1 strategy for the treatment of industrial wastewaters by coupling of chemical oxidation and...
TRANSCRIPT
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Strategy for the Treatment of Industrial Wastewaters by
Coupling of Chemical Oxidation and Biodegradation
Processes
MER Dr C. Pulgarin, GGEC, Institute of Chemical Science and Engineering
EPFL
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Water Cycle in the Center of Human Water Cycle in the Center of Human activitiesactivities
Drinking waterProduction
Drinking waterProduction
Domestic Industrial
Reject of used water(Only ~5% is treated)
Consumption
Wastewatertreatment
Wastewatertreatment
Agriculture
37% 59% 4%
Total available drinking water
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Pré-traitementphysico-chimiquesoxydation: chimique électrochimique photochimique
Contexte général
Caractérisation de l‘effluent charge débit composition toxicité biodégradabilité
Effluents biorécalcitrants
Traitements biologiquesspécifiques à la source
Traitements chimiques oxydation totale combustion
Traitements biologiquesspécifiques à la source
Effluents biodégradables Effluents toxiques et/ounon biodégradables
Boues
Adaptation,sélectionbactérienne
Eauxépurées
Eaux traitéesRésidus minéralisés
ÉpandageIncinérationDécharge
Pers
pect
ives
Pe
rspe
ctiv
es
The
ory
The
ory
Obj
ectiv
eO
bjec
tive
Con
text
Con
text
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Development and optimization, at pilot scale, of a system combining an AOP and a biological process for the treatment of biorecalcitrant wastewater.
AimAim
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Problem Wastewater containingbiorecalcitrant pollutants
Existingtreatments
Disadvantages
Activated carbon
Non-destructive
IncinerationWet-oxidation
High costToxic by-productsHigh-energy consumption
Bio-treatment
Non-viable with toxic and biorecalcitrant
AOPs
High costIf mineralizationaimed
Coupled systemCoupled system
proposition Advanced OxidationProcess
Biologicalprocess
Benefits Low energyconsumption
Complete degradation
Low/mediumcost
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Typical asymptotic mineralization during a photo-catalytic treatment
Typical asymptotic mineralization during a photo-catalytic treatment
0
20
40
60
80
100
0 1 2 3 4 5 6 7 8
Photo-treatment time (h)
TO
C r
em
ov
ed
(%
)
p-NTSIsoproturon
AMBI
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General strategy for coupling AOP-biological processesGeneral strategy for coupling AOP-biological processes
Coupled AOP-biological
treatment
Coupled AOP-biological
treatment
Comparison of different AOP´s
no
Optimization of the most appropriate AOP
Biorecalcitrant compound
Biodegradable?
Biological treatmentyes
Effluent
Wastewater
Biodegradable?
Pulgarin et al. Cat. Today 54 (1999) 341
no
Sarria et al. Cat. Today 76 (2003) 301
yes
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General strategy for coupling AOP-biological processesGeneral strategy for coupling AOP-biological processes
no yes
Wastewater
Biodegradable?
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CH3
NH2 NH
NHO
5-amino-6-methyl-2-benzimidazolone
Important intermedite in the industrial production of dyes
Very low biodegradability by conventional biological treatments
Table 1. Physicochemical characteristics of the wastewater under study
TOC (mg C l-1)
BOD5 (mg O2 l
-1) COD
mg O2 l-1
Cl- mg l-1
NH4+
mg l-1 PO4
3-
mg l-1 NO3
- mg l-1
pH
4368 136 18105 6265 6.8 0.9 0.0 9.3
• BOD5/COD = 0.0075• Zahn-Wellenst Test – Negative response• Simulation test – Negative response
