Professional Documents
Culture Documents
Summary
Objectives and selection criteria Full System Decontamination Decontamination of components/parts Conclusions One detail example (BR3 case) in each part
Definition
3 main reasons
To remove the contamination from components to reduce dose level in the installation (save dose during dismantling) To minimize the potential for spreading contamination during decommissioning To reduce the contamination of components to such levels that may be Disposed of at a lower category Recycled or reused in the conventional industry (clearance of material)
Pool, Tank Open system Hydro jet Method Blast Method Strippable coating Method
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Closed system
Decontamination Of Building
Objectives : Reduction of radioactive concrete waste or Release of building Concrete Surface Mechanical Method Scabbler Shaver Blast Method
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Some examples about the type of material Stainless steel: Resistant to corrosion, difficult to treat, needs a strong decontamination process to remove several m Carbon steel: Quite porous and low resistance to corrosion, needs a soft process but the contamination depth reaches several thousand m (more secondary waste) Concrete: The contamination will depend of the location and the history of the material, the contamination depth can be few mm to several cm.
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Some examples about the type of surface Porous: Avoid wet techniques which are penetrant. Coated: Do we have to remove paint ? (contamination level, determinant for the use of electrochemical techniques) Presence of crud: what are the objectives ? (reduce the dose or faciliting the waste evacuation)
Some examples about decontamination factor required Primary circuit of BWR and PWR reactors
Soft decontamination process
DF
1-5 5-50
1-5 m 2-10 m
Outer layer : Fe2O3, Iron rich Intermediate layer (CRUD) : FeCr2O4, Cr2O3, Chromium rich
5 30 m
50-10,000
Some examples about the treatment of secondary waste Availability of a facility to treat secondary waste from decontamination (chemical solutions, aerosols, debris, ) Final products (packaging, decontaminated effluent,) have to be conform for final disposal. In decontamination processes, the final wastes are concentrated, representing a significant radiation source.
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Decontamination Techniques Used in Decommissioning Activities Objectives and selection criteria Full system Decontamination
General consideration Chemical reagents Spent decontamination solutions Guidelines for selecting appropriate FSD The case of BR3 (CORD)
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Application
Decontamination of the primary circuit (RPV,PP, SG and auxiliary circuits) directly after the shutdown of the reactor Decontamination of components in a closed loop
Practical objectives
Remove the crud layer of about 5 to 10 m inside the primary circuit
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Chemical process
Chemical process commonly used
Siemens England Russia Westinghouse EPRI
CORD Chemical Oxidizing Reduction Decontamination based on the used of permanganic acid (AP). LOMI Low Oxidation State Metal Ion (AP) APCE Process based on the use of permanganate in alkaline solution NITROX or CITROX based on the use of nitric or citric acid. EPRI DFD (Decontamination For Decommissioning) based on the use of fluoroborique acid.
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Decontamination step
A dissolution step is carried out with oxalic acid to dissolve the crud layer The reduction / dissolution step is enhanced by complexing agent
Purification step
The excess of oxalic acid is removed using permanganate or hydrogen peroxide The dissolved cations and the activity are removed using Ion Exchange Resins.
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Chemical reagent
MnO4HNO3 HBF4
H2C2O4 oxalates anionic species
CrIII to CrVI
H2O2
Water
The Full System Decontamination of the primary system of the BR3-PWR reactor with the Siemens CORD Process Objectives
Reduce the radiation dose rate by a factor of 10 Remove the surface contamination, the so-called CRUD to avoid dispersion of contamination during dismantling of contaminated loops Minimize the amount of secondary wastes Minimize the radiation exposure of the workers Minimize the modifications to be done to the plant for the decontamination operation.
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Full System Decontamination of the primary and auxiliary loops in 1991 CORD: Chemical Oxidizing-Reducing Decontamination
MnO4-
Step nr 2: Reduction + Decontamination Injection of oxalic acid - Circulation Purification on ion exchange Step nr 3: Cleaning Destruction of organics + purification on ion exchange
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Dose rate before mSv/h 1.74 1.58 0.74 4.40 0.46 0.49 0.47 0.905
Dose rate after mSv/h 0.125 0.16 0.11 1.50 0.15 0.13 0.14 0.05
DF
HOT LEG COLD LEG 1 COLD LEG 2 MAKE UP EJECTOR PRIMARY PUMP 1 PRIMARY PUMP 2 PRESSURIZER STEAM GENERATOR
14 10 7 3 3 4 3.5 16
! In some points, still some hot spots due to redeposition in dead zones 28 horizontal line of the pressurizer, dead zones in heat exchangers..
