Bioleaching of vanadium from stone coal vanadium ore by Bacillus mucilaginosus:Influencing factors and mechanism

Vanadium and its derivatives are used in various industries,including steel,metallurgy,pharmaceuticals,and aerospace engineering.Although China has massive reserves of stone coal resources,these resources have low grades.Therefore,the effective extraction and recovery of metallic vanadium from stone coal is an important way to realize the efficient resource utilization of stone coal vanadium ore.Herein,Bacillus mucilaginosus was selected as the leaching strain.The vanadium leaching rate reached 35.5%after 20 d of bioleaching under optimal operating conditions.The cumulative vanadium leaching rate in the contact group reached 35.5%,which was higher than that in the noncontact group(9.3%).The metabolites of B.mucilaginosus,such as oxalic,tartaric,citric,and malic acids,dominated in bioleaching,accounting for 73.8%of the vanadium leaching rate.Interestingly,during leaching,the presence of stone coal stimulated the expression of carbonic anhydrase in bacterial cells,and enzyme activity increased by 1.335-1.905 U.Enzyme activity positively promoted the production of metabolite organic acids,and total organic acid content increased by 39.31 mg·L^(-1),resulting in a reduction of 2.51 in the pH of the leaching system with stone coal.This effect favored the leaching of vanadium from stone coal.Atomic force microscopy illustrated that bacterial leaching exacerbated corrosion on the surface of stone coal beyond 10 nm.Our study provides a clear and promising strategy for exploring the bioleaching mechanism from the perspective of microbial enzyme activity and metabolites.

Leaching kinetics of low-grade copper ore containing calcium-magnesium carbonate in ammonia-ammonium sulfate solution with persulfate

The leaching kinetics of copper from low-grade copper ore was investigated in ammonia-ammonium sulfate solution with sodium persulfate. The effect parameters of stirring speed, temperature, particle size, concentrations of ammonia, ammonium sulfate and sodium persulfate were determined. The results show that the leaching rate is nearly independent of agitation above 300 r/min and increases with the increase of temperature, concentrations of ammonia, ammonium sulfate and sodium persulfate. The EDS analysis and phase quantitative analysis of the residues indicate that bornite can be dissolved by persulfate oxidization. The leaching kinetics with activation energy of 22.91 kJ/mol was analyzed by using a new shrinking core model （SCM） in which both the interfacial transfer and diffusion across the product layer affect the leaching rate. A semi-empirical rate equation was obtained to describe the leaching process and the empirical reaction orders with respect to the concentrations of ammonia, ammonium sulfate and sodium persulfate are 0.5, 1.2 and 0.5, respectively.

Leaching of nickel-molybdenum sulfide ore in membrane biological reactor

The bioleaching of molybdenum from its sulfide ore using a Mo-resistant thermophilic bacterium sulfolobus metallics combined with a membrane biological reactor（MBR） was studied.The experimental results showed that the concentration of Mo can be controlled by filter of the membrane in MBR and the toxicity of Mo to microorganism is decreased in the process of bioleaching.It was also evidenced that there were different leaching rates of Ni and Mo when the concentration of Mo was different.After leaching for 20 d in the MBR at Mo concentration of 395 mg/L,the leaching rates of Ni and Mo reached the maximum of 79.57% and 56.23% respectively under the conditions of 100 g/L of mineral density,65 ℃,pH=2 and 1.0 L/min of the aeration rate.While 75.59% Ni and 54.33% Mo were leached out in column without membrane under the same conditions.

Upgrading and dephosphorization of Western Australian iron ore using reduction roasting by adding sodium carbonate

The technology of direct reduction by adding sodium carbonate （Na2CO3） and magnetic separation was developed to treat Western Australian high phosphorus iron ore. The iron ore and reduced product were investigated by optical microscopy and scanning electron microscopy. It is found that phosphorus exists within limonite in the form of solid solution, which cannot be removed through traditional ways. During reduction roasting, Na2CO3 reacts with gangue minerals （SiO2 and A1203）, forming aluminum silicate-containing phosphorus and damaging the ore structure, which promotes the separation between iron and phosphorus during magnetic separation. Meanwhile, Na2CO3 also improves the growth of iron grains, increasing the iron grade and iron recovery. The iron concentrate, assaying 94.12wt% Fe and 0.07wt% P at the iron recovery of 96.83% and the dephosphorization rate of 74.08%, is obtained under the optimum conditions. The final product （metal iron powder） after briquetting can be used as the burden for steelmaking by an alactrie a.re furnace to rer）la,ce scrar） steel.

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.