Case Study: AMBI a biorecalcitrant pollutantCase Study: AMBI a biorecalcitrant pollutant
Sarria et al. Wat. Sci. Tech. 40 (2001) 93
Peringer P. Rapport final. Mai 1997
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√ Haag et al., 1992√ Rupert et al., 1994√Serpone et al., 1996
•OH
Sonochemical Sonochemical
Sunlight/Fe3+/O2Sunlight/Fe3+/O2
Sunlight/Fe3+/H2O2Sunlight/Fe3+/H2O2
ElectrochemicalElectrochemical
Explored Advanced Oxidation Processes
Explored Advanced Oxidation Processes
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Energetic comparison of tested AOPs Energetic comparison of tested AOPs
0 400 800 1400
Sono
Electro
Photo
kWh m-3
Torres et al. Wat. Res. 37 (2003) 3118
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Fe(III)/AMBIFe(III)/AMBI
Fe(III)
AMBI
AMBI/Fe(III)
0.0
200 300 400 500nm
0.5
1.0
1.5
2.0
2.5
Abs
Sarria et al. Appl. Cat. B. 40 (2003) 231
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Fe(II)
AMBI
Fe(III) photoinduced degradation of AMBIFe(III) photoinduced degradation of AMBI
0
0.2
0.4
0.6
0.8
1
0 100 200 300
Time (min)
Con
cent
ratio
n (n
omal
ized
)
0
0.2
0.4
0.6
0.8
1
Fe
2+ (
mm
ol l
-1)
System Fe3+/h[AMBI] = 1.0 mmol l-1
[Fe3+] = 1.0 mmol l-1
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Fe(III) photoassisted degradation of AMBIFe(III) photoassisted degradation of AMBI
Sarria et al. Appl. Cat. B. 40 (2003) 231
AMBI oxidation[AMBI---Fe(III)]h
AMBI
Fe(III)
LMCT = Ligand to Metal Charge Transfer
Fe(II)
Balzani and Carassiti. Photochemistry of coordination compounds, 1970
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0
0.2
0.4
0.6
0.8
1
0 100 200 300
Time (min)
AM
BI
(mm
ol l
-1)
Isopropanol
He2
O2
Involvement of ·OH radicals Involvement of ·OH radicals
System Fe3+/h[AMBI] = 1.0 mmo l-1
[Fe3+] = 1.0 mmol l-1
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Fe(III) photoassisted degradation of AMBIFe(III) photoassisted degradation of AMBI
O2H
OH
OH
O2
Fe2+
Pollutant oxidation
H+H2O2
Fe(OH)2+
Feaq2+ +
O2hv
Pollutantoxidation
Fe2+
Fenton Reaction
+
hv
Castinini et al. The Sci. Total Environ. 298 (2002) 219
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H2O2 OH
O2H
Fe3+
Fe2+
Fe3+ + H2O + h •OH + H+ + Fe2+
Fe2+ + H2O2 •OH + -OH + Fe3+
Fe3+ + H2O2 Fe2+ + H+ + •O2H
Fe2+ + •OH Fe3+ + -OH
Fe2+ + •O2H Fe3+ + -O2H
H2O2 + •OH H2O + •O2H
•OH + RH R+ or [HORH] (R = organic)
Fenton and Photo-Fenton reactionFenton and Photo-Fenton reaction
H2O2
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Optimization of Fe3+ concentrationOptimization of Fe3+ concentration
0.000
0.001
0.002
0.003
0.004
0.005
0 1 2 3 4
Fe3+ concentration (mmol l-1)
k obs
(m
in-1
)
Real wastewater
Synthetic wastewater
System Fe3+/H2O2/h[AMBI] = 1.0 mmol l-1
[H2O2] = 25 mmol l-1
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Optimization of H2O2 concentrationOptimization of H2O2 concentration
0
0.0005
0.001
0.0015
0.002
0.0025
0 50 100 150
H2O2 concentration (mmol l-1)
k obs
(m
in-1
)
System Fe3+/H2O2/h[AMBI] = 1.0 mmol l-1
[Fe3+] = 1.0 mmol l-1
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Optimal Conditions Optimal Conditions
AMBI / Fe3+ / H2O2
1 / 1 / 25 1 / 1 / 25
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General strategy for coupling AOP-biological processesGeneral strategy for coupling AOP-biological processes
Comparison of different AOP´s
no
Optimization of the most appropriate AOP
Biorecalcitrant compound
Biodegradable?
Wastewater
Biodegradable?
Biodegradability?Toxicity?Global parameters?
