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Separation and Purication Technology 95 (2012) 172179

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Separation and Purication Technology


journal homepage: www.elsevier.com/locate/seppur

Degradation of methyl parathion using hydrodynamic cavitation: Effect of


operating parameters and intensication using additives
Pankaj N. Patil, Parag R. Gogate
Chemical Engineering Department, Institute of Chemical Technology, Matunga, Mumbai 400 019, India

a r t i c l e

i n f o

Article history:
Received 5 January 2012
Received in revised form 13 April 2012
Accepted 18 April 2012
Available online 7 May 2012
Keywords:
Methyl parathion
Hydrodynamic cavitation
Intensication
Additives
Kinetic analysis

a b s t r a c t
Methyl parathion (C8H10NO5PS), which is an organophosphorus pesticide that has been widely used as an
agricultural insecticide in India, can result in signicant water pollution due to its biorefractory nature
and longer stability. In the present work, degradation of methyl parathion has been investigated using
hydrodynamic cavitation reactors with possible intensication studies using different approaches. Effect
of different parameters like operating pressures (18 bar), operating temperatures (sets of intense cooling, moderate cooling and uncontrolled operation) and initial pH (2.28.2) has been investigated initially.
Under the optimized set of operating parameters, the effect of process intensifying parameters like
hydrogen peroxide (25200 mg/l), carbon tetrachloride (16 g/l) and Fentons reagent (H2O2:FeSO4 ranging from 1:1 to 1:6) on the extent of degradation has been investigated. Effect of radical scavengers like
sodium bicarbonate and tert-butanol on the extent of degradation was also investigated with an objective
of establishing the controlling mechanism. More than 90% degradation of methyl parathion was achieved
using combination of hydrodynamic cavitation with H2O2 and Fentons reagent. TOC analysis at optimum
conditions was also performed to quantify the extent of mineralization and it has been observed that a
maximum of 76% TOC reduction is obtained. The study has also focused on the determination of intermediate products formed during the degradation. It has been established that hydrodynamic cavitation in
the presence of additives can be effectively used for complete removal of methyl parathion.
2012 Elsevier B.V. All rights reserved.

1. Introduction
The pesticide and allied chemical industries are considered to
generate wastewaters containing toxic and non-biodegradable
compounds that remain in the environment even after conventional wastewater treatment approaches [1]. Existing wastewater
treatment methods such as adsorption on activated carbon, extraction, and chemical oxidation suffer from limitations such as limited
applicability and low efciency [2,3], thus imparting the need of
research into alternative treatment techniques. A promising way
to achieve the degradation of biologically and chemically stable
molecules is by application of advanced oxidation processes
(AOPs) based on the in situ production of hydroxyl radicals
under mild experimental conditions [4,5]. Among the AOPs, the
techniques used are: processes based on hydrogen peroxide
(H2O2 + UV, Fenton, photo-Fenton and Fenton-like processes), photocatalysis, processes based on ozone (O3, O3 + UV) and electrochemical processes [68]. These processes are often limited by
mass transfer barriers and/or catalyst poisoning which results in

Corresponding author. Tel.: +91 22 3361 2024; fax: +91 22 3361 1020.
E-mail address: pr.gogate@ictmumbai.edu.in (P.R. Gogate).
1383-5866/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.seppur.2012.04.019

lower effectiveness for wastewater treatment applications. Cavitation also results into formation of hydroxyl radicals and cavitation
based treatment approach can also be classied as an advanced
oxidation process. Cavitation can be generated by passage of ultrasonic energy in the liquid medium or by making use of the alternations of velocity/pressure in the hydraulic systems.
An intensive passage of ultrasonic energy through the liquid
medium results in the liquid bulk being pulled apart and pushed
to local points; causing drastic pressure differences, locally, which
are dynamic too. Such conditions can trigger the generation, subsequent growth and collapse of the cavities, releasing large magnitudes of energy over a very small area resulting in very high
energy densities and the overall process is described as cavitation.
Cavitation occurs at millions of locations in the reactor simultaneously and generates conditions of very high temperatures (in
the range 100015,000 K) and pressures (in the range 500
5000 bar) locally with overall ambient conditions. Cavitation generated by use of ultrasound has been referred to as acoustic cavitation. Hydrodynamic cavitation (HC) is another type of cavitation in
which similar effects can be generated using hydraulic means in a
much more energy efcient manner. In this case cavitation is produced by pressure variations, which can be obtained using geometry of the system creating velocity variation. Common devices
used for this purpose are the orice plates and venturi. Both the

