Stabilisation / solidification Stabilisation / solidification experience in France experience in France Starnet 2005 ; 12-13 April 2005
Stabilisation / solidification Stabilisation / solidification
experience in France experience in France
Starnet 2005 ; 12-13 April 2005
12-13 April 2005
IntroductionIntroductionIntroduction
• 1989-a special industrial wastes disposal is closed by the Authority.MONTCHANIN
• 1990 : Parliament report
• 1991 : new regulation for Incineration MSW
• 1991: First draft of European landfill Directive
• 1992: New regulation for HW landfill
• NIMBY process in development within population
• Transparency and political strategy is required by citizens
• A lack of storage capacity for hazardous wastes is planned
• Threshold limits values for admission wastes
• Ultimate waste + Pretreatment of waste before landfilling
Evolution Evolution of French of French political strategy concerning waste political strategy concerning waste management management
Development Development by main by main industrial industrial groups of groups of waste pretreatmentwaste pretreatmentprocesses processes ::
Creation of Inertec (SITA and Bachy Soletanche) in 1992 for development of specialised processes for HW
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INERTEC presentationINERTEC presentation
Soletanche Bachy GroupGround Technologies
Soletanche Bachy GroupGround Technologies
SITA GroupEnvironmentSITA GroupEnvironment
INERTECINERTEC50% 50%
ShareholdersShareholders
Since 1992, INERTEC has developed a new concept for waste processing particularly via its stabilisation / solidification processes, its adapted chemical formulae and specific engineering techniques.
INERTEC have develop 3 main knowledge :
The chemistry of the solid industrial waste,Capacity to design and adapt physico-chemical processing,Capacity to build up and run these treatments.
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InertizationInertization purposepurpose
Improve waste management and landfill security
French regulations (1992)
Classification of wasteSeparation of hazardous / non hazardous waste
Landfill regulationsAdaptation type of waste / type of landfill
Inertization in order to improve waste behaviour :Improve chemical fixation of pollutantReduce waste toxicityImprove mechanical characteristicsTransform waste into stable products
Application : 1995 or 1998, depending on waste type
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TO BE TREATED(INERTIZATION)
TO BE TREATED(INERTIZATION)
CLASS ICLASS ICLASS I CLASS ICLASS ICLASS IYESYES
NO NO
LEACHING TEST
Hazardous wasteHazardous waste
SOLIDITYCS > 1 MPa and
TS > 0.1 MPa
SOLIDITYCS > 1 MPa and
TS > 0.1 MPa
NOYES
(NON MONOLITHIC WASTE)(MONOLITHIC WASTE)
LEACHING TEST
Limit values Limit valuesSolubles < 10 %Phenol I < 100 mg/kgCOD < 2000 mg/kgCr 6+ < 5 mg/kgCr < 50 mg/kgPb < 50 mg/kgZn < 250 mg/kgCd < 25 mg/kgCN < 5 mg/kgNi < 50 mg/kgAs < 10 mg/kgHg < 5 mg/kg
Monolithic sampleØ 4 cm x 8 cm
Crushed wasteto 4 mm
HW HW landfilllandfill : admission : admission criteriacriteria(French (French regulationregulation 18/12/92 18/12/92 andand 18/02/94)18/02/94)
NF X 31-211standard
NF X 31-210 standard
Solubles < 10 %Phenol I < 100 mg/kgCOD < 2000 mg/kgCr 6+ < 5 mg/kgCr < 50 mg/kgPb < 50 mg/kgZn < 250 mg/kgCd < 25 mg/kgCN < 5 mg/kgNi < 50 mg/kgAs < 10 mg/kgHg < 5 mg/kg
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(French transcription 30/12/02)(French transcription 30/12/02)European landfill European landfill directivedirective
Same principle Same principle : : landfill landfill type // type // wastewaste classificationclassificationSlight Slight modifications in admission modifications in admission thresholds thresholds ::
TO BE TREATED(INERTIZATION)
TO BE TREATED(INERTIZATION)
CLASS ICLASS ICLASS I CLASS ICLASS ICLASS I
YESYES
NO NO
LEACHING TEST
Hazardous wasteHazardous waste
SOLIDITYCS > 1 MPa and
TS > 0.1 MPa
SOLIDITYCS > 1 MPa and
TS > 0.1 MPa
NOYES
(NON MONOLITHIC WASTE)(MONOLITHIC WASTE)
LEACHING TEST
Limit values Limit values
Monolithic sampleØ 4 cm x 8 cm
Crushed wasteto 4 mm
NF X 31-211standard
EN 12-457 - 2 standard
