EP2787509B1 - Method for decomposing an oxide layer - Google Patents
Method for decomposing an oxide layer Download PDFInfo
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- EP2787509B1 EP2787509B1 EP14158346.8A EP14158346A EP2787509B1 EP 2787509 B1 EP2787509 B1 EP 2787509B1 EP 14158346 A EP14158346 A EP 14158346A EP 2787509 B1 EP2787509 B1 EP 2787509B1
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- EP
- European Patent Office
- Prior art keywords
- decontamination
- acid
- loop
- methanesulfonic acid
- process according
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 54
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 87
- 238000005202 decontamination Methods 0.000 claims description 69
- 230000003588 decontaminative effect Effects 0.000 claims description 60
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 47
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 43
- 239000002253 acid Substances 0.000 claims description 40
- 150000001768 cations Chemical class 0.000 claims description 38
- 238000007254 oxidation reaction Methods 0.000 claims description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- 230000003647 oxidation Effects 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 32
- 239000011651 chromium Substances 0.000 claims description 29
- 239000011572 manganese Substances 0.000 claims description 29
- 150000002500 ions Chemical class 0.000 claims description 19
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 239000003456 ion exchange resin Substances 0.000 claims description 10
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 230000015556 catabolic process Effects 0.000 claims description 7
- 238000011282 treatment Methods 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000002826 coolant Substances 0.000 claims 2
- 230000003134 recirculating effect Effects 0.000 claims 2
- 238000009434 installation Methods 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 29
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 17
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- 230000009467 reduction Effects 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- 229910044991 metal oxide Inorganic materials 0.000 description 9
- 150000004706 metal oxides Chemical class 0.000 description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-M methanesulfonate group Chemical group CS(=O)(=O)[O-] AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 9
- 235000006408 oxalic acid Nutrition 0.000 description 8
- 239000011241 protective layer Substances 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000009390 chemical decontamination Methods 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- CXIHYTLHIDQMGN-UHFFFAOYSA-L methanesulfonate;nickel(2+) Chemical compound [Ni+2].CS([O-])(=O)=O.CS([O-])(=O)=O CXIHYTLHIDQMGN-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 206010010904 Convulsion Diseases 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- JJIJKNKBEFFVIK-UHFFFAOYSA-N manganese(2+);oxygen(2-);hydrate Chemical compound O.[O-2].[Mn+2] JJIJKNKBEFFVIK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- -1 metal oxalates Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002901 radioactive waste Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
Classifications
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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
- G21F9/001—Decontamination of contaminated objects, apparatus, clothes, food; Preventing contamination thereof
- G21F9/002—Decontamination of the surface of objects with chemical or electrochemical processes
- G21F9/004—Decontamination of the surface of objects with chemical or electrochemical processes of metallic surfaces
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
-
- 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
-
- 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 process for the decomposition of an oxide layer containing chromium, iron, nickel, zinc and radionuclides, in particular for the decomposition of oxide layers deposited on the inner surfaces of systems and components of a nuclear power plant, by means of an aqueous decontamination solution containing an acid.
- the invention relates to a method for the extensive degradation of radionuclides in the primary system and the auxiliary systems in a nuclear power plant using the existing operating medium and the power plant operating systems.
- oxidic protective layers are formed at an operating temperature of> 180 ° C on the medium wetted inner surfaces of the systems and components.
- Radionuclides are incorporated into the oxide matrix.
- the aim of chemical decontamination methods is to dissolve this oxide layer in order to be able to remove those with incorporated radionuclides. This is to ensure that in the case of a revision the radiation exposure of the inspection staff kept as low as possible or in the case of dismantling of the nuclear reactor, the metallic materials of the components can be easily fed to a recycling cycle.
- the oxide protective layers are considered to be chemically insoluble.
- the oxide structure By means of a preceding oxidative chemical treatment of the oxide structure, it can be broken up and the sparingly soluble oxide matrix converted into readily soluble metal oxides.
- This breakdown of the oxide matrix occurs by oxidation of the trivalent chromium into the hexavalent chromium: Fe 0.5 Ni 1.0 Cr 1 ⁇ 5 O 4 / NiFe 2 O 4 / Fe 3 O 4 ⁇ oxidation ⁇ CrO 4 2- , FeO, NiO, Fe 2 O 3 equation (1)
- the manganese ion is present in the permanganate in the oxidation state 7 and is reduced according to equation (2) in the oxidation state 4, at the same time present in the trivalent oxidation state chromium is oxidized to the oxidation state 6.
- chromium is oxidized to the oxidation state 6.
- steps I to V is in this case carried out three to six times (three to six decontamination cycles) in succession.
- manganese oxihydrate [MnO (OH) 2 ] or manganese dioxide (MnO 2 ) is formed in all the decontamination technologies used so far, as equations (2) illustrate.
- the manganese oxyhydrate / manganese dioxide is insoluble and precipitates on the inner surface of the components / systems. With increasing manganese oxyhydrate / manganese dioxide deposition, the desired oxidation of the oxide protective layer is hindered. In addition, the converted iron and nickel oxides remain undissolved on the surface, so that the barrier layer on the surface further amplified.
- Object of the present invention is to avoid the disadvantages of the prior art, in particular to allow a simplification of the process flow, the formation of manganese dioxide and metal oxalates to be avoided.
- the emergence of CO 2 should be excluded. Also, the release of oxide particles should be largely avoided.
- the dissolution of the oxide layer in a single treatment step by means of an aqueous in a first cycle (K1) flowing decontamination with methanesulfonic acid as acid that methanesulfonic acid throughout the decontamination process both as a proton supplier for adjusting the decontamination solution remains at a pH ⁇ 2.5 and as an oxide solvent in the decontamination solution that the digestion of chromium-containing oxide layers with permanganic acid takes place and that after degradation of permanganic acid the solution while maintaining the operation of the first circuit (K1) via a bypass line in a second circuit (K2) flows through an ion exchanger (IT), in which the present in the decontamination solution 2- and 3-valent cations and the dissolved radionuclides are fixed, with simultaneous release of methanesulfonic acid.
- K1 aqueous in a first cycle
- I ion exchanger
- the pH is set by metered addition of methanesulfonic acid.
- methanesulfonic acid there is no need for further addition of methanesulfonic acid.
- the decontamination can be carried out with power plant own systems without the help of external decontamination auxiliary systems, the activity reduction without manganese formation and other cation precipitations and without CO 2 -Anfall and without release of oxidic particles take place and the metal oxides are simultaneously dissolved chemically and as cations / Anions are fixed together with the manganese and the nuclides (Co-60, Co-58, Mn-54, etc.) on ion exchange resins.
- the process may be carried out using the cycle or a subcircuit that is present in a nuclear facility such as a nuclear power plant.
- a nuclear facility such as a nuclear power plant.
- proprietary as well as power plant own systems are used.
- the chemical conversion of the sparingly soluble oxides into readily soluble oxides, the dissolution of the oxides / radionuclides and the discharge and fixing of the dissolved cations to ion exchangers take place in a single process step.
- the permanganic acid used is completely converted to the Mn 2+ cation in the course of the preoxidation step.
- Manganese oxyhydrate / manganese precipitation does not occur.
- methanesulfonic acid is still available at the end of the "oxidative decontamination step" for the subsequent steps.
- the oxides (NiO, Ni 2 O 3 , FeO,) formed in the course of the "oxidative decontamination step" are already dissolved by the methanesulfonic acid during the "HMnO 4 phase".
- methanesulfonic acid is used for pH adjustment.
- the amount of methanesulfonic acid required to prevent MnO (OH) 2 formation is based on the permanganate concentration. As the permanganate concentration increases, the pH must be lowered, ie a higher acid concentration has to be set ( Fig. 1 ).
- the amount of individual cations released in the respective "HMnO 4 phase" can be calculated in each case in advance , This is possible because the amount of HMnO 4 used converts to 100% in Mn 2+ and stoichiometrically produces the amount of dichromate produced.
- the amount of oxidized Cr-III gives the amount of Fe / Cr / Ni / Zn oxides converted and thus the Fe / Ni / Zn / Mn ions produced in the "HMnO 4 phase" ,
- the system to be decontaminated is operated in the circuit K1 without ion exchange integration, ie without circulation K2. This should be based on principle Fig. 3 be clarified.
- the circuit K1 is in operation.
- the circuit K2 is switched in bypass to circuit 1 when the conversion of the HMnO 4 amount to 100% in Mn 2+ is completed.
- Ni-II-oxide Ni (CH 3 SO 3 ) 2 + H 2 O Equation (5)
- a process temperature of preferably 60 ° C to 120 ° C is set.
- the decontamination is preferably carried out in a temperature range of 85 ° C to 105 ° C.
- the divalent and trivalent cations (Mn-II, Fe-II, Fe-III, Zn-II and Ni-II) as well as the radionuclides (Co-58, Co-60, Mn-54 etc .) removed from the solution.
- the methanesulfonic acid is released and is available to the process again. See equations (8) through (11).
- the operation of the ion exchanger IT takes place at a process temperature of ⁇ 100 ° C.
- the operation of the ion exchanger IT is carried out in the bypass until all dissolved cations, anions and radionuclides are fixed on the ion exchange resin.
