advanced oxidation process: fundamentals & process … · 2012-03-08 · advanced oxidation...
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Advanced Oxidation Process: Advanced Oxidation Process: Fundamentals & ProcessFundamentals & ProcessFundamentals & Process Fundamentals & Process Applications in Water and Applications in Water and Wastewater Treatment/ReuseWastewater Treatment/ReuseWastewater Treatment/ReuseWastewater Treatment/ReuseKhalil Z. Atasi, Ph.D., P.E., BCEE, F.ASCE Khalil Z. Atasi, Ph.D., P.E., BCEE, F.ASCE S i ViS i Vi P id tP id tSenior Vice Senior Vice PresidentPresidentCamp Dresser & McKee Inc.Camp Dresser & McKee Inc.&&Kathy A. Traexler, P.E. Kathy A. Traexler, P.E. Project Engineer Project Engineer Camp Dresser & McKee IncCamp Dresser & McKee IncCamp Dresser & McKee Inc.Camp Dresser & McKee Inc.
Air Products Technology SymposiumAir Products Technology Symposiumgy ygy yDeerfield Beach, FloridaDeerfield Beach, Florida
July July 22, 200922, 2009
Presentation OutlinePresentation Outline What is advanced oxidation (AO)?What is advanced oxidation (AO)?
Basic principle of AOBasic principle of AO ChemistryChemistry ChemistryChemistry KineticsKinetics Electrical Energy Dose(E ED)Electrical Energy Dose(E ED) Electrical Energy Dose(E ED)Electrical Energy Dose(E ED)
Type of AO processes (AOP)Type of AO processes (AOP) Type of AO processes (AOP)Type of AO processes (AOP)
AOP for treatment of emergingAOP for treatment of emerging AOP for treatment of emerging AOP for treatment of emerging contaminantscontaminants
Technology for AOPsTechnology for AOPs
Wh t i Ad d O id ti ?Wh t i Ad d O id ti ?What is Advanced Oxidation?What is Advanced Oxidation?
High rate kineticsHigh rate kinetics
Fast reactionFast reaction
Generates hydroxyl radicals (Generates hydroxyl radicals (●●OH)OH)
NonNon-- “discriminatory” reaction (non“discriminatory” reaction (non--y (y (selective)selective)
Wh t i Ad d O id ti ?Wh t i Ad d O id ti ? (C t )(C t )What is Advanced Oxidation? What is Advanced Oxidation? (Cont.)(Cont.)
E t l f tE t l f t i l ti l h ti l ti l h t Extremely fast Extremely fast –– requires relatively short requires relatively short time (on the order of seconds to minutes)time (on the order of seconds to minutes)
Small footprintsSmall footprints ideal for large flow ratesideal for large flow rates Small footprints Small footprints –– ideal for large flow ratesideal for large flow rates Detoxification/Transformation and/or Detoxification/Transformation and/or
mineralization of emerging contaminants ofmineralization of emerging contaminants ofmineralization of emerging contaminants of mineralization of emerging contaminants of concern (ECCs)concern (ECCs)
No Solid waste or residuals generation (e.g. No Solid waste or residuals generation (e.g. g ( gg ( gsludge; spent activated carbon; IX brine sludge; spent activated carbon; IX brine solution)solution)
NN l ti til ti ti id l f lti lid l f lti l NonNon--selective reaction selective reaction ideal for multiple ideal for multiple simultaneous treatment objectivessimultaneous treatment objectives
Wh t i Ad d O id ti ?Wh t i Ad d O id ti ? (C t )(C t )What is Advanced Oxidation? What is Advanced Oxidation? (Cont.)(Cont.)
