High-efficiency trace Na extraction from crystal quartz ore used for fused silica-A pretreatment technology

Trace Na sources, extraction dynamics of trace Na, and influences of calcination temperature on quartz lattice, fluid inclusions, and muscovite were studied in detail herein for trace Na extraction from the quartz ore with water leaching at 90℃. Experimental results suggested that the trace Na sources included quartz lattice, fluid inclusions, and muscovite. The extraction rate of the trace Na in quartz ores can reach 31.0wt% after calcination at 900℃ for 5 h and water leaching at 90℃ for 24 h. The extraction process consisting of the dissolution of unfree Na and diffusion of free Na was dominated by calcination temperature. Calcination at 900℃ for 5 h was effective for extraction of the trace Na in fluid inclusions and muscovite. The extraction of the trace Na was mainly affected by the decrepitation of fluid inclusions when the calcination temperature ranged from 400 to 600℃ and by the damage of muscovite when the calcination temperature ranged from 600 to 900℃. Based on the extraction rates at different calcination temperatures, approximately 20.1wt% of the trace Na occurred in fluid inclusions, approximately 10.9wt% existed in muscovite, and 69.0wt% mainly occurred in quartz lattice.     

Chlorination roasting-coupled water leaching process for potash recovery from waste mica scrap using dry marble sludge powder and sodium chloride

The present paper reports the effective utilization of marble sludge powder(MSP) for the recovery of potash values from waste mica scrap using chlorination roasting–water leaching method. Characterization studies indicated the presence of dolomite as the major mineral phase in MSP, whereas muscovite and quartz were observed in the mica sample. The acid leaching studies suggest a maximum of 22% potash recovery under conditions: 4 M H_2SO_4 acid, particle size of ～100 μm, stirring speed of 600 r/min, leaching temperature of 75℃, and leaching time of 90 min. The chlorination roasting–water leaching process was adopted to achieve the lowest level of 80%–90% potash recovery. The optimum conditions for the recovery of ～93% potash from mica(～8.6 wt% K_2O) requires 900℃ roasting temperature, 30 min roasting time,and 1:1:0.75 mass ratio of mica : MSP : Na Cl. The roasting temperature and amount of Na Cl are found to be the most important factors for the recovery process. The reaction mechanism suggests the formation of different mineral phases, including sylvite(KCl), wollastonite, kyanite,and enstatite, during roasting, which were confirmed by X-ray diffraction(XRD) analyses and scanning electron microscopy(SEM) morphologies. The MSP-blended Na Cl additive is more effective for potash recovery compared with the other reported commercial roasting additives.     

Comparison of the mechanisms of microwave roasting and conventional roasting and of their effects on vanadium extraction from stone coal

Experiments comparing microwave blank roasting and conventional blank roasting for typical vanadium-bearing stone coal from Hubei Province in central China, in which vanadium is present in muscovite, were conducted to investigate the effects of roasting temperature, roasting time, H₂SO₄ concentration, and leaching time on vanadium extraction. The results show that the vanadium leaching efficiency is 84% when the sample is roasted at 800℃ for 30 min by microwave irradiation and the H₂SO₄ concentration, liquid/solid ratio, leaching temperature, and leaching time are set as 20vol%, 1.5:1 mL·g-1, 95℃, and 8 h, respectively. However, the vanadium leaching efficiency achieved for the sample subjected to conventional roasting at 900℃ for 60 min is just 71% under the same leaching conditions. Scanning electron microscopy (SEM) analysis shows that the microwave roasted samples contain more cracks and that the particles are more porous compared to the conventionally roasted samples. According to the results of X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) analyses, neither of these roasting methods could completely destroy the mica lattice structure under the experimental conditions; however, both methods deformed the muscovite structure and facilitated the leaching process. Comparing with conventional roasting, microwave roasting causes a greater deformation of the mineral structure at a lower temperature for a shorter roasting time.     

Characteristics and evolution of ore-forming fluids of the Chongjiang copper deposit in the Gangdise porphyry copper belt,Tibet

Petrography, microthermometry, and scanning electron microscope/energy dispersive spectrometer (SEM/EDS) studies were performed on the fluid inclusions in the ore-beating quartz veins and quartz phenocrysts in the porphyry of the Chongjiang porphyry copper deposit. The analyses of the fluid inclusions indicate that the ore-forming fluids were exsolved from magma. They are near-saturated, supercritical, rich in volatile constituents, and have the capture temperature of 362-389℃ and salinities of 17.7wt%- 18.9wt% NaC1 eq. With the decreasing of temperature and pressure, the supercritical fluids were separated into a low salinity vapor phase and a high salinity liquid phase. During quartz-sericitization, the high salinity fluid boiled and separated into a low salinity vapor phase and a high salinity liquid phase. The high salinity inclusions that formed in the boiling process had daughter mineral melting temperatures higher than the homogenization temperatures of the vapor and liquid phases. The late fluids that are responsible for argillization are of lower temperature and salinity.     

