Metal Decontamination Techniques used in Decommissioning Activities

Mathieu Ponnet SCKCEN

Summary
Objectives and selection criteria Full System Decontamination Decontamination of components/parts Conclusions One detail example (BR3 case) in each part

Definition

Decontamination is defined as the removal of contamination from surfaces by

Washing Heating Chemical or electrochemical action Mechanical action Others (melting)

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)

Decontamination for decommissioning

In maintenance work, we must avoid any damage to the component for adequate reuse In decommissioning, decontamination techniques can be destructive, the main goal being the removal of as much activity as possible (high DF)

Decontamination before Dismantling

Objectives : Reduction of occupational Exposure

Pipe Line System Decontamination

Pool, Tank Open system Hydro jet Method Blast Method Strippable coating Method
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Closed system

Chemical Method Mechanical method

Decontamination after Dismantling

Objectives : Reduction of radioactive waste or recycling Pipes, Components Open or closed system Chemical Immersion Method Electrochemical Method Blast Method Ultrasonic wave Method Gel Method
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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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Concrete Demolition Explosives Jackhammer Drill &Spalling

Selecting a specific decontamination technique

Need to be considered
Safety: Not increase radiological or classical hazards Efficiency: Sufficient DF to reach the objectives Cost-effectiveness: should not exceed the cost for waste treatment and disposal Waste minimization: should not rise large quantities of waste resulting in added costs, work power and exposure Feasibility of industrialization: Should not be labour intensive, difficult to handle or difficult to automate.

Parameters for the selection of a decontamination process

Type of plant and plant process Operating history of the plant Type of components: pipe, tank Type of material: steel, Zr, concrete Type of surface: rough, porous, coated Type of contaminants: oxide, crud, sludge Composition of the contaminant (activation products, actinides and radionuclide involved) Ease of access to areas/plant, internal or external contaminated surface Decontamination factor required Destination of the components after decontamination Time required for application Capability of treatment and conditioning of the secondary waste generated

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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)

Right decontamination technique

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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

Thorough decontamination process

5 30 m

Base alloy : Fe, Cr, Ni

50-10,000

Right decontamination technique

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Some examples about the type of components

Pipes, tanks, pools

Decontamination in a closed system? (avoids the spreading of contamination) Decontamination in an open system after dismantling? (secondary waste) Connection to the components, dose rate, the total filling up of the component, auxiliary

Right decontamination technique

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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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Overview of decontamination process for metals

Chemical process
In closed system (APCE, TURCO, CORD, SODP, EMMA, LOMI, DFD, Foams or various reagents) In open system on dismantled components (MEDOC, Cerium/nitric acid, CANDEREM, DECOHA, DFDX or various reagents, HNO3, HCl, HF,)

Electrochemical process (open or close system)

Phosphoric acid, Nitric acid, Oxalic or citric acid, sulfuric acid or others process

Physical process (open system)

Wet or dry abrasives, Ultrasonic cleaning, HPW, CO2 ice blasting, others

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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)

Decontamination of components/parts Conclusions

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Full system and closed system Decontamination Objectives

Reduce the dose rate and avoid spreading of contamination during dismantling Typical decontamination factor 5 to 40

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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Multi-step decontamination process

Oxidation step
Oxidation of the insoluble chromium with permanganate in alkaline or acidic media, Nitric acid or fluoroboric acid

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

Oxidizing agent for chromium oxide

CrIII to CrVI

Dissolving agent Minimize secondary waste

CO2 After destruction

H2O2

Destruction agent Minimize secondary waste

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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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with a particular attention to:

The BR3 primary loop

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Full System Decontamination of the primary and auxiliary loops in 1991 CORD: Chemical Oxidizing-Reducing Decontamination

3 Decontamination Cycles at 80 to 100 C in 9 days For each cycle : 3 steps

oxidation step with HMnO4 Reduction step with H2C2O4 Cleaning step with anionic and cationic IEX resins and removal of excess oxalic acid by oxidation with HMnO4 or with H2O2 on catalysts
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Chemistry of the process

Oxidation Step with Permanganic Acid HMnO4 at 0.3 g/l

For the oxidation of the Chromium from Cr3+ to Cr6+ Temperature 100C

Decontamination step with Oxalic Acid H2C2O4 at 3 g/l

Dissolution step for the hematite dissolution and the activity dissolution Temperature 80C to 100C

Cleaning step: Destruction of the excess oxalic acid by oxidation

with permanganic acid or with hydrogen peroxide on a catalyst Combined with fixation of corrosion products on Ion Exchange resins Temperature: 80 to 60C (last cycle)
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Process steps for each cycle

