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WATER RESEARCH 40 (2006) 61– 66

ARTICLE IN PRESS WATER RESEARCH 40 (2006) 61– 66 Available at journal homepage: Electrokinetic
ARTICLE IN PRESS WATER RESEARCH 40 (2006) 61– 66 Available at journal homepage: Electrokinetic

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ARTICLE IN PRESS WATER RESEARCH 40 (2006) 61– 66 Available at journal homepage: Electrokinetic
ARTICLE IN PRESS WATER RESEARCH 40 (2006) 61– 66 Available at journal homepage: Electrokinetic

Electrokinetic dewatering of Turkish glass sand plant tailings

O. Bayat a, , O. Kilic a , B. Bayat b , M. Anil a , H. Akarsu c , C. Poole d

a Mining Engineering Department, Cukurova University, Balcali, 01330 Adana, Turkey b Environmental Engineering Department, Cukurova University, Balcali, 01330 Adana, Turkey c CAMIS Mining Co., Mersin, Turkey d Department of Mining and Mineral Engineering, University of Leeds, Leeds LS2 9JT, UK

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Article history:

Received 19 November 2003 Received in revised form 18 July 2005 Accepted 18 October 2005


Tailings disposal




Waste processing

In this study, the dewatering of glass sand plant tailings from Mersin, Turkey was investigated using an electrokinetic technique. The particle size ðd 80 Þ of the solid waste material tested was less than 0.020 mm and consisted mainly of silica, orthoclase, alumina, potassium and iron oxides. In current plant practice, Larox high-pressure filters are used to produce a filter cake containing 22–25% moisture. As an alternative, a laboratory-scale

dewatering pond using an electrokinetic technique was designed and a final product (cake) containing 34% moisture was obtained after 24 h treatment using 14.6 V direct current applied for 40 min. When the treatment continued up to 48 h, a firm-to-hard cake was produced.

& 2005 Elsevier Ltd. All rights reserved.



Silica sand occurs in abundance in varying degrees of purity, but only a small percentage is suitable for glassmaking and other high-grade industrial applications, including foundry, ceramics, chemicals, fillers and the construction industry. Mineral processing is an essential step in upgrading the raw sand to meet industrial specifications, such as a high silica content (495.4% SiO 2 ), narrow size distribution and small amount of clay combined with low levels of TiO 2 , Al 2 O 3 and Fe 2 O 3 . Sedimentation of glass sand tailings is frequently difficult and lengthy, owing to their nature and small particle size. Chemical dosing with metal ions is often used in primary treatment to remove colloidal materials from waste- water, but new technologies such as electrocoagulation (EC)

are now able to produce flocs of larger size and density (Newman, 1984; Koren and Syverson, 1995; Mollah et al., 2001; Larue and Vorobiev, 2003). It is generally accepted that the EC process involves three successive stages: (a) formation of coagulants by electrolytic oxidation of the ‘sacrificial elec- trode’; (b) destabilization of the contaminants, particulate suspension, and breaking of emulsions; and (c) aggregation of the destabilized phases to form flocs. The destabilization mechanism of the contaminants, particulate suspension, and breaking of emulsions has been described in broad steps and may be summarized as follows (Mollah et al., 2001):

(i) Compression of the diffuse double-layer around the charged species, which is achieved by the interac- tions of ions generated by dissolution of the sacrificial

Corresponding author. Tel.: +90 322 3386119; fax: +90 322 3386126. E-mail addresses: (O. Bayat), (O. Kilic), (B. Bayat), (M. Anil), (H. Akarsu), (C. Poole). 0043-1354/$ - see front matter & 2005 Elsevier Ltd. All rights reserved.




