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(QUICK) Overview of PCB disposal technologies. Carlo Lupi – UNIDO consultant [email protected]. Thank you very much for your Kind attention. ….sorry – any question ?. Commercial technologies for PCB treatment. TECHNOLOGIES FOR HIGH CONCENTRATED OR PURE PCBs. - PowerPoint PPT Presentation
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PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
(QUICK)OVERVIEW OF PCB
DISPOSAL TECHNOLOGIES
Carlo Lupi – UNIDO [email protected]
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
THANK YOU VERY MUCH FOR YOUR KIND ATTENTION
….sorry – any question?
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
COMMERCIAL TECHNOLOGIES FOR PCB TREATMENT
Thermal technologi
es
Incineration
Co-Incineration
(Cement kiln)
Plasma
Chemical technologi
es
Sodium based dechlorination
Hydro-dehalogenatio
n
Post -Treatment
Solvent Washing
Retrofilling
Thermal desorption
Vacuum washing
Pre-treatment
Draining
Shredding
Vacuum extraction
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
TECHNOLOGIES FOR HIGH CONCENTRATED OR PURE PCBS
Oil
Thermal technologies
Transformers
Thermal technologies
Cleanup of carcasses
Post - treatment
Capacitors
Pre treatment
Thermal technologies
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
TECHNOLOGIES FOR LOW-MEDIUM CONCENTRATED PCBS (I.E. UP TO 10000 PPM )
Oil
Chemical dehalogenatio
n
Oil reprocessing
New transformer
s
Pretreatment (draining, flushing)
Chemical dehalogenation (of the oil)
Retrofilling
Old transformer
s
Pretreatment (draining,
dismantling)
Chemical dehalogenatio
n
Post treatment
Recovery of scrap metal
Capacitor (very rare)
Draining or shredding
Chemical dehalogenatio
n or incineration
Thermal treatment of
the waste
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
DECONTAMINATION TARGETS
•Stockholm Convention: <50 ppm•National regulations: <2ppm to <50 ppmRegulatory level for equipment
and dieletric oil
•Burning oil: (40 CFR 761.20) <2ppm (if greater only incineration is allowed)
•Unused oil: not detectable (IEC 60296 / IEC 61619)
Other uses by sector
•Cleanup level for soils (from 0.1 ppm to 15 ppm)Environmental
standards
•Low POPs content: <50 ppm (cann be landfilled)
•High POPs content: >50 ppm (cannot be landfilled)
POPs waste
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
REQUISITES FOR DISPOSAL TECHNOLOGIES UNDER THE SC
•“destroyed or irreversibly transformed”
• otherwise disposed of in an environmentally sound manner (low POPs content)
•In compliance with all other national and international rulesArticle 6.1(d)(ii) of the
Stockholm Convention
on POPs requires that Stockpiles of
POPs and waste
contaminated by POPs must be
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
BAT AND BEP UNDER THE STOCKHOLM CONVENTION
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
EFFICIENCY MEASUREMENT: DE AND DRE
•((Input mass – Sum of ALL outputs)/Input mass)*100
•>99,99%
DE•((Input mass – mass released
in the atmosphere) / input mass)*100
•>99.9999%
DRE
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
NEED TO PERFORM TRIAL BURN TESTSID
123456789101112131415161718192021222324252627282930313233343536373839
PCB soil (1-2%)200 kg/h
400 kg/h600 kg/hPCDD/F sampling
12
3Sampling flue gas for other pollutantsSampling waste, bottom ashes, fly ashes, sludge
PCB oil (20%)100 kg/h
140 kg/hPCDD/F sampling
12
3Sampling flue gas for other pollutants
Sampling waste, bottom ashes, fly ashes, sludgePCB Soil and capacitors (10%)
200 kg/h400 kg/h
600 kg/hPCDD/F sampling
23
Sampling flue gas for other pollutantsSampling waste, bottom ashes, fly ashes, sludge
200 kg/h400 kg/h
600 kg/hPCDD/F sampling
12
3Sampling flue gas for other pollutants
Sampling waste, bottom ashes, fly ashes, sludge
16 18 20 22 0 2 4 6 8 10 12 14 16 18 20 22 0 2 4 6 8 10 12 14 16 18 20 22 0 2 4 6 8 10 12 14 16 18 20 22 0 2 4 6 8 10 12 14 16 18 20 22 0 2 4 6 8Mon 14 Sep Tue 15 Sep Wed 16 Sep Thu 17 Sep Fri 18 Sep Sat 19 Sep
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
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
PRE-TREATMENT AND FEEDING
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
INHERENTLY AND DEMONSTRABLY SAFE
•A technology that achieves the highest possible level of occupational safety and has a history of safe operation.
