Wastewater Treatment

Technology AOP

TableofContents
CinkarnaCeljeandgreentechnologies ................................................................................................... 4
Ultrafinetitaniumdioxideaswatertreatmentcatalyst.......................................................................... 4
Magneticphotocatalyst(MP).................................................................................................................. 5
TheefficiencyoftheMPincomparisontootherphotocatalysts ........................................................... 5
WastewatertreatmenttechnologyusingMPs ....................................................................................... 6
Wastewatertreatment ....................................................................................................................... 6
RetrievingandreusingMPs ............................................................................................................... 6
Developmentapproachtothecustommadesolutionfortheuser................................................... 6
MPtechnologyadvantagesincomparisontootherAOPtechnologies ............................................. 7
MPtechnologylimitations .................................................................................................................. 8
GeneralinformationconcerningphotocatalysisMPenergysource.................................................... 8
AOPgloballyoverview.......................................................................................................................... 9
ExistingAOPtechnologies ..................................................................................................................... 10
References............................................................................................................................................. 10

CinkarnaCeljeandgreentechnologies
Ultrafinetitaniumdioxideaswatertreatmentcatalyst
UltrafineTiO2producedbyCinkarnaCelje(CCA100AS,CCA100BSand200BS)hasphotocatalytic
features,whichischaracteristicoftitaniumdioxidenanoparticles.Thischaracteristicisusedin
wastewatertreatmentbecause,inordertowork,themethodonlyneedsultrafineTiO2andUVlight.
Thismethodisclassifiedamongthemoreadvancedoxidationtreatmenttechniques(AOP
AdvancedOxidationProcesses).

AOPtreatmentmethodsareusedglobally,mainlyinordertoremovesmallamountsofhealth
hazardouspollutants,someofwhichareeventoxicformunicipaltreatmentplants(e.g.hormone
disruptors,pesticides,etc.)andthusneedtobetreatedusingothermethodsbeforetheyare
releasedintomunicipalwaters.Thismethodisalsousefulforthepretreatmentofcertaintypesof
pollutedwaterswherecomplexmoleculesarebrokenupintosmallerandlesshazardousones,
makingwatermorebiologicallydegradable.

Advancedoxidationprocessesarebeingusedforthetreatmentofindustrialwastewatermoreoften
thanever.UltrafineTiO2ischaracterizedbynonselectiveremovalofawiderangeofpollutants.In
cooperationwithuniversities(theUniversityofLjubljana,MariborandNovaGorica),institutes(Joef
tefanInstitute,InstituteofChemistry),andhealthcareorganizations,wemonitoredtheefficiency
andselectivityofourmaterialusingsomeofthemostadvancedtechniques,whichgivesusabetter
overviewoverthetreatmentprocessefficiency.

Amongalloftheadvantagesofwastewatertreatmentusingtitaniumdioxidenanoparticles,the
mainissueisremovingthemfromwateroncethetreatmentprocessisconcluded.Inorderto
achievethemaximumefficiencyofthematerial,theparticlesneedtobesuspendedinpolluted
water,incontrasttosomeproducts,inwhichthecatalystlayerisappliedonsolidcarriers(smaller
specificsurfaceoftheactivematerialincomparisontosuspendedparticles).

Ourcompanyhasdevelopedatreatmenttechnologyusingacompositecatalystwithtitanium
dioxidenanoparticlesboundtomagneticnanoparticles.Theadvantagethatoursolutionhasover
othercompetingproductsonthemarketisthetechnologyofmaterialseparationfromtreated
water,whichonlytakesplaceifanexternalmagneticfieldispresent(withoutusingadditional
energy),enablingtheremovalofthecatalystafterwatertreatment(recycling).Atthesametime,the
materialkeepsitslargespecificsurfaceduetothesuspendedcatalystparticles.

Themostcommonareasofapplication[1]:

textilewastewater,
foodindustrywastewater,
pharmaceuticalwastewater,
ballastwater(disinfectionenvironmentalrequirements),
closedloopwater(microorganismremoval,coolingwaterconditioning).

