Non-Varnishing PAG-based Turbine Fluid and GEK Spec 32568h Recommendations. Govind Khemchandani, Ph. D. The Dow Chemical Company Freeport, TX, USA

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Non-Varnishing PAG-based Turbine Fluid and GEK Spec 32568h Recommendations Govind Khemchandani, Ph. D. The Dow Chemical Company Freeport, TX, USA STLE May 18-22, 2014, Florida Dow.com

Presentation Objectives Polyalkylene Glycols( PAGs) Chemistry and Varnish Free Technology Characteristics PAG-based Turbine Fluid In-Service Monitoring of PAG-based Turbine Oils Inclusion of PAG-based Synthetic Turbine Fluid in GEK 32568h 2

Varnish, Varnish, Varnish TLT Magazine, January Varying degrees of varnished servo valve filters 2008 TLT Magazine, April 2011

Defining the Opportunity Year 2007 Heavy Duty Gas and Steam Turbines Common sump - lube oil & hydraulic system varnishing IGV s and/or GCV s are driving trips Significant cost due to varnish related trips (lost revenue & maintenance) Standard lube oil tests incapable of varnish detection Degradation of hydrocarbon turbine oils continue to persist 4

Why should a gas turbine operator evaluate and specify PAG-based turbine fluid technology? End Users will have less trips and longer service-life by using PAGbased turbine fluids with outstanding varnish-free performance End Users can implement a varnish-free solution faster by leveraging DOW s experience and data in turbo machinery applications 5

PAG Technology: Designed to Refined OSP PO BO

What is different? Degradation by-products of hydrocarbon oils are polar compounds but not soluble in non-polar base oil Mineral Oil Petroleum- based Hydrocarbon Group I Base stock Non-Polar PAO- Poly Alpha Olefin- Synthetic Hydrocarbon Oil Group IV Heavily additized for oxidation stability and has poor solvency H(Me) R1 O O O O O O PAG Poly Alkylene H(Me) Glycol Base H(Me) Fluid Group H(Me) V H(Me) H(Me) O Degradation by-products of PAGs are polar compounds soluble in polar parent base oil R2 Polar Inherently thermooxidatively stable with high VI 7

Equipment Reliability - Varnish Elimination Oxidation of hydrocarbon oils and PAGs 8

Aniline Point for Various Base stocks 160 140 120 100 Group I (MO) VI 95 Group II (MO) VI 102 Group III (MO) VI 135 Group IV (PAO) VI 136 Group V (Napthenic oil) VI 45 Poor Aniline Point (ºC) 80 60 40 Solvating Power 20 0 Group V (PAG) VI >200-20 -40 Strong

TURBO COMPRESSORS - Varnish Elimination 10+ Years Experience Over 100,000 Installations Group I-III Produce Heavy Sludge and Varnish Group IV s Produce Hard Yellow Varnish PAG Technology is Non-Varnishing Polyalkylene Glycol Chemistry Produces NO SLUDGE These Applications Are More Challenging Than Typical Turbine Conditions Leveraged experience to solve varnish problems in gas turbines that used hydrocarbon based fluids 10

Comparative Properties Typical Properties PAG-Based Synthetic Turbine Fluid Vs. A Petroleum-Based Turbine Oil Polyalkylene Glycol Petroleum-Based ISO Viscosity Grade 25 32 @40 C (104 F) cst @100 C (212 F) cst 26.23 32.44 5.19 5.56 Viscosity Index 132 109 Thermal Conductivity @40C watts/m ⁰K 0.145 0.1 Four Ball Wear Scar mm 0.63 0.65 Air release Results ASTM D 3427 Minutes to 0.2% Entrained Air volume 0.4 4.0-5.0 Biodegradable Yes ---- Hydrolytic Stability No Reaction With Water Forms Acids, Degrades 11

Evidence of Technical Solution VISCOSITY COMPARISON 12

Evidence of Technical Solution TURBINE FLUID CONVERSONS, HOURS Converted 41 gas turbines since November 07 All fluid conditions track well Consistent measurements of TAN, Particle Count, Metals, AO, Water Content Base Load, >50K Hrs Cyclic, 21K Hrs Base Load, >40K Hr Peaker 13

