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Hydrometallurgy 72 (2004) 159 165 www.elsevier.

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Dissolution kinetics of malachite in sulphuric acid


lu b,* D. Bingo l a, M. Canbazog
a

Department of Mining Engineering, Dumlupnar University, Ku tahya, Turkey b Department of Mining Engineering, Cumhuriyet University, Sivas, Turkey

Received 28 May 2003; received in revised form 1 October 2003; accepted 5 October 2003

Abstract A kinetic study of the sulphuric acid leaching of oxidised copper ore, primarily malachite, was carried out. The effects of leaching time, stirring speed, acid concentration, solid to liquid ratio, reaction temperature, and particle size of the ore were investigated. Using the best conditions, the copper recovery was nearly 94% at 25 jC and 99% at 80 jC after 180 min leaching. Dissolution of malachite during the leaching was described by a logarithmic function, y = a ln(x) + b. The data obtained for the leaching kinetics indicated that the initial dissolution of malachite is a diffusion controlled reaction. D 2003 Elsevier B.V. All rights reserved.
Keywords: Malachite; Dissolution; Copper; Sulphuric acid; Leaching; Kinetics

1. Introduction Copper was the first metal to which hydrometallurgical processes including leaching, solvent extraction and electrowinning (L-SX-EW) were applied (Seward, 1997, 1999; Hopkins, 1994). During the leaching of copper minerals, such as chalcopyrite (CuFeS2) or tenorite (CuO), sulphuric acid and ammonia are generally the most used leaching mediums (Bingo l et al., 1994; Amores et al., 1997; Navarro and Alguacil, 1999; Alguacil, 1999). Copper oxide minerals contain copper in the divalent state (e.g. azurite (Cu3(OH)2(CO3)2), malachite (Cu2(OH)2CO3), tenorite (CuO) and chrysocolla (CuSiO3.2H2O)), and these are completely soluble in sulphuric acid at room

temperature. Typical reactions of oxidised copper ores with sulphuric acid can be given as follows (Blazy, 1970; Barlett, 1992), Cu3 OH2 CO3 2 3H2 SO4 ! 3CuSO4 2CO2 4H2 O 1

Cu2 OH2 CO3 2H2 SO4 ! 2CuSO4 CO2 3H2 O 2 CuO H2 SO4 ! CuSO4 H2 O 3

CuSiO3 :2H2 O H2 SO4 ! CuSO4 SiO2 3H2 O 4 The cost of acid may be the most important economic factor in the leaching of oxidised copper ores. Carbonate rocks, such as limestone and dolo-

* Corresponding author. lu). E-mail address: mcanbaz@cumhuriyet.edu.tr (M. Canbazog 0304-386X/$ - see front matter D 2003 Elsevier B.V. All rights reserved. doi:10.1016/j.hydromet.2003.10.002

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mite, are often significantly found in the ores and consume additional acid according to the reaction given below (Blazy, 1970; Barlett, 1992): CaCO3 H2 SO4 H2 O ! CaSO4 :2H2 O CO2 5 To determine the leaching parameters, the dissolution of malachite in sulphuric acid solutions has been recently studied by the Taguchi method (Ata et al., 2001). In this study, the kinetics of malachite leaching was not evaluated and the optimum leaching conditions were determined as: temperature, 40 jC; solid to liquid ratio, 0.1 g cm 3; sulphuric acid concentration, 10%; reaction time, 45 min; particle size, 10 mesh and stirring speed, 480 rpm. Under these optimum working conditions, the recoveries of copper and iron from malachite ore were 100% and 58%, respectively. The aim of this present study is to determine and discuss the dissolution kinetics of malachite in sulphuric acid. For this purpose, the initial dissolution rate and activation energy were determined and the effect of other minerals on leaching reactions were taken into the consideration.

and the sulphur from the base metal minerals. Quartz was determined using the conventional hydrofluoric acid method. The ore was first crushed, ground and then screened to obtain the desired particle size fractions for the leaching experiments. The leaching experiments were performed in a 600 mL Pyrex beaker in a thermostatically controlled water bath, and equipped with a thermometer and Teflon stirrer agitated mechanically. The ground copper ore was added into the agitated sulphuric acid solution at the required temperature. After pre-determined time intervals, 5 mL of leaching solution sample was withdrawn from the reactor and 5 mL of fresh sulphuric acid solution was added immediately to leaching medium. After filtration, the clear leach solution sample was analysed for copper by AAS. The weight loss during leaching was calculated by difference. The acid consumption was determined by titration of the leach solution with NaOH, using dimethyl yellow + methylene blue as indicators. For the leaching experiments where the acid concentration and solid to liquid ratio were examined, the ore sample has a P80 of 0.65 mm was used, the 100 150 Am size fraction was used to test the effect of temperature.

