TLM2013,TransformerLifeManagement,Hannover/Dubai

NewIEC60296(ed.4)
FromaTransformerOilManufacturersPerspective

Nils Herlenius
ErgonEuropeMEAInc. DrveRichelle161,BuildingC B1410Waterloo,Belgium nils@ergon.com

Jimmy Rasco and Edward Casserly

Ergon,Inc. Jackson,Mississippi392151639,USA

ABSTRACT
ThispaperhighlightssomeofthemajorupdatesinthenewIEC60296(ed.4,publishedin2012),Fluidsforelectrotechnical applications Unused mineral transformer oils for transformers and switchgear [1], and some of the considerations a transformeroilmanufacturerneedstotakeinordertofullymeetthenewIEC60296standard.

1. INTRODUCTION

The IEC 60296 (ed. 4) published in February 2012 replaces the IEC 60296 (ed.3) from 2003 [2]. Since 2003, various findings made an update of the IEC 60296 necessary. Few ofthemmentionedbelow: In 2005, Doble conducted testing for presence of corrosive sulphur in some 500 unused transformer oils. The tests showed that more than 40 percent of the oils were corrosive as per ASTM 1275A [3] which was the existing testmethodforcorrosivesulphur. In 2006, the laboratory of Sea Marconi Technologies and the Italian utility Terna, together with Italian and US Universities, identified a single compound, suspected to been added to the oil as an antioxidant, in declared un inhibitedtransformeroils[4]. In 2009 Cigre published a report on the copper corrosion problem Copper sulphide in transformer insulation [5] and IEC published the new corrosive test method IEC 62535 [6], complimenting the already existing corrosive testsDIN51353[7]andASTM1275B[8]. In 2010 Cigre started the new working group A240, Copper sulphide longterm mitigation and risk assessment [9], and IEC initiated work to establish an official IEC method of detecting Dibenzyl Disulfide [10]. Professor Kapila from the University of Missouri Rolla presentedattheMyTransfo2010thedetectionofan

undeclared metal deactivator in transformer oils in his presentation Rapid and Specific Determination of Additives, Contaminants and Byproducts in Transformer Mineral Oils with Electrospray Mass Spectrometry and TandemMassSpectrometry[11] In 2011, the Belgian laboratory Laborelec [15] presented a paper on its discovery of an undeclared metal deactivator intransformeroils.

2. MajorchangeofIEC60296(ed.4) versusIEC60296(ed.3)
Newinterpretationofuninhibited andinhibitedtransformeroil Metalpassivators/deactivators Dibenzyldisulfide Otheradditives Corrosivesulfurtest

2.1Newinterpretationofuninhibited andinhibitedtransformeroil

In the previous IEC 60296 (ed. 3) inhibitors improving the oxidation stability of the transformer oil were strictly limited to those described in the IEC 60666 Detection and
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TLM2013,TransformerLifeManagement,Hannover/Dubai

determinationofspecifiedadditivesinmineraltransformer oils [13]. No other additives improving the result the oxidation stability were allowed as per the IEC 60296 (ed. 3). If any of the antioxidant of the IEC 60666 were added, the oil should have been declared as either trace inhibited or inhibited transformer oil depending on the amountofinhibitorused. In the new IEC 60296 (ed.4), the definition of un inhibited and inhibited transformer oils is only linked to the antioxidants of the IEC 60666. As before, if any of the antioxidant described in the IEC 60666 are added the transformer oil should be declared as either trace inhibited or inhibited. Furthermore, in the new IEC 60296 (ed. 4) any additives may be used, including those which as per IEC 60296 definition are defined as an antioxidants.Thechoiceofantioxidantsisnolongerlimited tothosedescribedintheIEC60666. As a consequence, the transformer oil manufacture can addanyantioxidantadditivethatisnotdescribedintheIEC 60666 and declare the oil as uninhibited, even though thetransformeroilcontainsasyntheticantioxidant.

2.3DibenzylDisulfideDetection

MethodfordetectionofdibenzyldisulfideasperIEC62535 [6] is added as a compulsory requirement. For more informationregardingthisadditive,see:[4],[16]and[17].

