Ferromanganese Ore Research Articles

Hydrometallurgical enrichment of polymetallic and ferromanganese ore

The article presents the results of theoretical and experimental studies of leaching of polymetallic manganese-containing and ferromanganese ore. Thermodynamic calculations and experimental studies on enrichment of manganese-containing raw materials made it possible to determine the main technological parameters of the extraction of manganese, iron and non-ferrous metals, and to develop technological schemes for enrichment of various types of manganese-containing raw materials. The studies were carried out for polymetallic and ferromanganese ores of the Kaigadat deposit, the Selezen deposit, the Sugul site, located in the Kemerovo Region – Kuzbass. Before carrying out laboratory studies, the authors have performed thermodynamic analysis of ore leaching, chemical and X-ray structural analyzes of the samples. Laboratory tests were carried out on a multichamber autoclave unit MKA-4-75 using calcium and iron chlorides as solvents. Since the introduction of a reducing agent into the charge during leaching significantly improves the conditions for dissolution of oxides and hydroxides of manganese in calcium chloride, a series of experiments was conducted with the use of charcoal in the charge. Thermodynamic calculations have shown that the leaching process is fully implemented in the temperature range from 323 to 673 K. The results of the experiments confirmed the theoretical research results. The obtained data allowed the authors to propose a technological scheme for hydrometallurgical enrichment of polymetallic and ferromanganese ores to produce high-quality concentrates. All processed products are suitable for use. The use of optimal technological parameters of enrichment allows 95–97 % of manganese, up to 80 % of nickel, up to 99 % of cobalt, and 96–98 % of iron to be extracted from polymetallic manganese-containing raw materials. As a result of the deposition of these elements, high-quality concentrates of manganese, nickel, iron, cobalt are obtained. According to the proposed technological scheme for ferromanganese raw materials with a high content of silicates, it is possible to obtain high-quality concentrates of manganese and iron, while the extraction of manganese is 90–92 %, and of iron – 86–90 %.

Improving the technology of manganese ore X-ray radiometric separation

Introduction. In addition to the classical methods of manganese ore processing, a lower-cost and more environmentally friendly technology of X-ray radiometric separation (XRS) has been developed in the last twenty years. The technology has been embraced by enterprises and applied to improve the efficiency of manganese deposits development. The article provides original results of the research carried out by Irgiredmet institute concerning the development of the procedure and technology of manganese ore XRS. Research methodology. The XRS methodology is based on the X-ray fluorescence (XRF) method of elements detection common in geophysical practice. A methodological task of these method is to find manganese in ore containing not only manganese but also iron, as soon as the two elements possess characteristic X-ray radiation (CXR) close in energy and mutually affect the accuracy of their detection by the X-ray fluorescence analyzers. The chosen research methodology allowed developing a new way of keeping records of the elements when solving the problems of manganese ore sampling and sorting. Research results. A new and efficient algorithm of sampling manganese and iron has been developed and tested on different types of manganese and ferromanganese ore. The ratio of CXR of the detected elements to the total sum of the scattered radiation (SR) and these elements CXR intensity set by a special spectral coefficient k is such universal criterion which promotes to more accurate detection of manganese and iron content in lumps.

Mineralogical Characterization and Optimization of Fe and Mn Through Roast-Leaching of Ferromanganese Ore

Iron and manganese both are important ferrous metals, and they usually need to be extracted separately for better usage. Ferromanganese ore from the Yunnan Province of China was investigated by subjecting it to reduction roasting, leaching, magnetic separation, hydrometallurgical separation process, X-ray diffraction (XRD), electron probe micro-analysis (EPMA) and scanning electron microscopy/energy-dispersive spectroscopy (SEM-EDS). It is noted that the ferromanganese ore contains valuable components or elements of 21.41 wt% Fe2O3 and 19.88 wt% MnO, which are 14.99% and 15.40% of the total of Fe and Mn, respectively, with a large amount of impurities comprising 33.00 wt% SiO2, 9.81%wt% Al2O3, etc. After roasting, microscopic examination showed the presence of haematite, magnetite, pyrolusite, psilomelane, hollandite, marcasite, pyrite, limonite, braunite and manganite, while XRD analysis showed that the magnetite content increases with the increase in roasting temperature, reflecting the increase in conversion of haematite to magnetite. Based on EPMA and SEM-EDS analysis, it was shown that the haematite and magnetite interface were the main Fe-bearing minerals; however, the dissemination of the two minerals, that is, haematite and magnetite with the coexistence of Fe- and Mn-bearing minerals, will result in difficulty in effective separation of Fe and Mn. The effective roasting temperature and roasting time were 800 °C and 60 min, respectively, to avoid the formation of a composite oxide of MnxFe3-xO4 beyond 800 °C. The Fe recovery via roasting and magnetic separation only was 66.56%, whereas a combination of magnetic separation which ensued after the leaching process showed a recovery of 80.08% and 59.95% of Fe and Mn, respectively.

