Reductive leaching of pyrolusite ore by using sawdust for production of manganese sulfate

Manganese compounds, such as manganese sulfate, can be obtained from pyrolusite, a manganese ore. Low-grade manganese ores is usually treated by hydrometallurgical methods. In this study, the leaching and recovery of manganese from pyrolusite ore in sulfuric acid solutions containing sawdust as reducing agent was investigated. The effects of experimental parameters, such as sulfuric acid concentration, sawdust amount, solid-to-liquid ratio, stirring speed, particle size, reaction temperature, and leaching time, on the manganese extraction from ore were examined. The results showed that the leaching rate of pyrolusite ore increased with an increasing sulfuric acid concentration, sawdust amount, stirring speed, reaction temperature and leaching time, and decreasing in solid to liquid ratio and particle size. The kinetic analysis of leaching process was carried out, and it was determined that the reaction rate was controlled by diffusion through the product layer under the experimental conditions in this work. The activation energy was found to be 22.35 kJ mol^?1. Manganese can be recovered as manganese sulfate by the evaporative crystallization of the purified leach liquor.     

Removal of Phosphorus From High Phosphorus Iron Ores by Selective HCl Leaching Method

  The selective HCl leaching method was used to remove phosphorus from high phosphorus iron ores. The hydroxyapatite in high phosphorus iron ores was converted into soluble phosphate during the process of HCl leaching. The effects of reaction time, particle size, hydrochloric acid concentration, reaction temperature, liquid solid ratio and stirring strength on the dephosphorization ratio were studied. The results showed that the dephosphorization ratio can exceed 98% under the conditions of reaction time 30-45 min, particle size ＜0147 mm, hydrochloric acid concentration 25 mol/L, reaction temperature 25 ℃, liquid solid ratio 5∶1 and stirring strength 502-1276 s-1. After dephosphorization reaction, the content of phosphorus in iron ore complied completely with the requirements of steel production.     

Reaction Kinetics of magnesite ore in dilute ethanoic acid

The leaching of naturally occurring magnesite in dilute ethanoic acid is achieved to optimize the reaction conditions affecting the reaction kinetics. In the current study effect of various reaction parameters (The particle size of ore, concentration of leaching agent, the reaction temperature and rate of stirring) on the dissolution of magnesium carbonate ore with aqueous solutions of acetic acid is probed. It is inferred that the rate of leaching reaction of magnesium carbonate ore in the aqueous solutions of acetic acid rises with a rise in temperature of reaction medium, acetic acid solution strength and decreases with the increase in particle size of the magnesite ore samples. The analysis of kinetic data done by the application of graphical and statistical approaches reveals that the leaching kinetics of magnesite ore in dilute solutions of acetic acid follows a surface chemically controlled mechanism. The calculated value of energy of activation for the dissolution reaction of magnesium carbonate in acetic acid is 46.39 kJ mol^–1.     

Dissolution kinetics of malachite in ammonia/ammonium carbonate leaching

The leaching of oxide copper ore containing malachite, which is the unique copper mineral in the ore, by aqueous ammonia solution has been studied. The effect of leaching time, ammonium hydroxide, and ammonium carbonate concentration, pH, [NH₃]/[NH₄⁺] ratio, stirring speed, solid/liquid ratio, particle size, and temperature were investigated. The main important parameters in ammonia leaching of malachite ore are determined as leaching time, ammonia/ammonium concentration ratio, pH, solid/liquid ratio, leaching temperature, and particle size. Optimum leaching conditions from malachite ore by ammonia/ammonium carbonate solution are found as ammonia/ammonium carbonate concentrations: 5 M NH₄OH+0.3 M (NH₄)₂CO₃; solid/liquid ratio: 1:10 g/mL; leaching times: 120 min; stirring speed: 300 rpm; leaching temperature: 25 °C; particle size finer than 450 μm. More than 98% of copper was effectively recovered. During the leaching, copper dissolves as in the form of Cu(NH₃)₄⁺² complex ion, whereas gangue minerals do not react with ammonia. It was determined that interface transfer and diffusion across the product layer control the leaching process. The activation energy for dissolution was found to be 15 kJ mol⁻¹.     

