Oil & PCBs Free Program - Solution for PCB decontamination

“Oil & PCBs Free” Program:
BAT/BEP – LCM (Life Cycle Management) for
Inventory, Control, Management,
Decontamination of Electrical Transformer
PCBs contaminated (On Site & On Load)
Sea Marconi Technologies sas - All Right Reserved

Vander Tumiatti
• President and Founder of Sea Marconi Technologies, Turin (Italy) since 1968
• Ass. Secretary IEC TC 10 (International Electrotechnical Commission) Geneve-CH
• IEC «1906 Award» - 2009
• Expert PEN - UNEP (POPs-PCBs Elimination Network- United Nations Environment
Programme) Geneve - CH
©2012

May 2012

Sea Marconi - Key Information
• Foundation: 1968, by Vander Tumiatti
• Mission: Protection of company assets
and environmental resources
• Activities: Research, Technologies and
Services for Energy & Environment
• Clients: > 3,000 users in the energy,
industry and service sectors, worldwide

• Human resources: about 100
employees
• Quality & accreditation: ISO 9001-
2008, Globe (Sea Marconi
Technologies), ACCREDIA
• Patents: over 40 in EEC, USA, etc.
• Expertise: members in WGs (IEC,
CEN, CIGRE)
©2012

Headquarters (North Italy)
May 2012

Where we are

Karlsruhe – Germany
Homécourt – France
2007
2002
Collegno (Turin) – Italy
Barakaldo – Spain 1968
2002

Lecce – Italy
1992
©2012

Buenos Aires – Argentina
2004 May 2012

Sea Marconi - Technical Capabilities
Power transformers treated per year (2011) 670
PCBs Dehalogenation (CDP Process®) 226
Depolarisation and Reclaim 106
Reconditioning 338
Oil mass treated per year (2011) 5.971 ton
PCBs Dehalogenation (CDP Process®) 1.831ton

Reclaim and depolarisation 1.796 ton
Reconditioning 2,344 ton
Number of decontamination units (DMU by Sea Marconi) 25
Oil samples analysed per Year (2011) 13.287
Transformers analysed per Year (2011) 8.409
Oil test performed per Year (2011) 71.104

Transformers database > 50.000
©2012

Diagnostics database > 150.000

May 2012

Key References of PCBs dehalogenation
• EDF (France): Framework Agreement for PCBs decontamination of
at least 200 power transformers per year (since 2003)
• SNCF (France): Framework Agreement for PCBs decontamination
(since 2007)
• RTE (France)
• ENEL (Italy): >200 power transformers decontaminated (since
1993)

• Italian Army (Italy)
• Endesa (Spain): about 30 power and distribution transformers
(2007-2009)
• C.E.R.N. (Switzerland)

More than 8000 power transformers in the last 25 year…
©2012

May 2012

©2012 Sea Marconi Technologies sas - All Right Reserved

May 2012
Focus on the Transformer

Scenario

Protection of Resources Assets & Environment
Failure Explosion Fire

Old age
Occasional
Infancy

Damages

• Direct: Assets & Personal
• Indirect: Production
• Environment: soil, water, air
©2012

Black-Out
May 2012

PCBs: Regulation & Standards

UN initiatives for mitigation of POPs/PCBs
1) Protocol to the Convention on Long-range Transboundary Air Pollution on
Persistent Organic Pollutants (1979) and Executive Body Decision (1998)
2) “Stockholm Convention on POPs”, 22/05/01
3) Several UN-promoted projects worldwide for Environmentally Sound
Management of PCBs

The UN/ECE Protocol on POPs defines the 16 most hazardous substances for
human kind and the environment: PCBs is between them

 In the framework of the Stockholm Convention on POPs recently was launched the PEN
(PCBs Elimination Network)
AIM: promotion of the cost-effective completion of the environmentally sound
management (ESM) of liquids and equipment contaminated with PCBs
©2012

 Sea Marconi is an Expert and Founding Member of PEN

May 2012


Decontamination Regulatory References

 IEC 60422 Ed. 4 2012 Supervision and maintenance
guide for mineral insulating oils in electrical equipment
 IEC 61619 insulating liquids – Contamination by PCBs.
Methods of determination by capillary column Gas

chromatography
 CENELEC CLC/TR 50503 (02/2010)- Guidelines for the
inventory control, management, decontamination and/or
disposal of electrical equipment and insulating liquids
containing PCBs
 Brochure CIGRE n. 413 (April 2010)- Insulating oil
©2012

