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.

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.

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.

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.

Hydration vs.oxidation:Modelling implications for Fe-Ti oxide crystallisation in mafic intrusions,with specific reference to the Panzhihua intrusion,SW China

Recent work on the Panzhihua intrusion has produced two separate models for the crystallisation of the intrusion：（1） low-Ti,high CaO and low H2O（0.5 wt.%） parent magma（equivalent to Emeishan low-Ti basalt） at FMQ;and（2） high-Ti,low CaO and higher H2O（＆gt;1.5 wt.%） parent magma（equivalent to Emeishan high-Ti basalt） at FMQ ＋ 1.5.Modelling of these parent magma compositions produces significantly different results. We present here detailed f（O2） and H2O modelling for average compositions of both Emeishan high-Ti and low-Ti ferrobasalts in order to constrain the effects on crystallisation sequences for Emeishan ultra-mafic -mafic layered intrusions.Modelling is consistent with numerous experimental studies on ferro-basaltic magmas from other localities（e.g.Skaergaard intrusion）.Modelling is compared with the geology of the Panzhihua intrusion in order to constrain the crystallisation of the gabbroic rocks and the Fe-Ti oxides ore layers.We suggest that the gabbroic rocks at the Panzhihua intrusion can be best explained by crystallisation from a parent magma similar to that of the high-Ti Emeishan basalt at moderate H2O contents（0.5-1 wt.%） but at the lower end of TiO2 content for typical high-Ti basalts（2.5 wt.%TiO2）. Distinct silicate disequilibrium textures in the Fe-Ti oxide ore layers suggest that an influx of H2O may be responsible for changing the crystallisation path.An increase in H2O during crystallisation of gabbroic rocks will result in the depression of silicate liquidus temperatures and resultant disequilibrium with the liquid.Continued cooling of the magma with high H2O then results in precipitation of Mt-Uv alone. The H2O content of parent magmas for mafic layered intrusions associated with the ELIP is an important variable.H2O alters the crystallisation sequence of the basaltic magmas so that at high H2O and f（O2） Mt -Uv crystallises earlier than plagioclase and clinopyroxene.Furthermore,the addition of H2O to an anhydrous magma can explain silicate disequilibrium texture observed in the Fe-Ti oxide ore layers.

Study on the pre-treatment of oxidized zinc ore prior to flotation

The pre-treatment of zinc oxide bearing ores with high slime content is important to ensure that resources are utilized optimally. This paper reports an improved process using hydrocyclone de-sliming, dispersion reagents, and magnetic removal of iron minerals for the pre-treatment of zinc oxide ore with a high slime and iron content, and the benefits compared to traditional technologies are shown. In addition, this paper investigates the damage related to fine slime and iron during zinc oxide flotation, the necessity of using hydrocyclone de-sliming together with dispersion reagents to alleviate the influence of slime, and interactions among hydrocyclone de-sliming, reagent dispersion, and magnetic iron removal. Results show that under optimized operating conditions the entire beneficiation technology results in a flotation concentrate with a Zn grade of 34.66% and a recovery of 73.41%.

Early Crystallized Titanomagnetite from Evolved Magmas and Magma Recharge in the Mesoproterozoic Zhuqing Oxide-Bearing Gabbroic Intrusions,Sichuan,SW China

The ca. 1.5 Ga mafic intrusions in the Zhuqing area, predominantly composed of alkaline gabbroic rocks in the Kangdian region of SW China, occur as dykes or irregular small intrusions hosting Fe–Ti–V mineralization. All of the intrusions that intrude the dolomite or shales of the Mesoproterozoic Heishan Formation of the Huili Group are composed of three cyclic units from the base upward： a marginal cyclic unit, a lower cyclic unit and an upper cyclic unit. The Fe–Ti–V oxide ore bodies are hosted in the lower and upper cyclic units. The textural relationships between minerals in the intrusions suggest that titanomagnetite formed earlier than silicate grains because euhedral magnetite and ilmenite grains were enclosed in clinopyroxene and plagioclase. Both the magnetitess–ilmenitess intergrowths due to subsolidus oxidation–exsolutions and the relative higher V distribution coefficient between magnetite and silicate melts in the gabbros from the Zhuqing area are different from those of other typical Fe–Ti bearing mafic rocks, suggesting that the oxygen fugacity was low in the gabbric rocks from the Zhuqing area. This finding was further confirmed by calculations based on the compositions of magnetite and ilmenite pairs. The clinopyroxene, magnetite and ilmenite in the intrusions from the Zhuqing area had considerably lower Mg O than those of other typical Fe–Ti oxide-rich complexes, suggesting that the titanomagnetite from the intrusion may have crystallized at a relatively late stage of evolution from a more evolved magma. Titanomagnetite first fractionally crystallized and subsequently settled in the lower parts of the magma chamber, where it concentrated and formed Fe–Ti–V oxide ore layers at the bases of the lower and upper cycles. Moreover, the occurrence of multiple Fe-Ti oxide layers alternating with Fe-Ti oxide-bearing silicate layers suggests that multiple pulses of magma were involved in the formation of the intrusions and related Fe-Ti-V oxide deposits in the Zhuqing area.

