EP0252166B1 - Verfahren zur kontinuierlichen oder quasi-kontinuierlichen Abtrennung von Cäsium-Ionen aus wässrigen Lösungen durch Ionenaustausch an Ammonium-molybdatophosphat - Google Patents
Verfahren zur kontinuierlichen oder quasi-kontinuierlichen Abtrennung von Cäsium-Ionen aus wässrigen Lösungen durch Ionenaustausch an Ammonium-molybdatophosphat Download PDFInfo
- Publication number
- EP0252166B1 EP0252166B1 EP86109194A EP86109194A EP0252166B1 EP 0252166 B1 EP0252166 B1 EP 0252166B1 EP 86109194 A EP86109194 A EP 86109194A EP 86109194 A EP86109194 A EP 86109194A EP 0252166 B1 EP0252166 B1 EP 0252166B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solution
- container
- ions
- cesium
- continuous
- 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
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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
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
Definitions
- the invention relates to a process for the continuous or quasi-continuous separation of cesium ions from aqueous solutions having high sodium and / or potassium ion concentrations by ion exchange on ammonium molybdate phosphate (AMP).
- AMP ammonium molybdate phosphate
- the invention is therefore based on the object of providing a method with which quantitative cesium separation from aqueous, strongly saline solutions, in particular from nitrate-containing, strongly nitric acid, highly active solutions can be ensured without bleeding out of the AMP and / or undesirable local overheating in the Have to accept exchangers.
- the method should be able to be carried out continuously or quasi-continuously, i.e. H. it should be ensured that a large number of bed volumes of solution containing cesium ions can be passed through the exchanger before the amount of AMP has to be replaced by a fresh amount.
- the uniform flow of the starting solution is advantageously adjusted with the proviso that the suspended volume of the quantity of AMP microcrystals used does not exceed 7/8 the height of the liquid column in the container.
- the porous base for the loose layer of microcrystalline AMP can consist, for example, of a stainless steel sintered metal frit.
- the throughput rate of the starting solution which is the small amounts of cesium ions and which, on the other hand, contains very high salt concentrations, through the AMP or through the column or through the container can vary within a wide range depending on the size of the usable volume of space. Conveniently, the flow rate will be adjusted so that the AMP microcrystals in the lower part of the volume of the starting solution are kept in suspension but never reach the exit opening of the decontaminated solution container.
- the feed with the starting solution is interrupted and the solution standing above the re-deposited AMP layer is sucked out or pressed out of the column using a pipe which is attached at a suitable height.
- the solution freed from cesium ions is replaced by water.
- the AMP is freed from residues of the acidic solution.
- the excess washing solution is then removed by suction.
- the exchanger loaded with cesium ions can now be dissolved in ammonium hydroxide solution or sodium hydroxide solution and the resulting waste solution can be drawn off at the lower end of the container without any changes to the equipment or cumbersome handling of the equipment.
- the AMP can also be rinsed out of the device.
- the cesium-containing exchange solution or suspension can then easily be mixed homogeneously with the matrix intended for deposition (for example for the glazing of radioactive waste or for the cementing of such waste) or be subjected to a further chemical treatment with the aim of commercial cesium production.
- Sodium hydroxide solution is more suitable as a solvent in highly active systems because of its greater radiation resistance.
- fresh AMP can be added to the apparatus, for example, via the decanting line, e.g. B. with the help of a pump.
- the decanting line immersed in the solution can be designed such that it can be moved in the vertical direction if required. In another embodiment, it can be introduced laterally into the column.
- the figure shows schematically an example of a device as it can be used to carry out the method.
- the device essentially consists of a container or a column, for example of a cylindrical tube 1, which is provided at both ends with inlets 4, 6 or outlets 5, 6, 7 and at least at the lower end with a frit 2.
- the AMP is filled in as powder via the riser pipe 6 so that it lies loosely on the frit 2.
- the AMP can be filled in as a suspension in the medium that is to be decontaminated later, via 6.
- the porosity of the frit 2 is irrelevant, since it is only intended to prevent the AMP from falling through, and the pore size of the frit is normally 3 to 15 ⁇ m.
