RECENT ADVANCES IN PHOTOCATALYTIC

REACTORS

Submitted by:Madhura N. Chincholi

Guided by:Dr. PRG

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INTRODUCTION

• Background• Photocatalysis?• Catalysts• Light sources• Reactors• Applications

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LITERATURE REVIEW

• Organics and microorganisms • Dyes • Drugs• Toxic components

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ORGANICS & MICROORGANISMS

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• Sraw et al. (2013) degraded monocrotophos (MCP), an organophosphorous insecticide

• Catalysts- Aeroxide P-25 and LR grade TiO2

• UV (8 blue black UV florescent lamps (Philips, 20W)) and sunlight

• Ambient T & P, t = 3 h• 84% degradation • Degradation rate increased by 15 % by H2O2 addition with LR TiO2

Fig. 1. Skurry batch photocatalytic reactor setup (Sraw et al. 2013)

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• Grcic et al.(2015)• Household greywater (GW) • Solar photocatalysis• Followed by flocculation by chitosan• TiO2-coated textile fibers by applying TiO2–

chitosan pasteous dispersion on polyester/wool blend textile

• The reactor assembled mostly from waste materials

• Results showed significant decrease in organic content (50.8%), COD and toxicity over a period of 4 h.

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• Complete degradation of dye molecules and certain aromatic compounds.

• The chitosan dissolved at certain extent during photocatalytic treatment

• An efficient flocculant in treated wastewater.• Flocs observed shortly after treatment, complete

sedimentation 12 h in dark.

Fig.2 Schematics of reactor for solar photocatalysis (a) front view, (b) top view (c) side view. (Grcic et al. 2015)

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• Carra et al. (2015) • Acetamiprid (ACTM), thiabendazole (TBZ) and their transformation products (TPs) in

an agro-food industry effluent • Solar photo-Fenton treatment. • Novel

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Fig. 3 Scheme of the raceway pond reactor (RPR) used in the experiments. (Carra et al. 2015)

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• Avg. UV irradiance of 15 ± 1Wm-2 (winter conditions) measured by a global UV radiometer

• Avg. wastewater T: 26 ± 2 °C.• High degradation achieved (>99% TBZ

and 91% ACTM in 240 min). • Analyses indicated that after the

treatment only three TPs from ACTM were still present in the effluent, while the

others had been removed.

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• García-Fernández et al. (2015) • Disinfection of urban effluents using solar

TiO2 photocatalysis• E. coli and F.solani spores• Compound parabolic collectors (CPC)

reactor• Two CPC mirror titled at 37◦• T= 45 °C• Qair= 60 L/h• TiO2= 100 mg/L• ~99.9

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Fig.4 The 60 L-CPC reactor . Front view (4.5 m2of collector mirrors) with air injection points indicated (a), side view: air injection and DO probe (b), and cooling and heating systems (c)(García-Fernández et al. 2015)

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DYES• Esparza et al. (2011)• Methylene blue (MB) • Natural volcanic ashes (VA) particles and

nanostructured titania supported on volcanic ashes (TVA)

• High-pressure Na vapour lamp (Philips, model 400-W G/92/2) placed 50 cm far from thereactor

• Fixed-bed photocatalytic reactor. (designed and built in the lab)

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• Easy and efficient method to carry out photocatalytic reactions without requiring water filtration post-processing

• Conversions in case of TVA, independent of the flow rate were about 90.3% for 3 h reaction time

• 96.4%.

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Fig. 5. Schematic view of experimental setup (Esparza et al. 2011)

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• Lin et al. (2012) • Methyl orange(MO) • A novel multi-layer rotating disk

reactor(600 rpm)• Four stacked cells • Eight UV-light lamps (4 W each) and an Al

disk (dia. 12 cm) • TiO2 nano-particles coated• Inlet 4×10−5 M MO • At 5 ml/min conversion >95%• High conversion at high flow rate 04/15/2023

Fig.6. Schematic diagram of the MLRDR system (Lin et al. 2012)

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• Byberg & Cobb (2012) • Direct Red 23, 80, and 81, Direct Yellow 27

and 50, and Direct Violet 51• 25 mg/L• Paper embedded TiO2• Equalized for 30 min, run for 24 h• Complete color removal• 80% TOC reduction, toxicity increased

04/15/2023Fig. 7. Photo and sketch of reactor used at ENSIC. (Byberg & Cobb 2012)