P.N. Patil, P.R. Gogate / Separation and Purication Technology 95 (2012) 172179

types of cavitational reactors i.e. ultrasound based sonochemical


reactors and hydrodynamic cavitation reactors have been used
for wastewater treatment [5,912]. Cavitation can also be combined with advanced oxidation techniques or intensied using different additives to result in enhanced degradation of pollutants.
Different types of additives that can be added into the system
are H2O2, TiO2, coal ash, activated carbon supported TiO2, Fe (Fenton), salts (NaCl, Na2SO4), chloroalkanes, CuSO4, NiSO4, etc. These
additives can be used in combination with cavitational reactors
for intensication [13,14]. The present work will deal with the
application of hydrodynamic cavitation reactors for wastewater
treatment contaminated with methyl parathion, which is an
important pesticide most commonly used in India.
Methyl parathion is used to control boll weevils and many biting insects of agricultural crops, primarily cotton. Methyl parathion, known as the cotton poison, is applied in elds
containing crops such as cotton, corn, apples, soybeans, rice, wheat,
peaches, alfalfa, sunower, and sweet corn [15]. It readily degrades
to methyl paraoxon in human body which acts as acetyl cholinesterase inhibitor creating problems with nervous systems [16].
There have been some reports on degradation of methyl parathion
using cavitation or in general advanced oxidation processes. Wang
et al. [17] have studied the sonocatalytic degradation of methyl
parathion in the presence of micron-sized and nano-sized rutile
titanium dioxide catalysts and observed that sonocatalytic performance of micron-sized TiO2 powder is better than that of nanosized rutile TiO2 powder. Wang et al. [18] have investigated the
degradation of methyl parathion using anatase titanium dioxide
powder as heterogeneous sonocatalysts. The degradation of methyl
parathion was shown to depend on the amounts of anatase TiO2
catalysts, initial concentrations of methyl parathion, acidity, temperature, ultrasonic frequency and intensity.
Moctezuma et al. [19] have performed the photocatalytic degradation of methyl parathion and also identied the reaction pathways and intermediate reaction products. Shriwas and Gogate
[16] have worked on ultrasonic degradation of methyl parathion
in aqueous solutions and investigated the effects of presence of different process intensifying additives like TiO2, CCl4, H2O2 and Fenton type chemistry on the degradation. Fan et al. [20] have
investigated parathion degradation and its intermediate formation
by Fenton process whereas Yao et al. [21] have studied the mechanism and kinetics of parathion degradation under ultrasonic irradiation. Arapoglou et al. [22] have performed the detoxication of
methyl-parathion in aqueous solutions by using electrochemical
oxidation. Overall it can be said that methyl parathion degradation
has been investigated in details using different advanced oxidation
processes including the ultrasound induced acoustic cavitation
based reactors, however, use of hydrodynamic cavitation reactors
for parathion degradation has not been observed to the best of
our knowledge. The present work deals with the use of hydrodynamic cavitation alone and in combination with different additives
with an objective of process intensication, for the degradation of
methyl parathion.

2.2. Experimental set-up


The hydrodynamic cavitation set-up used in the present study
is schematically shown in Fig. 1. It essentially consists of a closed
loop circuit including a holding tank, a reciprocating pump (power
rating 1.1 kW), control valves at appropriate places, orice plate
and pressure gauges. The suction side of the pump is connected
to the bottom of the tank and the discharge from the pump
branches into two lines. The rst main line consists of an orice
plate having the specications of diameter 25 mm with a 2 mm
hole inside, which acts as a cavitating device. The exact geometric
details of the orice have also been provided in Fig. 1. A by-pass
line is provided to control the liquid ow through the main line.
Control valves and pressure gauges are provided at appropriate
places to control the ow rate through the lines and to measure
the pressures respectively.
2.3. Experimental methodology
For a typical experiment of degradation, 4 l aqueous solution of
desired concentration of methyl parathion was placed in feed tank.
The pump was then started and inlet pressures were adjusted by
controlling the ow through by-pass line using the by-pass valve.
The temperature was kept constant by circulating water through
the jacket of tank. Experiments were performed up to 120 min of
reaction time and samples for analysis were removed at regular
time intervals. Initially, the effect of initial concentration of the
pollutant has been investigated over the range of 2050 ppm. To
study the effect of inlet pressure on degradation, the pressure
was varied from 1 to 8 bar. In the case of experiments related to
different operating temperatures (32, 35 and 39 C), the temperature of feed was kept constant at desired value by changing the

