EP0321352B1 - Procédé d'immobilisation de résines échangeuses d'ions provenant des circuits secondaires des réacteurs nucléaires à eau pressurisée et des réacteurs graphite-gaz - Google Patents

Procédé d'immobilisation de résines échangeuses d'ions provenant des circuits secondaires des réacteurs nucléaires à eau pressurisée et des réacteurs graphite-gaz Download PDF

Info

Publication number: EP0321352B1
Authority: EP; European Patent Office
Prior art keywords: resins; exchange resins; ion; water; graphite
Prior art date: 1987-12-16
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

Application number

EP88403208A

Other languages

German (de)

English (en)

French (fr)

Other versions

EP0321352A1 (fr

Inventor

Guy Magnin

Claude Jaouen

Marie-Françoise épouse Magnin Champeaud

Véronique Aubert

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.)

Societe Generale pour les Techniques Nouvelles SA SGN

Original Assignee

Societe Generale pour les Techniques Nouvelles SA SGN

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.)

1987-12-16

Filing date

1988-12-16

Publication date

1992-11-25

1988-12-16 Application filed by Societe Generale pour les Techniques Nouvelles SA SGN filed Critical Societe Generale pour les Techniques Nouvelles SA SGN

1989-06-21 Publication of EP0321352A1 publication Critical patent/EP0321352A1/fr

1992-11-25 Application granted granted Critical

1992-11-25 Publication of EP0321352B1 publication Critical patent/EP0321352B1/fr

2008-12-16 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

238000000034 method Methods 0.000 title claims description 11
230000008569 process Effects 0.000 title claims description 10
239000003456 ion exchange resin Substances 0.000 title claims description 7
229920003303 ion-exchange polymer Polymers 0.000 title claims description 7
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 7
230000003100 immobilizing effect Effects 0.000 title description 2
239000011347 resin Substances 0.000 claims description 31
229920005989 resin Polymers 0.000 claims description 31
QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
229910021529 ammonia Inorganic materials 0.000 claims description 8
125000000129 anionic group Chemical group 0.000 claims description 7
VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
239000011230 binding agent Substances 0.000 claims description 4
150000001875 compounds Chemical class 0.000 claims description 3
229920006395 saturated elastomer Polymers 0.000 claims description 3
235000010344 sodium nitrate Nutrition 0.000 claims description 3
239000004317 sodium nitrate Substances 0.000 claims description 2
239000002609 medium Substances 0.000 description 11
-1 NH4+ ions Chemical class 0.000 description 5
125000002091 cationic group Chemical group 0.000 description 5
150000001450 anions Chemical class 0.000 description 3
150000001768 cations Chemical class 0.000 description 3
238000005342 ion exchange Methods 0.000 description 3
238000004806 packaging method and process Methods 0.000 description 3
239000010426 asphalt Substances 0.000 description 2
VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
235000011114 ammonium hydroxide Nutrition 0.000 description 1
150000001449 anionic compounds Chemical class 0.000 description 1
239000012736 aqueous medium Substances 0.000 description 1
RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical class [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
239000011575 calcium Substances 0.000 description 1
229910052791 calcium Inorganic materials 0.000 description 1
230000015556 catabolic process Effects 0.000 description 1
239000004568 cement Substances 0.000 description 1
239000011248 coating agent Substances 0.000 description 1
238000000576 coating method Methods 0.000 description 1
238000001816 cooling Methods 0.000 description 1
238000006731 degradation reaction Methods 0.000 description 1
238000006073 displacement reaction Methods 0.000 description 1
230000000694 effects Effects 0.000 description 1
230000008570 general process Effects 0.000 description 1
230000009931 harmful effect Effects 0.000 description 1
238000010348 incorporation Methods 0.000 description 1
150000002500 ions Chemical class 0.000 description 1
239000000203 mixture Substances 0.000 description 1
239000008188 pellet Substances 0.000 description 1
239000011591 potassium Substances 0.000 description 1
229910052700 potassium Inorganic materials 0.000 description 1
238000002203 pretreatment Methods 0.000 description 1
230000002035 prolonged effect Effects 0.000 description 1
230000001737 promoting effect Effects 0.000 description 1
238000000746 purification Methods 0.000 description 1
239000011734 sodium Substances 0.000 description 1
229910052708 sodium Inorganic materials 0.000 description 1
239000007787 solid Substances 0.000 description 1
230000006641 stabilisation Effects 0.000 description 1
238000011105 stabilization Methods 0.000 description 1
230000000087 stabilizing effect Effects 0.000 description 1
238000003756 stirring Methods 0.000 description 1
238000010408 sweeping Methods 0.000 description 1
239000002699 waste material Substances 0.000 description 1

