Oviedo, 4-5 de julio de 2019
Angel Fernández Mohedano
UNIVERSIDAD AUTONOMA DE MADRID
Industrial wastewater treatment through combined processes
INDUSTRIAL WASTEWATER TREATMENTTechnical Workshop
PhenolsChlorophenols
MetalsSolvents
DrugsPersonal care
products
HerbicidesPesticides
Priority and Emerging Contaminants
Industrial wastewater Wastewater derived from any industrial or commercialactivity, not directly related to sanitary uses (washbasins,toilets, showers).
Non destructive Destructive
Stripping
Coagulation
Floculation
Sedimentation
Filtration
Adsorption
Chemical Oxidation
WAO
CWAO
AOPs
AC
Agricultural wastesSludge biosolids
ChitosanMineral clays
OzonationPhotocatalysis
UltrasoundsElectrochemical
FentonPhoto-Fenton
Biological
Anaerobic
Aerobic
CASSBRMBR
Mild P and T ·OH
Refractoryintermediates
Recalcitrantcompounds
Cost
AOPs
Biological
High toxicity Low biodegradability
Biodegradable organic matter Recalcitrant compounds
(non toxic)
OPTIMIZATION
Intermediates
ToxicityBiodegradability
Advanced Oxidation Processes (AOPs)
Photocatalysis
High cost AOPs as treatment to enhance biodegradabilityand reduce toxicity
Fenton oxidation
h+
e-
Conduction band
Valence band
Eg
O2
O2•-
Photo-reduction
Photo-oxidation
H2O
HO•
TiO2hv
Biological Oxidation (SBR)
OLR 0.15-0.3 kg COD kg-1 SSV d-1
Biomass concentration: 2-4 g VSS L-1
Cellular retention time: 25 d
Hydraulic residence time: 6 d
Cycle: 6-8 h
Anoxic filling (0.5 h)
Aerated reaction (4.75-7 h)
Settle and draw (0.5-0.75 h)
Second generationNeonicotinoids
Source ofwater
contamination
Beepopulationdeclination
Bio-recalcitrant
High toxicitymicroorganism
Widespreaduse and
goodstability
Broadspectrum
insecticidalactivity
European Union expands ban of three neonicotinoid pesticides (2018)Imidacloprid, clothianidin and thiamethoxam
Time course of TMX concentration, COD removal,
H2O2 and TOC conversion in the Fenton-like
oxidation of pure TMX (a) and its commercial
formulation (b) with a stoichiometric H2O2 dose.
[TMX] = 100 mg L-1
pH = 3700 rpm
50ºCt = 4 h
0 40 80 120 160 200 240 280
0
20
40
60
80
100
TMX
XTOC
XH2O2
b
TM
X (
mg L
-1),
XT
OC (
%),
XH
2O
2 (
%)
T
MX
(m
g L
-1),
XT
OC (
%),
XH
2O
2 (
%)
Time (min)
a
0 50 100 150 200 250 300
0
20
40
60
80
100
TMX
XTOC
XH2O2
Time (min)
0,0
0,2
0,4
0,6
0,8
1,0
COD
0,0
0,2
0,4
0,6
0,8
1,0
COD
CO
D (m
g L
-1)
CO
D (m
g L
-1)
H2O2(%)
TMX (commercial) TMX (pure)
XH2O2 XTMX XTOC XCOD XH2O2 XTMX XTOC XCOD
100 > 99 > 99 60.5 63.2 > 99 > 99 49.09 69.47
75 > 99 > 99 60.0 59.7 > 99 > 99 45.58 66.71
50 > 99 > 99 52.6 52.5 > 99 > 99 42.26 69.13
25 > 99 76.25 49.9 43.9
TMX, TOC conversion and COD removal (%) upon Fenton oxidation at
different H2O2 doses
50-100 %≈ COD-TOC removal
(%) H2O2 dose
m/z = 278
m/z = 265
m/z = 274
m/z = 232
m/z = 247 m/z = 205
m/z = 205
m/z = 173
m/z = 116
m/z = 177
m/z = 115m/z = 149
m/z = 74
m/z = 75
Identified by-products for Thiamethoxam oxidation
0 25 50 75 1000
10
20
30
40
50
60
0
10
20
30
40
50
60
TOCTMX
TOCacids
TOCunidentified
TN
(m
g L
-1)
TO
C (m
g L-
1 )
H2O
2 Dose (%)
TNTMX
TNN-NO
-
2,N-NO
-
3
TNunidentified
Measured and unidentified TN and TOC
balance closure from Fenton oxidation.
