Tested technologies for HW Sofia 26 5 05 allÃgÃe

TREDI InternationalTried & Tested Treatmentsfor Hazardous Wastes : 

TREDI International Tried & Tested Treatments for Hazardous Wastes Les Hêtres - BP 20 - 53810 Changé - Tél. 02 43 59 60 00 - - 33 rue de Mogador - 75009 Paris - Tél. 01 53 21 53 53 MOB 24/06/04

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Introduction Tredi has developped with its Research Departement, over the past 15 years, new solutions for the treatment of highly hazardous wastes : Thermal Process Thermal vacuum extraction Thermal desorption Catalytic hydrogenation and wet air oxidation Autoclaving Incineration Chemical Process Physical Treatment Filtration Solvent extraction Biological degradation

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The system is designed to reach in vacuum conditions feed material temperatures of up to 400°C allowing an effective treatment of soils and sludge polluted with a wide range of low and high boiling point compounds. The system is suitable for PCBs and mercury The gases produced during the process are treated by a vapour recovery system which includes a condensing unit and a vapour phase carbon adsorption unit. The condensed mixture is incinerated Fraysse, G. & Thauront, J. (1989). Procédé et dispositif de décontamination de produits solides. Brevet d’invention n° 2 653 044. Thermal vacuum extraction

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The Technology is based on thermal desorption followed by combustion. The main operational units of the system include an indirectly heated rotary reactor, a cooler, and multi venturi scrubbers, a gas combustion chamber and a full water treatment The rotary reactor is the main component of the system. Waste is vaporized and treated in gas combustion chamber. The operating temperature in the reactor ranges from 450 to 600 °C. The process applications include the treatment of PCBs contaminated soils and of a full range of chlorinated hydrocarbons, organochlorine pesticides. This technology is not applicable for treatment of liquids (water, flammable liquids and solvents), and materials that cannot be decomposed by thermal treatment at 600 °C Thermal Desorption Process

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The TREDECO Unit used for the treatment and destruction of contaminated soils in 2001 in Denmark Thermal Desorption Process Risoul, V., Pichon, C., Trouvé, G., Peters, W.A., Gilot, P. & Prado. G. (1999). Thermogravimetric study of thermal decontamination of soils polluted by hexachlorobenzene, 4-chlorobiphenyl, naphtalene or n-decane. Journal of Hazardous Materials B, 64, 295-311.

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Catalytic hydrogenation and wet air oxidation Béziat, J.C., Besson, M., Gallezot, P. & Durécu, S. (1999). Ing. Eng. Chem. Res., 38, 1310-1315. Felis, V., De Bellefon, C., Fouilloux, P. & Schweich, D. (1999). Applied Catalysis B : Environmental, 20, 91-100.

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Handling procedure for Thermal Treatment

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Autoclaving PCB oils and solids decontamination by liquid – liquid extraction using a third part solvent

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Apparatus in service on the site of St Vulbas Optimisation by recycling of the third part solvent (perchlorethylen) Autoclaving

Incineration: 

Incineration ROTARY KILN PCB and halogenated wastes SLAGS Gaz Instantaneous cooling  No dioxins recomposition 1200°  70 ° First Combustion chamber Secondary Combustion Chamber 1200 °C Liquids GAZ CLEANING WASTE WATER TREATMENT

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Incineration STATIC KILN specific kiln for liquids PCB OIL POLLUTED WITH PCBs PCBs 1200°  70 ° GAZ CLEANING WASTE WATER TREATMENT 1200 °c Gaz Instantaneous cooling  No dioxines recomposition

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Waste water treatment Quench chamber ending treatment column Colonne de lavage 1 Wet electrofilter Soda column 1 Soda column 2 HCl SO2 HF... Heat exchanger HCl, HF... Halogenated gaz traces (HBr, HI, ... ) + SO2 dust dusts < 10 mg/Nm3 HCl < 10 mg/Nm3 HF < 1 mg/Nm3 Gaz cleaning facility for both kilns

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Chemical Treatment Substitution Reaction -for the treatment of low level PCBs wastes usually between 50 - 2000 ppm -the process involves the treatment of the PCB with NaH (Sodium Hydrid) -a mobile installation using this process is working in Europe since about 10 years

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Chemical Treatment Regenerative treatment : the transformer is ready for re-use after decontamination Decontaminated oil fits to the EU norms for brand new dielectric material

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Chemical Treatment Transformer Mobile unit P01 P18 S03 R01 V P16 P04 P01 : Feeding pump with contaminated oil P04 : Feeding pump of the de-watering devices P16 : Filter press pump P18 : Dewatered oil discharge pump R01 : Nitrogen cylinder S03 : Nitrogen production device V : expansion tank   Treatment rates : up to 1000 l / h, depending of PCBs initial concentration

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Chemical Treatment Works directly at the feet of the transformer Can be deployed into operational state in about 6 hours Transportation doesn’t need extra weight Standard trucks are used

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Extraction of PCBs by microfiltration process in liquids to concentrate the polluted fraction in a minimum volume to be incinerated. The permeate is reused. Physical Treatment

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This microfiltration process is operationnal since two years at TREDI Saint-Vulbas Plant. Fraysse, G., Dudouit, J., Petit, M.T., Cheradame, G. & Durécu, S. (1994). Microfiltration tangentielle d’effluents industriels contenant des traces de produits organiques halogénés. Interfiltra 94. Recueil des conférences édité par la Société Française de filtration, Paris, 327-330. Physical Treatment

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Solvent Extraction techniques are cost-effective methods to treat PCBs and other chlorinated compounds, but the main limitation is that the contaminants transferred to another phase must be destroyed through a secondary method. TREDI has tested a carbon dioxide extration in supercritical conditions. CO2 extraction technology has been tested to soils and to transformers contaminated with PCBs. Zaragoza, R., Blanchard, J.M. & Barna, L. (1997). Supercritical fluid extraction applied to soils contaminated by chlorinated compounds. 4th Meeting on Supercritical fluids and Environment. 20-21 January 1997, INSA Villeurbanne, France Solvent extraction

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Enhanced bioremediation, also called biostimulation or bioaugmentation, is a process to increase the biodegradation rate of contaminated soil by the addition of nutrients and oxygen. Lab scale trials proved very successful At TREDI Saint-Vulbas, Pilot plant trials had proven successful at a PCB concentration limit of 60% of chlorine. Over 60% PCB’s are not easily biodegradable. Biological degradation

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Biological degradation Lab scale and pilot plant at TREDI Saint-Vulbas

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The difference between technologies that only separate and/or concentrate a pollutant (e.g. solvent extractions, thermal desorption, filtration) and those which destroy the contaminant (e.g. oxidation, reduction, and biodegradation) must be considered when setting site remediation goals. The applicability and availability of the different treatment technologies depend on the location of treatment systems and whether the waste can be transported to the treatment facility. Social, environmental, technical and economical criteria should be considered during the technology process selection. Conclusions