Treating Metal Finishing Wastewater

SultanI.Amer,Ph.D.
AQUACHEMINC.

EnvironmentalTechnologyMarch/April1998

Wastewaterfrommetalfinishingindustriescontainshighconcentrationsofcontaminants
whicharehazardoustotheenvironmentandposepotentialhealthriskstothepublic.With
increasinglystringentregulationsgoverningwastewaterdischargeandgreaterquantitiesof
wastewaterbeingproduced,thereisagrowingneedformoreefficientandcosteffective
methodstoremoveheavymetals.

InaccordancewiththeNationalPollutantDischargeEliminationSystem(NPDES),asrequiredbythe
CleanWaterAct,metalfinishersarerequiredtopretreattheirwastewaterpriortoreleasingitto
municipalsewersorsurfacewaters.Astheregulationsgoverningthedischargeofwastewaterbecome
morestringent,publiclyownedtreatmentworkshavesetlowerdischargelimitsonheavymetalsand
othercontaminantsofconcern.Withthegreaterquantitiesofwastewaterbeingproducedanddischarge
limitsbeinglowered,thereisaneedformoreefficientprocessestoremoveheavymetals.

Wastewaterfrommetalfinishingindustriescontainscontaminantssuchasheavymetals,organic
substances,cyanides,andsuspendedsolids,atlevelswhicharehazardoustotheenvironmentandpose
potentialhealthriskstothepublic.Heavymetals,inparticular,areofgreatconcernbecauseoftheir
toxicitytohumanandotherbiologicallife.Heavymetalstypicallypresentinmetalfinishingwastewater
arecadmium,chromium,copper,lead,nickel,silver,tin,andzinc.Table1showstheEPAbestpractical
controltechnology,BPT,limitsformetalfinishingeffluent.

Table1:BPTLimitsforMetalFinishingEffluent

Parameter

Maximumallowablein1
day(ppm)

TotalCadmium
TotalChromium
TotalCopper
TotalLead
TotalNickel
TotalSilver
TotalZinc
TotalCyanide
pH

0.69
2.77
3.38
0.69
3.98
0.43
2.61
1.20
6.09.5

DailyAveragefor30
consecutivedays(ppm)
0.26
1.71
2.07
0.43
2.38
0.24
1.48
0.65
6.09.5

Conventionally,metalfinishingwastestreamsaretreatedbychemicalmeansandthequalityoftreated
effluentsmustmeetdischargestandards.Thetechniquesusedintheconventionaltreatmentofmetal
finishingwastewaterinvolveprecipitationofheavymetals,flocculation,settling,anddischarge.Such
techniquestakeconsiderabletimeandrequireextensivesetup.Eachsteptakesplaceinaseparatetank,
andtheentiretreatmentrequiresseveraladjustmentsofpHaswellastheadditionofacid,coagulant,
limeorcaustic,andpolymericflocculant.Inaddition,theprocessgenerateslargevolumesof
sludge/wastewhichrequiresdisposalandisnormallyhazardousduetothehighconcentrationsofheavy
metals.
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Thecurrentacceptedbestavailabletechnology(BAT)forremovalofheavymetalsandotherhazardous
contaminantsfromwastewaterisstabilizationinanonleachingmatrix(waste),sothattheydonotposea
hazardtotheenvironmentoncethewasteisplacedinalandfill.Thismanipulationisnormallycarriedoutat
wastetreatmentplantsbyreactingthegeneratedwastewithchemicalsknownasamendmentsandallowing
themixturetocure.Thisincreasesthecostofthetreatmentandplacesanextraburdenontreatment
facilities.Disposalofhazardouswastegeneratedbythecurrentpracticeofwastewatertreatmentincreases
theoverallcostofthetreatmentby50%to200%,dependingonthenatureandlevelofmetalsinthewaste.
Itisfairtoassumethatthecostofdisposalofnonhazardousmaterialisabout50%to70%cheaperthanfor
hazardousmaterialofequalvolumeorweight.Theoverallcostofwastewatertreatmentincludesboththe
costoftreatingthewaterandthedisposalofwaste.Forexample,afacilityinMichigangenerates2,000
gallonsofchromiumladenwastewaterdaily.Thecostoftreatingthewateraloneisestimatedat$25,000to
$30,000peryear,plus,thefacilitypaysapproximately$16,000to$20,000annuallyforwastedisposal
whichresultsinatotalof$41,000to$50,000.Disposalcostsometimesexceedsthatofwatertreatment,
dependingonthenatureandlevelofcontaminants.

