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WO1997027595A1 - Fluorination - Google Patents

Fluorination Download PDF

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Publication number
WO1997027595A1
WO1997027595A1 PCT/GB1997/000198 GB9700198W WO9727595A1 WO 1997027595 A1 WO1997027595 A1 WO 1997027595A1 GB 9700198 W GB9700198 W GB 9700198W WO 9727595 A1 WO9727595 A1 WO 9727595A1
Authority
WO
WIPO (PCT)
Prior art keywords
fuel
plasma
fluorination
reprocessing
slurry
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB1997/000198
Other languages
French (fr)
Inventor
Mark Fields
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sellafield Ltd
Original Assignee
British Nuclear Fuels PLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by British Nuclear Fuels PLC filed Critical British Nuclear Fuels PLC
Publication of WO1997027595A1 publication Critical patent/WO1997027595A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B60/00Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02Obtaining thorium, uranium, or other actinides
    • C22B60/0204Obtaining thorium, uranium, or other actinides obtaining uranium
    • C22B60/0213Obtaining thorium, uranium, or other actinides obtaining uranium by dry processes
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G43/00Compounds of uranium
    • C01G43/04Halides of uranium
    • C01G43/06Fluorides
    • C01G43/063Hexafluoride (UF6)
    • C01G43/066Preparation
    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21CNUCLEAR REACTORS
    • G21C19/00Arrangements 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
    • G21C19/42Reprocessing of irradiated fuel
    • G21C19/44Reprocessing of irradiated fuel of irradiated solid fuel
    • G21C19/48Non-aqueous processes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00Energy generation of nuclear origin
    • Y02E30/30Nuclear fission reactors
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies

Definitions

  • This invention relates to fluorination and in particular to the fluorination of irradiated fuel in nuclear fuel reprocessing.
  • Plant size contributes significantly to the cost of a facility for reprocessing irradiated nuclear fuel. For any process, if one or more ofthe process stages can be earned out in smaller apparatus and at increased rate, this is likely to lead to considerable cost savings, provided overall throughput is not compromised.
  • Fluonde volatility reprocessing involves fluorination of irradiated fuel and the subsequent separation of fission product fluorides and actinide fluo ⁇ des from UF 6 . Fluorination is currently carried out using a fluidised bed to nullify the effect ofthe highly exothermic fluo ⁇ nation reaction. A large vessel is required and a large volume of highly contaminated fluid bed material is produced, which matenal ultimately has to be treated and disposed of. Fluo ⁇ nation of all the UO or U O g and fission products and actinides takes approximately one day per fuel assembly. Accordingly the throughput per fluid bed is limited.
  • a fluonde volatility reprocessing procedure in the reprocessing of irradiated nuclear fuel wherein fluo ⁇ nation of the fuel is earned out by feeding the fuel to an ionised gas plasma and contacting the resultant excited species with a fluo ⁇ nating agent whereby fluonnation is affected.
  • the ionised gas plasma provides a source of intense heat and avoids the need for a fluid bed. allowing the fluonnation reaction to be speeded up.
  • the ionised gas plasma may be, for instance, an inductively-coupled plasma (ICP) or a microwave plasma.
  • ICP inductively-coupled plasma
  • regions of intense heat may be created by means of a laser or by the use of infra-red light.
  • ICPs are commonly used in analytical chemistry for the determination of concentrations of metals in solution. They provide a small and intense source of heat (temperatures up to 10,000 K are routinely achievable) and thus break down all known material to elements and ions.
  • the plasma is created by the application of a radio frequency (rf) field, through a cooled induction coil, to an inert gas such as argon or nitrogen.
  • the gas is ionised and the ions and electrons produced interact with the fluctuating magnetic field produced by the induction coil. Ohmic heating occurs as a consequence of resistance to movement of the ions and electrons and causes the high temperature.
  • solutions containing the species to be analysed are sprayed into the centre ofthe plasma as an aerosol.
  • the present invention it has been found possible very efficiently to introduce solids in the form of a slurry into the plasma. A 100% conversion of solids to atoms and ions is readily achievable.
  • a powder fluidised by an inert gas could be supplied to the plasma.
  • a feedstock of UO 2 and/or U 3 O 8 in slurry form when fed to an ICP results in the formation of excited U atoms (U*). These excited atoms react with a fluorinating (or chlorinating) agent to produce volatile uranium species, such as UF 6 .
  • the process ofthe present invention produces relatively little waste (no bed material waste in contrast ofthe fluidised-bed process) and the plant volume requirements are small. Furthermore, the process provides rapid chemical conversion of oxide fuel and fission products into separable species. An additional benefit is that the constituent parts of the apparatus are small in size and therefore readily disposable.
  • the accompanying drawing shows, diagrammatically, apparatus of use in the present invention.
  • the apparatus includes a vessel 1 within which is located an induction coil 3 to the interior of which an inert gas such as argon is fed via tubes 5. Between tubes 5 is located a further tube 7 by which fuel slurry may be fed to a central position within the induction coil.
  • Application of a radio frequency field to the induction coil results in the formation of an ICP 9 , into which the fuel slurry is fed.
  • This results in the formation of excited U atoms (U*) which pass through an orifice in plate 1 1 to an upper region of vessel 1 which comprises a fluorinating atmosphere.
  • This atmosphere is typically fluorine gas but may also be provided by another fluorinating agent including a novel reagent such as XeF 2 , KrF 2 , O 2 F 2 , HF, BrF 3 or BrF 5 .
  • a novel reagent such as XeF 2 , KrF 2 , O 2 F 2 , HF, BrF 3 or BrF 5 .

