Rare earth elements(REE)and isotope composition(δ^(13)C andδ^(18)O)of manganese ores of Chiatura deposit(Georgia):features of ore formation and genesis

The rare earth elements(REE)geochemistry and the isotope(δ^(13)C,δ^(18)O)composition of manganese ores of the Chiatura(Georgia)deposit were studied.One of the major features of all types of manganese ores is negative cerium(Ce/Ce*_(PAAS))anomaly and the absence of europium(Eu/Eu*_(PAAS))anomaly.Oxide oolitic manganese ores were formed in oxic shallow marine environments.The content and distribution of REEs(in particular Ce and Eu)in these ores are connected mainly with ferrous oxides.The performed C-and O-isotope research in Mn-carbonates(oolitic and massive)has indicated that carbonate ores were formed by the participation of isotopic ally light CO_(2)which is a result of the oxidation of organic matter in the sediment strata by reducing environments of early diagenesis(and,partially,catagenesis)zone.Obtained negative cerium anomalies in the studied carbonate ores reflect the specific REE patterns in pore waters of sediments of earlier isdiagenesis zone of the Oligocene Chiatura's basin.The deficiency of cerium in this zone remains debatable and requires further study.Formation of manganese carbonates took place multistage by the input of incisional solutions of different chemistry into sea bottom waters and sediments.The absence of europium anomaly indicates about lack of hydrothermal solution input.

Sulfur resource recovery based on electrolytic manganese residue calcination and manganese oxide ore desulfurization for the clean production of electrolytic manganese

An environmentally friendly and resource-conserving route to the clean production of electrolytic manganese was developed,in which the electrolytic manganese residue(EMR)was initially calcined for cement buffering;then the generated SO2-containing flue gas was managed using manganese oxide ore and anolyte(MOOA)desulfurization;at last,the desulfurized slurry was introduced to the electrolytic manganese production(EMP).Results showed that 4.0 wt%coke addition reduced the sulfur of calcined EMR to 0.9%,thereby satisfying the cement-buffer requirement.Pilot-scale desulfurization showed that about 7.5 vol%of high SO2 containing flue gas can be cleaned to less than 0.1 vol%through a five-stage countercurrent MOOA desulfurization.The desulfurized slurry had 42.44 g·L-Mn2+and 1.92 g·L-1 S2 O62-,which was suitable for electrowinning after purification,and the purity of manganese product was 99.93%,satisfy the National Standard of China YB/T051-2015.This new integrated technology fulfilled 99.7%of sulfur reutilization from the EMR and 94.1%was effectively used to the EMP.The MOOA desulfurization linked the EMP a closed cycle without any pollutant discharge,which promoted the cleaner production of EMP industry.

Manganese leaching in high concentration flue gas desulfurization process with semi-oxidized manganese ore

Manganese leaching during high concentration flue gas desulfurization process with semi-oxidized manganese ore was studied in this paper.It was found that there were different reaction pathways among which MnO2,Mn2O3 and MnCO3 in semi-oxidized manganese ore during flue gas desulphurization and manganese leaching.High SO2 concentration facilitated redox reaction between MnO2 and SO2,and high concentration of H2SO4 accelerated MnCO3/Mn2O3 leaching from semi-oxidized ore.Kinetics study showed that manganese leaching in flue gas desulfurization process with semi-oxidized ore was controlled by a mixed-control model,that is the surface chemical reaction and mass diffusion dominated both the oxidation of SO2 and manganese leaching process.The apparent activation energy was 13.05 k J·mol-1 and the reaction orders with respect to SO2 and H2SO4 concentration were 1.38 and 0.10,respectively.Finally,a semi-empirical rate equation based on shrinking core model was derived to describe the process.

