Advanced Materials Research Vols.

781-784 (2013) pp 2184-2188 Online: 2013-09-04

© (2013) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.781-784.2184

The Degradation of Organophosphorous Pesticide Wastewater by

sonophotocatalytic oxidation technology
Li Zhaoyan1 Song Wei2 Zhang Li3
1
Bio-chemistry department of Nanyang Institute of Technology in Henan 473004, China
2
Bio-chemistry department of Nanyang Institute of Technology in Henan 473004, China
2
Changchun Terumo Medical Products Co.ltd
1
email : xlxunyil@163.com), 2email : leirentsw@sohu.com 3email : zhang-momo-123@163.com) ，
Keywords: organophosphosphous pesticides wastewater, sonophotocatalytic oxidation technology,
degradate

Abstract： ： Organophosphosphous pesticides wastewater was degradated by sonophotocatalytic

oxidation technology,and some factors affecting sonophotocatalytic oxidation reaction were studied
in details such as different degradation modes,the time of degradation, initial solution concentration ,
initial pH value, the amount of catalyst and the effect of Fenton,etc.In the end the optimal conditons
were determined.The conclusion we drawed was that the optimal time of degradation was 100min ,
initial solution concentration was 100mg／L, the amount of catalyst AgBr/TiO2 was 0.6g,moreover
the adding of Fenton could greatly enhance the degradation rate.

intruduction
Nowadays Organophosphorus pesticide is applicated widely in the word Because of its high
efficiency, easy to be used, easy to be degraded under natural condition. However, due to the large
amounts of application, the organphosphorous pesticide residues have brought serious environment
pollution and begin to threat the health of human beings .Thus,how to degradate organphosphorous
pesticide residues efficiently has been social concern problem[1].
Ultrasonic irradiation method and photocatalytic oxidation method are all the new wastewater
treatment technique and develop rapidly in rencent years. Ultrasonic irradiation method uses the
cavatition effect to treat organic pollutant in the wastewater,.The technique has the advantages of low
energy consumption,no pollution or little pollution, simple equipment and easy to operate[2].
However, photocatalytic oxidation method is a new type of environment clean technology which can
efficiently degrade most pollutant to be CO2 and H2O at last, and phosphorus atoms, sulphur atoms
and nitrogen atoms in pollutant can be transformed into ions such as PO43-, SO42-, NO3-, NH+[3] .In
the end the organic pollutant is degradated completely. Because of having many prominent characters
such as easy equipment, easy to control operation conditions, non-selective oxidation organic
pollutants, low operation fees and no the second pollution, it has gradually become a hot research area
in treating wastewater and also widely be used in dying, surfactants, pesticide and other wastewater
treatment. But it is hard to reach ideal treatment efficiency to degrade organphosphorous pesticide
wastewater only by means of simple ultrasonic irradiation method or simple photocatalytic oxidation
method ,thus the experiment will combine the two ways to degradate theorganophosphorus pesticide.
In the experiment we choosed methamidophos as organic pollutant to prepare simulation
organphosphorous pesticide wastewater with certain concentration, and treated the wastewater by
sonophotocatalytic oxidation technology . In the progress of degradation some factors affecting
sonophotocatalytic oxidation reaction were studied and reaction conditions were explored.

Experimental section
1. Materials and instruments
78% (w/w) methamidophos emulsifiable concentrates was purchased from Jiahua Company in
Zhejiang; AgBr/TiO2 was made by labs;Fenton Reagent was propared by labs; Probing type
ultrasonic generator was purchased from Tianhong testing equipment company in Siping ;500W