As < 25 mg/kg DMBa < 300 mg/kg DMCd < 5 mg/kg DMTotal Cr < 70 mg/kg DMCu < 100 mg/kg DMHg < 2 mg/kg DMMo < 30 mg/kg DMNi < 40 mg/kg DMPb < 50 mg/kg DMSb < 5 mg/kg DMSe < 7 mg/kg DMZn < 200 mg/kg DMTDS < 10 % DMTOC < 1000 mg/kg DMFluoride < 500 mg/kg DM
As < 25 mg/kg DMBa < 300 mg/kg DMCd < 5 mg/kg DMTotal Cr < 70 mg/kg DMCu < 100 mg/kg DMHg < 2 mg/kg DMMo < 30 mg/kg DMNi < 40 mg/kg DMPb < 50 mg/kg DMSb < 5 mg/kg DMSe < 7 mg/kg DMZn < 200 mg/kg DMTDS < 10 % DMTOC < 1000 mg/kg DMFluoride < 500 mg/kg DM
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INERTIZATION : SEVERAL PROCESSESINERTIZATION : SEVERAL PROCESSES
Three main types :
Transformation of pollutantsin chemically stable compounds in a durable matrix.Water washing, extraction.Washing, extraction andtransformation.
Transformation of pollutantsin chemically stable compounds in a durable matrix.Water washing, extraction.Washing, extraction andtransformation.
Low temperature treatment :- hydraulic binders / mineral binders,- washing / extraction,- combined processes
Encapsulation :- asphalts, plastics
Encapsulation of waste in asphalt or plastic.
Encapsulation of waste in asphalt or plastic.
High temperature treatment :- vitrification- ceramization
High temperature treatments by waste melting
High temperature treatments by waste melting
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Inertization Inertization treatment : choice criteriatreatment : choice criteria
Main goal = comply with regulation
• Decrease pollutant solubility,
• Retention of pollutants,
• Inprove physical characteristics of waste
Additionnal criteria
• Optimised treatment cost, acceptable by industry and collectivity
• No pollution transfer (no water discharge),
• Long term effect.
Choice of cold treatment, with hydraulic binders addition
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Inertization Inertization principlesprinciples
Physico-chemical treatment in several steps
StabilisationTransformation of pollutantsby chemical reactions to obtain :
very low solubility productsimmobilize these products in the matrix.
SolidificationFormation of initial waste intoa solid and monolithic product :
high mechanical propertiesvery low permeability
Hazardous waste : release of pollutants in water
Waste after treatment : stable and solid waste
+ First separation step if needed
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INERTEC INERTEC processesprocesses : Stabilisation / solidification: Stabilisation / solidification
Hydraulic binders :for solidification + properties in pollutant chemical fixation...
Soluble anionsComplex formation with aluminium phase (C3A)Adsorption on CSH surface
Example : diffusion coefficient measured on inertized MSWI fly ash 10 -12 m2/s
Metallic pollutantsComplex formation with aluminium phase (C3A)Substitution in CSH crystalsPrecipitate formation (hydroxides, iron and calcium salts…).
… Completed with chemical reagents
For pollutant fixationoxidising agents, reducing agents, complexing agents, selective adsorbing agents, precipitating agents …
For final product consistencyrheology, setting time ...
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Treatment developmentTreatment development
11
22
Three phases aregenerally necessary :
1. Laboratory Study- characterisation / analysis of waste,- development of specific formula.
2. Test- test of treatment process on real scaleon industrial prototype,- number of cycles and formulafor optimum treatment.
3. Operations- mobilisation of necessary equipment,- design and start-up- checking of final product.
33
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Inertization Inertization process adaptationprocess adaptation
Process development according Process development according to :to :
Waste type and composition
Waste variability
Admission criteria for storage
Inertization efficiency (abatement coefficient…)
Reagent availability
INERTECDATABASE
EVALUATION
NEWWASTE
Characterisation
Preliminaryformulation
Objectives
Adjustedformulations
Industrialscale
Long term behaviour : tests, analysis...
Organisation chart :Organisation chart :
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ExampleExample of flue of flue gas cleaning gas cleaning in MSWIin MSWI
Flue gas
Gasscrubbing
Water +reagents
(lime,soda...)
