Reductive leaching of manganese oxide ores using waste tea as reductant in sulfuric acid solution

Manganese oxide ores from Gabon and Xiangxi were leached with waste tea as reductant in dilute sulfuric acid solution. The effects of waste tea dosage, concentration of sulfuric acid, liquid-to-solid ratio, leaching temperature and reaction time on leaching process were explored. The leaching efficiency of Gabonese manganese oxide ore reached almost 100% under the optimal condition which was determined as follows： manganese oxide ore to waste tea mass ratio of 10：1, sulfuric acid concentration of 2.5 molFL, liquid-to-solid ratio of 7.5：1, leaching temperature of 368 K, time of 8 h. The leaching efficiency of Xiangxi manganese oxide ore reached 99.8% under the optimal condition which was determined as follows： manganese oxide ore to waste tea mass ratio of 10：1, sulfuric acid concentration of 1.7 mol/L, liquid-to-solid ratio of 7.5：1, leaching temperature of 368 K, time of 8 h. The leaching process followed the internal diffusion controlled kinetic model, and the apparent activation energies of Gabonese manganese oxide ore and Xiangxi manganese oxide ore were calculated to be 38.2 kJ/mol and 20.4 kJ/mol, respectively. The morphological changes and mineralogical forms of the ore before and after the chemical treatment were discussed with the support of XRD analysis and SEM analysis.

Leaching of low grade zinc oxide ores in Ida^(2-)-H_2O system

Ida2--H2O system（iminodiacetate aqueous solution） was used to leach a low grade zinc oxide ore for Zn extraction.The effects of leaching time,liquid-solid ratio（L/S）,total concentration of Ida2-（[Ida2-]T）,leaching temperature and pH on Zn leaching recovery and the dissolution of impurities such as Ca,Mg,Cu,Ni,Fe,Pb and Cd were investigated.Results show that Ca,Mg and Fe in ores were hardly dissolved in alkalescent iminodiacetate aqueous solution,while valuable metals such as Cu,Ni,Pb and Cd were partly dissolved into leaching liquor with Zn.The recovery of Zn reaches 76.6% when the ores were leached for 4 h at 70 ℃ by 0.9 mol/L iminodiacetate aqueous solution with pH of 8 and L/S of 5：1.

Preparation of ammonium jarosite from clinker digestion solution of nickel oxide ore roasted using(NH_4 )_2SO_4

To obtain the appropriate conditions for eliminating Fe3＋from NiSO4 solution, the digestion solution of the clinker was used as raw material, which was obtained from roasting the nickel oxide ore with （NH4）2SO4. The ammonium jarosite was successfully synthesized from the solution with analytic grade NH4HCO3. The effects of reaction temperature, reaction time, end pH value of reaction on the removal rate of iron were investigated, and the effect of the initial concentration of Fe3＋was also discussed. All of those factors had significant effects on the removal rate of Fe3＋, among which the reaction temperature was the most prominent. The appropriate reaction conditions were concluded as follows： reaction temperature 95 ℃ reaction time 3.5 h, end pH value of reaction 2.5 at initial concentration of Fe3＋19.36 g/L. The physical aspect of （NH4）2Fe6（SO4）4（OH）12 was cluster figure composed of sheet or prismatic particles with smooth surface.

Manganese extraction by reduction-acid leaching from low-grade manganese oxide ores using CaS as reductant

The extraction of manganese from low-grade manganese oxide ores using Ca S derived from Ca SO4 as reductant was investigated. The effects of mass ratio of Ca S to ore, reduction temperature, reduction time, liquid to solid ratio（L/S ratio）, stirring speed, leaching temperature, leaching time and H2SO4 concentration on the leaching rates of Mn and Fe during the reduction–acid leaching process were discussed. The leaching rates of 96.47% for Mn and 19.24% for Fe were obtained under the optimized conditions of mass ratio of Ca S to manganese oxide ore 1：6.7, L/S ratio 5：1, stirring speed 300 r/min, reduction temperature of 95 °C for 2.0 h in the reduction process and leaching stirring speed of 200 r/min, H2SO4 concentration of 1.5 mol/L, leaching temperature of 80 °C for 5 min in the leaching process. In addition, this process can be employed in the recovery of manganese from various manganese oxide ores, and Mn leaching rate above 95% is obtained.

