Pre-treatment of acrylic fiber wastewater by complex process made up of internal electrolysis and Fenton oxidization

Meng Zhi-guo, Wang Jin-sheng

College of Water Sciences Beijing Normal University Beijing, China zhiguomeng@163.com
AbstractIn this paper a process of combining internal electrolysis and Fenton was used to pre-treat acrylic fiber wastewater based on investigating the optimization parameters of internal electrolysis and Fenton oxidization. Four kinds of combining processes were studied. Results showed that both the processes of Fenton oxidization next to internal electrolysis and internal electrolysis coupled Fenton oxidization were efficiency. COD of the effluents from these two processes were less than 400 mg.L-1 with a COD removal of more than 70% and the ratio of BOD/COD enhancing to 0.3, CN- concentration in effluent less then 0.3mg.L-1, meeting bio-treatment requirement steadily. While COD and CN- concentration and biodegradability of effluents from the processes of internal electrolysis next to Fenton oxidization and both reactions in one reactor could not meet biotreatment requirement. Keywords-acrylic fiber wastewater; internal electrolysis; Fenton oxidization; Pre-treatment.

dyeing wastewater, electroplating wastewater, petrochemical wastewater and arsenic-containing and cyanide-containing wastewater some of which have already been put into practical operation [5-8]. In this paper, process combining internal electrolysis with Fenton was used to pre-treat acrylic fiber wastewater, studying the treatment effect and process technology feasibility under different combining patterns to get better understand of improvement of biodegradability by different combining methods. II. A. MATERIALS AND METHODS

I.

INTRODUCTION

Acrylic fiber wastewater is one of the typical hardlydegradable industrial wastewater due to its complex composition of varied pollutants including toxic materials that causes its hard-biodegradability [1]. Thus it is impossible to treat acrylic fiber wastewater to meet the National Discharge Standards by bioprocess alone[2-4]. At present, acrylic fiber wastewater is usually treated by a process combining physichemistry unit and biochemistry unit. The key-point to improve the treat efficiency of acrylic fiber wastewater is to improve its biodegradability by pretreatment. Enhancing biodegradability of acrylic fiber wastewater becomes a research hotspot [3-4]. Internal electrolysis and Fenton advanced oxidation are promising method to pre-treat acrylic fiber wastewater. The former one can form primary battery to treat wastewater basing on metal corrosion principle. Using iron scraps as raw material also has the meaning of using waste to control waste. The latter one, Fenton advanced oxidation, is a technique which makes use of strong oxidation of OH to decompose organic compounds while the Fe2+ is oxidized to Fe3+ simultaneously with a result of coagulation sedimentation. Currently, there are several researches reporting utilization of Internal electrolysis and Fenton advanced oxidation, like treatment of printing and

Experimental material and method The internal electrolysis tower is made of organic glass, having an inner diameter of 150mm and a height of 1000mm. The filling ratio of iron scraps and activated carbon is 1:1. The iron scraps have been taken from the Project Training Center of Dalian University of Science and Technology. Before filling, iron scraps are rubbed repeatedly by hot alkaline solution to eliminate the oil, then soaked in 3% dilute hydrochloric acid with activated carbon to activate 30min in order to clean the surfaces oxide of iron scraps. The activated carbon is almond activated carbon. Before being used, activated carbon is soaked in the original water for 24 hours to make its adsorption saturated, and then activated. The flow rate of influent is controlled to control hydraulic retention time of wastewater. The pH value is adjusted with sulfuric acid or sodium hydroxide. After changing the operation parameter each time, the reactor has been operated steadily with 3 times of hydraulic retention time, and then samples are taken. In order to eliminate the influence of Fe2+ to COD analysis, pH of samples are adjusted to 9 to precipitate Fe2+ and settled 30min, then supernatant is taken to analyze COD. For investigating the influence of flocculation by the settling process of ferric hydroxide to the analysis of COD, the iron-carbon effluent is aerated directly without pH adjustment. COD is measured after Fe2+ has been oxidized to Fe3+. The result shows that both of the COD are nearly the same which illustrates that the flocculation has no obvious effect during the settling process of Fe2+.

