Hydrometallurgy 77 (2005) 3 7 www.elsevier.

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Influence of mechanical activation on selectivity of acid leaching of arsenopyrite

M. Achimovicova*, P. Balaz
Institute of Geotechnics, Slovak Academy of Sciences, Watsonova 45, 043 53 Kosice, Slovakia Received 27 May 2004; received in revised form 13 July 2004; accepted 12 September 2004

Abstract Mineral arsenopyrite (FeAsS) was exposed to leaching in H2SO4 solution. Surface changes of mechanically activated sulphide were investigated before and after leaching using infrared spectroscopy and scanning electron microscopy. Mechanical activation of the mineral resulted in mechanochemical surface oxidation and in the formation of sulphates. Furthermore, the specific surface area and the disordering of mineral crystal structure increased. These aspects influence the kinetics and selectivity of acid leaching of arsenopyrite. D 2004 Published by Elsevier B.V.
Keywords: Mechanical activation; Selective acid leaching; Arsenopyrite

1. Introduction Arsenopyrite is the most common arsenic containing mineral of many ore deposit but it is of limited economic importance and generally is discarded as solid waste during mining operation. When arsenopyrite present in an ore is not associated with gold values, it is viewed as a troublesome impurity. Smelters at present prefer to receive concentrates which are essentially free of arsenic (Landsburg et al., 1980; Nesbitt et al., 1995; Beattie and Poling, 1987). In

T Corresponding author. Fax: +421 55 63 234 02. E-mail address: achimovic@saske.sk (M. Achimovicova). 0304-386X/$ - see front matter D 2004 Published by Elsevier B.V. doi:10.1016/j.hydromet.2004.09.008

some sulphide concentrates, arsenopyrite contains binvisibleQ gold that can be released only by some type of pretreatment, e.g. by chemical oxidation in acidic medium (Cruz et al., 1997; Balaz, 2000). Mechanical activation as a process of creating new surfaces and structural defects of minerals as well as the selection of proper leaching agent can accelerate the process of alternative hydrometallurgical processing of arsenopyrite with the aim to extract the valuable metals contained in this type of ore or concentrate (Balaz, 2000). The aim of this paper is to analyse the influence of mechanical activation of arsenopyrite FeAsS on kinetics and leaching selectivity of arsenic and iron in sulphuric acid medium.

M. Achimovicova, P. Balaz / Hydrometallurgy 77 (2005) 37

2. Experimental 2.1. Materials The investigations were carried out with arsenopyrite FeAsS mineral of Slovak origin (Pezinok). The samples contained admixtures of ankerite, calcite and quartz. The chemical composition was as follows: 0.05% Cu, 21.20% Fe, 10.48% S, 25.12% As, 3.42% Ca, 20.55% SiO2 and 0.77% insoluble rest. 2.2. Mechanical activation Mechanical activation of the mineral under study was performed in a planetary mill Pulverisette 4, (Fritsch, Germany) under the following conditions: weight of sample20 g, grinding means25 pieces of balls with diameter 15 mm and 5 pieces of balls with diameter 25 mm, material of grinding means and chambertungsten carbide, grinding time 530 min, relative acceleration of the millb/g=10.3. 2.3. Leaching

Zeiss, Germany). Sample of arsenopyrite for spectra measurements was prepared by KBr disc technique (Kossler, 1970). 2.5. X-ray diffractometry The structural disorder of mechanically activated samples as well as the quantitative diffraction data were obtained by X-ray diffraction phase analysis on a diffractometer Dron 2.0 (Russia) in the following regime: radiation Cu Ka, 30 kV, 20 mA; time constant 1 s ; limit of measurement 10 impulsesd s1, rate of detector movement 28d min1; paper drive 2.4 m h1. The lattice microstrains e (Klugg and Alexander, 1972) were calculated according to the equation: e Da b d1000 a 4Rtanh 2

where Da/a stands for the relative microstrains (x), b is the physical half width of the diffraction line (200) FeAsS (mm), R is the goniometer radius (mm) and h is the diffraction angle (8). 2.6. Specific surface area

The leaching was investigated in a 500 mL glass reactor into which 400 mL of leaching solution (170 g L1 H2SO4) and 0.5 g of sulphide were added. The leaching was performed for 120 min at 90 8C at a stirring rate of 8.33 s1. Aliquots (1 mL) of the solution were withdrawn at appropriate time intervals for determination of the contents of the dissolved arsenic and iron by atomic absorption spectroscopy. The selectivity of leaching has been defined as As/Fe ratio. The leaching selectivity of FeAsS was described by the equation derived by Dutrizac (Dutrizac, 1982):
2 eMe k 1 k 2:tL k 3:tL

The specific surface area, S A, was determined by the low temperature nitrogen adsorption method in a Gemini 2360 sorption apparatus (Micromeritics, USA). The specific surface area, S G, was statistically determined from the particle size distribution data measured on Helos and Rodos granulometer (Sympatec, Germany).

