Kinetics of saprolitic laterite leaching by sulphuric acid at atmospheric pressure

Mineralogical analyses of the saprolitic laterite material have been characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, thermal analysis, scanning electron microscope (SEM) and energy dispersive X-ray analysis (EDAX). Results showed that the saprolitic laterite material consists mainly of nickel-substituted lizardite showing the pebble-like morphology and traces of magnetite and phlogopite. Leaching results showed that as much as 84.8% nickel could be leached under the experimental conditions of 10% (v/v) H₂SO₄, 90 °C reaction temperature, leached within 5 min, particle size d₅₀ = 25 μm, stirring at 500 rpm and liquid to solid ratio 3:1. The kinetics of nickel and magnesium leaching from the saprolitic laterite material have been investigated in a mechanically stirred reactor and the activation energies were determined to be 53.9 kJ mol^?1 for nickel and 59.4 kJ mol^?1 for magnesium respectively, which are characteristic for a chemical reaction controlled process. The similarity of the activation energies of nickel and magnesium leaching from the saprolitic laterite material by sulphuric acid means that nickel in lizardite is loosely bound within the octahedral layer and almost all of the nickel could be leached simultaneously with magnesium but without complete decomposition of the silicate structure.     

Agglomeration and column leaching behaviour of goethitic and saprolitic nickel laterite ores

Processability of complex, low-grade nickel (Ni) laterite ores via heap leaching is very limited due to some intractable geotechnical and hydrological challenges such as poor heap porosity/permeability and structural stability. This work presents some investigations on laboratory batch drum agglomeration and continuous column leaching behaviour of saprolitic (SAP) and goethitic (G) Ni laterite ores as part of the quest for an effective ore pre-treatment process for enhanced heap leaching. As a focus, the effect of ore mineralogy/chemistry on the agglomeration and column leaching behaviour of −2 mm (crushed from −15 mm run-of-mine) G and SAP Ni laterite ores was examined. To produce ∼5–40 mm agglomerates in <15 min, the SAP ore required a higher H₂SO₄ (30 wt.%) binder dosage compared with the G ore, although both ores displayed substantially similar, coalescence-controlled agglomeration mechanism. The resulting G agglomerates were more robust than the SAP ones based upon their compressive strength and acidic solution soak test measurements. However, over 100 days of continuous column leaching, the structural stability of the SAP agglomerate bed was slightly greater than that of G agglomerates, reflecting a lesser slump of the former. The pregnant leach solution analysis revealed greater Ni/Co extraction rates from the SAP than the G agglomerates. Whilst the total mass of acid consumed per ton dry ore processed was greater for the SAP ore, the total kg acid per kg Ni extracted was markedly lower. Incongruent leaching of gangue minerals’ constituent elements (e.g., Fe, Mn, Mg, Al and Si) occurred and contributed significantly to the overall acid consumption. The findings show the relevance of agglomeration and column leaching tests for providing useful information for plant designing and optimization of Ni laterite heap leaching operations.     

Innovative technology for processing saprolitic laterite ores by hydrochloric acid atmospheric pressure leaching

An innovative technology for processing saprolitic laterite ores from the Philippines by hydrochloric acid atmospheric leaching and spray hydrolysis is proposed. The factors that affect the hydrochloric acid atmospheric leaching of the laterite ores and spray hydrolysis of the atmospheric acid leach solution are investigated. Experimental results show that the leaching of Ni, Fe, and Mg is 98.9 wt%, 97.8 wt%, and 80.9 wt%, respectively, under optimal acid leaching conditions. The hydrolysis of Ni and Fe by the atmospheric acid leach solution approaches 100 wt% at the temperature range of 450–500 °C. Characterization results show that a serpentine mineral, nominally Mg₃Si₂O₅(OH)₄, is the major component and goethite, FeO(OH), is the minor one in the laterite ores. Treatment by hydrochloric acid atmospheric leaching breaks the mineral lattices of the laterite ores and makes amorphous silica the primary product in the atmospheric acid leach residue. The grade of Ni in the hydrolyzate increases to 4.55%. The hydrolyzate with high Ni content can be utilized for ferro-nickel production.     

