INVISTA DBA Dibasic AcidFor Flue Gas DesulfurizationN b 17 2010November17,2010© 2010 INVISTADisclaimer**The information set forth herein is furnished free of charge and is based on technical data thatINVISTA believes to be reliable, provided that INVISTA makes no representation or warranty as to thecompleteness or accuracythereof.The information is intended tobe used for informationalpurosesyponly and on a without prejudice basis and should not beviewed as giving technical advice, instruction,or otherwise.It is intended for use by persons having technical skill, at their own discretion and risk,who will make their own determination as to its suitability for their purposesprior to use. The handlingprecaution information contained herein is given with the understanding that those using it will satisfythemselves that their particular conditions of use present no health or safety hazards As with anythemselvesthattheirparticularconditionsofusepresentnohealthorsafetyhazards.Aswithanymaterial, evaluation of any compound under end-use conditions prior to specification is essential.Nothing herein is to be taken as a license tooperate under or a recommendation to infringe anypatents. In no event will INVISTA be responsiblefor damages of any nature whatsoever resulting fromthe use of or reliance upon the information containedherein or the productto which the informationrefers. NO REPRESENTATION OR WARRANTIES, EXPRESSED OR IMPLIED, OF MERCHANTABILITY,FITNESS FOR A PARTICULAR PURPOSE, OR ANY OTHER NATURE ARE MADE HEREUNDER WITHRESPECT TO THE INFORMATION CONTAINEDHEREIN OR THE PRODUCT TO WHICH THEINFORMATION REFERS. The data and information contained herein are the exclusive property ofINVISTA and nothing herein shall be construed as authorization or license to use print or distribute anyINVISTAandnothinghereinshallbeconstruedasauthorizationorlicensetouse,print,ordistributeanysuch data or information.Unless explicitly stated, no license or immunity under any patent is either granted or implied throughthis presentation or through the technical information provided herein.© 2010 INVISTAINVISTA overview• INVISTA: one of the world’s largest integrated producers ofl dfbpoymers andfibers– Primarily nylon, spandex and polyester applications• Subsidiaries of Koch Industries, Inc. acquired INVISTA fromDuPont in 2004 and combined it with KoSa• History of innovation and leadership•Enriching daily life:clothing carpetsEnrichingdailylife:clothing,carpets,luggage, plastic bottles, automobile parts,airbags and moreh 00 d• More tan 700unique patents andsignificant intellectual property•www.INVISTA.com© 2010 INVISTAINVISTA’s shareholder• INVISTA is an independently managed,h ll d b idi f K h I d t i Iwholly ownedsubsidiary ofKochIndustries,Inc.