Dissertations / Theses on the topic '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.

Ni-bearing Mg-phyllosilicates (commonly known as garnierites) are significant ore minerals in many Ni-laterite deposits worldwide. However, the characterisation of these mineral phases is complex, as well as their classification and nomenclature, due to their fine-grained nature, low crystallinity and frequent occurrence as mixtures. The aim of this study is to shed some light to the nature of the Ni-bearing Mg-phyllosilicates occurring at the Falcondo Ni-laterite. In this deposit, these minerals are found within the saprolite horizon mainly as fracture-fillings, coatings on joints and as breccias. The Falcondo garnierites display easily distinguishable different shades of green and characteristic textures, which correspond to different mineral phases. Five garnierite types were defined by X-ray diffraction (XRD), optical and electron microscopy, and electron microprobe (EMP) analyses: I) Ni-Fe-bearing serpentine-like, II) Ni-(Al)-bearing serpentine-like with minor talc-like, III) Ni-rich mixture of serpentine- and talc-like, IV) talc-like and V) sepiolite-falcondoite. The characterisation was completed with differential thermal analysis and thermogravimetry (DTA-TG), transmission electron microscopy (TEM), Raman spectroscopy, microfocus X-ray absorption spectroscopy (i.tXAS) and dissolution experiments, in order to gain further insight on these mineral phases from different points of view. EMP oxide totals and DTA-TG indicate that talc-like contain higher H2O than talc sensu stricto (about 4.5% mass loss at 200°C, and up to 5% at 650°C), and therefore the names kerolite-pimelite [(Mg,Ni)3Si4010(OH)2• nH20] should be used instead of talc-willemseite [(Mg,1•103Si401o(OH)21. Compositional data showed continuous Mg-Ni solid solution along the joins lizardite-nepouite/chrysotile-pecoraite (serpentine-like), kerolite-pimelite (talc-like) and sepiolite-falcondoite. The phases with larger amounts of talc-like displayed the highest Ni contents (up to 2.2 apfu out of 3 octahedral atoms). In addition, EMP analyses of the mixed phases showed deviations from the stoichiometric Mg-Ni solid solutions of serpentine and talc. This is best explained by mixing at the nanoscale, which was confirmed by XRD and high resolution TEM imaging. Furthermore, a detailed textural study by means of EMP quantified X-ray element imaging was used to explain the relationships between textural position, sequence of crystallization and mineral composition of the studied Ni-phyllosilicates. These results indicate several stages of growth with variable Ni content, pointing to recurrent changes in the physical-chemical conditions during the precipitation of the different Ni-phyllosilicates. HRTEM and low magnification imaging enabled to measure the characteristic basal spacings of these phyllosilicates and to observe a wide variety of nanotextures, respectively: 15-sectored polygonal serpentine, chrysotile tubes, lizardite lamellae, kerolite-pimelite lamellae and sepiolite ribbons. In accordance with EMP results, chemical analyses by TEM showed that Ni is more concentrated in the kerolite-pimelite lamellae than in the serpentine particles. In addition, the HRTEM revealed that kerolite-pimelite lamellae replace the Ni-poor serpentine particles. These observations evidence the processes of progressive Ni-enrichment within some Ni-bearing Mg-phyllosilicates. Characteristic Raman bands were observed for serpentine-, talc- and sepiolite-like phases, and therefore this technique allowed discriminating the different garnierite types. The synchtrotron radiation-based µXAS analyses were conducted to investigate the speciation of Fe (by Fe K-edge X-ray absorption near edge structure, XANES) and the local environment of Ni (by Ni K-edge extended X-ray absorption fine structure, EXAFS). The XANES results indicate that Fe in the weathered saprolite and in the garnierites is mostly oxidised, whereas in the primary serpentine from the ultramafic protolith it is in the ferrous form. The EXAFS spectra indicate that Ni is homogeneously distributed in the unweathered rock, and is accumulated in discrete domains (clusters) in the weathered saprolite and in all the garnierite types. Finally, the dissolution experiments of a set of garnierites which cover a wide range of mineral compositions at acidic pH suggest that the dissolution rates are faster in serpentine- dominated garnierites than in talc (kerolite)-dominated garnierites or sepiolite-falcondoite, and that the dissolution is not congruent, being the serpentine component the first to dissolve in the garnierite mixtures of serpentine and talc (kerolite). In summary, the various analytical techniques applied to the garnierites of this study provide an accurate outlook of their complex mineralogy, structures, textures and chemistry at different scales that provides further details on the formation of these Ni-bearing Mg- phyllosilicates in a lateritic environment.
Els fil- losilicats de níquel (comunament anomenats "garnierites") són importants menes en molts jaciments laterítics de Ni del món. La seva caracterització, classificació i nomenclatura és complexa, ja que normalment es troben en forma de mescles íntimes de diferents fil- losilicats de gra molt fi i baixa cristal• linitat. L'objectiu d' aquesta tesi és avançar en el coneixement de la mineralogia dels fil- losilicats de Ni del dipòsit de laterites niquelíferes de Falcondo, a la República Dominicana, per mitjà de l'ús d'un ampli espectre de tècniques analítiques: difracció de pols de raig X, anàlisi tèrmica diferencial i termogravimetria, microscòpia òptica, microscòpia electrònica de rastreig, microsonda electrònica, microscòpia electrònica de transmissió, espectroscòpia Raman, espectroscòpia d' absorció de raigs X (EXAFS i XANES, amb radiació sincrotró) i per mitjà d'experiments de dissolució. Les garnierites de Falcondo es localitzen a la part baixa de l'horitzó saprolftic en forma de rebliment de fractures i vetes, i ciments i clasts en bretxes. Els principals resultats indiquen que hi ha cinc tipus de garnierites, segons el seu color, la seva mineralogia i la química mineral. La majoria són barreges de serpentina i talc hidratat (kerolita-pimelita), tot i que també hi ha fases de la sèrie sepiolita-falcondoita. La fase que concentra més Ni és la kerolita-pimelita, mentre que a la serpentina el Ni és sistemàticament molt baix i a la sepiolita-falcondoita és molt variable. Les imatges d' alta resolució obtingudes amb microscopi electrònic de transmissió indiquen que els fil- losilicats que componen les garnierites formen una gran varietat de textures: serpentina poligonal, tubs de crisòtil, lamel• les de lizardita, lamel• les de talc hidratat i cintes de sepiolita. A més, s'ha observat que la kerolita-pimelita (rica en Ni) reemplaça sistemàticament la serpentina (pobra en Ni). L'espectroscòpia Raman permet distingir els cinc tipus descrits de garnierites i per tant, s'ofereix com una tècnica ràpida, senzilla i no destructiva per analitzar aquest tipus de minerals al camp. L' absorció de raigs X per mitjà de radiació sincrotró ha permès identificar que tot el Fe contingut en les garnierites i en les serpentines de la saprolita està en forma de Fe3+, i que tot el Ni es troba acumulat formant clusters, i no pas en forma de solució sòlida homogènia, a la capa octaèdrica. Finalment, els experiments de dissolució suggereixen que les velocitats de dissolució són més ràpides en les garnierites que contenen molta serpentina, i que la dissolució no és congruent, sent el Mg el primer element en ser posat en solució, seguit del Si i del Ni.

Embankments are key elements in the infrastructural development of structures such as dams, bridges, and roads. Residual soils are generally used as fills in the construction of embankments in areas were residual soils such as laterite is the dominant soil types. Laterite soils have the characteristics of losing its shear strength with time and in fully saturated conditions and its properties varies from region to region. The soil property is influenced by the chemical composition and the environment. The binding agent iron oxide in such soils changes its composition with time and in the presence of moisture. Sudden failures of embankments founded of laterite soils which were, otherwise, checked and found to be safe with high factor of safety, have been observed. This study is performed to investigate the stability of embankments with sudden loss of strength with time and when it is fully saturated. The research includes an investigation of the properties of laterite soils around the world, with particular emphasis on Nigeria. Initially, information is gathered from different sources about the strength-based properties of such soils. Previous research in Nigeria is used as a basis for obtaining real-world soil data. Next, stability analyses are performed using SLOPE/W with shear strength parameters for total stress (short-term), effective stress (long-term), and fully saturated soil conditions. A probability analysis is conducted for the fully saturated conditions because of the variability in the input parameters. Three slope configurations (1:1, 2:1, and 3:1) are considered. The study revealed that the laterite soils embankments lose most of its stability over time period and in full saturation soil conditions. Both these conditions significantly compromise the strength of the soil and the related stability of slopes. To consolidate all information, a database of the properties of laterite soils in some localities of Nigeria was created on the geographic information system (GIS), in order provide a quick access to information on laterite soils in Nigeria.
M.S.
Department of Civil and Environmental Engineering
Engineering and Computer Science
Civil Engineering

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.

