Economic and Ecologically Favorable Detoxification of Polyhalogenated Pollutants Applying the DMCR...
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Economic and Ecologically Economic and Ecologically Favorable Favorable
Detoxification of Detoxification of Polyhalogenated Pollutants Polyhalogenated Pollutants
Applying the DMCR TechnologyApplying the DMCR Technology
LüneburgBuxtehudeSuderburg
Universityof Applied Sciences
FachhochschuleNordostniedersachsen
Department of Civil Engineering (Water and Environmental Management)
Dr. Volker Birke Prof. Dr. Martin Brodowski
DMCR = Dehalogenation by Mechanochemical Reaction
R–R–HalHal R–YR–Y
R–R–HalHal R–HR–H
DEHALOGENATION:(schematic, simplified)
REDUCTIVEREDUCTIVEDEHALOGENATIONDEHALOGENATION:
R–Hal
R–H
R–MR–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
inside a vibratory mill inside a vibratory mill at room temperature and in a short timeat 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:
TOXICTOXIC HARMLESSHARMLESS
R–R–ClCl ++ SodiumSodium ++ “H“ “H“ R–H + NaCl R–H + NaCl
(PCB)(PCB) Base MetalDonor
Rock SaltBiphenyl
REAGENTSREAGENTS
Dehalogenation Reaction
(schematic, simplified)
Hydrogen-
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
DMCR Technology
Reductive Dehalogenation Under Reductive Dehalogenation Under Mechanochemical ConditionsMechanochemical Conditions
Hardware/Equipment: Hardware/Equipment: ((Vibratory) ball millVibratory) ball mill
Reagent A:Reagent A: Base metal Base metal (sodium, magnesium, aluminium, (sodium, magnesium, aluminium,
zinc, iron or alloys et cetera)zinc, iron or alloys et cetera) Reagent B: Reagent B:
Hydrogen donor Hydrogen donor On site and/or off site Operations (On site and/or off site Operations (ex situex situ)) High flexibility, wide scope of areas of applicationHigh flexibility, wide scope of areas of application
Process Characterization
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
Elimination
Every pollutant can be eliminated directly inside a contaminated material ex situ
Virtually regardless of the material´s state, Virtually regardless of the material´s state, how complex its structure may be and how complex its structure may be and how strongly the pollutants may be bound how strongly the pollutants may be bound adsorptively compounds adsorptively compounds
(e.g., clays regarding soils)(e.g., clays regarding soils)
Elimination Directly Inside Complex Matter
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)
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
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: Only one well-defined reaction mechanism:
total reductive dehalogenationtotal reductive dehalogenation of the parent of the parent polyhalogenated contaminantspolyhalogenated contaminants
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
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
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
Selection of Solvable Problems
Filter dustsFilter dusts containing polyhalogenated containing polyhalogenated pollutants like dioxins and PCBspollutants like dioxins and PCBs
Contaminated Contaminated adsorptive materialsadsorptive materials like like activated carbon, clays, molecular sieves etc. activated carbon, clays, molecular sieves etc. applied for purifications of waste streamsapplied for purifications of waste streams
Soils Soils contaminated by hazardous contaminated by hazardous polyhalogenated substancespolyhalogenated substances
Harbour/river sedimentsHarbour/river sediments contaminated by contaminated by polyhalogenated pollutantspolyhalogenated pollutants
Selection of Solvable Problems
PCB contaminated PCB contaminated construction materialsconstruction materials
PCB contaminated PCB contaminated sewage sludgessewage sludges
Remediation ofRemediation of industrially produced industrially produced hazardous wastehazardous waste, , for instance, associated for instance, associated with the production of hexachlorocyclo-with the production of hexachlorocyclo-hexane (HCH), pentachlorophenol (PCP) et hexane (HCH), pentachlorophenol (PCP) et ceteracetera
Recycling of PCB contaminatedRecycling of PCB contaminated transformer transformer and used lubricating oilsand used lubricating oils
Areas of Application
Wood and Timber Industry
Agriculture
Energy and Electricity Supplying Companies
Industrial Wastes
Residence Areas, Municipal Buildings
Military
Areas of Application
Electrical Industry
Recycling Plants, Scrap Metal Recycling Plants
Garbage Incineration Plants,
Hazardous Waste Incineration Facilities
Petrochemical Industry, Refineries
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)
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:
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)
Analytical Results: Treatment of PCB Contaminated Soils (appr. 5000 ppm PCB)
MSD-GC: MSD-GC: prior to millingprior to milling
MSD-GC: MSD-GC: after milling after milling
Analytical Results: Treatment of PCB Contaminated Soils (appr. 5000 ppm PCB)
MSD-GC: after milling, MSD-GC: after milling, normalnormal resolution resolution
MSD-GC: after milling, MSD-GC: after milling, highhigh resolution resolution
Analytical Results: Treatment of PCB contaminated soils (appr. 250 ppm PCB)
ECD-GC: prior toECD-GC: prior to PCB dechlorinationPCB dechlorination
ECD-GC: after ECD-GC: after PCB dechlorinationPCB dechlorination
(> 99,9 %)(> 99,9 %)
Analytical Results: Treatment of PCB contaminated soils (appr. 250 ppm PCB)
ECD-GC: prior to ECD-GC: prior to PCB dechlorinationPCB dechlorination
highhigh resolution resolution
ECD-GC: after ECD-GC: after PCB dechlorinationPCB dechlorination
highhigh resolution resolution
Vibratory Mill Dehalogenation Pilot Device
Transformer OilTransformer Oil (batch (batch process)process)
L+Z Transforma-L+Z Transforma-toren-Servicetoren-Service
Vibratory Mill Dehalogenation Pilot Device
Lubricating oilsLubricating oils (batch process) (batch process)
Vibratory Mill Dehalogenation
Soil washing fractions (continuous)Soil washing fractions (continuous)
Outline of an off site vibratory mill plant capable of treating solid materials
Sketch by Sketch by Siebtechnik GmbH, Siebtechnik GmbH, Muelheim/Ruhr, Muelheim/Ruhr, GermanyGermany
PCB contaminated coils/capacitors
PCB contaminated coils/capacitors
PCB contaminated coils/capacitors
PCB contaminated coils/capacitors
PCB contaminated coils/capacitorsand formerly encapsulating soil
1st 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
PCB contaminated coils/capacitors and formerly encapsulating soil
2st 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
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.
More Information
URLs:
www.tribochem.dewww.mechanochemistry.de
www.fhnon.de
Co-operation Partners:
Thank you for your attention!
The mill is now empty!