EP0278379B1 - Method to remove radioactive metallic isotopes from liquid groceries or foodstuffs - Google Patents
Method to remove radioactive metallic isotopes from liquid groceries or foodstuffs Download PDFInfo
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- 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
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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- the cesium cycle of an "in vivo" method is broken and the cesium isotopes can do this Circulation can be largely withdrawn.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- the cesium isotopes withdrawn from the cycle can be obtained in a concentrated form and thus deposited in accordance with regulations or used for other purposes.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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Abstract
Description
Die Erfindung betrifft ein Verfahren zum Entfernen von radioaktiven Metallisotopen aus flüssigen Lebens- oder Futtermitteln mit den Merkmalen des Oberbegriffs des Patentanspruches 1.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.
Weiterhin betrifft die Erfindung eine Austauschersäule zur Durchführung eines solchen Verfahrens sowie die Verwendung von in Wasser und verdünnten Säuren unlöslichem Eisen(III)hexacyanoferrat(II).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.
Aus der FR-PS 15 17 279 ist ein gattungsgemäßes Verfahren zum Entfernen von radioaktiven Metallisotopen aus flüssigen Lebens-oder Futtermitteln bekannt. Dort werden Ionenaustauscherharze verwendet, die im Gegensatz zu Verbindungen vom Typ Berliner Blau nicht vorwiegend auf Cäsium wirken, sondern auch andere Ionen, die zum Beispiel in Milch in ganz anderen Größenordnungen vorkommen, austauschen.From FR-
Aus der DE-PS 26 07 292 ist ein Verfahren bekannt, bei dem es um die Regenerierung von im Kernreaktorbetrieb verbrauchten Ionenaustauscherharzen geht. Es soll dort eine vereinfachte Abfallbeseitigung einschließlich einer möglichen Wiedergewinnung von Konditionierungsstoffen erreicht werden. Es wird die Adsorption von radioaktiven Ionen in Salzsäureauszügen an nicht näher definierte Verbindungen wie Ferroferricyanide oder Silberverbindungen beschrieben.From DE-PS 26 07 292 a method is known which involves the regeneration of ion exchange resins consumed in the operation of a nuclear reactor. Simplified waste disposal, including possible recycling of conditioning substances, is to be achieved there. The adsorption of radioactive ions in hydrochloric acid extracts on unspecified compounds such as ferroferricyanides or silver compounds is described.
In der DE-A-22 42 412 wird vorgeschlagen, radiaktive Flüssigkeiten durch Ionenaustauscher und Sekundärregenerierflüssigkeiten dieser Ionenaustauscher mittels wasserlöslicher Ferricyanide in Verbindung mit Bariumcarbonat durch Ausfällen zu dekontaminieren.In DE-A-22 42 412 it is proposed to decontaminate radioactive liquids by ion exchangers and secondary regeneration liquids of these ion exchangers by means of water-soluble ferricyanides in connection with barium carbonate by precipitation.
Beim in der FR-A-15 84 018 vorgeschlagenen Verfahren werden Flüssigkeiten mit sehr hohen Gehalten an radioaktiven Substanzen verarbeitet. Wegen des hohen Gehaltes an radioaktiven Substanzen werden diese durch geeignete Fällungsmittel niedergeschlagen und aus diesen Niederschlägen wieder rückgewonnen. Die genannten Fällungsmittel sind für Lebensoder Futtermittel nicht geeignet.In the process proposed in FR-A-15 84 018, liquids with very high levels of radioactive substances are processed. Due to the high content of radioactive substances, these are precipitated by suitable precipitants and recovered from these precipitates. The mentioned precipitants are not suitable for food or feed.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren der gattungsgemässen Art zu schaffen, bei dem die Lebensoder Futtermittel hinsichtlich der gewünschten Eigenschaften unbeeinträchtigt bleiben und die radioaktiven Metalle in konzentrierter und somit einfach deponierbarer Form abgetrennt werden können.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.
