Hydrometallurgy 121-124 (2012) 116119

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Hydrometallurgy
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Technical note

Extraction of copper from bacterial leach liquor of a low grade chalcopyrite test heap using LIX 984N-C
S. Panda a, c, P.K. Parhi b,, N. Pradhan a, U.B. Mohapatra c, L.B. Sukla a, K.H. Park b
a b c

Bioresources Engineering Department, Institute of Minerals & Materials Technology (IMMT), CSIR, Bhubaneswar-751013, India Mineral Resources Research Division, Korea Institute of Geoscience & Mineral Resources (KIGAM), Daejeon, 305-350, Republic of Korea North Orissa University, Baripada-757003, Odisha, India

a r t i c l e

i n f o

a b s t r a c t
Low grade copper ore (ball mill spillage) obtained from Malanjkhand Copper Mine was processed through heap bioleaching at pilot scale. Bioleach liquor (Pregnant Leach Solution) from the heap contains (g/L of) Cu (II) 0.45, Fe (III) 0.838, Zn (II) 0.006, Ni (II) 0.0014, Mn (II) 0.011 and Pb (IV) 0.004. Solvent extraction of copper from Pregnant Leach Solution was carried out using LIX 984N-C. Effect of different operational factors such as equilibrium pH (pHe), extractant concentration, strip solution concentration, phase ratio was examined to optimize the condition for selective and quantitative extraction of copper. Based on the results of extraction as well as stripping isotherm, a 6-cycle counter current simulation study (CCS) was conducted for the conformational study. The extraction of copper was quantitative in 2-stages using 1.5% (v/v) LIX 984N-C at A: O ratio of 1:2 and pHe 1.85. The CCS condition (two stages, phase ratio A:O = 1:4) obtained from the stripping isotherm study, further attributes to the enrichment (4 folds) of copper concentration in the strip solution. 2012 Elsevier B.V. All rights reserved.

Article history: Received 13 March 2012 Accepted 27 March 2012 Available online 5 April 2012 Keywords: Low grade ore Heap bioleaching Copper Solvent extraction LIX 984N-C

1. Introduction Over the past few years, hydrometallurgical copper production from low grade ores is being routed through bioleachingsolvent extractionelectrowinning (BLSXEW) (Wenjian et al., 1995). At about 2025% of the world's total copper production is through solvent extraction followed by electrowinning processes (Munoz et al., 2007). Heap bioleaching of low grade chalcopyrite ore is gaining importance for waste treatment vis--vis with a substantial recovery of the valuable metals (Pradhan et al., 2008; Sukla et al., 2009). During heap bioleaching of chalcopyrite, some other metal ion impurities also get leached and are present along with the copper. Iron is found as one of the major impurities in the leach solution since its concentration is as high as compared to the other impurities. The separation of copper by solvent extraction process from the iron bearing solution is well proven and a suitable method in hydrometallurgy (Cvetkovski et al., 2009; Minango et al., 2005; Stevanovic et al., 2009). Stevanovic et al. (2009) have developed the processing ow sheet to recover the copper from overburden of an abandoned mine Cerovo in Eastern Serbia which follows the hydrometallurgical route including leachingSXEW methods. In view of the industrial and economic importance of copper extraction process, there is a great need for separation and recovery of the metal values using cost

Corresponding author. Tel.: + 82 42 868 3604. E-mail address: parhi_pankaj@yahoo.co.in (P.K. Parhi). 0304-386X/$ see front matter 2012 Elsevier B.V. All rights reserved. doi:10.1016/j.hydromet.2012.03.008

