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

A STABILIZATION PROCESS OF MINERAL RESIDUE CONTAMINATED WITH HEAVY METALS AND ORGANIC COMPOUNDS. G. Depelsenaire – SOLVAY. [ Presentation Outline ]. 1. The Novosol ® process 2. Potential applications 3. Process R&D 3.1. The process as applied to fly ash

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

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  1. A STABILIZATION PROCESS OF MINERAL RESIDUE CONTAMINATED WITH HEAVY METALS AND ORGANIC COMPOUNDS G. Depelsenaire – SOLVAY

  2. [ 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. 1. THE PROCESS TWO-STEP STABILIZATION OF MINERAL RESIDUE CONTAMINATED WITH HEAVY METALS AND ORGANIC COMPOUNDS Step A HEAVY METAL STABILIZATION by binding to a calcium phosphate ( [Ca3(PO4)2]xH2O ) matrix formed by adding H3PO4 Step BORGANIC COMPOUND DESTRUCTION by calcination (650°C - 900°C) H3PO4 Calories Usable stabilized mineral residue Calcium phosphate formation Organic compound destruction Contaminated mineral residue StepA StepB

  4. POTENTIAL APPLICATIONS • 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

  5. 3. NOVOSOL® PROCESS R&D • 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)

  6. 3.1. THE NOVOSOL® PROCESS AS APPLIED TO FLY ASH 3.1.1. Patents • 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)

  7. 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 Flue gas process Sodium bicarbonate Activated carbon Furnace + boiler Filtration Filtration Stack Waste Raw flue gasses Processed gasses Dust-free gasses Fly ash Sodium-rich residue REVASOL pilot plant – Dombasle 1999 - 2003 Water Scrubbing-------------------------------------NOVOSOL Scrubber solution H3PO4 Chemical treatment Calories Concentrated dioxin-free, furan-free standardized brine Dioxin-free, furan-free solid residue Ultimate wastes Incorporation in road-building materials Grade I landfill site Sodium carbonate production

  8. 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 • 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

  9. 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 • 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

  10. 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 • 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

  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)

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

  14. 3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS 3.2.1. Patents • 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”

  15. 3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS 3.2.2. Novosol foam Process operating chart Calcination H3PO4 Maturation and drying bed Sediments/Soil cont. 50% H2O Site A Interim storage - 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 Value recovery from stabilized materialsValue recovered as calories for drying or electricity generation Site B

  16. 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 sediments17 05 05 * Dredging sludges containing hazardous substances Heavy metal levels above which sediments are considered hazardous

  17. 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 • Laboratory research 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)

  18. 3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS 3.2.3. Study of process and value recovery from products • Phosphatation mini pilot unit (Capacity: 400 l/h of sediments containing 50% H2O)

  19. 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% H2O

  20. 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. 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 (designed and realized by Bertin Technologies) Capacity: 20 t / month of processed sediments

  22. 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. 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. 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. 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 materialsRiver 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. 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 • 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.

  27. 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 Detail of membranes

  28. 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 2- initial compaction with vibrating roller 1- spreading and collecting of samples for molding 3- compaction with P1 tires 4- final screeding e= 0.25 m

  29. 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) * cas de percolation contaminée par de la chaux répandue sur la route * Composition of the material (cement-stabilized sand) - Limestone 0/6 mm 63% - NOVOSOL®-treated sediments 30% - ROC SG hydraulic binder 7%

  30. 3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS 3.2.4. Marketing strategy 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.

  31. 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 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

  32. INDUSTRIAL ECOLOGY- NOVOSOL® / FOAM Mineral residues Combustible waste Sediments with 50 % H2O pump H3PO4 Refuse-derivedfuel (RDF) pump Dried sludgefrom wastewatertreatment plant Flying ash GastreatmentNEUTREC Gas treatment Mineral fineshredder residues Others Others Unit APhosphatation - Drying Unit BCalcination End product for reuse inroad – brick - concrete

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