Accepted Manuscript

Title: Fixed Bed Recirculation Type Photocatalytic Reactor

with TiO2 Immobilized Clay Beads for the degradation of
Pesticide Polluted Water

Authors: Abhishek Sraw, Taranjeet Kaur, Yamini Pandey,

Amit Sobti, Ravinder K. Wanchoo, Amrit Pal Toor

PII: S2213-3437(18)30671-7
DOI: https://doi.org/10.1016/j.jece.2018.10.062
Reference: JECE 2748

To appear in:

Received date: 14-8-2018

Revised date: 25-10-2018
Accepted date: 28-10-2018

Please cite this article as: Sraw A, Kaur T, Pandey Y, Sobti A, Wanchoo RK, Toor
AP, Fixed Bed Recirculation Type Photocatalytic Reactor with TiO2 Immobilized
Clay Beads for the degradation of Pesticide Polluted Water, Journal of Environmental
Chemical Engineering (2018), https://doi.org/10.1016/j.jece.2018.10.062

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Fixed Bed Recirculation Type Photocatalytic Reactor with TiO2

Immobilized Clay Beads for the degradation of Pesticide Polluted

Water

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Abhishek Srawa, Taranjeet Kaura, Yamini Pandeya, Amit Sobtib, Ravinder

SC
K. Wanchoob and Amrit Pal Toora,b,*

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a N
Energy Research Centre, Panjab University, Chandigarh-160014, India
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b
Dr. SSB University Institute of Chemical Engineering and Technology, Panjab University,
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Chandigarh-160014, India
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*
Corresponding author’s Email:aptoor@yahoo.com
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Graphical abstract
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Highlights
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  Development of a recirculation type photocatalytic reactor for MCP degradation
 Synthesis of low cost and eco-friendly TiO2 coated clay beads as solid support
 Low electrical energy per order (EEO) proves the economic viability of the reactor
 The catalyst withstands upto 30 cycles without reactivation of the catalyst
 The probable degradation pathway for MCP is proposed

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Abstract

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A recirculation type photocatalytic reactor (RTPR), using ultraviolet radiations (Blue black lamp)

and

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filled with titanium dioxide (TiO2) coated local clay beads, has been designed and used for the
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degradation of extremely toxic and water persistent pesticide Monocrotophos (MCP). Further, the
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present study has made an effort to use low cost, easily available, eco-friendly clay material as the
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support for the immobilization of catalyst for treating the pesticide polluted water by photocatalytic
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degradation. The economic viability of the developed reactor has been addressed in terms of
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Electrical energy per order (EEO) for photocatalytic degradation of MCP, which is found to be very

less compared to the literature values. The effect of various parameters like light conditions,
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recirculation rate, light intensity and initial MCP concentration has been determined for optimization

of the designed RTPR. MCP degradation of 78.57% was obtained with optimum conditions as
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25mg/L MCP, 600 beads and pH 5. In addition to this, the recyclability of the immobilized TiO2

over clay beads in the developed RTPR was studied up to 30 continuous cycles without reactivation
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of catalyst. The mineralization of the MCP was studied using COD and was determined to be

73.75% and the degradation pathway is also proposed. Further, the degradation obeys pseudo first

order kinetics.

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Keywords: Clay Beads, Recirculation reactor, TiO2, Photocatalytic degradation, Monocrotophos

1. Introduction

Increasing population and their elevated demand for food grains, exerts high pressure for the

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increment in gross agricultural production, that intern favors the excessive use of pesticides.

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Pesticides are now the second largest contaminant in drinking water and; are one of the main culprits

behind human and animal toxicity [1]. Monocrotophos is a widely used organophosphorus pesticide

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in India as it quiet cheap and is effective against large variety of insects. But, it is classified as an

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endocrine disrupting chemical and according to WHO and EPA it is a highly toxic class I chemical

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[2, 3]. Photo-catalytic degradation using titanium dioxide (TiO2) has been established as an efficient
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and reasonable means for the removal of varied range of contaminants from water [4-8]. The most
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striking feature of this process is the generation of strong oxidizing radicals that results in

destruction of chemical substrate [9]. TiO2 is the most common, commercially available
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photocatalyst that is widely applied in slurry based photo-reactors because of its low band gap, large
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specific surface area, stable and inert behavior, non-toxic nature and long life span [10]. However

the use of such a nanometric size material in aqueous suspensions requires an additional or
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somewhat complicated recovery operation [11]. This separation process is sparingly critical to evade
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economic loss due to catalyst washout and its introduction in treated water [12].