P ibl hi h it l d O&M tP ibl hi h it l d O&M t Possible high capital and O&M costs Possible high capital and O&M costs (mainly power)(mainly power)
Issues with treated water stability due to Issues with treated water stability due to potential formation of AOC/BDOCpotential formation of AOC/BDOCpotential formation of AOC/BDOCpotential formation of AOC/BDOC
Generally difficult to predict the reactionsGenerally difficult to predict the reactions Generally difficult to predict the reactions Generally difficult to predict the reactions involved (mechanism and/or kinetics)involved (mechanism and/or kinetics)
Excess HExcess H22OO22 needs to be quenchedneeds to be quenched
T h lT h l AOPAOPTechnology Technology -- AOPAOP
Ad d O id ti P (AOP) fAd d O id ti P (AOP) f Advanced Oxidation Process (AOP) for Advanced Oxidation Process (AOP) for oxidizing, altering, or mineralization of oxidizing, altering, or mineralization of “Microconstituents” that otherwise can not “Microconstituents” that otherwise can not c oco st tue ts t at ot e se ca otc oco st tue ts t at ot e se ca otbe oxidized by “regular” oxidation processbe oxidized by “regular” oxidation process
Contaminants such as:Contaminants such as: EDCsEDCs PPCPsPPCPs Pesticides Pesticides HerbicidesHerbicides CyanotoxinsCyanotoxins Organoleptic compoundsOrganoleptic compounds Xenobiotic compoundsXenobiotic compounds
AOPAOP Ch i tCh i tAOP AOP -- ChemistryChemistry
Involves the generation of chemical radicalsInvolves the generation of chemical radicals Strong oxidizing reagentsStrong oxidizing reagents Hydroxyl radicals Hydroxyl radicals ●●OHOH
Highly accelerated reactionsHighly accelerated reactions Hydroxyl radicals react with many reduced Hydroxyl radicals react with many reduced
d t t t i f h i ld t t t i f h i lcompounds to start a series of chemical compounds to start a series of chemical degradation reactionsdegradation reactions
AOPs performance impacted by reactionAOPs performance impacted by reaction AOPs performance impacted by reaction AOPs performance impacted by reaction kinetics and reactor hydraulicskinetics and reactor hydraulics
AOPAOP Ch i tCh i t (C t )(C t )AOP AOP –– Chemistry Chemistry (Cont.)(Cont.)
Hydroxyl radicals react with Hydroxyl radicals react with organic organic contaminantscontaminants by different/several reaction by different/several reaction mechanisms including:mechanisms including:mechanisms, including:mechanisms, including: Hydrogen abstraction from aliphatic compounds Hydrogen abstraction from aliphatic compounds
(CH(CH33 OHOH CHCH22 OH), andOH), and(CH(CH33 OH OH CHCH22 OH), andOH), and Addition to unsaturated compoundsAddition to unsaturated compounds Followed by reaction with OFollowed by reaction with O22 initiating a seriesinitiating a series Followed by reaction with OFollowed by reaction with O22 initiating a series initiating a series
of degradation reactionsof degradation reactions In general sequence of reactions: contaminants In general sequence of reactions: contaminants
t t ft t f ld h dld h d th idi d tth idi d treact to form react to form aldehydesaldehydes, then are oxidized to , then are oxidized to carboxylic acids and ultimately become carboxylic acids and ultimately become COCO33
AOPAOP R ti Ki tiR ti Ki tiAOP AOP –– Reaction KineticsReaction Kinetics
Generation of chemical radicals Generation of chemical radicals –– strong strong id tid toxidantsoxidants
●●OH radicals are the most known and OH radicals are the most known and studiedstudied
“Advanced” as compared to “regular” “Advanced” as compared to “regular” REDOX reaction due to high rate kineticsREDOX reaction due to high rate kineticsREDOX reaction due to high rate kineticsREDOX reaction due to high rate kinetics
●●OH radicals generate series of reactionsOH radicals generate series of reactions ●●OH radicals generate series of reactionsOH radicals generate series of reactions
AOPAOP R ti Ki tiR ti Ki ti (C t )(C t )AOP AOP –– Reaction Kinetics Reaction Kinetics (Cont.)(Cont.)
