solar detoxification of water rodriguez

7/30/2019 Solar Detoxification of Water Rodriguez

1/21

Sixto Malato RodrguezSixto Malato Rodrguez

o ar e ox ca on o wa er.o ar e ox ca on o wa er.

Recent overview and trendsRecent overview and trends

Plataforma Solar de Almeria, SPAINPlataforma Solar de Almeria, [email protected]@psa.es

Biodegradable substances:

Biofilter treatment/ activated sludge treatment

IntroductionIntroduction

Non-biodegradable substances can show

Non-toxic / inert behaviour

Acute toxicity

Chronic toxicity

Alternativetreatment

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Phenols, nitrophenols and halophenols.Phenols, nitrophenols and halophenols.


Chlorinated hydrocarbons (solvents, VOCs, etc).Chlorinated hydrocarbons (solvents, VOCs, etc).

, ... ., ... .

Gasoline additivesGasoline additives (MTBE, ETBE,..).(MTBE, ETBE,..).

Agrochemical wastes (pesticides).Agrochemical wastes (pesticides).

Residues from textile industry (dyes).Residues from textile industry (dyes).

WATERBORNE PATHOGENS


BACTERIA Salmonella Shigella Campylobacter Vibrio Escherichia coli

VIRUS Poliovirus Hepatitis A Parvovirus Adenovirus Rotavirus

PROTOZOA Giardia lamblia

Entamoeba

histolytica

Crystosporidium

HELMINTHS Taenia saginata

Ascaris

lumbricoides

Schistosoma

InactivationInactivation

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Bacterial inactivation under solar radiation

Indirect action


Direct action

UV absorption by

DNA molecules of

microorganisms

Photocatalytic effect

of TiO2 attacks the

cell membrane.

Decrease of

Coenz me-A levels

UV

TiO2H2O OH

by photo-oxidation,

which induces celular

death.

PhotocataysisPhotocataysis may be used for decontaminationdecontamination of water containingorganic pollutants, classified as bio-recalcitrant, and/or for disinfectiondisinfection


removng curren an emergng pa ogens.

The overarching goal for the future ofreclamation and rereclamation and re--useuse of water is tocapture water directly from non-traditional sources such as industrial ormunicipal wastewaters and restore it.

Futuristic direct re-use systems envisioned should involve a photocatalyticphotocatalyticreactor to provide an absolute barrierreactor to provide an absolute barrierto pathogens and to destroy organic

contaminants that ma ass the nanofiltration barrier. Nevertheless, technical applications are still scarcetechnical applications are still scarce. Process costs may be

considered the main obstacle to their commercial application

M.A. Shannon et al., Nature, 452 (2008) 301.

C. Comninell is et al., J. Chem. Technol. Bio technol., 83 (2008) 769.

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Integration of AOPs as part of a treatment t rainIntegration of AOPs as part of a treatment t rain


Pathogens

Biological Treatment

Biodegradablewastewater

Water

reuse

Se arationTechnolo

Micropollutants passthrough the bioreactor

Generation of a concentrated effluent

Entails a transference of the problem to

another phase

PHOTOCATALYSISPHOTOCATALYSIS

Elimination of pathogens and micropollutants

Integration of AOPs as part of a treatment t rainIntegration of AOPs as part of a treatment t rainIntroductionIntroduction

Pulgarn et al., Catalysis Today 54, 1999.

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To minimize tTo minimize tRR and reagent by an optimized coupl ing strategyand reagent by an optimized coupl ing strategy

Real WWReal WW


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-1Na+ 2 g.L-1

Ca2+ 0.02 g.L-1C. Sirtori et al., Wat Res. 43, 661668, 2009.

To minimize tTo minimize tRR and reagent by an optimized coupl ing strategyand reagent by an optimized coupl ing strategy

AOP BIO vs. BIO AOPIntroductionIntroduction

10022ndnd

40

60

80

O

C

reduction

Biotr.

time =

4 days

Biotr.

time =

4 days

t30w = 21 min (elim. NXA) !!!

11stst

22ndnd

C. Sirtor i et al., Env. Sci. Technol., 43, 1185, 2009.

0

20%

t30w = 350

min

(elim.NXA)

Photocatalysis

11stst

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Sunlight as the irradiation sourceSunlight as the irradiation source


CATALYSIS+

SUNS. Malato et al., Catalysis Today 147, 1, 2009.

