EP0278379B1 - Procédé pour l'enlèvement des isotopes radioactifs métalliques des aliments ou fourrages liquides - Google Patents

Procédé pour l'enlèvement des isotopes radioactifs métalliques des aliments ou fourrages liquides Download PDF

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Publication number
EP0278379B1
EP0278379B1 EP88101535A EP88101535A EP0278379B1 EP 0278379 B1 EP0278379 B1 EP 0278379B1 EP 88101535 A EP88101535 A EP 88101535A EP 88101535 A EP88101535 A EP 88101535A EP 0278379 B1 EP0278379 B1 EP 0278379B1
Authority
EP
European Patent Office
Prior art keywords
liquid
milk
ion
substance
radioactive
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.)
Expired - Lifetime
Application number
EP88101535A
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German (de)
English (en)
Other versions
EP0278379A1 (fr
Inventor
Hans Dieter Kalscheuer
Roland Pässler
Rainer Schönegge
Walter Schmelz
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.)
Societe des Produits Nestle SA
Original Assignee
Societe des Produits Nestle SA
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Filing date
Publication date
Application filed by Societe des Produits Nestle SA filed Critical Societe des Produits Nestle SA
Priority to AT88101535T priority Critical patent/ATE70659T1/de
Publication of EP0278379A1 publication Critical patent/EP0278379A1/fr
Application granted granted Critical
Publication of EP0278379B1 publication Critical patent/EP0278379B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids

Definitions

  • the invention relates to a method for removing radioactive metal isotopes from liquid food or feed with the features of the preamble of claim 1.
  • the invention further relates to an exchange column for carrying out such a method and to the use of iron (III) hexacyanoferrate (II) which is insoluble in water and dilute acids.
  • FR-PS 15 17 279 a generic method for removing radioactive metal isotopes from liquid food or feed is known.
  • ion exchange resins are used which, in contrast to compounds of the Berlin blue type, do not primarily act on cesium, but also exchange other ions, which occur in milk of completely different sizes, for example.
  • the invention has for its object to provide a method of the generic type, in which the food or feed remain unaffected in terms of the desired properties and the radioactive metals can be separated in a concentrated and thus easily deposited form.
  • the cesium cycle of an "in vivo" method is broken and the cesium isotopes can do this Circulation can be largely withdrawn.
  • the procedures can be applied centrally, so that control and precise dosing is guaranteed.
  • the cesium isotopes withdrawn from the cycle can be obtained in a concentrated form and thus deposited in accordance with regulations or used for other purposes.
  • the device shown in FIGS. 1a, 1b and 1c enables the discontinuous removal of radioactive metals from contaminated milk or milk products (so-called batch process).
  • the milk 12 is filled into a container 10.
  • the fill level of the milk (or the milk product) 12 in the container 10 is designated 10..
  • the milk 12 in the container 10 is to be disposed of.
  • the milk to be disposed of is transferred to an ultrafiltration device 18 via a line 14 and a pump 16.
  • Ultrafiltration devices are known as such and need not be described in more detail here.
  • Liquid, including the radioactive cesium is secreted by the semipermeable membrane in the ultrafiltration device 18.
  • the liquid that has passed through the semipermeable membrane, including the radioactive cesium, is called permeate and reaches a container 22 via line 20.
  • Permeate 24 in container 22 has a fill level of 22 ⁇ .
  • the milk 12 components (retentate) retained by the semipermeable membrane of the ultrafiltration device 18 are returned to the container 10 via the line 26, a control valve 28 and a return line 30.
  • the state shown in Fig. 1b is reached, i.e. A liquid containing radioactive cesium has been removed from the milk (or the milk product) 12 in the container 10 and transferred into the container 22. 1b (right), the radioactively contaminated permeate 24 is stirred in the container 22 by means of an agitator 32 to accelerate the process.
  • the temperature of the permeate 24 in the container 22 is between 20 and 60 ° C.
  • a substance binding and / or ion-exchanging the cesium atoms is introduced into the container 22, which is indicated in FIG. 1 b (right) by the arrows 34.
  • complex compounds such as iron cyano compounds of the Berlin blue type, or aluminum silicates, such as bentonites and zeolites. Combinations of the substances mentioned above are also possible.
  • the dosage for the complex salts is in the per mille range and for the aluminum silicates in the percentage range.
  • the liquid contaminated with radioactive cesium can also be removed as a permeate by reverse osmosis.
  • the permeate 24 in the container 22 is treated by the radioactive cesium absorbing or ion-exchanging substance, the cesium being bound to the substance.
  • the treated permeate 24 is subjected to ultrafiltration in the ultrafiltration device 18 in the reverse direction.
  • Isotope-free liquid penetrates the semipermeable membrane in the ultrafiltration device 18 and passes via line 36 back into the container 10, so that the fill level 10 ⁇ of the milk (or the milk product) 12 almost reaches the original level according to FIG. 1a.
  • the residues filtered off during the ultrafiltration are fed via the control valve 38 and the line 40 back into the container 22, in which the radioactive residue 24 ⁇ , ie the isotope-binding or ion-exchanging substances including the radioactive isotopes, remains.
  • This radioactive residue 24 ⁇ is highly concentrated and can be stored according to regulations without polluting the environment.
  • Figure 2 illustrates a continuous process for decontaminating radioactive isotopes such as cesium, milk contaminated or milk products.
  • the milk to be cleaned (or the milk product) reaches an ultrafiltration device 54 via a line 50 and a pump 52 (in the figures, the flow directions of the substances or liquids are indicated by arrows).
  • Liquid, including the radioactive isotopes, is separated as permeate in the ultrafiltration device 54 and reaches a container 58 via a line 56, the fill level of which is designated 58 ⁇ .
  • An agitator 60 stirs the liquid in the container 58.
  • a substance absorbing and / or ion-exchanging the radioactive isotopes is introduced into the container 58 via a feed line 62.
  • This substance, including the radioactive isotopes bound to it, can be removed in a concentrated form by means of a discharge line 64 and can be disposed of in accordance with regulations.
  • Liquid ie the permeate from the ultrafiltration device 54 and the isotope-binding and / or ion-exchanging substance
  • a second ultrafiltration device 70 via a line 66 and a regulating member 68.
  • the permeate of the ultrafiltration device 70 passes through a line 72 to line 82, where it is brought together with the retentate from the ultrafiltration device 54 (line 78, control element 80).
  • the cleaned milk or milk product is continuously removed from the device by means of the line 82.
  • the retentate formed in the ultrafiltration device 70 passes back into the container 54 via the line 74 and the control valve 76.
  • This retentate contains the isotope-binding and / or ion-exchanging substance.
  • the fill level 58 ⁇ in the container 58 remains constant and the regulating elements or valves are set such that the throughput through line 56 (ie the permeate from the ultrafiltration device 54) is equal to the throughput through line 72 (i.e. the permeate from the ultrafiltration device 70).
  • the ultrafiltration resistance in the ultrafiltration device 54 is considerably larger than in the ultrafiltration device 70. Accordingly, the membrane area in the ultrafiltration device 54 is designed to be significantly larger than in the ultrafiltration device 70.
  • the device shown in FIG. 2 and the method described are suitable not only for the decontamination of milk or milk products but also for the decontamination of other liquids, such as beverages, drinking water or waste water.
  • the continuous process described with reference to FIG. 2 can be carried out repeatedly, either by recycling of the product removed via the line 82 into the line 50 or by connecting a plurality of devices according to FIG. 2 in series in order to improve the efficiency of the decontamination.
  • the method according to the invention in such a way that the milk to be treated (or the milk product) flows through thin tubes from a semi-permeable membrane, the isotope-absorbing and / or ion-exchanging substance flowing in countercurrent outside the tubes.
  • the decontamination agent ie the isotope-binding and / or ion-exchanging substance
  • FIG 3 shows a cartridge 100 in which the iron (III) hexacyanoferrate (II) described above is contained.
  • the insoluble iron (III) hexacyanoferrate (II) is freed from dust particles and sieving ensures that the grain size is larger than 100 ⁇ m, preferably 300 ⁇ m.
  • the iron (III) hexacyanoferrate (II) arranged in the cartridge 100 is pre-rinsed with water for about 10 minutes.
  • the food or feed to be decontaminated flows through the cartridge 100 and has to be prepared beforehand chemically and / or physically.
  • the pH of the liquid flowing through the cartridge 100 must be less than 8. A pH in the range from 3.5 to 7 is preferred. Milk or milk products decontaminated, these must be carefully untucked before entering the cartridge 100, ie coagulated protein substances etc. must be removed, since otherwise the cartridge would clog after a short time. The silt and solids are removed by prefilters (not shown).
  • the cartridge 100 shown in FIG. 3 has, in addition to a jacket 102, which may have a lead protection, two flanges 104, so that the cartridge can be connected on both sides to hose lines through which the food or feed to be decontaminated flows by means of the union nut 106 .
  • sieve / filter arrangements 108 are provided, through which the iron (III) hexacyanoferrate (II) is fixed in the jacket 102 of the cartridge 100.
  • FIG. 4 shows the sieve-filter arrangement 108 in detail.
  • Three layers of screens 112 are provided, as well as a filter layer 114 and a perforated disk 116.
  • the direction of flow of the food or feed to be disposed of through the cartridge 100 is reversible.
  • the reversal of the flow direction has the advantage that both the loosening of the iron (III) hexacyanoferrate (II) 110 in the cartridge 100 and a better utilization of the same take place.
  • a pH-neutral disinfectant can be sent through the cartridge 100 after predetermined periods of time.
  • the cartridge 100 As soon as the iron (III) hexacyanoferrate (II) arranged in the cartridge 100 has been loaded with radioactive cesium to a predetermined extent, the cartridge 100 as a whole is exchanged and replaced by a new one. Since the cartridge 100 can be secured by a protective jacket, it is possible to remove and deposit the contaminated goods without any risk for the operating personnel.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Fodder In General (AREA)
  • Dairy Products (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
  • Treatment Of Water By Ion Exchange (AREA)