Polluted water
Cleaned water
Filter cake10%
Fly ashes90%
Filter
Flue gas afterdust removal
Cleaned flue gas
Water treatment
Possible recycling(ex : Ludres)
Flue gasFly ashes
Neutralisation productsExcess reagents
Cleanedflue gas
Water(semi-dry process)
Reagents(lime, bicar...)
Reactor
Filter
Wet type :• without liquid recycling• with liquid recycling
Process :• dry (lime, bicar) • semi-dry (dry lime, lime slurry)
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MSWI MSWI fly ash characterisationfly ash characterisation
Composition :Soluble salts (chlorides, sulphates..)Heavy metals (lead, zinc...) up to several %“Inert” compounds (silica, alumina, lime…)
Physical properties :Fine particles (< 100 µm)Low density (0.4 < bulk density < 0.6)Hygroscopic material (salts, excess lime content…)
Soluble compounds :Salts (chlorides, sulphates..) up to 70 %Lead, Zinc, Cadmium, Chromium...
And variability withAnd variability with time : time : exampleexampleVariability of soluble salt content
0
5000
10000
15000
20000
25000
30000
35000
40000
03-avr-95 12-juil-95 20-oct-95 28-janv-96 07-mai-96 15-août-96
Sampling date
Con
d. µ
S/cm
Average
Incinerated waste
Incineration running (tonnage/capacity, temperature…)
Flue gas cleaning (neutralisation reagent quantity, temperature, filtration…)
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Results Results on inertized MSWI on inertized MSWI fly ashfly ashLeaching test results before / after treatment
0
500
1000
1500
Pb (mg/kg)
Before After Before After
Before After Before AfterBefore After
Results checking after treament Results checking after treament
0
50
100
Solubles (%)
0
5
10
Cr (mg/kg)
0
200
400
600
Cd (mg/kg)
0
5000
10000
Zn (mg/kg)
0
5
10
15
Compressive strength (MPa)
Before After
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Type of hazardous wasteType of hazardous waste
From various types of industrial activities :incineration plants : municipal solid waste incineration, hospital waste incineration, industrial waste incineration...metallurgy : dusts, sludge, slags,chemical industries : used catalysts, sludge,polluted soils
= Various polluting compoundsvery soluble compounds : chlorides, sulphates, fluorides...heavy metals : lead, zinc, cadmium, nickel, chromium...organic compounds : hydrocarbons, phenols, PAH, PCB...chromium VI, arsenic, mercury, cyanides..
Adaptation of specific inertization processes : more than 1500 for INERTEC since 10 years
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VilleparisisVilleparisis LaimontLaimont
VaivreVaivre
JeandelaincourtJeandelaincourt
DrambonDrambon
BellegardeBellegarde
ChampteusseChampteusse / / BaconneBaconne
HW treatment before landfillingHW HW treatment treatment before landfillingbefore landfilling
GraulhetGraulhet
St Cyr des St Cyr des GâtsGâts
LavalLaval
ArgencesArgences
Tourville Tourville la la RiviRivièèrereLimayLimay
13 industrial units
Location : HW landfills
Opening date : 1995 (to 2002)
Globaltreatment capacity :
~ 600.000 tons / year
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Treatment unit, global scheme
Type of waste:
- Fly ash- Industrial
sludge,- Chemical
waste,- Metallurgical
waste,- Polluted soil
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Example of industrial applicationExample of industrial application
NAME : Villeparisis UnitCOUNTRY : France (77)OPERATOR : France Déchets
=> The largest in EuropeProcessing capacity : 100.000 tonnes / year
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Example of industrial applicationExample of industrial application
NAME : Bellegarde UnitCOUNTRY : France (30)OPERATOR : SITA FD
=> A middle size plant Processing capacity : 50.000 tonnes / year
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Example of industrial applicationExample of industrial application
NAME : Laimont UnitCOUNTRY : France (55)OPERATOR : DECTRA
=> A smaller oneProcessing capacity : 20.000 tonnes / year
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PRINCIPLE OF A HW DISPOSALPRINCIPLE OF A HW DISPOSAL
Sampling on production site
Preliminary analyses
Controls / admission on
landfill siteDisposal
Treatment validation
Inertization
treatment
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Use of S/S in polluted site remediationUse of S/S in polluted site remediation
In some cases, not possible to treat on a collective plant :
Necessity of a pretreatmentHigh volumesToxicity or conditioningCost
Goal :to propose tailoredand comprehensiveon-site operations.
