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Biotechnology Letters, Vol 20, No 3, March 1998, pp.

257–259

CO2 supply in the biooxidation of an enargite-pyrite gold concentrate
F. Acevedo*, J.C. Gentina and N. Garc´ ıa
School of Biochemical Engineering, Universidad Catolica ´ de Valpara´ ıso, Casilla 4059 ,Valpara´ ıso, Chile CO2 supply at 4% (v/v) in air increased the biooxidation of a gold concentrate (41% enargite, 43% pyrite) with Thiobacillus ferrooxidans in a 2-l bioreactor at 4% (w/v) solids concentration, 35°C and pH 2.4. Extraction increased from 21 to 69% for Fe, 19 to 25% for As, and 16 to 19% for Cu. Suspended biomass increased from 2.6·107 to 1.2·108 cells/ml. It is concluded that the biooxidation of this gold concentrate is limited by the rate of CO2 supply.

Introduction In the bioleaching of minerals with chemoautotrophic bacteria, the carbon source, CO2, is usually supplied by air. Because of the very low CO2 content of air (0.03% v/v), the growth of the bacteria may become CO2 limited if the aeration is set to satisfy the oxygen demand. In fact, it is thought that CO2 limitation is more likely to occur than oxygen limitation (Acevedo and Gentina, 1989 ; Boogerd et al., 1990). If that is the case, CO2 enrichment of the air should cause an increase in the growth, and consequently, in the leaching rate. CO2 limitation in Thiobacillus ferrooxidans growth and bioleaching ability have been analysed and experimentally confirmed by several authors (Nagpal et al., 1993). Nevertheless, the available information on this topic is not easy to compare because of differences in mineral composition, bacterial strains and experimental conditions. Moreover, in many cases data on mass transfer capabilities of the equipment involved are not reported. The carbon dioxide limitation is relieved at some critical value that varies from one condition to another. It has also been found that high CO2 concentrations are inhibitory (Nagpal et al., 1993). The large scale biooxidation of gold concentrates has become a reality in the past few years (Brierley, 1995). Most of the work done in this area have been performed with arsenopyrite and pyrite minerals, but no more than three papers can be cited on the biooxidation of enargite, Cu3AsS4 (Escobar et al., 1997). The objective of this work was to test the hypothesis of carbon dioxide limitation when the aeration rate is based on the oxygen demand and to determine the optimum CO2 enrichment in the biooxidation of a gold concentrate of high enargite and pyrite content.
© 1998 Chapman & Hall

Table 1 Composition (w/w) of the enargite-pyrite gold concentrate.
Au µg/g 42.0 Cu % 21.1 Fe % 22.6 S % 37.8 As % 7.7 Cu3AsS4 % 40.7 FeS2 CuFeS2 % % 42.8 3.9

Experimental Microorganism and mineral Strain R-2 of Thiobacillus ferrooxidans, supplied by the Laboratory of Microbiology, Faculty of Biological Sciences, Universidad Cat´ olica de Chile, Santiago, was grown in a 9K-type medium (Silverman and Lundgren, 1959), with ferrous sulphate replaced by 4% (w/v) gold concentrate as the energy source. The mineral concentrate was kindly supplied by Minera El Indio (La Serena, Chile), and had the composition detailed in Table 1. Equipment and operating conditions Experiments were performed batchwise in a 2-l fermenter operated with 1.3 l medium. Agitation at 500 rpm was provided by two six-bladed disc turbines. The temperature was controlled at 35°C and the pH at 2.4. The aeration rate was 1.2 vvm. Air was supplemented with 1, 2, 4, or 6% v/v CO2. A control run gassed with regular air (0.03% CO2) was also performed. The Eh was measured with a combination probe with a Ag/AgCl reference electrode. Determination of the volumetric CO2 mass transfer coefficient kLa for CO2 was determined by the dynamic method of Andr´ e et al. (1981), following the response of the CO2 concentration in the exit gas to a step change in flow rate. It was also calculated from kLa measurements for oxygen by the stationary method described by Sobotka et al. (1982), considering that (Nagpal et al.,1993):
Biotechnology Letters ⋅ Vol 20 ⋅ No 3 ⋅ 1998