Genetic Type and Age of Ferromanganese Sediments of the Taloi Deposit, Transbaikalia

The paper reports petrochemical and isotope data on the ferromanganese ores and host volcanosedimentary rocks of the Taloi–Usoi interfluve of the Ikat terrane, the Central Asian Fold Belt. Obtained data indicate that the formation of the Taloi ferromanganese mineralization was related to the explosive and volcanic activity of synsedimentation suprasubduction volcanism. The age of the volcanogenic rocks is 799 ± 3 Ma. This indicates the manifestation of Neoproterozoic (Riphean) epoch of manganese accumulation related to active continental margin setting in the Transbaikalian segment of the CAFB.

Kinetic Features of the Hydrogen Sulfide Sorption on the Ferro-Manganese Material

The kinetics of hydrogen sulfide sorption by the surface of a ferromanganese material containing in its composition a mixture of iron (II) and (III) oxides FeO × Fe2O3, takanelite (Mn, Ca) Mn4O9 × 3H2O and quartz SiO2, and which is samples of unrefined ferromanganese ore, was studied in this work. Sorption rate constant and activation energy constant values were calculated. The catalytic effect of iron (III) oxide was established, the presence of which in natural material contributes to a decrease in the H2S sorption activation energy. Based on the results of X-ray phase and chromatographic analysis methods, a chemical (redox) reaction of the conversion of hydrogen sulfide into elemental sulfur and H2O was revealed. The overall process rate is expressed in terms of the physical sorption stage and chemical transformation of the components; the influence of the rate of the third stage—reaction products desorption—on the overall rate of the process is taken into account. The limiting stage of the process is determined—a chemical reaction. The relation between the heat and the activation energy of the chemical transformation is used according to the Bronsted—Polanyi rule for catalytic processes. It was found that with an increase in the chemisorption heat, the activation energy of the chemisorption stage decreases and, as a consequence, its rate increases. The sorption process parameters were calculated—the Fe2O3 coverage degree with the initial substances and reaction products providing the maximum sorption rate, which can be a criterion for evaluating the catalytically active sites of the catalyst surface for carrying out catalytic reactions.

Definition of conditions of selective iron reduction from iron-manganese ore

The article presents thermodynamic modeling results of reduction roasting of ferromanganese ore with a high phosphorus content in the presence of solid carbon. The modeling was carried out using TERRA software package. Influence of the process temperature in the range 950 – 1300 K and carbon content in the amount of 8.50 – 8.85 g per 100 g of ore on reduction of iron, manganese and phosphorus was investigated. With these parameters of the system, iron is reduced by both solid carbon and carbon monoxide CO to the metallic state, and manganese is reduced only to MnO oxide. The degree of phosphorus reduction depends on the amount of reducing agent. With an excess of carbon relative to the reduction of iron, all phosphorus is converted into metal at a temperature of 1150 K. Phosphorus is not reduced at temperatures below 1150 K and such amount of carbon. The process of solid-phase reduction of iron from manganese ore with the preservation of manganese in the oxide phase was researched in laboratory conditions. Experimental results of direct reduction of these elements with carbon and indirect reduction with carbon monoxide CO are presented. The experiments were carried out in the laboratory Tamman furnace at a temperature of 1000 – 1300 °C and holding time of 1 and 3 hours. Results of the research of phase composition of the reduction products, as well as chemical composition of the phases are considered. The possibility of selective solid-phase reduction of iron with solid carbon to the metallic state was confirmed. Iron in the studied conditions is reduced by carbon monoxide CO and passes into magnetic part. During the magnetic separation of the products of ore reduction roasting with solid carbon and carbon monoxide CO, the non-magnetic part contains oxides of manganese, silicon and calcium. The work results can be used in development of theoretical and technological foundations for the processing of ferromanganese ores, which are not processed by existing technologies.