2. Experimental
2.1. Materials
The commercial grade methyl parathion was obtained from
Dhanuka Industries, Haryana. Carbon tetrachloride was obtained
from Central Drug House (P) Ltd., New Delhi. All other chemicals
used in the work were purchased from S.D. Fine-Chem Pvt. Ltd.,
Mumbai, India. All the chemicals were used as received from the
supplier. Distilled water was used for the preparation of solutions,
which was prepared in the laboratory using distilled water plant.

173

Fig. 1. Schematic of hydrodynamic cavitation set-up.

174

P.N. Patil, P.R. Gogate / Separation and Purication Technology 95 (2012) 172179

ow rate of cooling water in the cooling jacket. Experiments were


carried out at different pH ranging from 2.2 to 8.2 and it was adjusted using 0.2 M sulfuric acid and 0.2 M NaOH. The experiments
regarding the combination of hydrodynamic cavitation and different additives were performed by setting the initial pH of the feed
solution to 3. The different additives used in the present work for
intensication includes H2O2 over a concentration range of 25
200 mg/l), CCl4 over a range of 16 g/l and Fentons reagent with
the ratio of H2O2:FeSO4 as 1:0.5 to 1:4. The experiments regarding
the effect of radical scavengers were performed by adding sodium
bicarbonate (1 and 2 g/l) and 1 g/l of tert-butanol in the system.
2.4. Analysis
The concentration of methyl parathion at any instance of time
was determined using high pressure liquid chromatography
(HPLC). HPLC instrument used comprised of a HPLC pump (K501) with a UV detector (K-2501) and a Eurosphere 100-5 C18 column of dimensions 250  4 mm supplied by KNAUER, Germany.
The mobile phase used in HPLC determination consists of 75% acetonitrile and 25% deionized water mixture with ow rate of 1 ml/
min. The determination wavelength for methyl parathion was set
at 278 nm. The concentration of the solution was determined from
the calibration chart prepared earlier with known concentrations.
In addition, some of the samples were also analyzed to determine
the total organic carbon (TOC) content using ANATOC II total organic carbon analyzer from SGE International Pvt. Ltd., Australia.
The intermediate product formations during the treatment were
monitored using liquid chromatographymass spectroscopy supplied by Thermo Electron Corporation. Kinetic analysis of the degradation process was also carried out under different operating
conditions viz. varying pressure, temperature, pH, etc. and for the
use of different additives. Integral method of analysis was followed
in the present work and it has been observed that rst order kinetics explains the degradation reaction very well.

respect to the initial concentration. It can be seen from the gure


that the extent of degradation decreases with an increase in the
initial concentration of methyl parathion. It was also observed that
the rate constant decreased from 5.41  103 to 3.88  103 min1
for an increase in the concentration from 20 ppm to 50 ppm. The
maximum extent of degradation as 44.44% was obtained at initial
concentration of 20 ppm. The observed decrease in the degradation
with an increase in the initial concentration may be due to the fact
that pollutant and byproducts formed are known to compete for
the OH radicals in the solution. So the initial concentration of the
methyl parathion has a fundamental effect on the extent of degradation. Similar results for the dependency of degradation of pnitrophenol on the initial concentration have been reported by
Sivakumar et al. [11] over the concentration range of 10
500 ppm. Mishra and Gogate [23] have also reported similar results for the sonophotocatalytic degradation of p-nitrophenol in
the concentration range of 10100 ppm.
3.2. Effect of inlet pressure

The effect of initial concentration of methyl parathion on the


extent of degradation has been investigated. The experiments were
performed at four different initial concentrations as 20, 30, 40 and
50 ppm. Fig. 2 depicts the variation of extent of degradation with