WATER R ESEARCH 40 (2006) 61– 66

electrode, due to passage of current through the solution. (ii) Charge neutralization of the ionic species present in wastewater, which is caused by the counter ions, produced by the electrochemical dissolution of the sacrificial elec- trode. These counter ions reduce the electrostatic inter- particle repulsion sufficiently so that the van der Waals attraction predominates, thus causing coagulation. (iii) Floc formation, and the floc formed as a result of coagulation creates a sludge blanket that entraps and bridges colloidal particles that have not been complexed.

Differences in the mobilities of ions, molecules, or particles in an electric field can also be exploited to perform useful separations. For electrolytic solutions, the migration of charged species in an electric field constitutes an additional mechanism of mass transfer. Thus, the flux of an ionic species

N i in gmol/cm 2 s in dilute solutions can be expressed as N i ¼ z i u i Ic i rE D i c i þ c i v,


where the ionic mobility u i is the average velocity imparted to the species under the action of a unit force (per mole); v is the stream velocity in cm/s. In the present case, the electric field rE is in V/cm and the charge z i I per mole, where I is the Faraday constant in C/g equivalent, D i is the ionic-diffusion coefficient, cm 2 /s, and z i is the valence of the ith species. Multiplication of this force by the mobility and the concen- tration c i (gmol/cm 3 ) yields the contribution of migration to the flux of the ith species (Robinson and Stokes, 1959). Particle sedimentation can be accelerated by imposing an electrical field in the proper orientation; that is, for negatively charged particles, horizontal placement of the anode (positive elec- trode) near the bottom of the slurry, with the negatively charged cathode floating on the surface (Sprute and Kelsh, 1974). When sedimentation is complete, further drainage can

be stimulated by reversing the polarity, with the bottom cathode acting as a drain. In an electrical field established between two separated electrodes buried in slurry, the solid particles will not move appreciably because of their relatively dense packing, but the water will be carried toward the negatively charged cathode by the viscous drag of the migrating positive ions. The effectiveness of electrokinetic techniques (direct current application) in consolidating slur- ries of fine-grained solids in watery suspensions has been investigated since the 1970s (USBM, 1974a, b, 1975; Mollah et al., 2001, 2004; Larue and Vorobiev, 2003; Larue et al., 2003). Matteson et al. (1995) investigated the EC of aqueous suspensions of ultrafine kaoline particles in a single stirred cell apparatus and in a continuously flowing system consist- ing of three cells in series. By taking advantage of the electrical surface charge on solid particles in water, fast particle settlement and sediment dewatering can be achieved by imposing a relatively large dc voltage (60–240 V/m) between electrodes placed in the slurry. This technique has already been successful for treating siliceous tailings from Idaho, USA, metal mines. Slurry properties found to affect response included electrical conductivity, particle size distribution, water content, and surface charge density. Chemical proper- ties also influenced behaviour, but their importance was specific to each sample and difficult to characterize (Sprute and Kelsh, 1980). Camis Madencilik AS has been operated in Mersin (a southern province of Turkey) since 1970. The ore contains quartz (88%), orthoclase (10%), iron oxides (0.25%) and trace elements such as Zr, Cr, Ca and Ti (Bayat and Akarsu, 2002). As shown in Fig. 1, froth flotation is used for the removal of the colouring impurities, including pyrite, garnet, chromite, ilmenite, haematite, mica, etc. The capacity of the concen- trator is 450,000 tonnes per year and tailings (approximately 50,000 tonnes per year) are thickened and filtered by Larox

Feed (glass sand; -2 cm) Grinding (Rodmill) Hydrocyclone +0.6-0.106 mm -0.106 mm Froth Flotation H 2
Feed (glass sand; -2 cm)
Grinding (Rodmill)
+0.6-0.106 mm
-0.106 mm
Froth Flotation
H 2 SO 4
Aero 801+825; 370 g/t
(from Cytec Int., Holland)
Superfloc A 110; 70 g/t
Larox Filter
Spiral Classifier
Alcopol; 80 g/t
Dewatered Tailings
(20-25% moisture)





62 ARTICLE IN PRESS WATER R ESEARCH 40 (2006) 61– 66 electrode, due to passage of

Dewatered Tailings (20-22% moisture)

Fig. 1 – Flowsheet of glass sand-processing plant.


