TP 1906 Trans. Indian Inst. Met. Vol.57, No. 5, October 2004, pp. 485-490 BIOFLOTATION OF THE LOW GRADE SARCHESHMEH COPPER SULFIDE M. Kolahdoozan1, S.M Tabatabaei Yazdi2 , W.T.Yen3, R. Hosseini Tabatabaei4, A.R Shahverdi2, M. Oliazadeh1, M. Noaparast1, A. Eslami5, Z. Manafi5 1 Dept. of Mining Eng., University of Tehran, Tehran, 11365, Iran. 2 Dept. of Biotech., Tehran Medical Sciences University, Tehran, 11365, Iran. 3 Dept. of Mining Eng., Queen’s University, Kingston, Ontario, Canada, K7l 3N6. 4 M.Sc Graduate, Dept. of Mining Eng., University of Tehran, Tehran, 11365, Iran. 5 Mineral Processing Expert, Sarcheshmeh R & D Division, Sarcheshmeh, Kerman. Email: [email protected] (Received 10 March 2004 ; in revised form 29 June 2004) ABSTRACT Application of Thiobacillus ferrooxidans bacteria in the flotation of Sarcheshmeh low-grade sulfide copper ore was studied. Sarcheshmeh low-grade ore contains pyrite that cause some problems in flotation process of copper minerals. In this study, pure strain of T.Ferrooxidans was used to bring about surface chemical changes of pyrite and sulfide copper ores, and consequently their flotation behavior. In presence of Thiobacillus ferrooxidans and xanthate as collector, pyrite was depressed whereas chalcopyrite and other sulfide minerals were unaffected. Also the pulp pH remained unchanged. It was shown that the surface chemical properties of bacteria can be manipulated successfully to achieve desired effects in flotation process. The results showed that recovery of pyrite in the presence of bio-depressant is 50% lower than the time when no bacteria applied. At the same time recovery of chalcopyrite was not affected. 1. INTRODUCTION Thiobacillus ferrooxidans is a gram negative, chemolithotrophic bacteria that grows in acidic drainage water of mines 1. It’s ability to oxidize Fe+2 to Fe+3 ions and elemental sulphur in acidic solution is well established. Although, bioleaching of low-grade ores is being practiced for a long time, application of bacteria to flotation is relatively new and few studies have been reported 2-7. Sarcheshmeh copper deposit is the major producer of copper and molybdenum of the country located in south eastern Iran, 160 km from the city of Kerman. Pyrite is the main gangue mineral and for long it has been depressed by lime while floating copper. In present work, an attempt was made to use chemolithotrophic bacteria such as Thiobacillus ferrooxidans as a depressant for pyrite in flotation of Sarcheshmeh copper ore. The growth kinetics of Thiobacillus ferrooxidans is slow and its fully-grown culture can be achieved after 48 hours. The bacterium surface properties depend on the growth conditions 3,7,8. The chemical components of bacterial surface play an important role in its adhesion on the mineral surface 7. Since flotation is dependent on the surface properties of minerals, any changes in this property can introduce direct effects on the whole process of bacteria application. 2. EXPERIMENTAL 2.1 Materials and Methods A representative sample of low-grade sulfide copper ore, pure pyrite and chalcopyrite from Sarcheshmeh were collected and used in this study. Table 1 shows the chemical composition of the sample. Also sodium TRANS. INDIAN INST. MET., VOL. 57, NO. 5, OCTOBER 2004 isopropyl xanthate (Z 11 ) and Methyl Isobutyl Carbonyl (MIBC) were used as the collector and frother respectively. 2.1.1 Bacterial strain & adaptation A pure strain of Thiobacillus ferrooxidans isolated from acidic water drainage of Sarcheshmeh mine was used in this study. Thiobacillus ferrooxidans was cultured and maintained in 9k medium (3g/l (NH4)2SO4, 0.5g/l MgSO4.7H2O, 0.5g/l K2HPO4, 0.1g/l KCl and pH 1.9) given by Silverman and Lundgren. A 10% active cell culture was added to the medium and incubated in rotary shaker at 150rpm and 320C. The cells were harvested from the culture just at the beginning of the stationary phase of their growth. Cell 5 grown in the presence of ferrous ions and elemental sulfur, were filtered through Whatman filter paper to remove cells from the suspended solid material. The liquid containing the cells then filtered through biological filter paper and washed twice with acidic water (pH of 1.9). During tests, cells were counted by Petroff-Hauser counter as this method is comparatively quick and convenient. 