CaseStudy:ExcessiveSulfuricAcidDosingResultinginIrreversibleScaleFormation M.Malki,AmericanWaterChemicals,Inc.

Abstract ManyconsultantsintheROwatertreatmentindustryrecommendsulfuricaciddosingintothefeedwaterasa safetymeasure.Thiscasestudyreviewsasituationwhereaciddosingwasusedwiththeintentionof improvingsystemperformancebutresultedinseveresulfatescaling.Thedifficultiesincleaningsulfatescales arediscussedandafternumerouslengthytrials,aneffectivecleaningprocedureisfoundandimplemented. Introduction: OneoftherulesofthumbrecommendedbymostindustryexpertsisthedosingofsulfuricacidintoROfeed waterasaprecautionarymeasure.ManycautiontoalwaysdoseenoughacidtomaintainareducedpH.They arguethatsulfuricacidwillactasabackupscaleinhibitorshouldtheantiscalantdosingpumpfail.WhilepH reductionprovidesexcellentcontrolforcalciumcarbonateandcalciumphosphatescaleformations,bothare reversiblescalesthatareamongtheeasiesttoclean.Theadvantagesprovidedbysulfuricaciddosinghaveto beweighedagainsttherisksofintroducingexcesssulfatesintothefeedwater.Sulfatesathighconcentrations cancombinewithcertaincationstoformsparinglysolublesaltsatlevelsbeyondtheirsaturationlimits. SulfatescalesarenotpHdependent;theyareformedbyirreversiblereactionswhichmakethemverydifficult ifnotimpossibletoclean. Background WhenarecentlycommissionedROplantinSouthwestFloridacouldnotachievedesignpermeatethehead operatorcontactedthesystemmanufacturer.Theplanthadbeeninoperationforonly6months. AWCsservicesweresolicitedandafieldserviceengineerwassentouttoinvestigate.Hediscoveredthata prominentscalehadformedonthetailendelementsofthesecondstage.Whenheappliedafewdropsof hydrochloricacidtoasmallpieceofthescale,itdidnotdissolveorbubble.Sulfatescalingwasimmediately suspectedandtheplantslogsheetswerereviewed. Apparentlytheplanthadbeingexperiencingheavyelementalsulfurprecipitationintheclearwellafter degassification.TheoperatorswereadvisedbytheircounterpartsinneighboringmunicipalROplantsto furtherdepressthefeedpHto5.4inordertomaintainH2Ssolubilityinwater(SeeFig.1) Acid addition drives the equilibrium to the left thereby maximizing H2S formation. is removed by the degassifier at very high efficiency H2S(aq) + H2O H3O+(aq) + HS-(aq) HS-(aq) + H2O H3O+(aq) + S2-(aq) Sulfide ions when exposed to oxygen in the degassifier oxidize to form elemental sulfur 2H2S + O2 2S + 2H2O Fig.1:Formationofelementalsulfurinpermeatewaterafterdegassifier 1 H2S gas

Indoingso,theplantoperatorsoverlookedthemanufacturersrecommendationtomaintainapHof7orto avoidaciddosingatall.Thereasonthisrecommendationhadoriginallybeenimplementedwasbecauseof extremelyhighsulfateandstrontiumlevelsinthefeedwater(seeTable1). Adosageofabout100ppmSulfuricacid(93%)isrequiredtoreducethepHfrom7.4to5.4.Thisincreasedthe sulfatesinthetailendelementsbyabout420ppm,raisingthetotalsulfatesto3046ppm. Sulfuricaciddissociatesintohydroniumionsandsulfateionsonceitisdosedintowater: H2SO4+2H2O2H3O++SO42 ThesulfateanionscancombinewithCalcium,BariumandStrontiumcationstoformsparinglysolublesalts thatcanresultinirreversibleadhesivescales.Sulfatescalescanbeimpossibletocleanleavingnochoicebut toreplacethetailendmembranes. Ca2++SO42CaSO4 Ba2++SO42BaSO4 Sr2++SO42SrSO4 FeedwaterEvaluation: Inordertofurtherinvestigate,anewfeedwatersamplewascollectedandanalyzed.Thewaterchemistryhad notchanged.Theanalysiswasenteredintoanantiscalantprojectionprogramtoreviewthesaturationsofthe variousscalants(Table2).CalciumSulfateandStrontiumSulfatewerewellabovetheirsaturationlimitsbut withinthelimitsoftheantiscalantbeingused. FeedwaterParameters Mg/L(asions) Calcium 350 Barium 0.04 Strontium 30 Iron 0.06 Manganese ND Sulfate 525 Bicarbonate 120 Carbonate 0.11 Silica 17 pH 7.4 Table1:Feedwateranalysis 2