WATER RESEARCH 40 (2006) 61– 66


high-pressure filters. A filter cake containing 22–25% moisture is conveyed to the tailings disposal area and the current dewatering cost is about $1/tonne. In this study, dewatering of the tailings from the glass sand- processing plant using an electrokinetic technique was investigated on a laboratory scale.

  • 2. Materials and methods

Physical and chemical properties of the solid waste (tailings) before treatment are summarized in Table 1. Chemical analysis of the sample was carried out at the Camis plant by XRF spectrometry using a method described in detail by Skoog et al. (1998). The particle size of the sample ranged from 0.005 to 0.105mm and the d 80 was less than 0.020mm. X- ray measurements were performed using a Philips X-ray difractometer employing nickel-filtered CuKa radiation. X-ray diffraction data for crystalline phases of the tailings are given in Table 2. The mineralogy was found to be mainly orthoclase (KAlSi 3 O 8 ), alumina (Al 2 O 3 ), potassium (K 2 O), iron oxides (Fe 2 O 3 ) and silica (SiO 2 ). The zeta potential (ZP) measurements of the suspensions were made in distilled water of a constant ionic strength (0.01 M NaCl) by Zeta-Meter 3.0. Prior to ZP measurements powder sample was dispersed at 0.1% (w/v) solid ratio in distilled water, pH and ionic strength were adjusted to desired values and stirred on a magnetic stirrer for 5min at room temperature. Required amount of suspen- sion was transferred into the electrophoresis cell of the zeta meter. During the ZP measurement 10 particles were tracked and the average of their ZP values was taken. Consequently, the ZP changes of the suspensions as a function of pH were determined. The working principle of the zeta meter 3.0 is based on the electrophoresis method and it computes automatically the ZP using the Smoluchowski equation. Laboratory electrokinetic dewatering tests were conducted at the Camis plant using a specially built Plexiglas model (see Fig. 2) 112 cm long 24 cm wide 24 cm deep. Two series of

tests were performed using various dewatering arrangements (Kilic, 1998). Optimum results were achieved with the follow- ing procedure. Two iron pipes, with an outside diameter of 2.1 cm and 36 cm long, placed on the horizontal floor and embedded in gravel, served as a cathode. A 36 cm 20 cm rectangular grid of a 0.95 cm iron rod acted as the moveable anode: this was placed on the surface of the cell. For each test, a 32 litre-suspension containing 3–5% solids was taken from the plant thickener and poured into the cell after 10min of mixing. In the first stage of a two-stage dewatering procedure, power was applied to the front section at a rate of 14.5 V between electrodes, with an average current density of 11.88 A/m 2 until drainage ceased. For the second stage (after 10min), the anode was moved to a position 6 cm below the surface over the cathode, and power was applied at 14.6 V between electrodes at an average current density of 5.63 A/m 2 until water discharge from the pump well ceased. The power was then switched off after 40min and the cake was left for 24 h for additional settlement. The final product in the model was sampled for moisture content. During electrolysis, the positive side underwent anodic reactions, while on the negative side, a cathodic reaction was encountered. Consum- able metal plates, such as iron or aluminium, were usually used as sacrificial electrodes to continuously produce ions in the system. The released ions neutralized the charges of the particles and thereby initiated coagulation.