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.

Orientadores: Francisco Sergio Bernardes Ladeira, Fabiano Tomazini da Conceição
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Geociências
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Resumo: A teoria de pediplanação proposta por King em 1956 ganhou atenção no Brasil a partir da sua publicação sobre a evolução do relevo da porção oriental brasileira. Este trabalho de King suscitou críticas e reflexões da comunidade geomorfológica nacional. Além de King, muitos autores publicaram trabalhos com este enfoque, podendo-se destacar Moraes Rego (1932), De Martonne (1943), Freitas (1951), Almeida (1964), Bigarella e Ab¿Sáber (1964), Barbosa (1965), Bigarella e Andrade (1965), Braun (1971), entre outros. Apesar de uma certa estagnação após a década de 1980, a temática "paleosuperfícies" ganhou destaque nas últimas duas décadas, principalmente devido ao surgimento de novos métodos de análise, inclusive a possibilidade de datações absolutas em perfis de intemperismo. Este trabalho busca associar os perfis lateríticos de ferro aos patamares altimétricos, tratando os perfis lateríticos como marco cronoestratigráfico passível de datação, através de análises químicas, mineralógicas, macromorfológicas e de datação por (U-Th)/He dos perfis lateríticos de ferro. Duas áreas principais foram estudadas mais a fundo: o quadrante leste do Quadrilátero Ferrífero (região de Catas Altas), nas imediações da Serra do Caraça, apresentando uma superfície laterítica de ferro a 890m de altitude, com 10 Km de extensão, sob a Formação Fonseca, na qual foi amostrado um perfil laterítico de ferro; e o quadrante oeste do Quadrilátero Ferrífero, a região da Serra do Rola Moça e norte da Serra da Moeda, onde foi também amostrado um perfil laterítico de ferro, a 1400m de altitude aproximadamente, sob o itabirito in situ (na Serra do Rola Moça). Nestas áreas foram mapeadas a superfície laterítica de ferro e realizada analise geoquímica, mineralógica e de datação (U-Th)/He dos perfis lateríticos amostrados. As idades encontradas variam no perfil da região de Catas Altas de 33,09±1,11Ma a 0,71±0,05Ma e no perfil da Serra do Rola Moça de 6,08±0,20Ma a 0,43±0,04Ma. Os dados apontam que a superfície laterítica de ferro teve o início da sua elaboração a 33Ma atrás na região de Catas Altas, sendo que a goethita desde este momento vem dissolvendo e recristalizando, por isso as idades mais recentes. Portanto, a área do Quadrilátero Ferrífero estava exposta há 60Ma, isso significa que a configuração do relevo com os topos eram os mesmos há 60Ma, principalmente em se tratando da região da Serra do Caraça. Os materiais datados na Serra do Rola Mola vão ao encontro das idades elencadas para as áreas vizinhas, como é o caso da Mina do Capão Xavier na Serra da Moeda (em torno de 6 a 8 Ma). Por fim, na análise de paleosuperfícies não se pode associar os patamares altimétricos a antigas superfícies de aplainamento de forma direta. De acordo com o estudo regional no Quadrilátero Ferrífero, pode-se afirmar que independente dos patamates altimétricos o que prevalece na paisagem é a superfície Sul-Americana e não encontrou-se evidências seguras da Superfície Gondwana, mais antiga
Abstract: The theory of pediplanation proposed by King em 1956 has gained attention in Brazil since his publication about the evolution of the relief of the Brazilian eastern portion. This King's work has given rise to reviews and reflections from the national geomorphological community. Besides King, many authors have published with this approach, highlighting Moraes Rego (1932), De Martonne (1943), Freitas (1951), Almeida (1964), Bigarella and Ab¿Sáber (1964), Barbosa (1965), Bigarella and Andrade (1965), Braun (1971), among others. In spite of a certain stagnation after the decade of 1980, the theme "paleosurfaces" has been highlighted in the last two decades, mainly due to the uprising of new methods of analysis, including the possibility of absolute dating in intemperism profiles. This work aims to associate the iron laterite profiles with elevation levels by using laterite profiles as a chronostratigraphic mark possible to be dated, through chemical, mineralogical, macromorphological analysis and dating by (U-Th)/He of the laterite iron profiles. Two main areas have been studied deeper: the eastern quadrant of Quadrilátero Ferrífero (Catas Altas region), next to Serra do Caraça, showing a laterite iron profile at 890m of altitude, with 10km of extension, under Fonseca Formation, in which a laterite iron profile was sampled; and the western quadrant of Quadrilátero Ferrífero, Serra do Rola Moça region and northern Serra da Moeda, where a laterite iron profile was also sampled, at about 1400m of altitude, under the itabirite in situ (in Serra do Rola Moça). In these areas the iron laterite surface was mapped and the geochemical, mineralogical analysis and dating (U-Th)/He of the sampled laterite profiles was done. The ages found range in the Catas Altas region from 33,09±1,11Myr ago to 0,71±0,05Myr ago and in the profile of Serra do Rola Moça from 6,08±0,20 Myr ago to 0,43±0,04 Myr ago. The data show that the laterite iron surface began its forming 33Myr ago in Catas Altas region, regarding that from this moment goethite has been dissolving and recrystallizing, then, the more recent ages. Thus, Quadrilátero Ferrífero area was exposed 60Myr ago, this means that the configuration of the relief with the tops was the same 60Myr ago, especially being the Serra do Caraça region. The material dated in Serra do Rola Moça meet the ages listed for the neighboring areas, as Mina do Capão Xavier in Serra da Moeda (about 6 to 8 Myr ago). Finally, in paleosurface analysis altitude levels cannot be associated with former flattening surfaces in a direct way. According to the regional study in Quadrilátero Ferrífero, we can state that independently of the altitude levels, what prevails in the landscape is the Sul-Americana surface and we did not find secure evidence of the Gondwana surface, older
Doutorado
Análise Ambiental e Dinâmica Territorial
Doutora em Geografia

This study was carried out to evaluate the sorption capacity of Pb, As, Cd, Zn, and Mn by laterite from Tam Duong District (Vinh Phuc Province) and Thach That District (Hanoi City). Laterite samples were exposed to different initial concentrations of heavy metals in solutions (2.5, 5.0, 10, 20, and 50 mg/l) at pH = 5.5 during 24 hours. The results demonstrated that sorption capacity of heavy metals was in the following order: Pb> As> Cd> Zn>Mn. The highest sorption capacity of Pb, As, Cd, Zn, and Mn of laterite from Tam Duong was 1553, 756, 397, 281, and 143 mg/kg, respectively and the highest removal efficiency was 94, 76, 70, 56 and 37%. The results indicated that laterite from Tam Duong District showed lower sorption capacity than that from Thach That District. The disparity sorption capacity of Pb, As, Cd, Zn, Mn between laterite from Thach That and Tam Duong was 10.3–11.6, 11.9–17.9, 11.5–13.7, 9.5–17.6, and 11.1–14.3%, respectively. Laterites from Tam Duong and Thach That are a promising environmental material which can be used in the removal of heavy metals from wastewater.
Nghiên cứu này được thực hiện nhằm đánh giá khả năng hấp phụ Pb, As, Cd, Zn, và Mn bởi laterit đá ong khu vực huyện Tam Dương (Vĩnh Phúc) và huyện Thạch Thất (Hà Nội). Mẫu đá ong được tiến hành thí nghiệm trong các dung dịch có hàm lượng kim loại nặng ban đầu khác nhau (2,5; 5,0; 10; 20 và 50 mg/l) tại pH=5,5 trong 24 giờ. Kết quả nghiên cứu cho thấy mức độ hấp phụ kim loại nặng bởi laterit đá ong lần lượt là Pb> As> Cd> Zn>Mn. Dung lượng hấp phụ Pb, As, Cd, Zn và Mn cao nhất của laterit Tam Dương lần lượt là 1553, 756, 397, 281 và 143 mg/kg và hiệu suất hấp phụ cao nhất lần lượt là 94, 76, 70, 56 và 37%. Dung lượng hấp phụ kim loại nặng của laterit huyện Tam Dương thấp hơn khu vực huyện Thạch Thất. Sự chênh lệch về dung lượng hấp phụ Pb, As, Cd, Zn và Mn giữa laterit Thạch Thất và laterit Tam Dương lần lượt là 10,3–11,6; 11,9–17,9; 11,5– 13,7; 9,5–17,6 và 11,1–14,3%. Kết quả nghiên cứu bước đầu cho thấy đá ong khu vực huyện Tam Dương và Thạch Thất là vật liệu hấp phụ tiềm năng phục vụ ứng dụng trong xử lý nước thải bị nhiễm kim loại nặng.