Influence of acid leaching and calcination on iron removal of coal kaolin

Calcination and acid leaching of coal kaolin were studied to determine an effective and economical preparation method of calcined kaolin. Thermogravimetric-differential thermal analysis (TG-DTA) and X-ray diffraction (XRD) demonstrated that 900℃ was the suitable temperature for the calcination. Leaching tests showed that hydrochloric acid was more effective for iron dissolution from raw coal kaolin (RCK), whereas oxalic acid was more effective on iron dissolution from calcined coal kaolin (CCK). The iron dissolution from CCK was 28.78wt%, which is far less effective than the 54.86wt% of RCK under their respective optimal conditions. Through analysis by using M?ssbauer spectroscopy, it is detected that nearly all of the structural ferrous ions in RCK were removed by hydrochloric acid. However, iron sites in CCK changed slightly by oxalic acid leaching because nearly all ferrous ions were transformed into ferric species after firing at 900℃. It can be concluded that it is difficult to remove the structural ferric ions and ferric oxides evolved from the structural ferrous ions. Thus, iron removal by acids should be conducted prior to calcination.     

Effects of the mineral phase and valence of vanadium on vanadium extraction from stone coal

The influence of roasting on the leaching rate and valence of vanadium was evaluated during vanadium extraction from stone coal. Vanadium in stone coal is hard to be leached and the leaching rate is less than 10% when the raw ore is leached by 4 mol/L H₂SO₄ at 90℃ for 2 h. After the sample is roasted at 900℃ for 2 h, the leaching rate of vanadium reaches the maximum, and more than 70% of vanadium can be leached. The crystal of vanadium-bearing mica minerals decomposes and the content of V(V) increases with the rise of roasting temperature from 600 to 900℃, therefore the leaching rate of vanadium increases significantly with the decomposition of the mica minerals. Some new phases, anorthite for example, form when the roasting temperature reaches 1000℃. A part of vanadium may be enwrapped in the sintered materials and newly formed phases, which may impede the oxidation of low valent vanadium and make the leaching rate of vanadium drop dramatically. The leaching rate of vanadium is not only determined by the valence state of vanadium but also controlled by the decomposition of vanadium-bearing minerals and the existence state of vanadium to a large extent.     

Upgradation of bauxite by molecular hydrogen and hydrogen plasma

An approach was developed to upgrade the bauxite ore by molecular hydrogen and hydrogen plasma. A gibbsite-type bauxite sample was obtained from National Aluminium Company (NALCO), Odisha, India. The obtained sample was crushed and sieved (to 100 μm) prior to the chemical analysis and grain-size distribution study. The bauxite sample was calcined in the temperature range from 500 to 700°C for different time intervals to optimize the conditions for maximum moisture removal. This process was followed by the reduction of the calcined ore by molecular hydrogen and hydrogen plasma. Extraction of alumina from the reduced ore was carried out via acid leaching in chloride media for 2 h at 60°C. X-ray diffraction, scanning electron microscopy, thermogravimetry in conjunction with differential scanning calorimetry, and Fourier transform infrared spectroscopy were used to determine the physicochemical characteristics of the material before and after extraction. Alumina extracted from the reduced ore at the optimum calcination temperature of 700°C and the optimum calcination time of 4 h is found to be 90% pure.     

Extraction and separation of nickel and cobalt from saprolite laterite ore by microwave-assisted hydrothermal leaching and chemical deposition

Extraction and separation of nickel and cobalt from saprolite laterite ore were studied by using a method of microwave-assisted hydrothermal leaching and chemical deposition. The effects of leaching temperature and time on the extraction efficiencies of Ni2+ and Co2+ were investigated in detail under microwave conditions. It is shown that the extraction efficiencies of Ni2+ and Co2+ from the ore pre-roasted at 300℃ for 5 h were 89.19% and 61.89% when the leaching temperature and time were about 70℃ and 60 min, respectively. For the separation process of Ni and Co, the separation of main chemical components was performed by adjusting the pH values of sulfuric leaching solutions using a NaOH solution based on the different pH values of precipitation for metal hydroxides. The final separation efficiencies of Ni and Co were 77.29% and 65.87%, respectively. Furthermore, the separation efficiencies of Fe of 95.36% and Mg of 92.2% were also achieved at the same time.     

