Corrosive Sulphur IEC

7/21/2019 Corrosive Sulphur IEC

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Technical Market Support

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The NOVA GradesPresentation

Dipl.Ing.Gerfrid NeweselyGmunden, 27.Feb.2007


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Properties

Class IA Class IIA Class IIIA

Kinematic viscosity, mm2/s at 40C < 16,5 < 11,0 < 3,5

at -15C < 800 -- --

at -30C -- < 1.800 --

at -40C -- -- < 150Flash point, C > 140 > 130 > 95

Pour point, C < -30 < -45 < -60

Appearance

Density, kg/dm3 at 20C

Interfacial tension, N/m at 25CNeutralisation number, mg KOH/g

Corrosive sulphur

Water content, mg/kg

Anti-oxidant additives

Oxidation stability

Breakdown voltage:as delivered, kV

after treatment, kV

Dissipation factor, at 90C and 40 to 60 Hz

see note

< 0,895

Non - corrosive

30 / 40; see note

0; 0,3; see note

Limits

clear, free from sediment and suspend matter

< 0,895

> 40; see note

> 30

> 50

< 0,005

IEC 60296 Ed.2/1982


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Revision Requirements

Viscosity classification, Pour point etc.

Acidity test

Corrosive sulfur test

Oxidation stability criterions

New requirements


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Properties

Transformer Oil Low Temp. Switchgear Oil

Kinematic viscosity, mm2/s at 40C max. 12 max. 3,5

(LCSET) at -30C max. 1.800 --

at -40C -- max. 400

Pour point, C max. -40 max. -60

Water content, mg/kg

Breakdown voltage, kV

Dissipation factor, a t 90C and 40 to 60 HzAppearance

Acidity, mg KOH/g

Interfacial tension, mN/m at 25C

Total sulphur

Corrosive sulphur

Anti-oxidant additives, %

2-Furfural content, mg/kgOxidation stability

Total acidity, mg KOH/g

Sludge, %

DDF / 90C

Test duration, h

Gassing

Flash point, C min. 135 min. 100

Density, g/ml at 20C

PCA

PCB

No general requirement

max. 3% DMSO Extract

Not detectable

Limits

clear, free from sediment and suspend matter

max. 0,895

min. 40; see note

max. 0,005

min. 30 / min. 70

max. 1,2

max. 0,8

max. 0,500

164 (U) / 332 (T) / 500 (I) ; see note

max. 0,1

max. 0,01

Non corrosive

max. 30 / max. 40

0 (U) / 0 - 0,08 (T) / 0,08 - 0,4 (I) ; see note

No general requirement

IEC 60296 Ed.3/2003


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IEC 60296 Ed.3/2003

LCSET Max. viscosity Max. pour point0 C 1800 mm 2/s -10 C

-20C 1800 mm 2/s -30 C

-30 C 1800 mm 2/s -40 C

-40 C 2500 mm 2/s -50 C

Lowest cold start energizing temperature (LCSET)


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Neutralisation number

Coulometric titration (IEC 296 Ed.2/1982)


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IEC 62021-1 AcidityPotentiometric method


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Touch control screen or PC monitor control available

IEC 62021-1 AcidityPotentiometric method


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Corrosive Sulphur ASTM D 1275

250 ml Oil

Cu Strip

140 C

19 hrs


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Corrosive sulphur Test ISO/ASTM


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Corrosive sulphurCopper strip / Silver strip


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Corrosive sulphurDIN 51353

100 ml Oil

Ag strip

100 C18 h


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IEC 60296 Ed.2 Oxidation tests

Test Conditions Measured Criterions

IEC 61125 A 100C Acidity

(IEC 74) 30 cm Cu Sludge1 l O2/h

IEC 61125 B 120C Induction period(IEC 474) 90 cm Cu (until volatile acids

1 l O2/h have neutralized thecaustic solution)


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IEC 60296 Ed.2 Oxidation testsIEC 61125A (uninhibited oils)