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The intermittent method is used for Fenton oxidation. 400ml of internal electrolysis effluent has been put into a 500ml beaker, adjusted pH with the sulfuric acid and stirred with magnetic agitator. Ferrous sulfate and hydrogen peroxide have been added into successively and reacted for certain time. For eliminating the influence of hydrogen peroxide and Fe3+ to COD, pH is adjusted to 9 with sodium hydroxide after reaction. After being settled for 60min, supernatant is taken to analyze COD. Feeding media In this experiment, water fed into reactor is taken from a factory of Da Qing. In order to simulate the actual wastewater of treatment plant, acrylic fiber wastewater and acrylonitrile wastewater are mixed with a ratio of 1:3.The composition of original wastewater is shown in Table 1. C. Analytical procedures [9] According to the fast sealed microwave resolution method, COD can be got. The Dilution inoculation method is for BOD. The o-phenathroline spectrophotometry is used to get the concentrate of Fe2+, while the silver nitrate titrimetric method is for the concentrate of Cyanate ion. The glass-electrodes method is used to measure pH. D. Main reagents Hydrogen peroxide solution (30%), ferrous sulfate (analytical reagent), sulfuric acid (98%) and sodium hydroxide are used in this experiment. III. RESULTS AND DISCUSSION B.

TABLE II.

OPTIMIZATION PARAMETERS OF INTERNAL ELECTROLYSIS AND FENTON OXIDIZATION Internal electrolysis 2 3 0 Fenton oxidation 2 3-4 600 1500 -

Parameters Reaction timeh pH Fe2+mg/L H202mg/L Aeration amountL/h

Internal electrolysis - Fenton oxidation combination system The acrylic fiber wastewater passes through internal electrolysis tower firstly. After the pH value of effluent being adjusted, the ferrous sulfate and the hydrogen peroxide solution are added for Fenton oxidation. The characteristic of this craft is that both of internal electrolysis and Fenton oxidizes are running under the optimum operation parameters separately, therefore it is easier to manage and the performance is stable. The effect of combination system is shown in Figure 1. The result indicates that the average COD value of influent and effluent are 1328mg/L and 772 mg/L, respectively. The removal rate is above 40%. The COD of Fenton advanced oxidation process effluent is 347 mg/L on average, COD removal rate is 55.1%. The total COD removal rate of combination of internal electrolysis and Fenton advanced oxidation is 73.9%, and the COD of the final effluent stabilizes is below 400 mg/L.
1400

B.

COD(mg/L)

Before you begin to format your paper, first write and save the content as a separate text file. Keep your text and graphic files separate until after the text has been formatted and styled. Do not use hard tabs, and limit use of hard returns to only one return at the end of a paragraph. Do not add any kind of pagination anywhere in the paper. Do not number text headsthe template will do that for you. Finally, complete content and organizational editing before formatting. Please take note of the following items when proofreading spelling and grammar. The optimum operation condition of internal electrolysis and Fenton oxidation The optimum operation condition of internal electrolysis and the Fenton oxidation have been determined separately according to the beaker experiment which becomes the foundation for combination of internal electrolysis and the Fenton oxidation. In further experiment, internal electrolysis and Fenton oxidation are both carried on separately under the same operating condition described in Table 2.
TABLE I. CODmg/L 1180-1520 .WASTEWATER COMPONENTS BOD5/COD 0.14-0.18 PH 5-6 CN mg/L 4.24-8.6
-

1200

influent internal electrolysis fenton oxidation

1000

800

600

A.

400

10

Times of experiment

Figure 1. COD concentration in the influent, internal electrolysis effluent and Fenton oxidization effluent in internal electrolysis - Fenton oxidation combination system

C.

BOD5mg/L 165-210

Fenton oxidation - internal electrolysis combination system Although internal electrolysis - Fenton oxidation combination system is stable enough to meet the request of

