International Review of Chemical Engineering (I.RE.CH.E.), Vol. 3, N.

5 September 2011

Cadmium Removal from Potable Water of Mujamma Aldour by Electrocoagulation Process Using Aluminum Electrodes
Maha I. Al-Ali

Abstract Electrocoagulation (EC) process is an effective method for the removal of heavy
metal ions from water and wastewater effluents. In the present study, the removal of Cadmium (Cd) ions from potable water of Al-Mujamma Alsakany of Aldour city in Salahaddin Province north of Baghdad in Iraq has been studied by EC process with aluminum electrodes. The effect of several parameters such as pH(3-10), voltage(v) (20-40volt), time(t) (5-25min) and electrodes spaces (d) (3-6cm) on the performance of EC process has been investigated. The results indicated that the initial pH has no significant effect on the removal efficiency. The applied voltage and electrolysis period has a positive effect on the Cd removal efficiency. In which that the optimum operating conditions were determined as an electric potential of 40 volt, operating time of 25 min at pH 3. Also, the electrical energy consumption and electrode consumption were examined. Indeed the kinetic of contaminant (Cd) removal was calculated as a first order kinetic model. Copyright 2011 Praise Worthy Prize S.r.l. - All rights reserved.

Keywords: Aluminum Electrodes, Cadmium Removal, Electrocoagulation, Potable Water

I.

Introduction

The Contamination of water by toxic heavy metals, Cadmium, in particular, is a world-wide environmental problem [1]. Cadmium is introduced in to bodies of water from smelting, metal plating, Cadmium-Nickel batteries, phosphate fertilizer, mining, pigments, stabilizers, alloy industries sewage sludge and may also be caused by impurities in the zinc of galvanized pipes and solders and some metal fittings [2]. Particularly, cadmium can be released to drinking water from the corrosion of some galvanized plumbing and water main pipe materials [3]. The drinking water guideline value recommended by World Health Organization (WHO) is 0.005 mg Cd/L [4]. There are certain substances which, if present in supplies of drinking water at concentrations above certain levels, may give rise to actual danger to health such as itai-itai disease, renal damage, emphysema, hypertension, and testicular atrophy [2], [5]. In recent years, EC shows the greatest potential for application in the treatment of drinking water [6]-[10] and wastewaters of different sources as well as of textile industry [11], tannery [12], laundry [13], polishing [14], paper industry [15], oily bilge water [16] and many others wastewater sources. The advantages of EC over conventional technologies include high removal efficiency, compact treatment facility, and possibility of complete automation. Therefore tap water that was contaminated with higher concentrations of Cd(II) can

excellently treated by EC. EC is an electrocoagulation waste water treatment technique, in which an electric current is applied to sacrificial electrodes and metal ions are released as coagulant/sorbent into the water by electrolysis [17].In the environment Cd is usually present as mineral combined with other elements such as oxygen, chlorine, or sulphur (cadmium sulphate, cadmium sulphide) in zinc, lead, and copper ores. All these forms are solids that dissolve in water to varying degree [17]. Cadmium is considered as carcinogen and has a high biological half-time of 10 to 30 year. Its toxicity is therefore accumulative even at low dosages. The removal of cadmium from water or aqueous solution was carried out by electrocoagulation using various types of electrodes such as iron [18]-[20], magnesium [21], aluminum [22], [23] or aluminum alloy [24], zinc [25], stainless steel [26], commercial laminate steel [27] and other metals of electrodes. I.1. Reactions at the Electrodes

A simple electro-coagulating reactor is made up of one anode and one cathode. When a potential is applied from an external power source, the anode material undergoes oxidation, while the cathode will be subjected to reduction or reductive deposition of elemental metals. The electrochemical reactions with metal M as anode may be summarized as follows [28]-[31].