Magneticphotocatalyst(MP)
Bydevelopingourownproduct,wecombinednumerouspositivefeaturesofthemethodsthatwere
listedaboveinordertobenefitthemaximumefficiencyandsimplicityofwastewatertreatment.A
Magnetnifotokatalizator(MF)
magneticphotocatalyst(MP)usesthephotocatalyticpropertiesoftitaniumdioxidetodisintegrate
Zrazvojemlastnegaproduktasmozdruilivepozitivnihlastnostizgorajnatetihmetodvpridimveji
pollutantsandthemagneticpropertiesofthecarriertorecyclematerial.Theultrafinetitanium
uinkovitosti
in enostavnosti ienja onesnaenih vod. Magnetni fotokatalizator (MF) izkoria
dioxide,CCA100AS,whichisusedforpreparingthemagneticphotocatalyst(MP),isalsoCinkarna
dioxide,CCA100AS,whichisusedforpreparingthemagneticphotocatalyst(MP),isCinkarnaCeljes
fotokatalitine
lastnosti titanovega dioksida za razgradnjo onesnail ter magnetne lastnosti nosilca za
ownproduct.
Celjesownproduct.
recikliranje
materiala. Za pripravo magnetnega fotokatalizatorja uporabljamo lasten ultrafini titanov

dioksid,tipCCA100AS.

TheefficiencyoftheMPincomparisontoother
TheefficiencyoftheMPincomparisontootherphotocatalysts
photocatalysts
UinkovitostMFvprimerjavizdrugimifotokatalizatorji

AtCinkarnaCelje,wehavebeenusingourownmethodfordecomposingformicacidinorderto
AtCinkarnaCelje,wehavebeenusingourownmethodfordecomposingformicacidinorderto
determinetheefficiencyofthephotocatalyst.Thediagrambelowshowstheefficiencyofvarious
determinetheefficiencyofthephotocatalyst.Thediagrambelowshowstheefficiencyofvarious
Za
doloevanje fotokatalitske uinkovitosti uporabljamo v Cinkarni Celje interno metodo razgradnje
samples(MP,thesuspension,andthedepositsontheglassofourproductsandcompetingproducts)
samples(MP,thesuspension,andthedepositsontheglassofourproductsandcompetingproducts)
mravljinne
kisline. Na spodnjem grafu so prikazane uinkovitosti razlinih vzorcev (MF, suspenzije in
asthechangeoftheconversioninacertaintimeperiod.
asthechangeoftheconversioninacertaintimeperiod.
nanosinasteklulastnihterkonkurennihproizvodov)kotspremembakonverzijevasovnienoti.

PhotocatalyticHCOOH
HCOOH degradation
PhotocatalyticHCOOHdegradation
Photocatalytic
degradation
1
CCA 100 AS

0,8
CCA 200 BS

0,6
[H]/[Ho]

MF CC 2.4.2013

0,4
Competing sample
in a Competing
suspension sample

0,2

in a suspension

CCA 100 AS on plates

0
0

4
Time

CCA 100 AS on
plates sample
Competing
on plates

Competing sample

on plates
Time
Graf1:HitrostrazgradnjevzorcevTiO2vsuspenzijiinnatrdnihnosilcihterMFvsuspenziji.

Diagram1:degradationspeedofTiO
2samplesinasuspensionandonsolidcarriersaswellasMPina
Diagram1:degradationspeedofTiO
samplesinasuspensionandonsolidcarriersaswellasMP
2
Najnijo aktivnost izkazujeta vzorca, ki stainasuspension
nanesena
na trdnih nosilcih (CCA 100 AS na ploah in
suspension
konkurenni vzorec na ploah). Pri teh vzorcih je aktivna povrina dosti manja, kot v primeru
Thelowestactivitiesarenoticedinthesamplesthatwereappliedonthesolidcarriers(CCA100AS
suspendiranihnanodelcev.Temuprimernojeaktivnostmnogonija,vendarjenjihovoodstranjevanjepo
onplatesandthecompetingproductonplates).Inthesesamples,theactivesurfaceismuchsmaller
ienju
enostavno. Suspenzije lastnih in konkurennih proizvodov izkazujejo primerljivo aktivnost,
thaninsuspendednanoparticlesandtheactivitylevelsarecorresponding.However,theirremovalis
najhitrejorazgradnjomravljinnekislinepasmodoseglizmagnetnimfotokatalizatorjem.
simple.Theactivityofthesuspensionsofourownproductsandthecompetingproductsare
comparable.Thefastestdegradationofformicacidwasachievedwithamagneticphotocatalyst.

