Slide 1

Film Forming Metal Passivation Technology

TH Wharton Generation Texas

Cost of corrosion in the Power Industry

Corrosion of water/steam touched components cost USA fossil-fueled steam plants in excess of $3.5 Billion/year by James Mathews Program Manager, EPRI, 2013 Metrohm Conference

Thermoelectric Plant corrosion damage is attributable to poor chemistry and impurities in the steam/water cycle by James Mathews Program Manager, EPRI, 2013 Metrohm Conference

Eight of the fifteen highest corrosion costs are associated with the water/steam cycle and water cooled generator by James Mathews Program Manager, EPRI, 2013 Metrohm Conference

The water/steam purity demands of the thermoelectric industry is the 3rd greatest after the microchip technology and pharmaceutical industries by James Mathews Program Manager, EPRI, 2013 Metrohm Conference

The world production of thermoelectric generation exceeds 16.6 TWh (1012 watt hrs), requiring more than 2 billion Mg/hr of high purity steam at conditions of up to 25 MPa and 600C by James Mathews Program Manager, EPRI, 2013 Metrohm Conference

corrosion increases the cost of electricity more than it increases the cost of any other product, adding over 10 % to its price. Neil B. Caris (PPChem Volume 8 (2006), No. 3)

The total cost of corrosion to U.S. industry is in excess of $276 billion annually, half of the forced outages are caused by corrosion failures. More than 30 % of the cost of corrosion failures could be prevented through the use of optimum corrosion management practices. Neil B. Caris (PPChem Volume 8 (2006), No. 3)

Corrosion failures are the fifth highest cause of forced outages

23% of turbine outage hours are due to corrosion failures

Efficiency Losses due to corrosion per Year

Turbine blade deposits U$ 500,000

Feedwater heater foulingU$ 80,000

Boiler blowdowns U$1,000,000

Impact of CorrosionComponent Cost Outage DurationPartial economizer U$ 6 - 7 million25 40 weeksRow of LP turbine bladesU$ 6 - 21 million15 30 weeksHP heater U$ 150 200,0004 8 weeksO2 Depleted

Metal**Trapped contaminants can promote corrosion of base metalLimitationsConventional Filming AminesIsolation & trapping of contaminantscreates a hydrophobic surface but also a very dangerous under deposit corrosion mechanism. The oxidecontaminants (typically always inorganic in nature) wouldattack the under sideof the film architecture & result inrelease of the protective film, its subsequentdegradation,loss of basemetal protection and the formation of waxy, slimy degradation products, a commonly reported problem with filming aminesTrapped and isolated inorganic contaminants would beallowed toconcentrate below the film andresult inan aggressive attach on the base metal.

Water

Experiences Using A Full Standards Compliant Organic Film Forming Technology in High Pressure Boilers.

Presentation by:-

Paul R Hattingh President Anodamine IncIndustry First

Green Organic Cycle Chemistry For High Pressure Boilers

U.S.A.South AfricaColumbiaThailandIndonesiaChilePanamaOver 10 years of experience in the USA (25 years internationally).Currently treating 27 power stations in the US. with 3 more power groups soon to be online. Distributors currently in 7 countries.

The Mutual GoalProtect & Ensure Safety Of All Staff & Site Personnel.Avoid Exposure of People & Environment to Toxic Chemistries.Prevention Of Corrosion In All Steam / Water Sections.Preventing Scale and/or Deposits Efficiency Of Heat Transfer.Eliminating Boiler Cleaning.Protecting Utilities Exposed To Operational PeculiaritiesEase Of Application.Economics Of Treatment.Technical Support & Service

Innovation in Cycle Chemistry Creating Real Solutions To Complex Utility Metal Protection Problems.Anodamine CorporationAll formulations are exclusively manufactured in the United States using locally sourced US Raw materials. Protection of all ferrous and mixed metallurgies. Protection against FAC in single and 2 phase areas. Protection of Mixed & All Ferrous Metallurgies irrespective of oxygen and residual ammonia concentrations. Full standards compliant cycle chemistry. Volatile liquid ratio approx. 60/40 protection throughout the entire steam water cycle. No negative effects to online instrumentation Can be easily quantified spectrophotometrically Has been scientifically proven to slow/eliminate SCC **