Claims (7)

  1. Procédé pour enlever des isotopes radioactifs métalliques de produits alimentaires ou d'aliments pour animaux, sous forme liquide,
    a) par exemple du césium radio-actif,
    b) en utilisant des substances liant les isotopes métalliques ou des substances d'échange ionique, dans lequel
    c) on conditionne les produits alimentaires ou les aliments pour animaux, sous forme liquide, si nécessaire, à un pH de valeur inférieure à 8,
    d) on sépare éventuellement du liquide les dépôts et les matières solides en particulier par des pré-filtres ou par centrifugation,
    e) on fait passer un courant des produits alimentaires ou des aliments pour animaux, sous forme liquide, sur une colonne échangeuse qui contient des ferrocyanures ferriques comme substance fixant les métaux ou substance d'échange ionique,
    f) que l'on débarrasse des particules de poussière et qui présente une grosseur de grains d'au moins 100 µm, caractérisé en ce que
    g) les produits alimentaires ou les aliments pour animaux, sous forme liquide, consistent en du lait ou en des produits laitiers liquides,
    h) une partie du liquide contenant des électrolytes est séparée du lait ou du produit laitier par centrifugation ou par ultra-filtration et est traitée avec la substance fixant les isotopes métalliques ou d'échange ionique,
    i) la substance chargée de radio-activité est séparée et
    j) le cas échéant, le liquide débarrassé des isotopes radio-actifs est recyclé au lait ou au produit laitier, la substance fixant les métaux ou substance d'échange ionique étant du Fe₄ (III) [Fe(II) (CN)₆]₃ (bleu de Prusse) insoluble.
  2. Procédé suivant la revendication 1, caractérisé en ce que le diamètre des grains est supérieur à 300 µm.
  3. Procédé suivant l'une des revendications 1 et 2, caractérisé en ce qu'on inverse périodiquement la direction d'écoulement du liquide à travers la colonne échangeuse.
  4. Procédé suivant l'une des revendications 1 à 3, caractérisé en ce qu'on fait couler périodiquement un agent désinfectant à pH neutre à travers la colonne échangeuse après des temps d'écoulement prédéterminés.
  5. Colonne échangeuse pour la mise en oeuvre du procédé suivant l'une des revendications 1 à 4 sous forme d'un récipient ou d'une cartouche à usage unique, avec
    A) une douille cylindrique (102) en matière plastique, en verre ou en matière similaire, qui comporte aux deux extrémités les éléments suivants:
    B) dispositifs (108) à passoires/filtre,
    C) raccords pour une arrivée et un départ de liquide et
    D) éléments de fermeture éliminables, caractérisée en ce que
    E) la douille contient une charge d'hexacyanoferrate (II) de fer (III) solide en fines particules.
  6. Colonne échangeuse suivant la revendication 5, caractérisée en ce que
    F) la douille cylindrique (102) et les éléments de fermeture sont revêtus extérieurement d'une feuille de plomb.
  7. Utilisation d'hexacyanoferrate (II) de fer (III) insoluble dans l'eau et dans des acides dilués, présentant
    G) des diamètres de particules de 100 à 1000 µm, de préférence de 100 à 500 µm,
    H) une teneur en fer de 28 à 34%, de préférence de 31% (par rapport à la substance séchée à l'air),
    I) une extinction dans l'eau à 686 nm de moins de 0,01 avec moins de 0,01% de fer pouvant être élué à l'eau comme charge active, pour une colonne échangeuse suivant l'une des revendications 5 et 6.
EP88101535A 1987-02-10 1988-02-03 Procédé pour l'enlèvement des isotopes radioactifs métalliques des aliments ou fourrages liquides Expired - Lifetime EP0278379B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88101535T ATE70659T1 (de) 1987-02-10 1988-02-03 Verfahren zum entfernen von radioaktiven metallisotopen aus fluessigen lebens- oder futtermitteln.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873704046 DE3704046A1 (de) 1987-02-10 1987-02-10 Verfahren zum entfernen von radioaktiven metallen aus fluessigkeiten, lebens- und futtermitteln
DE3704046 1987-02-10