- the bypass circuit K2 is closed and again permanganic acid is added to the circuit K1. The method steps explained above are repeated until no further activity discharge from the system K1 to be decontaminated takes place.
- Fig. 2 shows by way of example the courses of the cation concentrations in a four-time HMnO 4 dosage in the course of a DWR primary system decontamination.
- step II it is customary, after the completion of the pre-oxidation, to reduce the excess permanganate with oxalic acid (step II) and then to initiate the decontamination step (step III) by adding further decontamination chemicals.
- step II all the ingredients of the pre-oxidation step (residual permanganate, colloidal MnO (OH) 2 , chromate and nickel permanganate) and all converted metal oxides are present in the system in the conventional solution. or component surface.
- metal ions are present partially in dissolved form (MnO 4 - , CrO 4 2- ) and as easily soluble metal oxides (NiO, FeO, MnO 2 / MnO (OH) 2 ), already in the course of the second process step of the reduction ( Step II) high cation contents in the solution.
- the CO 2 formation and release of oxide particles described above does not occur in the present invention.
- the oxalate compounds formed from divalent cations and the reduction chemical "oxalic acid” have limited solubility in water. Depending on the process temperature, the solubility of the divalent cations is: 50 ° C 80 ° C unit NiC 2 O 4 about 3 about 6 mg Ni-II / liter FeC 2 O 4 about 15 about 45 mg Fe-II / liter MnC 2 O 4 about 120 about 170 mg Mn-II / liter
- the oxidic protective layers of a primary system of a pressurized-water nuclear power plant usually give a total total NOx inventory of 1,900 kg to 2,400 kg [Fe, Cr, Ni oxide].
- the already dissolved radionuclides (Co-58, Co-60, Mn-54) are incorporated into the oxalate layer. This leads to a recontamination in the systems.
- Each nuclear power plant [PWR, SWR, etc.] has its own specific oxide structure, oxide composition, oxide dissolving behavior, and oxide / activity inventory.
- For the preliminary planning of a decontamination only assumptions can be made. Only in the course of carrying out the decontamination then shows whether the preliminary assumptions were correct.
- a decontamination concept must therefore be able to adapt to the respective changes during execution.
- NPP nuclear power plants
- the process parameters can be quickly adapted to the respective new requirements (chemical dosing, chemical concentrations, process temperature, time of IT exchanger integration, step sequences, etc.).
- process variations can be carried out until the desired activity output or the desired dose rate reduction has been achieved.
- the methanesulfonic acid present in the solution remains in the solution during the performance of all the process steps. The concentration is not changed. Only at the end of the aromatickontaminations diery the methanesulfonic acid is bound in the course of final cleaning on ion exchange resins.
- FIGS. 1 to 3 that are self-explanatory.
- the decontamination according to the invention is purely in principle of Fig. 2 refer to.
- the decontamination solution is underlaid with methanesulfonic acid to ensure a pH of ⁇ 2.5.
- methanesulfonic acid is metered into the solution in order to convert the insoluble Fe, CrNi oxide dressing into readily soluble metal oxides, the metal oxides at the same time dissolve and form readily soluble methanesulfonates.
- the Cr-III oxide is oxidized to Cr-VI and is present in the solution as dichromic acid.
- the solution flows through the ion exchanger IT (circuit K 2) via a bypass in the "IT operation" step, in which the dissolved cations and radionuclides are fixed.
- IT operation the methanesulfonic acid is released again and is available to the process again.
- the conversion of the poorly soluble Fe, Cr, Ni structure into slightly soluble oxide forms by means of permanganic acid takes place chemically.
- the dissolved oxide forms are dissolved with methanesulfonic acid.
- this is done in a circulation mode (cycle K1) ( Fig. 3 ) in a methanesulfonic acid / permanganic acid solution. Circulation K1 is maintained until the permanganic acid has been completely consumed and converted to Mn 2+ .
- the permanganic acid concentration is set in the range between 30 and 50 ppm at the beginning of the process, the conversion of permanganic acid to Mn 2+ lasts for 2 to 4 hours.
- the conversion of the oxide structure and the dissolution of the converted oxides takes place at the same time.
- the final products of the dissolution process are metal salts of methanesulfonic acid.
- the "IT phase” begins.
- the metal cations present as methanesulfonates and nuclides in the bypass (circulation K2) are passed over ion exchange resins and fixed there.
- both circuits K1 and K2 are in operation. In the exchange process, the methanesulfonic acid is released again and is the decontamination solution available again.
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- High Energy & Nuclear Physics (AREA)
- General Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- Food Science & Technology (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
Die Erfindung bezieht sich auf ein Verfahren zum Abbau einer Chrom, Eisen, Nickel, Zink und Radionuklide enthaltenden Oxidschicht, insbesondere zum Abbau von auf Innenflächen von Systemen und Komponenten eines Kernkraftwerks abgeschiedenen Oxidschichten, mittels einer eine Säure enthaltenden wässrigen Dekontaminationslösung.The invention relates to a process for the decomposition of an oxide layer containing chromium, iron, nickel, zinc and radionuclides, in particular for the decomposition of oxide layers deposited on the inner surfaces of systems and components of a nuclear power plant, by means of an aqueous decontamination solution containing an acid.
Die Erfindung betrifft insbesondere ein Verfahren zum umfassenden Abbau der Radionuklide im Primärsystem sowie der Hilfssysteme in einem Kernkraftwerk unter Nutzung des vorhandenen Betriebsmediums und der kraftwerkseigenen Betriebssysteme.In particular, the invention relates to a method for the extensive degradation of radionuclides in the primary system and the auxiliary systems in a nuclear power plant using the existing operating medium and the power plant operating systems.
Während des Leistungsbetriebes eines Kernkraftwerkes werden bei einer Betriebstemperatur von > 180°C auf den mediumbenetzten Innenflächen der Systeme und Komponenten oxidische Schutzschichten gebildet. Dabei werden Radionuklide mit in die Oxidmatrix eingebaut. Ziel chemischer Dekontaminationsverfahren ist es diese Oxidschicht aufzulösen um die mit eingebundenen Radionuklide entfernen zu können. Hierdurch soll erreicht werden, dass im Falle einer Revision die Strahlenbelastung des Revisionspersonals so gering wie möglich gehalten oder im Falle des Rückbaus des Kernreaktors die metallischen Werkstoffe der Komponenten problemlos einem Wiederverwertungskreislauf zugeführt werden können.During the power operation of a nuclear power plant oxidic protective layers are formed at an operating temperature of> 180 ° C on the medium wetted inner surfaces of the systems and components. Radionuclides are incorporated into the oxide matrix. The aim of chemical decontamination methods is to dissolve this oxide layer in order to be able to remove those with incorporated radionuclides. This is to ensure that in the case of a revision the radiation exposure of the inspection staff kept as low as possible or in the case of dismantling of the nuclear reactor, the metallic materials of the components can be easily fed to a recycling cycle.
Die oxidischen Schutzschichten gelten auf Grund ihrer Zusammensetzung und Struktur (Fe0.5Ni1.0Cr1.5O4, NiFe2O4) als chemisch nicht auflösbar. Durch eine vorlaufende oxidative chemische Behandlung der Oxidstruktur kann diese aufgebrochen und die schwerlösliche Oxidmatrix in leichtlösliche Metalloxide überführt werden. Dieses Aufbrechen der Oxidmatrix geschieht mittels Oxidation des dreiwertigen Chroms in das sechswertige Chrom:
Fe0.5Ni1.0Cr1·5O4 / NiFe2O4 / Fe3O4 → Oxidation → CrO4 2-, FeO, NiO, Fe2O3 Gleichung (1)
Due to their composition and structure (Fe0.5Ni1.0Cr1.5O4, NiFe2O4), the oxide protective layers are considered to be chemically insoluble. By means of a preceding oxidative chemical treatment of the oxide structure, it can be broken up and the sparingly soluble oxide matrix converted into readily soluble metal oxides. This breakdown of the oxide matrix occurs by oxidation of the trivalent chromium into the hexavalent chromium:
Fe 0.5 Ni 1.0 Cr 1 × 5 O 4 / NiFe 2 O 4 / Fe 3 O 4 → oxidation → CrO 4 2- , FeO, NiO, Fe 2 O 3 equation (1)
Als Oxidationsbehandlung hat sich weltweit die sogenannte "Permanganat-Voroxidation" entsprechend Gleichung (2) durchgesetzt, wobei folgende drei Oxidationsbehandlungen zur Verfügung stehen:
- "NP" Oxidation = Salpetersäure + Kaliumpermanganat (nitric acid, permanganate) (siehe z. B.
EP 0 675 973 B1 - "AP" Oxidation = Natriumhydroxid + Kaliumpermanganat (alkaline, permanganate) "HP" Oxidation = Permangansäure (siehe z. B.
EP 0 071 336 A1 EP 0 160 831 B1
Mn-VII + Cr-III → Mn-IV + Cr-VI 2 MnO4 1- + Cr2O3→ 2 MnO2 + Cr2O7 2- Gleichung (2)
As an oxidation treatment, the so-called "permanganate pre-oxidation" according to equation (2) has become established worldwide, the following three oxidation treatments being available:
- "NP" oxidation = nitric acid + potassium permanganate ( n itric acid, p ermanganate) (see eg.
