1 strategy for the treatment of industrial wastewaters by coupling of chemical oxidation and...

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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

2

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

3

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

4

Development and optimization, at pilot scale, of a system combining an AOP and a biological process for the treatment of biorecalcitrant wastewater.

AimAim

5

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?

9

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

42

Process parameters

43

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