EP2791945A2 - Traitement de déchets radioactifs carbonés comportant du chlore. - Google Patents
Traitement de déchets radioactifs carbonés comportant du chlore.Info
- Publication number
- EP2791945A2 EP2791945A2 EP12816710.3A EP12816710A EP2791945A2 EP 2791945 A2 EP2791945 A2 EP 2791945A2 EP 12816710 A EP12816710 A EP 12816710A EP 2791945 A2 EP2791945 A2 EP 2791945A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- waste
- treatment
- chlorine
- solution
- acid solution
- 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- Withdrawn
Links
- 239000002901 radioactive waste Substances 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract description 24
- 229910052799 carbon Inorganic materials 0.000 title abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title description 10
- 239000000460 chlorine Substances 0.000 title description 10
- 229910052801 chlorine Inorganic materials 0.000 title description 10
- 239000002253 acid Substances 0.000 claims abstract description 23
- 239000002699 waste material Substances 0.000 claims abstract description 19
- 238000002791 soaking Methods 0.000 claims abstract description 16
- 230000035939 shock Effects 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000012857 radioactive material Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000003929 acidic solution Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-OUBTZVSYSA-N chlorane Chemical compound [36ClH] VEXZGXHMUGYJMC-OUBTZVSYSA-N 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 3
- 238000002407 reforming Methods 0.000 claims description 3
- 238000007669 thermal treatment Methods 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 239000010439 graphite Substances 0.000 description 16
- 229910002804 graphite Inorganic materials 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000629 steam reforming Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000002285 radioactive effect Effects 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000005202 decontamination Methods 0.000 description 3
- 230000003588 decontaminative effect Effects 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OKTJSMMVPCPJKN-NJFSPNSNSA-N Carbon-14 Chemical compound [14C] OKTJSMMVPCPJKN-NJFSPNSNSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical class OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 229910052722 tritium Inorganic materials 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
- G21F9/001—Decontamination of contaminated objects, apparatus, clothes, food; Preventing contamination thereof
- G21F9/002—Decontamination of the surface of objects with chemical or electrochemical processes
-
- 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
-
- 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
-
- 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
- G21F9/32—Processing by incineration
Definitions
- the present invention relates to the treatment of radioactive waste, in particular but not exclusively based on graphite.
- the decontamination of an irradiated graphite matrix may be carried out using a so-called “steam reforming” technique (or “steam reforming” in Anglo-Saxon terms) as defined in particular in document US-6. , 625, 248.
- steam reforming or “steam reforming” in Anglo-Saxon terms
- the technique presented in this document does not ensure acceptable radioactive releases.
- organic chlorine a form of chlorine termed "organic” chlorine, defined by C-Cl bonds specific to “aromatic carbon” (in particular of the high energy double bond type), and directly linked to the carbon of the carbon matrix usually forming graphite, and
- chlorine a form of chlorine
- inorganic chlorine in the form of oxychlorides of undetermined composition, probably located in the porosity of the graphitic material (called “chlorite compounds (C102-) and chlorate (C103-)").
- the acidic solution may comprise sulfuric acid (H 2 SO 4 ). Tests with this type of acid have given good results.
- the acidic solution further comprises an oxygen supply element in the acidic solution, for example hydrogen peroxide (H 2 O 2 ) in a range of proportions typically comprised between 0.1% and 20%. % (a proportion of 5% yielding good results presented below).
- H 2 O 2 hydrogen peroxide
- the soaking in the acidic solution can be carried out in a time range of between 15 and 20 hours, for example about 18 hours.
- the aforementioned thermal shock made for example by roasting, can be carried out in a temperature range between 800 and 1200 ° C (for example about 1000 ° C) for a period of between 15 and 30 minutes (for example about twenty minutes).
- the present invention thus makes it possible to extract chlorine 36, of organic type, as demonstrated in the exemplary embodiments presented in detail below.
