EP0245588B1 - Procédé de purification poussée du molybdène de fission - Google Patents

Procédé de purification poussée du molybdène de fission Download PDF

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Publication number
EP0245588B1
EP0245588B1 EP87102017A EP87102017A EP0245588B1 EP 0245588 B1 EP0245588 B1 EP 0245588B1 EP 87102017 A EP87102017 A EP 87102017A EP 87102017 A EP87102017 A EP 87102017A EP 0245588 B1 EP0245588 B1 EP 0245588B1
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EP
European Patent Office
Prior art keywords
chamber
oxide
molybdenum
sorption
fission
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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.)
Expired - Lifetime
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EP87102017A
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German (de)
English (en)
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EP0245588A3 (en
EP0245588A2 (fr
Inventor
Jochen Bürck
Sameh Dr. Abdel Hadi Ali
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Forschungszentrum Karlsruhe GmbH
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Kernforschungszentrum Karlsruhe GmbH
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Publication of EP0245588A3 publication Critical patent/EP0245588A3/de
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    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21G—CONVERSION OF CHEMICAL ELEMENTS; RADIOACTIVE SOURCES
    • G21G4/00—Radioactive sources
    • G21G4/04—Radioactive sources other than neutron sources
    • G21G4/06—Radioactive sources other than neutron sources characterised by constructional features
    • G21G4/08—Radioactive sources other than neutron sources characterised by constructional features specially adapted for medical application

Definitions

  • the radioactive, relatively short-lived nuclide technetium-99m is used in nuclear medicine. For this purpose, it is separated from the mother nuclide / daughter nuclide equilibrium as a daughter of molybdenum-99 as shortly as possible before its use.
  • the production of the mother nuclide Mo-99 is known.
  • a uranium-aluminum alloy with the approximate composition UAI 3 which is often referred to as UAl x due to the often different aluminum proportions, is subjected to forced cooling in a nuclear reactor after five to ten days of neutron irradiation and after a subsequent cooling period of approximately one day for the UA1 3 targets the Mo-99 obtained after a series of chemical process steps.
  • the target plates are dissolved, for example, in three to six molar sodium hydroxide solution, with a solid residue and exhaust gas being formed in addition to the alkaline solution.
  • the exhaust gas includes Xe-133, Xe-135, Kr-85 and J-131.
  • U0 2 and Na 2 U 2 0 7 are found in the solid residue.
  • the solution contains aluminum ions and fission products, such as. B. ions of alkali and alkaline earth metals, as well as iodine, tin and molybdenum and smaller amounts of ions of poorly soluble elements such as cerium, ruthenium and zirconium.
  • the desorption step of the method according to the invention is carried out in a device as described in the characterizing part of claims 7 to 10.
  • a carrier amount of inactive molybdate in the form of (NH4) 6 M 07 0 24 is added to each sublimation flask for more complete sublimation of the Mo-99, which should not exceed 40 mg Mo per sublimation flask.
  • a direct sublimation of the Mo-99 activity from A1 2 0 3 is not possible.
  • the concentrations of the elements investigated in the sorption and desorption experiments corresponded to those molarities (10- 5 -10 -3 mol / l) of fission products occurring in the known fission molybdenum-99 separation process, if due to process disturbances in the previous chromatographic separation steps (pre-cleaning) complete breakthrough in activity would take place until the final fine cleaning measures of the method according to the invention.
  • additional Mo decontamination by means of the described method the most unfavorable conditions with regard to the presence of other fission products were chosen.
  • the carrier gas not only acted upon with H 2 O impinged nitrogen or oxygen with H 2 O can be used, but also other H 2 0-containing gas mixtures, such. B. air, noble gases with or without 0 2 etc.
  • FIG. 2 shows the Mo retention from 0.02 M HN0 3 solutions, curve 21 representing sorption on acidic A1 2 0 3 , curve 22 representing sorption on Sn0 2 and curve 23 for sorption on Zr0 2 .
  • the curve values of FIG. 3 were obtained from 1 M HN0 3 solutions.
  • Curve 31 shows the Mo retention on acidic Al 2 O 3 , curve 32 on SnO 2 and curve 33 on ZrO 2 . From these results it can be seen that Mo sorption from weakly acidic solutions on Al 2 O 3 is achieved up to a charge of about 30 mg Mo / g exchanger. When using Sn0 2 a charge of only about 4 mg Mo / g exchanger is useful, but this up to a high acidity of the aqueous solution. The Mo retention on Zr0 2 (curve 23) is comparable to that on Sn0 2 (approx. 4 mg Mo / g Zr0 2 breakthrough capacity).
  • Curve 33 shows the Mo retention from 1 M HN0 3 solution, it being evident that the sorption is reduced with a higher acid strength of the feed solution, as was also found with the other oxides.
  • the capacity loss of the Zr0 2 is slightly larger than that of the Sn0 2 , but far less than that of the Al 2 O 3 system. ZrO 2 is therefore largely comparable to Sn0 2 in terms of its sorption behavior.
  • Metal oxide exchanger particles 1 loaded with molybdate anions were introduced into a sublimation device according to FIG. 1 into the sublimation space 2, which is closed off on the side of the carrier gas supply 4 by a gas-permeable quartz frit 6.
  • An induction heater 8 generator for this purpose not shown in FIG. 1
  • the sublimation space 2 is closed off from the space 3, in which the desublimation of the Mo oxide takes place, by a quartz frit 7.
  • the sublimation space 3 has quartz packing 10, which facilitate the sublimation.
  • the part 11 of the device, which contains the desublimation space 3, the quartz frit 7 and the gas discharge pipe 5, is designed to be removable from the rest of the device.
  • an insert made of, for example, a Pt crucible with a drilled or perforated bottom, which receives the loaded metal oxide, can seal off the space 2 from the gas supply 4 during the sublimation of the Mo-99 oxide.
  • the heater 8 of the device is not limited to an inductive heater, but can be formed by other usable heating devices which act on the room 2 from the outside.
  • the decontamination factors of the fission products Ru, Sn, and Zr, based on Mo, in the SnO z system are as follows:

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Claims (10)

1. Procédé de purification poussée de molybdène de fission dissous sous forme anionique en présence d'anions de produits de fission de I, Sn, Ce, Ru et Zr dans une solution aqueuse d'acide minéral, dans lequel:
a) dans une étape d'adsorption le molybdène de fission est fixé sur un oxyde métallique et,
b) dans une étape de désorption, il est libéré, caractérisé en ce que:
c) on fait passer la solution aqueuse pour adsorber les anions de Mo, I, Ce, Ru, Sn et Zr sur un oxyde amphotère,
d) l'oxyde chargé est séché et ensuite pour sublimer Mo, on chauffe à une température comprise entre 1200°C et 1300°C et on balaye simultanément avec un gaz porteur contenant de la vapeur d'eau,
e) par refroidissement à une température inférieure à 600°C, on condense du courant de gaz porteur le Mo et le reste de Mo ainsi formé, après refroidissement à température ambiante est dissous dans une solution aqueuse d'un alcali fort et est transformé en une solution de molybdate.
2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise Sn02 comme oxyde amphotère.
3. Procédé selon la revendication 1, caractérisé en ce qu'on utilise y-AI203 comme oxyde amphotère.
4. Procédé selon la revendication 1, caractérisé en ce qu'on utilise Zr02 comme oxyde amphotère.
5. Procédé selon la revendication 1, caractérisé en ce que le gaz porteur, outre la vapeur d'eau, contient de l'oxygène.
6. Procédé de purification poussée de molybdène de fission dissous sous forme anionique en présence d'anions de produits de fission de I, Sn, Ce, Ru, et Zr dans une solution aqueuse d'acide minéral, dans lequel:
a) dans une étape d'adsorption, le molybdène de fission est fixé sur un oxyde métallique et,
b) dans une étape de désorption, il est libéré, caractérisé en ce que:
c) on fait passer la solution aqueuse pour adsorber des anions de Mo, I, Ce, Ru, Sn et Zr sur Sn02,
d) l'oxyde Sn02 chargé est séché et ensuite pour sublimer Mo, on chauffe à une température comprise entre 1200°C et 1300°C et on balaye simultanément avec un gaz porteur contenant de l'oxygène,
e) par refroidissement à une température inférieure à 600°C, on condense, par un courant de gaz porteur, le Mo et le reste de Mo ainsi formé, après refroidissement à température ambiante, est dissous dans une solution aqueuse d'un alcali fort et est transformé en une solution de molybdène.
7. Dispositif pour réaliser l'étape de désorption du procédé selon la revendication 1 ou 6, caractérisé par une première chambre (2) recevant l'oxyde métallique (1) amphotère chargé qu'on peut chauffer, et une deuxième chambre (3) qui reçoit le sublimé entre une entrée de gaz (4) et une sortie de gaz (5), qui sont délimitées par deux membranes ou frittes (6, 7) perméables au gaz, disposés avec un intervalle entre eux, la première fritte (6) fermant la première chambre (2) du côté de l'entrée de gaz (4) et l'autre fritte (7) séparant la première chambre (2) de la deuxième chambre (3) disposée en aval de l'introduction de gaz, et caractérisé par un chauffage (8).
8. Dispositif selon la revendication 7, caractérisé en ce que le chauffage (8) est constitué en dispositif de chauffage inductif avec une couche de graphite (9) enveloppant la première chambre (2).
9. Dispositif selon la revendication 7, caractérisé en ce que la deuxième chambre (3) est munie de corps de remplissage en quartz.
10. Dispositif selon la revendication 7, caractérisé en ce que la pièce (11) du dispositif, qui comprend la deuxième chambre (3), la fritte (7) et la sortie de gaz (5) est démontable du reste du dispositif.
EP87102017A 1986-05-15 1987-02-13 Procédé de purification poussée du molybdène de fission Expired - Lifetime EP0245588B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3616391 1986-05-15
DE19863616391 DE3616391A1 (de) 1986-05-15 1986-05-15 Verfahren zur feinreinigung von spaltmolybdaen