Dissolution behaviour of a beryl ore for optimal industrial beryllium compound production

This study involves the leaching of the beryl ore with sulphuric acid (H₂SO₄) solution for predicting optimal beryllium extraction conditions with the aim of assessing the importance of leachant concentration, reaction temperature and particle size on the extent of dissolution. A kinetic model to represent the effects of these variables on the leaching rate was developed. It was observed that the dissolution of beryl ore increases with increasing H₂SO₄ concentration, temperature, decreasing particle size and solid to liquid ratio. At optimal leaching conditions, 89.3% of the ore was reacted by 1.25?mol/L at 75°C temperature and 120 minutes with moderate stirring, where 1612.0?mg/L Be²⁺, 786.7?mg/L Al³⁺, 98.1?mg/L Fe³⁺ and 63.4?mg/L Ag⁺ were found as major species in the leach liquor. The unleached products constituting about 10.7% were examined by X-ray diffraction (XRD) and found to contain primarily, siliceous compounds such as Xonotlite, Antigorite, Chrysolite and Kaolinite.     

The dissolution of galena in ferric chloride media

The dissolution of galena (PbS) in ferric chloride-hydrochloric acid media has been investigated over the temperature range 28 to 95 °C and for alkali chloride concentrations from 0 to 4.0 M. Rapid parabolic kinetics were observed under all conditions, together with predominantly (>95 pet) elemental sulfur formation. The leaching rate decreased slightly with increasing FeCl₃ concentrations in the range 0.1 to 2.0 M, and was essentially independent of the concentration of the FeCl₂ reaction product. The rate was relatively insensitive to HCl concentrations <3.0 M, but increased systematically with increasing concentrations of alkali or alkaline earth chlorides. Most significantly, the leaching rate decreased sharply and linearly with increasing initial concentrations of PbCl₂ in the ferric chloride leaching media containing either 0.0 or 3.0 M NaCl. Although the apparent activation energy was in the range 40 to 45 kJ/mol (∼10 kcal/mol), this value was reduced to 16 kJ/mol (3.5 kcal/mol) when the influence of the solubility of lead chloride on the reaction rate was taken into consideration. The experimental results are consistent with rate control by the outward diffusion of the PbCl₂ reaction product through the solution trapped in pores in the constantly thickening elemental sulfur layer formed on the surface of the galena.     

Decomposition of mixed rare earth concentrate by NaOH roasting and kinetics of hydrochloric acid leaching process

A new clean extraction technology for the decomposition of Bayan Obo mixed rare earth concentrate by NaOH roasting is proposed.The process mainly includes NaOH roasting to decompose rare earth concentrate and HCl leaching roasted ore.The effects of roasting temperature,roasting time,NaOH addition amount on the extraction of rare earth and factors such as HCl concentration,liquid-solid ratio,leaching temperature and leaching time on the dissolution kinetics of roasted ore were studied.The experimental results show that when the roasting temperature is 550℃ and the roasting time is 60 min,the mass ratio of NaOH:rare earth concentrate is 0.60:1,the concentration of HCl is 6.0 mol/L,the ratio of liquid to solid(L/S) 6.0:1.0,and the leaching temperature 90℃,leaching time 45 min,stirring speed 200 r/min,and the extraction of rare earth can reach 92.5%.The relevant experimental data show that the process of HCl leaching roasted ore conforms to the shrinking core model,but the control mechanism of the che mical reaction process is different when the leaching temperature is different.When the leaching temperature is between 40 and 70℃,the chemical reaction process is controlled by the diffusion of the product through the residual layer of the inert material.The average surface activation energy of the rare earth element is E_a=9.96 kJ/mol.When the leaching temperature is 75-90℃,the chemical reaction process is controlled by the interface transfer across the product layer(product layer interface mass transfer) and diffusion.The average surface activation energy of rare earth elements is E_a=41.65 kJ/mol.The results of this study have certain significance for the green extraction of mixed rare earth ore.     

Leaching and kinetic modelling of low-grade calcareous sphalerite in acidic ferric chloride solution

The leaching kinetics of a low grade-calcareous sphalerite concentrate containing 38% ankerite and assaying 32% Zn, 7% Pb and 2.2% Fe was studied in HCl–FeCl₃ solution. An L₁₆ (five factors in four levels) standard orthogonal array was employed to evaluate the effect of Fe(III) and HCl concentration, reaction temperature, solid-to-liquid ratio and particle size on the reaction rate of sphalerite. Statistical techniques were used to determine that pulp density and Fe(III) concentration were the most significant factors affecting the leaching kinetics and to determine the optimum conditions for dissolution. The kinetic data were analyzed with the shrinking particle and shrinking core models. A new variant of the shrinking core model (SCM) best fitted the kinetic data in which both the interfacial transfer and diffusion across the product layer affect the reaction rate. The orders of reaction with respect to (C_Fe³⁺), (C_HCl), and (S/L) were 0.86, 0.21 and − 1.54, respectively. The activation energy for the dissolution was found to be 49.2 kJ/mol and a semi-empirical rate equation was derived to describe the process. Similar kinetic behavior was observed during sphalerite dissolution in acidic ferric sulphate and ferric chloride solutions, but the reaction rate constants obtained by leaching in chloride solutions were about tenfold higher than those in sulphate solutions.     