Demonstrably safe
•Closed system of the technology as a whole (pre-treatment + destruction process)
Inherently safe
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
MONITORING AND PERMITTING ISSUES
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
METALLIC SODIUM DEHALOGENATION OF PCBSMain reactions / Description
Technologies based on the use of metallic sodium to dechlorinate the PCB molecules.
PCB Concentration Generally not suitable for pure PCBProcess temperature 100° - 200°Process pressure AtmosphericReagents Metallic sodium.By products, outflows and waste streams
Sludge,
Applicability OilsNeeds for post or pre treatment
The process requires the dewatering and degassing of the matrix to be treated.
Main advantage Short time. Oil may be reused after treatment.
Main limitations Hazardous substances (Metallc sodium explodes when in contact with water)
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
COST FACTORS: METALLIC SODIUMSupplier Technology A Technology BArochlor type 1242 1254Amount PCB (tons) 1 1Moles PCB 3883 3063Moles Cl 11649 15318Moles Na 11649 15318Cl (tons) 0.41 0.54Na (tons) 0.27 0.35Na consumption declared
0.41 0.93
Reaction efficency 65.09 37.90Nacl produced 0.68 0.90BiPhenils produced 0.60 0.47Waste (sludge) 1.28 1.37
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
MOBILE DEHALOGENATION FACILITY
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
MOBILE DEHALOGENATION PLANT
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
MOBILE DEHALOGENATION PLANT
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
STATIONARY DEHALOGENATION PLANT
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
A-PEG DEHALOGENATION OF PCBSMain reactions / Description
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.
PCB Concentration
Reported up to 45,000 ppm. – usually not suitable over 2000 ppm.
Process temperature
70° - 200°
Process pressure
From atmospheric to 3.5 bar (CDP)
Main Reagents 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, outflows and waste streams
Mainly non toxic salts, and muds; be to when the process is used for the decontamination of transformer, the oil containing de-halogenated aromatics compound is re-used into the 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 pre treatment
It may be necessary in the case of treatment of contaminated soil or wastes.
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
MOBILE DEHALOGENATION FACILITY
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
STATIONARY DEHALOGENATION FACILITY FOR SMALL TRANSFORMERS
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
MOBILE DEHALOGENATION
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
HYDRODEHALOGENATION OF PCBSMain reactions / Description 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.
PCB Concentration Usually up to around 5000 ppm.Process temperature 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.
Process pressure
Main Reagents Hydrogen or a hydrogen donor; catalyst; phase transfer agent; Applicability Soil, PCB oils.Needs for post or pre treatment
Pretreatment is needed if soil or contaminated devices are treated;
Main limitations Hydrodehalogenation processes are often operated at high temperature and pressure, requiring complex plants.
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
INCINERATION
Process DescriptionCombustion in presence of an excess of oxygen
PCB Concentration 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 and waste streams
Ashes; flue gases; secondary reagents after the flue gas treatment
Applicability Any kind of waste may be treatedNeeds for post or pre treatment
Depending on the incinerator type.