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
- G21F9/16—Processing by fixation in stable solid media
- 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
- 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 present invention relates to a method for immobilizing ion exchange resins originating from the secondary circuits of pressurized water nuclear reactors and graphite-gas reactors.
the present invention relates to a process for the immobilization, with a view to their storage, of said resins.
the immobilization process chosen according to the invention is that of concreting, that is to say the general process - known in itself - consisting of coating the products to be immobilized in a hydraulic binder.
the problem consists in carrying out a pretreatment of the resins making it possible to implement this immobilization process and, if possible, to obtain a product having the best properties.
the pretreatment method according to the invention is characterized in that the ion exchange resins are saturated with a base, preferably sodium hydroxide, under conditions such that the pH of the medium is greater than approximately 9 and that the release of ammonia is favored.
a base preferably sodium hydroxide
base a compound such as sodium, potassium, calcium or barium hydroxides.
sodium hydroxide is preferred. This product can be used in solid form or in solution.
the base used in the present invention is intended to ensure, by ion exchange, saturation of all the sites of the resins comprising an NH4+ ion, it is obviously necessary to carry out this exchange in an aqueous medium which can be consisting wholly or in part of the water which is generally present in the charge of the resins which have to be treated.
the pH of the (aqueous) medium should be above about 9; in fact, the pH must be high enough for the NH4+ ions released from the resins by exchange with the basic cation (Na+) not to remain in the dissolved state in said medium but to give rise to gaseous ammonia which will emerge from said medium
the amount of "base” used must be at least that which allows total displacement of the NH4+ ions by the cation of said base.
an amount of "base” is used which is at least sufficient for the cation of said base to saturate all the sites of the resins, assuming that all the resins treated are cationic it will be noted that the use of a quantity of base greater than that necessary to ensure the saturation of the sites can, to a certain extent, promote and accelerate the phenomenon of saturation.
the process as described above only causes ionic exchanges on the cationic resins contained in the resins to be treated. It turns out that, given the very low radioactivity of the treated resins and the specifications current to be respected, it has been determined that the anionic resins did not have too great harmful effects on the phenomena of setting of the hydraulic binder.
the process according to the invention can be improved by also stabilizing, by ion exchange, the anionic resins present in the resins to be treated.
This stabilization can be done by carrying out the ion exchange of OH ⁇ contained in the anionic resins with ions such as NO4 ⁇ , SO4 ⁇ , CH3COO ⁇ ...
ions such as NO4 ⁇ , SO4 ⁇ , CH3COO ⁇ ...
NO3 ⁇ ion the most interesting, because of the stability obtained, because of the ease of its use and because of its inertia with respect to the anions present during concreting, is the NO3 ⁇ ion.
the amount of this anion (NO3 ⁇ preferably) to be used can advantageously be calculated by assuming that all of the treated resin is of the anionic type and that the aim is to saturate all the sites of this resin.

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)
Treatment Of Water By Ion Exchange (AREA)
Ceramic Products (AREA)
Carbon And Carbon Compounds (AREA)

EP88403208A 1987-12-16 1988-12-16 Procédé d'immobilisation de résines échangeuses d'ions provenant des circuits secondaires des réacteurs nucléaires à eau pressurisée et des réacteurs graphite-gaz Expired - Lifetime EP0321352B1 (fr)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
FR8717596A FR2624769B1 (fr)	1987-12-16	1987-12-16	Procede d'immobilisation de resines echangeuses d'ions provenant des circuits secondaires des reacteurs nucleaires a eau pressurisee et des reacteurs graphite-gaz
FR8717596		1987-12-16

Publications (2)

Publication Number	Publication Date
EP0321352A1 EP0321352A1 (fr)	1989-06-21
EP0321352B1 true EP0321352B1 (fr)	1992-11-25

Family

ID=9357948

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP88403208A Expired - Lifetime EP0321352B1 (fr)	1987-12-16	1988-12-16	Procédé d'immobilisation de résines échangeuses d'ions provenant des circuits secondaires des réacteurs nucléaires à eau pressurisée et des réacteurs graphite-gaz

Country Status (6)

