EP0278379B1 - Verfahren zum Entfernen von radioaktiven Metallisotopen aus flüssigen Lebens- oder Futtermitteln - Google Patents
Verfahren zum Entfernen von radioaktiven Metallisotopen aus flüssigen Lebens- oder Futtermitteln Download PDFInfo
- 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
Links
- 230000002285 radioactive effect Effects 0.000 title claims abstract description 28
- 239000007788 liquid Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 26
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 18
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 18
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005342 ion exchange Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000000428 dust Substances 0.000 claims abstract description 3
- 239000008267 milk Substances 0.000 claims description 35
- 210000004080 milk Anatomy 0.000 claims description 35
- 235000013336 milk Nutrition 0.000 claims description 35
- 238000000108 ultra-filtration Methods 0.000 claims description 25
- 150000002500 ions Chemical class 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 235000021056 liquid food Nutrition 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000000645 desinfectant Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- 230000008033 biological extinction Effects 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000010419 fine particle Substances 0.000 claims 1
- 239000011888 foil Substances 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- 229960003351 prussian blue Drugs 0.000 abstract 1
- 239000013225 prussian blue Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 239000012466 permeate Substances 0.000 description 13
- 235000013305 food Nutrition 0.000 description 7
- 239000012528 membrane Substances 0.000 description 6
- 238000005202 decontamination Methods 0.000 description 5
- 230000003588 decontaminative effect Effects 0.000 description 5
- 239000012465 retentate Substances 0.000 description 5
- 238000010924 continuous production Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- -1 aluminum silicates Chemical class 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 235000012216 bentonite Nutrition 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000000941 radioactive substance Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 150000001663 caesium Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011169 microbiological contamination Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- 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.
Landscapes
- 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)
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 (de) | 1988-08-17 |
EP0278379B1 true EP0278379B1 (de) | 1991-12-18 |
Family
ID=6320646
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88101535A Expired - Lifetime EP0278379B1 (de) | 1987-02-10 | 1988-02-03 | Verfahren zum Entfernen von radioaktiven Metallisotopen aus flüssigen Lebens- oder Futtermitteln |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0278379B1 (enrdf_load_stackoverflow) |
AT (1) | ATE70659T1 (enrdf_load_stackoverflow) |
DE (1) | DE3704046A1 (enrdf_load_stackoverflow) |
ES (1) | ES2028142T3 (enrdf_load_stackoverflow) |
GR (1) | GR3003655T3 (enrdf_load_stackoverflow) |
Families Citing this family (8)
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 (de) * | 1989-09-02 | 1991-03-21 | Noell Gmbh | Verfahren und anlage zur entfernung von radioaktivem caesium aus suspensionen, lösungen und ähnlichen flüssigkeiten sowie hierfür geeignetes ionenaustauscher-granulat |
US5707592A (en) * | 1991-07-18 | 1998-01-13 | Someus; Edward | Method and apparatus for treatment of waste materials including nuclear contaminated materials |
FI933677L (fi) * | 1991-12-24 | 1993-08-20 | Sovmestnoe Sovetsko Kanadskoe | Foerfarande foer framstaellning av kompositsorbent |
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)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL237783A (enrdf_load_stackoverflow) * | 1958-04-03 | |||
BE678719A (enrdf_load_stackoverflow) * | 1966-03-30 | 1966-09-30 | ||
FR1563936A (enrdf_load_stackoverflow) * | 1968-02-28 | 1969-04-18 | ||
FR1584018A (enrdf_load_stackoverflow) * | 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 |
-
1987
- 1987-02-10 DE DE19873704046 patent/DE3704046A1/de active Granted
-
1988
- 1988-02-03 AT AT88101535T patent/ATE70659T1/de not_active IP Right Cessation
- 1988-02-03 EP EP88101535A patent/EP0278379B1/de not_active Expired - Lifetime
- 1988-02-03 ES ES198888101535T patent/ES2028142T3/es not_active Expired - Lifetime
-
1992
- 1992-01-27 GR GR920400084T patent/GR3003655T3/el unknown
Also Published As
Publication number | Publication date |
---|---|
ES2028142T3 (es) | 1992-07-01 |
GR3003655T3 (enrdf_load_stackoverflow) | 1993-03-16 |
ATE70659T1 (de) | 1992-01-15 |
DE3704046A1 (de) | 1988-08-18 |
EP0278379A1 (de) | 1988-08-17 |
DE3704046C2 (enrdf_load_stackoverflow) | 1989-01-05 |
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