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further biochemical treatment process, too much acid and alkali consumption for pH adjusting before and after internal electrolysis process is still a problem which leads to increasing of operation cost. It is observed that during the experiment there is decreasing tendency of pH which will meet the pH requirement of internal electrolysis (PH=3). It is also reported that the order of internal electrolysis and the Fenton oxidation had tremendous influence to treatment performance. According to the above, Fenton oxidation - internal electrolysis combination system experiment is carried on, of which the treatment effect is shown in Figure 2. The result shows that the COD of original water decreases from 1373 mg/L to 687 mg/L on average and the COD removal rate is 50%. But COD of the effluents from internal electrolysis is 483 mg/L on average with COD removal of only 29.7%. The good removal performance cant be ensured under the condition that internal electrolysis is carried followed Fenton oxidation as a result of that despite of the strong removal ability both of electrolysis and Fenton oxidation to large molecular organics, Fenton oxidation seems to be stronger than internal electrolysis oxidation so that Fenton oxidation can still continue to degrade reaction products of internal electrolysis when Fenton oxidation followed internal electrolysis oxidation. While following Fenton oxidation, internal electrolysis oxidation hardly have any effect on elimination of reaction product of Fenton oxidation. Meanwhile, internal electrolysis tower tends to be blocked if precipitate production of Fenton oxidation enters into the tower which means backwashing frequency of electrolysis tower will be increased leading to the increasing of operating cost. During the experiment, the backwashing has been required per 24hrs if Fenton oxidation coming first, while internal electrolysis tower can run continuously 4 weeks without backwashing if Fenton oxidation coming after internal electrolysis oxidation. Therefore, process
1400

D.

Internal electrolysis Fenton oxidation coupling craft Effluent from internal electrolysis tower contains a highlevel ferrous ions which can act as catalyst of Fenton oxidation in order to reduce or totally replace the adding ferrous sulfate for further oxidation process. Controlling pH value of influent and hydraulic retention time of internal electrolysis tower can get the optimum pH for Fenton oxidation so that the pH neednt to be adjusted repeatedly. Therefore, the best operation condition of internal electrolysis tower should be reconsidered in order to create a efficient reaction condition for the further Fenton oxidation. Through adjusting HRT and pH of internal electrolysis tower, the pH value and the ferrous ion content (were been) are investigated. Meanwhile, COD removal effect of Fenton oxidation is also investigated by adding hydrogen peroxide solution (1500mg/L) into internal electrolysis effluent (Table 3). The result shows that the primary factor affecting ferrous ion content of internal electrolysis effluent is the pH of influent. With the decreasing of pH, the ferrous ion content of internal electrolysis effluent increases gradually while the HRT doesnt have obvious influence to ferrous ion content and the effluent pH slightly increases with the increasing of HRT. Among the 7 test conditions investigated, only when pH=1, HRT=60min or 45min, effluent COD is under 400 mg. Under these two kinds of operating conditions, the pH and ferrous ion content of internal electrolysis effluent approached the optimum operating condition by Fenton oxidation running independently. After coupling system running 15days stably under the operating condition of Table 3, influent and effluent COD reach to 1286 mg/L and 352 mg/L on average respectively, and the COD removal rate is 72.6% which illustrate that it is feasible to use effluent of internal electrolysis for Fenton oxidation so that repeated pH adjusting and ferrous sulfate adding can be avoided to decrease the cost of operation. But with the decreasing of pH of internal electrolysis influent, iron ion content of effluent increases leading to much iron chip consumption so that iron chip should be supplied in time.
TABLE III. OPERATIONAL PARAMETERS AND RESULTS OF INTERNAL ELECTROLYSIS - FENTON OXIDIZATION COUPLING EXPERIMENT Fenton 488 375 349 553 587 756 722

1200

influent internal electrolysis fenton oxidation

1000

COD(mg/L)

800

Operation parameters PH Fe2+ influent internal electrolysis PH1HRT=30min 2.2 PH1HRT=45min 3.3 PH1HRT=60min 3.6 PH2HRT=30min 4.5 PH2HRT=15min 4.0 PH3HRT=15min 5.4 PH3HRT=30min 6.8 523 562 549 256 277 154 122 1265 1265 1265 1265 1265 1265 1265 698 672 661 712 789 827 792

600

400

10

Times of experiment

Figure 2. COD concentration in the influent, Fenton oxidization effluent and internal electrolysis effluent in Fenton oxidation - internal electrolysis combination system

Note1. Unit is mg/L except for pH; 2. The data of this table are all the average of ten experiments.

of internal electrolysis - Fenton oxidation combination craft takes advantages over that of Fenton oxidation - internal electrolysis combination craft on aspects of treatment performance and operating cost.

On the other hand, if the influent pH is too low, the equipment corrosion will be serious thus higher requirement of treatment equipment material is put forward. In the actual application, PH=1, HRT=45min may be used which means lower HRT to reduce the internal electrolysis tower volume therefore capital investment will be decreased.

