5 avril 2006 - 0 a stabilization process of mineral residue contaminated with heavy metals and...

5 avril 2006 - 1

A STABILIZATION PROCESS OF A STABILIZATION PROCESS OF MINERAL RESIDUE MINERAL RESIDUE CONTAMINATED WITH HEAVY CONTAMINATED WITH HEAVY METALS AND ORGANIC METALS AND ORGANIC COMPOUNDSCOMPOUNDS

G. Depelsenaire – SOLVAY

5 avril 2006 - 2

[ Presentation Outline ][ Presentation Outline ]

1. The Novosol® process

2. Potential applications

3. Process R&D

3.1. The process as applied to fly ash

3.2. The process as applied to polluted river or port sediments

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Step A HEAVY METAL STABILIZATION

Step B ORGANIC COMPOUND DESTRUCTION

1. THE PROCESS

TWO-STEP STABILIZATION OF MINERAL RESIDUE CONTAMINATED WITH HEAVY METALS AND ORGANIC COMPOUNDS

Calcium phosphate formation

Contaminated mineral residue

H3PO4

Step A Step B

by binding to a calcium phosphate ( [Ca3(PO4)2]xH2O ) matrix formed by adding H3PO4

by calcination (650°C - 900°C)

Calories

Organic compound destruction

Usable stabilized mineral residue

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Potential applications

Port and waterway dredging sediments

Fly ash from municipal waste incinerators

Automotive shredder residue

Contaminated soil

Industrial sludge ...

Among these, the following have been so far treated in industrial pilot facilities:

Fly ash from municipal waste incinerators

River sediments

2. POTENTIAL APPLICATIONS

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Research program - Began in 1993, with the Université Libre de Bruxelles (ULB – Professor DERIE) - Continued uninterruptedly since then, in partnership with several research institutes:

* Ecole des Mines d’Albi (F)* Laboratoire des matériaux et de la durabilité des constructions à

Toulouse (F)* BRGM – Orléans (F)* Ecole Centrale de Lille (F)* NJIT (USA)* Laboratoire Central des Ponts et Chaussées – Nantes (F)* EUROVIA (F)* Ecole Nationale de Travaux Publics de l’Etat – Lyon (F)* EEDEMS – Lyon (F)

3. NOVOSOL® PROCESS R&D

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Europe - EP 0883585 B1 (Jan. 12, 2000)

- EP 0899000 B1 (Nov. 3, 2004)

USA - 6 132 355 (Oct. 17, 2000)- 6 254 846 (Jul. 3,

2001)

3.1. THE NOVOSOL® PROCESS AS APPLIED TO FLY ASH3.1.1. Patents

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Incorporation in road-building materials

Sodium-rich residue

WasteFurnace +

boiler Raw flue gasses

FiltrationDust-free gasses Processed gassesFiltration Stack

Sodium bicarbonate

Activated carbon

Flue gas process

Fly ash

Chemical treatmentScrubber solution

Dioxin-free, furan-free solid residue

Grade I landfill site Sodium carbonate production

Scrubbing-------------------------------------

NOVOSOL

H3PO4

Water

Calories

3.1. THE NOVOSOL® PROCESS AS APPLIED TO FLY ASH3.1.2. Study of process and value recovery from products

The REVASOL program: value recovery from flue gas scrubbing residue produced by the sodium bicarbonate-based Neutrec® dry process

Concentrated dioxin-free, furan-free

standardized brineUltimate wastes

REVASOL pilot plant – Dombasle 1999 - 2003

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ADEME - Agence De l'Environnement et de la Maîtrise de l'Energie - Angers BERTIN Technologies - Tarnos BRGM - Bureau de recherches Géologiques et Minières - Orléans EMAC - Ecole des Mines d'Albi/Carmaux - Albi LCPC - Laboratoires Central des Ponts et Chaussées - Nantes Ets. Jean LEFEBVRE - Metz - Dourdan LMDC - Laboratoires des Matériaux et de la Durabilité des Constructions - INSA - Toulouse POLDEN - INSA - Lyon


REVASOL program – Development of partnership studies

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Carried out by BERTIN in 1998 Built by SOLVAY at its Dombasle (Nancy) research centre in 1999 Operated by Solvay

Process developed in 2000 20 metric tons of fly ash treated in the first half of 2001