Atmospheric acid leaching of siliceous goethitic Ni laterite ore: Effect of solid loading and temperature

In this study, atmospheric acid leaching behaviour of siliceous goethitic nickel (Ni) laterite ore is investigated. Specifically, the effect of −200 μm feed solid loading (30 vs. 45 wt.%) and temperature (70 vs. 90 °C) on leach kinetics, acid consumption capacity and Ni and cobalt (Co) extraction was studied under isothermal, batch (4 h) leaching conditions at pH 1. Incongruent leaching was observed for constituent elements reflecting slow but steady release of value (Ni and Co) and some of gangue metals such as Fe, Mg and Al accompanied by faster and sharp release of Na and Si. Higher temperature and lower pulp solid loading, both led to a 40–50% increase in overall Ni and/or Co extraction and higher acid consumption. At 70 °C and 45 wt.% solid loading, Ni/Co extraction after 4 h was the lowest (∼14/16%) whilst the highest extraction (∼67/56%) was observed at 90 °C and 30 wt.% solid loading. Temperature appeared to have dramatic influence on Ni/Co and other impurity metals’ extractions revealing the chemical reaction controlled nature of the leaching. Higher solid loading and longer leaching time also both slowed down the leach kinetics. A two-stage chemical reactions-controlled leaching mechanism involving a faster initial leaching kinetics followed by a slower leaching at lower rate constants and higher activation energies was established for release of Ni, Co, Fe and Mg. The mechanism reflects the fast leaching of reactive host mineral phases (e.g., clays and Mg–silicates) during first 30 min followed by slow leaching of more refractory mineral phases (e.g., goethite and quartz) during the rest of leaching period. The findings provide a greater understanding for enhanced atmospheric acid leaching process of siliceous goethitic laterite ores.     

Acid leaching and rheological behaviour of a siliceous goethitic nickel laterite ore: Influence of particle size and temperature

This study investigates the isothermal, batch, H₂SO₄ acid leaching behaviour of siliceous goethitic (SG) nickel (Ni) laterite ore and its links to pulp rheology. Specifically, the effect of feed ore particle size (−0.2 vs −2.0 mm), leaching temperature (70 vs 95 °C) and pulp rheology on Ni and pay metal, cobalt (Co) extraction kinetics and yield was studied for 4 h on 40 wt.% solid dispersions at pH 1. The leaching behaviour was distinctly incongruent, reflecting the disproportionate proliferation of major gangue mineral’s constituent elements (e.g., Fe, Al, Mg, Na, Si) alongside Ni and Co in the pregnant leach solution. At 70 °C, Ni/Co extraction rates were notably lower (<20%) in contrast with 95 °C where a significant increase in Ni/Co extraction to 78/77% and 74/77%, respectively, for the −0.2 and −2.0 mm feeds occurred. The slurries displayed a non-Newtonian, shear thinning Bingham plastic rheological behaviour of which the viscosity and shear yield stress increased markedly in the course of 4 h leaching. The pulp viscosity and shear yield stress were greater at lower temperature than at higher temperature and they were also greater in slurries with finer than coarser feed particles. The dynamic pulp rheology, however, had no marked effect on the overall Ni/Co extraction rates. Whilst the feed ore particle size had no remarkable impact on overall Ni/Co extraction, it led to noticeably higher acid consumption and enhanced slurry rheology in the finer sized ore. The mechanism of leaching the SG ore followed a two-stage, first order chemical reaction-controlled shrinking core model, the kinetics of which gave higher rate constants and lower activation energies for the release of Ni, Co, Fe and Mg in the first stage. A faster leaching process involving more reactive minerals during the first 30 min is envisaged to be followed by leaching of the more refractory minerals.     