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 Advanced Materials Research Vols. 781-784 2185

high-voltage mercury lamp were supplied by Shanghai Ouwei Lighting Equipment company.; high
performance liquid chromatography (Dionex UltiMate 3000 HPLC)was purchased from USA.
2 .Degradation experiment and analysis method
(1) degradation experiment：At first, A certain concentration of Methamidophos solution 400ml
and certain quality of AgBr/TiO2 powder were added to the 500ml beaker, then the AgBr/TiO2 power
was uniformly dispersed in solution by entering air and stiring for 30 minutes. So AgBr/TiO2-
methamidophos suspension was made. Adjust the frequency of ultrasonic generator to be 20KHz.
Open high-voltage mercury lamp and ultraviolet rags flash out the reaction solution. Then, record
experimental beginning time after high-voltage mercury lamp was pre-heatted for 5 minutes . After
lighting for a certain time, we took sample for high-speed centrifugal separation. Take the upper clear
liquid to analyze the change of concentration of methamidophos solution before and after
sonophotocatalytic oxidation.
(2) Analysis method [4,5]：:In the experiment ,we determined organophosphosphous pesticide
residue in methamidophos wastewater by high-performance liquid chromatography(HPLC). The
following were the chromatography conditions : APOLLOC18 column; mobile phase of mixture of
methanol and water (V:V) at a rate of 70:30 ;the flowrate was 1.0ml/min;injection volume was 10ul;
column tempreture was room tempreture;detection wavelengh was UV-254.
Y=(1－Ct／Co)×100%
Y—the degradation rate
CO— Initial concentration of methamidophos wastewater
Ct—the residual concentration of methamidophos wastewater after sonophotocatalytic oxidation
degradation

Results and discussion

1. the influence of different modes on the degradation rate
Respectively taking 0.6g AgBr/TiO2 powder into 400ml , 100mg/L methamidophs
solution.,entering air and stirring for half an hour, the organicphosphorus pesticide wastewater was
degragated respectively by photocatalytic oxidation, ultrasonic irradiation and sonophotocatalytic
oxidation. The degradation time was controlled 60 minutes ,then compared degradation effect of the
three methods. Please See Fig .1.

Fig.1The influence of different modes on the rate of degradation

From Fig. 1 we could see that, by using ultrasonic irradiation method to treat 100mg / L
methamidophos wastewater, after 60 minutes the degradation rate was 15.3%; and by using
photocatalytic oxidation method , the degradation rate was 26.2% after 60 minutes. However, by
combination with ultrasonic oxidation and photochemical catalysis oxoprocess, the rate of
degradation improved largely as high as 78.2%, higher than the efficiency of simple ultrasonic
oxidation or simple photochemical catalysis oxoprocess ,even higher than their adding。from above
we knew that ultrasonic oxidation and photochemical catalysis oxoprocess together would produce
synergistic effect[6], which could improve the rate of degradation largely. The reason may be that 1)
Ultrasonic wave can be stirred to be particles and form oxidation hydrogen which can improve
2186 Advances in Chemical Engineering III

photocatalytic degradation reaction. hydroxy is the main reason of photocatalytic degradation,

however, ultrasonic wave can induce the formation of these perssad in water[7]. 2) Photochemical
catalyst's particle fragmentation can increase surfacel area of fixed particles, and provide more
efficient activity to increase hydroxy and the other oxidation perssad. 3) Ultrasonic wave's surface
cleaning function can get rid of absorbing material on the surface of catalyst to prevent it inactivation.
2. the influence of initial concentration on the degradation rate
Preparing respectively methamidophos waste solution with concentration of 100 mg/L, 300
mg/L and 600mg/L, adding 0.6g anatase AgBr/TiO2 powder, entering air and stirring for 30
minutes ,then the wastewater was degradated by sonophotocatalytic oxidation technology . Every 10
minutes a sample was took out for analyzing . 60 minutes later we recorded the concentration
changes of methamidophos pesticide wastewater. Please see Fig. 2.
From Fig. 2 we could see that, initial concentration of the solution would produce significant
influence on degradation efficiency. When initial concentration of methamidophos was 100mg/L,
60min later the final Ct was 0.218 and the rate of degradation could reach 78.2%. When initial
concentration was 600mg/L, after the same time thel Ct／Cowas 0.8 and the rate of degradation
could reach 20%. Thus, with the increase of initial concentration, the degradation rate of
methamidophos pesticide waste declined gradually, so the optimal initial concentration of
methamidophos pesticide wastewater was 100mg/L.

