The potential use of manganese oxidation in treating metal effluents

A technique of using microbially formed manganese oxides to takeup and immobilise metal effluents is described. An algal facilitated bacterial oxidation of manganese (Mn²⁺, which overcomes slow rates of bacteria-only manganese oxidation, was used to produced high yields of oxides using 1.6 g/L Mn²⁺ at neutral pH. Metals such as Cu, Zn, Co and Ni can be immobilised in stable co-precipitated manganese oxides. This effect was achieved either by the direct addition of metals during oxidation or by pretreating algal cells with metals prior to oxidation. Acid leaching (pH 2 H₂SO₄) showed that the immobilised metals were tightly bound by the manganese oxides. Transmission electron microscopy and X-ray analysis (TEM/EDAX) confirmed that bioformed manganese oxides had physically encapsulated the added metal ions, thereby preventing their release.     

Review of theory and practice of measuring proton activity and pH in concentrated chloride solutions and application to oxide leaching

The leaching of oxides in high strength brines is advantageous because of favourable leaching kinetics even at atmospheric conditions due to enhanced proton activity, and the catalytic effect of chloride ions due to complexation with metal ions. A proper understanding of hydration theory, practice of measuring proton activities in concentrated acid–chloride systems, and their applications to rationalise leaching kinetics is beneficial for further development of chloride processes. In the present study, a hydration number of 1 or 2 for the chloride ion and a constant ionic activity coefficient for the hydrated chloride ion has been proposed for the theoretical evaluation of pH of concentrated hydrochloric acid solutions. A comparison of the results based on hydration theory and extended Debye–Hückel equation with the experimental results based on acidity functions, glass electrode, and hydrogen electrode shows the importance of liquid junction potential corrections for measured values based on potentiometric methods. The proton activity based on electrode potentials reveals a hydration number of 6–7 which is consistent with an ion-pair hydration model (H₃O⁺)(H₂O)_6–7Cl⁻. Chloride ions facilitate the dissolution of copper(II) oxide and goethite in acid solutions. The rates of dissolution of these oxides in hydrochloric acid solutions are first order with respect to proton activity due to the formation of adsorption complexes such as Cu(OH)Cl⁰ and Fe(OH)₂Cl⁰. Hydration, chloro-complexation and hydrolysis of metal ions play important roles in the selective leaching of nickel over iron from laterite ores by acid–chloride lixiviant system.     

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).     

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.     

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.     

Atmospheric leaching characteristics of nickel and iron in limonitic laterite with sulfuric acid in the presence of sodium sulfite

Atmospheric leaching of nickel from limonitic laterite ores is regarded as a promising approach for nickel production, despite its low nickel recovery and slower leaching rate than high pressure acid leaching. Sulfur dioxide can enhance the sulfuric acid leaching of laterite, but its behavior for enhancing atmospheric sulfuric acid leaching was uncertain due to SO₂ losses and emission. In this study, sodium sulfite was used as a substitute for SO₂ gas in the leaching and the sulfuric acid leaching characteristics of Ni and Fe from a limonitic laterite in the presence of sodium sulfite were investigated. A linear correlation exists between the extraction of Ni and Fe, indicating the difficulty in selective leaching of Ni over Fe. Most nickel is isomorphically substituted within the goethite and it is difficult to dissolve in a high oxidation–reduction potential solution environment, resulting in a low nickel recovery. SO₂(aq) generated from the reaction of sodium sulfite in sulfuric acid solution, lowers the potential for the reducing reaction of FeOOH to give Fe²⁺, accelerating the iron extraction and nickel liberation from goethite.     

Ferric sulphate/chloride leaching of zinc and minor elements from a sphalerite concentrate

Atmospheric leaching of a sphalerite concentrate in sulphate and chloride media was performed and the effect of several variables, such as solid/liquid ratio and oxidant (Fe(III)) concentration were investigated. The behaviour of minor elements, such as Cu, In, As, Sb, Bi, Sn and Pb, was also studied under different conditions. The results showed that using a solid/liquid ratio of 5% (w/v) it was possible to leach 95% of zinc after 2 h, with a solution of 0.5 M H₂SO₄ and Fe₂(SO₄)₃ at 80 °C. The minor elements As, Sb and Bi were also completely leached whereas copper leaching was favoured by the use of chloride medium. The oxidation of Fe(II) during the leaching tests was studied and an improvement of 20% zinc extraction was observed in an oxygenated system. Cross-current leach tests using two/three stages and a solid/liquid ratio of 10% (w/v) were performed to achieve 90% of zinc extraction. The electron microprobe analysis of the leaching residues showed no change on the sphalerite composition after the leaching, which indicates that the leaching of sphalerite involves the break down of the sulphide structure.     

