Precise regulation of the phase transformation for pyrolusite during the reduction roasting process

The mechanism involved in the phase transformation process of pyrolusite (MnO_(2)) during roasting in a reducing atmosphere was systematically elucidated in this study,with the aim of effectively using low-grade complex manganese ore resources.According to single-factor experiment results,the roasted product with a divalent manganese (Mn^(2+)) distribution rate of 95.30% was obtained at a roasting time of 25 min,a roasting temperature of 700℃,a CO concentration of 20at%,and a total gas volume of 500 mL·min^(-1),in which the manganese was mainly in the form of manganosite (MnO).Scanning electron microscopy and Brunauer–Emmett–Teller theory demonstrated the microstructural evolution of the roasted product and the gradual reduction in the pyrolusite ore from the surface to the core Thermodynamic calculations,X-ray photoelectron spectroscopy,and X-ray diffractometry analyses determined that the phase transformation of pyrolusite followed the order of MnO_(2)→Mn_(2)O_(3)→Mn_(3)O_(4)→MnO phase by phase,and the reduction of manganese oxides in each valence state proceeded simultaneously.

Hydrogen-based mineral phase transformation mechanism investigation of pyrolusite ore

Pyrolusite comprises the foremost manganese oxides and is a major source of manganese production.An innovative hydrogenbased mineral phase transformation technology to pyrolusite was proposed,where a 96.44%distribution rate of divalent manganese(Mn^(2+))was observed at an optimal roasting temperature of 650℃,a roasting time of 25 min,and an H2 concentration of 20vol%;under these conditions.The manganese predominantly existed in the form of manganosite.This study investigated the generation mechanism of manganosite based on the reduction kinetics,phase transformation,and structural evolution of pyrolusite and revealed that high temperature improved the distribution rate,and the optimal kinetic model for the reaction was the random nucleation and growth model(reaction order,n=3/2)with an activation energy(E_(a))of 24.119 kJ·mol^(−1).Throughout the mineral phase transformation,manganese oxide from the outer layer of particles moves inward to the core.In addition,pyrolusite follows the reduction sequence of MnO_(2)→Mn_(2)O_(3)→Mn_(3)O_(4)→MnO,and the reduction of manganese oxides in each valence state simultaneously proceeds.These findings provide significant insight into the efficient and clean utilization of pyrolusite.

Response surface optimization of process parameters for reduction roasting of low-grade pyrolusite by bagasse

The reduction roasting processes for low-grade pyrolusite using bagasse as the reducing agent was statistically analyzed. The central composite rotatable design （CCD） was used to optimize this reduction roasting processes. The three process parameters studied were the mass ratio of bagasse to ore, the roasting temperature and the roasting time. Analysis of variance （ANOVA） was used to analyze the experimental results. The interactions between the process parameters were done by using the linear and quadratic model. The results revealed that the linear and quadratic effects as well as the interaction are statistically significant for the mass ratio and roasting temperature but insignificant for the roasting time. The optimal conditions of 0.9：10 of mass ratio, the roasting temperature of 450 ~C, the roasting time of 30 min were obtained. Under these conditions, the predicted leaching recovery rate for manganese was 98.1%. And the satisfied experimental result of 98.2% confirmed the validity of the model.

Enhancement of bio-oxidation of refractory arsenopyritic gold ore by adding pyrolusite in bioleaching system

Pyrolusite was added in the bioleaching process to enhance the bio-oxidation process. Bioleaching tests at different dosages of pyrolusite ore, pH and inoculation amounts of Acidithiobacillus ferrooxidans were studied. The results showed that the time of the bio-oxidation process was decreased obviously and the arsenic leaching rate reached 94.4% after the bioleaching. The bio-oxidation of arsenopyrite and the effective extraction of manganese from pyrolusite were achieved by the bioleaching process. After bioleaching, the leaching rate of gold from the reaction residues reached 95.8% by cyanide leaching. In the bio-oxidation process, pyrolusite increased the redox potential of the solution to accelerate the bioleaching rate. The experiment showed that there were two reaction modes in the bioleaching process.

