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:
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
HydrogenDonor
REAGENTS
R–H + NaCl
Biphenyl
Rock Salt
HARMLESS
(schematic, simplified)
DMCR Technology
Treatable: Hazardous Polyhalogenated
Pollutants
Selected compounds:
 Polychlorinated
biphenyls (PCBs)
 Dioxins (PCDD),
Dibenzofuranes (PCDF)
 Hexachlorocyclohexane
(Lindane, HCH)
 Dichlorodiphenylethane
(DDT)
 Aldrin (HHDN)
 Dieldrin (HEOD)

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Toxaphene
(Champhechlor)
Pentachlorophenol
(PCP)
Chlorofluorocarbons
(CFC)
Trichloroethylene
(TCE)
Chemical Weapons:
Adamsite, Lost
DMCR Technology
Process Characterization

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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
• Soils
• filter dusts
• sludges or oils
• Pure contaminants
or mixtures of them
Treatable
Contaminated
Materials
Solid
Solid-liquid
Liquid
Treatable
Pollutants
Every halogenated
pollutant in principle
Treatable
Concentration
Levels
From ppb to pure
contaminants
Elimination
Elimination Directly Inside Complex Matter

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
(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


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

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
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

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
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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 dusts containing polyhalogenated
pollutants like dioxins and PCBs

Contaminated adsorptive materials like
activated carbon, clays, molecular sieves etc.
applied for purifications of waste streams

Soils contaminated by hazardous
polyhalogenated substances

Harbour/river sediments contaminated by
polyhalogenated pollutants
Selection of Solvable Problems

PCB contaminated construction materials

PCB contaminated sewage sludges

Remediation of industrially produced
hazardous waste, for instance, associated
with the production of hexachlorocyclohexane (HCH), pentachlorophenol (PCP) et
cetera

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
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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:

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)
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:
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 GmbH,
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
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)
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.de
www.mechanochemistry.de
www.fhnon.de
Co-operation Partners:
Thank you for your attention!
The mill is now empty!