Dissertations / Theses on the topic 'Nickel laterite'

Falconbridge Dominicana C. Por A. operating in the Dominican Republic produces nickel as an iron-nickel alloy from laterite ore. Material that is rejected from their mining operations due to its incompatible chemistry is currently being stockpiled against mine depletion. Recent interest in recuperating nickel from this reject material led to the examination of the suitability of carbothermic reduction followed by magnetic separation for nickel recovery from this reject ore. Five parameters were considered in a Design of Experiment framework, namely: heating time; temperature; material type, coke addition and oxygen partial pressure. Magnetic separation was conducted with a Davis Tube and a low intensity hand magnet.
It was found that this reject material can successfully be treated using a carbothermic reduction process to produce 50 to 75 mum diameter metallic components within a gangue matrix. The recovery of nickel ranged from 61.7% to 21.9% to 16.4% in the high, low and non magnetic fractions, respectively, separated from the reduced material. The grade of nickel ranged from 1.97 wt% Ni to 1.58% to 0.75 wt% Ni in the high, low and non magnetic fractions, respectively.
Heating temperature had the greatest positive influence on the performance of the process followed by material type and heating time. Oxygen activity and coke addition were seen not to influence the performance. The Boudouard reaction was considered to be the rate controlling step and a maximum possible operating temperature was considered to depend on the physical properties of the material, specifically the softening temperature.

Atmospheric leaching (AL) of low-grade nickel laterite ores can produce a pregnant leach solution (PLS) containing significant amounts of impurities such as trivalent iron, aluminium and chromium ions. Purification of PLS by precipitation of the impurities with an alkaline reagent often causes an associated loss of nickel. This thesis documents an investigation of the physicochemical processes that occur during the precipitation of iron, aluminium and chromium from both synthetic and real nickel laterite AL leach liquors and associated nickel losses.A chemical equilibrium model in the Fe(III)–Ni(II)–H2SO4–H2O system was developed with the effects of ionic strength and temperature taken into account. This model was able to calculate the concentration distribution of iron and nickel species over the pH range from 0 to 4 and temperature from 25 to 100 °C, and predict the pH value of the solution. In addition, the model can calculate the saturation index of iron oxides such as goethite, ferrihydrite and schwertmannite to predict whether a specific iron oxide will precipitate or dissolve under particular conditions. The solubility of goethite, ferrihydrite and schwertmannite decreased substantially with increasing pH value. Goethite, ferrihydrite and schwertmannite were all undersaturated below pH 2. With increasing pH, ferric ions tended to precipitate first in the form of ferrihydrite followed by goethite and schwertmannite. A mixture was formed above pH 2.5, of which schwertmannite was the dominant phase.Considerable effort has been put into the experimental study on the relationships between impurities removal and nickel losses from nickel laterite AL liquors. The precipitation experiments were conducted in either single- or multi-stage simulation using synthetic and real PLS. For the single-stage precipitation experiments conducted using a synthetic PLS containing Fe(III)+Ni(II), the effects of the factors governing the iron precipitation process upon nickel losses were investigated by statistical analysis and modelling. Temperature, pH and the initial Fe/Ni ratio in PLS were found to be the important factors affecting iron removal efficiency and the level of nickel loss to solid. These factors were studied using a three-level Box-Behnken design combined with response surface methodology. Quadratic models were fitted to the experimental data, to enable construction of 3D response surfaces and corresponding contour plots. These graphs clearly demonstrated the links between responses and the interactions of factors.Further single-stage precipitation experiments performed using PLS containing Fe(III)+Ni(II)+Al(III), Fe(III)+Ni(II)+Cr(III), and Fe(III)+Ni(II)+Al(III)+Cr(III) showed that greater losses of nickel to solids occurred in the presence of aluminium and chromium. Increasing the pH value of solution and precipitation temperature favored the removal of iron, aluminium and chromium, but at a cost of greater nickel losses. By carefully controlling pH and temperature using a multi-stage precipitation process, however, the iron, aluminium and chromium can be effectively rejected with a minimal nickel loss and desirable sludge properties. The optimum conditions for a multi-stage precipitation process were found to be at pH 3 and 55 ºC in the first stage followed by a second stage operated at pH 3 and 85 ºC. Using this precipitation procedure, as much as 95% iron and chromium together with above 80% aluminium can be removed; the level of nickel loss to the solid can be reduced to below 1%. The sludge showed a fast settling rate of 5.05 m/h with the addition of a cationic flocculant. Similar satisfactory results were also obtained when performing this multi-stage precipitation procedure on real leach solutions.The effect of water salinity on impurities removal and nickel losses was also examined due to variable nature of process water available in Western Australia to process nickel laterite during atmospheric leaching. This was achieved by conducting single-stage precipitation experiments in Fe(III)+Ni(II)+Al(III)+Cr(III) systems with various amounts of sodium chloride added. The presence of high concentration of salts resulted in higher removal efficiencies for iron, aluminium and chromium, and less nickel losses to the solids, particularly when the precipitation reactions were carried out at 85 ºC. XRD analysis of the residues confirmed that the poorly structural-ordered schwertmannite and/or ferrihydrite were the dominant phases. Natrojarosite (NaFe3(SO4)2(OH)6) can be detected when the precipitation reaction was conducted at pH 2 and 85 ºC from synthetic solution with high salinity.The presence of large amounts of poorly structural-ordered schwertmannite and ferrihydrite in the iron-rich residues complicates mineralogical identification using routine XRD technique. A comprehensive characterization was performed using a combination of several techniques that include selective Acidified Ammonium Oxalate (AAO) dissolution, differential XRD, SEM and FTIR spectroscopy. These techniques in combination allowed reliable mineralogical identification for samples containing high proportions of schwertmannite and ferrihydrite. The effects of foreign metallic cations on the crystallization, dissolution behaviour and surface sulphate coordination were investigated. The results suggested that the presence of goethite in the precipitates can be identified after removing the schwertmannite and/or ferrihydrite. Nickel, aluminium and chromium retarded the transformations of schwertmannite and/or ferrihydrite to goethite, but aluminium and chromium supressed the formation of 6-line ferrihydrite. Also, aluminium and chromium influenced the symmetry of the sulphate absorbed onto the iron-rich precipitates. The structural order of the phases became less pronounced with the presence of foreign metallic cations, particularly aluminium and chromium. Aluminium and chromium can strongly stabilize iron-rich precipitates making these resistant to leaching by AAO solution. FTIR analysis confirmed the presence of goethite in the bi-metallic precipitates and suggested that the sulphate is present to a greater extent in lower symmetry environments.

In recent years nickel is mostly produced from lateritic ore deposits such as nontronite, limonite, etc. Resource estimation is difficult for laterite deposits as they have a weak and heterogeneous form. 3D modeling software are rather suitable for deposits having tabular or vein type ores. In this study the most appropriate estimation technique for resource estimation of nickel laterite deposits was investigated. One of the known nickel laterite deposits in Turkey is located at Tü
rkmenç
ardagi - Gö
rdes region. Since the nickel (Ni) grade recovered from drilling studies seem to be very low, a reconciliation pit having dimensions of 40 m x 40 m x 15 m in x-y-z directions was planned by Meta Nikel Kobalt Mining Company (META), the license owner of the mine, to produce nickel ore. 13 core drilling and 13 reverse circulation drilling (RC) and 26 column samplings adjacent to each drillholes were located in this area. Those three sampling results were compared to each other and as well as the actual production values obtained from reconciliation pit. On the other side 3D computer modeling was also used to model the nickel resource in Tü
rkmenç
ardagi - Gö
rdes laterites. The results obtained from both inverse distance weighting and kriging methods were compared to the results of actual production to find out the applicability of 3D modeling to laterite deposits. Modeling results showed that Ni grade of the reconciliation pit in Tü
rkmenç
ardagi - Gö
rdes, considering 0.5% Ni cut-off value, by using drillholes data, inverse distance weighting method estimates 622 tonnes with 0.553% Ni and kriging method estimates 749 tonnes with 0.527% Ni. The actual production pit results provided 4,882 tonnes of nickel ore with 0.649% Ni grade. These results show that grade values seem to be acceptable but in terms of tonnage, there are significant differences between theoretical estimated values and production values.

With the dramatic growth of interest in nickel laterite resource exploitation, fueled by increasing demand and new processing technologies, the need for accurate resource delineation and careful mine planning becomes paramount. The traditional use of borehole grids to calculate mineral resources has proven to be neither sufficiently accurate nor cost-effective at many sites due to the complexity of tropical weathering profiles. Although an unconventional approach to laterite mine planning and resource delineation, emerging near-surface geophysical methods, particularly ground penetrating radar (GPR), hold tremendous potential for addressing project geology, resource delineation, and mine planning issues. GPR acquisition and processing techniques have been developed specifically for laterite applications and have been successfully utilized in the field. Preliminary test work has been performed at varied sites in Papua New Guinea, Indonesia, Venezuela, Guatemala, the Philippines, and Brazil. Two projects in New Caledonia were selected as comprehensive test sites for experimentation with GPR. Test surveys with GPR were performed at these sites to determine the effectiveness of the method in mapping the lateritic weathering profile. A description of the geology of various humid laterite deposits and the geophysical consequences of their complex nature is discussed, as well as the correlation of the acquired geophysical data to geological borehole information. Geophysics in general, and GPR in specific, has been proven to increase the database of knowledge with respect to project geology, as well as provide invaluable assistance in mine planning by high resolution imaging of the bedrock depth and texture as well as the accurate location of subsurface pinnacle structures at many sites.

A systematic research study was carried out in order to characterize the rheology of concentrated slurries prepared from eight nickel laterites. The experiments were carried out using a rotational viscometer, and the behavior of the laterites was evaluated in terms of the apparent viscosity and yield stress obtained through flow curve modeling. An attempt was made to correlate the results obtained for the laterite samples with data obtained for model single mineral systems as well as for model mixed mineral systems. In combination with detailed mineralogical characterization of the laterite samples, all the rheological results allowed a rheology-based laterite classification system to be proposed. Accordingly, the laterite samples gave the following responses: the SAPSIL samples (high-quartz) generally producedl ow yield stress values, the SAPFE samples (high-iron) were characterized by intermediate to high yield stress values, while the SAP samples (saprolite) gave the highest yield stress values. Interestingly, these dominant rheological responses of laterites could actually be predicted based on rheological tests carried out on model mineral suspensions (particularly goethite and quartz). Since the rheology of fine mineral suspensions is largely determined by the surface properties (surface charge) of the particles, a series of electro-acoustic measurements were also performed on model minerals and laterite samples to analyze the surface charge characteristics of the tested samples. It was demonstrated that the current electro-acoustic theory developed for single mineral systems can readily be used for modeling the behavior of mixed mineral systems. The modeling and experimental data agreed exceptionally well when constituent minerals were of the same surface charge under given pH. Clear but rather small deviations between experiment and theory were observed under conditions when the minerals were oppositely charged. This observation strongly suggested that inter-particle aggregation was most likely responsible for the observed discrepancies. Overall, the results of this thesis show that laterite slurries exhibit a wide range of rheological responses due to highly variable mineralogy, differences in particle size distributions, and difference in the surface properties of the many constituent minerals. It also shows that the surface properties of the minerals relates to rheology.

This thesis investigated the impact of secondary reactions; adsorption and precipitation, on nickel and cobalt recovery from bioleaching of nickel laterite ores. Although bioleaching is considered an ecologically and energy friendly technique to process laterite ores, low recoveries of target metals have inhibited its commercialisation. The secondary reactions occurrence in bioleaching of limonite, fresh and weathered saprolite ores was verified by performing chemical leaching tests using sulphuric and citric acid that would be generated by chemolithotrophs and heterotrophs respectively. The following leaching parameters were kept constant; pulp density at 10 (g/ml)%, particle size of the ore at 64 – 180 µm and stirring speed at 500 rpm. Metal loss was observed typically after 5 – 10 days and it increased as the acid to ore (A/O) ratio was reduced. At the lowest A/O ratio (0.1:1 (g/g)), up to 74% of nickel and 89% of cobalt were lost from target metals leached from saprolites while only 9% of nickel and negligible cobalt were lost from limonite. The mineralogical transformation of the residues resulting from the leaching process contributed to the alteration of the mineral isoelectric point (IEP) and consequently adsorption behaviour. The lower IEP in the saprolite residue (2.5 – 3.5) were attributed to the residual serpentine mineral (3.3) and quartz (2.2). While goethite (6.1 – 6.7) contributed to the higher IEP of the limonite residue (6.9). Systematic tests verified that adsorption can be overcome by maintaining the solution pH below the IEP of residues and adding complexing agent, 15 g/L of citric acid. A simulation of iron precipitation revealed little effect on metals recovery suggesting adsorption was as the primary secondary reaction affecting nickel laterite bioleaching. It is concluded that secondary reactions can have a huge impact on the metal recoveries and controlling its effect is critical in driving the commercialisation of the laterite bioleaching

An oxidative precipitation technique using potassium permanganate was explored for the removal of manganese from pregnant leach solution (PLS) generated from the pressure acid leaching (PAL) of nickel laterite ores. The results revealed that the right combination of pH and molar ratio is important in order to achieve maximum removal of manganese (II) with minimum nickel (II) and cobalt (II) losses.

Nickel and cobalt are key additives to metal alloys in modem industry. The largest worldwide nickel-cobalt resources occur in nickel laterite deposits that have formed during the chemical weathering of ultramafic rocks at the Earth's surface. At the Murrin Murrin mine in Western Australia, the nickel laterite deposits occur as laterally extensive, undulating blankets of mineralisation with strong vertical anisotropy, near normal nickel distributions, and positively skewed cobalt distributions. The mineral resources in nickel laterite deposits in Murrin Murrin are usually estimated from drilling and sampling on relatively wide-spaced drill patterns that are supported by local clusters of close-spaced sampling. The combination of deposit geometry and sampling configuration presents several estimation challenges for geostatistical resource estimation methods. In this thesis, close-spaced grade control drill sampling data from Murrin Murrin is used to quantify the estimation effectiveness of the wider spaced actual exploration pattern used to define the original resource, and an alternative cost saving stratified sampling pattern. Additionally, an unfolding of the laterite blanket by vertical data translation prior to nickel and cobalt grade estimation is tested for each exploration pattern. The unfolding essentially removes undulations in the laterite blanket prior to grade estimation by vertical translation of the sample data relative to a surface of high grade nickel-cobalt connectivity. Unfolding is expected to improve estimation accuracy in terms of grade and volume, as well as improve the quality of variography analyses. The stratified pattern is expected to give similar estimation accuracy to the actual exploration pattern. The effectiveness of ordinary kriging and full indicator kriging estimation algorithms from GSLIB software are compared for the combinations of in situ and unfolded cases of the actual sampling pattern used to define the deposit and an alternative stratified sampling pattern. For each combination, the estimates are made at the data locations of closed spaced grade control ‘reality'. The accuracy of each estimate is quantified by comparing the error, degree of bias and pseudo grade-volume relationships of the estimate to the 'reality' data. Additionally, the quality of exploration pattern variography is assessed against the grade continuity of the grade control information. Importantly, the main focus of these comparisons is on the correct estimation of local high grade nickel and cobalt resources that are preferentially processed in the early years mining. The results of comparisons between estimation methods and sample configuration combinations investigated show that the combination of unfolding and indicator kriging gives the best correspondence (in terms of grade and volume) of the various estimates to the grade control reality. The results of comparisons between the actual and the alternative stratified exploration pattern show that the cost saving' alternative pattern produces estimates similar to the actual exploration estimates.

