Carlo Lupi – UNIDO consultant
carlolupi@wasteandchemicals.eu
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
….sorry – any question?
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Thermal
technologies
Chemical
technologies
Post Treatment
Pretreatment
Incineration
Sodium based
dechlorination
Solvent Washing
Draining
Co-Incineration
(Cement kiln)
Hydrodehalogenation
Retrofilling
Shredding
Thermal
desorption
Vacuum
extraction
Plasma
Vacuum
washing
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Oil
Thermal
technologies
Transformers
Capacitors
Thermal
technologies
Pre treatment
Cleanup of
carcasses
Thermal
technologies
Post treatment
Post-treatment
or thermal
technologies
Other waste
(paper,
wood, soil)
Thermal
destruction
Thermal
desorption
followed by
thermal
destruction
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
New
transformers
Old
transformers
Capacitor
(very rare)
Chemical
dehalogenation
Pretreatment
(draining,
flushing)
Pretreatment
(draining,
dismantling)
Draining or
shredding
Oil reprocessing
Chemical
dehalogenation
(of the oil)
Chemical
dehalogenation
Chemical
dehalogenation
or incineration
Retrofilling
Post treatment
Thermal
treatment of
the waste
Oil
Recovery of
scrap metal
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Regulatory level
for equipment and
dieletric oil
•Stockholm Convention: <50 ppm
•National regulations: <2ppm to <50 ppm
Other uses by
sector
•Burning oil: (40 CFR 761.20) <2ppm (if greater
only incineration is allowed)
•Unused oil: not detectable (IEC 60296 / IEC 61619)
Environmental
standards
•Cleanup level for soils (from 0.1 ppm to 15 ppm)
POPs waste
•Low POPs content: <50 ppm (cann be landfilled)
•High POPs content: >50 ppm (cannot be landfilled)
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Article
6.1(d)(ii) of
the Stockholm
Convention on
POPs requires
that Stockpiles
of POPs and
waste
contaminated
by POPs must
be
• “destroyed or irreversibly
transformed”
• otherwise disposed of in an
environmentally sound
manner (low POPs content)
• In compliance with all other
national and international
rules
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Designed to prevent or to reduce
releases of chemicals listed in Part
I of Annex C (PCDD/F, HCP and PCB
and their impact on the
environment as a whole.)
Destruction of PCBs must
not result in the release
of Dioxins!!
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
DE
• ((Input mass – Sum of ALL
outputs)/Input mass)*100
• >99,99%
DRE
• ((Input mass – mass released in
the atmosphere) / input
mass)*100
• >99.9999%
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Trial burn with
PCB
contaminated soil
(PCB 1-2%)
Trial burn with
PCB oil (PCB 20%)
Trial burn with
PCB soil and
capacitors (PCB
10%)
DE / TEq test trial burn
with PCB soil and
capacitors (PCB 10%)
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Pre-treatment (including
meshing, shredding, feeding)
may be an important source
of release.
It may also represent a risk
for workers (exposure to
chemicals and other
accidents)
Pre-treatment equipment
and operations must be
properly designed to avoid
human exposute and prevent
release of toxic wate
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
No matter how good is the
downstream disposal
technology…
If the pre-treatment is
poorly managed, it will
result in the release of
POPs (low DE)
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Demonstrably
safe
Inherently
safe
• A technology that achieves
the highest possible level of
occupational safety and has a
history of safe operation.
• Closed system of the
technology as a whole (pretreatment + destruction
process)
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
EIA, IPPC (BAT compliance)
Building permits and land use
Licensing (waste handling,
transportation)
Monitoring of releases in
atmosphere and water
Environmental monitoring
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Main reactions /
Description
PCB Concentration
Process temperature
Process pressure
Reagents
By products, outflows and
waste streams
Applicability
Needs for post or pre
treatment
Main advantage
Main limitations
Technologies based on the use of metallic
sodium to dechlorinate the PCB molecules.
Generally not suitable for pure PCB
100° - 200°
Atmospheric
Metallic sodium.
Sludge,
Oils
The process requires the dewatering and
degassing of the matrix to be treated.
Short time. Oil may be reused after treatment.