The effect of inlet pressure has been investigated over the operating range of 18 bar. The obtained results have been depicted in
Fig. 3. It was observed that the extent of degradation increases
with an increase in the pressure from 1 bar till an optimum value
of 4 bar and then it decreases at higher pressures. The observed increase in the degradation with an increase in the pressure may be
attributed to the enhanced cavitational activity at higher operating
pressures. At higher operating pressures the collapse of the cavity
becomes more violent leading to a higher pressure pulse generated
at the collapse of the cavity which in turn enhances the extent of
dissociation of water molecules leading to higher number of hydroxyl radicals. As the pressure increases beyond the optimum value of 4 bar, the extent of degradation decreases which may be
attributed to the onset of super cavitating conditions in which
indiscriminate growth of the bubbles takes place at downstream
of the constriction resulting in splashing and vaporization of the
ow. The formation of numerous cavities results in a slug like ow
(large vapor pocket) where the collapse of cavities are dampened
leading to lower extent of formation of free radicals. Kinetic studies
revealed that the rst order degradation rate constant increased
from 1.40  103 min1 to 2.37  103 min1 with an increase in
the pressure from 1 bar to 4 bars and then a decrease was observed
as shown in Table 1. The maximum extent of degradation obtained
was 22.4% at 4 bar of operating pressure and hence the remaining

Fig. 2. Effect of initial concentration of the pollutant on degradation.

Fig. 3. Effect of operating pressure on degradation.

3. Results and discussion


3.1. Effect of initial methyl parathion concentration

P.N. Patil, P.R. Gogate / Separation and Purication Technology 95 (2012) 172179

175

sets of experiments have been performed at 4 bar pressure. Similar


effects regarding increase in the extent of degradation with an increase in pressure have also been reported in some of the earlier
literature illustrations. Chakinala et al. [24] have studied the oxidation of 20 g/l of KI in the presence of CH2Cl2, at pressures in the
range of 34102 atm and observed increase in the extent of oxidation with an increase in the inlet pressure. In this case, they have
not observed any optimum pressure where supercavitation can
be occurring. Also, Wang and Zhang [25] reported the increase in
the degradation rate of alachlor pesticide with increasing inlet
pressures from 0.2 to 0.6 MPa using swirling jet cavitation, though
no optimum pressure for maximum benets have been reported.
The observed variations can be attributed to the fact that the onset
pressure is strongly dependent on the design of the hydrodynamic
cavitation reactor, which is also conrmed from the fact that much
lower operating pressures as used in the present work have also
shown degradation of pollutants. Efcient design of the reactor allows generation of enough free radicals/oxidizing species so as to
initiate the desired application even at substantially lower operating pressures, which eventually reduces energy consumption and
operational costs.
Fig. 4. Effect of operating temperatures on degradation.

3.3. Effect of operating temperature


In the case of experiments related to different operating temperatures, experiments were performed at three different temperatures as 32 C (intense cooling), 35 C (moderate cooling) and
39 C (uncontrolled operation). The desired temperature of the system was maintained by controlling the ow rate of cooling water
owing through the cooling jacket. The lowest temperature of
32 C was obtained by keeping the maximum ow rate of cooling
water whereas a temperature of 35 C was maintained by keeping
intermediate ow rate of cooling water and a temperature of 39 C
was achieved without circulating the cooling water through the
jacket. The obtained results for the extent of degradation using
these sets of experiments have been depicted in Fig. 4. It can be
seen that the extent of degradation marginally increases as the
operating temperature of the system increases from 32 C to
39 C. It was also observed that the rate constant increases marginally from 2.24  103 to 2.50  103 min1 for increase in the temperature from 32 C to 39 C as shown in Table 2. Similar results for
increase in degradation with increase in temperature were reported by Wang and Zhang [25] for the degradation of alachlor
pesticide in the range of 30 C to 40 C temperature whereas any
temperature increase beyond 40 C resulted in a decrease in the
extent of degradation. Due to an increase in the temperature, the
cavitational efciency decreases due to the formation of vaporous
cavities. On the other side, enhanced temperatures increases the
kinetic rates of degradation and also can lead to enhanced presence
of pollutants in the collapsing cavities. Braeutigam et al. [26] and
Wu et al. [27] have also conrmed that the effect of temperature
on the extent of degradation in hydrodynamic cavitation reactor
is by way of higher volatility of the substances at higher temperatures and decreased cavitational efciency due to generation of

Table 1
Kinetic rate constants at different operating pressures.
Operating pressure
(bar)

First order rate constant k  103


(min1)

Extent of
degradation (%)

