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Separation and Purication Technology 51 (2006) 374378

Removal of nitrate from aqueous solution by using red mud


Yunus Cengeloglu a, , Ali Tor b , Mustafa Ersoz a , Gulsin Arslan a
b

Selcuk University, Department of Chemistry, Campus, 42031 Konya, Turkey Selcuk University, Department of Environmental Engineering, Campus, 42031 Konya, Turkey

Received 12 August 2005; received in revised form 7 February 2006; accepted 15 February 2006

Abstract The objective of this study is to remove the nitrate from aqueous solution by using the original and activated red mud in batch adsorption technique. The effects of pH, adsorbent dosage and contact time on the adsorption were investigated. The nitrate adsorption capacity of activated red mud was found to be higher than that of the original form and decreased above pH 7. Adsorption process was expressed by using Langmuir and Freundlich isotherms. Langmuir isotherm curves was found to be signicant compared to Freundlich isotherm. Adsorption capacity of the original and activated red mud was found to be 1.859 and 5.858 mmol nitrate/g red mud, respectively. It was found that sufcient time for adsorption equilibrium of nitrate ions is 60 min. The mechanism for nitrate removal was explained by considering of chemical nature of red mud and interaction between metal oxides surface and nitrate ions. 2006 Elsevier B.V. All rights reserved.
Keywords: Red mud; Activated red mud; Adsorption; Removal of nitrate; Utilization

1. Introduction Nitrate is mainly found in most of natural waters at moderate concentrations but is often enriched to over the contaminant levels from the excessive using of fertilizers and uncontrolled discharge of raw [13]. Most important environmental problems caused by nitrate are eutrophication in water supplies and infectious disease [4]. Excess nitrate in drinking water may cause blue baby disease called as methemoglobinemia in newborn infants as well as other illness [5,6]. In order to protect public health from the adverse effects of high nitrate intake, World Health Organisation (WHO) set the standard as 50 mg/L to regulate the nitrate concentration in drinking water [7]. The conventional processes such as coagulation, ltration, chlorination, etc. for water treatment are not useful with regard to nitrate ion elimination from water [3]. Therefore, the traditional biological treatment [811], adsorption [5], ion exchange [1215], Donnan dialysis [16], electrodialysis [1720] methods have been applied to remove excessive nitrate from water. In addition the different adsorbents such as activated carbon, sepiolite, slag, synthetic ion exchanger, etc. have been also used for removing of nitrate. In recent years, considerable attention has

been devoted to the study of different types of low-cost materials such as tree bark, wood charcoal, saw dust, alum sludge, red mud and other waste materials for adsorption of some toxic substances [21]. Red mud (bauxite wastes of alumina manufacture) emerges as unwanted by-products during alkaline-leaching of bauxite in Bayer process. About 500 000 m3 of strongly alkaline (pH 1213) red mud-water pump is dumped annually into specially constructed dams around Seydisehir Aluminum Plant (Konya, Turkey). Since the plant began to process, red mud has accumulated over years and causes a serious environmental problem. Therefore, in the present paper, the possibility of utilization of the red mud in the original or activated form as an adsorbent for removal of nitrate from drinking water was studied. 2. Experimental NaNO3 , NaCl, NaOH, HCl were of analytical grade obtained from Merck Co. Darmstadt, Germany. Red mud was supplied from the Etibank Seydisehir Alu minum Plant (Konya, Turkey). The grain size of red mud was mostly (>94%) less than 10 m and average composition of red mud was given in Table 1. Original red mud was prepared by suspending the red mud in distilled water with a liquid to solid ratio of 2/1 on a weight basis, stirring it until the equilibrium pH is around 8.08.5, than

Corresponding author. Fax: +90 332 241 0106. E-mail address: ycengel@gmail.com (Y. Cengeloglu).

1383-5866/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.seppur.2006.02.020

Y. Cengeloglu et al. / Separation and Purication Technology 51 (2006) 374378 Table 1 Average composition of red mud used (% by wt.) Al2 O3 Fe2 O3 TiO2 Na2 O CaO SiO2 LOIa
a

375

18.7 39.7 4.9 8.8 4.5 14.5 8.1

0.6 0.7 0.5 0.9 0.6 0.4 0.4

Loss on ignition.