Existence and release of fluid inclusions in bornite and its associated quartz and calcite

The existence and release of fluid inclusions in bornite and its associated minerals, namely, quartz and calcite were investigated and confirmed. The structures, forms, and phases of these large quantities of fluid inclusions were also studied. A mass of fluid inclusions with various sizes, distributions, shapes, and phases exist in bornite and its associated minerals. Their sizes vary from a few micrometers to tens of micrometers, and the forms appear as negative crystals, or elongated, elliptical, and irregular. At room temperature, fluid inclusions were mainly characterized as gas-liquid twophase. However, small amounts of fluid inclusions with pure gas phase and pure liquid single-phase were also observed in quartz and calcite. These fluid inclusions initially broke during the ore crushing and grinding process and then released into the flotation pulp in the flotation process. The quantitative analysis of fluid inclusions in the solution and the comparisons of mineral dissolution show that the amount of copper and iron released by fluid inclusions in the bornite sample is higher than the amount dissolved by the mineral; fluid inclusions in the associated gangue minerals, quartz, and calcite also make contribution.     

Extraction of vanadium from high calcium vanadium slag using direct roasting and soda leaching

The extraction of vanadium from high calcium vanadium slag was attempted by direct roasting and soda leaching. The oxidation process of the vanadium slag at different temperatures was investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). The effects of roasting temperature, roasting time, Na₂CO₃ concentration, leaching temperature, leaching time, and liquid to solid ratio on the extraction of vanadium were studied. The results showed that olivine phases and spinel phases in the vanadium slag were completely decomposed at 500 and 800℃, respectively. Vanadium-rich phases were formed at above 850℃. The leaching rate of vanadium reached above 90% under the optimum conditions:roasting temperature of 850℃, roasting time of 60 min, Na₂CO₃ concentration of 160 g/L, leaching temperature of 95℃, leaching time of 150 min, and liquid to solid ratio of 10:1 mL/g. The main impurities were Si and P in the leach liquor.     

Linking leach chemistry and microbiology of low-grade copper ore bioleaching at different temperatures

The effects of temperature on chalcocite/pyrite oxidation and the microbial population in the bioleaching columns of a low-grade chalcocite ore were investigated in this study. Raffinate from the industrial bioleaching heap was used as an irrigation solution for columns operated at 20, 30, 45, and 60℃. The dissolution of copper and iron were investigated during the bioleaching processes, and the microbial community was revealed by using a high-throughput sequencing method. The genera of Ferroplasma, Acidithiobacillus, Leptospirillum, Acidiplasma, and Sulfobacillus dominated the microbial community, and the column at a higher temperature favored the growth of moderate thermophiles. Even though microbial abundance and activity were highest at 30℃, the column at a higher temperature achieved a much higher Cu leaching efficiency and recovery, which suggested that the promotion of chemical oxidation by elevated temperature dominated the dissolution of Cu. The highest pyrite oxidation percentage was detected at 45℃. Higher temperature resulted in precipitation of jarosite in columns, especially at 60℃. The results gave implications to the optimization of heap bioleaching of secondary copper sulfide in both enhanced chalcocite leaching and acid/iron balance, from the perspective of leaching temperature and affected microbial community and activity.     

Fluid mineralization of the Dajing Sn-polymetal deposit： Evidence from LA-ICP-MS analysis of individual fluid inclusions

LA-ICP-MS analyses on single fluid inclusions trapped in fluorite and quartz from the Sn-Cu orebody of the Dajing deposit and from the Sn ore-body of the Huanggangliang deposit were conducted to trace the source and evolution of Cu-rich and Sn-rich fluids in the Dajing deposit using the Rb/Sr and Sn/Cu ratios of the fluids. The results show that the Cu-rich fluids in the Dajing deposit, relatively rich in Na and probably derived from deep-seated basic magma, contain Cu several to several tens of times more than Sn, and Sr several to several tens of times more than Rb, while the Sn-rich fluids, relatively rich in K and probably derived from high level granitic magma, contain Sn several to several tens of times more than Cu, and Rb several to several tens of times more than Sr. It is suggested that the Sn-rich and the Cu-rich fluids were mixed at the stage of moderate to low temperature and low salinity, resulting in the formation of Cu-Sn orebodies at the central part of the Dajing deposit.     

