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By Éder Domingos Oliveira, Leandro Viana Teixeira, Carlos Antonio Morais, Ruberlan Gomes Silva

The purity of rare earth products depends on the ability of the reagents used to selectively promote the precipitation of the rare earth elements (REE) from impurities present in sulfuric liquors. The present study aims at investigating the conditions required to precipitate REE, either as rare earth oxalates or carbonates, from purified rare earth sulfuric liquor with a low Al3+ and UO2 2+ and a very high Ca2+, Mg2+, Mn2+, and SO4 2− impurity content. The rare earth sulfuric liquor was obtained in a previous study by the reaction of a rare earth ore with sulfuric acid, pyrolysis at 700 °C/2 h, cooling at 20 °C, and water leaching. The impurities such as Fe3+, Th4+, and PO4 3− were completely removed from the liquor in two consecutive neutralization steps. In order to recover the REE, the purified rare earth liquor was then treated with oxalic acid and sodium carbonate. Rare earth oxides (REO) precipitated with oxalic acid displayed a very high purity (99.2% w/w) and low impurity content. In contrast, the rare earth carbonates precipitated with sodium carbonate presented a comparatively lower REO content (68.5% w/w) and 94.2% of purity, but with a higher content of impurities. Better precipitating conditions were achieved at 60 °C, compared with 20 °C, and under stoichiometric reagent consumption, with REE precipitation efficiencies higher than 96%. The dosage above the stoichiometric condition caused the precipitation of calcium oxalates and co-precipitation of rare earth sulfates when oxalic acid is used, and precipitation of calcium, manganese, and uranium carbonates and also a co-precipitation of rare earth sulfate when sodium carbonate were used. An integrated flowsheet to produce a high-quality rare earth product from rare earth sulfuric liquor containing some impurities is proposed.

By José Maria Silva, Eugênio Oliveira, Ruberlan Silva, Thiago Souza, Lucas Reis, Lorena Guimarães, Matheus Bianchetti

Copper mine operations consistently generate a large quantity of tailings after their concentration processing. These tailings are either piled up or stored in a dam, where both alternatives of disposal lead to environmental impacts. The dam copper tailings have a huge potential for by-product production thus improving sustainability and profitability in industrial operations. This paper describes a study aiming at producing a magnetite pellet feed as a by-product from a dam chalcopyrite flotation tailings and generating free magnetite non-magnetic rougher tailings. The chemical assay and mineralogy analysis of dam copper flotation tailings indicate low Fe grade (6.34 wt%), high SiO2 grade (63.14 wt%), low magnetite (3.6 wt%), and high iron silicates content (22.72 wt%). The complex mineralogy of these tailings leads to the need of grinding the rougher magnetite pellet feed as fine as 80% of particles smaller than 20 μm ( P80) aiming at improving magnetite liberation. The proposed process route comprises a scalping screen, low field rougher, and cleaner magnetic separations using a drum magnetic separator (80 kA/m or 1000 Gauss), followed by silicates reverse cationic flotation as a recleaner step. With this process route, it was possible to produce a high-quality magnetite pellet feed reaching 68.00 wt% of Fe, 2.13 wt% of SiO2, 0.51 wt% of Al2O3, and 95.1 wt% of magnetite. The Blaine specific surface area was 2300 cm2/ g, being in the range recommended for pelletizing (1900 up to 3000 cm2/ g). The total mass, Fe, SiO2, Al2O3, and magnetite recoveries were 2.77%, 29.71%, 0.09%, 0.12%, and 73.17%, respectively. Most of the magnetite losses, around 20% of total magnetite fed, occurred in the oversize of the scalping screen. Additionally, it generated non-magnetic rougher tailings with less than 1.0 wt% of magnetite that could be used as by-products and reduced the amount of tailings disposal in a dam. This study contributes toward the sustainability of operation, minimizing tailings disposal.

Sep 28, 2022

By NEHA PANDEY, V.K. REDDY KALLAM, SUNIL KUMAR TRIPATHY, ARIJIT BISWAS

This work discusses the sulfur dioxide (SO2) leaching of low-grade ferruginous manganese ores to selectively recover manganese (Mn) as manganese sulfate (MnSO4), followed by electrowinning of the purified MnSO4 to produce electrolytic manganese dioxide (EMD). The effects of the leaching process parameters on Mn recovery were studied, and the leaching duration and SO2 flow rate were found to have significant effects. Under the optimum conditions derived for grade 1 ore (with total Mn content of approximately 17.16 percent), the specific SO2 requirement (SSR) — that is, the SO2 flow rate per gram of Mn in the leach slurry — was calculated to be 0.014 L/min. At the SO2 flow rate calculated using SSR for grade 2 ore (with total Mn content of approximately 26.29 percent), a Mn recovery rate of 94 percent was realized. Electrowinning of the purified MnSO4 generated after leaching resulted in EMD with 88.01 percent purity and a γ structure.

