EP0073263B1 - Procédé pour séparer les ions de césium de solutions aqueuses - Google Patents

Procédé pour séparer les ions de césium de solutions aqueuses Download PDF

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EP0073263B1
EP0073263B1 EP81106784A EP81106784A EP0073263B1 EP 0073263 B1 EP0073263 B1 EP 0073263B1 EP 81106784 A EP81106784 A EP 81106784A EP 81106784 A EP81106784 A EP 81106784A EP 0073263 B1 EP0073263 B1 EP 0073263B1
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adduct
solution
sbcl
mol
phase
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EP0073263A1 (fr
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Ewald Prof. Dr Ing. Blasius
Karl-Heinz Dipl.-Chem. Nilles
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Karlsruher Institut fuer Technologie KIT
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Kernforschungszentrum Karlsruhe GmbH
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Priority to DE8181106784T priority patent/DE3173134D1/de
Priority to JP57150613A priority patent/JPS5845744A/ja
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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
    • G21F9/06—Processing
    • G21F9/12—Processing by absorption; by adsorption; by ion-exchange
    • G21F9/125—Processing by absorption; by adsorption; by ion-exchange by solvent extraction

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  • the invention relates to a process for separating cesium ions from aqueous solutions using an adduct compound of a macrocyclic polyether and an inorganic, complex acid or salts thereof.
  • medium-radioactive, aqueous wastes such as those obtained as waste solutions, concentrates or sludges in the reprocessing of irradiated nuclear fuels and / or broods, is due to the presence of small amounts of the cesium isotopes 134CS and 137Cs difficult.
  • LAW low active waste
  • dibenzo crown ethers In contrast to the previous extraction agents for Cs + , dibenzo crown ethers have a very low solubility in water and are therefore (at least in part) suitable for use in continuous extraction operations.
  • crown ethers are neutral ligands, the anion is also extracted during the extraction. However, this has a decisive influence on the extraction coefficient. It is very difficult to extract simple cesium salts (chloride, nitrate) with crown ethers in polar solvents (with the exception of nitromethane and nitrobenzene solutions). It was therefore decided to combine crown ethers with known Cs + -specific reagents (these contain voluminous, polarizable anions).
  • the invention has for its object to provide a process for the separation of cesium ions from aqueous solutions, which in the discontinuous and / or in the continuous operation without problems, even in the presence of larger amounts of sodium and potassium ions and without restriction to certain pH ranges of the starting solutions, with good Success can be done.
  • the use of DB-21-C-7 / NaTPB also allows extractions from strongly acidic solutions such as the aforementioned MAW with its high Na + content.
  • the decomposition of the NaTPB is not prevented by using a 100% excess of crown ether and converting the adduct phase into the K + form, but it is greatly slowed down.
  • 30% of the NaTPB used was hydrolyzed by the introduction of 40 ml of a 0.018 mol / l DB-21-C-7 / KTPB (2: 1) adduct solution in nitrobenzene over a total duration of 6 h.
  • Nitrobenzene and 1,2-dichloroethane are particularly suitable as solvents. While NaTPB in nitrobenzene or nitromethane even without DB-21-C-7 provides very high D values for the Cs extraction from strongly alkaline MAW solutions with a high Na + content, an extraction with e.g. B. 1,2-dichiorethane as a solvent is only possible in the presence of DB-21 -C-7. As the corresponding example shows, the D value for the extraction with NaTPB in nitrobenzene is higher in the absence of the crown ether. This is because the somewhat lower Cs selectivity of DB-21-C-7 counteracts the high Cs selectivity of NaTPB (anti-synergism). In the case of DB-18-C-6, this even leads to the fact that extractions from solutions of higher Na + content are no longer possible (cf. CS-B-149 404).
  • the DB-21-C-7 / NaTPB or DB-21-C-7 / NaTPCB adduct solutions can be obtained by directly dissolving the individual components or by redissolving one by precipitation from a homogeneous solution (e.g. dioxane / H 2 0 or Methanol / H 2 0) or by evaporation of a solid adduct obtained (e.g. acetone) containing the two components in stoichiometric ratios.
  • a homogeneous solution e.g. dioxane / H 2 0 or Methanol / H 2 0
  • a solid adduct obtained e.g. acetone
  • An advantageous embodiment of the process according to the invention is characterized in that for the preparation of the adduct compound 2,3,11,12-dibenzo-l, 4,7,10,13,16-hexa-oxa-cyclo-octadeca-2,11- diene (dibenzo-18-crown-6, abbreviated DB-18-C-6) or 2,5,8,15,18,21-hexa-oxa-tricyclo- [20.4.0.0 9.14 ] -hexacosane (dicyclohexyl -18-krone-6, abbreviated DB-18-C-6) or higher homologues thereof with up to 30 ring atoms, including 10 O atoms, or benzo-15-krone-5 (B-15-C-5) .