R t d t i ti i i t t fR t d t i ti i i t t f Rate determination is very important for:Rate determination is very important for: Evaluation of contaminants transformationEvaluation of contaminants transformation
R t d iR t d i Reactor designReactor design
G ll d l d ( it ifi )G ll d l d ( it ifi ) Generally modeled (site specific) as :Generally modeled (site specific) as : Zero order, orZero order, or
Fi t dFi t d First orderFirst order
M tl fi t d ki tiM tl fi t d ki ti Mostly first order kineticsMostly first order kinetics
AOPAOP R ti Ki tiR ti Ki ti (C t )(C t )AOP AOP –– Reaction Kinetics Reaction Kinetics (Cont.)(Cont.) First order:First order: First order:First order:
CCe e = C= Coo exp[exp[--k (V/Q)]k (V/Q)]
CCe e , C, Coo effluent/influent concentrationeffluent/influent concentrationk first order rate constant (tk first order rate constant (t--11 ))k, first order rate constant (tk, first order rate constant (t--11 ))V, reactor volumeV, reactor volumeQ fl tQ fl tQ, flow rateQ, flow rate
High k value High k value smaller V (for a given Q)smaller V (for a given Q) Treatability studies important to determine k Treatability studies important to determine k
and feasibility of the processand feasibility of the process
Why AOs are so potent?Thermodynamics Thermodynamics (energy/feasible)(energy/feasible)
Why AOs are so potent?
ΔΔGGoo = = -- n F n F EEoonetnet
EEoonetnet = = EEoo
oxox + + EEooredred
When When EEoonetnet > 0, > 0, ΔΔGGoo < < 0, and the reaction is 0, and the reaction is
spontaneousspontaneousTh hi h th d ti t ti lTh hi h th d ti t ti l EEoo thth The higher the reduction potential, The higher the reduction potential, EEoo
redred, the , the more probable more probable EEoo
netnet to be > 0 and to be > 0 and ΔΔGGoo to be < 0 to be < 0 KineticsKinetics (reaction rate)(reaction rate)Kinetics Kinetics (reaction rate)(reaction rate)
AtrazineAtrazine + O+ O33 k = 2.3 k = 2.3 -- 24 L/mol24 L/mol--ssAt iAt i OHOH k 1 2k 1 2 2 6 102 6 1099 L/ lL/ l AtrazineAtrazine + + OH OH k = 1.2 k = 1.2 -- 2.6 x102.6 x1099 L/molL/mol--ss
[Source: Radiation Chemistry Data Center of the Notre Dame Radiation Laboratory] [Source: Radiation Chemistry Data Center of the Notre Dame Radiation Laboratory] [ y y][ y y]
AOPAOP O id ti PO id ti PAOP AOP –– Oxidation PowerOxidation Power
AOPAOP C d idi d bC d idi d b OHOHAOP AOP ––Compounds oxidized by Compounds oxidized by ●●OHOH
AOP AOP –– REACTION RATE (1REACTION RATE (1STST ORDER) ORDER) (L MOL(L MOL--11 SECSEC--11 ))(L MOL(L MOL--11 SECSEC--11 ))
Normally , hydroxyl radical Normally , hydroxyl radical concentration ranges between concentration ranges between 101088 to 10to 101010 mol.Lmol.L--1 1
PseudoPseudo--first order rate first order rate constant is between 1 and 10constant is between 1 and 10--44
secsec--11 (Glaze and Kang 1989)(Glaze and Kang 1989)secsec 1 1 (Glaze and Kang, 1989)(Glaze and Kang, 1989)
AOP AOP –– Water Treatment Technologies Water Treatment Technologies Suitability based on CODSuitability based on COD(Rodriguez, 2003)(Rodriguez, 2003)
Contaminant Levels Evolution Contaminant Levels Evolution ––Sustainable DevelopmentSustainable Development(Rodriguez, 2003)(Rodriguez, 2003)
Industrial
FecalECCs
Nutrients
AOP AOP –– Emerging ContaminantsEmerging Contaminants
AOPAOP El t i l E D (EED)El t i l E D (EED)AOP AOP –– Electrical Energy Dose (EED)Electrical Energy Dose (EED)