WastewatertreatmenttechnologyusingMPs
Thetreatmenttechnologyincludestwomainstages:

1. Wastewatertreatment,
2. RetrievingandreusingMPs.
Wastewatertreatment
Thecatalyst,theamountofwhichisdeterminedbeforehandbyalabdevice(theconcentrationstend
torangebetween20and250mg/L),isdispersedinthewaterthatwewishtotreat.Apumpthen
movesthewaterincludingthesuspendedMPparticlesthroughaUVreactor(seeFigure1)wherethe
pollutantdegradationtakesplace.Theresidencetimechangesaccordingtothewaterpollutionlevel,
pollutanttype,andrequiredtreatmentlevel.

Theresidencetimeisdeterminedaccordingtothetypeofthewaterpollutantthedegradation
levelismeasuredasthechangeofCODandBOD5values.Intheeventofmorecomplexpollutants,
morecomplexanalyticalmethodsareappliedthathelpuspreciselydeterminetheconcentrationof
theselectedpollutant.
Pollutedwaterinflow

Mixer
reactor

UV
reactor

Magnetic
separator
Treatedwater
outflow

Treatmentcycledescription:

1. Pollutedwaterisputintothemixer
reactor,
2. thecatalystisaddedtothepolluted
water,
3. thewaterwiththecatalystcirculates
throughtheUVreactor,
4. thetreatedwaterflowsoutthrough
themagneticseparator,
5. thecatalystisrecycled.

Figure1:Depictionoftreatmentplantoperation

RetrievingandreusingMPs
Thecatalystispreparedintheformofawatersuspensionwhichisaddedtowastewater.Afterthe
reactionisconcluded,thetreatedwaterwiththeMPisledthroughamagneticseparator(MS).The
separationisperformedonthebasisofmagnetismanddoesnotrequireanadditionalenergysource.
Aftertheseparationprocessisconcluded,thecatalystremainsintheseparator.Thetreatedwateris
pumpedoutofthesystem(Figure2)andreplacedwithnewwastewaterthatfirstneedstocirculate
throughtheseparatortocollectthecatalystparticles.Thetreatmentandrecyclingstagesarethen
interchangeduntilallofthewaterthatisbroughttothesystemistreated.

Developmentapproachtothecustommadesolutionfortheuser
Thevisionofthecompanyistouseitsownhightechproductswiththepurposeofreducingharmful
substancesintheenvironment.Thedevelopmentofthewastewatertreatmentapplicationusinga
magneticphotocatalystrequiresasolutioncustommadeforthebuyersbecausetheapplication

dependsonthewaterpollutanttype.Thereisapilotdevicesetupatthecompanywhich
demonstratesthetreatmenttechnologyusingvarioustypesofwastewater.

Table1:Thelevelofthedegradationofindustrialwastewatersamplewithamagnetic
photocatalyst.

54.2123Jan2012
BOD5
mg/LO2
27
COD
mg/LO2
165
UV0,1TiO224Jan2012
BOD
mg/LO2
<3.0LOD#
COD
mg/LO2
57

Optimalprocessparametersneedtobedeterminedfortheselectedwastewater:catalyst
concentration,residencetime,batch/continuousoperation,UVstrengthinput,etc.CinkarnaCelje
constructeditsownmobilelaboratorydevicethatenablescapacitycalculations.Later,thisdatahelps
uscalculatetheparametersfortheneedsoftheindustrialplant(Figure2).