Bioleaching of vanadium from barren stone coal and its effect on the transition of vanadium speciation and mineral phase

This study determined the optimal conditions required to obtain maximum vanadium extraction and examined the transition of mineral phases and vanadium speciation during the bioleaching process. Parameters including the initial pH value, initial Fe2+ concentration, solid load, and inoculum quantity were examined. The results revealed that 48.92wt% of the vanadium was extracted through bioleaching under optimal conditions. Comparatively, the chemical leaching yield (H₂SO₄, pH 2.0) showed a slower and milder increase in vanadium yield. The vanadium bioleaching yield was 35.11wt% greater than the chemical leaching yield. The Community Bureau of Reference (BCR) sequential extraction results revealed that 88.62wt% of vanadium existed in the residual fraction. The bacteria substantially changed the distribution of the vanadium speciation during the leaching process, and the residual fraction decreased to 48.44wt%. The X-ray diffraction (XRD) and Fourier transform infrared (FTIR) results provided evidence that the crystal lattice structure of muscovite was destroyed by the bacteria.     

Roasting and leaching behaviors of vanadium and chromium in calcification roasting–acid leaching of high-chromium vanadium slag

Calcification roasting–acid leaching of high-chromium vanadium slag (HCVS) was conducted to elucidate the roasting and leaching behaviors of vanadium and chromium. The effects of the purity of CaO, molar ratio between CaO and V₂O₅ (n(CaO)/n(V₂O₅)), roasting temperature, holding time, and the heating rate used in the oxidation–calcification processes were investigated. The roasting process and mechanism were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetry–differential scanning calorimetry (TG–DSC). The results show that most of vanadium reacted with CaO to generate calcium vanadates and transferred into the leaching liquid, whereas almost all of the chromium remained in the leaching residue in the form of (Fe_0.6Cr_0.4)₂O₃. Variation trends of the vanadium and chromium leaching ratios were always opposite because of the competitive reactions of oxidation and calcification between vanadium and chromium with CaO. Moreover, CaO was more likely to combine with vanadium, as further confirmed by thermodynamic analysis. When the HCVS with CaO added in an n(CaO)/n(V₂O₅) ratio of 0.5 was roasted in an air atmosphere at a heating rate of 10℃/min from room temperature to 950℃ and maintained at this temperature for 60 min, the leaching ratios of vanadium and chromium reached 91.14% and 0.49%, respectively; thus, efficient extraction of vanadium from HCVS was achieved and the leaching residue could be used as a new raw material for the extraction of chromium. Furthermore, the oxidation and calcification reactions of the spinel phases occurred at 592 and 630℃ for n(CaO)/n(V₂O₅) ratios of 0.5 and 5, respectively.     

Science Letters： Discovery of ultrahigh-T spinel-garnet granulite with pure CO2 fluid inclusions from the Altay orogenic belt, NW China

We first report discovery of the spinel-garnet-orthopyroxene granulite with pure CO2 fluid inclusions from the Fuyun region of the late Paleozoic Altay orogenic belt in Central Asia, NW China. The rock is characterized by an assemblage of garnet, orthopyroxene, spinel, cordierite, biotite, plagioclase and quartz. Symplectites of orthopyroxene and spinel, and orthopyroxene and cordierite indicate decompression under UHT conditions. Mineral chemistry shows that the orthopyroxenes have high XMg and Al2O3 contents (up to 9.23 wt%). Biotites are enriched in TiO2 and XMg and are stable under granulite facies conditions. The garnet and quartz from the rock carry monophase fluid inclusions which show peak melting temperatures of around -56.7℃, indicating a pure CO2 species being presented during the ultrahigh-T metamorphism in the Altay orogenic belt. The inclusions homogenize into a liquid phase at temperatures around 15.3-23.8℃ translating into CO2 densities of the order of 0.86-0.88g/cm^3. Based on preliminary mineral paragenesis, reaction textures and petrogenetic grid considerations, we infer that the rock was subjected to UHT conditions. The CO2-rich fluids were trapped during exhumation along a clockwise P-T path following isothermal decompression under UHT conditions.     

Structural,mechanical and corrosion properties of CNT-304 stainless steel nanocomposites

In this work, a systematic investigation was performed on the structural, mechanical and corrosion properties of CNT incorporated 304 stainless steel. Various concentrations of CNT from 0.5 to 4 wt% were incorporated into the 304 stainless steel matrix to investigate the feasibility of fabrication and enhancement of strength and other material properties. The fabrication of CNT-steel composite was achieved through a spark plasma sintering process at a sintering temperature of 800℃. Raman and morphological studies confirmed that the CNT structure was retained in the sintered pellets. Optimum performance was found at 0.5 wt% CNT giving a Vickers hardness of 351 Hv and compressive yield strength of 404 MPa which were 5.5 and 2.0 times, respectively, those of pristine steel. Corrosion studies with 3.5 wt% Na Cl solution revealed a slight increase in the corrosion rate for CNT dispersed samples.     