AOP d i b l t i lAOP d i b l t i l AOP are driven by electrical energyAOP are driven by electrical energy
Basis of Comparison: Electrical Energy Dose Basis of Comparison: Electrical Energy Dose EEDEED
Units of kWUnits of kW--hr/1,000galhr/1,000gal
EED = P/(Q*0.06) EED = P/(Q*0.06) (P i R t P i kW Q i R t(P i R t P i kW Q i R t (P is Reactor Power in kW, Q is Reactor (P is Reactor Power in kW, Q is Reactor
Flow in gpm)Flow in gpm)
AOP AOP –– Electric Energy per Order (EEO)Electric Energy per Order (EEO)gy p ( )gy p ( )
Electrical Energy per Order, EEOElectrical Energy per Order, EEO Electrical Energy per Order, EEOElectrical Energy per Order, EEO
EEO is the EED required to achieve oneEEO is the EED required to achieve one--loglog EEO is the EED required to achieve oneEEO is the EED required to achieve one--log log removal of a particular chemicalremoval of a particular chemical
EEO = EED * log(Co/EEO = EED * log(Co/CeCe)])](Co &(Co & CeCe are influent & effluent concentrations)are influent & effluent concentrations)(Co & (Co & CeCe are influent & effluent concentrations)are influent & effluent concentrations)
AOP AOP –– Electric Energy per Order Electric Energy per Order (EEO)(EEO) UVUV(EEO) (EEO) -- UVUV
EEO is a function of particular chemical, and UVEEO is a function of particular chemical, and UV EEO is a function of particular chemical, and UV EEO is a function of particular chemical, and UV reactor hydraulics, optical & electrical reactor hydraulics, optical & electrical efficienciesefficiencies
Lower EEO desiredLower EEO desired Higher EEO implies that greater electrical Higher EEO implies that greater electrical
i i d t hi l l fi i d t hi l l fenergy is required to achieve same level of energy is required to achieve same level of removalremoval
First Order Reaction: Plot of EED vs LogFirst Order Reaction: Plot of EED vs Log First Order Reaction: Plot of EED vs. Log First Order Reaction: Plot of EED vs. Log Removal is linear; slope of this plot will give Removal is linear; slope of this plot will give EEOEEO
Reactor hydraulics will affect EEOReactor hydraulics will affect EEO Use “Rated” power draws to calculate EEO’sUse “Rated” power draws to calculate EEO’spp 2 kW for LPHO2 kW for LPHO--UV, and 4 kW for MPUV, and 4 kW for MP--UVUV
AOPAOP TTAOPs AOPs -- TypesTypes
Fenton’s ProcessFenton’s Process
Ozone/Peroxide Ozone/Peroxide
UV/OzoneUV/Ozone
UV/PeroxideUV/Peroxide
UV/Peroxide/OzoneUV/Peroxide/Ozone U / e o de/O o eU / e o de/O o e
AOPAOP F t ’ PF t ’ PAOPs AOPs -- Fenton’s ProcessFenton’s Process
Ferric complexes can adsorb in the near UV andFerric complexes can adsorb in the near UV and Ferric complexes can adsorb in the near UV and Ferric complexes can adsorb in the near UV and up to 500 nm visible rangeup to 500 nm visible range
Fe(II) +peroxide at pH= 3Fe(II) +peroxide at pH= 3--4 will generate 4 will generate ●●OHOH
Fenton Reaction occurs without photochemical Fenton Reaction occurs without photochemical initiationinitiation
Effective with:Effective with:hi h t i t t tihi h t i t t ti high contaminant concentration high contaminant concentration
low UVT water, orlow UVT water, or High natural concentrationHigh natural concentration High natural concentrationHigh natural concentration
AOPAOP F t ’ PF t ’ PAOPs AOPs –– Fenton’s ProcessesFenton’s Processes
the Fenton Reagentthe Fenton ReagentHalf ReactionsHalf Reactions
