Anal. Bioanal. Electrochem., Vol. 2, No.

3, 2010, 165- 177

Analytical &
Bioanalytical
Electrochemistry
2010 by CEE www.abechem.com

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Phosphorous removal from wastewater effluent using electro-coagulation by aluminum and iron plates
Hamed Gharibi,1 Amir Hossein Mahvi,1,2 ,* Mohammad Chehrazi,3 Razih Sheikhi,1 Sara Sadat Hosseini1 School of Public Health and Center for Environmental Research, Tehran University of Medical Sciences, Tehran, Iran 2 National Institute of Health Research, Ministry of Health, Tehran, Iran 3 Department of biostatistics and epidemiology, Tehran university of medical sciences, Tehran, Iran * Corresponding Author; Tel.:88954914; Fax: 88950188
E-Mail: ahmahvi@yahoo.com
1

Received: 24 July 2010 / Accepted: 5 October 2010 / Published online: 20 October 2010

Abstract- In this study, phosphorous removal from wastewater effluent performed using electro-coagulation by aluminum and iron plates. This work had 3step: assessment of electrocoagulation for phosphate removal with phosphate concentration based on wastewater effluent in standard conditions (6mg/l), and evaluation of pH (3, 5.5, 7, 8.5, 10), voltage (20 V, 30 V, 40 V), and contact time(10 min, 20 min, 40 min, 60 min) for elucidation of best condition in phosphate removal; evaluation of the process according to the best conditions obtained in step 1 in different concentrations of 4, 8, and 10 mg/l; test of optimum conditions obtained in first two steps on real wastewater. Result obtained from synthetic waste water showed that the most effective phosphate removal with AL/AL plates is >99% in pH 8.5 and 40 V and 40 min after starting process and for IR/IR plates is >99% in pH 5.5 and 40 V and 40 min after starting process. Result obtained from 2th step revealed that the removal efficiency was high whenever concentration of phosphate decreased and efficiency of removal with AL plates is higher than IR plates. In 3th step, efficiency of phosphorous removal using electro-coagulation assessed and efficiency of this step with aluminum plates on real wastewater under different conditions is >99%. Keywords- Phosphorous removal, Electro-coagulation, Wastewater effluent

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1. INTRODUCTION As known, phosphate discharged into the surface waters, accelerates eutrophication [1, 2]. This can in turn disturb the balance of organisms present in the water and affect water quality, mainly through the depletion of oxygen level as the algae decay. Reduced oxygen level can have harmful effects on fish and other aquatic life, causing reductions in biodiversity. Eutrophication can also affect the recreational value of natural resources [3]. Phosphorus removal techniques are chemical treatments like adsorption, chemical precipitation, ion exchange, electro dialysis, hybrid systems containing fly-ash adsorption and membrane filtration and electrocoagulation [4].Biological treatment for phosphorous removal also used but removal efficiency usually does not exceed 30%, which means that remaining phosphate should be removed by another technique [5]. Phosphate removal with adsorption and chemical precipitation also have been explored [6,7], but chemical precipitation with use of aluminum sulphate and ferric chloride need further costs for purchase and installation of dosing equipment and operating costs for power, disposal of additional sludge, manpower, and surely chemicals used [8]. Electrocoagulation for wastewater treatment has been tested in recent years. Electrocoagulation is a process that creating metallic hydroxide flocks within the wastewater by electro-dissolution of soluble anodes, usually made of iron or aluminum [9]. Phosphate removal with electrocoagulation has a several advantages, such as no need of additional chemical matter after or before treatment, relatively low area demand [10], also sludge from this process is intensive and has low water [11]. For this reasons, in this work, phosphate removal from wastewater effluent has been studied with electrocoagulation. Choosing plates for this process is very important and common plate materials are aluminum and iron. They are cheap, readily available, and proven effective [12]. As known, Al3+ and Fe3+ ions dissolve and combine with hydroxyl ions in the water [13], when direct current passes through the Al and Fe anodes, they form metal hydroxides, which are partly soluble in the water under definite pH values. This step results in the colloidal particles formation with metal hydroxides as nuclei of the latter. Around a nucleus, the adsorption layer of cations and anions is being organized. Taken together, the nucleus and adsorption layer form a granule of the colloidal particle, which has a small positive charge. To compensate the charge, a diffusion layer is being formed around the granule, which makes the particle a neutral one. The main reactions that occur during the electrolysis reactions are shown in below. When aluminum is used as plate materials, the reactions are as follows: At the cathode: (1) 3H2O + 3e3/2 H2O+3OH