2.1.2 Adhesion experiments Adhesion experiments were carried out on all three samples (low-grade sulfide copper ore, pyrite and chalcopyrite). In this case 0.5g of each sample was added to 2ml cell suspension (0.5-3.5 *107 cells/ ml). The suspension was then shaken for 1 min with a vortex shaker and allowed to settle for 5 min. At that point, the optical density of the supernatant was measured to determine the cell density. The number of adherent cells was determined by subtracting in the number of cells in the supernatant from the number initially added. 2.1.3 Determining Parameters of Bioflotation In bioflotation process, there are important parameters that should be determined carefully before doing any bioflotation tests. These parameters are as follows: z Degree of grinding of minerals z Dosage of collector z Retention time in conditioning stage z Speed of rotation in conditioning stage One of the important stages in bioflotation process is its conditioning stage. In this stage mineral sample first conditioned with predetermined bacteria that time of conditioning and speed of rotation should be determined carefully. 2.1.4 Flotation tests The flotation tests were carried out in 2.5-liter Denver laboratory cells. 820g of low-grade sulfide copper ore sample was used in each test. The mineral sample was first conditioned with predetermined bacteria for 15 min and then the collector and frother were added and conditioned for 5 min after which floated for 6 min. The effect of initial cell concentration on the flotation of low-grade sulfide copper ore was examined. Tests were carried out in two different dosage of collector and some tests were also performed in the absence of bacteria and without any depressant. All tests were performed at natural pH. 3. RESULTS AND DISCUSSION 3.1 Adhesion of Thiobacillus ferrooxidans to sulfide minerals In case of low-grade sulfide copper ore and pyrite mineral samples Thiobacillus ferrooxidans adhesion increased with the number of cells added, although there were significant differences in the affinity of the bacteria for the samples (Fig. 1). By far the largest number of cells adhered to pyrite. The results showed that when Thiobacillus ferrooxidans cells were added to pyrite, adhesion increased almost linearly and in the case of low-grade copper sample Table 1 CHEMICAL COMPOSITION OF SAMPLE Element Cu(Total)(%) Sample 1.01 CuO(%) Fe (%) SiO2 (%) S (%) Al2O3 (%) Mo (%) 0.13 9.00 59.34 5.86 16.22 0.017 486 KOLAHDOOZAN, et.al., : BIOFLOTATION OF THE LOW GRADE SARCHESHMEH COPPER SULFIDE Fig. 1 : Number of cells adhering to 0.5 g of each sample the trend was almost the same. However in the case of chalcopyrite the adherent cells were not increased and it did not show any dependence on the number of cells adhered. It is concluded that bacteria cells do not attach on the surface of copper ore. 3.2 Flotation Parameters Results, shown in Fig. 2, demonstrate that the finer the sample, the more will be the degree of attachment of bacteria on the surface of pyrite. However as the slime will also be increased it produces some problems in flotation. The optimized grinding condition was evaluated as 70 percent -200 mesh size. 3.2.1 Grinding 3.2.2 Collector Dosage To optimize this parameter low-grade copper sulfide ore samples were grind in different percentage of ore less than 200 mesh (65–85 %< 200 mesh). Results are shown in Fig. 3. Different collector dosages (50-300 gram per ton) were examined and the optimum condition achieved at 150 gram per Fig. 2 : The effect of grinding on the recovery of Cu & Fe 487 TRANS. INDIAN INST. MET., VOL. 57, NO. 5, OCTOBER 2004 Fig. 3 : The effect of collector dosage on recovery of Cu & Fe tons which presented the highest recover for copper. However with increasing the dosage of collector beyond this point the recovery dropped as a result of hemi micelle formation. 3.2.3 Retention Time and Rotation Speed in Conditioning Stage Results are shown in Figs. 4 and 5. These two parameters are quiet important in bioflotation and should be determined accurately. Results demonstrate that with increasing the retention time and speed of rotation from adequate point in conditioning stage the bacteria can not depress pyrite and recovery of pyrite were increased since it destroys bacteria’s wall and increases shear stress (in increasing speed of rotation). Results show that these parameters play a vital role in bioflotation that even their little fluctuations cause considerable consequences in outcome of the operation. 