HH22OO22 + 2H+ 2H++ + 2e+ 2e-- 2H2H22OOHH OO OH OHOH OHHH22OO22 + e+ e-- OH + OHOH + OH--
FeFe2+ 2+ FeFe3+3+ + e+ e--
OverallOverallOverallOverall
FeFe2+2+ + H+ H OO FeFe3+3+ ++ OH + OHOH + OH--FeFe22 + H+ H22OO22 FeFe33 + + OH + OHOH + OH
AOPAOP O /P id (“O /P id (“PP ”)”)AOPs AOPs –– Ozone/Peroxide (“Ozone/Peroxide (“PeroxonePeroxone”)”)
OO OHOH OO33 OHOH–– in neutral to basic solutions Oin neutral to basic solutions O33 will decompose will decompose
to OHto OHto OHto OH
HH22OO22 + O+ O33 ●●OHOH–– HH OO accelerates the decompositionaccelerates the decomposition–– HH22OO22 accelerates the decompositionaccelerates the decomposition
Issues with bromate formation (depending on Issues with bromate formation (depending on the source water); however, controllablethe source water); however, controllable); ,); ,
Very attractive cost as compared to other Very attractive cost as compared to other AOPs processesAOPs processes
Meets LT2ESWTR and S2DBP requirementsMeets LT2ESWTR and S2DBP requirements
AOPSAOPS UV/OUV/OAOPS AOPS –– UV/OzoneUV/Ozone Ozone absorbs UV in the 200Ozone absorbs UV in the 200--300 nm300 nm Ozone absorbs UV in the 200Ozone absorbs UV in the 200 300 nm 300 nm
resulting in a singlet Oresulting in a singlet O22 generation, which generation, which results in results in ●●OH formationOH formation
UVUV--C (C ( = 200 = 200 –– 280 nm)280 nm) HH22OO22 2 2 ●● OHOH
Rarely used due to high cost and can not Rarely used due to high cost and can not compete with other AOPscompete with other AOPs
Inefficient method to produce Inefficient method to produce ●●OHOH
AOPs AOPs –– UV/PeroxideUV/Peroxide
Has received a lot of interest in drinking Has received a lot of interest in drinking ggwater due to the LT2 ESWTR barrier against water due to the LT2 ESWTR barrier against Cryptosporidium and Giardia Cryptosporidium and Giardia (disinfection) (disinfection) concurrently with organic compoundconcurrently with organic compoundconcurrently with organic compound concurrently with organic compound oxidation. Attractive with adenovirus.oxidation. Attractive with adenovirus.
Organic pollutant “removal” is achievedOrganic pollutant “removal” is achieved Organic pollutant removal is achieved Organic pollutant removal is achieved either by photolysis or AO (hydroxyl radical)either by photolysis or AO (hydroxyl radical)
Significant concentrations (>5 mg/L) of HSignificant concentrations (>5 mg/L) of H22OO2222 22are required due to molar absorption are required due to molar absorption coefficients of peroxide at 200coefficients of peroxide at 200--300 nm300 nm
UVUV C (C ( 200200 280 ) ( t i ld i280 ) ( t i ld i UVUV--C (C ( = 200 = 200 –– 280 nm) (quantum yield is 280 nm) (quantum yield is optimal) up to optimal) up to HH OO 22 ●● OHOH HH22OO22 2 2 ●● OHOH
AOPAOP UV/P idUV/P idAOPs AOPs –– UV/PeroxideUV/Peroxide
Key water quality parameters have impacts:Key water quality parameters have impacts: pHpH TemperatureTemperature TOCTOC UVT UVT Carbonate alkalinityCarbonate alkalinity IronIron ManganeseManganese
AOPsAOPs-- UV/PeroxideUV/PeroxideF ti f UV Ab b d b 10 /L HF ti f UV Ab b d b 10 /L H OOFraction of UV Absorbed by 10 mg/L HFraction of UV Absorbed by 10 mg/L H22OO22Anipsitakis, FWEAAnipsitakis, FWEA 20082008
25%
20%UV254 abs = 0.05 cm-1
10%
15%
1
5%
10% UV254 abs = 0.2 cm-1
0%Drinking Water Wastewater