Effect of desliming on the magnetic separation of low-grade ferruginous manganese ore

In the present investigation, magnetic separation studies using an induced roll magnetic separator were conducted to beneficiate low-grade ferruginous manganese ore. The feed ore was assayed to contain 22.4% Mn and 35.9% SiO2, with a manganese-to-iron mass ratio （Mn：Fe ratio） of 1.6. This ore was characterized in detail using different techniques, including quantitative evaluation of minerals by scan- ning electron microscopy, which revealed that the ore is extremely siliceous in nature and that the associated gangue minerals are more or less evenly distributed in almost all of the size fractions in major proportion. Magnetic separation studies were conducted on both the as-received ore fines and the classified fines to enrich their manganese content and Mn：Fe ratio. The results indicated that the efficiency of separation for deslimed fines was better than that for the treated unclassified bulk sample. On the basis of these results, we proposed a proc- ess flow sheet for the beneficiation of low-grade manganese ore fines using a Floatex density separator as a pre-concentrator followed by two-stage magnetic separation. The overall recovery of manganese in the final product from the proposed flow sheet is 44.7% with an assay value of 45.8% and the Mn：Fe ratio of 3.1.

Preparation of manganese sulfate from low-grade manganese carbonate ores by sulfuric acid leaching

In this study, a method for preparing pure manganese sulfate from low-grade ores with a granule mean size of 0.47 mm by direct acid leaching was developed. The effects of the types of leaching agents, sulfitric acid concentration, reaction temperature, and agitation rate on the leaching efficiency of manganese were investigated. We observed that sulfuric acid used as a leaching agent provides a similar leach- ing efficiency of manganese and superior selectivity against calcium compared to hydrochloric acid. The optimal leaching conditions in sul- furic acid media were determined; under the optimal conditions, the leaching efficiencies of Mn and Ca were 92.42% and 9.61%, respec- tively. Moreover, the kinetics of manganese leaching indicated that the leaching follows the diffusion-controlled model with an apparent ac- tivation energy of 12.28 kJ·mol-l. The purification conditions of the leaching solution were also discussed. The results show that manganese dioxide is a suitable oxidant of ferrous ions and sodium dimethyldithiocarbamate is an effective precipitant of heavy metals. Finally, through chemical analysis and X-ray diffraction analysis, the obtained product was determined to contain 98% of MnSOa4·H20.

Hydrometallurgical leaching and kinetic modeling of low-grade manganese ore with banana peel in sulfuric acid

Manganese was leached from a low-grade manganese ore(LGMO)using banana peel as the reductant in a dilute sulfuric acid medium.The effects of banana peel amount,H2SO4 concentration,reaction temperature,and time on Mn leaching from the complex LGMO were studied.A leaching efficiency of~98%was achieved at a leaching time of 2 h,banana peel amount of 4 g,leaching temperature of 120°C,manganese ore amount of 5 g,and sulfuric acid concentration of 15vol%.The phase,microstructural,and chemical analyses of LGMO samples before and after the leaching process confirmed the successful leaching of manganese.Furthermore,the leaching process followed the shrinking core model and the leaching rate was controlled by a surface chemical reaction(1−(1−x)^1/3=kt)mechanism with an apparent activation energy of 40.19 kJ·mol^−1.

Reductive leaching of manganese from low-grade pyrolusite ore in sulfuric acid using pyrolysis-pretreated sawdust as a reductant

Manganese （Mn） leaching and recovery from low-grade pyrolusite ore were studied using sulfiaric acid （H2SO4） as a leachant and pyrolysis-pretreated sawdust as a reductant. The effects of the dosage of pyrolysis-pretreated sawdust to pyrolusite ore, the concentration of sulfuric acid, the liquid/solid ratio, the leaching temperature, and the leaching time on manganese and iron leaching efficiencies were inves- tigated. Analysis of manganese and iron leaching efficiencies revealed that a high manganese leaching efficiency was achieved with low iron extraction. The optimal leaching efficiency was determined to be 20wt% pyrolysis-pretreated sawdust and 3.0 mol/L H2SO4 using a liq- uid/solid ratio of 6.0 mL/g for 90min at 90℃. Other low-grade pyrolusite ores were tested, and the results showed that they responded well with manganese leaching efficiencies greater than 98%.

