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KINETIC MODELLING OF GOLD LEACHING AND CYANIDE CONSUMPTION IN INTENSIVE CYANIDATION OF REFRACTORY GOLD CONCENTRATE

Waroonkarn Srithammavut1, Saija Luukkanen2, Arto Laari1, Timo Kankaanp3, Ilkka Turunen1

Lappeenranta University of Technology, Department of Chemical Technology, P.O. Box 20, FI-53851 Lappeenranta, Finland E-mail: firstname.lastname@lut.fi 2 Geological Survey Finland, Tutkijankatu 1, FI-83500 Outokumpu, Finland, Fax +358 13557557 3 Outotec Research Center, Kuparitie 10, FI-18101 Pori, Finland, E-mail: waroonkarn.srithammavut@lut.fi

ABSTRACT Intensive cyanidation of a refractory gold concentrate was studied experimentally and by mathematical modelling. Experiments were carried out in stirred tank reactors at different conditions varying oxygen and cyanide concentrations. Samples taken from the reactor were analyzed for gold and other compounds using fire assay AAS and ICP methods, respectively. Based on the experimental results, kinetic models were developed for gold leaching and for cyanide consumption. In the kinetic models, the effects of dissolved oxygen concentration, free cyanide concentration, amount of leachable gold in the concentrate and solid-liquid mass transfer were taken into account. Kinetic parameters were estimated by fitting the models to the experimental data. The obtained results show good agreement between the measured and predicted concentrations. The reliability of the estimated parameters was studied using Markov chain Monte Carlo methods. All experimental parameters were found to be well-identified. The rate controlling step was determined by comparing the surface reaction and mass transfer limited models. Based on the obtained results, it was concluded that the leaching rate is limited by surface reaction rate. Keywords: gold leaching, intensive cyanidation, kinetic modelling, parameter estimation.

INTRODUCTION Cyanidation process is a well-known extraction technique for leaching of precious metals such as gold and silver. Gold cyanidation is an electrochemical process which relies on the fact that gold dissolves in alkaline cyanide solutions and forms gold cyanide complex [Au(CN)2-] in the so called anodic reaction. Another half reaction, in which oxygen is reduced, is called cathodic reaction [1, 2]. Many studies have revealed that the concentration of reagents, cyanide and oxygen, plays significant roles in gold cyanidation. Kinetics of gold leaching for different types of concentrate have, there-

fore, been extensively studied, especially the effects of cyanide and oxygen concentrations on the leaching rate [3-8]. In general, the kinetics is also dependent on ore mineralogy. It is, therefore, difficult to develop a universally valid model which would be applicable for all ore types. In principle, the leaching rate is limited either by mass transfer of oxygen or cyanide from liquid bulk to the particle surface, by rate of the intrinsic leaching reactions on the surface of the particles or by intraparticle diffusion. Typically, the effect of intraparticle diffusion is omitted in gold cyanidation studies due to the generally nonporous characteristics of the ore particles.

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Different kinetic models have been presented based on either diffusion or reaction rate limitations. The Habashi rate equation [2] derived for pure gold surfaces is based on electrochemical mechanism in which the leaching rate is limited by diffusion of the reacting species over laminar boundary layer at the particle surface. Similar approach has been used by Rubisov et al. [10] who applied the diffusion model to pure gold by introducing a stoichiometric factor representing the number of moles of leached gold per moles of consumed oxygen. Recently, Bellec et al. [11] further developed the diffusion model by taking into account the dissolution of exposed gold surfaces and gold accessibility through ore porosity. The model for gold dissolution rate, including gold accessible through ore porosity, is given as:

rS , Au = 4 RKDCN CCN DO2 CO2 ( K ( + 1 ) + P ) ( DCN CCN + 8 RDO2 CO2 )

mass fraction of gold in the particles in the range of c CN 25-156 mg dm-3, cO2 8.5-40 mg dm-3 and x Au 4.713.2 mg kg-1.

