recovery of sf6 gas

DILO Armaturen und Anlagen GmbH Frundsbergstr. 36 D-87727 Babenhausen

Tel.: (49) 8333/302-0 Fax.: (49) 8333/302-52

Presentation

for training

“Acquisition of the permission to carry out the Recovery of SF6-gas“

Table of contents R

DILO D-87727 Babenhausen

Basic knowledge of relevant environmental issues - Kap.2 1

Sulphurhexafluoride (SF6) - Kap. 3 2

Checking the SF6 quality - Kap. 4 3

Use of SF6 in electric power equipment 4

Recovery of SF6 and SF6 mixtures and

purification of SF6 – Kap. 7.1 5

Determination of the gas state –

Carrying out a measurement – Kap. 7.2 6

Different filter types and adsorbents used in

service devices or mobile prefilter units – Kap. 7.3 7

Safety precautions and - Kap. 7.6.4

Neutralising SF6 decomposition products - Kap. 7.7 8

SF6 data recording obligations - Kap. 8 9

Maintenance equipment for SF6-gas recovery 10

12/10/09

Folie 1Andreas Büscher

AREVA Energietechnik GmbH, Sachsenwerk Mittelspannung

Basic knowledge of relevant environmental issues (T)

(Chapter 2 of the SF6 training documents)

12/10/09



Basic knowledge of relevant environmentalissues

Contents

● Characteristics of SF6

• Greenhouse gases and the greenhouse effect

• Impact of the anthropogenic greenhouse effect

• The Kyoto Protocol

• Global warming potential of SF6

• The Voluntary Commitment on SF6

• European Regulations on certain fluorinated greenhouse gases

12/10/09




Greenhouse gases and the greenhouse effect (1)• These are gases in the

atmosphere that prevent long-wave infra-red radiation frombeing emitted directly fromthe Earth‘s surface into space.

• Chlorofluoro-carbons FCKW´s

(freezing agents in refrigeration systems)• Hydrofluorocarbons FKW´s

(Propellants in spray cans/foams, freezing agents in refrigeration systems)

• Sulphur hexafluoride SF6

• Water vapour H2O• Carbon dioxide C02

• Ozone O3

• Methane CH4

• Nitrous oxide N2O (laughing gas)

Man-made greenhouse gases(long-therm: global heating of the earth‘s surface)

Natural greenhouse gases(increase of 33 0C – necessary fornormal temperatures on earth)

sun

short-wave solar radiation

atmosphere

long-waveradiation

long-waveradiation

earth‘s surface

12/10/09




Greenhouse gases and the greenhouse effect (2)• artificial greenhouse effect cause by man-made greenhouse gases

Heating of the atmosphere caused by greenhouse gases produced by man

The greenhouse effect

Atmosphere

4.) Short-wave radiationpenetrates the Earth‘satmosphere

8.) The atmosphereheats up

6.) Short-wave radiation isconverted into long waveheat radiation

7.) The heat radiationremains in theatmosphere

3.) CO2 flows in theatmosphere

1.) CO2 produced byburning

2.) Emission containlarge quantities of CO2

5.) The surfacereflects radiation

Atmosphere

Greenhousegases

Short-waveradiation of

the sun

Long waveradiation isreflected fromthe surfaceand plants

Glasspanes ofa green-house

12/10/09




The Kyoto Protocol• It is a supplementary protocol to the United

Nations Framework Convention on Climate Change (UNFCC) aimed at protecting the climate.

- Kyoto Conference (Japan) on 11th December 1997• binding target values for emissions of

greenhouse gases 2008 until 2012 5.2% reduction compared to 1990

• gases regulated in the Protocol- carbon dioxide CO2- methane CH4- nitrous oxide N2O- Hydrofluorocarbons H-FKW/HFCs- Perfluorocarbons FKW/PFCs- Sulphur hexafluoride SF6 ratified by 170

states (2007)

12/10/09




The global warming potential

The (relative) global warming potential (GWP) or CO2 equivalent is a measure of how much a given mass of a greenhouse gas contributes to the greenhouse effectCarbon dioxide is used as a comparison value CO2

