University of Applied Sciences Fachhochschule Nordostniedersachsen Lneburg Department

University of Applied Sciences Fachhochschule Nordostniedersachsen Lüneburg Department of Civil Engineering (Water and Environmental Management) Buxtehude Suderburg Dr. Volker Birke Prof. Dr. Martin Brodowski Economic and Ecologically Favorable Detoxification of Polyhalogenated Pollutants Applying the DMCR Technology DMCR = Dehalogenation by Mechanochemical Reaction

DEHALOGENATION: (schematic, simplified) R–Hal R–Y REDUCTIVE DEHALOGENATION: DEHALOGENATION R–Hal R–H

Different Dehalogenation Reaction Types In Principle Relevant to The Destruction of Toxic Halogenated Hydrocarbons: R–H reductive dehalogenations R–M organometallic reactions R–Hal R–R´ coupling reactions Wurtz type etc. R–OH R–OR´ R–SH R–SR´ nucleophilic substitutions

Hazardous polygenated pollutants in complex matter or pure toxic compounds are destroyed by: in one single universal step inside a vibratory mill at room temperature and in a short time

Dehalogenation Reaction R–Cl + Sodium + “H“ (PCB) TOXIC Base Metal Hydrogen. Donor REAGENTS R–H + Na. Cl Biphenyl Rock Salt HARMLESS (schematic, simplified)

DMCR Technology Treatable: Hazardous Polyhalogenated Pollutants Selected compounds: n Polychlorinated biphenyls (PCBs) n Dioxins (PCDD), Dibenzofuranes (PCDF) n Hexachlorocyclohexane (Lindane, HCH) n Dichlorodiphenylethane (DDT) n Aldrin (HHDN) n Dieldrin (HEOD) n n n Toxaphene (Champhechlor) Pentachlorophenol (PCP) Chlorofluorocarbons (CFC) Trichloroethylene (TCE) Chemical Weapons: Adamsite, Lost

DMCR Technology Process Characterization n n n Reductive Dehalogenation Under Mechanochemical Conditions Hardware/Equipment: (Vibratory) ball mill Reagent A: Base metal (sodium, magnesium, aluminium, zinc, iron or alloys et cetera) Reagent B: Hydrogen donor On site and/or off site Operations (ex situ) High flexibility, wide scope of areas of application

DMCR Technology Treatable Contaminated Materials • Soils Solid • filter dusts Solid-liquid • sludges or oils Liquid • Pure contaminants or mixtures of them Treatable Pollutants Every halogenated pollutant in principle Treatable Concentration Levels From ppb to pure contaminants

Elimination Directly Inside Complex Matter n Every pollutant can be eliminated directly inside a contaminated material ex situ n Virtually regardless of the material´s state, how complex its structure may be and how strongly the pollutants may be bound adsorptively compounds (e. g. , clays regarding soils)

Elimination Room Temperature and Short Time Every dehalogenation can be performed at room temperature, ambient pressure and in a short time (below 1 minute up to appr. 1 hour) Simple and Readily Available Reagents n n Base metals (e. g. , sodium, magnesium, aluminium, zinc, iron or alloys) Some additives (hydrogen donors)

Re-use of Scrap Metals/Alloys Different scrap metals and alloys in various shapes (e. g. , small lumps, filings, granules, coarse or fine powders) are used as dehalogenation reagents and, therefore, have to be considered as valuable materials that are usefully re-used No Particular Preprocessing

Defined Degradation Products n One or very few well-defined, harmless and/or easier disposable and/or even profitably usable degradation products n Only one well-defined reaction mechanism: total reductive dehalogenation of the parent polyhalogenated contaminants

Processing Recycling of Contaminated Matter Combinations with Other Processes Possible Simple Process Design Only one single universal key step is required to destroy hazardous compounds completly and forever

On Site and Off Site Operations n Small plants n Vibratory mills as the "core units": highly efficient mixing devices and reactors in one single operation step simultaneously n Low energy, equipment, personal and reagent costs n Mobile units: transportation to and operation at the contaminated site directly n Alternatively: stationary off site units

Scale/Throughput n n n Some kilograms/hr up to several tons of contaminated matter per hour For high throughputs: off site treatment is strongly recommended Pilot scale devices are being available at the moment only Full scale operating plants are still under development We are still looking for cooperation partners for particular and currently emerging applications in particular regions of the world High Rentability expected

Selection of Solvable Problems n Filter dusts containing polyhalogenated pollutants like dioxins and PCBs n Contaminated adsorptive materials like activated carbon, clays, molecular sieves etc. applied for purifications of waste streams n Soils contaminated by hazardous polyhalogenated substances n Harbour/river sediments contaminated by polyhalogenated pollutants