Test duration: 164 hours

Oxygen, 1l/min

30 cm Cu-wire

25 ml oil

Test temperature:100C

Limits:

Acidity: max. 0,4 ml KOH/g oil

Sludge: max. 0,1 %


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IEC 60296 Ed.2 Oxidation testsIEC 61125B (inhibited oils)

Test duration: see Induction period

Oxygen, 1l/min


90 cm Cu-wire

25 ml oil

Caustic solution

(corresponding to0,28 mg KOH/g oil)

+ indicator

Limit:Induction period: min 120 hrs

until change of colour


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Test Condition Measured Criterions

IEC 61125 C 120C Total acidity (soluble+volatile)

(IEC 813) 90 cm Cu Sludge0,15 l Air /h Diel.Dissipation Factor

IEC 60296 Ed.3 Oxidation tests


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IEC 60296 Ed.2 Oxidation testsIEC 61125C (uninhibited and inhibited oils)

Test duration: uninhibited: 164 hrs, inhibited 500 hrs

Air 0,15 l/min


90 cm Cu-wire

25 ml oil

Distilled water

soluble acid

sludge

Volatile acid

Limits:

Total acids: max. 1,2 mgKOH/gSludge: max. 0,8 %

DDF: max. 0,500

DDF


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2 options

General specification

(for general application)

Specific Requirements

(for special application)

Limits:


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IEC 60296 Ed.3/2003

Compilation of limits

General requirements Specific requirements

standard ox. stability high ox. stabilitytotal acidity max. 1,2 mg KOH / g max. 0,3 mg KOH / g

sludge max. 0,8 % max. 0,05 %

DDF / 90 C max. 0,500 max. 0,050

total sulphur --- max. 0,15 %

to be agreed

uninhibited oils (U) ---trace inhib. oils (T) ---

inhibited oils (I) ---

Oxidation stability (IEC 1125 C)

Electrostatic tendency ECT

Gassing (IEC 60628 A)


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0

0,02

0,04

0,06

0,08

0,1

0,12

0,14

0,16

0,18

0 5 10 15 20 25 30 35 40 45 50

Jahre

NZ[mgKOH/g]

BLW 12 BLW 13 BLW 14 BLW 23 BLW 28 BLW 30 BLW 35 BLW 45

Acidity of Nynas-Technol Insulating Oilin service in transformers in the Austrian High Voltage Grid


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0

5

10

15

20

25

30

35

40

45

0 5 10 15 20 25 30 35 40 45 50Jahre

Grenzflchenspannung

[mN/m]

BWL 12 BWL 13 BWL 14 BWL 23 BWL 28 BWL 30 BWL 35 BWL 48

Interfacial Tension of Nynas-Technol Insulating Oilin service in transformers in the Austrian High Voltage Grid


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0

5

10

15

20

25

30

35

40

45

0 5 10 15 20 25 30 35 40 45 50

Jahre

tgdelta

BLW 12 BLW 13 BLW 14 BLW 23 BLW 28 BLW 30 BLW 35 BLW 45

Diel.Dissipation Factor of Nynas-Technol Insulating Oil

in service in transformers in the Austrian High Voltage Grid


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The Copper Corrosion Phenomenon


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The Copper Corrosion Phenomenon:Damages in Brazil


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Strong indications:

Sealed or nitrogen blanketed transformers/reactors (rubberdiaphragm equipped conservator, lack of oxygen)

High operating ambient temperature but within design limits

Transients

In combination with certain components in oil

The Copper Corrosion Phenomenon:Criteria and indications


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Conditions where this phenomen is less likely to occur:

In open breathing transformers (conservators)

When varnished copper is used

The lower the temperature, the lower the risk

The Copper Corrosion Phenomenon:Criteria and indications


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Oil reactionswith copper

Low presence of oxygen and high temperatures will promote sulfur/copperreactions on the conductor surface and form deposits which might migrate to theinner cellulose layers.