Contrasting REE Signatures on Manganese Ores of Iron Ore Group in North Orissa, India

The distribution pattern of Rare Earth Elements （REE） in three categories of manganese ores viz. stratiform, stratabound-replacement, and detrital of Precambrian Iron Ore Group from north Orissa, India was reported. These categories of Mn-ore differed in their major and trace chemistry and exhibited contrasting REE signature. The stratiform ores were relatively enriched in ∑REE content （697 μg·g^-1） and their normalized pattern showed both positive Ce and Eu anomalies, whereas the stratabound-replacement types were comparatively depleted in ∑REE content （211 μg·g^-1） and showed negative Ce and flat Eu signatures. The detrital categories showed mixed REE pattern. The data plotted in different discrimination diagrams revealed a mixed volcaniclastic and chemogenic source of material for stratiform categories, and LREE （Light Rare Earth Elements） and HREE （Heavy Rare Earth Elements） are contributed by such sources, respectively. In contrast, the stratabound ore bodies were developed during the remobilization of stratiform ores, and associated Mncontaining rocks under supergene condition followed by the redeposition of circulating mineralized colloidal solutions in structurally favorable zones. During this process, some of the constituents were found only in very low concentration within stratabound ores, and this is attributed to their poor leachability/mobility. The detrital ores did not exhibit any significant characteristic in respect of REE as their development was via a complex combination of processes involving weathering, fragmentation, recementation, and burial under soil cover.

Reductive Acid Leaching of Low Grade Manganese Ores

Manganese recoveries from low-grade ores using organic acids as reducing agents were investigated in the present work. The acid leaching potential of both oxalic acid and citric acid were estimated. Manganese leaching amount were measured by using standard manganese curve and estimated by titration method. Effects of various acid concentrations on leaching efficiency were studied. The observed result suggested prominent manganese recovery of 66% by oxalic acid at 2 M concentration whereas citric acid had less effect on leaching showing leaching percentage upto 40% in 6 days. Acid leaching of manganese ore with both the acids gave a comparative data stating that oxalic acid leached better than citric acid.

Hydrometallurgical Processing of Manganese Ores: A Review

Hydrometallurgy is the most suitable extractive technique for the extraction and purification of manganese as compared to all other techniques including biometallurgy and pyrometallurgical processes. In the hydrometallurgical processing of manganese from its ore, the leach liquors often contain divalent ions such as iron, manganese, copper, nickel, cobalt and zinc along with other impurities which make manganese very difficult to separate. The processes employed for solution concentration and purification in the hydrometallurgical processing of manganese include precipitation, cementation, solvent extraction and ion exchange. Solvent extraction also proves more efficient and it plays vital roles in the purification and separation of the manganese as compared to all other techniques. A detailed review of the various steps involved in the hydrometal-lurgical manganese processing, concentration and purification processes and newer processes of extraction of manganese from ores and waste materials were discussed.

A Comprehensive Utilization Process for Black Manganese-silver Ores by Pyrite Reducing Method

On a 5 kg bench scale, the separating of Mn-Ag from black manganese-silver ores by pyrite reducing method was investigated. Leached Mn content of 98.3% (mass fraction) along with silver loss of 1.5% is achieved. The purification of solution by the precipitation method was effectively used. Chemical grade gamma -MnO2 with TMn content of 60.13% (mass fraction) and MnO2 content of 92.28% (mass fraction) is obtained. Mn recovery efficiency is 94.04%. The residues from leaching Mn process of black Mn-Ag ores was employed for silver extraction by cyanidation with leached silver content of 92.17% (mass fraction), displacement ratio of 99.5%, recovery efficiency of 90.79%. Therefore, the present study provides a feasible process for making full use of black manganese-silver ore resources.

Reductive leaching of low-grade manganese ore with pre-processed cornstalk

Cornstalk is usually directly used as a reductant in reduetive leaching manganese. However, low utilization of cornstalk makes low manganese dissolution ratio, In the research, pretreatment for cornstalk was proposed to improve manganese dissolution ratio. Cornstalk was preprocessed by a heated sulfuric acid solution （1.2 M of sulfuric acid concentration） for 10 min at 80℃. Thereafter, both the pretreated solution and the residue were used as a reductant for manganese leaching. This method not only exhibited superior activity for hydrolyzing cornstalk but also enhanced manganese dissolution. These effects were attributed to an increase in the amount of reductive sugars resulting from lignin hydrolysis. Through acid pretreatment for cornstalk, the manganese dissolution ratio was improved from 50.14% to 83.46%. The present work demonstrates for the first time the effective acid pretreatment of cornstalk to provide a cost-effective reductant for manganese leaching.