A direct solvent extraction system was developed to recover nickel and cobalt from nitrate-based nickel laterite liquors, as opposed to traditional sulphate-based liquors. The development and optimisation of promising solvent systems is reported, along with a comparison of three potential options to inform recommendations for commercial applications. Finally, an investigation into the chemical stability of the solvent extraction reagents is detailed to determine if a nitrate-based process affected reagent stability compared to a sulphate-based process.

In light of fast depleting nickel sulfide ore reserves and increasing demand for nickel, the future of the nickel industry lies in the hydrometallurgical processing of the relatively abundant low-grade nickel laterite ores. The purification of the leach solutions, however, has proven difficult. Hydroxide and oxidative precipitation processes using a variety of reagents were developed for processing synthetic sulfate solutions simulating nickel laterite leach solutions and nickel and cobalt solutions following iron precipitation process.

The aim of this study was to extract nickel and cobalt from the lateritic nickel ores of Gö
rdes region by hydrometallurgical methods under the optimum conditions. Limonitic and nontronitic types of Gö
rdes lateritic nickel ores were used during experiments. Agitative and column leaching experiments at atmospheric pressure were conducted with various parameters
these were duration, temperature and initial sulfuric acid concentration of leach solution. It was shown that in agitative leaching, under the optimum conditions that were determined as 24 hours of leaching at 95°
C with initial sulfuric acid concentration of 192.1 g/L for nontronite and 240.1 g/L for limonite, nickel and cobalt extractions were 96.0% and 63.4% for nontronite
93.1% and 75.0% for limonite, respectively. Overall acid consumptions of ores were calculated as 669 kg H2SO4/ton dry ore for nontronitic type nickel ore and 714 kg H2SO4/ton dry ore for limonitic type nickel ore. Column leaching experiments also showed that nickel and cobalt could be extracted from both ore types by heap leaching. Nontronite type of laterite was found to be more suitable for column leaching by sulfuric acid. In column leaching, the calculated nickel and cobalt extractions were 83.9% and 55.2% for nontronite after 122 days of leaching with 100 g/L sulfuric acid concentration. Acid consumption of nontronite was found to be 462 kg H2SO4/ton dry ore.

Leaching is the most widely used process for extraction of nickel metal from lateritic ores. In this study, nickel extraction from Manisa-Gö
rdes region laterites by hydrochloric acid leaching is aimed. The mineralogical analysis of sample showed that hematite, goethite, dolomite, quartz and smectite are the main minerals in the ore. Attrition scrubbing, cycloning and magnetic separation with permroll were used as preconcentration processes but results were unsatisfactory. HCl leaching experiments were conducted both at room temperature and at elevated temperatures. The effects of various parameters such as leaching duration, particle size, concentration of HCl, pulp density, Cl- concentration and temperature on nickel recovery were examined. The results showed that under the optimised leaching conditions (particle size: 100 % -1 mm, HCl concentration: 3 N, leaching duration: 3 hours, leaching temperature: 100 oC, pulp density: 1/30 solid to liquid ratio by volume) it was possible to extract 87.26 % of nickel in the ore.

Nickel extracting industries have been facing challenges reflecting, inter alia, low recoveries of Ni and Co, high acid consumption and inadequate knowledge of dissolution kinetics. In oxic laterite, Ni is mostly associated with goethite. Consequently, for effective extraction of Ni and Co from oxic Ni laterites, a clear understanding of their chemistry, mineralogy and mechanism of sorption in goc;!thite during laterite ore formation is essential. The result from experiment of Ni sorption on goethite revealed that at surface loadings of 0.003 to 0.2 wt. % Ni, only the >Fe(OH)2Ni complex was needed to, fit the data whereas both >Fe(OH)2Ni and (FeOH)2Ni complexes were invoked to fit surface loadings of >0.2 to 0.35 wt. % Ni. At 0.75 wt. % Ni and above, however, the polynuclear complex (FeOH)3Nh was required to fit the data. Similar results were obtained for Co sorption and co-sorption of Ni and Co on goethite. EXAFS results support the existence of Ni surface precipitate or extended polynuclear Ni complex in the Ni-sorbed goethite and Ni laterite. In all the samples, Ni and Co dissolve incongruently with iron. However, there exist disparities in their dissolution and desorption kinetics as a function of aging and concentration, which indicate differences in chemical structure. Modelling of Ni laterite using PHREEQC and equilibrium constants obtained from EQLFOR provides information on the processes of Ni laterite formation and the zones of supergene Ni enrichment as well as prediction of the weathering profile. The solubility product (Ksp) of Ni or Co substituted goethite increases with increasing metal substitution. Similar results were obtained for bi-metal substituted goethite. In general, leaching with dilut~ 2.75 M aqua regia is best for Ni laterites formed at low loading as well as those formed via surface precipitation with Fe content less than 33 wt. % Fe whereas 2.75 M HCI is effective for those formed at high loading containing> 33 wt.% iron.

This study investigated the development of a novel bacterial fungal interaction (BFI) technology involving co-growth of sulphur oxidising bacteria, Acidithiobacillus thiooxidans, and fungi Aspergillus niger. The bacterial fungal consortia (BFC) have unique synergistic properties that could improve the conventional hydrometallurgical processing of Nickel (Ni) and Cobalt (Co) from low-grade Ni saprolitic laterites. The key challenge in this is the lack of research and understanding of their BFI as co-growth of mixed strains of such types have not been attempted before. To investigate the potential of BFC, four studies were undertaken. The first study focused on the effects of secondary reactions, and the second examined the efficacy of the mixed chemical leaching using sulphuric (H₂SO₄) and organic acids (citric, malic, and oxalic). The third study on fermentation explored BFI feasibility using abiotic and biotic tests. The last study utilised the biogenic acids from the BFI study for their leaching efficacy. The outcomes of the first and second studies established that mixed acids were able to improve the selectivity of Ni and Co against iron (Fe) and magnesium (Mg) and highlighted the importance of low pH (pH < 1.5) for high Ni and Co recoveries. The BFI study successfully achieved the formation of the mixed microbial consortia of A. thiooxidans and A. niger, but with some antagonistic behaviours observed. Despite this challenge, the BFC bioleaching using the mixed biogenic acids has shown the benefits of the BFI technology in leaching saprolitic Ni laterites. This bioleaching study expanded the current understanding using A. thiooxidans and A. niger with the novel BFI technology. In particular, the findings of glucose and S⁰ supplementation on the A. thiooxidans and A. niger, respectively, indicated a new technique to improve existing bioleaching processes and opened new opportunities to further optimise the BFI technology for future development and application.

The aim of this thesis study was to extract nickel and cobalt from Sivrihisar limonitic nickel laterite ore by high pressure acid leaching (HPAL) method under most economical operating parameters. Optimizing the conditions to yield a saleable quality mixed hydroxide product from the pregnant leach solution (PLS) was also investigated. To extract high amounts of nickel and cobalt from the laterite matrix
leaching duration, leaching temperature and sulfuric acid/ore ratio were studied at fixed conditions of -850 µ
limonitic ore particle size and 40% solids concentration. The Sivrihisar limonitic nickel laterite ore was found to be readily leachable. It was found that 95.4% of Ni and 91.5% of Co were extracted at the optimized conditions of 235oC, 0.23 acid/ore ratio in 60 minutes. The real pregnant leach solution produced at the optimized conditions of HPAL was purified in two iron removal stages under the determined optimum conditions. Nearly all of the Al and Cr were removed from the PLS in the two stages of iron removal. Then, nickel and cobalt were taken out from the PLS in the form of mixed hydroxide precipitates (MHP) in two stages. A MHP 1 product containing 33.41 wt.% Ni, 2.93 wt.% Co was obtained with a Mn contamination of 3.69 wt.% at the optimized conditions of pH=7, 50oC and 60 minutes. The MHP 1 product was also contaminated with Fe (2.83 wt.%) since it could not be completely removed from the PLS without the critical losses of nickel and cobalt during the two iron removal stages.

The processing of laterite ores for the recovery of nickel and cobalt has increased as the reserves of exploitable sulphide ores have become depleted. The pressure acid leach process (PAL) has become the preferred option for the treatment of laterite ores. Difficulties associated with the poor settling characteristics of the pulp in the counter current decantation (CCD) circuit after pressure leaching has resulted in as much as 10% of the soluble nickel and cobalt reporting to the tailings. The objective of this project is the development of an alternative processing step for the recovery of soluble nickel and cobalt from the PAL tailings using resin-in-pulp (RIP) technology. Commercially available chelating resins with the iminodiacetate functional group have been studied for their suitability for the adsorption of nickel and other metal ions from PAL tailings pulp. The Amberlite IRC 748 resin was found to be superior despite its lower nominal loading capacity. The resin with the highest nominal capacity was observed to adsorb less nickel as a result of the adsorption of greater amounts of the impurity ions. The equilibrium loading for nickel on the preferred resin was found to be similar from the ammonium and protonated form of the resin although the kinetics of adsorption is greater when the resin is initially in the ammonium form. A comprehensive study has been made of the equilibrium adsorption of several metal ions on the resin as a function of the equilibrium pH of the solution. A relatively simple model of the equilibrium adsorption which includes the effect of pH has been developed and the results compared with the experimental data obtained in the M2+/Na+/H+ system. The model which requires two equilibrium constants has been found to fairly well describe the experimental results. A study of the kinetics of the loading of nickel and cobalt from both solutions and pulp has shown that the rate can be described in terms of a first-order approach to equilibrium. The kinetic and equilibrium parameters were used to simulate the performance of a multi-stage counter current resin-in-pulp operation A semiquantitative study of the elution of the adsorbed metal ions from the resin by dilute sulphuric acid solutions was also undertaken. The technical feasibility of the RIP process for the recovery of nickel and cobalt from the PAL tailings has been successfully demonstrated in both laboratory and pilot-plant studies using a five-stage adsorption process. Important parameters such as the operating pH and the residence times of pulp and resin in each stage were identified through the batch test work coupled to the simulation procedure. The optimum pH for adsorption was found to be in the range 4 to 5 as this pH is high enough to maximise the adsorption of nickel and cobalt while preventing precipitation of nickel and cobalt as hydroxides from the pulp. A method for minimizing the competition from more strongly loaded ions such as iron(II) and chromium(III) which are present in the pulp was also developed in the initial laboratory phase of the project and utilized during the pilot operation. Problems associated with the preparation of the pulp preparation, elution of the loaded resin and control of the adsorption train were resolved during several pilot plant runs on site at a local PAL plant. These and other minor improvements and adjustments to the operating procedure culminated in a successful continuous run for several days during which the target recovery of 90% for nickel and 60% for cobalt was exceeded throughout the run.

The processing of laterite ores for the recovery of nickel and cobalt has increased as the reserves of exploitable sulphide ores have become depleted. The pressure acid leach process (PAL) has become the preferred option for the treatment of laterite ores. Difficulties associated with the poor settling characteristics of the pulp in the counter current decantation (CCD) circuit after pressure leaching has resulted in as much as 10% of the soluble nickel and cobalt reporting to the tailings. The objective of this project is the development of an alternative processing step for the recovery of soluble nickel and cobalt from the PAL tailings using resin-in-pulp (RIP) technology. Commercially available chelating resins with the iminodiacetate functional group have been studied for their suitability for the adsorption of nickel and other metal ions from PAL tailings pulp. The Amberlite IRC 748 resin was found to be superior despite its lower nominal loading capacity. The resin with the highest nominal capacity was observed to adsorb less nickel as a result of the adsorption of greater amounts of the impurity ions. The equilibrium loading for nickel on the preferred resin was found to be similar from the ammonium and protonated form of the resin although the kinetics of adsorption is greater when the resin is initially in the ammonium form. A comprehensive study has been made of the equilibrium adsorption of several metal ions on the resin as a function of the equilibrium pH of the solution. A relatively simple model of the equilibrium adsorption which includes the effect of pH has been developed and the results compared with the experimental data obtained in the M2+/Na+/H+ system. The model which requires two equilibrium constants has been found to fairly well describe the experimental results. A study of the kinetics of the loading of nickel and cobalt from both solutions and pulp has shown that the rate can be described in terms of a first-order approach to equilibrium. The kinetic and equilibrium parameters were used to simulate the performance of a multi-stage counter current resin-in-pulp operation A semiquantitative study of the elution of the adsorbed metal ions from the resin by dilute sulphuric acid solutions was also undertaken. The technical feasibility of the RIP process for the recovery of nickel and cobalt from the PAL tailings has been successfully demonstrated in both laboratory and pilot-plant studies using a five-stage adsorption process. Important parameters such as the operating pH and the residence times of pulp and resin in each stage were identified through the batch test work coupled to the simulation procedure. The optimum pH for adsorption was found to be in the range 4 to 5 as this pH is high enough to maximise the adsorption of nickel and cobalt while preventing precipitation of nickel and cobalt as hydroxides from the pulp. A method for minimizing the competition from more strongly loaded ions such as iron(II) and chromium(III) which are present in the pulp was also developed in the initial laboratory phase of the project and utilized during the pilot operation. Problems associated with the preparation of the pulp preparation, elution of the loaded resin and control of the adsorption train were resolved during several pilot plant runs on site at a local PAL plant. These and other minor improvements and adjustments to the operating procedure culminated in a successful continuous run for several days during which the target recovery of 90% for nickel and 60% for cobalt was exceeded throughout the run.

Approximately 70% of the western world's known nickel reserves are contained in laterite ores, but only 30% of the world's nickel production comes from these ores. This is due to the lack of economically viable technology to extract the nickel from these ores. However, recent advances in pressure acid leaching technology have resulted in new commercial attempts to extract nickel and its valuable by-product, cobalt, from laterite ores. The commissioning of three nickel laterite projects in Western Australia in the late 1990s represents the first of these new generation nickel operations, with several other projects; in Australia and overseas, in various stages of development. Unfortunately, several technical issues have hindered full production in these new refineries. Some of these problems are directly attributable to the mixer-settler contactors used in the solvent extraction process. This has highlighted a need to develop alternative contactors for industrial use. Electrostatic Pseudo Liquid Membrane (ESPLIM) is an alternative, novel technique to conduct the solvent extraction process. It combines the basic principles of solvent extraction, liquid membrane and electrostatic dispersion into a simple, compact reactor that utilises many advantages of each technique. The aim of this study w as to develop a method of extracting and separating cobalt from an acidic nickel laterite leach solution using ESPLIM. Bench scale tests using synthetic and actual leach solutions have shown that: the design and construction materials of the baffle plate and electrodes have a significant effect on the performance of the reactor; an AC power supply provided better droplet dispersion than a DC power supply; an increase in the applied electric field strength above a critical value resulted in a decrease in the aqueous droplet size and an increase in residence tune.These effects increased the extraction efficiency and the concentration of the loaded strip solution. However, further increases in applied electric field strength decreased efficiency due to excessive levels of swelling and leakage; the known extraction isotherms for cobalt and nickel apply in the ESPLIM technique; salts of soluble organic acids influence extraction efficiency by changing the aqueous pH and interfacial tension; the use of ammonia was found to be effective as a replacement for salts of soluble organic acids; the ESPLIM reactor can cope with large changes in the flow rates of both feed and strip solutions. However, an increase in the feed flow rate should be accompanied by a relative increase in the ship flow rate to maintain high extraction efficiencies; the baffle design has a significant impact on the levels of swelling and leakage; provided the electrostatic field strength is maintained and flow rates are increased proportionately to the size of the reactor, no significant scale-up issues were observed, indicating that the data generated in bench scale studies could be applied to plant scale contactors. The optimum conditions, devised as a result of this investigation, to extract cobalt from an acidic nickel laterite leach solution using the ESPLIM technique are as follows: an applied electric field strength of 5.5 kV/cm. a raffinate pH of 5.5, a solvent containing 10% Cyanex 272 with 5% TBP in Solvent HF diluent, a feed to strip flow ratio of approximately 5 and a 1 M H[subscript]2S0[subscript]4 strip solution. At these conditions, almost complete cobalt extraction is achieved after only two extraction stages. A comparable extraction using conventional mixer-settlers could only be achieved after five stages.