INERTEC's services include several phases :• Initial studies,• Preparation (sorting, crushing), excavation,• Internal or external storage,• Stabilisation / solidification,• Removal to collective processing sites,• Etc.
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ON SITE WASTE TREATMENT : PRINCIPLEON SITE WASTE TREATMENT : PRINCIPLE
Sampling on production site
Preliminary analyses
Treatment validation
On site inertization treatment
Lab controls / admission
process with the
administration
Pilot test(if needed)
Internalor external disposal
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MYRIADNorth of France - 1999
Treatment of an acid salt dumpTreatment of an acid salt dump
In 7 months, processing of :- 28.700 tonnes of solid residues,- 6.000 m3 of acidic waters.
Rehabilitation of a dump containing acid and soluble residues :
in situ stabilisation treatment.
Extraction and treatment of acidic water
Screening and processing of residues
Reorganisationof the site
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MYRIADNorth of France - 1999
Treatment of an acid salt dumpTreatment of an acid salt dump
1- Extraction / treatment of acid waters to neutralise them,2- Excavation, sifting and treatment of the sulphate residues3- Put back in place and compactage of the treated residues by successive coats, reorganisation of the site
Initial siteProblematic : Various residues under various forms= necessity to create a dike to allow the separation and the simultaneous treatment of the residues :
Sulfates cristallisés
Sulfatesboueux Acid waters
Eau
Sulfates cristallisésSulfates
Sulfates boueuxSulfates boueux
Eauet sulfates boueux
Transfert des eaux et des sulfatessous forme boueuse
Digue
Eau
Sulfates cristallisés
Sulfates
Coulis
Eau traitée
Sulfates boueux
Traitementdes eaux
Digue
Sulfates cristallisésSulfates
Sulfates boueuxCoulis
Fin du traitementdes eaux
Digue
Sulfates cristallisésSulfates
Digue
Coulis
Traitement des sulfates boueux- Excavation,- Traitement,
Remise en place
Sulfates boueux
Aire de transfert
Sulfates cristallisés
Sulfates
Coulis
Traitement des sulfates- Excavation,- Traitement,
- Remise en place
Sulfates
Aire de transfertSulfates traités
Digue
Réaménagement final :coupe de principe
Coulis = 6.000 m3
Remblai
Terre végétale 0,5 m
1 m
4 à 5 m
Sulfates traités = 28.075 tonnes
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MOUTIERSFrance - 1999/2000
Treatment of an arsenic dumpTreatment of an arsenic dump
Replacement33Excavation11
Treatment22
Different problems :General principle : Rehabilitation of an old arsenic residue dump
- 100.000 tons of arsenic residues,- Mechanical stability of deposits,- Risks linked to presence of NaK.
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Treatment of an arsenic dumpTreatment of an arsenic dump
Initial site
May 2000
November 2000
final viewJune 2001
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In situ treatmentIn situ treatmentPetroleum waste treatment
- France - 2001 - 2002Sometimes its better not to excavate the waste for chemical and technical reason
Analysis, design and administrative file Operation : treatment and controlsA quiet efficient technique for lagoon and sludge deposit without smell or gas emission.