Process Steps Step nr 1: Oxidation Injection of permanganic acid Circulation during several hours Chemicals in solution Ion exchange Resins

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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C2O42Cr, Fe oxalates anionic species

Ni2+, Mn2+, Co2+

Fixation on cationic IEX

Cr, Fe oxalates Water, CO2

Fixation on anionic IEX

Total activity removed for each cycle

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Primary loop Decontamination factors

Component

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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Main data and results

Contaminated surface treated Primary system volume Corrosion products removed Mean Crud layer removed IEX Waste volume produced Final waste volume Dose rate in primary system Dose rate purification system Mean Decontamination factor Collective Dose exposure
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1200 m2 15 33 5 1.35 8 0.08 ~ 10 0.16 man.Sv m3 kg m m3 m3 mSv/h

0.06 mSv/h

Lessons drawn from the operation

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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Guidelines for selecting appropriate FSD

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

T (C) SODP REDOX MEDOC Amb 60-80C 80C

Acid HNO3 HNO3 H2SO4

Regene ration O3 Electrochemical O3

Origin Sweden Japan Belgium

Application Closed loop Open system Open and closed loop

Speed Low High High

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MEDOC process at BR3

The MEDOC process has been selected for its high decontamination efficiency

Objectives Clearance of material

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MEDOC : Only one step treatment

Cerium solution Ce 4+

O2

Contaminated Material Free release

Ozone gas Regeneration of cerium IV

Ce 3+ Decontamination

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BR3 industrial plant is characterized by three stages

O2
1 Decon. loop

Rinsing loop

O3
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3 waste treatment

Effluents are partially treated by SCK and transported to Belgoprocess

10 T 0.3 T
Asphalt Waste 15 kg/m3 total 4 Gbq/m3 Cerium neutralization Nitric acid Ph Neutralization Precipitation Filtration

<5%

SCK-CEN
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Belgoprocess

Medoc workshop after installation

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Control room

43

Safety precautions taken in the MEDOC installation

Due to the combined radioactive and chemical hazards
construction materials selected to resist to the aggressive process unreacted ozone thermally destroyed before release O3 and H2 detectors with automatic actions on the process two independent ventilation systems

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Material after decontamination

45

25 tons of contaminated material have already been treated

Treatment capacity is 0.5 ton per treatment (20 m2) Average corrosion rate 2.5 m/h The treatment time is about 4 to 10 hours Very low residual contamination < 0.1 Bq/g
0,1 0,08

Specific activity of material after decontamination in 200 Liters drums

0,06 0,04 0,02 0

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Steam generator and pressurizer decontamination in May 2002

Main goal
Make the demonstration of large components decontamination using MEDOC Reach the clearance contamination level after melting

7,94 m

Steam generator characteristics (primary loop - SS)

30 tons of mixed stainless and carbon steel Number of tubes 1400 in stainless steel Total length of tubes 15 km Total surface 620 m2 Volume 2.7 m3

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Handling of the SG before decontamination

The SG has been removed and placed horizontally to allow the total filling up of the primary side

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Main circulation loop between SG and MEDOC plant

RBS 87 RBS 86 RBS 84 RBS 82

PCV 02

RBS 85

Decontamination step I
Treatment gas Medoc ROV 07

RBS81

R01

ROV 01 ROV 22 ROV 05

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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Reach the clearance contamination level after melting

10 m or 42 kg of material were removed on the overall surface. 2.06 Gbq of Co60 The tube bundle was manually rinsed via the primary head with pressurized water. Low radiation level in the primary head (few Sv/h) - no free contamination

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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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HBF4 processes Decoha or DfD processes

The fluororic acid is able to dissolve both the oxide layer and the base alloy on stainless or carbon steel This process is used in batch treatment or in pulverization process The fluoroboric acid can be regenerated by electrodeposition of the metal.