Technological conditions and kinetics of leaching copper from complex copper oxide ore

The kinetic behavior of leaching copper from low grade copper oxide ore was investigated. The effects of leaching temperature, H2SO4 concentration, particle size of crude ore and agitation rate on the leaching efficiency of copper were also evaluated. And the kinetic equations of the leaching process were obtained. The results show that the leaching process can be described with a reaction model of shrinking core. The reaction can be divided into three stages. The first stage is the dissolution of free copper oxide and copper oxide wrapped by hematite-limonite ore. At this stage, the leaching efficiency is very fast （leaching efficiency is larger than 60%）. The second stage is the leaching of diffiuent copper oxides, whose apparent activation energy is 43.26 kJ/mol. During this process, the chemical reaction is the control step, and the reaction order of H2SO4 is 0.433 84. The third stage is the leaching of copper oxide wrapped by hematite-limonite and silicate ore with apparent activation energy of 16.08 kJ/mol, which belongs to the mixed control.

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.

Leaching kinetics of low grade zinc oxide ore in NH_3-NH_4Cl-H_2O system

The leaching kinetics of low grade zinc oxide ore in NH3-NH4Cl-H2O system was studied. The effects of ore particle size, reaction temperature and the sum concentration of ammonium ion and ammonia on the leaching efficiency of zinc were examined. The leaching kinetics of low-grade zinc oxide ore in NH3-NH4Cl-H2O system follows the kinetic law of shrinking-core model. The results show that diffusion through the inert particle pores is the leaching kinetics rate controlling step. The calculated apparent activation energy of the process is about 7.057 kJ/mol. The leaching efficiency of zinc is 92.1% under the conditions of ore particle size of 69 μm, holding at 80 ℃ for 60 min, sum ammonia concentration of 7.5 mol/L, the molar ratio of ammonium to ammonia being 2-1, and the ratio (g/mL) of solid to liquid being 1-10.

Techniques of copper recovery from Mexican copper oxide ore

Mexican copper ore is a mixed ore containing mainly copper oxide and some copper sulfide that responds well to flotation. The joint techniques of flotation and leaching were studied. The results indicate that an ore containing 19.01% copper could be obtained at a recovery ratio of 35.02% by using sodium sulfide and butyl xanthate flotation. Over 83.33% of the copper oxide can be recovered from the railings by leaching in suitable conditions, such as 1 h stirring at a temperature around 25 ℃with a mixing speed of S00 r/min, an H2SO4 concentration of 1.0 mol/L and a mass ratio of the ore-slurry-liquid to solid （mL/ms） of 3. The overall yield of refined ore after flotation and leaching is over 89.18% of the copper, which is much better than sole flotation or leaching. A copper product containing more than 99.9% copper was obtained by using the process： flotation-agitation leaching- solvent extraction-electro-winning.

Kinetics of reductive leaching of manganese oxide ore using cellulose as reductant

The kinetics of reductive leaching of manganese from a low-grade manganese oxide ore were studied using cellulose as reductant in dilute sulfuric acid medium.It was found that when the stirring speed was higher than 200 r/min,the effect of gas film diffusion on manganese extraction efficiency could be neglected,and the kinetic behavior was investigated under the condition of elimination of external diffusion influence on the leaching process.Effects of leaching temperature,mass ratio of cellulose and ore,and the sulfuric acid concentration on manganese extraction efficiency were discussed.The kinetic data were analyzed based on the shrinking core model,which indicated that the leaching process was dominated by both ash layer diffusion and chemical reaction at the initial stage,with the progress of leaching reaction,the rate-controlling step switched to the ash layer diffusion.It was also concluded that the sulfuric acid concentration had the most significant influence on the leaching rate,the reaction orders with respect to the sulfuric acid concentration were 2.102 in the first 60 min,and 3.642 in the later 90 min,while the reaction orders for mass ratio of cellulose and ore were 0.660 and 0.724,respectively.An Arrhenius relationship was used to relate the temperature to the rate of leaching,from which apparent activation energies were calculated to be 46.487 kJ/mol and 62.290 kJ/mol at the two stages,respectively.Finally,the overall leaching rate equations for the manganese dissolution reaction with cellulose in sulphuric acid solution were developed.The morphological changes and mineralogical forms of the ore before and after the chemical treatment were discussed with the support of SEM and XRD analyses.