ABSTRACT HIGH PRESSURE ACID LEACHING OF TURKISH LATERITES Kaya, Serif M.Sc., Department of Metallurgical and Materials Engineering Supervisor: Prof. Dr. Yavuz A. Topkaya January 2011, 91 pages The aim of this thesis study was to investigate and find the most cost effective way of extracting nickel and cobalt into the pregnant leach solution (PLS) from Gö
rdes lateritic nickel and cobalt ore by means of sulphuric acid leaching under high temperature and high pressure conditions.The high pressure acid leach (HPAL) experiments were conducted with nontronitic and limonitic types of Gö
rdes lateritic nickel ore, respectively. Leaching experiments of nontronite ore have shown that almost all of the nickel and cobalt contained in the nontronitic ore were easily extracted into the (PLS). Therefore, the rest of the experiments were concentrated on difficult to leach limonitic sample when compared with the nontronitic one, and higher nickel and cobalt extractions were aimed to be obtained. By taking economic and technical considerations into account, the basic (HPAL) process parameters for the limonitic sample were optimized as
leaching at 255 °
C with a particle size of 100% -850 &mu
with 0.30 sulphuric acid to ore weight ratio in 1 hour of leaching duration. The experiments were conducted with 30% solids ratio and it was found that 87.3% of nickel and 88.8% of cobalt present in the limonitic ore could be extracted into the pregnant leach solution. Nevertheless, these results were found to be below the desired values. Therefore, the possible reasons of this behavior were investigated and the presence of hematite mineral in the limonitic ore was found to be the most probable one. Therefore, in order to dissolve the nickel and cobalt present in the hematite mineral, the additions of HCl, ferrous ions, cuprous ions and sulphur were tried, respectively and they were found to be beneficial in order to increase the degree of nickel and cobalt extractions.

Approximately 70% of the western world's known nickel reserves are contained in laterite ores, but only 30% of the world's nickel production comes from these ores. This is due to the lack of economically viable technology to extract the nickel from these ores. However, recent advances in pressure acid leaching technology have resulted in new commercial attempts to extract nickel and its valuable by-product, cobalt, from laterite ores. The commissioning of three nickel laterite projects in Western Australia in the late 1990s represents the first of these new generation nickel operations, with several other projects; in Australia and overseas, in various stages of development. Unfortunately, several technical issues have hindered full production in these new refineries. Some of these problems are directly attributable to the mixer-settler contactors used in the solvent extraction process. This has highlighted a need to develop alternative contactors for industrial use. Electrostatic Pseudo Liquid Membrane (ESPLIM) is an alternative, novel technique to conduct the solvent extraction process. It combines the basic principles of solvent extraction, liquid membrane and electrostatic dispersion into a simple, compact reactor that utilises many advantages of each technique. The aim of this study w as to develop a method of extracting and separating cobalt from an acidic nickel laterite leach solution using ESPLIM. Bench scale tests using synthetic and actual leach solutions have shown that: the design and construction materials of the baffle plate and electrodes have a significant effect on the performance of the reactor; an AC power supply provided better droplet dispersion than a DC power supply; an increase in the applied electric field strength above a critical value resulted in a decrease in the aqueous droplet size and an increase in residence tune.
These effects increased the extraction efficiency and the concentration of the loaded strip solution. However, further increases in applied electric field strength decreased efficiency due to excessive levels of swelling and leakage; the known extraction isotherms for cobalt and nickel apply in the ESPLIM technique; salts of soluble organic acids influence extraction efficiency by changing the aqueous pH and interfacial tension; the use of ammonia was found to be effective as a replacement for salts of soluble organic acids; the ESPLIM reactor can cope with large changes in the flow rates of both feed and strip solutions. However, an increase in the feed flow rate should be accompanied by a relative increase in the ship flow rate to maintain high extraction efficiencies; the baffle design has a significant impact on the levels of swelling and leakage; provided the electrostatic field strength is maintained and flow rates are increased proportionately to the size of the reactor, no significant scale-up issues were observed, indicating that the data generated in bench scale studies could be applied to plant scale contactors. The optimum conditions, devised as a result of this investigation, to extract cobalt from an acidic nickel laterite leach solution using the ESPLIM technique are as follows: an applied electric field strength of 5.5 kV/cm. a raffinate pH of 5.5, a solvent containing 10% Cyanex 272 with 5% TBP in Solvent HF diluent, a feed to strip flow ratio of approximately 5 and a 1 M H[subscript]2S0[subscript]4 strip solution. At these conditions, almost complete cobalt extraction is achieved after only two extraction stages. A comparable extraction using conventional mixer-settlers could only be achieved after five stages.

This thesis focuses on development of new regents which are suitable for recovering nickel, cobalt and copper from laterite leach solutions, specifically focusing on reagent requirements for novel base metal flowsheets developed by Anglo American. The work aims to design reagents which can extract nickel(II), cobalt(II) and copper(II) from a highly acidic aqueous sulfate solutions whilst showing selectivity over iron(II) and iron(III). Chapter 1 reviews current extractive metallurgy processes for separating and concentrating metals in laterite ores and describes new flowsheets proposed by Anglo American. Chapter 2 considers whether single reagent molecules with sets of tridentate donor atoms can generate sufficiently stable nickel(II) complexes to allow selective extraction of nickel from an aqueous sulfate solution. The salicylaldimines, 3-X-4-alkyl-6-(quinolin-8-imino)phenol, 3-X-4-alkyl-6-(2- methoxyphenylimino)phenol and 3-X-4-alkyl-6-(2-thiomethoxyphenylimino)phenol (alkyl = tert-butyl or tert-octyl; X = H, Br or NO2), were selected for study. The synthesis and characterisation of these proligands and their nickel(II) complexes are reported. XRD structures of Br-substituted salicylaldimines and their nickel(II) complexes are compared and discussed. The 4-tert-octylsalicylaldimines were used to extract nickel(II) from an aqueous sulfate solution with a pH > 2.8 and 3- nitro-4-tert-octyl-6-(quinolin-8-imino)phenol was found to be the strongest extractant in the series with a pH0.5 of 3.5. Computational studies of an analogous series of salicylaldimine proligands in the gas phase calculated the formation energies of their nickel(II) complexes and the predicted trend follows the experimentally determined solvent extraction results. Chapter 3 investigates modifications to phenolic pyrazoles, which are known copper(II) extractants. A series of 6-X-4-methyl-2-(5-alkyl-1H-pyrazol-3-yl)-phenols (X = H, OMe, Br and NO2) was synthesised and characterised. Varying the 6-X-substituent of the phenolic pyrazole altered the strength of copper extraction and 6-nitro-4-methyl-2-(5-(1,3,5-tri-methyl-pentyl)-1H-pyrazol-3-yl)-phenol was found to be the strongest extractant in the series. Analysis of XRD structures of related phenolic pyrazoles and their copper(II) complexes showed evidence of inter- and intra-molecular hydrogen bonding. Computational DFT studies in the gas phase were carried out to calculate the formation energies of analogous phenolic pyrazole copper complexes. The predicted order of these energies followed the same trend shown by experimental solvent extraction studies. The double deprotonation of 4-tert-butyl-(pyrazol-3-yl)-phenol at high pH forms a polynuclear complex in the organic phase with a copper(II) to ligand ratio of 1:1, thereby increasing the mass transport efficiency of copper by the reagent. The synthesis and characterisation of the [Cu16(4-tert-butyl-(pyrazol-3-yl)- phenolate)16(EtOH)4(H2O)2] wheel complex was carried out to demonstrate how such polynuclear copper(II) complexes could be formed under solvent extraction conditions. Chapter 4 explores the solvent extraction of nickel(II) and cobalt(II) by novel combinations of neutral nitrogen-donor heterocyclic ligands with organic acids, such as dinonylnaphthelenesulfonic acid (DNNSAH). The synthesis and characterisation of 2,6-bis(5-alkyl-1H-pyrazol-3-yl)-pyridine, 2-(5- alkyl-1H-pyrazol-3-yl)-pyridine and 5,5'-alkyl-3,3'-bi-1H-pyrazole (alkyl = tert-butyl or nonyl) and their nickel(II) complexes were reported. Also reported are synthesis and 6-N-alkyl-2-(2-pyridinyl)- benzothiazole (alkyl = n-butyl or n-decyl) and 2-(1-Isopropyl-benzimidazol-2-yl)-pyridine. The extraction of nickel(II) from highly acidic mixed metal aqueous sulfate solutions by some of these ligands was studied. These synergistic mixtures demonstrated remarkable strength and selectivity for nickel(II), and cobalt(II) over iron(II). XRD structures of nickel(II) complexes of 2,6-bis(5-tert-butyl- 1H-pyrazol-3-yl)-pyridine, 2-(5-tert-butyl-1H-pyrazol-3-yl)-pyridine and 5,5'-tert-butyl-3,3'-bi-1Hpyrazole with sulfonates or perchlorates as ion-pairs have intermolecular hydrogen bonding interactions between the inner-sphere ligands and the counterions.