  • solutions of adducts obtained with complex salts or their salts can also be prepared by extracting the complex acid from (6-10 mol / l) hydrochloric acid with a crown ether, dissolved in nitrobenzene or 1,2-dichlorobenzene or 1,1. 2,2-tetrachloroethane or 1,2-dichloroethane, at a molar ratio
  • M + Na + , K + , NH 4 + and T1 +.
  • the preparation of the adduct solution via the detour via the adduct compounds previously obtained in the solid state and dissolving of the solid, easily metered adducts as required has the advantage that the adducts, stored in a stable form, directly in the desired M (l) loading form come into use.
  • H 2 [ HgJ 4] (the adduct solution in contact with an aqueous solution actually contains the [HgJ 3] --lon) or H [BiJ 4] and their salts form 1: 1 with DB-21-C-7 Adducts, the corresponding adduct solutions similar to those of the hexachloroantimonates (V) being able to be prepared by extraction or direct dissolution of the individual components or by redissolving an adduct obtained by precipitation. All of the abovementioned solvents are suitable for the preparation of adduct solutions with tetraiodomercurates. For adducts with tetraiodobismutates (111) only nitrobenzene shows sufficient solvency.
  • H 2 [ HgJ 4] and its salts are insoluble or only minimally soluble in the solvents mentioned. Solutions of H [BiJ 4] in nitrobenzene have already been described as extractants for Cs + (M. Kyrs, S. Pedesva, Anal. Chim. Acta 27 (1962) 183), but not in combination with a crown ether.
  • the tetraiodobismuth acid or its salts bleed heavily and are quickly destroyed in an oxidizing medium. If an excess of crown ether is used and the K + form is used, bleeding is prevented or oxidative destruction is suppressed.
  • Adducts of DB-21-C-7 with tetraiodomercurate and tetraiodobismutate cannot, however, be used for extractions from the MAW given as an example (formation of J 2 , HgJ 2 or BiJ 3 ).
  • the disturbance is caused by Fe (111) and probably also by ruthenium.
  • the exemplary embodiments listed below for these adducts therefore work with Ru and Fe-free MAW solutions.
  • tetraiodobismutate and tetraiodomercurate adducts should therefore be restricted to non-oxidizing MAW solutions in a continuous procedure.
  • Fe- and Ru-free, HN0 3 -acidic MAW solutions can be used to perform simple batch operations with good success.
  • the synergistic adducts that form with complex acids are liquid exchangers in the H + form, each with an exchangeable proton.
  • liquid exchangers e.g. Na + , K + , NH 4 + , TI + form
  • M (I) nitrate solution e.g. the NH 4 + form by shaking for 1 hour with 3 mol / I NH 4 N0 3 solution or the K + form by shaking with 2 mol / I KN0 3 solution.
  • the loaded adducts can be regenerated in a simple manner by continuous or discontinuous back-extraction of the cesium ions from the organic phase with alkali metal or ammonium salt solution and can then be reused for a further batch.
  • the salt solution containing the radioactive cesium obtained after such a regeneration can be evaporated and the concentrate or the salt cake that forms can be transferred to a solidification matrix suitable for final storage.
  • the concentrate or the salt cake can also be added to the highly radioactive waste.
  • the chloroantimonate adducts have a very high solubility in some chlorinated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane) and in 1,2-dichlorobenzene.
  • chlorinated hydrocarbons diichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane
  • 1,2-dichlorobenzene 1,2-dichlorobenzene.
  • adducts are also suitable for use in continuously operating extraction systems.
  • tetrachloroethane, dichlorobenzene and nitrobenzene are best used as solvents for the adducts, as can be seen in the following comparison of the solvent properties relevant for the extraction:
  • Dichloromethane and chloroform are eliminated as solvents because they have too high a vapor pressure. In chloroform, more bleeding is observed despite a 50% excess of crown ether (DK too low).
  • the dichloromethane phase which contains the DB-21-C-7 / H [SbCl 6 ] adduct in pure form, is siphoned off using a pipette into a template with 10 cm 3 of the corresponding 3 mol / 1 M + Cl - solution transferred (at Tl + with TIN03 or Tl 2 SO 4) and 1/2 hours, shaken vigorously. This step can be repeated again, which is particularly recommended when producing the Na + form.
  • the organic phase which contains the corresponding M (I) loading form, is dried over MgS0 4 after separation from the aqueous phase and then evaporated in a rotary evaporator.
  • the K + , NH 4 + and TI + forms can be left as they are. However, they can also be overturned by taking up the residues in 5 cm 3 of dichloromethane and precipitating yellow to yellow-orange etherates with 20 cm 3 of diethyl ether, which split off the ether again when the solvent residues were separated off at 120 ° C. and thereby pass into orange-brown powder.
  • a yellow etherate of the H + or Na + forms can be precipitated from the oily residues, which turns into a deep yellow powder when the solvent residues are separated off at 80.degree.
