stabilisation / solidification experience in france

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)


CLASS ICLASS ICLASS I CLASS ICLASS ICLASS IYESYES

NO NO

LEACHING TEST

Hazardous wasteHazardous waste

SOLIDITYCS > 1 MPa and

TS > 0.1 MPa


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 ::



CLASS ICLASS ICLASS I CLASS ICLASS ICLASS I

YESYES

NO NO

LEACHING TEST

Hazardous wasteHazardous waste


TS > 0.1 MPa


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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NAME : Bellegarde UnitCOUNTRY : France (30)OPERATOR : SITA FD

=> A middle size plant Processing capacity : 50.000 tonnes / year

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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

Coulis

Eau traitée

Sulfates boueux

Traitementdes eaux

Digue


Sulfates boueuxCoulis

Fin du traitementdes eaux

Digue


Digue

Coulis

Traitement des sulfates boueux- Excavation,- Traitement,

Remise en place

Sulfates boueux

Aire de transfert


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

stabilisation / solidification experience in france

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