The GWP describes the average warming effect over a given period

• usually 100 years

22 200Sulphur hexafluoride SF6298Nitrous oxide N2O

up to 14 400

Chlorofluoro-carbons

FKW/HFKW

25Methane CH4

1 430Tetrafluoroethane R-134a, HFC-134a

1Carbon dioxide CO2

Global warming potential GWP (examples)

12/10/09




The global warming potential of SF6

22 200Sulphur hexafluoride SF6

1 kg SF6, which has been released into the atmosphere influences the greenhouse effect like 22 200 kg CO2

GWP

SF6 has the highest global warming potential of all known greenhouse gases!Comparison:

1 kg SF6 released into the atmosphere makes the same

contribution to the anthropogenic greenhouse effect as a

petrol-driven mid-class car with a total mileage of around

120,000 km (emitting around 185 g CO2 per km).

1 kg SF6 emissionabout 120 000 km

12/10/09




SF6 Voluntary Comittment

The Voluntary Commitment of the SF6 producers and the manufacturers and operatorsof electric power equipment > 1 kVfor electrical power transmission and distribution in the Federal Republic of Germany on SF6 as an insulation and quenching gas

Manufacturers and operators work according to the following principles :

• SF6 emissions should be avoided wherever possible.• Quantities of SF6 required to fulfill specific functions should be minimised.

12/10/09




SF6 Voluntary Comittment

In the 2005 version of the Voluntary Commitment the signatories havepledged to reduce SF6 emissions significantly in:

• the manufacture of electric power equipment• its commissioning and operation, and in the• and in the recovery,• recycling (including re-use) and• disposal of SF6.

Is controlled annually by the Federal Environment Ministry / Federal Environment Agency via the national SF6 reporting system.

12/10/09




The European Regulation on certain fluorinated greenhouse gases

Regulation (EC) No. 842/2006 of the European Regulation (EC) No. 842/2006 of the European Parliament and of the Council Parliament and of the Council

of 17 May 2006of 17 May 2006on certain fluorinated greenhouse gaseson certain fluorinated greenhouse gases

Its primary objective is to reduce the emissions of the fluorinated greenhouse gases specified above and thus protect the environment. (need to be reduced by approximately 70% compared to 1990 levels)

Reason• the high global warming potential of fluorinated

greenhouse gases

Validity • all member states of the European Union

- Imports of products, equipment and services into the EU are also subject to the regulation

Member states of the EU

12/10/09




The European Regulation on certain fluorinated greenhouse gases

This regulation applies to:• Certain fluorinated greenhouse gases or gas mixtures containing as listed

in Annex 1, Part 1 of the Regulation• Products and equipment containing these fluorinated gases:

- refrigeration systems- air-conditioning systems - heat pumps- fire protection systems and fire-extinguishers- equipment containing solvents based on fluorinated greenhouse gases- high-voltage switchgear

• Processes and manufacturing procedures that use fluorinated greenhouse gases

• „Avoidable applications“(such as windows, footwear, tyres, single-component foams and novelty aerosols)

12/10/09



Prohibition of using SF6

04.07.2007 04.07.2007

04.07.2007Magnesium melting process in case the annual amount of 850 kg has been exceeded.

12/10/09



Article number

Title of article in the (EC) No. 842/2006 regulation

(additional) detailed

specification in each member state of the EU

3 Reduction of emissions(Control of density)

4 Recovery

5 Training and certification Miniumumrequirements

6 Reporting

7 Labelling (only manufacturer)

8 Control of uses

9 Restrictions on the placing of such products and equipment on the market

10 Revision

11 (Promotion of alternative solutions)

13 Sanctions

Concernment of T&D industry: “High voltage switchgear”also valid for equipment and services imported in the EU

Standardised for and in all member states of

the EU


12/10/09



Definition of the new regulation (EC) No. 305/2008

WhatWhat areare ““highhigh--voltagevoltage switchgearswitchgear““??Switching devices and their combinationwith associated control, measuring, protective and regulating equipment, and assemblies of such devices and equipmentwith associated interconnections, accessories, enclosures and supporting structures, intended for use in connection with - generation- transmission- distribution- conversionof electric energy at rated voltages above 1,000 V.