effective commercial extractants. A considerable amount of work have been devoted towards the investigation on solvent extraction of copper from acid or ammoniacal medium using LIX series extractants (Lazarova and Lazarova, 2005, 2007; Panigrahi et al., 2009; Parija and Sarma, 2000). Off these LIX reagents, LIX 984N-C is found to be an efcient and effective extractant owing to its exclusive applications in extraction of several metals (Cu, Ni, Fe and Zn) by solvent extraction processes (Kul and Cetinkaya, 2009a, 2009b, 2010). In addition, the selectivity of the LIX 984N-C towards any of the above metals was again governed by the change of suitable pH range of the aqueous solutions (Kul and Cetinkaya, 2009b). From the reported literatures (Kul and Cetinkaya, 2009b; Lazarova and Lazarova, 2005), LIX 984N-C was notably found as a very selective chelating extractant towards the extraction of copper metal ion despite of the presence of other impurities in the aqueous solution, while separating the copper ion from the leach solution bearing other metals such as Zn, Pd and Ni. Nevertheless, LIX 984N-C is considered as a strong extractant towards the extraction of copper because of its very good physical performance property. Its predominance performances by mean of extraction efciency and selectivity, is due to the mixed effect of LIX 860N-C and LIX 84-IC in LIX 984N-C (Asghari et al., 2009; Cheng et al., 2000; Fouad, 2009). The mixed reagent for example LIX 984N, shows faster kinetics because of the synergism behavior as compared with other LIX reagents (LIX 860N-I, LIX 84-I, LIX 65N) during the investigation on the extraction of copper from the nitrate/nitric acid solution (Lazarova and Lazarova, 2005). LIX 984N acts as a very good synergist with

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117

Cyanex 301 and their mixture lead to enhance the metal stripping efciency more effectively from the loaded organic with H2SO4. Nonetheless, it could also lower the acid consumption rate while stripping the metal ion from the loaded organic phase (Fouad, 2009). Unlike solvent extraction, several authors have also proposed for the use of LIX 984N in dispersive (ELM and BLM) as well as non dispersive type liquid membranes (SLM) separation process, in which LIX 984N provides a very good overall transport performance for copper from the acidic and dilute solutions (Sengupta et al., 2006; Yang and Fane, 1999a, 1999b). Copper extraction was obtained to be quantitative with 30% LIX 984N-C at an equilibrium pH 2, O: A ratio of 8:1 in 2 stages to enhance the loading of copper (20.4 g/L) into the organic phase and subsequent stripping of copper from loaded organic using 550 g/L H2SO4 in two counter current stages (Kul and Cetinkaya, 2009b). Xie et al.(2008) have developed the process ow diagram for the separation of Cu(II), Zn(II), and Cd(II) from a rich sulfate leachate of zinc slag by solvent extraction in which the copper extraction was carried out with LIX 984N followed by separation of Zn and Cd using of mixture of D2EHPA and tri-butyl-phosophate. Extraction of copper from the rich sulphate leach solution was carried out as the function of the factors namely extraction time, pH, LIX 984 concentration and phase ratio and the optimal condition for copper extraction was determined as: concentration of LIX 984N 25%(v/v), extraction time 7 min., phase ratio O/A 3:2 and pH= 1.7. Furthermore, from the results of it was observed that LIX 984N is highly selective and very efcient in the extraction of Cu (II) in presence of the metal like Zn (II) and Cd (II). The purpose of the present paper is to explore the optimal condition for selective extraction of copper from the Pregnant Leach Solution (PLS) obtained through heap bioleaching of low grade copper ore (ball mill spillage) using LIX 984N-C. The effect of different operating parameters such as equilibrium pH (pHe), LIX 984N-C concentration, strip solution (H2SO4) concentration, phase ratio, were studied. A suitable extraction and stripping condition was established to enrich the copper concentration more effectively and that attributes to achieve a high copper concentration the nal strip solution. 2. Experimental 2.1. Description of the heap bioleaching pilot plant set up A heap of low grade ore copper ore (ball mill spillage material) of 1000 t capacity was constructed at Malanjkhand, India. Chemical composition of the sample showed 0.26% Cu, 1.5% Fe, 0.46% S, and 92.8% of acid insoluble material. Chemical composition of each size fraction with their percentage weight in construction of the heap is shown in Table 1. The detailed mineralogical analysis of the sample is presented in Table 2. The ore material was stacked on an impervious leach pad. Bottom of the heap had layered network of pipelines for aeration of heap. Sprinklers were tted at the top for spraying of the lixiviant. The heap was acid conditioned prior to the start of the experiment. A specially designed BACFOX tank (Bacterial Film Oxidation Unit) of 108 m 3 capacity was built for the growth of microorganisms. A mixed culture of mesophillic acidophillic chemolithotrophic consortia, predominantly Acidithiobacillus ferrooxidans acted as inoculum. The BACFOX tank was also used for collection of pregnant