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1500

1.0 0.9 0.8 0.7

E.

Internal electrolysis and the Fenton oxidation (carry on) carried out simultaneously If hydrogen peroxides solution is put into internal
COD(mg/L)

1400 1300 1200 1100 1000 900 800 700 600 500 400 0 1 2 3 4 5 6 7 8 9 10

means internal electrolysis and Fenton oxidation will be carried out in the same reactor, thus Fenton oxidizing reactor could be reduced. The pH of original water is adjusted to 1.Hydrogen peroxide solution is put into the original water which concentration is 1500 mg/L. HRT is maintained at 45min and ten experiments are carried out. COD of influent and effluent of simultaneously oxidation and removal rate are shown in Figure 3 which shows that internal electrolysis and Fenton oxidation are carried on simultaneously in the identical reactor with a maximum COD removal rate of 65% only and average effluent COD of 576 mg/L. This may be mainly because reaction time of internal electrolysis and Fenton oxidation can be independent each which means that Fenton oxidation will not be carried on sufficiently due to the short HRT of internal electrolysis tower leading to the performance of effluent unstable. Furthermore, the reaction mechanism in internal electrolysis tower is complex increasing the difficulty of operation controlling.
TABLE IV. RESULT OF INTERNAL ELECTROLYSIS - FENTON OXIDIZATION
COUPLING EXPERIMENT

0.5

influent

effluent

removal rate

0.4 0.3 0.2 0.1 0.0 11

Times of experiment

Figure 3. the COD concentration in the influent, effluent and COD removal efficiency of simultaneously oxidization experiment

F.

Biochemistry research

Frequence 1 1 2 3 4 5 Average 3.2 3.3 3.0 3.4 3.3 3.2

2 551 547 522 518 505 529

3 1308 1279 1343 1196 1285 1286

4 698 683 721 647 702 691

5 372 353 349 325 361 352

BOD5/COD and CN-ion concentration of final effluent of each kind of combined craft are measured. Whether each combined form could enhance the biochemistry of acrylic fiber wastewater is tested to create good condition for the following biochemistry processing. Results indicate that the ratio of BOD5/COD of acrylic fiber wastewater treated by combined form 1 and 3 reach up to 0.3 belonging to scope of being biodegradable. But BOD5/COD of acrylic fiber wastewater treated by combined form 2 and 4 do not increase obviously, which is only 0.2 which will not satisfy the request of further biological process. CN- ion has toxicity to microorganism. CNconcentration of original water is up to 8.6 mg/L and the biological toxicity may be serious. After treatment of combined form 1 and 3, CN-ion concentration is only 0.22 mg/L and the toxicity of CN- ion to the further biological treatment may be reduced. Although treatment of combined form 2 and 4 have some effect on removal of CN- ion, CN-ion concentration of effluent is still up to 2.3 mg/L which means the toxicity of CNion to the further biological treatment remains serious.
TABLE V. RESULTS OF BIODEGRADABILITY RESEARCH 2 500 105 0.21 1.50 3 361 126 0.35 0.18 4 575 127 0.22 2.26

Combined form original water 1 CODmg.L-1 1180-1520 BOD5mg.L-1 165-210 BOD5/COD 0.14-0.18 CN-mg.L-1 4.24-8.6 352 117 0.33 0.215

Note1: (1) (5) replace Influent pH, Influent Fe2+, Influent COD, Internal electrolysis effluent COD and Fenton effluent COD, respectively

Note: combined forms contain: 1. internal electrolysis - Fenton oxidation combination system; 2. Fenton oxidation - internal electrolysis combination system; 3. internal electrolysis Fenton oxidation coupling craft; 4. internal electrolysis and the Fenton oxidation carried out simultaneously system.The data of this table are all the average of ten experiments.

Removal rate

electrolysis tower, Fenton reagent could be formed which

0.6

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IV.