Radiological aspects
Phase I : Preparatory phase manual closure of the reactor pressure vessel maintenance of the components modifications to the circuits Phase II : Decontamination operation hot run 3 decontamination Cycles Phase III : Post decontamination operations evacuation of the liquid wastes evacuation of the solid wastes
135.3 man*mSv
6.4
man*mSv
16.9 man*mSv
The total dose amounted to only 159 man*mSv The dose saving up to now is over 500 man*mSv
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0.06 mSv/h
Expected ...
Smooth process, minor operational problems Careful and detailed preparation is a must Requires a reactor in full satisfactory conditions To be performed shortly after the operation Man-Sv savings for future dismantling justify the operation
Unexpected ...
More ion exchange resins needed and higher liquid waste volume Pollution of the reactor pool during reactor opening due to the presence of insoluble iron oxalate and loose crud: could be easily removed by the plant filtration Internals of RPV remarkably clean facilitating inspection and dismantling and allowing to evacuate waste in a lower category LAW vs MAW
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Objectives in terms of Decontamination Factor Type of material: Acidic solution is not appropriate for carbon steel Volume of secondary waste: preferred regenerative process (Lomi, DfD, CORD) Composition of secondary waste: avoid organic element like EDTA (Complexing agent) Type of oxide layer: Select an oxidizing process for high chromium content in the CRUD Capability of treatment and conditioning of the secondary waste generated (Evaporation, IEX, Precipitation, filtration)
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Decontamination Techniques Used in Decommissioning Activities Objectives and selection criteria Full system decontamination Decontamination of components/parts
General considerations Chemical decontamination Electrochemical decontamination Mechanical decontamination Decontamination by melting Guidelines for selecting appropriate decontamination techniques The case of BR3 (ZOE - MEDOC)
Conclusions
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Decontamination of components/parts
To reduce the contamination of components to such levels that they may be Disposed of at a lower category decategorization Recycled or reused in the conventional industry (clearance of material) The decontamination can be applied: In a closed system on an isolated component (circuits, steam generator) In an open system on dismantling material in batch treatment.
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Chemical decontamination
Multi-step processes Same processes : Lomi, Cord, Canderem Processes in one single step (Hard decontamination process) Cerium IV process : SODP, REDOX, MEDOC HNO3/HF HBF4 : Decoha, DfD..
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Cerium IV process
The cerium IV process is a one step treatment. The cerium is a strong oxidizing agent (Eo = 1.61 V) in mixture with acid (Nitric acid or Sulfuric acid) The cerium IV dissolves oxide layer and the base metal. Cerium can be regenerated and recycled. The neutralization of cerium IV and the treatment of the solution for final conditioning are simple.
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Cerium IV process
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The MEDOC process has been selected for its high decontamination efficiency
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O2
Ce 3+ Decontamination
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O2
1 Decon. loop
Rinsing loop
O3
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3 waste treatment
<5%
SCK-CEN
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Belgoprocess
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Control room
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7,94 m
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PCV 02
RBS 85
Decontamination step I
Treatment gas Medoc ROV 07
RBS81
R01
ROV 13
RBS83
MEDOC
MS01
RBS 80 ROV 21
T01
ROV 08
ROV 04
T02
ROV 09
ROV 03
HV 02 FLT 01
ROV 17
ROV 18
P02
ROV 16
F01
ROV 19
P05
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Workload
30 decontamination cycles are needed : Decontamination (2 hours) Regeneration of cerium IV (4 hours) After 15 cycles, the SG was rotated for homogenous attack on the primary side. 60 hours decontamination and 130 hours of regeneration about 3 weeks with 2 working teams.
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Conclusions on MEDOC
Contaminated materials are successfully decontaminated using a batchwise technique in MEDOC plant. Up to now, 80% of treated materials have been cleared and sold to a scrap dealer (including primary pipes) Remaining 20% can be cleared after melting (< 1 Bq/g) The loop treatment of the BR3-SG was also a success It will easy the post-operation dismantling (HPWJC), It will avoid the evacuation of huge components in a waste category.
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HNO3/HF processes
The sulfonitric mixture is commonly used for the etching of stainless steel
in batch process in pulverization solution
The liquid penetrates the oxide layer to attack the base metal (thorough decontamination process). The oxides come off the surface and stay in the solution. The oxides are eliminated by filtration.
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HNO3/HF processes
The efficiency increases with the concentration and the temperature. However, it decreases with the increasing of dissolved material. This is not a regenerative process, new HF has to be added to the solution and produces more effluents.