Sunlight as the irradiation sourceSunlight as the irradiation sourceIntroductionIntroduction

Photocatalysis3500

4000

sSolar

Photocatalysis

1000

1500

2000

2500

3000

Numberofpublication

(source: www.scopus.com,www.scopus.com, Feb 2011, search terms phot ocatalysis and solar photocatalysis

98 99 00 01 02 03 04 05 06 07 08 09 10

0

500

Year of publ ication

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1. Solar photocatalysis hardware1. Solar photocatalysis hardware

OutlookOutlook

2. Solar photocatalytic treatment plants2. Solar photocatalytic treatment plants

3. Solar photocatalytic disinfection3. Solar photocatalytic disinfection

4. Concluding remarcks4. Concluding remarcks

1. Solar photocatalysis hardware1. Solar photocatalysis hardware

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2forr a

aa

a

aa

2

3

2for

sin1

cos2r

Part A-B

Part B-C

y

asin

1

C

y

asin

1

C

Solar photocatalysis hardwareSolar photocatalysis hardware

Ox

R C

r

Ox

R C

r

Ifa = 90 C = 1

One Sun CPC collector manufacturing:One Sun CPC collector manufacturing: aa = 90= 90 all direct and diffuseall direct and diffusesolar photons can be col lected and used (diffuse UV radiation is a verysolar photons can be col lected and used (diffuse UV radiation is a very

important fraction of total solar UV)important fraction of total solar UV)

A BA B

1 Sun CPCs

Turbulent flow conditions


o vapor za on o vo a e

compounds

No trackingNo OverheatingDirect and Diffuse radiationLow cost

contamination)

High optical efficiency

Malato et al., Sol ar Energy, 77, 2004.

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LVRPA* distribution in aLVRPA* distribution in a

CPC in sunny (a) andCPC in sunny (a) andcloudy (b) day.cloudy (b) day.

Considerations:Considerations:

I Constant = 30 W/mI Constant = 30 W/m22Direct/diffuse =Direct/diffuse =

ConstantConstant

75% UV trasmittance75% UV trasmittanceby cloudsby clouds

ColinaColina--Mrquez , MachucaMrquez , Machuca--Martnez , Li Puma. Env. Sci. Technol., 43, 2009Martnez , Li Puma. Env. Sci. Technol., 43, 2009

**LVRPA= local volumetric rate ofLVRPA= local volumetric rate ofphoton absorption, W/mphoton absorption, W/m33

2. Solar photocatalytic treatment plants2. Solar photocatalytic treatment plants

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30 x 20 km (West of

Almer ia)

The intensive

agriculture activity is avery important

economical sector in

5,200 Tm pest icide =

2 x 106

plasticcontainers (2L)

Solar photocatalytic treatment plantsSolar photocatalytic treatment plants

Almer a. There are

more than 350 km2 of

greenhouses in

Almera.

These greenhouses

yearly consumes 5.200

Tm of phytosanitary

Selective recovery

Recycling plant

.

bot tles; 1.9 L average

volume).

Plastic washing

Wastewater wi thhundreds of mg/L

of pesticides


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Solar fi eld figures:

a) Individual CPC modulesformed by 20 parallel


tubes (surface: 2.7m2/module)

b) 4 parallel rows with 14modules each mountedon a 37-tilted platform(local latitude)

c) total collectors surface:m

d) Total photoreactorvolume: 1061 L

e) Total volume per batch:1500 to 2000 LMalato et al., Catalys is Today , 122 (2007).

Zapata et al., Chemical Engineering Journal, 160 (2010).

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Installed at DSM-DERETIL

Villaricos (ALMERIA)http://www.psa.es/webeng/projects/cadox/index.html

O2

PH

OUT

IBR

BIOLOGICAL

LOOP

IBR

1 m3

BIOREACTOR

Neutralisation

Tank

O2

PH

OUT

IBR

BIOLOGICAL

LOOP

IBR

1 m3

BIOREACTOR

Neutralisation

Tank


CONDITIONER

OUT

OUT

F

F

NEUTRALIZATIONTANK

PH

SOLAR

LOOP

BLOWER

Solar

photoreactor

100 m2

Conditioner

2 m3

5 m3

CONDITIONER

OUT

OUT

F

F

NEUTRALIZATIONTANK

PH

SOLAR

LOOP

BLOWER

Solar

photoreactor

100 m2

Conditioner

2 m3

5 m3

BUFFER

OUT

OUT

PH

O2

F

H2O2

Recirculation

tank

3 m3

BUFFER

OUT

OUT

PH

O2

F

H2O2

Recirculation

tank

3 m3

I. Oller et al. Ind . Eng. Chem. Res. 46 (2007).

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3. Solar photocatalytic disinfection3. Solar photocatalytic disinfection

OH

O2-

A d s o r b e d

T iO2

Photocatalytic inactivation


TiO2

h+

OH

e-

So ar UV

e-/h+

V e r y sm a l l

p a r t i c l e s

o f T iO2

Malato, Fernandez-Ibez and Blanco, J. Solar Energy Engi neering 129 (2007) 1-12.