Effect of biological pretreatment on flotation recovery of pyrolusite

Bacillus mucilaginosus was used in pretreatment ofpyrolusite to facilitate the flotation removal of quartz from pyrolusite minerals. Quartz was activated by B. mucilaginosus, whereas pyrolusite was unaffected at pH 7 with laurylamine as collector. Flotation recovery of pyrolusite with B. mucilaginosus pretreatment is 73.62%, slightly lower than that of the process without biopretreament, namely 74.70%. The grade of concentrate of recovered pyrolusite is 19.44%, 2.18% higher than that of the recovered pyrolusite without B. mucilaginosus pretreatment （17.26%）. The results of FTIR and SEM showed that no bacteria were adsorbed on the surface of quartz or pyrolusite, indicating that the better selectivity and collectability of flotation resulted from bacterial byproducts. And interaction of bacterial byproducts such as extracellular bacterial polysaccharide, extracellular bacterial protein and acetic acid, on minerals were studied by FTIR and adsorption.

A pilot-scale jet bubbling reactor for wet flue gas desulfurization with pyrolusite

MnO2 in pyrolusite can react with SO2 in flue gas and obtain by-product MnSO4· H2O. A pilot scale jet bubbling reactor was applied in this work. Different factors affecting both SO2 absorption efficiency and Mn2^＋ extraction rate have been investigated, these factors include temperature of inlet gas flue, ration of liquid/solid mass flow rate（ L/S）, pyrolusite grade, and SO2 concentration in the inlet flue gas. In the meantime, the procedure of purification of absorption liquid was also discussed. Experiment results indicated that the increase of temperature from 30 to 70 K caused the increase of SO2 absorption efficiency from 81.4% to 91.2%. And when SO2 concentration in the inlet flue gas increased from 500 to 3000 ppm, SO2 absorption efficiency and Mn2^＋ extraction rate decreased from 98.1% to 82.2% and from 82.8% to 61.7%, respectively. The content of MnO2 in pyrolusite had a neglectable effect on SO2, absorption efficiency. Low L/S was good for both removal of SO2 and Mn2^＋ extraction. The absorption liquid was filtrated and purified to remove Si, Mg, Ca, Fe, Al and heavy metals, last product MnSO4· H2O was obtained which quality could reach China GB1622-86, the industry grade standards.

Kinetics of Reductive Leaching of Low-grade Pyrolusite with Molasses Alcohol Wastewater in H_2SO_4

The kinetics of reductive leaching of manganese from low grade pyrolusite in dilute sulfuric acid in the presence of molasses alcohol wastewater was investigated. The shrinking core model was applied to quantify the effects of reaction parameters on leaching rate. The leaching rate increases with reaction temperature, concentrations of H 2 SO 4 and organic matter in molasses alcohol wastewater increase and ore particle size decreases. The leaching process follows the kinetics of a shrinking core model and the apparent activation energy is 57.5 kJ·mol –1 . The experimental results indicate a reaction order of 0.52 for H2SO4 concentration and 0.90 for chemical oxygen demand (COD) of molasses alcohol wastewater. It is concluded that the reductive leaching of pyrolusite with molasses alcohol wastewater is controlled by the diffusion through the ash/inert layer composed of the associated minerals.

Fluidized roasting reduction kinetics of low-grade pyrolusite coupling with pretreatment of stone coal

Based on the fluidized roasting reduction technology of low-grade pyrolusite coupling with pretreatment of stone coal, the manganese reduction efficiency was investigated and technical conditions were optimized. It is found that the optimum manganese reduction efficiency can be up to 98.97% under the conditions that the mass ratio of stone coal to pyrolusite is 3：1, the roasting temperature of stone coal is 1000℃, the roasting temperature of pyrolusite is 800℃, and the roasting time is 2 h. Other low-grade pyrolusite ores in China from Guangxi, Hunan, and Guizhou Provinces were tested and all these minerals responded well, giving -99% manganese reduction efficiency. Meanwhile, the reduction kinetic model has been established. It is confirmed that the reduction process is controlled by the interface chemical reaction. The apparent activation energy is 36.397 kJ/mol.

Effects of sodium carbonate and calcium chloride on calcite depression in cationic flotation of pyrolusite

In the cationic flotation of pyrolusite using dodecyl ammine(DDA),the depressive effect of sodium carbonate andcalcium chloride on the calcite mineral was investigated systematically through flotation experiments,FTIR analysis,contact anglemeasurements and zeta potential tests.The microflotation experiments showed that both depressant agents decrease the flotationrecovery of calcite significantly.In addition,sodium carbonate acts as activator agent for pyrolusite,and increases its floatability.Theflotation experiments and contact angle measurements indicated that the selective depression effect of sodium carbonate on thecalcite mineral is more than that of calcium chloride.As evidenced by zeta potential and FT-IR analysis,sodium carbonate decreasesthe negative charges on the surface of calcite mineral and subsequently reduces the adsorption of DDA collector through electrostaticforces.At a pH of7.5,using2000g/t DDA and1500g/t sodium carbonate,a pyrolusite concentrate containing almost40%MnOwith71.5%recovery is achieved by carrying out the ore flotation experiments on the tabling pre-concentrate.