2. Experimental 3. Results Oxidised copper ore was used for the leaching experiments. Mineralogical analysis, performed using a Rigaku DMAX IIIC model X-ray diffractometer using CuKa radiation at 35 kV and 15 mA, indicated that malachite, pyroxene group minerals, quartz, goethite and magnetite were the major mineral phases in the ore. The chemical analysis of the malachite ore sample is presented in Table 1. Copper, iron, nickel, cobalt and chrome value were determined by using Atomic Absorption Spectrophotometer (AAS). Sulphur and carbon content were determined by using LECO-444 SC analyser. The carbon in the ore originates from carbonate content of malachite mineral,
Table 1 Chemical analysis of ore Component (%) Cu 28.36 Fe 15.74 Ni 0.044 Co 0.010 Cr 0.019 S 0.10 C 2.72 SiO2 15.34

3.1. Effect of leaching time The effect of leaching time on the dissolution of malachite is shown in Fig. 1. Clearly, the copper recovery increased with increasing leaching time with the initial dissolution of copper being very rapid. After 5 min, 77% copper recovery was achieved and this increased to 97% after 210 min. In practice, 30 min of leaching time was found to be optimum. It is clear that chemical reaction of malachite with sulphuric acid determines the dissolution rate of malachite during the leaching. 3.2. Effect of sulphuric acid concentration The effect of sulphuric acid concentration on the dissolution of malachite was investigated. The copper recovery, acid consumption and weight loss are given in Fig. 2. It can be seen that there is a direct

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3.3. Effect of stirring speed Fig. 3 shows that stirring speed has a significant effect on the dissolution of malachite. The copper recovery obtained under the same experimental conditions without agitation was 39%, while it was nearly 87% when 170 350 rpm stirring speed was applied. The same effect of stirring speed was observed on the dissolution of the iron minerals. There was no apparent iron dissolution in the absence of agitation, but it was 21% at 300 rpm. It can be concluded that this effect occurs by the increased diffusion rate of ions in leaching medium with increasing agitation. 3.4. Effect of solid/liquid ratio Fig. 4 gives the copper recovery and the weight loss that occurred during leaching, as the function of the solid to liquid ratio (weight of solid/volume of liquid). According to experimental results presented in Fig. 4, it was found that the copper recovery increased until the solid/liquid ratio was 1:5, where 87% of copper was recovered. At ratios higher than 1:5, there was no significant increase in the copper recovery. During the

Fig. 1. The effect of leaching time on the recovery of copper from the malachite ore (acid concentration, 2.04 mol/L; temperature, 25 jC; particle size, 80% 650 Am; the amount of ore, 20 g; solid to liquid ratio, 1:5 g/mL; stirring speed, 250 rpm).

relationship between the copper recovery and the acid consumption. The consumption was high until 1.02 mol/L sulphuric acid was used, e.g. the copper recovery was 87% and the acid consumption was about 85% when 1.02 mol/L sulphuric acid was used. Acid in the leaching solution (97%) was consumed while 0.61 mol/L sulphuric acid was used and the copper recovery was approximately 57%. For the acid concentrations higher than 1.02 mol/L, both acid consumption and copper dissolution rate decreased. When 2.04 mol/L of sulphuric acid was used, the acid consumption was 20% and the copper recovery remained 91%. The weight loss increased with acid concentration and reached 48% when 2.04 mol/L of sulphuric acid was used. It was found that this value was also equivalent to the malachite dissolution from the sample. The experimental results showed that the acid consumption was 0.92 mol/L for 90% copper recovery. From reaction (2), the theoretical amount of acid consumed during leaching can be calculated. Under the experimental conditions, 0.80 mol/L acid is required for malachite dissolution. It is suggested that the slightly higher value in practice is due to acid consumption by gangue minerals.

Fig. 2. Effect of sulphuric acid concentration on the recovery of copper from the malachite ore, and on the acid consumption and the weight loss during the leaching (temperature, 25 jC; particle size, 80% 650 Am; the amount of ore, 20 g; solid to liquid ratio, 1:5 g/ mL; stirring speed, 250 rpm; time, 30 min).

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Fig. 3. Effect of the stirring speed on the recovery of copper and iron from the malachite ore (acid concentration, 1.02 mol/L; temperature, 25 jC; particle size, 80% 650 Am; weight of ore, 25 g; solid/liquid, 1:10; time, 30 min).

leaching, the weight loss pattern was found similar to malachite dissolution. Consequently, it was suggested that the weight loss be related to the dissolution of malachite. The recovery was 90% and the weight loss was 40% for a solid to liquid ratio of 1:5.

3.5. Effect of temperature As seen from Fig. 5, the copper recovery increased as the temperature was increased. The recovery after 120 min reached 94% and 98% for 25

Fig. 4. Effect of solid to liquid ratio (w/v) on the recovery of copper from the malachite ore and on the weight loss during the leaching (acid concentration, 1.02 mol/L; temperature, 25 jC; particle size, 80% 650 Am; weight of ore, 20 g; stirring speed, 250 rpm; time, 30 min).