0
30
60
90
120
150
180
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0 50 100
Ecoto
xic
ity (T
U)
BO
D5/C
OD
H2O2 dose (%)
Variation of Ecotoxicity (TU) and
BOD5/COD ratio.
Effluents from Fenton oxidation with H2O2 doses of 50% and 75% from stoichiometric were selected for a subsequent biological treatment
OLR: 0.15-0.3 kgCOD kg-1
VSS d-1
0
10
20
30
40
50
60
70
80
0 5 10 15 20 25 30 35
TOC
, COD
(mg
L-1)
Time (d)
0
10
20
30
40
50
60
70
80
0 5 10 15 20 25 30 35Time (d)
Accl.Accl. ORL 0.15ORL 0.15 ORL 0.30 ORL 0.30
0.5 h 4.75 h 0.75 h
Anoxicfilling Aerobic stage Settling and Draw
SBR: 6-hours cycle
XTOC =↑20 %
H2O2 H2O2
0.5 h 4.75 h 0.75 h
Anoxicfilling Aerobic stage Settling and Draw
SBR: 6-hours cycle
75 %
H2O
250 %
H2O
2
Time-course over a 6-h SBR cycle.
Coupling Fenton and biological oxidation is an adequate alternativefor TMX removal, according to the TOC conversion and CODremoval above 80% for the combined treatment.
IONIC LIQUIDS (ILs)
Alternative
to VOCs
o Negligible vapor pressure
o High solvent capacity
o Non – flammability
o Thermal stability
“Design” products
“GREEN” compounds
BmpyrCl HmimCl
1-butyl-4-methylpyridinium 1-hexyl-3-methylimidazolium
0
0,2
0,4
0,6
0,8
1
0
0,2
0,4
0,6
0,8
1
0 200 400 600 800 1000 1200 1400
XC
OD, X
CO
T
C/C
0
Time (min)
0
0,2
0,4
0,6
0,8
1
0
0,2
0,4
0,6
0,8
1
0 200 400 600 800 1000 1200 1400
XC
OD
, X
CO
T
C/C
0
Time (min)
Photolysis Photocatalysis Adsorption XCOD XTOC
BmpyrCl HmimCl
[IL] = 0.35 g L-1
[TiO2] = 0.25 g L-1
24 h
Xe lamp = 600 W m-2
35 ºC
Sunset solar simulator
TiO2
0
50
100
150
200
250
300
0 10 20 30
TO
C,
CO
D,
TN
(m
g L
-1)
Time (d)
TOC TOCi COD CODi TN TNi
BmpyrCl HmimCl
0
50
100
150
200
250
0 5 10 15 20 25 30 35
TO
C,
CO
D,
TN
(m
g L
-1)
Time (d)
Sludge
Acclimat.
Sludge
Acclimat.
0
20
40
60
80
100
120
140
160
0 100 200 300 400 500
TO
C,
CO
D,
Co
nce
ntr
ati
on
(mg
L-1
)
Time (min)
0
20
40
60
80
100
120
140
160
0 100 200 300 400 500
TO
C,
CO
D,
Co
nce
ntr
ati
on
(m
g L
-1)
Time (min)
TOC COD AcidsShort-chain
acids
• Fenton oxidation and solar photocatalysis generatedeffluents with low ecotoxicity values and highbiodegradability index.
• Working at 75 and 50% of the stoichiometric doseof H2O2 in Fenton oxidation gave rise to suitableeffluents for the combined treatment.
• Coupling Fenton/solar photocatalysis and biologicaloxidation is an adequate alternative for TMX or ILsremoval, according to TOC conversion and CODremoval values, higher than 80% for the combinedtreatment.
ACKNOWLEDGEMENTS
Spanish MCI (CTM2016-76564-R)
THANK YOU
Madrid’s Regional Government
(S2013/MAE-2716)
UAM-Santander (CEAL-AL/2015-08)
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