ConventionalTechnology

Inconventionaltreatment,precipitationisthetechniqueofchoicefortheremovalofdissolvedheavy
metals.Precipitationofheavymetalslowerstheconcentrationsofallmetals.Thesolubilityof
precipitatedmetalcompoundsisthekeytothismethod'ssuccess;ifametalcanformaninsoluble
compound,thenthecompoundcanberemovedviaclarificationandfiltration.

Thereareafewmethodsfortheprecipitationofheavymetals,namelyashydroxides,sulfides,and
carbonates.However,thetwomainmethodscurrentlyinusearehydroxidesandsulfides.Table2shows
solubilityofmetalhydroxidesandsulfides.Bothmethodsinvolveareactionofthemetalcationwith
eitherOHorS2toformthecorrespondinginsolublemetalhydroxideorsulfide,asshownbelow.

2+
M + 2 OH2+

2-

+S

M(OH)2

MS

Table2.SolubilityofHydroxidesandSulfidesofHeavyMetals

Metal(Ion)
Cadmium(Cd2+)
Chromium(Cr3+)
Cobalt(Co2+)
Copper(Cu2+)
Iron(Fe2+)
Iron(Fe3+)
Lead(Pb2=)
Manganese(Mn2+)
Mercury(Hg2+)
Nickel(Ni2+)
Silver(Ag+)
Tin(Sn2+)
ZincZn2+)

Themostwidelyusedmethod
isprecipitationofheavy
metalsashydroxides,a
processwhichispHsensitive.
Inmetalfinishingwastewater,
multiplemetalsarepresentat
highlevels.Therefore,the
mosteffectivepHmustbe
determinedpriorto
treatment.Most,butnotall,
heavymetalhydroxides
precipitateatapHinthe
rangeof8.59.5.Beyondthis
narrowrange,metal
hydroxide
mayresolubilizeornotform

ConcentrationofmetalIon,mg/L
Hydroxide
Sulfide
2.3x105
8.4x104
2.2x101
2.2x102
8.9x101
1.0x104
2.1
1.2
3.9x104
6.9x103
13.3
1.1x104
1.1

6.7x1010
Noppt.
1.0x108
5.8x1018
3.4x105
Noppt.
3.8x109
2.1x103
9.0x1020
6.9x108
7.4x1012
3.8x108
2.3x107

completely.Table3showspHrangesfortheformationofmetalhydroxides.
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Table3.RangesofpHforPrecipitationOfMetalHydroxides
Metal

pHRange

Cadmium
Chromium(III)
Copper
Iron(III)
Lead
Nickel
Silver
Zinc

9.011.0
6.57.0
7.07.5
5.05.5
8.59.0
9.011.0
9.012.0
8.08.5

Heavymetalhydroxidesprecipitateascolloidal,chargedparticlesthat
requiretheadditionofcoagulantssuchasalumorironcompoundsto
reducethechargeandallowtheparticlestogrowinsize.Tofacilitate
sedimentation,thecoagulatedparticlesareflocculatedusing
flocculants.Sedimentationofmetalladenfloc/sludgetakesplaceina
clarifierorsettlingtank.Theclearsupernatantcanthenbe
discharged,ifitmeetsregulatorylimitsandthesludgeispressed
throughafilterpresstoproduceasemisolidwaste.Figure1showsa
diagramofaconventionaltreatmentsystemsetup.