Country	Link
US (1)	US4834915A (es)
EP (1)	EP0321352B1 (es)
KR (1)	KR970004357B1 (es)
DE (1)	DE3876224T2 (es)
ES (1)	ES2053790T3 (es)
FR (1)	FR2624769B1 (es)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DE4137947C2 (de) *	1991-11-18	1996-01-11	Siemens Ag	Verfahren zur Behandlung von radioaktivem Abfall
US5545798A (en) *	1992-09-28	1996-08-13	Elliott; Guy R. B.	Preparation of radioactive ion-exchange resin for its storage or disposal
TW365009B (en) *	1996-09-24	1999-07-21	Jgc Corp	Method of disposal of metallic aluminum-containing radioactive solid waste
US5960368A (en) *	1997-05-22	1999-09-28	Westinghouse Savannah River Company	Method for acid oxidation of radioactive, hazardous, and mixed organic waste materials
ES2207479T3 (es) *	2000-03-20	2004-06-01	Institute Of Nuclear Energy Research, Taiwan, R.O.C.	Procedimiento de co-solidificacion de residuos humedos debilmente radioactivos producidos en centrales nucleares de agua hirviendo.
RU2217825C2 (ru) *	2001-08-27	2003-11-27	Государственное предприятие Научно-исследовательский технологический институт им. А.П. Александрова	Способ включения радиоактивных ионообменных смол в портландцементное связующее
RU2253162C2 (ru) *	2003-04-24	2005-05-27	ФГУП "Производственное объединение "Маяк"	Способ локализации отработанных ионообменных смол
RU2278429C2 (ru) *	2004-07-01	2006-06-20	ФГУП "Производственное объединение "Маяк"	Способ локализации отработанных ионообменных смол
RU2353011C1 (ru) *	2007-11-19	2009-04-20	Закрытое акционерное общество "ИНТРА"	Способ подготовки радиоактивных ионообменных смол к иммобилизации в монолитные структуры
RU2381579C1 (ru) *	2008-12-08	2010-02-10	Федеральное государственное унитарное предприятие "Научно-исследовательский технологический институт имени А.П. Александрова"	Способ переработки радиоактивных ионообменных смол и промышленных токсичных жидких отходов
RU2600940C2 (ru) *	2015-03-27	2016-10-27	Открытое акционерное общество "Красная Звезда"	Способ подготовки твердой фазы жидких радиоактивных отходов к захоронению
RU2735858C1 (ru) *	2020-06-02	2020-11-09	Акционерное общество "Научно-исследовательское проектно-технологическое бюро "Онега" (АО "НИПТБ "Онега")	Установка для сушки радиоактивных ионообменных смол

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
FR1560332A (es) *	1967-12-04	1969-03-21
DE2628286C2 (de) *	1976-06-24	1986-04-10	Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe	Verfahren zur Verbesserung der Auslaugbeständigkeit von Bitumenverfestigungsprodukten radioaktiver Stoffe
FR2361724A1 (fr) *	1976-08-12	1978-03-10	Commissariat Energie Atomique	Procede de stockage de resines echangeuses d'ions contaminees
SE7902685L (sv) *	1978-04-13	1979-10-14	Sgn Soc Gen Tech Nouvelle	Forfarande for foretredesvis kontinuerlig behandling av radioaktivt fluidum av lagaktivt eller medelaktivt slag
DE2910677C2 (de) *	1979-03-19	1983-12-22	Kraftwerk Union AG, 4330 Mülheim	Verfahren zur Behandlung von borhaltigen radioaktiven Konzentraten aus Abwässern von Druckwasserreaktoren
IT1195040B (it) *	1981-05-11	1988-09-28	Snial Resine Poliestere Spa Ca	Composizioni di materia contenenti materiale radioattivo a base di resine scambiatrici di ioni
JPS58213300A (ja) *	1982-06-04	1983-12-12	株式会社日立製作所	放射性廃棄物の処理方法
US4530723A (en) *	1983-03-07	1985-07-23	Westinghouse Electric Corp.	Encapsulation of ion exchange resins
FR2561812B1 (fr) *	1984-03-21	1989-02-17	Commissariat Energie Atomique	Procede de bitumage de dechets radioactifs constitues par des resines echangeuses de cations et/ou par des resines echangeuses d'anions
CH664843A5 (de) *	1984-11-12	1988-03-31	Industrieorientierte Forsch	Verfahren zur verbesserung der stabilitaetseigenschaften von verfestigten radioaktiven ionenaustausch-harzpartikeln.
SE455656B (sv) *	1986-01-15	1988-07-25	Eka Nobel Ab	Sett for behandling av avfall fran en kernreaktoranleggning innehallande med radioaktiva metaller bemengd, organisk jonbytarmassa