Effect of temperature on leaching behavior of copper minerals with different occurrence states in complex copper oxide ores

The effect of temperature on leaching behavior of copper minerals with different occurrence states in complex copper oxide ores was carried out by phase analysis means of XRD, optical microscopy and SEM-EDS. The results indicated that at ambient temperature, the easily leached copper oxide minerals were completely dissolved, while the bonded copper minerals were insoluble. At lukewarm temperature of 40℃, it was mainly the dissolution of copper in isomorphism state. With increasing temperature to 60℃, the copper leaching rate in the adsorbed state was significantly accelerated. In addition, when the temperature increased to 80℃, the isomorphic copper was completely leached, leaving 11.2% adsorbed copper un-leached. However, the copper in feldspar-quartz-copper-iron colloid state was not dissolved throughout the leaching process. Overall, the leaching rates of copper in different copper minerals decreased in the order: malachite, pseudo-malachite > chrysocolla > copper-bearing chlorite > copper-bearing muscovite > copper-bearing biotite > copper-bearing limonite > feldspar-quartz-copper-iron colloid.

Recovery prediction of copper oxide ore column leaching by hybrid neural genetic algorithm

The artificial neural network(ANN)and hybrid of artificial neural network and genetic algorithm(GANN)were appliedto predict the optimized conditions of column leaching of copper oxide ore with relations of input and output data.The leachingexperiments were performed in three columns with the heights of2,4and6m and in particle size of<25.4and<50.8mm.Theeffects of different operating parameters such as column height,particle size,acid flow rate and leaching time were studied tooptimize the conditions to achieve the maximum recovery of copper using column leaching in pilot scale.It was found that therecovery increased with increasing the acid flow rate and leaching time and decreasing particle size and column height.Theefficiency of GANN and ANN algorithms was compared with each other.The results showed that GANN is more efficient than ANNin predicting copper recovery.The proposed model can be used to predict the Cu recovery with a reasonable error.

Laboratory Study on the Removal of Fluorine from High Fluorine Bearing Zinc Oxide Ore

An ever increasing demand for zinc has resulted in worldwide efforts to exploit complex and lean grade reserves of zinc oxide ore. In this study experiments were done on zinc recovery from high-fluorine bearing zinc oxide ore. First the effect of different variables on fluorine removal was investigated. Optimum experimental conditions occurred when the temperature was 1173 K, roasting time was 90 min and air flow was at a velocity of 5 m/min, the fluorine removal from the samples reached over 93%. The results obtained indicate that fluorine removal is not enhanced by adding diluted sulfuric acid or water as a binder. Second the roasted materials were leached with a diluted sulfuric acid, neutralized, flocculated and filtrated. The which satisfies the requirement of fluorine residual fluorine content in the leached content in the leached solutions for the solutions was less than 38 mg/L production of electrolytic zinc.

Some Characteristics of Niobium Mineral Resources of Low and Medium Grade Oxide Ores in the Main and Eastern Mining Areas at the Bayan Obo Mine

Since the low and medium grade oxide ores in the Main and Eastern Mining Areas at the Bayan Obo Mine have a high grade of Nb_2O_5 and large ore reserves and are rich in many elements,they are of greater value to use in development and recovery than other kinds of niobium minerals resources.The dissemination characteristics and processing properties of four types of niobium minerals are summarised and methods and results of niobium mineral processing are also described.