Die erfindungsgemässe Lösung dieser Aufgabe ist im Patentanspruch 1 gekennzeichnet.The inventive solution to this problem is characterized in claim 1.
Vorteilhafte Ausgestaltungen sind in den Unteransprüchen 1 bis 4 beschrieben.Advantageous configurations are described in subclaims 1 to 4.
Eine beim erfindungsgemässen Verfahren anwendbare Austauschersäule sowie eine Ausgestaltung derselben sind in den Patentansprüchen 5 bzw. 6 beschrieben. Eine Verwendung von in Wasser und verdünnten Säuren unlöslichem Eisen(III) hexacyanoferrat(II) ist im Patentanspruch 7 beschrieben.An exchange column which can be used in the method according to the invention and an embodiment thereof are described in patent claims 5 and 6, respectively. The use of iron (III) hexacyanoferrate (II) which is insoluble in water and dilute acids is described in claim 7.
Die Vorteile des erfindungsgemässen Verfahrens liegen auf der Hand: Der Cäsium-Kreislauf eines "in-vivo"-Verfahrens wird durchbrochen und die Cäsium-Isotope können dem Kreislauf weitgehend entzogen werden. Die Verfahren lassen sich zentral anwenden, so daß eine Kontrolle und genaue Dosierung gewährleistet ist. Die dem Kreislauf entzogenen Cäsium-Isotope können in konzentrierter Form gewonnen und somit vorschriftsmäßig deponiert oder für andere Zwecke verwendet werden.The advantages of the method according to the invention are obvious: 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.
Nachfolgend werden Ausführungsbeispiele der Erfindung anhand der Zeichnung näher erläutert. Es zeigt:
- Fig. 1
- schematisch ein diskontinuierliches Verfahren zum Dekontaminieren von Milch oder Milchprodukten;
- Fig. 2
- schematisch ein kontinuierliches Verfahren zum Entsorgen von Milch oder Milchprodukten, und
- Fig. 3
- schematisch eine Eisen(III)hexacyanoferrat(II) enthaltende Patrone zum Dekontaminieren von mit radioaktivem Cäsium kontaminierten Lebens- oder Futtermitteln.
- Fig. 1
- schematically a batch process for decontaminating milk or milk products;
- Fig. 2
- schematically a continuous process for the disposal of milk or milk products, and
- Fig. 3
- schematically a cartridge containing iron (III) hexacyanoferrate (II) for decontaminating food or feed contaminated with radioactive cesium.
Die in den Fig. 1a, 1b und 1c gezeigte Vorrichtung ermöglicht die diskontinuierliche Entfernung von radioaktiven Metallen aus kontaminierter Milch oder Milchprodukten (sogenanntes Batch-Verfahren).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).
