Solar Photocatalysis for Urban and Industrial Waste Water Reclamation
Sixto MalatoPlataforma Solar de Almería (PSA-CIEMAT),
Tabernas (Almería), Spain.
1. Central receiver technology
7. Solar furnaces
4. Parabolic-trough technology (DSG)
2. Parabolic dishes + Stirling engines
3. Parabolic-trough technology (thermal oil)
8. Water desalination
9. Water photocatalysis
1
1
3
10. Passive architecture 10
8
97
2
4
6. Linear Fresnel Collector
6
5. Parabolic-troughs (gas) + Molten Salt TES
5
driven by solar energy
Solar Advanced Oxidation Processes
“near ambient temperature and pressure
water treatment processes driven by solar energy which involve the generation
of hydroxyl radicals in sufficient quantity to effective water purification”
Introduction
1/38
Introduction
Fe3+ activity, l540-580 nm
0.2 0.4 0.8 1.0 1.2 1.40
200
400
600
800
1000
1200I,
W/m
2m
O3 O2
O3
H2O
H2O
CO
H2O
0.60
200
400
600
800
1000
1200
Wavelength, µm
O3 O2
O3
H2O
H2O
2
H2O
TiO
2ac
tivity
, l3
90nm
Wavelength, µm
2/38
Introduction
CATALYSIS+
SUN
3/38
Introduction
4/38
1 Sun CPCs
Turbulent flow conditions
No vaporization of volatile compounds
No solar tracking
No overheating
Direct and Diffuse radiation
Low cost
Weatherproof (no contamination)
Introduction
5/38
Introduction
6/38
Give sound examples of techno-economic studies.
Assessment of the environmental impact: life cycle analysis (LCA).
To lead to industry application it will be critical that the processes can be developed up to a stage, where the process:
can be compared to other processes.
is robust, i.e. small to moderate changes to the wastewater stream do not affect the plant’s efficiency and operability strongly.
is predictable, i.e. process design and up-scaling can be done reliably.
gives additional benefit to the industry applying the process (e.g. giving the company the image of being “green”).
Introduction
The current lack of data for comparison of solar photocatalysis with other technologies definitely presents an obstacle towards an industrial application. Therefore, it is necessary:
7/38
AOP-BIO and BIO-AOP
Lanfill leachate
Treatment of Ecs
Combination NF/AOPs
Examples of techno-economic studies
Sound examples of techno-economic studies:
8/38
AOP-BIO and BIO-AOP
9/38
WW characterization: TOC, COD, BOD, main inorganics, contaminants (LC-MS/GC-MS)
Non-toxic or partially toxic (<50%)
TOXICITY
Toxic (>50%)EVALUATION OF
BIODEGRADABILITY
2: Biodegradable. COD>Guideline
AOP EVALUATION OF BIODEGRADABILITY DURING AOP
1: Partially or not biodegradable
BIOLOGICAL TREATMENT
COD and toxicity<Guideline
DISCHARGE
TOC<500 mg/LTOC>500 mg/L
DILUTION AND EVALUATION OF BIODEGRADABILITY
AOPEVALUATION OF
BIODEGRADABILITY DURING AOP
BIOLOGICAL TREATMENT
AOP
Biorecalcitrant compounds COD and toxicity<Guideline
DISCHARGE
BIOLOGICAL TREATMENT
AOPEVALUATION OF
BIODEGRADABILITY DURING AOP
1
12
2
2
21
1 12
AOP-BIO and BIO-AOP
10/38
Combined photo-Fenton and biotreatment
Biological treatment (IBR)
Solar Photo-Fenton
Industrial wastewater
DOC0: 480 mg/L
Non-biodegradable pesticides
Biodegradable compounds
Decontaminated water
DOC: 75 mg/L• 20 mg/L Fe / pH: 2.8• 44 % mineralization
• DOCf: 270 mg/L
• 21 mM H2O2 consumed
• DOC0: 300 mg/L
• 1.5 days of
biotreatment• 75 % mineralization
• DOCresidual: 75 mg/L
0 4 8 12 16 20 24 280
20
40
60
80
100%
BIO
DE
G.