Alternatively the use of binders for the catalyst immobilization onto a suitable solid support matrix
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were used to solve the problem of separation and reuse [13, 14]. Wide-ranging researches have been

stated for the immobilization of TiO2 on to the photochemically stable but less durable substrates

such as perlite granules [15], silica sheets [16] , thin films [17], quartz wool [18], activated carbon

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[19], glass beads [20, 21], glass plates, cement slabs, alginate balls [22], stainless steel plates [23],

magnetite [24], zeolites [25], and silicates [26] etc; either with the help of catalyst binders or by

directly mixing them with the powdered substrate in the form of suspensions. These immobilizing

fibers shows truncated resilience as the deposited TiO2 crystals may lessen-off over reaction time,

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resulting in a loss of photoactivity with increased pressure drop in the reactor [27]. Moreover, the

selection of binder is a typical process, as it may differ significantly in accordance to the purpose of

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its application. Also, it will considerably add up to the cost for the large scale applications.

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Mixing of catalyst with the powdered substrate and its conversion into solid structures [6] is also not

a good approach, because in the process of photo-degradation, light radiations can activate only the

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open surface (top layer) of the immobilized catalyst. Therefore, fixing of TiO2 on the surface of
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porous structures using low cost methods such as sol-gel dip coating [28], thermal treatment [29] and
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wet impregnation[30] etc, has attracted vast interest, owing to the increase in oxidation potential and
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surface area of the catalyst [6, 31-33]. It was also testified that the nature of support material have a
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strong impact over the adsorption characteristics and decomposition rate of several contaminants
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[34].

Supporting material should have strong and durable bonding of the surface with the catalyst in
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addition to high specific surface area, effortless availability, good separability and environmental
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friendly nature [35]. Portland cement modified using TiO2 have also been examined by few

researchers for the degradation of phenol [36], insecticide imidacloprid degradation [37],
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development of self cleansing building surfaces [38], and degradation of dye [39] etc. Mixture of

cement [40], POP with TiO2 [41], was tested for degradation but the post separation problem

persists.

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Local clay is one of the materials exhibiting all the required qualities. Different types of processed

clays such as laponite [6], purified clay [42], and montmorillonite [43], in suspension along with

TiO2, have been used for the photo-catalytic degradation of pesticides and other organic pollutants;

however, the application of local pottery clay for the immobilization of catalyst has not been

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explored much [41]. Clay along with fly ash and foundry sand has been used for immobilization

[44]. Fuller’s Earth and Foundry sand beads have also been examined for immobilization of TiO2 to

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carry out degradation of Phenazone [45]. In India, for the last so many centuries, water was used to

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store in clay pots to keep it cold and clean. Clay have good adsorption, absorption and show

catalysis because of the physico-chemical properties like large surface areas, great ion exchange

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capacity and active broken edge metal-oxygen bonds (M-O-) [46].

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Hence, the present work is aimed to develop an easily available, recyclable, reusable, bio-degradable
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and eco-friendly solid support (clay) for the application in photo-catalytic degradation processes. An
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energy efficient recirculation type photocatalytic reactor (RTPR) has also been developed to test the
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applicability of the prepared TiO2 clay beads. Monocrotophos (MCP) has been taken as a model
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pesticide compound due to its wide application, toxic nature and water persistency. The impact of

various parameters such as light conditions, recirculation rate, light intensity and initial MCP
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concentration on degradation rate of MCP were explored. Electrical energy per order (EEO) was used

to compute the electrical energy required for the degradation using RTPR. Lastly, the TiO2-coated
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clay beads immobilized RTPR was compared with the fixed bed photoreactors reported in literature
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for the degradation of various pesticides.