  • 3. Results and discussion

    • 3.1. Zeta potential measurements

The surface charge characteristics of precipitated metal hydroxides are of great importance in coagulation. In common with oxides and other minerals they show an isoelectric point (i.e.p.) at which the apparent (electrokinetic) surface charge is zero. At pH values below the i.e.p. the

Table 1 – Properties of the suspension of the glass sand tailings




Conductivity (3 4% solids, pH 8, 2372 1C) Solid content


12 mS/cm 3–4% by weight

Zeta potential at 2372 1C 3% solids, at pH 4



at pH 6


at pH 8

35 mV

5% solids, at pH 4


at pH 6 at pH 8 Grain-size distribution


55mV 58 mV 94% finer than 0.075 mm 80% finer than 0.020 mm 50% finer than 0.010 mm

pH at 2372 1C



(% by weight)


SiO 2

Al 2 O 3

Fe 2 O 3

TiO 2



Na 2 O

K 2 O

Cr 2 O 3 MnO



















a LOI, loss on ignition.




WATER R ESEARCH 40 (2006) 61– 66

Table 2 – XRD data for crystalline phases of the tailings

Crystalline phase

d spacing (A ˚ )

Fe 2 O 3 _A




Al 2 O 3 _A


FeTiO 3 _B


Fe 3 O 4 _A


FeCr 2 O 4


Fe 2 O 3 _B


ZrSiO 4




SiO 2 _qrz




FeS 2 _B




Cu 2 O


FeTiO 3 _A


FeS 2 _A




Fe 2 O 3 _A


Al 2 O 3 _A


FeTiO 3 _B


Fe 3 O 4 _A


Ca 2 _A




Cr 2 O 4


CaSO 4 _h 2


Anode (Oxidation) + Colloidal Particle Fe 2+ E DC power Fe(OH) 2 supply OH − Suspension
Colloidal Particle
Fe 2+
DC power
Fe(OH) 2
OH −
H 2

Fig. 2 – Schematic of longitudinal cross section of test cell.

precipitate is positively charged and at higher pH values it has a negative charge (Duan and Gregory, 2003). The ZPs of the suspension versus pH are given in Table 1. The isoelectrical point at about pH 7 was found at 5% solids and the magnitude of the ZP increased dramatically with increasing pH of the suspension. The sample consists of over 75% SiO 2 (see Table 1), and may thus be considered as a quartz mineral. The ZP of quartz is zero at pH 2.0 (Fuerstenau and Jia, 2004). However, when their surface properties, especially ZP (Table 1), associated impurities i.e., colouring metal oxides (Fe 2 O 3 , TiO 2 ) or other metal oxides (MgO, Al 2 O 3 ), and geologic formation are considered, they may indicate some physical, chemical and mechanical differences with regard to the pure quartz mineral. Murugananthan et al. (2004) have revealed that the i.e.p. of iron oxide/hydroxide and aluminium oxide/hydroxide was

observed at a pH of 7.7 and 8.8, respectively. These values are in accordance with the values reported by earlier researchers (Syed Ahmed, 1975; Rudzinski et al., 1992). Below the pH of i.e.p., precipitates of oxy-hydroxides are positively charged. From the results it is apparent that the magnitude of positive ZP of iron and aluminium oxy-hydroxides reduces in the presence of sulphate and sulphite ions without any shift in i.e.p. This clearly indicates that there is no chemical interac- tion between these ions and metal hydroxy precipitates. At the same time, a decrease in the magnitude of ZP of metal hydroxides in the presence of these ions clearly suggests an electrical interaction. This reduction in positive charge may be due to a weak electrical interaction between negatively charged sulphite and sulphate ions and positively charged oxy-hydroxy species of iron and aluminium. Transmission electron microscopic (TEM) studies conducted by earlier researchers (He et al., 1996) have revealed that at a pH of 6.0, the aggregated Fe(OH) 2 colloids exist as three-dimen- sional (branched or spread out) porous sponge-like precipi- tates. Thus, better dewatering under slightly acidic conditions can be explained in the light of the ZP results.

  • 3.2. Electrokinetic dewatering

Iron upon oxidation in an electrolytic system produces iron hydroxide, Fe(OH) n , where n ¼ 2 or 3. When a dc current flows between two iron electrodes, the following electrolysis reactions are expected to occur in the vicinity of the electrodes (Mollah et al., 2001):



Fe ðsÞ ! Fe


ðaqÞ þ

2e ,




ðaqÞ þ 2OH


ðaqÞ ! FeðOHÞ 2ðsÞ .



