Advanced Materials Research Vols.

726-731 (2013) pp 2804-2807 Online: 2013-08-16

© (2013) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.726-731.2804

Treating Industrial Pesticide Wastewater by Distillation Method

Changhai Li 1 , Yuejin Li1, 2,a, WangRuan3

1
（ Department of Chemistry and Chemical Engineering, Binzhou University, Binzhou 256603,
2
China Key Laboratory for Comprehensive Utilization of liquid pollutants of Binzhou City, Binzhou
3
256603, China College of Chemical Engineering, Changchun University of Technology,
Changchun 130012, China）
a
email:liyuejin83@163.com

Keywords: pesticide wastewater; batch distillation; chemical oxygen demand (COD).

Abstract. The experiments for treating the pesticide wastewater, which had been produced by
Shandong pesticide factory when it produced the Nicosulfuron, were carried out. Through the small
test, treatment of pesticide wastewater by batch distillation was studied. The results showed that the
top temperature of the recovery samples were about from 98.5˚C to 100.2˚C，the COD of the
recovery samples were about from 10000mg/L to 200 mg/L.With the increasing of the reflux ratio, the
average of the COD of these samples and the recoveries reduced gradually, and the removal rate of
COD increased gradually, which is above 92% when R≥4.

Introduction
China is the largest pesticide producer and consumer in the world[1]. Once produce 1 ton products,
they get even more than ten tons of waste water, Which have been processed accounted for 7% and
which reached the sewage emission control regulations accounted for only 1% of the total processing
[2]. The process methods of the pesticide wastewater have extraction, adsorption, wet oxidation and
micro-electrolytic method. But these methods have a lot of problems[3-5].The operation cost of
extraction method is high and Liquid membrane extraction exists technology barriers; The resin price
and regeneration cost of adsorption are high; Wet oxidation method has harsh conditions and high
processing cost; micro-electrolysis technology is easily produce second pollution. This experiment is
for pesticide wastewater-Nicosulfuron ,which the optimum conditions for were studied in a batch
distillation column.
The production process flow of nicosulfuron has four stages: chlorinated section, sulfonated
section, esterification section and synthesis section. Among them, the main pollutants for chlorinated
section are sulfurous acids; The main pollutants for sulfonated section are nitrogen heterocyclic
compounds, sulfonamide and a small amount of hydrogen sulfide weak acid water; The main
pollutants for esterification section are acetone and amine ester; The main pollutants for synthetic
phase are toluene, acetone and pyridine amine. The characteristics of the pesticide wastewater is a
wide range variety, with a high concentration, color depth, organic matter complex composition,
toxic, and poor characteristics of bio-degradable[6-8].

Experimental Procedure
Materials and Chemicals. The pesticide wastewater was collected from a pesticide company in
Shandong Province． The wastewater contained various organic compounds．The characteristics of
the pesticide wastewater are followed as: pH 4.12, COD15,000 mg/L -30,000mg/L. The rectification
device is KM-DL computer controlled rectification device (Jilin Keman). The determination methods
of COD is potassium dichromate method.
Distillation experiments. Washed and dried the distillation with 95% ethanol and distilled water
before the experiment. The wastewater showed acid, so the filler should be chosen on the acidproof
class. Weighed 350ml pesticide wastewater and joined it in the column reactor, and then heated the
column reactor. The Heating process was controlled by computer. Steam rose from the top of the

All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of Trans
Tech Publications, www.ttp.net. (ID: 128.119.168.112, Univ of Massachusetts Library, Amherst, USA-07/07/15,04:57:46)
 Advanced Materials Research Vols. 726-731 2805

tower into the condenser, the liquid part of the condensate as reflux liquid to return into the distillation
tower, the rest is removed as distillate. With potassium dichromate method measured the COD of the
distillate, and recorded column top temperature at the same time. Changed the reflux ratio to repeat
the previous step.

Results and Discussion

Effect of Separation Temperature Figures.