This article presents nano composite TiO2.Fe2O3/laterite materials, which were successfully prepared by hydrometallurgical method. The materials were modified using urea as the nitrogen source. The particles size of the materials is from 20-30 nanometers. The obtained materials can not only absorb arsenic compounds but also enhance the ability of converting As (III) or As (V) into Aso, which is removed from solution. Arsenic removal efficiency of these materials is high. Using sunlight in a hydraulic retention time, about 180 minutes, the arsenic value at the inflow was about 10 mg/L but the outflow was negligible. Covering TiO2.Fe2O3 nano on laterite have brought high economical efficiency, on one hand, it saved material and on the other hand, it can be continuously operated without the centrifugal separation of the nano material
Bài báo này giới thiệu về phương pháp điều chế vật liệu nano TiO2.Fe2O3 biến tính nitơ được phủtrên đá ong bằng phương pháp thủy luyện. Vật liệu nano thu được có kích thước 20-30 nm. Vật liệu thu được không những có khả năng hấp phụ các hợp chất của asen mà còn có khả năng khử As (III) hoặc As (V) thành Asokhi được chiếu sáng. Sử dụng ánh sáng mặt trời chiếu vào hệ thống xử lý trong thời gian 180 phút có thể loại bỏ được gần như hoàn toàn asen ra khỏi nước mặc dù hàm lượng đầu vào là 10 mg/l. Việc phủ vật liệu TiO2.Fe2O3 nano lên đá ong đã mang lại hiệu quả kinh tế cao, một mặt nó tiết kiệm được vật liệu, mặt khác, vật liệu có thể sử dụng một cách liên tục mà không cần phải tách bằng phương pháp ly tâm

The SOLSA project aims to construct an analytical expert system for on-line-on-mine-real-time mineralogical and geochemical analyses on sonic drilled cores. A profilometer is indispensable to obtain reliable and quantitative data from RGB and hyperspectral cameras, and to get 3D definition of close-to-surface objects such as rheology (grain shape, grain size, fractures and vein systems), material hardness and porosities. Optical properties of minerals can be analyzed by focusing on the reflectance. Preliminary analyses were performed with the commercial scan control profilometer MI-CRO-EPSILON equipped with a blue 405 nm laser on a conveyor belt (depth resolution: 10 μm; surface resolution: 30x30 μm2 (maximum resolution; 1m drill core/4 min). Drill core parts and rocks with 4 different surface roughness states: (1) sonic drilled, (2) diamond saw-cut, polished at (3) 6 mm and (4) 0.25 μm were measured (see also abstract Duée et al. this volume). The ΜICRO- EPSILON scanning does not detect such small differences of surface roughness states. Profilometer data can also be used to access rough mineralogical identification of some mineral groups like Fe-Mg silicates, quartz and feldspars). Drill core parts from a siliceous mineralized breccia and laterite with high and deep porosity and fractures were analyzed. The determination of holes’ convexity and fractures) is limited by the surface/depth ratio. Depending on end-user’s needs, parameters such as fracture densities and mineral content should be combined, and depth and surface resolutions should be optimized, to speed up “on-line-on-mine-real- time” mineral and chemical analyses in order to reach the target of about 80 m/day of drilled core.

The SOLSA project aims to construct an analytical expert system for on-line-on-mine-real-time mineralogical and geochemical analyses on sonic drilled cores. A profilometer is indispensable to obtain reliable and quantitative data from RGB and hyperspectral cameras, and to get 3D definition of close-to-surface objects such as rheology (grain shape, grain size, fractures and vein systems), material hardness and porosities. Optical properties of minerals can be analyzed by focusing on the reflectance. Preliminary analyses were performed with the commercial scan control profilometer MI-CRO-EPSILON equipped with a blue 405 nm laser on a conveyor belt (depth resolution: 10 μm; surface resolution: 30x30 μm2 (maximum resolution; 1m drill core/4 min). Drill core parts and rocks with 4 different surface roughness states: (1) sonic drilled, (2) diamond saw-cut, polished at (3) 6 mm and (4) 0.25 μm were measured (see also abstract Duée et al. this volume). The ΜICRO- EPSILON scanning does not detect such small differences of surface roughness states. Profilometer data can also be used to access rough mineralogical identification of some mineral groups like Fe-Mg silicates, quartz and feldspars). Drill core parts from a siliceous mineralized breccia and laterite with high and deep porosity and fractures were analyzed. The determination of holes’ convexity and fractures) is limited by the surface/depth ratio. Depending on end-user’s needs, parameters such as fracture densities and mineral content should be combined, and depth and surface resolutions should be optimized, to speed up “on-line-on-mine-real- time” mineral and chemical analyses in order to reach the target of about 80 m/day of drilled core.

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.

Madagascar - Ambatovy region, AMBATOVY Project - Sherritt International. The Ambatovy Project, a mine for nickel and cobalt ore located in the centre of the country, required the construction of a slurry pipeline to transport the ore 220 km to be processed on the east coast. The pipeline and its maintenance road traverses primary forests, the sensitive Torotorofotsy Wetlands and include 172 stream crossings in sensitive laterite soils. The restoration and rehabilitation of the cut and fill geotechnical works and stream crossings is important technical works within the environmental portfolio and for project cost reductions.The surface water erosion of the soil and the associated stream sedimentation are studied. These processes are classified based on the characteristics of the vegetation/land use, the slopes and the type of laterite soil. Three representative sites are chosen for a detailed study using field observations and field measurements (TSS in streams). These results are compared to numerical modeling results using RUSLE (Revised Universal Soil Loss Equation model) for surface erosion within GeoWEPP (Geo-spatial interface for Water Erosion Prediction Project), a USGS (US Geological Survey) –LESAM (Landscape-based Environmental System Analysis & Modeling) model which conducts continuous and process-based simulations of small watersheds, for soil erosion and sedimentation.At the three selected sites, the use of GeoWEPP as a tool to explore possible mitigation measures using geotechnical engineering methods combined with revegetation is investigated and discussed. The results of these studies will be used to suggest measures to mitigate environmental impacts associated with the pipeline construction for the Ambatovy Project.
Madagascar – région d'Ambatovy, Projet AMBATOVY - Sherritt International. Le Projet Ambatovy, une mine de nickel et cobalt située au centre de l'ile, a requiert la construction d'un pipeline de pulpe pour pouvoir transporter le minerai sur 220kms, pour pouvoir être acheminé et transformé sur la côte Est. Le pipeline et son réseau routier de maintenance traverse des forêts primaires, la sensible région du marais de Torotorofotsy et incluant 172 cours d'eau sensibles reposant sur le sol latéritique. La restauration et la réhabilitation des tranchées de remblai et déblai grâce aux travaux géotechniques sont d'importants travaux techniques pour les cours d'eaux notamment au niveau de l'impact environnemental et jouant sur la réduction des couts du projet. Le phénomène de l'érosion de surface au niveau des cours d'eau et la sédimentation des rivières y associée ont été étudiés. Les processus sont classés sur base des caractéristiques de la végétation, de la pente et du type de sol latéritique. Trois sites représentatifs sont choisis aux fins d'une étude détaillée avec usage des données et observations de terrain (MES dans les rivières). Ces résultats sont par la suite comparés aux résultats avec usage des modèles numériques utilisant RUSLE (Revised Universal Soil Loss Equation model) pour l'érosion de surface dans GeoWEPP (Geo-spatial interface for Water Erosion Prediction Project), un modèle provenant de USGS (US Geological Survey) –LESAM (Landscape-based Environmental System Analysis & Modeling) qui conduit notamment des simulations en mode continu et sous base de processus pour les petits bassins versants, concernant l'érosion et la sédimentation.Au niveau de ces trois sites sélectionnés, l'utilisation de GeoWEPP comme utile de prédiction et de « design » des mesures de mitigation possibles par usage de solutions d'ingénierie géotechnique combinée à la re-végétalisation ont pu être étudiés et comparés. Les résultats de ces études pourront être utilisés en tant que suggestion de mesures de mitigation des impacts environnementaux relatifs à la construction du pipeline du Projet Ambatovy.

