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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
Abstract—In 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



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 surface’s 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+.

Demonstration Project and Key Technology of Ground water pollution control along the SongHua River Item Number: 2008ZX07207-007

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RESULTS AND DISCUSSION B. COD can be got. ferrous sulfate (analytical reagent). Main reagents Hydrogen peroxide solution (30%).internal electrolysis combination system Although internal electrolysis . 400ml of internal electrolysis effluent has been put into a 500ml beaker. complete content and organizational editing before formatting. TABLE I. In order to simulate the actual wastewater of treatment plant. sulfuric acid (98%) and sodium hydroxide are used in this experiment. The glass-electrodes method is used to measure pH. internal electrolysis effluent and Fenton oxidization effluent in internal electrolysis . Finally. C.18 PH 5-6 CN (mg/L) 4. In further experiment. Please take note of the following items when proofreading spelling and grammar. Do not use hard tabs.24-8. and limit use of hard returns to only one return at the end of a paragraph.Fenton oxidation combination system C.Fenton oxidation combination system The acrylic fiber wastewater passes through internal electrolysis tower firstly. The Dilution inoculation method is for BOD. TABLE II. Keep your text and graphic files separate until after the text has been formatted and styled. pH is adjusted to 9 with sodium hydroxide after reaction. the ferrous sulfate and the hydrogen peroxide solution are added for Fenton oxidation. supernatant is taken to analyze COD.6 - 1200 influent internal electrolysis fenton oxidation 1000 800 600 A. Downloaded on July 17. BOD5(mg/L) 165-210 Fenton oxidation .2010 at 17:23:12 UTC from IEEE Xplore. COD removal rate is 55. 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. Analytical procedures [9] According to the fast sealed microwave resolution method. adjusted pH with the sulfuric acid and stirred with magnetic agitator. water fed into reactor is taken from a factory of Da Qing.WASTEWATER COMPONENTS BOD5/COD 0. The COD of Fenton advanced oxidation process effluent is 347 mg/L on average. The effect of combination system is shown in Figure 1. COD(mg/L) 1180-1520 .14-0.Fenton oxidation combination system is stable enough to meet the request of 2 Authorized licensed use limited to: UNIVERSIDADE NOVA DE LISBOA. Do not add any kind of pagination anywhere in the paper. D.The intermittent method is used for Fenton oxidation.9%. OPTIMIZATION PARAMETERS OF INTERNAL ELECTROLYSIS AND FENTON OXIDIZATION Internal electrolysis 2 3 0 Fenton oxidation 2 3-4 600 1500 - Parameters Reaction time(h) pH Fe2+(mg/L) H202(mg/L) Aeration amount(L/h) Internal electrolysis . The total COD removal rate of combination of internal electrolysis and Fenton advanced oxidation is 73. The o-phenathroline spectrophotometry is used to get the concentrate of Fe2+. III. therefore it is easier to manage and the performance is stable. COD concentration in the influent. For eliminating the influence of hydrogen peroxide and Fe3+ to COD. while the silver nitrate titrimetric method is for the concentrate of Cyanate ion. The result indicates that the average COD value of influent and effluent are 1328mg/L and 772 mg/L. 400 0 2 4 6 8 10 Times of experiment Figure 1. The removal rate is above 40%. Feeding media In this experiment. . respectively.1%. Ferrous sulfate and hydrogen peroxide have been added into successively and reacted for certain time. acrylic fiber wastewater and acrylonitrile wastewater are mixed with a ratio of 1:3. After being settled for 60min. The characteristic of this craft is that both of internal electrolysis and Fenton oxidizes are running under the optimum operation parameters separately. and the COD of the final effluent stabilizes is below 400 mg/L. 1400 B. internal electrolysis and Fenton oxidation are both carried on separately under the same operating condition described in Table 2. Do not number text headsthe template will do that for you. After the pH value of effluent being adjusted. first write and save the content as a separate text file.The composition of original wastewater is shown in Table 1. Restrictions apply. COD(mg/L) Before you begin to format your paper.