2.4OtherAdditives
Known by few and used by even less, in the previous IEC 60296 (ed.3), article 5.4C gave the buyer an option to requestthesuppliertodeclarealladditivesintheoil.Inthe newIEC60296(ed.4)alladditivesshallbedeclared. An transformer oil that fully complies with the new IEC 60296 (ed.4) shall include the following information on additivesintheProductDataSheet(PDS): Antioxidantadditives,aspertheIEC60666 MetalPassivators,aspertheIEC60666 DibenzyldisulfideaspertheIEC62535 OtherAdditivesshallbedeclared

2.2MetalDeactivators
The discovery of metal deactivators in some transformer oilsonthemarket[11and12]raisedconcerns.Thesetypes of additives could hide potentially corrosive oil and give so called false negative results on corrosion tests. These additives additionally sabotage the oxidation test and do not give a fully representative result of the oxidation test, though the known metal deactivators are consumed quickly in service. The use of such additives without declaration and agreement with the buyer of the transformer oil is a violation of both the previous IEC 60296(ed.3)andthenewIEC60296(ed.4). Chemical literature classifies metal deactivators into two major groups as per their functioning mechanism, which either can be of chelant or of passivating type [19]. The new IEC 60296 (ed. 4) describes both metal deactivators and metal passivators as examples of antioxidant additive, but it is important to note that the IEC60666canonlydetectsmetalpassivators,i.e.notmetal deactivatorofthechelanttype. As per the new IEC 60296 (ed.4) the oil shall be tested for metal passivator additives of IEC 60666. Some of the other metal deactivators found declared or undeclared in transformer oils and that is not described in the IEC60666, can be detected by independent laboratories such as: Sea Marconi[14]andLaborelec[15].

It is important to note that as per the new IEC 60296 (ed.4), if any additives are added that improve the oxidation stability, i.e. not only those described in the IEC 60666,thetransformeroilshallbesubjecttothe500hours oxidation test as per IEC 61125 C [18]. Example: any oil containingametaldeactivator,passivatingorchelanttype.

2.5CorrosiveSulfurTest
Additionally to the corrosive sulphur test DIN 51353, the IEC 62535 [6] test on potentially corrosive sulphur is included in the new IEC 60296 (ed. 4). An informative annex has also been added with information on potentially corrosive sulfur. The annex includes useful information on how to detect corrosive sulphur compounds in oil containing a metal passivator additive (declaredorsuspected),[1]

3. ManufacturingofTransformerOil MeetingtheIEC60296(ed.4)

For a mineral transformer oil to meet the new IEC 60296 (ed.4) standard: crude oil selection and correct oil fractionation by distillation are important to meet the requestedviscosityat40and30degreeCelsius(ISO3104), sufficient amount of polycyclic aromatic compounds must be removed in order to pass the health requirements (IP 346), corrosive sulphur has to be removed in order to pass the not corrosive requirements tested as per IEC 62535
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TLM20 013,TransformerLifeManagement, ,Hannover/Duba ai

and DIN 513 353. As per the IEC 6029 96 (ed. 4), the t t transformeroi ilshallmeetmore m than20re equirements. T To manufactu ure mineral na aphthenic tran nsformer oil that meets the IEC C 60296 (ed.4), , there are basically four ste eps as illustrated in picture 1: Crude C oil selec ction, Distillation, d Blending. Paraffinic transformer t oil Cleaning and additionallyne eedstounderg goadewaxingprocess.

3.1Crude eOilSelection
Atypicalmisun nderstandingisthatthecorr rosivebehavior rof t the oil is depe endent on the e origin of the crude oil. The ere are several so ources of good d quality naph hthenic crude oil, appropriate for f premium transformer oil production, w with very diffe erent total sulp phur content, such a North Sea S crude with ap pproximately 0,5 0 weight perc cent sulphur and a V Venezuelan cr rude with approximately 2,7 7 weight perce ent s sulphur. But th here is no link between tran nsformer oils that are corrosive, i.e. do not pass p the corro osive tests of IEC e DIN 51353, and a the origin of the crude oil. 62535 and the Insteadoilfoundtobecorro osivehaveoriginatedfrombo oth low sulphur containing crud de to high sulphur level cru ude otal sulphur co ontent of a crude oil is not an oils. So the to indicator if the finished d transforme er oil will be ot. corrosiveorno

oil dist illate and it i is only the hi igher molecular weight uted dibenzot thiophene molecu les, such as the substitu unds, that are present in the e oil after the d distillation compou process s. In the cas se of benzot thiophene or dibenzo thiophe ene compound ds, there are s substituted hyd drocarbon groups attached to th he carbons on the base ring structure. eight of the molecule increases the As the molecular we hat is listed in the table. ease above wh boiling point will incre er,thebasebe enzothiophene echemistryisr retained. Howeve