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Analysis Previous experiments showed that in this system.28 1. µ1 (h–1) air 1% 2% 4% 6% 1 Fe2 (mg/l·h) 5. and As exhibit a maximum at 4% CO2 in the inlet gas.9 g/L at day 12 and then declined due to Fe3ϩ precipitation (Figure 2). Table 2 presents a summary of the results of the five runs. the Eh increased from initial values of 250–280 mV to steady figures of 500–505 mV after 5 to 8 days of leaching. Furthermore.2 vvm.015 0.8 g Cu/l is less than the copper that stoichiometrically corresponds to the 0. Suspended cell concentration was determined by direct counting in a Petroff-Hausser chamber and by alkaline hydrolysis and Lowry protein.03 17. pH 2. ferric iron was reduced with hydroxylamine hydrochloride and then assayed with phenanthroline. 1. 1969). 35°C.. At 6% CO2 the final population dropped to 7·107.019 Calculated from cell count data. Table 2 Effect of CO2 enrichment on the maximum specific growth rate and leach rates of Fe.4.58 As (mg/l·h) 1. Figure 2 Kinetics of iron and copper solubilisation in the bioleaching of an enargite-pyrite gold concentrate by Thiobacillus ferrooxidans in a 2-l agitated tank at 4% pulp density.1.022 0.04 1. and DC and DO are the diffusivities of CO2 and O2 in water. a longer growth period could be expected. Acevedo et al.012 0. kLa]C ϭ kLa]O (DC/DO)2/3 where kLa]C and kLa]O are the mass transfer coefficients for CO2 and O2. Cu. Ferrous ion was quantified by a modified phenanthroline method (Herrera et al. Cu and As after 24 days of biooxidation. the reason for this behaviour is not clear at this time.6·107 cells/ml in the case of regular air to 1.4. 4% CO2.93 3. Almost all of the iron in the liquid was present as ferric ion.04 1. respectively.. 500 rpm. some copper should also be supplied by chalcopyrite and other minor species present in the concentrate. and arsenic by reduction.82 2. Soluble iron accumulated in the leachate up to 5.84 3.00 20. pH 2.2 vvm. In all runs.79 g As/l present in the liquid. Typical kinetic patterns are shown in Figures 1 and 2 for the case of 4% CO2.77 3. The suspended cell population also increased significantly from 2. 35°C. 258 Biotechnology Letters ⋅ Vol 20 ⋅ No 3 ⋅ 1998 . Copper was analysed by iodometry (Flashka et al.027 0. the cell population is distributed roughly 50% attached to the mineral and 50% suspended in the liquid. 500 rpm. distillation and iodometry (Brescia et al. but it may be a combined effect of inhibition by Fe3ϩ and other ions and cell adhesion to precipitated jarosite.00 3. Dissolved oxygen was monitored with a galvanic probe. 4% CO2.00 5. 2 calculated at the time of maximum concentration before precipitation. Because at that time all nutrients were in excess. after the first few days of operation..F. 1989). Very slow growth can be appreciated after a nine-day period of fast growth (Figure 1). assuming an average cell composition of 37% protein. CO2 CO2 CO2 CO2 0.65 Cu (mg/l·h) 2.2·108 cells/ml in the run with 4% CO2. denoting a very efficient bacterial oxidation of the ferrous ion.35 1. some precipitation must occur because 1. Results and discussion The results show a marked effect of carbon dioxide concentration on the kinetics of growth and bioleaching. The specific growth rates and the extraction rates of Fe. Although the copper curve apparently does not suggest it. 1970).14 Figure 1 Kinetics of cell growth and arsenic solubilisation in the bioleaching of an enargite-pyrite gold concentrate by Thiobacillus ferrooxidans in a 2-l agitated tank at 4% pulp density. CO2 in the exit gas was measured with a Beckman infrared analyser.