Time (days)
S1 (DOC0: 490 mg/L) S5 (DOC
0: 345 mg/L)
S2 (DOC0: 460 mg/L) S6 (DOC
0: 255 mg/L)
S3 (DOC0: 440 mg/L) S7 (DOC
0: 170 mg/L)
S4 (DOC0: 400 mg/L) S8 (DOC
0: 145 mg/L)
Biodegradability limit
0 1 2 3 20 400
250
500
750
1000
1250
0.0
0.2
0.4
0.6
0.8
1.0IBR
Illumination time (hours)
DOC COD H
2O
2 consumed
C (
mg/
L)
Treatment time (hours)
Photo-Fenton
AOS
AO
S
AOP-BIO
11/38
Compound % Reduction combined system
Final conc(g/L)
Imidacloprid 96.4 25
Dimethoate 99.4 5
Pyrimethanil 81 161
Thiacloprid 84.2 88
Azoxystrobin 99.4 3
Malathion 100 < 0.1
Carbofuran 100 < 0.1
Metalaxyl 100 < 0.1
Spinosyn a 100 < 0.1
Bupirimate 100 < 0.1
Fenamiphos 100 < 0.1
Tebufenozide 100 < 0.1
Concentration of all pesticides decreased gradually throughout the process (mainly during the photo-Fenton process).
After the combined system: totally removed, except pyrimethanil and thiacloprid, found in range of g/L
1. SPE extraction
Oasis® HLB
1 2 3 4
2. LC-TOF-MS
AOP-BIO
12/38
Parameter Amount pH 3.98
Conductivity 7 mS.cm-1 TOC 775 mg.L-1 COD 3420 mg.L-1
Nalidixic acid 45 mg.L-1 TSS 0.407 g.L-1 Cl- 2.8 g.L-1
PO43- 0.01 g.L-1
SO42- 0.16 g.L-1
Na+ 2 g.L-1 Ca2+ 0.02 g.L-1
Real WW
N N
O
OH
O
BIO-AOP
13/38
0 50 100 150 200 250 3000
150
300
450
600
750
900
TOC H
2O
2 consumed
t30W
(min)
TO
C (
mg
/L)
0
10
20
30
40
50
60
70
H2O
2 co
nsu
med
(m
M)
0 50 100 150 200 250 300
0
10
20
30
40
50
Nalid
ixic
acid
(m
g/L
)
t30W
(min)
0 50 100 150 200 250 3000
150
300
450
600
750
900
TOC H
2O
2 consumed
t30W
(min)
TO
C (
mg
/L)
0
10
20
30
40
50
60
70
H2O
2 co
nsu
med
(m
M)
0 50 100 150 200 250 300
0
10
20
30
40
50
Nalid
ixic
acid
(m
g/L
)
t30W
(min)
INITIAL CONDITIONS (photo-Fenton)• Nalidixic acid: 39 mg/L • Initial TOC: 822 mg/L • [NaCl] : 6.5 g/L
• Total degradation of the nalidixic acid at 350 minutes (illumination time) (65 mM H2O2)• 28% of the initial TOC was removed
• Nalidixic acid: 38 mg/L
• Initial TOC: 725 mg/L
• [NaCl] : 4.3 g/L
INITIAL CONDITIONS (Biotreatment)
• NH4+ : <0.1 mg/L
• NO3- : <0.1 mg/L
• pH: 6.6
• 96% of the initial TOC was removed• Nalidixic acid persists after biological treatment (~15 mg/L)
0 1 2 3 40
100
200
300
400
500
600
700
800
TOC Nalidixic acid
Time (days)
TO
C (
mg
/L)
0
10
20
30
40
50
Nal
idix
ic a
cid
(m
g/L
)
BIO-AOP
14/38
AOP-BIO and BIO-AOP
0
20
40
60
80
100
% T
OC
red
ucti
on
AO
P
BIO
Biotr. time = 4 days Biotr.
time = 4 days
BIO
A
OP
t30w = 350 min; H2O2 = 65 mM (elim.NXA)
t30w = 21 min (elim. NXA) !!!
H2O2 = 12 mM (elim. NXA) !!!