DOW PAG-based Turbine Fluid: Monitoring Tests Sample Base Line PAG-based- Turbine Fluid 7 Years, Peaker 21000 Hours 7 Years Base Load >50000 Hours GE Specs GEK 32568G ASTM D 445 Viscosity 26 27.1 26.2 28-35 ASTM D 972 mg KOH/g 0.08 0.2 0.16 0.4 Max ASTM D 6971 Ruler 100 91( 85( 25% Min NOV ASTM D 2272 Minutes 750 509 490 25% Min NOV ASTM D 7843 (MPC Test) 3 11( 9( Trend Monitor Particle Count ISO 4406 12/11/9 14/13/11 15/12/10 - ICP ASTM D 6595 - Sodium 3 6 4 --- Calcium 2 3 2 - Zinc - 1 ---- Phosphorous 1 5 4 4 14

PAG-based Turbine Fluid: Cooler Bearings Bearing Metal Temp - Generator Bearing # Bearing Metal Temp Generator Bearing # Bearing Metal Temp Turbine Bearing #1 Bearing Metal Temp Turbine Bearing #2 Bearing Metal Temp Thrust Active Bearing Metal Temp Thrust Inactive 15

Bearing temp graph -10.77 o - 8.36-7.65-8.47-6.25-5.04 Dow.com

Foaming & Air release Specification Foam Tendency, ASTM D892, ml PAG-based Turbine Fluid PAG-based Turbine Fluid After 5 years use in Peaker Turbine Seq. 1 10/0 10/0 Seq. II 0/0 0/0 Seq. III 0/0 5/0 Air Release, ASTM D3427 (Minutes @ 50 C) 0.4 0.7** Excellent air release for both neat fluid and fluid after five years in peaking Turbine, ** 7 year Peaker sample Lower air release times than those typical of petroleum and hydrocarbon-based turbine fluids 4.0 to 5.0 recently tested) - GEK 32568G Spec requires 5.0 max Prolonged air release times can lead to pump cavitations, micro dieseling, premature oxidation, and component wear. 17

Corrosion Characteristics Sample ASTM D 665 A Rust Prevention Base Line PAGbased-Turbine Fluid 7 Years, Cyclic 21,000, Hrs 7 Years Base Load >50,000 Hrs Pass No Corrosion No Corrosion AST M D 4378 & 6224 Light Fail ASTM D 130 24 Hours @100⁰C Copper Corrosion 1A 1B 1B - 1B Max is GE New Fluid Spec 18

PAINT COMPATIBILITY TEST: P23E-AL-0204 REV. E Experimental Paint: A8B95 1-part Gold Phenolic-Epoxy Primer ( GE approved paint ). Thinner: D5E11 n-butyl Acetate Oils: Dow Turbine Fluid TF-25 and Texaco R&O 32 Surface Preparation Sec 4.5 : Sand blasted steel panels Paint Preparation Sec 4.6 Coating Application Sec 4.7 30 days Immersion testing @ 200 F Delta E is defined as total color difference between sample and the standard BYK Colorimeter S 124026 A. Oil Type Delta E Dow Turbine Fluid TF-25 11.81 Dow Turbine Fluid TF-25 11.42 Dow Turbine Fluid TF-25 12.12 Texaco R&O 32 21.30 Texaco R&O 32 20.46 Texaco R&O 32 20.49

GE Paint Coated Panels: 30 days immersed in @ 200F Standard No Sign of wrinkling, blistering, or peeling, Texaco 32 darker in color vs. Dow TF-25 Dow Turbine Fluid TF-25 Texaco R&O 32

Base Load Turbine - Filter Analysis Experimental: Filter Analysis Method: Oblique reflected light microscopy (LM) Instrument: Leica WILD MZ-16 stereo-zoom light microscope equipped with a Nikon DXM 1200 digital camera and ACT-1 image acquisition software Sample Preparation: samples were imaged using oblique reflected light (fiber optic light and ring lamp) Extracted Oil subjected to ICP analysis All metals were <1 ppm (Fe, Ni,Al,Sn,Ag,Cr, Pb,Si,B) K, Ca were <10ppm 21

Base Load Turbine - Filter Analysis Four Years Used Last Chance Filter Tear Down Filter Body/Baffle with ends Stainless Steel Mesh Paper Filter Wire screen 22

http://www.geenergy.com/tools_and_training/tools/technical_manuals_gas_and_steam_turbine_generator_units.jsp

Conclusions In-service monitoring of PAG based Turbine Fluid track well after 48 thousand hours of use in GE Heavy Duty 7 FA Gas Turbines Polyalkylene Glycols( PAGs) Technology eliminates varnish and deposits in Heavy Duty Gas Turbine applications 24

Thank You gvkhemchandani@dow.com (979) 238-4045 cell: (804) 896-2352 25