0.81 0.73 r = 0.0016 cCN ( x Au x Au , )1.5 cO 2

(3)

(1)

where rS , Au is the molar kinetics of gold dissolution per unit of surface, R is the stoichiometric factor for oxygen, K is the rate constant, DCN is the cyanide diffusivity, DO2 is the oxygen diffusivity, c CN is the cyanide concentration, cO2 is the concentration of oxygen, 1 is the distance between gold and bulk solution at any time, P is the threshold distance from ore surface above which the gold grains are not accessible to chemical attack by cyanide and is the thickness of boundary layer. On the other hand, some researchers have found that the rate is kinetically controlled by surface reactions [5, 6, 12]. Based on electrochemical reactions, a model in which the leaching rate is controlled by the rate of the intrinsic reactions and not by diffusion over the boundary layer is presented below [4].

where r is in units mg (kg h)-1, x Au is the mass fraction of gold in concentrate and x Au , is the mass fraction of gold in concentrate after infinite leaching time. According to Eq. (3) gold leaching rate decreases rapidly as the gold mass fraction in solids is decreased as leaching proceeds. This can be explained to be caused by the intrinsic size distribution of gold particles in the solids. Small particles with large interfacial area are leached first at high rate. The remaining larger particles have less interfacial area and are leached at lower rate. Some part of the gold particles, x Au , , are completely locked inside the matrix and cannot be leached no matter how long leaching times are used. A similar form for the rate equation, which also includes the effect of particle size is presented in Eq. (4). The equation was obtained by using cCN of 260 and 650 mg dm-3, c O2 of 8 and 40 mg dm-3 and x Au of 1.5-2.3 mg kg-1 [6].

0.961 0.228 r = (1.13 10 3 4.37 10 11 d 2.93 )cCN ( x Au x Au, ) 2.13 cO 2

r=

(2)

where F is the Faraday constant in units C mol-1 and ka and kc are rate constants. Many leaching models, which have been proposed previously, lump a number of effects together considering a homogeneous kinetics in which the diminishing surface area is excluded. Ling et al. [3] proposed a rate equation based on the assumption of pseudohomogeneous ore behavior. This rate equation is expressed in terms of cyanide and oxygen concentrations in the liquid and

(4) where r is in units mg (kg h) and d is in units m. Another important rate equation in gold cyanidation is the rate by which cyanide is consumed. In addition to reactions with gold, cyanide is also consumed in other reactions, for instance, in reactions with competing metals. The amount of information about cyanide consumption kinetics available in literature is scarce. De Andrade Lima and Hodouin [6] have studied cyanide consumption in gold cyanidation. They presented a cyanide consumption model in which the rate is a function of cyanide concentration and particle size.

-1

(5)

where r is in units mg dm-3 h-1 and d is in units m. More recently, Bellec et al. [11] further developed cyanide consumption models taking into account cyanide concentration and particle size as well as the

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Waroonkarn Srithammavut, Saija Luukkanen, Arto Laari, Timo Kankaanp, Ilkka Turunen

concentration of copper and sulphur in the ore, as shown in Eq. (6). They also considered three classes of gold (liberated, exposed and accessible through ore porosity) in the solid phase.

(6)