Zinc extraction from zinc oxidized ore using(NH4)2SO4 roasting−leaching process

An improved method of(NH4)2SO4 roasting followed by water leaching to utilize zinc oxidized ores was studied.The operating parameters were obtained by investigating the effects of the molar ratio of(NH4)2SO4 to zinc,roasting temperature,and holding time on zinc extraction.The roasting process followed the chemical reaction control mechanism with the apparent activation energy value of 41.74 kJ·mol^−1.The transformation of mineral phases in roasting was identified by X-ray diffraction analysis combined with thermogravimetry–differential thermal analysis curves.The water leaching conditions,including the leaching temperature,leaching time,stirring velocity,and liquid-to-solid ratio,were discussed,and the leaching kinetics was studied.The reaction rate was obtained under outer diffusion without product layer control;the values of the apparent activation energy for two stages were 4.12 and 8.19 kJ·mol^−1.The maximum zinc extraction ratio reached 96%while the efficiency of iron extraction was approximately 32%under appropriate conditions.This work offers an effective method for the comprehensive use of zinc oxidized ores.

SYNERGISTIC ACTIVATION OF CHELATING AGENT ON XANTHATE DURING THE FLOTATION OF REFRACTORY COPPER OXIDIZED ORES

For realizing the effective flotation of refractory copper ox-idized ores and developing the activation-flotation theory , the influences of nine different organic chelating agents on xanthate collection pcnver and its adsorption characteristics ivere studied in the flotation of malachite and chrysocolla representatively selected by means of XPS,IR, absorbed quanti-ty measurements and flotation tests.For easily-dissolved malachite flotation , a small amount of chelating agent can obviously enhance xanthate collecting power and make malachite floated easily , and so reduces the consumption of xanthate. For hard-dis-晄olved chrysocolla, chelating agent is able to increase its recovery to 90% , but the chelating agent consumption is high. Chelating agent and xanthate can produce synergistic adsorptions, which follmv Freundlich's adsorption equation on malachite and Chrysocolla surfaces. The high chemical activity of chelating agent and its synergistic activation on xanthate are the key to improving xanthate collection poiver. The synergistic activation of chelat-ing agent on xanthate on melachite surfaces is clearly stronger than on chrysocolla surfaces. According to experimental results, it can be thought that the synergistic activation results from the synergistic complexation of chelating agent and xanthate with copper ions to form biligand-tribasic co-ordination complex.

Preliminary Study of the Characteristics and Genesis of Arsenate Minerals in the Oxidized Zone of the Debao Skarn-Type Cu-Sn Ore Deposit in Guangxi

Through the study of the oxidized zone of the Debao skarn-type Cu-Sn deposit in Guangxi, the authorshave found 14 arsenate minerals, most of which are for the first time reported in China. They are mainly Cuarsenate minerals with subordinate Cu-Pb arsenate minerals and minor Fe-Pb-Ba varieties. Based on their paragenesis these minerals may be divided into the following series: (1) the clinoclasite-olivenite-cornwallite- cornubite- debaoite- copper silicarsenate association, (2) the scorodite- carminite- beudan-tite-bayldonite- duftite association, and (3) the scorodite-Ba-bearing pharmacosiderite- dussertite association. Arsenate minerals are formed generally in the oxidized zone of the sulfide-type deposits which lie in thewarm, humid and rainy torrid-subtropical zone with pH=6-8 and contain large amounts of arsenopyrite andcarbonate rocks.