Table 2 Mineralogical analysis of low grade Malanjkhand Copper ore (Mill Spillage). Silicate minerals Sulphide minerals Accessory minerals Quartz, orthoclase, microcline, plagioclase, biotite and chlorite Muscovite, sericite, epidote, hornblende and clay minerals Chalcopyrite, bornite, pyrite, chalcocite, sphalerite, covellite, molybdenite Malachite, apatite, uorite, pyrophyllite, titanite, zircon tourmaline, zoisite and clinozoisite

leach solution (PLS) from the heap. The heap was operated at ambient temperature. The tank also had a compressed air supply. Initial volume of the bacterial solution was 30 m3 and was pumped at the rate of 1.1 L/min/m 2. The concentration of copper and other elements in the PLS was analyzed by Atomic Absorption Spectrophotometer (Perkin Elmer Model AA-400). 2.2. Extraction of copper from pregnant heap leaching solution 2.2.1. Reagents The organic solvents such as LIX 984N-C (Cognis, Ireland) and commercial grade kerosene were used as obtained from the supplier. The kerosene was used as the diluent in all cases. The organic extractant namely LIX 984N-C used in present investigation, is the well known as the combination of 1:1 volume of LIX 860N-C and LIX 84-IC. (Asghari, et al., 2009). The pH adjustment of the aqueous solution was made to a desired value before extraction by addition of dilute H2SO4 or NaOH and all the pH readings were recorded using a pH meter (pH meter Orion, USA, provided with combined glass electrode). All the chemical reagents used were of analytical grade (Merck, German). 2.2.2. Solvent extraction procedure All the solvent extraction experiments were performed manually by contacting the desired volume of aqueous and organic phases in a separating funnel (shake ask) for time period of 5 min. After phase disengagement, the two phases were allowed to separate followed by measurement of equilibrium pH (pHe) and analysis of metal ion concentration of rafnate using atomic absorption spectrophotometer. The metal ion concentration in the organic phase was determined from the difference between the concentration of metal before and after extraction. As and when required, the metal concentrations in the organic phase were estimated after ltration through 1PS phase separation paper and stripping a suitable aliquot of it with 10% (v/v) H2SO4 followed by dilution and analysis. All the experiments were conducted at the ambient temperature (25 1 C). The distribution coefcient D (ratio of metal ion concentrations in the organic and aqueous phases) and the percentage (%) of metal extraction were determined accordingly. Some of the solvent extraction experiments in present investigation were repeated in order to assure reproducibility and the experimental error was found to be of 2%. 3. Results and discussion The bacterial lixiviant prepared in the BACFOX tank was recirculated, which allowed the copper to dissolute from the ore and build up in the BACFOX tank. The composition of PLS from heap, used for copper solvent extraction study was presented in Table 3. The bioleach liquor (PLS) was then subjected to various optimization

Table 1 Chemical composition of each size fraction used in heap. Size (mm) + 12 12 + 6 6+4
a b

Weight % 24 43 33

Cu (O)a Nil Nil Nil

Cu(S)b 0.50 0.23 0.09

Cu (Total) 0.50 0.23 0.09

Si as SiO2 77.72 73.88 61.96

Table 3 Analysis result of pregnant leach solution of heap used for solvent extraction studies. Cu(II), g/L 0.45 Fe(III), g/L 0.838 Zn(II), g/L 0.006 Ni (II), g/L 0.0014 Mn (II), g/L 0.011 Pb (IV), g/L 0.004

Cu (O)copper oxides. Cu(S)copper sulphides.

