Water Cycle in the Center of Human

activities

Strategy for the Treatment of Industrial Wastewaters by

Drinking water Consumption
Coupling of Chemical Oxidation and Biodegradation Production
37% 59% 4%

Processes
Total available drinking water
MER Dr C. Pulgarin, GGEC, Institute of Chemical Science and Engineering
EPFL
Agriculture Domestic Industrial

Wastewater
treatment Reject of used water
(Only ~5% is treated)

1 2

Contexte général
Aim
Context

Caractérisation de l‘effluent
• charge
Objective

• débit
• composition
• toxicité
• biodégradabilité
Development and optimization, at
pilot scale, of a system combining
Theory

Effluents biodégradables Effluents biorécalcitrants Effluents toxiques et/ou

non biodégradables
an AOP and a biological process for
Adaptation,sélection
Traitements chimiques
the treatment of biorecalcitrant
Perspectives

bactérienne
• oxydation totale
• combustion

Traitements biologiques
wastewater.
spécifiques à la source Eaux traitées
Résidus minéralisés

Traitements biologiques
spécifiques à la source
Pré-traitement
physico-chimiques
oxydation:
• chimique
Épandage Eaux • électrochimique
Boues Incinération épurées • photochimique
Décharge
3 4
 High cost

Disadvantages Non-destructive
Toxic by-products
Non-viable with
toxic and
High cost
If mineralization
Typical asymptotic mineralization during
High-energy biorecalcitrant
consumption aimed
a photo-catalytic treatment
Existing Activated Incineration Bio-treatment AOPs
treatments carbon Wet-oxidation
100
Isoproturon
p-NTS
80

TOC removed (%)

Problem Wastewater containing
60
biorecalcitrant pollutants

40
AMBI

20
Biological
proposition Advanced Oxidation
process 0
Process
0 1 2 3 4 5 6 7 8
Photo-treatment time (h)
Coupled system

Benefits Low energy Low/medium

Complete
consumption cost
degradation
5 6

General strategy for coupling AOP-biological processes General strategy for coupling AOP-biological processes

Wastewater Wastewater

Biorecalcitrant no yes no yes

Biodegradable? Biological treatment Effluent Biodegradable?
compound

Comparison of different AOP´s

Coupled
yes
AOP-biological
Optimization of the treatment
most appropriate AOP Biodegradable?

no

Pulgarin et al. Cat. Today 54 (1999) 341

Sarria et al. Cat. Today 76 (2003) 301

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 Case Study: AMBI a biorecalcitrant pollutant Explored Advanced Oxidation
Processes
Important intermedite in the industrial
5-amino-6-methyl-2-
production of dyes
benzimidazolone
CH3 NH Very low biodegradability by conventional
O biological treatments
NH2 NH Electrochemical Sonochemical

•OH
Table 1. Physicochemical characteristics of the wastewater under study

TOC BOD5 COD Cl- NH4+ PO43- NO3- pH

(mg C l-1) (mg O2 l-1) mg O2 l-1 mg l-1 mg l-1 mg l-1 mg l-1
4368 136 18105 6265 6.8 0.9 0.0 9.3 Sunlight/Fe3+/H2O2
Sunlight/Fe3+/O2

• BOD5/COD = 0.0075
√ Haag et al., 1992
• Zahn-Wellenst Test – Negative response Peringer P. Rapport final. Mai 1997 √ Rupert et al., 1994
• Simulation test – Negative response √Serpone et al., 1996
Sarria et al. Wat. Sci. Tech. 40 (2001) 93

9 10

Energetic comparison of tested AOPs Fe(III)/AMBI

Abs
2.5
Photo
2.0
AMBI/Fe(III)
Electro Torres et al. Wat. Res. 37 (2003) 3118 1.5
AMBI
1.0

Sono 0.5 Fe(III)

0.0
nm
0 400 800 1400 200 300 400 500
kWh m-3 Sarria et al. Appl. Cat. B. 40 (2003) 231

11 12
Fe(III) photoinduced degradation of AMBI Fe(III) photoassisted degradation of AMBI
1 1

Fe(II)

Concentration (nomalized)
0.8 0.8 hν
AMBI [AMBI---Fe(III)] AMBI oxidation

(mmol l )
-1
0.6 0.6
Fe(II)
Fe(III)
0.4 0.4

2+
AMBI

Fe
0.2 0.2
LMCT = Ligand to Metal Charge Transfer
0 0
0 100 200 300
Time (min)

[AMBI] = 1.0 mmol l-1 Balzani and Carassiti. Photochemistry of coordination compounds, 1970
System Fe3+/hν [Fe3+] = 1.0 mmol l-1 Sarria et al. Appl. Cat. B. 40 (2003) 231

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Involvement of ·OH radicals Fe(III) photoassisted degradation of AMBI

Pollutant oxidation

1 Isopropanol

He2 OH
AMBI (mmol l )

0.8
-1

O2 Fenton
Reaction Fe(OH)2+
0.6 hv

0.4 Fe2+

Pollutant
0.2 H2O2 Feaq2+ + OH oxidation
H+
0 +
O2 O2
0 100 200 300 hv

Time (min)
Fe2+
O2 H
[AMBI] = 1.0 mmo l-1
System Fe3+/hν [Fe3+] = 1.0 mmol l-1 Castinini et al. The Sci. Total Environ. 298 (2002) 219
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 Fenton and Photo-Fenton reaction Optimization of Fe3+ concentration