High pressure acid leaching of a refractory lateritic nickel ore

This paper describes the experimental findings of the extraction of nickel and cobalt by high pressure acid leaching (HPAL) of a refractory limonitic nickel laterite ore from the Gördes region of Manisa in Turkey. By optimizing the basic HPAL process parameters: leaching at 255 °C with 0.30 sulfuric acid to ore weight ratio with a particle size of 100% −850μ for 1 h of leaching, it was found that 87.3% of nickel and 88.8% of cobalt present in the ore could be extracted into the pregnant leach solution (PLS). However, these extraction results were found to be relatively low compared with other similar studies. In order to understand the possible reasons for this relatively lower extraction, further investigations have shown that together with a problem related to the kinetics of the dissolution reactions, a persistent acid resistant refractory mineral present in this sample also limited the leaching process. Attempts were made with different additives to solve this problem. The effects of chemical additives such as HCl, Na₂SO₄, FeSO₄, Cu⁺ and sulfur were tested and the effect of each addition on the degree of extraction of nickel and cobalt was determined.     

Hydrogeochemistry and Contamination of Trace Elements in Cu-Porphyry Mine Tailings: A Case Study from the Sarcheshmeh Mine,SE Iran

Geochemical and hydrochemical investigations were performed to understand the contamination potential of the Sarcheshmeh mine tailings. The geochemical mobility for the tailings is as follows: Cu > Cd > Co > Zn > Ni > Mn > S > Cr > Sn > As > Se > Fe = Bi > Sb = Pb = Mo. Highly mobile and contaminant elements (Cd, Cu, Zn, Mn, Co, Ni, S, and Cr), which significantly correlated with each other, were mainly concentrated in the surface evaporative layer of the old, weathered tailings, due to the high evaporation rate, which causes subsurface water to migrate upward via capillary action. The contamination potential associated with the tailings is controlled by: (1) dissolution of secondary evaporative soluble phases, especially after rainfall on the old weathered tailings, accompanied by low pH and high contamination loads of Al, Cd, Co, Mg, Cr, Cu, Mn, Ni, S, Se, and Zn; (2) processing of the Cu-porphyry ore under alkaline conditions, which is responsible for the high Mo (mean of 2.55 mg/L) and very low values of other contaminants in fresh tailings in the decantation pond; (3) low mobility of As, Fe, Pb, Sb, Mo, and Sn due to natural adsorption and co-precipitation in the tailings oxidizing zone. Speciation modeling showed that sulfate complexes (MSO₄ ⁺, M(SO₄)_(aq), M(SO₄) ₂ ^?2 , and M(SO₄) ₂ ^? ) and free metal species (M⁺² and M⁺³) are the dominant forms of dissolved cations in the acidic waters associated with the weathered tailings. In the alkaline and highly alkaline waters, trace element speciation was controlled by various hydroxide complexes, such as M(OH)⁺, M(OH) ₃ ^? , M₃(OH) ₄ ⁺² , M₂(OH) ₃ ⁺ , M(OH)_2(aq), M(OH) ₄ ^?2 , Me(OH) ₂ ⁺ , Me(OH) ₄ ^? , Me(OH) ₂ ⁺ , Me(OH)_3(aq), and Me(OH) ₄ ^? (where M represents bivalent and Me represents trivalent cations). The speciation pattern of As, Mo, and Se is mainly dominated by oxy-anion forms. The obtained results can be used as a basis for environmental management of the Cu-porphyry mine tailings.     

Recovery of manganese from electric arc furnace dust of ferromanganese production units by reductive leaching

Recovery of manganese from electric arc furnace dust (EAFD) of a ferromanganese production unit was investigated using reductive leaching in sulfuric acid (H₂SO₄). Three different reducing reagents, oxalic acid, hydrogen peroxide and glucose, were tested. Effect of different leaching parameters on the leaching and separation selectivity of manganese from iron was investigated. Iron concentration in solution was also determined, since iron was the major contaminant in the leach liquor. From the results complete leaching of manganese was achieved at 0.31 mol/L oxalic acid concentration, 2 mol/L H₂SO₄, a liquid/solid ratio of 30/1 at 70 °C and with 90 min leaching time.     