Iron solubilization during anaerobic growth of acidophilic microorganisms with a polymetallic sulfide ore

Acidithiobacillus ferrooxidans at 30 °C and Sulfobacillus thermosulfidooxidans at 47 °C were selected from a preliminary screening of various acidophiles for their ferric iron reduction capacities during anaerobic, autotrophic growth on sulfur. The selected cultures were used with a polymetallic sulfide ore under anoxic conditions to demonstrate enhanced solubilization of iron during leaching in shaken flasks and enhanced removal of iron from laboratory ore-leaching columns, compared to leaching with continuous aeration. Ore-associated, ferric iron-rich precipitates, which were formed under previously oxidizing conditions, were a potential influence on extraction of target metals and percolation through ore columns and were available as the source of ferric iron for anaerobic sulfur oxidation. Over twice as much iron was removed by moderate thermophiles when anoxic phases were introduced during the leaching. Enhanced removal of iron and some improvement in extraction of base metals from ore fragments were also demonstrated with a selected “Sulfolobus”-like strain during growth and leaching with alternating periods of aeration and anoxic conditions at 70 °C.     

Calcination of low-grade laterite for concentration of Ni by magnetic separation

With the continuous depletion of high-grade nickel ores such as millerite and niccolite, nickeliferous laterites have become the major source for the production of nickel metal. However, only 42% of the world’s production of nickel comes from laterites, since the concentration of Ni is relatively low (ca. 2 wt.%). In addition, other metals, such as magnesium, iron and silicon can be found in laterite, which make the concentration of nickel even more difficult.In this study, a low-grade nickeliferous laterite ore was first calcinated and then processed by using a wet magnetic separator in order to recover nickel. Since, the ore contains both Ni and Fe, the calcination of laterite is effective in altering the crystalline structure of Fe species and therefore its magnetic properties, which in turn enable the selective concentration of nickel by magnetic separation that is an easy and environmentally-friendly technique. The experimental results have indicated the importance of carefully controlling: (1) the calcination temperature; (2) the pulp density and (3) applied magnetic field strength. The main finding of this work was that magnetic separation is effective in recovering 48% of nickel from laterite, increasing the Ni grade in the recovered product from 1.5% to 2.9%, when prior to the separation the ore was calcinated at 500 °C for 1 h.     

Selective pressure leaching of Fe (II)-rich limonitic laterite ores from Indonesia using nitric acid

The selective extraction of nickel and cobalt over iron from an Indonesian limonitic laterite was investigated using nitric acid pressure leaching (NAPL). The mineralogical analysis showed that the major minerals were goethite and magnetite, and the content of the divalent iron was as high as 7.06%. Nickel and cobalt were mainly distributed in these two minerals; however, the distribution was non-uniform. A series experiments were conducted to examine the basic parameters and propose the optimal conditions for the extraction. When the ore was treated via HPAL under the optimal condition, the extracted nickel and cobalt were less than 75%, and the iron concentration in the leach liquor was over 12.5 g/L. By contrast, over 85% of nickel and cobalt were extracted and about 1.8 g/L iron was achieved using NAPL. The loss of nickel and cobalt can be mainly attributed to the undissolved magnetite and manganese minerals. The leaching process of NAPL is a dissolution–oxidation–precipitation mechanism, and in this process nitric acid acts as both a lixiviant and an oxidant. The formation of hematite results in a low iron concentration in the leach liquor without oxygen injected. Meanwhile, the oxidation and the precipitation of dissolved divalent iron results in a calculated savings in acid consumption of about 120 kg nitric acid per ton of ore can be obtained, which is equal to over 93 kg of sulfuric acid per ton of ore. Moreover, lower residual acid (20 g/L nitric acid) is a significant advantage of NAPL. The iron residues had a high iron content (>56 wt%) with no sulfur, making it suitable as raw materials for ironmaking.     

Copper leaching from waste electric cables by biohydrometallurgy

This study examines the leaching of copper from waste electric cables by chemical leaching and leaching catalysed by Acidithiobacillus ferrooxidans in terms of leaching kinetics and reagents consumption. Operational parameters such as the nature of the oxidant (Fe³⁺, O₂), the initial ferric iron concentration (0–10 g/L) and the temperature (21–50 °C) were identified to have an important influence on the degree of copper solubilisation. At optimal process conditions, copper extraction above 90% was achieved in both leaching systems, with a leaching duration of 1 day. The bacterial leaching system slightly outperformed the chemical one but the positive effect of regeneration of Fe³⁺ was limited. It appears that the Fe²⁺ bio-oxidation is not sufficiently optimised. Best results in terms of copper solubilisation kinetics were obtained for the abiotic test at 50 °C and for the biotic test at 35 °C. Moreover, the study showed that in same operating conditions, a lower acid consumption was recorded for the biotic test than for the abiotic test.     