Ore Genesis of the Kalatongke Cu-Ni Sulfide Deposits, Western China: Constraints from Volatile Chemical and Carbon Isotopic Compositions

The Kalatongke Cu-Ni sulfide deposits located in the East Junggar terrane, northern Xinjiang, western China are the largest magmatic sulfide deposits in the Central Asian Orogenic Belt （CAOB）. The chemical and carbon isotopic compositions of the volatiles trapped in olivine, pyroxene and sulfide mineral separates were analyzed by vacuum stepwise-heating mass spectrometry. The results show that the released volatiles are concentrated at three temperature intervals of 200-400°C, 400-900°C and 900-1200°C. The released volatiles from silicate mineral separates at 400-900°C and 900-1200°C have similar chemical and carbon isotopic compositions, which are mainly composed of H2O （av. ~92 mol%） with minor H2, CO2, H2S and SO2, and they are likely associated with the ore-forming magmatic volatiles. Light δ13CCO2 values （from -20.86‰ to -12.85‰） of pyroxene indicate crustal contamination occurred prior to or synchronous with pyroxene crystallization of mantlederived ore-forming magma. The elevated contents of H2 and H2O in the olivine and pyroxene suggest a deep mantle-originated ore-forming volatile mixed with aqueous volatiles from recycled subducted slab. High contents of CO2 in the ore-forming magma volatiles led to an increase in oxygen fugacity, and thereby reduced the solubility of sulfur in the magma, then triggered sulfur saturation followed by sulfide melt segregation; CO2 contents correlated with Cu contents in the whole rocks suggest that a supercritical state of CO2 in the ore-forming magma system under high temperature and pressure conditions might play a key role in the assemblage of huge Cu and Ni elements. The volatiles released from constituent minerals of intrusion 1# have more CO2 and SO2 oxidized gases, higher CO2/CH4 and SO2/H2S ratios and lighter δ13CCO2 than those of intrusions 2# and 3#. This combination suggests that the higher oxidation state of the volatiles in intrusion 1# than intrusions 2# and 3#, which could be one of key ore-forming factors for large amounts of ores and high contents of Cu and Ni in intrusion 1#. The volatiles released at 200-400°C are dominated by H2O with minor CO2, N2＋CO and SO2, with δ13CCO2 values （-25.66‰ to -22.98‰） within the crustal ranges, and are considered to be related to secondary tectonic-hydrothermal activities.

Preparation of crystalline rare earth carbonates with large particle size from the lixivium of weathered crust elution-deposited rare earth ores

Crystalline rare-earth(RE)carbonates having large particle size were prepared from the lixivium of weathered crust elution-deposited rare-earth ores using the precipitation method with ammonium bicarbonate as the precipitant.Their chemical composition was studied using elemental and thermogravimetric analyses(TGA),and their structure and morphology were characterized using Fourier transform infrared(FTIR)spectroscopy,X-ray diffraction(XRD),and scanning electron microscopy(SEM).The results demonstrate that the crystalline rareearth carbonate is a hydrated basic carbonate or oxycarbonate and not astable intermediate carbonate in the process of thermal decomposition.The particle size of crystalline rare-earth carbonates with large particle size is in the range of 50–200μm.With an RE2O3 content of up to 95wt%,the quality of crystalline rare-earth carbonates is higher compared to the Chinese National Standard(GB/T 28882–2012).The quality of the product is superior to the Chinese National Standard.

Effect of CaO and CaCO3 on Reduction Rate of Iron Ore Pellets Containing Carbon

The effect of metallurgical fluxes CaO and CaCO3 on the reduction rate of iron ore pellets containing carbon in nitrogen atmosphere has been studied by a weight-loss thermal balance. The experimental results showed that adding CaO or CaCO3 can promote reduction reaction as the added CaO or CaCO3 probably decrease the apparent activation energy of iron ore concentrate-carbon-CaO or CaCO3 reaction, and the reduction rate constant changes with mass percent of CaO and CaCO3. The kinetic analysis also showed that the rate-controlling step of the reaction is inner gas diffusion.

Acid leaching decarbonization and following pressure oxidation of carbonic refractory gold ore

Carbonate decomposition of carbonic refractory gold ore and the following pressure oxidation were studied.In the carbonate decomposition procedure,the effects of liquid-to-solid ratio and reaction time on decomposition ratio of carbonate were investigated.The experimental result shows that the decomposition ratio of carbonate is 98.24%under the conditions of liquid-to-solid ratio of 5:1,Fe^(3+)concentration of 20 g/L,sulfuric acid concentration of 20 g/L,reaction temperature of 80 ℃ and reaction time of 2 h.Then,the slurry obtained from carbonate decomposition was put into the titanium autoclave for pressure oxidation leaching.Effects of liquid-to-solid ratio,temperature,time and oxygen partial pressure on sulfur oxidation ratio were studied during pressure oxidation.With the prolonged time,pyrite and arsenopyrite are oxidized to ferric subsulfate,hydrated ferric sulfate and jarosite,resulting in the increasing residue ratio.The residue ratio and the sulfur content in the residue can be decreased by ferric subsulfate dissolution.The oxidation ratio of the sulfur is 99.35% under the conditions of oxidation time of 4 h,temperature of 210 ℃,oxygen partial pressure of 0.8 MPa and stirring speed of 600 r/min.