KINETICS OF LEACHING SPHALERITE WITH PYROLUSITE SIMULTANEOUSLY BY MICROWAVE IRRADIATION

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Study on Decoloration of Acidic Scarlet GR by Pyrolusite Oxidation under an Acid Condition

Decoloration of acidic scarlet GR by pyrolusite is studied in this paper. The effects of pH in solution, dosage and granularity of pyrolusite, reaction temperature, and vibration speed on decoloration efficiency are discussed. According to experiment results, the decoloration efficiency may exceed 95% for 40 mg/L GR solution by pyrolusite, pH is most important among all factors which impact the decoloration of acidic scarlet GR. Dosage and granularity of pyrolusite, reaction temperature, and vibration speed have a little benitfit on decoloration. The high decoloration efficiency and low removal efficiency of COD as well as FT-IR spectra of products between pyrolusite and acidic scarlet GR indicate that acidic scarlet GR undergoes the redox reaction on the interface of mineral and its chromophore is oxidated and decolored, but it is not removed thoroughly by oxidation.

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%.

TG–FTIR analysis of pyrolusite reduction by major biomass components

Pyrolusite reduction processes by three major biomass components cellulose,hemicelluloses and lignin,represented by CP,HP and LP,respectively,were investigated by thermogravimetric analyzer coupled with Fourier transform infrared spectrometry(TG-FTIR).The Sestak-Berggren(SB) equation was used to evaluate the kinetics of reduction processes.TG analysis reveals that the main reduction processes occur at 250-410 ℃,220-390 ℃,and 190-410 ℃ for CP,HP,and LP,respectively.FT-IR and XRD results indicate that various reducing volatiles(e.g.aldehydes,furans,ketones and alcohols) are produced from the pyrolysis with the three major components,which directly reduce MnO_2 in ore to MnO.The processes are described by the SB equation with three parameters(m,n,p).Their non-zero values suggest that pyrolusite reduction is controlled by the diffusion of reducing gaseous products through an ash/inert layer associated with minerals.The apparent activation energies for pyrolusite reduction by CP,HP and LP are 40.48,25.70 and 40.10 kJ·mol^(-1),respectively.

Galena-pyrolusite co-extraction in sodium chloride solution and its electrochemical analysis

The co-extraction behavior of galena-pyrolusite in a sodium chloride solution and the electrochemical mechanism of this process were investigated,and some factors affecting the leaching rate of Pb and Mn were optimized.The results show that all the factors such as the concentration of NaCl,HCl and pyrolusite ore,reaction time,temperature,adding times of HCl,affect the leaching rate of Pb.The main affecting factors are the concentration of NaCl,reaction time and temperature.The Tafel polarization curves and EIS plots of the galena and pyrolusite in the NaCl solution demonstrate that during the oxidation process of galena mineral electrode,film forms on the galena surface,which prevents galena from deeper oxidation.However,the film resistance can be greatly reduced in the presence of sodium chloride,thus promoting the reaction rate of galena.

Neutral Leaching of Low-Grade Pyrolusite with High Silica Content

Leaching studies of low-grade pyrolusite, containing 11.84﹪ Mn with high silicon, were carried out using sodium sulfite as a reductant in ammonium sulfate medium. Various process parameters including temperature, leaching time, solid-liquid ratio, quantity of ammonium sulfate, as well as the amount of reducing agent were studied in detail. The manganese extraction yield was the response of the process. Temperature and reagent concentration exerted the most important positive effect on the manganese extraction. The optimized conditions showed that when the amount of reducing agent was a stoichonmetric amount, over 90﹪ manganese extraction and the lowest impurities were achieved, the amount of heavy metal impurities in the manganese leaching liquid was less than 5 mg/L, and almost no iron and aluminum were extracted in 3 mol/L ammonium sulfate concentration at 100 ℃ in 45 min.

