Solar Photocatalysis for Urban and Industrial Waste Water Reclamation Sixto Malato Plataforma Solar de Almería (PSA-CIEMAT), Tabernas (Almería), Spain.

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