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

1
 Water Cycle in the Center of Human
activities

Drinking water Consumption

Production
37% 59% 4%

Total available drinking water

Agriculture Domestic Industrial

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

2
 Contexte général
Context

Caractérisation de l‘effluent
 charge
Objective

 débit
Objective

 composition
 toxicité
 biodégradabilité
Theory

Effluents biodégradables Effluents biorécalcitrants Effluents toxiques et/ou

Theory

non biodégradables

Adaptation,sélection
Traitements chimiques
bactérienne
Perspectives

 oxydation totale
Perspectives

 combustion

Traitements biologiques
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
 Aim
Aim

Development and optimization, at

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

4
 High cost
Non-viable with
Toxic by-products High cost
Non-destructive toxic and
Disadvantages High-energy
biorecalcitrant
If mineralization
consumption aimed

Existing Activated Incineration Bio-treatment AOPs

treatments carbon Wet-oxidation

Problem Wastewater containing

biorecalcitrant pollutants

Biological
proposition Advanced Oxidation
process
Process

Coupled
Coupledsystem
system

Benefits Low energy Low/medium

Complete
consumption cost
degradation
5
Typical
Typical asymptotic
asymptotic mineralization
mineralization during
during
aa photo-catalytic
photo-catalytic treatment
treatment

100
Isoproturon
p-NTS
80
TOC removed (%)

60

40
AMBI

20

0
0 1 2 3 4 5 6 7 8
Photo-treatment time (h)

6
General
Generalstrategy
strategyfor
forcoupling
couplingAOP-biological
AOP-biologicalprocesses
processes

Wastewater

Biorecalcitrant no yes
Biodegradable? Biological treatment Effluent
compound

Comparison of different AOP´s

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

no

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

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

7
General
Generalstrategy
strategyfor
forcoupling
couplingAOP-biological
AOP-biologicalprocesses
processes

Wastewater

no yes
Biodegradable?

8
 Case
CaseStudy:
Study:AMBI
AMBIaabiorecalcitrant
biorecalcitrantpollutant
pollutant
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

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

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

9
Explored
Explored Advanced
Advanced Oxidation
Oxidation
Processes
Processes

Electrochemical
Electrochemical Sonochemical
Sonochemical
•OH

Sunlight/Fe
Sunlight/Fe3+/H
3+
/H2O
Sunlight/Fe 2O2
Sunlight/Fe /O
3+ 2
/O22
3+

√ Haag et al., 1992

√ Rupert et al., 1994
√Serpone et al., 1996

10
Energetic
Energetic comparison
comparison of
of tested
tested AOPs
AOPs

Photo

Electro Torres et al. Wat. Res. 37 (2003) 3118

Sono

0 400 800 1400

kWh m-3
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 Fe(III)/AMBI
Fe(III)/AMBI
Abs
2.5

2.0
AMBI/Fe(III)
1.5
AMBI
1.0

0.5 Fe(III)

0.0
nm
200 300 400 500
Sarria et al. Appl. Cat. B. 40 (2003) 231

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

Fe(II)
Concentration (nomalized)
0.8 0.8

(mmol l )
-1
0.6 0.6

0.4 0.4

2+
AMBI

Fe
0.2 0.2

0 0
0 100 200 300
Time (min)

[AMBI] = 1.0 mmol l-1

System Fe3+/h [Fe3+] = 1.0 mmol l-1

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Fe(III)
Fe(III) photoassisted
photoassisted degradation
degradation of
of AMBI
AMBI

h
AMBI [AMBI---Fe(III)] AMBI oxidation

Fe(II)
Fe(III)

LMCT = Ligand to Metal Charge Transfer

Balzani and Carassiti. Photochemistry of coordination compounds, 1970

Sarria et al. Appl. Cat. B. 40 (2003) 231

14
 Involvement
Involvement of OH
of ··
OH radicals
radicals

1 Isopropanol
AMBI (mmol l-1) He2
0.8 O2

0.6
0.4
0.2
0
0 100 200 300
Time (min)
[AMBI] = 1.0 mmo l-1
System Fe /h 3+
[Fe3+] = 1.0 mmol l-1
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Fe(III)
Fe(III) photoassisted
photoassisted degradation
degradation of
of AMBI
AMBI
Pollutant oxidation

OH
Fenton
Reaction Fe(OH)2+
hv

Fe2+

Pollutant
H2O2 Feaq2+ + OH oxidation
H+
+
O2 O2
hv

Fe2+
O2H
Castinini et al. The Sci. Total Environ. 298 (2002) 219
16
Fenton
Fenton and
and Photo-Fenton
Photo-Fenton reaction
reaction
O2H Fe2+ H2O2

H2O2 Fe3+ OH

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)