Recovery of nickel from lateritic nickel ore using Aspergillus niger and optimization of parameters

The present study deals with the extraction of nickel from lateritic nickel ore of Sukinda mines, Orissa, through microbial leaching using Aspergillus niger. The presence of significant metals in oxidic nickel ores, are potential sources of nickel for the future. Thus, experiments were carried out with ore to optimize the conditions for maximum nickel recovery. Experiments designed as per central composite design technique, were carried out for fitting an empirical reduced second order model. The factors studied were sucrose concentration, pulp density, temperature and duration. In addition to main effects of four factors, sucrose concentration, pulp density and duration had quadratic effect on the percentage extraction and there were interactions between different factors also. There was also significant interaction between temperature and duration as well as sucrose and pulp density. The F-value for the model shows that model is significant at less than a 0.01% level (i.e. at 99.99% confidence level). The predicted maximum nickel extraction was 31.34% with a pulp density of 8.75%, sucrose concentration of 10.04 g/l, temperature 33.8 °C and duration of 37.5 days.     

TGA kinetic study on the hydrogen reduction of an iron nickel oxide

Reduction of a mixed iron nickel oxide by hydrogen to produce ferronickel alloy was investigated by thermo-gravimetric analysis (TGA). The iron nickel oxide, which contains 50 wt% Fe and 10 wt% Ni mainly in the form of hematite (Fe₂O₃) and nickel ferrite (NiFe₂O₄), is a residue produced from the water leaching of a selectively sulfation roasted nickel calcine. Continuous heating tests with a fixed heating rate as well as isothermal tests were performed. Results indicate that the reduction of the mixed oxide began above 350 °C. The reduction reactions occurred in a non-topochemical mode at low temperatures between 350 °C and 600 °C with its rate controlled by the solid–gas chemical reactions. The reduction rate increased with the increase in temperature from 350 °C up to 1100 °C. Between 600 °C and 1200 °C, the rate controlling step was the diffusion of reducing gas through the pores of the sample bed with an apparent activation energy of 34.1 kJ/mol. Due to the melting of the silicate material at 1200 °C which substantially reduced the sample porosity, the reduction rate decreased. Above 1200 °C, the reduction rate increased again due to the increased diffusion of the reducing gas through the molten sample at higher temperatures.     

Changes in an Australian laterite ore in the process of heat treatment

This paper examines an Australian garnieritic-type ore and changes in phase composition and morphology caused by heating in argon at 400–1000 °C using XRF, XRD, DTA/TG, SEM/EDS and BET analyses. The mineral phases detected by XRD in the original ore include chlorite, talc, hematite and quartz. Traces of iron silicate, Fe–Cr spinel and monoxide phase (predominantly manganese oxide) were observed by EDS. Nickel was detected in chlorite, talc, iron silicate and monoxide phase. Heat treatment at 400–500 °C did not change XRD patterns. At 600 °C, dehydroxylation of the brucitic phase of chlorite occurred. Chlorite was converted into olivine (forsterite) and enstatite at 600–800 °C. Upon heating to 900–1000 °C, talc was also converted into olivine and enstatite. Ni-bearing phases after heat treatment at 800–850 °C were forsterite, enstatite, talc, iron silicate and monoxide.     