1) Installation 2) Starting 3) Stabilisation in situ
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CCI Brest CCI Brest –– 2001 2001 –– Stabilisation and PRBStabilisation and PRB
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Slurry wall
Stabilisation Filtering gates
Brest : Brest : generalgeneral viewview of of thethe workwork sitesite
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Hydrocarbon sludge lagoonHydrocarbon sludge lagoonTOTALFINAELF -Refinery - France2002
TREATMENT PHASING :
1) WATER PUMPING AND TREATMENT2) MOBILISATION OF THE REAGENT PRODUCTION UNIT3) FIRST LINE OF IN SITU STABILISATION4) QUALITY CONTROL CHECK5) SECOND LIN OF IN SITU STABILISATION,ETC6) RE-COVERING7) RE-USE OF THE SITE
1 2 3
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-- REMEDIATION WORKS REMEDIATION WORKS --SEVERAL REFERENCESSEVERAL REFERENCES……
1997 : Avranches (50) - France-> Demolition, crushingand stabilisation of concrete polluted with CrVI-> Quantity = 120 tons
1999-2000 : Moutiers (73) - France-> Rehabilitation of a sitepolluted with arsenic,-> Quantity = 100.000 tons
1998-1999 : Maubeuge (59) - France-> In situ treatment / rehabilitation ofan area of water polluted with iron sulphate-> Quantity = 30.000 tons
1999 : Brussels (Berlaymont Complex) - Belgium-> Processing of cladding contaminatedwith asbestos before dismantlingwithout any containment
1997 : Nangis (77) - France-> Processing of oil drilling residuewith high hydrocarbon content-> Quantity = 200 m3
1996 : Port du Dragon (59) - France-> Stabilisation of dredging sludge polluted with heavy metalsand organic compounds-> Quantity = 2.000 m3
1996 : Miramas (13) - France-> Stabilisation of sludge with high mercury content-> Quantity = 40 tons
1996 : Caen (14) - France-> Bottom ash stabilisation and valorisation in quarry backfilling-> Quantity = 40.000m3
1996 : La Voulte (07) - France-> Stabilisation ofsoils polluted with PAH-> Quantity = 650 tons
1994-1995 : Ayshire - United Kingdom-> Treatment of acidic soilspolluted by heavy metals-> Quantity = 2.000 m3
ArsenicArsenic AsbestosAsbestos Iron Iron sulfatesulfate
Chromium VIChromium VI HydrocarbonHydrocarbon Heavy metalsHeavy metals+ Organic + Organic compoundscompounds
MercuryMercury
Bottom ash Bottom ash valorisationvalorisation
P.A.H.P.A.H. Heavy metalsHeavy metals
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CurrentCurrent developmentsdevelopments
New New processesprocesses developmentdevelopment or or improvementsimprovements
Life cycle Life cycle analysisanalysis of S/S of S/S technologytechnology
DevelopmentDevelopment andand acknowledgementacknowledgement of of sharedshared assessmentassessmenttoolstools (ENV12920 standard) to (ENV12920 standard) to validatevalidate long long termterm behaviorbehaviorandand durabilitydurability of s/s of s/s materialsmaterials
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S/S for waste valorisation : S/S for waste valorisation : CaenCaen (1996)(1996)
Stabilisation : 40,000 tof MSWI bottom ashesFilling : 40,000 m3 of mortar
Stabilisation of MSWI bottom ashes and valorisation for
quarry filling.
Quarry
Mortarpump
Bottomashes
Stabilisation unit
Waterlight storage
Metal removal and screening
Bottomashes
Stabilisedmortar
Controls
Filled Quarry
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Experience of Experience of CaenCaen (1996(1996--1997)1997)
Impact study with ADEME (ENV 12920)
First iteration :First iteration :Description of the scenario,Characterisation of materials,Long term leaching tests,Evaluation of the impact of a quarry filled on the water table,Instrumentation on site for validation.
Following steps :Following steps :More precise study of the parameters of the scenario,Numeric modelling of the impact,Adjustment of the model with the data of the site.
Follow up since 1996 No Follow up since 1996 No signifiantsignifiant impactimpact
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ConclusionsConclusions
A proved technology since 1995.
- Treatment of 3 M tons since 1995 including about 60% of FGC residues, - Positive results on long term behaviour
Exportation of French technology, which is demonstrating its validity.
- Spain and Portugal, - Projects in Mexico, Czech Rep, Middle East...
If recycling not possible, BDAT
- Best ratio quality / price, - Adaptability and traceability
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Challenges for Challenges for thethe comingcoming yearsyears
Development of contaminated site remediation
Acknowledgement of shared methodology to validate proposed solutions :Durability, long term behavior, ecocompatibility…
Development of waste valorisation
- Development of civil engineering materials with some waste- Acknowledgement of shared methodology to validate new materials
Relying on large industrial experiences and a lot of existing tools…
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The entire INERTEC team is at your service :
Technical Departments :6, rue de Watford
F - 92000 NANTERRETel.: +33 1 47 76 55 70Fax: +33 1 46 92 03 65
P. De P. De RochebouRochebouëëttDirectorDirectorEE--mail: mail: [email protected]@inertec.fr
M.C. M.C. MagniMagniééAssistant managerAssistant managerEE--mail: mail: [email protected]@inertec.fr
Web siteWeb sitewww.inertec.frwww.inertec.fr