- leaching of the radionuclides out of the irradiated graphite can be obtained by soaking in a highly acidic and oxidizing solution, followed by a thermal shock.
- the present invention also aims at a facility for the treatment of carbonaceous radioactive waste, for the purpose of process according to one of the preceding claims, characterized in that it comprises: a tank for storing said waste in an acidic solution, and
- Heating means shaped to apply a thermal shock to said waste after soaking in said acid solution.
- FIG. 1 diagrammatically illustrates the main steps of the process within the meaning of the invention
- Carbonaceous radioactive waste was crushed into powder form to constitute the different samples of the table above.
- Each sample having a mass of 5 grams and observed particle sizes distributed typically between 2380 and 4000 microns after crushing, was: soaked for 18 hours in a solution of the aforementioned type (H 2 SO 4 and H 2 O 2 ),
- o by rapid heating in a range of 5 to 60 minutes, for example for 20 minutes
- o high temperature between 900 and 1200 ° C, for example at 1000 ° C.
- FIG. 1 summarizes the main steps of the process within the meaning of the invention, comprising: for example, during a first step S1, the recovery of radioactive carbonaceous waste, for example in the form of graphite,
- step S3 after identifying a sufficient soaking time (for example 18 hours) in step S3, applying a heat treatment, by roasting, at a temperature of the order of 1000 ° C, in step S4;
- step S5 After identifying a sufficient duration of heat treatment (for example 20 minutes) in step S5,
- chlorine 36 can be recovered in the acid solution and treated separately, and the carbonaceous waste can then be subjected to a vapor reforming treatment as described, for example, in the document cited above.
- WO-2010/103210 step S6.
- the installation for the implementation of this process may then comprise, with reference to FIG. 2, a tank CU and a conveyor C1 of GR waste products pouring into a highly acidic and oxygenated solution (H 2 SO 4 H 2 O 2 ) contained in the tank CU, which is surrounded (in the example shown) heating means MC to apply a heat shock type treatment.
- the GR waste thus treated can then be recovered by the second conveyor C2 (after filtering, for example, the acid solution now containing chlorine-36) to be conveyed to a steam reforming installation.
- Chlorine 36 can be recovered for example from the solution remaining under the tank CU, as presented as a purely illustrative example in Figure 2.
- hydrogen peroxide is a good oxygen delivery element in a solution.
- step a) the proportions of the oxygen supply element in the acid solution are susceptible to variations depending on the acids and elements employed.
- the soaking time in step a) is capable of variations. The same goes for the temperature and the duration of the thermal shock.
- step a) of soaking in the acid solution is preceded by a crushing of the carbonaceous waste to reduce it to powder.
- this implementation is not essential and it can be alternatively provided to directly dipping solid graphite for example up to heart in an acid solution.
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Food Science & Technology (AREA)
- Processing Of Solid Wastes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Gasification And Melting Of Waste (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1161814A FR2984583A1 (fr) | 2011-12-16 | 2011-12-16 | Traitement de dechets radioactifs carbones comportant du chlore. |
| PCT/FR2012/052883 WO2013088059A2 (fr) | 2011-12-16 | 2012-12-11 | Traitement de déchets radioactifs carbonés comportant du chlore. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2791945A2 true EP2791945A2 (fr) | 2014-10-22 |
