1. 5 avril 2006 - 0 A STABILIZATION PROCESS OF MINERAL RESIDUE CONTAMINATED WITH HEAVY METALS AND ORGANIC COMPOUNDS G. Depelsenaire – SOLVAY

2. 5 avril 2006 - 1 [ 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

3. 5 avril 2006 - 2 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 H 3 PO 4 Step AStep B by binding to a calcium phosphate ( [Ca 3 (PO 4 ) 2 ]xH 2 O ) matrix formed by adding H 3 PO 4 by calcination (650°C - 900°C) Calories Organic compound destruction Usable stabilized mineral residue

4. 5 avril 2006 - 3  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

5. 5 avril 2006 - 4 u 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

6. 5 avril 2006 - 5 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 ASH 3.1.1. Patents

7. 5 avril 2006 - 6 Incorporation in road-building materials Sodium-rich residue Waste Furnace + boiler Raw flue gasses Filtration Dust-free gasses Processed gasses Filtration Stack Sodium bicarbonate Activated carbon Flue gas process Fly ash Chemical treatment Scrubber solution Dioxin-free, furan-free solid residue Grade I landfill siteSodium carbonate production Scrubbing ------------------------------------- NOVOSOL H 3 PO 4 Water Calories 3.1. THE NOVOSOL ® PROCESS AS APPLIED TO FLY ASH 3.1.2. 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 brine Ultimate wastes REVASOL pilot plant – Dombasle 1999 - 2003

8. 5 avril 2006 - 7  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 3.1. THE NOVOSOL ® PROCESS AS APPLIED TO FLY ASH 3.1.2. Study of process and value recovery from products REVASOL program – Development of partnership studies

9. 5 avril 2006 - 8  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 3.1. THE NOVOSOL ® PROCESS AS APPLIED TO FLY ASH 3.1.2. Study of process and value recovery from products REVASOL program – Pilot plant process development

10. 5 avril 2006 - 9  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 m 2 ) and a ‘control road’ (100 m 2 ) at Dombasle. Their leachates can be collected on impermeable membranes and continuously monitored. Construction of mini pilot units (4 m 2 ) for running accelerated aging tests on road-building materials. Their leachates, also collected on impermeable membranes, have been monitored until June 2003 3.1. THE NOVOSOL ® PROCESS AS APPLIED TO FLY ASH 3.1.2. Study of process and value recovery from products REVASOL program – Assessment of value recovery strategies

11. 5 avril 2006 - 10 3.1. THE NOVOSOL ® PROCESS AS APPLIED TO FLY ASH 3.1.2. Study of process and value recovery from products Test road at Dombasle: placement of the sand-gravel aggregate base course containing 12% treated fly ash (June 2002)

12. 5 avril 2006 - 11 3.1. THE NOVOSOL ® PROCESS AS APPLIED TO FLY ASH 3.1.2. Study of process and value recovery from products Test road at Dombasle: placement of the sand-gravel aggregate base course containing 12% treated fly ash (June 2002)

13. 5 avril 2006 - 12 * cas de percolation contaminée par de la chaux répandue sur la route 3.1. THE NOVOSOL ® PROCESS AS APPLIED TO FLY ASH 3.1.2. Study of process and value recovery from products Quality of the leach water collected beneath the ‘test’ road

14. 5 avril 2006 - 13  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 SEDIMENTS 3.2.1. Patents

15. 5 avril 2006 - 14 Value recovery from stabilized materials Value recovered as calories for drying or electricity generation Sediments/Soil cont. 50% H 2 O Maturation and drying bed H 3 PO 4 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 SEDIMENTS 3.2.2. Novosol foam Process operating chart

16. 5 avril 2006 - 15 3.2. THE NOVOSOL ® PROCESS AS APPLIED TO POLLUTED SEDIMENTS 3.2.3. Study of process and value recovery from products European classification of contaminated sediments 17 05 05 * Dredging sludges containing hazardous substances Heavy metal levels above which sediments are considered hazardous

17. 5 avril 2006 - 16 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 3.2. THE NOVOSOL ® PROCESS AS APPLIED TO POLLUTED SEDIMENTS 3.2.3. Study of process and value recovery from products Process demonstration in pilot units

18. 5 avril 2006 - 17  Phosphatation mini pilot unit (Capacity: 400 l/h of sediments containing 50% H 2 O) 3.2. THE NOVOSOL ® PROCESS AS APPLIED TO POLLUTED SEDIMENTS 3.2.3. Study of process and value recovery from products