2. Experimental

2.1 Material and Chemicals

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Technical grade pesticide MCP having purity 78% was received from Markfed Agro Chemicals,

India. Double distilled water was used for preparing all the experimental solutions. Common clay

used for the pottery, was obtained from the local pot makers. Aeroxide P25 (TiO2) having anatase to

rutile ratio of 80:20, average particle size of 30 nm with 97% purity, BET surface area of 50 m2/g

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was obtained from Aeroxide (China) Co., Ltd.

2.2 Preparation of support beads and their coating

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For preparing solid support as spherical beads, semi-solid mixture of clay was prepared in water.

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The detailed method of preparation has been reported in our previous study [41]. The images of the

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prepared clay beads (plain, surface modified and TiO2 coated) are given in fig 1.

(i)
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Further the immobilization of TiO2 over clay beads was done through simple heat attachment
(ii)
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method as reported in our earlier paper [41].
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The mesoporous nature of clay beads was confirmed by the type IV isotherms [47] obtained by BET
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analysis. The average surface areas for bare and TiO2 coated clay beads were found to be 14.011 and
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16.910 m2g-1respectively.
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2.3Recirculation type Photo-catalytic Reactor

A novel RTPR was designed for the photocatalytic study that can operate with TiO2 coated clay
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beads, as represented in fig. 2. The photoreactor comprises three concentric cylindrical jackets of

borosil glass (height-575mm, inner diameters of the central, middle and external glass tubes: 30mm,
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55mm & 78mm respectively) and a blue black UV lamp (Philips, Power-20 W, λmax-365 nm,

length-600 mm, diameter-28 mm) inserted axially within the central tube. The diameter of the three

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jackets was thus selected to have a gap of 12.50 mm between the central and middle jacket, for the

filling of TiO2 coated clay beads.

The reactor was filled with around 600 TiO2 coated clay beads (1121.7 g), having average diameter-

12.46 mm and total TiO2 loading 26.68 g. The outer jacket of reactor was designed for the

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circulation of cooling water. The outermost surface of the reactor was covered with a UV reflective

aluminium foil to prevent the energy loss. The working volume of the developed photocatalytic

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reactor is 1000 mL. A local submersible pump attached with a control valve was used for the

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continuous circulation of pesticide solution through the reactor. An overflow pipe was also attached

with the valve that helps in vigorous mixing of the pesticide stock solution.

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2.4 Experimental Procedure N
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Two liter of 25 mg L-1 MCP solution was filled into a reservoir, and circulated continuously through
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the RTPR using a manually regulated submersible pump. All reactions were performed under

controlled temperature (25±1oC) and at natural pH of the MCP solution (pH 5). A blank experiment
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was performed by circulating the prepared solution under dark and UV irradiations through RTPR
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filled with uncoated clay beads, to check their adsorption or degradation characteristics. Thereafter,
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photocatalytic reactions were carried out over TiO2 coated clay beads. Appropriate aliquots (3.0 mL)

of samples were withdrawn at an interval of 1 h up to 7 h using 5 mL syringe and analyzed for the
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concentration using UV-visible spectra against the calibration curve (concentration vs absorbance)

of MCP solution. Absorbance spectra of MCP were recorded in the wavelength rage of 200-800 nm
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and the λmax was observed to be 292 nm.

2.5Analytical methods

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Morphological structure of the prepared beads was determined using scanning electron microscope

(SEM) (model: JSM-6510 LV; JEOL, Japan). Nitrogen adsorption-desorption was carried out using

an autosorb Brunauer Emmett Teller (BET) apparatus (Quantum Chrome NOVA 20400E, USA) for

the determination of BET surface area. Further, the elemental analysis was obtained by energy-

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dispersive x-ray spectroscopy (EDS) (INCAx-act, Oxford Instruments, UK). To detect the

degradation of MCP, the respective absorption spectra were analyzed using UV-Vis

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spectrophotometer (Shimadzu UV 2450, Japan) operated in the wavelength range of 200-800nm.

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COD Vario photometer, Tintometer GmbH (Germany) was used for the measurement of COD.

Photometer/ radiometer (Solar Light Co. PMA2100, USA) was used to measure the intensity of UV

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light.