• Koch Industries, Inc. is one of the largestprivately held companies in the world• Koch companies: 60 countries, approximately 70,000 employees• Businesses/industries:Refining and ChemicalsPolymers and Fibers–RefiningandChemicals–PolymersandFibers– Process and Pollution Control – Commodity TradingEquipment and Technologies and ServicesMineralsForest & Consumer Products––Forest&ConsumerProducts– Fertilizers – Ranching•www.kochind.com© 2010 INVISTARole of INVISTA DBA in flue gas desulfurization (FGD)• Organic acid additives have been successfully used in coal-burningpower plant wet scrubbers since the 1980’s• Drivers for the use of DBA in FGD Systems– Regulatory compliance– Reduce cost (maintenance, energy, capital)Flexible fuel strategy–Flexiblefuelstrategy•Organicacidadditivessuch DBAoffer:ga c ac d add t es suc o e– Improved scrubbing efficiency & operational flexibility– Improved reliability– Reduced operating cost© 2010 INVISTAUtility of DBA additive in FGD systems•Retrofitto existing wet scrubbers– Improve performance– Overcome design limitation– Increase operational flexibilityT h l f h i f t fit li ti–Technology ofchoicefor retrofitapplications•Originalequipment for new wet scrubbers– Reduce capital cost (minimize the amount of overdesign necessary to ensuremeetingSO2-removal requirements)– Increase SO2removal efficiency (95% +)– Increase limestone utilization or use lowergrade limestone– Reduce coal cost– Reduce maintenance cost– Contingency planningfor spray header or recirculation pump problems© 2010 INVISTALimitations of wet limestone scrubbersGasl dl d l dh• Dissolvedlimestone providesliquid-paseneutralizing capability (LOW solubility)• At high pH, SO2dissolves and is rapidly neutralizedLi tGasGypsum– Neutralization of SO2consumes liquid-phaseneutralizing capability• Rapid depletion of neutralizing capacity at surface of dropletAirLimestone& water– Replenished more slowly by diffusion of dissolved reagent from interiorof droplet to the surface• Depletion of dissolved reagent from interiorg– Limited replenishment due to low solubility of limestone and slowdissolution rate•When dissolution of limestone cannot keep up with consumption of liquidWhendissolutionoflimestonecannotkeepupwithconsumptionofliquidphase neutralizing capacity, pH drops and SO2adsorption slows© 2010 INVISTAChemistry of wet limestone scrubbers (simplified)Without DBA• CaCO3(limestone) is virtually insoluble,but dissolves to provide a small amountWith DBA• DBA “predissolves” limestone.•CaDBA is soluble and provides much moreof SO2-neutralizingcapacity•CaDBAissolubleandprovidesmuchmoreSO2-neutralizing capacity than limestone aloneCaCO3+DBACaDBA+ CO2+ H2OCaCO3(solid) CaCO3(aq)SO2(aq)SO2(g)H2SO3+CaDBACaSO3+DBAH2SO3SO2(aq)SO2(g)SO2(aq) + H2OH2SO3H2SO3+ CaCO3CaSO4SO2(aq) + H2OCaSO3+ H2O + CO2CaSO3+Air• Liquid-phase neutralizing capacity isdepleted by SO2neutralization•Rate of replenishment depends on• More liquid-phase neutralizing capacity isl bl flCaSO4CaSO3+ AirCaSO4CaSO3+AirRateofreplenishmentdependsonlimestone dissolution• When LS dissolution cannot keep up withSO2neutralization, pH drops and SO2bbiavailablefor SO2neutralization• Rate of replenishment is increased• pH does not drop as much, so SO2scrubbingffi i i i dscrubbingstops efficiencyisimproved© 2010 INVISTATypical FGD unit with DBA additionFlue gas outDBA(solutionFlue gas inReagentor flake)ReactiontankDewateringLimestoneGrindingReagentstoragetankSolidsWater (recycle)© 2010 INVISTATypical benefits of DBA on FGD scrubber100Improved SO2removalefficiency