REVASOL program – Pilot plant process development

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Studies carried out by different research teams from 1998 to 2001 Selected strategies:

Incorporation in concrete

Incorporation in road-building materials Tested strategy: road construction (in juin 2002)

Construction of a ‘test road’ (100 m2) and a ‘control road’ (100 m2) at Dombasle. Their leachates can be collected on impermeable membranes and continuously monitored. Construction of mini pilot units (4 m2) for running accelerated aging tests on road-building materials. Their leachates, also collected on impermeable membranes, have been monitored until June 2003


REVASOL program – Assessment of value recovery strategies

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Test road at Dombasle: placement of the sand-gravel aggregate base course containing 12% treated fly ash (June 2002)

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Test road at Dombasle: placement of the sand-gravel aggregate base course containing 12% treated fly ash (June 2002)

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* cas de percolation contaminée par de la chaux répandue sur la route

After

1 week After

1 month After

4 months After

12 months After

40 months 1

Tank 02.07.02

2 Tank

18.07.02

3 Tank

18.10.02

4 Tank

09.07.03

5 Tank

24.01.06

SEQ*/Ground water,

drinking water production, acceptable

quality pH 6.200 7.400 8.6 ** 7.600 10.6500 8.5 – 9

Conductivity P mg/l

Cl-

µ S/cm

14.385 0.690 4.010

7.053 0.260 1.959

3080.000 0.160

8080.000

3000.000 NM*** 656.000

9830.0000 NM***

3169.0000

400 – 2300 250.000

SO4 mg/l 811.000 763.000 446.000 573.000 734.0000 250.000 As id < 0.001 < 0.001 < 0.001 < 0.001 < 0.0010 0.010 Cd id < 0.005 < 0.050 < 0.050 NM*** < 0.0005 0.005

Cr (total) id 0.080 0.160 0.210 0.100 0.1100 0.050 Ni id < 0.050 < 0.050 < 0.050 NM*** < 0.0050 0.020 Cu id < 0.050 < 0.050 < 0.050 NM*** 0.0090 0.200 Ag id < 0.001 < 0.001 < 0.001 < 0.001 < 0.0010 0.020 Pb id < 0.050 < 0.050 < 0.050 NM*** < 0.0050 0.010 Zn id < 0.050 < 0.050 < 0.050 NM*** 0.0100 5.000

* SEQ = Système d’Evaluation de la Qualité des eaux (France – Agences de l’eau) ** Percolating water was contaminated by lime spilt on the road *** Not measured


Quality of the leach water collected beneath the ‘test’ road

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Patent applied for in October 2000 for processing port and waterway dredging sediments

* European patent EP 1 341 728 B1 (Nov. 23, 2005)

Patent applied for in October 2002 due to technological advances – “NOVOSOL–Foam”

3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS3.2.1. Patents

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Value recovery from stabilized materials

Value recovered as calories for drying or electricity generation

Sediments/Soil cont. 50% H2O

Maturation and drying

bed

H3PO4

Interim storage

Calcination

Site A

Site B

- Interim storage makes for:

* Fast completion of the phosphatation & drying phase

* Extra time for planning the calcination & value recovery phase

* Extra time for selecting the best fuel for the calciner

3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS3.2.2. Novosol foam

Process operating chart

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in mg/kg dry matter

FRANCE GEODE

THE NETHERLANDS – FLANDERS KLASSE 4

BELGIQUE WALLONIA

As 50.00 173.8 50.0 Cd 2.40 6.0 6.0 Cr 180.00 268.6 200.0 Hg 0.80 0.8 1.5 Cu 90.00 126.4 150.0 Ni 74.00 173.8 75.0 Pb 200.00 221.2 250.0 Zn 552.00 1058.6 1200.0

3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS3.2.3. Study of process and value recovery from products

European classification of contaminated sediments17 05 05 * Dredging sludges containing hazardous substancesHeavy metal levels above which sediments are considered hazardous

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Research and doctoral dissertation agreements with:

- Ecole des Mines (Albi-Carmaux, France)- Ecole Centrale (Lille, France)- Ecole Nationale des Travaux Publics (Lyon, France)- Université P. Sabatier (Toulouse, France)

Laboratory research


Process demonstration in pilot units

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Phosphatation mini pilot unit (Capacity: 400 l/h of sediments containing 50% H2O)