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.

This article presents nano composite TiO2.Fe2O3/laterite materials, which were successfully prepared by hydrometallurgical method. The materials were modified using urea as the nitrogen source. The particles size of the materials is from 20-30 nanometers. The obtained materials can not only absorb arsenic compounds but also enhance the ability of converting As (III) or As (V) into Aso, which is removed from solution. Arsenic removal efficiency of these materials is high. Using sunlight in a hydraulic retention time, about 180 minutes, the arsenic value at the inflow was about 10 mg/L but the outflow was negligible. Covering TiO2.Fe2O3 nano on laterite have brought high economical efficiency, on one hand, it saved material and on the other hand, it can be continuously operated without the centrifugal separation of the nano material.
Bài báo này giới thiệu về phương pháp điều chế vật liệu nano TiO2.Fe2O3 biến tính nitơ được phủtrên đá ong bằng phương pháp thủy luyện. Vật liệu nano thu được có kích thước 20-30 nm. Vật liệu thu được không những có khả năng hấp phụ các hợp chất của asen mà còn có khả năng khử As (III) hoặc As (V) thành Asokhi được chiếu sáng. Sử dụng ánh sáng mặt trời chiếu vào hệ thống xử lý trong thời gian 180 phút có thể loại bỏ được gần như hoàn toàn asen ra khỏi nước mặc dù hàm lượng đầu vào là 10 mg/l. Việc phủ vật liệu TiO2.Fe2O3 nano lên đá ong đã mang lại hiệu quả kinh tế cao, một mặt nó tiết kiệm được vật liệu, mặt khác, vật liệu có thể sử dụng một cách liên tục mà không cần phải tách bằng phương pháp ly tâm.

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.

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Locally available building materials are proven energy efficient and eco-friendly, making them a sustainable building material. In the last two decades, use of raw earth as building material is augmented, owing to the environmental concerns construction industry is also reconsidering the use of raw earth, researchers on the other hand are working to understand the mechanical and dynamic behaviour of earthen buildings, yet the study of mechanical parameters possess multiple challenges due to material inert properties exposing the need of new experimental approaches to extract accurate mechanical parameters. Building techniques such as adobe, compressed earth blocks, rammed earth, and laterite building stones are on a verge of reclaiming elite position in construction industry. In this study, experimental investigation on two naturally available building materials, unstabilised rammed earth (USRE) and laterite building stones (LBS) are carried out. The work focuses on the parameters that need to be considered in the experimental procedures, which influences the mechanical properties of USRE and LBS are seen. The locally available soils in the region of Rhone-alps, France and laterite building stones from Burkina Faso are used in this experimental campaign. Rammed earth walls are constructed by compacting moist soil in layers, due to manufacturing technique there is a density gradient within the layer that leads to heterogeneity. On the other hand, the manufacturing parameters of the USRE such as compaction energy and manufacturing water content have a direct influence on the dry density of the material and therefore the strength. The manufacturing parameters and specimens replicating the in-situ condition are very important to understand the behaviour of USRE wall. Hence an experimental procedure to study the unconfined compressive strength, considering the influence of manufacturing parameters and specimens replicating in-situ conditions are performed along with the cyclic loading and unloading to study the elasto-plastic property of the USRE. The test procedure is performed on two different soils that are used to build USRE structures. Along with the compressive strength of USRE, the tensile strength and flexural strength are also presented by subjecting specimens under split tensile test and four point bending test. Another important parameter is the mechanical strength properties of USRE layer interface under lateral loads. A novel experimental procedure to study the interface strength properties are discussed in this study. The experimental procedure is simple and xii compact that can be performed using a simple uniaxial press using inclined metallic wedges that allows rectangular prism to undergo bi-axial loading. With the help of inclined metallic wedges, shear stress and normal stress can be induced on the specimen interface allowing to obtain coulomb’s failure criteria and hence the strength properties of the interface. Laterite building stones (LBS) which are mainly used in tropical countries are porous in nature. The moisture retention capacity of porous building material will bring indoor comfort, but the presence of water molecules within the material and their variation to the outdoor environment is responsible for complex mechanical behaviour. Hence an experimental investigation to analyse the moisture ingress of LBS and their influence on mechanical strength is designed. The moisture ingress is studied by subjecting LBS for moisture sorption and desorption test and moisture buffering test. Then the influence of moisture ingress on mechanical strength (flexure and compression) are investigated using three point bending test and unconfined compression test with loading and unloading cycles. This experimental investigation allows studying the moisture ingress and their influence on strength along with elasto-plastic behaviour of LBS

Lateritisation is associated with tropical climates and geomorphic conditions of peneplanation where hydromorphic processes of weathering predominate. Laterites are products of relative (residual) and absolute(chemical) accumulation after leaching of mobile constituents. Their major element chemistry is controlled by the aluminous character of bedrock and drainage. Bauxitisation is characterised by residual gibbsite neoformation and lateritisation, by both residual accumulation and hydromorphic precipitation of goethite controlled by the redox front at the water table. The laterite forms part of a weathering profile that is underlain by saprock, saprolite, the mottled zone and overlain by a soil horizon. The secondary gold in laterites has its source invariably with mineralised bedrock. The distribution of secondary gold is controlled by mechanical eluviation and hydromorphic processes governed by organic, thiosulphate and chloride complexing. The precipitation of secondary gold is controlled by pH conditions, stability of the complexing agent and ferrolysis. Gold-bearing laterites are Cainozoic in age and are best developed on stable Archean and Proterozoic cratons that have suffered epeirogenesis since lateritisation. Mechanical eluviation increases in influence at the expense of hydromorphic processes as a positive function of topographic slope and degradation rate. Gradients greater than 10⁰ are not conducive for lateritisation, with latosols forming instead. High vertical degradation rates may lead to the development of stone lines. In the Western Australian case, post-laterite aridification has controlled the redistribution of secondary gold at levels marked by stabilisation of the receding palaeowater table. Mineable reserves of lateritic ore are located at Boddington, Westonia and Gibson toward the south-west of the Yilgarn Block. A significant controlling variable appears to be the concentration of chloride in the regolith. Based on the Boddington model, the laterite concentrates the following elements from bedrock gold lodes: i) Mo, Sb, W, Hg, Bi and Au as mobile constituents. ii) As and Pb as immobile constituents. Geochemical sampling of ferruginous lag after bedrock and laterite has provided dispersed anomalies that are easily identifiable. "Chalcophile corridors" up to 150 km in length are defined broadly by As and Sb but contain more discrete anomalies of Bi, Mo, Ag, Sn, W, Se or Au, in the Yilgarn Block. The nature of the weathered bedrock, the tabular distribution of secondary gold ore deposition and the infrastructural environment lends the lateritic regolith to low cost, open-cut mining. The western Australian lateritic-gold model perhaps can be adapted and modified for use elsewhere in the world.