Kinetics of galena dissolution in nitric acid solutions with hydrogen peroxide

The extraction of lead from a galena concentrate in nitric acid solutions with additional hydrogen peroxide was studied taking stirring speed, temperature, hydrogen peroxide and nitric acid concentrations, and particle size as dissolution parameters. The dissolution curves followed the surface chemical reaction controlled shrinking core model over the whole range of parameters, except at high nitric acid concentrations where the reaction was diffusion-controlled. The activation energy of 42 kJ mol^− 1 and a linear relationship between rate and inverse particle size support the reaction controlled dissolution mechanism. Hydrogen peroxide addition accelerated the reaction compared with nitric acid alone. It was concluded that the dissolution process is favourable, since the acid consumed for oxidation of galena can easily be regenerated in the same reactor by means of hydrogen peroxide.     

Treatment of a Nigerian covellite ore. Part I: Dissolution kinetics study by ammonia solution

In the present work, the leaching kinetics of covellite ore in ammonia solution was studied and the following variables, the solution concentration, reaction temperature and particle size were considered. A kinetics model representing the effects of these variables on the leaching rate was developed and it was ascertained that the leaching rate increases with increasing solution concentration, reaction temperature and decreasing particle size. At optimal conditions, 75.1% of covellite ore was reacted within 120 min and the leaching reaction was diffusion controlled by surface chemical mechanism. The calculated activation energy of 56.98 kJ/mol supported the proposed dissolution process.     

烧结矿应用于化学链燃烧的反应特性

本文通过热重实验研究了烧结矿作为载氧体的H₂还原反应特性,将其与通过溶解法制备的Fe₂O₃/Al₂O₃载氧体进行了氧化还原反应性比较,在500~1250℃范围内研究了温度对于烧结矿还原反应过程的影响,在950℃下进行了30次循环反应实验,采用四种模型进行了反应动力学分析.结果表明,烧结矿的H₂还原转化率大于80%,可以完全再氧化,并具有良好的循环反应性能.在500~950℃范围内,随温度升高还原反应速率及最终转化率都显著增加;而当温度高于1100℃时,在反应后期还原反应速率和最终转化率有下降的趋势.在500~950℃范围内,对烧结矿的还原过程第一反应阶段(Fe₂O₃-Fe₃O₄/FeO,还原转化率< 25%)可采用二阶反应模型(M2)拟合,得到表观活化能为E=36.018 kJ·mol^-1,指前因子为A₀=1.053×10^-2 s ^-1;第二反应阶段(Fe₃O₄/FeO-Fe,还原转化率> 25%)采用收缩核模型(M4)拟合,得到的表观活化能为E=51.176 kJ·mol^-1,指前因子为A₀=1.066×10^-2 s ^-1.     

Kinetics of galena dissolution in ferric chloride solutions

A leaching investigation of galena with ferric chloride has been carried out as a function of concentration of ferric chloride and sodium chloride, temperature, and particle size. Three size fractions were considered in this investigation, namely, 48 × 65, 35 × 48, and 28 × 35 mesh. The concentration ranges of ferric chloride and sodium chloride used in this investigation were 0 to 0.25 M and 0 to 3 M, respectively. The reaction rate mechanism has been discussed in terms of a shrinking core model developed for cubic systems. Mass transport of ferric chlorocomplex through the product sulfur layer appears to be responsible for establishing the overall leaching rate under most of the conditions used in this investigation. The apparent activation energy for the leaching of 28 × 35 mesh galena with 0.1 M FeCl₃, 1 M HC1, and 3.0 M NaCl was found to be about 8.05 kcal/mol (33.7 kJ/mol), which was partially contributed by diffusion and partially by the heat of reaction of the formation of ferric chlorocomplexes. Rate of dissolution at both 50° and 90 °C is greatly affected by ferric chloride concentration up to 0.2 M and is essentially constant with ferric chloride concentration above this value.     