Fig.2 The influence of initial concentration on the rate of degradation

3. the influence of catalyst quantity on the rate of degradation
Respectively taking photochemical catalyst - AgBr/TiO2 powder 0.4g, 0.6g, 0.8g, 1.0g and 1.2g ,
each of which was added methamidophos pesticide wastewater with concentration of 100mg/L. After
entering air and stirring for 30 minutes, conducting sonophotocatalytic oxidation degradation for 100
minutes.,the degradation results could be seen from Fig. 3 .

Fig.3 The influence of catalyst quantity on the rate of degradation

 Advanced Materials Research Vols. 781-784 2187

From Fig. 3 we knew that, at the begainning of the reaction ,with the increase of catalyst's
dosage,the degradation rate of sonophotocatalytic oxidation increased gradually . When the amount
of catalyst was 0.6 g, the rate of degradation reached 98 .6% to be the highest.But after that, if we
kept on adding catalytic dosage ,the rate of degradation began to decline. The reason was that at the
beginning of reaction, with the increase of catalytic dosage, ultrasonic cavitation effect was
enhancedand , concentration of generated oxidant increased,reaction speed of the degradation
accelerated, then led to the increase of degradation rate of organophosphorus pesticide waste.
However, after the catalyst was added to a certain amount, the photon in the suspension that could be
absorbed had been fully absorbed, and synergistic effect of the ultrasonic cavitation on photocatalytic
degradation decreased gradually. All that led to the·OH which produced on the surface of catalyst to
keep stable basicly. Thus, degradation rate would not increase , even tended to decrease because of
high concentration. So, suitable catalytic dosage would be a crucial factor. Under the experiment
conditions, it iwas advisable for AgBr/TiO2 dosage to prefer 0.6g.
4. the influence of degradation time on degradation rate
Put 0.6g anaase AgBr/TiO2 powder into 100mg/L methamidophos solution, which was radiated
with a frequency of 20kHz, a certain sound intensity of ultrasonic radiation.Every 20min we took out
a sample to analyze. 120min later comparing the concentration changes after degradation
methamidophos pesticide wastewater, the degradation rate Changing with time was shown in Fig.4.
As could be seen from Fig.4, with the performance of reaction, the degradation rate began to
increase gradually. When Ultrasound time was 100min the degradation rate could reach 98.6%. But
after the 100min, Athough the degradation rate increased modestly, but tend to be even. Considering
time and economic efficiency, the best degradation time was 100min.

Fig.4 The influence of degradation time on degradation rate

5. the influence of adding Fenton reagent on the degradation rate

Putting 0.6g TiO2 powder into 100mg/L methamidophos solution, then adding 0.4mL Fenton
reagent to conduct sonophotocatalytic oxidation degradation.,every 10min we took out a sample to
analyze, and determined the Ct ／ Co and degradation rate. 60min later we compared the
concentration changing ,then compared the influence on degradation rate of adding Fenton reagent
and without adding Fenton reagent. Please see Fig.5.
2188 Advances in Chemical Engineering III

Fig. 5 The influence of Fenton reagent on degradation rate

From Fig.5 we could see that in the progress of sonophotocatalytic oxidation degradation ,adding
Fenton reagent could improve largely the rate of degradation . The reason was that adding a small
amount of Fenton reagent could promote to produce the oxidizing substances such as hydroxyl
radical and hydrogen peroxide on the interface of bubble during cavitation ,which could improve
oxidation strength of ultrasonic wave degradation, speed up reaction rate and promote degradation
reaction of organophosphorus wastewater.

Conclusions
In the experiment we choosed methamidophos wastewater as research objective, studyed the
progress of sonophotocatalytic oxidation degradation and discussed some factors affecting
sonophotocatalytic oxidation reaction. The conclusion we could drawn was that: sonophotocatalytic
oxidation technology could deal with methamidophos wastewater efficiently. Moreover, the
synergistic effect between ultrasonic wave and photochemical catalysis could improve the efficiency
largely in degradating organophosphorus wastewater.

Acknowledgements
This research was financially supported by the Youth Fund Project of Nanyang Institute of
Technology in Henan Province(2012GG032).

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The Degradation of Organophosphorous Pesticide Wastewater by Sonophotocatalytic Oxidation

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