Sep 1, 2022

By V. K. Reddy Kallam, NEHA PANDEY, Sunil Kumar Tripathy, ARIJIT BISWAS

The study investigates SO2 leaching of low-grade ferruginous manganese ores to selectively recover manganese as MnSO4 and produce battery-grade electrolytic manganese dioxide (EMD). The effects of leaching parameters (duration, temperature, SO2 flow rate) on Mn recovery were studied. Under optimum conditions, 97.9% Mn recovery was achieved. The MnSO4 leach liquor was purified and used for electrowinning EMD with 88.01% purity and battery-active γ structure.

Apr 20, 2022

By W. A. Rickelton, A. J. Robertson

The ability of triisobutylphosphine sulfides to selectively recover silver from acidic sulfate solutions containing zinc and copper is described. Selectivity is explained in terms of the concept of hard and son Lewis acids and bases. Silver is stripped from the solvent using a novel strip feed (thiosulfate salt), and the recovery of metallic silver from the strip liquor by electrolysis or cementation is suggested. The high selectivity of extraction for silver and the utility of the stripping reagent are demonstrated in continuous, countercurrent, mini-plant tests. Important reagent properties, such as hydrolytic stability and low aqueous solubility, are discussed.

Jan 1, 1988

By K. L. Gabby

Selective removal of mercury from cyanide leaching solutions while retaining silver has been a long-standing problem, due to the chemical similarity of mercury and silver. In order to be practical, a mercury removal process needs to be both highly selective and use inexpensive materials. This paper reports the use of zinc sulfide (ZnS) as a precipitant for mercury. The mercury cyanide complex (Hg(CN)4 2-) undergoes a replacement reaction with the zinc sulfide, forming insoluble HgS, while the silver cyanide complex (Ag(CN)2 -) remains in solution. Under appropriate conditions, the separation of mercury from silver is nearly quantitative, with close to 100% removal of mercury, while nearly none of the silver is precipitated.

By E. O. Jacobs

A coupled solid and rock fracture mechanics model is used to analyze the blast driven fracture propagation phase, predict propagation rates, and directly measure shockwave and particle velocity. The study incorporates quasi-static pre-stress conditions for different depths below the surface. The scaled experiments include dynamic material properties and quasi-dynamic fracture mechanics which are shown to significantly affect the fracture propagation. The study was performed using three-dimensional cube-type laboratory models fabricated from Polymethylmethacrylate (PMMA). The test cubes are loaded with explosives and resulting fracture networks are studied. The dynamic evaluation of the spatial crack system is monitored using a high speed image camera. An experimental model set-up is designed to indicate the pre-stress effect on deep borehole blasting and is shown that the pre-stress conditions have a decisive influence on fracture profiles and orientation. It is found that shockwaves rapidly exceed the slower dynamic fractures and a majority of cracks occur due to detonation pressure. Experimental testing using different parameters validate that explosive fracturing can predict the outcome of fracture and crack propagation in any rock type with known material properties. This can be accomplished under great stress conditions deep below ground surface. The experimental study results can be applied to a variety of industries such as mining and quarrying, tunneling, oil and gas, and construction.

Feb 23, 2014

By S. Svoronos, B. Moudgil, R. Stana, A. El-Midany

Due to their similar surface properties, it is not always easy to separate carbonate minerals from other salt type minerals by froth flotation. A particular example is the difficulty of separating dolomite impunities from phosphate minerals. Such challenging fundamental and practical problems have inspired several research efforts in various laboratories around the globe to find methods for economically removing the dolomite. However, a universal and cost effective process is not in commercial use. In this paper, a new process for separation of carbonate minerals (dolomite or calate) from other associated minerals is presented. Differential solubility of carbonates in slightly acidic solution is utilized to generate micro GO, bubbles at the carbonate mineral/ water interface. Particle (e.g., dolomite)/ bubble aggregates float to the surface leaving phosphate concentrate with low MgO content. Interestingly, up to 6.0 mm particles can be floated by such micro bubble/particle aggregates. Different sutface-active agents were tested to stabilize the bubbles. Results of these tests are presented and the mechanisms involved are discussed.