Recovery of copper,nickel and cobalt from acidic pressure leaching solutions of low-grade sulfide flotation concentrates

Recovery of copper, nickel and cobalt from the acidic pressure leaching solutions of Jinbaoshan (YN Province, PRC) low-grade sulfide flotation concentrates was investigated. The proposed technique includes four major steps: (1) the acidity adjustment of the acidic pressure leaching solutions; (2) solvent extraction (SX) separation of copper by organic reagent XD5640, and then stripped from the loaded organic phase by H₂SO₄ solution for copper recovery; then (3) iron in raffinates after copper extracting is selectively removed by high-temperature hydrolysis precipitation in an autoclave; and lastly (4) nickel and cobalt are selectively precipitated by Na₂S from the final solutions after removing iron. The experimental results for treating 1 L acidic leaching solutions per batch by this new technique were reported, and some evaluation and further comparisons with previous investigations were also carried out. It was reported that the total percent recovery of Cu could reach 95% or more, and that of Ni and Co were all more than 99%. In the processing, the percent removal of impurities, such as Fe, Mg and Ca, were all also near to 99%.     

Preparation of layered nickel aluminium double hydroxide from waste solution of nickel

The separation of nickel has been carried out from a waste solution containing 3.18 g/L Ni with other impurities such as Fe, Zn, Cu and As. Iron was removed by precipitation and Cu and Zn were removed by solvent extraction using LIX 622N and NaTOPS-99, respectively. After removal of all these impurities nickel was extracted by 1.5 M NaTOPS-99 in two counter-current stages at A:O ratio of 3:1 and the loaded organic was stripped with 30 g/L H₂SO₄ at phase ratio of unity. The strip solution of nickel was treated with Al₂(NO)₃ · 9H₂O for co-precipitation by increasing the pH of solution with 1 M NaOH up to 10. The Ni–Al layered double hydroxide was confirmed through XRD characterization.     

Geochemical and Mineralogical Characterization of a Pyritic Waste Pile at the Anjir Tangeh Coal Washing Plant, Zirab, Northern Iran

Coal washing at the Anjir Tangeh plant, in Zirab, northern Iran, has produced more than 1.5 Mt of coal wastes. These waste materials were geochemically and mineralogically characterised to guide development of an appropriate remediation scheme. Three vertical trenches up to 4 m deep were excavated from the coal waste pile surface and 25 solid samples were collected at 0.5 m intervals. The samples were analysed for total concentrations of 54 elements, paste pH, SO ₄ ^?2 , CO ₃ ^?2 , and HCO₃ ^?. The lowest pH values were measured at a depth of 0.3 m. The upper portion (1 m) of one profile was moderately oxidised, while oxidation in the other two profiles did not extend more than 0.8 and 0.5 m beneath the pile surface. The waste piles have low acid-producing potential (15–21.87 kg CaCO₃/t) and high values of acid-neutralizing potential (0.06–96.2 kg CaCO₃/t). Fe, Al, S, Na, Mn, Pb, Zn, Cd, and Ag increased with increasing depth, while Mo, Sr, Zr, and Ni decreased with increasing depth. The results show pyrite oxidation at depth and subsequent leaching of the oxidation products. Mn, Zn, Cu, Pb, Ag, and Cd are the most important contaminants of concern at this site.     

Kinetic factors for oxidative and non-oxidative dissolution of iron sulfides

The dissolution behaviour of iron sulfides is significant in the minerals industry for both the recovery of more precious metals and the treatment of waste materials (pyrite being the major contributor to acid rock drainage). The dissolution behaviour of pyrrhotite, Fe_(1−x)S, and troilite, FeS, in deoxygenated acid was studied using approaches established for the study of binary metal oxides in acid conditions. A feature of pyrrhotite (Fe_(1−x)S) is that a relatively slow dissolution rate (10⁻⁸ mol m⁻² s⁻¹) can increase suddenly by three orders of magnitude (to 10⁻⁵ mol m⁻² s⁻¹) in the same solution. The sudden increases have been shown to be due to the onset of non-oxidative dissolution.Correlation was found between the non-oxidative dissolution of pyrrhotite and that of ionic and semi-conducting binary metal oxides dissolving in acid with reaction controlled kinetics. In both situations -log (Rate) was proportional to pH, implying that the rate-determining step is ionic transfer across the surface - electrolyte interface.The strongly ionic nature of the S²⁻ bonding within semi-conducting troilite is made evident by dissolution rates of the order of 10⁻⁴–10⁻³ mol m⁻²s⁻¹. As with ionic oxides with dissolution rates of this magnitude, the dissolution kinetics of troilite are no longer reaction-controlled, but are controlled by bulk solution diffusion factors.     