Kinetics Analyzing of Direction Reduction on Manganese Ore Pellets Containing Carbon

Using high temperature carbon tube furnace, reduction of manganese ore pellets containing carbon was investigated. The reaction was divided into two stages at five minutes after reaction, and the kinetics model of reduction process was established. The experimental results showed that, the reaction rate in the earlier stage was controlled by the chemical reactions between FeO, MnO and carbon reductant, and the activation energy was 28.85 KJ/mol. In the later stage, as the carbon reductant replaced by CO, the reaction rate was controlled by CO-diffusing in solid products, and the cor- responding activation energy was 86.56 KJ/mol. Reaction rate of the later stage was less than the earlier one.

Phase, Microstructure and Beneficiation of Manganese Ore by Acid Leaching

In this research work, sawdust was used as a reducing agent for sulphuric acid leaching of manganese ore from Prang Ghar, Lower Mohmand Agency, Pakistan. X-ray diffraction of the powdered sample indicated the presence of Hausmannite (Mn3O4), Calcium Aluminum Silicate Hydrate, Silica (SiO2) and Hematite (Fe2O3). X-ray diffraction and the energy dispersive spectroscopic analysis show that the manganese ore sample was siliceous in nature. In the present study, six process parameters were investigated i.e. the particle size of the ore, leaching temperature, time duration, Mn ore amount, sulphuric acid concentration and amount of sawdust. Manganese extraction of 88.93 (wt%) was achieved for a leaching time of 60 minutes at 120°C using 5% (v/v) H2SO4 concentration for 10 g Mn ore and 5 g sawdust. The results demonstrate that sawdust is a low cost, renewable and non-hazardous reducing agent in comparison to other available reagents.

Reductive recovery of manganese from low-grade manganese dioxide ore using toxic nitrocellulose acid wastewater as reductant

The hydrometallurgical strategy of extracting Mn from low-grade Mn ores has attracted attention for the production of electrolytic manganese metal(EMM). In this work, the reductive dissolution of low-grade Mn O2 ores using toxic nitrocellulose acidic wastewater(NAW) as a reductant was investigated for the first time. Under the optimized conditions of an Mn O2 ore dosage of 100 g·L-1, an ore particle size of-200 mesh, concentrated H2 SO4-to-NAW volume ratio of 0.12, reaction temperature of 90°C, stirring speed at 160 r·min-1, and a contact time of 120 min, the reductive leaching efficiency of Mn and the total organic carbon(TOC) removal efficiency of NAW reached 97.4% and 98.5%, respectively. The residual TOC of 31.6 mg·L-1 did not adversely affect the preparation of EMM. The current process offers a feasible route for the concurrent realization of the reductive leaching of Mn and the treatment of toxic wastewater via a simple one-step process.

The Occurrence of Sc, Co and Ni in Manganese Ore from Western China

China’s manganese resources are usually associated with the valuable elements such as silver, lead, zinc, cobalt, nickel, scandium, etc which should be comprehensively recovered during the manganese beneficiation. A manganese ore from western China contains Mn 23.18%, Co 0.073%, Ni 0.21% and Sc 0.013%. The mineralogy composition of ore and the occurrence of associated elements of Sc, Co as well as Ni are studied in this paper. According to the results, the manganese minerals in this ore are mainly lithiophorite and a little secondary pyrolusite. The lithiophorite in this ore is rich in aluminum and actually it is the generic name for the multi-mineral aggregates mixed by silicon, aluminum and iron, which is quite different with the ordinary psilomelane. There is not any Sc, Ni or Co mineral in this ore and more than 98% of Sc, Ni and Ni exists in lithiophorite and pyrolusite. The distribution of Sc, Co and Ni in lithiophorite is further studied by EPMA and the results indicate that Sc and Co in lithiophorite is sparse and dispersed distribution while Ni usually distributes in the argillaceous lithiophorite and is local enrichment. Reduction-sulfuric acid leaching tests show that the dissolution of Sc and Co happens before lithiophorite dissolves; the dissolution rate of Sc and Co is almost the same, which is significantly higher than the dissolution rate of manganese. However, the dissolution rate of Ni is extremely low with the dissolution of manganse, which indicates that Ni is hard to dissolve and its dissolution rate obviously lags behind that of Mn, Sc and Co. The conclusion can be drawn that Sc and Co exist in the lithiophorite crystals as interface adsorption while Ni exists in the clay (kaolinite) mixed up with lithiophorite as interface adsorption. The conclusion indicates that Sc and Co can dissolve before the dissolution of manganese at a high dissolution rate in the hydrometallurgical process while Ni is also into the solution through desorption from the interface of clay but its dissolution rate is rather slow because of the insoluble nature of clay.

