EP1786000A1 - Procédé pour le traitement des résines échangeuses d'ions - Google Patents

Procédé pour le traitement des résines échangeuses d'ions Download PDF

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Publication number
EP1786000A1
EP1786000A1 EP05024365A EP05024365A EP1786000A1 EP 1786000 A1 EP1786000 A1 EP 1786000A1 EP 05024365 A EP05024365 A EP 05024365A EP 05024365 A EP05024365 A EP 05024365A EP 1786000 A1 EP1786000 A1 EP 1786000A1
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EP
European Patent Office
Prior art keywords
ion exchange
exchange resins
exchange resin
salt
slurry
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.)
Withdrawn
Application number
EP05024365A
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German (de)
English (en)
Inventor
Horst-Otto Bertholdt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Areva GmbH
Original Assignee
Areva NP GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Areva NP GmbH filed Critical Areva NP GmbH
Priority to EP05024365A priority Critical patent/EP1786000A1/fr
Publication of EP1786000A1 publication Critical patent/EP1786000A1/fr
Withdrawn legal-status Critical Current

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    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/28—Treating solids
    • G21F9/30—Processing

Definitions

  • the invention relates to a method for conditioning radioactive ion exchange resins.
  • Ion exchange resins are used, for example, in the operation of nuclear facilities to clean the coolant of the primary system, ie water. The aim of this cleaning is the avoidance of unwanted deposits, the prevention of corrosion and the reduction of contamination in the primary circuit of the plant.
  • acidic cation exchangers which extract radioactive metal ions, for example cobalt 60, from the primary coolant, basic anion exchangers are also used.
  • spent ion exchange resins Before spent ion exchange resins can be put into a repository, they must be conditioned. This is generally understood as the transfer of a radioactive waste into a final storable form.
  • the object of the invention is to propose a method for conditioning radioactive ion exchange resins, with which the waste volume can be reduced with low equipment and cost.
  • ion exchange resins which are usually present in granular form, mixed with water, that is, a slurry is prepared.
  • a slurry is now preferably passed through a reaction zone at a temperature of more than 30 ° C. in a circuit in which hydroxyl radicals are formed by means of a device present there, whereby the oxidative degradation of the ion exchange resins is considerably accelerated.
  • An overpressure that requires pressure-resistant and therefore expensive containers and pipelines is not required.
  • a plasma is generated by means of the device.
  • the required energy supply can be done in various ways, namely by thermal excitation, by radiation excitation, such as by UV light, and by electrostatic and electromagnetic Fields.
  • a plasma is generated by means of an arc.
  • the oxidative degradation of the ion exchange resins is significantly accelerated by the energetic particles, in particular radicals such as hydroxyl radicals attack not only already formed fragments of the macromolecules but also act decomposing on the surface of macroscopic particles of the ion exchange resins.
  • radicals such as hydroxyl radicals attack not only already formed fragments of the macromolecules but also act decomposing on the surface of macroscopic particles of the ion exchange resins.
  • oxygen-containing oxidants in particular of hydrogen peroxide
  • a very high proportion of hydroxyl radicals is present.
  • the interaction of the resulting radicals and the added oxidizing agent thus results in a considerable acceleration of the oxidative degradation of the ion exchange resins.
  • the majority of the technically relevant resins based on crosslinked styrene-divinylbenzene copolymers which in the case of acidic cation exchanger sulfone, phosphonic or carboxylic acid groups and in the case of basic anion exchangers, eg. B. quaternary ammonium groups or primary, secondary or tertiary ammino groups.
  • the reaction products of the oxidative degradation are mainly CO 2 and water, the CO 2 is discharged from the process cycle.
  • Remains essentially water, in which the acid groups of the acidic exchange resins in the form of the corresponding acids or the ammonium and amino groups of the basic exchange resins are dissolved in the form of corresponding ammonium or amino salts.
  • the volume of waste can be reduced by a factor of about 10 using the proposed method.
  • a device for UV irradiation is present in the reaction section.
  • the energy of the UV radiation is chosen so that a plasma does not arise, at least to a considerable extent.