Manuscript received and revised August 2011, accepted September 2011

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Maha I. Al-Ali

At the anode:
M M n + ne nH 2O 2nH + + O2 + 2ne

(1)

the electrocoagulation time (hr) & V is the volume (m3) of the treated water [31], [32]. Also, the amount of electrode dissolved was calculated theoretically by using Faraday's law:
Celectrode = l t M z F V

At the cathode:
M n + + ne M n nH 2O + ne H 2 + nOH 2

(4)

(2)

The purpose of this work is to achieve lower concentration of Cd to the permissible level of it using Al electrodes by the EC process and to reduce the energy and electrode consumption by shortening the treatment time for Cd removal from drinking water. Influence of operation parameters that affect the EC process; initial pH, applied voltage, operating time and electrodes spacing were determined for better removal efficiency.

where Celectrode (kg Al electrode/m3 of treated water) is the theoretical amount of ion produced by current intensity I (A) passed for a duration of operating time t (min), z is the number of electrons involved in the oxidation/reduction reaction; for Al, zAl = 3. Mw is the atomic weight of anode material (Mw Al = 0.02698 kg/mol), F is the Faradays constant (96485C/mol) and V is the volume (m3) of the potable water in the EC reactor. Hence, the amount of aluminum adsorption increased with the increase in adsorbent concentration, which indicated that the adsorption depended on the availability of binding, sites for aluminum hydroxides flocs [31][34].

II.

Materials and Method

III. Results and Discussion

In the present study, electrocoagulation process has been evaluated as a treatment technology for cadmium removal from potable water. Cadmium removal efficiency (Re%) at different condition pH, voltage (v), time (t) and electrodes space (d) were evaluated. III.1. Effect of pH on Metals Removal It has been established that the influent pH is an important operating factor influencing the performance of the EC process [17], [35]. To examine its effect, the sample water was adjusted to the desired pH for each experiment by using 0.1M NaOH solution and 0.1M H2SO4 solution. But as illustrated in Table I, the influent pH did not affect the removal efficiencies significantly over a wide range. Therefore, pH adjustment before treatment is not required. Also the pH was varied in the range (3-10) to investigate the influence of this parameter on the removal of cadmium. As seen, the final pH for pH 3 and 7 of experiments is higher than initial pH, which is in agreement with Peulen and Vik et al. [17], [35], a pH increase occurs when the initial pH is lower than7 according to hydrogen evolution at cathodes by the release of carbon dioxide from water owing to hydrogen bubble disturbance or when the initial pH is acidic, reactions would shift towards which causes a pH increase. For initial pH =10, the final pH was lower than 10. In alkaline medium pH more than 8, the final pH does not vary very much and a slight drop was recorded and suggested that electrocoagulation can act as pH buffer [36], finally notice that the highest efficiency of cadmium removal observed at pH=10 in alkaline medium of 99.4%.
International Review of Chemical Engineering, Vol. 3, N. 5

The EC experiments were carried-out in a batch mode using a 1000mL Plexiglas reactor 194mm inside diameter and 125mm height by vertically positioned Al/Al electrodes spaced by (3, 4.5 & 6) cm were dipped in the water sample and connected to a digital DC power supply (Type SDR 4010, SODILEC Model; 40V, 10A). The cathode and anode consist of separated sheets; each one dimensions of (100602mm), the submerged surface area of the each electrode plate was 45cm2. The applied voltage was adjusted according to a desirable value (20, 30 and 40 volts). pH of solutions before and after the EC process were measured by a pH meter (LUTRON PPH-2108). In each run, 1L of potable water samples containing Cd average concentration of 260g/L was placed in to the EC reactor at a constant temperature of 25 C. At the end of EC process, the solution was filtered and then was analyzed. Samples of 3 ml were periodically taken from the EC cell then filtered to eliminate sludge formed during electrolysis. The residual concentrations of metal ions were determined by atomic absorption spectrophotometer. At the end of the run, the electrodes were washed thoroughly with dilute acid and water to remove any solid residues on the surfaces, dried and re-weighted. Electrical energy consumption is a very important economical parameter in the electrocoagulation process. The electrical energy consumption was calculated using the following equation [32]:
E= v l t V