2H 2 O ðlÞ þ 2e ! 2OH

ðaqÞ þ H 2ðg Þ .




Fe ðsÞ þ 2H 2 O ðlÞ ! FeðOHÞ 2ðsÞ þ H 2ðgÞ .


The Fe(OH) n (s) formed remains in the aqueous stream as a gelatinous suspension, which can remove the pollutants from wastewater either by complexation or by electrostatic attrac- tion, followed by coagulation. In the surface complexation mode, the pollutant acts as a ligand (L) to chemically bind hydrous iron:

L-H ðaqÞ ðOHÞOFe ðsÞ ! L-OFe ðsÞ þ H 2 O ðlÞ . (6) The prehydrolysis of Fe 3+ cations also leads to the forma- tion of reactive clusters for water treatment. Structural models for these oxyhydroxy iron cations have been extensively reported in the literature (Schneider and Schwyn, 1987). For instance, wastewater containing Cr 6+ (CrO 2 4 ) ions can be removed by the EC technique using iron as the sacrificial anode. The ferrous ion (Fe 2+ ) generated by electro- oxidation of the iron anode can reduce Cr 6+ to Cr 3+ under alkaline conditions and is itself oxidized to ferric (Fe 3+ ) ion


WATER RESEARCH 40 (2006) 61– 66


according to



4 ðaqÞ þ 3Fe 2þ ðaqÞ þ 4H 2 O ðlÞ

! 3Fe 3þ ðaqÞ þ Cr 3þ ðaqÞ þ 8OH





4 ðaqÞ þ 3Fe 2þ ðaqÞ þ 4H 2 O ðlÞ

þ 4OH ðaqÞ 3FeðOHÞ 3 þ CrðOHÞ 3 .



The Cr (aq) 3+ ion is then precipitated as Cr(OH) 3(s) by raising the

pH of the solution. The Fe (aq) 2+ ions can also reduce Cr 2 O 2


under acidic conditions according to the following reaction:

Cr 2 O 2


ðaqÞ þ 6Fe 2þ ðaqÞ

þ 14H

ðaqÞ þ 2Cr 3þ ðaqÞ þ 6Fe 3þ ðaqÞ þ 7H 2 O ðlÞ .


The generation of iron hydroxides is followed by an electrophoretic concentration of particles containing mainly mica, clays, iron oxides and silica particles, which are swept by the electric field into the region close to the anode. Particles interact with the iron hydroxides and can be removed either by surface complexation or electrostatic attraction. Therefore, the EC process improves coagulation (Larue and Vorobiev, 2003). For initial experiments, tailings taken directly from the plant thickener were poured into the model and after complete settlement of solids, the moisture content of the product was determined as 62% after 24 h. The effects of pH and solids content of the suspension were also evaluated with the laboratory test model. The slimes responded well to electrokinetic dewatering procedures in these small-scale laboratory tests. The solid content of the cake was readily increased from an initial 3–5% to 39%, 46% and 44% at pH 4, 6

and 8, respectively, after 10 h (see Fig. 3) with an applied

current density of 5.63–11.88 A/m 2 . The tests were performed

with the bottom electrode negatively charged, thereby draw- ing water downwards. The power consumption (costing $0.13/ kWh) required to obtain these results ranged between 1.37 and 2.11 kWh per tonne of final product. The overall efficiency was poor in these initial experiments, so several modifications were made. Three more by-pass holes were opened on the right side of the cell, allowing water to be pumped more efficiently. A thick layer of sand, 1.5 cm deep, was placed on top of the gravel to provide additional filtering. The cycle consisted of applying potential to the

