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.

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.

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.

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.

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.

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.

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.

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%.

Effect of Calcium on the Vanadium Extraction from High Calcium Type Stone Coal

The high calcium type stone coal from Hubei province was leached by water and dilute acid separately after being roasted with different dosage of Na Cl. The water leaching rate of vanadium（WLRV） was low and only 26.8% of vanadium can be leached by water when 4% Na Cl was added, but the acid leaching rate of vanadium（ALRV） was relatively high. Calcium in the high calcium type stone coal is greatly superfl uous relative to vanadium, hence, the calcium reacts with vanadium to form Ca（VO3）2, Ca2V2O7 and Ca3（VO4）2orderly during the stone coal roasting process and high temperature is beneficial to the reactions between calcium and vanadium, which was validated by simulated reactions between pure calcium carbonate and vanadium pentoxide. These calcium vanadates are all water insoluble but acid soluble and this causes the low WLRV and relatively high ALRV. After calcium removal by HCl, the WLRV is highly enhanced and reaches about 50% when only 2% Na Cl was added. If the HCl content is too high, the stone coal is easily sintered and the formed glass structure can enwrap vanadium, which leads the WLRV to decline. Single water leaching process is not appropriate to extract vanadium from high calcium type stone coal.

Desiliconisation of alkaline leaching solution of roasted stone coal with carbonation method

The effects of reaction time,reaction temperature,stirring speed and flowrate of CO2 gas on desilication rate and loss rate of vanadium were studied.The results indicated that desilication rate increases with the increase of flowrate of CO2 gas and reaction time.Reaction temperature and stirring speed have little effect on desilication rate,while influence the loss rate of vanadium significantly.Under the condition of reaction time of 2 h,reaction temperature of 95℃,stirring speed of 180 r/min,flowrate of CO2 gas of 60 mL/min and aging time of 2 h,desilication rate is more than 96%and the loss rate of vanadium is about 4.24%.The residue of desilication process can be processed for silicon materials,such as high-grade hydrated silica,which commonly known as white carbon black.In addition,with this carbonation method,leaching regents NaOH can be recycled by simple treatments.

陕西紫阳某废弃石煤矿酸性废水的产生机理探讨

在自然环境中,黄铁矿容易发生氧化反应导致酸性矿山废水(AMD)污染,进而威胁人类的健康安全。石煤及矸石中伴生的黄铁矿及重金属(镉、镍、钒、锰、锌等)成分复杂,经大气降雨、地表水以及基岩裂隙水的长期浸泡淋溶,产生酸性水,加剧有毒有害重金属元素浸出。AMD因产量大、形成时间跨度长、产源地分散等问题,成为矿山环境修复者们的最棘手问题之一。对陕西紫阳废弃石煤矿进行采样分析,掌握废渣的化学成分及矿物组成,为酸性水的产生查找根源。依据《固体废物浸出毒性浸出方法水平振荡法》(HJ 557—2010),将样品破碎后分别采用蒸馏水浸泡、曝气浸泡及密封浸泡方法,来模拟自然环境下酸性水产生过程,并在模拟过程中定期采集水样进行分析测定,为后续的矿上修复治理提供依据。

蒿坪河流域石煤矿区河流铝的白色污染及其成因分析

矿山酸性水及其伴生的重金属污染是含黄铁矿矿山最主要、综合治理难度最大的污染问题。为了查明蒿坪河流域废弃石煤矿开采河流铝的白色污染及成因问题,2021年以来进行了卫星遥感解译、无固定翼无人机航测、样品采集与分析、主要河流断面水质动态监测等工作。结果表明:(1)研究区河流普遍存在铝的白色污染,其形成可见3种模式:两条沟道不同酸碱度的河水混合后形成白水带;河道河水自然跌水后在河床形成白色污染物;河水自然演化形成酸性水、酸性磺水与酸性白水。(2)河水铝离子污染普遍且超标严重,216件河水中Al离子平均含量为8.6mg/l,样品超标率65.8%,19条河流断面3次河水中Al离子的平均超标率90.48%。(3)河流中铝来自于石煤矿及其围岩中酸性溶解作用长石的结果,废渣堆底部流水是河流铝的主要污染源。(4)河水中铝离子与pH具有显著的负相关关系,河水酸度愈大,河水中铝离子含量愈高;河水中白色无定形胶凝状物形成后,河水中铝离子含量显著降低。河水pH的升高,是河流白色污染物形成的主要因素。河水中铝的白色污染物具有无定形特点,化学组分复杂,是硫酸根、氢氧根及铝构成的复杂化合物。铝的白色无定形胶凝状物具有吸附河水中重金属离子的能力。研究成果可为研究区铝的污染防治提供重要的理论依据。