Manganese in the hydrosphere of the Jewish autonomous region: surface water

At present, knowledge about the content of manganese in the surface waters of the Jewish Autonomous Region is becoming more and more relevant, since the development and extraction of iron-manganese ores has already begun in the area of the Bidzhan deposit in the north-west of the region. It is planned to develop iron-manganese deposits in other regions of the autonomy. However, we are not sufficiently aware of the migration of this element, its spread by watercourses along the hydraulic network, the change in the forms of transportation due to the boggy territory of the autonomy, and the possible negative impact on aquatic organisms. The purpose of our work is to study the distribution of manganese in surface watercourses, taking into account the geological features and natural conditions of the Jewish Autonomous Region. The content of total manganese in the surface waters of the Bira River and mainly its northern tributaries located on the territory of the autonomy was determined by the method of atomic absorption spectrophotometry. The article presents the results of determining manganese and iron, as well as indicators that affect their migration ability, in the surface watercourses of the Jewish Autonomous Region for two years. The paper describes and analyzes the natural conditions and geological features of the autonomy that affect the distribution of manganese in its surface waters. As a result of the study, it was revealed that all rivers reflect the specific nature of the natural conditions of their formation. In the watercourses of the northwestern part of the region, draining the foothills of the Small Khingan, the influence of deposits of ferromanganese ores is clearly manifested. In the rivers flowing from the southern spurs of the Bureinsky ridge, manganese ore content is not felt. Bira's sharp turn from the mountainous north to the south, to the Amur, occurs against the background of a contrasting change in the relief and close contact of the river with the adjacent swampy plain. Natural processes and sources of Mn input into river waters change: the input of soluble humid metal complexes from the bog drainage begins.

Estimation of selective reduction of iron and phosphorus from manganese ores of different genesis

The possibility of selective reduction of iron from complex oxides by carbon monoxide gas is investigated. Brazilian ore rich in manganese oxide, ferromanganese ore from the Selezenskoye Deposit (Russia) and concentrate from the Zhayrem GOK (Kazakhstan) were used as samples. Experiments have shown that it is possible to selectively reduce iron from complex manganese ores to a metallic state not only with solid carbon, but also with carbon monoxide. Experimental results of solid-phase reduction showed that at a temperature of 900 °C. With an exposure time of 1.5 hours, the release of metallic iron is detected. At the same time, in the atmosphere with the metal phase, there is no presence of other elements other than iron in the metal. As the temperature rises to 1000 °C, the amount of metallic iron, as well as manganese and phosphorus, increases. At a temperature of 1000 °C, phosphorus turns into metal, despite the type of reducing agent. In all experiments, oxides of manganese, silicon and calcium remained in the oxide part.

Characteristics of Natural Mineral Sorbent for Water Treatment of Drinking Water from Underground Sources

The results of research of sorption characteristics of natural mineral material – marsh ferromanganese ore are presented. Indicators of physical properties and mechanical strength, specific surface area of grains of ore samples were determined. The high efficiency of extraction of manganese and iron ions from underground waters by this natural material without the use of additional reagents is revealed. The kinetics of the sorption process was studied. It is shown that the extraction of manganese and iron ions from water solutions by marsh ferromanganese ore proceeds by a sorption-catalytic mechanism. For each ion, the values of the sorption capacity of the sorbent, the sorption equilibrium constants, and the kinetic parameters of the sorption process are calculated.