5.9

is partly locked in the sulphide matrix. The major mineralogical component is quartz. The main sulfides are pyrrhotite, chalcopyrite, arsenopyrite and pyrite. The concentrate was pre-treated by oxidation at 180C for 2 h. Oxidation was required due to high concentration of sulfide in the ore which prevents the access of cyanide to the surface of gold particles and also increases cyanide consumption during leaching. The pre-treated concentrate contains 124.1 mg kg-1 of gold, 33.5 g t-1 of silver, 15.5 % of iron, 1.1 % of copper, 1.3 % of arsenic and 6.4 % of sulfur. The concentrate with a density of 3.21 g cm-3 was ground in a ball mill for 30 minutes to 80 % -36 m and had a mean size of 33.88 m. Experimental apparatus and procedure The experiments were carried out at ambient temperature at pH of 11-12. The cyanidation experiments were carried out in two different reactors. Atmospheric experiments were carried out in a 1 dm3 glass reactor, equipped with stainless steel baffles. The diameter of the reactor was 10 cm and the diameter of the impeller (turbine) was 76 mm. Pressurized experiments were carried out in a 2.7 dm3 autoclave reactor, equipped with stainless steel baffles. The diameter of the reactor was 15.4 cm and the diameter of the impeller was 76 mm. The stirring speed for the atmospheric and pressurized experiments was in both cases 600 rpm. It was experimentally observed that at this mixing rate the leaching is not anymore limited by mixing or solid-liquid mass transfer. The concentrate was divided to approximately 380 g batches for atmospheric experiments and about 760 g batches for pressurized experiments. In atmospheric experiments 890 cm3 and in pressurized experiments 1780 cm3 of solution containing NaCN and Ca(OH)2 was added to the reactor in order to obtain a 30 wt. % slurry. Samples were taken from the atmospheric experiment reactor at times 0.5, 2, 5, 10 and 24 h from the start and from the pressurized experiment reactor at times 0.5, 1, 2, 4, 5, 10 and 24 h from the start. The experimental conditions including the initial amount of gold are given in Table 1. The initial amount of gold in different batches can vary due to the heterogeneous nature of the concentrate. The initial amounts of gold given in Table 1 are obtained from mass balances calculated from the analyzed concentrations of gold in liquid phase and in the solid reside at the end of each experiment.

where r is the cyanide consumption per unit of time and mass of liquid, cCu is the ore copper concentration, c S is the ore sulphur concentration and d P is the length of cubic ore particle sides. In refractory ore gold is partly locked up in a matrix of sulphide minerals, such as pyrrhotite and pyrite. The presence of these reactive sulphides often inhibits gold dissolution by forming sulphide film on the gold surface [13]. Consequently, gold leaching under normal conditions is difficult. High concentrations of cyanide, typically from 3000 up to 50000 mg dm-3, and oxygen, the socalled intensive cyanidation, can be possibly used to treat this kind of ore. The gold cyanidation models presented in literature are obtained in conditions which are typical for normal cyanidation process, i.e. at relatively low concentration of cyanide and oxygen According to the best knowledge of the authors no kinetic model has been given which is valid in intensive conditions. The objective of this work was, therefore, to develop kinetic models for gold leaching and cyanide consumption for the studied ore in conditions of intensive cyanidation. Advanced mathematical methods were used for parameter estimation and assessment of parameter reliability. Kinetic models based on surface reaction and mass transfer were investigated and compared. The developed leaching rate equation takes into account the reagent concentration, the concentrate particle size and the decrease of the active surface area of the concentrate particles during leaching. EXPERIMENTAL Materials The gold concentrate under study was produced by flotation. It is a refractory concentrate where the gold

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Operation mode Atmospheric Leaching Pressurized Leaching Run No. 1 2 3 4 5 Pressure kPa (abs) 100 100 400 100 1000 oxygen air oxygen oxygen oxygen Gas

cCN c O2

Run mode C C V V V

*) initial concentration In the atmospheric experiments, the free cyanide concentration and pH were kept at almost constant level by analyzing liquid samples and adding corresponding amount of cyanide to the reactor (run mode C in Table 1). In the pressurized experiments, all the cyanide was added at the beginning and the cyanide concentration and pH was allowed to change during the leaching (run mode V in Table 1). In atmospheric leaching experiments the dissolved oxygen concentration was continuously monitored. In pressurized experiments, this was not possible. Instead, it was assumed that the dissolved oxygen concentration obeys Henrys law and that the dissolved oxygen concentration is 40 mg dm-3 at 100 kPa, 160 mg dm-3 at 400 kPa and 400 mg dm-3 at 1000 kPa. Analytical methods Gold concentration from solution samples was analyzed by atomic absorption spectrometry (AAS; Perkin Elmer Analyst 400) and from solid residues by Fire Assay method. Other elements (e.g. Cu, Fe) from solution were analyzed by inductively coupled plasma spectrometry (ICP-OES; Thermo Electron iCAP 6500 ICP-OES ) and from solid residue by X-ray fluorescence spectrometry (XRF: PANalytical AXIOS equipped with additional RR Fundamental Parameters correction program). Anions, like S2-and SO42-, from solution were analyzed ionchromatographically (Dionex DX-120). KINETIC MODELLING The chemistry of the dissolution of gold can be described by the well-known Elsner equation as [1]: 4Au + 8CN- +O2+2H2O 4Au(CN)2- +4OH(7) Gold leaching is a heterogeneous reaction in which either chemical reaction kinetics or mass transfer can possibly be the rate limiting step. Therefore, kinetic models, based on surface reaction and mass transfer, were studied and compared in this work. The gold dissolution rate is given by multiplying the surface reaction rate by the area of the concentrate particle and the number of the particles in the slurry. Actually, the leaching rate depends on the area and size distribution of gold particles in the concentrate. However, as this information is generally not available, it is assumed that gold is homogeneously distributed on the surface of the concentrate particles.