EP 0 675 973 B1 - "AP" = sodium hydroxide + potassium permanganate oxidation (a lkaline, p ermanganate) "HP" = permanganic oxidation (see, for. Example,
EP 0 071 336 A1 EP 0 160 831 B1
Mn-VII + Cr-III → Mn-IV + Cr-VI 2 MnO 4 1- + Cr 2 O 3 → 2 MnO 2 + Cr 2 O 7 2- Equation (2)
Das Mangan-Ion liegt im Permanganat in der Oxidationsstufe 7 vor und wird entsprechend Gleichung (2) in die Oxidationsstufe 4 reduziert, zeitgleich wird das in dreiwertiger Oxidationsstufe vorliegende Chrom in die Oxidationsstufe 6 aufoxidiert. Für die Oxidation von 1 mol Cr2O3 werden, unter sauren Bedingungen entsprechend Gleichung (2), 2 mol MnO4- benötigt.The manganese ion is present in the permanganate in the oxidation state 7 and is reduced according to equation (2) in the oxidation state 4, at the same time present in the trivalent oxidation state chromium is oxidized to the oxidation state 6. For the oxidation of 1 mol of Cr 2 O 3 , 2 mol of MnO 4 are required under acidic conditions in accordance with equation (2).
Eine chemische Dekontamination eines gesamten Primärsystems einschließlich aller aktivitätsführenden Hilfssysteme wurde bisher nur in wenigen Kernkraftwerken durchgeführt. Weltweit wurden in den letzten Jahren an die 50 unterschiedlichste Dekontaminationsverfahren entwickelt. Von all diesen Verfahren haben sich nur die Technologien durchgesetzt, die auf einer vorlaufenden Voroxidation mit Permanganaten (MnO4-) aufbauen.A chemical decontamination of an entire primary system, including all activity-carrying auxiliary systems, has so far only been carried out in a few nuclear power plants. Worldwide, over 50 different decontamination processes have been developed in recent years. Of all these processes, only the technologies that rely on a preliminary pre-oxidation with permanganates (MnO 4- ) have prevailed.
Zur Verfügung stehende chemische Dekontaminationsverfahren werden grundsätzlich derzeit mit folgender Verfahrens-Sequenz (= Dekontaminations-Zyklus) durchgeführt:
- Schritt I: Voroxidations-Schritt
- Schritt II: Reduktions-Schritt
- Schritt III: Dekontaminations-Schritt
- Schritt IV: Zersetzungs-Schritt
- Schritt V: Endreinigungs-Schritt.
- Step I: Pre-oxidation step
- Step II: Reduction Step
- Step III: Decontamination step
- Step IV: Decomposition Step
- Step V: Final cleaning step.
Die Schrittfolge I bis V wird hierbei drei bis sechs Mal (drei bis sechs Dekontaminations -Zyklen) hintereinander durchgeführt.The sequence of steps I to V is in this case carried out three to six times (three to six decontamination cycles) in succession.
Alle Verfahren verwenden Permanganate (Kaliumpermanganat, Permangansäure) zur Voroxidation (I) und Oxalsäure zur Reduktion (II). Unterschiede weisen die Verfahren nur im Dekontaminationsschritt (III) auf. Hier werden unterschiedliche Chemikalien und Chemikalienmischungen eingesetzt.All processes use permanganate (potassium permanganate, permanganic acid) for pre-oxidation (I) and oxalic acid for reduction (II). The methods only show differences in the decontamination step (III). Here different chemicals and chemical mixtures are used.
Die bisherigen Dekontaminationsverfahren bauen auf das zuvor erläuterte Konzept auf. Die schwerlöslichen oxidischen Schutzschichten werden im Zuge eines Voroxidationsschrittes in leichter lösliche Oxidverbindungen umgewandelt und verbleiben auf der Systemoberfläche. Während der Voroxidation erfolgt daher kein Aktivitätsaustrag aus den zu dekontaminierenden Systemen. Ein Abbau der Dosisleistung findet in dieser Zeitphase einer Dekontamination bisher nicht statt.The previous decontamination methods build on the previously discussed concept. The sparingly soluble oxide protective layers are converted into more soluble oxide compounds during a preoxidation step and remain on the surface of the system. During the pre-oxidation therefore no activity discharge from the systems to be decontaminated. Degradation of the dose rate does not take place in this period of decontamination.
Erst nach dem zweiten Verfahrensschritt (II) der Reduktion der Permanganate und des gebildeten Braunsteins mittels Oxalsäure sowie im Dekontaminationsschrittes (III) werden die Oxide gelöst und die gelösten Kationen/Radionuklide ausgetragen und auf Ionenaustauscherharze gebunden.Only after the second process step (II) of the reduction of the permanganate and of the formed manganese dioxide by means of oxalic acid and in the decontamination step (III) are the oxides dissolved and the dissolved cations / radionuclides discharged and bound to ion exchange resins.
Während der Voroxidation (I) bildet sich bei allen bisher zum Einsatz gelangten Dekontaminations-Technologien Manganoxihydrat [MnO(OH)2] bzw. Braunstein (MnO2), wie Gleichungen (2) verdeutlichen.During pre-oxidation (I), manganese oxihydrate [MnO (OH) 2 ] or manganese dioxide (MnO 2 ) is formed in all the decontamination technologies used so far, as equations (2) illustrate.
Das Manganoxyhydrat/Mangandioxid ist unlöslich und scheidet sich auf der Innenoberfläche der Komponenten / Systeme ab. Mit zunehmender Manganoxyhydrat / Mangandioxid Abscheidung wird die gewünschte Oxidation der oxidischen Schutzschicht behindert. Zusätzlich verbleiben die umgewandelten Eisen und Nickeloxide ungelöst auf der Oberfläche, so dass sich die Sperrschicht auf der Oberfläche weiter verstärkt.The manganese oxyhydrate / manganese dioxide is insoluble and precipitates on the inner surface of the components / systems. With increasing manganese oxyhydrate / manganese dioxide deposition, the desired oxidation of the oxide protective layer is hindered. In addition, the converted iron and nickel oxides remain undissolved on the surface, so that the barrier layer on the surface further amplified.
Am Ende des Voroxidationsschrittes liegen im zu dekontaminierenden System folgende neue, im Verfahrensschritt (I) eingebrachte bzw. entstandene chemische Verbindungen vor:
- auf der Systemoberfläche: MnO2, NiO, FeO, Fe2CO3, Fe3O4
- in der Voroxidationslösung: KMnO4, NaOH bzw. HNO3, kolloidales MnO(OH)2, CrO4 2- bzw. Cr2O7 2-.
- on the system surface: MnO 2, NiO, FeO, Fe 2 CO 3 , Fe 3 O 4
- in the pre-oxidation solution: KMnO 4 , NaOH or HNO 3 , colloidal MnO (OH) 2 , CrO 4 2- or Cr 2 O 7 2- .
Am Ende des Voroxidationsschrittes liegen demnach noch sämtliche Metalloxide einschließlich der Radionuklide im zu dekontaminierenden System vor. Das sich gebildete Manganoxyhydrat/Mangandioxid wurde teilweise in nicht durchströmte Systembereiche eingetragen und kann in den weiterführenden Verfahrensschritten nicht mehr ausgetragen/entfernt werden.Accordingly, at the end of the pre-oxidation step, all the metal oxides, including the radionuclides, are still present in the system to be decontaminated. The manganese oxyhydrate / manganese dioxide formed was partially introduced into non-perfused system areas and can no longer be discharged / removed in the subsequent process steps.
Nach dem Stand der Technik erfolgt im Zuge der Oxidation der Oxidschicht kein Abbau von Radioaktivität, also keine Dekontamination, da praktisch keine Kationen aus der Oxidschicht heraus gelöst werden, welche mit Hilfe eines Kationentauschers entfernt werden könnten. Die Auflösung der Oxidschicht erfolgt vielmehr in einem zweiten Verfahrensschritt mit Hilfe von Oxalsäure, dem ein Reduktionsschritt zur Reduktion überschüssiger Permangansäure sowie von Manganoxidhydrat vorgeschaltet ist. Erst nach diesen Verfahrensschritten werden Kationen durch Ionentausch aus der Reinigungslösung (Dekontaminationslösung) entfernt.According to the state of the art, in the course of the oxidation of the oxide layer no degradation of radioactivity takes place, ie no decontamination, since virtually no cations are dissolved out of the oxide layer, which could be removed with the aid of a cation exchanger. Rather, the oxide layer is dissolved in a second process step with the aid of oxalic acid, which is preceded by a reduction step for reducing excess permanganic acid and manganese oxide hydrate. Only after these process steps are cations removed by ion exchange from the cleaning solution (decontamination solution).
Aufgabe der vorliegenden Erfindung ist es, die Nachteile des Standes der Technik zu vermeiden, insbesondere eine Vereinfachung des Verfahrensablaufs zu ermöglichen, wobei die Bildung von Braunstein und Metall-Oxalate vermieden werden soll. Das Entstehen von CO2 soll ausgeschlossen werden. Auch soll das Freisetzen oxidischer Partikel weitgehend vermieden werden.Object of the present invention is to avoid the disadvantages of the prior art, in particular to allow a simplification of the process flow, the formation of manganese dioxide and metal oxalates to be avoided. The emergence of CO 2 should be excluded. Also, the release of oxide particles should be largely avoided.