3. Results and discussion 3.1. Mechanochemical surface oxidation of arsenopyrite The complexity of surface alterations of arsenopyrite during mechanical activation can be observed on the infrared spectra shown in Figs. 1A and 2A. During mechanical activation a sulphate layer forms on the surface of the mineral that results from the mechanochemical surface oxidation. The infrared spectrum shown in Fig. 1A contains a variety of absorption bands. Apart from the 441450 cm1 band, induced by FeAs valence vibration in the

where e Methe leached metals yield in the solution (in 01 interval); k(2), k(3)reaction rate constants and t Ltime of leaching. Initial rate constants k(2) were deduced by fitting the data to Eq. (1) and deducing the scope at t=0 min. 2.4. Infrared spectroscopy Measurements of infrared spectra were performed using an infrared spectrometer SPECORD IR 75 (Carl

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layers thus become heterogenous from both morphological and energy point of view. Here, the chemical bonds are broken and that affects the sulphide reactivity during acid leaching. If the infrared spectra of arsenopyrite mechanically activated for 10 min and its spectrum after leaching in H2SO4 are compared (Fig. 1A, B), it can be seen that no significant change of surface occurred, with the exception of the disappearance of ankerite (Fe,Ca)CO3 bands. Ankerite is decomposed during leaching according to the equation shown below: 2(Fe,Ca)CO3+2H2SO4=FeSO4+CaSO4 +2H2O+2CO2

(2)

Fig. 1. Infrared spectrum of arsenopyrite FeAsS mechanically activated 10 min: Abefore leaching, Bafter leaching.

mineral (Syrtlanova et al., 1979), the rest of the bands belong to the products of mechanochemical oxidation and mineral admixtures. The 10711077 cm1 bands indicate the presence of products of mechanochemical oxidation of sulphides to sulphates. The sulphides are characterised also by the 450 cm1 band, that is probably superimposed on the FeAs valence vibration band situated at the same place. The carbonates 2 are represented in the spectrum by CO3 group 1 vibrations at 866 and 14231433 cm . The samples thus contain ankerite. The admixture of quartz yielded a double band at 790 cm1 and bands in the 510518 cm1, 687 and 1150 cm1 region. The 1620 cm1 band corresponds to water in KBr pellet (Nakamoto, 1978). 3.2. Effect of mechanochemical surface oxidation on acid leaching of arsenopyrite The effect of mechanical activation on sulphide reactivity has been studied for a number of years. The mechanical activation changes the surface layers of the studied sulphide minerals and introduces the defects into bulk structure (Balaz, 2000; Avvakumov, 1986; Kulebakin, 1983; Tkacova, 1989). The surface

Non-activated FeAsS is very resistant against the influence of H2SO4. Fig. 2A shows that probably only the solubilization of Fe in ankerite occurred. Arsenic and iron in FeAsS are not leached out under the given conditions. In case of mechanically activated sample, As and Fe from arsenopyrite are transferred into the leachate. The maximum yield is 29% for As and 31% for Fe, provided the sample was mechanically activated for 30 min (Fig. 2B). The chemical processes of FeAsS leaching are very complicated as all the three elements present in the mineral usually form a number of insoluble and soluble compounds. Thus, e.g. Fe enters

Fig. 2. Recovery of metals into the solution e Me, vs. time of leaching, t L for FeAsS: Aas received, Bmechanically activated 30 min.

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the leachate as Fe2+ or Fe3+, As can be present as As3+ or As5+, sulphur in sulphides can be present in the form of S2 or according to the level of oxidation up to S6+. 3.3. Effect of deformation of arsenopyrite crystalline structure on the kinetics and leaching selectivity of acid leaching Mechanical activation as a method of sulphide mineral pretreatment results in the increase of reactive surface and deformation of crystalline structure of minerals. Thisin generalleads to accelerating the leaching process (Balaz, 2000). At the end, the increased reactivity of mechanically activated sulphides leads to the decrease of activation energy and the acceleration of leaching of the metals presented in the mineral. This in turn affects also the selectivity of leaching. Fig. 3 shows initial reaction rate constant values, k Me=k(2) of Fe and As leaching from arsenopyrite in relation to the duration of mechanical activation. It can be seen that with the increase of activation time, the reaction rate for both metal increase. The maximum values are achieved after 20 min of activation. It follows that leaching after mechanical activation for 20 min is the most rapid and effective. The relationship between the specific reaction rate con-