Regeneration and Dehalogenation
May 2012


CENELEC CLC/TR 50503 (02/2010)

Scope:
“….toward the Life Cycle Management (LCM) of insulating liquids … with
the following objectives :

a) Reduction of risks for workers, public health and environment, arising
from human error, malfunction, or failures of the equipment that
cause fires or spillage of hazardous and Persistant Organic Pollutants

(POPs);
b) Implementation of the “Best Available Techniques” (BAT) “Best
Environmental Practices” (BEP) and methodologies available for
safety, whilst taking into account the surroundings and the criteria of
self-sufficiency and functional recovery;
c) Technical faisability of the activities within the prescribed time
schedules, taking into account current legislation and economical
feasability .”
©2012

May 2012


EUROPEAN DIRECTIVE n. 59/96 of 16.09.1996
ARTICLE 2 ARTICLE 3
(a) PCBs means “…….DECONTAMINATION and or
- POLYCHLORINATED BIPHENYLS DISPOSAL shall be effected at
- POLYCHLORINATED TERPHENYLS (PCTs) the last by the end of ……
- MONOMETIL-TETRACHLORO DIPHENIL “2010”
METHANE, ……. (PCBT)
- ANY MIXTURE CONTAINING ANY OF THE
ABOVE MENTIONED ARTICLE 4
SUBSTANCES IN A TOTAL OF MORE THAN INVENTORY
“…..within 3 years of the adoption

0,005% BY WEIGHT
of this Directive ….”

PCBs INVENTORY IN FRANCE
(30 June 2002)

545,610 units
©2012

May 2012

SEA MARCONI approach

“Oil & PCBs Free” Program:
BAT/BEP – LCM (Life Cycle Management) for
Inventory, Control, Management,
Decontamination of Electrical Transformer
PCBs contaminated (On Site & On Load)
©2012

May 2012

SEA MARCONI approach

“PCBs Free” Program:
Sea Marconi provides an integrated service including
• Support for PCBs-inventory (training, analysis, data management)
• Decontamination of PCBs-containing oil/equipment
• Risk analysis and evaluation of transformer’s operational condition
• Survey and control of contaminated sites

In accordance with the European Directives 59/96/EC, art. 4:
- Test methods IEC-EN 61619
- EN 12766-1
- prEN 12766-2
- prEN 12766-3
©2012

- prEN 50503

May 2012

SEA MARCONI: Life Cycle Management (LCM) approach

INSULATING FLUID like “HUMAN BLOOD”
©2012

May 2012


Sampling for Diagnostic Tests

Transformer oil “Human blood”
©2012

May 2012


Laboratory for analyses

Sea Marconi lab Typical “Hospital” lab
©2012

May 2012


Sea Marconi Laboratory
Advanced analysis methods

Accreditation internationally accepted
Quality certification:
ISO 9001; ISO 17025-2000

Our laboratory analysis is among the best
in the world:
• for the range of tests performed
• for the technologically advanced

instrumentation
• for the methodologies used
Accreditated tests:
- PCBs, PCT, PCBsT, (IEC 61619:1997-
04; EN 12766 -3:2004)
- Dissolved water (IEC 60814:1997-08)
- Furfural and derivative compounds
(IEC 61198:1993-09;)
©2012

- Dissolved gases in oil (IEC
60567:2005-06)

May 2012


Diagnosis for identification of functional and
environmental criticalities (According to IEC 61619, EN 12766)
PCBs test report Diagnosis with health index
Test results with and Suggested actions
method, uncertainty
Trend analysis
©2012

May 2012


Oil & Transformer decontamination

Decontamination Mobile Unit (DMU) “Human blood dialysis”
©2012

for oil & transfo, On site & On load

May 2012

SEA MARCONI solution: PCBs dehalogenation

Dehalogenation & Detoxification of PCBs
Chemical process capable to eliminate or reduce PCBs
contamination from insulating oils.

Several type of process are available, the best compromise
between efficiency and safety conditions is the
dehalogenation in continuous mode by closed circuit

process (CDP Process®) by Sea Marconi.

The process uses a solid reagent consisting of a high molecular
weight glycol mixture, a base and a radical promoter for the
chemical conversion organic chlorine to inert salts.