(3)

where; E is the energy consumption (Wh/m3), v is the applied voltage (volt), I is the current intensity (A), t is
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Maha I. Al-Ali

TABLE I pH CHANGE DURING EC PROCESS AND CADMIUM REMOVAL WITH pH CHANGE AT 20 volt, 20 min, d=3cm pHfinal Re% pHinitial 3 7.3 98.5 7 8.3 99.3 10 8.53 99.4

III.2. Effect of Applied Voltage on Metals Removal The effect of applied voltage was investigated in the range (20-40 volt) using two aluminum electrodes at pH 3.2. Table II shows the effect of applied voltage on Cd removal from potable water. An increase in applied voltage from 20 to 40 volt yields an increase in the efficiency of Cd removal from 87.7 to 99.7% for a given time of electrocoagulation. Consequently Cd removal increased with increasing applied voltage because more Al3+ passed to water at higher voltage and the formation rate of Al(OH)3 increased. The aluminum hydroxide flocs act as adsorbents for metal ions and eliminate them from the potable water. Simultaneously, the OH ions which are produced at the cathode increase the pH of water [21], [33]. The energy and electrode consumptions (eqn. (3) & (4)) respectively were determined as shown in Table II. Energy consumption increased from 0.42 to 16.7Wh/m3 and electrode consumption increased from 0.12 to 2.33g/L when current density increased from 2.5 to 10 mAcm2 at (5-25min) of electrocoagulation time. The weight of the electrode consumed in the process has been increased when a higher voltage of the system applied. The Cd was completely removed after 25 min of electrocoagulation at an electric potential of 40volt.
TABLE II PERCENT OF CADMIUM REMOVAL, ELECTODE AND ENERGY CONSUMPTION AND KINETIC CONSTANT DURING EC PROCESS; pHinitial = 3.2, d=3 cm Kinetic Cd Electrode Energy voltage Time constant rem- consumption consumption v t K oval Celectrode E (volt) (min) (min-1) Re% (g/L) (Wh/m3) 20 5 87.7 0.12 0.42 -0.091 20 10 90.1 0.23 0.83 -0.067 20 15 92.0 0.35 1.25 -0.059 20 20 95.5 0.47 1.70 -0.073 20 25 96.9 0.58 2.10 -0.073 30 5 88.5 0.23 1.25 -0.232 30 10 91.6 0.47 2.50 -0.120 30 15 95.3 0.70 3.75 -0.090 30 20 98.2 0.93 5.00 -0.116 30 25 98.9 1.20 6.25 -0.156 40 5 95.2 0.50 3.30 -0.156 40 10 95.4 0.93 6.70 -0.110 40 15 96.0 1.40 10.0 -0.112 40 20 98.5 1.86 13.0 -0.132 40 25 99.7 2.33 16.7 -0.125

according to Faraday's law Eq. (4) when the electrolysis time increases, an increase occurs in the concentration of Al3+ ions and their hydroxide flocs so the EC process yield is enhanced [10], [33]. The efficiency of EC process depends directly on the concentration of aluminum ions, which is produced by the electrode dissolution. Fig. 1 shows the effect of electrolysis time on the Cd removal efficiency. The results indicate that the Cd ions removal efficiency increased from 87.7 to 96.9% at 5 to 25 min respectively at 20volt, also Re% ranged from 88.5 to 98.9% at 30volt and from 95.2 to 99.7% at 40 volt for the same interval time.

