WO2009090209A1 - Verfahren zur konditionierung radioaktiver ionenaustauscherharze - Google Patents
Verfahren zur konditionierung radioaktiver ionenaustauscherharze Download PDFInfo
- Publication number
- WO2009090209A1 WO2009090209A1 PCT/EP2009/050415 EP2009050415W WO2009090209A1 WO 2009090209 A1 WO2009090209 A1 WO 2009090209A1 EP 2009050415 W EP2009050415 W EP 2009050415W WO 2009090209 A1 WO2009090209 A1 WO 2009090209A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- ion exchange
- resin
- cement
- exchange resins
- Prior art date
Links
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
- G21F9/28—Treating solids
-
- 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
- G21F9/301—Processing by fixation in stable solid media
- G21F9/302—Processing by fixation in stable solid media in an inorganic matrix
- G21F9/304—Cement or cement-like matrix
Definitions
- the invention relates to a method for conditioning radioactive ion exchange resins.
- Ion exchange resins which are generally present as approximately spherical particles, 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 to avoid unwanted deposits on the surfaces of the primary circuit components, to prevent corrosion and to reduce the build-up of contamination in the primary circuit of the system.
- Both acid cation exchangers and basic anion exchangers are used in this purification, the former retaining metal cations and the latter anionic compounds, for example metal complexes. Since some of the metals are radionuclides, spent or loaded ion exchangers are radioactive waste and must be disposed of temporarily or permanently.
- Radioactively contaminated exchange resins are also used in the decontamination of nuclear facilities, eg in primary circuit decontamination.
- metal oxide layers present on the surfaces of the primary circuit components are removed by means of decontamination solutions, the solutions being passed through ion exchangers during or after the decontamination in order to remove activity or metal cations contained therein.
- contaminated ion exchangers which are essentially organic resins with acidic or basic groups, must be conditioned. Conditioning is generally understood to mean the transfer of a radioactive waste into a storable form.
- spent ion exchange resins are usually dried and after a certain storage period or decay time, in which the radioactivity has dropped to a predetermined limit, for the purpose of storage embedded in a solid matrix, for example, cemented.
- the embedding of the ion exchange resins in a solid matrix leads to an increase in volume by more than six times the volume of the resin. Due to the large amount of waste arising for the operator of a nuclear power plant considerable costs for the intermediate or final disposal. Therefore, concepts have been developed to reduce the volume of the ion exchange resins.
- One of these concepts provides for combustion. However, this requires complex filter systems to prevent leakage of radioactivity into the environment. In addition, the combustion does not work very well due to the acidic or basic groups commonly present in the resins.
- the metals and thus the activity with the aid of acids or alkalis are completely removed from the resins, so that the resins can be reused.
- the respective acid or alkali is passed over a purely organic, i. neither acid nor basic groups containing and therefore more easily combustible resin passed, the metals (and the
- the object of the invention is to propose a method for conditioning contaminated ion exchange resins, with which compared to the direct embedding in a solid matrix, a volume reduction is connected and can be carried out with little time and material.
- a method according to claim 1 namely in that the ion exchange resin is mixed with water and with the aid of an oxidizing agent added to the water is at least partially decomposed into water-soluble fragments, wherein the resulting aqueous solution is solidified with a binder.
- the volume reduction achieved by the process over cementation of solid resin particles is mainly due to the transition from the solid phase in which the resin is in the form of a bulky network of macromolecules to dissolved fragments of that network. Essentially, the process does not require more than one tank to carry out the resin oxidation and possibly a second tank for the Consolidation.
- the added oxidizing agent causes the polymer network of the resin, for example a copolymer of vinylbenzene and divinylbenzene, to break up, forming water-soluble fragments.
- the water solubility results from acid or base groups present on the fragments (eg sulfonic acid groups or aminoethyl groups).
- the oxidation is preferably continued until all or almost all of the resin has gone into solution.
- the exchange resin is treated oxidatively only until it is preferably completely in the form of water-soluble fragments.
- the resulting amount of carbon dioxide is relatively low.
- Preliminary tests can be determined empirically.
- the solidification takes place in a simple manner by the fact that at the end of the oxidation
- the present mixture is stirred with at least the same mass of cement.
- other binders such as water glass may also be used.
- Compared to the above-mentioned direct involvement of the untreated ion exchange resin in cement which results in an increase in volume compared to the original resin bulk volume by a factor of 6, in accordance with the invention - depending on the present water / resin ratio and water / Cement value - a factor of only 2 to 4 achieved. This factor can be further reduced if part of the water is removed from the solution by evaporation before solidification.
