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.

Enhanced properties of stone coal-based composite phase change materials for thermal energy storage

Phase change materials (PCMs) can be incorporated with low-cost minerals to synthesize composites for thermal energy storage in building applications.Stone coal (SC) after vanadium extraction treatment shows potential for secondary utilization in composite preparation.We prepared SC-based composite PCMs with SC as a matrix,stearic acid (SA) as a PCM,and expanded graphite (EG) as an additive.The combined roasting and acid leaching treatment of raw SC was conducted to understand the effect of vanadium extraction on promoting loading capacity.Results showed that the combined treatment of roasting at 900℃ and leaching increased the SC loading of the composite by 6.2%by improving the specific surface area.The loading capacity and thermal conductivity of the composite obviously increased by 127%and 48.19%,respectively,due to the contribution of 3wt% EG.These data were supported by the high load of 66.69%and thermal conductivity of 0.59 W·m^(-1)·K-1of the designed composite.The obtained composite exhibited a phase change temperature of 52.17℃,melting latent heat of 121.5 J·g^(-1),and good chemical compatibility.The SC-based composite has prospects in building applications exploiting the secondary utilization of minerals.

Process mineralogy approach to optimize curing-leaching in vanadiumbearing stone coal processing plants

The purpose of this study is to apply process mineralogy as a practical tool to further understand and analyze the reasons for low leaching rates in the curing-leaching process of vanadium-bearing stone coal and to find a solution or improvement to optimize the leaching index.Using vanadium-bearing stone coal with the V2O5 mass fraction of 0.88%as the research object,the effects of particle size,mineral composition,and sulfuric acid curing on the feed,intermediate,and final products of curing-leaching were analyzed.The main vanadium-bearing minerals in the feed samples included sericite/illite,montmorillonite,kaolinite,limonite,and schreyerite.Through the penetration depth analysis of sulfuric acid,the reason for the high vanadium content in the coarse leaching residue(0.205%V2O5)was found,mainly due to the poor curing effect and incomplete washing after screening.Therefore,thorough washing after sieving and further optimizing the curing process are necessary.The vanadium content of the fine leaching residue(0.078%)was low and the curing-leaching effect was good.However,the vanadium content in the thickened residue(0.296%)exceeded that in the fine leaching residue,which was attributed to the neutralization reaction in the#1 thickener.To solve this problem,the neutralization and thickening processes should be performed in separate equipment.The analysis and detection of key products is helpful for identifying problems and improving the curing-leaching circuit process.

Bioleaching and biosorption behavior of vanadium-bearing stone coal by Bacillus mucilaginosus

The recovery of vanadium(V)from stone coal by bioleaching is a promising method.The bioleaching experiments and the biosorption experiments were carried out,aiming to explore the adsorption characteristics of Bacillus mucilaginosus(B.mucilaginosus)on the surface of vanadium-bearing stone coal,and the related mechanisms have been investigated.After bioleaching at 30℃ for 28 d,the cumulative leaching rate of V reached 60.2%.The biosorption of B.mucilaginosus on stone coal was affected by many factors.When the pH value of leaching system is 5.0,strong electrostatic attraction between bacteria and stone coal promoted biosorption.Bacteria in the logarithmic growth phase had mature and excellent biosorption properties.The initial bacterial concentration of 3.5×10^(8) CFU/mL was conducive to adhesion,with 38.9%adsorption rate and 3.6×10^(7) CFU/g adsorption quantity.The adsorption of B.mucilaginosus on the stone coal conformed to the Freundlich model and the pseudo-second-order kinetic model.Bacterial surface carried functional groups(-CH_(2),-CH_(3),-NH_(2),etc.),which were highly correlated with the adsorption behavior.In addition,biosorption changed the surface properties of stone coal,resulting in the isoelectric point(IEP)approaching the bacteria.The results could provide an effective reference for the adsorption laws of bacteria on minerals.