Figure2:Themobilepilotdevice
Whendeterminingtheefficiencyofthedegradationofmorecomplexpollutants,sampleanalyses
needtobecarriedoutbymeansofchromatographyincombinationwithamassspectrometer.CLP
SemivolatilesCalibrationMixisusedasastandardmixofpollutantsthataredegradedwithmore
difficulty.

MPtechnologyadvantagesincomparisontootherAOPtechnologies
Thesynthesisofinnovativematerialmadeitpossibleforustodevelopanewwastewatertreatment
technologythathassomekeyadvantagesovercompetingtechnologies:

MPparticlesaredispersedinpollutedwaterandthushaveasignificantlylargerspecific
surfaceincomparisonwithcatalyststhatarefixedonreactororcarriersurfaces,
duringthetreatmentreaction,nosubstancesneedtobeaddedtoenablethepollutant
degradationreaction,
inordertofunction,thetechnologyonlyusesUVenergyandMPs,
thecatalystisrecycledfollowingeachtreatmentcycle,
MPscausethedegradationofawiderangeoforganicpollutants(hormonedisruptors,
pesticides,antibiotics,carbohydrates,phenols,bacteria,algae,etc.),
MPsdegradesmicroorganismsandnotmerelydeactivatestheirreproduction,
thecatalystisnotharmfultotheenvironmentandpeople.

MPtechnologylimitations
-

thewaterpHvalueneedstobebetween3and9,
thewatermaynotincludeanynondissolvedpollutants1,
theoxygenconcentrationinthewaterneedstobeascloseaspossibletosaturated
concentration,
watertemperaturemaynotbehigherthan45C,
thistechnologyismoresuitableforlowerconcentrationpollution,exceptinthecaseof
specificpollutantswherethehighestefficiencylevelisachieved.

GeneralinformationconcerningphotocatalysisMPenergy
source
Thetermphotocatalysisdenotestypesofreactionsthattakeplaceinthepresenceoflightanda
catalyst.UltrafinetitaniumdioxideneedsaUVlightsourceforitsfunctioning.Thislighttheninduces
theprocessofchargeseparationinmaterialaTiO2isasemiconductorthatbecomescharged
undertheinfluenceofUVlightwithspecificenergy.

Theelectronsandelectronholesthatarecreatedduetothemigrationofelectronscontributetothe
creationofactiveradicals.Onthesurfaceofthecatalyst,theelectronsandelectronholesreactwith
oxygenandwatermolecules.Theproductsofthisreactionarehydroxylandsuperoxideradicalsthat
triggerthedegradationofpollutantsinwater[2].

Oxidant
OxidationPotential(eV)
2.80
OH
2.07
O3
1.77
H2O2
1.70
HydroperoxylRadicals
1.67
Permanganate
1.50
ChlorineDioxide
1.36
Chlorine
1.23
O2

Table2:Thecomparisonofoxidationpotentialvaluesofindividualoxidants[3].

Intheeventofnondissolvedsubstances,preliminaryfiltrationisrequired.

REDUCTION

Conductionband
Electron
excitation
Photon
absorption

Valenceband
OXIDATION

UVphoton
Figure3:DepictionofthephotocatalysisprocessonTiO2nanoparticle 4.

AOPgloballyoverview
Thetechnologyofadvancedoxidationmethodshasbeenknownintheworldforapproximately20
years.Nowadays,mainlythecombinationofUVlightandanoxidationagentisusedforwastewater
treatment,andnotsomuchanyindividualmethods.

PhotocatalysiswithtitaniumdioxideisanAOPwastewatertreatmentmethodthatrequiresaUV
lightsourceforitsfunctioning.InadditiontothestrengthoftheUVlightsource,thelifespanofUV
lightbulbsisalsoveryimportantfromthetechnoeceonomicpointofview.Inpractice,thislifespanis
12to18monthsifused24/7.Equipmentcostsarecalculatedonthebasisoftheamountof
wastewaterandthedesiredeffectofthedegradationofthepollutant(powerinput).