upper electrode for 15min, followed by 5min of no power. This 20-min cycle was repeated throughout the dewatering period. The effects of pH and solid content of the suspension using the modified model are shown in Fig. 4. The solid content of the cake was readily increased from an initial 3–5% to 50%, 62% and 50% at pH 4, 6 and 8, respectively, after 10 h (see Fig. 4) with an applied current density of 5.63–11.88 A/m 2 . These tests demonstrated that a final product containing 34% moisture could be obtained after 24 h treatment at pH of 6 for a power expenditure of 2.15 kWh per tonne final product. Larue and Vorobiev (2003) have indicated that the flocs obtained by this technique are larger or have a higher effective density when compared with those generated by the addition of chemicals. In a recent article Jiang et al. (2002) reported the treatment of wastewater by a hybrid EC technique using aluminium electrodes. The authors designed two different EC reactors to evaluate their water treatment performance and found out the best configurations to maximize the treatment efficiency. The EC reactors were configured with water up-flow or cross-flow arrangements.

70 Initial 68 pH = 4 66 pH = 6 pH = 8 64 62 60
pH = 4
pH = 6
pH = 8
Moisture of the cake (%)

Dewatering time (min)

ARTICLE IN PRESS WATER RESEARCH 40 (2006) 61– 66 65 according to CrO 2 4 þ

Fig. 3 – Effects of pH and suspension solid content on dewatering of glass sand process tailings at 2372 1C.

62 58 54 50 46 42 38 Initial pH = 4 34 pH = 6 pH
pH = 4
pH = 6
pH = 8
Moisture of the cake (%)

Dewatering time (min)

ARTICLE IN PRESS WATER RESEARCH 40 (2006) 61– 66 65 according to CrO 2 4 þ

Fig. 4 – Effects of pH and suspension solid content after modification of the model at 2372 1C.



WATER R ESEARCH 40 (2006) 61– 66

Kovatcheva and Parlapanski (1999) applied a low-frequency (25–75 Hz) sonic field at current densities of 0.1–0.4 A/m 2 to improve the performance of the EC cell with carbon steel electrodes. It has been reported to increase the quantity of iron hydroxides, and thereby enhance coagulation. Using optimized conditions, after 24 h treatment, a final cake containing 34% moisture was obtained, but the product could be converted into a firm-to-hard cake with 20% moisture content when the process time was extended to 48 h. As a result of all of these test modifications, the following operating procedures were found to be necessary:

water should be constantly pumped from the sump, since an accumulation at the cathode prevents efficient dewa- tering, cathodes should be embedded on the floor of the settling pond, cathodes must be well embedded to ensure good electrical contact throughout the experiment when lowering the anode onto the fill, and natural drainage should be initiated as soon as the material has thickened sufficiently to discharge clean water; this reduces electrokinetic treatment time and results in a better final product.

These encouraging results led to a plant-scale electrokinetic system being suggested as an alternative to the Larox plant filters for dewatering the glass sand tailings. An evaluation of the new system showed that six large ponds (55 30 16m) would be required for efficient tailings disposal at a predicted lower overall disposal cost of $0.89/tonne. One of the most important considerations in lowering the cost of the EC process is to minimize the IR-drop to enhance current efficiency. Evolution of oxygen at the anode represents an unwanted leakage of current, which reduces the overall current efficiency. This problem can be minimized through the choice of an anodic material that presents a high over potential for the oxygen evolution reaction near the anode. This high over potential allows the realization of anodic reactions, which are not possible with other materials and in particular, the oxidation of organic compounds with a very high current efficiency.



Laboratory-scale dewatering experiments demonstrated that an electrokinetic process could effectively dewater and densify unclassified tailings from a glass sand processing plant with moderate power consumption. A-firm-to-hard cake with 20% moisture content was obtained when the process time was extended to 48 h.


The authors extend their sincere thanks to Camis Madencilik AS, Mersin, Turkey, for their technical support. This study was supported by the Cukurova University Scientific Research Projects Directorate (project no. FBE.98.YL.65).


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