Soil vanadium pollution and microbial response characteristics from stone coal smelting district

A field investigation was performed to study the content, speciation and mobility of vanadium, as well as microbial response in soil from a stone coal smelting district in Hunan province of China. The results showed that the contents of soil V ranged from 168 to 1538 mg/kg, which exceeded the maximum permissible value of Canadian soil quality for V. The mean soil V content from wasteland area reached 1421 mg/kg, and those from the areas related with slag heap, ore pile and smelting center were 380, 260 and 225 mg/kg, respectively. Based on the results of the modified BCR sequential extraction procedure, V contents in the mobile fractions varied from 19.2 to 637 mg/kg accounting for 7.4%-42.3% of total V, and those of V(+5) species were between 21.9 and 534.0 mg/kg. Soil enzyme activity and microbial basal respiration were adversely affected by high level of soil V. More attention should be paid to soil V pollution and potential hazardous surrounding the stone coal smelting district.

Flotation recovery of vanadium from low-grade stone coal

Pre-concentration of vanadium from low-grade stone coal by the method of desliming-flotation was investigated. The mineral composition and microstructure of stone coal were studied systematically by means of X-ray fluorescence spectrometry （XRF）, X-ray diffraction （XRD） and scanning electron microscopy （SEM）. The results show that selective separation of vanadium-bearing minerals can be achieved by flotation in acidic solution using melamine （EA）. The final vanadium concentrate with V2O5 grade of 1.88% and recovery rate of 76.58% is obtained by desliming-flotation process and 72.51% of the raw ore is rejected as tailings. The pre-concentration of vanadium from low-grade stone coal can increase V2O5 grade and decrease the content of acid consuming minerals, which would enable economical utilization of metallurgical vanadium extraction technology.

Recovery of vanadium and carbon from low-grade stone coal by flotation

Flotation technology of high-carbon stone coal bearing vanadium was investigated based on mineralogical study. Carbon and vanadium flotation circuits were included in the flotation process for carbon and vanadium mineral concentrates. Carbon and vanadium minerals were efficiently separated via regrinding process in the carbon flotation circuit. The results show that the grade and recovery of V2O5 in flotation concentrate are 1.32% and 88.38%, respectively, and the tailings yield is 38.36%. Meanwhile, the grade and recovery of the carbon mineral are 30.08% and 75.10%, respectively, which may be utilized as the fossil fuels directly. The leaching rates of the flotation products are as high as 85%. The results demonstrate that there is no direct adverse effect of flotation process on vanadium leaching. This technology could potentially reduce cost and increase the treatment capacity of vanadium extraction and provide reference to stone coal flotation technology.

Loose-stratification model in separation process for vanadium pre-concentration from stone coal

A technology of one-stage roughing and one-stage scavenging vanadium pre-concentration with shaking table was investigated for improving vanadium grade and decreasing acid consumption minerals content based on the quantitative evaluation of minerals by scanning electronic microscopy （QEMSCAN）. In order to visually illustrate how the vanadium-bearing minerals were separated from system, a loose-stratification model was established with Bagnold shear loose theory and Kelly stratification hypothesis. Through the model, it was inferred that fine fraction and coarse fraction of vanadium-bearing muscovite particles easily became the concentrate in roughing and scavenging stages, respectively. The type of the dominant effect on the loose-stratification was confirmed. In the roughing stage, gravity sedimentation played a leading role in the loose-stratification process. However, in the scavenging stage, shearing dispersion pressure caused by asymmetric motion of table deck took an important part in the loose-stratification process. Finally, the correction of the loose-stratification model was validated by the practical experiment.

Vanadium recovery from stone coal through roasting and flotation

A new process for vanadium recovery from stone coal by roasting-flotation was investigated based on the mineralogy. The process comprised four key steps： decarburization, preferential grinding, desliming and flotation. In the decarburization stage, roasting at 550 ℃ effectively avoided the negative effect of the carbonaceous materials in raw ore and generation of free CaO from calcite decomposition during roasting. Through preferential grinding, the high acid-consuming minerals were enriched in the middle fractions, while mica was enriched in the fine and coarse fractions. Through flotation, the final concentrate can be obtained with V2O5 grade of 1.07% and recovery of 83.30%. Moreover, the vanadium leaching rate of the final concentrate increased 13.53% compared to that of the feed. The results reveal that the decarburization by roasting at 550 ℃ is feasible and has little negative impact on mica flotation, and vanadium recovery from stone coal is conducive to reducing handling quantity, acid consumption and production cost.