Publications (2)

Publication Number Publication Date
EP0278379A1 EP0278379A1 (fr) 1988-08-17
EP0278379B1 true EP0278379B1 (fr) 1991-12-18

Family

ID=6320646

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88101535A Expired - Lifetime EP0278379B1 (fr) 1987-02-10 1988-02-03 Procédé pour l'enlèvement des isotopes radioactifs métalliques des aliments ou fourrages liquides

Country Status (5)

Country Link
EP (1) EP0278379B1 (fr)
AT (1) ATE70659T1 (fr)
DE (1) DE3704046A1 (fr)
ES (1) ES2028142T3 (fr)
GR (1) GR3003655T3 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3912702C2 (de) * 1989-01-31 1994-10-20 Roiner Franz Verfahren zur Dekontaminierung von mit Metallionen und/oder radioaktiven Stoffen befallenen Substanzen
WO1991003815A1 (fr) * 1989-09-02 1991-03-21 Noell Gmbh Procede et installation pour l'elimination du cesium radioactif des suspensions, solutions et liquides similaires et granule echangeur d'ions correspondant
US5707592A (en) * 1991-07-18 1998-01-13 Someus; Edward Method and apparatus for treatment of waste materials including nuclear contaminated materials
US5407889A (en) * 1991-12-24 1995-04-18 Compomet Cantec Method of composite sorbents manufacturing
NL9401686A (nl) * 1994-10-13 1996-05-01 Drs Jacobus Maria Verzijl Werkwijze en inrichting voor het verwijderen van (radioactief) cesium uit vloeistoffen.
FI111765B (fi) * 1996-06-26 2003-09-15 Fortum Nuclear Services Oy Menetelmä cesiumin erottamiseksi ydinjäteliuoksista sekä menetelmä heksasyanoferraattien valmistamiseksi
DE102009019474A1 (de) 2008-05-04 2009-11-05 Fugmann, Winfried, Dr. Mittel und Verfahren zur Modulation der Radioaktivität eines lebenden Körpers
CN111569670B (zh) * 2020-04-24 2022-05-20 江苏大学 一种聚酚介导的普鲁士蓝/石英纳米复合膜及其制备方法与用途

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL237783A (fr) * 1958-04-03
BE678719A (fr) * 1966-03-30 1966-09-30
FR1563936A (fr) * 1968-02-28 1969-04-18
FR1584018A (fr) * 1968-07-09 1969-12-12
DE2242412A1 (de) * 1972-08-29 1974-03-07 Belgonucleaire Sa Verfahren zum dekontaminieren von radioaktiven fluessigkeiten
DE2607292C2 (de) * 1976-02-23 1985-08-29 Kraftwerk Union AG, 4330 Mülheim Verfahren zur Befreiung von im Kernreaktorbetrieb verbrauchten Ionenaustauscherharzen von radioaktiven Korrosionsprodukten
JPS59231493A (ja) * 1983-06-15 1984-12-26 住友金属鉱山株式会社 低レベル放射性廃液の処理方法

Also Published As

Publication number Publication date
ATE70659T1 (de) 1992-01-15
DE3704046A1 (de) 1988-08-18
ES2028142T3 (es) 1992-07-01
DE3704046C2 (fr) 1989-01-05
EP0278379A1 (fr) 1988-08-17
GR3003655T3 (fr) 1993-03-16

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