Corrosion Fatigue & Stress Corrosion Cracking on LP Turbine Blades

pitting

Cost of corrosion in the Power IndustryPresentation at Metrohm Analytical Conference, March 2013 by James Mathews Program Manager, EPRI

Cycle Chemistry Challenges

Utility Reliability&AvailabilityOperational ComplianceCycle Chemistry

How Is Success MeasuredCompliance

Non Compliance

How Is Success MeasuredMisconceptions (FALSE ASSUMPTIONS)I have added an oxygen scavenger, I have removed oxygen, I cant have corrosion, my plant must be well protected. FALSEI always measure adequate treatment chemical residuals, my treatment performance is optimum. FALSE

Cathode Example O2 + 2e- + 2H2O 2OH-WaterMoistureCorrosion MonsterFe2O3 Hematite (Iron 111 oxide)O2xFe3O4 Magnetite FeO.Fe2O3 (Iron 11 & 111 oxide)Oxygen removal14Anode Fe Fe2+ + 2e-

Magnetite Metal Protection152H2O + 2 e- H2 +2OH- (cathodic reaction) reduction of water in an OXYGEN FREE environment

Fe(OH)2 Fe3O4 + 2H2O + H2 ** (Magnetite) FeO.Fe2O3promotes HYDROGEN embrittlement 2+ 3+

Hydrogen Damage in Boiler Tubing

Cost of corrosion in the Power IndustryPresentation at Metrohm Analytical Conference, March 2013 by James Mathews Program Manager, EPRI

Existing Treatment ProtocolsAVT (R) All Volatile Treatment Reducing (ideal involving complete oxygen removal)

AVT (O) All volatile Treatment (oxidizing) Maintaining oxygen at approx 20 ppb

OT Oxygenated Treatment Addition of oxygen to maintain residual 150 300 ppbFACFlow Assisted CorrosionSingle & 2 Phase Flow

AVT (R)Chemical Protocol FAC LimitationsO2 Depleted

Reducing Environmentin Aqueous PhaseO2 DepletedSingle Phase FACWhen Physical & Chemical Conditions Are Correct,Destabilization & Release of Magnetite, Corrosion of Base Metal & Tube Wall Thinning

Fe3O4 + 4H+ + 2e- 3Fe2+ + 4OH-Fe2+Fe2+Fe2+Fe2+Fe2+Fe0 Fe2+ + 2 e-

AVT (O) & OTChemical Protocol 2 Phase FAC LimitationsOxidizing Environmentin Vapor PhaseReducing Environmentin Aqueous PhasePotential FAC zoneDestabilization & Release of Magnetite, Corrosion of Base Metal & Tube Wall ThinningDue to Poor Solubility of Oxygen at High TemperatureOxygen will Partition in Vapor Creating Oxidizing EnvironmentLeaving Aqueous Layer in a Reducing EnvironmentO2O2 DepletedFe2O3 + 3H+ + 2e- - 2Fe2+ + 3OH-

Fe3O4 + 4H+ + 2e- - 3Fe2+ + 4OH-Oxygen Free Water, Low pH Conditions & Changes in FlowPromote Destabilization, Dissolution& Loss of MagnetiteFe2+Fe2+Fe0 Fe2+ + 2 e-

Copper Oxides, Corrosion and AminesO2 Depleted3 N2H4 4NH3 + N2 (ammonia is added or produced and/or addition of neutralizing or filming amines)

Cu + O2 + H2O CuII(OH)2CuII(OH)2 + 4NH3 (amines) Cu(NH3)4(OH)2

flow of liquid washes away the protective patina. More copper will corrode to replace that lost.