- the cesium-containing process solution is then introduced through the feed line 4 into the device at a uniform flow rate. This can be done by hydrostatic pressure or by a pump etc.
- the AMP slowly rises with the flow, distributes itself in the liquid and forms a density gradient from the frit 2 upwards.
- the flow rate is selected so that the upper end of the column, from which the decontaminated solution flows out through outlet 5, remains free of AMP particles.
- a 0.5 ⁇ m frit 3 can be attached to the upper end, which is caused when the AMP is swirled up, be it by pumping too quickly or by air bubbles, which prevents it from escaping from the column.
- this filter can also be installed instead as an “in-line filter” in the outlet line 5 before the solution enters the storage vessel (not shown in the figure). If certain procedural conditions are observed, frit 3 is not required.
- the column is emptied for the solution above the AMP via the suction pipe 6 or for the solution portion still remaining in the device by draining off via the discharge line 7, with compressed air (air, N2, Ar etc.) in the line 5 Device can be given to accelerate the drainage process.
- compressed air air, N2, Ar etc.
- the column can be blown dry if necessary.
- the solutions required to dissolve the AMP or rinse the device are fed in via the inlet (the feed line) 4 or, if necessary, via the lines 5, 6, 7 and leave the column 1 in the most suitable manner via the outlet pipe 5 in the case of continuous operation , the riser pipe 6, after the AMP has settled or (after emptying via the riser pipe 6) through the drain pipe 7.
- the continuous or quasi-continuous method according to the invention has a serious problem both in relation to a discontinuous method, for example in a beaker (batch method) which works with pure AMP, and also to a method in which the AMP has been drawn up from a support structure and surprising advantage: While a batch process can achieve a decontamination factor (DF) for cesium ions of the order of 102, the process according to the invention ensures a DF of> 60,000, with higher radioactivity due to the still low residual activity> 100,000.
- DF decontamination factor
- the term ">" used means that the numerical value mentioned may well be higher, however, it cannot therefore be calculated quite correctly because the residual activity is close to the detection limit.
- the solution was collected in a storage vessel and subjected to a ⁇ measurement. Only Cs-134 and Cs-137 were removed with a decontamination factor of DF> 60,000, given by the detection limit of the ⁇ -spectrometer. This continuous operation means that there is no local overheating, since the AMP-1 is continuously cooled and dissolved in NaOH solution after it has been used.
- the pump was then switched off and after a quick sit down of the AMP-1 the protruding one was already Aspirated decontaminated solution through the riser and added to the decontaminated stock solution.
- the total dose at the storage vessel was still 0.7 R / h.
- the supernatant aqueous solution was also removed from the column via the riser pipe (after the AMP-1 had settled); the Amp-1, which was loaded with Cs, was dissolved with 20 ml of 1 M NaOH solution, which was fed into the column from below.
- the waste solution was then drained down from the column. After washing the column with H2O, the column was again charged with fresh AMP-1 via the riser and the procedure was repeated with fresh MAW.
- the column was then rinsed with 5 liters of water from bottom to top, the majority of the rinsing water still remaining in the column likewise being removed via the riser pipe after the AMP-1 had settled.
- the Cs-containing AMP-1 was then dissolved in 100 ml of 1 M NaOH solution which was fed in from below. This waste solution was drained down.