Jan 1, 2005

By L. H. Michaud

A mining company plans to extend its surface coal-mining operations in central Pennsylvania. Although the proposed site contains pyritic material, the results of the acid-base accountings for the site shows an overall Neutralization Potential to Maximum Potential Acidity Ratio (NP:MPA) of 4.26:1 for the entire site. The pyritic material is, however, associated with the lower of the three seams to be mined. If traditional dragline-mining methods are used, this would result in the acidic material being placed at the top of the spoil piles, exposing it to air and water, and therefore to the formation of acid mine drainage (AMD). Further concerns are associated with the fact that the alkaline material is not distributed evenly over the mine site. To prevent the formation of AMD, the company has proposed to mine the area using truck-shovel mining methods. This technique offers a more flexible alternative for cut sequencing and for the selective placement of waste material. Working with the Department of Mineral Engineering at The Pennsylvania State University, amine plan was developed for this site. This plan results in the layering of the alkaline and acidic spoil to achieve an overall net alkalinity in all spoil areas. Therefore, mining this site should not result in the formation of AMD.

Jan 1, 1996

By L. H. Michaud

An existing mining company plans to extend their surface coal mining operations in central Pennsylvania. Although the proposed site contains pyritic material, the results of the acid-base accounting for the site show an overall NP:MPA ratio of 4.26:1 for the entire site. The pyritic material is, however, associated with the lower of the three seams to? be mined. If traditional dragline mining methods were used, this would result in the acidic material being placed at the top of the spoil piles, exposing it to air and water, and therefore to the formation of Acid Mine Drainage (AMD). Further concerns are associated with the fact that the alkaline material is not distributed evenly over the mine site. In order to prevent the formation of AMD, the company has proposed to mine the area using Truck/Shovel mining methods. This technique offers a more flexible alternative for cut sequencing and for the selective placement of waste material. Working with the Department of Mineral Engineering at The Pennsylvania State University, a mine plan was developed for this site. This plan results in the layering of the alkaline and acidic spoil in order to achieve an overall net alkalinity in all spoil areas. Mining of this site should therefore not result in the formation of AMD.

Jan 1, 1994

By T. Y. Yan

O2, NaCl03, H202, NaOCI and Ce+4 have been examined as oxidants in an alkaline carbonate system for uranium in situ leaching. The South Texas and New Mexico ores contained up to 2.6 meq/g of reducing compounds that consume oxidants in the leaching operation. Leaching rates did not increase linearly with the oxidation potential of the oxidants. A mild oxidant can be used to maximize uranium oxidation selectivity and oxidant efficiency. 02 can oxidize most of the uranium mineral with an adequate rate and high oxidant efficiency.

Jan 1, 1993

By Éder Domingos Oliveira, Carlos Antonio Morais, Ruberlan Gomes Silva

The objective of this work was to assess the influence of parameters such as residence time, solid content, and temperature in a process route towards purified rare earth liquor which could be adequate to produce marketable rare earth products. The steps of the process route proposed in this study comprised water leaching of a sulfated rare earth ore and removal of impurities through the purification of the rare earth sulfuric liquor, which is the product of the water leaching step. The sample used in the water leaching experiments was a sulfated rare earth ore produced by the reaction of a beneficiated rare earth ore with sulfuric acid followed by roasting at 700 °C for 2 h in a muffle furnace and cooling at 20 °C. The water leaching experiments showed that the best condition comprised a residence time of 30 min, temperature of 20 °C, and solid content of 10% w/w, resulting in a recovery of 71.3% of the rare earth elements (REE) and a lower impurity extraction, e.g., only 15.0% of Fe, representing the main impurity in the rare earth ore. Even when presenting low amounts of impurities, the rare earth sulfuric liquor still needed to be purified before it can be used in the production of marketable rare earth products. In the study, the rare earth sulfuric liquors were purified in two consecutive neutralization steps, first by dosing the limestone pulp to pH up to 3.5 and secondly by adding the lime pulp to raise the pH from 3.5 to 5.0. The application of two consecutive purification steps at 20 °C resulted in the highest overall REE recoveries (65.4%) throughout all the steps of the process, being 71.3% in the water leaching, 99.6% in the partial purification with limestone pulp, and 92.1% in the purification with lime pulp at 20 °C. Under this condition, there was a total elimination of Fe, P, and Th and a significant reduction in the Al, U, and sulfate concentrations in the purified rare earth liquor. The purified rare earth liquor attained through the experiment is expected to be amenable to be used in the production of marketable products due to the lower impurities/REO mass ratios.

