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WO1997038785A1 - Separation de fluorures metalliques - Google Patents

Separation de fluorures metalliques Download PDF

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Publication number
WO1997038785A1
WO1997038785A1 PCT/GB1997/001023 GB9701023W WO9738785A1 WO 1997038785 A1 WO1997038785 A1 WO 1997038785A1 GB 9701023 W GB9701023 W GB 9701023W WO 9738785 A1 WO9738785 A1 WO 9738785A1
Authority
WO
WIPO (PCT)
Prior art keywords
mof
gas
fluoπne
separation
band
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/GB1997/001023
Other languages
English (en)
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 WO1997038785A1 publication Critical patent/WO1997038785A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D59/00—Separation of different isotopes of the same chemical element
    • B01D59/34—Separation by photochemical methods

Definitions

  • This invention relates to the separation of metal fluo ⁇ des and specifically to the separauon of molybdenum hexafluo ⁇ de from uranium hexafluo ⁇ de.
  • the rnixture will be present in the form of a UF 6 gas stream in which the MoF 6 is present as an unpu ⁇ ty
  • Uranium may be en ⁇ ched by converting it to UF 6 and usmg cent ⁇ fuges to separate the 235 isotope.
  • va ⁇ ous metal fluo ⁇ des are present as impu ⁇ ues.
  • the vapour pressures of several hexafluo ⁇ des are similar to that of UF 6 and therefore fractional disullation is not a suitable techmque for separating out these impu ⁇ ues.
  • MoF 6 may be present as an impu ⁇ ty if the UF 6 has been prepared from uranium ore.
  • the present invention provides a method of removing MoF 6 from a gas containing both UF 6 and MoF 6 , the method comprising irradiating the gas with ultraviolet light and allowmg the M0F 5 which is formed to condense from said gas.
  • Photolysis was carried out through the quartz window of the vacuum shroud using a mercury lamp to provide UV radiation, the wavelength being 254nm.
  • Each of the deposited samples was examined by infrared spectroscopy before and after irradiation with UV light. .All infrared spectra were recorded with 2cm ' resoluuon and 128 scans or 0.5cm ' resoluuon and 256 scans.
  • the results obtained at the cryogenic temperatures used here can be directly translated to gaseous samples.
  • the matrix-isolauon technique has been used for ease of handling the samples. In fact, the process is expected to be more efficient in the gas phase due to the much greater mobility of the species. and 621cm "1 which are attributed to MoF 6 and UF 6 respectively. In addition a band was observed for MoF 6 at 264cm "1 .
  • the infrared spectrum of MoF 6 shows three new bands at 721cm “1 , 707cm *1 and 678cm “1 , all of which grew in intensity with increased irradiation.
  • the band at 737cm "1 showed a marked decrease in intensity as irradiation of the sample proceeded. In total. the sample of MoF 6 was irradiated for 225 minutes and other new bands were not observed.
  • the band at 674cm “1 is attributed to the formation of MoF 5 in the matrix.
  • the bands at 580cm “1 and 560cm “1 are attributed to UF 5 . It is apparent that both MoF 6 and UF 6 were reduced to MoF 5 and UF 5 .
  • a fluorme radical scavenger is present.
  • scavengers are xenon or carbon monoxide.
  • the photolysis reaction occurs much more rapidly because fluo ⁇ ne radicals are effectively removed from the system by the scavenger and regeneration of UF 6 then has to occur by removal of a fluo ⁇ ne radical from MoF 6 by UF 5 .
  • Figure 1 is a schematic diagram of apparatus for carrying out the method of the present mvention.
  • Figure 2 is a schematic diagram of the reaction vessel of the apparatus m Figure 1
  • the reacuon vessel 1 is fed with a mixture of UF 6 and MoF 6 from storage vessel 3 and with fluorme from vessel 5
  • the pipework between vessels 3 and 5 and vessel 1 is equipped with suitable valves 7 to allow passage of either gas mto the reaction vessel 1.
  • Reaction vessel 1 is shown in more detail m Figure 2. It is made from nickei or Monel and is passivated to prevent reaction of UF 6 with the vessel.
  • a senes of ultraviolet sources are held in the walls of the vessei at suitable positions to enable them to irradiate the whole internal volume of the vessei. These sources may be high, medium or low pressure mercury lamps, xenon lamps or any other convenient sources of UV radiation mcluding lasers operated in the UV range. They should provide sufficient energy to photodissociate MoF 6 and UF 6 .
  • the UF 6 and MoF 6 mixture is irradiated with UV radianon to remove MoF 6 from the vapour phase by reduction to invoiatile MoF 5 .
  • UF 6 is reduced to UF 5 but. smce UF 5 is more reacnve than MoF 5 , UF 6 is regenerated preferentially by the reaction of UF 5 with other molecules of MoF 6 and/or free fluo ⁇ ne atoms.
  • UF 6 is allowed to flow from the reacuon vessel through filter 11 (preventing passage of pamculate matter) mto cryogenic trap 13. Trap 13 condenses UF 6 , whilst any fluorme gas produced du ⁇ ng the process passes through the system to a fluorme store at 15 for recycling. The mvolatile MoF 5 remains in the reaction vessei. The UF 6 may then be revoiarilised and passed into a vessel 17 for storage.
  • Fluo ⁇ ne (or an aitemauve fluo ⁇ natmg agent) is then introduced into reaction vessel 1 to react with MoF 5 and regenerate MoF 6 Depending on the fluo ⁇ nating agent which is used, vessel 1 may be heated or irradiated with UV radiation to speed up the reaction to reform the MoF 6 .
  • the MoF 6 is passed through the cryogenic trap to remove any fluo ⁇ ne (for recycling) and is then passed to storage vessei 19 for disposal.
  • a senes of reaction vessels 1 are operated sequentially so as further to pu ⁇ fy the UF 6 .