Typically it includes: heating to 90-100 C, filtration, vacuum
treatment, chemical reaction and percolation under pressure
©2012

through suitable materials.

May 2012


CDP Process®
Patents CEE n.0675 748 - USA n. 5.663.479

1982 First patent
1983 Successful application for the complete dehalogenation
of the 2,3,7,8 TCDD, Dioxin of the “Seveso Case” in Italy
1985 Industrial application on power transformers oil in non-

continuous mode (batch process)
1992 Development of continuous process (Close cycle)
2003 On load application on high voltage power transformers
2007 from the BAT Reference Italian Ministry of the
Environment as Best Available Technique for PCBs
decontamination of electrical equipment in service
(Official Gazette n.133)
©2012

May 2012


CDP Process®
Dehalogenation of PCBs and environmental protection

Patent:
EEC 0675 748
USA 5.663.479

The closed-loop,
continuous-mode,
risk-free

decontamination of
PCBs

CDP Process® is the exclusive and safe technology for the
Decontamination of transformers and the Dehalogenation/Detoxification
©2012

of PCBs in insulating oils with the functional recovery and “PCBs-
FREE” re-classification of transformers
May 2012

PCBs decontamination, alternative techniques

Sodium, Litium and derivates
(Ref IEC 60422, Ed. 4 2012, 12.4.2)

 Alkaline metals sodium, lithium and derivates
 Oil Temperature > flash point (150-300 C)
 Risks of explosion and fire with water and air
 Non continuous process

NON CONFORMITY
(EC Directive 96/61/CE)
©2012

May 2012


Sodium, Litium and derivates
(Ref IEC 60422, Ed. 4 2012, 12.4.2)

News /video sent by TGR - Piemont (2010)

Explosion, FIRE and BLACK OUT
©2012

May 2012


Polyethyilene-glycole and hydroxide of
potassium (KPEG) (Ref IEC 60422, Ed. 4 2012, 12.4.3)
 Liquid reagent formed by Polyethyilene-glycole and
hydroxide of alkaline metal (K, Na)
 Oil Temperature > flash point (130-150 C)
 Limited efficiency for some PCB congeners

(Aroclor 1242)
 Non continuous process

DANGER
©2012

May 2012

PCBs decontamination Techniques comparison

CDP Process®: Best Available Technique (BAT)
Italian Ministry of the Environment, the Territory and the Seas
Decree 29/01/2007 – Published on the Official Gazette n.133:

Guidelines for the identification and utilization of the
Best Available Techniques on Treatment of PCBs, apparatuses
and wastes containing PCBs and stocking systems

Table E3 – Decisional matrix for the various available techniques

Functional Environmental Operator Eco-balance Global
METHODS Cost/Benefit
Safety safety Safety and Emissions
Ratio
Retrofilling
*** ** *** * **
Sodium, Lithium and
Derivates * * * ** *
KPEG ** *** *** ** **
Continuous Closed-
©2012

Loop Dehalogenation *** *** *** **** ****
(CDP Process®)
**** = OPTIMUM; *** = GOOD; ** = AVERAGE; * = CRITICAL
May 2012


CDP Process®: features of the process
(CENELC TR 50503 8.4.2.3; IEC 60422 Ed 3 12.4.4; Cigre Brochure no. 413 10.1.4)

 Exclusive Technology developed by Sea Marconi
 Use of solid reagent for de-chlorination of PCBs
 Low operational pressures and temperatures (< 80 -100 C)

CDP Process® = PCBs dehalogenation + oil regeneration simultaneously =

recovery of oil properties and extension of transformer life-time

• ON-SITE Process: No need for transportation of
“big” transformers
• PCB-decontamination of oil in continuous, closed
loop (without draining the equip.)
• Performed by DMU – Mobile Decontamination Units –
©2012

safety and high automated

May 2012


CDP Process® - Schema of PCBs dehalogenation

PCBs
PCBs
PCBs
PCBs

PCBs PCBs
©2012

Desludging effect on core and active parts

May 2012

©2012

DMU (Decontamination Mobile Unit) by Sea Marconi
May 2012

PCBs Dehalogenation Sea Marconi – How does it work?
The dehalogenation (CDP Process®) is performed using
Decontamination Mobile Units (DMU) by Sea Marconi.
The reaction takes while the oil is circulated through
DMU a percolation columns, filled with a solid reagent
containing glycols (PEG, PPG) and strong basis on a
solid matrix.
©2012

