07-16 General Atomics Methods and apparatus for selective gaseous extraction of molybdenum-99 and other fission product radioisotopes
CN104870370A (zh) * 2012-11-16 2015-08-26 霍尼韦尔国际公司 钼值从铀过程馏出物的分离和回收
US9567237B2 (en) 2012-11-16 2017-02-14 Honeywell International Inc. Separation and recovery of molybdenum values from uranium process distillate
RU2713745C1 (ru) * 2019-06-25 2020-02-07 Федеральное государственное унитарное предприятие "Научно-исследовательский институт Научно-производственное объединение "ЛУЧ" (ФГУП "НИИ НПО "ЛУЧ") Способ переработки уран-молибденовой композиции

Also Published As

Publication number Publication date
FR1272542A (fr) 1961-09-29
CH435227A (fr) 1967-05-15
DE1141628B (de) 1962-12-27
BE606034A (fr) 1961-11-03
GB927735A (en) 1963-06-06
NL267653A (de) 1900-01-01
LU40388A1 (de) 1961-09-11

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