 Forfurtherverification,alabstudywasconducted.Thewaterchemistryintherejectwasreconstitutedand testingwasperformedonacontrolsamplevs.asamplecontainingantiscalant.Itwasconfirmedthatthe antiscalantwasabletocontrolallscalantsincludingstrontiumsulfateatlevelsfarhigherthanthosewhichhad resultedinscalingattheROplant. PotentialScalants CalculatedSaturations CalciumCarbonate(LSI) 0.56(indexvalue) CalciumSulfate 233% BariumSulfate 2066% StrontiumSulfate 782% Silica 56% Table2:%Saturationofvariousscalantsat80%recoverywithsulfuricaciddosingtoreducepHto5.4 Designandoperationalflawscontributingtotheproblem Itisalwaysgoodpracticetolookbeyondtheobviouswhentryingtofindthecauseofaproblem.Inthiscase, thesystemcouldnotbeoperatedatfulldesigncapacitybecauseoffeedwelllimitations.Each2.5MGDtrain wasonlyprovidedwithenoughfeedwatertoproduce2MGD.Thereducedcrossflowmayhaveresultedina largerboundarylayerarea,consequentlycontributingtothescalingpotential.Theboundarylayer,also knownasconcentrationpolarization,describesaphenomenonwhereionsexistathigherconcentrationlevels atthemembraneboundarythanthegeneralbodyoftheoutgoingconcentratestream;thisregionexperiences alessturbulentflowprovidingabetterenvironmentforprecipitatedsaltstosettle. Theplanthadbeendesignedwithflowmetersonthetotalpermeateandconcentratestreamsonly,withno flowmetersonthefeedside.Monitoringoftheindividualstageswasnotpossibleduetotheabsenceofflow meterstomeasurethefirststagepermeateorsecondstagefeed.Ifaflowmeterwasgivingincorrect readings,itwouldhavegoneunnoticedbecausesimplemassbalancecalculationscouldnotbeperformedwith thelimitedflowdataavailable. Whentheexistingflowmeterswerecalibratedusingportablemagneticflowmeters,theywereallfoundtobe outofcalibration.Thismayhaveledtotheoperationoftheplantbeyonditsdesignrecovery. Uponreviewingplantdata,theserviceengineerfoundthatitwasbeingcollectedonadailybasisbutnot plottedornormalized.Withoutanormalizationcurve,scalingmayhavebeenoverlookedforquitesometime; theproblemwouldnotbecomeapparentuntilthescalingwasatanadvancedenoughstagetocauseadrastic decreaseinpermeateproductivity. Itwasalsofoundthattheantiscalantdosingpumpswerenotbeingregularlycalibrated;Aswithanyother equipment,regardlessoftechnologyorsophistication,dosingpumpcalibrationisanabsolutelynecessary practiceandshouldbeperformedweekly. Basedonalltheprojectionswhichwerelaterverifiedbylabtests,theantiscalantwasfullycapableof preventingstrontiumsulfatescaleformationwellbeyondthedesignparameters.Thisleadsustobelievethat asystemupsetmayhaveoccurredthatwasfurtherexaggeratedbytheincreasedsulfatesintroducedthrough thesulfuricaciddosing. 3

MembraneEvaluation: Inordertotestthemembraneinanoffsitefacility,theserviceengineerreplacedoneofthetailelement membraneswithamembranespacer.Duetothesizeofthesystem,theabsenceofasinglemembrane elementforashortperiodoftimedidlittletoaffectthetotalwaterquality. AsmallpieceofprotrudingscalewasscrapedoffandanSEM/EDSanalysiswasperformedtodetermineits elementalconstituents(Fig2,3).Thescalewasdeterminedtobemostlystrontiumsulfatewithtracesof calciumsulfate.

Figure2:StrontiumSulfateScaleonmembranesurfaceat1000timesmagnification

 Figure3:EnergyDispersiveSpectroscopyshowingelementalmakeupofthescaleonthemembranesurface consistedmainlyofstrontiumandsulfur. Themembranewasweighedandfoundtobe43LBS,about9LBSheavierthananewelement.Theelement wasaToraymembrane,TMG20430.Itwasevaluatedbyperformingawettestidenticaltotheprotocol providedbythemembranemanufacturer.Themembranewasonlycapableofa3.5%recovery(Table3) comparedto15%recordedbythemembranemanufacturer.Thisindicatedtheextentofthescaleformation.

Date TypeofMembrane Feedtemperature,C Permeateflow,gpm Differentialpressure,psi %Recovery %Saltrejection Comments/Remarks

June02,2008 TMG20430(membrane1) 29.6 0.778 5 3.49 81.9

June23,2008 TMG20430(membrane2) 28.8 0.44 10 2.06 52.8

Weightofmembrane Weightofmembrane beforecleaningat43lbs beforetestingat41lbs Table3:Resultsofperformancetestofscaledmembranepriortocleaning.

