WASTE MANAGEMENT AND TECHNOLOGY Physico chemical processing of (hazardous) waste Treatment of solid waste polluted by polychlorinated contaminants in Spolana Neratovice WASTE MANAGEMENT AND TECHNOLOGY Mecislav Kuras Institute of Chemical Technology in Prague

Contamination in Spolana Neratovice Historical Background - a large chemical plant built up in 1939 - situated 25 km north from Prague 1961 – 1968 - production of insecticides, herbicides and other agricultural chemicals (hexachlorocyclohexane, hexachlorobenzene, sodium pentachlorophenolate, butylester of 2,4,5-trichlorophenoxyacetic acid) - undesirable (at that time unexpected) reactions occurred in a technology resulting in formation of extremely toxic compounds of dioxin type, which concentrated in recycled sodium hydroxide and spread out through air venting system - the presence of dioxine compounds in air inside technological building first detected in 1968 - there were 78 people suffering from serious health problems with inexplicable diagnosis and unknown therapy - contaminated technological installations closed from 1968 to 2000 without any action

Spolana Neratovice – total view Dioxins polluted site

Contaminated technological building

Monitoring of contamination and risk assessment - the first complex monitoring of the contaminated technological building as well as the area around it was carried out in 2001 dioxins TEQ (ng/g) soil 100 - 400 concrete 2 500 – 5 000 plaster 4 - 8 chemicals 10 - 2000 - risk assessment underlined an acute need of immediate site remediation

Feasibility study on suitable cleaning technique - carried out by the USA company Resource Applications, Inc. - three cleaning strategies were examined: 1) incineration of solid contaminated waste in a plant outside the Spolana area, 2) building up a new incineration plant in Spolana to process contaminated waste close to the source of pollution, and 3) application of a non-incineration approach for the destruction of the chlorinated compounds recommendation - to utilise the non-incineration approach BCD (developed by US EPA), since it promised safe and cheapest performance among the three possibilities without necessity to transport polluted material out of the Spolana area. amount to treat 23 000 tons of contaminated soil 8 900 tons of demolition waste 3 000 tons of steel constructions and 160 tons of chemicals

Pilot-scale demonstration of the technology selected for treatment of contaminated waste Since the level and extent of pollution by polychlorinated contaminants at the site were extremely high even in comparison with the localities where the recommended BCD technology was successfully applied in the past, it was decided by the Czech state authorities to perform a pilot scale demonstration in Spolana Neratovice to prove suitability of this technological process. Pilot-scale installation included thermal desorption unit BCD reactor The both technological systems were placed in an underpressurized tent to prevent contaminants escape into atmosphere. The air leaving inner space of the tent was passing through high capacity active carbon filtration system.

Pilot-scale demonstration Polluted solids Chemicals Detoxicated solids Condensate Water Organics Oil THERMAL BCD

Pilot-scale demonstration – thermal desorption unit

Pilot-scale demonstration – BCD reactor

Pilot-scale demonstration Sampling and analysis of polluted materials

Pilot-scale demonstration Sampling and analysis of polluted materials

Results of pilot-scale thermal desorption treatment - temperature of treatment 600 – 700oC - time of desorption 1 – 4 hours Table: Effect of thermal desorption treatment inicial contamination residual contamination Sample compounds of dioxin type (TEQ – ng/g) hexachloro- benzene (mg/kg) lindane mixed sample 2 420 0.0063 49 000 1.0 11 soil 45 0.0030 2 640 1.7 concrete 4 780 0.066 5 100 1.0 18 plaster 7.2 0.13 270 1.1

Results of pilot-scale BCD treatment compounds of dioxin type - temperature in the reactor - 325 – 350oC - decomposition time – 1 hour Table: Effect of BCD process inicial contamination residual contamination  Sample compounds of dioxin type (TEQ – ng/g) hexachloro- benzene (mg/kg) lindane chemicals 1 input output (oil/condensate) 209 (0/0.60) 29 000 (1.0/3 500) 1 500 (1.0/2.7) chemicals 2 125 (0.0043/0.83) 200 000 (2.0/6 000) 950 (2.0/4.1) chemicals 3 11 (0.00023/0) 550 000 (2.0/130) 1 000 (2.0/2.0)

Conclusions of the pilot-scale treatment - Processing of solid waste showing extremely high contents of polychlorinated compounds (including dioxins) was successfully carried out within the pilot-scale demonstration project at former pesticides producing plant in Spolana Neratovice. - The treatment system consisting of thermal desorption unit and a BCD reactor proved its capability to effectively detoxicate soil, concrete, bricks, plaster, steel and dust contaminated by polychlorinated compounds as well as to provide more than satisfactory destruction of these chemicals in their concentrated form. - The demonstration results confirmed the ability of these technological processes to clean up the solid waste with extraordinary high efficiency thus providing an effective remediation tool for this heavily polluted site.

Full-scale installation (2005 – 2008) installation of protection underpressurized envelope

Full-scale installation (2005 – 2008) installation of protection underpressurized envelope

Full-scale installation contaminated building demolition

Full-scale installation contaminated building demolition

Final monitoring at the decontaminated site