15/38
LC-TOF-MS chromatograms
10 20 30 40 50
Initial wastewater IBR IBR + photo-Fenton
Time (min)
Retention time (min)
N N
O
O
OH
O
O
P34
N N
OH
OO
OH
P2
N N
OH
OO
NXA
N N
O
O
O
OH
OH
P3
N ON
O
O OH
P4
N N
OH
OO
P5
N N
OH
OO
OH
P9
N NH
OH
OO
P6
N N
OH
OH
P14
N N
OH
OHP1
N N
OH
O
O
O
HO
P11
N NH
O
O
OH
OH
P12
N NH
OH
O
P15
N NH
O
P13
N N
OH
O
O
P7
N N
HO
OO
OH
ClP17
N N
OH
O
HO
OHP22
N N
OH
O
OHO
P27
No DPs
BIO-AOP
16/38
TC = 15615 mg/L COD = 42630 mg/L
IC = 5.9 mg/L Conduct. = 77.3 mS/cm
DOC = 15610 mg/L Cl-= 40.2 g/L
pH = 7.4 Na+= 32 g/L
SO42-= 15.7 g/L K+= 5.7 g/L
NH4+ = 445 mg/L
Landfill leachate (COD: 15615 mg/L; DQO: 42630 mg/L)
3. Evaluation of toxicity and biodegradability
3.a Respirometry activated sludge
3.b Biodegradability by Zahn-Wellens
1. Pre-treatment (Coagulation/floculation)
2. Photo-Fenton (Fe 1 mM)
Landfill leachate
17/38
Res
pir
atio
n(m
gO
2/L
h)
Time, s
SAMPLE 6
SAMPLE 4
SAMPLE 2
SAMPLE 0
Res
pir
atio
n(m
gO
2/L
h)
Time, s
SAMPLE 6
SAMPLE 4
SAMPLE 2
SAMPLE 0
Respirometry activated sludge
Landfill leachate
18/38
0 4 8 12 160
20
40
60
80
100
D,
%
time, days
M0 M1 M2 M3 M4 M5 M6 M7 REF
BIODEGRADABILITY, 70%
-1- 100
-t B
tA BA
C CD
C C
Biodegradability by Zahn-Wellens
Landfill leachate
19/38
1. Pre-treatment (Coagulation/floculation)
2. PHOTO-FENTON(<20 % mineralization)
3. BIOTREATMENT
Landfill leachate
TC= 15615 mg/L COD= 42630 mg/L
DOC= 15610 mg/L Conduct.= 77.3 mS/cm
€/m3 %
M1 M3 M1 M3
Chemicals (H202) 21.5 30.1 73 60
Electricity 0.1 0.1 1 1
Man power 1.4 1.4 5 5
CPC + facilities 6.4 11.7 22 27
Total (€/m3) 29.4 43.3
20/38
(ng-μg/L)
NATURAL WATERS
Photochemical transformations
TRANSFORMATION PRODUCTS
EMERGING CONTAMINANTS
• Until recently unknown
• Commonly use
• Emerging risks (EDCs,
antibiotics)
• Unregulated
WWTPs
INCOMPLETE REMOVAL
CONTINUOUS INTRODUCTION INTO THE ENVIRONMENT
Treatment of ECs
21/38
Caf
fein
e4-
AA
AP
arax
anth
ine
4-F
AA
Nic
otin
eC
otin
ine
Ibup
rofe
nG
emfib
rozi
lF
uros
emid
e4-
MA
AH
idro
chlo
roth
iazi
de4-
AA
Nap
roxe
nD
iclo
fena
cO
floxa
cin
Ate
nolo
lR
aniti
dine
Cod
eine
Sul
fam
etho
xazo
leA
ntip
yrin
eIs
opro
turo
nC
ipro
floxa
cin
Ace
tam
inop
hen
Diu
ron
Ket
opro
fen
Trim
etho
prim
Vel
afax
ime
Azi
thro
myc
inS
ulfa
pyrid
ine
Pra
vast
atin
Cla
rithr
omyc
in
102
103
104
c [n
g L
-1]
Atr
azi
ne
Su
lfam
eth
azi
ne
Ery
thro
myc
in
Ch
lorf
en
vin
ph
os
Cita
lop
ram
HB
r
Fe
no
fibri
c A
cid
Ca
rba
ma
zep
ine
Lin
com
ycin
Pri
mid
on
e
Be
nza
fibra
te
No
rflo
xaci
n
Sa
licili
c_A
cid
Ind
om
eth
aci
ne
Sim
azi
ne
Me
tro
nid
azo
le
Pro
pyp
he
na
zon
e
So
talo
l
Pro
pa
no
lol
Me
top
rolo
l
Ep
oxi
de
Ca
rba
ma
zep
ine
Me
fen
am
ic A
cid
Fa
mo
tidin
e
Me
piv
aca
ine
Su
lfath
iazo
le
Na
do
lol
Am
itrip
tylin
HC
l
Clo
fibri
c A
cid
Dia
zep
an
Ifo
sfa
mid
e
Te
rbu
talin
e
Fe
no
fibra
te
100
101
102
c [n
g L
-1]
Treatment of ECs
22/38
CHARACTERIZATION
29/62 Compounds with
higher contribution in
MWTP Effluent
LC-QLIT-MS/MS
Treatment of ECs
23/38
75 L, 4.1 m2, control T (35 ºC)
50 L, 0.69 g O3 h-1
Treatment of ECs
24/38
Contaminants > 1000 ng L-1.∑C = rest of contaminants at less than 1000 ng L-1
1-Bisphenol A; 2-Ibuprofen; 3-Hydrochlorothiazide; 4-Diuron; 5-Atenolol; 6-4-AA; 7-Diclofenac; 8-Ofloxacin; 9-Trimethoprim; 10-Gemfibrozil; 11-4-MAA; 12-Naproxen; 13-4-FAA; 14-∑C; 15-4-AAA; 16-Caffeine; 17-Paraxanthine
Solar photo-Fenton
Solar TiO2.