3. Results and Discussion N

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3.1Adsorption, photolysis and photocatalytic degradation of MCP
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The degradation of MCP (25 mgL-1) was studied in the RTPR under different experimental
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conditions using bare clay beads under dark & UV light, and TiO2 coated clay beads under dark &
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UV irradiations. The results show that even a 7 h long contact with the bare clay beads under dark

shows only 2.6% decrease in MCP concentration, thus confirm poor adsorption of MCP molecules
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over the surface of clay beads. Whereas, comparatively higher decrease in concentration (7.14%)

under UV light may be attributed due to the UV assisted photolysis of MCP [48]. When the reaction
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was carried out under dark using TiO2 coated CL beads, slight decrease in the concentration of MCP

was observed due to the adsorption of pesticide over the surface of TiO2 [49]. Due to very low
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adsorption, the factor was not considered for further studies. After 7 h UV irradiation, the RTPR

with TiO2 coated clay beads demonstrated a degradation of 78.57% for MCP. Generation of

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electron-hole pairs due to activation of TiO2 surface by the UV radiations [50] could be the possible

reason behind the observed trend.

The UV-Vis spectra of the photocatalytic degradation of MCP under UV light using developed

RTPR is presented in fig. 3. MCP solution gives the main absorption peak at 292 nm, which starts

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decreasing gradually on reaction with TiO2 and shows a blue shift, which was also observed by

Sivagami et. al. [1]. The variation in the peak intensity and shape confirms that the developed

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photocatalytic reactor had degraded the complex MCP effectively rather than converting it to

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another form.

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3.2 Effect of recirculation rate on the photocatalytic degradation

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The two main factors which influence the photoactivity of the catalyst in fixed bed reactors are the
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contact time between the pollutant particles & the catalyst surface; and appropriate recirculation of
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the solution through the reactor [51]. To assure optimum mass transfer, the degradation of MCP was

optimized by varying the recirculation rates of the solution (100, 200, 400, 600 and 800 mL min-1)
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through the developed RTPR and obtained results are given in fig 4. On increasing recirculation rate
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from 100 to 400 mL min -1 degradation was observed to increase from 57.79% to 78.57% , however
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with more increase in recirculation rate up to 800 mL min-1 degradation was observed to decrease

upto 66.23%. The same trend was noticed with apparent rate constant, with the highest value (3.92 x
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10-3 min-1) obtained at the recirculation rate 400 mL min-1. Low recirculation speed may not allow

the optimum catalyst – pesticide contact and leads to low degradability of MCP at recirculation rates
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less than 400 mL min-1. However, on increasing the recirculation rate (up to 400 mL min-1), more &

more MCP molecules come across the UV active TiO2 surface and degrades by the so generated

reactive hydroxyl (●OH) radicals [52]. Increase in solution recirculation rate above 400 mL min-1

may further decrease the contact time between MCP particles and TiO2 surface, and thus resulted in
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low photocatalytic degradation. Therefore a constant (400 mL min-1) recirculation rate was

maintained in this study to obtain a steady state resistance time and to avoid the removal of catalyst

from the supporting material by turbulence [53].

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3.3 Effect of varying the size of clay beads

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Size of the beads have a very important role to play in any reaction. Decrease in the bead size results

in higher surface area which causes more active sites to be available for photoactivity.

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Effect of three different sizes of beads i.e. 5.87, 12.42 and 16.74 nm were studied on MCP with
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number of beads of each size decided by keeping the catalyst loading constant to 1.5g. As shown in
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fig 5 the rate of degradation increases with decrease in bead size upto 12.42 nm but, on further
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decrease to 5.87 nm degradation was found to decrease. This decrease could be possibly because of
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poor catalyst holding by the bead surface on decreasing the size beyond a particular value.
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3.4 Effect of UV light intensity

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TiO2 coated clay beads are solid and opaque in nature, hence do not let the UV light pass through

them. The developed RTPR has TiO2 coated clay beads filled in such a way that there one side will
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always be opposite to the UV light source (fig. 2) and consequently receive UV light by the

reflection from aluminium foil and illumination of the MCP solution only. To check for the optimum
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photocatalytic activity of the developed reactor, two different sets of reactions were performed; first

with a single axially inserted UV tube (20 W) and second by placing three extra-tubes surrounding

the reactor (20*4 W). However, the results obtained do not shows much effect of additional light

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source on the degradation efficiency of the developed reactor, as only 2% increment in the rate of

degradation was obtained by the additional UV light (fig.6).