Anal. Bioanal. Electrochem., Vol. 2, No. 3, 2010, 165 177 At the anode: Al Al3++3e In the solution: Al (aq)+3H2OAl(OH)3 + 3H+(aq)
3+

167

(2)

(3)

When iron is used as plate materials, the reactions are: At the cathode: 3H2O + 3e 3/2 H2(g) + 3OH At the anode: 4Fe(s) 4Fe2+(aq) + 8e And with dissolved oxygen in solution: 4Fe2+(aq) + 10H2O(l) + O2 (g) 4Fe(OH)3 + 8H+(aq) Overall reaction: 4Fe(s) + 10 H2O (l) + O2 (g) Fe (OH) 3(S) + 4H2(g) (5) (4)

(6)

(7)

As seen in the above reactions, electrocoagulation is a combination of oxidation, flocculation and flotation. Electrocoagulation has occurred in three steps. In first step, coagulant has formed because of oxidation of anode. In second step, pollutants have destabilized. In last step, destabilized matters have united [14]. Aim of this work was to study the feasibility of phosphorous removal with electrocoagulation and determine the optimum operating conditions under different values such as pH, current density(CD), contact time and different plates (aluminum and iron) for doing the best conditions that found in real wastewater effluent.

2. EXPERIMENTAL 2.1. Reagent and Solutions All chemicals used were analytical grade and used without further treatment. All chemical were purchased from Merck chemicals. Distilled water was used in step 1 and 2 of study and for 3th step reactor was filled with real wastewater that collected from wastewater treatment effluent. Phosphate solutions were prepared from KH2PO4 (Merck) in 1 and 2th step. NaCl 1%(Merck), was used as supporting electrolyte. When necessary, pH was adjusted by using 0.1N HCl or 0.1N NaOH. After collecting samples, in distinguished time (10, 20, 40, 60 min) spectrophotometer (PERKINELMER lambda25) was used for the analysis of

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phosphate in accordance with the standard methods (vanadomolybdophosphoric acid calorimetric method) [16]. 2.2. Experimental setup For this study, a glass tank in 1 litter volume with two plates (5 11 cm) was used Fig. 2. The plates were vertically in to the tank and the gap between the plates was 1.5 cm. One of the aims in this study was determine of operating efficiency between aluminum and iron plates for phosphorous removal with electro-coagulation and in according this, plates were made of aluminum and iron separately. Plates were connected to terminal of direct supply power characterized by 5 A for current and the ranges 040 V for voltage. Temperature (21-22 c) was stable in during of the work. Synthetic phosphate solutions(6 mg/l) was used in the first step and in 2th step, in best efficiencies that elucidated in the first step, concentration of phosphate changed to 4 mg/l and 8 mg/l and 10 mg/l for evaluating of process and best operating conditions that caught in first step. At the beginning of each run the solution of phosphate (900 ml) of the desired concentration was fed into the reactor and 100 ml of 1% solution of NaCl (as electrolyte) was added to it to increase the solution conductivity. Each run was timed starting with the DC power supply switching on.

Fig.1. A schematic diagram of the experimental set up

3. RESULTS AND DISCUSSION This work had 3step: assess of electro coagulation for removal of phosphate with phosphate concentration based in wastewater effluent standard condition (6 mg/l), and evaluating of pH, current density and contact time for elucidating of best condition in phosphate removal and in 2th step, in best efficiencies that elucidated in first step, concentration of phosphate changed to 4 mg/l and 8 mg/l and 10 mg/l for evaluating of

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process and best conditions that caught in first step. In 3th step, efficiency of phosphorous removal using electro-coagulation assessed. 3.1. First step Percentage of phosphorous removal using electro-coagulation with iron plates on synthetic wastewater that was containing phosphate in concentration of 6 mg/l was studied in first step. As seen in table 1, phosphorous removal under pH 5.5 and 40 V and 40 min after electro-coagulation process was >99% .it must be noted that in pH 5.5 and 30 V, after 60 min of electro-coagulation process, efficiency of phosphorous removal was >99% too.