Arsenic (As) contaminated groundwater has been a major concern due to the negative impacts to exposed people. This research was conducted to assess and compare the removal efficiency of As from groundwater by laterite, sand, and ash. The experiment was carried out in 14 days in a household scale in Son Dong commune, Hoai Duc district, Ha Noi. Groundwater was pumped directly from a well and flowed through 20 cm (diameter) x 80 cm (length) columns. The initial As concentration in groundwater was 526 μg/L decreasing to an average of 189, 192 and 154 μg/L after being filtrated using sand, ash, and laterite, respectively. Average removal efficiency of sand, ash and laterite during the experiment was 63.3, 63.9, and 70.5%, respectively. Laterite had higher As removal efficiency may be due to higher content of goethite and kaolinite in this sorbent which resulted in better adsorption of As. The concentrations of As in the outflow water were higher than the allowable limit set by the national technical regulation on drinking water quality (QCVN 01:2009/BYT). Therefore, it requires higher volume of sorbents or additional treatment technologies for removal of As from groundwater.
Ô nhiễm asen (As) trong nước ngầm hiện nay là một vấn đề cấp bách đối với xã hội bởi những rủi ro tiềm ẩn với sức khoẻ con người. Nghiên cứu được thực hiện nhằm đánh giá và so sánh khả năng hấp phụ As trong nước ngầm của đá ong, cát và tro. Thí nghiệm được tiến hành trong vòng 14 ngày đặt tại một hộ gia đình có nguồn nước ngầm bị ô nhiễm As thuộc xã Sơn Đồng, huyện Hoài Đức, Hà Nội. Nước ngầm được bơm từ giếng và chảy qua các cột đựng vật liệu có đường kính và chiều dài lần lượt là 20 cm và 80 cm. Nồng độ As ban đầu là 526 μg/L đã giảm xuống còn 189, 192 và 154 μg/L sau khi lọc bằng cát, tro và đá ong. Hiệu suất xử lý As trung bình của cát, tro và đá ong lần lượt là 63,3, 63,9 và 70,5 μg/L. Đá ong xử lý As tốt hơn có thể do hàm lượng goethit và kaolinit cao hơn trong vật liệu hấp phụ này dẫn đến khả năng hấp phụ As tốt hơn. Tuy nhiên hàm lượng As trong nước đầu ra vẫn chưa đạt quy chuẩn cho nước uống (QCVN 01:2009/BYT). Do đó, cần tăng thêm lượng vật liệu hoặc kết hợp với các phương pháp khác để xử lý As hiệu quả hơn.

In several parts of Burkina Faso, there is an urgent need of making arsenic contaminated water potable. The shallow, dug out wells traditionally used in the rural areas provides small, inconsistent yields and are vulnerable to microbes. Consequentially, many of them have now been replaced with drilled tube-wells, intercepting water from fractures in the bedrock and providing reliable water sources. However, as arsenic is naturally present in the bedrock in many parts of the country, previous studies has shown that water from a lot of these wells is not safe to drink. In some cases, the wells had to be closed due to high arsenic concentrations. The medical effect of the arsenic exposure has also been evaluated among the inhabitants of affected villages, indicating that the problem is critical. Previous studies in this project were focused on using the commercial material Granular Ferric Hydroxide (GFH) as a possible method for arsenic removal in the villages. As the price of GFH however is too high, other methods has been researched instead. In this study, natural laterite rock has been crushed and used as adsorbent in column experiments, but indicating a low arsenic capacity. The same lateritic sand has then been coated in ferrihydrite both by drying the materials together in the oven and by a centrifugation method previously evaluated in Uppsala, Sweden. Although results after the ferrihydrite-coating improved, the adsorption capacity was still significantly lower than that of GFH. The results from the ferrihydrite-coated sand also differed largely from those previously found in Uppsala, and though this could be due to the fact that this study was made with natural water instead, it is thought that the inevitable alterations in the coating method might have affected the result of the coating to a great extent. The conclusion of this study is therefore that ferrihydrite-coated sand still is a possible low-cost adsorbent material for arsenic contaminated water in developing countries, though factors such as sand material, grain size and coating method should be evaluated further.

The bulk of the world's known nickel reserves are contained in laterite ores but sulphidic ores remain the main source of the Western world's nickel production. With the continuing increase in nickel consumption and the depletion of sulphidic ores, the traditional source of nickel, the extraction of nickel from lateritic ores has been the subject of research interest worldwide. Advances in pressure acid leaching (PAL) technology have resulted in significant commercial attempts to extract nickel from these ores. Leaching the ore with sulphuric acid at elevated temperatures and pressures allows almost complete dissolution of the nickel and cobalt, a valuable byproduct of these ores, but yields highly contaminated pregnant leach solutions. Separating and purifying the nickel and cobalt from these solutions remains a hindrance to full commercial production. Several purifying techniques have been commercialised but all suffer from continuing technical problems. Among them, however, the direct solvent extraction (DSX) technique offers several advantages. Direct solvent extraction involves the separation of the nickel and cobalt directly from the partially neutralised pregnant liquor stream (PLS) by solvent extraction with Cyanex(R) 272 as the extractant. However certain contaminants adversely affect the solvent extraction process. Among them is chromium and little is known about the solvent extraction behaviour of this metal. The present work investigated the solvent extraction of chromium with Cyanex(R) 272. It was found that the solvent extraction behaviour of chromium(III) and chromium(VI), both of which could be found in PAL-generated PLS, are distinctly different.For chromium(III), solvent extraction tests showed that (a) it is extracted in the pH range 4-7; (b) the extraction is partly influenced by diffusion; (c) the apparent equilibration time is significantly longer than most transition metals; (d) increases in temperature from 22 to 40 C resulted in increases in the extraction; (e) the pH0.5 increases in the order nitrate < chloride < sulphate in the presence of these anions; (f) the presence of acetate depresses extraction of chromium(III) when the solution is allowed to stand before extraction; (g) in the PLS, chromium(III) precipitated at lower pH than that predicted by the solubility product principle; and (h) the pH0.5 decreases as the Cyanex(R) 272 concentration increases. Chromium(III) is initially extracted by solvation of its inner sphere complex, which then undergoes further reaction in the organic phase leading to the formation of a much more stable species that is difficult to strip. A reaction scheme together with a description of both the initially extracted and resulting stable species is proposed. Extraction of chromium(VI), on the other hand, (a) occurs at pH less than 2 by solvation of chromic acid; (b) is independent of the aqueous phase composition; (c) does not occur in the pH range (3-6) used in the separation of nickel and cobalt. The latter is irrespective of temperature up to 40 C, the use of industrial PLS as the aqueous phase or the presence of an anti-oxidant in the organic phase. The stripping of chromium(III) from a loaded organic phase can be achieved using 1-4 mol L-1 mineral acids provided the stable organic species have not formed making industrial scale stripping of chromium(III) from Cyanex(R) 272 difficult. The exact composition of the aqueous phase during extraction affects the stripping efficiency.

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.