Zur Lösung der Aufgabe ist im Wesentliche vorgesehen, dass das Auflösen der Oxidschicht in einem einzigen Behandlungsschritt mit Hilfe einer wässrigen in einem ersten Kreislauf (K1) strömenden Dekontaminationslösung mit Methansulfonsäure als Säure erfolgt, dass Methansulfonsäure während der gesamten Dekontaminationsdurchführung sowohl als Protonenlieferant zur Einstellung der Dekontaminationslösung auf einen pH-Wert ≤ 2,5 als auch als Oxidlösemittel in der Dekontaminationslösung verbleibt, dass der Aufschluss von chromhaltigen Oxidschichten mit Permangansäure erfolgt und dass nach Abbau der Permangansäure die Lösung bei Aufrechterhaltung des Betriebs des ersten Kreislaufs (K1) über eine Bypass-Leitung in einem zweiten Kreislauf (K2) einen Ionenaustauscher (IT) durchströmt, in dem die in der Dekontaminationslösung vorhandenen 2- und 3-wertigen Kationen sowie die gelösten Radionuklide fixiert werden, bei gleichzeitiger Freisetzung von Methansulfonsäure.To solve the problem is essentially provided that the dissolution of the oxide layer in a single treatment step by means of an aqueous in a first cycle (K1) flowing decontamination with methanesulfonic acid as acid that methanesulfonic acid throughout the decontamination process both as a proton supplier for adjusting the decontamination solution remains at a pH ≤ 2.5 and as an oxide solvent in the decontamination solution that the digestion of chromium-containing oxide layers with permanganic acid takes place and that after degradation of permanganic acid the solution while maintaining the operation of the first circuit (K1) via a bypass line in a second circuit (K2) flows through an ion exchanger (IT), in which the present in the decontamination solution 2- and 3-valent cations and the dissolved radionuclides are fixed, with simultaneous release of methanesulfonic acid.
Erfindungsgemäß wird die Aufgabe im Wesentlichen dadurch gelöst,
- dass die Oxidation der Oxidschicht und deren Auflösung in einem einzigen Behandlungsschritt mit Hilfe einer wässrigen Dekontaminationslösung erfolgt,
- dass Methansulfonsäure als Dekontaminationssäure eingesetzt wird,
- dass die Methansulfonsäure sowohl zum Einstellen des pH-Wertes als auch zum Auflösen der Metalloxide verwendet wird, und
- dass die löslichen Methansulfonate, nach Abbau des Permangansäure, über eine Bypass-Leitung einen Ionenaustauscher durchströmt, in dem die gelösten Kationen und Radionuklide fixiert werden, bei gleichzeitiger Freisetzung von Methansulfonsäure.
- the oxidation of the oxide layer and its dissolution take place in a single treatment step with the aid of an aqueous decontamination solution,
- that methanesulfonic acid is used as decontamination acid,
- that the methanesulfonic acid is used both for adjusting the pH and for dissolving the metal oxides, and
- that the soluble methanesulfonates, after degradation of permanganic acid, flows through an ion exchanger via a bypass line, in which the dissolved cations and radionuclides are fixed, with simultaneous release of methanesulfonic acid.
Dabei ist erfindungsgemäß vorgesehen, dass zu Beginn des Verfahrensablaufs der pH-Wert durch Zudosieren der Methansulfonsäure vorgegeben wird. Während des oxidativen Abbaus der Schicht und der in diesem Zusammenhang durchgeführten Verfahrensschritte bedarf es keiner weiteren Zugabe von Methansulfonsäure. Erfindungsgemäß ist ein Verfahren zum Abbau des Aktivitätsinventars in Komponenten und Systemen vorgesehen, wobei mit einer Dekontaminationslösung die Oxidschichten der mediumbenetzten Innenflächen entfernt werden. Dabei können die Dekontamination mit kraftwerkseigenen Systemen ohne Hilfe von externen Dekontaminationshilfssystemen durchgeführt werden, der Aktivitätsabbau ohne Braunstein-Bildung und sonstige Kationen-Ausfällungen sowie ohne CO2-Anfall und ohne Freisetzung von oxidischen Partikeln stattfinden und die Metalloxide zeitgleich chemisch gelöst werden und als Kationen / Anionen zusammen mit dem Mangan und den Nukliden (Co-60, Co-58, Mn-54 etc.) auf Ionenaustauscherharzen fixiert werden.It is inventively provided that at the beginning of the procedure, the pH is set by metered addition of methanesulfonic acid. During the oxidative degradation of the layer and the process steps carried out in this context, there is no need for further addition of methanesulfonic acid. According to the invention, a method for reducing the inventory of activity in components and systems is provided, wherein the oxide layers of medium wetted inner surfaces are removed with a decontamination solution. The decontamination can be carried out with power plant own systems without the help of external decontamination auxiliary systems, the activity reduction without manganese formation and other cation precipitations and without CO 2 -Anfall and without release of oxidic particles take place and the metal oxides are simultaneously dissolved chemically and as cations / Anions are fixed together with the manganese and the nuclides (Co-60, Co-58, Mn-54, etc.) on ion exchange resins.
Das Verfahren kann unter Verwendung des Kreislaufs oder eines Teilskreislaufs durchgeführt werden, der in einer kerntechnischen Anlage wie Kernkraftwerk vorhanden ist. Insoweit werden anlageeigene wie kraftwerkseigene Systeme genutzt.The process may be carried out using the cycle or a subcircuit that is present in a nuclear facility such as a nuclear power plant. In that regard, proprietary as well as power plant own systems are used.
Im Gegensatz zu den bisherigen zuvor erläuterten Dekontaminations-Konzepten erfolgt erfindungsgemäß die chemische Umwandlung der schwerlöslichen Oxide in leichtlösliche Oxide, das Auflösen der Oxide/Radionuklide und der Austrag und das Fixieren der gelösten Kationen an Ionenaustauscher in einem einzigen Verfahrensschritt.In contrast to the previously discussed decontamination concepts, according to the invention the chemical conversion of the sparingly soluble oxides into readily soluble oxides, the dissolution of the oxides / radionuclides and the discharge and fixing of the dissolved cations to ion exchangers take place in a single process step.
Des Weiteren und im Gegensatz zum Stand der Technik wird erfindungsgemäß im Zuge des Voroxidationsschrittes die eingesetzten Permangansäure vollständige zum Mn2+- Kation umgewandelt. Eine Manganoxyhydrat /Braunstein-Ausfällung findet nicht statt.Furthermore, and in contrast to the prior art, according to the invention, the permanganic acid used is completely converted to the Mn 2+ cation in the course of the preoxidation step. Manganese oxyhydrate / manganese precipitation does not occur.
Durch die Reaktion von Mn-VII zu Mn-II stehen 5 Äquivalente (Elektronen) für die Oxidation von Cr2O3 zur Verfügung. Dies bedeutet, dass im Vergleich mit den bisherigen Dekontaminationsverfahren entsprechend der erfindungsgemäßen Lehre nahezu die doppelte Cr2O3 Menge zu Chromat/Dichromat aufoxidiert werden kann.Through the reaction of Mn-VII to Mn-II, 5 equivalents (electrons) are available for the oxidation of Cr 2 O 3 . This means that in comparison with the previous decontamination according to the teaching of the invention almost twice the amount of Cr 2 O 3 can be oxidized to chromate / dichromate.
Bei den bisherigen permanganatbasierten Dekontaminations-Konzepten werden pro 100 g eingesetzter Permanganat-Ionen:
- 43 g Cr-III zu Cr-VI aufoxidiert
- 72,5 g MnO(OH)2 fallen aus.
- 43 g Cr-III oxidized to Cr-VI
- 72.5 g of MnO (OH) 2 precipitate.
Beim Dekontaminations-Konzept entsprechend der vorliegenden Erfindung werden pro 100 g eingesetzter Permanganat-Ionen
73 g Cr-III zu Cr-VI aufoxidiert
es treten keine MnO(OH)2 / MnO2 - Ausfällungen auf.In the decontamination concept according to the present invention, per 100 g of permanganate ions used
73 g Cr-III oxidized to Cr-VI
no MnO (OH) 2 / MnO 2 precipitations occur.
Nach der erfindungsgemäßen Lehre werden sowohl der pH-Wert als auch die Permangansäure und der Protonenlieferant (Methansulfonsäure) nach einem festen logistischen Schema so aufeinander abgestimmt, dass im Zuge der Dekontamination-Durchführung:
- kein Braunstein entstehen kann
- die durch den Zerfall der schwerlöslichen Spinell- / Magnetit-Oxide entstehenden Einzeloxide (FeO, Fe2O3, Fe3O4, NiO) zeitgleich chemisch gelöst werden
- die sich bildende Mangan-, Eisen- und Nickel-Methansulfonate eine hohe Löslichkeit aufweisen
- die gelösten Kationen (Fe3+, Fe2+ ˙ Ni2+ und Mn2+) sowie die Radionuklide auf Ionenaustauscher fixiert werden.