O2H Fe2+ H2O2

0.005

0.004 Synthetic wastewater

kobs (min-1)
H2O2 Fe3+ OH 0.003

0.002 Real wastewater

Fe3+ + H2O + hν Î •OH + H+ + Fe2+

Fe2+ + H2O2 Î •OH + -OH + Fe3+

0.001
Fe3+ + H2O2 Î Fe2+ + H+ + •O2H
0.000
Fe2+ + •OH Î Fe3+ + -OH
0 1 2 3 4
Fe2+ + •O2H Î Fe3+ + -O2H
Fe3+ concentration (mmol l-1)
H2O2 + •OH Î H2O + •O2H

•OH + RH Î R+ or [HORH]• (R = organic) [AMBI] = 1.0 mmol l-1

System Fe3+/H2O2/hν [H2O2] = 25 mmol l-1

17 18

Optimization of H2O2 concentration Optimal Conditions

0.0025

0.002

AMBI / Fe3+ / H2O2

kobs (min-1)

0.0015

0.001 1 / 1 / 25

0.0005

0
0 50 100 150
-1
H2O2 concentration (mmol l )

[AMBI] = 1.0 mmol l-1

System Fe3+/H2O2/hν [Fe3+] = 1.0 mmol l-1

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General strategy for coupling AOP-biological processes Toxicity and AOS evolution during the
Photo-treatment
Wastewater
0.07 3

Toxicity 1/EC 50 (l x mg C -1)

Averange Oxidation State

Biorecalcitrant no
Biodegradable? 0.06 2
compound 400

0.05 300

DOC (mg C/l)

1
200
0.04
Comparison of different AOP´s
9Biodegradability? 100
0
Microtox
9Toxicity? analysis 0.03 0

Optimization of the 9Global parameters? 0.02

0 400 800
Time (min)
1200
-1
most appropriate AOP Biodegradable?
BOD5
-2
COD 0.01

AOS 0 -3
0 200 400 600 800 1000

Time (min)
DOC − COD
Average Oxidation State = 4 ×
DOC
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Biodegradability before and after Photochemical-biological coupled flow reactor

photo-treatment
BOD5/COD yields a measurement
0.45 of biodegradability

0.40

0.35
Biodegradability (BOD/COD)

0.30

0.25

0.20 Initial
Final
0.15

0.10
Domestic wastewater typically
0.05 has a BOD5/COD around 0.4

JPKradolfer
0.00

produit pur
Syntetic wastewater
Eaux réelles
Real wastewater

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Assessment of the optimal pretreatment time O2(air) vs H2O2 as electron acceptors

100
90 Coupled reactor
% of initial DOC removed

80
70
60 Bioreactor
50
40
30 Photoreactor
20
10
0
0 100 200 300 400 500 600
Photo pre-treatment time (min)

[AMBI] = 1.0 mmol l-1

System Fe3+/hν [Fe3+] = 1.0 mmol l-1 2h 5h

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Coupled solar-biological system at field

pilot scale

Scaling UP Type of solar photoreactor

Optimization of the photo-catalytic

conditions

Type of bioreactor

Performances of the coupled system

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 Choice of the solar photoreactor
Reflection of the solar radiation
in a Compound Parabolic
Collector (CPC)
CPC reactor at the EPFL – Parabolic-Through Concentrator at
Switzerland the PSA

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Optimization of Fe3+ and H2O2 using

Bioreactors used in bioremediation,
Surface Response Methodology
suspended and fixed biomass

9 Suspended growth bioreactors consist of batch,

plug flow, and completely mixed reactors.
Microorganisms here are suspended in the
medium in the reactor.

9 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.

NEMROD software

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 Advantages of immobilized biomass in Coupled solar-biological reactor at pilot scale
biological reactors
9 Larger microbial diversity
9 Larger spectra of biochemical activities
9 Cells live for a much greater period of time
9 More biomass per volume of reactor
9 Higher rates of degradation
9 More resistant to toxic loading
9 Efficiency independent of flow rate

JPKradolfer
9 Prevents washout of biomass
9 Easier to operate
Sarria et al. J. Photochem. Photob. 159 (2003) 89

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Coupled solar-biological reactor at pilot scale Solar-biological degradation of AMBI

in dark
1.2
Solar Biological
1 treatment treatment

Concentration (%)
0.8 DOC

0.6
0.4
AMBI
0.2
0
0 10 6 18 24
-1
Quv (kJ l ) Time (h)

Sarria et al. J. Photochem. Photob. 159 (2003) 89

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Performances and cost of solar treatment Demonstration plant scheme
of Isoproturon pesticide by CPC reactor
Photoreactor volume 22 L
Total reactor volume 39 L
Collector surface3.08 m2
Residence time 1.0 h
Isoproturon removed 100 %
TOC removed 60 %

40 L / h / m2

In a sunny day (900 w/m2)

It is possible to render
biodegradable around 3 m3 of 1m3 ~ 1.25 $
Isoproturon solution with 10 m2
of CPC reactor

37 38

Process parameters
Demonstration plant

39 40
Process parameters Process parameters

41 42

Process parameters Final result

Photochemical

Biological

Toxic and/or
Biorecalcitrant

JPKradolfer
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 Parameter Value
PESTICIDES AND POLLUTION
COD (mg O2/l) 108.7
¾ Aerial and manual
pesticides pH (Unit) 6.81
application
¾ Cleaning recipients Temperature (° C) 26.0

Turbidity (UNT) 1.4

Flow (l/s) 1.85
Inicial wastewater characterization

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Expected Results: Acknowledgements

Agroindustrial wastewater treatment by a coupled Helio-
photocatalytical-biological system

Contract nº: EVK1-CT2002-00122

OFES nº: 01.0443

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Coupled chemical-biological ÉCOLE POLYTECHNIQUE
FÉDÉRALE DE LAUSANNE
process group

Coupled Advanced Oxidation and

Biodegradation

Cesar Pulgarin,

Electrochemical Engineering Group, Institute of Chemical

Sciences and Engineering

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