Adsorption of Ni (II) ions from aqueous solution on anode dust: Effect of pH value Adsorbcija Ni(II) ionov iz vodne raztopine anodnega prahu: učinek pH vrednosti Anita Štrkalj1-*, Ankica Rabenovic1, Jadranka Malina1 'University of Zagreb, Faculty of Metallurgy, Alej a narodnih heroj a 3, 44 000 Sisak, Croatia Corresponding author. E-mail: strkalj@simet.hr Received: November 20, 2009 Accepted: January 28, 2010 Abstract: In this study, the anode dust, a solid residue of aluminium production, was examined as a non-conventional and low-cost sorbent for the removal of Ni (II) from aqueous solution. The adsorption capacity was found to be pH dependent and decreased along with an increase pH. The maximum adsorption was obtained at pH 4.5. The results were analyzed by the Langmuir and Freundlich isotherm at the best pH value. Izvleček: V članku je opisan poskus z anodnim prahom, ki je trdna usedlina pri pridobivanju aluminija, za neobičajno in cenovno odstranjevanje Ni(II) iz vodne raztopine. Dokazano je bilo, da je adsorbcijska kapaciteta odvisna od pH in se zmanjšuje z naraščajočo vrednostjo pH. Največja adsorbcija je bila pri pH 0.5. Rezultati so bili analizirani z Langmuirovo in Freundlichovo izotermo pri najboljši vrednosti pH. Key words: anode dust, adsorption, Ni (II) ions, aqueous solution, pH value Ključne besede: anodni prah, adsorbcija, Ni (II) ioni, vodna raztopina, vrednost pH Introduction The removal of toxic heavy metals such as cadmium, copper, lead, nickel, mercury, and zinc from aqueous environment has received considerable attention in recent years due to their toxicity and carcinogenicity which may cause damage to various systems of the human body. [1] Nickel is metal frequently encountered in raw wastewater streams from industries such as mining, electroplating, metallurgy, electroplating, pigment and ceramics industries. [2] This metal is non-biodegradable toxic heavy metal and may cause dermatitis, allergic sensitization and cancer.[3, 4] It is essential to remove Ni (II) ions from industrial wastewater before being discharged. For this reason, generally are used the advanced treatment processes such as chemical reduction, ion exchange, reverse osmosis, electro dialysis, and adsorption. Since the cost of these processes is rather expensive, the use of agricultural residues or industrial by-product was received with considerable attention [5] In recent years, a number of industrial by-product as waste mould sand,[6] blast furnace sludge, [7] steel slag, [8] red mud[9] were used for the removal of toxic metals from aqueous solutions. For reduction of alumina in aluminium production by the electrolytic process, carbon anodes are used. The remaining parts of the anodes after use for aluminium production are called anode butts. The cleaned anode butts are crushed and reused for the production of new anodes (about 20 % of the anode is recycled). Anode dust originates from the baking process and during the transport of anodes. Owing to its granulometry and chemical composition, the anode dust is considered as a waste material. [10, 11] In this study, the anode dust, a solid residue of aluminium production, was investigated as a non-conventional and low-cost adsorbent for the removal of Ni (II) ions from aqueous solution. The influence of pH value on adsorption capacity of anode dust is examined. Materials and methods Preparation and characterization of anode dust Anode dust, which is a solid residue of aluminium production, was used as the adsorbent. For analysis, a representative sample of anode dust was obtained using a quartering technique. The sample was dried at 105 °C for 4 h and sieved to particle size 0.125-0.2 mm. The chemical composition of the sample was determined by atomic absorption spectroscopy (the AAS method). The