The result shows that the primary factor affecting ferrous ion content of internal electrolysis effluent is the pH of influent. During the experiment. HRT=60min or 45min. the best operation condition of internal electrolysis tower should be reconsidered in order to create a efficient reaction condition for the further Fenton oxidation.7%. Restrictions apply. COD removal effect of Fenton oxidation is also investigated by adding hydrogen peroxide solution (1500mg/L) into internal electrolysis effluent (Table 3). 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. if the influent pH is too low. The data of this table are all the average of ten experiments. only when pH=1. It is observed that during the experiment there is decreasing tendency of pH which will meet the pH requirement of internal electrolysis (PH=3).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.internal electrolysis combination system experiment is carried on. Therefore. COD concentration in the influent. Fenton oxidation .0 PH=3,HRT=15min 5. OPERATIONAL PARAMETERS AND RESULTS OF INTERNAL ELECTROLYSIS . 3 Authorized licensed use limited to: UNIVERSIDADE NOVA DE LISBOA. 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. Fenton oxidization effluent and internal electrolysis effluent in Fenton oxidation . influent and effluent COD reach to 1286 mg/L and 352 mg/L on average respectively. 2. . process 1400 D. According to the above. But with the decreasing of pH of internal electrolysis influent. of internal electrolysis .8 523 562 549 256 277 154 122 1265 1265 1265 1265 1265 1265 1265 698 672 661 712 789 827 792 600 400 0 2 4 6 8 10 Times of experiment Figure 2.further biochemical treatment process.2 PH=1,HRT=45min 3. 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 needn’t to be adjusted repeatedly. Through adjusting HRT and pH of internal electrolysis tower. 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. With the decreasing of pH. iron ion content of effluent increases leading to much iron chip consumption so that iron chip should be supplied in time. while internal electrolysis tower can run continuously 4 weeks without backwashing if Fenton oxidation coming after internal electrolysis oxidation. internal electrolysis oxidation hardly have any effect on elimination of reaction product of Fenton oxidation. the pH and ferrous ion content of internal electrolysis effluent approached the optimum operating condition by Fenton oxidation running independently. In the actual application. After coupling system running 15days stably under the operating condition of Table 3. On the other hand. Under these two kinds of operating conditions.internal electrolysis combination craft on aspects of treatment performance and operating cost.Fenton oxidation combination craft takes advantages over that of Fenton oxidation . Meanwhile. PH=1.6 PH=2,HRT=30min 4. Unit is mg/L except for pH. the pH value and the ferrous ion content (were been) are investigated. But COD of the effluents from internal electrolysis is 483 mg/L on average with COD removal of only 29. It is also reported that the order of internal electrolysis and the Fenton oxidation had tremendous influence to treatment performance.internal electrolysis combination system Note1. Downloaded on July 17. and the COD removal rate is 72.3 PH=1,HRT=60min 3.4 PH=3,HRT=30min 6. HRT=45min may be used which means lower HRT to reduce the internal electrolysis tower volume therefore capital investment will be decreased. the backwashing has been required per 24hrs if Fenton oxidation coming first. 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%. Meanwhile. While following Fenton oxidation. 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. The good removal performance can’t 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. Therefore. the equipment corrosion will be serious thus higher requirement of treatment equipment material is put forward. Among the 7 test conditions investigated.2010 at 17:23:12 UTC from IEEE Xplore. of which the treatment effect is shown in Figure 2. effluent COD is under 400 mg.5 PH=2,HRT=15min 4. the ferrous ion content of internal electrolysis effluent increases gradually while the HRT doesn’t have obvious influence to ferrous ion content and the effluent pH slightly increases with the increasing of HRT.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 PH=1,HRT=30min 2. TABLE III.

RESULT OF INTERNAL ELECTROLYSIS .26 Combined form original water 1 COD(mg.FENTON OXIDIZATION COUPLING EXPERIMENT 0. The pH of original water is adjusted to 1. . 3. 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. Although treatment of combined form 2 and 4 have some effect on removal of CN.21 1.18 4 575 127 0.ion. 2. But BOD5/COD of acrylic fiber wastewater treated by combined form 2 and 4 do not increase obviously. CN-ion concentration is only 0.Hydrogen peroxide solution is put into the original water which concentration is 1500 mg/L.5 influent effluent removal rate 0. CN-ion concentration of effluent is still up to 2.0 0.0 3. Downloaded on July 17.22 2.internal electrolysis combination system. Influent Fe2+.2 which will not satisfy the request of further biological process.6 352 117 0.2 3. thus Fenton oxidizing reactor could be reduced. Influent COD. Biochemistry research Frequence (1) 1 2 3 4 5 Average 3.33 0. internal electrolysis .L-1) 165-210 BOD5/COD 0.18 CN-(mg. the COD concentration in the influent. Results indicate that the ratio of BOD5/COD of acrylic fiber wastewater treated by combined form 1 and 3 reach up to 0. internal electrolysis – Fenton oxidation coupling craft. which is only 0.3 3.4 0. 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.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.50 3 361 126 0. After treatment of combined form 1 and 3.0 11 Times of experiment Figure 3.3 3. CNconcentration of original water is up to 8. effluent and COD removal efficiency of simultaneously oxidization experiment F. RESULTS OF BIODEGRADABILITY RESEARCH 2 500 105 0.7 E.6 mg/L and the biological toxicity may be serious. 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. TABLE V. Internal electrolysis effluent COD and Fenton effluent COD. Furthermore.3 belonging to scope of being biodegradable.35 0. CN.3 mg/L which means the toxicity of CNion to the further biological treatment remains serious.L-1) 4.The data of this table are all the average of ten experiments.2 0.ion to the further biological treatment may be reduced.8 0. internal electrolysis and the Fenton oxidation carried out simultaneously system. the reaction mechanism in internal electrolysis tower is complex increasing the difficulty of operation controlling. HRT is maintained at 45min and ten experiments are carried out. Fenton reagent could be formed which 0. 4. TABLE IV.6 4 Authorized licensed use limited to: UNIVERSIDADE NOVA DE LISBOA.ion has toxicity to microorganism.1500 1.2010 at 17:23:12 UTC from IEEE Xplore.24-8.4 3. respectively Note: combined forms contain: 1. Removal rate electrolysis tower.L-1) 1180-1520 BOD5(mg.Fenton oxidation combination system.1 0.215 Note1: (1) –(5) replace Influent pH.9 0. Restrictions apply.22 mg/L and the toxicity of CN.14-0. Fenton oxidation .3 0.