Superior lithium storage performance in MoO_(3) by synergistic effects:Oxygen vacancies and nanostructures

Molybdenum trioxide(MoO_(3))has recently attracted wide attention as a typical conversion-type anode of Li-ion batteries(LIBs).Nevertheless,the inferior intrinsic conductivity and rapid capacity fading during charge/discharge process seriously limit large-scale commercial application of MoO_(3).Herein,the density function theory(DFT)calculations show that electron-proton co-doping preferentially bonds symmetric oxygen to form unstable HxMoO_(3).When the-OH-group in HxMoO_(3) is released into the solution in the form of H_(2)O,it is going to form MoO_(3-x)with lower binding energy.By the means of both electron-proton co-doping and high-energy nanosizing,oxygen vacancies and nanoflower structure are introduced into MoO_(3) to accelerate the ion and electronic diffusion/transport kinetics.Benefitting from the promotion of ion diffusion kinetics related to nanostructures,as well as both the augmentation of active sites and the improvement of electrical conductivity induced by oxygen vacancies,the MoO_(3-x)/nanoflower structures show excellent lithium-ion storage performance.The prepared specimen has a high lithium-ion storage capacity of 1261 mA h g^(-1)at 0.1 A g^(-1)and cyclic stability(450 cycle),remarkably higher than those of previously reported MoO_(3)-based anode materials.

Diffusion behavior and distribution regulation of MgO in MgO-bearing pellets

In this paper, the diffusion behavior between MgO and Fe2O3（the main iron oxide in pellets） is investigated using a diffusion couple method. In addition, the distribution regulation of MgO in MgO-bearing pellets is analyzed via pelletizing experiments. The results illustrate that MgO is prone to diffuse into Fe2O3 in the form of solid solution; the diffusion rate considered here is 13.64 μm·min^（-1）. Most MgO content distributes in the iron phase instead of the slag phase. The MF phase {（Mg（1-x）Fex）O·Fe2O3, x ≤ 1} is generated in the MgO-bearing pellets. However, the distribution of MgO in the radial direction of the pellets is inconsistent. The solid solution portion of MgO in the MF phase is larger in the outer layer of the pellets than in the inner layer. In this work, the approximate chemical composition of the MF phase in the outer layer of the pellets is {（Mg（0.35-0.77）·Fe（0.65-0.23）） O·Fe2O3} and in the inner layer is {（Mg（0.13-0.45）·Fe（0.87-0.55））O·Fe2O3}.

螯合活化剂对孔雀石的活化及其对氧化铜矿石浮选应用

对采自云南红河、兰坪、东川及湖北大冶铜绿山的四个孔雀石样品,进行了分别使用D2(2、5——二硫酚——1、3、4——硫代二唑)及硫化钠作活化剂,黄药作捕收剂的单矿物浮选试验。研究了不同矿区孔雀石浮选基本行为间的差别、D2药剂作用规律及适用范围。对于以D2作活化剂,用黄药从氧化矿石中直接浮选未经预先硫化的氧化铜矿物新工艺的实践经验及结果也作了报道。

Effect of Ca-Fe oxides additives on NOx reduction in iron ore sintering

As the emission control regulations get stricter,the NO;reduction in the sintering process becomes an important environmental concern owing to its role in the formation of photochemical smog and acid rain.The NOxemissions from the sintering machine account for 48% of total amount from the iron and steel industry.Thus,it is essential to reduce NO;emissions from the sintering machine,for the achievement of clean production of sinter.Ca-Fe oxides,serving as the main binding phase in the sinter,are therefore used as additives into the sintering mixture to reduce NOxemissions.The results show that the NO;reduction ratio achieves 27.76% with 8% Ca-Fe oxides additives since the Ca-Fe oxides can advance the ignition and inhibit the nitrogen oxidation compared with the conventional condition.Meanwhile,the existence of Ca-Fe oxides was beneficial to the sinter quality since they were typical low melting point compounds.The optimal mass fraction of Ca-Fe oxides additives should be less than 8%since the permeability of sintering bed was significantly decreased with a further increase of the Ca-Fe oxides fines,inhibiting the mineralization reaction of sintering mixture.Additionally,the appropriate particle size can be obtained when mixing an equal amount of Ca-Fe oxides additives of-0.5 mm and 0.5-3.0 mm in size.