In einen Behälter 10 wird die Milch 12 eingefüllt. Die Füllhöhe der Milch (oder des Milchproduktes) 12 im Behälter 10 ist mit 10ʹ bezeichnet. Die Milch 12 im Behälter 10 soll entsorgt werden.The
Gemäß Fig. 1 wird die zu entsorgende Milch über eine Leitung 14 und eine Pumpe 16 zu einer Ultrafiltrationsvorrichtung 18 überführt. Ultrafiltrationsvorrichtungen sind als solche bekannt und brauchen hier nicht näher beschrieben zu werden. Durch die semipermeable Membran in der Ultrafiltrationsvorrichtung 18 wird Flüssigkeit einschließlich des radioaktiven Cäsiums abgesondert. Die durch die semipermeable Membran durchgelassene Flüssigkeit einschließlich des radioaktiven Cäsiums wird Permeat genannt und gelangt über die Leitung 20 in einen Behälter 22. Das Permeat 24 im Behälter 22 hat den Füllstand 22ʹ.1, the milk to be disposed of is transferred to an
Die von der semipermeablen Membran der Ultrafiltrationsvorrichtung 18 zurückgehaltenen Bestandteile der Milch 12 (Retentat) werden über die Leitung 26, ein Regelventil 28 und eine Rückführleitung 30 zum Behälter 10 zurückgeführt.The
Nach Durchführung der vorstehend beschriebenen Ultrafiltration wird der in Fig. 1b gezeigte Zustand erreicht, d.h. aus der Milch (oder dem Milchprodukt) 12 im Behälter 10 ist eine radioaktives Cäsium enthaltende Flüssigkeit entfernt und in den Behälter 22 überführt worden. Gemäß Fig. 1b (rechts) wird das radioaktiv kontaminierte Permeat 24 im Behälter 22 mittels eines Rührwerkes 32 zur Beschleunigung des Verfahrens durchgerührt. Die Tempeatur des Permeats 24 im Behälter 22 liegt zwischen 20 und 60°C. Zur Absonderung des radioaktiven Cäsiums aus dem Permeat 24 im Behälter 22 wird eine die Cäsiumatome bindende und/oder ionenaustauschende Substanz in den Behälter 22 eingegeben, was in Fig. 1b (rechts) durch die Pfeile 34 angedeutet ist.After carrying out the ultrafiltration described above, 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
Als absorbierendes bzw. ionenaustauschendes Material kommen folgende Stoffe in Betracht: Komplexverbindungen, wie Eisencyanoverbindungen vom Typ Berliner Blau, oder Aluminiumsilikate, wie Bentonite und Zeolithe. Auch Kombinationen der vorstehend genannten Substanzen sind möglich. Die Dosierung liegt bei den Komplexsalzen im Promillebereich und bei den Aluminiumsilikaten im Prozentbereich.The following substances are suitable as absorbent or ion-exchanging material: 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.
Statt durch Ultrafiltration kann die mit radioaktivem Cäsium kontaminierte Flüssigkeit auch durch eine Umkehrosmose als Permeat abgetrennt werden.Instead of using ultrafiltration, the liquid contaminated with radioactive cesium can also be removed as a permeate by reverse osmosis.
In der in Fig. 1b gezeigten Verfahrensstufe wird das Permeat 24 im Behälter 22 durch die radioaktives Cäsium absorbierende oder ionenaustauschende Substanz behandelt, wobei das Cäsium an die Substanz gebunden wird.In the process stage shown in FIG. 1b, the
Gemäß Fig. 1c wird in der folgenden Verfahrensstufe das behandelte Permeat 24 in umgekehrter Richtung einer Ultrafiltration in der Ultrafiltrationsvorrichtung 18 unterzogen. Dabei durchdringt isotopenfreie Flüssigkeit die semipermeable Membran in der Ultrafiltrationsvorrichtung 18 und gelangt über die Leitung 36 zurück in den Behälter 10, so daß der Füllstand 10ʹ der Milch (oder des Milchproduktes) 12 fast den ursprünglichen Pegel gemäß Fig. 1a erreicht. Die bei der Ultrafiltration abgefilterten Rückstände (das Retentat) werden über das Regelventil 38 und die Leitung 40 zurück in den Behälter 22 geführt, in dem der radioaktive Rest 24ʹ, also die Isotope bindenden oder ionenaustauschenden Substanzen einschließlich der radioaktiven Isotope, verbleibt. Dieser radioaktive Rest 24ʹ ist hochkonzentriert und kann vorschriftsmäßig gelagert werden, ohne die Umwelt zu belasten.According to FIG. 1c, the treated
Fig. 2 illustriert ein kontinuierliches Verfahren zum Dekontaminieren von mit radioaktiven Isotopen, wie Cäsium, kontaminierter Milch oder Milchprodukten.Figure 2 illustrates a continuous process for decontaminating radioactive isotopes such as cesium, milk contaminated or milk products.