1987
- 1987-12-16 FR FR8717596A patent/FR2624769B1/fr not_active Expired - Fee Related
1988
- 1988-02-16 US US07/157,039 patent/US4834915A/en not_active Expired - Lifetime
- 1988-12-08 KR KR1019880016343A patent/KR970004357B1/ko not_active Expired - Fee Related
- 1988-12-16 DE DE8888403208T patent/DE3876224T2/de not_active Expired - Fee Related
- 1988-12-16 EP EP88403208A patent/EP0321352B1/fr not_active Expired - Lifetime
- 1988-12-16 ES ES88403208T patent/ES2053790T3/es not_active Expired - Lifetime

Also Published As

Publication number	Publication date
FR2624769B1 (fr)	1991-04-19
DE3876224T2 (de)	1993-05-19
DE3876224D1 (de)	1993-01-07
ES2053790T3 (es)	1994-08-01
EP0321352A1 (fr)	1989-06-21
KR970004357B1 (ko)	1997-03-27
US4834915A (en)	1989-05-30
FR2624769A1 (fr)	1989-06-23
KR890010932A (ko)	1989-08-11

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1989-05-06	PUAI	Public reference made under article 153(3) epc to a published international application that has entered the european phase	Free format text: ORIGINAL CODE: 0009012
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1991-06-12	17Q	First examination report despatched	Effective date: 19910429
1992-10-09	GRAA	(expected) grant	Free format text: ORIGINAL CODE: 0009210
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1994-08-01	REG	Reference to a national code	Ref country code: ES Ref legal event code: FG2A Ref document number: 2053790 Country of ref document: ES Kind code of ref document: T3
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Publication	Publication Date	Title
EP0321352B1 (fr)	1992-11-25	Procédé d'immobilisation de résines échangeuses d'ions provenant des circuits secondaires des réacteurs nucléaires à eau pressurisée et des réacteurs graphite-gaz
US4671897A (en)	1987-06-09	Process and apparatus for solidification of radioactive waste
EP0127490B1 (fr)	1987-07-22	Procédé de conditionnement de déchets contaminés en milieu acide, notamment de matériaux échangeurs de cations
EP0144440B1 (en)	1988-08-10	Process for solidifying radioactive wastes
EP2552849B1 (fr)	2016-05-04	Utilisation d'agents anti-corrosion pour le conditionnement de magnésium métal, matériau de conditionnement ainsi obtenu et procédé de préparation
CN115286429A (zh)	2022-11-04	一种防腐型水性渗透型无机防水剂及其制备方法和应用
JP4173222B2 (ja)	2008-10-29	負荷イオン交換樹脂、その調製方法及び使用方法
EP0522931B1 (fr)	1997-04-02	Bloc contenant des résines échangeuses d'ions contaminées et son procédé de préparation
US2567855A (en)	1951-09-11	Rapid-wetting bentonite-calcium sulfate backfill for cathodic protection
JPS6333118B2 (es)	1988-07-04
JPH09101398A (ja)	1997-04-15	放射性廃棄物の処理方法および装置
GB2205562A (en)	1988-12-14	Process for water-repellent treatment of gypsum building units
JPS5815080B2 (ja)	1983-03-23	固形化方法
NL8006789A (nl)	1981-07-16	Waterstoffosfide afgevend preparaat, alsmede bestrijdingsmiddelen, die deze preparaten bevatten.
FR2564632A1 (fr)	1985-11-22	Procede de concentration de solutions de dechets radioactifs provenant de centrales nucleaires
WO1988009040A1 (fr)	1988-11-17	Procede d'immobilisation de resines echangeuses d'ions radioactives par un liant hydraulique
JP3524555B2 (ja)	2004-05-10	樹脂粉末及び不活性合成樹脂繊維からなる混合物の容積減少方法
US4992208A (en)	1991-02-12	Stabilization of solid sodium chloride against mushing in an aqueous medium
GB2130428A (en)	1984-05-31	A process for reducing the volume of aqueous radioactive waste
FR2841895A1 (fr)	2004-01-09	Materiau a base de chaux constitue de cao partiellement hydrate, procede de preparation et utilisation en tant que liant, capteur d'eau et/ou source d'energie
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