Optimization of reaction conditions for the electroleaching of manganese from low-grade pyrolusite

In the present study, a response surface methodology was used to optimize the electroleaching of Mn from low-grade pyrolusite. Ferrous sulfate heptahydrate was used in this reaction as a reducing agent in sulfuric acid solutions. The effect of six process variables, including the mass ratio of ferrous sulfate heptahydrate to pyrolusite, mass ratio of sulfuric acid to pyrolusite, liquid-to-solid ratio, current density, leaching temperature, and leaching time, as well as their binary interactions, were modeled. The results revealed that the order of these factors with respect to their effects on the leaching efficiency were mass ratio of ferrous sulfate heptahydrate to pyrolusite 〉 leaching time 〉 mass ratio of sulfuric acid to pyrolusite 〉 liquid-to-solid ratio 〉 leaching temperature 〉 current density. The optimum conditions were as follows： 1.10：1 mass ratio of ferrous sulfate heptahydrate to pyrolusite, 0.9：1 mass ratio of sulfuric acid to pyrolusite, liquid-to-solid ratio of 0.7：1, current density of 947 A/m^2, leaching time of 180 min, and leaching temperature of 73°C. Under these conditions, the predicted leaching efficiency for Mn was 94.1%; the obtained experimental result was 95.7%, which confirmed the validity of the model.

Preparation of sodium manganate from low-grade pyrolusite by alkaline predesilication-fluidized roasting technique

Low concentration alkaline leaching was used for predesilication treatment of low-grade pyrolusite. The effects of initial NaOH concentration, liquid-to-solid ratio, leaching temperature, leaching time and stirring speed on silica leaching rate were investigated and the kinetics of alkaline leaching process was studied. The results show that silica leaching rate reached 91.2% under the conditions of initial NaOH concentration of 20%, liquid-to-solid ratio of 4：1, leaching temperature of 180 ℃, leaching time of 4 h and stirring speed of 300 r/min. Shrinking-core model showed that the leaching process was controlled by the chemical surface reaction with activation energy Ea of 53.31 k J/mol. The fluidized roasting conditions for preparation of sodium manganate were optimized by the orthogonal experiments using the desiliconized residue. The conversion rate of sodium manganate was obtained to be 89.7% under the conditions of silica leaching rate of 91.2%, NaOH/MnO2 mass ratio of 3：1, roasting temperature of 500 ℃ and roasting time of 4 h, and it increased with the increase of silicon leaching rate.

Pyrolusite and Chalcophanite Forming in Qixiashan, Nanjing

Weathering of manganese-bearing carbonate could form chalcophanite. In this paper, the occurrence of Fe (hydro) oxides and Mn-bearing minerals in Qixiashan were identified by XRD and SEM, mainly consisted of goethite, hematite, pyrolusite and chalcophanite. From the microscope investigation, stromatolite-like structure phenomenon is widespread existed, which may be caused by microbial activities. To identify the mineral structure in the Fe-Mn crust, Raman and XPS were used to identify the mineral structure and valence of Fe, Mn and Zn. This work could help us to know the relationship of Fe and Mn during the weathering of manganese-bearing carbonate. And the enrichment of Mn and Zn from the supergene environment could provide a path for the contamination of heavy metals.

Comparative Study between D2EHPA and Cyanex 272 as Extractants of Mn(II) from a Leached Liquor Produced by Reductive Leaching of a Pyrolusite Ore with SO₂

This paper compares the efficiency of D2EHPA and Cyanex 272 to extract the divalent manganese cation from an actual leaching solution obtained by reductive leaching of a low-grade pyrolusite ore, using SO2 gas. The studied variables were the extractant concentration in the organic phase, the pH of the leached liquor and the volume ratio between organic phase and leached liquor. It was observed that D2EHPA is a better extractant than Cyanex272. Therefore, with the best experimental conditions found, both extractants reach a manganese recovery around 95% with five extraction stages conducted under the following conditions: 25?C, O/A = 2, 10% volume of extractant concentration in the organic phase, pH of the leached liquor before the mixing between 8 and 8.5, and one minute of mixing time for each extraction stage.

CFD simulation for reduction of pyrolusite in fluidized beds

In this study,a CFD model coupled with heterogeneous flow structure,mass transfer equations,and chemical reaction kinetics is established to forecast the pyrolusite reduction reaction behavior.Compared with the previous studies which ignore the volume change of solids phase,the influence of volume shrinkage on reaction and flow behavior is explored in this research.Volume shrinkage of pyrolusite is proved to be non-negligible in predicting the conversion rate.The negligence of volume shrinkage leads to the overestimation of conversion rate for its inaccurate estimation of surface area for reaction.Besides,the influence of volume shrinkage on the reaction is found smaller in the scaled-up reactor.