Die zu reinigende Milch (bzw. das Milchprodukt) gelangt über eine Leitung 50 und eine Pumpe 52 in eine Ultrafiltrationsvorrichtung 54 (in den Figuren sind die Strömungsrichtungen der Stoffe oder Flüssigkeiten durch Pfeile angeben). In der Ultrafiltrationsvorrichtung 54 wird Flüssigkeit einschließlich der radioaktiven Isotope als Permeat abgeschieden und gelangt über eine Leitung 56 in einen Behälter 58, dessen Füllstand mit 58ʹ bezeichnet ist. Ein Rührwerk 60 rührt die Flüssigkeit im Behälter 58.The milk to be cleaned (or the milk product) reaches an
Über eine Zuleitung 62 wird eine die radioaktiven Isotope absorbierende und/oder ionenaustauschende Substanz in den Behälter 58 gegeben. Mittels einer Ableitung 64 kann diese Substanz einschließlich der an sie gebundenen radioaktiven Isotope in konzentrierter Form abgeführt und einer vorschriftsmäßigen Deponierung zugeführt werden.A substance absorbing and / or ion-exchanging the radioactive isotopes is introduced into the
Über eine Leitung 66 und ein Regelorgan 68 wird aus dem Behälter 58 Flüssigkeit (also das Permeat aus der Ultrafiltrationsvorrichtung 54 sowie die Isotope bindende und/oder ionenaustauschende Substanz) zu einer zweiten Ultrafiltrationsvorrichtung 70 geführt. Das Permeat der Ultrafiltrationsvorrichtung 70 gelangt über eine Leitung 72 zur Leitung 82, wo es mit dem Retentat aus der Ultrafiltrationsvorrichtung 54 (Leitung 78, Regelorgan 80) zusammengeführt wird. Mittels der Leitung 82 wird die gereinigte Milch oder das Milchprodukt aus der Vorrichtung kontinuierlich entnommen.Liquid (ie the permeate from the
Das in der Ultrafiltrationsvorrichtung 70 gebildete Retentat gelangt über die Leitung 74 und das Regelventil 76 zurück in den Behälter 54. Dieses Retentat enthält die Isotope bindende und/oder ionenaustauschende Substanz.The retentate formed in the
Während des kontinuierlichen Prozesses bleibt der Füllstand 58ʹ im Behälter 58 konstant und die Regelorgane bzw. -ventile werden derart eingestellt, daß der Durchsatz durch die Leitung 56 (also das Permeat aus der Ultrafiltrationsvorrichtung 54) gleich dem Durchsatz durch die Leitung 72 (also dem Permeat aus der Ultrafiltrationsvorrichtung 70) ist.During the continuous process, the fill level 58ʹ in the
In der Regel, insbesondere bei der Dekontamination von eiweißhaltigen Produkten, ist der Ultrafiltrationswiderstand in der Ultrafiltrationsvorrichtung 54 erheblich größer als in der Ultrafilterungsvorrichtung 70. Dementsprechend wird die Membranfläche in der Ultrafiltrationsvorrichtung 54 wesentlich größer ausgelegt als in der Ultrafiltrationsvorrichtung 70.As a rule, especially in the decontamination of protein-containing products, the ultrafiltration resistance in the
Die in Fig. 2 gezeigte Vorrichtung und das beschriebene Verfahren eignen sich nicht nur zur Dekontamination von Milch oder Milchprodukten sondern auch zur Dekontamination von anderen Flüssigkeiten, wie Getränken, Trinkwasser oder Abwasser.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.