Algumas indicações morfológicas sugerem que as superfícies de paisagem tropicais onde encontram-se os duricrusts ferruginosos, podem apresentar idades que variam desde o Quaternário até o Cretáceo, e que a laterização sobre estas superfícies pode ter sido iniciada simultaneamente ou não, estabelecendo-se uma sequência cronológica de formação escalonada de acordo com a elevação, em função da evolução geomorfológica das superfícies. Sabendo-se que no Planalto de Diamantina na Serra do Espinhaço Meridional (SdEM) são reconhecidos três níveis geomorfológicos correlatos aos ciclos de aplainamento da plataforma Sul-americana, o objetivo deste trabalho foi estudar as variações mineralógicas, geoquímicas e morfológicas de duricrusts ferruginosos da Serra do Espinhaço Meridional buscando entender os processos genéticos envolvidos e as implicações disto sobre a distribuição e evolução da paisagem regional e suas relações com os ciclos de aplainamento do continente Sul-americano. Para atingir estes objetivos, foram realizadas análises de difratometria de raios X, suscetibilidade magnética, microscopia eletrônica de varredura com sistema de energia dispersiva acoplado e análise elementar a partir da dissolução total dos minerais constituintes. Os resultados mostraram que no Planalto de Diamantina na SdEM coexistem níveis de ferricretes e lateritas na superfície correspondente ao ciclo erosivo Pós-Gondwanico. As superfícies lateríticas são provavelmente as formações supérgenas mais antigas da paisagem regional, originadas durante os processos denudacionais que ocorreram ao longo do ciclo erosivo Pós-Gondwanico. A erosão parcial de seu perfil laterítico constituíram o material fonte de Fe e Al para a gênese dos ferricretes distribuídos em superfícies elevadas (> 1200 m), especialmente aqueles em superfícies em torno de 1400 m de altitude. As variações paleoclimáticas do ciclo Pós-Gondwanico também proporcionaram ciclos erosivos alternados que resultaram no subescalonamento desta superfície, criando condições geomorfológicas favoráveis à gênese de ferricretes mais recentes (1200 - 1400 m). Além disso, os duricrusts ferruginosos do Planalto Diamantina (SdEM) sob influência do maciço quartzítico do Supergrupo Espinhaço e situados superfícies erosivas elevadas (> 1200 m), além de policíclicos, também podem apresentar características poligenéticas.
Some morphological indications suggest that the tropical landscape surfaces where the iron-rich duricrust are present may have ages varying from the Quaternary to the Cretaceous, and that the laterization on these surfaces may have been initiated simultaneously or not, establishing a sequence chronological formation according to the elevation, according to the geomorphological evolution of the surfaces. Three geomorphological levels correlated to the South American platform planing cycles are known on the Diamantina Plateau, for this the objective of this work was to study the mineralogical, geochemical and morphological variations of the iron-rich duricrust of the SdEM, trying to understand the genetic processes involved and the implications of this on the distribution and evolution of the regional landscape and its relations with the planning cycles of the South American continent. In order to reach these objectives, X-ray diffraction, magnetic susceptibility, scanning electron microscopy with dispersive energy system coupled and elemental analysis carried out from the total dissolution of the constituent minerals. The results showed that in the Diamantina Plateau at the SdEM, coexist levels of ferricretes and laterites on the surface corresponding to the Post-Gondwanic erosive cycle. The laterite surfaces are probably the oldest surviving formations of the regional landscape, originated during the denudation processes that occurred along the Post-Gondwanic erosive cycle. Partial erosion of its lateritic profile was source material of Fe and Al for the genesis of ferricretes distributed on high surfaces (> 1200 m), especially those on surfaces at 1400 m of altitude. The paleoclimatic variations of the Post-Gondwanic cycle also provided alternating erosive cycles that resulted in sub-scaling of this surface, creating geomorphological conditions favorable for genesis of earlier ferricretes (1200 - 1400 m). In addition, the ferricretes of the Diamantina Plateau (SdEM) under influence of the Quartzite massif of the Espinhaço Supergroup and located in elevated erosive surfaces (> 1200 m), besides polycyclics, may also present polygenetic characteristics.

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Sulfides exposition to atmosphere promotes its oxidation resulting in acid drainage and mobilization of heavy metals and metalloids in water. Arsenic (As) mobilization can be a serious problem due to anthropogenic activities in the presence of sulfide minerals such as arsenopyrite (FeAsS). The use of limestone gravel is a common practice to neutralize the acid drainage. In this process, mobilization of metals and metaloids is decreased by precipitation, co-precipitation or adsorption onto recently precipitated Fe oxides. In this work, the efficiency of limestone filters for As remotion from water and neutralization of acid drainage was evaluated under field conditions. Arsenic stability in sediments next to a gold exploitation area was evaluated by sequential extraction chemical analyzes. The efficiency of horizontal filters prototypes, containing soil materials combined with limestone, for acidity neutralization and As remotion from acid solutions, was also evaluated in laboratory. Water and sediment samples were collected from creeks in area close to a gold mineralization. Water samples were collected during wet and dry seasons, while sediments were collected only during the wet season. Measurements of pH, Eh, electric conductivity (EC), dissolved oxygen and temperature were registered immediately after water sampling and As concentrations were determined in laboratory. In sediment samples, it was determined texture, particle density, remaining As, organic carbon (OC); As, Al, Ca, Mg and P contents extracted by Mehlich-3, pH in water, potential acidity, As sequential extractions and total contents of As and Fe. In order to evaluate the prototypes, in laboratory, acid solutionswith approximately 58 mg L-1 As were applied throughout PVC modules filled with Laterite (LAT), an Oxisoil (SOLO), a 3:1 mixture of SOLO and organic waste (SOLO+RO), and with limestone gravel (BRITA). Twelve filtration cycles, totalizing applications of 6.2, 67.21, 99.74, 20.22, 10.13 g As, Fe, S, Mg and Ca per filter, respectively, were performed. The residence time of the solution in the filters, as well as pH, CE, acidity and As, Fe, S, Mg and Ca contents in the input and output solutions were monitored. In the field, contents of As in water samples were low, except in two points which presented values above 100 ug L-1. There was not a consistent behavior for As in water samples respective to the collection time, but it could be observed a trend to decrease As concentrations during dry season. In general, As content in sediments was related to the organic matter content. It was observed that sediments and limestone filters play an important role in As mobility in water streams affected by acid drainage. Arsenic was mainly associated to stable fractions of the sediments, with a mean of 58% of the As linked to Fe oxides and residual fractions, which present practically null mobility. In the laboratory, prototypes of limestone gravel filters removed approximately 26 and 23% of the As and Fe applied, respectively. There was no significant sulfate removing or pH alteration in the filtered solutions for all prototypes. However, significant levels of the total acidity neutralization were observed, directly related to the residence time. Prototypes with SOLO+RO presented the highest residence times. The use of soil containing filters associated to limestone filters removed 2.6 and 2.45 times the As and Fe, respectively, removed by the limestone filter. The prototype LAT/BRITA/SOLO presented highest As removal capacity, around 70% of the applied As, and the highest As removal rate, by 1.2 mg min-¹, among soil containing filters. However, the residence time was higher to the filters containing soil materials than to the limestone filters. This can be a disadvantage to the use of soil filters. Notwithstanding, the use of soil materials combined with limestone can be an important strategy to increase the safety of the systems for As removal and acid drainage neutralization during rainy season.
A exposição dos sulfetos ao ar atmosférico promove a sua oxidação, o que pode resultar na acidificação de águas de drenagem e a mobilização de metais pesados e de metalóides. A mobilização de arsênio (As) pode ser um sério problema decorrente de atividades antropogênicas, na presença de minerais sulfetados, como a arsenopirita (FeAsS). O uso de britas de calcário é uma prática bastante utilizada para neutralizar a drenagem ácida. Neste processo ocorre a limitação da mobilização de metais por precipitação, co-precipitação e adsorção em óxidos de Fe recentemente precipitados. O presente trabalho avaliou a eficiência de filtros de brita calcária na remoção de As; e a neutralização da drenagem ácida, em condições de campo. Também foi avaliada a estabilidade do As em sedimentos próximos a área de exploração de ouro, por meio análises químicas de extrações seqüenciais. Paralelamente, foi avaliada a eficiência de protótipos de filtros horizontais contendo materiais de solo em conjunto com filtros de brita calcária na neutralização da acidez e remoção de As de solução ácida, em laboratório. Em condições de campo, foram coletadas amostras de água e de sedimentos em córregos de áreas próximas a mineralização de ouro. As amostras de água foram coletadas nos períodos chuvoso e seco, ao passo que os sedimentos foram coletados apenas no período chuvoso. Foram determinados pH, Eh, condutividade elétrica (CE), oxigênio dissolvido e temperatura das amostras de água, imediatamente após a coleta e em laboratório foram determinadas as concentrações de As . Nos sedimentos foram determinados a textura, a densidade de partícula, o pH em água, a acidez potencial, o As-remanescente, o carbono orgânico (CO), os teores de As, Al, Ca, Mg e P extraídos por Mehlich-3, extrações seqüenciais de As, e os teores totais de As e Fe. Para avaliação dos protótipos, em laboratório, foram aplicadas soluções ácidas com aproximadamente 58 mg.L-1 de As através de módulos de PVC preenchidos com laterita (LAT), com Latossolo Vermelho-Amarelo (SOLO), com uma mistura do SOLO e um resíduo orgânico, na proporção 3:1 (SOLO+RO), e com brita calcária (BRITA). Foram realizados 12 ciclos de filtração, totalizando uma aplicação de 6,2; 67,2; 99,7; 20,2; 10,1 g de As, Fe, S, Mg e Ca por filtro, respectivamente. Foram monitorados o tempo de residência da solução nos filtros e os valores de pH, CE, acidez e teores de As, Fe, S, Mg e Ca nas soluções de entrada e saída dos filtros. Em condições de campo, as concentrações de As nas águas foram baixas, com exceção de dois pontos que apresentaram valores acima de 100 ug L-¹. Não se observou um comportamento consistente do As nas águas em relação às épocas de coleta, mas houve uma tendência de diminuição nas concentrações de As no período seco. De modo geral,o teor de As nos sedimentos apresentou certa relação com o teor de matéria orgânica. Verificou-se que os sedimentos e os filtros de brita calcária desempenham importante função no controle da mobilidade do As em cursos d água afetados por drenagem ácida. Nos sedimentos, o As está associado a frações mais estáveis, em média 58 % do total ligado a óxidos de Fe e à fração residual, de mobilidade praticamente nula. Em laboratório, os protótipos dos filtros de brita calcária retiveram aproximadamente 26 e 23 % do As e Fe aplicados, respectivamente. Não houve remoção significativa de sulfatos ou alteração significativa do pH nas soluções filtradas para todos os protótipos de filtros. No entanto, foram observados níveis significativos de neutralização da acidez total na solução filtrada, diretamente relacionados com os tempos de residência. Os protótipos com SOLO+RO apresentaram os maiores tempos de residência. O uso de filtros contendo solo associados a filtros de brita calcária promoveu retenções de até 2,6 e 2,45 vezes mais As e Fe, respectivamente, em relação aos filtros de brita apenas. O protótipo de composição LAT/BRITA/SOLO apresentou maior capacidade de remoção, cerca de 70 % do As aplicado, e maior taxa de remoção de As, cerca de 1,2 mg min-¹. No entanto, o tempo de residência dos protótipos com materiais de solo foi acentuadamente superior aos de brita calcária, o que pode ser uma desvantagem para seu emprego. Não obstante, o uso de materiais de solo em conjunto com brita calcária pode ser uma estratégia importante nos períodos de chuva para aumentar a segurança do sistema de remoção do As e neutralização da acidez das águas de drenagem.

