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.     

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.     

A study of atmospheric acid leaching of a South African nickel laterite

Nickel and cobalt acid leaching from a low-grade South African saprolitic laterite using sulphuric acid was studied. Ore characterisation was performed by XRD and XRF. Batch agitation leaching tests were conducted at atmospheric pressure investigating main parameters: particle size and percent solids at 25 °C and 90 °C. Ore characterisation showed that the ore is a saprolitic laterite with nickel present in lizardite. Leaching tests showed that nickel and cobalt could be leached from the ore at atmospheric pressure. Nickel was found to be more leachable from the coarser −106 + 75 μm fraction, with 98% Ni being extracted at 90 °C after 480 min. Cobalt was not favoured by variation in particle size and increased percent solids. Increasing ore percent solids improved nickel extraction at 25 °C however at 90 °C extraction decreased due to a diffusion layer build-up as a result of amorphous colloidal silica. The co-dissolution of magnesium and iron was elucidated. Nickel leaching data at increased temperature and percent solids fit the shrinking core model equation, k_dt = 1−2/3x − (1 − x)^2/3 showing that nickel leaching reaction was diffusion controlled under the set conditions.     

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.     

Nickel and cobalt precipitation from sulphate leach liquor using MgO pulp as neutralizing agent

The research work presented in this paper determined the conditions at which nickel and cobalt can be recovered, as easily filterable precipitates, from leach liquors, which are produced by sulphuric acid leaching of nickel oxide ores, at atmospheric pressure. More specifically, nickel and cobalt were precipitated as hydroxides at pH = 9, using MgO pulp as a neutralizing agent, by 99.9% and 99.0%, respectively. At this pH value, manganese, which was contained in the leach liquor, was precipitated having a concentration of about 3% in the final mixed precipitate. Statistical design and analysis of experiments were used in order to determine the main effects and interactions of the precipitation factors, which were the pH at equilibrium and the addition of seed material. The characterization of the produced mixed precipitate was carried out by X-ray diffraction, TG–DTA, scanning electron and optical microscopy and particle size distribution analyzer. The main mineralogical phases in the precipitate were theophrastite (Ni(OH)₂) and brucite (Mg(OH)₂). The microscopic observation revealed that the presence of brucite was, mainly, due to the un-reacted MgO pulp, during the precipitation process. This brucite content acted as seed material for nickel precipitation.     

Activation pretreatment of limonitic laterite ores by alkali-roasting method using sodium carbonate

Activation pretreatment of Cr-containing limonitic laterite ores by Na₂CO₃ roasting to remove Cr and Al, as well as its effect on Ni and Co extraction in the subsequent pressure acid leaching process were investigated. X-ray diffraction (XRD), thermogravimetric (TG), and scanning electron microscopy/X-ray energy dispersive spectroscopy (SEM/XEDS) techniques were used to characterize the laterite ores and the water leaching residues of alkali roasting and found that goethite is the major Ni-bearing mineral and chromite the minor one. Alkali-roasting pretreatment breaks the mineral lattices of the laterite, exposing their Ni and Co, which leads to higher extraction of these two metals under milder operation conditions in the subsequent pressure acid leaching process. Experimental results showed that the leaching of Cr and Al were up to 99 wt% and 80 wt%, respectively, under optimal alkali roasting and water leaching conditions. Compared with the direct pressure acid leaching of the raw laterite ores, leaching of Ni and Co increased from 79.96 wt% to 97.52 wt% and 70.02 wt% to 95.33 wt%, respectively, after alkali-roasting activation pretreatment was performed. Meanwhile, the grade of acid leaching iron residues increased from 55.31 wt% to 62.92 wt%, and these residues with low Cr content could be more suitable as the raw materials for iron-making.     

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.     

Use of oxidation roasting to control NiO reduction in Ni-bearing limonitic laterite

Use of limonitic laterite as an iron source in conventional ironmaking is restricted due to its gangue composition and small particle size. Even direct reduction cannot effectively produce direct reduced iron (DRI) because NiO would be reduced together with iron oxide to form Fe–Ni. A small amount of Ni (about 2 wt.%) in DRI degrades the physical properties of final steel products. The current study investigated how oxidation roasting of limonitic laterite ores affected NiO reduction, with the goal of producing Ni-free DRI and Ni-bearing slag. Ni-bearing slag can be a good secondary Ni resource. Oxidation roasting made NiO inert under H₂ reduction at 900 °C by forming Ni-olivine. Optimum roasting temperature was proposed by examining phase transformation of limonitic laterite ores during heating and by FactSage calculation of the equilibrium Ni fraction in Ni-bearing phases. Furthermore, the effect of Mg–silicate forming additives on the control of NiO reducibility was clarified to maximize the suppression of NiO reduction. Among various additives such as MgSiO₃, Mg₂SiO₄ and Fe–Ni smelting slag, Ni-free olivine-typed flux was found to be the most effective form of Ni-olivine because Ni–Mg ion exchange between Ni-bearing phase and Ni-free olivine occurs more readily than other Ni-olivine formation schemes. Finally, the mechanism of Ni-olivine formation during roasting was studied using a diffusion couple test. Calculated diffusivity values of Ni in Mg₂SiO₄ indicated that the two major routes of Ni-olivine formation while roasting limonitic laterite ore are (1) Ni partitioning within Mg–Ni silicate before crystallization and (2) Ni diffusion from spinel to Ni free olivine after crystallization.     