1
3
4
5
6
8

1.40
2.20
2.37
2.29
2.16
1.98

13.6
20.8
22.4
21.4
20.2
18.4

vaporous cavities. In the present work, since the boiling points of


the methyl parathion pesticide is substantially higher (around
143 C), the effect of presence of pollutants in the collapsing cavities will not be dominating and hence only a marginal increase has
been observed initially. The results of Wang and Zhang [25] also
conrm this hypothesis where decreased extents of degradation
are obtained at higher temperatures due to the controlling action
of the cavitation events. Since only marginal effect on the degradation rate was observed in the present work, higher operating temperatures have not been selected in the present study considering
the fact that the costs associated with heating are not introduced
into the total treatment costs considering possible commercial
application.
3.4. Effect of feed pH
The experiments related to pH effect were carried out at different pH ranging from 2.2 to 8.2 and it was adjusted using H2SO4 and
NaOH. It can be seen from Fig. 5 that the degradation of methyl
parathion was maximum at pH value of 3. At alkaline conditions
the extent of degradation was lower than that observed under
acidic conditions. The observed results can be attributed to the fact
that under acidic conditions generation of hydroxyl radicals is favored and also the oxidation capacity of hydroxyl radicals is higher
under acidic conditions [16,28,29]. Some similar illustrations can
be observed in the literature where acidic conditions are found
to be better for degradation of organic pollutants using cavitation,
though not much for the hydrodynamically generated cavitation.
Shriwas and Gogate [16] have reported that the ultrasonic degradation of methyl parathion was higher at pH value of 2.5. Pradhan
and Gogate [28] have studied the removal of p-nitrophenol at three
different pH values 2.0, 3.75 and 8.0 using hydrodynamic cavitation and observed that maximum removal of 63.2% was observed
at pH value of 3.75. Saharan et al. [30] have also investigated the
effect of pH on the decolorization rate of Acid Red 88 dye by using
hydrodynamic cavitation at different pH in the range 211 and reported that the rate of decolorization increases with a decrease in
solution pH. A much lower decolorization rate was observed at pH
10.0 and about 92% decolorization was obtained at pH 2.0. Kotronarou et al. [31] have studied the sonodegradation of p-nitrophenol and reported the enhanced degradation under acidic
conditions. Rahman and Muneer [32] have also observed increased

176

P.N. Patil, P.R. Gogate / Separation and Purication Technology 95 (2012) 172179

Table 2
Kinetic rate constants at different operating temperatures.
Operating
temperature (C)

First order rate constant


k  103 (min1)

Extent of
degradation (%)

32
35
39

2.24
2.37
2.50

21.1
22.4
23.1

Fig. 6. Effect of different loadings of H2O2 on degradation.

Fig. 5. Effect of feed pH on degradation.

rates of degradation of pesticides at lower pH values whereas Currel et al. [33] have reported that sonodegradation of phenol is favored at low pH. From Table 3, it can be seen that at optimum
pH of 3, maximum degradation of 44.4% with kinetic rate constant
of 5.42  103 min1, was obtained. Based on these results, it was
decided to investigate the effect of other operating parameters at
initial pH of 3.

rmed by a comparison with the literature illustrations. Wang


et al. [34] have reported that the extent of degradation of Rhodamine B in a hydrodynamic cavitation reactor increases with an increase in the hydrogen peroxide concentration from 0 to 150 mg/l.
Similarly Mishra and Gogate [35] have observed the similar effects
for degradation of Rhodamine B using hydrodynamic cavitation
over a range of 0200 mg/l of hydrogen peroxide. Pradhan and
Gogate [36] have studied the degradation of p-nitrophenol using
combination of ultrasound with hydrogen peroxide (0.55 g/l)
and observed that maximum of 59% degradation was obtained
with 5 g/l loading of H2O2. Similarly Shriwas and Gogate [16] have
reported that 15% degradation of methyl parathion was obtained
using ultrasound in presence of H2O2 at an optimum loading of
200 mg/l.

