INVESTIGATION OF SOLVENT EXTRACTION OF Zn(II) FROM NIGERIAN SPHALERITE BY CYANEX272

Dr. Alafara A. BABA (+), Lecturer I and Assoc. Prof. Folahan A. ADEKOLA(+) Department of Chemistry, University of Ilorin, P.M.B. 1515, Ilorin 240003, Nigeria.

(+) Corresponding authors: (E-mail: alafara@unilorin.edu.ng (A.A. Baba); Tel: +2348035010302, fadekola@unilorin.edu.ng (F. A. Adekola); Tel: +2348067332320.

Abstract The extraction and purification of Zn(II) with bis(2,4,4-trimethylpentyl)phosphinic acid, commonly known as Cyanex272 in kerosene from aqueous chloride sphalerite leached liquor was investigated. The results of fundamental studies on solvent extraction of synthetic solutions of Zn(II) showed that extraction of metal ions increased with increasing pH, extractant concentration and temperature. The stochiometry of the extracted metal species by Cyanex272 with Zn(II) was 1:1. The apparent standard molar enthalpy (H), molar entropy(S) and Gibbs free energy(G) of -26.81kJ/mol, 21JK-1 mol-1 and -5.48kJ/mol were calculated for the process respectively. These values showed that Zn(II) extraction with Cyanex 272 is entropy controlled. The number of the theoretical stages for this process evaluated by the McCabe-Thiele diagram was six. An extraction efficiency of 95% Zn(II) by 0.047M Cyanex272 in kerosene was obtained from an initial sphalerite leach liquor containing 603.4mg/L Zn, 121.4mg/L Fe and 16.3mg/L Pb as a major constituents. Pb(II), Ag(I), Cu, Sn, and Al (less than 5mg/L) present in the liquor were firstly separated by cementation with Zn granules, followed by Iron removal by precipitating with 4M ammoniacal solution to a pH of 3.5 at 25oC2oC. A 0.1M HCl was found to be adequate for the stripping of at least 95% of Zn from the organic phase. The stripped Zn(II) solution was recovered as zinc oxide (ZnO) via precipitation with sodium hydroxide followed by calcination at 600 oC during 120 minutes. A practicable hydrometallurgical scheme summarizing the operational procedure for the extraction of Zn(II) and Pb(II) from the Sphalerite ore was presented. Key words: Beneficiation, sphalerite, Zinc, Solvent extraction, hydrochloric acid, Cyanex272.

Introduction: The mineral sphalerite, ZnS, is the most important zinc mineral and is generally treated pyrometallurgically. However, zinc smelting faces difficulties with respect to the environmental restrictions. (Adebayo, et al, 2006). Therefore, the hydrometallurgical solvent extraction processes have become major purification operations in practice with special emphasis on Zn(II) separation from its coexistent species such as Pb(II), Co(II), Ni(II) and Cu(II), etc. Presence of these impurities in dissolved low grade Zinc ores and need of concentrated Zinc electrolytes for ultra high grade Zinc production made solvent extraction a very attractive pretreatment sequence for electrowinning process (Sayar, et al, 2007). As the world wide high grade ore reserves are falling at appalling rate as most are worked out because of high metal demand (Kesari, et al, 2009), hydrometallurgical route has been an alternative to pyrometallurgical processes for sulphidic ores and concentrates, particularly for small scale production and for remote metal resources not acceptable by pyrometallurgy. (Rotuska and Chmielewski, 2008). Zinc has a wide variety of application including its use in metallic coating to improve corrosion resistance of various types of steel. The pickling of steel goods is usually carried out using 20% HCl and the process is stopped when HCl concentration reaches 10% (Regel, et al, 2001). The use of organophosphorus extractants including Cyanex302, Cyanex921, Cyanex923 and TBP have been widely reported for the separation and recovery of Zn(II) from HCl medium (Daoud, et al, 2008; Tait, 1992). Therefore, the present study centered on the solvent extraction and separation of Zinc(II) from associated impurities such as lead, iron, copper, silver etc. contained in Nigerian sphalerite mineral. This is a first in-depth study on the hydrometallurgical recovery of Zinc(II) and lead(II) from a Nigerian sphalerite origin by Cyanex 272. It is worthy to note that the first part of the studies on the beneficiation of the sphalerite mineral had earlier been published (Baba and Adekola, 2010).

Experimental The experimental approach adopted for this study comprises a preliminary work aimed at establishing conditions for the optimal extraction of Zinc from synthetic Zn(II) solutions by Cyanex272 with subsequent application to the recovery and beneficiation of Zinc(II) from sphalerite leachate (Baba, 2008; Daoud, et al, 2006; Sayar, et al, 2007). In all extraction experiments, the ratio of Zn(II) in the extract to its concentration in the aqueous phase, otherwise known as distribution ratio, Dc is given by: Dc = [Zn(II)]org/[Zn(II)]aq (1)

Dc is the index of metal extractability and it is related to percentage of the metal extracted (Sayar, et al, 2007).

Result, discussion and conclusion: The results on fundamental studies on solvent extraction of synthetic solutions of Zn(II) showed that extraction of metal ions increased with increasing pH, extractant concentration and the system temperature. Also, the values of the thermodynamic parameters such as the apparent molar enthalpy, molar entropy and Gibbs free energy change showed that Zn(II) extraction by Cyanex 272 is entropy controlled. These results were used in the optimization of the systematic study of the Zinc(II) and Pb(II) extraction and its beneficiation from sphalerite ore.

Consequently, a hydrometallurgical flow diagram summarizing all analytical procedures for the recovery of Zinc(II) and production of pure Zinc oxide from Nigerian sphalerite origin by Cyanex272 is presented in Fig. 1.

Sphalerite sample collection and preparation (crushing, pulverizing) Leaching of Sphalerite in HCl medium Sphalerite leachate in 4M HCl at 360rpm at 80; pH adjusted to 3.0 Cementation Pb 92.28% efficiency Zn, Fe, other trace elements Zn: 648.65mg/L Pb: 1.26mg/L Fe: 104.55mg/L Zn: 603.45mg/L Pb: 16.33mg/L Fe: 121.40mg/L * Other elements: Ag, Mn, Sn, Cu are present in traces

Fe 98.85% efficiency

Ammoniacal solution, pH 3.5

Zn, other trace elements n3

Zn: 646.22mg/L Fe: <2mg/L

0.032M Cyanex 272 pH 3.0 Temperature: 250C20C Zn-Cyanex: 613.98mg/L Zn-aqueous: 32.24mg/L Extraction efficiency = 95.01%

re-use

Zn - Cyanex

Cyanex 272

Stripping with 0.1M HCl

Zn(II) in 0.1M HCl

Zn-aqueous: 586.23mg/L Zn-recovery = 95.48%

NaOH/Calcination ZnO

Figure 1: Hydrometallurgical flow diagram for the recovery of Zn(II) extraction and production of pure ZnO from Abakaliki (Nigeria) Sphalerite ore.

Acknowledgements: The authors wish to thank Dr. Oliber Rouher and Mrs. Christine Salomon of Cytec Industries, Rungis Cedex, France for their benevolence by supplying Cyanex272. A.A. Baba also thanks the University of IlorinNigeria, for the 2005/2006 Staff Development Award for Ph.D. research in Chemistry.

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