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.

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.

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.

La repartition dans les profils des concentrations cobaltiferes est controlee par deux mecanismes qui interferent: le premier consiste en une accumulation progressive du cobalt dans une tranche donnee de profil correspondant au toit des alterites silicatees, au fur et a mesure de l'approfondissement de l'alteration; le second consiste en une migration progressive du cobalt depuis les zones hautes vers les depressions du toit silicate, formees par la roche en cours d'alteration. Le cobalt est porte par des produits noirs caracteristiques des divers milieux de depot

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.

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.

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.

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.

Estimates of the depth and variation of lateritic weathering profiles are especially important in tropical areas such as Oahu, HI. Shear-wave velocity data were obtained by a new application of Multi-channel Analysis of Surface Waves (MASW) to map the base of the critical zone, to show variations in the LWP, and to derive weathering rates. The MASW technique proved highly capable of imaging the base of the critical zone, confirmed by lithological well data and direct field measurements. Profile thickness can be obtained without drilling, which has applications in engineering and geochemical studies. The measured rate of advance of the weathering front derived from the thickness measured by MASW ranged from 0.019 m/ka to 0.30 m/ka in mesic zones; about 1500 mm of annual rainfall, while a zone of 800 mm of annual rain fall revealed rates ranging from 0.011 m/ka to 0.013 m/ka. These rates are comparable to geochemically derived rates in previous studies. Standard p-wave seismic reflection data were insufficient for detecting boundaries as the weathering boundaries are gradational and do not produce reflections. Shear-wave models also showed internal velocity variations that may be caused by weathering heterogeneity due to textural differences in parental lava flows. Soil chemistry revealed the nature of weathering products as enriched in Al, Fe, Ni, and Cr, and commonly contain alteration minerals such as halloysite, kaolinite, maghemite, and ferrihydrite. Imaging depth limitations were overcome by innovative experiment designs, pushing the boundaries of the current technology. Increasing offsets and combining dispersion curves allowed for a more objective picking of the dispersion curve into the lower frequency domain. Even further improvements were made from a newly developed form of the active/passive technique. These advancements in technology allowed for detailed imaging of the subsurface with greater modeling confidence. This study showed that velocity models derived from MASW are accurately able to describe laterite weathering profiles in terms of depth and variability, expanding the use of the MASW technique beyond its traditional applications and making it a potential tool of interest for many fields of geoscience.

The bulk of the world's known nickel reserves are contained in laterite ores but sulphidic ores remain the main source of the Western world's nickel production. With the continuing increase in nickel consumption and the depletion of sulphidic ores, the traditional source of nickel, the extraction of nickel from lateritic ores has been the subject of research interest worldwide. Advances in pressure acid leaching (PAL) technology have resulted in significant commercial attempts to extract nickel from these ores. Leaching the ore with sulphuric acid at elevated temperatures and pressures allows almost complete dissolution of the nickel and cobalt, a valuable byproduct of these ores, but yields highly contaminated pregnant leach solutions. Separating and purifying the nickel and cobalt from these solutions remains a hindrance to full commercial production. Several purifying techniques have been commercialised but all suffer from continuing technical problems. Among them, however, the direct solvent extraction (DSX) technique offers several advantages. Direct solvent extraction involves the separation of the nickel and cobalt directly from the partially neutralised pregnant liquor stream (PLS) by solvent extraction with Cyanex(R) 272 as the extractant. However certain contaminants adversely affect the solvent extraction process. Among them is chromium and little is known about the solvent extraction behaviour of this metal. The present work investigated the solvent extraction of chromium with Cyanex(R) 272. It was found that the solvent extraction behaviour of chromium(III) and chromium(VI), both of which could be found in PAL-generated PLS, are distinctly different.
For chromium(III), solvent extraction tests showed that (a) it is extracted in the pH range 4-7; (b) the extraction is partly influenced by diffusion; (c) the apparent equilibration time is significantly longer than most transition metals; (d) increases in temperature from 22 to 40 C resulted in increases in the extraction; (e) the pH0.5 increases in the order nitrate < chloride < sulphate in the presence of these anions; (f) the presence of acetate depresses extraction of chromium(III) when the solution is allowed to stand before extraction; (g) in the PLS, chromium(III) precipitated at lower pH than that predicted by the solubility product principle; and (h) the pH0.5 decreases as the Cyanex(R) 272 concentration increases. Chromium(III) is initially extracted by solvation of its inner sphere complex, which then undergoes further reaction in the organic phase leading to the formation of a much more stable species that is difficult to strip. A reaction scheme together with a description of both the initially extracted and resulting stable species is proposed. Extraction of chromium(VI), on the other hand, (a) occurs at pH less than 2 by solvation of chromic acid; (b) is independent of the aqueous phase composition; (c) does not occur in the pH range (3-6) used in the separation of nickel and cobalt. The latter is irrespective of temperature up to 40 C, the use of industrial PLS as the aqueous phase or the presence of an anti-oxidant in the organic phase. The stripping of chromium(III) from a loaded organic phase can be achieved using 1-4 mol L-1 mineral acids provided the stable organic species have not formed making industrial scale stripping of chromium(III) from Cyanex(R) 272 difficult. The exact composition of the aqueous phase during extraction affects the stripping efficiency.

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 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.