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Geology (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
  • Plasma & Fusion (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

In the reprocessing of irradiated nuclear fuel, fluorination of the fuel is carried out by feeding the fuel to an ionised gas plasma and then contacting the resultant excited species with a fluorinating agent, for example, fluorine, so as to effect fluorination. The ionised gas plasma is an inductively-coupled plasma or a microwave plasma, and the fuel is fed to the plasma in the form of a slurry or a powder fluidised by a gas. Where the slurry is formed from LWR fuel, a variety of volatile and involatile fission product fluorides and actinide fluorides is produced, so enabling the separation of UF6 from the involatile fission product fluorides.

Description

FLUORINATION
This invention relates to fluorination and in particular to the fluorination of irradiated fuel in nuclear fuel reprocessing.
Plant size contributes significantly to the cost of a facility for reprocessing irradiated nuclear fuel. For any process, if one or more ofthe process stages can be earned out in smaller apparatus and at increased rate, this is likely to lead to considerable cost savings, provided overall throughput is not compromised.
Fluonde volatility reprocessing involves fluorination of irradiated fuel and the subsequent separation of fission product fluorides and actinide fluoπdes from UF6. Fluorination is currently carried out using a fluidised bed to nullify the effect ofthe highly exothermic fluoπnation reaction. A large vessel is required and a large volume of highly contaminated fluid bed material is produced, which matenal ultimately has to be treated and disposed of. Fluoπnation of all the UO or U Og and fission products and actinides takes approximately one day per fuel assembly. Accordingly the throughput per fluid bed is limited.
According to the present invention there is provided a fluonde volatility reprocessing procedure in the reprocessing of irradiated nuclear fuel wherein fluoπnation of the fuel is earned out by feeding the fuel to an ionised gas plasma and contacting the resultant excited species with a fluoπnating agent whereby fluonnation is affected.
The ionised gas plasma provides a source of intense heat and avoids the need for a fluid bed. allowing the fluonnation reaction to be speeded up.
The ionised gas plasma may be, for instance, an inductively-coupled plasma (ICP) or a microwave plasma. In other embodiments of the present invention regions of intense heat may be created by means of a laser or by the use of infra-red light. Reference will be made hereinafter to ICPs but it should be understood that this is by way of example only. ICPs are commonly used in analytical chemistry for the determination of concentrations of metals in solution. They provide a small and intense source of heat (temperatures up to 10,000 K are routinely achievable) and thus break down all known material to elements and ions. The plasma is created by the application of a radio frequency (rf) field, through a cooled induction coil, to an inert gas such as argon or nitrogen. The gas is ionised and the ions and electrons produced interact with the fluctuating magnetic field produced by the induction coil. Ohmic heating occurs as a consequence of resistance to movement of the ions and electrons and causes the high temperature.