Fig. 1. The effect of time on Cd Removal% at 20, 30 and 40 volts

III.4. Effect of Electrode Spacing on Metals Removal Once distance between the electrodes increases, the electrical current decreases, less interaction of ions with hydroxide polymers is expected. In other words, decreasing both local concentration and electrostatic attraction are the reasons for decreasing the removal of Metals [10]. So, increased distance between each couple of anode and cathode electrodes leads to increased voltage. Because of diminished ions aggregation, hydroxide polymers, decreased rate of absorption of ions and electrostatic force, enhancing electrolyte constancy and spacing will eventually lead to decreased removal efficiency [10], [28]. In the current study, when the distance of the electrodes is increased from 3 to 6 cm, the removal efficiency decreases Table III. These results indicating the distance between anode and cathode electrodes was chosen to be 3 cm.
TABLE III CADMIUM REMOVAL WITH ELECTRODE SPACING CHANGE AT 20 volt, 20 min Electrode spacing (cm) Re% 3 98.5 4.5 98.0 6 96.2

III.3. Effect of Electrolysis Time on Metals Removal The production rate of Al3+ ions is related to the time and current flow (electric potential) in the EC cell,

IV.

Kinetic Study

In the EC process, the kinetics of Cd removal is proportional to its concentration. From Fig. 2, it is clear

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Maha I. Al-Ali

that the changing rate of Cd concentrations can be expressed as a first order kinetic model, as follows:
dCt = kCt dt

(5)

Eq. (5) can be rewritten by integration:

Ct = Co e kt

voltage of 40volt with an energy consumption of 0.0167kWh/m3 and an electrode consumption of 2.33g/L. On the other hand, in this study it was shown that electrocoagulation process achieves a fast and effective reduction of cadmium (more than 99%) present in potable water.

(6)
[1]

References
D. Tilaki and R. Ali, STUDY ON REMOVAL OF CADMIUM FROM WATER ENVIRONMENT BY ADSORPTION ON GAC, BAC AND BIOFILTER, Diffuse Pollution Conference Dublin, 8B Ecology (2003) 35-39. R. Leyva-Ramos , P. E. Diaz-Flores, A Aragon-Pia., J. Mendoza-Barron & R. M, Guerrero-Coronado, Adsorption of Cadmium (II) from aqueous solution on to Activated Carbon, Separation Science and Technology (2005) 2079-2094. G.M. Murthy, Cadmium Analysis Using Field Deployable Nanoband Electrode System and its Removal Using Electrocoagulation, M.Sc. Dissertation, Dept. Chem. Eng. LAMAR Univ. - BEAUMONT, 2008. Drinking-water Quality Committee members, Guidelines for Drinking-water Quality- 4th Ed., (WHO Press 2011). P.D. NATIONS, International Standards for Drinking-Water, (GENEVA press, 1958). M. Kobya, U. Gebologlu, F. Ulu, S. Oncel and E. Demirbas, Removal of Arsenic from Drinking Water by The Electrocoagulation Using Fe and Al Electrodes, Electrochimica Acta 56 (2011) 50605070. D. Ghosh, C.R. Medhi and M.K. Purkait, Treatment of fluoride containing drinking water by electrocoagulation using monopolar and bipolar electrode connections, Chemosphere 73 (2008) 1393 1400. W. Wana, T.J. Pepping, T. Banerji, S. Chaudhari and D.E. Giammar, Effects of water chemistry on arsenic removal from drinking water by electrocoagulation, Water Research 45 (2011) 384-392. N. S. Kumar, S. Goel, Factors influencing arsenic and nitrate removal from drinking water in a continuous flow electrocoagulation (EC) process, Journal of Hazardous Materials 173 (2010) 528533. M. Malakootian, H.J. Mansoorian and M. Moosazadeh, Performance evaluation of electrocoagulation process using ironrod electrodes for removing hardness from drinking water, Desalination 255 (2010) 6771. S. Aoudj, A Khelif., N. Drouiche, M. Hecini and H. Hamitouche, Electrocoagulation process applied to wastewater containing dyes from textile industry, Chemical Engineering and Processing 49 (2010) 11761182. I. A. Sengil S. Kulac and M. Ozacar, Treatment of tannery liming drum wastewater by electrocoagulation, Journal of Hazardous Materials 167 (2009) 940946. J. Ge, J. Qu, P. Lei and H. Liu, New bipolar electrocoagulation electroflotation process for the treatment of laundry wastewater, Separation and Purification Technology 36 (2004) 3339. C.Y. Hu, S.L. Lo, C.M. Li and W.H. Kuan, Treating chemical mechanical polishing (CMP) wastewater by electro-coagulationflotation process with surfactant, Journal of Hazardous Materials A120 (2005) 1520. Zaieda M., Bellakhal N., Electrocoagulation treatment of black liquor from paper industry, Journal of Hazardous Materials 163 (2009) 9951000. M. Asselin, P. Drogui, S. K. Brar, H. Benmoussab and J. Blais, Organics removal in oily bilge water by electrocoagulation process, Journal of Hazardous Materials 151 (2008) 446455. T. O. Peulen, Electoflotation of water containing Cd(II),Cu(II), and Pb(II) with aluminum electrodes, Dept. de Quimica Fisica Molecular, Grupo de Qumica Ambiental (2007).