17
 Optimization
Optimization of Fe3+concentration
of Fe 3+
concentration

0.005

0.004 Synthetic wastewater

kobs (min-1)
0.003

0.002 Real wastewater

0.001

0.000
0 1 2 3 4

Fe3+ concentration (mmol l-1)

[AMBI] = 1.0 mmol l-1

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

18
 Optimization
Optimizationof
ofH
H22O
O22concentration
concentration
0.0025

0.002

kobs (min-1) 0.0015

0.001

0.0005

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

[AMBI] = 1.0 mmol l-1

System Fe /H2O2/h
3+
[Fe3+] = 1.0 mmol l-1

19
Optimal
Optimal Conditions
Conditions

AMBI / Fe3+ / H2O2

11 // 11 // 25
25

20
General
Generalstrategy
strategyfor
forcoupling
couplingAOP-biological
AOP-biologicalprocesses
processes

Wastewater

Biorecalcitrant no
Biodegradable?
compound

Comparison of different AOP´s Biodegradability?

Toxicity?
Optimization of the Global parameters?
most appropriate AOP Biodegradable?
BOD5
COD
AOS

21
 Toxicity
Toxicity and
and AOS
AOS evolution
evolution during
during the
the
Photo-treatment
Photo-treatment
0.07 3

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

Averange Oxidation State

0.06 2
400

0.05 300

DOC (mg C/l)

1
200
0.04
100
0
Microtox
analysis 0.03 0
0 400 800 1200
-1
0.02 Time (min)

0.01 -2

0 -3
0 200 400 600 800 1000

Time (min)
DOC  COD
Average Oxidation State  4 
DOC
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Biodegradability
Biodegradability before
before and
and after
after
photo-treatment
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

0.00

produit pur
Syntetic wastewater
Eaux réelles
Real wastewater

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Photochemical-biological
Photochemical-biological coupled
coupled flow
flow reactor
reactor

JPKradolfer
24
Assessment
Assessment of
of the
the optimal
optimal pretreatment
pretreatment time
time

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+/h [Fe3+] = 1.0 mmol l-1

25
O
O22(air)
(air) vs
vs HH22O
O22 as
as electron
electron acceptors
acceptors

2h 5h

26
Scaling
Scaling UP
UP

27
Coupled
Coupledsolar-biological
solar-biologicalsystem
systemat
atfield
field
pilot
pilotscale
scale

Type of solar photoreactor

Optimization of the photo-catalytic

conditions

Type of bioreactor

Performances of the coupled system

28
 Choice
Choiceof
ofthe
thesolar
solarphotoreactor
photoreactor

CPC
CPCreactor
reactoratatthe
theEPFL
EPFL–– Parabolic-Through
Parabolic-ThroughConcentrator
Concentratoratat
Switzerland the
thePSA
PSA
Switzerland

29
Reflection of the solar radiation
in a Compound Parabolic
Collector (CPC)

30
Optimization
Optimization of Fe3+and
of Fe 3+
andH
H22O
O22using
using
Surface
SurfaceResponse
ResponseMethodology
Methodology

NEMROD software

31
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.

32
 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

33
Coupled
Coupledsolar-biological
solar-biologicalreactor
reactorat
atpilot
pilotscale
scale

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

34
Coupled
Coupledsolar-biological
solar-biologicalreactor
reactorat
atpilot
pilotscale
scale

35
 Solar-biological
Solar-biologicaldegradation
degradationof
ofAMBI
AMBI
in dark
1.2
Solar Biological
Concentration (%)
1 treatment treatment

0.8 DOC

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

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

36
Performances
Performances andand cost
cost of
of solar
solar treatment
treatment
of
of Isoproturon
Isoproturon pesticide
pesticide by
by CPC
CPC reactor
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 1m
1m3~~1.25
3
1.25$$
Isoproturon solution with 10 m2
of CPC reactor

37
Demonstration plant scheme

38
Demonstration plant

39
Process parameters

40
Process parameters

41
Process parameters

42
Process parameters

43
 Final
Finalresult
result

Photochemical

Biological

Toxic and/or
Biorecalcitrant

JPKradolfer
44
PESTICIDES AND POLLUTION
 Aerial and manual
pesticides
application
 Cleaning recipients

45
 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

46
 Expected Results:
Agroindustrial wastewater treatment by a coupled Helio-
photocatalytical-biological system

47
 Acknowledgements
Acknowledgements

Contract nº: EVK1-CT2002-00122

OFES nº: 01.0443

48
Coupled
Coupled chemical-biological
chemical-biological
process
process group
group

49
 ÉC O LE PO L Y T E C H N IQ U E
FÉ DÉR A LE D E LA U S A N N E

Coupled Advanced Oxidation and

Biodegradation

Cesar Pulgarin,

Electrochemical Engineering Group, Institute of Chemical

Sciences and Engineering

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