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.     

A novel approach for recovery of rare earths and niobium from Bayan Obo tailings

It is difficult to economically recover rare earths (RE) and niobium (Nb) from Bayan Obo tailings by the existing metallurgical processes. In this study, a novel hydrometallurgy process was employed for separating and recovering RE and Nb from Bayan Obo tailings. Firstly, by sulfating roasting at 250 °C and subsequent leaching at 60 °C, the RE and Nb present in the polymetallic minerals can be efficiently extracted into the leach solution. Secondly, after the reduction of Ti⁴⁺ and Fe³⁺ ions (to Ti³⁺ and Fe²⁺ ions) with iron powders followed by hydrolysis at pH 2.01, the Nb can be efficiently precipitated from the leach solution. The impurities present in the precipitated product can then be removed by treating with NH₃⋅H₂O–H₂C₂O₄ system at pH 4.50. Thirdly, the RE can be efficiently precipitated at pH 7.15 from the filtrate of above hydrolysis reaction mixture. Finally, the impurities present in the crude RE can be removed by oxalate co-precipitation method. The yield of RE and Nb in this novel process reaches up to 90% and 78%, respectively. Both the Nb (60.67 wt% Nb₂O₅) and RE products (>88.65 wt% RE_xO_y) have high application value.     

Simulated small-scale pilot plant heap leaching of low-grade oxide zinc ore with integrated selective extraction of zinc

The leaching of low-grade oxide zinc ore and simultaneous integrated selective extraction of zinc were investigated using a small-scale leaching column and laboratory scale box mixer-settlers. Di-2-ethylhexyl phosphoric acid (D2EHPA) dissolved in kerosene was used as an extractant. The results showed that it was possible to selectively leach zinc from the ores by heap leaching. The zinc concentration of the leach liquor in the first leaching–extraction circuit was 32.57 g/L, and in the 16th cycle the zinc concentration was 8.27 g/L after the solvent extraction. The leach liquor was subjected to solvent extraction, scrubbing and selective stripping for the enrichment of zinc and the removal of impurities. The pregnant zinc sulfate solution produced from the stripping cycle was suitable for zinc electrowinning.     

Leaching behaviour of natural and heat-treated brannerite-containing uranium ores in sulphate solutions with iron(III)

Uranium leaching tests were conducted on two naturally occurring, highly metamict brannerite ores from the Crockers Well and Roxby Downs deposits, South Australia. The ores were leached over a range of temperatures and Fe^(III) and H₂SO₄ concentrations. As well, samples of the ores were calcined at 1200 °C in air to investigate the effect of thermally induced recrystallisation on uranium dissolution. For the unheated samples, a maximum of ∼80% U dissolution was obtained using an Fe^(III) concentration of 12 g/L, an acid concentration of 150 g/L H₂SO₄ and a temperature of 95 °C. The heat treated samples performed poorly under identical conditions, with maximum uranium dissolution of <10% recorded. High uranium dissolution from natural brannerite can be achieved providing; (i) acid strength, oxidant strength and temperatures are maintained at elevated levels (compared to those traditionally used for uraninite leaching), and, (ii) the brannerite has not undergone any significant recrystallisation (e.g. through metamorphism).     

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.     

Complex treatment of mining and metallurgical wastes for recovery of base metals

A complex process for the recovery of copper and zinc from mining and metallurgical wastes has been investigated and proposed. It includes sulfuric acid leaching of old pyrite flotation tailings to produce ferric containing leach solution; followed by ferric leaching of copper converter slag flotation tailings with the leach solution. A sample of old pyrite flotation tailings from the concentrator containing 0.36% of copper and 0.23% of zinc was leached with 10% sulfuric acid in the column. Recovery of copper and zinc reached 47.1% and 47.2%, respectively. The pregnant leach solutions contained 15.9 g/L of ferric iron. The subsequent ferric leaching of copper converter slag flotation tailings containing 0.53% copper and 2.77% zinc with the pregnant leach solution was conducted. The effects of various process parameters on the leaching dynamics of metals under batch conditions were investigated. Under the best conditions (temperature 70 °C, pulp density 30%, ferric iron concentration 15.9 g/L, initial pH of the pulp 0) the recovery of copper and zinc reached 79.6% and 43.7%, respectively. It was concluded that acid leaching of base metals from old pyrite flotation tailings with pregnant leach solution for the ferric leaching of copper converter slag flotation tailings is a prospective and promising technique for the complex treatment of mining and metallurgical wastes.     