c yLower liquid/gasratio for reduced95

a l Efficien c100

nt)140Chloride tolerance3ratioforreducedenergy consumption490

O 2 Remov a859095

v al Efficiency (perceNoadditive100120

G, gallons/kc f

S75800 20000 40000 60000Chloride, ppm

SO2 Remo vo add t e500 ppm DBA1000 ppm DBA801000 500 1000 1500 2000DBA Additive, ppm

L/850 500 1000 1500 2000ppm DBA© 2010 INVISTAPotential DBA benefits to FGD(on Large Utility Boilers)ParameterWet Scrubber on Large UtilityBoilers 

# without DBAWet Scrubber on Large Utility Boiler



# with DBASO2Removal efficiency 80-90% (typical) 90-98%1Limestone consumptionIncreasing limestone feed to improveSO2removal may result in poorlimestone utilization.Improved SO2removal may reduce theneed for excess limestone and improvelimestone utilization.GypsumqualityStandard FGD solids Higherpurityat no additional costq ypySolids disposal (non-gypsumproducers) Typical FGD solidsLess solids and lower disposal cost dueto better limestone utilizationIncreasing liquid/gas ratio to improveImproved SO2removal may allowoperation at lower liquid/gas ratio,Slurry recirculation energyIncreasingliquid/gasratiotoimproveSO2removal may increase energy use.operationatlowerliquid/gasratio,reducing energy useScaling and pluggingScaling and plugging may causedowntime and reduced removalefficiency.Reduced scaling and plugging may resultin less downtime and improved removalefficiencyChloride inhibitionBuildup of chloride reduces limestoneutilization and scrubbing efficiency Higherefficiency even at high chlorideFuel (i.e. coal) selectionChoice of fuel may be limited byemission constraintsImproved SO2removal may allow widerrange of fuel optionsThe DBA benefits described above are a general summary of modeling and industry experience. Actualbenefits will vary with individual scrubber and operational parameters.1 – Percent reduction will depend upon FGD scrubberdesign and individual unit operational parameters.© 2010 INVISTADBA consumptionDBA is slowly depleted through several different mechanisms:• Slow oxidation (chemical degradation)- Oxidation and decarboxylation- Some oxidation products remain functional•System purges (blow down)Systempurges(blowdown)• Co-precipitation with solids in natural or inhibited oxidation scrubbers– Not significant with forced oxidation• Solution losses (process liquor entrained with solids)The dominant mechanism(s) will be determined by mode of operationof the FGD unit© 2010 INVISTATesting DBA in FGD scrubbers10095

a l Efficiency90

SO2 Remov850 500 1000 1500 2000ppm DBAThe shape and curve will be unique for each scrubber and must bedetermined by testing.© 2010 INVISTABarriers to DBA testing and use• People and time (motivated site advocate, support services)•Regulatory (e g potential impact on air and water permits)Regulatory(e.g.potentialimpactonairandwaterpermits)• Aversion to change (potential disruption to operations, concern aboutgypsum quality, new chemical, uncertainty about DBA benefits)•Cost (of testing equipment and additive)Cost(oftesting,equipmentandadditive)• Misalignment of corporate and site objectives (e.g. corporate goal tominimize overall SO2compliance costs vs. site goal to minimize siteoperating expenses)operatingexpenses)• Implementation – lack of physical facilities to store and meter DBAinto system•Lack of large scale testing facilities (i e no DBA storage tank)Lackoflargescaletestingfacilities(i.e.noDBAstoragetank)© 2010 INVISTADBA addition and testing conceptsDBAHot water supplyFlush water suppliedto all required points10001200

h )4.55 )pph SO2DBA tank level, feet2. DBA feed started1. Baselinedata acquiredTypical permanent facilityDBAStorageTankHeaterBackpressureRegulationtoallrequiredpointsDBA feed toi di id lDBAStorageTankHeaterBackpressureRegulationtoallrequiredpointsDBA feed toi di id l400600800

SO2 emissions (pp h33.54 DBA tank level (feet )3. Virtually immediatedecrease in SO2emissionsRecirculatingPumpsRegulatingValvesFlowMetersindividualFGD unitsRecirculatingPumpsRegulatingValvesFlowMetersindividualFGD units0200012345678Day22.5Temporary / test facilityLimestoneslurrytank orDBA TrailerFeed and control systemFGD unitDBATrailerPumpRegulatingvalveFlowmeter•Transfer lines electrically heated to prevent DBA crystallization© 2010 INVISTATemporary facility for testing DBA• DBA added directly from trailer to two scrubber reaction tanks to obtain aconcentration of approximately 1200 ppm in scrubber• The response was immediate. Performance was monitored as DBAconcentration declined to develop efficiency curve1 0100%0 50.81.0

O 2 EmissionsBaseline data(before DBA addition)Adding trailer #1 to97%98%99%

v al Efficiency0 00.30.5

Relative S OAddingtrailer#1toreaction tank #1Adding trailer #2 toreaction tank #294%95%96%