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.

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.

Regeneration of Nickel-Molybdenum Catalysts DN-3531 and Criterion 514 Used in Kerosene and Gas Oil Hydrotreating by Supercritical Carbon Dioxide Extraction

Results of research of supercritical fluid CO2-regeneration process of Nickel-Molybdenum Catalysts DN-3531 and Criterion 514 are given. Regeneration was carried out with the use of pure supercritical carbon dioxide and mixture of supercritical carbon dioxide and various polar cosolvents. Regeneration process is carried out along isotherms, in the temperature range of 323 - 383 K, at pressures of P = 20 MPa and 30 MPa. Results of surface assessment of the catalyst samples regenerated show high effectiveness of suggested method.

REDUCTION BEHAVIOR OF IRON ORE PELLETS CONTAININGCARBON UNDER NON-ISOTHERMAL CONDITION

The reduction behavior of iron ore pellets containing carbon under non-isothermal condition in the temperature range from 573 to 1373 K was investigated in a laboratory scale setup. The test results show that carbon content has no obvious effect on reduction degree of composite pellets (C/O mole ratio=1.0) by CO in the temperature range from 573 to 1373 K under linear temperature-rising program; reduction degree of iron ore pellets containing carbon is large in 90%CO-10%CO2 mixture than that of in 100%CO atmosphere or in 80%CO-20%CO2 mixture; the s type temperature-rising program has a better effect than that of linear one in increasing the reduction degree; and reduction degree of slower linear temperature-rising program is greater than that of faster one, but the final reduction degrees, i.e., those at the highest temperature are about the same for various CO partial pressures or temperature-rising programs. The kinetic analysis also shows that the reduction of iron ore-carbon composite pellets by CO or CO-CO2 mixture under non-isothermal condition should be controlled by surface reaction, and the apparent reduction activation energy changes with the reduction progress under various test conditions.

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.

Application of carbon composite iron ore hot briquette to innovative ironmaking process

As a new type of ironmaking raw materials,carbon composite iron ore hot briquette(CCB) is the product of fine iron ore and fine coal by hot briquetting process.On basis of experimental research on the manufacturing and metallurgical properties of CCB,this study focused on the application of CCB to blast furnace ironmaking and newly-developed shaft furnace smelting reduction processes.Firstly,the metallurgical properties of CCB are experimentally tested and compared with the common iron-bearing burdens.Then,the effects of charging CCB on blast furnace operation are numerically analyzed by means of multi-fluid blast furnace model,and the flowchart and pilot test of CCB-Shaft furnace smelting reduction process are briefly introduced.

The Effect of the Grinding Time on the Mechanical Activation of MnO2 Ore and Tea Plant Waste Carbonization Product

In this study, pyrolusiteore （MnO2） was subjected to mechanical milling with a high-energy mill with carbonized tea plant wastes and the effect of grinding time on the crystal structure of the material was investigated. The ratio of Mn/Fe was 8/1, the ratio of C/（MnO2 ＋ Fe3O4） was 2 and the ratio of ball to ore was 10/1. The samples were mechanically ground at 10, 15, 20, 30, 60, 90 and 120 hours. In the processes performed on the attritor, the rotation speed of the mill shaft was determined to be 350 rpm. The results were characterized by TG-DTA, SEM and XRD analyzes. As a result of the experimental studies, it was observed that the samples subjected to mechanical grinding for 120 hours were gradually reduced due to the increasing grinding time at all the diffraction peaks when the XRD peaks were compared with the grinding times. In the thermogravimetric analysis, the sample milled for 120 hours, 50% weight loss was observed at 470 ℃, weight loss of up to 56% was observed at progressive temperatures.

Extraction of molybdenum and nickel from Ni-Mo ore by pressure acid leaching

A direct hydrometallurgical route for nickel and molybdenum extraction from a nickel-molybdenum （Ni-Mo） ore using pressure acid leaching was studied. The nickel and molybdenum were extracted by acid leaching under oxygen pressure. Compared with traditional roasting methods, this hydrometallurgical method eliminates SO2 and As203 emission （the Ni-Mo ore containing 15%-25% S）. Compared with existing alkali leaching recovery of molybdenum process, almost all the nickel and considerable molybdenum were extracted in the acid leaching process. Under oxygen pressure conditions, almost all the nickel and a substantial part of the molybdenum were dissolved into the acid leaching liquor and the other part of the molybdenum was left in the acid leach residue. The acid leach residue was further leached under alkaline （NaOH） conditions. Under optimal experimental conditions, the extraction rates nickel and molybdenum reached 97% and 96%, respectively.