mineralogical composition of the anode dust sample was determined by the X-ray diffraction method (XRD method). The chemical composition of the examined anode dust is presented in Table 1. It was found that the anode dust was dominated by C (w(C) = 94.49 %), followed by Si (w(Si) = 1.73 %), Al (w(Al) = 1.69 %), S (w(S) = 1.50 %), and Fe (w(Fe) = 0.34 %). The mineralogical composition (XRD analysis) of anode dust is shown in Figure 1. Batch experiment A stock solution of Ni (II) ions was prepared by dissolving NiCl2-6H2O in 1000 mL deionized water. This solution was diluted as required to obtain the standard solutions. The initial concentrations of the solutions contained 50-500 mg L1 of Ni (II) ions. The batch experiments were carried out in 100 mL conical flasks by agitating 0.375 mg anode dust with 25 mL of the aqueous Ni (II) ions solution for a period of 30 min (equilibrium time) at 20 °C on a mechanical shaker. The adsorption of nickel ions by anode dust was studied in a pH range of Table 1. Chemical composition of anode dust sample in mass fractions (w/%) Components C Si Al S Fe Na V Ca Ni w/% 94.49 1.73 1.69 1.50 0.34 0.089 0.072 0.044 0.043 Figure 1. XRD pattern of the anode dust sample 4.5-7. Solutions of 0.5 M HCl and 0.5 M NaOH were used for pH adjustments. The concentration of Ni (II) ions before and after the adsorption was determined spectrophotometrically with standard method.[12] The amount of Ni (II) ions adsorbed at equilibrium i. e. the adsorption capacity, qe/(mg/g), was calculated according to the formula: Ve = C0 - Ce m ■ F (1) where, qe - adsorption capacity, mg/g c0 - initial concentration of nickel ions, mg/L ce -equilibrium concentration of nickel ions, mg/L V - volume of solution, L m - adsorbent mass, g Results and discussion One of the most critical parameter in the adsorption process of metal ions from aqueous solution is the pH of medium. [1] The capacity of Ni (II) ions removed is shown in Figure 2. The effect of pH on the adsorption capacity of anode dust may be attributed to the combination of the nature of the surface and amount of Ni (II) ions. Change of pH value causes the ionization of the acid groups (hydroxyl, carboxyl, phenol etc.) present in anode dust surface.[13]This suggest that electrostatic interaction between divalent Ni (II) ions and anode dust nega- tives sites could be the most prevalent mechanism of metal-binding. It is evident from Figure 2 that the capacity is higher at lower pH. The best adsorption of Ni (II) ions was obtained at the pH value of 4.5. For higher pH values, Ni (II) ions precipitate in the form of metallic hydroxides and adsorption capacity was decreased. [14] Adsorption equilibrium data were fitted to the Langmuir and Freundlich isotherms at pH value of 4.5-7 with linear regression analysis. The linear equations of Langmuir and Freundlich are represented as follows (Equations (2) and (3), respectively): [8] Figure 2. Effect of pH value on the adsorption capacity (qe) of anode dust with different equilibrium concentration (c ) of Ni (II) ions ■*-.pH=7; £ - 0,9328; y = 0,2202 + 27,3008*x ^pH=5,7; ^ = 0,9767; y = 0,1645 + 23,1477*x v r = 0,994-7; y = 0,1157 + 17r78S3*x 0,1 -------- ■———■ ............——— ■ --------- ■ ------ ■ ■ -——1 0.000 0,005 0,010 0,015 0.020 0,025 0,030 0,035 0,040 Mce, l/mg Figure 3. Langmuir isotherms for adsorption of Ni(II) ions on anode dust at pH value of 4.5-7 Figure 4. Freundlich isotherms for adsorption of Ni(II) ions on anode dust at pH value of 4.5-7 Table 2. Values of Langmuir/Freundlich constants and correlation coefficients Langmuir isotherm Freundlich isotherm PH q / (mg/g) KJ (L/mg) R2 n kf R2 7 4.54 8.06 • 10-3 0.9328 1.775 0.140 0.9098 5.7 6.08 7.11 • 10-3 0.9767 1.707 0.157 0.9701 4.5 8.64 6.50 • 10-3 0.9947 1.755 0.230 0.9532 1 1 1 (2)