Kinetics of galena leaching in hydrochloric acid-chloride solutions

This article presents a series of studies on the nonoxidative leaching of galena with hydrochloric acid in the presence of a metallic chloride. A systematic study was carried out using a succession of metallic chlorides with cations of different valencies in an attempt to generalize the leaching behavior of these solutions. The reaction order for leaching galena, in terms of the mean ionic activity of HCl, is 3/2 over a wide range of concentration. The addition of soluble chlorides to a HCl solution increases the leaching rate of the galena by augmenting the mean ionic activity of the acid. A reaction order of 3/2 for the mean HCl activity in the solution is maintained for solutions in which the acid concentration is constant and the metallic chloride varies, as well as for the opposite situation. Therefore, the only activity that must figure in the kinetic equation is that of the HCl. The activation energy (58.5 kJ/mole) is independent of the chloride used to increase the activity of the hydrochloric acid. The same is true for the Arrhenius prefactor.     

高磷鲕状赤铁矿酸浸脱磷动力学

在HSC6.0计算软件热力学分析的基础上,采用正交实验确定了高磷鲕状赤铁矿酸浸脱磷保铁的最佳工艺,并以最佳工艺为基础进行了酸浸过程中脱磷和铁损反应的动力学研究。热力学分析表明H_2SO_4为最佳酸浸用酸。正交实验得出最佳酸浸条件为:H+浓度为0.5mol/L的H_2SO_4溶液、酸浸时间40min、温度298K、液固比200mL∶14g、搅拌速度100r/min。在该条件下,脱磷率可达98.89%,铁损率仅为0.51%。通过SEM-EDS对酸浸前后高磷鮞状赤铁块矿试样分析表征得出:经H_2SO_4浸出后,磷灰石基本完全溶解,含铁矿相未发生明显反应。动力学分析显示:优化条件下,酸浸脱磷反应在298~328K内符合收缩未反应核模型,浸出过程主要受内扩散控制,表观活化能为11.24kJ/mol;铁损反应在298~328K内遵循收缩未反应核模型,浸出过程主要受化学反应控制,表观活化能为42.24kJ/mol。     

Kinetics of Dissolution of Tenorite in Ammonium Media

In this work, the dissolution kinetics of tenorite (CuO) in a NH₄OH-H₂O system was studied. The studied temperature range was 5–55°C, ammonium hydroxide concentration between 0.1 and 0.75 M, and a particle size range of 5–24 µm. The stirring speed, pH of the ammonia solution, and various agents were also studied. The results indicated that the leaching of tenorite occurred quickly with a particle size of 5 µm in a 0.45 M solution of NH₄OH for a pH value equal to 10.5. Dissolution of CuO also increases as temperature and the concentration of NH₄OH increase. For concentrations less than 0.10 M, there is almost no leaching tenorite. By decreasing the particle size, the dissolution of CuO increase. Results show the stirring speed had no significant effect on the leaching rate of tenorite for values above 250 rpm. Leaching kinetics was analyzed using the model of the surface chemical reaction. The reaction rate was of the order of 2.2 with respect to the concentration of ammonium hydroxide and inversely proportional to the initial particle size. Activation energy of 59 kJ/mol was estimated for the temperature range of 5–55°C.     

Recovering copper from volcanic ASH by NH<Subscript>3</Subscript> · H<Subscript>2</Subscript>O–NH<Subscript>2</Subscript>COONH<Subscript>4</Subscript>

Volcanic ash from Xinjiang in the PRC contains malachite and cuprite. The volcanic ash has a copper content of 1.29%. However, because of severe argillization it is difficult to recover the copper through enrichment by flotation. Because the ash contains significant amounts of calcium and magnesium carbonates leaching the ash with acid requires a large amount of acid. We thus studied the use of ammonia-water and ammonium carbamate as effective leaching agents for copper. Leaching with ammonia-water and ammonium carbamate does not affect gangue minerals such as quartz and calcite and it can also promote the dissolution of minerals that contain copper. This leaching agent is highly specific. Using this system we recovered more than 90% of the copper from the volcanic ash. Higher reaction temperatures, smaller ore particle sizes, a higher stirring speed, a higher liquid to solid ratio and an increase in the agent’s concentration increased the copper leaching rate. SEM analysis, the activation energy (7.827 kJ/mol) and kinetics data comprehensively indicate that the reaction of copper minerals in the ammonia-water and ammonium carbamate system is controlled by internal diffusion.     