where K, Co and Ct are the kinetic constant and the concentration of Cd at 0 & t time respectively. The reaction rate constant K, can be calculated from the plot ln [Ct/Co] versus electrolysis time. K values are reported in Table II, and their equations with its correlation coefficient, R2 are represented in Table IV. The results indicated that the removal rate constants of Cd were dependent on the initial concentration and decreased with an increase in the metal ion concentrations in the solution. These results confirmed the effect of the initial Cd concentration on the EC removal rate.

[2]

[3]

[4] [5] [6]

[7]

[8]

[9]

[10] Fig. 2. The kinetics of Cd removal proportional to its concentration at 20, 30 and 40 volts [11] TABLE IV KINETIC EQUATIONS FOR Cd REMOVAL AT 20, 30, 40 volts Applied Voltage Kinetic Correlation v Equation Coefficient (volt) (R2) 20 y = -0.1324x - 1.8761 0.7939 30 y = -0.1241x - 1.3791 0.9743 40 y = -0.0707x - 1.6406 0.9631

[12]

[13]

[14]

V.

Conclusion
[15]

It can be concluded that electrocoagulation method is a reliable, safety, efficient and cost-effective method for removal of cadmium from potable water, especially designed for voltage = 40 V and t=25 min with d=3cm of potable water pH of 3.2. When the higher voltage of the system applied, the weight of the electrode consumed in the process has been increased. The Cd was completely removed after 25 min of electrocoagulation at an applied

[16]

[17]