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• Pastrana-Martínez et al. (2013) • TiO2 catalysts: large titania sol–gel

nanoparticles (ECT), surface modified titania nanoparticles (m-TiO2) and graphene oxide-TiO2 composite (GOT-3.3)

• Under near-UV/Vis and visible light.• Methyl orange (MO) • Quartz cylindrical reactor(7.5 mL solution)• A Heraeus TQ 150 medium pressure Hg

vapor lamp (visible light a cut-off long pass filter)

• pH 4.4, catalyst loading 0.5 mg/L• Composite (GOT-3.3) quite active, (m-TiO2)

visible light04/15/2023

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• Rasoulifard et al. (2014)• Direct Red 23 (DR23)• UV-LED/S2O8

2-

• Continuous photoreactor (octagonal cylindrical )

• 72 UV-LEDs (1 W each)• S2O8

2- (12.5 mM), dye conc. (20 ppm), current intensity (80%)

Fig. 8 Schematic representation of continuous photoreactor (3.6 W)( Rasoulifard et al. 2014)

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• Li et al. (2014)

• Rhodamine B (RhB)

• Novel double-cylindrical-shell (DCS)

photoreactor

• Monolyer TiO2-coated silica gel beads

• An UV black light lamp (Tokyo Metal BM-

10BLB)

•  t= 12h, RhB= 10 mg/L

• 49.6% and 90.4% in dark and in UV, resp.

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• Higher efficiency, lower energy consumption and better repetitive operation performance

• Promising alternative for recalcitrant decomposition

Fig. 9. Schematic of the TiO2-coated silica gel beads immobilized double-cylindrical-shell (DCS) photoreactor and the photocatalytic system.( Li et al. 2014)

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DRUGS• Wang et al. (2012)•  17-ethinylestradiol(EE2)•  Modified flat plate serpentine reactor

(MFPSR)•  TiO2

• Three lamps (Philips TUV8W)• t= 120 min, TiO2 =0.04 g/L, u= 0.03 m/s,• 98 %

04/15/2023Fig.10. Geometry of MFPSR and flow sheet of the experimental setup (Wang et al. (2012)

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• Pastrana-Martínez et al. (2013)• Diphenhydramine (DP)• ECT, m-TiO2 and GOT-3.3• Quartz cylindrical reactor• Heraeus TQ 150 medium pressure Hg

vapor lamp• T= 25 °C, pH 5.9, 1 g/L catalyst • Under near-UV/Vis irradiation, ECT most

active for the degradation of DP.

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• Rodríguez et al. (2013)• Atenolol (ATL), hydrochlorothiazide (HCT),

ofloxacin (OFX) and trimethoprim (TMP)• Photocatalytic oxidation, ozonation and

photocatalytic ozonation• Borosilicate cylindrical reactor• A porous plate for gas• Black wooden box (50x30x30 cm)• Two 15 W black light lamps• TiO2 ,pH 4, t= 2 h• TPC and TOC removal of 80% and 60%

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TOXIC • Abhang et al. (2011)• Phenol• Three phase fluidized bed type of reactor

(TPFBR)• TiO2 coated on solid silica gel particles• Four lamps of 8 W • P = 1 atm, T = 25 °C• W/o aeration only 50% • 95.27% within 1.5 h

Fig.11 .Schematics of TPFBR Abhang et al. (2011)

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• Shengyong et al. (2012)• Hexachlorobenzene• Quartz photocatalytic reactor• Nano-TiO2 catalyst film on a glass plate• Two 8W UV lamps• 50-mL ice-bathed hexane and acetone

mixture• T=25 to 35 °C, t= 9.5 h, 12 µg , 5 mW/cm2

• ~99%

Fig. 12 .Schematic diagram of the photocatalysis reactor.(Shengyong et al. 2012)

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• Tang et al. (2012)

• Perfluorooctanoic acid (PFOA)

• Water-jacketed cylindrical quartz

photoreactor

• Ferrous sulfate and H2O2

• 9W UV lamp

• PFOA 20.0 _M, H2O2

30.0 mM, Fe2+ 2.0 mM,

pH 3.0

•  95%

Fig. 13. A diagram of the experimental set-up for photodegradation of PFOA. (Tang et al. 2012)

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• Choi et al. (2012)

• Anodized nano-structured TiO2 membrane

• N-nitrosodimethylamine (NDMA) under UV

• Micro-porous tubular-type pure Ti (12-mm

inner dia., 100-mm length) was prepared

for anode materials.