- no brownstone can arise
- the individual oxides (FeO, Fe 2 O 3 , Fe 3 O 4 , NiO) formed by the decomposition of the sparingly soluble spinel / magnetite oxides are simultaneously dissolved chemically
- the forming manganese, iron and nickel methanesulfonates have a high solubility
- the dissolved cations (Fe 3+ , Fe 2+ ˙ Ni 2+ and Mn 2+ ) and the radionuclides are fixed on ion exchangers.
Die zuvor beschriebene Bildung von Mangandioxid nach der NP-, AP- bzw. HP-Oxidation wird erfindungsgemäß durch Einsatz von Permangansäure im sauren Bereich (pH < 2,5, vorzugsweise pH ≤ 2,2 , insbesondere pH ≤ 2) vermieden. Das sich im sauren Medium bildende Mn2+ wird entsprechend der Erfindung mittels Ionenaustauscher bereits während des "Dekontaminations-Schritts" aus der Lösung entsprechend Gleichung (3) entfernt:
a) 6HMnO4 + 5Cr2O3 + 2H+ → 6Mn2+ + 5Cr2O7 2- + 4H2O Gleichung (3)
b) Mn2+ + H2KIT→ [Mn2+-KIT] + 2 H+ Gleichung (4)
The above-described formation of manganese dioxide after NP, AP or HP oxidation is avoided according to the invention by using permanganic acid in the acidic range (pH <2.5, preferably pH ≦ 2.2, in particular pH ≦ 2). The Mn 2+ which forms in the acid medium is removed from the solution according to the invention by means of an ion exchanger during the "decontamination step" according to equation (3):
a) 6HMnO 4 + 5Cr 2 O 3 + 2H + → 6Mn 2+ + 5Cr 2 O 7 2- + 4H 2 O Equation (3)
b) Mn 2+ + H 2 → KIT [Mn 2 + - KIT] + 2 H + Equation (4)
Die
Entsprechend vorliegender Erfindung wird der erforderliche pH-Wert von < 2,5, insbesondere ≤ 2,2, bevorzugt pH ≤ 2,0 durch Zugabe von Methansulfonsäure eingestellt. Von allen zur Verfügung stehenden Säuren erfüllt Methansulfonsäure die für den erfindungsgemäßen Dekontaminationsprozess erforderlichen Bedingungen, wie
- Methansulfonsäure ist gegenüber Permanganat beständig
- sie wird weder oxidativ zerstört noch chemisch verändert
- Permangansäure wird durch Methansulfonsäure nicht reduziert, eine Braunsteinbildung (MnO2) findet nicht statt
- Metalloxide werden aufgelöst und bilden leichtlösliche Methansulfonate
- eine zusätzliche Zugabe von Mineralsäuren (Schwefelsäure, Salpetersäure), organischen Carbonsäuren (Oxalsäure, Ascorbinsäure etc.) und Komplexbildner ist nicht erforderlich
- die gelösten Kationen werden auf Kationenaustauscherharze gebunden, die Methansulfonsäure steht dem Prozess wieder zur Verfügung
- ein Grundmaterialangriff findet nicht statt.
- Methanesulfonic acid is resistant to permanganate
- it is neither oxidatively destroyed nor chemically altered
- Permanganic acid is not reduced by methanesulfonic acid, a manganese formation (MnO 2 ) does not occur
- Metal oxides are dissolved to form readily soluble methanesulfonates
- an additional addition of mineral acids (sulfuric acid, nitric acid), organic carboxylic acids (oxalic acid, ascorbic acid, etc.) and complexing agents is not required
- the dissolved cations are bound to cation exchange resins, the methanesulfonic acid is the process again
- a base material attack does not take place.
Aufgrund der vorstehend aufgeführten Eigenschaften steht Methansulfonsäure am Ende des "oxidativen Dekontaminations-Schrittes" für die Folgeschritte weiterhin zur Verfügung.Due to the properties listed above, methanesulfonic acid is still available at the end of the "oxidative decontamination step" for the subsequent steps.
Die im Zuge des "oxidativen Dekontaminations-Schrittes" entstehenden Oxide (NiO, Ni2O3, FeO,) werden von der Methansulfonsäure bereits während der "HMnO4-Phase" aufgelöst.The oxides (NiO, Ni 2 O 3 , FeO,) formed in the course of the "oxidative decontamination step" are already dissolved by the methanesulfonic acid during the "HMnO 4 phase".
Entsprechend vorliegender Erfindung wird für die pH Einstellung Methansulfonsäure verwendet. Die Menge der Methansulfonsäure, die zur Vermeidung der MnO(OH)2 Bildung erforderlich ist, orientiert sich an der Permanganat-Konzentration. Mit steigender Permanganat-Konzentration muss der pH Wert erniedrigt, das heißt eine höhere Säurekonzentration eingestellt werden (
Als Richtwert gelten folgende pH-Werte:
bei 0,1 mol Permangansäure pro Liter ein pH-Wert von ca. 1- bei 0,01 mol Permanganat pro Liter ein pH-Wert von ca. 2.
- at 0.1 mol of permanganic acid per liter, a pH of about 1
- at 0.01 mol permanganate per liter, a pH of about 2.
Während der Durchführung der "HMnO4-Phase" wird die Konzentration der freien Protonen (H+) durch die Bildung von Metall-Methansulfonate reduziert. Die Menge der gelösten Fe-, Ni-, Zn-, Mn-Kationen werden daher in die Ermittlung des zusätzlichen Methansulfonsäure-Bedarfs entsprechend folgender Formeln mit einbezogen:
mg CH3SO3 -1/Liter = [mg Kation/Liter] x [Kationen-spezifischer Faktor].
During the execution of the "HMnO 4 phase", the concentration of free protons (H + ) is reduced by the formation of metal methanesulfonates. The amount of dissolved Fe, Ni, Zn, Mn cations are therefore included in the determination of the additional methanesulfonic acid requirement according to the following formulas:
mg CH 3 SO 3 -1 / liter = [mg cation / liter] x [cation specific factor].
In Abhängigkeit von der Fe/Cr/Ni/Zn - Zusammensetzung der Schutzschicht kann entsprechend vorliegender Erfindung in Abhängigkeit von der eingesetzten HMnO4 - Menge jeweils vorlaufend exakt die Menge der Einzelkationen berechnet werden, die in der jeweiligen "HMnO4-Phase" freigesetzt werden. Dies ist möglich, da sich die eingesetzte HMnO4-Menge zu 100% in Mn2+ umwandelt und dabei die erzeugte Dichromat-Menge stöchiometrisch entsteht. Die Menge des oxidierten Cr-III gibt wiederum die Menge der umgewandelten Fe-/Cr-/Ni-/Zn - Oxide und somit der in der "HMnO4-Phase" entstehenden Fe-/Ni-/Zn-/Mn - Ionen vor.Depending on the Fe / Cr / Ni / Zn composition of the protective layer, according to the present invention, depending on the amount of HMnO 4 used , the amount of individual cations released in the respective "HMnO 4 phase" can be calculated in each case in advance , This is possible because the amount of HMnO 4 used converts to 100% in Mn 2+ and stoichiometrically produces the amount of dichromate produced. The amount of oxidized Cr-III, in turn, gives the amount of Fe / Cr / Ni / Zn oxides converted and thus the Fe / Ni / Zn / Mn ions produced in the "HMnO 4 phase" ,
Während der Oxidumwandlung in der "HMnO4-Phase" und des zeitgleich ablaufenden Auflösens der neuen Oxidstrukturen wird das zu dekontaminierende System im Kreislauf K1 ohne Ionenaustauscher - Einbindung, also ohne Kreislauf K2 betrieben. Dies soll prinzipiell anhand
Um den erforderlichen Einsatz von Methansulfonsäure zu minimieren, wird die oxidative "HMnO4-Phase" vorzugsweise mit einer HMnO4-Konzentration von ≤ 50 ppm HMnO4 durchgeführt. Während des "HMnO4-Phase" laufen folgende chemische Teilreaktionen ab (Gleichungen (4) bis (7)):
- Oxidieren und Lösen des in der Schutzschichte (Fe0.5Ni1.0Cr1.5O4) eingebundenen Cr2O3:
6HMnO4 + 5Cr2O3 + 12CH3SO3H → 6 [Mn (CH3SO3)2] + 5H2Cr2O7 + 4H2O Gleichung (4)
- Oxidizing and dissolving the Cr 2 O 3 incorporated in the protective layer (Fe 0.5 Ni 1.0 Cr 1.5 O 4 ):
6HMnO 4 + 5Cr 2 O 3 + 12CH 3 SO 3 H → 6 [Mn (CH 3 SO 3 ) 2 ] + 5H 2 Cr 2 O 7 + 4H 2 O Equation (4)
Durch die Oxidation des Cr-III-Oxids unter Bildung von wasserlöslichem Dichromat werden Ni-II-Oxid (NiO), Fe-III-Oxid (Fe2O3) und Zn-II-Oxid (ZnO) aus der Oxidmatrix freigesetzt und von der Methansulfonsäure aufgelöst (Gleichung (5) bis (7)).