Individual enrichment of manganese and iron from complex refractory ferromanganese ore by suspension magnetization roasting and magnetic separation

Owing to its complex characteristics, the large-scale utilization of ferromanganese ore is limited by the traditional processes. In this study, suspension magnetization roasting and magnetic separation technology was proposed, and the thermodynamics, phase and magnetic transformation, and microstructure evolution of the main minerals were systematically investigated during roasting. Results show that iron concentrate with iron grade of 68.31% at a recovery of 96.34% can be obtained in the magnetic separation concentrate, and manganese concentrate with manganese grade of 33.70% at a recovery of 86.83% can be obtained in magnetic separation tailings under optimum conditions. Pyrolusite and braunite were reduced to weak magnetic manganosite, and weak magnetic hematite was selectively transformed into strong magnetic magnetite. Many cracks appeared in the ores owing to the multiple reduction and dehydration reactions of ferromanganese ore, which was favorable for grinding and separation of manganese and iron.

Manganese ores of the Kemerovo region – Kuzbass and methods of their enrichment

Manganese ores of the vast majority of domestic deposits are of low quality: with low content of manganese (18 – 24 %) and high specific content of phosphorus (ratio P/Mn > 0.006). They have an increased content of iron and silicon and they are difficult to enrich. The main part of balance reserves of manganese ores – 98.5 million tons (64.2 %) is concentrated in large Usinskoye field in the Kemerovo region. In addition to Usinskoye, there are also deposits in this region Kaigadatskoye (32.7 million tons), Durnovskoye (300 thousand tons), Selezenskoye fields and the Chumay plot. For a comprehensive approach to solving the proposed problem it is needed to assess technical and economic feasibility of all stages (exploration, extraction and enrichment of manganese ores, their subsequent processing and consumption) of involvement of manganese ores from these deposits in production. Using developed technology of calcium-chloride enrichment, high-quality manganese concentrates are obtained from carbonate, including high-phosphorous ores of the Usinskoye field, poor oxide and ferromanganese ores of the Selezenskoye and the Durnovskoye fields. Extraction of manganese from manganese-containing raw materials into concentrate was at least 90 %. The resulting concentrate contains 58 – 64 % of manganese, less than 0.01 % of phosphorus, 0.02 – 0.05 % of iron oxide, 0.5 – 1.0 % of silica and sulfur. Thermodynamic calculations and experimental studies on the enrichment of polymetallic manganese-containing ores from the Chumay plot allowed us to determine the main technological parameters for extracting valuable components. The use of optimal technological parameters of enrichment allows extraction of up to 95 – 97 % of manganese and 98 – 99 % of nickel from raw materials.

Separation of manganese and iron for low-grade ferromanganese ore via fluidization magnetization roasting and magnetic separation technology

As a potential solid waste resource, low-grade ferromanganese ore has not been fully utilized or recycled. In this study, fluidization magnetization roasting and magnetic separation technology were used to recycle low-grade ferromanganese ore. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), sample vibrating magnetometer (VSM), X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM) were used to systematically detect the process mechanism. The results show under the optimized conditions, high-quality products of iron concentrate with iron grade of 69.05% at iron recovery of 95.94%, and a manganese concentrate with manganese grade of 53.30% at manganese recovery of 90.41% were obtained. The fluidization magnetization roasting technology can make the weak magnetic hematite in raw ore transform to the strong magnetic magnetite, while it makes the pyrolusite and braunite transform to manganosite. The newly formed mineral lattice had clear stripes and remarkable magnetization properties. After magnetic separation, magnetite and manganosite were individually separated at individual concentrates, which efficiently transforms and utilises this low-grade ferromanganese ore without any residue using this process.

Spinel MnFe2O4 nanoparticles (MFO-NPs) for CO2 cyclic decomposition prepared from ferromanganese ores

Ferromanganese ores with high contents of Mn and Fe are abundant worldwide. In this study, spinel-type MnFe2O4 nanoparticles (MFO-NPs) were first synthesized via a novel solid-state reaction process followed by ball-milling, magnetic separation, and nano-grinding. The synthetic MFO-NPs presented a stable spinel structure, fine granularity, and large specific surface; these characteristics highlight their potential in the preparation of thermochemical catalysts. We additionally conducted H2 reduction (HR) and CO2 decomposition reaction (CDR) cyclic tests to investigate the catalytic performance of MFO-NPs. The MFO-NPs showed excellent recyclability and thermal stability during CO2 decomposition; moreover, oxygen-defect MFO-NPs were able to completely decompose CO2 into carbon quantum dots. The mechanism of CO2 decomposition on the MFO-NPs’ surfaces was analysed in detail by XRD, SEM, TEM, TG, Raman, XPS.