IMPROVED LEACHING METHOD AND KINETICS OF MANGANESE CARBONATE ORE AT ROOM TEMPERATURE

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Characterization of Egyptian Manganese Ores for Production of High Carbon Ferromanganese

This work aims at studying the reactivity of Egyptian manganese ores to be used in the production of ferromanganese alloys in submerged electric arc furnace. Ores with different manganese content (high-medium and low) were selected and characterized by X-Ray Fluorescence (XRF), X-Ray Diffraction (XRD) and Scanning Electron Microscope (SEM). The main mineralogical compositions in the three ores are pyrolusite (MnO2) and hematite (Fe2O3). Porosity of selected Mn ores was determined. The reactivity of the different ores was carried out through pre-reduction of the selected ores using thermobalance at 900°C and 1100°C and mixture of CO and CO2 gases. The reduction process was done until steady weight. The reduced ores were examined using XRD and SEM. The results showed that pyrolusite in high and medium ores are converted completely to MnO at 1100°C. However, the ore with low manganese content was converted to MnO and Mn3O4. Consequently, it is clear from the results that Mn ores with high and medium MnO2 content are more reactive than those with low MnO2. Therefore, high MnO2 content Mn ores are preferable to get good economic impact during the production of high carbon ferromanganese.

Occurrence of Manganese Ore Deposits and Their Mineralogy in Vizianagaram-Visakhapatnam Manganese Ores Belt (Andhra Pradesh) India

The Manganese deposits of Andhra Pradesh are associated with a thick sequence of Precambrian rocks, belonging to Khondalite and Charnockite groups of Dharwar Supergroup that forms part of 2500 to 3000 m.y. old Eastern Ghat complex of India. The study area is the Manganese deposits of Vizianagram-Visakhapatnam Manganese Belt of Andhra Pradesh. The study area lies about 150 km NE of Visakhapatnam between 18°12′N - 18°30′N and 83°20′E - 83°45′E. The mineralization of Manganese ores is confined to different rock types, belonging to both Khondalite and Charnockite groups, where they are dispersed throughout the country rocks as small lenses, pockets, veins and irregular bodies of varying dimensions. Quartz, garnet, clay, limonite and apatite are the common gangue minerals in the Manganese ores. The presence of quartz, garnet and apatite brings down the grade of the ore. Ferruginous laterite and ochre generally work as capping of the Manganese deposits. The various Manganese ore minerals present in these deposits are indentified as 1) Primary minerals-braunite, bixbyite, vredenburgite, jacobsite and hausmannite, 2) secondary minerals-psilomelane, cryptomelane, hollandite, pyrolusite and wad. The primary ore minerals are considered to be syngenetic and regionally metamorphosed while, the associated secondary ore minerals are formed due to alteration of the primary ores.

Influence of Microstructure on Beneficiation of Low-Grade Siliceous Manganese Ore from Orissa, India

Two low-grade siliceous manganese ores such 1) siliceous crystalline and 2) siliceous cherty types from north Orissa, Indiawas mineralogically characterized and investigated for their possible upgradation. Both the Mn-ore types were subjected to different physical beneficiation techniques under identical conditions and results reported. The results revealed that in the case of low-grade siliceous crystalline type Mn-ore a feed having 26% Mn could be upgraded to more than 45% Mn by dry magnetic separation with 69% recovery at 1.00 tesla magnetic intensity. But the cherty type Mn-ore could not respond well to any of the beneficiation techniques, particularly dry magnetic separation, because of poor liberation even at a size fraction below 100 mesh, though the other type gives best result at this size fraction.