Oxidation of Fe(II) in a synthetic nickel laterite leach liquor with SO2/air

Under specific controlled conditions, the addition of SO₂ to oxygen or air produces the peroxy-monosulphate free radical in solution, which is a stronger oxidant than oxygen alone. In this study, the practical strategies required to optimise the oxidation of Fe(II) with SO₂/air was investigated at 75 °C as part of a process to remove iron as Fe(III) oxides from a synthetic nickel laterite high pressure acid leach solution containing 5 g/L Fe(II), 1 g/L Fe(III), 8 g/L Ni, 30 g/L Mg in sea water at pH about 2. The rate of Fe(II) oxidation was optimised in the pH range of 1.2–2.0 with respect to SO₂/air ratio and gas flow rates for minimum production of H₂SO₄ and maximum utilisation of SO₂. In order to minimise the air flow rates into the reactor vessel, the maximum rate of SO₂ addition that could be employed with air was established whilst maintaining oxidising conditions. The results provide strategies for commercial applications of the SO₂/air oxidising system and indicate important factors for reactor design.     

Copper leaching from chalcopyrite concentrate in Cu(II)/Fe(III) chloride system

This study was conducted to develop a novel process for copper recovery from chalcopyrite by chloride leaching, simultaneous cuprous oxidation and cupric solvent extraction to transfer copper to a conventional sulfate electrowinning circuit, and hematite precipitation to reject iron. Copper leaching from chalcopyrite concentrate in ferric and cupric chloride system was investigated using a two-stage countercurrent leach circuit under a nitrogen atmosphere at 97 °C to minimize the concentrations of cupric and ferric ions in pregnant leach solution for subsequent copper solvent extraction while maintaining a maximum copper extraction. A high calcium chloride concentration (110–165 g/L) was used to maintain a high cuprous solubility and enhance copper leaching. With 3–4 h of leaching time for each stage, the copper extraction reached 99% or higher while that of iron was around 90%. With decreasing concentrate particle size from p80 of 26 to 15 μm, the copper extraction increased by about 0.2% while the iron extraction increased by about 2.0%. The concentration of Cu(II) + Fe(III) in the pregnant leach solution was able to be reduced to 0.04 M. When the cupric concentration fell below the above limiting value, the elemental sulfur present was reduced by cuprous ions to form copper sulfide, eventually stopping the leaching of copper. Under this condition, only iron was leached. A very small amount of sulfur (1.2–1.4%) was oxidized to sulfate, resulting in an increase from 3 to 9 g/L in HCl concentration. The extractions of trace metals (Cr, Pb, Ni, Ag and Zn) were 96–100%.     

Ligand-promoted dissolution of serpentine in ultramafic nickel ores

The ligands catechol, citrate, EDTA, oxalate and tiron were investigated for their ability to improve the dissolution of serpentine in ultramafic nickel ores at neutral to alkaline pH to enhance mineral carbon sequestration. It is desirable to leach magnesium from serpentine in ores at neutral to alkaline pH so that leaching and carbonation can be conducted at the same pH value, and ultimately so that the reagent requirements of mineral carbon sequestration can be reduced. Both solution modeling and experimental work were conducted. The solution modeling revealed that each of the ligands studied is able to enhance the solubility of magnesium at the desired pH, with the order of effectiveness being EDTA > tiron > citrate > catechol > oxalate. Experimentally it was shown that the ligands studied could improve both the total amount and rate of magnesium leaching from ultramafic nickel ores. The order of ligand effectiveness based on the experimental work for the Pipe ore was EDTA ⩾ tiron > catechol > oxalate ⩾ citrate. For the OK ore, the order was tiron > EDTA = catechol > oxalate > citrate. Overall, the ligands studied in this work, particularly EDTA, tiron, and catechol, appear promising for enhancing the dissolution of serpentine in ultramafic nickel ores at neutral to alkaline pH.     

Extraction of indium from zinc plant residues

The main purpose of this study was to extract indium from the Irankoh zinc plant residue. The Irankoh zinc plant residue contained 145 ppm indium. The optimum conditions for leaching of indium and reduction of ferric ion in reductive leaching were obtained at temperature of 90 °C for a leaching duration of 3 h with sulfuric acid concentration of 100 g/L and the amount of required sodium sulfide for reduction of ferric was 1.5 times of stoichiometric quantity of iron. Then, to prepare concentrated indium solution, indium was selectively precipitated from the leach solution. The pH of leach solution was adjusted to 6 with ammonia solution in 90 °C for selective indium precipitation, and reaction time was considered to be 10 min. Then the resulting precipitation was dissolved using hot sulfuric acid solution, and the solution was subject to solvent extraction and cementation using zinc powder to recover indium.