ThelargestusersofUVequipmentaremunicipaltreatmentplantsthatneedUVlightfortertiary
treatment(systemswithaflowrateofafewhundredm3/min).TheMPtechnologyisanupgradeof
theUVwatertreatment/preparationsystemthatcombinestheremovalofmicroorganismsandthe
degradationoftoxicsubstanceswhichmaynotbedegradedusingstandardmethodsortheremoval
ofwhichisnoteconomicallyviable.TheuseofMPtreatmenttechnologyalsomakessenseforusers
whoalreadyhavesetupUVdisinfection/wastewatertreatmentsystemsbecauseitreducesthe
residencetime(savesenergy)orincreasestheleveloftreatment,evenupto40percent2.However,
themainadvantagethattheuseoftheMPtechnologyhasoverothertechnologiesisthattheuseof
MPsdoesnotrequiretheadditionofchemicalsorothersubstancesinordertoachievethedesired
treatmenteffect.
ThelargestAOPwatertreatmentsystemsarecurrentlyintheUSA(theremovalofNDMA,1,4
dioxane)wheretreatmentcostsarealreadyapproximately0.01EUR/m3ofwastewater[5].

Thepercentageoftheincreasedtreatmenteffectdependsonthetypeofwater.

Theapplicationforballastwatertreatmentisalsoveryinteresting.Inthefuture,thisapplicationwill
berequiredbylaw.Therearesystemsonthemarketthatprovidetheremovalofallmicroorganisms
withthehelpofTiO2UVtechnology[6].

Thisapplicationisalsosuitableinthefieldofprovidingdrinkingwater.Withintheprojectsofthe
EuropeanresearchinititativeSeventhFrameworkProgramme,thephotocatalyticremovalofvarious
pollutantsthataffecttheendqualityofdrinkingwaterisbeingtested[7].

ExistingAOPtechnologies
AOPoradvancedoxidationprocessesconsistofadozenpollutantremovaltechnologies,inwhich
hydroxylradicalsserveastheactivemedium.Themethodsareseparatedaccordingtothesourceof
theformationofOH*radicals[8]:
- TiO2photocatalysis,
- ozonization,
- UVdisinfection,
- UVwastewatertreatment,
- theapplicationofhydrogenperoxide(H2O2),
- Fenton/PhotoFentonreaction,
- variouscombinationsoftheabovemethods.

References
[1]MohajeraniM,MehrvarM.,EinMozaffariF.Anoverviewoftheintegrationofadvancedoxidation
technologiesandotherprocessesforwaterandwastewatertreatment.Internationaljournalof
Engineering3,120(2009).

[2]ChongM.N.,JinB.,ChowC.,SaintC.Recentdevelopmentsinphotocatalyticwatertreatment
technology:Areview.Waterresearch44,2997(2010).

[3]SharmaS.,RupareliaJ.P.,PatelM.L.Ageneralreviewonadvancedoxidationprocessesforwaste
watertreatment.Internationalconferenceoncurrenttrendsintechnology,Nuicone(2011)

[4]http://projekti.gimvic.org/2009/2a/kataliza/fotokataliza_teorija.html(6June2013).

[5]KanekoM.,OkuraE.PhotocatalysisScienceandTechnology.Springer,Japan,2002.

[6]MatheickalJ.,RaaymakersS.2ndInternationalballastwatertreatmentR&Dsymposium.
Globallastmonographseries15(2003).

[7]http://www.observatorynano.eu/project/(6June2013).

[8]Kommineni,S.et.al.3.0AdvancedOxidationProcesses.http://www.nwri
usa.org/pdfs/TTChapter3AOPs.pdf(11June2013).

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Contact:
Peter Bastl M.Sci.
Product sales manager
tel.: 00386 3/427 - 6083
gsm: 00386 41/271 - 615
e-mail: peter.bastl@cinkarna.si

Alja Selinik
Research and development
tel.: 00386 3/427 - 6087
fax.: 00386 3/427 - 6116
e-mail: aljaz.selisnik@cinkarna.si