Figure1.ConventionalTreatmentSystem

Process Water
pH

Equalization Tank

Precipitation

Coagulation

Flocculation

Treated Water

Clarifier

Filter Press
Back To Equalization Tank

Sludge

Sludge Bin

AlthoughsulfideandcarbonateprecipitationarelesspHdependentandaffordeffluentsofhighquality,theyare
notgenerallythemethodsofchoicedueto:toxicityofsulfide;reactivityofsulfidecontainingsludgewithacidsto
generatetoxichydrogensulfidegas;andthatsulfidecontainingsludgemaynotdisposableinsomestates.In
addition,thechemicalcostishigh;carbonateprecipitatecostsaboutfourtoeighttimesthatofhydroxide,and
sulfideprecipitationisabout10t020timesthatofhydroxide.

SludgeDisposal

Disposalofsludgegeneratedinthecurrentpracticeisachallengingproblemforenvironmentalauthorities.There
isalwaysthepotentialthatprecipitatedheavymetalswillresolubilizeifthepHdropsbelowtheoptimumrange.
Decompositionofmunicipalgarbageandhumicmaterialgeneratesorganicacids(lowersthepH)whichinturn
increasesthesolubilityofheavymetals(leachingout).Sulfideandcyanidecontainingwastes,inparticular,posea
greathazardastheycanreactwithsuchorganicacidsandgeneratetoxichydrogensulfideandhydrogencyanide
gases.

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Wasteisgenerallyplacedindisposalpitsorlandfillsthathaveminimalimpactongroundwater.Wherethese
conditionsdonotexist,itmaybenecessarytoinstallcollectionsystemstocollectleachatesforsubsequent
removalofheavymetalsbyprecipitationorothermeans(pumpandtreattechnique).

Chemicaltreatmenttominimizetheleachibilityofheavymetalsludgehavebeendeveloped.Metalscontaining
sludgearetreatedwithamendmentsthatrenderthemstableorlesssoluble.Suchtreatmentofhazardouswaste
isanintegralpartofmostlandfillprograms.However,thesemanipulationsaddtothealreadyhighcostof
wastewatertreatment;theytypicallyaccountfor60%to80%ofthewastedisposalcost.

ANewAlternativetoConventionalTreatment

Thechemicalprecipitationtechnique,currentlyusedbymostmetalfinishingbusinesses,istimeconsumingand
requiresextensiveequipmentandhandling,especiallyifitwereabatchprocess.Theprocessusesseveral
dangerousandsometimestoxicliquidchemicals,someofwhichareknowntofreezeincoldclimates.Someofthe
problemsassociatedwithsuchconditionsincludecloggingoffeedlinesandaccumulationofsolidonthebottom
offeedtanks,whichcouldresultinasignificantchangeintheconcentrationoftheliquidchemicalsolution.This
upsetsthetreatment,astheymayrequireinterruptingtheprocessaltogether,orhavingtoaddmoreliquidto
achievethedesiredresult.Itcouldalsorequireheatingtheareawherefeedtanksarelocatedinordertomaintain
thefluidnatureofthechemicals,which,inturn,addstothetreatmentcost.Inaddition,intheeventofaspill,
liquidchemicalarenoteasytocontainorcleanup.

Theprecipitationmethoddoesnotensuretotalcomplianceforallmetalspresentinthewastestreamsinceall
hydroxidesarenotcompletelyprecipitatedatasinglepH.Polishingwithscavengersisoftenrequiredinorderto
meetregulatorydischargestandards.Ifthetreatedwaterdoesnotmeetdischargestandards,thewateris
returnedandgoesthroughthetreatmentagainuntilitsqualityisacceptable.

Arecentlydevelopedalternativetreatmentusesamineralbasedagenttoremovecontaminantssuchasheavy
metals,oil&grease,andsuspendedsolidsfromwastewater.Theagenthasahighaffinityforheavymetals,and
thetreatmentitselfislessdependentonpHthanmetalhydroxideprecipitation.Theagentreactswithmetalssuch
aszinc,copper,lead,andchromiumatlevelsashighas10,000mg/Lorhigher.Thehighcapacityformetalsis
independentofpHorthepresenceofoil,surfactants,chelants,complexingagents,suspendedsolids,and
hardness.