ENGLISH ABSTRACT: Leaching of nickel laterite was conducted with a solution of ammonia and ammonium carbonate in a closed vessel. The vessel used in this study was designed to leach and perform solid-liquid separation at the same time. For solid-liquid separation, stainless steel sintered metal filter media were used. The sintered metal filter medium was selected for its high strength to withstand pressure, chemical resistance to caustic solution and back flushing properties. Optimum leaching conditions were determined by varying temperature, ammonia concentration, ammonium carbonate concentration and oxygen pressure. After leaching and filtration, the pH of the leach liquor was measured and samples were analyzed for dissolved metals (Ni, Fe and Co) using atomic absorption spectrophotometry. The most significant variable effect on leaching of nickel was the ammonia concentration. The maximum dissolution of nickel from the unroasted ore was 11.90% at 4 M NH3, 100oC, 2 M (NH4)2CO3 and 2 bar O2 pressure. Optimization from the leaching data was done using response profiling and desirability in Statistica software. Optimum leaching conditions were determined to be 3 M NH3, 2 M (NH4)2CO2, 100oC and 2 bar O2 pressure. The mineralogy of the ore before and after leaching was studied to understand why nickel extraction from unroasted ore was poor. XRF analysis of solids after leaching showed that iron, silicon, and magnesium remained the same. The only metal which showed significant decrease from solids was nickel. XRD analysis of solids after and before leaching showed that most mineral phases present in the ore are not affected by the leaching solution. SEM with EDS detection was used to determine nickel distribution within the ore. The results showed that nickel is mostly associated with iron. The iron is surrounded by magnesium and silicon. Silicate minerals do not react with ammonia and ammonium carbonate solution. From filtration experiments, the filtration differential pressure had no significant effect on the filtration rate. An average filtration rate of 0.29±0.07 ml/min.cm2 was obtained. The filtration rate from these experiments was very low. The main reason was due to quick pore clogging of sintered metals. Pore clogging was found to be mainly on the surface of the filter medium. Laterites have been found to have low permeability due a lot of clay present in the ore. Rheological studies on this ore showed that the ore has shear thickening behavior. However, a very clear filtrate was obtained. After each leach and filtration experiment, the sintered metals was unblocked by back flushing with water and air. Back flushing was successful because all 18 experiments were carried out using the same sintered filter medium. The effect of roasting the ore prior to leaching was investigated using optimum conditions obtained when leaching the unroasted ore. There was a slight improvement in nickel extraction when the ore was roasted. The average percentage extraction of nickel from 3 experimental runs was 19.25%±0.19 at 100oC, 3M NH3, 2M (NH4)2CO3, and 5 bar oxygen pressure. Some part of nickel in the ore was unextractable due to association of nickel with recrystallized silicate minerals in the reduced ore. Roasting improved permeability of the ore. The filtration rate improved significantly after roasting the ore. The average filtration rate was 2.60±0.05 ml/min.cm2. Dissolution kinetics of the unroasted and roasted saprolitic laterite were investigated with regard to the effects of temperature, ammonia concentration, ammonium carbonate concentration, and oxygen pressure. For the unroasted ore, it was found that dissolution rate and degree of nickel extraction increases with increasing temperature. Increase in ammonia concentration improves the degree of nickel extraction. Nevertheless, nickel extraction does not depend entirely on ammonia concentration because even when ammonia concentration is high and ammonium carbonate concentration is zero nickel extraction is low. An increase in ammonium carbonate concentration also increases the degree of nickel extraction. Ammonium carbonate is critical for the extraction, since ammonium ions in the solution prevent hydrolysis of the nickel ammine complex. Oxygen did not have a significant effect on the degree of nickel extraction. The leaching of nickel laterite was found to be a two stage leaching process. In the first stage, the dissolution of nickel is faster but after 15 minutes, the reaction rate is reduced. The reaction rate is reduced by inert minerals which host nickel. These minerals contain iron magnesium and silicon. The fast dissolution of nickel in the first stage represents leaching of free nickel in the ore. The data for the second stage of leaching was analyzed by the shrinking core model, and the results suggested that the dissolution rate is controlled by mixture kinetics (ash layer diffusion and surface reaction control). The activation energy for the dissolution reaction was calculated as 56.5 KJ/mol. The reaction order with respect to ammonia and ammonium carbonate were determined to be 0.3 and 0.26 respectively. For the roasted ore, the highest degree of nickel extraction was obtained at 60oC, 3M NH3, 2M (NH4)2CO3, and 5 bar oxygen pressure. The percentage extraction under these conditions was 28.7%. Temperature did not have a significant effect on the leaching rate. An increase in NH3 and (NH4)2CO3 increased the final extraction of nickel but did not have any effect on leaching rate in the first stage of leaching. In the absence of ammonium carbonate, nickel extraction is almost zero. The experimental data did not give linear fit to the shrinking core models investigated for the unroasted ore. The reason for this could be due to the sampling time interval which was too far apart, or the leaching behavior of roasted nickel is complicated and cannot explained by shrinking core model alone. Leaching experiments demonstrate that for a high degree metal extraction and improved reaction kinetics with ammonia and ammonium carbonate, the solution temperature should be high (>100oC) for the unroasted ore. In order to leach at high temperature with ammonia and ammonium carbonate a closed vessel is required to prevent reagent loses. The reaction kinetics showed that the reaction is controlled mostly by ash layer diffusion; this indicates that a low degree of nickel extraction in the unroasted saprolitic laterite is due to inert minerals (ash layer) which host nickel within the ore. In order to obtain a high degree of nickel extraction, the ore needs to be roasted under reducing conditions. Roasting conditions need to be carefully controlled to ensure high dissolution of nickel. In fact optimum roasting conditions which will give maximum dissolution of nickel, must be determined before working with the bulk of the ore.
AFRIKAANSE OPSOMMING: Logingstoetse van saprolitiese lateriet met 'n oplossing van ammonia en ammonium karbonaat is gedoen in 'n druk houer. Die logingsvat vir hierdie studie is ontwikkel om die loging sowel as die vloeistof – vastestof skeiding te doen. Gesinterde metaal filter medium was gebruik vir die vloeistof – vastestof skeiding aangesien dit die volgende eienskappe vertoon; die vermoë om druk te weerstaan, die chemiese weerstand teen bytsoda oplossing, asook voordelige terugspoel eienskappe. Optimum loogkondisies is bepaal deur die temperatuur, ammoniak konsentrasie, ammonium karbonaat konsentrasie, en suurstof druk te varieer. Na loging en filtrasie is die pH van die loogvloeistof gemeet en monsters is deur atoom absorpsie spektrofotometrie geanaliseer vir opgeloste metale (Ni, Fe en Co). Die veranderlike wat die grootste effek op die loging van nikkel gehad het was die ammoniak konsentrasie. Die maksimum herwinning van nikkel van uit ongeroosterde erts was 11.9 % by 4 M NH3, 100 oC, 2 M (NH4)2CO3 en 2 bar O2 druk. Optimisering van die loogdata is gedoen deur die respons profiel te analiseer met Statistica sagteware. Optimum loogkondisies was bepaal as 3 M NH3, 2 M (NH4)2CO2, 100 oC en 2 bar O2 druk. Die mineralogie van die erts voor en na loging is bestudeer om te bepaal waarom die nikel opbrengs van ongeroosterde erts so laag was. XRF analise van die vastestof na loging het gewys dat yster, silikon en magnesium nie deur loging affekteer is nie. Slegs nikkel het 'n merkwaardige afname getoon. XRD analsiese van die vastestof voor en na loging wys dat die meeste mineraal fases teenwoordig in die erts nie deur die loogoplossing affekteer is nie. SEM met EDS deteksie is gebruik om die nikkel verspreiding in die erts te bepaal. Die resultate wys dat nikkel meestal met yster assosieer. Die yster is omring deur magnesium en silikon. Silikaat minerale reageer nie met ammoniak en ammonium karbonaat oplossing nie. In filtrasie eksperimente is daar gevind dat die filtrasie differensiële druk geen noemenswaardige effek op die filtrasie tempo gehad het nie. Die gemiddelde filtrasietempo was 0.29+0.07 ml/min.cm2. Die filtrasie tempo van hierdie eksperimente was baie laag, hoofsaaklik as gevolg van blokkasie van porieë van die sinter metaal filter medium. Dit is gevind dat blokkasie van porieë hoofsaaklik op die oppervlak van die filter medium plaasvind. Lateriedes toon 'n lae deurlaatbaarheid as gevolg van die erts se hoë klei inhoud. Rheologiese studies op hierdie erts wys dat die erts skuif verdikking (“shear thickening”) gedrag vertoon. 'n Baie helder filtraat is egter verkry. Die gesinterde metale is na elke loog en filtrasie eksperiment skoongemaak deur terugspoeling met water en lug. Hierdie procedure was suksesvol, aangesien al 18 eksperimente met dieselfde filter medium uitgevoer is. Die effek van erts roostering voor loging is ondersoek by die optimum kondisies wat verkry was vir die loging van ongeroosterde erts. Nikkel ekstraksie het effens verbeter met geroosterde erts. Die gemiddelde persentasie ekstraksie van nikkel van drie eksperimentele lopies was 19.25 % + 0.19 by 100 oC, 3 M NH3, 2 M (NH4)2CO3, en 5 bar suurstofdruk. 'n Gedeelte van die nikkel in die erts was onherwinbaar as gevolg van die assosiasie van nikkel met her-gekristaliseerde sillikaat-minerale in die gereduseerde erts. Die porositeit van die erts is verbeter deur dit te rooster. Die filtrasie tempo het merkwaardig verbeter nadat die erts gerooster is. Die gemiddelde filtrasie tempo was 2.6+0.05 ml/min.cm2. Kinetika vir die oplossing van ongeroosterde en geroosterde saprolitiese lateriet is ondersoek, met in ag geneem die effekte van temperatuur, ammonia konsentrasie, ammonium karbonaat konsentrasie en suurstofdruk. Vir ongeroosterde erts is gevind dat die oplossingstempo en graad van nikkel ekstraksie toeneem met toenemende temperatuur. Toename in ammoniak konsentrasie lei tot 'n toename in nikkel ekstraksie, maar nikkel ekstraksie is nie alleenlik afhanklik van ammoniak nie. 'n Toename in ammonium karbonaat konsentrasie lei ook tot 'n toename in nikkel ekstraksie. Ammonium karbonaat is krities vir die ekstraksie, aangesien ammonium ione in die oplossing die hidrolise van die nikkel-amien kompleks verhoed. Suurstof het nie 'n merkwaardige effek op die totale nikkel ekstraksie gehad nie. Vir die bepaling van reaksie kinetika is 100˚C gebruik as die logingstemperatuur. Die loging van saprolitiese nikkel lateriet vind in twee stadia plaas. In die eerste fase is die oplossing van nikkel vinnig, maar na 15 minute neem die reaksietempo af. Die reaksietempo word verlaag deur inerte minerale wat teenwoordig is in die nikkel erts. Hierdie minerale bevat yster, magnesium en silikon. Die vinnige oplossing van nikkel in die eerste fase verteenwoordig die loging van vry nikkel in die erts. Die data vir die tweede stadium is geanaliseer deur die krimpende kern model, en die resultate dui aan dat die oplossingstempo deur 'n gemengde meganisme beheer word (as laag diffusie en oppervlak reaksie beheer). Die aktiveringsengergie vir die oplossingsreaksie was bereken as 56.5 kJ/mol. Die reaksieorde ten opsigte van ammoniak en ammonium karbonaat is onderskeidelik bepaal as 0.3 en 0.26. Die hoogste graad van nikkel ekstraksie vir die geroosterde erts is verkry by 60oC, 3 M NH3, 2 M (NH4)2CO3, en 5 bar O2 druk. Die persentasie ekstraksie by hierdie kondisies was 28.7 %. Temperatuur het nie 'n merkwaardige effek op loogtempo gehad nie. 'n Toename in NH3 en (NH4)2CO3 het die graad van nikkel ekstraksie laat toeneem, maar het nie enige effek op die loogtempo gehad nie. In die afwesigheid van ammonium karbonaat het byna geen nikkel ekstraksie plaasgevind nie. Die eksperimentele data het nie 'n lineêre passing vir die krimpende kern model soos vir die ongeroosterde erts ondersoek gegee nie. Die rede hiervoor is dat die monsternemings interval te groot was, of dat die logings karakteristiek van geroosterde nikel gekompliseerd is en nie alleen deur die krimpende kern model voorspel kan word nie. Logings eksperimente wys dat die temperatuur hoog moet wees (> 100 oC) om 'n hoë graad van nikkel ekstraksie te verkry met die ongeroosterde erts. 'n Geslote reaktor word benodig om by 'n hoë temperatuur met ammoniak en ammonium karbonaat te loog om reagens verliese te verhoed. Die reaksie kinetika word grootliks deur aslaag diffusie beheer. Hieruit kan gesien word dat 'n lae graad van nikkel ekstraksie uit die ongeroosterde saprolitiese lateriet die gevolg is van nie-reaktiewe minerale (aslaag) waarin die nikkel binne die erts bevat word. Om 'n hoë graad van nikkel ekstraksie te verkry moet die erts onder reduserende kondisies gerooster word. Rooster kondisies moet versigtig beheer word om hoë oplossing van nikkel te verseker. Optimum rooster kondisies om maksimum nikkel oplossing te verkry, moet bepaal word voordat daar met groter hoeveelhede erts gewerk kan word.

The processing of laterite ores for the recovery of nickel and cobalt has increased as the reserves of exploitable sulphide ores have become depleted. The pressure acid leach process (PAL) has become the preferred option for the treatment of laterite ores. Difficulties associated with the poor settling characteristics of the pulp in the counter current decantation (CCD) circuit after pressure leaching has resulted in as much as 10% of the soluble nickel and cobalt reporting to the tailings. The objective of this project is the development of an alternative processing step for the recovery of soluble nickel and cobalt from the PAL tailings using resin-in-pulp (RIP) technology. Commercially available chelating resins with the iminodiacetate functional group have been studied for their suitability for the adsorption of nickel and other metal ions from PAL tailings pulp. The Amberlite IRC 748 resin was found to be superior despite its lower nominal loading capacity. The resin with the highest nominal capacity was observed to adsorb less nickel as a result of the adsorption of greater amounts of the impurity ions. The equilibrium loading for nickel on the preferred resin was found to be similar from the ammonium and protonated form of the resin although the kinetics of adsorption is greater when the resin is initially in the ammonium form. A comprehensive study has been made of the equilibrium adsorption of several metal ions on the resin as a function of the equilibrium pH of the solution. A relatively simple model of the equilibrium adsorption which includes the effect of pH has been developed ii and the results compared with the experimental data obtained in the M2+/Na+/H+ system. The model which requires two equilibrium constants has been found to fairly well describe the experimental results. A study of the kinetics of the loading of nickel and cobalt from both solutions and pulp has shown that the rate can be described in terms of a first-order approach to equilibrium. The kinetic and equilibrium parameters were used to simulate the performance of a multi-stage counter current resin-in-pulp operation A semiquantitative study of the elution of the adsorbed metal ions from the resin by dilute sulphuric acid solutions was also undertaken. The technical feasibility of the RIP process for the recovery of nickel and cobalt from the PAL tailings has been successfully demonstrated in both laboratory and pilot-plant studies using a five-stage adsorption process. Important parameters such as the operating pH and the residence times of pulp and resin in each stage were identified through the batch test work coupled to the simulation procedure. The optimum pH for adsorption was found to be in the range 4 to 5 as this pH is high enough to maximise the adsorption of nickel and cobalt while preventing precipitation of nickel and cobalt as hydroxides from the pulp. A method for minimizing the competition from more strongly loaded ions such as iron(II) and chromium(III) which are present in the pulp was also developed in the initial laboratory phase of the project and utilized during the pilot operation. Problems associated with the preparation of the pulp preparation, elution of the loaded resin and control of the adsorption train were resolved during several pilot plant runs on site at a local PAL plant. These and other minor improvements and adjustments to the operating procedure culminated in a successful continuous run for several days during which the target recovery of 90% for nickel and 60% for cobalt was exceeded throughout the run.

Le gisement nickélifère latéritique de Nouvelle-Calédonie, développé au toit de la Nappe des Péridotites, représente près de 20% des ressources mondiales en nickel. Afin de mieux comprendre la formation de ce gisement, notre étude, portant sur le massif de Koniambo, se singularise par la volonté de ne pas se focaliser uniquement sur la zone minéralisée. L’approche employée a combiné : i) l’analyse de la déformation interne de l’ensemble du massif, ii) la caractérisation isotopique de deux sous-produits supposés de l’altération supergène que ont les veines de quartz et les veines de magnésite, iii) la modélisation 3D du gisement nickélifère, basée sur les données de plus de 6000 forages de subsurface et sur l’étude d’affleurements ponctuels au sein de la zone minéralisée. L’évolution spatiale et temporelle de la déformation associée à la serpentinisation est décrite au travers des ~800 m d’épaisseur structurale du massif de Koniambo. La partie supérieure du massif, très fracturée, préserve la marque d’au moins deux événements précoces de déformation. Le premier est associé au réseau de failles à antigorite et le second au réseau de failles à serpentine polygonale. La semelle serpentineuse, épaisse de ~200 m, est constituée de brèches et mylonites et enregistre un cisaillement tangentiel diffus associé à la serpentine polygonale et à la magnésite. La semelle représente ainsi un niveau de décollement majeur en base de nappe. Entre la semelle et le haut du massif, un niveau intermédiaire est identifié, caractérisé par la présence de zones de cisaillement plurimétriques probablement connectées à la semelle. La caractérisation 3D de la distribution du nickelau sein du niveau saprolitique, à l’échelle du gisement comme à l’échelle de l’affleurement, permetde mettre en évidence l’existence de processus impliquant une redistribution non pas seulement verticale, comme il est classiquement admis, mais aussi latérale, mécanique ou associée à des fluides, à l’origine d’importants enrichissements locaux. L’analyse isotopique des veines de quartz associées au minerai garniéritique met en évidence les conditions d’hydrothermalisme de basse température associées à leur formation. La caractérisation structurale et isotopique (couplage ''isotopes stables'' et ''clumped isotope thermometry'') des veines de magnésite situées dans la semelle serpentineuse permet de documenter leur caractère syn-tectonique et la nature météorique et de basse température du fluide dont elles sont issues. Ceci nous amène à proposer que la tectonique active a pu faciliter l’infiltration de l’eau météorique impliquée dans le processus de latérisation depuis le sommet jusqu’à la base de la nappe
The New Caledonia nickel laterite ore deposit, developed at the top of the Peridotite Nappe, hosts about 20% of the nickel resources worldwide. In order to better understand the formation of this eposit, our study, focusing on the Koniambo Massif, is not restricted to the ore zone but concerned with the whole peridotite pile. Our approach combined: i) the analysis of the internal deformation of the massif, ii) the isotopic characterization of quartz and magnesite veins which are suspected to represent by-products of the laterization process, iii) the 3D modelling of the lateritenickel ore deposit, based on a dataset of ~6000 subsurface boreholes and the study of some outcrops located into the mineralized area. The spatial and temporal evolution of the deformation associated with serpentinization is described across the ~800 m-thick rock pile of the Koniambo Massif. The upper part of the massif is densely faulted and preserves the record of two early deformation events. The first one is associated with synantigorite faults and the second one with syn-polygonal serpentine faults. The ~200m-thick serpentine sole is composed of breccias and mylonites and records pervasive tangential shearing associated with polygonal serpentine and magnesite. Thus, the serpentine sole represents a major décollement at the base of the nappe. Between the sole and the upper part of the massif, anintermediate structural level is identified, characterized by the presence of plurimetric shear zones that probably merge with the sole.The 3D characterization of the nickel distribution in the saprolite level, at both deposit and outcrop scales, gives evidence for processes implying not only vertical (as commonly assumed) but also lateral nickel redistribution. This lateral transport ismechanical or associated with fluids and leads to significant local enrichments. The isotopic characterization of the quartz veins associated with garnieritic ore shows that they formed under low temperature hydrothermal conditions. The structural and isotopic (coupling “stable isotope” and “clumped isotope thermometry”) characterization of the magnesite veins located at the serpentine sole shows that they are syn-tectonic and derived from low temperature meteoric water. As a result, we propose that active tectonics has enhanced the infiltration of the meteoric waters involved in the laterization process down to the base of the nappe