Many researchers have observed the dependent relationship between photocatalytic reactions on the

radiant flux (ɸ), which further keeps a check over the holes available during the electron-hole pair

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formation [54-56]. However in case of TiO2, the number of conduction-band electrons is much

higher than the photo-generated valence-band holes. At high intensity, saturation of the surface

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activation of TiO2 takes place which results in the mass transfer limitations in the adsorption-

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desorption phenomenon and finally leads to limit the effect of increasing light intensity [27].

Therefore, the results ]attained in this study show that the axially inserted UV lamp in the developed

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RTPR is more enough to illuminate the TiO2 coated clay beads sufficiently.
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3.5 Kinetic Studies of MCP degradation
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In case of photocatalytic degradation of organic pollutants in water, Langmuir–Hinshelwood (L–H)

kinetic model is considered to be highly suitable to study the variation in degradation rate with the
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concentration of pollutants [7]. During photocatalysis, the reaction kinetics may influence by the
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formation of various intermediates [57], therefore calculation were performed at the beginning of
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reaction. L-H model as a function of initial concentration can be expressed as:

𝑑𝐶𝑜 𝑘 𝐾𝐶
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𝑟 𝑜
𝑟= − = (1+𝐾𝐶 )
(1)
𝑑𝑡 𝑜
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where ro (mg L-1 min-1) is the initial rate of MCP degradation, Co (mg L-1) is the initial MCP

concentration, kr is the reaction rate constant and K is the equilibrium adsorption constant. At low

substrate concentration, KCo can be consider to be much less than 1, therefore neglected in the

denominator. Thus equation (1) can be expressed as apparent first order kinetic equation:

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 𝐶
ln( 𝑜 ) = 𝑘𝑟 𝐾𝑡 = 𝑘𝑎𝑝𝑝 𝑡 (2)
𝐶

Where, kapp (min-1) is the apparent rate constant for the photocatalytic degradation of MCP.

As shown in fig. 7, the first order rate constant decreased from 5.35*10-3 min-1 to 3.02*10-3 min-1

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with the increase in MCP concentration from 15 to 35 mg L-1. Following the same trend, 20% lesser

degradation was observed at higher concentration (35 mg L-1). The observed relation is supported

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by the fact that higher concentrations reduce the photoactive surface area of the catalyst by the

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excessive adsorption of pollutant; thus creates a light barrier and diminish the generation of ●OH [3,

8, 58, 59].

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The dependence of rate of MCP degradation on the initial concentration could be expressed by the

inverse of equation (1) as:

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1 1 1 1
= + (3)
𝑟𝑜 𝑘𝑟 𝑘𝑟 𝐾 𝐶𝑜
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The plot of 1/ro versus 1/Co gives a linear variation; therefore confirm the L-H relationship for the
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MCP degradation in the RTPR, as shown in fig. 8. From the intercept and slope of the straight line

having a regression coefficient of R2 = 0.977, the values of kr and K were determined as 0.21 mg L-1
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min-1 and 0.0291 L mg-1, respectively. The obtained values are comparable with our previous study
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(kr 0.847 mg L-1 min-1; K 0.02 L mg-1), which was carried out on hemispherical photocatalytic slurry

reactor for the degradation of MCP under UV light [7].

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3.6 Chemical Oxygen Demand (COD) analysis

The extent to which the mineralization or degradation of an organic species occurred could be

reflected in terms of COD [60], therefore, photocatalytic degradation of MCP was also studied in

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terms of Chemical oxygen demand. The comparative graph between the percentage degradation and

COD removal of MCP under UV light is represented by fig. 9. The obtained curves show that the

photo-degradation and mineralization of MCP goes hand in hand with respect to the reaction time.