Fig. 5. Effect of leaching time on the recovery of copper from the malachite ore (acid concentration, 1.02 mol/L; temperature, 25 jC; particle size, 100 150 Am; weight of ore, 25 g; solid/liquid ratio, 1:10; stirring speed, 350 rpm).

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3.6. Effect of particle size The effect of particle size was studied using eight crushed and five ground size fractions. For the copper recovery calculations, the copper grade of each fraction was considered. These samples were all leached using 1.02 mol/L sulphuric acid used at 25 jC. The results are given in Figs. 6 and 7. From these figures, it is clear that copper recovery is rapid at the beginning. If the particle size decreases, the dissolution is more rapid. However, the particle size effect decreases with increasing leaching times.

4. Discussion Malachite can be easily dissolved by acidic reactions. The experimental results showed once more that, as the amount of acid consumed is increased, the dissolution of malachite increases (Fig. 8). According to reaction (2), only about 90% of the acid is used for malachite dissolution. The acid consumption per mol malachite was found to be 2.22 2.37, the extra 10% is consumed in the dissolution of other minerals found in the ore, notably the iron oxides.

Fig. 6. Effect of particle size of the crushed ore for the dissolution of malachite (acid concentration, 1.02 mol/L; temperature, 25 jC; weight of ore, 20 g; solid/liquid, 1:5; stirring speed, 250 rpm; time, 30 min).

jC and 80 jC, respectively. However, the malachite dissolution hardly increased after a rapid dissolution in 5 min.

Fig. 7. Effect of particle size of the ground ore for the dissolution of malachite (acid concentration, 1.02 mol/L; temperature, 25 jC; weight of ore, 25 g; solid/liquid ratio, 1:10; stirring speed, 350 rpm).

Fig. 8. The graph showing the direct relationship between the acid consumption and the copper recovery.

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Accordingly, XRD analysis of the leaching residues showed malachite to be completely dissolved, whereas goethite, magnetite, pyroxenes and quartz were not dissolved in the acid leaching conditions applied. It was also determined that the amount of these gangue minerals in the residue increases as the copper recovery or the amount of dissolved malachite increased. Combining the chemical analysis and XRD analysis, it can be estimated that the ore consisted of 49.35% malachite, 22.56% goethite and magnetite, 27.36% quartz and pyroxene group, leaving only 0.73% unaccounted for by XRD analysis. The kinetic evaluation of reactions occurring during the acidic leaching of malachite indicated that neither chemical nor diffusion models applied. These models are unable to explain the dissolution of malachite for the rapid initial reaction and the complete leaching period studied. However, the initial dissolution can be modelled using a logarithmic function: y = a ln(x) + b; where y is the copper recovery, x is the leaching time, a and b are the constant coefficients. A significant part of dissolution has been achieved at the leaching times within 15 min and the values can be expressed by logarithmic

Fig. 10. The Arrhenius curve obtained for the dissolution of malachite ore.

curves as presented in Fig. 9. It was also observed that the values of a and b increase as the temperature increases. The value of a increased from 3.539 at 25 jC to 3.735 at 80 jC and the value of b increases from 81.683 to 86.141 over the same temperature range. It is possible to calculate the dissolution rate after 0.1 min of leaching at different temperatures by using the model. From these rates, an Arrhenius curve can be drawn (Fig. 10). It was determined that the activation energy, Ea, was 1.3 kJ/mol. This value is very low and indicates that the dissolution of malachite is solution diffusion-controlled during the initial dissolution. This is supported by the significant increase in dissolution due to stirring (Fig. 3). After the initial dissolution, the availability of readily accessible malachite had been greatly reduced and a change in rate determining step is likely.

5. Conclusions The following conclusions can be drawn from the kinetic study of the malachite dissolution: (i) Malachite was readily dissolved by sulphuric acid giving high recoveries of copper, other

Fig. 9. Effect of time on the dissolution of malachite at 40 jC leaching temperature (acid concentration, 1.02 mol/L; temperature, 25 jC; particle size, 100 150 Am; weight of ore, 20 g; stirring speed, 350 rpm).

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minerals, such as iron minerals, were only slightly affected from sulphuric acid medium. (ii) The most important parameters affecting the leaching were time, acid concentration, stirring speed and the temperature of medium. Acid concentrations of less than 1.02 mol/L were insufficient for complete dissolution, for higher concentrations there is a direct relationship between the acid concentration and the dissolution of malachite. Leaching was found to comprise two steps, an initial, very rapid dissolution with f 85% copper recovery within f 15 min and a slower second step. After 210 min of leaching, the effect of particle size on dissolution was found to be negligible. The malachite dissolution increased slightly with temperature, going from 94% to 98% as the temperature increased from 25 to 80 jC. (iii) The initial dissolution kinetics may be modelled by a simple logarithmic function. From this model, the activation energy was found to be 1.3 kJ/mol, clearly malachite dissolution is controlled by solution diffusion. (iv) Sulphuric acid consumption for 90% copper recovery was computed to be about 450 kg per ton ore.

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