Beruflich Dokumente
Kultur Dokumente
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
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
174
P.N. Patil, P.R. Gogate / Separation and Purication Technology 95 (2012) 172179
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
P.N. Patil, P.R. Gogate / Separation and Purication Technology 95 (2012) 172179
175
Table 1
Kinetic rate constants at different operating pressures.
Operating pressure
(bar)
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
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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)
Extent of
degradation (%)
32
35
39
2.24
2.37
2.50
21.1
22.4
23.1
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.
Table 3
Kinetic rate constants at different feed pH.
Feed
pH
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)
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.
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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)
Extent of
degradation (%)
H2O2:FeSO4
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.
P.N. Patil, P.R. Gogate / Separation and Purication Technology 95 (2012) 172179
179
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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