it was died in an oven at 105 C. Later activation of red mud was carried out as follows. The 10 g of water-washed and dried red mud was boiled in 200 mL of 20% wt. HCl for 20 min. The acid slurry is then ltered and the residue washed with distilled water to remove residual acid and soluble Fe and Al compounds. Finally, the residue is dried at 40 C, and used for the experiments without further treatment. The specic surface area of original and activated red mud was 14.2 and 20.7 m2 /g, respectively [22]. The nitrate solutions were prepared from stock solutions (1000 mg/L) prepared in laboratory to desired concentrations. The nitrate concentration was determined with a specic ionelectrode (Mettler Toledo) by use of ionic strength adjuster (ISA) solution (2 M (NH4 )2 SO4 ) to eliminate the interference effect of complexing ions. The ISA solution was added 100:2 into the nitrate standard and other solutions [23]. Nitrate concentration and pH were measured by an Orion EA940 ion meter. The adsorption experiments were carried out with batch method. All experiments were carried out at a constant ionic strength of 0.1 M maintained with NaCl. A known amount of red mud and nitrate solution were taken in a 100 mL stoppered conical ask. Sodium chloride was added to maintain ionic strength, and pH was adjusted to the desired level with 0.1 M NaOH or 0.1 M HCl solutions. The nal volume was adjusted to 50 mL with distilled water and agitated at constant speed (500 rpm) with magnetic stirrer in room temperature over a period of time and then ltered. The concentration of nitrate in ltrate was determined and the amount of nitrate removal was calculated from the ratio of nitrate taken and that remaining in the solution. Adsorbed nitrate was calculated from mass balance. The experimental parameters studied are: amount of adsorbent (18 g/L), contact time (5200 min), initial nitrate concentration (5250 mg/L), and the effect of pH (211). 3. Results and discussion 3.1. Effect of contact time The removal of nitrate versus time was illustrated in Fig. 1, and as can be seen that the removal of nitrate increases with time up to reach a steady state value in 60 min. The amount of nitrate ions adsorbed from water was expressed by Eq. (1): q= Q wd (1)

Fig. 1. Removal of nitrate as a function of equilibrium time. pH 6; initial nitrate concentration, 1.61 mmol/L and activated red mud dose is 0.2 g/50 mL.

where Q and wd are the amount (mmol) of nitrate ions adsorbed on the red mud and the weight (g) of the dry red mud, respectively. 3.2. Adsorption isotherms The adsorption isotherms of nitrate on red mud and activated red mud were illustrated in Fig. 2, in which q values increased with increasing of initial nitrate concentration (C) on both original and activated red mud. As shown in Table 2, the adsorption isotherm of nitrate was expressed both Langmuir and Freundlich isotherms. The Langmuir isotherm equation is written as C C 1 + = q Kb As As (2)

where C is the nitrate equilibrium concentration, the parameters Kb and As are the adsorption binding constant (L/mmol) and the saturation capacity (mmol nitrate/g dry wt. of red mud), respectively. The Freundlich isotherm equation is written as q = kC1/n (3)

where C is equilibrium concentration, k is the saturation capacity (mmol nitrate/g dry wt. of red mud) and n is an empirical parameter. The experimental data were tted to both Langmuir and Freundlich isotherm equations. Nitrate adsorption constants and correlation coefcients were calculated from Langmuir as

Table 2 Parameters of Langmuir and Freundlich isotherms for adsorption of nitrate on activated and original red mud Langmuir isotherm model As (mmol/g) Kb (L/mmol) R2 Activated red mud Original red mud 5.858 1.859 65.654 1.674 Freundlich isotherm model k (mmol/g) n R2

0.999 6.727 0.945 0.874

3.492 0.801 1.599 0.962

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Y. Cengeloglu et al. / Separation and Purication Technology 51 (2006) 374378

Fig. 2. (a) The adsorption of nitrate on the activated and original red mud; (b) Langmuir isotherm for activated red mud; (c) Freundlich isotherm for activated red mud; (d) Langmuir isotherm for original red mud; (e) Freundlich isotherm for original red mud. pH 6; contact time, 60 min; activated and original red mud dose is 0.2 g/50 mL.

well as Freundlich plots (Fig. 2(b)(e)) and are presented in Table 2. The adsorption data in respect to nitrate ions provide an excellent t to Langmuir isotherms, giving correlation coefcients of 0.999 and 0.945 for activated and original forms, respectively. As seen in Fig. 2(a) and Table 2, the adsorption capacity of activated red mud (5.858 mmol nitrate/g dry wt. of

red mud) is higher than that of original red mud (1.859 mmol nitrate/g dry wt. of red mud). It can be mentioned that monolayer coverage does not occur on the heterogeneous surface of original red mud [24]. This situation is attributed that various active sites or heterogeneous mixture of several minerals on original red mud has different afnities to nitrate anion [25].