Ozonation
Treatment of ECs
25/38
LC-MS chromatogram. Photo-Fenton.
t = 0t = 20 (t30W = 14) minLC-MS chromatogram. Ozonation.
t = 0 t = 60 min
Toxicity assays during ozonation and photo-
Fenton showed < 10% inhibition on V. fisheri
bioluminescence and in respirometric assays
with municipal activated sludge
SolarTiO2
Solarphoto-Fenton Ozonation
Treatment time, min 475 20 60
Accumulated solarEnergy, kJ L-1
212 2.3 -
ReagentConsumption
--
H2O2 54 mg L-1
Fe(II)5 mg L-1
O3
9.5 mg L-1
Treatment of ECs
26/38
H2O2 1.1 € kg-1
Fe(II) 0.72 € kg-1
H2SO4 0.20 € kg-1
NaOH 0.12 € Kg-1
Electricity 0.07 € Kwh-1
O2 0.15 € Kg-1
Labour 18.8 € h-1
23.1 € kg O3
Solar photo-Fenton Ozonation
€m3
90% 98% 90% 98%
Reagent 0.064 0.148 0.16 0.22
Labour 0.03 0.05 0.05 0.05
Electricity 0.004 0.010 0.010 0.020
Investment 0.09 0.15 0.23 0.27
Total 0.188 0.358 0.450 0.560
Treatment of ECs
Calculation basis:90% or 98% degradation
of micropollutants 5000 m3/day
27/38
MF
UF
NF
RO
SaltsWaterMacro-molecules
ECs andTPs
Suspended SolidVirus Bacteria
Multivalent
Monovalent
0.1-10
Pore Sizeµm
5.10-3 - 5.10-2
5.10-4 - 5.10-3
1.10-4 - 1.10-3
MBR
UF
WW+ECs
Effluent+ECs
Perm
eate
AOP
Concentrate+ ECs
NF/RO
For reuse
CAS
WW + ECsAOP
Concentrate+ ECs
NF/RO
For reuse
EffluentPre-treatment
Perm
eate
Combination NF/AOPs
28/38
SQ24
Permeate
Concentrate
Feed tank
SQ16
V12
V13PNF
SP11
V15
SC14
V14
F11
F12V21
V22 SP21
V24
ST27
Feed sample
SC16
V27SQ26Recirculation
NF in parallel (5.2 m2). 1.4 m3 h-1
Combination NF/AOPs
29/38
Carbamazepine
(anticonvulsant)
Flumequine (broadspectrum
antibiotic)
Ibuprofen (nonsteroidal
antiinflammatory)
Ofloxacin (gramnegative
antibiotic)
Sulfamethoxazole (bacteriostatic
antibiotic)
Micropollutants
at 15 µg L-1, each
Ions mg L-1
Na+
K+
Mg2+
Ca2+
SO42-
Cl-
HCO3-
380-4405-7
37-6085-100
250-280290-350813-915
Combination NF/AOPs
30/38
MF
UF
NF
RO
SaltsWaterMacro-molecules
ECs andTPs
Suspended SolidVirus Bacteria
Multivalent
Monovalent
0.1-10
Pore Sizeµm
5.10-3 - 5.10-2
5.10-4 - 5.10-3
1.10-4 - 1.10-3
Solar photocatalysis
Inorganic ions
R (%) Ce, CF=4 (mg L-1) Ce, CF=10 (mg L-1)
Na+
K+
Mg2+
Ca2+
SO42-
Cl-
HCO3-
76-8777-8291-9788-9396-9967-8472-88
1000-110015-19
140-18090-105
840-890770-860
1780-1930
2036-215631-31.1592-73170-105
2000-36001200-12602440-2500
Pharmaceuticals
R (%) Ce, CF=4 (mg L-1) Ce, CF=10 (mg L-1)
CarbamazepineFlumequineIbuprofenOfloxacin
Sulfamethoxazole
93-9697-10096-10097-9992-95
47-5258-6355-6158-6252-59
138-141148-152150-154140-145144-146
Combination NF/AOPs
