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Electrochemical treatment of

reverse osmosis concentrates


Jelena Radjenovic, Arseto Bagastyo, Korneel Rabaey

Reverse Osmosis Concentrate (ROC)


- normally comprises about 15-25% of the incoming water
- characterized by high salinity, recalcitrant organics, biological
materials and residuals from wastewater treatment process,
preconcentrated up to 7 times!!!
ROC disposal:
Ocean discharge of brine, discharge into the sewer system,
evaporation ponds and disposal in landfills, deep well injection, zero liquid discharge
ROC treatment:
Coagulation, granular activated carbon,
chemical oxidation - UV/H2O2, TiO2 photocatalysis, O3, UV/Fe2+/H2O2

 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).

Dimensionally stable anodes (DSA)


 Electrochemically stable and available in practical mesh geometry
in large-scale quantities.
 Investigated for the treatment of organic petroleum wastewater, textile effluents, pesticide
contaminated wastewater, landfill leachate and other hardly treatable waste streams.
ACTIVE
ANODES

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

The oxidizing power is determined by the anode


overpotential for O2 evolution reaction and
adsorption enthalpy of the electrogenerated OH.

OH are produced by the electrolysis of water at the electrode surface:


M (OH)+H++eM+H2O
However, this reaction is in competition with O2 evolution:
M (OH)

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-

Increased efficiency reported for electrolysis of individual solutions of organic


contaminants in concentrated NaCl solution (e.g. atrazine, chlorophenols,
BPA, antibiotics)...
...can it work for real wastewater with high Cl- content?

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

 Decreased electron density at the aromatic ring due to the presence of


electron-withdrawing groups (-Cl, -I, -COR, NH3+).

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)

- Higher electrical charge (Q, Ah/m3) applied.


- Accumulation of oxidants in the bulk liquid, thus more intense indirect oxidation.

1.0

100

0.8

80

0.6

60

0.4

40

0.2

20

0.0
0

10

20

50

100

150

200

Free and total Cl2, mg L-1

ROC/ROC0

Continuous oxidation, J=100-250 A/m2

SUVA254/SUVA254,0
Colour/Colour0
Free chlorine (DPD)
Total chlorine (DPD)

0
250

Current density, A m-2

TOC0 = 57.1mg/L

ROC
Batch oxidation, J=250

TOC/TOC0

A/m2

SUVA254,0 = 1.42 L/(mg*m)


Colour= 104.6 1/m

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

Free and total Cl2, mg L-1

ROC/ROC0

[Cl-]= 1.5 mg/L

V. Fischeri bioassay of the oxidized ROC


 Bioassays were always performed on the extracted samples (Oasis HLB).
 Toxic equivalency concept - expressing the toxicity of complex mixtures of compounds in baseline
toxic
equivalent concentration (TEQ) units, derived from a baseline toxicity QSAR model using a virtual
compound with log KOW= 3 & MW= 300 g/mol as a reference, which equates to an EC50 of 12 mg L-1.

B.I. Escher et al, J. Environ. Monitor. 10 (2008), 612.

 The contribution of each chemical is weighted only by its hydrophobicity.

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)

J, A/m2 (Q, Ah/m3)

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

ELOX pathway of metoprolol (MTPL)


P237

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

P281A-Cl (R: =O)

MTPL-OH

P225-Cl2

P281A (R: =O)

P283-Cl (R: -OH)

P283 (R: -OH)

25 products identified!

P279 (R: =O)


P281 (R: -OH)

rS
RB

RC
lS

P279-Cl2 (R: =O)


P281-Cl2 (R: -OH)
lS
RC

RC
lS
R

HN

P279-Br (R: =O)


P281-Br (R: -OH)

P279-Cl (R: =O)

O
Cl
O

P281-Cl (R: -OH)


Cl

Cl

P279-Cl3 (R: =O)


P281-Cl3 (R: -OH)

Influence of electrode material


1.8
1.6

MTPL
(MTPL-Cl)

P335

(MTPL-Cl2)

P345

(MTPL-Br)

P379

(MTPL-BrCl)

1.4
A/A0,MTPL (-)

P301

Ti/Ru0.7Ir0.3O2, J=250 A/m2

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

Ti/SnO2-Sb, J=250 A/m2

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)

 Faster formation and further degradation of ELOX products at Ti/SnO2-Sb anode.

Influence of current density (J, A/m2)


1.4

Ti/Ru0.7Ir0.3O2, J=100 A/m2

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

Ti/Ru0.7Ir0.3O2, J=250 A/m2

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.

Super-power BDD electrodes - complete COD removal reported


! 16,000 per m2

(DSA: 1-3,000 per m2)

Post-treatment
Activated carbon and anaerobic
degradation have been proposed.

? Electro-dialysis and electrochemical oxidation.

Thank you for your attention!

Urban Water Security Research Alliance

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