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Industrial-scale phosphation pilot unit (designed and realized by Bertin Technologies)

Capacity: 400 l/h of sediments containing 50% H2O

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3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS3.2.3. Study of process and value recovery from productsIndustrial-scale phosphatation and drying demonstration pilot unit at Farciennes (B)

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Mobile industrial-scale calcination pilot unit (designed and realized by Bertin Technologies)

Capacity: 20 t / month of processed sediments


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3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS3.2.3. Study of process and value recovery from productsMobile industrial-scale calcination pilot unit – General view

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Raw sediments Phosphated sediments Calcinated sediments

Composition mg/kg

dry matter

Leaching CH3COOH

0.5 M L/S=20 mg/kg

dry matter

Composition mg/kg

dry matter

Leaching CH3COOH

0.5 M L/S=20 mg/kg

dry matter

Composition mg/kg

dry matter

Leaching CH3COOH

0.5 M L/S=20 mg/kg

dry matter As 7.82 1.200 6.94 4.70 13.00 4.70 Cd 11.50 0.068 11.50 < 0.20 13.00 0.23 Cr 131.00 2.500 129.00 < 0.20 175.00 0.48 Hg 0.89 < 0.001 0.86 0.16 0.35 < 0.10 Cu 100.00 < 0.500 102.00 < 0.20 163.00 0.34 Ni 105.00 18.000 106.00 14.90 165.00 1.45 Pb 680.00 40.000 700.00 < 0.60 981.00 0.98 Zn 3590.00 900.000 3530.00 212.00 4290.00 109.70

TOTAL 4626.21 962.270 4586.30 232.96 5800.35 117.89 Evolution ratio of metals in the

mineral matrix 100 % 99.14% 125%

Metal leaching ratio 20.8 % 5.08 % 2.03 %


Stabilizing performances of the NOVOSOL® process when applied to river sediments in pilot units – Leaching with 0.5M acetic acid

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Raw sediments Phosphated sediments Calcinated sediments

Composition mg/kg

dry matter

Leaching H2O

L/S=10 mg/kg

dry matter

Composition mg/kg

dry matter

Leaching H2O

L/S=10 mg/kg

dry matter

Composition mg/kg

dry matter

Leaching H2O

L/S=10 mg/kg

dry matter As 7.82 0.1670 6.94 0.5980 13.00 0.1980 Cd 11.50 0.0250 11.50 0.0450 13.00 0.0450 Cr 131.00 0.0400 129.00 0.0300 175.00 4.0300 Hg 0.89 0.0006 0.86 0.0008 0.35 0.0004 Cu 100.00 0.1200 102.00 0.1500 163.00 0.2900 Ni 105.00 0.2600 106.00 0.4900 165.00 0.0800 Pb 680.00 0.3400 700.00 0.6500 981.00 0.3600 Zn 3590.00 0.4900 3530.00 0.4500 4290.00 0.2100

Metal leaching ratio 0.03 % 0.05 % 0.09 %


Stabilizing performances of the NOVOSOL® process when applied to river sediments in pilot units – Leaching with water

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Phosphated and calcinated river sediments from pilot units A and B

“Sand/cement road construction material

(base course) containing 40% NOVOSOL

sediments”

Inert material *

Composition mg/kg

dry matter

Lixiviation H2O L/S = 10 mg/kg

dry matter

Lixiviation H2O L/S = 10 en mg/kg

matières sèches

Lixiviation H2O L/S = 10 en mg/kg

matières sèches

Fraction soluble 16720.00 5530.0000 6000.00

As 21.30 < 0.10 < 0.1000 0.50

Cd 8.30 < 0.02 < 0.0200 0.04

Cr 122.50 < 0.05 0.3000 0.50

Hg 0.23 - < 0.0005 0.01

Cu 82.30 < 0.02 < 0.0200 2.00

Ni 70.30 < 0.05 < 0.0500 0.40

Pb 552.30 1.40 0.0500 0.50

Zn 1853.80 0.42 < 0.0500 4.00

* Council Directive 1999/31/EC of 26 April 1999 on the landfill of waste

3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS3.2.3. Study of process and value recovery from productsValue recovery through production of road construction materialsRiver sediment sample treated by the NOVOSOL® process for the ‘test’ road studyRoad construction material sample containing 40% treated river sedimentLeaching results (x30402.2)

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Construction in December 2005 of a test road (100m2) comprising a sand/cement base course prepared with 30% NOVOSOL®-treated river sediments

The environmental impact (analyses of leachate collected beneath the ‘test’ road) and the mechanical performance of this road will be monitored for at least 1 year and 3 years at most.