All SFAll SF6 6 equipmentequipment withwith a a generationgeneration, , transmissiontransmission, , distributiondistribution and and conversionconversion higherhigher thanthan 1 kV1 kV


12/10/09



EU regulation for „high-voltage switchgear“


(EC) No. 1493/2007 establishing the format for the report

Regulation (EC) No. 842/2006

Article 5 „Training and Certification“

Articel 7 „Labelling“

Article 6 „Reporting“

Article 4 „Recovery“

(EC) No. 1494/2007 establishing the form of labels

(EC) No. 305/2008 minimumrequirements for the certification of personnel

Recovery by certifiedpersonnel

12/10/09



Definition of handling SF6RecoveryRecovery

collection and storage from, for example, machinery, equipment and containers

extraction of SF6RecyclingRecycling

extraction of a recovered fluorinated greenhouse gas following a basiccleaning process

re-use of used SF6TreatmentTreatment

reprocessing of a recovered fluorinated greenhouse gas in order to meet a specified standard of performance

The SF6-gas producer Solvay Fluor GmbH, for example, isimplementing the reclamation of used and recovered SF6gas as part of ist re-use concept.

DestructionDestructiontransforming or decomposition into stable substances which are notfluorinated greenhouse gases

burning of SF6, which is not possible to reclaim


12/10/09



ResponsibilityOperators of “high-voltage switchgear“shall be responsible for:

the proper recovery of SF6

to ensure their recycling, reclamation or destruction 1)

Only certified personnel is allowed to carry out gas recovery (and its subsequent handling)

Requirements are stipulated in the commission regulation no. 305/2008

1) Regulation (EC) no. 842/2006, article 4


12/10/09



Activities only by persons holding a qualification certificate

Activities in connection with the recovery of SF6

from “High voltage switchgear“ 1)

Special notes:Not affected: filling or refilling of SF6.The end of life / maintenance / revision / repairworks of “High voltage switchgear” (> 1 kV) are affected in practiseCertificate in accordance with regulations not to be mistaken for company internal certificates

e. g. according to IEC 62271-303• are not accepted by law

1) regulation (EC) no. 842/2006


12/10/09



Content of the training - appendix 1 of the (EC) regulation 305/2008

No. Minimum knowledge and skillsTest type

1

Basic knowledge of relevant environmental issues (climate change, Kyoto Protocol, global warming potential), the relevant provisions Regulation (EC), No 842/2006 and of the relevant Regulations implementing provisions of Regulation (EC) No 842/2006

T

2 Physical, chemical and environmental characteristics of SF6 T

3 Use of SF6 in electric power equipment (insulation, arc quenching) T

4 SF6-quality, according to the relevant industrial standards (1) T

5 Understanding of the design of electric power equipment T

6 Checking the SF6-quality P

7 Recovery of SF6 and SF6-mixtures and purification of SF6 P

(1) For instance IEC 60376 and IEC 60480


T: Theoretical examination with one or several questions per training item P: practical examination

12/10/09



No. Minimum knowledge and skillsTest type

8 Storage and transportation of SF6 T

9 Operation of SF6-recovery equipment P

10Operation of tight drilling systems for suction lines, if necessary (gas tight drilling systems) P

11 Reuse of SF6 and different re-use categories T

12 Working on open SF6-components P

13 Neutralising SF6 by-products T

14Monitoring of SF6 and appropriate data recording obligations under national or Communitiy legislation or international agreements T

T: Theoretical examination with one or several questions per training item P: practical examination


Content of the training - appendix 1 of the (EC) regulation 305/2008

12/10/09



Dead-line and transition period for certification

1th August 2008 Effective as from 4th July 2009

Gas recovery etc. by personnel who carried out

these functions before 4th July 2008

Gas recovery etc. is to

be carried out only by a

certified person 1)

national transition period in Germany (without certificate for transition

period)


1) Exception: persons whoare educated undersupervision of a certifiedperson

12/10/09



Mutual acceptance of certificates for personnelMutual acceptance of certificates for personnel is necessary 1)

Requirement:• Translation of the certificate

into the official EU-language of the corresponding member state! 1)

1) EC regulation no. 3005/2008, article 8


Musterzertifikat

12/10/09



Period of validity of the certificates for personnelCertificate is bounded to a person