NiO + 2 CH3SO3H → Ni (CH3SO3)2 + H2O Gleichung (5)
Fe2O3 + 6 CH3SO3H → 2 [Fe (CH3SO3)3] + 3 H2O Gleichung (6)
ZnO + 2 CH3SO3H → Zn (CH3SO3)2 + H2O Gleichung (7)
Oxidation of the Cr-III oxide to form water-soluble dichromate releases Ni-II-oxide (NiO), Fe-III-oxide (Fe 2 O 3 ) and Zn-II-oxide (ZnO) from the oxide matrix the methanesulfonic acid dissolved (equation (5) to (7)).
NiO + 2CH 3 SO 3 H → Ni (CH 3 SO 3 ) 2 + H 2 O Equation (5)
Fe 2 O 3 + 6 CH 3 SO 3 H → 2 [Fe (CH 3 SO 3 ) 3 ] + 3 H 2 O Equation (6)
ZnO + 2CH 3 SO 3 H → Zn (CH 3 SO 3 ) 2 + H 2 O Equation (7)
Die vorstehend dargestellten chemischen Reaktion (Gleichungen (4) bis (7)) laufen zeitgleich ab.The above-described chemical reaction (equations (4) to (7)) occur at the same time.
Zur Beschleunigung der "HMnO4-Reaktion" sowie der "Methansulfonsäure-Reaktionen" wird eine Prozesstemperatur von vorzugsweise 60°C bis 120°C eingestellt.To accelerate the "HMnO 4 reaction" and the "methanesulfonic acid reactions", a process temperature of preferably 60 ° C to 120 ° C is set.
Entsprechend vorliegender Erfindung erfolgt die Dekontamination vorzugsweise in einem Temperaturbereich von 85°C bis 105°C.According to the present invention, the decontamination is preferably carried out in a temperature range of 85 ° C to 105 ° C.
Dies soll auch anhand des Schaubilds in
Voraussetzung für die Einbindung eines Ionenaustauschers ist, dass sich das Permanganat vollständig oder im Wesentlichen vollständig zu Mn2+ umgesetzt hat und die Lösung frei von MnO4 --Ionen ist (Richtwert < 2 ppm MnO4).The prerequisite for the incorporation of an ion exchanger is that the permanganate has reacted completely or essentially completely to Mn 2+ and the solution is free of MnO 4 - ions (standard value <2 ppm MnO 4 ).
Während des Betriebes des Ionenaustauschers IT werden die zwei- und dreiwertigen Kationen (Mn-II, Fe-II, Fe-III, Zn-II und Ni-II) sowie die Radionuklide (Co-58, Co-60, Mn-54 etc.) aus der Lösung entfernt. Zeitgleich wird die Methansulfonsäure freigesetzt und steht dem Prozess wieder zur Verfügung. Siehe Gleichungen (8) bis (11).During operation of the ion exchanger IT, the divalent and trivalent cations (Mn-II, Fe-II, Fe-III, Zn-II and Ni-II) as well as the radionuclides (Co-58, Co-60, Mn-54 etc .) removed from the solution. At the same time, the methanesulfonic acid is released and is available to the process again. See equations (8) through (11).
Mn(CH3SO4)2 + H2KIT → 2 CH3SO4H + [Mn2+-KIT] Gleichungen (8)
Ni(CH3SO4)2 + H2KIT → 2 CH3SO4H + [Ni2+-KIT] Gleichungen (9)
Fe(CH3SO4)2 + H2KIT → 2 CH3SO4H + [Fe2+-KIT] Gleichungen (10)
2 Fe(CH3SO4)3 + 3H2KIT → 6 CH3SO4H + [Fe3+-KIT] Gleichungen (11)
Mn (CH 3 SO 4 ) 2 + H 2 KIT → 2 CH 3 SO 4 H + [Mn 2+ -KIT] Equations (8)
Ni (CH 3 SO 4 ) 2 + H 2 KIT → 2 CH 3 SO 4 H + [Ni 2 + - KIT] Equations (9)
Fe (CH 3 SO 4 ) 2 + H 2 KIT → 2 CH 3 SO 4 H + [Fe 2+ -KIT] Equations (10)
2 Fe (CH 3 SO 4 ) 3 + 3H 2 KIT → 6 CH 3 SO 4 H + [Fe 3+ -KIT] Equations (11)
Der Betrieb des Ionenaustauschers IT erfolgt bei einer Prozesstemperatur von ≤ 100°C.The operation of the ion exchanger IT takes place at a process temperature of ≤ 100 ° C.
Der Betrieb des Ionenaustauschers IT erfolgt solange im Bypass, bis alle gelösten Kationen, Anionen und Radionuklide auf dem Ionenaustauscherharz fixiert sind.The operation of the ion exchanger IT is carried out in the bypass until all dissolved cations, anions and radionuclides are fixed on the ion exchange resin.
Entsprechend der vorliegenden Erfindung wird nach erfolgter Ionentauscher-Reinigung der Pypass Kreislauf K2 geschlossen und in den Kreislauf K1 erneut Permangansäure zugegeben. Die zuvor erläuterten Verfahrensschritte werden solange wiederholt, bis kein weiterer Aktivitätsaustrag aus dem zu dekontaminierenden System K1 mehr erfolgt.According to the present invention, after the ion exchanger has been cleaned, the bypass circuit K2 is closed and again permanganic acid is added to the circuit K1. The method steps explained above are repeated until no further activity discharge from the system K1 to be decontaminated takes place.
- HMnO4-Phase = Aufbrechen und Auflösen der Oxidmatrix, Kreislaufbetrieb K1
Methansulfonsäure + Permangansäure - IT-Betrieb = Fixieren der gelösten Kationen und Radionuklide an Ionenaustauscherharze
Kreislaufbetrieb K1 + paralleler Kreislaufbetrieb K2 Methansulfonsäure / Methansulfonate
- HMnO4 phase = break up and dissolution of the oxide matrix, cycle operation K1
Methanesulfonic acid + permanganic acid - IT operation = fixing the dissolved cations and radionuclides to ion exchange resins
Circulation mode K1 + parallel circulation mode K2 Methanesulfonic acid / methanesulfonates
Nach dem Stand der Technik ist es üblich, nach Ablauf der Voroxidation, das überschüssige Permanganat mit Oxalsäure zu reduzieren (Schritt II) und anschließend durch eine Zugabe von weiteren Dekontaminationschemikalien den Dekontaminationsschritt (Schritt III) einzuleiten.According to the prior art, it is customary, after the completion of the pre-oxidation, to reduce the excess permanganate with oxalic acid (step II) and then to initiate the decontamination step (step III) by adding further decontamination chemicals.
Zum Zeitpunkt der Reduktion (Schritt II) befinden sich bei diesen herkömmlichen Verfahren in der Lösung noch sämtliche Inhaltsstoffe des Voroxidationsschrittes (Rest-Permanganat, kolloidales MnO(OH)2, Chromat und Nickel-Permanganat) sowie alle umgewandelten Metall-Oxide auf der System- bzw. Komponentenoberfläche.At the time of the reduction (step II), all the ingredients of the pre-oxidation step (residual permanganate, colloidal MnO (OH) 2 , chromate and nickel permanganate) and all converted metal oxides are present in the system in the conventional solution. or component surface.
Da die Metall-Ionen teilweise in gelöster Form (MnO4 -, CrO4 2-) als auch als leichtlösliche Metalloxide (NiO, FeO, MnO2/MnO(OH)2) vorliegen, treten bereits im Zuge des zweiten Verfahrensschrittes der Reduktion (Schritt II) hohe Kationengehalte in der Lösung auf.Since the metal ions are present partially in dissolved form (MnO 4 - , CrO 4 2- ) and as easily soluble metal oxides (NiO, FeO, MnO 2 / MnO (OH) 2 ), already in the course of the second process step of the reduction ( Step II) high cation contents in the solution.
Zeitgleich entstehen durch die Reduktion des Permanganats, des Chromats und des Braunsteins mit der Oxalsäure große Mengen an CO2 (s. Gleichungen (12 bis 14)). Diese an der Oberfläche ablaufende CO2-Bildung führt zu einer Mobilisierung von Oxidpartikeln, die sich dann in strömungsarmen Zonen des Systems absetzen und dort zu einer Erhöhung der Dosisleistung führen.
2 HMnO4 + 7H2C2O4 → 2 MnC2O4 + 10 CO2 + 8 H2O Gleichung (12)
MnO2 + 2 H2C2O4 → MnC2O4 + 2 CO2 + 2 H2O Gleichung (13)
Cr2O7 2- + 3 H2C2O4 + 8 (H3O)+ → 2 Cr3+ + 6 CO2 + 15 H2O Gleichung (14)
At the same time, the reduction of permanganate, chromate, and manganese dioxide with oxalic acid produces large amounts of CO 2 (see Equations (12 to 14)). This CO 2 formation taking place on the surface leads to a mobilization of oxide particles, which then settle in low-flow zones of the system and lead there to an increase in the dose rate.