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
INCINERATION PLANT FOR HAZARDOUS WASTE (INCLUDING PCBS)
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
INCINERATION PLANT FOR HAZ. WASTE
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
THE ROTARY KILN OF THE SHENYANG INCINERATOR
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
NEED FOR AN LCA APPROACH IN PCB MANAGEMENT
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
PLASMA
Process DescriptionThermal destruction in the absence of oxygenPCB Concentration Up to pure PCBsMain Reagents Inert gasesBy products, outflows and waste streams
Syngas; Chlorinated salts
Applicability Liquid waste (oil)Needs for post or pre treatment
Depending on the plasma type.
Main advantage Reduced volumetric emission; very high process temperature
Main limitations 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
PLASMA (CONT’D)Parameter CSM Mobile Plasma for
solid wastePACTTM System for mixed waste
PLASCON liquid waste unit
Main scope of the plant Mainly pulverized or granulated solids (asbestos); suitable for semisolid waste or liquid waste.
Solids in drums; suitable also for semisolid, pulverized or granulated waste
Only liquids and gases
Capacity (t/hr) 0.3 0.2 (based on the duration of the whole cycle)
0.135 (for pure PCBs)
Maximum power 1MW 150KWMax current and voltage 2000A, 500VType of plasma Transferred arc,
computerized design plasma torches
Multimodal torch (nonTransferred for heating up, transferred for melting waste)
Non transferred arc, in flight destruction of waste.
Type of reactor Cylindrical reaction chamber (1mx1m)
Centrifugal chamber (1m3)
“In flight” tube.
Batch / continuous process
Batch (continuous for liquids)
Continuous Continuous
Operation temperature in the destruction zone
Over 1700°C 1650°C 3100°C
Flue gas flowrate (m3/hr)
500 Nm3/h 0.5 Nm3/hr
Mobile / Transportable / Fixed
Transportable Fixed Mobile
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
TRANSPORTABLE PLASMA PLANT
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
RETROFILLINGProcess description Technology based on the physical replacement of
contaminated dielectric oil in transformers with new dielectric oil.
PCB Concentration Not limited by concentration but the cost increases with increasing PCBs concentration.
Process temperature From ambient temperature to around 100°C, depending on the type of technology adopted.
Process pressure May be carried out at ambient pressure or under vacuum.Main Reagents NoneBy products, outflows and waste streams
The main waste stream is the replaced oil that need to be decontaminated or destroyed..
Applicability Transformers and capacitors with high residual value, not at their end of life. Large transformers with low PCB contamination.
Needs for post or pre treatment
None.
Main advantage Simple process very effective for low contaminated transformers .
Main limitations Not a stand alone technology. Requires further process for the subsequent destruction of PCBs.
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
COST FACTOR FOR RETROFILLING CYCLES
1
10
100
1000
10000
100000
1000000
0 1 2 3 4 5 6 7 8
Number of retrofilling cycles
Decontamination trends with retrofilling, starting from different concentrations. For pure PCBs, at least 6 cycles are required to bring PCBs contamination below 50 ppm
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
SOLVENT WASHINGProcess 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
May vary with the type of process considered. Critical solvent temperature processes require a variable temperature during the process.
Process pressureMay be conducted at ambient pressure (standard solvent processes); high pressure (near critical temperature solvent process) or under vacuum (solvent extraction in autoclave).
Main Reagents Organic solvents.By products, outflows and waste streams
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.
Applicability Transformers and capacitors at their end of life; contaminated soils and wastes.Needs for post or pre treatment
Pre treatment of contaminated wastes is necessary (opening of the capacitors and transformers 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
SOLVENT WASHING
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
SOLVENT WASHING
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
THERMAL DESORPTIONProcess 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 waste streams
Pure PCBs is extracted from the solvent after decontamination; sludge contaminated by PCBs; VOCs
Applicability Contaminated soil and PCBs contaminated carcasses
Needs for post or pre treatment
Treatment of the off gases (scrubbers, fabric 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
JIANGDE TDU
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
JIANGDE TDU
PPG Inception Meeting – Colombo, Sri Lanka 5-10 August 2013
THANK YOU VERY MUCH FOR YOUR KIND ATTENTION
….Questions ?