Fig. 4. Dependances of specific reaction rate constant of metal leaching, k Me/S G (Me=As,Fe) vs. FeAsS microstrains, e.

stant k Me/S G (i.e. reaction rate constant value over specific surface S G) and the structure deformation values of arsenopyrite defined by microstrains e is shown in Fig. 4. The curves could be decomposed to three segments that characterise the differences in the course of leaching. At stage I, As and Fe enter the leachate only from the surface layers of FeAsS. At stage II, with the increasing value of structure deformation, As and Fe are leached from whole volume of the FeAsS specimen. This means that the reaction is structure sensitive. At stage III, one can observe a rapid decrease of specific reaction rate constant value that is related to lattice microstrains. That is probably caused by the agglomeration effect (Balaz, 2000; Tkacova, 1989).

As/Fe[%]

0 2 2,2 2,4 2,6 2,8 3

SA[m2g-1]
Fig. 5. Selectivity of leaching, As/Fe from mechanically activated arsenopyrite vs. specific surface area, S A (time of leaching, t L=20 min).

Fig. 3. Dependance of leaching rate constants of metals k Me (Me=Fe,As) vs. time of mechanical activation of FeAsS, t G.

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The selective leaching of FeAsS as defined by the As/Fe ratio in relation to specific surface is shown in Fig. 5. The linear, decreasing trend indicates that with the increase of specific surface, the As/Fe yield rate decreases. It means that in contrast to the As yield, the Fe yield is increasing with the duration of mechanical activation. Mechanical activation makes the crystalline structure of FeAsS instable and in this process, in all probability the bonds between As and Fe are broken. This in turn makes their transfer to the leachate easier. The mutual ratio of both the discussed metals is also probably linked to the complicated leaching chemistry.

were in part (M.A., P.B.) kindly supported by VEGA (grant No. 2/5151/5), APVT (grant No. 20-018402) and Center of Excellence NANOSMART.

References
Avvakumov, E.G., 1986. Mechanicals Method of Activation of Chemical Processes. Nauka, Novosibirsk (in Russian). Balaz, P., 2000. Extractive Metallurgy of Activated Minerals. Elsevier, Amsterdam. Beattie, M.J.V., Poling, G.W., 1987. A study of the surface oxidation of arsenopyrite using cyclic voltametry. International Journal of Mineral Processing 20, 87 108. Cruz, R., Lazaro, I., Rodrgues, J.M., Monroy, M., Gonzales, I., 1997. Surface characterization of arsenopyrite in acidic medium by triangular scan voltametry on carbon paste electrodes. Hydrometallurgy 46, 303 319. Dutrizac, J.E., 1982. Ferric ion leaching of chalcopyrites from different localities. Metallurgical Transactions 13B, 303 309. Klugg, H.P., Alexander, L.G., 1972. X-ray Diffraction Procedures for Polycrystalline and Amorphous Materials. J. Wiley Inc., New York. Kfssler, I., 1970. Quantitative Infrared Spectroscopy of Minerals. SNTL, Prague. (in Czech). Kulebakin, V.G., 1983. Transformations of Sulphides by Activation. Nauka, Novosibirsk (in Russian). Landsburg, A., Mauser, J.E., Henry, J.L., 1980. Behaviour of Arsenic in a Static Bed During Roasting of Copper Smelter Feed. USBM R.I, p.8493. Nakamoto, K., 1978. Infrared and Raman Spectra of Inorganic and Coordination Compounds. J. Wiley and Sons, Inc., New York. Nesbitt, H.W., Muir, I.J., Pratt, A.R., 1995. Oxidation of arsenopyrite by air and air-saturated, distilled water, and implications for mechanism of oxidation. Geochimica et Cosmochimica Acta 59, 1773 1786. Syrtlanova, T.S., Minejev, G.G., Smagunov, V.N., Perepelica, L.S., 1979. Intensifikacija scelocnogo razlozenija arsenopyritpyritnogo koncentrata putjom suchogo dispergirovania. Izvestija SO AN SSSR 7, 50 55. Tkacova, K., 1989. Mechanical Activation of Minerals. Elsevier, Amsterdam, p. 155.

4. Conclusion Mechanical activation results in mechanochemical surface oxidation of the studied mineral. It causes the appearance of sulphates on the FeAsS surface. These products influence the speed of arsenopyrite leaching at stage of commencement as they are readily soluble in the leaching medium. Another effect of mechanical activation is the deformation of the mineral structure (defined by the value of microstrains e), that also effects positively the leaching speed of arsenopyrite. With an increasing time of mechanical activation agglomeration sets in, that negatively affects the FeAsS leaching speed. The acid leaching of mechanically activated FeAsS is selective.

Acknowledgement We would like to thank Dr. M. Balintova for the measurement of the IR spectra. The research activities