dc Au n = rS , Au Ai dt eL

(8)

where r S , Au is reaction rate of gold at surface in units mol m-2 h-1, Ai is surface area of one particle during leaching in units m2, n is number of particles per volume in units mR-3 and eL is liquid volume fraction in units mL3 mR-3. It is also assumed that the shrinkingcore model can be used to describe the decrease of the active surface area of the concentrate particles during leaching. Based on the shrinking core model, the active surface area of concentrate particles decreases continuously during the leaching and it can be calculated from the content of gold in the particles. Kinetic model based on surface reaction This model is built under assumption that the reaction of gold with cyanide and oxygen is considered as a surface reaction which depends on the cyanide and oxygen concentration at the reacting surface. Due to the fact that some amount of gold in the particles usually

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Waroonkarn Srithammavut, Saija Luukkanen, Arto Laari, Timo Kankaanp, Ilkka Turunen

remains unreacted, the reaction rate, therefore, also depends on the amount of gold in the solids that is available for leaching. The surface reaction rate, in mol m-2 s-1, is then given by:

The similar conclusion can be made by examining the Habashi leaching equation [3].

r=

kcCN cO2

rS , Au

c = k1 CN c CN ,m

a1

cO2 cO ,m 2

a2

x Au x Au , x Au , m

a3

(cCN + cO2 )

(11)

(9)

where k1 is the overall rate constant, a 1 is the reaction order for cyanide, a 2 is the reaction order for oxygen and a 3 is the reaction order for gold mass fraction in solids. Each term of reactants is divided by a mean value which is used to improve parameter identification in parameter estimation. The mean values used for cyanide concentration ( cCN ,m ), oxygen concentration ( cO2 , m ) and gold mass fraction ( x Au , ) are 6000 mg dm-3, 200 mg dm-3 and 70 mg Au kg-1, respectively. Gold is assumed to be homogeneously distributed on the surface of the particles. Kinetic model based on mass transfer In mass transfer limited rate model, the leaching rate depends on mass transfer of cyanide and oxygen from the bulk of the liquid to the reacting gold surface. Since the cyanide concentration in the current experiments is much higher than the oxygen concentration, the leaching rate becomes limited by oxygen. According to the film model for mass transfer, the leaching rate is then:

If cyanide is in excess to oxygen the leaching rate becomes directly dependent on the oxygen concentration and it is not dependent on the cyanide concentration. Cyanide consumption model The total consumption of cyanide is an important parameter of leaching process and it influences the economical profitability of the whole process. In practice, other metals than gold are also dissolved in alkaline cyanide solutions to form metal cyanide complexes consuming additional cyanide. Cyanide consumption models are not widely studied and published. Andrade Lima and Hodouin [6] have presented an equation for cyanide consumption equation in which the cyanide consumption depends on cyanide concentration and particle size. In the current work, the cyanide consumption model, as shown in Eq. (12), is developed taking into account the concentration of the reagents. The model considers the total amount of cyanide consumed by all the species that react with cyanide.

rS ,CN

c k 2 CN c CN , m

b1

cO 2 cO , m 2

b2

(12)

rS , Au = k L (cO2 cO2 , s )