TREATMENT REAGENT COST BUDGET

The main medicament used during the treating process contains sulfuric acid and sodium hydroxide for pH adjusting, hydrogen peroxide solution and ferrous sulfate for Fenton oxidation. According to the actual market price and the amount for treatment per ton, the cost of medicament is calculated and shown on Table 6 from which the medicament cost can be seen with a value of 4.26 RMB/ ton. The main medicament expense is on the hydrogen peroxide solution for Fenton oxidation which amount can be adjusted to reduce the cost according to the quality and biological treatment ability of original water in the practical application. There is another way to reduce the cost which is using Lime commonly used in the industry to replace the sodium hydroxide to adjust pH.You are now ready to style your paper; use the scroll down window on the left of the MS Word Formatting toolbar. V. CONCLUSIONS

The medicament treatment cost is 4.26 Yuan per ton water and the cost could be controlled by controlling the throwing amount of hydrogen peroxide solution. ACKNOWLEDGMENT

Thanks for Professor FengLin Yangs help and instruction from Dalian university of technology. REFERENCES
[1] Cai Xiao-dong, Zheng Guo. Problems in the treatment of wastewater from acrylic fiberproduction and its existing status of research. Industrial Water Treatment, 2006,Vol 26(3):12~15. [2] Yang Qi, Wen Xiang-hua, Meng Yao-bin, Qian Yi. Treatment of Propenylcyanide Waste Water by Using Membrane Hybrid Bioreactor. Enviromental science, 2000Vol 21(2):85~87. [3] Yang Xiao-yi, Shi Shao-qi, Jiang Zhan-peng, Guan Yun-tao, Zhou Shihui. Study on Treatment of Polyacrylonitrile Fiber Wastewater by Coagulation-Anaerobic-Anoxic-Aerobic Process. Water & Wastewater Engineering, 2001,Vol 27(6):40-46. [4] Zhao Cao-cheng, Wang Zhi-wei.The treatment of Acrylic fiber wastewater by ozonation. Environmental Protection of Chemical Industry, 2004,Vol 24: 56~59. [5] Liu Fa-qiang, Wang Peng, Zhao Ying, Pan Xin-ming, Cao Lan-hua, Wen Shan-xiong, Qiao Tong-sen. Purification of nitrile containing waste water by ozone/activated carbon catalytic oxidation. Pebrochemical Technology & Application, 2005,Vol 23(6):474~477. [6] Cai Gu-ping, Ge Xiao-xia, Zhang Yun-hui. Application of new type of iron chips filtering tower for internal electrolysis in industrialized treatment of dyeing wastewater. [7] Fan Bing-jun, Pang Shu-rong, Shen Cai-qin, Sun Xiao-xia. Pre-treating acrylic fiber wastewater by a combined process of microelectrolysis and biofilters. Water & Wastewater Engineering, 2002,Vol 28(8):31~33. [8] Xu Xun, Cao Jia-shun, Chang Fei. Engineering examples of the treatment of chemical wastewater by iron-carbon microelectrolysisFenton oxidization-secondary A/O process. Water & Wastewater, 2004,Vol 30(5):44~47. [9] Tang You-min, Guan Bao-hong, Wu Zhong-biao. The treatment of methyldopa wastewater by Fenton oxidization PAM flocculation A/O process. Water & Wastewater Engineering, 2006,Vol 32(11):49~51. [10] The National Environmental Protection Agency compilation. Water and waste water examination analysis method(3rd edition). Beijing: Environmental science press,1989. [11] Jian Zhang, Zibo Wang, Zhumei Ji. Experiments on Fenton reagent and micro-electrolysis technology to pre-treat wastewater containing nitrobenzene. Journal of Yangzhou University(Natural Science Edition), 2006,Vol.9(22):74~78.

The effect of internal electrolysis following Fenton oxidation was the best and most stable among all the internal electrolysis and Fenton oxidation combined forms. If influent COD is 1332 mg/L, the combination process average COD removal rate can be 73.6% and BOD5/COD can reach to 0.33, the CN-ion concentration of effluent is 0.215 mg/ L which could meet the request of further biological treatment perfectly. Internal electrolysis coupled Fenton oxidization has been proved to have good effects. The optimum operation condition of internal electrolysis tower are when pH is 1, HRT is 45min, and COD of influent and effluent are 1286mg/L and 352mg/L. The COD removal rate can get to 72.6%, BOD5/COD can reach to 0.35 the CN-ion concentration decreases to 0.18mg/L, ferrous sulfate neednt to be added. The only thing needed is to adjust the pH of influent to 1. But iron chips need to be supplied in time for internal electrolysis tower. For internal electrolysis and Fenton simultaneously oxidation craft, both of the reaction times cannot be independent and condition of interaction is complex, the performance of effluent and biochemistry are inefficiency.

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