Hazardous substances (Metallc sodium explodes
when in contact with water)
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Supplier
Arochlor type
Amount PCB (tons)
Moles PCB
Moles Cl
Moles Na
Cl (tons)
Na (tons)
Na consumption
declared
Reaction efficency
Nacl produced
BiPhenils produced
Waste (sludge)
Technology A
1242
1
3883
11649
11649
0.41
0.27
0.41
Technology B
1254
1
3063
15318
15318
0.54
0.35
0.93
65.09
0.68
0.60
1.28
37.90
0.90
0.47
1.37
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Main reactions /
Description
PCB
Concentration
Process
temperature
Process pressure
Main Reagents
The process consists of mixing and heating the contaminated media with the APEG reagent.
During heating, the alkali metal hydroxide reacts with the halogen from the contaminant to form
a non-toxic salt; and the PEG takes the location in the PCB molecule formerly occupied by the
halogen making it less hazardous. Process can be operated in batch or continuous mode.
Reported up to 45,000 ppm. – usually not suitable over 2000 ppm.
70° - 200°
From atmospheric to 3.5 bar (CDP)
Alkali metal hydroxide; polyethilene glycol; (APEG), Hydroxide tetraethilene glycol (ATEG), non
alkali metal, polyalkeneglycol and a alkali or alkaline earth metal hydroxide or alcoholate. (SEA
Marconi CDP process)
By products,
Mainly non toxic salts, and muds; be to when the process is used for the decontamination of
outflows and
transformer, the oil containing de-halogenated aromatics compound is re-used into the
waste streams
transformer; in the case of soil decontamination, de-halogenated aromatic compounds form a non
hazardous waste to be further destroyed or incinerated.
Applicability
PCBs Oils; transformers containing PCB oils; soil.
Needs for post or
It may be necessary in the case of treatment of contaminated soil or wastes.
pre treatment
Main limitations Following EPA (US EPA, 540/S-93/s 506), and regarding the soil treatment, the disadvantages of
the conventional APEG processes are that it often takes numerous cycles of the process to achieve
the desired results, the process only effects partial dehalogenation, and the formation of dioxin
and furans often occurs when the process is implemented”
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Main reactions / Description
PCB Concentration
Process temperature
Process pressure
Main Reagents
Applicability
Needs for post or pre
treatment
Main limitations
Under the category of hydrodehalogenation may be included all the
reductive dehalogenation processes involving the breaking of a single
bond between a carbon atom and the halogen with the subsequent
formation of a single bond between hydrogen and carbon. The process
may involve the use of molecular hydrogen, similarly to the
hydrogenation of crude oil, or may be based on processes of catalyzed
transfer of hydrogen from an hydrogen donor.
Usually up to around 5000 ppm.
Pressure and process temperature depend greatly on the type of process
adopted. The use of molecular hydrogen require temperature in the
order of 350°C and high pressure. Process based on hydrogen transfer
are performed at temperature ranging from 200 to 350 °C atmospheric
pressure.
Hydrogen or a hydrogen donor; catalyst; phase transfer agent;
Soil, PCB oils.
Pretreatment is needed if soil or contaminated devices are treated;
Hydrodehalogenation processes are often operated at high temperature
and pressure, requiring complex plants.
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Process Description
PCB Concentration
Combustion in presence of an excess of oxygen
Usually less than 15% PCB in the waste fed to the
plant
Main Reagents
Chemicals for the treatment of the exhaust gases;
By products, outflows Ashes; flue gases; secondary reagents after the flue
and waste streams
gas treatment
Applicability
Any kind of waste may be treated
Needs for post or pre Depending on the incinerator type.
treatment
Main advantage
Highly flexible; capable to deal with any kind of
hazardous waste; consolidated technology.
Main limitations
High energy requirement. Sophisticated air pollution
control system is needed to reduce PCDD/F
emissions.
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013



Trial burn test 1 (PCB contaminated soil, PCB 1-2%)
– PCDD/F 0.104 ngTEq/Nm3
Trial burn test 2 (PCB oil, PCB 20%)
– PCDD/F 0.042 ngTEq/Nm3
Trial burn test 3 (PCB soil+capacitors, PCB 10%)
– PCDD/F 0.080 ngTEq/Nm3
• Minimize release of POPs from the whole
process !!
Site cleanup
Transportation and
Storage
Final Disposal
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Process Description
PCB Concentration
Main Reagents
By products, outflows
and waste streams
Applicability
Needs for post or pre
treatment
Main advantage
Main limitations
Thermal destruction in the absence of oxygen
Up to pure PCBs
Inert gases
Syngas; Chlorinated salts
Liquid waste (oil)
Depending on the plasma type.