• 99.9 % pure Ta (thickness 0.25 mm,

surface area of 50x50 mm2) as a counter

electrode.

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Graph. 1 Removal of NDMA using RO membrane (conditions: contact time 100 min, temperature 20 ± 1 C, NDMA 1 mg L-1, initial pH 6 ± 0.2, UV intensity 64 W and ozone concentration 9.0 mg L-1). Here, anodized Ti membrane and reverse osmosis are denoted as A-Ti-M and RO,respectively.

• Electrolyte, 1 M KH2PO4 solutions with 0.35 wt% NH4F.

• Electrolyte stirred continuously and anodization was conducted at a constant potential with a DC power supply.

• Lead to the formation of distinct array of TiO2

nanotubes

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• Souzanchi et al. (2013)

• Phenol

• Annular sieve-plate column photoreactor

• Two concentric columns

• TiO2 immobilized on a stainless steel sieve

plate

• 15W UV-A lamp

• t= 6 h, T=35 °C, 0.5 mM phenol

• ~100%

• COD lowered by 95%

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Fig. 14. Details of size and dimensions of the ASCP photoreactor used in the present study in two sections: vertical (a), and horizontal (b). (1) Inner quartz tube; (2) outer Pyrex tube; (3)

15WUV-A lamp; (4) stainless steel sieve plate rings (i.e., TiO2 immobilized support); (5) inlet; (6) outlet.

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Paper Degradation of Reactor Catalyst Light source Operating Conditions

Result

Sraw et al (2013)

Monocrotophos(MCP)

Slurry batchreactor

Aeroxide P-25 and LR grade TiO2

Blue black UV florescent lamps (Philips, 20W)

t= 3 hMCP= 25 ppm P25= 0.5 g/L, pH = 5

84%

García-Fernández et al. (2015)

Escherichia coli and Fusarium solani spores

Compound parabolic collectors (CPC) reactor

Suspended TiO2

Sunlight T= 45 °CQair= 60 L/hTiO2= 100

mg/L

~99.9

Grcic et al.(2015)

Household greywater

Thin film reactor

TiO2 coated

textile fibre

Sunlight t= 4 h 50% organics,

significant reduction in other ingredients

Carra et al.(2015)

Acetamiprid(ACTM), thiabendazole(TBZ)and their transformation products(TPs)

Raceway pond reactor

Fenton(Ferrous iron)

Sunlight, UV irradiance of 15 ± 1Wm-2

pH= 2.8 ± 0.1T=26 ± 2 °Ct= 240 min

>99% TBZ, 91% ACTM,.only 3 TPs remained

PESTICIDES AND OTHER ORGANICS

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Paper Degradation of Reactor Catalyst Light source Operating Conditions

Result

Esparza et al. (2011)

Methylene blue Fixed-bed reactor Natural volcanic ashes (VA), nano-titania supported on volcanic ashes (TVA)

High-pressure Na vapour lamp (Philips,400-W G/92/2)

pH =7T= 20 °C

Degradation 85.6% with VA,96.4% with TVA

Lin et al. (2012) Methyl orange Multi-layerRotating disk reactor

Nano-sized tio2 particles

8 UV-light lamps (4 W each; Winstar Lighting Co., Ltd)

Ambient temperature,600 rpmWithin s of residence time

95% conversion

Byberg & Cobb (2012)

Direct Red 23, 80, and 81, Direct Yellow 27 and 50, and Direct Violet 51

Thin film reactor TiO2 paper

substrate

UV lamp Dye 25 mg/Lt= 24 h

TOC ~80%100 % color removal

Pastrana-Martínez et al. (2013)

Methyl orange Quartz cylindrical reactor

ECT, m-TiO2 and

GOT-3.3

Heraeus TQ 150 medium pressure Hg vapor lamp

T= 25 °C,0.5 g/L catalystpH 4.4

~99%

Li et al. (2014) Rhodamine B (RhB) Novel double-cylindrical-shell (DCS) photoreactor

MonolyerTiO2-coated silica gel beads

An UV black lightlamp (Tokyo Metal BM-10BLB)

t= 12hRhB= 10 mg/L

49.6% and 90.4% in dark aad in UV, resp.