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Biophysics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Treating Waste Gases (AREA)

Abstract

L'invention a pour objet un procédé destiné à retirer l'hexafluorure de molybdène d'un gaz contenant de l'hexafluorure d'uranium et de l'hexafluorure de molybdène. Ce procédé consiste à irradier le gaz avec un rayonnement ultraviolet et à laisser le pentafluorure de molybdène formé se condenser à partir du gaz.
PCT/GB1997/001023 1996-04-17 1997-04-15 Separation de fluorures metalliques Ceased WO1997038785A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9607901.7A GB9607901D0 (en) 1996-04-17 1996-04-17 Metal flourides separation
GB9607901.7 1996-04-17

Publications (1)

Publication Number Publication Date
WO1997038785A1 true WO1997038785A1 (fr) 1997-10-23

Family

ID=10792177

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1997/001023 Ceased WO1997038785A1 (fr) 1996-04-17 1997-04-15 Separation de fluorures metalliques

Country Status (3)

Country Link
GB (1) GB9607901D0 (fr)
WO (1) WO1997038785A1 (fr)
ZA (1) ZA973140B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2020188048A1 (fr) * 2019-03-21 2020-09-24 Technische Universität München Préparation de fluorures métalliques et procédés de séparation
CN115608023A (zh) * 2022-10-31 2023-01-17 中核四0四有限公司 一种用于液相六氟化铀过滤净化的装置
RU2817671C2 (ru) * 2019-03-21 2024-04-19 Технише Универзитет Мюнхен Приготовление фторидов металлов и процессы разделения

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4555318A (en) * 1984-01-06 1985-11-26 The United States Of America As Represented By The United States Department Of Energy Removal of fluoride impurities from UF6 gas

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4555318A (en) * 1984-01-06 1985-11-26 The United States Of America As Represented By The United States Department Of Energy Removal of fluoride impurities from UF6 gas

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEM. PHYS. LETT., vol. 53, no. 3, 1 May 1978 (1978-05-01), NL, pages 435 - 438 *
DATABASE INIS INTERNATIONAL ATOMIC ENERGY AGENCY (IAEA), VIENNA, AT; EERKENS ET AL.: "LASER SEPARATION OF MEDICAL ISOTOPES", XP002032784 *
DATABASE INIS INTERNATIONAL ATOMIC ENERGY AGENCY (IAEA), VIENNA, AT; FREUND ET AL.: "multiple-photon isotope separation in mof6", XP002032785 *
TRANSACTIONS OF THE AMERICAN NUCLEAR SOCIETY, vol. 75, 10 November 1996 (1996-11-10) - 14 November 1996 (1996-11-14), WASHINGTON. DC, USA, pages 20 - 22 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2020188048A1 (fr) * 2019-03-21 2020-09-24 Technische Universität München Préparation de fluorures métalliques et procédés de séparation
US20220153607A1 (en) * 2019-03-21 2022-05-19 Technische Universität München Preparation of metal fluorides and separation processes
RU2817671C2 (ru) * 2019-03-21 2024-04-19 Технише Универзитет Мюнхен Приготовление фторидов металлов и процессы разделения
US12319589B2 (en) * 2019-03-21 2025-06-03 Technische Universitaet München Preparation of metal fluorides and separation processes
CN115608023A (zh) * 2022-10-31 2023-01-17 中核四0四有限公司 一种用于液相六氟化铀过滤净化的装置

Also Published As

Publication number Publication date
GB9607901D0 (en) 1996-06-19
ZA973140B (en) 1998-01-29

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