BOD5
CODAOS
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0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0 200 400 600 800 1000
Time (min)
To
xici
ty 1
/EC
50 (
l x
mg
C-1
)
-3
-2
-1
0
1
2
3
Ave
ran
ge
Oxi
da
tio
n S
tate
0
100
200
300
400
0 400 800 1200Time (min)
DO
C (
mg
C/l
)
Microtox analysis
DOC
CODDOCStateOxidationAverage
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Toxicity and AOS evolution during thePhoto-treatment
Toxicity and AOS evolution during thePhoto-treatment
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produit pur
Eaux réelles
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
Bio
de
gra
da
bili
ty (
BO
D/C
OD
)
Initial
Final
Real wastewater
Syntetic wastewater
BOD5/COD yields a measurement of biodegradability
Domestic wastewater typically has a BOD5/COD around 0.4
Biodegradability before and after photo-treatment
Biodegradability before and after photo-treatment
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JPK
rad
olf
er
Photochemical-biological coupled flow reactorPhotochemical-biological coupled flow reactor
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0
10
20
30
40
50
60
70
80
90
100
0 100 200 300 400 500 600
Photo pre-treatment time (min)
% o
f ini
tial D
OC
rem
oved
Photoreactor
Bioreactor
Coupled reactor
Assessment of the optimal pretreatment timeAssessment of the optimal pretreatment time
System Fe3+/h[AMBI] = 1.0 mmol l-1
[Fe3+] = 1.0 mmol l-1
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O2(air) vs H2O2 as electron acceptors O2(air) vs H2O2 as electron acceptors
2h 5h
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Scaling UP Scaling UP
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Coupled solar-biological system at field pilot scale
Coupled solar-biological system at field pilot scale
Type of solar photoreactor
Optimization of the photo-catalytic
conditions
Type of bioreactor
Performances of the coupled system
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CPC reactor at the EPFL – Switzerland
CPC reactor at the EPFL – Switzerland
Parabolic-Through Concentrator at the PSA
Parabolic-Through Concentrator at the PSA
Choice of the solar photoreactorChoice of the solar photoreactor
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Reflection of the solar radiation in a Compound Parabolic
Collector (CPC)
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Optimization of Fe3+ and H2O2 using Surface Response Methodology
Optimization of Fe3+ and H2O2 using Surface Response Methodology
NEMROD software
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Bioreactors used in bioremediation, suspended and fixed biomass
Suspended growth bioreactors consist of batch, plug flow, and completely mixed reactors. Microorganisms here are suspended in the medium in the reactor.
Fixed-film bioreactors consist of fixed bed, fluidized beds, air-sparged, or rotating media reactors. Here, microorganisms grow on or within a solid medium in the reactor.
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Advantages of immobilized biomass in biological reactors
Larger microbial diversity
Larger spectra of biochemical activities
Cells live for a much greater period of time
More biomass per volume of reactor
Higher rates of degradation
More resistant to toxic loading
Efficiency independent of flow rate
Prevents washout of biomass
Easier to operate
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Coupled solar-biological reactor at pilot scaleCoupled solar-biological reactor at pilot scale
Sarria et al. J. Photochem. Photob. 159 (2003) 89
JPK
rad
olf
er
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Coupled solar-biological reactor at pilot scaleCoupled solar-biological reactor at pilot scale
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Solar-biological degradation of AMBISolar-biological degradation of AMBI
0
0.2
0.4
0.6
0.8
1
1.2
0 6 18 24
Quv (kJ l-1)
Con
cent
ratio
n (%
)
in dark
Time (h)
Biological treatment
10
DOC
AMBI
Solar treatment
Sarria et al. J. Photochem. Photob. 159 (2003) 89
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In a sunny day (900 w/m2)It is possible to render biodegradable around 3 m3 of Isoproturon solution with 10 m2 of CPC reactor
Photoreactor volume 22 LTotal reactor volume 39 LCollector surface3.08 m2 Residence time 1.0 hIsoproturon removed 100 %TOC removed 60 %
40 L / h / m2
1m3 ~ 1.25 $1m3 ~ 1.25 $
Performances and cost of solar treatment of Isoproturon pesticide by CPC reactor
Performances and cost of solar treatment of Isoproturon pesticide by CPC reactor
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Demonstration plant scheme
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Demonstration plant
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Process parameters
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Process parameters
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Process parameters
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Process parameters
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Final resultFinal result
Toxic and/orBiorecalcitrant
Biological
Photochemical
JPK
rad
olf
er
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PESTICIDES AND POLLUTION Aerial and manual Aerial and manual
pesticides pesticides applicationapplication
Cleaning recipientsCleaning recipients
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Parameter Value
COD (mg O2/l) 108.7
pH (Unit) 6.81
Temperature (° C) 26.0
Turbidity (UNT) 1.4
Flow (l/s) 1.85
Inicial wastewater characterization
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Expected Results:Expected Results:Agroindustrial wastewater treatment by a coupled Helio-Agroindustrial wastewater treatment by a coupled Helio-
photocatalytical-biological system photocatalytical-biological system
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AcknowledgementsAcknowledgements
Contract nº: EVK1-CT2002-00122
OFES nº: 01.0443
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Coupled chemical-biological process group
Coupled chemical-biological process group
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Cesar Pulgarin,
Electrochemical Engineering Group, Institute of Chemical Sciences and Engineering
ÉC OL E PO L Y T E C H N I Q U EFÉ DÉR A L E D E L A U SA N N E
Coupled Advanced Oxidation and
Biodegradation