Ciba Specialty Chemicals PROTECTION
Ashless Additive Technology For Modern Turbine Oils
Lubricants Russia 2006 WORD TRADE CENTER MOSCOW Picture: Schweiz Power Systems Ciba SC,Siemens Lubricants RussiaAG - November 2006
Steam-, Gas- and Combined Cycle Turbines Electricity
Gas Combustor
Gas turbine unit
Steam turbine unit
1250-1500°C
600°C Heat exchanger Steam generator
Generator
550°C
Steam
Generator
< 200°C Water
Condenser Ciba SC, Lubricants Russia - November 2006
DIN specification: 51515 ¾ DIN 51515 -1 (June 2001) TD (Turbine “Dampf” = Steam) ¾ normal duty, typical tests are ¾ TOST life: 2000 h ¾ Copper corrosion, rust method A, foam, air release, water separation ¾ The foaming requirements are very low: 450/0-450/0-450/0 to emphasize the importance of the air release. (Negatively affected from Antifoam agents) ¾ DIN 51515 – 2 (November 2004) TG (Turbine, gas) ¾ For higher Temperature services; typical tests are ¾ RPVOT: 800 min ¾ TOST life: 3000h ¾ RPVOT modified: 85% retention ¾ Copper corrosion, rust method A, foam, air release, water separation
Ciba SC, Lubricants Russia - November 2006
The new ISO 8068 (September 2006) TSA TGA
Steam turbine for normal (low) temperature Gas turbine, for normal (low) temperature
TSE TGE
Steam turbine for normal (low) temperature with EP Gas turbine for normal (low) temperature with EP
TGB TGSB
Gas turbine, B = higher temperature Gas + steam Turbine, higher temperature
TGF TGSE
Gas turbine, higher temperature with EP Gas turbine + steam, higher temperature, with EP
TGCH
Gas turbine for high temperature formulated from synthetic base oils
TGCE
Gas turbine for high temperatures used in aircrafts
THA THE
Turbine for normal temperature operating in the boundary/mixed lubrication regime Turbine for normal temperature operating in the boundary/mixed lubrication regime with EP additives
TSD TGD
steam Turbine, fluid based on phosphate ester = fire resistant gas Turbine, fluid based on phosphate ester = fire resistant
THCH THCE
Turbine, fluid environmentally acceptable based on PAO (almost AWHF: HEPR) Turbine, fluid environmentally acceptable based on Esters (almost AWHF: HEES)
Ciba SC, Lubricants Russia - November 2006
Typical requirements for TGB, TGSB, TGF and TGSE OXIDATION TESTS ¾TOST life: min 3500 h ¾ RPVOT: min 750 min ¾ RPVOT modified: 85% retention Pretreatment of the sample at 121°C for 48 h with a continuous steam of dry Nitrogen at a rate of 3l/h
Picture: Drew Troyer, "Looking Forward to Lubricant Oxidation?" Practicing Oil Analysis Magazine. March 2004
¾ Oxidation stability at high temperature ASTM D 4636-2: (72h at 175°C) ¾ viscosity change: report ¾ acid number change: report ¾ metal specimen mass change (steel, aluminum, cadmium, copper, magnesium): max 2.5 mg/cm2)
Ciba SC, Lubricants Russia - November 2006
OEM Specifications OEM/Organization
Specification
Turbine Type
Comments
Alstom
HTGD 90117
Gas/Steam
With and without FZG requirement; D2272 minimum of 300 minutes. D943 of 2000 h; Zinc max 5 ppm.
General Electric
GEK 101941A
Gas, Frame 6F
FZG requirement of 8 fail (minimum); D2272 minimum of 500 minutes
General Electric
GEK 107395A
Gas/Steam, Class H
D943 minimum of 7000 hours; D2272 minimum of 1000 minutes; modified D2272 test
General Electric
GEK 27070
Steam
General Electric
GEK 28143A
Gas, Frame 3, 5, & 6B
With and without antiwear additives
General Electric
GEK 32568f
Gas, Frame 7/9
D2272 minimum of 500 minutes; modified D2272 test
General Electric
GEK 46506D
Steam
D2272 minimum of 250 minutes
Mitsubishi Heavy Industries
MS04-MA-CL001
Gas/Steam
"Dry TOST" specification; low temperatures; D943 of 2000 h;
Mitsubishi Heavy Industries
MS04-MA-CL002
Gas/Steam
"Dry TOST" specification; high temperature; D2272 minimum of 700 minutes
Mitsubishi Heavy Industries
MS04-MA-CL003
Gas
"Dry TOST" specification; high temperature with EP; D2272 minimum of 700 minutes; D943 of 4000 h
Siemens
TLV 9013 04
Gas/Steam
With and without FZG requirement
Siemens Westinghouse
M spec 55125Z3
Gas
D2272 minimum of 350 minutes
Ciba SC, Lubricants Russia - November 2006
Dry TOST Requirements: ¾ Dry-TOST according to ASTM D943 however run at 120
without water.