Oil soluble copper ions might migrate into the oil and form copper sulfide on theoutside of the cellulose and/or spacers.

Copper

Paper

S

R

Cu-Sulfide

Cu-ion

Reaction on copper surfacecan deposit on paper andpenetrate to next layer

Copper ions dissolved in the oil

Copper sulphide deposits on paper

+Sulfur

Cu-Sulfide


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Development of Copper corrosion test methods:

ABB - CCCD Test (Covered copper conductor deposition)


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Development of Copper corrosion test methods:ABB - CCCD Test (Covered copper conductor deposition)


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Development of Copper corrosion test methods:ABB - CCCD Test (Covered copper conductor deposition)Results 1


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Development of Copper corrosion test methods:ABB - CCCD Test (Covered copper conductor deposition)Results 2


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Mineral oil chemistry

Basic hydrocarbon structures in mineral oil


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Mineral oil chemistry

Theoretical molecules in naphthenic oil


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Sulphur containing moleculesSmall sulphur containing molecules are more reactive than larger

Small sulphur containing molecules are not present in transformer oils

However, larger sulphur containing molecules are present in oils and arepotentially reactive towards copper and some are acting as inhibitors

S

RR

S

RR-S-R

R-S-S-R

R-SH

Decreased reactivity


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Nitrogen containing molecules

N

N

N

R

N N

Nitrogen are present in oil in various molecular structures

Nitrogen molecules are potential promoters for copper migrationand/or could act as copper passivators


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Hetero atoms in mineral oil molecules are necessary to achievegood oxidation stability

Mineral Oil Chemistry


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Hydrotreatment Refining- Optimization of properties

Need of optimization but you can not get everything


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A Modern Hydrotreatment Refinery


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Hydrotreating processes


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Tests of the new oil filled in one failed reactor


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Nynas Selected Passivator

Oil soluble BTA derivative

Commercially available

Developed for use in high temperature lube oil applications,e.g. turbine oil

Protects copper and yellow metals


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Passivators: Test results(ASTM 1275 B)

D = Oil C

passivated

B = Oil A passivated

after 15 h ageing

A = New Oil C = used OilE = New Oil

H = Oil Epassivated


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Technical solutions

In-service solutions

Add passivator to transformers at risk: Halts any further degradation

Nynas TRO products

Nynas offer special passivated products:

Nytro 10GBN passivated

Nytro 10 GBA passivated

Nytro 10 GBX passivated

Nytro 10 XN

Nytro 4000A/X


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Corrosivity Tests

Corrosive sulphur DIN*) DIN 51353

Corrosive sulphur ASTM**) ASTM D1275

These methods are mainly developed to detect contaminants frommanufacturing/handling of transformer oil.

*)IEC 60296

Potentially corrosive sulfur compounds in transformer oil ??


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Development of Copper corrosion test methods:Copper strip method to detect corrosive and potentially

corrosive sulphur in insulating oil

Corrosive sulphur ASTM D 1275

ASTM 1275 A ASTM 1275 B

140C 150C19 h 48 / 72 h


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Development of Copper corrosion test methods:CIGRE - CCD Test

for detection of potentially corrosive sulfur in insulating oil

Head space vial

15 ml Oil

30 mm Cu

150 C

72 h


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Development of Copper corrosion test methods:CIGRE - CCD Test

for detection of potentially corrosive sulfur in insulating oil


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Hydrotreatment Refining- Optimization of properties

Need of optimization but you can not get everything

NYNAS - NOVA GRADES:


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TaurusLibraSTANDARD

Lyra X10XN

Gemini X

HIGH

4000XSUPER

INHIBITEDUNINHIBITED


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10XNGasoil Arctic Grade

Gemini XLibraGasoil

4000XLyra X

TaurusNon Gasoil

INHIBITEDUNINHIBITED

NYNAS - NOVA GRADES:

Documents

Corrosive Sulphur IEC