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HNO3/HF processes
Application :
Not very attractive in batch treatment due to the consumption of reagent Good result in pulverisation process at low temperature followed by rinsing with pressurised water jet.
Safety
Need of special attention to the worker safety due to the presence of HF and fluoride.
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Regeneration of HBF4
Inlet solution
Fe + 2 HBF4
Ion Exchange Membrane
Fe(BF4)2 + H2
Fe + 2 BF4 H2
HBF4
Application
Compared to the cerium or sulphonitric process, it is less aggressive (lower rate) Due to the formation of hydrogen in the decontamination and regeneration steps, the process required special safety attention (monitoring, ventilation, dilution with air) The 137Cs which is not deposited has to be eliminated in IEX or by added chemical treatment.
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Electrochemical decontamination
Electrolytic polishing is an anodic dissolution technique Material to be decontaminated is the anode, the cathode being an electrode or the tank itself Objectives :
removed hot spot lowered dose rate decategorisation of material
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Electrochemical decontamination
+
bath with acid or salt High current density at low voltage
Electrolyte
chemical or electrochemical
Application
Electropolishing can be used for the treatment of Carbon steel, Stainless steel, Aluminum Electropolishing requires conducting surfaces (the paint must be removed) Not really adapted for small or complex geometry material with hidden parts (current density inside pipes, )
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Electropolishing
quick processing time reliability less secondary waste maximal recycling effect
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Principle of electropolishing
+
bath with phosphoric acid
before
after
Oxide skin
Base material
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190C
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Electropolishing processes
Electrolyte
Conc M 1
Electrode
Time Hours 2
HNO3
Ti
HNO3
100-300
Basket Ti NC
1-3
16 20
H2SO4
0.5
<1
60-240
Na2SO4
0.5
NC
<1
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Advantages of Electropolishing
Commercially available and relatively inexpensive Large panel of material and geometry (water box of SG, tanks, large pieces,) can be treated with this technique High corrosion rate and quick treatment Low volume of secondary waste.
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Disadvantages of Electropolishing
Electropolishing does not remove fuels, sludge or any insulating material Inside parts of tubes or hidden parts are treated poorly Like chemical processes, secondary liquid waste are generated. This method is less applicable for industrial decontamination of complex geometries:
limited by the size of the batch in immersion process The access to contaminated parts and free space are required when an electrode (pad) is used
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Mechanical decontamination Mechanical decontaminations are often less aggressive than the chemical ones but they are a bit simpler to use. Mechanical and chemical techniques are complementary to achieve good results The two basic disadvantages
The contaminated surface needs to be accessible Many methods produce air bone dust.
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Cleaning with ultrasons Projection of CO2 ice or water ice Pressurized water jet Decontamination with abrasives in wet or dry environment Mechanical action by grinding, polishing, brushing
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The cleaning in ultrasonic batch is only applicable for slightly fixed contamination Does not allow to remove the fixed contamination This technique is used in combination with detergent (Decon 90, ) However, it is mainly used to enhance the corrosion effect in chemical decontamination processes (Medoc,)
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CO2 ice pellets are projected at high speed against the surface The CO2 pellets evaporate and remove the contamination The operator works in ventilated suit inside a ventilated room to remove CO2 and contamination Needs some decontamination tests before selecting the process (not efficient for deep contamination)
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Operator at work
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The air contamination in dry sandblasting is much more important (cross contamination)
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Advantages/Disadvantages abrasive-blasting
Advantages
Effective and commercially available Removes tightly adherent material (paint, oxide layer)
Disadvantages
Produces a large amount of secondary waste (abrasive and dust) Care to introduce the contamination deeper in porous material.
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Large range of abrasive belts or rollers available on the market Ideal to remove small contaminated surface Due to the production of dust, used in a ventilated enclosure, the operator wears protection clothes
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Melting of metals
are eliminated in fumes and dust Heavy elements coming from oxide are eliminated in slag (radioactive waste)
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Melting of metals
Country Carla Studsvik Germany Sweden Capacity 3t 3t Material CS, SS, Al, Cu CS, SS, Al Product Ingot, shield blocks, containers Ingot
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Advantages of melting
Advantages of redistributing of radionuclides in ingots/slag and dust: decontamination effect Essential step when releasing components with complex geometries (allows the measurement after melting)
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Conclusions
Selection criteria of decontamination techniques for metals
The geometry and size of pieces The objectives of the decontamination (dose rate or waste management) The nature and the level of contamination The state of the surface and the type of material The availability of the process
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