3.2.4 Flotation results The flotation results obtained by using increasing cell concentrations of ferrous and sulfur grown Thiobacillus ferrooxidans at two different xanthate concentrations. Results are shown Figs. 6 and 7. Fig. 4 : The effect of retention time in conditioning stage on the recovery of Cu and Fe 488 KOLAHDOOZAN, et.al., : BIOFLOTATION OF THE LOW GRADE SARCHESHMEH COPPER SULFIDE Fig. 5 : The effect of rotation speed in conditioning stage on the recovery of Cu and Fe Fig. 6 : The effect of collector concentration on the recovery of Fe. In presence of sulfur & ferrous grown Thiobacillus ferrooxidans Fig 7 : The effect of collector concentration on the recovery of Cu. In presence of sulfur & ferrous grown Thiobacillus ferrooxidans 489 TRANS. INDIAN INST. MET., VOL. 57, NO. 5, OCTOBER 2004 These figures show the recovery of Fe and Cu respectively. For this sample, flotation recoveries of Cu and Fe at higher xanthate concentration (200 gram per ton) were 62% and 65% respectively compared to 55% and 64% at lower xanthate dosage (100 gram per ton). The preconditioning of minerals with bacterial cells prior to the addition of collector reduced the floatability of pyrite, but it did not affect the floatability of copper minerals. The sulfur grown cells, depressed more pyrite compared to the ferrous ion grown cells. The ferrous grown cells decreased the pyrite recovery at two different collector concentrations (200 and 100 gram per tons) from 65% to 40% and 42% but in sulfur grown cells the drop in recovery of pyrite was higher. Results demonstrated that recovery of copper minerals is not a function of their growth conditions i.e. bacterial cells do not attach on the surface of copper therefore do not have any depressing effect on copper minerals (Fig. 7). can be adsorbed on the surface of sulfide copper minerals promoting hydrophobicity. 5. ACKNOWLEDGMENTS This work was conducted under financial support of Research and Development Division of Sarcheshmeh copper complex as well as The Research Department of the University of Tehran, Faculty of Engineering. Authors wish to express their sincere appreciations. REFERRENCES 1. Brierley C L, Bacterial Leaching. Crit.Rev.Microbial, 6, (1987) 207-262 2. Sharma P K, Hanumanth Rao K, Nataraja K A, Forssberg K S E, Bioflotation of sulphide minerals in the presence of heterotrophic & chemolithotrophic bacteria. Proceeding of the XXI international mineral processing congress (1999). 3. Nagaoka T, Ohmura N, Saiki H, A novel mineral flotation process using Thiobacillus ferrooxidans. Appl. Environ. Microbial (1999) p. 3588-3593 4. Kawatra S K, Eisele T C, Depressuion of pyrite by yeast and bacteria. Minerals & metallurgical processing, 16(4) (1999). 5. Somasundaran P K, Deo N, Natarajan K A, Utility of bioreagents in mineral processing. Minerals & metallurgical processing, 17(2) (2000). 6. Devasia P, Natarajan K A, Sathyanarayana D N, Surface chemistery of Thiobacillus ferrooxidans relevant to adhesion on mineral surfaces. Appl. Environ. Microbial 59 (1993) pp.4051-4055 7. Bryner L C, Beck J V, Davis D B, Wilson D G, Int. Eng. Chem. 46 (1996) 2587 8. Lyalikova N N, Lyubavina L L, On the possibility of using a culture of Thiobacillus Ferrooaxidans to separate antimony and mercuric sulfides during floattion. In: Fundamental & Biohydrometallurgy, Elsevier, New York, (1986) p. 403-406 4. CONCLUSIONS It was shown that the selective flotation of copper sulfides from pyrite is possible by interaction of minerals with both ferrous and sulfur grown Thiobacillus ferrooxidans. Thiobacillus ferrooxidans bacteria do not have any motion for adhering to chalcopyrite. However it could selectively adhere to pyrite surface hindering its floatability and therefore Thiobacillus ferrooxidans can be used as a depressant for pyrite during the flotation of copper sulfides. This is because bacterial cells obtain their energy by oxidizing iron ion and elemental sulfide and therefore the cells might have strongly adsorbed on pyrite surface and xanthate could not replace the adsorbed cells. However in the case of chalcopyrite, the copper ions are toxic to the cells and bacteria do not adhere on the mineral surface. Therefore collector species 490
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