- Cement for example Portland cement
- Portland cement usually contains high proportions of calcium oxide, which together with silicates with the mixing water forms cement hardening hydrates during the setting process. If the water of the mixture to be solidified is acidic, the calcium oxide is dissolved and is no longer available for hydrate formation and thus for cement hardening.
- a base is added for the neutralization of acids or for raising the pH of the mixture, so that it is slightly acidic to basic at the end. Alkaline earth oxides and hydroxides are preferably used as the base.
- the oxidation of the ion exchange resins can in principle be carried out with any desired oxidizing agents. Preferably, however, those are used which form no reaction products in their reaction with the resin, which hinder the setting of the cement or other binder.
- oxidizing agents which have this property, water used toffperoxid and ozone. Hydrogen peroxide leaves only harmless water, and ozone is reduced to oxygen, which escapes for the most part from the mixture. Resin oxidation produces CO 2 (which mostly escapes) and water.
- Resins 1 and 2 are relatively low crosslinked polystyrene-based resins having a divinylbenzene content of about 4-6%. Resins 3 and 4 are more crosslinked and have a divinylbenzene content of about 8-12%. The experiments have shown that not all resins are equally degradable. The time required to get more highly crosslinked resins
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020107018247A KR101183002B1 (ko) | 2008-01-17 | 2009-01-15 | 방사성 이온 교환 수지의 컨디셔닝 방법 |
EP09702004A EP2248134B1 (de) | 2008-01-17 | 2009-01-15 | Verfahren zur konditionierung radioaktiver ionenaustauscherharze |
CA2711555A CA2711555C (en) | 2008-01-17 | 2009-01-15 | Method for conditioning radioactive ion exchange resins |
JP2010542625A JP5543926B2 (ja) | 2008-01-17 | 2009-01-15 | 放射性イオン交換樹脂のコンディショニング方法 |
AT09702004T ATE514168T1 (de) | 2008-01-17 | 2009-01-15 | Verfahren zur konditionierung radioaktiver ionenaustauscherharze |
US12/816,790 US8372289B2 (en) | 2008-01-17 | 2010-06-16 | Method for conditioning radioactive ion exchange resins |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102008005336A DE102008005336A1 (de) | 2008-01-17 | 2008-01-17 | Verfahren zur Konditionierung radioaktiver Ionenaustauscherharze |
DE102008005336.8 | 2008-01-17 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/816,790 Continuation US8372289B2 (en) | 2008-01-17 | 2010-06-16 | Method for conditioning radioactive ion exchange resins |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009090209A1 true WO2009090209A1 (de) | 2009-07-23 |
Family
ID=40756569
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2009/050415 WO2009090209A1 (de) | 2008-01-17 | 2009-01-15 | Verfahren zur konditionierung radioaktiver ionenaustauscherharze |
Country Status (10)
Country | Link |
---|---|
US (1) | US8372289B2 (de) |
EP (1) | EP2248134B1 (de) |
JP (1) | JP5543926B2 (de) |
KR (1) | KR101183002B1 (de) |
AT (1) | ATE514168T1 (de) |
CA (1) | CA2711555C (de) |
DE (1) | DE102008005336A1 (de) |
ES (1) | ES2367238T3 (de) |
TW (1) | TWI442414B (de) |
WO (1) | WO2009090209A1 (de) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102018131902B3 (de) | 2018-12-12 | 2020-02-27 | Framatome Gmbh | Verfahren zur Konditionierung von Ionenaustauscherharzen und Vorrichtung zur Durchführung des Verfahrens |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2065360A (en) * | 1979-11-08 | 1981-06-24 | Kernforschungsz Karlsruhe | Disposing of radioactive waste |
WO1985000922A1 (en) * | 1983-08-04 | 1985-02-28 | Studsvik Energiteknik Ab | A process for treatment of a spent, radioactive, organic ion exchange resin |
EP0257192A1 (de) * | 1986-08-20 | 1988-03-02 | Fuji Electric Co., Ltd. | Verfahren zur Beseitigung radioaktiver Ionenaustauscherharze mittels oxidierender Zerlegung |