On completion of the reaction the values obtained for the degradation and mineralization of MCP

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were 78.57 % and 73.75% respectively, and confirm the breakdown of the complex MCP to smaller

organic compounds.

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3.7 Probable Degradation Pathway

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On the basis of this study a probable pathway of degradation of MCP using TiO2 under UV

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radiations was prepared as shown in fig. 10.

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MCP undergoes fragmentation and breakdown in smaller compounds when it reacts with the OH•
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produced by the activation of TiO2 under UV light. The breakdown occurs in two possible ways;
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either to phosphate compound such as Trimethyl phosphate, or to nitrogenous compound such as N-

formyl-N-methyl-formamide. In both cases, these intermediate compounds shall further breakdown

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to simpler non toxic molecules such as NO3-, PO43-, CO2 and H2O etc, by means of hydrolysis and
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redox reactions.
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3.8 Recycle and durability studies of TiO2 coated clay beads using RTPR
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The major advantages of fixed bed reactor is that the cost of catalyst recovery is reduced and catalyst

can be reused. The durability and physio-chemical nature of the support material determines the
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commercial application of any fixed bed reactor. Generally, in the case of slurry mode, activity of

the catalyst reduces after five/six runs [37] and requires reactivation of catalyst by washing with a

solvent, oven drying & calcination at high temperature etc, before each reaction [61]. Such processes

are time consuming and practically unviable for large scale applications. Thus, in the present study,
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continuous cycles have been performed under UV light using RTPR filled with TiO2 coated CL

beads, for treating two liter (25 mg L-1) MCP solution a time. As shown in fig. 11, about 30 cycles of

7 h each have been performed under UV light, with highest 78.57% and lowest 70.11% degradation

of MCP in the 1st and 30th cycle respectively. The average degradation for the 30 cycles was

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calculated to be 75.78%, which shows that the developed RTPR is efficient enough and has high

repetitive performance. The morphology of the TiO2 coated beads before and after 30 cycles is

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shown in fig 12 using SEM-EDS spectral images. Fig. 12 (a) shows the smooth surface of clay due

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to the presence of consistent TiO2 coating, whereas the resulting peaks demonstrate the richness of

Ti & O2 particles. A little loss of TiO2 in terms of surface roughness can be seen in fig. 12 (b);

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however the respective EDS spectra confirm the presence of strongly bonded TiO2 particles.

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The SEM images of plain and TiO2 coated clay beads are given in fig 13 from which it is observed
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that a prominent layer of TiO2 coating is formed on the surface of clay bead with an average
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thickness 60.45 μm, which enables the photoactive characteristic of prepared beads for the
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degradation of organic pollutants.

3.9 Electrical energy consumption of the developed RTPR

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Field scale applications of fixed bed photocatalytic reactors and their economic viability for the
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degradation of polluted waste water, depends a lot on their electrical energy consumption.

Therefore, the obtained degradation data were analyzed in terms of electrical energy consumption
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per order (EEO) figure-of-merit, where EEO (kWh m-3 order-1) is defined as the as the number of

kilowatt hours (kWh) of electrical energy required to reduce the concentration of a pollutant by 1

order of magnitude (90%) in 1 m3 of contaminated water (by Photochemistry Commission of the

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International Union of Pure and Applied Chemistry) and expressed for batch type reaction by the

following equations [62]:

𝑃∗𝑡∗1000
𝐸EO = 𝐶𝑖 (4)
𝑉∗60∗log( )
𝐶𝑓

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38.4∗𝑃
𝐸EO = (5)
𝑉∗𝑘1 ′

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Where, P is the power input (kW) from the wall to derive UV lamp(s)

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t is the irradiation time (min)

V is the volume (l) of solution in the reactor

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Ci-C fis the initial & final concentrations of the pollutant
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k1’ is the pseudo-first order rate constant (min-1)
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38.4 is the conversion factor 1000 x ln (10)/60