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Regeneration of HBF4
Inlet solution

Dissolution reaction (Decontamination)

Cathode (-) Anode (+)

Fe + 2 HBF4
Ion Exchange Membrane

Fe(BF4)2 + H2

Cathodics reactions Fe(BF4)2 + 2e2H+ + 2 e-H+

Fe + 2 BF4 H2

Anodic reaction H2O 2 H+ + 2e- + O2

Metal Particles Outlet solution to filter

Recombination after membrane transfer 2H+ + 2 BF4 57

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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Advantages for chemical decontamination

Chemical decontamination allows the treatment of complex geometry material (hidden parts, inside parts of tubes,) With strong mineral acids, DF over 104 can be reached allowing the clearance of material With proper selection of chemicals, almost all radionuclides may be removed Chemical decontamination is a known practice in many nuclear plants and facilities (experience)

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Disadvantages for chemical decontamination

The main disadvantage is the generation of secondary liquid waste which requires appropriate processes for final treatment and conditioning The safety due to the chemical hazard with high corrosive products (Acid, gas,) and byproducts (H2, HF, ) Chemical decontamination is mostly not effective on porous surfaces
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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

Phosphoric acid Nitric acid Sulfuric acid Sodium sulfate

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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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Special technique at KRB A plant in Gundremmingen

Decontamination of stainless steel parts with phosphoric acid

Electropolishing
quick processing time reliability less secondary waste maximal recycling effect
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Principle of electropolishing
+
bath with phosphoric acid

6000 A at low voltage

before

after

H2PO4 chemical or electrochemical

Oxide skin

Base material

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Stainless Steel in Acid Bath

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Stainless Steel after Electropolishing

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Regeneration of Phosphoric Acid

Recycling of Phosphoric acid by - adding oxalic acid

- precipitate the dissolved iron as - iron oxalate

Reuse acid for decontamination

- extracting the iron oxalate - vaporization

Thermolysis of iron oxalat

- heating the iron oxalate - transformation into iron oxide for final storage
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Schematic principle of Regeneration

Dilute acid to concentrated

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Thermolysis plant for iron oxalate

190C

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Example Secondary Steam Generator

Vessels of three Steam Generators decontaminated from 20,000 Bq/cm to free release producing only 1,5% radioactive waste

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Electropolishing processes

Electrolyte

Conc M 1

Current density A/m2 20-30

Electrode

Time Hours 2

Corrosion rate m/h NC

AEA/ Harwell CEA/ UDIN Toshiba

HNO3

Ti

HNO3

100-300

Basket Ti NC

1-3

16 20

H2SO4

0.5

3000 10000 60C 10006000

72

<1

60-240

Eldecon ABB/ Sweden

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

Handling of components may lead to additional exposure to workers

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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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Typical Mechanical decontamination

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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Cleaning with ultrasons

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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Projection of CO2 ice or water ice

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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Pressurized water jet

Low pressure water Jet : 50 150 bar

Pre-decontamination technique Removal of sludge or deposited oxide Decontamination of tools

Medium pressure water Jet : 150 700 bar

Usually used for the decontamination of equipments or large surfaces (pool walls,) Large water consumption (60 6000 L/h) and contaminated aerosols Requires a suitable ventilation system and a recirculation loop with filtration (recycling of water)

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Decontamination with abrasives

Uses the power of abrasives projected at high speed against the surface Wet environment: fluid transporter is water Dry environment: fluid transporter is air Imperative to ensure the recycling of the abrasive to reduce the secondary waste production Needs a suitable ventilated system to remove contamination and aerosols.
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Abrasives in wet environment at BR3

Roof opening for large pieces

Operator at work

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Abrasives in dry environment

Working in enclosed area

Decontamination (Metal, plastics, concrete) Decoating Cleaning Degreasing

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Abrasives in dry environment at Belgoprocess

Automatic process in batch treatment
Declogging filter (ventilation) Load of material

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Comparison of the wet and dry sandblasting

Choose an abrasive with a long lifetime (recycling)
Minerals (magnetite, sand,) Steel pellets, aluminum oxide Ceramic, glass beads Plastic pellets Natural products

Wet and dry techniques allow to recycle the abrasive by separation

Filtration or decantation in wet sandblasting On declogging filter (ventilation) in dry sandblasting

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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Mechanical action by grinding, polishing, brushing

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

The melting of metal can be considered as a decontamination technique

137Cs

are eliminated in fumes and dust Heavy elements coming from oxide are eliminated in slag (radioactive waste)

The melting technique is used for

The recycling of material in nuclear field (container,..) The clearance of ingots after melting (measurement of activity easier )

87

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)

89

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

90

Needs for decommissioning

For decommissioning we need several complementary techniques
To reduce the dose rate before dismantling FSD To treat materials with complex geometries Chemical decontamination To treat materials with simple geometries Sand blasting or electrochemical decontamination To decontaminate tools or slightly contaminated pieces High pressure jet Manuel cleaning Other mechanical techniques To remove residual hot spot after decontamination Mechanical techniques : grinding, brushing To help in the evacuation route of materials Melting of metals

91