• analogue to driving license• not bounded to a company• not transferable to other persons

Certificate without “date of expiry”• one-time acquisition • however: can be revoked by

the certification body for some timeor forever

Basic knowledge of relevant environmental issues

Musterzertifikat

12/10/09



Administrative offence in connection with recovery of SF6

Offence against personal conditions

regarding the recovery of SF6

administrative offence:

in case gas recovery is carried out without the required certification with intent or wilful negligencecivil penalty up to 50,000.00 Euros

Offence against recovery of SF6

administrative offence:

in case the SF6-gas is not recovered or is not recovered in time.civil penalty up to 50,000.00 Euros


Solvay Fluor - SF6 Schulungsunterlagen

Solvay Fluor – RBU LS, [email protected]

Sulphurhexafluoride (SF6)

Kapitel 3: Sulphurhexafluoride

and

Kapitel 7.5: Storage and Transportation of SF6



What is Sulphurhexaflouride (SF6)?

colourless and odourless

• inert and not toxic

• not flammable

• not corrosive

• five times heavier than air – 6,08 g / Ltr.

• sound velocity is around 1/3 regarding to air

• excellent arc-quenching and insulation properties



What is Sulphurhexafluoride (SF6)?

• SF6 is thermally constant up to 500°C

• SF6 – is a relative ozone friendly gas

• SF6 – has the GWP 22.200

• Lifetime in the atmosphere of 3.200 years

• Space saving (Conventional/SF6-Technic = 5 : 1)

• higher switching performance (oil/air / SF6-Techn. = 1:3..4)

At the moment no alternatives to SF6-Gas are available



Gründe für die Verwendung in der Elektroindustrie

• Lichtbogenlöschen 100 Mal schneller als in Luft

arc radius

0.51.0 0

11

10

9

8

7

tem

pera

ture

in K

6

5

4

3

2

1

0.5 1.0

·103N2

SF6

lower limit ofionisation temperature

Temperaturprofil in SF6 and N2 im Lichtbogen(schematische Darstellung von Z. Angew. Physik12, [1960] 5, pp 231 to 237)



• Durchschlagfestigkeit 3 Mal stärker als in Luft

Durchschlagfestigkeit in Transformeröl, Luft und SF6

als Funktion des Gasdrucks(Kali und Steinsalz, 3, Ausgabe 10 [1963] 319)

12.5

12.5

75 m

m

Gründe für die Verwendung in der Elektroindustrie

Die Durchschlagsfestigkeit ist abhängig vom Druck - daher Druck-Kontrolle durchführen.



Advantages of using SF6

• Closed, compact electrical components

• Insensitive to environmental influences

(moisture, sand, salt)

• High personal safety

• Low maintenance efforts

• High reliability

Due to this positive characteristics SF6-Gasis used worlwide in the energy technology



• During an arc quenching the SF6 – Gas can react with the electrodes or the surface materials of the internalcomponents.

�� SF6-decomposition �� Metallfluorides

• Decomposition products

�� solid decomposition products (Partikels or grey dust) �� gaseous decomposition products (smell of rotten eggs)

Characteristics of SulphurhexafluoridDecomposition products



Solid decomposition products



• Solid decomposition products

- with particle filters in the pre filter unit and the particlefilter in the service cart

- with dry vacuum cleaner (dust class „H“)

• Gaseous decomposition products

- with filters in the gas compartment and with the filters in the service device

Characteristics of SulphurhexafluoridDecomposition products of SF6

• How to remove decomposition products



Specification of new SF6

IEC 60376

Specification

In ppm(mass)

Solvay Fluor Specification

in ppm(mass)

Air 2000 (1 Vol-%) 50

CF4 2400 10

Water 25

(Dewpoint -36°C)

0,65 (Dewpoint -65°C)

Oil 10 1

Acidity HF 1 0,3

Hydr. Fluoride not specified 1



SF6-ReUse-SpecificationIEC 60480 Specification

for used SF6

SF6-ReUse-Spezification(IEC62271-303)

Air (N2, O2)

< 3 Vol%

< (30 Vol%)

CF4 < (5 Vol%)

Water < 95 Gew.-ppm (Dewpoint at pa 1bar -23°C)

< 25 Gew.-ppm (Dewpoint at pa 1bar -36°C)

< 1000 ppmm

Oil < 10 Gew.-ppm < 1000 ppmm

HF < (50 Vol.-ppm)

(12 Vol.-ppm S02 und SOF2 / 25 ppm HF)

< 1000 ppmm

Regenerating at the SF6-producer



The SF6-ReUse-Concept

Established since 1991:

• 3 Cases

• Provisioning of ReUse cylinders

• Transport and Labeling

• Analysis of the used SF6

• Direct intigration in the production process withoutspecial cleaning process!