Effect of vanadium occurrence state on the choice of extracting vanadium technology from stone coal

The extraction technology of vanadium from stone coal by means of no-salt-roasting and dilute acid solution leaching treatment has the advantages of low pollution, low investment, as well as high vanadium leaching efficiency, which makes it the best technology for extending application. In the present study, the effects of vanadium occurrence state in stone coal, roasting temperature and additive agent on the leaching efficiency of vanadium were studied. The results indicate that the effect of vanadium occurrence state on the extracting vanadium technology is obvious. If the vanadium component in stone coal existed in amorphous phase form, this type of stone coal can be treated by no-slat-roasting and dilute acid solution leaching technology; while the vanadium-bearing crystalline phase existed in stone coal, the roasting additive must be added to destroy this crystalline form so as to acquire high vanadium leaching rate.

Leaching of vanadium from stone coal with sulfuric acid

The effects of roasting, mass ratio of H2SO4 to stone coal, leaching temperature, liquid-to-solid ratio, grinding fineness of stone coal, and two-stage counter-current leaching on the vanadium leaching ratio were studied. The results show that the vanadium leaching ratio of roasted stone coal through two-stage counter-current leaching can reach 65.1% at the mass ratio of H2SO4 to stone coal of 20%, leaching temperature of 95℃, leaching time of 30 h, liquid-to-solid ratio of 1.1 mL·g^-1, and grinding fineness of 0.1 mm, which can serve as an experimental basis for the production of vanadium from stone coal.

Mechanisms of aid-leaching reagent calcium fluoride in the extracting vanadium processes from stone coal

The mechanisms of aid-leaching reagent calcium fluoride in the extracting vanadium processes were researched by comparing the blank extraction with the extraction with calcium fluoride as aid-leaching reagent. The leaching experiments were carried out under the conditions of 95 ~C, 6 h, 1.5 ml.g-1, 15 vol % H2SO4, and 5 % calcium fluoride （mass ratio of CaF2 to stone coal）. The concentrations of hydrogen ion were adjusted from initial 1.82 and 4.79 mol.L-1 to the pH of 1.80 4- 0.05 by 200 g.L-1 lime milk, respectively. The solvent extraction experiments were carded out under the organic phase using 15 vol% D2EHPA, 5 vol% TBP, and 80 vol% sulfonated kerosene and O/A phase ratio of 1/4. The leaching rate of vanadium and six-stage countercurrent solvent extraction rate of vanadium can be remarkably improved from 66.71 to 92.97 % and 81.15 to 98.81%, respectively, when calcium fluoride was added as aid-leaching reagent. In the leaching process, fluorine can enhance the breakage of the structure of vanadium-bearing minerals. Meanwhile, fluoride ion can combine with iron ion to generate acid-insoluble iron fluoride hydrate （Fe2Fs.7H20） and consume all ferric ions and a portion of ferrous ions. In adjusting pH value process, the massive impurities are decreased to form KA1SO4 and FeA1Fs. In solvent extraction process, fluorine can prevent the formation of ferric hydroxide colloids and eliminate the formed unstable ferric hydroxide colloids and the silicon-containing colloids to promote the sufficient contact between the aqueous phase and the organic phase and the sufficient reaction.

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 moUL 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.

A new process of extracting vanadium from stone coal

A new process of extracting vanadium from the stone coal vanadium ore in Fangshankou, Dtmhuang area of Gansu Province, China was introduced. Various leaching experiments were carried out, and the results show that the vanadium ore in Fangshankou is difficult to process due to its high consumption of acid and the high leaching rate of impurities. However, the leaching rate can be up to 80% and the content of V2O5 in the residue can be between 0.22%-0.25% in the process of ore fme grinding→oxidation roasting→mixing and ripening→aqueous leaching→P2O4 solvent extraction→sulfuric acid stripping→oxidation and precipitation→decomposition by heat. Also, the quality of flaky V205 produced by this process can meet the requirements of GB3283--87. The total leaching rate of vanadium is 70%. Also, three types of wastes are easy to treat. The vanadium extraction process is better in relation to the aspect of environmental protection than the sodium method.