Heijnen. M´ etodos de Laboratorio Qu´ ımico: Fundamentos de Qu´ ımica. Biotechnol Bioeng 35: 1111–1119 Brescia. P.3 for As. Real. Kalgoorlie. In : Annual Report on Fermentation Processes. Kuenen. Again. H. Schrebler. JR (1997). GT Tsao. Biotechnol Lett 19: 719–722 Flashka. 1997). Arents. The effect of CO2 enrichment was also reflected in the degree of extraction obtained in each run (Table 3). Moo-Young. AJ and Sturrock. L. Biotechnol Bioeng 41: 459–464 Silverman. The limitation resulted from the combination of two factors: the low concentration of CO2 in air and an insufficient flow rate. E and Wiertz. 1993). FC.28 17. Barnard. New York: Barnes and Noble Herrera. pH 2. G´ omez. JG.2 vvm. project 1950974 and from DGIPUCV. The high figures reported for iron in Tables 2 and 3 imply a preferential biooxidation of pyrite over enargite.780/94. extractions increased by factors of 3. The bioreactor used in this work showed a kLa for oxygen of 60.29 Cu (%) 16.91 25. Received: 10 December Revisions requested: 19 December Revisions received: 22 January Accepted: 23 January 1998 1998 1998 1998 Biotechnology Letters ⋅ Vol 20 ⋅ No 3 ⋅ 1998 259 . the mass transfer capability of the equipment is important. F. 1. Ruiz. RG (1990). Cu and As extractions. A. JC and Fehrmann. G. DG (1959). 5.4. JV (1997). Although extractions were far from complete. IJ and Einsele. pp. which is a very refractory mineral with a slow dissolution rate (Escobar et al. A (1982). Biotechnol Bioeng 23: 1161–1122 Boogerd. (1997) working in the electrochemical oxidation of this same concentrate. Fe (%) air 1% 2% 4% 6% 21. R and Vilche. References Acevedo. Quantitative Analytical Chemistry.7 h–1. CW (1981).. CL (1995). Australian Gold Conference.48 19. Vol. Bos. JJ and van der Lans. D and Oolman..23 59. M and Robinson. J Chem Technol Biotechnol 44: 171–181 Nagpal. Bacterial oxidation: revolutionizing the gold industry. ferrooxidans growth and leaching activity by high carbon dioxide partial pressures has been noted previously (Nagpal et al.59 As (%) 19. Prokop.23 34. Meilich. 195–197. Dahlstrom. Cu. PE (1969). M´ exico: Editorial Continental Brierley. and As after 24 days of biooxidation. Huenupi.6 h–1. the results confirmed the carbon dioxide limitation in the biooxidation of this enargite-pyrite concentrate in a 2-l tank bioreactor operated at 35°C. The measured value for this coefficient was 47. JC (1989).38 20. Vol. Dunn.3 for Fe. B. The optimal carbon dioxide concentration in the inlet gas was 4%. Bioprocess Eng 4: 223–229 Andr´ e. HA.29 CO2 CO2 CO2 CO2 In conclusion. R. MP and Lundgren. J Bacteriol 77: 642–647 Sobotka. they caused an increase in gold recovery by cyanidation of over 100% (results not shown). The differences in the optimal CO2 concentrations reported by different authors are due to differences in mineral composition.17 18. S. J.8 h–1. At this condition. H and Turk. J Electrochem Soc 144: 2628–2636 Escobar. SG. A (1989). According to the results obtained by C´ ordova et al. F and Gentina. and 1. 500 rpm and 1.60 18. which gives a calculated value for the kLa of CO2 of 51.CO2 supply in the biooxidation of an enargite-pyrite gold concentrate Table 3 Effect of CO2 enrichment in the extraction of Fe. P. T (1993). Review of methods for the measurement of oxygen transfer in microbial systems. 1. project 203. pp 133–135.39 19. Australia C´ ordova. microbial strains and operating conditions. Aguill´ on.35 69. Acknowledgements The authors wish to acknowledge support received from FONDECYT-Chile. A (1970). In this respect. 4% carbon dioxide gave maximal Fe.24 21. New York: Academic Press The inhibition of T.2 for Cu.39 23. M. a much higher dissolution rate would be expected if the Eh values could be raised to 600 mV or higher. It is considered that the small difference between them is acceptable and in the range of experimental error. ed pp 127–210.