AOPsAOPs-- UV / PeroxideUV / PeroxideAOPsAOPs UV / Peroxide UV / Peroxide Overcoming Low Overcoming Low ●●OH YieldOH Yield
Increasing HIncreasing H22OO2 2 dose ( min 5 dose ( min 5 ppmppm))
AOPsAOPs-- UV / PeroxideUV / PeroxideAOPsAOPs UV / Peroxide UV / Peroxide Overcoming Low Overcoming Low ●●OH YieldOH Yield
Increasing HIncreasing H22OO2 2 dose ( min 5 ppm)dose ( min 5 ppm) Increasing UV Increasing UV fluencefluence
AOPsAOPs-- UV / PeroxideUV / PeroxideAOPsAOPs UV / Peroxide UV / Peroxide Overcoming Low Overcoming Low ●●OH YieldOH Yield
Increasing HIncreasing H22OO2 2 dose ( min 5 ppm)dose ( min 5 ppm) Increasing UV fluenceIncreasing UV fluence Reducing UVReducing UV254 254 absorbance (increasing absorbance (increasing
UVT):UVT): MixedMixed--media filtrationmedia filtration Membrane processesMembrane processes
AOPsAOPs-- UV / PeroxideUV / PeroxideAOPsAOPs UV / Peroxide UV / Peroxide Overcoming Low Overcoming Low ●●OH YieldOH Yield
Increasing HIncreasing H22OO2 2 dose ( min 5 ppm)dose ( min 5 ppm) Increasing UV fluenceIncreasing UV fluence Reducing UVReducing UV254 254 absorbance (increasing absorbance (increasing
UVT):UVT): MixedMixed--media filtrationmedia filtration Membrane processesMembrane processes
Alternatives to HAlternatives to H22OO22
Peracetic acid (Acetic acid with peroxide)Peracetic acid (Acetic acid with peroxide)
AOPsAOPs-- UV / PeroxideUV / PeroxideAOPsAOPs UV / Peroxide UV / Peroxide Overcoming Low Overcoming Low ●●OH YieldOH Yield
Increasing HIncreasing H22OO2 2 dose ( min 5 ppm)dose ( min 5 ppm) Increasing UV fluenceIncreasing UV fluence Reducing UVReducing UV254 254 absorbance (increasing absorbance (increasing
UVT):UVT): MixedMixed--media filtrationmedia filtration Membrane processesMembrane processes
Alternatives to HAlternatives to H22OO22
Peracetic acid (Acetic acid with peroxide)Peracetic acid (Acetic acid with peroxide) HOClHOCl
UV/HOClUV/HOCl UV/HUV/H OOUV/HOCl UV/HOCl vsvs UV/HUV/H22OO22
Rapid photochemical conversion of HOCl to OHRapid photochemical conversion of HOCl to OH Rapid photochemical conversion of HOCl to OHRapid photochemical conversion of HOCl to OH
●●OH from HOCl/OClOH from HOCl/OCl-- and Hand H22OO2222 22
Yield of Yield of ●●OHOHOClOCl-- < < < H< < < H22OO22 < HOCl< HOCl22 22
Energy required for Energy required for ●●OH generation and organics OH generation and organics id tiid tioxidationoxidation
–– At lowAt low--mgmg--LL--11 oxidant doses in surface wateroxidant doses in surface waterEnergyEnergyHOClHOCl ≤ Energy≤ EnergyH2O2H2O2 <<<< EnergyEnergyOClOClEnergyEnergyHOClHOCl ≤ Energy≤ EnergyH2O2H2O2 EnergyEnergyOClOCl--
AOPAOP UV/O /P idUV/O /P idAOPs AOPs –– UV/Ozone/PeroxideUV/Ozone/Peroxide
Addition of peroxide will further enhance the Addition of peroxide will further enhance the f ti f h d l di lf ti f h d l di lformation of hydroxyl radicalsformation of hydroxyl radicals
Not used in drinking water or wastewater Not used in drinking water or wastewater treatment due to costtreatment due to cost
Mainly used in the detoxification of RCRA Mainly used in the detoxification of RCRA types of waste materials such as PAHstypes of waste materials such as PAHstypes of waste materials, such as PAHs types of waste materials, such as PAHs
T h lT h l AOP/AOP/ HiPOXHiPOXTechnology Technology –– AOP/ AOP/ HiPOXHiPOX
T h lT h l AOP/AOP/ HiPOXHiPOX (C t )(C t )Technology Technology –– AOP/ AOP/ HiPOXHiPOX (Cont.)(Cont.)