Family
ID=47599056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP12816710.3A Withdrawn EP2791945A2 (fr) | 2011-12-16 | 2012-12-11 | Traitement de déchets radioactifs carbonés comportant du chlore. |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20140350320A1 (ko) |
| EP (1) | EP2791945A2 (ko) |
| JP (1) | JP2015505967A (ko) |
| KR (1) | KR20140133500A (ko) |
| CN (1) | CN104170019A (ko) |
| FR (1) | FR2984583A1 (ko) |
| RU (1) | RU2014129056A (ko) |
| WO (1) | WO2013088059A2 (ko) |
| ZA (1) | ZA201404590B (ko) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2624270C1 (ru) * | 2016-02-24 | 2017-07-03 | Акционерное общество "Радиевый институт имени В.Г. Хлопина" | Способ переработки отходов реакторного графита |
| RU2726145C1 (ru) * | 2019-04-25 | 2020-07-09 | Валерий Вадимович Крымский | Способ уменьшения радиоактивности отработавших графитовых блоков и установка для его осуществления |
| CN110715296B (zh) * | 2019-09-28 | 2021-01-12 | 山西方洁路路通净化技术有限公司 | 负压无烟筒式焚烧系统 |
| RU2765864C1 (ru) * | 2020-10-09 | 2022-02-03 | Акционерное Общество "Наука И Инновации" | Способ переработки облученного в реакторе АЭС углерода и устройство для его реализации |
| CN113658736A (zh) * | 2021-08-24 | 2021-11-16 | 浙江省辐射环境监测站 | 一种利用碳基纳滤膜去除溶液中放射性核素的方法 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1958464A1 (de) * | 1969-11-21 | 1971-06-03 | Alkem Gmbh | Verfahren zur nasschemischen Verbrennung von organischem Material |
| DE2916203A1 (de) * | 1979-04-21 | 1980-11-06 | K E W A Kernbrennstoff Wiedera | Verfahren zur behandlung von brennbaren, festen, radioaktiven abfaellen |
| DE3375051D1 (en) * | 1983-12-13 | 1988-02-04 | Kernforschungsz Karlsruhe | Process for the oxidative disposal of carbon particles contaminated by noxious material |
| FR2691524B1 (fr) * | 1992-05-20 | 1997-12-12 | Servithen Sarl | Procede et installation pour la destruction sans contamination de l'environnement de pieces de graphite eventuellement radioactives. |
| UA57884C2 (uk) | 1999-10-14 | 2003-07-15 | Дейвід БРЕДБЕРІ | Спосіб обробки радіоактивного графіту |
| JP2003014890A (ja) * | 2001-06-28 | 2003-01-15 | Toshiba Corp | 放射化黒鉛の処分方法及びその装置 |
| FR2943167B1 (fr) | 2009-03-11 | 2011-03-25 | Electricite De France | Traitement de dechets radioactifs carbones. |
| DE102010026936A1 (de) * | 2010-07-12 | 2012-01-12 | Forschungszentrum Jülich GmbH | Verfahren zur Teildekontamination radioaktiver Abfälle |
-
2011
- 2011-12-16 FR FR1161814A patent/FR2984583A1/fr not_active Withdrawn
-
2012
- 2012-12-11 WO PCT/FR2012/052883 patent/WO2013088059A2/fr active Application Filing
- 2012-12-11 JP JP2014546614A patent/JP2015505967A/ja active Pending
- 2012-12-11 US US14/365,360 patent/US20140350320A1/en not_active Abandoned
- 2012-12-11 KR KR1020147019074A patent/KR20140133500A/ko not_active Application Discontinuation
- 2012-12-11 CN CN201280065380.6A patent/CN104170019A/zh active Pending
- 2012-12-11 EP EP12816710.3A patent/EP2791945A2/fr not_active Withdrawn
- 2012-12-11 RU RU2014129056A patent/RU2014129056A/ru not_active Application Discontinuation
-
2014
- 2014-06-23 ZA ZA2014/04590A patent/ZA201404590B/en unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2013088059A2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2014129056A (ru) | 2016-02-10 |
| ZA201404590B (en) | 2015-12-23 |
| FR2984583A1 (fr) | 2013-06-21 |
| US20140350320A1 (en) | 2014-11-27 |
| KR20140133500A (ko) | 2014-11-19 |
| JP2015505967A (ja) | 2015-02-26 |
| CN104170019A (zh) | 2014-11-26 |
| WO2013088059A2 (fr) | 2013-06-20 |
| WO2013088059A3 (fr) | 2013-10-24 |
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