Selection of Solvable Problems n PCB contaminated construction materials n PCB contaminated sewage sludges n Remediation of industrially produced hazardous waste, for instance, associated with the production of hexachlorocyclohexane (HCH), pentachlorophenol (PCP) et cetera n Recycling of PCB contaminated transformer and used lubricating oils

Areas of Application Industrial Wastes Wood and Timber Industry Agriculture Energy and Electricity Supplying Companies Residence Areas, Municipal Buildings Military

Areas of Application Petrochemical Industry, Refineries Electrical Industry Recycling Plants, Scrap Metal Recycling Plants Garbage Incineration Plants, Hazardous Waste Incineration Facilities

Already Implemented Projects Relevant to Industrial Application n n Dehalogenation of PCBs and DDT in loamy soils in Oslo (Norway, 1995/1996) Dehalogenation of PCBs in transformer oils focussing on recycling of these oils (Germany, 1998) Dehalogenation of polyhalogenated pollutants and PCBs in used lubricating oils (Germany, 1999) Dehalogenation of PCBs and dioxins in filter dusts (worldwide, 2000, ongoing) Scale-up of dehalogenation of PCBs in transformer oils (Germany, 2001, ongoing)

Upcoming and Planned Novel Projects In Co-operation with National and International Partners: n Dehalogenation of several ten thousands of tons of pure PCB oils and hexachlorobenzene per year (South America) n Dehalogenation of DDT and other pesticides (South America, Pacific rim) n Dehalogenation of polyhalogenated pollutants in huge amounts of used lubricating oils (Germany)

Upcoming and Planned Novel Projects n Filter dusts, slags and ashes polluted by dioxins, PCBs and other polyhalogenated compounds (worldwide) n Dehalogenation of pure PCB oils (Pacific rim) n Dismantling of PCB contaminated electrical devices like capacitors and coils, destruction of PCBs by dehalogenation and recovery/recycling of valuable materials like copper (Asia) PCB dehalogenation in soil washing fractions (Scandinavia) n

Analytical Results: Treatment of PCB Contaminated Soils (appr. 5000 ppm PCB) MSD-GC: prior to milling MSD-GC: after milling

Analytical Results: Treatment of PCB Contaminated Soils (appr. 5000 ppm PCB) MSD-GC: after milling, normal resolution MSD-GC: after milling, high resolution

Analytical Results: Treatment of PCB contaminated soils (appr. 250 ppm PCB) ECD-GC: prior to PCB dechlorination ECD-GC: after PCB dechlorination (> 99, 9 %)

Analytical Results: Treatment of PCB contaminated soils (appr. 250 ppm PCB) ECD-GC: prior to PCB dechlorination high resolution ECD-GC: after PCB dechlorination high resolution

Vibratory Mill Dehalogenation Pilot Device L+Z Transformatoren-Service Transformer Oil (batch process)

Vibratory Mill Dehalogenation Pilot Device Lubricating oils (batch process)

Vibratory Mill Dehalogenation Soil washing fractions (continuous)

Outline of an off site vibratory mill plant capable of treating solid materials Sketch by Siebtechnik Gmb. H, Muelheim/Ruhr, Germany

PCB contaminated coils/capacitors

PCB contaminated coils/capacitors

PCB contaminated coils/capacitors

PCB contaminated coils/capacitors

PCB contaminated coils/capacitors and formerly encapsulating soil Proposal: Two major treatment trains 1 st treatment train: Getting rid of the electrical devices n Appropriate dismantling of PCB contaminated coils/capacitors n Separation into steel/iron, copper, resin, paper et cetera n Recycling of valuable steel/iron and copper n Removing PCBs n Dehalogenation of PCBs and PCB contaminated materials (DMCR)

PCB contaminated coils/capacitors and formerly encapsulating soil 2 st treatment train: Getting rid of the soil n Preconditioning of PCB contaminated soil (crushing, sieving, drying et cetera) n Dehalogenation step directly in a ball mill (DMCR) n Recovery of reagents n Disposal/re-use of PCB-free soil

Upcoming Events Hanover Industry Fair The University of Applied Sciences North-East Lower Saxony, TRIBOCHEM and SIEBTECHNIK Gmb. H will present the DMCR technology at the upcoming Hanover Industry Fair (April 15 -20 th) in Hanover, Germany, hall 18, booth 003, 1 st floor. We look forward to seeing you there.

More Information URLs: www. tribochem. de www. mechanochemistry. de www. fhnon. de Co-operation Partners:

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