Selective sulphidation and flotation of nickel from a nickeliferous laterite ore

The sulphidation of a nickeliferous lateritic ore was studied at temperatures between 450 and 1100 °C and for sulphur additions of 25–1000 kg of sulphur per tonne of ore. The experiments demonstrated that the nickel could be selectively sulphidized to form a nickel–iron sulphide. It was found that both the grade and the sulphidation degree largely depended upon the temperature and the sulphur additions, with temperatures above 550 °C exhibiting the highest nickel sulphidation degrees and grades. A DTA/TGA with mass spectrometer was used to further elucidate the nature of the phase transformations that occurred upon heating of the ore in the presence of sulphur.It was found that at low temperatures, the Fe–Ni–S phase was submicron in nature and heating to temperatures between 1050 and 1100 °C allowed for the growth of the particles, due to the increased sulphide mobility associated with the formation of a liquid sulphide matte phase, containing dissolved oxygen. Flotation studies conducted on 60 g samples showed that the sulphides responded to flotation with maximum grades of up to 6–7 wt.% nickel being achieved. Recoveries were approximately 50% on a sulphide basis and it was determined that the low nickel grades were due to the entrainment of magnetite fines.     

The effect of seawater based media on copper dissolution from low-grade copper ore

Due to the scarcity of water in the north of Chile, there is interest in small-scale mining using seawater to leach the minerals. This situation has led to this research aimed to determine the effect of different process variables on the extraction of copper based on the ore type of these small-scale mining activities. The extraction of copper from finely ground (<150 μm) low-grade mixed ore (0.36% Cu) was studied in different acidic media (H₂SO₄ and HCl). The effects of water quality (tap water, seawater and synthetic process water) and lixiviants on copper leaching were investigated at three temperatures (25 °C, 35 °C and 45 °C). Synthetic process water was prepared by adding Na⁺, Cl⁻, Cu²⁺ and SO₄²⁻ to seawater. Copper extractions between 70% and 80% were achieved in 48 h using seawater, similar to the extractions obtained using tap water. Rapid copper dissolution occurred when synthetic process water was used, from 90% to 97%. This marked increase was related to the addition of Cu²⁺, which promoted the formation of CuCl⁺. Seawater was comparable to freshwater in terms of leaching kinetics and yield potential by raising the chloride concentration and increasing the formation of copper chloride ions. The findings of this study also expanded our understanding of the consequences of substituting seawater for freshwater at industrial leaching operations.     

Leaching of manganese ores using sawdust as a reductant

In this study sawdust was used as reductant for sulphuric acid leaching of manganese ore. Effects of pulp density, amount of acid, temperature, particle size of ore and amount of sawdust were studied. Manganese extraction of ∼98% was achieved under the conditions: leaching time 8 h, 5% H₂SO₄ (v/v), 10% pulp density, 90 °C and 5% sawdust (w/w), i.e. 0.5 g/g ore. Other Mn containing materials like low grade manganese ore, manganese nodule and Mn-nodule leach residues were tested and all these materials responded well giving more than 98% Mn extraction.     

Determining the effect of acid stress on the persistence and growth of thermophilic microbial species after mesophilic colonisation of low grade ore in a heap leach environment

The microorganisms involved in the bioleaching of sulphidic mineral ores are acidophilic. Generally, a pH in the range of pH 1–2.5 is applied for optimal growth in these systems. In operating heaps, perturbation of conditions could result in changes in the pH outside this “safe” window, so an understanding of the effect of changes in pH on growth and activity of bioleaching microbes is needed. Previous work has shown that some microorganisms e.g. Acidithiobacillus thiooxidans, Leptospirillum ferriphilum and Leptospirillum ferrooxidans are able to adapt to low pH environments (∼pH 0.9). However, most studies on the response of micro-organisms implicated in mineral bioleaching to pH have been conducted under submerged, aerated culture conditions, with limited performance-based studies conducted under conditions mimicking a heap environment. In this study, the effect of acid stress on the persistence of the thermophilic micro-organisms in the ore bed inoculated at mesophilic conditions and their subsequent growth on reaching thermophilic conditions is considered.Following inoculation, five columns loaded with a low grade chalcopyrite ore were irrigated at a feed pH of 1.7 at 25 °C. After a few days, the temperature was sequentially increased from 25 °C through 37 °C to 50 °C, resulting in an Eh above 850 mV across all columns. The irrigation feed pH was then varied across the range pH 1.0 to 1.7 at 50 °C. Eh values greater than 800 mV could be attained in the columns with feed pH values between pH 1.2 and pH 1.7 at 50 °C. The Eh of the column receiving feed solution at a pH of 1.0 at 50 °C dropped to below 700 mV and did not recover. The temperature was then increased gradually to 60 °C. All the columns with feed pH of 1.2 and higher achieved Eh values above 800 mV. Quantitative analyses of the microbial community on selected PLS and ore samples indicated that lower pH affected the persistence of the thermophilic micro-organisms in the ore bed and their subsequent growth on reaching thermophilic conditions. The microbial population detached from the ore sample after 120 days decreased by a factor of 5–15 and 25–100 fold on decreasing the operating pH from 1.5–1.7 to 1.4 and 1.2 respectively. Poor microbial activity was found at pH 1.0, suggesting ineffective growth or persistence of the archaea.     