31/38
-30 0 30 60 90 1200
200
400
600
800
CF=1, C0=15 g/L
CF=4 CF=10
H2O
2co
nsum
ptio
n (m
g/L)
C (g
/L)
Illumintation time (min)
Fenton Photo-Fenton
0
5
10
15
20
H
2O
2 consumption
r = kC
Fe (II), 0.1 mM
H2O2, 25 mg L-1
Natural pH
Combination NF/AOPs
32/38
-30 -20 -10 0 10 20 300
200
400
600
800
C (g
/L)
CF=4 CF=10
Photo-Fenton
C (g
/L)
t30W
(min)
Fenton-like
0
20
40
60
80
100
120
CF=1
Fe(III)-L + hν → [Fe(III)-L]* → Fe(II) + L•
Fe (II), 0.1 mM
0.2 mM EDDS
H2O2, 25 mg L-1
Natural pH
HOOC
HOOC
COOH
NHNH COOH
Ethylenediamine-N,N'-disuccinic acid (EDDS)
Combination NF/AOPs
33/38
Operational requirements for attaining 95% of pharmaceuticals degradation present in NF concentrates (CF=4 and 10) when solar photo-Fenton and photo-Fenton like Fe(III)-EDDS
complex were applied. CF=1, no NF, only AOP.
Combination NF/AOPs
CF 1 4 10
Solarphoto-Fenton
H2O2 consumed (gm-3)
Quv (kJ L-1)
t(min) / CPC surface(1)
17.022.5
90/100
4.45.1
120/22.6
1.92.8
110/12.4
Solar photo-Fenton like
Fe (III)-EDDS complex
H2O2 consumed (gm-3)
Quv (kJ L-1)
t(min) / CPC surface(1)
24.92.7
14/15
6.20.6
10/3.3
2.50.5
19/2.7
34/38
Flow rate 20 L/min.
CPC with pyrex glass tubes, 1.375 m2.
Irradiated volume 9.79 L.
Total volume 25 L.
Catalyst loading 0.2-1 g/L, Pt/(TiO2-N) or Pt/(CdS-ZnS)
Sacrificial agents: formic acid (0.05 M), glycerol (0.001 M) and a municipal wastewater (97.7 mg/L of DOC).
Heterogeneous photocatalytic hydrogengeneration in a solar pilot plant
35/38
Security valve
H2O to CPC
Pump
to sample
TankH2O from CPC
N2+H2 to GC
Glass window
N2
10-500 mhn/min
0.4-20 mhn/minMFC
MFC
Heterogeneous photocatalytic hydrogengeneration in a solar pilot plant
36/38
0.05 M formic acid
0 5 10 15 20 25 30 35
0
500
1000
1500
2000
2500
3000
3500
H2 c
once
ntra
tion
(m
olL
)
Q (KJ /L)
TiO2-N-Pt
TiO2P25
TiO2-N
0 10 20 30 400
50
100
150
200
250
H 2
con
cent
ratio
n (
mol
/L)
Q(KJ /L)
Pt/(CdS-ZnS)
Real wastewater, 98 mg/L of DOC
Reaction conditions: 5 g of catalyst, 25 L of aqueous solution. Data corresponding to 5 hours of irradiation.
K. Villa, X. Domènech, S. Malato, M. I. Maldonado, J. Peral. Heterogeneous photocatalytic hydrogen generation in a solar pilot plant. Int. J. Hydrogen Energy, 38 (29), 2013, 12718-12724.
Heterogeneous photocatalytic hydrogengeneration in a solar pilot plant
37/38
Unidad de Tratamientos Solares de Agua (Solar Treatment of Water Research Group) .
Plataforma Solar de Almería (CIEMAT).
Acknowledgements
38/38
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