  • dioxane can also be used for reprecipitation, the corresponding dioxanates being obtained.
  • the hexachloroantimonate (V) adducts produced in this way have an unlimited shelf life (provided that they are stored in a dry place) and are thermally stable (NH 4 + form up to 200 ° C).
  • the hexachloroantimonate (V) adducts can also be obtained in a particularly simple manner by precipitation from homogeneous solution if the two exemplary regulations below are followed.
  • the display options from a homogeneous solution are not limited to these regulations.
  • Solution 11 was then introduced into solution I, cooled to about 30 ° C., with vigorous stirring, a voluminous, yellow to yellow-orange colored precipitate of the corresponding DB-21-C-7 / M [SbC1 6] dioxanate settling out , which was dried over a glass frit G 4 and washed with 20 cm 3 of 10 mol / l HCl in a desiccator over NaOH.
  • the adducts obtained according to regulations 1, 2a) and 2b), dissolved in acetone or dichloromethane, can be applied to silica gel with complete removal of the solvent.
  • the M [SbCI 6] dioxane adducts, dissolved in H 2 O, can also be used as Cs + -specific precipitation reagents in the qualitative analysis.
  • Cs + - specific reagents e.g. Kalignost, Caesignost, heteropolyacid, H 2 [PtCl 6 ], picric acid
  • K + and NH 4 + do not interfere.
  • they can be used in the entire pH range, while most of the customary precipitation reagents are restricted to certain pH ranges.
  • the DB-21-C-7 / hexachloroantimonate (V) adducts can also be used for the extraction of solutions with larger Cs + contents.
  • extractions in the pH range 0 to 7 and, if the K + form is used can also be carried out in addition.
  • a further possible application of all adduct solutions listed in the present invention is their use as a stationary phase in extraction chromatography (liquid-liquid distribution chromatography) with silica gel as the carrier material.
  • solid adducts can be used directly as column material in ion exchange chromatography.
  • Fig. 1 shows one of these units.
  • Each unit of the extraction apparatus consisted of a 100 cm 3 beaker 1 in which a glass cylinder 2 stood concentrically on small feet 3.
  • a connection gap 5 remained open just above the beaker bottom 4, through which the mobile MAW phase 6 could pass into the settling chamber 7 (space between the cylinder and the beaker wall).
  • the continuously introduced MAW solution 6 was mixed with the initially introduced (or likewise continuously enforced) adduct solution 9 by stirring with the aid of a stirrer 10.
  • the continuous throughput of adduct solution 9 is not shown in the figure.
  • the mixer-settler unit shown in the figure is not part of the invention, but was based on W. Fischer et al., Angew. Chem. 78 (1966) 19. However, other devices can also be used for the method according to the invention.
  • the KN0 3 solution containing the radioactive Cs was then evaporated with the aid of an IR lamp, a colorless salt cake of about 5 cm 3 volume being obtained. This results in a total restriction factor of approx. 2500.
  • a 16-stage mixer-settler apparatus based on the countercurrent principle according to W. Ochsenfeld, S. Krawczynski, Kerntechnik 5 (1963) 218, significantly higher DF values (> 10 4 ) and Throughputs between 20 and 30 liters of the named MAW solution with a total volume of 100 cm 3 of the adduct solution per extraction cycle may be possible.
  • the adduct concentration can be doubled or tripled, which results in extraction coefficients> 40 in the present adduct.
  • the adduct solution was prepared by dissolving 6.2 g of sodium tetraphenylborate and 14.6 g of DB-21-C-7 in 1 dm 3 of nitrobenzene. It contained 0.018 mol / I NaTPB and 0.036 mol / I DB-21-C-7 ( 2: 1 adduct). 20 ml of this solution was 1/2 h shaking with 20 ml MAW solution. An extraction coefficient of 23.0 was achieved for Cs + .
  • the adduct solution thus prepared contained 0.018 mol / l K [HgJ 3 ] and 0.036 mol / l DB-21-C-7.
  • the adduct solution was prepared by dissolving 11.2 gK [HgJ 3 ] and 14.6 g DB-21-C-7 in 1 dm 3 1,2-dichloroethane.
  • the resulting solution contained 0.018 mol / lK [HgJ 3 ] and 0.036 mol / IDB-21-C- 7.
  • the adduct solution was prepared by dissolving 23.0 g of the (1: 1) adduct thus prepared and 7.3 g of DB-21-C-7 in 1 dm 3 of 1,2-dichloroethane. It contained 0.018 mol / l K [HgJ 3] and 0.036 mol / I DB-21-C-7 ( 2: 1 adduct).
  • the adduct solution was prepared by dissolving 14.3 g of the adduct thus prepared and 5.4 g of DB-24-C-8 in 1 dm 3 of nitrobenzene. It contained 0.012 mol / l Na [BiJ 4 ] and 0.024 mol / l DB-24-C-8.
  • the adduct solution was prepared by redissolving 20.6 g of the DB-21-C-7 / Na [BiJ 4] adduct prepared as in Example 15 and 7.3 g of DB-21-C-7 in 1 dm 3 of nitrobenzene. It contained 0.018 mol / I Na [BiJ 4] and 0.036 mol / I DB-21-C-7 ( 2: 1 adduct).
  • Fig. 2 shows schematically the various possibilities for the preparation of DB-21-C-7 / hexachloroantimony (V) acid / salt adduct solutions.