• Producing of new SF6 according to IEC 60376 /

VDE 0373-1 quality



1. Reuse directly on site

Recover the measuring gas

Recover the measuring gas

IEC 60480Gasquality

1. Measurement of the gas quality

- Decomposition products- Volume percententage- Dewpoint

2. Recovery of the decomposed gas and cleaningof the gas to a better quality

3. Monitoring of the recovered gas

4. Measuring of the cleaned gas

5. ReUse the cleaned gas



Checking the gas quality on site

Measuring device Messmedium Measuring range

Accuracy

Volume-Percentage-Measuring device SF6/N2, SF6/Air

0-100Volumen-%

+/- 1 Vol-%

Electronic moisture measuring device H2O/Dewpoint -50°C - 0°C +/- 3°C

Mirror dewpoint measuring device H2O/Dewpoint -60°C - 5°C +/- 0,2°C

Measuring device for decompositionproducts with test tubes

SO2HFOil mist

1…500ppmv1,5…15ppmv0.16…1,6ppm

Keine Angabe

Multi measuring devices SF6/AirH2O/DewpointSO2

0-100%-60°C - +10°C0-500ppmv

+/- 1 Vol-%+/- 2°C+/- 0,4 bis +/- 10 ppmv

Tabelle: SF6-Measuring devices



New gas according to

IEC 60376

VDE 0373-1Checking the gas quality

�� SO2 decompositionproducts

�� H2O�� Air �� Oil mist

SF6producer

SF6 Service device

Recovery at the SF6 producer

ReUse-cylinders

Regeneration laboratory-gas analysis / ReUse-Specification

SF6 filledelectricalcomponent

2. Recovery and regeneration to produce new gas in accordance with IEC 60376



Einspeisung von gebrauchtem SF6 in den Produktionsprozess



3. Disposal of SF6

Checking the gas quality

�� SO2

�� H2O�� Air�� Oil mist

SF6 Service device

SF6

producerDisposal Special case

ReUse- cylinders

Laboratory gas analysisReUse-Specification

SF6 filledelectricalcomponent



SF6 Neugas

nachÜberprüfung des Gaszustandes� Luft, N2 � H2O� Öl �SO2, HF /

Zersetzungsprodukte

gut

HerstellerSOLVAY / SF6Trennanlage

HerstellerSOLVAY

Rückstands-verbrennungs-anlage

DILO Servicegerät

Inspektionsfall

Entsorgungsfall

Rückgewinnungsfall

New SF6

according

IEC 60376

VDE 0373-1

Checking the gas quality

� Air, N 2 � H2O� Oil�SO2, HF /

Decomposition products

good

SF6 producer

SF6 producer

SF6 Service device

Recovery on site

Special case

Regeneration at the SF6 producer

IEC 60376VDE 0373-1

IEC 60480

IEC 62271-303

SF6 filledelectricalcomponents

Summary of all SF6-ReUse-cases

Chemical wasteincinerationfacility



Storage of SF6 ???