Y. Cengeloglu et al. / Separation and Purication Technology 51 (2006) 374378

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For activated red mud, Langmuir isotherm exhibited a better t to experimental data compared to Freundlich isotherm. It is very well-known that Langmuir type adsorption is resulted with monolayer type adsorption, it means the adsorption is limited by surface site saturation and the sorption onto red mud is saturated one sites of the surface layer because of heterogeneous mixture of several minerals in its structure [25]. In other words, less heterogeneous mineral assemblage on the surface of activated red mud results in a homogeneous surface. It was pointed out by Genc-Fuhrman et al. [25] the adsorption capac ity of Bauxol (red mud) is hindered by the presence of surface impurities (i.e. salts and basic properties), thus, applying of activation process improve the adsorption capacity. This statement was also expressed that the acid treatment as well as heat treatment signicantly enhanced the adsorption capacity of the raw material of Bauxsol. On the contrary, adsorption of nitrate onto original red mud can be better dened by Freundlich isotherm which is assumed to be t for exponential increasing in adsorption and thus it gave lower saturation capacity compared to Langmuir isotherm. In other words, the nitrate sorption in the original red mud obeys the Freundlich isotherm model which is frequently encountered when solutes interact with heterogeneous substrate. According to the obtained results, the activation improves the adsorption capacity by increasing binding sites. It can be found that similar results in the literature [5,21,24,25], where removal efciency of different sorbates increased by following (the activation of red mud and sepiolite with acid.) Red mud is high in sodalite compounds ((Na, Ca)8 (AlSiO4 )6 (SO4 , OH, S, Cl)2 ) [26,27] which are expected to hinder the adsorption by blocking the available adsorption sites for nitrate. Therefore, the leaching out of the sodalite compounds during acid treatment increases the adsorption capacity [2830]. 3.3. Effect of pH The extent of adsorption of anions is strongly governed by the pH of the solution. Since anion adsorption is coupled with OH ions, the adsorption is favored in low or neutral pH values. Red mud is a metal oxide adsorbent containing different metal oxide in the structure. In a humid environment, hydroxylated surfaces of these oxides developed charge on the surface. The interaction between nitrate ion and metal oxide was modeled by assuming ligand exchange reactions as follows [21,31]:

Fig. 3. The effect of equilibrium pH on nitrate removal. Contact time is 60 min; activated red mud dose, 0.2 g/50 mL and initial nitrate concentration, 1.61 mmol/L.

ous interface. The adsorption of nitrate on activated red mud was studied at different pH values, ranging from 2 to 11. The obtained results are given in Fig. 3. It is evident that that removal of nitrate uctuates very little in the pH range 27. The obtained results for maximum adsorption are in agreement with the nitrate removal study on the sepiolite and activated sepiolite (about pH 6) [5]. It is seen from Fig. 3, the nitrate removal decreases at a pH above 7, due to stronger competition with hydroxide ions on adsorbent surface. In other words a high bias in the measured concentration could occur at pH values above 7 due to presence of high concentration of OH [27]. The solution pH relative to the point of zero charge (pHpzc) for the red mud also needs to be considered. At pH values above the pHpzc of the adsorber, the surface of adsorber particles is negatively charged and as the pH rises above the pHpzc, anion adsorption decreases. The pHpzc for red mud and activated red mud has been reported as about 8.3 and 8.5, respectively, in the literature [27,32], but the change from a strongly positive to a strongly negative zeta potential takes place gradually over 1.52 pH units [33]. 3.4. Effect of red mud dosage The percentage of nitrate adsorption with varying amounts of activated red mud is presented in Fig. 4. In general, the increase in adsorbent dosage increased the percent removal of adsorbate. This is consistent with the expectation that higher adsorbent dosages will result in lower q values. The concentration of surface hydroxyl groups is related to red mud concentration through surface site density [31]. Therefore percent of adsorption increased with red mud dosage, whereas q decreased (Fig. 4). Various anions in drinking water or waste water have relative binding ability on red mud surface [21]. Therefore, their effects on the adsorption of nitrate should be considered. In the literatures, it was reported that nitrate adsorption decreased from 41.4% to 31.4% in case of sulphate and 16% in phosphate on

(4)

(5) where M presents metal ions (Al, Fe or Si). The pH of the aqueous solutions is an important variable, and controls the adsorption between the adsorbent and aque-

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[8] [9] [10] [11] [12] [13] [14] [15] [16] [17]

Fig. 4. The variation of removal nitrate with activated red mud dose. pH 6; initial nitrate concentration, 1.61 mmol/L and contact time is 60 min.

activated carbon, and from 33.4% to 5.6% and 0.5% in sulphate and phosphate, respectively, on sepiolite. 4. Conclusion In this study, the possibility of utilization of red mud as adsorbent for removal of nitrate from aqueous solution was studied. The results are summarized as follows: The nitrate saturation capacity of activated and original red mud is 5.858 mmol nitrate/g dry wt. of red mud and 1.859 mmol nitrate/g dry wt. of red mud, respectively. In other words, the removal of nitrate with activated red mud was found as three times higher with regard to the original form. The effect of time for removal of nitrate was determined within 60 min. The removal of nitrate was decreased at a pH above 7. Acknowledgement The authors are grateful for kindly nancial support provided by Selcuk University Research Foundation (SUAF). References
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