(10)

where cO2 , s is the concentration of oxygen at the reacting surface and kL is the mass transfer coefficient. Since the gold leaching reaction is fast in the mass transfer limited model, cO2 , s is close to zero and the leaching rate is first order with respect to oxygen and zero order with respect to cyanide. In practice, the order for oxygen can be lower than one due to oxygen dependent deactivitation reactions taking place at the gold surface. This does not, however, explain the experimentally observed dependency of the leaching rate from cyanide concentration. Therefore, it seems likely that the leaching rate cannot be described by mass transfer of the reactants to the reacting surface.

where r S , CN is the reaction rate of cyanide in units mol m-2 h-1, k2 is the overall rate constant, b1 is the reaction order for cyanide and b2 is the reaction order for oxygen. The cyanide consumption rate is then given as:

dcCN dt

= rS ,CN Ai

n eL

(13)

RESULTS AND DISCUSSION From experimental work, the results show that the final gold conversion increases with increasing reagent concentrations, as seen from Table 2. The effect of oxygen concentration can be studied from experiments No. 1 and 2, and from experiments No. 3, 4 and 5. The results show that high oxygen concentration enhances

185

x Au , mg kg-1

the leaching rate. The effect of cyanide concentration is studied in experiments No. 1 and 4. A similar trend, that higher cyanide concentration increases conversion from solid samples, is also found. The highest conversion is found in experiment No. 5, in which the highest cyanide and oxygen concentrations were applied. The non-leachable amount of gold and conversion is presented in Table 2 as well. The gold leaching conversion was calculated as: Conversion (%) =

x Au ,ini x Au , x Au ,ini

100

(14)

where x Au ,ini is the gold mass fraction at the beginning of experiments in units mg kg-1. Others metals, such as copper, iron and silver, and elemental sulfur were found to be soluble in cyanide solution during leaching as well. These compounds

were dissolved more readily at high cyanide and oxygen concentrations, as seen in Fig. 1. The simultaneous dissolution of other metals and ions together with gold affect cyanide consumptions increasing it considerably. The kinetic parameters were estimated using the Modest computer software [9] by fitting the models to the experimental data using the least squares method (LSQ). In the estimation both gold and cyanide concentrations were used as the data and the kinetic parameters in Eqs. (9) and (12) were estimated simultaneously. The reacting area during leaching was calculated from gold content in the particles using the shrinking-core model assuming that the particles are spherical. The results show that the coefficient of determination for the rate equations shown in Eqs. (9) and (12) is 99.54 % which indicates a good agreement between the experimental data and the model predictions. The experimental and predicted results for gold leaching are shown in Fig. 2, presenting a good fit between simulated curve and the experimental data. Fig. 3 shows the concentration of the free cyanide during experiments. Lines No. 1 and 2 represent the cyanide concentration which was kept constant at about 3000 mg dm-3 and lines No. 4, 5 and 6 represent cyanide concentration falling from the initial value of 10 000 mg dm-3 due to reaction with gold and other substances. The values of the estimated pa-

Fig. 1. Concentration of copper, iron, silver and total sulfur in cyanide solution. l - run 1; - run 2; - run 3; - run 4; + - run 5.

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Waroonkarn Srithammavut, Saija Luukkanen, Arto Laari, Timo Kankaanp, Ilkka Turunen

Fig. 2. Comparison of the observed and simulated gold concentration in liquid. Lines (-) represent simulated values. l - run 1; - run 2; - run 3; - run 4; + - run 5. rameters are presented in Table 3. The results show that the leaching rate seems to depend strongly on the concentration of gold in the particles and is more sensitive to cyanide than oxygen. Additionally, it was discovered that the fit was improved when the continuously decreasing reactive surface area was included to the model instead of using constant surface area. The gold leaching and cyanide consumption rate equations can be then written as:

rS , Au c = 1.94 10 CN c CN , m

5

Fig. 3. Comparison of the measured and predicted cyanide concentrations. Lines (-) represent simulated values. l run 1; - run 2; - run 3; - run 4; + - run 5. The selectivity of the free cyanide to gold can be also predicted, using Eqs. (15), (16).