Níquel laterítico compõe 70% das reservas disponíveis do metal. A produção de níquel a partir dessas reservas representa 40%, dos quais é possível extrair também cobre e cobalto. Isso ocorre devido ao alto teor de impurezas, principalmente ferro. Com a crescente demanda desses metais, o uso das reservas de lateritas de níquel passou a ser mais profundamente investigado, assim como o desenvolvimento de processos hidrometalúrgicos. Nesse caso, o íon férrico prejudica a recuperação do níquel e do cobalto, uma vez que em trocas iônicas esse metal compete na ocupação dos sítios catiônicos. Em processos de extração por solvente um efeito semelhante é observado. Além disso, durante a eventual precipitação do ferro ocorre a coprecipitação. Assim, para a troca iônica, o íon ferroso pode ser menos prejudicial do que o férrico. O presente trabalho teve por objetivo o estudo do processo de redução do íon férrico em solução aquosa, e também a posterior obtenção de cobalto e níquel por meio de resinas quelantes. Estudou-se o processo de redução do íon férrico e o efeito na adsorção de metais por troca iônica. Os ensaios de redução química do íon férrico em solução foram estudados utilizando ditionito de sódio, metabissulfito de sódio e sulfito de sódio. Os ensaios com os agentes redutores ditionito e metabissulfito de sódio foram feitos em São Paulo, e os ensaios com o sulfito de sódio foram feitos na The University of British Columbia. Os agentes redutores foram adicionados na solução monoelementar de ferro para redução do potencial redox. As variáveis potencial redox, entre 860mV e 240mV; pH, entre 0,5 e 3,5; temperatura, entre 25°C e 60°C; e tempo, entre 30min e 96 horas, foram estudadas em frascos erlenmeyer sob agitação constante. Analisou-se, então, a redução do íon férrico em solução multielementar de níquel laterítico. Nos ensaios de troca iônica, realizados em batelada e em coluna, utilizou-se a resina quelante Lewatit TP 207, de grupo funcional iminodiacetato, e a resina Lewatit TP220, de grupo funcional bis-picolilamina. Três soluções foram estudadas: uma preparada com Fe(III), outra com Fe(II) e a terceira com Fe(III) após o processo de pré-redução. Os ensaios em batelada foram realizados com a utilização de frascos erlenmeyer, sob agitação constante, com 100mL de solução para 1mL de resina. Estudou-se o efeito do pH, entre 0,5 e 3,5; tempo, entre 30min e 480min; e temperatura, entre 25°C e 60°C. Nos ensaios em sistema contínuo, as três soluções foram alimentadas em colunas de vidro preenchidas com resina. A solução foi alimentada com bombas peristálticas a vazão constante. Para eluição das colunas, ácido sulfúrico 1mol.L-1 foi alimentado na coluna com utilização de bomba peristáltica. A segunda parte do trabalho, realizado na The University of British Columbia, foi o estudo do uso de sulfito de sódio no processo de pré-redução. Foram estudadas duas resinas: a Lewatit TP 207, seletiva para cobre; e a Lewatit TP 220, seletiva para níquel e cobalto. O sulfito de sódio foi adicionado na solução para redução do potencial, em frascos, e colocado sob agitação constante. Após reação, as soluções foram colocadas em contato com a resina quelante, e ficaram em agitação. Os ensaios em batelada foram realizados e o efeito do pH estudado entre 0,5 e 3,5. No processo em coluna, a Coluna 1, preenchida com a resina Lewatit TP 207, foi utilizada para remoção do cobre; e a solução de saída foi alimentada na Coluna 2, preenchida com a resina Lewatit TP 220. Para a eluição, foram estudados os ácidos clorídricos e sulfúricos em duas diferentes concentrações, 1mol.L-1 e 2mol.L-1. Hidróxido de sódio foi utilizado para remover o ferro na solução obtida na saída da Coluna 2. A separação do cobalto da solução foi feita utilizando a técnica de extração por solventes (Cyanex 272 20%), estudando o efeito do pH, 4,0 e 5,0, e da temperatura, 25°C e 65°C. Os resultados mostraram que a redução do íon férrico utilizando ditionito de sódio foi de 100% na solução monoelementar e de 70% na multielementar contendo os outros metais. Nos ensaios de troca iônica em batelada, utilizando a resina TP 207, 62% do cobre foi adsorvido na solução após processo de pré-redução. Para solução com Fe(II), a adsorção de cobre foi de 61%; e para solução com Fe(III), 49%. Nos ensaios de troca iônica após pré-redução do ferro com sulfito de sódio, a adsorção do cobre foi de 69% em pH 2,0 pela resina TP 207. A resina TP 220 foi mais seletiva para níquel e cobalto em pH 2,0, em que as adsorções destes metais foram 32,5% e 69%, respectivamente. Nos ensaios em coluna, a Coluna 1 foi utilizada para remoção de cobre, porém houve perda de 17% de níquel e 7% de cobalto. Na alimentação da Coluna 2, verificou-se que 98% do níquel e 84% do cobalto foram adsorvidos. A solução obtida da Coluna 2 teve concentração de 618mg.L-1 de ferro, 13231mg.L-1 de níquel e 179mg.L-1 de cobalto. A remoção de 100% do ferro foi possível em pH 4,0. Para separação do cobalto da solução rica em níquel, utilizou-se a extração por solventes com o Cyanex 272 20% em querosene, no qual 99% do cobalto foi separado da solução a 65°C e pH 5,0, sem perda de níquel. Para estudos futuros, a remoção do cobre no início do processo pode ser explorada com a utilização de outras técnicas, a fim de se evitarem perdas de níquel e cobalto. Outro ponto que pode vir a ser explorado é a máxima utilização das colunas de troca iônica nas mesmas condições deste trabalho - solução com Fe(III), com Fe(II) e após processo de pré-redução - sobretudo em escala piloto, para estudar o efeito do estado de oxidação do ferro em um possível envenenamento da resina.
Nickel laterite ores represent 70% of the available metal reserves. The nickel production from these reserves represents 40%, where it is also possible extract copper and cobalt. It occurs due to the high impurities content, mainly iron. With the growing demand of these metals, the use of nickel laterite reserves became more deeply investigated, as well as hydrometallurgical process development. In this case, the ferric iron difficult the nickel and cobalt recovery, once in ion exchange processes this metal competes in the occupation of the cationic sites. In solvent extraction processes the same effect is observed. Besides that, during the eventual iron precipitation there is a co-precipitation. Therefore, for ion exchange, ferrous iron may be less damaging than ferric iron. The aim of this work was to study the reducing process of ferric iron in aqueous solution, and also the subsequent obtaining of cobalt and nickel through chelating resins. It was studied the reducing process of ferric iron and the effect of it in metals adsorption by ion exchange. Experiments of chemical reduction of ferric iron in solution were studied using sodium dithionite, sodium metabisulfite and sodium sulfite. Experiments with reducing agents sodium dithionite and metabisulfite were performed in São Paulo, and experiments with sodium sulfite were performed in The University of British Columbia. Reducing agents were added in ferric iron mono-elementary solution to decrease the redox potential. The variables potential redox, between 860mV and 240mV; pH, between 0,5 and 3,5; temperature, between 25°C e 60°C; and time, between 30min and 96 hours were studied in erlenmeyer flasks under constant stirring. Then, analyzed ferric iron reduction in multielementary solution of nickel laterite. In ion exchange experiments, performed in batch and column, it was used chelating resin Lewatit TP 207, with iminodiacetate functional group, and resin Lewatit TP 220, with bis-picolylamine functional group. Three solutions were studied: prepared with Fe(III), other with Fe(III) and the third with Fe(III) after pre-reducing process. Experiments in batch system were performed using erlenmeyer flasks, under constant stirring, with 100mL of solution to 1mL of resin. It was studied the effect of pH, between 0,5 and 3,5, time, between 30min and 480min, and temperature, between 25°C e 60°C. In experiments in continuous system, the three solutions were fed in glass columns filled with resin. The solution was fed using peristaltic pumps at constant flow rate. For column elution, sulfuric acid 1mol.L-1 was fed to the column using peristaltic pumps. The second part of this work, performed at The University of British Columbia, was the study of sodium sulfite application at prereducing process. It was studied two resins: Lewatit TP 207, selective for copper, and Lewatit TP 220, selective for nickel and cobalt. Sodium sulfite was added to the solution to decrease the potential, in flasks and it was placed under constant stirring. After reaction, the solution was placed in contact to the chelating resin, which was placed under stirring. Batch experiments were performed, and the effect of pH was studied between 0,5 and 3,5. In column process, the Column 1, filled with Lewatit TP 207, was used for copper removal, and output solution was feed in Column 2, filled with Lewatit TP 220. For the elution, it was studied sulfuric and hydrochloric acids in two different concentrations, 1mol.L-1 e 2mol.L-1. Sodium hydroxide was used for iron removal from solution obtained in Column 2 output. Cobalt separation was performed using solvent extraction technique (Cyanex 272 20%), studying the effect of pH, 4,0 and 5,0, and temperature, 25°C e 65°C. Results shows that ferric iron reduction using sodium dithionite was 100% in mono-elementary solution and 70% in multi-elementary solution with other metals. In ion exchange experiments performed in batch using resin TP 207, 62% of copper was adsorbed by the resin after pre-reducing process. For solution with Fe(II), the copper adsorption was 61%, and for solution with Fe(III), 49%. In ion exchange experiments after pre-reducing process using sodium sulfite, the copper adsorption was 69% at pH 2,0 by the resin TP 207. The resin TP 220 was more selective for nickel and cobalt at pH 2,0, where these metals adsorptions were 32,5% and 69%, respectively. In experiments performed in column, the Column 1 was used for copper removal, however there were losses of nickel (17%) and cobalt (7%). In the feeding of Column 2, it was found that 98% of nickel and 84% of cobalt were adsorbed. Solution obtained in Column 2 had concentration of iron 618mg.L-1, nickel was 13231mg.L-1 and cobalt 179mg.L-1. The iron removal was 100% at pH 4,0. For cobalt separation in nickel-rich solution, it was used the solvent extraction with Cyanex 272 20% with kerosene, where 99% of cobalt was separated from solution at 65°C and pH 5,0, without nickel loss. For future studies, the copper removal in the beginning of the process can be explored using other techniques, in order to avoid nickel and cobalt losses. Another point that can be explored is the maximum use of ion exchange columns in the same conditions of this work - solution with Fe(III), with Fe(II) and after the pre-reducing process - mostly on a pilot scale, to study the effect of iron oxidation state on possible resin poisoning.

La Nouvelle-Calédonie détient d’importantes réserves de nickel latéritique et est devenue, en 2017, le cinquième producteur mondial de Ni. Ces dépôts sont habituellement considérés comme résultant d’altération latéritique intense de la péridotite, qui constitue la principale source de nickel. Ainsi, le principal modèle conceptuel de la formation des minerais de nickel latéritique en Nouvelle-Calédonie est un modèle per descensum où la plupart des éléments (Mg, Ni et Si) ont été lessivés depuis la surface, en particulier lors du développement du sol latéritique. Le nickel est ensuite reprécipité, soit dans la goethite de la latérite fine, soit au niveau de la saprolite, sous forme de goethite et de silicates Mg-Ni, dont des talc-like ou kérolite. Les observations minéralogiques et structurales récentes ainsi que les données minières ont cependant mis en évidence de nombreux types d’hétérogénéités dans les concentrations, et la distribution des porteurs de Ni. Comprendre les facteurs la mobilité de cet élément, ses mécanismes de piégeage ainsi que les paramètres chimiques et hydrodynamiques à l’origine de ce piégeage, est essentiel afin de prévoir la distribution du nickel dans les profils latéritiques en Nouvelle-Calédonie, et constitue l’objectif de cette thèse. Ce travail est basé sur le développement (i) d’un modèle 1D s’intéressant en particulier au comportement géochimique du nickel lors de l’altération de l’ophiolite, sa comparaison avec les observations in situ et une compréhension détaillée de la mobilité des éléments traces pendant le processus, et (ii) d’un modèle 2D hydro-géochimique couplé avec l’hydrodynamique complexe des profils latéritiques, améliorant ainsi la connaissance du contrôle structural sur la redistribution et la minéralisation du nickel. Tandis que les simulations 1D permettent de mieux comprendre les aspects chimiques contrôlant les processus de rétention du nickel au sein d’un profil, le modèle 2D se révèle être un outil puissant pour la compréhension de la formation des dépôts locaux les plus riches en nickel. Les résultats du modèle 2D montrent une remobilisation du nickel depuis les horizons supérieurs puis sa reprécipitation sous forme de silicates dans la saprolite. Le nickel remobilisé provient principalement de la zone saprolitique à cause de la dissolution des silicates de nickel formés précédemment ainsi que de l’olivine résiduelle de cette zone. Ce modèle a également révélé que l’horizon latéritique (et en particulier les oxy- hydroxydes de nickel) avait un faible impact dans la remobilisation du nickel. L’infiltration latérale de l’eau contenant le nickel dissout issu des formations surincombantes est à l’origine de la formation des zones les plus riches dans les parties inférieures du profil. Cette redistribution est entièrement contrôlée par l’hydrodynamique locale, la topographie ainsi que l’orientation et la position des fractures. Les modèles présentés permettent d’expliquer les processus de formation des minerais de nickel latéritique saprolitique, améliorant ainsi la compréhension des paramètres contrôlant la mobilité des éléments traces dans un environnement ultramafique. Ceci donne une nouvelle clé de distribution du nickel dans les profils actuels, qui peut devenir un outil pour la prospection minière, et la recherche de nouvelles ressources exploitables
New Caledonia hosts significant lateritic nickel reserves, and presently became the fifth largest Ni producer in the world. These deposits are generally thought to be closely as- sociated with the intense chemical and mechanical weathering of peridotite bedrock that is a principal source of nickel. Thus, the main ore genesis model for Ni ores in New Caledonia is based on a single per descensum model where most elements (Mg, Ni, and Si) are leached from the surface, particularly, during lateritic soil development. Nickel is then concentrated either in the fine-grained laterite where goethite is the main Ni bearer, the so-called ’lateritic ore’, or below the laterites, in the saprolite level, where nickel occurs as goethite and several types of Mg-Ni silicates, in particular kerolite. Recent mineralogical and structural observations together with mining data have revealed a lot of different types of heterogeneities associated with the distribution and mineralogy of Ni bearing minerals. Therefore, in depth investigations of Ni mobility, its retardation processes along with its governing chemical and hydrodynamic parameters are of big importance for understanding and subsequent prediction of Ni distribution in profiles of New Caledonia. Such an investigation is an objective of the present work. The concept is based on the development of i) a powerful 1D model with particular emphasis on Ni geochemical behavior during ophiolite weathering, its comparison with in situ observations, and detailed understanding of trace elements mobility, and ii) 2D hydro-geochemical model coupled with complex hydrodynamics, that would additionally provide new insight into the structural control on Ni redistribution and mineralization. While the 1D simulations provide a remarkable result for understanding the chemical features that drive Ni retention processes in a profile, 2D model appears to be a powerful tool for understanding how local Ni-enrichments may form. The results of this model show the reactivation of Ni from upper horizons and its concentration in neo-formed silicates in bottom of the saprolite. The reactivated Ni comes mostly from the saprolite horizon due to the redissolution of previously formed Ni-bearing silicates and still persisting in this olivine zone. Modeling has revealed minor contribution of the laterite horizon (Ni-oxi-hydroxides) into the Ni remobilization. The lateral infiltration of water with remobilized Ni from areas such as topographic highs to downstream slope areas leads to the formation of richest deposits in this lower part of profile. The manner of redistribution is fully governed by the topographic slopes, orientation and position of the fractures. Presented models appear to be of importance in attempt of explanation of Ni mineralization processes, revealing the main keys to understanding the control of trace elements mobility in ultramafic environment. The latter gives new insights into the Ni distribution in present day profiles and, therefore, may greatly help in mineral prospecting and forecasting the distribution of future resources