  • the wavelength range of the UV light is selected such that, on the one hand, covalent bonds of the ion exchange resin are separated and, on the other hand, hydroxyl radicals are formed, for example, from an oxygen-containing oxidizing agent. Even with such a procedure results in a significant acceleration of the oxidative degradation of the ion exchange resins.
  • the above-mentioned reaction products namely mainly CO 2 and water.
  • the solution specified in claim 4 provides, finally, that anodic oxidation of the ion exchange resins or of the molecule fragments formed therefrom is carried out with the device present in the reaction zone.
  • the device essentially comprises at least two electrodes, namely an anode and a cathode.
  • the added oxidizing agent is first effective in this process variant. This separates out of the polymer matrix of the ion exchange resin molecule fragments, which are then further oxidatively degraded at the anode and of course by the oxidant itself.
  • the oxidizing agents used in all process variants are preferably hydrogen peroxide, ammonium peroxide disulfate and gaseously metered-in oxygen, alone or in a mixture, although hydrogen peroxide is particularly preferred.
  • the oxidative decomposition may further by addition a catalyst can be accelerated.
  • a particularly in connection with hydrogen peroxide a significant acceleration of the oxidative degradation causing catalyst are iron-II and / or iron-II salts, Cu-I and / or Cu-II salts or mixtures of said Fe and Cu salts. These catalyze the formation of hydroxyl radicals from hydrogen peroxide. The proportion of these radicals in the reaction mixture is thereby further increased, so that accelerates the oxidative degradation of the ion exchange resins.
  • a portion of the water of the slurry is preferably vaporized during decomposition by energization to thereby further restrict the volume of residual liquid.
  • the energy supplied with one of the above-mentioned facilities used for evaporation so that additional heating devices may not be required.
  • the content of the water in the residual solution is adjusted by evaporation so that the subsequent incorporation of the residual solution into a solid matrix can be carried out without a further additional treatment.
  • the content of the water is in the range of about 10 to 15 wt.% Of the final matrix or the solidified end product.
  • the residual solution present at the end of the reaction is solidified with the aid of a binder, cement preferably being used.
  • Hardening with cement is carried out with the addition of salts whose cations with sulphate ions form a precipitate that is difficult to dissolve in water.
  • the harmful influence of sulfate ions on the solidification of the cement is thereby significantly reduced. Accordingly, a smaller amount of cement is required to bind the residual liquid.
  • alkaline earth oxides and hydroxides used.
  • oxides and / or hydroxides of aluminum and / or silicon may be added.
  • a pH ⁇ 8 preferably from 1 to 3 is set. Under such conditions, the oxidation effect of hydrogen peroxide is particularly pronounced. In addition, all cations and the activity as sulfate salts remain in solution, which facilitates the further processing of the residual solution.
  • a pH of> 7, preferably from 10 to 14 is maintained.
  • Such ratios are self-adjusting due to the basic exchanger groups.
  • Some oxidants, such as hydrogen peroxide, show a reduced oxidation effect in a basic environment. It is now conceivable to arrive by the addition of acids in the acidic range. However, this would have the disadvantage that it would increase the amount of waste to be disposed of.
  • the basic conditions are left and instead of a reduction in pH under these conditions, effective oxidizing agents, preferably oxygen and / or ozone, are used.
  • this procedure produces iron, nickel, chromium and activity hydroxides which are removed from the residual solution by means of a mechanical separation process (filtration, centrifuging, etc.).
  • the drawing shows in a greatly simplified schematized form a plant for the decomposition of ion exchange resins, which comprises a reaction zone or an oxidation reactor 1.
  • This is essentially formed by an example barrel-shaped container.
  • a ring line 2 is connected to the oxidation reactor 1 above and below a ring line 2 .
  • the oxidation reactor 1 can be charged with an aqueous slurry of ion exchange resins.
  • acids such as phosphonic or sulfonic acids are formed from their exchange groups, so that a pH value which is clearly in the acidic range is established on its own.
  • a concentration of hydrogen peroxide of 5 to 10,000 mg / l solution is set.
  • the amount of hydrogen peroxide is based on the particular technique used to generate hydroxyl radicals (underwater plasma, anodic oxidation, UV light).
  • iron (II) / iron (III) ions and / or copper (I) copper (II) ions are added in the form of soluble salts.