19. 5 avril 2006 - 18 3.2. THE NOVOSOL ® PROCESS AS APPLIED TO POLLUTED SEDIMENTS 3.2.3. Study of process and value recovery from products Industrial-scale phosphation pilot unit (designed and realized by Bertin Technologies) Capacity: 400 l/h of sediments containing 50% H 2 O

20. 5 avril 2006 - 19 3.2. THE NOVOSOL ® PROCESS AS APPLIED TO POLLUTED SEDIMENTS 3.2.3. Study of process and value recovery from products Industrial-scale phosphatation and drying demonstration pilot unit at Farciennes (B)

21. 5 avril 2006 - 20 Mobile industrial-scale calcination pilot unit (designed and realized by Bertin Technologies) Capacity: 20 t / month of processed sediments 3.2. THE NOVOSOL ® PROCESS AS APPLIED TO POLLUTED SEDIMENTS 3.2.3. Study of process and value recovery from products

22. 5 avril 2006 - 21 3.2. THE NOVOSOL ® PROCESS AS APPLIED TO POLLUTED SEDIMENTS 3.2.3. Study of process and value recovery from products Mobile industrial-scale calcination pilot unit – General view

23. 5 avril 2006 - 22 3.2. THE NOVOSOL ® PROCESS AS APPLIED TO POLLUTED SEDIMENTS 3.2.3. Study of process and value recovery from products Stabilizing performances of the NOVOSOL ® process when applied to river sediments in pilot units – Leaching with 0.5M acetic acid

24. 5 avril 2006 - 23 3.2. THE NOVOSOL ® PROCESS AS APPLIED TO POLLUTED SEDIMENTS 3.2.3. Study of process and value recovery from products Stabilizing performances of the NOVOSOL ® process when applied to river sediments in pilot units – Leaching with water

25. 5 avril 2006 - 24 3.2. THE NOVOSOL ® PROCESS AS APPLIED TO POLLUTED SEDIMENTS 3.2.3. Study of process and value recovery from products Value recovery through production of road construction materials River sediment sample treated by the NOVOSOL ® process for the ‘test’ road study Road construction material sample containing 40% treated river sediment Leaching results (x30402.2)

26. 5 avril 2006 - 25  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. 3.2. THE NOVOSOL ® PROCESS AS APPLIED TO POLLUTED SEDIMENTS 3.2.3. Study of process and value recovery from products Value recovery through production of road construction materials

27. 5 avril 2006 - 26 Detail of membranes 3.2. THE NOVOSOL ® PROCESS AS APPLIED TO POLLUTED SEDIMENTS 3.2.3. Study of process and value recovery from products Construction of the ‘test’ road at Dombasle Base course (25cm thick) made of cement-stabilized sand containing 30% NOVOSOL ® -treated river sediments

28. 5 avril 2006 - 27 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 SEDIMENTS 3.2.3. Study of process and value recovery from products Construction 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

29. 5 avril 2006 - 28 * cas de percolation contaminée par de la chaux répandue sur la route * Composition of the material (cement-stabilized sand) - Limestone 0/6 mm63% - NOVOSOL®-treated sediments30% - ROC SG hydraulic binder7% 3.2. THE NOVOSOL ® PROCESS AS APPLIED TO POLLUTED SEDIMENTS 3.2.3. Study of process and value recovery from products Value recovery through production of road construction materials Characteristics of the material* used to construct the ‘test’ road (cement-stabilized sand comprising 30% NOVOSOL ® -treated river sediments)

30. 5 avril 2006 - 29 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 SEDIMENTS 3.2.4. Marketing strategy

31. 5 avril 2006 - 30 3.2. APPLYING THE NOVOSOL PROCESS TO CONTAMINATED SEDIMENTS 3.2.4. Marketing elements Main economic data for an industrial unit with a treatment capacity of 100 000 m 3 /year raw sediments 50% H 2 O, 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

32. 5 avril 2006 - 31 Mineral residues Combustible waste Sediments with 50 % H 2 O Flying ash Mineral fine shredder residues Others Unit A Phosphatation - Drying H 3 PO 4 Unit B Calcination End product for reuse in road – brick - concrete pump INDUSTRIAL ECOLOGY- NOVOSOL® / FOAM Gas treatment Refuse-derived fuel (RDF) Dried sludge from wastewater treatment plant Others Gas treatment NEUTREC