The Combined Impact of Mine Drainage in the Ankobra River Basin,SW Ghana

This study assessed the combined effects of seven large-scale gold mines, one manganese mine, and scattered artisanal gold mining sites on the quality of water in the Ankobra Basin in a geologically complex terrain. Water samples from streams, boreholes, hand dug wells, and mine spoil were analysed. Scatter plots of trends among measured parameters were used to assess drainage quality and differential impacts. Drainage quality exhibits wide seasonal and spatial variations; the geology strongly influences the water chemistry. Areas with low pH (<5.5), and high sulphate ions and trace ions are suggestive of acid mine drainage while sites with high pH (>7.5), HCO₃ ⁻, subdued SO₄ ²⁻, and high trace ions are suggestive of sites where acid neutralization is effective. High metal sources are largely confined to mining operations in the Birimian formation with ores containing more than 2% sulphides. However, restricted high metal regimes are observed in drainage in the Tarkwaian formation associated with scatted sulphide-bearing dolerite dykes in the operational areas of the Tarkwa and Damang mines. Earlier studies disputed sulphides in the Tarkwaian formation until recently, when acid-generating dykes were discovered in operating pits. The most degraded waters emanate from the Prestea and Iduapriem mines, and to a lesser extent, the Nsuta mine sites, all mining Birimian rocks. The Tarkwa mine showed minimal metal loading. Zn, Cu, Ni, As, SO₄, pH, and specific conductance are essential and adequate parameters in determining if acid drainage is taking place at these sites, and are recommended for routine mine environmental monitoring.     

The controlled oxidative precipitation of manganese oxides from Mn(II) leach liquors using SO2/air gas mixtures

In the future, an oxidation approach using SO₂/O₂ could be an important technique for extracting manganese from leach liquors. The aim of this work was to analyse the effect of temperature on the oxidative precipitation of Mn(II) in solutions derived from low-grade ore leaching using a SO₂/air gas mixture. This oxidation method is frequently used to eliminate Mn impurities from Ni and Co leach liquors. It was observed that controlling the temperature favoured the selective oxidation of Mn(II) to produce different oxidised species, such as MnO₂, α-MnOOH, γ-MnOOH and Mn₃O₄. The experimental results also showed that higher temperatures promoted the production of species with a lower manganese oxidation state. Moreover, in the range of studied operation variables, it was found that the best oxidation kinetics were obtained at pH = 6, 5% SO₂/95% O₂ and 75 °C. In addition, for efficiency reasons, a gas mixture flow rate of 200 mL/min is suggested.     

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.     

A kinetic and electrochemical study of the ammonia cyanide process for leaching gold in solutions containing copper

One of the biggest challenges for the gold industry in the 21st century is the presence of copper in gold containing ore bodies. This is because copper consumes large quantities of cyanide. In addition, copper cyanide species are more stable than free cyanide, and hence are problematic in events of tailings spillage. One of the methods which has been suggested for treating copper containing ores is to leach with an ammonia cyanide solution. The effect of copper and ammonia addition on gold leaching kinetics was studied in the present paper. It will be shown that when the solutions do not contain copper, the addition of ammonia decreases the rate of gold leaching. When copper is added to solution, the leach rate does decrease due to the formation of the copper cyanide complexes. However it will be shown that under conditions of zero free cyanide, gold does leach readily via the Cu(CN)₃²⁻ complex. It was found that the addition of ammonia had little effect on the leaching of gold by Cu(CN)₃²⁻, but did increase the leaching kinetics when the major cyanide species present is Cu(CN)₂⁻. Under these conditions, leaching in the absence of ammonia is very slow. The effect of copper(II) addition was also studied, and it was found that in the absence of free cyanide the presence of copper(II) increases the leach rate, provided there is enough ammonia to stabilise it against reaction with the copper(I) cyanide complexes.     

矿区地下水环境演化的模拟试验研究

以皖北矿区恒源煤矿作为研究区域,通过室内模拟淋滤试验,检测淋滤液中的Na+,SO42-,F-,Fe,总溶解固体,总硬度等污染组分的质量浓度以及pH,电导率,分析研究岩样在淋滤作用下的污染组分的溶出规律以及其随淋滤量增加而衰减的拟合衰减幂数曲线。结果表明,淋滤液中pH值变化不明显,呈中性偏弱酸性,SO42-,F-,Mn等组分超标,其他重金属Cr,Cu,Pb,Cd等未检出;在淋滤试验前期,部分污染组分浓度很高,如Na+,总溶解固体和总硬度等,后期随着淋滤量的增加而呈现衰减趋势,并趋于稳定,其衰减方程基本符合幂数关系。表明在淋滤作用下岩样污染组分对地下水水质存在影响,且在一定程度上影响着地下水环境演化过程。