  • a concentration of greater than 0.05 mmol / l preferably adjusted from 0.05 to 0.25 mmol / l by continuously or intermittently the slurry is added a corresponding amount.
  • the iron or copper ions are preferably added simultaneously with the hydrogen peroxide.
  • a decomposition of the ion exchange resins into CO 2 , water and a residual solution can be carried out in a relatively short time.
  • a significant acceleration of the oxidative degradation of the resin is made possible by a device 4 arranged in the oxidation reactor 1.
  • the device 4 is a volume range of the reaction mixture Energy supplied eg in the form of electrical current or electromagnetic radiation. This energy supply is generally such that the oxidative processes are accelerated, preferably by formation of hydroxyl radicals.
  • the device 4 serves to generate a plasma.
  • at least two electrodes arranged at a distance from one another, for example made of chromium steel, are used.
  • the distance between the electrodes is selected so that the circulating through the circuit by means of a pump 5 can flow between the electrodes.
  • An alternating current of at least 30V and a frequency of more than 100 Hz is applied to the electrodes.
  • An alternative is a DC operation, in which a voltage of more than 100 V prevails between the electrodes and the current flowing between two opposing electrodes is regulated to values greater than 0.1 A, preferably from 0.1 to approximately 10 A.
  • the arc which forms between at least two electrodes generates a plasma in which, inter alia, hydroxyl radicals are formed which, with cleavage of covalent bonds, entrain an electron from the carbon skeleton of the ion exchange resin or the molecular fragments resulting therefrom.
  • the energy is supplied in the form of a UV irradiation, but their intensity is not sufficient to produce a plasma.
  • the frequency range of the UV source is in the range of 100 nm to 800 nm, preferably from 200 nm to 400 nm.
  • the UV irradiation on the one hand causes a cleavage of covalent bonds of the ion exchange resin or intermediates formed therefrom.
  • hydroxyl radicals are formed from the hydrogen peroxide added as oxidizing agent, which reacts further in accordance with the reaction scheme given above.
  • anodic oxidation is carried out with the aid of the device 4.
  • there are at least two pairs of electrodes that is to say an anode and a cathode, which are connected to a direct current source.
  • the electrode surface is about 100 to 200 cm 2 / l slurry.
  • the electrodes consist for example of solid metal material, graphite and / or, for example, with metals of the Pt group of the PSE or diamond coated material.
  • the reaction mixture is pumped in the circulation, where here, as in the other two process variants, the reaction volume up to 1000 times per hour through the oxidation reactor 1 is performed.
  • reaction products CO 2 and water and next to the from the exchange groups emerging substances such as sulfuric acid, sulfonic acid, phosphoric acid or in the case of basic exchangers ammonium compounds, possibly also nitrite and nitrate ions.
  • the carbon dioxide formed during the oxidative degradation is removed during the degradation process via a discharge port 6 of the reaction mixture.
  • the power supply via the device 4 can be controlled so that a portion of the water of the slurry evaporates, the water vapor exiting the oxidation reactor, for example via said opening 6.
  • a pH of equal to or less than 8, preferably from 1 to 3 is maintained.
  • the oxidizing agent used is preferably hydrogen peroxide, which is very effective at the indicated pH values, in particular at pH values of 1 to 3.
  • the sulfates or phosphates formed from the exchanger groups are soluble in the acidic and slightly basic range. A reduction in volume of such residual solutions is carried out by evaporation.
  • cation and anion exchange resins accumulate simultaneously in a nuclear installation, so that it is expedient to condition the two resins together, but to choose the mixing ratio of the resins such that acidic conditions are established in the slurry.
  • a residual solution is present in which all reaction products are in dissolved form, s that excess water is expediently carried out by evaporation.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Processing Of Solid Wastes (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
EP05024365A 2005-11-09 2005-11-09 Procédé pour le traitement des résines échangeuses d'ions Withdrawn EP1786000A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05024365A EP1786000A1 (fr) 2005-11-09 2005-11-09 Procédé pour le traitement des résines échangeuses d'ions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP05024365A EP1786000A1 (fr) 2005-11-09 2005-11-09 Procédé pour le traitement des résines échangeuses d'ions