Variouschemicalsweretestedinanattempttocleanthemembrane.TheseincludedEDTAandvariousblends ofEDTA,Trisodiumphosphateandsodiumtripolysphosphateasrecommendedinwidelyavailableliterature. Recoveryonlyimprovedby1%despitecontinuousrecirculationatmaximumtemperatureforabout18hours. Twoproprietaryproductswerethentested,AWCC237andthenAWCC239(Table4). Chemicalused AWCC237(2%solutionbyvol) Membrane1 June18,2008 TMG20430 28.3 2.1 0 9.0 94.8 Weightaftercleaningat38lbs AWCC239(2%solutionbyvol) Membrane2 July24,2008 TMG20430 28.9 5.656 0 22.6 94.7

Date TypeofMembrane Feedtemperature,C Permeateflow,gpm Differentialpressure,psi %Recovery %Saltrejection Comments/Remarks

Finalweightofmembranes aftercleaning=34lbs Table4:Resultsofperformancetestofscaledmembraneaftercleaning.

TheC237gavepartialcleaningresultswhiletheC239gaveexcellentcleaningresults,completelyremoving thescale.Forbothchemicals,temperaturehadmaintainedat122Fandatotalrecirculationtimeof48hours wasrequired.Thelowsaltrejection,whichistypicallyafterahighpHcleaning,partiallyrecoveredafterthe membraneswereplacedonlineforafewdays.However,theformedscalehadbeenthickenoughtoprythe membraneleavesapart,probablycausingsomeirreversiblestructuraltearing. Thesuccessfulresultswiththesingleelementcleaningpromptedanattemptatafullscalecleaning.TheAWC C239wascirculatedthroughthesecondstageforonly12hoursbecausethemunicipalityhadtocaterto waterdemandsandcouldnotshutdowntheirsystemforalongerperiodoftime.Thedesiredsolution temperaturecouldnotbeachievedbecausetheplantdidnothaveaheaterintheirmixingtank.Furthermore, theflowratesacrossthemembranesurfacewerenotcomparabletothoseachievedinasingleelement cleaning.Feedpressurestoachievedesignpermeateflowrateswerenotreducedandtherewereno improvementsinthepressuredropsacrossthesecondstageofeithertrain.Itwasdecidedthattheelements wouldallbecleanedoffsiteattheROmaintenancecompanysfacility. Thetailendelementsweretakenoutsixatatimeandtemporarilyreplacedwithmembranespacersuntiloff sitecleaningcouldbecompleted.Thescaleremovalwasextremelysuccessfulwithresultssimilartothosein table4. 6

Conclusion: ThereappeartobemanyfactorswhichcontributedtothescalingatthisROplant.Thelowfeedflowandthe consequentlyreducedcrossflowmayhaveplayedasignificantrole.Theflowmeterswhichwereoutof calibrationweregivingincorrectreadingswhichcouldhaveledtooperationathigherthandesignrecoveries. Butmostimportantly,thesulfuricaciddosingraisedthesulfateionsinthetailendelementstoextremelyhigh levelscreatinganenvironmentthatwasfavorableforscaleformation.Whenoperatingatsuchborderline conditions,theslightestsystemupsetcanresultindisaster.Movingtheaciddosingpointtothepermeateside caneliminatethescalingproblemswhileresolvingtheelementalsulfurprecipitationissuesinwatercontaining highH2Slevels.ThecostofreducingthepHinthepermeateisalsomuchlowerthandoingsointhefeed alkalinityisrejectedbythemembranesleavingthepermeatewithoutabufferingcapacitysothatafractionof theaciddosagewillresultinmaximalpHreduction. WhencleaninganROmembrane,thetemperature,cleaningtimeandflowrateareallequallyasimportantas thecleaningchemicalusedforremovingsulfatescales.Inthiscase,itwasfoundthatcleaningfor12hoursat lowflowratesandnearambienttemperatureswasineffectivedespitegreatsuccessusingthesamechemical offsite.Cleaningoffsiteallowedforhigherflowratesandwasmosteffectiveat122Ffor48hours,returning themembranestoacceptableoperatingconditions.EDTA,trisodiumphosphate,sodiumtripolyphosphate combinationswerefoundtobeineffectiveatremovingstrontiumsulfatescaledespitecontinuouscirculation atelevatedtemperaturesforseveraldays.Bycontrast,thespecialtychemicalsAWCC237andAWCC239 resultedinmeasurableimprovements,substantiallyremovingstrontiumsulfatescales,andreturning differentialpressuresandpermeateflowratestonearoriginaldesignconditions. SelectionofthecorrectcleaningchemicalsandprocedurescanresultingreatsavingsforROplantsthathave experiencedheavysulfatescales.Inadequatechemicalsorprocedurescanresultinthecostlyreplacementof alltailelementmembranesthelargertheplantthehigherthecost.Regardless,sulfatescaleremovalcan onlybeaccomplishedthroughsingleelementcleaningandthestructuraldamagecausedbytheformedscale canneverbereversed.Thebestapproachtocosteffectiveplantoperationisalwaysprevention.Thefeed wateranalysisshouldalwaysbecarefullystudiedandaqualifiedwaterchemistryexpertshouldalwaysbe consultedpriortomakingchangestochemicaldosagesoroperationalparameters.