¾ RPVOT and filtration (1 μm filter) used for the monitoring ¾ amount of sludge has to be at below 100mg/kg at 25% of RPVOT residual ratio ¾ Dry TOST live min. 500h@25%RPVOT
Ciba SC, Lubricants Russia - November 2006
Sludge Formation in modern Turbine oils ¾ Modern base oils have better oxidative stability but poorer solvency for any sludge generated. ¾ Acidic products can be insoluble in hydro treated oils and not increase the TAN ¾ Test results (e.g. TOST life) can be misleading Comparison of typical long life Turbine oils: A
B
C
D
TAN (after 10.000 h TOST ASTM D 943)
0.09
0.04
0.33
0.05
Sludge, mg
175
219
526
411
RPVOT, min
68
47
44
156
% of original
5.4
3.5
9.1
6.4
HPDSC, min
18.9
15.9
10.1
19.9
% of original
44.7
21.6
28.5
32.4
There was no significant increase in oil viscosity at 10,000 hours Ciba SC, Lubricants Russia - November 2006
Requirements for additives ¾“Operating experience has shown the antioxidant of the di-tertiary butyl-paracresol (DBPC) type is not suitable for this service. The inhibitor must be of a non-volatile type” (MS04-MA-CL002 and GEK 32568f) ¾“This (specification) exempts lubricating oil that includes phenol type antioxidants only as oxidation inhibitor.” (MS04-MA-CL001) 100
Weight loss [%w/w]
0
80
20
60 40
Low volatile Ciba Antioxidant
2,6-DTBP 40 60 20 80 DBPC 1000 0
50
100
150
200
250
300
350
400
Temperature [°C] Æ choose only thermally stable, non volatile Antioxidants Ciba SC, Lubricants Russia - November 2006
Primary AO Mechanism of Aminic AO ROOH
ROO RO
ROH
H N
N
N
HH
N
O
One molecule of aminic Antioxidant can convert app. 36 radicals = high stoichiometric factor
R"
ROO
ROO R' RO
N O
OOR
N
inactive
ROOR
R
ROO R O N
Ciba SC, Lubricants Russia - November 2006
Mechanism of phenolic AO ROOH
ROO RO
ROH
OH
O
O
R
R
H R
+
Synergistic effects Phenolic AO Degradation
Aminic AO
Mix of Aminic AO and Phenolic AO
R'OO
O
R
OOR'
inactive
Time Ciba SC, Lubricants Russia - November 2006
One molecule of phenolic Antioxidant can convert app. 3 radicals = lower stoichiometric factor
Metal deactivator ¾ To obtain good results in the Oxidation tests metal deactivation is necessary: Cu
2+
+
Cu
Cu
2+
Cu +
+ Cu
RH
+
oxygen
+
Cu
+
ROOH
+
ROOH
Cu
+
Cu
H
+
+
2+ +
H
+
+
ROO °
OH
-
+
RO
°
N N
3
R°
2+
N CH
+
R
N
N
N
H
CH NR' 2 2 Non volatile additive
Volatile additive
Ciba SC, Lubricants Russia - November 2006
Additives to meet the EP requirements ¾ Most Turbines operate in the hydrodynamic regime, anti-scuff protection is needed for geared turbines. ¾ All Specifications require an FZG (ASTM D 5182) ¾ Only mild EP Additives are suitable to prevent sludge formation. Suitable additives to meet an failure load stage of 12: O RO
P 1-2
OH
S * HNR'2 2-1
Amine phosphates
2-1
R
P O
S
R'
O
R
Dithioshosphates
¾ Required treat rate is only 300 ppm:
Ciba SC, Lubricants Russia - November 2006
Picture TU Dresden: FZG-torque change device
Ciba Turbine oil packages ¾ Providing a balanced formulation of ¾ Antioxidants ¾ Corrosion inhibitors ¾ Metal deactivators ¾ EP-AW additives and more ¾Typical Formulation: 0.42% of a base package and 300 ppm of an EP/AW additive TEST
Group I oil
Group II or III oil
TOST life
~ 3000 h
>10000 h
TOST sludge (1000 h)
< 20 mg
< 20 mg
~ 700 min
~ 1600 min
> 95%
> 95%
DRY TOST@25%RPVOT
-
~ 1200 h
DRY TOST@25%RPVOT
-
< 100 mg
12
12
RPVOT RPVOT retention
FZG failure stage load
Æ Only the right selection of an suitable additive packages and the right base stock yield the required performance Ciba SC, Lubricants Russia - November 2006
Ciba Specialty Chemicals PROTECTION
providing solutions for Modern Industrial oils with our ashless additives and packages meeting stringent specifications ensuring a long life of your equipment
Any questions !
Picture: Schweiz Power Systems Ciba SC,Siemens Lubricants RussiaAG - November 2006