Nickel laterites account for ?40 % of global nickel production and contain 60 % of the world's total land based nickel resources. Despite the importance of these deposits published studies, detailing their morphology and formation processes are relatively few and the interaction of variables responsible for the formation of different nickel laterites are poorly understood. To better understand the process of nickel laterite formation, the Caldag and Bitincke paleodeposits were studied and their geological history established. The Caldag laterite, western Turkey, formed by intense chemical weathering of a serpentinite protolith in a region with a high water table and relatively low topography, resulting in the formation of an oxide deposit. In addition silica precipitation is common in the upper horizons of the deposit, where it creates an indurated layer, protecting the deposit from erosion. The Bitincke Nickel laterite, Albania is composed of two distinct zones characterized by silicate nickel and iron oxide phases. At Bitincke laterite formation and variations in thickness were controlled by the interaction between topography, faulting and protolith fracture density. The morphological and geochemical study of the Caldag and Bitincke paleodeposits indicates that there is a complex interplay between structures, topography, water table height and climate. Therefore nickel laterite deposits developed on very similar protoliths can form deposits with distinct and different characteristics. By comparing climatic data for regions where suitable ultramafic rocks are exposed and defining the climatic conditions favourable for the formation of nickel laterite deposits, the optimum temperatures and precipitation rates for nickel laterite development can be identified. A compilation of paleoclimatic data from western Turkey and Albania allows for the optimum periods of laterite formation within these regions to be established. Calculation of temperatures of formation from goethite oxygen and hydrogen isotopes could provide additional data on paleoclimaitc conditions. However due to the heterogeneity of laterite deposits and an extended weathering history, data gained from goethite appears not to provide a robust measure of paleotemperature. The study of the Caldag and Bitincke deposits combined with the analysis of the optimum conditions for nickel laterite formation has shown that there are four main factors which effect laterite formation: 1) Exposure of a suitable protolith; 2) Optimum climatic condition; 3) Geological variables; 4) Environment of preservation. Knowledge of these variables will assist in future laterite studies and will improve predictability of the location of new deposits.

The objective of this thesis study is to recover nickel and cobalt at maximum efficiency from column leach liquor of lateritic nickel ores existing in Gö
rdes region of Manisa by performing various hydrometallurgical methods under the optimum conditions. This column leach solution of nontronite type lateritic nickel ore was initially neutralized and purified from its basic impurities by a two stage iron removal process under the optimum conditions determined experimentally. Then, nickel and cobalt were precipitated in the form of mixed hydroxide precipitate from the purified leach solution by a two stage precipitation method called &ldquo
MHP&rdquo
and a manganese removal process was carried out also under the optimum conditions determined. By decreasing Mn concentration with this process to an acceptable level yielding at most 10% Mn in hydroxide precipitate, it was possible to produce a qualified MHP product suitable to the current marketing and standard conditions. As a result of this thesis study, the experiments conducted showed that by recycle leaching with sulfuric acid about 81% of Ni and 63% of Co in the lateritic nickel ore (9.72 kg Ni / ton of ore and 0.28 kg Co / ton of ore) could be extracted as mixed hydroxide precipitate by MHP method. The MHP product contains 41.9% Ni, 1.0% Co, 2.3% Mn, 0.06% Al, 1.5% Mg, 0.02% Fe, 0.01% Cr, 0.25% Zn, 0.03% Cu and 4.73% S.

The purpose of this study was to investigate the process optimization of combined high pressure acid leaching (HPAL) and mixed hydroxide precipitation (MHP) route for the extraction of nickel and cobalt from Ç
aldag lateritic nickel ore. In order to extract nickel and cobalt values into pregnant leach solution (PLS), several process parameters of HPAL including acid load, temperature, leaching duration and particle size were investigated in comparative manner at constant solid concentration and agitation speed. After HPAL trials, it has been found that more than one combination of parameters offered higher than 90% extraction efficiencies for both nickel and cobalt. Among them, 0.325 kg/kg acid load, 250°
C, 1 hour duration and 100% -1 mm particle size was selected as the optimum conditions with 94.1% Ni and 94.0% Co extractions. A stock of PLS was prepared under the stated conditions that was treated by downstream operations in order to obtain MHP. Initially by two-stage iron removal of downstream operations major impurities iron, chromium and aluminum were nearly completely removed with acceptable nickel and cobalt losses from PLS. Then, the nickel and cobalt were precipitated by two-stage mixed hydroxide precipitation. In the first step of MHP, the optimum conditions were chosen as pH=7.10, 60°
C and 1 hour duration. The intermediate product obtained at these conditions contained 44.3% Ni, 3.01% Co with 3.06% Mn contamination. In summary, it was found that Ç
aldag nickel laterite ore was readily leachable under HPAL conditions and PLS obtained was easily treatable in order to produce saleable MHP.

An investigation of the segregation process applied to Western Australian nickel laterites, with a particular focus on the relatively unique nontronite zone, was carried out. The main aim was to provide a better understanding of the process through study of its underlying fundamental aspects. The results revealed the key to achieving high recoveries is promoting segregation over the parallel in-situ reduction process, with the mineralogy of the ore playing a key role.

A fundamental study was undertaken in order to establish the mechanisms of the leaching of pre-reduced nickel laterites in ammonia-ammonium carbonate solution. Although the process has undergone various improvements since it was first introduced, the total recoveries are still relatively low, averaging at 80% for nickel and 45-50% for cobalt. The lack of sound fundamental information regarding the mechanisms and the kinetics of the dissolution of nickel and cobalt from iron-alloy grains produced by the reduction roasting of lateritic ores is seen as the main obstacle to establishing the reasons for the lack of adequate recovery and to defining alternative processing strategies which would lead to improved extraction and better process optimisation. Based on fimdamental electrochemical studies and bench scale leaching tests, as well as on-site measurements at an industrial plant where this process is applied, the work presented in the thesis introduces significant new evidence and sheds more light on the understanding of the mechanism of the dissolution process and on the reasons for the low extractions of nickel and cobalt. It has been established that the oxidative dissolution of the iron-alloy grains formed during the reduction roasting takes place primarily via a reaction involving reduction of dissolved cobalt (111) to cobalt (11), and also that the reduction of water is not a significant component of the reactions involved in the dissolution process. Open-circuit potential measurements with various metals and iron-alloys selected to model the reduced material in various solutions which simulated the leaching conditions were also conducted and revealed that passivation takes place during the leaching process. This brings to light a possible new reason for the low recoveries of nickel and cobalt which has not been previously considered. In addition, a kinetic study was conducted, in which the dissolution rates for the various metals, iron-alloys and solutions were measured as a function of time, and the results of which shed more light on the development of the process of passivation. The passivation itself is attributed to formation of iron-oxide on the surface of the dissolving iron-alloy grains, which restricts the transfer of electrons to the reduced metal and brings the oxidative leaching reaction to an end. It has been shown that the passivation can occur in two ways. On the one hand, particularly high concentration of dispersed and dissolved oxygen in the leaching reactors causes passivation by overcoming the limiting current density for the oxidation of iron to divalent iron ions and taking the potential to the region where the direct oxidation to trivalent ions becomes favourable resulting in the formation of an iron-oxide film on the surface. On the other hand, in normally aerated solutions, the passivation of the dissolving ironalloy grains occurs due to the formation of a cobalt and nickel sulphide layer, as a byproduct of the reduction of thiosulphate on the metal surface, which in turn gradually shrinks the area available for the oxidation of iron, again leading to a situation where the oxidising agents present in the solution under standard aerated conditions become sufficient to shift the mixed potential to the region where the iron-oxide forming reaction becomes favourable. The presence of thiosulphate has a decisive role in the second type of passivation. What is more, besides preventing further dissolution of the nickel and cobalt locked in the iron-alloy matrix, the loss of nickel and cobalt by precipitation in the presence of thiosulphate can further reduce the recovery of these metals. For this reason, a method was developed for the oxidation and removal of thiosulphate fkom the actual plant liquor.

A fundamental study was undertaken in order to establish the mechanisms of the leaching of pre-reduced nickel laterites in ammonia-ammonium carbonate solution. Although the process has undergone various improvements since it was first introduced, the total recoveries are still relatively low, averaging at 80% for nickel and 45-50% for cobalt. The lack of sound fundamental information regarding the mechanisms and the kinetics of the dissolution of nickel and cobalt from iron-alloy grains produced by the reduction roasting of lateritic ores is seen as the main obstacle to establishing the reasons for the lack of adequate recovery and to defining alternative processing strategies which would lead to improved extraction and better process optimisation. Based on fimdamental electrochemical studies and bench scale leaching tests, as well as on-site measurements at an industrial plant where this process is applied, the work presented in the thesis introduces significant new evidence and sheds more light on the understanding of the mechanism of the dissolution process and on the reasons for the low extractions of nickel and cobalt. It has been established that the oxidative dissolution of the iron-alloy grains formed during the reduction roasting takes place primarily via a reaction involving reduction of dissolved cobalt (111) to cobalt (11), and also that the reduction of water is not a significant component of the reactions involved in the dissolution process. Open-circuit potential measurements with various metals and iron-alloys selected to model the reduced material in various solutions which simulated the leaching conditions were also conducted and revealed that passivation takes place during the leaching process. This brings to light a possible new reason for the low recoveries of nickel and cobalt which has not been previously considered. In addition, a kinetic study was conducted, in which the dissolution rates for the various metals, iron-alloys and solutions were measured as a function of time, and the results of which shed more light on the development of the process of passivation. The passivation itself is attributed to formation of iron-oxide on the surface of the dissolving iron-alloy grains, which restricts the transfer of electrons to the reduced metal and brings the oxidative leaching reaction to an end. It has been shown that the passivation can occur in two ways. On the one hand, particularly high concentration of dispersed and dissolved oxygen in the leaching reactors causes passivation by overcoming the limiting current density for the oxidation of iron to divalent iron ions and taking the potential to the region where the direct oxidation to trivalent ions becomes favourable resulting in the formation of an iron-oxide film on the surface. On the other hand, in normally aerated solutions, the passivation of the dissolving ironalloy grains occurs due to the formation of a cobalt and nickel sulphide layer, as a byproduct of the reduction of thiosulphate on the metal surface, which in turn gradually shrinks the area available for the oxidation of iron, again leading to a situation where the oxidising agents present in the solution under standard aerated conditions become sufficient to shift the mixed potential to the region where the iron-oxide forming reaction becomes favourable. The presence of thiosulphate has a decisive role in the second type of passivation. What is more, besides preventing further dissolution of the nickel and cobalt locked in the iron-alloy matrix, the loss of nickel and cobalt by precipitation in the presence of thiosulphate can further reduce the recovery of these metals. For this reason, a method was developed for the oxidation and removal of thiosulphate fkom the actual plant liquor.

In this study, an attempt has been made to hydrometallurgical extraction of cobalt and nickel by atmospheric pressure sulphuric acid leaching and a pug-roast-leach process using two stage roasting for lateritic ore. The ore used in the study was obtained from Ç
aldag Lateritic Ore, Manisa, Turkey. The metal contents of the ore are 2.1 % Ni, 0.12 % Co, 32.45 % Fe, 1.01 % Mn, 2.58 % Cr, 0.78 % Mg and 1.01 % Al. The reserve of lateritic ore deposit is approximately 40 million tonnes. In the study, first sulphuric acid leaching was applied at atmospheric pressure for leaching the Ç
aldag lateritic ore. The effect of various parameters, such as leaching time, leaching temperature, particle size, pulp density and acid strength on Ni and Co extractions were determined. By leaching at 80oC for 40 wt % H2SO4 addition of ore, 1/3 pulp density, Ni and Co extractions were found 44.49 % and 53.03 % respectively, yielded a pregnant solution containing 3.11 g/L Ni and 0.12 g/L Co. But the result of atmospheric pressure sulphuric acid leaching was considered insufficient from the recovery point of view. In the pug-roast-leach process, which is consisted of a two stage roasting followed by water leaching, decomposition temperature differences of sulphates of cobalt, nickel and iron are exploited. In this process, amount of acid, sulphatization and decomposition temperature, sulphatization and decomposition time, leaching temperature and time, solid/liquid ratio, and the effect of water addition during pugging were optimized. Under the optimized conditions (sulphuric acid: 25 wt % of ore
moisture: 20 wt % of ore
sulphatization temperature: 450oC
sulphatization time: 30 minutes
decomposition temperature: 700oC
decomposition time: 60 minutes
leaching temperature: 70oC
leaching time: 30 minutes and solid-liquid ratio: 1/4 by weight), Co and Ni extractions were found 91.4 and 84.4 percent, respectively. A pregnant solution containing 3.084 g/L Ni and 0.185 g/L Co was obtained. These results were considered sufficient for the leaching of lateritic nickel ores.

Nickel silicate laterite deposits developed on ultra-mafic rocks are similar in many general respects but they vary considerably in detail. The mineralogy of these surficial deposits is very complex and difficult to determine because of the fine grained nature and solid solution characteristics of the hydrous secondary minerals and because many of the phases are actually mineraloids that are poorly ordered or amorphous. To try some new approaches toward clarification of these phases, 24 samples from New Caledonia and Puerto Rico ranging from the ophiolite-ultramafic olivine-pyroxene-chromite-serpentine substrate rocks upward through intermediate phases of weathering to the final oxide -hydroxide iron cap phase were analyzed with the infrared spectrophotometer (IR -10) and with the automated X –ray diffractometer. Four limonite samples were also mineralogically analyzed. Goethite, secondary quartz, cryptomelane, hematite, chromite, talc, thuringite, and garnierite have been identified in various samples as weathering profile products.

Reasons for the variable acid leaching performance of the nickel laterite ore samples from Western Australia were investigated using numerous microstructural analytical techniques. Cementation of goethite-silica/silicate was identified as the main factor inhibiting acid leaching. Another major outcome of the research was significant improvement of quantitative phase analysis of turbostratically disordered nontronite by developing phase models with peak shape descriptions in X-ray diffraction analysis.