3.5. Combination of hydrodynamic cavitation and H2O2

3.6. Combination of hydrodynamic cavitation and CCl4

The effect of different loadings of hydrogen peroxide ranging


from 25 mg/l to 200 mg/l was investigated in the present study.
H2O2 acts as an additional source providing hydroxyl radicals to
intensify the degradation process. The obtained results have been
depicted in Fig. 6. It was observed that the extent of degradation
increases with an increase in the concentration of hydrogen peroxide over the entire range of concentration. It can be seen from the
gure that degradation of methyl parathion was enhanced from
44.4% for operation using only HC to complete degradation for
operation using combination of HC with 200 mg/l H2O2. The rst
order rate constant observed for this loading was 68.48 
103 min1as shown in Table 4. The TOC removal at this condition
was 56.4%. The obtained results can be attributed to the enhanced
formation of the free radicals due to continuous dissociation of
hydrogen peroxide under the cavitating conditions. This is con-

The effect of different loadings of carbon tetrachloride ranging


from 1 g/l to 6 g/l has been investigated in the present study. From
Fig. 7 it can be observed that as the concentration of CCl4 increases
from 1 to 6 g/l the degradation of methyl parathion also increases
till an optimum loading of 5 g/l beyond which the extent of degradation was almost constant. The observed enhancement due to the
use of carbon tetrachloride can be attributed to the additional radicals generated due to the dissociation of the additive in the presence of cavitating conditions. The enhancement in the degradation
can be explained on the basis of series of chain reactions occurring
in the system initiated by the dissociation of CCl4 under the cavitating conditions which leads to generation of highly reactive chlorine radicals upon bubble collapse. The series of chain reactions
leads to generation of additional oxidizing species which attack
the methyl parathion molecules. The observed enhancement in
degradation may be attributed to the fact that the amount of Cl
radicals formed by the degradation of the CCl4 is substantially
higher as compared to the scavenging action caused by a decrease
in the intensity of cavitation at higher concentration of the additives. Based on the oxidationreduction thermodynamics, CCl4 is
considered to be non-reactive with hydroxyl radicals and reactions
would proceed through reductive processes rather than chemical
oxidations [24]. Thus, the rate of degradation of methyl parathion
in the presence of CCl4 is directly proportional to the rate of Cl radical formation, which is again directly proportional to the degradation of CCl4. In this way the combined attack of additional oxidizing

Table 3
Kinetic rate constants at different feed pH.
Feed
pH

First order rate constant k  103


(min1)

Extent of degradation
(%)

2.2
3
4
5.2
8.2

4.56
5.42
5.07
2.07
1.87

38.3
44.4
41.4
20.8
18.7

P.N. Patil, P.R. Gogate / Separation and Purication Technology 95 (2012) 172179
Table 4
Kinetic rate constants at different loadings of H2O2.
Loadings of H2O2
(mg/l)

First order rate constant k  103


(min1)

Extent of
degradation (%)

25
50
100
120
150
200

5.81
14.13
23.64
31.45
51.21
68.48

48.3
81.2
95.1
96.9
99.6
99.8

species and hydroxyl radicals generated due hydrodynamic cavitation increases the extent of methyl parathion degradation.
The extent of degradation at loading of 6 g/l was nearly similar
to degradation at loading of 5 g/l which may be attributed to the
fact that the cavitational activity was insufcient for complete
pyrolysis of CCl4 added in the system [37]. Similar results for degradation using CCl4 were reported by Mahamuni and Pandit [38]
for degradation of phenol in the presence of CCl4. Wang et al.
[39] have reported that the rate constant for degradation for
methyl orange increased 160 times due to the addition of CCl4.
Mishra and Gogate [35] also reported a similar increase in the extent of degradation of Rhodamine B by the addition of CCl4 using
hydrodynamic cavitation. From Table 5 it can be seen that the rate
constant was also increased from 6.20  103 min1 to
15.56  103 min1 with increase in CCl4 concentration from 1 g/
l to 6 g/l.

3.7. Hydrodynamic cavitation coupled with Fenton oxidation


The concentrations considered for experiments related to Fentons reagent were on the basis of ratio of H2O2:FeSO4 as 1:0.5 to
1:4 at a xed loading of H2O2 as 100 mg/l. The loading of H2O2
was xed to 100 mg/l because more than 95% degradation of
methyl parathion was obtained using this loading. The obtained results for the combination of Fenton chemistry and hydrodynamic
cavitation have been shown in Fig. 8. It was observed that as the
ratio of H2O2:FeSO4 increases the extent of degradation also increases. The intensication in the degradation due to the addition

177

of Fentons reagent can be attributed to intensied production of


hydroxyl radicals due to the conversion of Fe2+ to Fe3+. The reaction
mechanism suggesting the generation of additional radical species
can be given as follows [40]:

Fe2 H2 O2 ! Fe3  OH OH


Fe3 H2 O2 ! Fe  OOH2 H
Fe  OOH2 ! Fe2  OOH
Fe3  OOH ! Fe2 O2 H
Kinetic data tting has also been done for the combination studies and the obtained values of the rate constant have been given in
Table 6. The second order rate constant for degradation of methyl
parathion was 6.36  103 (min1) (l/g) with TOC removal of 76.6%
at the ratio of 1:4 of H2O2:FeSO4. The results obtained in the present work can be conrmed with some similar literature reports.
Song et al. [7] have reported that the degradation of Acid Red 88
increased with an increase in the loading of Fe+2 from 0.036 mM
to 0.108 mM at constant H2O2 loading. Pradhan and Gogate [28]
have reported similar results for removal of p-nitrophenol using
the combination of hydrodynamic cavitation with FeSO4:H2O2 in
the ratio 1:5. For the combination of hydrodynamic cavitation with
Fentons oxidation, the added hydrogen peroxide is initially utilized for Fentons process and a small amount gets directly converted to hydroxyl radicals. The remaining hydrogen peroxide,
along with the hydrogen peroxide generated due to hydrodynamic
cavitation contributes to the continuous formation of the oxidizing
species. As mentioned earlier, xed loading of H2O2 as 100 mg/l
was taken and to this quantum of H2O2, FeSO4 was added to promote the generation of hydroxyl radicals by Fentons chemistry
route.
3.8. Effect of radical scavengers on degradation
In the case of experiments related to effect of radical scavengers
on the degradation, sodium bicarbonate and tert-butanol were
used as radical scavengers. The different sets of experiments were
carried out using 1 and 2 g/l of sodium bicarbonate and 1 g/l of

Fig. 7. Effect of different loadings of CCl4 on degradation.

178

P.N. Patil, P.R. Gogate / Separation and Purication Technology 95 (2012) 172179

Table 5
Kinetic rate constants at different loadings of CCl4.

Table 6
Kinetic rate constants at different loadings of Fenton reagent.

Loadings of CCl4
(g/l)

First order rate constant k  103


(min1)

Extent of
degradation (%)

H2O2:FeSO4

Second order rate constant


k  103 (min1) (l/g)

Extent of
degradation (%)

1
2
3
4
5
6

6.20
7.60
9.39
12.18
15.03
15.56

50.6
59.3
64.8
76.2
81.6
82.8

1:0.5
1:1
1:2
1:3
1:4

1.80
2.32
5.52
6.18
6.36

78.5
82.5
92.6
93.4
93.8

were diethyl phosphite, O, O, O-triethyl thiophosphate, O, O, S-triethyl phosphorothioate, 1-ethoxy-4-nitro-benzene, and parathion.
All these intermediates formed were reported with reference to
mass (m/z) observed by LCMS analysis [17]. One of the major distinctions in the intermediates observed in the current work as compared to earlier work of Yao et al. [21], is the absence of Nitrophenol
as one of the intermediates. This might be attributed to the fact that
nitrophenol readily gets converted to 1-ethoxy-4-nitro-benzene by
the attack of ethyl radical on OH group in 4-nitrophenol. The
sources of ethyl groups could come from decomposition of the
small molecular organic acids or intermediates containing alcohol
functional groups under cavitating conditions [21]. The oxidative
attack by OH on PAO bond which connects the thiophosphate
group to the aromatic ring might result in the formation of other
compounds containing phosphorus. The similarity between the
intermediates formed as analyzed in the present work and the earlier work of Yao et al. [21] leads us to a conclusion that the mechanism of degradation follows a similar path in terms of generation of
the hydroxyl radicals and its initial attack on the pollutant.
3.10. Comparison of cavitational yield in hydrodynamic cavitation and
sonochemical reactors
Fig. 8. Effect of different loadings of Fenton reagent on degradation.