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[18] L. I. Junguo, LI Jun and LI Yungang, Cadmium removal from wastewater by sponge iron sphere prepared by charcoal direct reduction, Journal of Environmental Sciences Supplement, (2009) S60S64. [19] E. Bazrafshan, A. H Mahvi, S. Nasseri, A. R Mesdaghinia, F. Vaezi, & S. Nazmara, Removal of Cadmium from Industrial Effluents by Electrocoagulation Process using Iron Electrodes, Iranian Journal of Environmental Health, Science and Engineering, 3 (2006) 261-26. [20] M. Kobya, E. Demirbasb, N. U. Parlaka & S. Yigit, Treatment of cadmium and nickel electroplating rinse water by electrocoagulation, Environmental Technology, 31 (2010) 14711481. [21] S. Vasudevan, J. Lakshmi and M. Packiyam, Electrocoagulation studies on removal of cadmium using magnesium electrode, J Appl Electrochem, 40 (2010) 20232032. [22] A. H. Mahvi and E. Bazrafshan, Removal of Cadmium from Industrial Effluents by Electrocoagulation Process Using Aluminum Electrodes, World Applied Sciences Journal, 2 (2007) 34-39. [23] E. Bazrafshan and A. H Mahvi., Removal of Cadmium from Aqueous Environments by Electrocoagulation Process using Aluminum Electrodes, ZAHEDAN JOURNAL OF RESEARCH IN MEDICAL SCIENCES, 9 (2007) 61-70. [24] S. Vasudevan, J. Lakshmi and G. Sozhan, Effects of alternating and direct current in electrocoagulation process on the removal of cadmium from water, Journal of Hazardous Materials, 192 (2011) 26-34. [25] Bazrafshan E., Kord Mostafapoor F., Zazouli M.A., Eskandari Z. and Jahed Gh.R, Study on Removal of Cadmium from Plating Baths Wastewater by Electrochemical Precipitation Method, Pakistan Journal of Biological Sciences, 9 (2006) 2107-2111. [26] A.H. Sulaymona, A. O. Sharifb, T. K. Al-Shalchi, Removal of cadmium from simulated wastewaters by electrodeposition on stainless steel tubes bundle electrode, Desalination and Water Treatment, 29 (2011) 218226. [27] C. Escobara, C. Soto-Salazarb and M. I. Toral, Optimization of the electrocoagulation process for the removal of copper, lead and cadmium in natural waters and simulated wastewater, Journal of Environmental Management, 81 (2006) 384-391. [28] B. Merzouka, B. Gourichb, A. Sekkic, K. Madanid and M. Chibane, Removal turbidity and separation of heavy metals using electrocoagulationelectroflotation technique: A case study, Journal of Hazardous Materials, 164 (2009) 215222. [29] I. Zongoa, J. Leclerca, H. A.Magab, J. Wthb and F. Lapicque, Removal of hexavalent chromium from industrial wastewater by electrocoagulation:Acomprehensive comparison of aluminum and iron electrodes, Separation and Purification Technology, Separation and Purification Technology, Vol.66, Issue 1 (2009) 159-166. [30] A. Shafaei, E. Pajootan, M. Nikazar and M. Arami, Removal of Co (II) from aqueous solution by electrocoagulation process using aluminum electrodes, Desalination, (2011), 6 pages. [31] I. Heidmann and W.Calmano, Removal of Ni, Cu and Cr from a galvanic wastewater in an electrocoagulation system with Fe- and Al-electrodes, Separation and Purification Technology, 71 (2010) 308314. [32] C. A. Martnez-Huitle and E. Brillas, Decontamination of wastewaters containing synthetic organic dyes by electrochemical methods: A general review, Applied Catalysis B: Environmental, 87 (2009) 105145. [33] E. Bazrafshan, A. H. Mahvi, S. Nasseri, A. R Mesdaghinia., F. Vaezi and Sh.Nazmara, Removal of Cadmium from Industrial Effluents by Electrocoagulation Process using Iron Electrodes, Iran. J. Environ. Health. Sci. Eng.,3 (2006) 261-266. [34] M. Kobya, F. Ulua, U. Gebologlua, E. Demirbas and M.S. Oncel, Treatment of potable water containing low concentration of arsenic with electrocoagulation: Different connection modes and FeAl electrodes, Separation and Purification Technology, 77 (2011) 283293.

[35] E. A. Vik, D. A. Carlson, A.S. Eikum and E.T. Gjessing, Electrocoagulation of potable water, Water Research, 18 (1984) 1355-1360. [36] Chen X., Chen G. and Po L.Y., Separation of pollutants from restaurant wastewater by Electrocoagulation, Sep. Purif. Technol, 19 (2000) 65-76.

Authors information
Maha I Al-Ali Iraq 1974 Gender: Female Nationality: Arabian Current Location: Iraq - Salahalddin Languages Known: Arabic, English E-mail: basmala17@yahoo.com MSc in Chemical Engineering Tikrit University/Salahaddin/Iraq 2002 Designation: Lecturer Education: -Bachelors in Chemical Engineering Science-Tikrit University / 1996. - M. Sc in Chemical Engineering Science - Tikrit University / 2002. - Courses in pharmaceutical science / 2009. Work Experience: - Lecturer in chemical engineering department for many subjects: .Basic of Chem. Eng. Principles and Calculations. .Unit Operation of Chem. Eng. .Petroleum Refinery. .Material Properties. .Organic Chemistry. - Experience in Chemical Plating Plant.

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