Table1:B BoilingPointforcertainsu ulphurcompound.Source e:ErgonandAlbermarle

3.3Cl leaningby ymeansof f Hydrotre eatment

The tr ransformer oil distillate is not accep ptable as transfor t will not pass the IEC 602 296 (ed.4) rmer oil as it require ments. The d distillate stock k still contain ns sulphur unds that are corrosive at t typical conditio ons found compou inatran nsformerinse erviceandtheo oxidationstabilityofthe distillat e is not suffici ient and would d not pass the oxidation C61125C[18]requiredaspe ertheIEC6029 96(ed.4). testIEC

P Picture1:TypicalTransfo ormerManufacturingPro ocess.

3.2Distillation D
T The distillation n of the crudeoil is a process where the oi il is being separate ed into differe ent fractions depending d on the t boiling tempe eratures. The light fractions s, i.e. the gas ses, distills at a te emperature of f less than 40 0 degrees Cels sius (<105F), while the heavies st fractions, i.e e. asphalt, would oximately 700 0 degrees Celsius (1290F) and a distill at appro above. A typic cal cut for transformer oil is i similar to lig ght g gasoil or die esel, i.e. typic cal 300370 degrees Cels sius (572698F).

There are several methods us sed for clea aning the rmer oil distillate but most commonly, us sed by the transfor major t transformer o oil manufactur rers, is hydrot treatment (also so ometimes calle ed hydrofinishi ing or hydropr rocessing). Hydrotr reatment(see picture2)isaprocesswhere eunstable molecu les such as those contain ning oxygen, nitrogen, r,andmetalsa areremovedan ndolefinsandaromatics sulphur are satu urated. By rem moving these unstable mole ecules and saturatiing the carb boncarbon do ouble bonds, we are eliminat ting the risk o of getting an o oil that is dang gerous for health (by removing the polycyclic c aromatic compounds) tions that and eli minating the possibility of adverse react the typical ope erating conditions found could h appen under t ansformer. Dur ring the hydro otreatment pr rocess the in a tra
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T Table 1 conta ains the boili ing points of certain sulph hur compounds. The T distillation process gener rally excludes the t lower molecul lar weight com mpounds from the transform mer

TLM20 013,TransformerLifeManagement, ,Hannover/Duba ai

oil is exposed to high pressure, approxim mately 2000 PS SIG h temperatu ure up to 385 5 degrees Cels sius ( ~140 bar), high (725F), plenty y of hydrogento feed chemical reactions and a a nickelmolyb bdenum orcob baltmolybdenu um catalyst tailor madeforremo ovalofreactive ecompounds.

bility is of The op timum point of maximum oxidation stab when manufac cturing an un ninhibited crucial importance w rmeroilmeetingtheIEC602 296(ed.4),i.e.anoilthat transfor will pas ss the 164 hours oxidation stability test a as per IEC 61125 C [18] without t the use of additives such as s peroxide decomp posers, metal passivators an nd deactivators that all havean nimpactonthe eoxidationtes st.

Picture2:Cleaningthe eTransformerOilDistillat tebyHydrotreating

T The severe conditions c fou und in the hydro h treatme ent process, you will w never find d in a transfor rmer even und der t the most seve ere conditions, see table 2, and the sulph hur containing compounds c that would survive the t hydrotreatmen nt process and a end up in the finish hed t transformer oil are very few w (typically 25150 ppm), stable osive, i.e. they easily pass the DIN 51353 and a and noncorro t theIEC62535requiredbyth henewIEC602 296(ed.4).

erOilDistillatebyHydrotr reating Picture3: CleaningtheTransforme

3.4Blend ding
The ble ending can be e either adding different strea ams of the g process or adding additi ives such as the ones refining describe 0666 for a trace or inhib bited type ed by IEC 60 transfor rmer oil. As de escribed in 3.4 4 Other Addit tives, the new IEC C 60296 (ed.4) ) open up for t the use of any additives, includin ng additives n not described in the IEC 60 0666, that improve es the oxidat tion stability as long as they are declare d in the pr roduct data sheet and c certificates pliance. ofcomp

4. .Conclusio onsandRe ecommend dations

Therea aremajorchan ngesinthenew wIEC60296(ed.4)from 2012 co ompared to previous IEC 60 0296 (ed. 3) fr rom 2003. The ne ew interpreta ation of unin nhibited and inhibited transfor rmer oils puts more focus on n the use of ad dditives in transfor rmerliquids.

