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!