EP0522931A1 (de) * | 1991-07-03 | 1993-01-13 | Commissariat A L'energie Atomique | Block kontaminierte Ionenaustauschharze enthaltend und Herstellung davon |
WO1994009904A1 (en) * | 1992-11-04 | 1994-05-11 | Abb Atom Ab | Method and device for treatment and disposal of spent ion-exchange resin |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT43561B (de) | 1909-02-15 | 1910-08-10 | Anton Wrana | Getreide-Mahl- und Sichtmaschine. |
JPS5341319B2 (de) * | 1971-08-17 | 1978-11-01 | ||
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 |
JPS5998740A (ja) * | 1982-11-30 | 1984-06-07 | Mitsui Eng & Shipbuild Co Ltd | 使用済イオン交換樹脂の分解処理方法 |
US4530723A (en) * | 1983-03-07 | 1985-07-23 | Westinghouse Electric Corp. | Encapsulation of ion exchange resins |
JPH0232600B2 (ja) * | 1983-03-07 | 1990-07-20 | Westinghouse Electric Corp | Ionkokanjushisuiseiekikongobutsuosementochunifunyusuruhoho |
JPS61165696A (ja) * | 1985-01-18 | 1986-07-26 | 三菱重工業株式会社 | 放射性廃棄物処理方法 |
DE3926252A1 (de) * | 1989-08-09 | 1991-02-14 | Ghattas Nader Khalil | Verfahren und vorrichtung zur zersetzung verbrauchter ionentauscherharze |
WO1992003829A1 (en) * | 1990-08-28 | 1992-03-05 | Electric Power Research Institute | Organic material oxidation process utilizing no added catalyst |
JP3846820B2 (ja) * | 1997-08-20 | 2006-11-15 | 株式会社東芝 | 固体廃棄物処理方法 |
JP4675521B2 (ja) * | 2001-08-15 | 2011-04-27 | 日揮株式会社 | 放射性有機廃棄物の処理方法及び処理装置 |
JP4414214B2 (ja) * | 2003-12-24 | 2010-02-10 | 行政院原子能委員會核能研究所 | 廃イオン交換樹脂の処理方法 |
EP1564188B1 (de) | 2004-02-13 | 2006-11-29 | Institute of Nuclear Energy Research, Atomic Energy Council | Verfahren zur Behandlung vor verbrauchten Ionenaustauschern |
EP1786000A1 (de) * | 2005-11-09 | 2007-05-16 | AREVA NP GmbH | Verfahren zur Konditionierung radioaktiver Ionenaustauscherharze |
-
2008
- 2008-01-17 DE DE102008005336A patent/DE102008005336A1/de not_active Withdrawn
-
2009
- 2009-01-15 CA CA2711555A patent/CA2711555C/en not_active Expired - Fee Related
- 2009-01-15 ES ES09702004T patent/ES2367238T3/es active Active
- 2009-01-15 AT AT09702004T patent/ATE514168T1/de active
- 2009-01-15 EP EP09702004A patent/EP2248134B1/de active Active
- 2009-01-15 WO PCT/EP2009/050415 patent/WO2009090209A1/de active Application Filing
- 2009-01-15 KR KR1020107018247A patent/KR101183002B1/ko active IP Right Grant
- 2009-01-15 JP JP2010542625A patent/JP5543926B2/ja not_active Expired - Fee Related
- 2009-01-16 TW TW098101513A patent/TWI442414B/zh not_active IP Right Cessation
-
2010
- 2010-06-16 US US12/816,790 patent/US8372289B2/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2065360A (en) * | 1979-11-08 | 1981-06-24 | Kernforschungsz Karlsruhe | Disposing of radioactive waste |
WO1985000922A1 (en) * | 1983-08-04 | 1985-02-28 | Studsvik Energiteknik Ab | A process for treatment of a spent, radioactive, organic ion exchange resin |
EP0257192A1 (de) * | 1986-08-20 | 1988-03-02 | Fuji Electric Co., Ltd. | Verfahren zur Beseitigung radioaktiver Ionenaustauscherharze mittels oxidierender Zerlegung |
EP0522931A1 (de) * | 1991-07-03 | 1993-01-13 | Commissariat A L'energie Atomique | Block kontaminierte Ionenaustauschharze enthaltend und Herstellung davon |
WO1994009904A1 (en) * | 1992-11-04 | 1994-05-11 | Abb Atom Ab | Method and device for treatment and disposal of spent ion-exchange resin |
Also Published As
Publication number | Publication date |
---|---|
CA2711555C (en) | 2015-04-14 |
ATE514168T1 (de) | 2011-07-15 |
TW200941502A (en) | 2009-10-01 |
DE102008005336A1 (de) | 2009-07-30 |
EP2248134B1 (de) | 2011-06-22 |
TWI442414B (zh) | 2014-06-21 |
CA2711555A1 (en) | 2009-07-23 |
EP2248134A1 (de) | 2010-11-10 |
KR101183002B1 (ko) | 2012-09-18 |
US8372289B2 (en) | 2013-02-12 |
US20100256435A1 (en) | 2010-10-07 |
ES2367238T3 (es) | 2011-10-31 |
JP2011510281A (ja) | 2011-03-31 |
KR20100120155A (ko) | 2010-11-12 |
JP5543926B2 (ja) | 2014-07-09 |
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