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From equation 5, the value of EEO by the developed RTPR for the degradation of 25 mg L-1 MCP, at
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optimized parameters, was calculated to be 0.09796 x 103 kWh m-3 order-1, which is significantly

less than the values reported in the literature for the photocatalytic degradation of pesticides using
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immobilized photoreactor [Table 1]. The lower value of EEO signifies the outstanding efficiency of

developed RTPR for the degradation of pesticide polluted water using TiO2 immobilized clay beads.
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3.10 Comparison of developed clay bead support and RTPR with the available literature
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To establish the effectiveness and efficiency of the developed system, a comparison with the

available literature on catalyst supports and photocatalytic reactors has been done. Catalyst

immobilization over solid supports has been studied earlier also. Un-economic support materials

such as polystyrene beads [63], quartz wool [18], glass beads [20, 64] and glass slides [65] etc have
15
been tested for the degradation of organic pollutants. Moreover, there is another problem of safe

disposal of such non bio degradable materials after use. Non porous supports such as steel plates

[23] do require strong binders and possess very weak catalyst holding capacity. Porous materials

such as zeolites and silicates [25, 26, 66], are widely considered as an option as they possess large

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surface area and chemical stability, but has poor recyclability. Whereas, in this work, locally

available clay (without any binder) is used as a support material for TiO2 which is readily available,

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economical, porous as well as eco-friendly. The developed photoreactor for these clay beads is

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highly energy efficient (Table 1) and cost effective as it is made up of glass & contains no costly &

sophisticated peristaltic pumps [67, 68]. Moreover, efficient degradation of MCP (75.78%) up to 30

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continuous cycles without reactivating the catalyst adds up to the adequate application of the system.

4. Conclusion
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A recirculation type photocatalytic reactor (RTPR) has been developed and used successfully for the

degradation of extremely toxic pesticide i.e. MCP under UV using TiO2 coated; low cost, eco-
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friendly and easily available local clay beads. The developed reactor (RTPR) has shown promising
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efficiency of about 79% for the degradation of high concentration of MCP with remarkably low

energy consumption of EEO=0.09796×103kWh m-3 order-1, which established the economic viability
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of the developed reactor. Further, the recyclability of the immobilized TiO2 over clay beads up to 30
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cycles without reactivation of the catalyst proves the acceptability of the developed reactor. The

photocatalytic degradation of MCP follows pseudo first order kinetics.

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Declaration of Interest

None

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Acknowledgement

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We would like to acknowledge the following for support and help:

TEQIP-II, TEQIP-III and PURSE Grant-II for providing financial support. The instrumental

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facilities provided by Central Instrumentation Laboratory (CIL), Punjab University, Chandigarh.

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Central Research Facilities provided by IIT Ropar (Punjab) for carrying out the SEM/EDS analysis.

Markfed Unit, Mohali (Punjab) for providing the sample of pesticide (MCP). Aeroxide (China) for

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donating a free sample of P25 TiO2.
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A
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References
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[1] K. Sivagami, R. R. Krishna, T. Swaminathan, Studies on photocatalytic degradation of

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monocrotophos in an annular slurry reactor using factorial design of experiments, Journal of Water

Sustainability 1 (2011) 75-84.

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 (i) (ii) (iii)

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Figure 1 Images of prepared clay beads (i) Plain (ii) Surface modified (iii) TiO2 coated clay bead.

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Figure 2 Experimental setup of RTPR for photocatalytic degradation experiments.
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 0.7
Initial
0.6 30min
60min
0.5
90min
Absorbance

0.4 120min
150min

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0.3
180min
0.2

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0.1

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200 250 300 350 400

Wavelength (nm)

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Figure 3 UV-Visible spectra of MCP degradation under UV light (MCP 25 mg L-1, 600 beads, UV

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30 W m-2, recirculation rate 400 mL min-1, pH 5±0.5, T 25±1oC)
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 100 4.5
90 Degradation %
4
rate constant

Rate constant (x 10-3 min-1)

80 3.5
70
Degradation (%)

3
60
2.5
50
2
40
1.5

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30
20 1
10 0.5

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0 0
100 200 400 600 800
Recirculation rate (mL min-1)

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Figure 4 Effect of recirculation rate on the degradation of MCP (MCP 25 mg L-1, 600 beads, UV 30

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Wm-2, pH 5±0.5, T 25±1oC)

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Figure 5 Effect of different sizes of clay beads on the degradation of MCP (MCP 25 mg/L, pH 6,

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temp 25±1°C, UV 30 W m-2, reaction time 5 h)
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 1
0.9
0.8
0.7
0.6
C/Co

0.5 1 UV
0.4
4 UV
0.3
0.2

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0.1
0
0 100 200 300 400 500

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Time in min

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Figure 6 Effect of UV light intensity on the degradation of MCP (MCP 25 mg L-1, 600 beads, pH

5±0.5, T 25±1oC, recirculation rate 400 mL min-1).