Table.1. Result of studies with iron plates

pH 3 VOLTAGE (V) 20 30 40 5.5 20 30 40 7 20 30 40 8.5 20 30 40 10 20 30 40 T=10 min 40.44 46.56 50.78 72.67 78.89 89.9 50.79 69.3 78.56 60.5 64.41 70.68 58.98 64.76 71.22 T=20 min 50.68 58.71 65.98 78.47 84.32 93.67 67.15 78.76 83.77 67.33 75.27 78.68 65.43 74.00 79.66 T=40 min 68.56 75.89 79.76 88.90 92.56 >99 80.10 85.42 87.68 84.77 87.80 90.56 78.33 83.22 88.24 T=60 min 73.34 79.65 83.79 97.90 >99 >99 91.87 93.88 95.4 95.45 97.21 98.00 91.32 93.45 95.2

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Phosphorous removal using electro-coagulation by aluminum plates on synthetic wastewater that was containing phosphate in concentration of 6 mg/l was studied in following of first step. As seen in table 2, phosphorous removal under pH 8.5 and 40 V and 40 min after electro-coagulation process was >99%.

Table.2. Result of studies with aluminum plates

pH VOLTAGE (V) 3 20 30 40 5.5 20 30 40 7 20 30 40 8.5 20 30 40 10 20 30 40 T=10 min 65.43 67.54 70.76 72.22 74.49 75.22 76.44 78.33 80.45 79.54 81.43 89.29 76.44 79.22 89.23 T=20 min 70.56 76.54 78.54 81.22 83.11 81.22 82.67 86.34 89.44 84.32 85.54 96.34 82.98 88.45 90.21 T=40 min 84.42 85.91 90.00 87.57 85.98 89.22 92.35 93.44 94.55 90.34 93.33 >99 90.65 92.65 95.22 T=60 min 92.21 95.32 98.59 93.67 95.86 96.66 97.10 97.33 98.33 98.12 >99 >99 98.43 97.22 98.11

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In 2th step, in best efficiencies that elucidated, concentration of phosphate changed to 4 mg/l and 8 mg/l and 10 mg/l for evaluating of process and best conditions that caught in first step. In best operating conditions that caught in respect with pH, efficiency of phosphorous removal with aluminum plates was high in pH 8.5 and for iron plates was high in pH 5.5. For this reason, concentration of phosphate in this pH that mentioned changed. Efficiency of phosphorous removal with using electro-coagulation with iron plates has shown in table.3. As seen in this table; with decrease of phosphate concentration, efficiency of process with iron plates gives better results.

Table.3. Result of studies with iron plates and pH 5.5 on synthetic wastewater Was containing phosphate
phosph ate 4 VOLTAGE (V) 20 30 40 8 20 30 40 10 20 30 40 T=10 min 97.34 98.12 >99 81.32 87.17 89.13 80.12 83.00 88.25 T=20 min >99 >99 >99 90.00 91.36 94.47 82.57 86.46 92.45 T=40 min >99 >99 >99 95.16 95.10 >99 90.55 93.19 96.76 T=60 min >99 >99 >99 98.22 98.34 >99 94.11 97.22 >99

Efficiency of phosphorous removal with using electro-coagulation with aluminum plates has shown in table 4. As seen in this table; with decrease of phosphate concentration, efficiency of process with aluminum plates gives better results.

Anal. Bioanal. Electrochem., Vol. 2, No. 3, 2010, 165 177 3.3. 3th step

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In 3th step, the optimum conditions that this work reached, on real wastewater tested. With results of 2th step and statistical analysis elucidated that efficiency of phosphorous removal with aluminum plates in electro-coagulation process is higher than iron plates, so phosphorous removal using electro-coagulation in real waste water tested with aluminum plates. Real wastewater was containing 5.5 mg/l phosphate. In this step, because efficiency of phosphorous removal with aluminum plates was high in ph8.5, this work was on real wastewater with natural pH 6.5 and pH 8.5. Efficiency of phosphorous removal with using electro-coagulation with aluminum plates in this step has shown in table.5.