Pigments on Late Bronze Age painted Canaanite pottery at Tel Esur: New insights into Canaanite–Cypriot technological interaction

The ceramics and pigments of Late Bronze Age (LBA) painted Canaanite pottery were studied using ceramic petrography and three microbeam methods: pXRF, LA-ICP-MS and EPMA. The analyses focused on specimens from Tel Esur in Israel’s northeastern Sharon Plain, which has yielded a well-preserved assemblage of the 15th/14th centuries BCE. We studied painted jars, biconical jugs and a bowl decorated with black, red or two-colored geometric patterns. The petrographic analysis revealed that the majority of the painted vessels were produced on the southern Levantine coastal plain. The microbeam analyses demonstrated the use of ferromanganese and ferric-iron pigments for the black and the red decorations respectively. The adoption of the manganese-based technique in Canaanite workshops seems to be an early LBA technological progress, which facilitated the production of black decoration while firing vessels in an oxidizing atmosphere; it explains the sharp increase in the production of two-colored Canaanite pottery during that period. Ferromanganese ore sources for the black pigment are rare in Canaan and absent from its coast; this required importation of raw ore from external sources. The analogous use of the manganese-based technique for black decoration on Cypriot wares suggests that both pigments and technology were transferred from Cyprus to Canaan, highlighting a ‘new’ aspect in the multi-faceted Cypro-Canaanite liaisons of this period.

The early stages of ferromanganese ore genesis on the guyots of the Magellan Seamounts (The Pacific Ocean)

Fe-Mn crusts play an important role in marine mineral deposit research because of their widespread occurrence and high concentrations of valuable and rare metals. Most Fe-Mn crust deposits occur on the tens of thousands of seamounts found in the ocean. Data on the structure, texture, composition, age, and deposit characteristics will help define which factors are key for the creation of mineral accumulation and which combination of factors leads to the formation of potentially economic concentrations of metals. In this paper, we address the structure and characteristics of the oldest Fe-Mn crust stratigraphic sections (Late Cretaceous and Paleocene) collected from the Magellan seamounts. A complete section of the crusts on the Magellan Seamounts includes four layers, each 2—4 cm thickness: the Late Paleocene (?) Early Eocene layer I 1, the Mid Late Eocene layer I—2, the Miocene layer II and the Quaternary layer III. In some cases, the main CMC section is underlain by relict layers. The chemical and mineral composition of the layers was determined both by X-ray diffraction and precision methods; concentrations of the main ore components and phosphorus were determined by the methods of classical chemistry. The age of 12 samples was determined, the mineral composition of four, the chemical composition of 22 samples. The results of the relict layers analysis allow to distinguish two groups of samples among them. Among the relict layers, two age ranges are established — the second half of Late Cretaceous (R1) and the first half of Paleocene (R2). High concentrations of barium, lithium, gallium, and zinc suggest that hydrothermal sources could be the source of the material. But not through direct delivery, but via the phase of transfer of sea bottom water. Thus, the analysis of lithological and geochemical parameters and fossil fauna of foraminifera in the relict layers of the Magellan Seamounts ore section indicates two stages of their formation: Late Campan Maastricht and Early Middle Paleocene. The discreteness of the formation of relict layers in time once again proves that the sharply changing environmental conditions controlled the growth of the CMC ore section.

The Microstructure of Oxide Ferromanganese Ores in the World Ocean as Proof of their Bacterial Origin

Study of the submicroscopic structure of oxide ores revealed their similarity to the present-day bacterial communities. It was shown that the structure of cobalt-bearing crusts and ferromanganese nodules is based on bacterial mats, which permits identifying them as stromatolites and oncolites. Data that support intense interaction between biofilms and the environment were found. Signs of formation of the mineral phase as a result of biochemical absorption and assimilation of iron and manganese by bacteria were observed.