Das anhand der Fig. 2 beschriebene kontinuierliche Verfahren kann wiederholt durchgeführt werden, entweder durch Rückführung des über die Leitung 82 entnommenen Produktes in die Leitung 50 oder durch Hintereinanderschaltung mehrerer Vorrichtungen gemäß Fig. 2, um den Wirkungsgrad der Dekontamination zu verbessern.The continuous process described with reference to FIG. 2 can be carried out repeatedly, either by recycling of the product removed via the
Werden durch den Ionenaustauscher, wie z.B. Bentonit, nicht nur radioaktive Cäsium-Isotope ausgetauscht, sondern auch andere Ionen, so muß gegebenenfalls dieser Verlust durch gezielte Mineralstoffzugabe in die Leitung 78 (Fig. 2) bzw. 36 (Fig. 1c) ausgeglichen werden.Are by the ion exchanger, such as Bentonite, not only exchanged radioactive cesium isotopes, but also other ions, this loss may have to be compensated for by adding minerals in line 78 (FIG. 2) or 36 (FIG. 1c).
Es ist auch möglich, das erfindungsgemäße Verfahren derart durchzuführen, daß die zu behandelnde Milch (oder das Milchprodukt) durch dünne Röhren aus einer semipermeablen Membran strömt, wobei außerhalb der Röhren die Isotope absorbierende und/oder ionenaustauschende Substanz im Gegenstrom fließt. Bei einer solchen Vorrichtung wird ein direkter Kontakt zwischen dem zu entsorgenden Gut und dem Dekontaminierungsmittel (also der Isotope bindenden und/oder ionenaustauschenden Substanz) vermieden.It is also possible to carry out 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. With such a device, direct contact between the material to be disposed of and the decontamination agent (ie the isotope-binding and / or ion-exchanging substance) is avoided.
Fig. 3 zeigt eine Patrone 100, in der das oben beschriebene Eisen(III)hexacyanoferrat(II) enthalten ist. Vor dem Einfüllen in den Mantel 102 der Patrone 100 wird das unlösliche Eisen(III)hexacyanoferrat(II) von Staubteilen befreit und durch Sieben sichergestellt, daß die Korngröße größer ist als 100 µm, vorzugsweise 300 µm.3 shows a
Bevor das zu dekontaminierende Lebens- oder Futtermittel durch die Patrone 100 strömt, wird das in der Patrone 100 angeordnete Eisen(III)hexacyanoferrat(II) für ca. 10 Minuten mit Wasser vorgespült.Before the food or feed to be decontaminated flows through the
Das zu dekontaminierende Lebens- oder Futtermittel durchströmt die Patrone 100 und muß zuvor chemisch und/oder physikalisch vorbereitet werden. Der pH-Wert der die Patrone 100 durchströmenden Flüssigkeit muß kleiner als 8 sein. Bevorzugt wird ein pH-Wert im Bereich von 3,5 bis 7. Werden Milch oder Milchprodukte dekontaminiert, so müssen diese vor Eintritt in die Patrone 100 sorgfältig entschlickt werden, d.h. koaggulierte Eiweißstoffe etc. müssen entfernt werden, da sich ansonsten die Patrone nach kurzer Zeit zusetzen würde. Die Schlick- und Feststoffe werden durch Vorfiltern (nicht gezeigt) entfernt.The food or feed to be decontaminated flows through the
Die in Fig. 3 gezeigte Patrone 100 weist neben einem Mantel 102, welcher einen Bleischutz aufweisen kann, zwei Flansche 104 auf, so daß mittels der Überwurfmutter 106 die Patrone beidseitig an Schlauchleitungen angeschlossen werden kann, durch welche das zu dekontaminierende Lebens- oder Futtermittel strömt. Am Eingang und am Ausgang der Patrone 100 sind jeweils Sieb/Filter-Anordnungen 108 vorgesehen, durch welche das Eisen(III)hexacyanoferrat(II) im Mantel 102 der Patrone 100 fixiert wird.The