Without S/CDP® reagent the dehalogenation of
PCBs would not be possible
May 2012


CDP Process® - Chemical mechanism
1 1 1 1
3 2 2 3 3 2 2 3
R-[O-CH2CH2]n-OH + MOH
4 4 1
4 4
1
+ MCl
5 6 61 51
80 - 100 C 5 6 61 51

Cl m Cl n Hm H n
m + n = 1 a 10 m + n = 1 a 10

Where:

MOH is an alkaline base
R-[O-CH2CH2]n-OH + MOH is a polyalkylene glycol
MCl is an inorganic alkaline chloride

The dehalogenation reaction promote the conversion of PCBs
into byphenyl and an inert and harmless inorganic salt,
©2012

THIS MEANS ELIMINATION OF PCBs WITHOUT PCBs WASTE

May 2012

Dehalogenation Sea Marconi – On Load Treatment

transformer is fully operational for
©2012

the entire duration of the
dehalogenation
May 2012

Decontamination Mobile Unit (DMU) by Sea Marconi

DMU = Multifunctional Technologies
According with CENELEC 50503, IEC 60422, CIGRE Brochure no. 413/2010

Physical CHEDCOS CDP PROCESS®
Main function
decontamination depolarisation dehalogenation

Recovery of dielectric properties   

Recovery of the chemical properties of

 
the oil (acidity, delta tg, colour)

Elimination of DBDS (main responsible of
 
corrosive sulfur problem)
Elimination of dissolved organo-metallic
 
contaminants

Dehalogenation / Detoxification of

PCB/PCT/PCBT, POPs, compounds etc.
©2012

May 2012

Multifunctional DMU: decontamination also for DBDS

Before Abatement of DBDS After

Concentration (mg/kg)
160

140 DBDS
Irgamet 39
120

100

80

60

40

20

ASMT Scale: 4c 0
0 1 2 3 4 5 6 7 8 9 10
ASMT Scale: 1a
Number of treatment cyles

DBDS
dibenzyldisulfide DBDS
dibenzyldisulfide
©2012

Oil change color during the process
May 2012

Decontamination Mobile Unit (DMU) by Sea Marconi

SAFETY FEATURES – Process Monitoring
• The DMU is equipped with process control
logical systems (PLC)

• Oil circulation is automatically stopped in
case of emergency

• Process control is independent from the
physical presence of an operator – the unit

operates 24h (GSM Remote Alarm and
Monitoring)

The monitoring is extended to
all relevant parameters:
• Temperature
• Pressure
• Flow rate
©2012

• Oil level in vacuum chamber
• Smoke detector
May 2012

REAL CASES: before and after PCBs Dehalogenation

CASE 1 – Macedonia, April 2012_______________________

PCBs [mg/Kg]
Initial contaminat.: 109
Final contaminat.: < 2
Treatment duration: 6 Hrs

CASE 2 – Korea, July 2009___________________________

PCBs [mg/Kg]
Initial contaminat.: 297
Final contaminat.: < 2
©2012

Treatment duration: 4 Hrs

May 2012


Power Transformer
REAL CASE (Sept 2011 – France)
Constr. Year 1975
of PCBs dehalogenation
Voltage 400 KV
with CDP Process® Power 250 MVA

Oil Weight 84.500 Kg
Before After Recommended Value
Parameter
Dehalogenation CDP Process® (96/59/CE)

PCB/PCT/PCBT (mg/kg) 107,6 < 10 < 50 mg/kg

Dissolved Gases (%) 4,2 1,1 -

Dissolved Water (mg/kg) 12,4 8,7 < 10

Dissipation Factor (tg delta) 0,1875 0,0352 < 0,1

TAN (mgKOH/g) 0,1460 <0,030 < 0,10

Colour 3,5 1,0 -
©2012

Breakdown Voltage (kV) 57,5 71,5 > 60

May 2012


REAL CASE (1996)
International Tender of the Electricity Authority of CYPRUS for:
“Elimination of PCBs from the insulating oil of distribution transformers”
Distribution Transformers: 520 units
Mass of contaminated oil: 94 ton
Power range: 10–1000 kVA
PCBs Contamination Range: 50–15.000 mg/kg