2 HMnO 4 + 7H 2 C 2 O 4 → 2 MnC 2 O 4 + 10 CO 2 + 8 H 2 O Equation (12)
MnO 2 + 2 H 2 C 2 O 4 → MnC 2 O 4 + 2 CO 2 + 2 H 2 O Equation (13)
Cr 2 O 7 2- + 3 H 2 C 2 O 4 + 8 (H 3 O) + 2 → Cr 3+ + 6 CO 2 + 15 H 2 O Equation (14)
Die vorstehend beschriebene CO2-Bildung und Freisetzung von Oxidpartikeln tritt bei der vorliegenden Erfindung nicht auf. Die Oxalat-Verbindungen, die aus zweiwertigen Kationen und der Reduktionschemikalie "Oxalsäure" gebildet werden, haben nur eine begrenzte Löslichkeit in Wasser. Je nach der Verfahrenstemperatur liegt die Löslichkeit der zweiwertigen Kationen bei:
Rechnerisch werden bei einer Primärsystemdekontamination bei Einsatz der bisherigen Dekontaminationsverfahren pro Dekontaminationszyklus große Kationenmengen freigesetzt. Dies führt bereits im Reduktions-Schritt zu Oxalat-Ausfällungen auf den Innenflächen der Systeme.Computationally, large quantities of cations are released during a primary system decontamination when using the previous decontamination methods per decontamination cycle. This leads already in the reduction step to oxalate precipitations on the inner surfaces of the systems.
Die oxidischen Schutzschichten eines Primärsystems eines Druckwasserkernkraftwerkes ergeben üblicherweise in Summe ein Gesamtoxidinventar von 1.900 kg bis 2.400 kg [Fe,Cr,Ni-Oxid].The oxidic protective layers of a primary system of a pressurized-water nuclear power plant usually give a total total NOx inventory of 1,900 kg to 2,400 kg [Fe, Cr, Ni oxide].
Bei der Dekontamination eines Primärsystems eines Druckwasserreaktors muss daher mit folgender maximaler Kationenfreisetzung gerechnet werden:
- Chrom → 70
bis 80 kg Cr - Nickel → 100
bis 120 kg Ni - Eisen → 190 bis 210 kg Fe
- Chromium → 70 to 80 kg Cr
- Nickel → 100 to 120 kg Ni
- Iron → 190 to 210 kg Fe
Bei der Primärsystemdekontamination werden üblicherweise 3 Dekontaminationszyklen durchgeführt. Bei einem Gesamtvolumen von ca. 600 m3 und einer gleichmäßigen Verteilung der Kationen über 3 Zyklen ist pro Zyklus mit folgenden Konzentrationen an zweiwertigen Kationen zu rechnen:
- Nickel → 67 ppm Ni
- Eisen → 117 ppm Fe
- Nickel → 67 ppm Ni
- Iron → 117 ppm Fe
Diese Überschlagsrechnung zeigt auf, dass bei allen bisherigen Dekontaminationsverfahren, die zur Reduktion und/oder Dekontamination Oxalsäure einsetzten, eine Fe2+ - und Ni2+- Oxalatbildung nicht vermieden werden kann.This rough calculation shows that in all previous decontamination processes that used oxalic acid for reduction and / or decontamination, Fe 2+ and Ni 2+ oxalate formation can not be avoided.
Liegen, wie zuvor beschrieben, nach Beendigung eines Dekontaminationszyklusses noch Oxalat Reste im System vor, muss im darauffolgenden Zyklus mehr Permanganat eingesetzt werden, wie die Gleichungen (15), (16) zeigen:
3NiC2O4 + 2HMnO4 + H2O 3 NiO + 2MnO(OH)2 + 6CO2 Gleichung (15)
3FeC2O4 + 2HMnO4 + H2O 3 FeO + 2MnO(OH)2 + 6CO2 Gleichung (16)
If, as described above, oxalate residues remain in the system after completion of a decontamination cycle, more permanganate must be used in the subsequent cycle, as shown by Equations (15), (16):
3NiC 2 O 4 + 2HMnO 4 + H 2 O 3 NiO + 2MnO (OH) 2 + 6CO 2 Equation (15)
3FeC 2 O 4 + 2HMnO 4 + H 2 O 3 FeO + 2MnO (OH) 2 + 6CO 2 Equation (16)
Dies führt, ohne dass das Dekontaminationsergebnis verbessert wird, zu einem höheren Permanganatbedarf und daraus resultierend zu einer erhöhten MnO(OH)2 Abscheidung auf den Oberflächen und letztendlich zu einem höheren Anfall an radioaktiven Abfall. Zusätzlichen erhöht sich der Kationeneintrag im Folgezyklus, die Gefahr einer erneuten Oxalatbildung steigt und der Anfall an Ionenaustauscherharzen wird weiter erhöht.This leads, without improving the decontamination result, to a higher permanganate requirement and, as a result, to an increased MnO (OH) 2 deposition on the surfaces and ultimately to a higher accumulation of radioactive waste. In addition, the cation addition increases in the subsequent cycle, the risk of re-oxalate formation increases and the accumulation of ion exchange resins is further increased.
Die bereits gelösten Radionuklide (Co-58, Co-60, Mn-54) werden in die Oxalat-Schicht mit eingebunden. Dies führt zu einer Rekontamination in den Systemen.The already dissolved radionuclides (Co-58, Co-60, Mn-54) are incorporated into the oxalate layer. This leads to a recontamination in the systems.
Wie bereits zuvor beschrieben, liegen entsprechend der vorliegenden Erfindung alle freigesetzten Kationen (Ni-II, Mn-II, Fe-II, Fe-III, Zn-II) sowie das Dichromat in der oxidativen "HMnO4-Phase" der Dekontamination gelöst vor und die Fixierung der Kationen und Anionen erfolgt durch Zuschalten des Bypasses (Kreislauf K2) zeitnah auf Ionenaustauscherharze.As already described above, according to the present invention, all liberated cations (Ni-II, Mn-II, Fe-II, Fe-III, Zn-II) and the dichromate are dissolved in the oxidative "HMnO 4 phase" of decontamination and the fixation of the cations and anions takes place by connecting the bypass (circulation K2) promptly ion exchange resins.
Jedes Kernkraftwerk [DWR, SWR etc.] hat eine eigene spezifische Oxidstruktur, Oxidzusammensetzung, Löseverhalten der Oxide und Oxid-/Aktivitätsinventar. Für die Vorplanung einer Dekontamination können nur Annahmen getroffen werden. Erst im Zuge der Durchführung der Dekontamination zeigt sich dann, ob die vorlaufend getroffenen Annahmen richtig waren.Each nuclear power plant [PWR, SWR, etc.] has its own specific oxide structure, oxide composition, oxide dissolving behavior, and oxide / activity inventory. For the preliminary planning of a decontamination only assumptions can be made. Only in the course of carrying out the decontamination then shows whether the preliminary assumptions were correct.
Ein Dekontaminationskonzept muss daher in der Lage sein, während der Durchführung sich den jeweiligen Veränderungen anzupassen.A decontamination concept must therefore be able to adapt to the respective changes during execution.
Mit vorliegender Erfindung kann gezielt auf alle nur denkbaren neuen Anforderungen reagiert werden. Die zuvor aufgezeigten Detailschritte können je nach Art und Menge des im System vorliegenden Oxid- /Aktivitätsinventars beliebig wiederholt werden.With the present invention, it is possible to respond specifically to all conceivable new requirements. The detailed steps outlined above can be repeated as desired, depending on the type and amount of the oxide / activity inventory present in the system.
Eine Dekontamination, entsprechend der vorliegenden Erfindung, benötigt im Vergleich zu den bisherigen Verfahrenstechniken eine sehr niedrige Chemikalien-Konzentration. Die benötigten Chemikalien-Mengen können daher mit in Kernkraftwerken (KKW) vorhandenen eigenen Dosiersystemen dosiert und die anfallenden Kationen mittels KKW eigenen Reinigungssystemen (Ionenaustauscher) entfernt werden. Große externe Dekontaminationseinrichtungen müssen nicht installiert werden.Decontamination, in accordance with the present invention, requires a very low level of chemicals compared to previous processing techniques. The required quantities of chemicals can therefore be dosed with existing in nuclear power plants (NPP) own dosing and the resulting cations are removed by means of NPP own cleaning systems (ion exchanger). Large external decontamination facilities do not need to be installed.
Durch Steuerung des Gesamtprozesses von der Kraftwerkswarte des Kernkraftwerkes aus können die Prozessparameter schnell den jeweiligen neuen Anforderungen angepasst werden (Chemikaliendosierung, Chemikalienkonzentrationen, Prozesstemperatur, Zeitpunkt der IT-Tauscher-Einbindung, Schrittfolgen etc.).By controlling the overall process from the nuclear power plant's power plant, the process parameters can be quickly adapted to the respective new requirements (chemical dosing, chemical concentrations, process temperature, time of IT exchanger integration, step sequences, etc.).
Die Verfahrensvariationen können bei Bedarf solange durchgeführt werden, bis der gewünschte Aktivitätsaustrag bzw. die gewünschte Dosisleistungsreduktion erzielt wurde.If necessary, the process variations can be carried out until the desired activity output or the desired dose rate reduction has been achieved.
Die in der Lösung vorliegende Methansulfonsäure verbleibt während der Durchführung aller Verfahrensschritte in der Lösung. Die Konzentration wird dabei nicht verändert. Erst am Ende der Gesamtdekontaminationsdurchführung wird die Methansulfonsäure im Zuge der Endreinigung auf Ionenaustauscherharze gebunden.The methanesulfonic acid present in the solution remains in the solution during the performance of all the process steps. The concentration is not changed. Only at the end of the Gesamtdekontaminationsdurchführung the methanesulfonic acid is bound in the course of final cleaning on ion exchange resins.