No Estado do Pará, convencionalmente são empregados rocha britada ou seixo rolado natural como agregados nas misturas asfálticas. Nas proximidades da região metropolitana de Belém, não há disponibilidade destes materiais, obrigando o transporte destes agregados de boa qualidade de pedreiras e jazidas distantes mais de 170 Km, aumentando consideravelmente os custos de pavimentação. Com o objetivo de redução de custos, buscou-se o estudo de um outro agregado natural nãoconvencional, a laterita, abundante nas proximidades de Belém. Três tipos de ligantes asfálticos foram utilizados nas misturas asfálticas pesquisadas: um asfalto convencional CAP de penetração 50-60 proveniente da refinaria da LUBNOR, no Ceará; um asfalto da refinaria da REMAN da Amazônia modificado por asfaltita; e um asfalto-borracha da região sudeste. Uma quarta alternativa da mistura asfáltica foi considerada, empregando conjuntamente laterita e seixo rolado como agregados. Foi realizada uma análise comparativa das misturas asfálticas baseada em ensaios laboratoriais tais como: dosagem Marshall, danos por umidade induzida, deformação permanente em simulador de tráfego, resistência à tração por compressão diametral, módulo de resiliência e fadiga. Um processo inovador foi concebido para separação e lavagem das lateritas. Os resíduos desta seleção de agregados foram testados de modo a viabilizar seu emprego como material de base ou sub-base. Foi realizada também uma breve análise mecanicista de estruturas de pavimentos com o auxílio do programa ELSYM 5. Concluiu-se que as misturas asfálticas com laterita lavada podem ser usadas em revestimentos de pavimento de vias públicas e de rodovias de baixo volume tráfego obtendo-se os melhores resultados para as misturas de lateritaasfalto com o ligante modificado por asfaltita.
Crushed igenous rocks and washed quartzite gravels are conventional aggregates for asphalt mixes in the State of Pará, northern Brazil. However, these materials are not available in many parts of the state, specially near the city of Belem, the state capital. The current practice is to import these high quality aggregates from the few quarries located in remote sites, leading to a considerable increase in construction costs. To cut down costs, it is necessary to look for alternative sources of natural aggregates. This study attempts to present an alternative solution for asphalt mixtures using a non-conventional natural aggregate: laterites, which are widely available in the metropolitan area. Three types of asphalt binders were used: a conventional one – AC penetration of 50-60, an asphalt cement modified by gilsonite, and an asphalt rubber. A fourth type of asphalt mix was considered, using washed quartzite gravels in addition to the laterite. A comparative analysis was conducted using parameters obtained from laboratory tests like Marshall design, stripping test, wheel tracking test, indirect tensile strength, resilient modulus, and fatigue life. An innovative process was developed to clean the laterite by water washing. Residuals from the process were tested regarding its possible use as a material for pavement base or subbase. Finally, a mechanistic analysis was performed, using ELSYM 5 software. Results indicate a good performance to the hot-mixes and the one with gilsonite modified binder presented the best performance.

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.

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.

O caulim do Rio Capim na Amazônia Oriental se constitui num depósito importante para o Brasil, ocupando lugar de destaque na produção mundial desta matéria prima mineral. Os modelos estabelecem uma origem para a caulinita vinculada ao intemperismo em condições lateríticas (Paleogeno Inferior) a partir de um substrato formado por rochas sedimentares da Formação Ipixuna (Cretáceo Superior). No perfil, destacam-se em ordem de importância entre os compostos de ferro, a hematita e a goethita, minerais pouco estudados no caulim do Rio Capim. A partir dos fácies principais do caulim (fácies caulim macio na base e caulim duro no topo), foram separados e concentrados os minerais de interesse para estudos de detalhe, utilizando a difratometria de raios X (DRX) e a espectrometria de infravermelho por transformada de Fourier (FTIR). Entre os parâmetros determinados, obtiveram-se estimativas da dimensão, forma, área superficial e substituição isomórfica. A interpretação dos resultados evidencia o potencial de aplicação das informações na estimativa do comportamento destes minerais durante o processo de beneficiamento e para a discussão do modelo genético dos perfis de caulim. As goethitas e hematitas de ambos os fácies possuem propriedades muito semelhantes, reforçando o modelo que especula sobre uma origem comum para a fácies caulim macio e caulim duro do perfil. Entre as propriedades, destacam-se a elevada cristalinidade e a baixa participação do alumínio em sua composição, proporcionando a estes minerais um comportamento com resistência moderada a elevada nos processos de lixiviação ácida e a tendência de dissolução preferencial da hematita. O conjunto de características dos óxidos e oxihidróxidos de ferro são compatíveis com uma formação em ambientes hidromórficos, com baixa influência da matéria orgânica a partir de soluções com baixa atividade do ferro, moderadamente redutoras a fracamente ácidas. Dentro do modelo genético da formação do caulim, sua origem não está associada à zona de laterização do perfil, sendo compatível com um ambiente saprolítico e hidromórfico. As propriedades observadas permitem afirmar que os processos naturais que favoreceram a formação da caulinita na base do manto de alteração foram suficientemente longos e intensos para promover a retirada do ferro destas fácies num processo não dissociado no tempo. No modelo, o caulim é uma fácies da base do perfil formado abaixo do nível freático de um espesso perfil laterítico em condições moderadamente redutoras e ácidas com elevada atividade do Si e do Al, porém, com carência de Al disponível para a formação da hematita e da goethita. Neste ambiente, haveria uma lenta mobilização do Fe dentro do perfil sem a necessidade do estabelecimento de um evento excepcional com uma elevada atividade da matéria orgânica, como previsto em alguns modelos.
The Rio Capim Kaolin from the eastern Amazon is recognized as one of the largest deposits of Brazil with a quality and volume that place this area amongst the most important deposits in the world. Despite the importance and the significant amount of studies about kaolin, many questions remain unanswered and the genesis of this occurrence is not well understood. Perhaps, the consensus today is the acceptance of the Rio Capim kaolin origin to be related to a lateritic weathering process during the Early Paleogene, period with favorable geotectonic, duration and climatic conditions to originate a thick cover with the development of a complete weathering profile above a substrate composed by sedimentary rocks of the Ipixuna Formation (Cretaceous). The models consider kaolin to be a bottom facies of a thick lateritic profile, but nowadays the upper lateritic facies was destroyed (probably by erosion periods along the middle to upper Paleogene). The kaolin profile has two facies: the bottom one, which is called soft kaolin, and the upper, differentiated one forming the flint kaolin. Most controversial points are related to the way that the flint kaolin was formed and the mechanism in which the iron was mobilized from the kaolin profile as a whole. This study aims to get some insight about the Rio Capim kaolin development using some properties measured from the iron oxides and oxyhydroxides. The iron and titanium minerals from the kaolin represent the most important contaminants, and a large effort is made by the industry to eliminate their influence but, despite this negative reputation, those minerals also represent a source of valuable information about the environmental conditions of the profile. Among them, hematite is the most widespread in the entire kaolin profile, followed by goethite, whose importance increases in the direction of the flint kaolin facies. Representative samples of kaolin facies were selected from the kaolin profile and submitted to an approach that allowed concentrating the iron minerals and eliminating the influence of kaolinite. Using X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR), a set of properties of the hematite and goethite were determined, including median crystal dimensions, shapes, specific surface area and mineral composition by estimating the isomorphous replacement of iron (Fe) by aluminum (Al). The results show that hematites and goethites do not have enough differences in their properties to support a genesis model with radical changes in their conditions . In terms of behavior to acid leaching, the observed variations were important to predict differences in the rate of mineral dissolution and possibilities of preferential dissolution of hematite in relation to goethite, promoting the increase of the yellow component with the leaching. Both hematite and goethite have high crystallinity and the isomorphous replacement of Fe by Al is low. Comparing the properties observed in synthetic and natural environments, the hematite and goethite from the Rio Capim kaolin profile have characteristics that relate these minerals to a formation environment in hydromorphic conditions where the influence of organic matter was low, with low iron activity, weakly reduced and acidic conditions. These conditions are found in a saprolitic domain in accordance with the bottom facies of a thick laterite profile. Despite agreeing with a laterite model, differences make it difficult to explain iron depletion by organic matter only (Pirabas Event) and the origin of flint kaolin facies by a subsequent and superimposed laterite period. With the hematite and goethite properties found in this study, it is possible to propose that the Rio Capim kaolin is the bottom facies of a laterite profile formed in the zone permanently below the water table. Contrasting with the upper laterite portion of the profile, the bottom zone is in hydromorphic conditions and allowed the fixation of Al and Si to form kaolinite by primary feldspar and mica minerals of the Ipixuna Formation. This environment promotes the slow depletion of iron without the need of an exceptional accumulation of organic matter. The flint kaolin facies was formed in the same period of the soft kaolin facies and the observed differences in the kaolinite morphology are only related to changes caused by the location of this facies in the intermediate zone characterized by the water table fluctuation, but again without the need of subsequent superimposed lateritic processes.