Dissolution studies of mechanically activated Manavalakurichi ilmenite with HCl and H2SO4

The effect of the change in phase constitution, particle size distribution, surface area, crystallite size, strain and lattice parameters introduced by mechanical activation of the altered beach sand ilmenite from Manavalakurichi region, India on the dissolution kinetics of HCl and H₂SO₄ was investigated. The altered ilmenite showed different physico-chemical characteristics and was found to be more resistant to acid leaching than the less altered ilmenite from the Chatrapur beach sands, India investigated earlier. The dissolution behavior was also different in H₂SO₄ and HCl. For sulfuric acid leaching, the dissolution of Fe and Ti increased monotonically with time of milling and showed a continuous increase with time of leaching, whereas hydrolysis of titanium occurs in HCl medium, especially for the activated samples at lower acid concentration, lower solid to liquid ratio and higher temperature leading to lower solution recoveries. The dissolution kinetics in both H₂SO₄ and HCl prior to hydrolysis conforms initially to the reaction rate control model and for higher leaching times to the shrinking core model where diffusion through the product layer is rate controlling. It is postulated that the anatase formed by hydrolysis in milled samples impedes the further progress of leaching. The activation energies for the dissolution of Fe and Ti decreased with time of milling and were marginally lower in HCl than in H₂SO₄. An attempt has also been made to correlate the decrease in activation energy to the increase in the energy input to the material through high-energy milling. The relative contribution of the increase in surface area and structural disorder on the enhancement of the dissolution rates has been evaluated.     

Kinetic study of nonoxidative leaching of cinnabar ore in aqueous hydrochloric acid-potassium iodide solutions

Results obtained in a kinetic study of nonoxidative leaching of cinnabar ore in aqueous hydrochloric acid-potassium iodide solutions and the basic reactions in a new process of cinnabar treatment for obtaining mercury are presented. Experiments were performed at stirring speeds fast enough to eliminate the effect of this variable in the overall reaction rate. Under these experimental conditions the dissolution rate appears to be controlled by chemical reaction on the cinnabar surface. An activation energy of 42.3 kJ/mole was found. The dissolution rate is of the first order with respect to hydrochloric acid activity and of second order with respect to potassium iodide activity. The reaction rate in the different leaching conditions was established through weight loss of very pure cinnabar spheres submerged in the attack solution for known periods of time.     

Preparation of Industrial Manganese Compound from a Low-Grade Spessartine Ore by Hydrometallurgical Process

The increasing global demands for pure manganese in steel production and manganese compound as dietary additives, fertilizer, pigment, cells and fine chemicals production cannot be over-emphasized. Thus, continuous efforts in developing low cost and eco-friendly route for purifying the manganese ore to meet some defined industrial demands become paramount. Therefore, this study focused on reductive leaching and solvent extraction techniques for the purification of a Nigerian manganese ore containing admixture of spessartine (O_96.00Mn_24.00Al_16.00Si₂₄.₀₀) and quartz (Si_3.00O_6.00). During leaching, parameters such as leachant concentration and reaction temperature on the extent of ore dissolution were examined accordingly for the establishment of extraction conditions. At optimal leaching conditions (1.5 mol/L H₂SO₄?+?0.2 g spent tea, 75 °C), 80.2% of the initial 10 g/L ore reacted within 120 min. The derived dissolution activation energy (Ea) of 35.5 kJ/mol supported the diffusion reaction mechanism. Thus, the leachate at optimal leaching was appropriately treated by alkaline precipitation and solvent extraction techniques using sodium hydroxide and (di-2-ethylhexyl) phosphoric acid (D2EHPA) respectively, to obtain pure manganese solution. The purified solution was further beneficiated to obtain manganese sulphate monohydrate (MnSO₄.H₂O, melting point?=?692.4 °C: 47-304-7403) of high industrial value. The unleached residue (~?19.8%) analyzed by XRD consisted of silicileous impurities (SiO₂) which could serve as an important by-product for some defined industries.     

The leaching of galena in cupric chloride media

The kinetics of dissolution of galena (PbS) in CuCl₂-HCl-NaCl media have been investigated using the rotating disk technique. Rapid nonlinear kinetics are observed over the temperature range 45 °C to 90 °C and for NaCl concentrations from 0 to 4.0 M. The leaching rate is in-dependent of CuCl₂ concentrations >0.1 M but increases with increasing concentrations of either HC1 or NaCl. The leaching rate decreases with the accumulation of either the PbCl₂ or CuCl reaction product in the leaching medium but is insensitive to the disk rotation speed. The apparent activation energy for the rate controlling process is 33 kJ/mol, and this value falls to about 15 kJ/mol when interpreted as a dissolution rate for PbCl₂, whose solubility increases with temperature. The above observations are shown to be consistent with rate control by the outward diffusion of the PbCl₂ and CuCl reaction products through the solution trapped in the pores of the constantly thickening elemental sulfur layer which forms on the surface of the galena. CANMET, Energy, Mines, and Resources Canada, 555 Booth Street, Ottawa, ON, K1A 0G1, Canada.