2-Phase Flow Accelerated Corrosion Damage in HP Feedwater Heater w/ Ancillary Damage

Cost of corrosion in the Power IndustryPresentation at Metrohm Analytical Conference, March 2013 by James Mathews Program Manager, EPRIElectrochemical Reaction

FACFlow Accelerated Corrosion in unit feedwater system

FACFlow Accelerated Corrosion - in unit feedwater system

FACFlow Accelerated Corrosion - in unit feedwater system

Black/shiny

Tiger-Striping

Orange Peel

Anodamine Preferred Oxide

Yang merah anodamine filming

MetalComparativeAdvanced Filming Amine ProtectionA slow, progressive molecular permeation through oxide layer resulting in proportional release of trapped inorganic contaminants (cycle clearance), and a temporary manageable increase in cycle cation conductivities, followed by absorption on the metal/oxide topotactic layer and a decline in cation conductivities to < 0.2 uS/cm.Inspection of exposed oxide at this stage may reveal only water bleeding, with little or no signs of water beading/hydrophobicitySurface loose non-adherent oxide can be brushed away to reveal base metal hydrophobicity

Step 1 (real site images illustrating this stage next)**FFA film protection at base metal topotactic layerSlow and controlled progressive release of inorganic oxide contaminants

WaterExample Step 1

When water is placed on a high temperature produced oxide surface and the protective film exists only at the metal topotactic layer, the water will be seen to bleed through the oxide. This is often in error confused as a sign of no protection.

The high pressure oxide produced surface is manually brushed or wiped off to remove any loose non adherent oxide and debri. The surface is once again checked by carefully placing a drop on to the metal surface. Now hydrophobicity is clearly evident thus demonstrating the permeation of the proprietary FFA through the oxide to the base metal surface.

Molecular absorption on the metal/oxide topotactic layer. This stage of molecular orientation and absorption is rapid. With sufficient dosage creating a driving force toward the metal, excellent metal protection is achieved within 24 hours. Progress from this stage is simply based upon volume chemical added vs. available surface area.Surface loose non-adherent oxide can be brushed away to reveal base metal hydrophobicityStep 2 (real site images illustrating this stage next)ComparativeAdvanced Filming Amine ProtectionMetal** FFA film protection at base metal topotactic layer

Water

Example of Step 2

Low Pressure Drum from HRSG inspection showingvarying levels of hydrophobicity with some oxide water bleed through the remaining loose surface oxide. Base metal topotactic layer is hydrophobic

Example Step 3Complete hydrophobicity achieved across all available oxide surface. Oxide is however very fine and competent. Image from LP drum feed water manifold.The same is found in feed water sections, LP Heaters, boiler drums, ACC ducts and saturated steam lines etc in both single and 2 phase areasExcellent proprietary FFA hydrophobicity with no oxide water bleeding

To achieve this stage requires an ongoing routine chemical treatment approach with chemical residuals maintained at 800 1000 ppb. This continual treatment results in a tenacious, competent, dense and very stable oxide to metal surface with an increased 3+ oxide content. Either the oxide is very thin and/or the base metal is protected and exposed oxides are all found hydrophobic. The extent/magnitude of oxides and time of treatment exposure will determine completion of this stage and final level of (water beading) hydrophobicity.Step 3 (real site images illustrating this stage next)ComparativeAdvanced Filming Amine ProtectionMetalFFA film protection at base metal topotactic layer & throughout the fine dense, competent oxide layer

Example Step 3

Complete hydrophobicity achieved across all available oxide surface. Oxide is however very fine and competent.The same can be found in feed water sections, LP Heaters, boiler drums, ACC ducts and saturated steam lines etc in both single and 2 phase areasExcellent proprietary FFA hydrophobicity with no oxide water bleeding

Understanding Paradigms

Hydrazine addition (complete oxygen removal + phosphonate chelant)Start Of Accelerated Corrosion Test

After 10 minutesAfter 4 hours

Start of Corrosion Test using anodamineZERO oxygen scavenging

Reaction after 24 hours

A Perfect Partnership Between Metal & WaterIntroducing PerformanceBoiler & Cooling WaterMetal Passivation Technologies

The LPR (Linear Polarization Resistance) Corrator instrument configuration was used having a dedicated Anode + Cathode + Reference electrode, Product Code: LP327EH0311000 Serial No. Y791.The instrument was set to give a duty cycle (activation of anode with a generated potential between the anode and cathode) of 15 minuteson and 1 minute off this ON / OFF sequence was continuedfor approx 24 36 hours.