Rasoulifard et al. (2014)

Direct Red 23 (DR23) Continuous photoreactor (octagonal cylindrical)

Potassium peroxydisulfate

72 UV-LEDs of 1 W each

S2O82- (12.5

mM), DR23

(20 ppm),

current I.

(80%)

90%

DYES

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Paper Degradation of Reactor Catalyst Light source Operating Conditions

Result

Wang et al.

(2012)

17-ethinylestradiol(EE2)

Modifiedflat plate serpentine reactor

TiO2 Three lamps (Philips TUV8W)

T=25±2 °Ct= 120 minTiO2 =0.04 g/L

u= 0.03 m/s,Iw = 282 W/m2

98 %

Pastrana-Martínez et al. (2013)

Diphenhydramine (DP)

Quartz cylindrical reactor

Large titania sol–gel nanoparticles, surface modified titania nanoparticlesGraphene oxide-tio2 composite

Heraeus TQ 150 medium pressure mercury vapor lamp

T= 25 °CpH 5.91 g/L catalystt= 240 minDP (3.40x104

mol/L)

~98%

Rodríguez et al. (2013)

Atenolol (ATL), hydrochlorothiazide (HCT), ofloxacin (OFX) and trimethoprim (TMP)

Borosilicate cylindrical reactor

TiO2 Two 15 W black light lamps (Lamp15TBL HQPowerTM

Velleman®)

pH 4t= 2 h

TPC and TOC removal of 80% and 60%

DRUGS

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Paper Degradation of Reactor Catalyst Light source Operating Conditions

Result

Abhang et al. (2011)

Phenol Three phase fluidized bed type of reactor(TPFBR)

TiO2 coated on

solid silica gel particles

Four lamps of8 W

P = 1 atmT = 25 °C t = 2 h

95.27% within 1.5 h

Shengyong et al. (2012)

Hexachlorobenzene Quartz photocatalytic reactor

Nano-TiO2

catalyst films

Two 8W UV lamps

T=25 to 35 °Ct= 9.5 h12 µg 5 mW/cm2

~99%

Tang et al. (2012)

Perfluorooctanoic acid (PFOA)

Water-jacketed cylindrical quartz photoreactor

Ferrous sulfate and H2O2

9W UV lamp PFOA 20.0 _M, H2O2

30.0 mM, Fe2+ 2.0 mM, pH 3.0, 5 h

95%

Choi et al. (2012)

N-nitrosodimethylamine

Membrane reactor

TiO2

nanotubes

UV(64 W)

t= 100 min, T= 20 ± 1 °C, NDMA= 1 mg L-1, initial pH= 6 ± 0.2

~100%

Souzanchi et al. (2013)

Phenol Annular sieve-plate column photoreactor

TiO2 immobilized

on a stainless sieve plate

15W UV-A lamp t= 6 h,T=35 °C,0.5 mM phenol

~100%COD lowered by 95%

TOXIC COMPONENTS

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PROJECT OUTLINE• Improve cooling tower efficiency• Biological fouling • Disinfection of water• Source• Identify the microorganisms• TiO2 • Reactor type• MOC• Light source

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REFERENCES• Abhang R. M., Kumar D. & Taralkar S. V.,

“Design of Photocatalytic Reactor for Degradation of Phenol in Wastewater”, Int. J. Chem. Eng. Appl. 2, 337–341 (2011).

• Choi W.-Y., Lee Y.-W. & Kim J.-O., “Performance of photocatalytic membrane reactor with dual function of microfiltration and organics removal”, 1517–1522 (2013).

• Izadifard M., Achari G. & Langford C. H., “Application of Photocatalysts and LED Light Sources in Drinking Water Treatment”, 726–743 (2013).

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• Lin C.-N., Chang C.-Y., Huang H. J., Tsai D. P. & Wu N.-L., “Photocatalytic degradation of methyl orange by a multi-layer rotating disk reactor”, Environ. Sci. Pollut. Res. 19, 3743–3750 (2012).

• Nakata, K. & Fujishima A., “TiO2 photocatalysis: Design and applications”, J. Photochem. Photobiol. C Photochem. Rev. 13, 169–189 (2012).

• Tang H., Xianga Q., Lei M., Yan Zhub L., & Zouc J., “Efficient degradation of perfluorooctanoic acid by UV – Fenton process”, Chem. Eng. J. 184, 156–162 (2012).

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THANK YOU!