Influence of Phanerochaete chrysosporium on degradation and preg-robbing capacity of activated carbon

The effect of Phanerochaete chrysosporium on degradation and preg-robbing capacity of activated carbon,which was used as a substitute of carbonaceous matter in carbonaceous gold ores,was studied.After 14 d treatment with Phanerochaete chrysosporium,the degradation rate of activated carbon reached 27.59%.The XRD and FTIR analyses indicate that Phanerochaete chrysosporium can distort the micro-crystalline structure of activated carbon,increase the number of oxygen-containing groups and aliphatics and make the aromatic structures be oxidized and exfoliated.The gold-adsorption tests show that Phanerochaete chrysosporium can reduce the preg-robbing capacity of activated carbon by 12.88%.This indicates that Phanerochaete chrysosporium is an available microorganism,and it can be employed to reduce the preg-robbing capacity of carbonaceous matter and improve the gold leaching rate.The combined effect of passivation,alkalization and oxidation of biological enzymes-free radicals of Phanerochaete chrysosporium on carbonaceous matter was also discussed.

Anatomy and genesis of the world’s largest carbonate-hosted Zn-Pb deposit:New insights from ore characteristics,Zn-Pb-C-O isotopes,and trace element constraints of the Huoshaoyun deposit,Karakorum Range,Xinjiang

The Huoshaoyun deposit in the Karakorum area of NW China is the world’s largest zinc-lead carbonate ore deposit.Here we investigate the genesis of the mineralization based on multiproxy investigations.The deposit contains zinc-lead carbonate and sulfide minerals,with smithsonite(Smt),cerussite(Cer),and sulfides accounting for 85%,10%,and 5%of the total lead and zinc resources,respectively.Three ore-forming stages,involving Smt,Cer,and sulfides ores were summarized.The Smt mineralization is characterized by veined,massive,and stratified Smt forming horizontal sedimentary layered ore and vertical feeder veins similar to the SEDEX-type deposits.The sulfide and Cer veins display typical hydrothermal characteristics and are superimposed on the massive Smt ores.The Smt ores show high Li,Be,Cr,Y,Ba,Nd,Yb,and Zr contents,whereas the Cer veins have extremely high Sr contents(up to 3814–9174 ppm)and low Zr contents(less than 0.01 ppm).Galena and sphalerite show higher Cd concentrations compared to Smt and Cer ores.The Smt ores differ with different spatial locations,with Smt ores formed at the vent haveδ^(66)Zn values of+0.15‰to+0.21‰,the massive Smt formed close to the vent show a value of+0.13‰,and those formed away from the vent show a value of 0.05‰,all values being close to 0.The sulfides haveδ^(66)Zn values of−0.09‰to+0.04‰.The C-O isotopes of Smt ores are similar to both altered and unaltered host limestone,suggesting that the limestone was a potential source for carbon and oxygen.Quartz with veined Smt shows magmatic signatures withδ^(18)OVSMOW of+1.14‰to+2.23‰,high Pb(115–401 ppm)and Zn concentrations(390–997 ppm),whereas quartz associated with sulfide has meteoric fluid signature with the lowestδ^(18)OVSMOW(−14‰to−10.7‰),low Pb(11.6–49.0 ppm)and Zn(18.1–72.8 ppm)concentrations.The temperature of equilibration computed based on oxygen isotope fractionation between Smt and coeval quartz indicate a dual source with that of quartz derived from an aqueous fluid,whereas the source for Smt might involve CO_(2)or HCO_(3)^(−).We trace multiple metallogenic stages for this deposit including exhalation,hydrothermal deposition,and fault-controlled sulfide vein formation.The largest orebody(III-1)preserves a 16 Mt reserve of Zn and was formed by crust-mantle interaction at ca.195 Ma in the early development of the Linjitang post-arc rift system.Fluid convection,zinc enrichment driven by granitic magma,volcanic activity,and karst alteration induced by acid rain in a lagoonal environment promoted ore enrichment.

Raman Spectroscopic Core Scanning for Iron Ore Characterisation

Automated core scanning technologies for mineralogical characterisation of diamond core, drill chips pulps is now an established technique, particularly in the Australian iron ore industry, for mineral analysis in exploration and mining. Application of reflectance spectroscopy over the 400–2500 nm, visible to near-infrared wavelength range, has been used to characterise the iron ore oxide mineralogy of bedded iron deposit (BID) derived iron ores in India (Thangavelu et al., 2011) and Brazil (da Costa et al., 2009), and used to define the ore and gangue (e.g., clay) mineralogy in ironstone or channel iron deposits (CID) in the Pilbara region of Western Australia (e.g., Haest et al., 2012).