Publications (1)

Publication Number Publication Date
EP1786000A1 true EP1786000A1 (fr) 2007-05-16

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Family Applications (1)

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EP05024365A Withdrawn EP1786000A1 (fr) 2005-11-09 2005-11-09 Procédé pour le traitement des résines échangeuses d'ions

Country Status (1)

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EP (1) EP1786000A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008005336A1 (de) * 2008-01-17 2009-07-30 Areva Np Gmbh Verfahren zur Konditionierung radioaktiver Ionenaustauscherharze
DE102018131902B3 (de) * 2018-12-12 2020-02-27 Framatome Gmbh Verfahren zur Konditionierung von Ionenaustauscherharzen und Vorrichtung zur Durchführung des Verfahrens
WO2024035902A1 (fr) * 2022-08-10 2024-02-15 Aclarity, Inc Système électroréducteur et régénératif

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4437999A (en) * 1981-08-31 1984-03-20 Gram Research & Development Co. Method of treating contaminated insoluble organic solid material
JPS5958400A (ja) * 1982-09-28 1984-04-04 日本原子力事業株式会社 放射性イオン交換樹脂の減容固化方法
JPH01313799A (ja) * 1988-06-13 1989-12-19 Fuji Electric Co Ltd 放射性イオン交換樹脂の酸化分解処理方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4437999A (en) * 1981-08-31 1984-03-20 Gram Research & Development Co. Method of treating contaminated insoluble organic solid material
JPS5958400A (ja) * 1982-09-28 1984-04-04 日本原子力事業株式会社 放射性イオン交換樹脂の減容固化方法
JPH01313799A (ja) * 1988-06-13 1989-12-19 Fuji Electric Co Ltd 放射性イオン交換樹脂の酸化分解処理方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 014, no. 116 (P - 1016) 5 March 1990 (1990-03-05) *
WPI WORLD PATENT INFORMATION DERWENT, DERWENT, GB, vol. 1, no. 89 PA - TOSHIBA PN - JP63282699 A, 18 November 1988 (1988-11-18), XP002021074 *
WPI WORLD PATENT INFORMATION DERWENT, DERWENT, GB, vol. 15, no. 90 PA - JCG CORP PN - JP2063595 A, 2 March 1990 (1990-03-02), 02.03.1990, XP002021073 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008005336A1 (de) * 2008-01-17 2009-07-30 Areva Np Gmbh Verfahren zur Konditionierung radioaktiver Ionenaustauscherharze
US8372289B2 (en) 2008-01-17 2013-02-12 Areva Np Gmbh Method for conditioning radioactive ion exchange resins
DE102018131902B3 (de) * 2018-12-12 2020-02-27 Framatome Gmbh Verfahren zur Konditionierung von Ionenaustauscherharzen und Vorrichtung zur Durchführung des Verfahrens
WO2020120143A1 (fr) * 2018-12-12 2020-06-18 Framatome Gmbh Procédé de conditionnement de résines échangeuses d'ions et dispositif pour mettre en œuvre le procédé
CN112655055A (zh) * 2018-12-12 2021-04-13 法玛通有限公司 调节离子交换树脂的方法和实施该方法的装置
JP2022512236A (ja) * 2018-12-12 2022-02-02 フラマトム ゲゼルシャフト ミット ベシュレンクテル ハフツング イオン交換樹脂のコンディショニング方法およびそれを実行するための装置
JP7247343B2 (ja) 2018-12-12 2023-03-28 フラマトム ゲゼルシャフト ミット ベシュレンクテル ハフツング イオン交換樹脂のコンディショニング方法およびそれを実行するための装置
CN112655055B (zh) * 2018-12-12 2024-03-15 法玛通有限公司 调节离子交换树脂的方法和实施该方法的装置
US12033766B2 (en) 2018-12-12 2024-07-09 Framatome Gmbh Method for conditioning ion exchange resins and apparatus for carrying out the method
WO2024035902A1 (fr) * 2022-08-10 2024-02-15 Aclarity, Inc Système électroréducteur et régénératif

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