Study on experiment and mechanism of thermal dissolved sulfuration of low grade lead-zinc oxide ore in lanpin

The thermal dissolved sulfuration technology is brought forward and performed based on the characteristic of low grade lead-zinc oxide ore in lanpin. Using sulfur as the sulphidizing agent in the experiment, the oxides in the sandstone and ignimbrite are changed into sulfides. The disproportionation reaction of sulfur in a solution is confirmed as 4S＋3H2O=2S^2-＋S2O3^2--＋6H^＋. The dynamics process is studied and the first-order reaction rate equation -1n（1-a）=ktt is obtained. The effects of the reactive products, stirring speed, dosage of sulfuration agent, value of pH and sulphidizing temperature on the sulfuration of oxide ore are investigated. The results indicate that the reactive apparent activation energy is 100.8 kJ/mol and the sulfuration ratio of lead-zinc oxide ore reaches 60% under the conditions of pH 5.9-7.5, the sulfuration temperature of 130 ℃, sulfuration time of 180 min and the stirring speed of 800 r/min.

Volatile and C-H-O isotopic compositions of giant Fe-Ti-V oxide deposits in the Panxi region and their implications for the sources of volatiles and the origin of Fe-Ti oxide ores

The Panzhihua,Hongge,and Baima Fe-Ti-V oxide deposits in the Panzhihua-Xichang(Panxi) region are hosted in large layered mafic-ultramafic intrusions.The layered intrusions intrude either the Neoproterozoic Dengying Formation,composed mainly of limestone,or the Paleoproterozoic Hekou Formation,composed of meta-sedimentary-volcanic rocks.It remains unclear if the wall rocks have been involved during the fractionation of magmas and have affected the sequence of crystallization of Fe-Ti oxide.Volatiles and their C-H-O isotopic compositions of magnetite,apatite,clinopyroxene,and plagioclase of different types of ores from the three intrusions are analyzed using a technique of stepwise heating mass spectrometer to evaluate the role of wall rocks in the formation of Fe-Ti oxide ores.Volatiles released from magnetite are composed mainly of H 2 O and CO 2,whereas the other minerals are composed mainly of H 2 O,CO 2 and H 2.At 800-1200°C temperature interval,the average 13 C values of CO 2 of all the minerals from the three intrusions range from 7.7‰ to 13.5‰ and the average 18 O CO 2 values from 19.1‰ to 19.5‰,which are scattered in a mixed field with basalt and the two types of wall rocks as end-members,indicating that CO 2 from the wall rocks may have been involved in the magmas from which the three intrusions formed.At 400-800 C temperature interval,both 13 C values(13.7‰ to 17.9‰ on the average) and 18 O values(16.2‰ to 19.2‰ on the average) of CO 2 of all the minerals are lower than those for 800-1200 C temperature interval,and much closer to the values of the wall rocks.Abundant H 2 O released at the 400-800 C temperature interval has relatively low D values ranging from 90‰ to 115‰,also indicating the involvement of fluids from the wall rocks.The average bulk contents of volatiles released from magnetite of the Hongge,Baima,and Panzhihua intrusions are 4891,2996,and 1568 mm 3 STP/g,respectively,much higher than those released from other minerals in total,which are 382,600,and 379 mm 3 STP/g,respectively,indicating that magnetite crystallized from magmas with much more volatiles than other minerals.This can be interpreted as that crystallization of clinopyroxene and plagioclase in the early fractionation of magmas resulted in volatiles such as H 2 O that were eventually enriched in the residual magmas and,at the same time,fluids from the wall rocks may have been involved in the magmas and were trapped in magnetite,which crystallized later than clinopyroxene and plagioclase.

Reduction of low-grade manganese oxide ore by biomass roasting

The reduction process of manganese dioxide in low-grade manganese ore by biomass roasting was investigated.The calcine of manganese oxide ore was further leached by sulphuric acid, the manganese in ore can be converted into manganese sulfate.Effects of the mass ratio of manganese ore to sawdust, roasting temperature and time, leaching temperature and time, leaching agent concentration and liquid-solid ratio were studied.97.71% of manganese recovery can be achieved under the optimal conditions：the mass ratio of manganese ore to sawdust of 5：1, roasting temperature at 500℃ for 40 min, leaching temperature at 60℃ for 40 min, sulphuric acid concentration of 1 mol/L and liquid-solid ratio of 10：1.Other types of low-grade manganese ore like Guilin ore, Nanning ore and Gongcheng ore were tested and the same results were obtained.