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP86109194A EP0252166B1 (de) | 1986-07-05 | 1986-07-05 | Verfahren zur kontinuierlichen oder quasi-kontinuierlichen Abtrennung von Cäsium-Ionen aus wässrigen Lösungen durch Ionenaustausch an Ammonium-molybdatophosphat |
DE8686109194T DE3680337D1 (de) | 1986-07-05 | 1986-07-05 | Verfahren zur kontinuierlichen oder quasi-kontinuierlichen abtrennung von caesium-ionen aus waessrigen loesungen durch ionenaustausch an ammonium-molybdatophosphat. |
US07/069,438 US4826604A (en) | 1986-07-05 | 1987-07-02 | Process for separation of cesium ions from aqueous solutions |
JP62167123A JPH07111474B2 (ja) | 1986-07-05 | 1987-07-06 | セシウムイオンを水溶液から連続的又は擬連続的に分離するための方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP86109194A EP0252166B1 (de) | 1986-07-05 | 1986-07-05 | Verfahren zur kontinuierlichen oder quasi-kontinuierlichen Abtrennung von Cäsium-Ionen aus wässrigen Lösungen durch Ionenaustausch an Ammonium-molybdatophosphat |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0252166A1 EP0252166A1 (de) | 1988-01-13 |
EP0252166B1 true EP0252166B1 (de) | 1991-07-17 |
Family
ID=8195242
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86109194A Expired - Lifetime EP0252166B1 (de) | 1986-07-05 | 1986-07-05 | Verfahren zur kontinuierlichen oder quasi-kontinuierlichen Abtrennung von Cäsium-Ionen aus wässrigen Lösungen durch Ionenaustausch an Ammonium-molybdatophosphat |
Country Status (4)
Country | Link |
---|---|
US (1) | US4826604A (ja) |
EP (1) | EP0252166B1 (ja) |
JP (1) | JPH07111474B2 (ja) |
DE (1) | DE3680337D1 (ja) |
Families Citing this family (10)
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 |
GB2264490A (en) * | 1992-02-18 | 1993-09-01 | John Douglas Bristowe | Recovery of heavy metals from water |
US20020121470A1 (en) * | 2000-10-23 | 2002-09-05 | Mann Nick R. | Composite media for ion processing |
US20040122141A1 (en) * | 2000-10-19 | 2004-06-24 | Todd Terry A | Composite media for ion processing and a method for making the composite media |
AU2002231316A1 (en) * | 2000-10-19 | 2002-04-29 | Bechtel Bwxt Idaho, Llc | Ion processing element with composite media |
US7629292B2 (en) * | 2000-10-19 | 2009-12-08 | Battelle Energy Alliance, Llc | Composite media for ion processing |
DK1876247T3 (da) * | 2002-07-08 | 2013-07-01 | Basf Corp | Metalforbindelse fjernelse |
CN104215999A (zh) * | 2013-05-30 | 2014-12-17 | 核工业北京地质研究院 | 一种海水中放射性核素分析前处理方法 |
JP2016211885A (ja) * | 2015-04-30 | 2016-12-15 | 株式会社神鋼環境ソリューション | 放射性物質の吸着装置、及び該吸着装置の使用方法 |
DE102017105004B4 (de) | 2017-03-09 | 2019-04-04 | Siempelkamp NIS Ingenieurgesellschaft mbH | Aufbereitung einer borhaltigen Flüssigkeit |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL237783A (ja) * | 1958-04-03 | |||
US3017242A (en) * | 1959-09-09 | 1962-01-16 | Lloyd L Ames | Removal of cesium by sorption from aqueous solutions |
US3296123A (en) * | 1964-04-01 | 1967-01-03 | William E Prout | Removal of cesium from aqueous solutions by ion exchange |
SE317051B (ja) * | 1965-02-23 | 1969-11-10 | Atomenergi Ab | |
US3453214A (en) * | 1967-02-14 | 1969-07-01 | Saint Gobain Techn Nouvelles | Method of cesium 137 removal |
EP0073261B1 (de) * | 1981-08-31 | 1985-11-13 | Kernforschungszentrum Karlsruhe Gmbh | Verfahren zum Abtrennen von Cäsiumionen aus Lösungen unter Verwendung einer Adduktverbindung in fester Form aus einem macrocyclischen Polyether und einer anorganischen Heteropolysäure |
-
1986
- 1986-07-05 DE DE8686109194T patent/DE3680337D1/de not_active Expired - Lifetime
- 1986-07-05 EP EP86109194A patent/EP0252166B1/de not_active Expired - Lifetime
-
1987
- 1987-07-02 US US07/069,438 patent/US4826604A/en not_active Expired - Lifetime
- 1987-07-06 JP JP62167123A patent/JPH07111474B2/ja not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0252166A1 (de) | 1988-01-13 |
DE3680337D1 (de) | 1991-08-22 |
JPS6327797A (ja) | 1988-02-05 |
JPH07111474B2 (ja) | 1995-11-29 |
US4826604A (en) | 1989-05-02 |
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Owner name: *KERNFORSCHUNGSZENTRUM KARLSRUHE G.M.B.H. Effective date: 20060705 |