Sea Marconi awarded the tender in
collaboration with Pawels Trafo Service –
Charleroi (Belgium)

• Alternative Solutions: incineration and replacement with new units
• Sea Marconi’s Solution:
• Reconditioning and classification as “PCB-free” of transformers
• Accomplishment of tender’s targets: PCBs < 10 mg/kg after 60 days
©2012

• Result: saving of 2 million USD
(avoided transformer replacement and waste disposal)
May 2012


Environmental Performance of CDP Process®
• Chemical destruction of PCBs (PCB-free waste)
• Top-level countermeasures to avoid PCBs release during process
• Low temperature process and heat-recovery technology
• Avoidance of massive CO2 emissions in comparison with incineration

LIFE CYCLE ANALYSIS-CO2 DIRECT EMISSIONS FOR 10000 LITERS OIL TREATED-

COMPARISSION RETRO FILLING AND DEHALOGENATION (CDP PROCESS)

DIRECT EM ISSIONS CO2/UF RETRO-FILLING DIRECT EM ISSIONS CO2/UF DEHA LOGENA TION
55 MILLION
DELTA=49,6
30,00 26,52
C O2 EM ISSION TONS CO2
50 ( T ON S / 1 0 0 0 0 LIT ER S
OIL T R EA T ED ) 48,6
45 25,00
40
35,31
35 20,00
30 RETRO FILLING DEHALOGENATION
25 15,00
DELTA=295
20
15 11,8 10,00
DELTA=1,6
10
5,00 0,53
5 1,49 0,94 0,04 0,98
0
0
PART OF CO2 EM ISSIONS PART OF CO2 EM ISSIONS PART OF CO2 EM ISSIONS TOTAL 0,00
DUE TO TRANSPORTS DUE TO PRODUCTION OF CO DUE TO ELIM INATION OF DIRECT CO2 EMISSIONS -RETRO-FILLING FOR 545 000 DIRECT CO2 EMISSIONS -DEHALOGENTION FOR 545 000
PRODUCTS (REAGENT OR WASTE (USED OIL)
TRANSFORMERS (MILLION TONS CO2) TRANSFORMERS (MILLION TONS CO2)
©2012

REM PLACEM EM T OIL)

LCA and CO2 emissions: CDP Process® vs Retrofilling

May 2012

SEA MARCONI Technology Transfer

Sea Marconi’s Technologies Worldwide
permanent presence of DMU Sea Marconi

United Kingdom
1999/2000 Macedonia 2012
South Korea 2009

Mongolia 2012

Argentina
2004/2005 Brazil 2008 South Africa 2007
©2012

May 2012

Conclusions

CDP Process®: PCBs dehalogenation + Functional
recovery/reuse of operational transformers

1. Non-Combustion Technology, no explosion risks, no leakage risk
2. Target: transformers and insulating liquids contaminated with up
to 50.000 ppm of PCBs
3. PCBs destruction  PCBs-free waste
4. On-site application without draining of transformer

5. Well proven Technology: more than 25 years experience and 8.000
transformers treated
6. Transfo energized and onload during the process
7. Sea Marconi: technological partner of top-level companies
worldwide
8. CDP Process®: Best Available Technology (BAT) - BEP in PCBs
©2012

decontamination of electrical equipment

May 2012

CDP Process®: PCBs dehalogenation

Stationary plant option - Batch technology
 Open cycle process (discontinuous mode)
 Off line and off site application
 Advantageous for heavy contaminated and waste oils
 Reaction takes place quickly in heated and stirred reactor
 Time consuming in separation of by-products

Empting of equipment
Chemical reaction
Decanting
Adsorption - Filtration
Degassing dehydration
(only for re-use)
©2012

Storage of clean oil

May 2012

Since 1968

www.seamarconi.com

Contacts

Vander Tumiatti Alessandro Capo
President and Founder Sales Manager

Sea Marconi Technologies Sea Marconi Technologies Sas
Via Ungheria 20 Via Ungheria 20
10093 Collegno (Turin - Italy) 10093 Collegno (Turin - Italy)
Tel. +39 011 234.34.34 Tel. +39 011 234.34.34
©2012

Fax +39 011 234.34.35 Fax +39 011 234.34.35
e-mail: tumiatti@seamarconi.it e-mail: capo@seamarconi.it

May 2012

Oil & PCBs Free Program - Solution for PCB decontamination

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