Microstructure of oxide ferromanganese ores in the World ocean as the proof of their bacterial origin

The study of submicroscopic structure of oxide ores revealed their similarity to the present-day bacterial communities. It is shown that the structure of cobalt-bearing crusts and ferromanganese nodules is based on bacterial mats, which permits identifying them as stromatolites and oncolites. The facts in favor of intense interaction between biofilms and the environment are found. The signs of mineral phase formation are registered as a result of biochemical absorption and assimilation of iron and manganese by bacteria.

Synergetic utilization of copper slag and ferruginous manganese ore via co-reduction followed by magnetic separation process

Attempts to economically and effectively treat copper slag (CS) and ferruginous manganese ore(FMO) using the traditional direct reduction–magnetic separation process have faced many challenges, such as low levels of metal recovery, poor cost-effectiveness and the need for a high proportion of additives. This paper proposes an eco-friendly process to synchronously utilise copper slag and ferruginous manganese ore by co-reduction followed by a magnetic-separation process to solve those problems. In the process, MnO2 within FMO acted as a catalyst to promote the reduction of fayalite and copper sulphide contained in CS, and thus improve the metallisation rate of Fe and Cu. Meanwhile, CS, possessing the low melting point, can enables more liquid phase generation and improve the growth of alloy particle, which is beneficial for the full liberation of Fe–Cu alloy. Under the optimum conditions, A crude Fe–Cu alloy powder containing 88.83% Fe and 1.07% Cu was prepared, which can be used in an electronic furnace to produce Cu-bearing steels. A high recovery of 85.89% Fe and 87.74% Cu can be obtained using this process, thereby confirming its efficiency. Additionally, Mn contained in the ferromanganese ore was enriched into the magnetic tailing in the form of low-valence manganese (II) oxides, which can be easily extracted by acid leaching. Moreover, the mechanism involved in the co-reduction of CS and FMO was investigated by XRD, SHTT and SEM-EDS techniques, which further confirmed the complementary advantages about an organic integration of CS and FMO can realise the efficient beneficiation of the valuable metals from them.

‘Gorceixite’, a Ba-Al phosphate mineral, from Mn-ores of Eastern Ghats Group of Rocks, Odisha, India

Gorceixite, a Ba-Al alunite supergroup mineral, associated with ferromanganese ores of the Precambrian Eastern Ghats Group is reported for the first time from Odisha. The characteristics of gorceixite are described using optical microscopy, XRD, FTIR, Raman, SEM-EDAX and EPMA techniques. The Odisha gorceixite is subhedral, with a broadly prismatic habit and occasional twinning. The calculated formula of present gorceixite is (Ba0.54 Ca00.39 Sr0.05)∑0.98 Al2.96 (PO4)2.05(OH)5.H2O. The Ba is partly substituted by Ca and Sr. Texture of the ores indicates that during supergene alteration, earlier silicate minerals, like celsian (Ba-feldspar), were replaced by gorceixite.

Selective enhancement of Mn bioleaching from ferromanganese ores in presence of electron shuttles using dissimilatory Mn reducing consortia

The present study describes anoxic Mn bioleaching of low grade ferromanganese ores using a dissimilatory Mn reducing consortia (MRC). Effect of external addition of electron shuttles such as humic acid and anthraquinone sulphonic acid was studied under same conditions. The MRC were found to be capable of utilizing MnO2 as electron acceptor as evidenced by Mn dissolution in media. In the presence of electron shuttles, Mn extraction was found to be enhanced by 2 to 4 times compared to the case without. A maximum of 58 (±3%) Mn was found to be leached from an amorphous ore while 38 (±2%) Mn was leached from a crystalline ore, in 50 days in presence of 100 μM electron shuttle at 20 g/L S:L ratio. A significant finding was consistently low leaching of Fe under all conditions studied (<50 mg/L or < 5%) and in-situ oxidation of Fe(II) by MnO2 to form insoluble ferric compounds as observed in residues. The presence of electron shuttle enhances reductive dissolution by MRC which favors dissolution of Mn more than Fe under anoxic conditions. X-ray fluorescence spectroscopy and X-ray diffraction peaks of residues confirm that MnO2 is preferentially dissolved than Fe2O3. These findings indicate that anoxic bioleaching can help to selectively recover Mn from low grade ferromanganese ores.