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 100 6
Degradation %
90
Rate constant 5

Rate constant (x 10-3 min-1)

80 5.35
70
Degradation (%)

4.53 4
60
3.92
50 3.49 3
40 3.02

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2
30
20
1
10

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0 0
15 20 25 30 35
Initial concentration of MCP (mg L-1)

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Figure 7 Degradation of MCP at different initial concentrations using RTPR(MCP 2 l, 600 beads, pH

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5±0.5, T 25±1oC, UV 30 W m-2, recirculation rate 400 mL min-1).
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 18
16 y = 163.94x + 4.7843
14 R² = 0.9803
1/ro (mg-1 L min)

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6
4

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2
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0.02 0.03 0.04 0.05 0.06 0.07

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1/Co (L mg-1)

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Figure 8 Plot showing Langmuir-Hinshelwood relationship

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 90
% Degradation/Mineralization 80
70
60
50
40 COD
30 Absorbance

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10

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0
0 100 200 300 400 500
Time (min)

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Figure 9 Plot showing % degradation and mineralization of MCP in terms of COD removal with the

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increase in irradiation time under UV light (MCP 2 l, 25mg L-1, 600 beads, pH 5±0.5, T 25±1 oC,

UV 30 W m-2, recirculation rate 400 mL min-1).

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Figure 10 Possible breakdown pathway of MCP degradation by UV activated TiO2
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 100
90
80
Degradation (%)

70
60
50
40
30

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20
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0

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1st 3rd 5th 7th 10th 13th 15th 17th 20tth 23rd 25th 27th 30th

Number of Cycles

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Figure 11 Recycling of TiO2 coated clay beads in terms of degradation of MCP using RTPR and UV

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light (MCP 2 l, 600 beads, pH 5±0.5, T 25±1oC, UV 30 W m-2, recirculation rate 400 mL min-1).

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 (a)

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(b)

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Figure 12 SEM-EDS analysis of TiO2 coated clay beads (a) before recycle and (b) after 30 recycles
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Figure 13 SEM images of plain (i) and TiO2 coated clay bead (ii)

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Table 1 Electrical energy consumption of different fixed bed reactors reported in literature for the

pesticide polluted waste water treatment

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Name of Catalyst used/ Power (kWh) Volume kapp EEO No. of Reference

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Pesticide Immobilizing Support treated (l) (x 10-3 min -1) (kWh/m3/order) cycles

MCP TiO2 0.02 2 3.92 0.09796 x 103 30 Present Study

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/ Clay Beads

2,5-DCP TiO2 0.03 0.7 3.443 0.478 x 103 1 [69]

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/Stainless Steel

Alachlor TiO2/Reactor walls 0.03 4 N 0.0145 0.00695 x 103 1 [68]

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Fenitrothion TiO2/Reactor walls 0.03 4 0.0222 0.01297 x 103 1
M

Fenamiphos ZnTNPc 0.375 0.025 8.5 6.776 x 104 3 [70]

/Mesoporous Silica
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ZnTPhOPc 0.375 0.025 3.0 19.2 x 104 1

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/Mesoporous Silica

ZnTTMAEOPcI 0.375 0.025 8.1 7.11 x 104 3

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/Mesoporous Silica

Imidacloprid TiO2 0.12 0.25 0.035 0.526 x 103 1 [65]

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/Glass Slides

Thimethoxam TiO2 0.12 0.25 0.019 0.970 x 103 1

A

/Glass Slides

Clothianidin TiO2 0.12 0.25 0.021 0.878 x 103 1

/Glass Slides

40
 A
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