Weitere Einzelheiten, Vorteile und Merkmale der Erfindung ergeben sich nicht nur aus den Ansprüchen - für sich und/oder in Kombination-, sondern auch sowohl aus den bereits zuvor beschriebenen als auch nachstehend ergänzend erläuterten
Die Figuren zeigen:
- Fig. 1
- der pH-Arbeitsbereich nach der Erfindung im Vergleich zum Stand der Technik,
- Fig. 2
- Änderung der Permangansäure-Konzentration und der Kationen- und Dichromsäure-Konzentration in Abhängigkeit von der Prozessdauer,
- Fig. 3
- Prinzipdarstellung des Dekontaminationskreislaufes (K1) sowie des IT-Reinigungskreislaufs (K2)
- Fig. 1
- the pH working range according to the invention in comparison to the prior art,
- Fig. 2
- Change in permanganic acid concentration and cation and dichromic acid concentration as a function of the duration of the process,
- Fig. 3
- Schematic representation of the decontamination cycle (K1) and of the IT cleaning cycle (K2)
Anhand des Schaubilds in
Die erfindungsgemäße Dekontamination ist rein prinzipiell der
Sodann wird erneut der Lösung, die nicht mehr den Kationenaustauscher durchströmt, entsprechend des zu oxidierenden Cr-3 im Fe,CrNi-Oxidverband erneut Permangansäure zugegeben.Then again the solution, which no longer flows through the cation exchanger, according to the to be oxidized Cr -3 in the Fe, CrNi oxide dressing again added permanganic acid.
Im Verfahrensschritt "HMnO4-Phase" erfolgt chemisch eine Umwandlung der schwer löslichen Fe, Cr, Ni-Struktur in leichter lösliche Oxidformen mittels Permangansäure. Das Lösen der umgewandelten Oxidformen erfolgt mit Methansulfonsäure. Verfahrenstechnisch wird dies in einem Kreislaufbetrieb (Kreislauf K1) (
Claims (10)
- A process for dissolving a chromium, iron, nickel, zinc and radionuclides containing oxide layer, in particular for breaking down oxide layers deposited on inner surfaces of systems and components of a nuclear power plant, by means of an aqueous decontamination solution containing an acid,
characterized in
that the dissolving of the oxide layer takes place in a single treatment step with the aid of an aqueous decontamination solution flowing in a first loop (K1) with methanesulfonic acid as the acid, such that during the entire carrying out of the decontamination methanesulfonic acid remains in the decontamination solution both as a proton donor to adjust the decontamination solution at a pH ≤ 2.5 and as oxide solvent, that the dissolution of chrome-containing oxide layers is done with permanganic acid and that following break-down of the permanganic acid the solution flows, while maintaining the operation of the first loop (K1) via a bypass line in a second loop (K2), through an ion exchanger (IT), in which the present 2- and 3-valent cations and the dissolved radionuclides are fixed, with simultaneous release of methanesulfonic acid. - The process according to claim 1,
characterized in
that in the decontamination solution, a methanesulfonic acid concentration of ≤ 3,500 ppm is set, preferably 500 to 1000 ppm. - The process according to claim 1 or 2,
characterized in
that in the oxidation stage of the decontamination process, during which the decontamination solution flows into the first loop (K1), the permanganic acid is set to a maximum concentration of 200 ppm, preferably 50 ppm. - The process according to at least one of the preceding claims,
characterized in
that the thickness of the oxide layer to be removed is controlled by the amount of permanganic acid used. - The process according to at least one of the preceding claims,
characterized in
that all stages of decontamination are carried out at a temperature between 60 °C and 120 °C, more preferably between 85 °C and 105 °C. - The process according to at least one of the preceding claims,
characterized in
that during flowing of the decontamination solution through the ion exchange resins in the second loop (K2) said methanesulfonic acid is regenerated by removing the Mn-II/Fe-II/Fe-III/Ni-II ions by means of said ion exchange resins. - The process according to preferably at least claim 1,
characterized in
that the oxide layer deposited on the inner surfaces of a coolant loop of a nuclear power plant or its components is oxidized and dissolved in layers by the decontamination solution containing permanganic acid and methanesulfonic acid recirculating in a first loop (K1) so that after complete consumption of said permanganic acid, in further recirculating operation the decontamination solution is recirculated in a second loop (K2) via a bypass through an ion exchanger to bind Fe, Ni, Zn, Mn cations and radionuclides present in the solution so that afterwards said methanesulfonic acid solution is again supplied with permanganic acid so that prior process steps (HMnO4 stage, IT stage) are repeated to an extent until no more discharge of activity (radionuclide release) from the system to be decontaminated (loop K1) is detectable. - The process according to at least claim 1 or claim 7,
characterized in
that at the beginning of breaking down the oxide layer the pH is set by means of methanesulfonic acid and that during breaking down the oxide layer and carrying out further process steps a further addition of methanesulfonic acid is stopped. - The process according to at least claim 1 or claim 7,
characterized in
that the pH is set by means of methanesulfonic acid to a value < 2.5, preferably < 2.2, in particular ≤ 2.0. - The process according to at least claim 1 or claim 7,
characterized in
that a loop or a partial loop thereof of a nuclear installation, in particular a coolant loop or part thereof is used as the first loop (K1).
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AT18822B (en) | 1903-01-19 | 1905-01-10 | Skodawerke Actiengesellschaft | Upper mount for guns with barrel return. |
EP0071336B1 (en) * | 1981-06-17 | 1986-03-26 | Central Electricity Generating Board | Process for the chemical dissolution of oxide deposits |
DE3413868A1 (en) | 1984-04-12 | 1985-10-17 | Kraftwerk Union AG, 4330 Mülheim | METHOD FOR CHEMICAL DECONTAMINATION OF METAL COMPONENTS OF CORE REACTOR PLANTS |
BE904139A (en) | 1986-01-30 | 1986-05-15 | Lemmens Godfried | PROCESS FOR THE DECONTAMINATION OF RADIOACTIVALLY CONTAMINATED MATERIALS. |
US4678552A (en) * | 1986-04-22 | 1987-07-07 | Pennwalt Corporation | Selective electrolytic stripping of metal coatings from base metal substrates |
EP0355628B1 (en) * | 1988-08-24 | 1993-11-10 | Siemens Aktiengesellschaft | Process for chemically decontaminating the surface of a metallic construction element of a nuclear power plant |
FR2648946B1 (en) * | 1989-06-27 | 1994-02-04 | Electricite De France | PROCESS FOR THE DISSOLUTION OF OXIDE DEPOSITED ON A METAL SUBSTRATE AND ITS APPLICATION TO DECONTAMINATION |
FR2699936B1 (en) | 1992-12-24 | 1995-01-27 | Electricite De France | Process for dissolving oxides deposited on a metal substrate. |
DE4410747A1 (en) * | 1994-03-28 | 1995-10-05 | Siemens Ag | Method and device for disposing of a solution containing an organic acid |
DE19818772C2 (en) * | 1998-04-27 | 2000-05-31 | Siemens Ag | Process for reducing the radioactivity of a metal part |
DE102004045297A1 (en) | 2004-09-16 | 2006-03-23 | Basf Ag | A method of treating metallic surfaces using low methane sulfonic acid based formulations |
ES2365417T3 (en) * | 2005-11-29 | 2011-10-04 | Areva Np Gmbh | PROCEDURE FOR DECONTAMINATION OF A SURFACE OF A COMPONENT OR A SYSTEM OF A NUCLEAR INSTALLATION THAT PRESENTS AN OXIDE LAYER. |
DE102009002681A1 (en) * | 2009-02-18 | 2010-09-09 | Areva Np Gmbh | Method for the decontamination of radioactively contaminated surfaces |
JP6009218B2 (en) * | 2011-05-24 | 2016-10-19 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーRohm and Haas Electronic Materials LLC | Alpha particle emitter removal |
-
2013
- 2013-03-08 DE DE102013102331.2A patent/DE102013102331B3/en not_active Expired - Fee Related
-
2014
- 2014-03-07 EP EP14158346.8A patent/EP2787509B1/en active Active
- 2014-03-07 US US14/200,327 patent/US9502146B2/en active Active
- 2014-03-07 ES ES14158346.8T patent/ES2566353T3/en active Active
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102017115122A1 (en) | 2017-07-06 | 2019-01-10 | Framatome Gmbh | Method for decontaminating a metal surface in a nuclear power plant |
DE102017115122B4 (en) | 2017-07-06 | 2019-03-07 | Framatome Gmbh | Method for decontaminating a metal surface in a nuclear power plant |
US11244770B2 (en) | 2017-07-06 | 2022-02-08 | Framatome Gmbh | Method of decontaminating a metal surface in a nuclear power plant |
Also Published As
Publication number | Publication date |
---|---|
DE102013102331B3 (en) | 2014-07-03 |
ES2566353T3 (en) | 2016-04-12 |
EP2787509A1 (en) | 2014-10-08 |
US20140338696A1 (en) | 2014-11-20 |
US9502146B2 (en) | 2016-11-22 |
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