High density methane inclusions in Puguang Gasfield: Discovery and a T-P genetic study

Based on measurement of homogenization temperature of inclusions and Raman spectral analysis, high density methane inclusions were discovered in the Triassic reservoirs of Puguang Gasfield. The methane inclusions show a homogenization temperature Th = -117.5― -118.1℃, a corresponding density of 0.3455―0.3477 g/cm3, and a Raman scatter peak v1 shift varying between 2911―2910 cm-1, which signifies a very high density of methane inclusions. The salt water inclusions paragenetic with methane inclusions show a homogenization temperature Th=170―180℃. Based on the composition of methane inclusions as determined by Raman spectra, PVTsim software was used to simulate the trapping pressure for high density methane inclusions in geologic history, and the trapping pressure was found to be as high as 153―160 MPa. Even though Puguang Gasfield is currently a gas pool of normal pressure, and the fluid pressure for the gas pool ranges between 56―65 MPa. However, data from this study indicates that remarkable overpressure may be generated at the stage of mass production of gas cracked from oils in Cretaceous, as high density methane inclusions constitute key evidence for overpressure in gas pool in geologic history. Meanwhile, discovery of small amounts of H2S, CO2 or heavy hydrocarbon in part of the high density methane inclusions indicates that the geochemical environment for trapping of inclusions may be related to formation of H2S. Therefore, the observation results can help to explore the thermochemical sulfate reduction （TSR） conditions for oil cracking and H2S formation.     

Mechanochemical leaching of chalcopyrite concentrate by sulfuric acid

This study aimed to introduce a new cost-effective methodology for increasing the leaching efficiency of chalcopyrite concentrates at ambient temperature and pressure. Mechanical activation was employed during the leaching (mechanochemical leaching) of chalcopyrite concentrates in a sulfuric acid medium at room temperature and atmospheric pressure. High energy ball milling process was used during the leaching to provide the mechanochemical leaching condition, and atomic absorption spectroscopy and cyclic voltammetry were used to determine the leaching behavior of chalcopyrite. Moreover, X-ray diffraction and scanning electron microscopy were used to characterize the chalcopyrite powder before and after leaching. The results demonstrated that mechanochemical leaching was effective; the extraction of copper increased significantly and continuously. Although the leaching efficiency of chalcopyrite was very low at ambient temperature, the percentages of copper dissolved in the presence of hydrogen peroxide (H₂O₂) and ferric sulfate (Fe₂(SO₄)₃) after 20 h of mechanochemical leaching reached 28% and 33%, respectively. Given the efficiency of the developed method and the facts that it does not require the use of an autoclave and can be conducted at room temperature and atmospheric pressure, it represents an economical and easy-to-use method for the leaching industry.     

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 sulfuric 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 investigated. 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 liquid/ solid ratio of 6.0 mL/g for 90 min at 90℃. Other low-grade pyrolusite ores were tested, and the results showed that they responded well with manganese leaching efficiencies greater than 98%.     

Recycling of Spent Nickel-Cadmium Batteries

A technique for recycling spent nickel-cadmium batteries, which makes separaion of cadmium and nickel possible, is developed by laboratory-scale experiments. NH₃-H₂CO₃ aqueous solution was used in this leaching technique. Since neutralization and/or solvent extraction were not required in the separation procedure of nickel and cadmium, the closed systemizaion of the process becomes possible. Experimental results show that, (1) if the NH₃ concentraion of leaching solution is sufficiently high and the ratio of H₂CO₃ to NH₃ is properly adjusted, both Ni(OH)₂ and Cd(OH)₂ react with NH, and quickly dissolve into leaching solution, and (2) Ni(OH)₂ can be converted into insoluble NiO by calcination at 500℃, and CdO from Cd(OH)₂ by calcination maintains good solubility in NH₃-H₂CO₃ aqueous solution. As a conclusion, the recycling technique characterized by two step leaching can be developed based on such changes in dissolution behavior by calcination. Meanwhile, the yields of 99.8% for nickel and 97.6% for cadmium are obtained, and the purities of recovered nickel and cadmium are 99.9% and 98.6%, respectively.