Table2:Typicalvaluesfo orhydrotreatingprocessversus v apowertransform mer

Picture 3 illust trates the bala ance of various s parameters the t t transformermanufacturer m needstotakein ntoconsideration w when produci ing transforme er oil meeting g the IEC 602 296 (ed.4). As seen n from the pict ture 3: all para ameters, with the t exception of gassing g tenden ncy and oxidat tion stability, are a improvedbyamoresevererefining,i.e.more m severehyd dro t treatment / cleaning of theoil. With more e severe cleaning, t the ability of the t oil to absorb gasses decr reases due to the t reduction of aromatic a carbo ons. There is an optimum po oint w where maximu um oxidation stability s is achieved by keep ping enough stable e sulfur and nitrogen compo ounds in the oil.

To secu ure premium quality, it is important that t users of transfor equestthatthe esupplierfully ymeetthe rmerliquidsre new IEC C 60296 (ed.4 4) including the full decla aration of additive esintheProdu uctDataSheet(PDS).

Thispap perhighlightss majorchangesinthenew someofthem IEC60 0296(ed.4)but titisnotasub bstituteforthenewIEC 60296 (ed.4). It is the erefore highly recommended that the ownloadsthela atestIEC60296 6fromtheIEC. userdo
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Reference es
Fluidsforelectr rotechnicalapplica ationsUnusedmineralinsulating oilsfortransfor rmersandswitchgear IEC60296(ed.4), 4 IEC,2012 [2] Fluidsforelectr rotechnicalapplica ationsUnusedmineralinsulating oilsfortransfor rmersandswitchgear IEC60296(ed.3), 3 IEC,2003 osive Sulfur in Electrical Insulating g [3] Standard Test Method for Corro Oils 0 ASTM Interna ational, 2003 (Re evised or Edited) ) ASTM D127503, [A] [B] [C] [4] Riccardo Maina , Fabio Scatiggio , Shubhen Kapila , [A] [A] [D], VanderTumiatt ti ,MichelaTumiatti andMassimoPompilli Dibenzyldisulfide(DBDS)ascorro osivesulphurCont taminant usedmineraltrans sformeroils,2006, , inusedandunu [A] [B] Sea Marconi Technologies, Co ollegno (TO) Italy, Terna S.p.A, [C] [D] Venezia Italy y, University of Missouri Rolla USA, Universit degliStudidiRo omaLaSapienza RomaItaly Dibenzyl disulfide (DBDS) as co orrosive sulfur con ntaminant in used d o presented at a the CIGRE Task k and unused mineral insulating oils, ForceA232.01, ,Paris,France,200 07. [5] CIGREWGA232, 3 CoppersulphideintransformerinsulationFinal Report,2009,Brochure B 378,URL: http://a2.cigre.org/cigre_search/ /result/%28Search hText%29/378 Accessed:October30,2012 [6] Insulatingliquid dsTestmethodfor f detectionofpo otentially corrosivesulphurinusedandunu usedinsulatingoil 1),IEC,2008 IEC62535(ed.1 [7] Testingofinsula atingoils;detectio onofcorrosivesulphur;silverstrip test,DIN51353 3:1985,1985 [8] Standard Test Method for Corro osive Sulfur in Electrical Insulating g rnational,2006 Oils,ASTMD127506,ASTMInter [9] CIGREWGA240 4 Coppersulphidelongtermmitiga ationandriskasse essment ea/WGA2.40copp persulphidelong URL: http://a2.cigre.org/WGAre termmitigation nandriskassessm ment Accessed:October30,2012 [10] Testmethodsfo orquantitativedeterminationofcor rrosivesulfur compoundsinunused u andusedinsulatingliquidsPart1:Test methodforqua antitativedetermin nationofdibenzyldisulfide(DBDS) IEC626971(ed d.1),2012 [11] R.Seemamahan nnop(1),KyleAnde erson(1)andS.Ka apila(1) V.Tumiatti(2), Carlo C Roggero(2), Michela Tumiatt ti(2) and Riccardo o Maina(2), Rap pid and Specific Determination of Additives, Contaminants and Byproducts in Transformer Mineral M Oils with h M Spectrometr ryandTandemMa assSpectrometry ElectrosprayMass PresentedatMyTransfo2010,Tu urin,Italy [1]