Experimental ProcedureThe water used for all experimental tests was raw water (untreated) and softened water (after sodium ion exchange softening) in both cases with zero oxygen scavenging (oxygen saturated > 5 ppm).

The LPR (Linear Polarization Resistance) Corrator instrument configuration was used having a dedicated Anode + Cathode + Reference electrode and a Product Code:LP327EH0311000 Serial No. Y791. The instrument was set to give a duty cycle (activation of anode with a generated potential between the anode and cathode) of 15 minutes on and 1 minute off this ON / OFF sequence was continued for approx 24 36 hours.A Perfect Partnership Between Metal & Water

Interpretation of Results

Untreated Raw water gave a corrosion rate of 11 mpySoftened water gave a corrosion rate of 14 mpy

The corrosion rate on both waters treated with Anodamine were reduced to 0.01 0.03 mpy. This rate of corrosion is equivalent to a max 0.0003 per annum; or equivalent to 0.00762 mm per annum. Assuming a pipe wall thickness of 8mmthis would give an approx.50 % service life expectancy of5,250 years

A Perfect Partnership Between Metal & WaterBASIC CHEMICAL PHILOSOPHY

ISOLATION OF THE ANODE.METAL PROTECTION INDEPENDENT OF OXYGEN.NO OXYGEN CONTACT.NO CORROSION.THERMAL STABILITY.FULL COMPLIANCE WITH 0.2uS/cm.ENVIRONMENTALLY COMPATIBLE.SINGLE PACK, MULTI-COMPONENT DOSING.PROGRAM SIMPLICITY & MONITORING.ANODIC SURFACE ACTIVEBARRIER PROTECTIONA Perfect Partnership Between Metal & WaterSome fouling of the corrosion probes leads to a temporary reduction in corrosion but under deposit pitting corrosion increases

Corrosion rate increases due to presence of residual brine in softened water

Best Industry Standard0.01 0.02 mpy within 8 hoursAnodamine LP boiler formulation employs a larger more branched thermally stable molecule that takes time to orientate to metal passivation is immediately better than industry standard and improves to optimum within 8 hoursCarbon Steel

Admiralty

A Perfect Partnership Between Metal & Water

Typical Case StudiesAdvanced Proprietary Filming Amine ProtectionAverages from > 10 Power Plants (natural and forced circulation) operational pressures ranging from 1,800 psig 2,500 psig (124 to 172 bar), reheat 1050 oF 566 oC MIXED METALLURGYAll circuits were previous treated under strict AVT (R) reducing treatment protocol.Treatment changed to proprietary FFA and now operational under AVT(O)

Averages from > 10 Power Plants (natural and forced circulation) operational pressures ranging from 1,800 psig 2,500 psig (124 to 172 bar), reheat 1050 oF 566 oC MIXED METALLURGY

Ferrozine Method TOTAL Iron Adapted from Stookey, L.L., Anal. Chem., 42(7), 779 (1970)Information & DataCourtesy George Verib FirstEnergy Corp USA., Published PPChem June 2012, page 338

Ferrozine Method TOTAL Iron Adapted from Stookey, L.L., Anal. Chem., 42(7), 779 (1970)Typical Case Studies1,980 MW Cyclic Operational Once Through Units using OT Chemistry + Proprietary FFAAll Ferrous Supercritical Once Through Pressure 4,500psi / 310 bar.Full Compliance FFA Cycle Chemistry.Steam Reheat 1,000 oF / 538 oC Cation Conductivity