40 nm 300 nm >1mTiO2 TiO2-aggregates cells

O2-

s u s p e n d e d

T iO2

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TiO2-aggregates in contact w ith F. equiseti

Solar photocatalytic disinfectionSolar photocatalytic disinfection

TiO2Macroconidia ofF. Equiseti before andafter the photocatalytic treatment (5h)

C. Sichel, et al. Appl. Cat. B:

Enviro n., 74 (2007) 152-160.


BACTERIA: Enterococcus faecalis (Gram+) Escherichia coli (Gram-)

VIRUS AND BACTERIOPHAGE: Poliovirus 1, Phage MS2 (RNA-bacteriophage)

CANCER CELLS: HeLa cells (cervical carcinoma), T24 (bladder cancer), U937 (leukemia).

FUNGI AND YEATS:

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Pilot plant with CPC modules, catalyst sedimentation and tankPilot plant with CPC modules, catalyst sedimentation and tankfilters for postfilters for post-- treatment developed for photocatalytictreatment developed for photocatalytic

disinfectiondisinfection


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102

QUV

needed to Detection Limit

MACROCONIDIA

L)

QUV needed to Detection Limit

CHLAMYDOSPORE

Water quality

100

101

DL

Controls

F.solaniConcentration(CFU/mL)

39,4

kJ/L

30,4

kJ/L

Solar disinfection

Well water

Distilled water

28,5

kJ/L

100

101

102

DL

Controls

F.equisetiConcentration(CFU/m

45,3

kJ/L

37,2

kJ/L

Well water

Distilled water

Solar Disinfection36,4

kJ/L

11:00 12:00 13:00 14:00 15:00 16:00

Local Time (HH:MM)

11:00 12:00 13:00 14:00 15:00 16:00

Local Time (HH:MM)


E. col i Fusarium

F. equiseti

Different microorganisms

0 2 4 6 8 10 12 14

1

10

100

Concentration(CFU/mL)

QUV

(kJ/L)

F. antophilum

F. verticillioides

F. solani

F. oxysporum

L

)

12:00 14:00 16:0010

0

101

102

103

100

101

102

10

F. equisetimacroconidia

Concentration(CFU/

Local time (hh:mm)

.

chlamydospores

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4. Concluding remarcks4. Concluding remarcks

To lead to indus try application it will be critical that the photocatalyticTo lead to indus try application it will be critical that the photocatalytic

processes can be developed up to a stage, where the process:processes can be developed up to a stage, where the process:

is costis cost--efficient compared to o ther processes.efficient compared to other processes.

Concluding remarcksConcluding remarcks

, . ., . .

affect the plants efficiency and operability s trongly.affect the plants efficiency and operability s trongly.

is predictable, i.e. process design and upis predictable, i.e. process design and up--scaling can be done reliably.scaling can be done reliably.

is easy to implement, i.e. suppliers and engineering companies can startis easy to implement, i.e. suppliers and engineering companies can startmarketing the process without huge initial investment costs, which couldmarketing the process without huge initial investment costs, which could

only be recovered by high turnovers.only be recovered by high turnovers.

is easy to operate and maintain, operation error must not lead tois easy to operate and maintain, operation error must not lead to catastrophic events . catastrophic events .

is safe regarding the environment (minimize risks of leakage, discharge ofis safe regarding the environment (minimize risks of leakage, discharge ofnot su fficiently treated effluent).not su fficiently treated effluent).

gives additional benefit to the industry applying the process (e.g. giving thegives additional benefit to the industry applying the process (e.g. giving thecompany the image of being green ).company the image of being green ).

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More information... The last...More information... The last...

Decontamination and disinfection of water by solar photocatalysis: Recent overview andtrends. Catalysis Today 147, 159, 2009. MONOGRAPH.

Decontamination of industrial wastewater containing pesticides by combining large-scalehomogeneous solar photocatalysis and biological treatment. Chemical EngineeringJournal, 160, 447456, 2010.

Degradation study of 15 emerging contaminants at low concentration by immobilized TiO2 ina pilot plant. Catalysis Today, 151, 107113, 2010

Integration ofSolar Photocatalysis and Membrane Bioreactorfor Pesticides Degradation.Separation Science and Technology, 45, 15711578, 2010.

Hydrogen peroxide automatic dosing based on dissolved oxygen concentration duringsolar photo-Fenton. Catalysis Today, 161, 247254, 2011.

emova o xeno ot c compoun s rom water an wastewater y a vance ox atonprocesses. In: Xenobiotics in the Urban Water Cycle. D. Fatta-Kassinos, K. Bester and K.Kmmerer (Eds.). Springer, Germany. pp. 387-412. 2010.

Technologies for advanced wastewater treatment in the Mediterranean Region. En: Wastewater tratment and reuse in the Mediterranean Region. D. Barcel and M. Petrovic (Eds.).Springer-Verlag, Berlin Heidelberg, Germany. pp. 1-28. 2011.

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solar detoxification of water rodriguez

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