T h lT h l AOP/AOP/ HiPOXHiPOX (C t )(C t )Technology Technology –– AOP/ AOP/ HiPOXHiPOX (Cont.) (Cont.)
Meets California Meets California Tile 22 for total Tile 22 for total coliform of 2.2 coliform of 2.2 MPN/100mLMPN/100mLMPN/100mLMPN/100mL
AOPAOP O l tiO l ti C dC dAOP AOP –– OrganolepticOrganoleptic CompoundsCompounds
A- Geosmin B- MIB
F t Aff ti O ti fF t Aff ti O ti fFactors Affecting Ozonation of Factors Affecting Ozonation of Odorants Odorants (Atasi et. al, 2001)(Atasi et. al, 2001)
200
100
150
Effe
ct, %
Test A error bars represent
50
100
dard
ized
E Test B standard errors for effect estimation
0Sta
nd
-50
atur
e
dose
2O2
atio
nnt do
se
H2O
2
poin
t
Tem
pera
O3
d H2
Ozo
napo
in
Tem
p-d
Tem
p-H
Tem
p-p
AOP AOP –– Ozone/PeroxideOzone/PeroxideG iG iGeosminGeosmin(Atasi et.al. 1999)(Atasi et.al. 1999)
150
R2 = 0.9958100c., n
g/L O3, raw
O3/H2O2, raw
R2 = 0.878850
100
min
Con
,
O3, settled
R2 = 0.9628
0
50
Geo
sm
00 1 2 3 4
T f d O D /LTransferred Ozone Dose, mg/L
AOP AOP –– Ozone/PeroxideOzone/PeroxideMIB, MIB, GeosminGeosmin, and IPMP Treatment, and IPMP Treatment(Atasi et.al., 2001) Isopropyl (Atasi et.al., 2001) Isopropyl MethanopirazineMethanopirazine
100 100
80
val,
%
80
val,
%
40
60
nt R
emov
MIB C 100 /L40
60
ant R
emov
MIB 1 5 /L O3
20
40
Odo
ra MIB, Co = 100 ng/L
Geosmin, Co = 125 ng/L
IPMP, Co = 182 ng/L 20
40
Odo
ra MIB,1.5 mg/L O3Geosmin, 1.5 mg/L O3IPMP, 1.5 mg/L O3
00.5 1 1.5 2 2.5
0200 300 400 500 600
Transferred Ozone Dose, mg/L Total Odorant Spike, ng/L
AOPAOP UV/P idUV/P idAOP AOP –– UV/PeroxideUV/Peroxide
AOPAOP UV/P idUV/P idAOP AOP –– UV/PeroxideUV/Peroxide
AOP AOP –– UV/PeroxideUV/PeroxideMIB treatment LPHO UVMIB treatment LPHO UV(Atasi et. al. 2004)(Atasi et. al. 2004)
100
80
H2O2 = 6 mg/L
60
egrada
tion
H2O2 = 4 mg/L
40
Percent De
H2O2 = 0 mg/L
20
0
0.0 0.2 0.4 0.6 0.8 1.0EED (kW-Hr/1,000 gal)
AOP AOP –– UV/PeroxideUV/PeroxideATZ Degradation LPHO UVATZ Degradation LPHO UV(Atasi, et. al., 2004)(Atasi, et. al., 2004)
100H2O2 = 6 mg/L
80
on
H2O2 = 4 mg/L
60
t Deg
rada
tio
H2O2 = 0 mg/L
20
40
Perc
ent
0
20
0.0 0.2 0.4 0.6 0.8 1.0
EED (kW-Hr/1,000 gal)
AOP AOP –– UV/PeroxideUV/PeroxideMIB D d ti MP UVMIB D d ti MP UVMIB Degradation MP UVMIB Degradation MP UV(Atasi et. al., 2004)(Atasi et. al., 2004)
100
H2O2 = 6 mg/L
80
tion H2O2 = 4 mg/L
60
nt D
egra
dat