Normally, in analytical applications, solutions containing the species to be analysed are sprayed into the centre ofthe plasma as an aerosol. In the case ofthe present invention, however, it has been found possible very efficiently to introduce solids in the form of a slurry into the plasma. A 100% conversion of solids to atoms and ions is readily achievable. Alternatively, a powder fluidised by an inert gas could be supplied to the plasma.
A feedstock of UO2 and/or U3O8 in slurry form when fed to an ICP results in the formation of excited U atoms (U*). These excited atoms react with a fluorinating (or chlorinating) agent to produce volatile uranium species, such as UF6.
In the case where the slurry is formed from irradiated LWR fuel, a variety of volatile and involatile fission product fluorides and actinide fluorides is produced, thereby enabling the separation of UF6 from the involatile fission product fluorides.
The process ofthe present invention produces relatively little waste (no bed material waste in contrast ofthe fluidised-bed process) and the plant volume requirements are small. Furthermore, the process provides rapid chemical conversion of oxide fuel and fission products into separable species. An additional benefit is that the constituent parts of the apparatus are small in size and therefore readily disposable.
The accompanying drawing shows, diagrammatically, apparatus of use in the present invention. The apparatus includes a vessel 1 within which is located an induction coil 3 to the interior of which an inert gas such as argon is fed via tubes 5. Between tubes 5 is located a further tube 7 by which fuel slurry may be fed to a central position within the induction coil. Application of a radio frequency field to the induction coil (which is cooled) results in the formation of an ICP 9, into which the fuel slurry is fed. This results in the formation of excited U atoms (U*) which pass through an orifice in plate 1 1 to an upper region of vessel 1 which comprises a fluorinating atmosphere. This atmosphere is typically fluorine gas but may also be provided by another fluorinating agent including a novel reagent such as XeF2, KrF2, O2F2, HF, BrF3 or BrF5. The UF6 and other volatile fission products produced by the reaction then pass into a storage tank and ultimately into the plant designed for separation ofthe fission product fluorides and the actinide fluorides.

Claims

1. A fluoride volatility reprocessing procedure in the reprocessing of irradiated nuclear fuel wherein the fluorination ofthe fuel is carried out by feeding the fuel to an ionised gas plasma and contacting the resultant excited fuel with a fluorinating agent whereby fluorination is effected.
2. A procedure according to Claim 1 wherein the ionised gas plasma is an ICP or a microwave plasma.
3. A procedure according to Claim 1 or Claim 2 wherein the fuel is fed to the ionised gas plasma in the form of a slurry or a powder fluidised by a gas.
4. A procedure according to any ofthe preceding claims wherein the fluorinating agent is fluorine.
5. A procedure according to any ofthe preceding claims wherein the fuel is irradiated LWR fuel.
6. A fluoride volatility reprocessing procedure in the reprocessing of irradiated nuclear fuel substantially as described herein.
7. A procedure according to Claim 1 and substantially as described with reference to the accompanying drawing.
PCT/GB1997/000198 1996-01-26 1997-01-23 Fluorination Ceased WO1997027595A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9601590.4 1996-01-26
GB9601590A GB9601590D0 (en) 1996-01-26 1996-01-26 Flourination

Publications (1)

Publication Number Publication Date
WO1997027595A1 true WO1997027595A1 (en) 1997-07-31

Family

ID=10787620

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1997/000198 Ceased WO1997027595A1 (en) 1996-01-26 1997-01-23 Fluorination

Country Status (2)