Inthetreatmentprocess,theagentisaddedtotheagitatedwastewaterinatreatmenttankwhereadensefloc
forms,settlesveryfast,andiseasilydewatered.Onaverage,ittakesbetween3to10minutesafterturbulence
hasceasedforthefloctosettlecompletely.Thetreatmentcanbeusedinbothcontinuousandbatchprocesses
andisimplementedusingexistingequipment.Inaddition,thetreatmentagentcanbetailoredtofitthechemistry
ofthewastestream.Figure2showsatypicalsetupforthistreatment.

Wastegeneratedinthenewtreatmentdoesnotrequireposttreatmenttorenderitsafefordisposal.The
compositionofthetreatmentchemicalstabilizescontaminantsinthewaste,especiallyheavymetals,andrenders
themlessavailable.Inotherword,itlowersthesolubilityofmetalsand,consequently,thewastepassesthe
ToxicityCharacteristicLeachingProcedure(TCLP)testandmeetstheregulatoryrequirementsfornonhazardous
materials.

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Figure2.TypicalSetupforTreatmentSystemUsingMineralBasedAgent

Process Water

pH

Equalization Tank

- If Needed

Treatment Tank
Treated Water

Clarifier

Filter Press
Back To Equalization Tank
Sludge

Sludge Bin

CaseStudies

Case1:MetalPlating

AplatingfacilityinMichiganhasahighlyacidicwastestream(pH<1)thatcontainshighlevelsofchromium,zinc,
andironaswellasanumberofchelatingandcomplexingchemicals.Thefacilityhasatreatmentsystemthat
2+
operatesinacontinuousprocessataflowrateof56gpm.ThesystemutilizesFe fromtheacidpicklingbathto
reducechromium(VI)inthewastestream.Limeslurryisaddedtotheacidicwaterinamixingtanktoprecipitate
metalhydroxides.Aflocculantisaddedtothewatertoenhancesedimentationintheclarifier.Thetreatedeffluent
overflowstoaholdingtank,passesthroughasandfilterandthenreleasedtothesewer.Sodiumdithiocarbamate
isusedtoprecipitatemetalsinchelatedorcomplexedformsandtomaintainmetalconcentrationsintheeffluent
atthecompliancelevel.Accumulatedsludgeintheclarifieriswithdrawnperiodicallyandforcedthroughafilter
pressandthewasteisdriedonabeddrierandhauledawayashazardousmaterial.

Case1
DailyMaximum
BeforeTreatment
AfterTreatment
Parameters
ppm
ppm
ppm
Cadmium
Chromium
Zinc
Iron
PH

1.20
7.00
4.20
1,000.00
6.09.5

1.30
127.00
145.20
>10,000
<1

<0.002
<0.05
0.22
<1.0
8.70

Withthenewtreatment,mixingtheproductwiththewastestreamtookaboutthreetofourminutestobring
abouttheformationoflargeflocthatsettledcompletelywithinthreetofiveminutes.Treatedeffluentshowed
concentrationsformetalsabout10timeslowerthanmunicipaldischargelimits.Thistreatmenteliminatedthe
needtouselime,flocculantandthenoxiousdithiocarbamate.Analysisofleachate(TCLP)showedzincand339
ppmandchromiumat<0.5ppm;regulatorylimitsare500ppmforzincand5ppmforchromium.Thewasteis
nonhazardouswhichresultsinasignificantsavingontransportcost.

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Case2:CircuitboardManufacturing

AnIllinoisbasedcircuitboardmanufacturinghasawastewatertreatmentsystemthatoperatesat130gpmdaily.
Thewastestreamcontainsmainlycopperandlead,withotherheavymetalsfoundinsolderandfluxasminor
constituents.

Thesystemoperatesbydrawingwastewaterfromthevarioussumps(etching,plating,etc.)toanequalization
tank.Thestreamisthenfedtothreemixingtanksinseries.Inthefirsttank,acid/inorganiccoagulantmixtureis
added.CausticsodaisaddedinthesecondtanktoraisethepHandprecipitatemetalhydroxides.Inthethirdtank
apolymericflocculantisaddedtoeffecttheformationoflargeflocandenhancesedimentationintheclarifier.
Overflowfromclarifierflowstoaneutralizationtank,wherepHisadjustedwithacidandthenflowstoaholding
tank.Theneutralizedeffluentispumpedthroughasandfilter,thentoaholdingtank,andfinallyreleasedtothe
sewer.Sludgefromtheclarifierisdrainedintoatankwhereitismixedwiththickenersandisperiodicallyforced
throughafilterpress.Thesemidrywasteishauledawayasahazardousmaterial.

