A fundamental evaluation of the atmospheric pre-leaching section of the nickel-copper matte treatment process
Thesis (PhD (Process Engineering))--University of Stellenbosch, 2007.
Nickel-Copper sulphide ores are the most important Platinum Group Metal bearing ores. The South African deposits are exceptionally rich in the platinum group metals (PGMs) and production of the PGMs is the primary purpose of treating these ores. The methods used in the recovery of the PGMs from the nickel-copper ores generally consists of ore concentration by physical techniques, pyrometallurgical concentration and hydrometallurgical extraction of the base metals followed by the PGMs. Pyrometallurgical concentration produces Ni-Cu matte, which is treated by hydrometallurgical processes to recover the nickel, copper, cobalt and the precious metals. In this study, the leaching behaviour of a Ni–Cu matte in CuSO4–H2SO4 solution during the repulping (pre-leach) stage at Impala Platinum Refineries was studied. The repulping stage is basically a non–oxidative atmospheric leach stage, in which nickel, iron and cobalt are partially dissolved, while the copper is precipitated. To understand the nature of the leaching process during this stage of the base metal refining operation, the effects of variations in the key process variables such as temperature, stirring rate, particle size, pulp density, residence time, initial copper and acid concentrations were investigated. The pre-leached matte was then pressure leached to ascertain the effect of process conditions in the pre-leach stage on the subsequent pressure leach stage. It was found that the leaching mechanism entails dissolution of metal alloys out of sulphide minerals with transformation of Ni3S2 to NiS. Aqueous copper precipitates as metallic copper and as chalcocite. The matte is leached by both acid and the cementation process, especially in the early stage when the Cu2+ ions are present. Galvanic interaction of the sulphide minerals and/or the Ni alloy also enhances the leaching process. The leaching kinetics of Ni was characterized with the shrinking core model and was found to be controlled by diffusion through surface layer. An activation energy of 31 kJ/mol was obtained, which also suggested a diffusion controlled leaching reaction. Atmospheric leaching tests indicated that Ni extraction increased slightly in the temperature range 50 – 60 oC, however no significant increase was observed from 60 to 80 oC, probably because the leaching process was found to be diffusion controlled. The slight increase in nickel dissolution at higher temperatures (>60 oC) may be attributed to the transformation of Ni3S2 to NiS, which is easier to leach. Co extraction appeared to be insensitive to temperature changes, while Fe extraction was low at 50 oC but increased significantly at 60 – 80 oC. The Ni extraction increased gradually with increase in the stirring rate from 145 to 400 rpm while Co and Fe extractions were insensitive at 145 and 205 rpm, but increased substantially at 400 rpm. This was probably due to increased mass transfer rate and transformation of Ni3S2 to NiS. With pulp density, Ni and Co extractions appeared to be insensitive to changes in the pulp density as only a slight increase in extractions was observed when the density was reduced from 1.7 kg/L to 1.6 kg/L. Similar iron extractions were achieved at 1.7 and 1.75 kg/L but increased significantly at 1.6 kg/L. It was found that Ni and Co extractions were not significantly affected by changes in the particle size, probably because metal alloys were liberated and hence exposed to the leaching solution. Iron extraction could not be determined accurately because of iron precipitation at pH above 3. Generally the leaching of metals did not depend on the initial copper concentration in the investigated range of 25 - 48 g/L Cu. It was also observed that initial acid concentration did not have an effect on Ni extraction, probably due to the fact that most of the nickel was leached by the process of cementation. However, Co and Fe extractions increased when the acid increased from 90 g/L to 110 g/L, but no further increase was noted at 125 g/L. A residence time of 5 hours was found to be adequate as there was no significant increase in metal extractions when the residence time was increased beyond 5 hours. As much as 20% Ni, 40% Co and 80% Fe can be extracted from the Ni-Cu matte during the repulping stage of the leaching process studied, provided the investigated conditions prevail. Generally the rate of Cu cementation increased with increasing temperature and pulp density, but decreased with an increase in particle size, acid and copper concentrations. The rate of stirring did not affected Cu cementation. It was found that aqueous copper precipitated from the solution within 90 minutes when the temperature was raised to 80 oC. However, under the present pre-leach temperature of about 60 oC complete Cu cementation can only be achieved after about 5 hours. The cementation reaction was found to follow a mixed control mechanism, with two distinct activation energies namely 18.2 kJ/mol at 70 – 80 oC and 74.6 kJ/mol at 50 – 70 oC. This suggested that the rate of cementation reaction is probably controlled by a boundary layer diffusion mechanism at higher temperatures. At low temperatures the rate is probably controlled by a surface reaction mechanism. The pressure leaching experiments, which were aimed at investigating the response of pre-leached matte to the subsequent pressure leaching process, showed that Ni extractions were similar for the investigated pre-leach temperature of 50 – 80 oC and stirring rate of 145 – 400 rpm. For the pre-leach stage conditions of 60 – 80 oC and 205 – 400 rpm Ni3S2 was transformed into NiS, which is easier to leach in the pressure leaching stage. However, because of the aggressive conditions prevailing in the pressure leaching stage, all the nickel minerals were leached at about the same rate. In the case of pulp density, Ni extraction was comparable for all the investigated pulp densities (1.6 – 1.75 kg/L). This was probably due to the fact that Ni3S2 transformed to NiS in the pre-leach stage. It was found that Ni extraction increased with increasing residence time for the investigated time of 1 hour to 9 hours, probably due to the changes in the mineral phases of the matte as indicated above. The copper minerals (Cu2S and Cu1.96S) transformed into Cu2S and Cu1.8S with aqueous copper being precipitated, and were not leached under the applied conditions. All the cobalt and iron dissolved in the pressure leaching stage. A semi-empirical kinetic model was developed for the pre-leaching stage. A comparison of the model predictions and the experimental data for the dissolved species during the batch leaching process showed that the model can satisfactorily fit the trends in the leaching of the metals.