Reduced volumetric emission; very high process
temperature
High electric energy requirement. May require a
system for the cleaning and storage of syngas
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Parameter
Main scope of the plant
Capacity (t/hr)
Maximum power
Max current and voltage
Type of plasma
Type of reactor
CSM Mobile Plasma for
solid waste
Mainly pulverized or
granulated solids
(asbestos); suitable for
semisolid waste or liquid
waste.
0.3
1MW
2000A, 500V
Transferred arc,
computerized design
plasma torches
Cylindrical reaction
chamber (1mx1m)
Batch / continuous process Batch (continuous for
liquids)
Operation temperature in Over 1700°C
the destruction zone
Flue gas flowrate (m3/hr)
500 Nm3/h
Mobile / Transportable /
Transportable
Fixed
PACTTM System for mixed
waste
Solids in drums; suitable
also for semisolid,
pulverized or granulated
waste
PLASCON liquid waste unit
0.2 (based on the duration
of the whole cycle)
0.135 (for pure PCBs)
Only liquids and gases
150KW
Multimodal torch
(nonTransferred for
heating up, transferred for
melting waste)
Centrifugal chamber (1m3)
Non transferred arc, in
flight destruction of waste.
Continuous
Continuous
1650°C
3100°C
Fixed
0.5 Nm3/hr
Mobile
“In flight” tube.
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Process description
PCB Concentration
Process temperature
Process pressure
Main Reagents
By products, outflows and
waste streams
Applicability
Needs for post or pre
treatment
Main advantage
Main limitations
Technology based on the physical replacement of contaminated
dielectric oil in transformers with new dielectric oil.
Not limited by concentration but the cost increases with increasing
PCBs concentration.
From ambient temperature to around 100°C, depending on the type
of technology adopted.
May be carried out at ambient pressure or under vacuum.
None
The main waste stream is the replaced oil that need to be
decontaminated or destroyed..
Transformers and capacitors with high residual value, not at their end
of life. Large transformers with low PCB contamination.
None.
Simple process very effective for low contaminated transformers .
Not a stand alone technology. Requires further process for the
subsequent destruction of PCBs.
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Decontamination trends with retrofilling, starting from
different concentrations. For pure PCBs, at least 6 cycles
are required to bring PCBs contamination below 50 ppm
1000000
100000
10000
1000
100
10
1
0
1
2
3
4
5
6
7
8
Number of retrofilling cycles
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Process
description
Technology based on the partition of chemical species between two immiscible phases.
PCB Concentration Not limited by concentration but the cost increases with increasing PCBs concentration.
Process
temperature
Process pressure
Main Reagents
By products,
outflows and
waste streams
Applicability
May vary with the type of process considered. Critical solvent temperature processes require a
variable temperature during the process.
May be conducted at ambient pressure (standard solvent processes); high pressure (near critical
temperature solvent process) or under vacuum (solvent extraction in autoclave).
Organic solvents.
Different waste streams (contaminated oil, debris, water, sludge, metal scraps) may be
generated during the pre-treatment steps. The use of volatile solvent may require a careful
control of the atmospheric emissions. The outflow of a solvent extraction system is typically a
concentrated extract of PCB, which has to be destroyed.
Transformers and capacitors at their end of life; contaminated soils and wastes.
Needs for post or Pre treatment of contaminated wastes is necessary (opening of the capacitors and transformers
pre treatment
carcasses; meshing and fracturing of the soil, etc.) After the extraction, concentrated PCBs
must be stored and destroyed.
Main advantage
Flexible process capable of treat any kind of media.
Main limitations
Not a stand alone technology The use of solvents may require an high level of safety
countermeasures to prevent exposure of workers.
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
Process Description
Physical desorption of PCB by means of
heating in presence of vacuum or a carrier
gas.
PCB Concentration
Up to 10000 ppm in soil; Equipment carcasses
contaminated with pure PCBs
Main Reagents
Carrier gas for the removal of PCB; solvents
By products, outflows and Pure PCBs is extracted from the solvent after
waste streams
decontamination; sludge contaminated by
PCBs; VOCs
Applicability
Contaminated soil and PCBs contaminated
carcasses
Needs for post or pre
Treatment of the off gases (scrubbers, fabric
treatment
filters, condenser);
Main advantage
Consolidated technology;
Main limitations
High energy requirement; high moisture
content may be a limitation to the process
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
….Questions ?
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013