160000
160000
140000
140000
120000
120000
COD/(mg/L)

100000

COD/(mg/L)
100000
80000
80000
60000
60000
40000
40000
20000
20000
0
0
99.1 99.4 99.7 100.1 100.1 100.1 100.2 98.9 99 99.7 99.9 99.9 100.1 100.1
T/℃ T/℃

Fig. 1 Reflux ratio R=1, Fig. 2 Reflux ratio R=2,

the top temperature—COD diagram the top temperature—COD diagram

160000
160000
140000
140000
120000 120000
COD/(mg/L)

COD/(mg/L)

100000 100000
80000 80000
60000 60000
40000 40000
20000 20000
0 0
98.7 99.4 99.8 99.8 99.9 99.9 100 100 98.6 99.8 100 100 100 100 100 100
T/℃ T/℃

Fig. 3 Reflux ratio R=4, Fig. 4 Reflux ratio R=5,

the top temperature—COD diagram the top temperature—COD diagram

200000
180000
160000
140000
COD/(mg/L)

120000
100000
80000
60000
40000
20000
0
98.5 99.5 100 100 100 100 100 100 100
T/℃

Fig. 5 Reflux ratio R=10, the top temperature—COD diagram

2806 Advances in Environmental Technologies

From figure 1 to figure 5 ,when R=1,R=2,R=4,R=5 and R=10,the corresponding top temperature
were 99.1˚C, 98.9˚C, 98.7˚C, 98.6˚C and 98.5˚C, the first sample of the COD value is about
1.3×105mg/L-1.8×105 mg/L. As the program went on, the samples of COD value had decreased trend
as temperature increased.The last few samples of COD is about 200-900mg/L.
The results showed that，before the temperature rose up to 100˚C,the samples of COD were very
high. It was because the boiling point of some organic compounds are lower than water. When the
temperature of samples were between 99.9˚C and 100.2 ˚C,the distillates of COD value were low.
That was because the distillate of water content was higher.The residuals at the tower kettle in all
reflux ratio had higher COD than the raw water. The main reason is that the tower kettle contained
high boiling point organic matter.

Effect of Reflux Ratio on Recovery

Table 1 The relationship between reflux ratio R and the COD of the sample ,the recoveries
reflux ratio 1 2 4 5 10
COD(mg/L) 3341.26 2783.26 2390.12 2000.93 1904.96
recovery 77.7% 68% 50.5% 49.7% 45.7%

As can be seen from Table 1, both COD and recovery were declined with the increasing of the reflux
ratio. The COD fallen from 3341.26 mg/L to 1904.96 mg/L and the recovery fallen from 77.7% to
45.7%.
Effect of Reflux Ratio on the Removal Rate of COD
With the increasing of reflux ratio，the COD removal efficiency also increased. When R=4, the COD
removal efficiency was 92.30%.When R≥4 ， the COD removal efficiency increased slowed.
Considering the recovery of the sample gradually reduced, so the best reflux ratio was 4.

35000 100%

30000 95%

25000
90%
COD/(mg/L)

20000
the average COD
of distillates 85%
15000
the COD of raw
water 80%
10000
the removal rate
5000 of COD 75%

0 70%
1 2 4 5 10
reflux ratio

Fig. 6 Effect of reflux ratio on the removal rate of COD

Summary
The largest recovery was 77.7% when R=1. the largest COD removal efficiency was 93.25%when
R=10. When R≥4，the COD removal efficiency increased slowed, the recovery was declined with
the increasing of the reflux ratio.so the optimal reflux ratio was R=4.
 Advanced Materials Research Vols. 726-731 2807

Acknowledgements
This work was financially supported by the Shandong Provincial Natural Science Foundation, China
(No. ZR2009BL001), the Science Technology Development Program of Binzhou([2010] 25) and
the Binzhou University Provincial Natural Science Foundation, China (Grant No. BZXYG1115).

References
[1] Q.Pan,W.Xie and Y.L.Li: Agro-Environment & Development. Vol. 3 (2012), p. 58.
[2]Y.S.Lin: Pesticide and Ecological Environment Protection. Chemical Industry Press,Beijing
(2000).
[3] Y.Cheng,Q.X.Zhou and Q.Y.Ma: Techniques and Equipment for Environmental Pollution
Control. Vol. 6 (2003), p. 57.
[4] K.Juttner,U.Galla and H.Schmieder: Eledrochim Acta. Vol. 45 (2000), p. 2578.
[5] J.W.Zhao: World Pesticides. Vol. 32 (2010), p. 39.
[6]W.Y.Chen,Z.H.Zhao and Z.X.Xue: Pesticide Production and Synthesis. Chemical Industry
Press,Beijing (2000).
[7] D.Cheng: Environmental Protection of Chemical Industry. Vol. 6 (1992), p.209.
[8]Y.Z.Wei,Q.S.Li and W.Zhao: Environment and Ecology in the Three Gorges. Vol. 32 (2010),
p.44.
Advances in Environmental Technologies
10.4028/www.scientific.net/AMR.726-731

Treating Industrial Pesticide Wastewater by Distillation Method

10.4028/www.scientific.net/AMR.726-731.2804