SeaMarconiTech nologiessas [14] S v viaUngheria20,1 10093Collegno(TO O),Italia T Tel+39011234.34 4.34 F Fax+39011234.3 34.35 E mailinfo@seam marconi.it U URL:www.seamar rconi.com A Accessed:October r30,2012 [15] L Laborelec 630Linkebeek R Rodestraat125,16 T Tel+32(0)23820 211 F Fax+32(0)23820 0241 E mail:info@labo relec.com U URL:www.laborellec.com/ A Accessed:October r30,2012 [16] C C.Qiu,S.Han,X.C ChengandT.Ren D Determining the a antioxidant activit ties of organic sulfides by rotary b bomb oxidation test and pre essurized differential scanning c calorimetry,Therm mochimicaActa,V Vol.447,2006,pag ges3640

[17] S S.Plaza,B.Mazurk kiewiczandR.Gru uzinski T Thermal decompo osition of dibenzy yl disulfide and it ts load carrying m mechanism,Wear r,Vol.174,1994,p pages209216

[18] U Unused hydrocar bon based insula ating liquids Tes st methods for e evaluatingtheoxidationstability,IE EC61125,IEC,1992 [19] J J. Dong, C. Mig gdal, Antioxidants, in Lubrican nt Additives C Chemistry and Ap pplications, L. Ru udnick, ed., 2nd Ed., CRC Press, T Taylor&FrancisG Group,USA,2009,pages350. Nils s Herlenius was b born in Sweden. He has a MSc. Che emical Engineering g from Royal Tech hnical University (KTH H) in Stockholm a and an Executive MBA from the Univ versity of Strathc clyde in Glasgow. He is a well kno wn speaker and adviser at man ny utilities and MS with nearly 2 20 years in the t transformer oil OEM bus iness. Active me ember of both C CIGRE and IEC, pers and reviewing g author for IEEE. He is currently autho r of technical pap nical & Marketing Director for Ergo on Europe MEA In nc. He is also a Techn onatemusicianand daprivatepilot. passio

Jimm myM.Rascowasb bornintheUnitedStates.

served d as Manager o of Technical Serv vice for Ergon Refini ng, Inc, Vicksbur rg Refinery respo onsible for the atory and Technic cal Services for 1 15 years. Jimmy Labora also s served as Vice Pr residentProduct Services, Ergon Refini ng, Inc responsible for quality and d development of napht henic and paraff finic base oils. Jimmy has worked d in petroleum ng for 38 years in the area of Qualit ty Control and Tec chnical support. refinin He cu urrently has globa al responsibility for base oil techn nology for both paraff finicandnaphthen nicproducts.HehasaBSdegreeinChemistryfrom Alcorn nStateUniversity.

[12] A. Schaut, S. Au utru, A. De Rop, S. Eeckhoudt, Effec cts of Irgamet 30 0 as Additive in Transformer T Oil, IEEE Trans. Diele ectr. Electr. Insul., Vol.19,No.1,February, F 2012,p.175. [13] Detection and determination of specified add ditives in mineral insulatingoils,IEC60666(ed.2),IEC,2010

Edw ardCasserly was bornintheUnited dStates.Hehas A. in Chemistry fr rom the University y of St. Thomas a B.A in H ouston, Texas an nd a Ph.D. in Org ganic Chemistry mRiceUniversityin nHouston.Hehasbeeninvolved from in R& &D and technical support for specialty petroleum prod ducts for over 28 years. He has c coauthored 18 scien ntific publications s and is coinve entor on 7 US patent ts.Heiscurrently yDirectorRefine eryR&DforErgonRefining.

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