Ni laterites are considered worthy targets for critical metals (CM) exploration as rare earth elements (REE), Sc and platinum group elements (PGE) can be concentrated during weathering as a result of residual and secondary enrichment. In this investigation geochemical and mineralogical data of CM from two different nickel laterite types (i) from the Moa Bay mining area in Cuba (oxide type) and (ii) from the Falcondo mining area in the Dominican Republic (hydrous Mg silicate type) are presented. Emphasis is given on examining their potential to accumulate CM and on processes involved. Results show that CM are concentrated towards the surface in specific zones: (i) REE in clay minerals rich horizons and within zones composed of secondary Mn oxide(s) (ii) Sc within zones rich in secondary Fe and Mn bearing oxide(s) and (iii) PGE in zones with high concentrations of residual chromian spinel and secondary Fe and Mn bearing oxide(s) at upper levels of the Ni laterite profiles. Concentration factors involve (i) residual enrichment by intense weathering (ii) mobilization of CM during changing Eh and pH conditions with subsequent reprecipitation at favourable geochemical barriers (iii) interactions between biosphere and limonitic soils at highest levels of the profile (critical zone) with involved neoformation processes. Total contents of CM in both Ni laterite types are low when compared with conventional CM ore deposits but are of economic significance as CM have to be seen as cost inexpensive by-products during the Ni (+Co) production. Innovative extraction methods currently under development are believed to boost the significance of Ni laterites as future unconventional CM ore deposits. Two Ni laterite profiles from the Falcondo mining area have been compared for their platinum group element (PGE) geochemistry and mineralogy. One profile (Loma Peguera) is characterized by PGE-enriched (up to 3.5 ppm total PGE) chromitite bodies incorporated within the saprolite, whereas the second profile is chromitite-free (Loma Caribe). Total PGE contents of both profiles slightly increase from parent rocks (36 and 30 ppb, respectively) to saprolite (-50 ppb) and reach highest levels within the limonite zone (640 and 264 ppb, respectively). Chondrite-normalized PGE patterns of saprolite and limonite reveal rather flat shapes with positive peaks of Ru and Pd. Three types of platinum group minerals (PGM) were found by using an innovative hydroseparation technique: (i) primary PGM inclusions in fresh Cr-spinel (laurite and bowieite), (ii) secondary PGM (e.g., Ru-Fe-Os-Ir compounds) from weathering of preexisting PGM (e.g., serpentinization and/or laterization), and (iii) PGM precipitated after PGE mobilization within the laterite (neoformation). Results provide evidence that (i) PGM occurrence and PGE enrichment in the laterite profiles is independent of chromitite incorporation; (ii) PGE enrichment is residual on the profile scale; and (iii) PGE are mobile on a local scale leading to in situ growth of PGM within limonite, probably by bioreduction and/or electrochemical metal accretion. Free grains of PGM with delicate morphologies were discovered in limonite hosted chromitite samples (“floating chromitites”) from highest levels in the Falcondo Ni laterite deposit (Dominican Republic). Textural and chemical evidence obtained via SEM and EMP analysis points to a multistage formation: (i) primary PGM formation at magmatic stage; (ii) transformation to highly porous secondary Os-Ru PGM during serpentinization; (iii) neoformation of Ir-Fe-Ni-(Pt) mineral phases during early stages of lateritization; (iv) neoformation of Pt-(Ir) mineral phases within the critical zone of the profile resulting in nugget shaped accumulation of rounded particulates during late stages of lateritization. The observation of accumulations of most likely biogenic mediated in situ growth of Pt rich nanoparticles in supergene environments could help to explain (i) why Pt bearing nuggets are the most abundant PGM found in surface environments, (ii) why Pt nuggets from placer deposits generally surpass the grain sizes of Pt grains found in parent rocks by several orders of magnitude (few micrometers vs. several millimeters) and (iii) how anthropogenic PGE contamination may affect our biosphere. Osmium chromitite, saprolite and limonite (Falcondo mining area), suggest that serpentinization of the Loma Caribe peridotite has not significantly affected the Re-Os system in Os-rich PGM. This is noted by the fact, that primary PGM formed at magmatic stage and secondary Ru-Os-Mg- isotope characteristics from primary and secondary PGM, separated from Si PGM formed due desulphurization of primary PGM with significant incorporation of Mg silicates, have almost identical Os isotope characteristics, typical of the mantle. However, the Re-Os system can be significantly disturbed during stages of lateritization when porous secondary PGM react with Fe-rich fluids, thus forming hexaferrum and magnetite in the 187 188 interstices of secondary PGM. Here presented data indicate that more radiogenic ratios in higher levels of the weathering profile are linked to steady mobilization of PGE within secondary PGM resulting in subsequent loss of Os counterbalanced by the incorporation of Fe. Os/ Os In this investigation presented data clearly states that PGE are neither noble nor inert in surface environments, at least in those related to tropical Ni laterites from the Northern Caribbean.

Em virtude das várias aplicações do cobre, acredita-se que a demanda por esse metal irá aumentar nos próximos anos, e consequentemente, o seu preço. Dessa forma, as mineradoras enfrentam o desafio de aprimorar e aperfeiçoar os processos produtivos a fim de atender sua futura demanda. Frações de cobre podem ser encontradas no licor de lixiviação do minério limonítico de níquel e a troca iônica com adsorvente sólido é uma das tecnologias disponíveis para promover a sua recuperação e o seu reaproveitamento. O presente trabalho teve como objetivo estudar o processo de adsorção dos íons de cobre presente em um licor sintético baseado no licor de lixiviação atmosférica do minério limonítico de níquel através de um sistema de resina de troca iônica utilizando a resina quelante Dowex XUS43605. A viabilidade da técnica escolhida foi analisada em função da influência de parâmetros por meio de ensaios em batelada e coluna de leito fixo utilizando uma solução sintética. O tempo de contato, o pH, a massa de resina e a temperatura foram avaliados. A resina quelante Dowex XUS43605 mostrou-se mais seletiva para o cobre em pH igual a 1,5, tendo sido definido esse pH como o de trabalho. Verificou-se que 1g é uma dosagem suficiente para recuperar o cobre da solução em escala laboratorial considerando 50mL de solução sintética. O incremento na temperatura não alterou a adsorção do cobre pela resina, sendo determinado que a temperatura de trabalho esteja entre 25-35°C. O modelo de isotermas de adsorção de Langmuir apresentou melhor ajuste entre a resina e o cobre do que os modelos de Freundlich e de Temkin. O modelo cinético pseudosegunda-ordem descreveu o processo de adsorção considerando a quimiossorção como a etapa limitante. Os ensaios em coluna de leito fixo possibilitaram a produção de uma solução com concentração reduzida de Cu2+ em 93% na etapa de carregamento. Pela etapa de eluição com ácido sulfúrico (H2SO4) 1mol/L, obteve-se uma solução 10 vezes mais concentrada em Cu2+ com relação à solução sintética. A solução resultante da etapa de eluição seguiu para os ensaios de precipitação, a qual permitiu a separação do cobre dos íons metálicos pela ação do agente precipitante CaCO3 e a geração de um precipitado composto por três fases: brochantite [Cu4SO4(OH)6], posnjatike [Cu4SO4(OH)6.H2O] e gesso (CaSO4.2H2O).
Considering the various applications of copper, it is believed that the demand for copper will increase in the coming years and, consequently, its price. Hence, the mining companies face the challenge of improving the productive processes to supply their future demand. Copper fractions can be found in liquor leaching nickel limonite ore and ion exchange with solid adsorbent is one of the available technologies which promote its recovery and reuse. The present work was aimed at studying the adsorption process of copper ions present in a synthetic liquor based on the atmospheric leaching liquor of the nickel limonite ore through an ion exchange resin system using Dowex XUS43605 chelating resin. The feasibility of the chosen technique was analyzed in relation to the influence of parameters by means of batch and fixed bed tests using a synthetic solution. The contact time, pH, amount of resin and temperature were evaluated. Dowex XUS43605 chelating resin showed to be more selective for copper at pH 1.5, and this pH was defined as the working pH. It has been found that 1g is a sufficient dosage to recover copper from the solution on a laboratory scale considering 50mL of synthetic solution. The increase in temperature did not change the adsorption of the copper by the resin, and it was determined that the working temperature is between 25-35°C. The Langmuir adsorption isotherms model showed a better fit between resin and copper than the Freundlich and Temkin models. The pseudosecond-order describes the sorption process and it indicates that the rate-limiting step is chemisorption. The fixed bed column tests allowed the production of a solution with reduced concentration of Cu2+ in 93% the loading step. By the elution step with 1mol/L of sulfuric acid (H2SO4), a solution 10 times more concentrated in Cu2+ was obtained in relation to the synthetic solution. The solution from the elution step followed to the precipitation tests, which allowed the separation of copper from the metal ions by the action of the precipitating agent CaCO3 and the generation of a precipitate composed of three phases: brochantite [Cu4SO4(OH)6], posnjatike [CuSO4(OH)6.H2O] and gypsum (CaSO4.2H2O).

O depósito de níquel laterítico de Niquelândia, GO, Brasil, é considerado um dos mais importantes depósitos desta natureza no país, em razão de sua dimensão, seus teores ligeiramente mais elevados e associação com argilominerais. Desde a década de 70, autores como Trescases e Santos já estudavam seus argilominerais detentores de níquel. Este depósito difere dos cubanos e australianos, pois os primeiros têm o níquel associado aos minérios oxidados e os segundos à serpentina. Em Niquelândia, o níquel está associado principalmente às esmectitas e vermiculitas. A existência destes argilominerais ricos em níquel torna o processo hidrometalúrgico aplicado em Niquelândia o menos recomendado, o que pode ser verificado através de perdas significativas de níquel no rejeito, principalmente no que se refere ao minério silicatado. Estas perdas estão relacionadas com a formação de silicatos de magnésio, como piroxênios, anfibólios e olivinas ainda durante o processo de moagem do minério, isto ocorre devido à técnica aplicada para a redução da umidade. A formação destes minerais retém o níquel em suas estruturas, não permitindo que este seja solubilizado na etapa de lixiviação amoniacal. Em Niquelândia, o principal portador de níquel é a esmectita, no entanto, são identificadas esmectitas di e trioctaédricas, quase sempre associadas. Estas variam desde um extremo trioctaédrico rico em níquel, praticamente refratário ao processo Caron, à esmectitas dioctaédricas de ferro, de baixos teores de níquel, mas com boa recuperação junto ao processo. Contudo, predominam no depósito esmectitas di e trioctaédricas de composições variadas de Fe-Mg-Ni, classificadas como montmorillonitas/stevensitas. Uma maneira de minimizar as perdas de recuperação de níquel seria exercer maior controle sobre a alimentação da usina, de forma a reduzir a proporção de minério silicatado do tipo esmectita trioctaédrica, aumentando a proporção de minério oxidado+minério silicatado de esmectitas dioctaédricas.
The nickel lateritic ore from Niquelândia Goiás - is one of the most important and well known Ni lateritic deposits in Brazil. High nickel contents, the deposit dimension and also, their associations with clay minerals are the main reasons for researchers, such as Trescases and Santos, to have studied it in the 1970s. The Cuban and Australian deposits have nickel associated to oxidized ores and serpentine, respectively, but at Niquelandia, nickel is specially associated to smectites and vermiculites. The Caron Process is not the most suitable for treating Ni-bearing clay minerals, as those present in Niquelândia. Consequently, there are many losses related to silicated ore. The reduction temperature used in the Caron process in the reduction step can form minerals, such as pyroxene, amphibole and olivine. These minerals trap Ni inside their structure; hence, the ammoniacal solution can not access this element and solubilize it. The main Ni-bearing clay mineral observed in Niquelândia is smectite. Actually, the silicated ore is composed by a mixture of smectites. One of them is a Ni-trioctahedral one, which is not affected by ammoniacal leaching; however, it has a significant amount of nickel. On the other hand, a dioctahedral Fe-rich smectite, has high Ni recoveries, but its nickel content is lower. Samples composed by a mixture of di and trioctahedrals smectites - Fe-Mg-Ni montmorillonite/stevensite are the most common. Considering all these factors, the losses related to Ni-recoveries can be avoided by a better feed control. The ideal feed should be an oxidized ore + silicate ore composed by dioctahedrals smectites. The Ni trioctahedral smectite should be avoided.

Pressure acid leaching is an acceptable process for the treatment of nickel laterites. This process offers many advantages such as low energy consumption, low capital cost and high nickel and cobalt recoveries. The dissolution process is coupled to selective thermal hydrolysis of iron and aluminum. The dissolution of laterite and precipitation of iron and aluminum are strongly dependent on the temperature and the acid-to-ore ratio, which is determined by ore compositions and mineralogy. Because of the complex nature of the laterites, a knowledge of the mineralogy of laterites, the nickel association with the various constitutional minerals and the reactivity of these mineral phases is fundamental to an understanding of the kinetics of nickel extraction and to the process optimization. The mineralogy of the laterite ore samples from two ore bodies in New Caledonia and a variety of locations in an Ivory Coast ore body was examined by X-ray diffraction, scanning electron microscope (SEM) and energy dispersive X-ray spectrometer (EDX). X-ray diffraction and SEM-EDX studies showed that goethite, maghemite, quartz and lithiophorite are common minerals in these laterite samples. Spinel and gibbsite are present as minor phases in the New Caledonia laterite samples. Silicates such as talc, kaolinite and clinochlore were found in the Ivory Coast laterites. EDX results indicated that goethite is the major host mineral for nickel. Nickel also showed association with maghemite, lithiophorite and silicates (to various extents in Ivory Coast laterites). Interruptive autoclave leaching experiments were carried out on a blended sample from the Ivory Coast ore body. With a 30% pulp density slurry treated at 260°C, with acid/ore = 0.19, nickel and cobalt extractions reached 96% within 15 minutes as goethite and maghemite had completely dissolved. Hydronium alunite was detected by XRD in the leach residue after 30 minutes of leaching, indicating that the amount of alunite increased with leaching time. Interruptive pressure acid leaching experiments were also performed at 250°C on the samples from five different locations of the Ivory Coast ore body. Process conditions such as acid/ore ratio and pulp density were calculated from a spreadsheet provided by Falconbridge Limited. Nickel and cobalt extractions obtained from 30 minute leaching tests as well as the free acid concentrations in the filtrates differed significantly among the five samples. The goethite dissolution rate also varied among samples and showed a dependence on free acid concentration. Goethite fully dissolved from samples LD-97-13, LD-97-18 and LD-97-32 within 30 minutes at 250°C when the free acid concentration was >32 g/1 in the filtrate. However some of the goethite was detected in the leaching residue of LD-97-24 after 1 hour of leaching with a filtrate free acid concentration of 27.15 g/1. In the experiments, maghemite exhibited the same reactivity as goethite. Clinochlore appeared to be dissolved at free acid concentration of approximately 40 g/1 from sample LD-97-13. Talc, kaolinite, and quartz showed resistance to pressure acid leaching at prescribed leaching conditions. The results of the free acid measurement showed that acid consumption during leaching was dependent not only on the chemical composition, but also the mineralogy of the ore.