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

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

Acid leaching of vanadium from roasted residue of stone coal

Through leaching from residue directly and leaching after a roasting treatment,respectively,the experimental research on sulfuric leaching of vanadium from residue of stone coal that came from power generation was conducted.Factors which influence the leaching of vanadium such as concentration of sulfuric acid,leaching temperature,leaching time and liquid-to-solid ratio were investigated in both processes.In the process of direct leaching,to achieve a leaching rate of 74.49%,H2SO4 concentration of up to 5.4%,leaching temperature of 90℃and leaching time of 8 h were necessary reaction factors.The results show that after a roasting treatment at the optimum condition of 950℃at 1 h,76.88%vanadium can be leached under the experimental condition of 0.45% of H2SO4,30℃for 1 h with a liquid-to-solid ratio of 2 mL/g.Leaching after an oxidation roasting treatment is an efficient way to leach vanadium from the residue of stone coal,which has some advantages,such as high recovery,low economic cost and less impurities in leaching solution.

Leaching vanadium by high concentration sulfuric acid from stone coal

An effectively new technology of extracting vanadium from stone coals by high concentration sulfuric acid was researched. The effect of the concentration of sulfuric acid,leaching temperature,leaching time and helper leaching agent on the extraction of vanadium was explored.The results show that the optimal conditions of extraction are as follows:the concentration of sulfuric acid is 6 mol/L,the ratio of liquid to solid is 3-1;the temperature is 90℃;the leaching time is 3-5 h,the diameter of the ore particle is less than 180μm,and the concentration of helper leaching agent R is 6%.Under these conditions,the extraction of vanadium can reach 95.86%.

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 tempera- ture, 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 20vo1%, 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.

Improving vanadium extraction from stone coal via combination of blank roasting and bioleaching by ARTP-mutated Bacillus mucilaginosus

In order to improve leaching efficiency of vanadium from stone coal,the combination of blank roasting and bioleaching using Bacillus mucilaginosus(B.mucilaginosus)mutants was evaluated.The atmospheric and room temperature plasma(ARTP)technique was used to generate B.mucilaginosus mutants.The results showed that a mutant B.mucilaginosus BM-50,after ARTP irradiation for 50 s,had the highest acid production.The total content of the organic acid produced by B.mucilaginosus BM-50 was nearly doubled compared with the wild strain after 2 days.After 20 days,vanadium leaching rate with B.mucilaginosus BM-50 reached 18.2%,which was improved compared with the original bacteria(15.3%).A pretreatment via blank roasting for stone coal further improved the vanadium dissolution by bioleaching,namely,68.3%vanadium was extracted,which was much higher than that without blank roasting.It is shown that bioleaching by bacterial mutants by ARTP irradiation combined with blank roasting has great potential for improving vanadium recovery from low-grade vanadium bearing stone coal.

Extraction of vanadium from stone coal by modified salt-roasting process

In order to reduce the pollution of Cl2 and HCl released during extracting vanadium from stone coal by sodium chloride roasting, a modified salt-roasting process was proposed by adding calcined lime in roasting process followed by H2SO4 leaching. The effects of parameters including roasting temperature, roasting time, addition mass ratio of NaCI, calcined lime upon leaching rate of vanadium and curing rate of chlorine were investigated, and the effects of leaching time and leaching temperature on leaching rate of vanadium were also studied. The results show that the vanadium leaching rate and the curing rate of chlorine are 67.3% and 51.5% （mass fraction）, respectively, at roasting temperature of 750℃, roasting time of 4 h, 15% sodium chloride and 8% （mass fraction） calcined lime, leaching temperature of room temperature, and leaching time of 4 h.