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Economic and Ecologically Favorable Detoxification of Polyhalogenated Pollutants Applying the DMCR Technology Lüneburg Buxtehude Suderburg University of.

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Presentation on theme: "Economic and Ecologically Favorable Detoxification of Polyhalogenated Pollutants Applying the DMCR Technology Lüneburg Buxtehude Suderburg University of."— Presentation transcript:

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

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

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

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

6 TOXICHARMLESS R–Cl +Sodium+“H“ R–H + NaCl R–Cl +Sodium+“H“ R–H + NaCl (PCB)Base Metal Donor Rock Salt Biphenyl REAGENTS Dehalogenation Reaction (schematic, simplified) Hydrogen-

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

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

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

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

11 Elimination Base metals (e. g., sodium, magnesium, aluminium, zinc, iron or alloys) Some additives (hydrogen donors) Some additives (hydrogen donors) Simple and Readily Available Reagents 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)

12 Re-use of Scrap Metals/Alloys No Particular Preprocessing 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

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

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

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

16 Scale/Throughput 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

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

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

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

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

21 Already Implemented Projects Relevant to Industrial Application 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)

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

23 Upcoming and Planned Novel Projects Filter dusts, slags and ashes polluted by dioxins, PCBs and other polyhalogenated compounds (worldwide) Dehalogenation of pure PCB oils (Pacific rim) 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)

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

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

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

27 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

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

29 Vibratory Mill Dehalogenation Pilot Device Lubricating oils (batch process)

30 Vibratory Mill Dehalogenation Soil washing fractions (continuous)

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

32 PCB contaminated coils/capacitors

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

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

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

39 More Information URLs: Co-operation Partners:

40 Thank you for your attention! The mill is now empty!

41 Areas of Application Industrial Wastes Waste from production of hexachlorocyclo- hexane (other HCH-isomers than  -HCH, Lindane) can be dehalogenated to the profitably usable solvent cyclohexane. Thus, in addition to the detoxification, profit can be made. Soils contaminated by HCH can be detoxified entirely using the same approach, which has to be modified slightly only.

42 Areas of Application Wood and Timber Industry Wood preservatives consisting of orcontaining pentachlorphenol (PCP) or other polyhalo- genated compounds or contaminated premises, e. g., soils, can be decontaminated effectively.

43 Areas of Application Agriculture Contaminated sludges and areas with pesticides or residues of pesticides can be decontaminated.

44 Areas of Application Energy and Electricity Supplying Companies Contaminated materials coming out of production plants or of leakages or contaminated soil around those facilities, e. g., PCB contaminated transformer oils or PCB contaminated soils around transformer stations, can be treated successfully.

45 Areas of Application Residence Areas, Municipal Buildings PCBs have been used in huge amounts as softeners for concrete adhesives worldwide and, therefore, jeopardize public health in many countries. Contaminated construction materials like concrete can be detoxified and recycled.

46 Areas of Application Military Toxic chemical agents and combat gases containing halogen like lost, lewisite, adamsite et cetera can be destroyed at room temperature in principle.

47 Areas of Application Petrochemical Industry,Refineries Used lubricating oils containing polyhalogenated pollutants can be detoxified at room temperature and can be recycled after the dehalogenation step. So far, most of them have been high- temperature incinerated causing an considerable increase of the carbon dioxide content of the atmosphere.

48 Areas of Application Electrical Industry Recycling of contaminated transformers, capacitors, trash from disassembled electronic devices. Decontamination and recycling of PCB transformer and capacitor oils.

49 Areas of Application Recycling Plants, Scrap Metal Recycling Plants Because of the use of base metals as dehalogenating agents also scrap metals can be applied in the process. This opens up the interesting opportunity to combine usefully two problems to each other and solve them in one single, universal step: On one hand, very toxic and hazardous pollutants are destroyed and contaminated materials are detoxified, on the other hand scrap metals, which perform the dehalogenation, are re-used.

50 Areas of Application Garbage Incineration Plants, Hazardous Waste Incineration Facilities Ashes and filter dusts contaminated by dioxins and related toxic compounds can be treated in order to destroy the contaminants.


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