With China’s continuing economic boom, the demand for nickel has seen unprecedented growth over the past 10 years. Most of the world’s nickel is present in nickel laterite deposits. These high volume, low grade deposits are now being exploited and processed. An understanding of nickel laterite rheology and the ability to obtain meaningful rheological data is essential to process intensification and stability.
The properties and physical characteristics of 8 industrial nickel laterite slurries as well as two alumina slurries were examined using various rheological techniques. The samples chosen covered a wide range of physical conditions such as differing pH, particle size distributions, solids densities and mineralogy as well as country and deposit of origin. The rheological parameters investigated were the yield stress and shear stress vs. shear rate of the particulate slurries. Considerable attention was focused on the techniques used in shear stress vs. shear rate characterisation, including capillary rheometry, smooth and roughened cup and bob rheometry and the vane in infinite medium technique.
This work confirmed the finding of previous works, showing nickel laterite slurry rheological behaviour ranging from time independent to thixotropic to rheopectic. It found the vane in infinite medium technique highly suitable for testing nickel laterites at process relevant yield stresses. This technique gave data that correlated well with vane yield stresses and capillary rheometry data. Cup and bob tests showed significant slip at lower shear rates. In a number of cases, the cup and bob techniques also showed erroneously high stresses at higher shear rates.
The vane yield stress was found to be a fast and accurate method for monitoring nickel laterite sample aging and the samples tested exhibited 100 Pa yield stresses at solids fractions ranging from 0.389 to 0.524. Blending of nickel laterites was found to be nonlinear, and confirmed that characterisation at various blend ratios is necessary if blending is to be utilised during production.

博士
國立成功大學
材料科學及工程學系
104
This research is divided into three parts, which include in calcination process, calcining temperatures and high temperature melting for limonite laterite. First, compared with reduced uncalcined laterite, when calcined limonite pellets were reduced at 1100oC for 30 min and carbon-oxygen ratio=1, the Nickel grade increased from 4.7% to 11.4% and the recovery of Nickel decreased from 84.5% to 57.1%. Second, 400oC-calcined limonite ore possesses a higher specific surface area of 48.84m2/g, and an average pore size of 29.68 Å, which provide better activity for reduction. And 400oC-calcined limonite ore obtained the best nickel grade of 78.2 % and the best recovery rate of 90.2 % under a reduction temperature of 1100oC, a reduction time of 30 min and a carbon-oxygen ratio of 0.6. Finally, 400oC-calcining limonite added graphite (C/O=0.35) and SiO2 (10%) which can obtain nickel grade 16.8% and nickel recovery 86.5% under a reduction temperature of 1100oC for a reduction time of 30 min and a melting temperature of 1550oC for a reduction time of 60 min. And also 400oC-calcining limonite added bio-coal (C/O=0.3) which can obtain nickel grade 16.7% and nickel recovery 87.7% under a reduction temperature of 1100oC for a reduction time of 30 min and a melting temperature of 1550oC for a reduction time of 60 min.

M. Tech. Chemical Engineering
The depreciation of high grade sulphide ores has resulted to the use of low grade laterites to meet the global nickel demand. Available low grade laterite ore reserves in South Africa are underutilised. Suitable metallurgical process for recovery of nickel from these reserves is not yet implemented because the mineralogy is not well understood. Hence, in this research the mineralogy and recovery of nickel from low grade laterites was studied through electrochemical process. The research shows that it is feasible to selectively recover nickel from the low grade laterite ore using electrochemical leaching method. It is recommended that optimization of the electrochemical cell design be looked into to evaluate the possibility of scaling up for industry application.

Masters Research - Master of Science
The jarosite group of compounds are yellow/brown clay like substances, both naturally occurring and synthetically produced in metallurgical processes. Jarosites have the structure MFe3(SO4)2(OH)6, where M can be numerous elements or compounds, most often potassium or sodium. The term jarosite refers specifically to the potassium form of the compound, but is synonymous with the whole group of compounds, often leading to confusion. In nature, jarosites can be associated with acid mine drainage and acid sulphate soils as an intermediate product of the oxidation of pyrite and other iron/sulphur bearing minerals. In industry, jarosites are used in metallurgical processes, synthetically produced to precipitate an easily filterable form of solid iron. Jarosites have properties that make them a chemically unstable solid. Upon decomposition the jarosite group of compounds will generate sulphuric acid. A literature review found many references to jarosites, their stability, methods of conversion to iron oxides, methods to extract reusable materials and environmental concerns. Most methods of recycling were unsuccessful. Accelerated conversion of jarosites to a form of iron oxide was a successful method of mitigating the risk of future acid generation. There were numerous specific ways of completing this task. The BHP Billiton patented nickel atmospheric leach process generates natrojarosite (sodium form of the compound) as a by-product, when extracting nickel from lateritic ores. The by-product of this process was tested for stability to understand the decomposition process. Accelerated decomposition of natrojarosite was attempted using limestone and hydrated lime at 90OC. Limestone did not react with the natrojarosite. Hydrated lime caused extensive dissolution of sodium and sulphur from the solid. However XRD analysis still reported natrojarosite as the solid material, suggesting incomplete decomposition and the formation an amorphous form of iron oxide not detected by XRD. Further decomposition tests were completed using elevated temperatures and pressures in an autoclave. Natrojarosite was not detectable in the solid phase after treatment at a temperature of 212OC, converting to haematite at temperature above 150OC. The stability of natrojarosite was measured using a number of methods on two natrojarosite samples sourced from the atmospheric leach process. The methods used were batch agitation, column testing and permeability testing. The aim was to provide a holistic result for the stability of natrojarosite if stored in a waste facility. Results obtained were compared against the standard TCLP test and found to be a more accurate method for measuring the stability of natrojarosite. The tests are more time consuming than TCLP testing but showed that natrojarosite was capable of decomposing to form sulphuric acid with time. This result was not obtained from TCLP tests, which suggested the solid material was stable. It was also found that salt water stabilised natrojarosite. Decomposition occurred in 40 and 80 days respectively, for two natrojarosite samples tested in deionised water. There was no evidence of decomposition after 150 and 280 days respectively for the same two samples. The common ion theory is thought to stabilise the natrojarosite which decomposes in an equilibrium reaction. Excess ions present in solution decrease the propensity for the solid to decompose. The two natrojarosite samples tested varied in calcium concentration. Limestone and hydrated lime were added to the natrojarosite during the nickel extraction process. Gypsum is theorised to form an impermeable layer around the natrojarosite, increasing the stability of the compound. Gypsum is sourced from the neutralisation reaction between limestone or hydrated lime and the acid generated from natrojarosite decomposition.

Masters Research - Master of Science
The jarosite group of compounds are yellow/brown clay like substances, both naturally occurring and synthetically produced in metallurgical processes. Jarosites have the structure MFe3(SO4)2(OH)6, where M can be numerous elements or compounds, most often potassium or sodium. The term jarosite refers specifically to the potassium form of the compound, but is synonymous with the whole group of compounds, often leading to confusion. In nature, jarosites can be associated with acid mine drainage and acid sulphate soils as an intermediate product of the oxidation of pyrite and other iron/sulphur bearing minerals. In industry, jarosites are used in metallurgical processes, synthetically produced to precipitate an easily filterable form of solid iron. Jarosites have properties that make them a chemically unstable solid. Upon decomposition the jarosite group of compounds will generate sulphuric acid. A literature review found many references to jarosites, their stability, methods of conversion to iron oxides, methods to extract reusable materials and environmental concerns. Most methods of recycling were unsuccessful. Accelerated conversion of jarosites to a form of iron oxide was a successful method of mitigating the risk of future acid generation. There were numerous specific ways of completing this task. The BHP Billiton patented nickel atmospheric leach process generates natrojarosite (sodium form of the compound) as a by-product, when extracting nickel from lateritic ores. The by-product of this process was tested for stability to understand the decomposition process. Accelerated decomposition of natrojarosite was attempted using limestone and hydrated lime at 90OC. Limestone did not react with the natrojarosite. Hydrated lime caused extensive dissolution of sodium and sulphur from the solid. However XRD analysis still reported natrojarosite as the solid material, suggesting incomplete decomposition and the formation an amorphous form of iron oxide not detected by XRD. Further decomposition tests were completed using elevated temperatures and pressures in an autoclave. Natrojarosite was not detectable in the solid phase after treatment at a temperature of 212OC, converting to haematite at temperature above 150OC. The stability of natrojarosite was measured using a number of methods on two natrojarosite samples sourced from the atmospheric leach process. The methods used were batch agitation, column testing and permeability testing. The aim was to provide a holistic result for the stability of natrojarosite if stored in a waste facility. Results obtained were compared against the standard TCLP test and found to be a more accurate method for measuring the stability of natrojarosite. The tests are more time consuming than TCLP testing but showed that natrojarosite was capable of decomposing to form sulphuric acid with time. This result was not obtained from TCLP tests, which suggested the solid material was stable. It was also found that salt water stabilised natrojarosite. Decomposition occurred in 40 and 80 days respectively, for two natrojarosite samples tested in deionised water. There was no evidence of decomposition after 150 and 280 days respectively for the same two samples. The common ion theory is thought to stabilise the natrojarosite which decomposes in an equilibrium reaction. Excess ions present in solution decrease the propensity for the solid to decompose. The two natrojarosite samples tested varied in calcium concentration. Limestone and hydrated lime were added to the natrojarosite during the nickel extraction process. Gypsum is theorised to form an impermeable layer around the natrojarosite, increasing the stability of the compound. Gypsum is sourced from the neutralisation reaction between limestone or hydrated lime and the acid generated from natrojarosite decomposition.

An electrochemical cell consisting of a flow-through yttria-stabilized zirconia (YSZ) sensor and a flow-through Ag/AgCl reference electrode has been employed to measure pH of high-temperature acidic sulphate solutions relevant to the pressure acid leaching (PAL) of nickel laterites. In a previous study, this cell was used to measure pH of H2SO4, Al2(SO4)3-H2SO4 and MgSO4-Al2(SO4)3-H2SO4 solutions at 250oC. In this work, the solutions range in complexity from the binary MgSO4-H2SO4, NiSO4-H2SO4, and Al2(SO4)3-H2SO4, through the ternary MgSO4-Al2(SO4)3-H2SO4 and NiSO4-Al2(SO4)3-H2SO4, to the PAL process solutions, whereas the temperature ranges from 200oC to 250oC. The measured and theoretical pH values typically agree within less than 0.1 pH unit and 0.2 pH units in synthetic solutions and PAL solutions, respectively. This is an improvement over the results of the previous study in synthetic solutions, which show differences between theory and experiment as high as 0.4 pH units. The conversion of measured potentials into pH values is based on the new mixed-solvent electrolyte (MSE) speciation model of the OLI Systems software calibrated independently based on solubility measurements. Both Henderson’s equation and the exact definition of the diffusion potential were employed in treating the obtained experimental data. Experimental pH values calculated using the diffusion potentials evaluated by either approach are essentially the same. This finding suggests that Henderson’s equation, which is based on readily available limiting ionic mobilities, can be effectively used. Lithium chloride is found to be a suitable alternative to sodium chloride as the reference electrode solution for the measurement of pH of aluminium-containing solutions, because it did not induce precipitation of aluminium as an alunite-type compound. The experimental results indicate that the high-temperature behaviour of Ni, Co and Mn sulphates can be satisfactorily approximated with that of MgSO4. The experimental findings also support the postulation that acid should be added to a PAL process so that the solution pH is around 1 at the leach temperature, regardless of the feed composition. The cell can be used for hydrometallurgical process research and development on a laboratory scale with very satisfactory performance, provided that a well-behaved YSZ sensor is available.

The processing of nickeliferous laterites to produce nickel metal is both complex and energy intensive. Since most laterites are found in remote regions, the capital costs for the infrastructure can exceed those for the process itself. The low temperature sulphidation of lateritic ores to produce an intermediate nickel concentrate for further processing offers a number of potential advantages, such as lower energy consumption and a relatively simple flowsheet. In this research, the sulphidation of a nickeliferous lateritic ore was investigated between the temperatures of 450-1100oC and sulphur additions of between 25-1000 kg of sulphur per tonne of ore. The experiments demonstrated that the nickel oxide within the ore can be selectively sulphidized to a nickel-iron sulphide. It was found that both the grade and the sulphidation degree largely depended upon the temperature and the sulphur additions, with temperatures above 550oC exhibiting the highest nickel sulphidation extents and grades. A DTA/TGA with mass spectrometer was used to further elucidate the nature of the phase transformations that occur upon heating of the ore, in the presence of sulphur. It was found that the Fe-Ni-S phase formed at low temperatures was submicron in nature and heating to temperatures of 1050oC-1100oC allowed for the growth of the sulphides to a d80 of up to 14 µm due to increased sulphide mobility, associated with the formation of a liquid sulphide matte with dissolved oxygen. Flotation studies conducted on 60 g samples showed that the sulphides formed respond to flotation with maximum grades of up to 6-7 wt% nickel being achieved and average grades of between 4-5 wt% nickel. Recoveries were approximately 50% on a sulphide basis and it was determined that the low nickel grades were due to the entrainment of magnetite fines.
Thesis (Ph.D, Mining Engineering) -- Queen's University, 2012-01-29 14:14:18.704

Η επεξεργασία των νικελιούχων λατεριτικών μεταλλευμάτων της χώρας μας για την παραγωγή σιδηρονικέλιου στη Λάρυμνα συνοδεύεται με την εκπομπή 200000t/y λεπτομερούς σκόνης που συλλέγεται στα συστήματα αντιρρύπανσης των περιστροφικών κάμινων (Π/Κ), μέσης περιεκτικότητας 1.2-1.5% σε Ni και 4-5% σε C. Η διατριβή αυτή συνέβαλε στην ανάπτυξη μεθόδου ανακύκλωσης της σκόνης αυτής με απευθείας αναγωγική της τήξη σε ηλεκτρική κάμινο συννεχούς ρεύματος (DC-HEP) με εμφυσησή της μέσω του κεντρικού διάτρητου γραφιτικού ηλκετρόδιου. Την προκαταρκτική θεωρητική διερεύνηση και τις εργαστηριακές προδοκιμές ακολούθησαν βιομηχανικές δοκιμές στην κάμινο 125t DC-HEP στη χαλυβουργία Georgsmarienhutte της Γερμανίας, όπου έλαβε χώρα τήξη 70t σκόνης και 2.5t φιλομερούς μεταλλεύματος.Η ανάκτηση Ni ήταν πολύ υψηλή 93-99%. Παρήχθησαν χάλυβες χαμηλής κραμάτωσης σε σε Ni καθώς και ποικίλοι τύποι σκωρίας προς διερεύνηση της χρήσης τους στην παραγωγή σύνθετων τσιμέντων Portland και σκωριωτσιμέντων. Πραγματοποιήθηκε μεταλλουργική αξιολόγηση των δοκιμών και αναπτύχθηκε μοντέλο προσομοίωσης της αναγωγικής τήξης της σκόνης.
The tratment of the laterite nickel ferrous ores in Hellas for the production of ferronickel at Larymna is associated with the emission of 200000t/y of fine dust collected in the gas cleaning systems of the rotary kilns (R/Ks), with 1.2-1.5% and 4-5% . Average Ni and C contents respectively . This thesis contributed to the development of a method for the recycling of this dust by means of its direct reduction smelting in a DC-HEP furnace (Direct Current-Hollow Electrode Powder) by its injection through the central hollow graphite electrode. The preliminary theoretical study and the laboratory trials were followed by industrial heat campaigns in the 12st DC-HEP furnace at georgsmarienhutte steelwork in Germany, where around 70t of dust and 2.5t of ore fines were smelted. The Ni-recovery was very high 93-99.9%. Low Nickel alloyed steel grades were produced and various slag types for the investigation of their utilization for the production of composite-portland cements and slag cements. The metallurgical evaluation of the trials was performed and model for the dust reduction smelting process was developed.