2rS , Au rS ,CN

or

(17)

0.51

c O2 cO , m 2

0 .2

x Au x Au , x Au , m

1.66

(15)

c = 1.35 10 CN c CN , m

3 0 .95

rS ,CN

cO 2 cO , m 2

0.25

(16)

The selectivity can be also considered as the ratio of cyanide consumed in the reaction with gold over the total amount of cyanide consumed in all reactions. In ideal case, all cyanide is consumed, according to the stoichiometry shown in Eq. (7), in reaction with gold and the value of the selectivity is 1.0. According to Eq. (17) the selectivity is proportional to the order of -0.44 for free cyanide concentrations and to the order of -0.05 for dissolved oxygen concentration. This means that the selectivity is improved by decreasing the cyanide and oxygen concentrations.

Table 3. Estimated parameter values and their standard errors. Coefficient of determination is 99.54%.

Parameters k1 k2 a1 a2 a3 b1 b2

Values 1.94 10-5 mol m-2 h-1 1.35 10-3 mol m-2 h-1 0.507 0.204 1.66 0.951 0.248

187

Fig. 4. Initial selectivity of free cyanide concentration to gold. The dependency of the initial selectivity from cyanide and oxygen concentrations at the beginning of the experiments is illustrated in Fig. 4. At later stages of leaching, the selectivity decreases according to Eqs. (15) and (17) when the amount of gold in the particles decreases. The maximum selectivity was found for the lowest cyanide and oxygen concentrations. This implies that at higher cyanide concentrations cyanide is consumed mainly by other competing ions. It should be noted, however, that the results below cyanide concentration of 3000 mg dm-3 were obtained by extrapolating the results to lower concentrations which probably creates some uncertainty to the results. To evaluate the accuracy of the estimated parameters in a non-linear multiparameter model it is important to consider possible cross-correlation and identifiability of the parameters. Classical statistical analysis giving optimal parameter values is approximate, based on linearization of the model, and may sometimes be quite misleading. This problem may be properly treated by Markov chain Monte Carlo (MCMC) methods. When using MCMC methods, estimation of model parameters and predictions is performed according to the Bayesian paradigm. All the uncertainties in the data, as well as the modelling results, are treated as statistical distributions. A distribution of the unknown parameters is generated using available prior information and statistical knowledge of the observation noise. Computationally, the distribution is generated using the Markov chain Monte Carlo (MCMC) sampling approach. Up-to-date adaptive computational schemes are employed in order to make the simulations as ef-

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Waroonkarn Srithammavut, Saija Luukkanen, Arto Laari, Timo Kankaanp, Ilkka Turunen

fective as possible [14, 15]. In this study a FORTRAN 90 software package MODEST [9] was used for both the least squares estimation and the MCMC estimation. The methods mentioned above are also implemented in a MATLAB package [15]. The distribution of the parameters shows how well the parameters have been identified. Each dot in the figures is a sample from the distribution of possible solutions to the parameter estimation problem. The contour lines in the figures represent 95 % and 50 % probability regions. As seen in Fig. 5, all the estimated parameters are well identified with the Markov chain samples centered around the most probable point and there is no cross-correlation between the parameters. From Fig. 5, it can be also seen that, for both gold leaching and cyanide consumption models, all estimated parameters have a narrow distribution. From the 1-dimensional probability distribution project on the axis, it can be seen that the most probable point for the reaction orders for cyanide and oxygen concentrations and gold mass fraction of gold leaching equation are approximately 0.6, 0.19 and 1.7, respectively. The reaction rate coefficients, k1 and k2, are around the value of 1.9 x 10-5 and 1.4 x 10-3, respectively. For parameters in cyanide consumption model, the reaction orders are 1.0 for cyanide and approximately 0.24 for oxygen. These values are the same as those obtained by the LSQ method in parameter estimation, as shown in Table 3. Thus, it can be said that the used advanced mathematical methods show that, even though the amount of experimental data was quite limited, reliable parameters and kinetic models were still obtained. CONCLUSIONS Cyanidation of gold from a refractory gold concentrate was studied experimentally and by mathematical modelling. The experimentally observed conversion of gold is from 88 to 96 % calculated from the solid gold content. Kinetic models were developed for gold leaching and cyanide consumption. The model parameters were estimated and fitted to the experimental data. In the conditions studied, the results show that the gold leaching is kinetically controlled by surface reaction. The leaching rate depends on cyanide concentration in liquid bulk, oxygen concentration at the particle surface and leachable amount of gold in the particles. The reaction orders for cyanide, oxygen and gold are approxi-