Microstructure of Solid Phase Reduction on Manganese Oxide Ore Fines Containing Coal by Microwave Heating

Microstructure of solid phase reduction on manganese oxide ore fines containing coal （MOOFCC） is one of important kinetics conditions of influencing microwave heating. On condition thai an atomic molar ratio of ro ： rc in MOOFCC is 1 ： 1.06 as well as a molecular molar ratio of rSiO2： rCaO is 1 ： 1.28, 1 kg of MOOFCC is heated by microwave to reach 1 000-1 300℃ and hold different time respectively. Experiments show that the metal phase takes the iron-based metal compounds containing manganese as the main content. The manganese content of metal phase increases with the xise of temperature. The particle size of the metal phase is within the range from 0. 01 to 0.05 mm. MO2 phase in the stuff is entirely changed into MnO phase and the slag phase is mainly composed of wollastonite and manganese olivine. The stuff reduced is loose and massive as a whole and its porosity is from 30% to 45%. The low softening-melting property and the low density of the stuff impact, to some degree, the solid phase reduction of powder by microwave heating.

Reduction of Low-grade Manganese Dioxide Ore Pellets by Biomass Wheat Stalk

An investigation on reducing low-grade manganese dioxide ore pellets was carried out by using wheat stalk as reductant. The main impact factors of reduction percent such as particle size, biomass/ore ratio, heating rate, nitrogen flow rate, temperature and time in reduction process were discussed. The morphology and component of manganese dioxide ore particle at different stages were also analyzed by scanning electron microscopy （SEM） and energy dispersive X-ray spectroscopy （EDS）. The results show the increase of the reduction temperature and time, biomass/ore ratio, and the decrease of particle size, heating rate and nitrogen flow rate can significantly enhance reduction efficiency. The reduction kinetic of the manganese ore is controlled by three-dimensional mass diffusion of gaseous reductive volatiles passing from the surface to the core of the ore particles. The activation energy E and frequency factor A were calculated to be 24.15 kJ.mol^-1 and 166 min^-1, respectively. Biomass pyrolysis volatiles adsorbed onto the surface of the ore particle leads to serious variation of the microstructures and chemical composition of the manganese ore particles.

An investigation on stability of biomass reduced manganese dioxide ore

In this study, how to improve the stability of reduced manganese oxide ore was dis- cussed by investigating reoxidation conditions and kinetics mechanism in the cooling process of manganese dioxide ore reduced by biomass. The effects of the temperature and time, chip size of biomass, raw materials thickness and different additives on stability of the products were determined. The valence variation of manganese in ore and the reoxidation kinetics of reduced products were studied. The results show that decrease of reduction temperature and time, and increase of raw materials thickness and little H2SO4 additive are favorable for the stability of the reduced products. The kinetics mechanism of the reoxidation is controlled by diffusion with dynamic appar- ent activation energy of E1--25.10 kJ.mol-1, and conformation of manganese in the process is changed from MnO to Mn3O4.

Mechanochemical sulfidization of a mixed oxide-sulphide copper ore by co-grinding with sulfur and its effect on the flotation efficiency

Mechanochemical sulfidization of a mixed sulfide/oxide copper ore by co-grinding with sulfur and additives including Mg(NO3)2 and Fe(NO3)3 salts and iron,aluminum and magnesium powders was investigated for the first time.Also,the influence of sulfidization during the wet-milling process was examined on the separation efficiency and recovery of copper in detail.The results demonstrated that co-grinding with sulfur solely had the best flotation performance at the value of 0.5 wt.%and it was attributed to the possible existence of S\\O bonding on copper oxides surfaces.In addition,adding magnesium nitrate salt,magnesium powder,iron nitrate salt and aluminum powder as additive associated with 0.5 wt%sulfur into ball milling caused the flotation improvement at the amounts of 0.2 wt%,0.2 wt%,0.5 wt%and 0.5 wt%,respectively.Also,the effect of grinding time and sulfidization pH with 0.5 wt%sulfur solely was determined and pH s of 7.5 to 8.5 gave the best results.The highest recovery(75.76%)and separation efficiency(63.44%)were achieved at pH of 7.5 and 8.5,respectively.