Country Link
GB (1) GB9601590D0 (en)
WO (1) WO1997027595A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000042229A3 (en) * 1999-01-15 2001-10-11 British Nuclear Fuels Plc Processing of uranium materials by fluorination and dissociation of uranium hexafluoride in plasma separator
KR100407728B1 (en) * 2001-03-21 2003-12-01 한국원자력연구소 Oxidation-Reduction Apparutus using Plasma for a Spent Nuclear Fuel
RU2371792C2 (en) * 2007-08-20 2009-10-27 Леонид Георгиевич Бабиков Method and plant for recycling of spent nuclear fuel
RU2396212C2 (en) * 2008-07-24 2010-08-10 Открытое акционерное общество "Новосибирский завод химконцентратов" Method of obtaining uranium tetrafluoride
US8192704B1 (en) * 2011-02-25 2012-06-05 The United States Of America As Represented By The Department Of Energy Spent nuclear fuel recycling with plasma reduction and etching
CN113795894A (en) * 2020-10-14 2021-12-14 中广核研究院有限公司 Plasma-based dry reprocessing of spent fuel
WO2025122228A1 (en) * 2023-12-04 2025-06-12 Terrapower, Llc Chloride based volatility for the recovery of uranium from nuclear fuel salt

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1462256A (en) * 1964-08-14 1966-04-15 Atomic Energy Commission Process for the continuous treatment of nuclear fuel by volatilization in the gas phase
GB1158287A (en) * 1965-11-26 1969-07-16 Ct D Etude De L En Nucleaire C Method of Fluorination of Nuclear Fuel.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1462256A (en) * 1964-08-14 1966-04-15 Atomic Energy Commission Process for the continuous treatment of nuclear fuel by volatilization in the gas phase
GB1158287A (en) * 1965-11-26 1969-07-16 Ct D Etude De L En Nucleaire C Method of Fluorination of Nuclear Fuel.

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000042229A3 (en) * 1999-01-15 2001-10-11 British Nuclear Fuels Plc Processing of uranium materials by fluorination and dissociation of uranium hexafluoride in plasma separator
US7427386B1 (en) 1999-01-15 2008-09-23 Nexia Solutions Ltd. Processing materials
KR100407728B1 (en) * 2001-03-21 2003-12-01 한국원자력연구소 Oxidation-Reduction Apparutus using Plasma for a Spent Nuclear Fuel
RU2371792C2 (en) * 2007-08-20 2009-10-27 Леонид Георгиевич Бабиков Method and plant for recycling of spent nuclear fuel
RU2396212C2 (en) * 2008-07-24 2010-08-10 Открытое акционерное общество "Новосибирский завод химконцентратов" Method of obtaining uranium tetrafluoride
US8192704B1 (en) * 2011-02-25 2012-06-05 The United States Of America As Represented By The Department Of Energy Spent nuclear fuel recycling with plasma reduction and etching
CN113795894A (en) * 2020-10-14 2021-12-14 中广核研究院有限公司 Plasma-based dry reprocessing of spent fuel
WO2022077250A1 (en) * 2020-10-14 2022-04-21 中广核研究院有限公司 Dry aftertreatment method for spent fuel employing plasma
GB2606640A (en) * 2020-10-14 2022-11-16 China Nuclear Power Technology Res Inst Co Ltd Dry aftertreatment method for spent fuel employing plasma
EP4060681A4 (en) * 2020-10-14 2023-02-22 China Nuclear Power Technology Research Institute Co., Ltd. DRY AFTER-TREATMENT METHOD FOR SPENT FUEL USING PLASMA
CN113795894B (en) * 2020-10-14 2024-07-12 中广核研究院有限公司 Spent fuel dry post-treatment method based on plasma
WO2025122228A1 (en) * 2023-12-04 2025-06-12 Terrapower, Llc Chloride based volatility for the recovery of uranium from nuclear fuel salt

Also Published As

Publication number Publication date
GB9601590D0 (en) 1996-03-27

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