By Éder Domingos Oliveira, Carlos Antonio Morais, Ruberlan Gomes Silva

The objective of this work was to assess the influence of parameters such as residence time, solid content, and temperature in a process route towards purified rare earth liquor which could be adequate to produce marketable rare earth products. The steps of the process route proposed in this study comprised water leaching of a sulfated rare earth ore and removal of impurities through the purification of the rare earth sulfuric liquor, which is the product of the water leaching step. The sample used in the water leaching experiments was a sulfated rare earth ore produced by the reaction of a beneficiated rare earth ore with sulfuric acid followed by roasting at 700 °C for 2 h in a muffle furnace and cooling at 20 °C. The water leaching experiments showed that the best condition comprised a residence time of 30 min, temperature of 20 °C, and solid content of 10% w/w, resulting in a recovery of 71.3% of the rare earth elements (REE) and a lower impurity extraction, e.g., only 15.0% of Fe, representing the main impurity in the rare earth ore. Even when presenting low amounts of impurities, the rare earth sulfuric liquor still needed to be purified before it can be used in the production of marketable rare earth products. In the study, the rare earth sulfuric liquors were purified in two consecutive neutralization steps, first by dosing the limestone pulp to pH up to 3.5 and secondly by adding the lime pulp to raise the pH from 3.5 to 5.0. The application of two consecutive purification steps at 20 °C resulted in the highest overall REE recoveries (65.4%) throughout all the steps of the process, being 71.3% in the water leaching, 99.6% in the partial purification with limestone pulp, and 92.1% in the purification with lime pulp at 20 °C. Under this condition, there was a total elimination of Fe, P, and Th and a significant reduction in the Al, U, and sulfate concentrations in the purified rare earth liquor. The purified rare earth liquor attained through the experiment is expected to be amenable to be used in the production of marketable products due to the lower impurities/REO mass ratios.

By Eti Purwaningsih, Widi Astuti, Erik Prasetyo

Increasing demand for high-grade manganese (Mn) ore has led to the practice of selective mining, which produced low-grade Mn ore as waste and in the long term could lead to environmental pollution. Research had been carried out to extract Mn from low-grade ore, which mostly exists as black Mn(IV) oxide (MnO2). Most extraction methods involved the reduction of insoluble MnO2 to soluble Mn2+ in acidic media. Metals other than Mn are also transferred to the pregnant leach solution (PLS) during the leaching process, especially iron (Fe). Due to high Mn concentration in PLS, precipitation is considered the best method to isolate Mn from PLS compared with solvent extraction and ion exchange/absorption. However, due to unselective leaching, the presence of Fe in the PLS makes the Mn separation and purification difficult. Therefore, in this research, the parameters affecting the selectivity of Mn over Fe in leaching process were investigated.

By Eti Purwaningsih, Widi Astuti, Erik Prasetyo

Selective-reductive leaching of manganese from low-grade manganese ore using tannic acid as a reductant in acidic media was demonstrated by XRD, SEM-EDX characterization, and batch leaching studies at room temperature. The pH change in the liquid phase before and after leaching revealed that selectivity of manganese over iron was due to the hydrolysis of iron. The acidity in the liquid phase during leaching was dictated by two mechanisms: proton-consuming reaction (manganese oxide reduction by tannic acid) and proton-producing reaction (ferric ion reduction by tannic acid to produce ferrous ion). Based on the leaching studies, the more prevalent reaction between these two was determined by initial leaching conditions: tannic acid concentration, sulfuric acid concentration, liquid-solid ratio, temperatures, and agitation time. Kinetic studies revealed that maximum recovery was attained within 6-h agitation, which indicated a product layer diffusion process.