Case2
DailyMaximum
BeforeTreatment
AfterTreatment
Parameters
ppm
ppm
ppm
Copper
Lead
Nickel
PH

3.00
1.00
3.00
6.09.5

25.20
7.30
<0.05
7.80

1.30
<0.05
<0.05
8.50

Laboratorytestsshowedthatadoseof500ppmoftheproductwassufficienttoreducethelevelofcopperto0.30
ppmandthatofleadto<0.05ppm.Theproductalsoreducedtheconcentrationsofphosphorus,CODandtotal
dissolvedsolids,TDS.Thetreatedwaterisclearandcanberecycled.Treatmentwiththenewproducteliminated
theneedforallliquidchemicals,neutralizationtank,andsludgethickening,producedaverycleareffluentthat
meetsmunicipalstandardsandgeneratednonhazardouswaste.

Case3:PlatingOperation

AplatingserviceineasternMichigangeneratesabout6000gallonsofwastewaterdaily.Themainmetallic
contaminantsinthewaterarezinc,chromium,copper,andcadmium.Localdischargestandardsareverystringent
andrequirethatalimitof1ppmbemetforzinc,chromiumandcopperand0.004ppmforcadmium.Thefacility
hasatreatmentsystemthatconsistsofanequalizationtank,atreatmenttankwherecausticisaddedto
precipitatemetalhydroxides,andasettlingtank,whereaflocculantisintroducedtoeffectsedimentation.
PrecipitationofzincandcadmiumrequiresthatpHissetat12.Asaresult,waterfromthesettlingtankhastobe
neutralizedwithacidtobringpHto9.5.Thewaterthenflowstoaholdingtankandfinallypassesthroughasand
filterbeforeitisreleasedtothesewer.Liquidsludgefromsettlingtankiswithdrawnperiodicallyandhauled
away.Itwasalwaysdifficulttomeetdischargerequirementonaroutinebasis.

Case3
DailyMaximum
BeforeTreatment
AfterTreatment
Parameters
ppm
ppm
ppm
Cadmium
Chromium
Copper
Zinc
PH

0.004
1.00
1.00
1.00
6.59.5

0.790
5.10
4.12
37.40
7.40

<0.005
<0.10
0.35
0.50
8.08.5

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Treatmentwiththemineralbasedagentatadoseofabout1000ppmbroughtaboutcomplianceandmaintained
thelevelsofmetalintreatedeffluentat0.5ppmforzinc,0.1ppmforchromium,0.35ppmforcopper,<0.004for
cadmium,andeffluentspHisintherangeof8.0to8.5.Inaddition,theagentreducedthelevelsofphosphorus
andCODinthedischarge.Thetreatmenteliminatedtheneedforaneutralizationtank,holdingtank,andsand
filter.

Conclusion

Whilechemicalprecipitationiswidelyusedinthetreatmentofmetalfinishingeffluent,theprocessistediousand
requirestheuseofseveralliquidchemicalstocompletethemetalremovalstep.Theheavymetalsmayalsobe
presentincomplexedformsandnotamenabletoprecipitationwhichmeansfailuretomaintaincompliance.
Theprocessgeneratesmostlyhazardouswastethatrequiresfurthertreatmentthat,inturn,addstothecostof
thetreatment.

Anewprocessthatusesamineralbasedagentprovidesaneffectivealternativefortheremovalofheavymetals
andothercontaminantsfrommetalfinishingwastestreams.Thetreatmentproduceshighqualityeffluentsthat
meetorexceeddischargestandardsandgeneratesnonhazardouswastethatdoesnotendangertheenvironment
orpublichealth.

MOREINFORMATION

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AQUACHEMINC.
Tel:8325391020
Fax:8325391389
info@aquacheminc.com

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