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studies using LIX 984N-C as the extractant. The major impurity in the leach liquor was Fe while other metals namely Ni, Zn, Mn and Pb, were present in minor amount (b0.012 g/L). In preliminary study for kinetics on extraction of copper from the pregnant heap was studied and from the results it was ensured that copper extraction occurs rapidly (with in contact time limit as mentioned in Experimental section) indicating very fast extraction kinetics. The observation is quite similar to the behavior of other commercial LIX reagents such as LIX 84-I, LIX 622N and LIX 64 (Lazarova and Lazarova, 2007; Panigrahi et al., 2009; Parija and Sarma, 2000). 3.1. Effect of equilibrium pH To study the copper extraction as the function of pH, the pHe values of the aqueous leach solution was varied from 0.38 to 2.24 with using 1.0%(v/v) LIX 984N-C, at the phase ratio: A:O = 1:1 and contact time 5 min. From the results of Fig. 1, it can be seen that the extraction of copper was increased from 37.78% to 97.56% with increase in pHe from 0.38 to 1.85 and on further increase in the pHe to 2.24, the copper extraction was more or less remains constant. Coextraction of Fe(III) was not observed up to the pHe of 1.85, however, at pHe 2.24, a small quantity of Fe (3.25 mg/L) was extracted to organic phase along with copper. The separation factor of copper from Fe (SFCuFe = DCu/DFe) at the solution pHe 2.24 was determined to be 16,254.7, indicating the selectivity of the LIX 984N-C on extraction of copper. The co-extraction of other metals such as Mn (II), Zn (II), Ni (II) and Pb (IV), are not observed within the studied pH range. The suitable pH ranges of present investigation was capable of avoiding iron precipitation (since Fe (III) starts precipitation greater than equilibrium pH 2.24) (Nathasarma, and Sarma, 1987; Parhi et al, 2011) and minimizing the co-extraction of other metal ions from the leach solution. From the above results it is cleared that, the Initial pH value of original leach solution (pH 2.0) is well within the optimum solvent extraction pH range and also consistent with the observations of previous work (Sukla et al., 2009). 3.2. Effect of LIX 984N-C concentration

100

Copper extraction, %

80 60 40 20 0 0 0.5 1 1.5 2 2.5 3

[LIX 984N-C], %
Fig. 2. Effect of LIX 984N-C concentration on copper extraction, Conditions: pHe 1.85, time: 5 min and A:O = 1.

LIX 984N-C was sufcient to recover 99.56% of copper from the leach solution in a single contact of aqueous and organic phases. 3.3. Extraction isotherm The extraction isotherm was studied to nd out the number of stages required for a quantitative extraction of copper at a chosen A:O phase ratio. Both aqueous and organic phases were contacted at different phase ratios (A: O = 1:5 to 5:1), while keeping rest of the parameters like pHe 1.85, 1.5%( v/v) LIX 984N-C and total volume of phases constant. After phase separation, the two phases were analyzed and based on the results, concentration of copper in organic and the aqueous phases, were plotted to obtain McCabeThiele diagram (Fig. 3). It illustrated the quantitative extraction of copper in 2 stages at A: O ratio of 2:1. Furthermore, to conrm this, a 2-stage counter-current simulation (CCS) study was carried out up to 6 cycles, at the above predicted conditions. The analysis of the rafnate obtained in CCS study reads to contain 0.009 mg/L of copper, conrming ~99.9% of copper extraction. Desired quantity of loaded organic containing 0.9 g/L of copper was generated for stripping study. 3.4. Effect of H2SO4 concentration on stripping of copper

The extraction of copper from the leach solution was carried out with different concentration of LIX 984N-C (0.252.5%) and at pHe 1.85 and phase ratio of 1. As shown in Fig. 2, the copper extraction was increased from 22.67% to 97.56% with increase in extractant concentration from 0.25% to 1.5%(v/v) LIX 984N-C. The extraction of copper seems to be plateau beyond 1.5% (v/v) LIX 984N-C. The co-extraction of Mn (II), Fe (III), Zn (II), Ni (II) and Pb (IV) was not observed within the above studied LIX 984N-C concentration range. Thus, from the above study, 1.5% (v/v) of
100