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Claims (11)

1. Procédé pour séparer des ions césium de solutions aqueuses par utilisation d'un composé d'addition d'un polyéther macrocyclique et d'un acide organique complexe ou de ses sels, caractérisé en ce qu'il consiste à exécuter les étapes de procédé suivantes:
a) fabriquer le produit d'addition d'un polyéther macrocyclique, constitué d'au moins un type des éléments de structure suivants, en cycles polyéther
Figure imgb0020
Figure imgb0021
Figure imgb0022
dans lesquels R=H, alcoyl ou aryl, et n=un des chiffres 0, 1 ou 2, avec un acide anorganique complexe, ou un sel de cet acide, et constitué d'un élément polyvalent du groupre Bore, Antimoine, Mercure, Bismuth, jouant le rôle d'atome central, et de plusieurs atomes d'un élément du 7ème groupe principal de la classification périodique des éléments, ou plusieurs radicaux phényl ou cyanure, comme ligands dans une solution polaire organique, - excepté la fabrication d'un produit d'addition de dibenzo-18-couronne-6 avec du tétraphénylborate de sodium (DB-18-C-6/NaTPB) -,
b) mettre en contact la solution aqueuse contenant des ions Césium avec le produit d'addition, selon a), pour l'extraction du Césium de la solution aqueuse dans la phase organique, et
c) séparer la phase organique, chargée en ions Césium, de la solution aqueuse, exempte de Césium ou ne contenant plus que de faibles quantités de Césium.
2. Procédé suivant la revendication 1, caractérisé en ce que le composé d'addition est utilisé dissous dans un solvant organique du groupe des nitrobenzène, 1,2-dichlorbenzène, 1,1,2,2-tétrachloréthane, 1,2-dichloréthane.
3. Procédé suivant la revendication 1, caractérisé en ce que le composé d'addition est utilisé sous la forme d'une phase liquide échangeuse d'ions, sur du gel de silice, comme matériau de support.
4. Procédé suivant la revendication 1, caractérisé en ce que le composé d'addition est utilisé sous la forme d'une phase échangeuse d'ions solide (sous la forme solide exempte de solvant), sur gel de silice ou d'oxyde d'aluminium comme matériau de support.
5. Procédé suivant la revendication 1, caractérisé en ce que le composé d'addition est utilisé, directement, après élimination du solvant organique, sous la forme solide, comme phase fixe.
6. Procédé suivant la revendication 1, caractérisé en ce que pour la fabrication du produit d'addition, on utilise les 2,3,11,12-Dibenzo-1,4,7,10,13,16-hexa-oxa-cyclo-octadéca-2,11-diène (dibenzo-18-couronne-6, en abrégé: DB-18-C-6), ou 2,5,8,15,18,21-hexa-oxa-tricyclo(20.4.0;09,14-hexacosane(dicyclohe- xyl-18-couronne-6, en abrégé: DC-18-C-6), ou des homologues supérieurs de ces produits, comportant jusqu'à 30 atomes dans le cycle, dont 10 atomes d'oxygène, ou benzo-15-couronne-5 (B-15-C-5).
7. Procédé suivant la revendication 1, caractérisé en ce que l'on utilisé, pour la fabrication du composé d'addition, l'acide hexa-chloro-antimonique(V) H+(SbCl6)- ou ses sels, dont: M+(SbCl6)-où M+ représente Na+, K+, NH4 + ou TI+ (Thallium).