Value recovery through production of road construction materials

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Detail of membranes


Construction of the ‘test’ road at DombasleBase course (25cm thick) made of cement-stabilized sand containing 30% NOVOSOL®-treated river sediments

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1- spreading and collecting of samples for molding

2- initial compaction with vibrating roller

3- compaction with P1 tires

3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS3.2.3. Study of process and value recovery from productsConstruction of the ‘test’ road at Dombasle

4- final screeding e= 0.25 m

Base course (25cm thick) made of cement-stabilized sand containing 30% NOVOSOL®-treated river sediments

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* cas de percolation contaminée par de la chaux répandue sur la route

Leaching x 30402.2

Samples kept at the laboratory

Road leachates SEQ – Ground water

Drinking water production, acceptable quality

Composition mg/kg

After 7 days

mg/l

After 28 days

mg/l

Obtained after 10 days

mg/l

Obtained after 2 months

mg/l

mg/l

As 20.7 0.015 0.015 0.0008 0.0008 0.010

Cd 13.3 0.020 0.020 0.0010 0.0010 0.005

Cr 120.0 0.020 0.040 0.0020 0.0020 0.050

Hg 0.1 0.001 0.001 0.0001 0.0001 0.001

Cu 73.3 0.020 0.030 0.0030 0.0010 0.200

Ni 63.3 0.030 0.050 0.0050 0.0050 0.020

Pb 500.0 0.005 0.005 0.0070 0.0050 0.010

Zn 1667.0 0.090 0.050 0.0050 0.0050 5.000

* Composition of the material (cement-stabilized sand) - Limestone 0/6 mm 63% - NOVOSOL®-treated sediments 30% - ROC SG hydraulic binder 7%


Value recovery through production of road construction materialsCharacteristics of the material* used to construct the ‘test’ road (cement-stabilized sand comprising 30% NOVOSOL®-treated river sediments)

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Solvay grants access to the NOVOSOL® technology by selling patent licenses for the use of the process.

A separate license is granted for each individual project. Licenses are therefore time-limited and concern a limited geographic area.

3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS3.2.4. Marketing strategy

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OPTION 1 – Production of dried phosphated sediments + landfilling OPTION 2 – Production of sand (1) for reuse in road construction

Investment k€

Cost/tonne (2) €

Annual Cost k€

Investment

k€ Cost/tonne (2)

€ Annual Cost

k€

Novosol A 3500 23.5

for 150000 t : 3525 Novosol A 3500 23.5

for 150000 t : 3525

Landfilling (3) 60 75

for 90000 t (4): 5400 6750

Novosol B 11500 90 80

for 82560 t (5) : 7425 6600

Total

3500 8925 10275

Total (6) 15000 10950 10125

Cost / ton raw sediments 50% H2O

59.5 68.5

73 67.5

3.2. APPLYING THE NOVOSOL PROCESS TO CONTAMINATED SEDIMENTS3.2.4. Marketing elements

Main economic datafor an industrial unit with a treatment capacity of 100 000 m3/year raw sediments50% H2O, representing 150 000 tonnes/year dry material

Assumptions :

(1) Option 2 produces a material described as “Sand” by road manufacrurers

(2) Novosol A : per tonne raw material, excluding the profit margin of the Novosol operator

(3) Current landfilling costs – estimated trend

(4) Landfilled material with a 20% water content

(5) Material with a 10% water content before calcination

(6) Road manufacturer takes the sand at zero cost

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Mineral residues Combustible waste

Sediments with 50 % H2O

Flying ash

Mineral fineshredder residues

Others

Unit APhosphatation - Drying

H3PO4

Unit BCalcination

End product for reuse inroad – brick - concrete

pump

pump

INDUSTRIAL ECOLOGY- NOVOSOL® / FOAM

Gas treatment

Refuse-derivedfuel (RDF)

Dried sludgefrom wastewatertreatment plant

Others

GastreatmentNEUTREC

5 avril 2006 - 0 a stabilization process of mineral residue contaminated with heavy metals and...

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