[10] The National Environmental Protection Agency compilation. 2004. hydrogen peroxide solution and ferrous sulfate for Fenton oxidation. Zhou Shihui.1989. Industrial Water Treatment. Zhang Yun-hui.26 Yuan per ton water and the cost could be controlled by controlling the throwing amount of hydrogen peroxide solution. 2006. Restrictions apply. Enviromental science. Guan Bao-hong.You are now ready to style your paper. [7] Fan Bing-jun.Vol. Treatment of Propenylcyanide Waste Water by Using Membrane Hybrid Bioreactor. Cao Jia-shun.33. Pre-treating acrylic fiber wastewater by a combined process of microelectrolysis and biofilters.18mg/L.6%. Downloaded on July 17. [4] Zhao Cao-cheng. According to the actual market price and the amount for treatment per ton. Shi Shao-qi. Meng Yao-bin. REFERENCES [1] Cai Xiao-dong. Jiang Zhan-peng. 2006. Pang Shu-rong. Water and waste water examination analysis method(3rd edition). Problems in the treatment of wastewater from acrylic fiberproduction and its existing status of research. Shen Cai-qin. Wu Zhong-biao. Zheng Guo. If influent COD is 1332 mg/L. Experiments on Fenton reagent and micro-electrolysis technology to pre-treat wastewater containing nitrobenzene.Vol 32(11):49~51. 2004. Zhumei Ji. 2006. [11] Jian Zhang. Study on Treatment of Polyacrylonitrile Fiber Wastewater by Coagulation-Anaerobic-Anoxic-Aerobic Process. Qiao Tong-sen. Internal electrolysis coupled Fenton oxidization has been proved to have good effects. Beijing: Environmental science press. Engineering examples of the treatment of chemical wastewater by iron-carbon microelectrolysisFenton oxidization-secondary A/O process. Environmental Protection of Chemical Industry. Sun Xiao-xia. The treatment of methyldopa wastewater by Fenton oxidization – PAM flocculation – A/O process. the cost of medicament is calculated and shown on Table 6 from which the medicament cost can be seen with a value of 4.Vol 23(6):474~477.Vol 28(8):31~33. [8] Xu Xun. The effect of internal electrolysis following Fenton oxidation was the best and most stable among all the internal electrolysis and Fenton oxidation combined forms.215 mg/ L which could meet the request of further biological treatment perfectly. 2000,Vol 21(2):85~87.Vol 24: 56~59. The only thing needed is to adjust the pH of influent to 1. Wen Xiang-hua.9(22):74~78. HRT is 45min. the performance of effluent and biochemistry are inefficiency. 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.2010 at 17:23:12 UTC from IEEE Xplore.IV. Wang Zhi-wei. Cao Lan-hua. 2005. both of the reaction times cannot be independent and condition of interaction is complex. use the scroll down window on the left of the MS Word Formatting toolbar.6% and BOD5/COD can reach to 0. the combination process average COD removal rate can be 73.Vol 30(5):44~47.The treatment of Acrylic fiber wastewater by ozonation. ferrous sulfate needn’t to be added. Wang Peng. Water & Wastewater Engineering. The optimum operation condition of internal electrolysis tower are when pH is 1. The COD removal rate can get to 72. TREATMENT REAGENT COST BUDGET • The main medicament used during the treating process contains sulfuric acid and sodium hydroxide for pH adjusting. Journal of Yangzhou University(Natural Science Edition). BOD5/COD can reach to 0.Vol 26(3):12~15. ACKNOWLEDGMENT Thanks for Professor FengLin Yang’s help and instruction from Dalian university of technology. 2002. Zibo Wang. Pebrochemical Technology & Application. Qian Yi. . V. Water & Wastewater. Water & Wastewater Engineering. Purification of nitrile containing waste water by ozone/activated carbon catalytic oxidation. Guan Yun-tao. Ge Xiao-xia. • CONCLUSIONS The medicament treatment cost is 4. [2] Yang Qi. [9] Tang You-min. Pan Xin-ming. and COD of influent and effluent are 1286mg/L and 352mg/L. 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. Wen Shan-xiong. For internal electrolysis and Fenton simultaneously oxidation craft.Vol 27(6):40-46. • • 5 Authorized licensed use limited to: UNIVERSIDADE NOVA DE LISBOA. [5] Liu Fa-qiang. [6] Cai Gu-ping. Application of new type of iron chips filtering tower for internal electrolysis in industrialized treatment of dyeing wastewater. Water & Wastewater Engineering. Chang Fei.26 RMB/ ton. the CN-ion concentration of effluent is 0. [3] Yang Xiao-yi. 2001. Zhao Ying. But iron chips need to be supplied in time for internal electrolysis tower.35 , the CN-ion concentration decreases to 0.