By Yongjun Peng, Yufan Mu

Pyrite depression in the flotation of copper ores is difficult due to the activation of Cu2+ ions on pyrite surface. In this study, the radical chain reaction involving the redox cycling of Cu(I/II) induced by sodium metabisulphite (MBS) was exploited to selectively depress the flotation of copper-activated pyrite at pH 8.0. Electrochemical measurements revealed that the presence of Cu2+ and O2 was essential to the formation of SO•− 5 through sulphite oxidation, the main entity to convert the activating species Cu(I)S on pyrite to Cu(II)-hydroxide/sulphate, causing deactivation of pyrite. The depression role ofMBS on pyrite flotation was closely associated with the type of grinding media which affected the electrochemical conditions of flotation. When forged steel was used as the grinding media, a high dosage of MBS was required to depress pyrite, but a low dosage of MBS could almost completely depressed pyrite when high chrome steel grinding media was used. This is because high chrome steel produced a stronger oxidation condition with a higher amount of Cu2+ and O2 which promoted the formation of SO•− 5

Jan 26, 2021

By M. B. Mooiman

It has recently been discovered that the pH at which gold can be extracted from cyanide solution with primary, secondary, and tertiary amines can be increased 2 to 5 pH units by the addition of modifiers. Under these circumstances gold can be extracted at pH values from 9 to 11, commensurate with the pH range found in cyanide leach liquors. The selectivity of the amines and amine/modifier combinations for AU (CN)[-2] over other metal -cyanide complexes is presented and discussed. In addition, potential applications for the solvent extraction of gold from cyanide solutions are discussed.

Jan 1, 1983

By Phil Pennington, D. Jack Adams

Mining and processing of minerals, metals, and fossil fuels can release selenium and arsenic into wastewaters. Both selenium and arsenic are difficult to remove to levels that meet current drinking water and discharge criteria. These metalloids can be used as electron acceptors by microorganisms transforming them back to reduced states, thus removing or stabilizing them. Bioremediation cost effectiveness will be discussed in terms of site information required, microbial populations, co-contaminants, pH, redox, and nutrients. Full-scale, economical ex situ and in situ biotreatments are possible and can produce 1,000’s of times less sludge than conventional precipitation technologies.

Jan 1, 2005

By Doug Williams, Kent J. McGrew, Dr. Jack Murphy

For some time, selenate has eluded water treatment by conven­tional means such as precipitation and clarification. This has been due to the nearly universal solubility of all oxidized sele­nium species, the low levels required for surface discharge, and almost identical chemical behavior to all forms of oxidized sul­fur. The last characteristic makes selenate particularly difficult to deal with in acid mine waters where sulfate can easily be on the order of one gram per liter. Approaches such as ion exchange or reverse osmosis often tum into total demineraliza­tion schemes for the sake of removing a "trace" selenium species that may be present on the order of 108 sulfate/selenate. Reduction of selenate to selenite or elemental selenium by chemical means has been relatively unresearched. Some limit­ed success has been reported (Murphy, 1988) using ferrous hydroxide as a reducing agent; however, the reaction time as reported is too slow to be useful in a practical plant design. One significant difference between selenate and sulfate is that selenate has been discovered to be reducible in acid solution by elemental iron when catalyzed by soluble copper. Since the +4 or zero valence states of selenium are rather easy to deal with by coprecipitation with iron salts or alum, the elemental iron dis­solved in the process contributes to the overall process by pro­viding sludge upon raising the pH that can be separated by con­ventional clarification. Commercial production of selenium using copper catalyzed reduction of selenite to selenium metal via sulfur dioxide is well established, however, at the < 5 ppb requirements for surface discharge this reduction process equili­brates at levels far too high to be useful to low level selenate removal criteria. The reaction reported herein uses elemental iron for reduction of selenate with copper acting either as a cata­lyst or as a coprecipitation agent. This method, employed with conventional sludging, clarification and filtration can provide an economic method to achieve non detectable selenium (< 0.005 mg/I). Iron consumptions for the conditions tested have been on the order of 3 lbs/1,000 gallons treated. This represents as little as $0.06 or $2.00 per 1,000 gallons based on using a scrap source of iron or the purchase of electrolytic iron for the process.

Jan 1, 1996

By Paul D. Chamberlin

In the author's selenium report of 1994 (1), the literature was culled for selenium removal technologies that had a chance of producing effluents with <10 ppb of total selenium. Very few processes could achieve such low concentrations. The EPA dictates such low concentrations. Discharges to fishery waters must be <5 ppb total selenium. The federal max­imum contaminant level ( MCL) for drinking water is 50 ppb. The EPA regulations are for total selenium, not for the species, perhaps because an approved EPA assay method is atomic absorption and it cannot distinguish between species.

Jan 1, 1996