The efciency of H2SO4 on stripping of copper from the copper loaded organic was examined and presented. The concentration of H2SO4 was varied from 10 to 200 g/L while other parameters like phase ratio of A: O = 1:1 and contact time of 5 minutes were kept xed. The rate of copper stripping as the function of H2SO4 concentration was shown in Fig. 4. This showed that the percentage of copper stripping was linearly increased from 19.24 to 99.55% with increase in H2SO4
1.6

Metal extraction,%

80 60 40 20 0 0 0.5 1 1.5 2 2.5 Cu Fe

1.2

[Cu]org, g/L

0.8

0.4

O:A=1:2

0 0 0.1 0.2 0.3 0.4 0.5

Equilibrium pH (pHe)
Fig. 1. Effect of pHe on copper extraction, Conditions: A:O = 1, time: 5 min and 1%(v/v) LIX 984N-C.

[Cu]aq, g/L
Fig. 3. McCabeThiele plot on extraction of copper, Conditions: pHe 1.85, time: 5 min 1.5% (v/v) LIX 984N-C.

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[Cu]SS, g/L

concentration from 10 to 180 g/L and thereafter it reached to a plateau value. As the summary of the above results, 180 g/L of H2SO4 was chosen to be the suitable concentration for quantitative stripping of copper from the loaded organic phase and therefore this concentration was xed for further experimental investigations. 3.5. Stripping isotherm study The stripping isotherm for copper was constructed to nd out the number of stages required for stripping at chosen phase ratio (A: O). The Cu-loaded LIX 984N-C and 180 g/L H2SO4 was contacted at different phase ratio (A: O = 1:5 to 5:1), while keeping the total volume of the phases constant. After phase separation, both phases are analyzed for metal concentration The McCabeThiele plot (Fig. 5) illustrated the possibility of >99% of copper stripping at 2 countercurrent stages at A: O ratio of 1:4. To conrm the above prediction, a 2-stages counter-current simulation (CCS) study was performed (up to 6 cycles) at the above mentioned conditions, which resulted a quantitative stripping of copper. Spent organic analysis result reveals 92% and 99.9% of stripping in the rst and second stages, respectively. The nal stripped solution obtained after two stage CCS study which reads to contain 3.6 g/L copper (>99.9% stripping efciency), conrming the copper enrichment in the stripped solution was up to 4 times as compared to copper concentration in the loaded organic. 4. Conclusions Solvent extraction of copper was carried out using LIX 984N-C from the pregnant leach solution obtained from a test heap bioleaching experiment on low grade copper ore (ball mill spillage) of Malanjkhand. Copper was preferentially extracted from pregnant leach solution using 1.5% (v/v) LIX 984N-C and it shows quantitative with 2-extraction stages with A: O ratio of 2:1 at solution pHe 1.85. Co-extraction of Fe, Zn, Co, Ni was not observed under the optimum conditions, indicating the selectivity extraction behavior of LIX 984N-C towards copper. Stripping isotherm study was carried out using 180 kg/m 3 H2SO4 which predicts the optimum stripping condition (2-stage at A:O ratio of 1: 4) and furthermore, it was conrmed by CCS study. Subsequently, the stripped solution, generated after CCS study contains 3.6 g/L of copper, was ensuring about the copper enrichment up to 4 folds and 8 folds as compared to the copper concentration in loaded organic and initial leach solution phase, respectively. Acknowledgments The authors are thankful to M/s Hindustan Copper Limited for nancial support for carrying out heap bioleaching. They also thank staff of Institute of Minerals and Materials Technology and Hindustan Copper Limited involved in this project. The rst author, S. Panda is

5 4 3 2
O:A=4:1

1 0 0 0.2 0.4 0.6 0.8 1

[Cu]LO, g/L
Fig. 5. McCabeThiele plot on stripping of copper from loaded organic, Conditions: 180 g/L H2SO4 and time 5 min.

thankful to CSIR for the award of Senior Research Fellowship and one of the co-author, P.K. Parhi is grateful to KIGAM for the award of postdoctoral fellowship. References
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90

Copper stripping, %

70

50

30

10

50

100

150

200

[H2SO4], g/L
Fig. 4. Effect of contact time on stripping of copper from loaded organic, Conditions: [H2SO4] :180 g/L and A: O = 1.