mately 0.51, 0.2 and 1.66, respectively. The cyanide consumption rate, in this work, is dependent on cyanide and oxygen concentrations. The reaction orders are 0.95 for cyanide and 0.25 for oxygen. The selectivity of cyanide to gold was found to be the highest at low cyanide concentrations and high oxygen concentrations. The reliability of the estimated kinetic parameters was studied using Markov chain Monte Carlo method. It is shown that, although the kinetic models contain 7 experimental parameters and the number of data is quite limited, the estimated parameters are all well-identified and reliable. Acknowledgements Financial support by Outotec Research Oy is gratefully acknowledged. The experimental work was conducted by the Geological Survey of Finland. REFERENCES 1. J. Marsden, I. House, The Chemistry of Gold Extraction, Ellis Horwood, West Sussex, 1992. 2. F. Habashi, Textbook of Hydrometallurgy, 2nd edn., Mtallurgie Extractive Qube, Qubec, 2002. 3. P. Ling, V.G. Papangelakis, S.A. Argyropoulos, P.D. Kondos, An improved rate equation for cyanidation of a gold ore, Can. Metall. Q., 35, 1996, 225-234. 4. F.K. Crundwell, S.A. Godorr, A mathematical model of the leaching of gold in cyanide solutions, Hydrometallurgy, 44, 1997, 147-162. 5. M.E. Wadsworth, X. Zhu, J.S. Thompson, C.J. Pereira, Gold Dissolution and Activation in Cyanide Solution: Kinetics and Mechanism, Hydrometallurgy, 57, 2000, 1-11. 6. L.R.P. de Andrade Lima, D. Hodouin, A lumped kinetic model for gold ore cyanidation, Hydrometallurgy, 79, 2005, 121-137. 7. S.C. Bouffard, D.G. Dixon, Evaluation of kinetic and diffusion phenomena in cyanide leaching of crushed and run-of-mine gold ores, Hydrometallurgy, 86, 2007, 63-71. 8. H. Kasaini, K. Kasongo, N. Naude, J. Katabua, Enhanced leachability of gold and silver in cyanide media: effect of alkaline pre-treatment of jarosite minerals, Miner. Eng., 21, 2008, 1075-1082. 9. H. Haario, Modest Users Guide, ProfMath Oy, Helsinki, 2002.

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10. D.H. Rubisov, V.G. Papangelakis, P.D. Kondos, Fundamental kinetic models for gold ore cyanide leaching, Can. Metall. Q., 35, 1996, 353-361. 11. S. Bellec, D. Hodouin, C. Bazin, M.R. Khalesi, C. Duchesne, Modelling and simulation of gold ore leaching, World gold conference 2009, Gauteng, Republic of South Africa, 2009, The Southern African Institute of Mining and Metallurgy, Johannesburg, 2009, pp.51-60. 12. M.E. Wadsworth, Surface processes in silver and gold

cyanidation, Int. J. Miner. Process, 58, 2000, 351-368. 13. P.D. Kondos, G. Deschnes, R.M. Morrison, Process Optimization Studies in Gold Cyanidation, Hydrometallurgy, 39, 99, 1995, 235-250. 14. H. Haario, E. Saksman, J. Tamminen, An adaptive Metropolis Algorithm, Bernoulli. 7, 2001, 223-242. 15. M. Laine, Adaptive MCMC Methods with Applications in Environmental and Geophysical Model, Ph.D. Dissertation, Finnish Meteorological Institute, Helsinki, Finland, 2008.

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