8. Procédé suivant la revendication 1, caractérisé en ce que l'on utilise pour la fabrication du composé d'addition, l'hexachlorantimonate(V)-dioxanate M+(SbCl6)―-dioxane, où M+=Na+, K+, NH4 + ou TI+.
9. Procédé suivant la revendication 1, caractérisé en ce que la fabrication des composés d'addition s'effectue par dissolution de différents composants dans les nitrobenzène, dichlorobenzène-1,2 tétrachloréthane-1,1,2,2, ou dichloréthane-1,2 dans un rapport moléculaire polyéther macrocyclique/acide complexe, ou ses sels, tel que ≥ 1 : 1.
10. Procédé suivant la revendication 1, caractérisé en ce que la fabrication de la solution de produit d'addition s'effectue par redissolution d'un produit d'addition obtenu sous la forme cristalline dans les conditions suivantes:
a) Extraction de H+(SbCl6)- de 6 à 10 molécules d'acide chlorhydrique avec une solution dibenzo-éther-couronne/Dichlorométhane, traitement de la phase dichlorométhane avec une solution aqueuse chlorure M+, (avec M+=Na+, K+ ou NH4 +), séparation de la phase aqueuse et de la phase dichlorométhane, séchage et évaporation du produit d'addition, solide ou huileux, et contenant la phase dichlorométhane, ou
b) selon a) et précipitation, au moyen de l'étherat correspondant, avec diéthyléther ou dioxane, du produit d'addition obtenu, sous forme cristalline, ou bien
c) préparation, à l'aide d'une solution de H+(SbCl6)- dans de l'acide chlorhydrique, à partir d'un mélange limpide de solution d'un dibenzo-éther-couronne avec une solution aqueuse de M+CI, où M a la même signification que dans l'étape a).
11. Procédé suivant la revendication 4, caractérisé en ce que le dépôt des produits d'addition du polyéther X+(SbCl6)- où X+=H+, Na+, K+, NH4 + ou Tl+, sur gel de silice ou A1203, s'effectue dans l'acétone, le dichlorméthane, le chloroforme, ou le 1,2-dichloréthane.
EP81106784A 1981-08-31 1981-08-31 Procédé pour séparer les ions de césium de solutions aqueuses Expired EP0073263B1 (fr)

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EP81106784A EP0073263B1 (fr) 1981-08-31 1981-08-31 Procédé pour séparer les ions de césium de solutions aqueuses
DE8181106784T DE3173134D1 (en) 1981-08-31 1981-08-31 Process for separating cesium ions from aqueous solutions
JP57150613A JPS5845744A (ja) 1981-08-31 1982-08-30 水溶液からセシウムイオンを分離する方法

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EP81106784A EP0073263B1 (fr) 1981-08-31 1981-08-31 Procédé pour séparer les ions de césium de solutions aqueuses

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EP0073263B1 true EP0073263B1 (fr) 1985-12-04

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Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Angew. Chemie 84 (1972) Nr. 1, S. 16-26 *

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JPS5845744A (ja) 1983-03-17
EP0073263A1 (fr) 1983-03-09
DE3173134D1 (en) 1986-01-16

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