A novel method to recover zinc and iron from zinc leaching residue

A novel method to recover zinc and iron from zinc leaching residue (ZLR) by the combination of reduction roasting, acid leaching and magnetic separation was proposed. Zinc ferrite in the ZLR was selectively transformed to ZnO and Fe₃O₄ under CO, CO₂ and Ar atmosphere. Subsequently, acid leaching was carried out to dissolve zinc from reduced ZLR while iron was left in the residue and recovered by magnetic separation. The mineralogical changes of ZLR during the processes were characterized by XRF, TG, XRD, SEM–EDS and VSM. The effects of roasting and leaching conditions were investigated with the optimum conditions obtained as follows: roasted at 750 °C for 90 min with 8% CO and CO/CO + CO₂ ratio at 30%; leached at 35 °C for 60 min with 90 g/l sulfuric acid and liquid to solid ratio at 10:1. The iron was recovered by magnetic separation with magnetic intensity at 1160 G for 20 min. Under the optimum operation, 61.38% of zinc was recovered and 80.9% of iron recovery was achieved. This novel method not only realized the simultaneous recovery of zinc and iron but also solved the environmental problem caused by the storage of massive ZLR.     

Combined extraction of metals and production of Mg(OH)2 for CO2 sequestration from nickel mine ore and overburden

Carbon storage by mineralisation (CSM) is an option for CO₂ emissions mitigation that has been under intensive study at Åbo Akademi (ÅA), Finland. Magnesium from silicate rocks is extracted with recoverable ammonium salts at 250–500 °C. The extracted elements are separated by selective precipitation and Mg is subsequently carbonated in a pressurised fluidised bed. This work studies the applicability of the process for co-extraction of Ni, Cu, Fe and Mg from nickel ore and nickel mine waste rock (overburden). The rock samples were collected from the Hitura Nickel mine, Finland. The results show that it is possible to co-extract the listed elements and integrate CSM (by the ÅA process) with steelmaking and Ni production industries.     

Bioleaching of six nickel sulphide ores with differing mineralogies in stirred-tank reactors at 30 °C

A bioleaching study was conducted with six nickel sulphide ores from different geographical locations across Canada. Mineralogical and chemical examination revealed considerable variability between the samples, particularly in the silicate phases. The ores contain 0.3–1% nickel, primarily in pentlandite and secondarily in pyrrhotite. Copper is present primarily in chalcopyrite, and cobalt in pentlandite. The ores were subjected to the same crushing and grinding procedure, and bioleached under the same conditions for 3 weeks with a mixed culture of iron- and sulphur-oxidizing bacteria. Stirred-tank experiments with finely ground ore (−147 μm) at 30 °C were conducted to assess the effect of pH (2–5) and the impact of the bacteria. Nickel extraction from pentlandite and pyrrhotite during bioleaching at pH 2 and 3 was generally good (49–86% after 3 weeks), and cobalt extraction tracked nickel extraction over most conditions. All six ores showed a similar response to a change in pH; an increase in pH from 2 to 3 resulted in approximately the same nickel and cobalt extraction (within statistical error), and a statistically significant reduction in sulphuric acid consumption, dissolved iron, and magnesium extraction.