H2O2 = 0 mg/L
H2O2 4 mg/L
20
40
Perc
en
2 2 g
0
20
0
0.0 0.4 0.8 1.2 1.6 2.0
EED (kW-Hr/1,000 gal)
AOP AOP –– UV/PeroxideUV/PeroxideMIB Degradation MP UVMIB Degradation MP UV(Atasi et.al., 2004(Atasi et.al., 2004
100
80
tion
H2O2 = 4 mg/L
H2O2 = 6 mg/L
60
nt D
egra
dat
H2O2 = 0 mg/L
40
Perc
en
0
20
0
0.0 0.4 0.8 1.2 1.6 2.0
EED (kW-Hr/1,000 gal)
AOPAOP C l iC l iAOP AOP -- ConclusionsConclusions
Very effective in detoxifying ECC by Very effective in detoxifying ECC by transformation/ breakdown and/or transformation/ breakdown and/or mineralizationmineralizationmineralizationmineralization
Hi h t ki ti lti i ll f t i tHi h t ki ti lti i ll f t i t High rate kinetics resulting in small foot printHigh rate kinetics resulting in small foot print
N id l t dN id l t d No residuals are generatedNo residuals are generated
Can address multiple contaminants Can address multiple contaminants simultaneously simultaneously
AOP – Conclusions (Cont )Energy requirements for UV systemsEnergy requirements for UV systems
AOP – Conclusions (Cont.) gy q ygy q y
DisinfectionDisinfection–– Depending upon upstream filtration, UV dose needs Depending upon upstream filtration, UV dose needs p g p p ,p g p p ,
to be 60 to be 60 –– 100 100 mJmJ/cm/cm22
–– A 3A 3--6 MGD WWTP requires 132.8 kW input to the UV 6 MGD WWTP requires 132.8 kW input to the UV f di i f if di i f isystem for disinfectionsystem for disinfection
Chemical decontaminationChemical decontamination–– Energy to activate the peroxidesEnergy to activate the peroxides
–– More energy (~ by one order of magnitude) than just More energy (~ by one order of magnitude) than just disinfectiondisinfectiondisinfectiondisinfection
– Larger reactors or bigger and more lamps–– Electrical energy per order is the figure of merit usedElectrical energy per order is the figure of merit usedElectrical energy per order is the figure of merit used Electrical energy per order is the figure of merit used
in this casein this case
Th k Y !Th k Y !Thank You!Thank You!
Khalil Z. Atasi, P.E.: Khalil Z. Atasi, P.E.: [email protected]@cdm.com
Kathy A. Traexler, P.E.: Kathy A. Traexler, P.E.: [email protected]@cdm.com
Camp Dresser & McKee Inc.Camp Dresser & McKee Inc.2301 Maitland Center Parkway, Suite 3002301 Maitland Center Parkway, Suite 300y,y,Maitland, FL 32751 Maitland, FL 32751