SO 2 Remo v** As each scrubber is unique, it is important to run a test to determine scrubberperformance as a function of DBA concentration in the scrubber0.002468Time (hours)94%0 200 400 600 800 1000 1200ppm DBAperformanceasafunctionofDBAconcentrationinthescrubber© 2010 INVISTAWastewater issues6,7•Highly site specific– Some sites are “zero discharge” – no issue– Others have varying outfall requirements (BOD, aquatic tox., etc.)•DBA is an organic diacid and contributes toward BOD / COD– DBA is “readily biodegradable” – the most easily degradable class– Some degradation occurs in the scrubber and downstream equipment–Activated sludge ponds wetlands are all effective bio-oxidizers to varyingActivatedsludge,ponds,wetlandsarealleffectivebiooxidizerstovaryingdegrees•Studies to date show no adverse effect on Se removal by biotreatmentStudiestodateshownoadverseeffectonSeremovalbybiotreatmentat DBA levels up to 2000 ppm in the waste water7•Several specialized firms can assist with wastewater treatment issues© 2010 INVISTAINVISTA DBA supply update• September 2008–Hurricane IKE hits Texas gulf coast nearHurricaneIKEhitsTexasgulfcoastnearGalveston– Extensive flooding forces shutdown anddamages INVISTA’Orange TX facilitydamagesINVISTA sOrange,TXfacility• 2009-2010– INVISTA repositionsglobal adipic acidgpbusiness for world-class competitivenessand growth•First quarter 2011Firstquarter2011– INVISTA anticipates re-start of theOrange, TX adipic acid facility© 2010 INVISTAUsed with permission from The Orange Leader newspaper, Orange, TexasINVISTA DBA• INVISTA can provide free trial quantities of DBAsolution – contact us for detailsT h i l d il bl i l d•Technicaldocuments available on requestinclude:– DBA shipping and handling guidelines for flue gas desulfurization–Measurement of buffer capacity of FGD scrubber liquidMeasurementofbuffercapacityofFGDscrubberliquid– Testing INVISTA dibasic acid (DBA) in wet scrubbers– DBA in FGD brochure• If you face any hurdles planning your trial, please callus. INVISTA may be able to help!Contact Us:1-800-231-0998db i i t© 2010 INVISTAwww.dba.invista.comReferences1. “The Role of Organic Acids in FlueGas Desulfurization”, INVISTA publication.2.“TestingINVISTA Dibasic Acid (DBA) in Wet Scrubbers”, INVISTA publication3. Overview on the Use of Additives in West FGDSystems, R.E. Moser and E.R. Owens, Proceedings:1991 SO2 Control Symposium. Vol 1. ElectricPower Research Inst., Palo Alto, CA, Nov 1992, pp3A.1-3A.214. Incorporating Full-Scale Experience into AdvancedLimestone Wet FGD Designs., P.C. Rader, E.Bakke(ABB Environmental Systems). Proceedings: 1991SO2 control symposium. Volume 3. ElectricPower Inst., Palo Alto, CA (United States) Nov 1992. p. 8A.43-8A.665.“Testingand Commercialization of Byproduct Dibasic Acids as Buffer Additives for Limestone FlueypGas Desulfurization Systems,” J. C. S. Changand J. D. Mobley,J.A.P.C.A., 33(10) 955-962 (1983).6. Duke Power WFGD Retrofit Program: Compliancevia Standardization and Selective Site-specificInnovations, Jim McCarthy, Jurgen Dopatka, PhilRader, Clark Bussell (Alstom and Shaw Group),Power-Gen International 2005. Available on the web athttp://www.power.alstom.com/home/events/past_events/power_gen_international/_files/file_20379_56769.pdf7. ABMet Biological Selenium Removal from FGD Wastewater. Jill Sonstegard, Tim Pickett, ZenonEnvironmental (includes the former Applied Biosciences Corp) Official Proceedings - InternationalWater Conference (2005), 66th, IWC.05.72/1-IWC.05.72/5. Available from www.eswp.com.© 2010 INVISTA