Fig. 4 zeigt die Sieb-Filter-Anordnung 108 im Detail. Es sind drei Lagen Siebe 112 vorgesehen sowie eine Filter-Lage 114 und eine Lochscheibe 116.4 shows the sieve-
Die Strömungsrichtung des zu entsorgenden Lebens- oder Futtermittels durch die Patrone 100 ist umkehrbar. Die Umkehrung der Strömungsrichtung hat den Vorteil, daß sowohl eine Auflockerung des Eisen (III) hexacyanoferrats (II) 110 in der Patrone 100 als auch eine bessere Ausnutzung derselben erfolgt.The direction of flow of the food or feed to be disposed of through the
Um mikrobiologische Verunreinigungen zu vermeiden, kann nach vorgegebenen Zeitspannen ein pH-neutrales Desinfektionsmittel durch die Patrone 100 geschickt werden.In order to avoid microbiological contamination, a pH-neutral disinfectant can be sent through the
Sobald das in der Patrone 100 angeordnete Eisen(III)hexacyanoferrat(II) über ein vorgegebenes Maß mit radioaktivem Cäsium beladen ist, wird die Patrone 100 insgesamt ausgetauscht und durch eine neue ersetzt. Da die Patrone 100 durch einen Schutzmantel gesichert werden kann, ist es möglich, das kontaminierte Gut ohne jegliche Gefahr für das Bedienungspersonal abzutransportieren und zu deponieren.As soon as the iron (III) hexacyanoferrate (II) arranged in the
Claims (7)
- A process for removing radioactive metal isotopes from liquid foods or feedsa) such as, for example, radioactive caesium,b) using substances which bind the metal isotopes or ion exchangers,c) the liquid foods or feeds if necessary being adjusted to a pH value below 8,d) any slime and solids being removed from the liquid by, in particular, preliminary filtration or centrifugation,e) the liquid foods or feeds being passed through an exchanger column in which ferroferricyanides are present as the metal-binding or ion-exchanging substance,f) having been freed from dust and having a particle size of at least 100 µm,characterized in thatg) the liquid food or feed is milk or a liquid milk product.h) part of the electrolyte-containing liquid is removed from the milk or the milk product by centrifugation or ultrafiltration and is treated with the substance binding metal isotopes or the ion-exchanging substance,i) the radioactively charged substance is removed andj) the liquid freed from the radioactive isotopes is optionally returned to the milk or the milk product, the metal-binding or ion-exchanging substance being insoluble Fe₄(III) [Fe(II) (CN)₆]₃ (Berlin Blue).
- A process as claimed in claim 1, characterized in that the particle size is greater than 300 µm.
- A process as claimed in claim 1 or 2, characterized in that the throughflow direction of the liquid through the exchanger column is periodically reversed.
- A process as claimed in any of claims 1 to 3, characterized in that a pH-neutral disinfectant is periodically passed through the exchanger column after predetermined throughflow times.
- An exchanger column for carrying out the process claimed in any of claims 1 to 4 in the form of a nonreuseable container or cartridge, comprisingA) a cylindrical sleeve (102) of plastic, glass or the like provided at either end with the following:B) sieve/filter arrangements (108),C) connections for the supply and removal of liquid andD) removable closure means,characterized in thatE) the sleeve contains a filling of fine-particle solid iron(III) hexacyanoferrate(II).
- An exchanger column as claimed in claim 5, characterized in thatF) the cylindrical sleeve (102) and the closure means are externally covered with a lead foil.