tert-butanol at xed loading of methyl parathion as 20 ppm. The


obtained results for these loadings of radical scavengers are presented in Fig. 9. It can be seen from Table 7 that extent as well
as rate of degradation of methyl parathion decreases in presence
of sodium bicarbonate and tert-butanol solution. From the results,
it can be concluded that the degradation of methyl parathion was
inhibited by the presence of sodium bicarbonate and tert-butanol
in the system. Similar results were reported by Yao et al. [21] for
parathion degradation under ultrasonic irradiation. They have indicated that free radical reactions predominate in the parathion degradation under ultrasonic irradiation and the reaction zones are
predominately at the interfacial regions between cavitation bubbles and bulk solution and, to a much lesser extent, in bulk solution. Merouania et al. [41] have also reported that bicarbonate
ions had a negative effect on the removal of dye. Based on the obtained results, it has been established that the free radical attack is
the dominating mode of degradation in the case of methyl parathion removal using hydrodynamic cavitation.
3.9. Intermediate analysis
Probable intermediates formed during the degradation of
methyl parathion at an optimum loading of hydrogen peroxide,
where maximum extent of degradation has been obtained among
all the treatment schemes, have been identied using the liquid
chromatographymass spectroscopy (LCMS) analysis. At the
beginning of degradation reaction, paraoxon was one of the major
byproduct formed via the replacement of sulfur of methyl parathion by oxygen in the P@S bond. The other compounds detected

As the mechanism of the degradation is similar in the case of


sonochemical and hydrodynamic cavitation, it was thought desirable to compare the effectiveness of the two different modes of
generation of cavitational events in terms of the energy consumption. The criterion for comparison used was the cavitational yield
which can be dened as extent of degradation per unit energy consumed (mg/J). In the case of sonochemical reactors, the main energy consuming component is the generator used for introducing
the ultrasonic irradiations into the system whereas in the case of
hydrodynamic cavitation reactors, the main energy consuming
component is the pump which is used for recirculation of the aqueous solution of the pollutant through the cavitation chamber. In
our earlier work [16], ultrasonic degradation of methyl parathion
(20 ppm initial concentration) has been investigated using ultrasonic horn reactor operating at 20 kHz and a power rating of
270 W. It has been reported that under acidic conditions (pH of
2.5), the extent of degradation obtained using ultrasonic horn
alone was 10.2% in 60 min of treatment time. Considering the supplied power and the operating volume of 100 ml, the power density for the reactor has been found to be 2700 W/L. The net
cavitational yield (mg/J) is obtained to be equal to 2.098 
107 mg/J.
Considering the rating of the pump used in the present work
(1.1 kW) and, the total power dissipation per unit volume has been
obtained to be equal to 275 W/L. With the use of hydrodynamic
cavitation alone, the extent of degradation was observed to be
equal to 44% for the 20 ppm initial solution of the pollutant and
hence the cavitational yield has been obtained to be equal to
4.44  106 mg/J. Comparison of the cavitational yields indicate
that the hydrodynamic cavitation is around 20 times more energy
efcient in degrading the given pollutant and hence can be considered as more efcient approach to generate cavitating conditions
for intensication of chemical processing applications.

P.N. Patil, P.R. Gogate / Separation and Purication Technology 95 (2012) 172179

179

Fig. 9. Effect of radical scavengers on degradation.

References

Table 7
Kinetic rate constants at different loadings of radical scavengers.
System

Rate constant
k  103 (min1)

Extent of
degradation (%)

Only HC
HC + sodium bicarbonate 1 g/l
HC + sodium bicarbonate 2 g/l
HC + tert-butanol 1 g/l

5.41
3.30
2.65
1.92

44.4
29.3
23.9
17.9

4. Conclusions
The degradation of methyl parathion using hydrodynamic cavitation combined with different additives has been investigated.
Depending on the obtained results, following important conclusions can be established for the degradation of methyl parathion:
 Hydrodynamic cavitation can be effectively used for degradation of methyl parathion at relatively large operating capacity
(4 l as used in the present work).
 Typically optimum operating pressure and acidic conditions are
recommended for enhancing the extent of degradation. However, extent of degradation of methyl parathion varies marginally with the operating temperature.
 The combination of hydrodynamic cavitation with 200 mg/l
H2O2 results in almost complete degradation of methyl parathion in 30 min of operation time with 56.4% TOC reduction.
 Similarly it has been observed that combination of hydrodynamic cavitation with CCl4 and Fentons reagent results in
enhanced extents of degradation.
 The degradation of methyl parathion using hydrodynamic cavitation is dominated by the free radical attack as conrmed by
the fact that presence of radical scavengers such as sodium
bicarbonate and tert-butanol in the system decreases the rate
of degradation.

Acknowledgment
PRG would like to acknowledge the funding of the Department
of Science & Technology, New Delhi, India under the Fast Track
program for the research work presented in this manuscript.

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