Table.4. Result of studies with aluminum plates and pH 8.5 on synthetic wastewater Was containing phosphate
phospha te 4 VOLTAGE (V) 20 30 40 8 20 30 40 10 20 30 40 T=10 min >99 >99 >99 82.22 88.07 86.63 82.22 83.56 88.45 T=20 min >99 >99 >99 90.65 93.76 95.97 87.67 89.66 95.45 T=40 min >99 >99 >99 94.76 96.00 >99 92.65 97.89 >99 T=60 min >99 >99 >99 98.12 >99 >99 98.11 >99 >99

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Table.5. Result of studies with aluminum plates on real wastewater was containing 6 mg/l phosphate
pH VOLTAGE (V) T=10 min T=20 min T=40 min T=60 min

Real

20 30

97.68 98.56

>99 >99

_ _

_ _

40 8.5 20

>99 98.7

>99 >99

_ _

_ _

30

>99

>99

40

>99

>99

As seen in table.5, efficiency of phosphorous removal using electro-coagulation with aluminum plates on real wastewater is >99% in 40 V and after 10min of starting process and in pH 8.5, efficiency is >99% in 30 V and after 10min of starting process. 3.4. Statistical analysis Statistical method used in this study is analysis of variance with repeated measurements. Whole tests were performed with significance level of 0.05[p<0.05]. In this study, time variable had a significant effect on removal process [p<0.0005] when iron plates were used. In Fig. 2, diagram of phosphate removal is shown along with the time. Also the voltage and pH have a significant effect on phosphate removal (p). Maximum of the phosphorous removal was seen in voltage 40 and pH 5.5 which corresponding means are 84.027 and 89.685, respectively.

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Fig. 2. Diagram of phosphate removal using iron electrodes along with the time

Difference of each mean with other level of corresponding variable is statistically significant [p<0.0005 and p<0.0005]. Using aluminum plate, it was shown that time variable has a significant effect on the removal process [p<0.0005]. Diagram of time effect for aluminum plate is shown in the Fig. 3. The pH and voltage have a significant effect on phosphorous removal too.

Fig. 3. Diagram of phosphate removal using aluminum electrodes along with the time

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The maximum of phosphorous removal in this plate was seen in voltage 40 and pH 8.5 which mean removal is 89.971 and 91.271, respectively. Finally, results show that mean removal using aluminum plates is higher than iron plates. This difference is statistically significant [p<0.0005]. In the next step, it was illustrated that phosphate variable had a significance effect on removal percentage [p=0.007] when phosphate added to reactor. The maximum removal using iron plates achieved in phosphate concentration of 4 mg/l which mean difference of this phosphate level with the other levels was significant [p= 0.03 and p= 0.008]. Along with the time, removal percentage increased in phosphate concentrations of 4 mg/l, 8 mg/l, and 10 mg/l; this process is shown in Fig. 4. However, removal percentage in phosphate concentration of 4 mg/l is higher than other concentrations.

Fig. 4. Removal percentage of phosphate concentration using iron electrodes along with the time

When aluminum plates were used, the maximum removal was observed in the concentration of 4 mg/l. Mean difference of the phosphate level with the other levels are significant [p= 0.02 and p= 0.01]. Removal percentage of phosphate concentration with aluminum plates is shown in Fig. 5. Removal percentage increased along with the time in concentrations of 4 mg/l, 8 mg/l, and 10 mg/l.

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Fig. 5. Removal percentage of phosphate concentration using aluminum electrodes along with the time

4. CONCLUSION In this work, electro-coagulation process was used for removal of phosphate from wastewater effluent. Result obtained from experiments on synthetic waste water showed that the most effective phosphate removal by AL/AL plates is >99% in pH 8.5 and voltage 40 and 40min after starting process and for IR/IR plates is >99% in pH 5.5 and voltage 40 and 40 min after starting process. Result obtained from 2th step revealed that the removal efficiency was high whenever concentration of phosphate decreased and efficiency of removal with AL/AL plates is higher than IR/IR plates. In 3th step, efficiency of phosphorous removal using electro-coagulation assessed and efficiency of this step with aluminum plates on real wastewater under different conditions is >99%. According to these results, it can be concluded that electro-coagulation process for phosphorous removal using aluminum plates is better than iron plates and is able to operate for phosphate removal with high efficiency from wastewater effluent.

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