- The use of iron (III) hexacyanoferrate(II) insoluble in water and dilute acids and havingG) a particle size of 100 to 1,000 µm and preferably 100 to 500 µm,H) an iron content of 28 to 34% and preferably 31% (based on air-dry substance),I) an extinction in water at 686 nm of less than 0.01 and less than 0. 01% water-elutable iron as active filling for the exchanger column claimed in claim 5 or 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT88101535T ATE70659T1 (en) | 1987-02-10 | 1988-02-03 | PROCESS FOR REMOVAL OF RADIOACTIVE METAL ISOTOPE FROM LIQUID FOOD OR FEED. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3704046 | 1987-02-10 | ||
| DE19873704046 DE3704046A1 (en) | 1987-02-10 | 1987-02-10 | METHOD FOR REMOVING RADIOACTIVE METALS FROM LIQUIDS, FOOD AND FEED |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0278379A1 EP0278379A1 (en) | 1988-08-17 |
| EP0278379B1 true EP0278379B1 (en) | 1991-12-18 |
Family
ID=6320646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88101535A Expired - Lifetime EP0278379B1 (en) | 1987-02-10 | 1988-02-03 | Method to remove radioactive metallic isotopes from liquid groceries or foodstuffs |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0278379B1 (en) |
| AT (1) | ATE70659T1 (en) |
| DE (1) | DE3704046A1 (en) |
| ES (1) | ES2028142T3 (en) |
| GR (1) | GR3003655T3 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3912702C2 (en) * | 1989-01-31 | 1994-10-20 | Roiner Franz | Process for the decontamination of substances contaminated with metal ions and / or radioactive substances |
| WO1991003815A1 (en) * | 1989-09-02 | 1991-03-21 | Noell Gmbh | Process and installation for the removal of radioactive caesium from suspensions, solutions and similar liquids, and ion-exchange beads suitable for this purpose |
| 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 (en) * | 1994-10-13 | 1996-05-01 | Drs Jacobus Maria Verzijl | Method and apparatus for removing (radioactive) caesium from liquids |
| FI111765B (en) | 1996-06-26 | 2003-09-15 | Fortum Nuclear Services Oy | A process for the separation of cesium from nuclear waste solutions and a process for the preparation of hexane cyanoferrates |
| DE102009019474A1 (en) | 2008-05-04 | 2009-11-05 | Fugmann, Winfried, Dr. | Agent, useful for modulating natural radioactivity of living body and to prepare e.g. medicines, dietary supplements and functional foods, comprises material composition, in which frequency of naturally occurring radionuclide is changed |
| CN111569670B (en) * | 2020-04-24 | 2022-05-20 | 江苏大学 | Polyphenol-mediated prussian blue/quartz nano composite film and preparation method and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL237783A (en) * | 1958-04-03 | |||
| BE678719A (en) * | 1966-03-30 | 1966-09-30 | ||
| FR1563936A (en) * | 1968-02-28 | 1969-04-18 | ||
| FR1584018A (en) * | 1968-07-09 | 1969-12-12 | ||
| DE2242412A1 (en) * | 1972-08-29 | 1974-03-07 | Belgonucleaire Sa | Radioactive decontamination of liqs - by adsorbing ions on a mixt of barium salt, metal ferrocyanide (and metal sulphide) |
| DE2607292C2 (en) * | 1976-02-23 | 1985-08-29 | Kraftwerk Union AG, 4330 Mülheim | Process for the removal of radioactive corrosion products from ion exchange resins used in nuclear reactor operation |
| JPS59231493A (en) * | 1983-06-15 | 1984-12-26 | 住友金属鉱山株式会社 | Method of treating low level radioactive waste liquid |
-
1987
- 1987-02-10 DE DE19873704046 patent/DE3704046A1/en active Granted
-
1988
- 1988-02-03 AT AT88101535T patent/ATE70659T1/en not_active IP Right Cessation
- 1988-02-03 EP EP88101535A patent/EP0278379B1/en not_active Expired - Lifetime
- 1988-02-03 ES ES198888101535T patent/ES2028142T3/en not_active Expired - Lifetime
-
1992
- 1992-01-27 GR GR920400084T patent/GR3003655T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE3704046C2 (en) | 1989-01-05 |
| DE3704046A1 (en) | 1988-08-18 |
| GR3003655T3 (en) | 1993-03-16 |
| EP0278379A1 (en) | 1988-08-17 |
| ATE70659T1 (en) | 1992-01-15 |
| ES2028142T3 (en) | 1992-07-01 |
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