Beruflich Dokumente
Kultur Dokumente
Electrochemical treatment
No use of chemicals!
Using appropriate electrode material and anode potential, a series of oxidants
is generated at the anode (e.g. OH, H2O2, O2 , O3).
DSA
OXIDATION
POTENTIAL (V)
OVERPOTENTIAL
FOR O2
EVOLUTION (V)
Ti/RuO2
1.4-1.7
0.18
Ti/IrO2
1.5-1.8
0.25
Ti/Pt
1.7-1.9
0.3
Ti/PbO2
1.8-2.0
0.5
Ti/SnO2
1.9-2.2
0.7
p-Si/BDD
2.2-2.6
1.3
NON-ACTIVE
ANODES
ADSORPTION
OXIDATION ENTHALPY
OF M-OH
POWER
M +1/2 O2+H++e-
Non-active electrodes (i.e. BDD, Ti/SnO2-Sb, Ti/PbO2) have a weak electrode-OH interaction
and are capable of combusting organic compounds.
M (OH)+R
M+mCO2+nH2O+H++e-
Active electrodes (i.e. Ti/IrO2, Ti/RuO2) adsorb OH and reactants interaction and are capable
only of converting organic compounds.
C. Comninellis, Electrochimica Acta,
39 (11-12), 1857-1862, 1994.
(OH)+R
M+RO+H++e-
Continuous oxidation of ROC amended with target analytes using Ti/RuO2-IrO2 anode at
different current densities, J=100-250 A/m2
100 A/m2
150 A/m2
200 A/m2
250 A/m2
80
60
40
20
N
T
LN
A C
C
TP
D
C
F
D
ZN
EN
R
SD
Z
TM
P
N
FL
SR
L
G
M
F
C
TP
VN
F
M
TP
D
IU
H
C
C T
AF
F
R
O
X
TM
L
C
B
Z
A
TZ
M
ET
IB
U
PN
T
IP
M
2,
4D
TP
R
D
EE
T
0
R
Removal, %
100
Iopromide
2,4-D
Triclopyr
DEET
RNT-ranitidine
LNC-lincomycin
ACTP-acetaminophen
DCF-diclofenac
DZN-diazinon
ENR-enrofloxacin
SDZ-sulfadiazine
TMP-trimethoprim
NFL-norfloxacin
SRL-sertraline
GMF-gemfibrozil
CTP-citalopram
VNF-venlafaxine
MTP-metoprolol
DIU-diuron
HCT-hydrochlorothiazide
CAFF-caffeine
ROX-roxithromycin
TML-tramadol
CBZ-carbamazepine
ATZ-atrazine
MET-metoprolol
IBU-ibuprofen
PNT-phenytoin
IPM-iopromide
2,4-D
TPR-triclopyr
DEET
Batch oxidation of ROC amended with target analytes using Ti/RuO2-IrO2 anode at J=250 A/m2
IBUPROFEN
100
METALOCHLOR
Removal, %
80
ATRAZINE
60
2,4-D
IOPROMIDE
40
PHENYTOIN
DEET
20
TRICLOPYR
0
0.0
Q=
I*t
V
0.2
kA h
m3
0.4
0.6
0.8
1.0
Q, kA h m-3
1.2
1.4
1.6
Q=1456 Ah/m3
(Continuous exp: J=250 A/m2
Q=769 Ah/m3)
1.0
100
0.8
80
0.6
60
0.4
40
0.2
20
0.0
0
10
20
50
100
150
200
ROC/ROC0
SUVA254/SUVA254,0
Colour/Colour0
Free chlorine (DPD)
Total chlorine (DPD)
0
250
TOC0 = 57.1mg/L
ROC
Batch oxidation, J=250
TOC/TOC0
A/m2
2.0
125
1.8
100
1.6
75
1.4
1.2
50
1.0
25
0.8
0.6
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
ROC/ROC0
Continuous ELOX
Batch ELOX
180
Toxic Equivalent
Concentration (TEQ), mg/L
Toxic Equivalent
Concentration (TEQ), mg/L
250
200
150
100
50
0
0
50
(154)
100
(308)
150
(461)
200
(615)
250
(769)
160
140
120
100
80
60
40
20
0
0
122
246
Q,
Ah/m3
437
1457
Batch oxidation of ROC amended with model compound using Ti/RuO2-IrO2 and Ti/SnO2-Sb
anode at J=100 and 250 A/m2
Model compound: METOPROLOL
MW=267.36 g/mol
Log KOW=1.88
pKa=9.68
positively charged in the pH range of the experiment (pH 7.8 to 2.2)
QqLIT-MS employed for qualitative analysis:
- Structural elucidation of known unknowns in MSn experiments
- Determination of qualitative profiles
Q0
Q1
Q2
Q3/LIT
P237-Cl
RClS
S
RBr
ROS
RHS
ROS
MTPL-Br
MTPL
P253
ROS-reactive oxygen species
RHS-reactive halogen species
R: =O, -OH
MTPL-BrCl
RC
lS
RClS
S
RO
MTPL-Cl2
MTPL-Cl
S
RO
P225
P133
RHS
MTPL-OH
P225-Cl2
25 products identified!
rS
RB
RC
lS
RC
lS
R
HN
O
Cl
O
Cl
MTPL
(MTPL-Cl)
P335
(MTPL-Cl2)
P345
(MTPL-Br)
P379
(MTPL-BrCl)
1.4
A/A0,MTPL (-)
P301
1.2
1.0
0.8
0.6
0.4
0.2
0.0
0.0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.7 0.8 0.9 1.05 1.2 1.4
1.4
A/A0,MTPL (-)
1.2
1.0
0.8
0.6
0.4
0.2
0.0
0.0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.7 0.8 0.9 1.05 1.2 1.4
Q (A h L-1)
P281
1.2
A/A0,MTPL (-)
P279
MTPL
1.0
P315
(P281-Cl)
P313
(P279-Cl)
0.6
P349
(P281-Cl2)
0.4
P347
(P279-Cl2)
0.8
0.2
0.0
1.2
P279
P281
0.04
0.08
0.12
0.16
0.2
0.24
0.32
0.44
0.52
0.6
0.68
HOCl/ClO-
HOCl/ClO-
A/A0,MTPL (-)
1.0
0.8
0.6
0.4
0.2
0.0
0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.7 0.8 0.9 1.05 1.2 1.4
Q (A h L-1)
Faster formation and further degradation of ELOX products at higher current density.
Conclusions
Under the conditions of the experiments, radical and non-radical RHS outcompeted the OH on both
anodes. Identical initial mechanism of degradation of MTPL was observed on the Ti/RuIrO2 and Ti/SnO2-Sb
anode, with a combined effect of ROS and RHS on the formation and degradation of the identified
oxidation by-products, likely in the bulk solution. Faster oxidation rates were observed for the Ti/SnO2-Sb
anode.
H2O
eANODE
OCl-/HOCl
METOPROLOL
O2, OH , O3
Cl-, Br-
HO
e-
HOCl/OClHOBr/OBr-
Br
Cl
HN
Solutions?
Higher electrical charge (Q, Ah/m3)?
Uneconomic.
Longer residence times?
Uneconomic & Impractical.
Post-treatment
Activated carbon and anaerobic
degradation have been proposed.