Storage of SF6

• Pressurised in steel cylinders• Cool and well ventilated places• Storing away from direct sunlight,

Storage temperature < 50°C according TRG 310, Abschnitt 3.3

• Keep away from heat and flames• Secure the cylinder from overturning and rolling

away



Transportation of SF6

New SF6 Used SF6

Different wall thickness (TRG) and bottle connections (Typ A, DIN 477)

SF6-ReUse-Cylinders



Valves

New SF6 Used SF6

Different materials and threads (Typ A, DIN 477)

Nr.: 6

W21,8 x 1/14“

Nr.: 8

1“



Different labels

New SF6



Different labels

Used SF6



Markings for the transportation on road

New SF6 Used SF6 Used SF6according IEC60480

UN-Nummer:

3308

Classification code:

2TC

Dangerous category:

2.3 + 8

UN-Number:

1080


2

Dangerous category:

2.2

UN-Number:

3163


2A

Dangerous category

2.2



Additional Labelling acc. GHS/CLP regulation

GHS = GLOBAL HARMONIZED SYSTEMCLP = CLASSIFICATION, LABELLING, PACKING

Gas cylinders with SF6 gas according to IEC60480 must be labelled with the following labeland sentences since 01.12.2010:

Label GHS04compressed gases

- H280 Contains gas under pressure;may explode if heated

-P410 Storing away from direct sunlight

-P403 Store at cool and well ventilated places



Label GHS04compressed gases

- H280 Contains gas under pressure; may explode if heated

- H331 Toxic if inhaled- H302 Harmful if swallowed- H312 Harmful in contact with skin- H315 Causes skin irritation- H319 Causes serious eye irritation- H335 May cause respiratory irritation

- P261 Avoid breathingdust/fume/gas/mist/vapours/spray

- P280 Wear protective gloves/protectionclothing/eye protection/face protection

- P305+P351+P338 If in eyes: Rinse cautiously with water for several minutes. Remove contact lenes, if present and easy to do

- P302+P352 If on skin: Wash with plenty of soap and water

- P309+P311 If exposed or if you feel unwell: Call a PoisonCenter or doctor/physician

- P410+P403 Protect from sunlight. Store in well-ventilatedplace

Signal Word: Danger

Sicherheitshinweise:

Label GHS06Danger

Gas cylinders with SF6 gas which does not meet the requirements according to IEC60480 must be labelled with the following labels and sentences since 01.12.2010:

Additional Labelling acc. GHS/CLP regulation



Road transport

Rating based on point system

1.000 points may be transported without driving licence for transport of

hazardous goods, without labeling of the vehicle, without tunnel limitation

and without vehicle registration for transporting hazardous goods.

UN No. 1080 New gas 1 kg corresponds to

1 point1.000 kg

UN No. 3163Used gas according to IEC 60480

1 kg corresponds to 1 point

1.000 kg

UN No. 3308 Re-use gas1 kg corresponds to

50 points20 kg



EN 1089-1 Lage der Stempelung für verflüssigte Gase

Kennzeichnung der Zulassungen auf den Druckgasflaschen



Repeated tests

for compressed gas cylinders and containers

Gas cylinders

(5 – 40kg)

New gas every 10 years Hydrostatic test ??

Containers

(600kg)

New gas every 10 years Hydrostatic test ??

Containers (40kg and 600kg)

Re-Use gas every 5 years Hydrostatic test ??



Identification of checking the SF6 cylinders



Assessment of the used SF6 – Product or Waste

WasteWaste……

Gas AnalysisOn site

Lab/Manufactureror

Gas manufacturer

Compliant withIEC 60480

(DIN EN 60480)

Compliant withIEC TR 62271-303

Not Compliant with IEC TR 62271-303

Suitable for reuse on site:„Used SF6 complying with the maximum acceptable3 impurity level“ according to

IEC 60480

Suitable for reuse at the gas manufacturer:

„Used SF6 suitable for Reuse at the gas manufacturers“:

It has to be disposedaccording to local or

internation reulation on waste management

ProductProduct ProductProduct

04/10/10

Folie 1Kapitel 4 der Schulungsunterlagen

Peter Pilzecker, G.A.S.

Checking the SF6 quality(Kap. 4 der Schulungsunterlagen)

04/10/10

Folie 2Kapitel 4 der Schulungsunterlagen

Peter Pilzecker, G.A.S.

Checking the SF6-quality Gliederung

Introduction

Limit values

Measuring methods

Which parameters should be measuredResults of the parametersMeasuring methodsUse of Combination measuring devices

recovery of sf6 gas

Documents

recovery of sf6

purification of sf6

sulphurhexafluoride

sf6 quality kap

sf6 mixtures

use of sf6

anthropogenic greenhouse

greenhouse effectatmosphere4