Publications (3)

Publication Number Publication Date
EP0245588A2 EP0245588A2 (fr) 1987-11-19
EP0245588A3 EP0245588A3 (en) 1988-07-06
EP0245588B1 true EP0245588B1 (fr) 1990-06-27

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EP87102017A Expired - Lifetime EP0245588B1 (fr) 1986-05-15 1987-02-13 Procédé de purification poussée du molybdène de fission

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US (1) US4981658A (fr)
EP (1) EP0245588B1 (fr)
DE (2) DE3616391A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2633000B2 (ja) * 1989-01-28 1997-07-23 動力炉・核燃料開発事業団 高放射性廃棄物の処理方法
DE4231997C1 (de) * 1992-09-24 1994-01-05 Kernforschungsz Karlsruhe Verfahren zum Abtrennen von Spaltmolybdän
US5802439A (en) * 1997-02-19 1998-09-01 Lockheed Martin Idaho Technologies Company Method for the production of 99m Tc compositions from 99 Mo-containing materials
US5802438A (en) * 1997-02-19 1998-09-01 Lockheed Martin Idaho Technologies Company Method for generating a crystalline 99 MoO3 product and the isolation 99m Tc compositions therefrom
US6337055B1 (en) * 2000-01-21 2002-01-08 Tci Incorporated Inorganic sorbent for molybdenum-99 extraction from irradiated uranium solutions and its method of use
RU2548033C2 (ru) * 2010-02-19 2015-04-10 БЭБКОК ЭНД ВИЛКОКС Текникал Сервисез Груп, Инк. Способ и устройство для экстракции и обработки молибдена-99
US8450629B2 (en) * 2010-05-10 2013-05-28 Los Alamos National Security, Llc Method of producing molybdenum-99
RU2525127C1 (ru) * 2012-12-27 2014-08-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский государственный машиностроительный университет (МАМИ)" Способ сорбционного извлечения молибдена
BE1023851B1 (fr) * 2016-06-28 2017-08-14 Institut National Des Radioéléments Procédé de production d'une fraction de radio-isotopes d'iode, en particulier d'i-131, fraction de radio-isotopes d'iode, en particulier d'i-131
CN110129573A (zh) * 2019-06-25 2019-08-16 国家能源投资集团有限责任公司 含钼催化剂中钼金属的回收装置及回收方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3799883A (en) * 1971-06-30 1974-03-26 Union Carbide Corp Production of high purity fission product molybdenum-99
US3830746A (en) * 1972-07-27 1974-08-20 Mallinckrodt Chemical Works Method for preparing technetium-99m generators loaded with fission product molybdenum-99
NL165872C (nl) * 1973-02-20 1981-05-15 Byk Mallinckrodt Cil Bv Isotopengenerator voor de produktie van 99m tc bevattende vloeistoffen.
JPS5233280B2 (fr) * 1974-02-07 1977-08-26
DE2610948C3 (de) * 1976-03-16 1980-01-10 Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe Verfahren zur Gewinnung von Molybdän -99 aus mit Neutronen bestrahlter, spaltbare Stoffe und Spaltprodukte enthaltender Matrix
US4123498A (en) * 1977-02-17 1978-10-31 General Electric Company Process for separating fission product molybdenum from an irradiated target material
DD136385B1 (de) * 1978-05-05 1982-05-26 Akad Wissenschaften Ddr Verfahren zur gewinnung von hoch 99 mo

Also Published As

Publication number Publication date
US4981658A (en) 1991-01-01
DE3763468D1 (de) 1990-08-02
DE3616391A1 (de) 1987-11-19
EP0245588A3 (en) 1988-07-06
EP0245588A2 (fr) 1987-11-19

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