湖南某石煤矿区重金属污染现状及生态风险评价

为研究湖南某石煤矿区重金属污染现状,采用ICP法测定了水体和土壤中多种重金属含量,并分别采用内梅罗污染指数法和潜在生态危害指数法进行风险评价。结果表明,水中Cd、Cr(Ⅵ)、Zn、Fe和Mn平均浓度分别为1.935 5、0.025 3、6.024 9、16.222 0和4.214 9 mg/L,污染指数分别为387.10、5.06、3.01、54.07和42.15,污染程度从大到小排序为:Cd>Fe>Mn>Cr(Ⅵ)>Zn;土壤中Pb、Zn、Cr、As、Hg和Cd平均含量分别为8.51、38.59、18.65、10.01、0.18和3.41 mg/kg,平均生态风险系数分别为2.13、0.98、0.85、18.00、28.55和339.80,污染程度从大到小排序为:Cd>Hg>As>Pb>Zn>Cr,整个矿区的综合潜在生态风险指数为390.31,污染程度为较高生态危险。矿区受到多种重金属复合污染,废石堆和沉淀池的排水口下游区域较严重。

某地陈家沟河水中重金属元素时空变化及影响因素研究

河水重金属污染一直是环境污染防治领域的热点。秦岭某地石煤矿区陈家沟河水中重金属含量严重超标,但重金属来源不明,为污染治理带来困扰。为了查明陈家沟河水中重金属来源和时空变化情况,采集了2期河水、废弃石煤矿硐排水、废渣堆淋溶水等地表水样品,采用污染指数法、主成分分析法和Pearson相关性分析方法,研究河水中重金属污染程度、空间分布,并对河水中重金属来源进行了解析。研究表明,陈家沟源头河水(对照点)重金属含量可以达到地表水的Ⅰ类标准,中游受废弃石煤矿矿硐排水及废渣堆淋溶水的影响,河水中重金属含量显著升高,汇入干流前河水中重金属含量是对照点的3.5~312倍;河水中Cd、Cu、Zn、Ni、Mn等重金属元素同源,均来源于矿硐排水、废渣淋溶水。河水中重金属含量的空间分布与地质体、污染源分布以及河水pH、盐度等因素有关。研究结果可为陈家沟河水重金属污染防治提供科学依据。

石煤钒矿直接硫酸浸出试验研究

石煤钒矿中的钒一般均以类质同象形式取代六次配位的三价铝而存在于伊利石或云母晶格中,为将钒从伊利石或云母中浸出,必须破坏含钒矿物伊利石或云母的结构。将矿石粉碎至全部通过0.15 mm(100目)标准筛,在加热和有添加剂的协同作用下,可直接用硫酸浸出石煤钒矿中的钒,再将浸出浆液固液分离,得到蓝色硫酸钒溶液。结果表明:正常试验条件下,通过合理调整添加剂配比,可实现对石煤钒矿粉浸出、固液分离,钒的回收率78%以上,该浸出溶液的取得,为后续提钒工艺提供了技术保障。

石煤浸出液离子交换法提钒的研究

选择了几种离子交换树脂，对石煤酸浸含钒液在不同条件下进行离子交换实验。结果表明：采用离子交换法能够很好地除去浸出液中大部分杂质，并能使钒得到富集；不同树脂对钒的吸附均受吸附时间、溶液pH值等实验条件的影响，不同解吸剂与解吸时间也会影响树脂解吸的效果；1#树脂吸附率在4h左右可达到99％的最大吸附能力，选择合适的解吸剂可在4h内使钒的解吸率达到95％以上；解吸液经过净化，沉钒，煅烧后得到的五氧化二钒纯度在99％以上。

麦饭石SRB污泥固定颗粒的稳定性及生物活性实验

针对我国煤矿酸性废水(ACMD)腐蚀性强、锰硫含量高的特点,基于微生物固定化技术,将改性麦饭石与硫酸盐还原菌污泥(SRB)有机结合,制成一种用于处理ACMD的改性麦饭石固定化SRB污泥颗粒。通过进行颗粒对酸碱盐溶液的稳定性试验及对比有无麦饭石颗粒膨胀率、OD600和SO42-的处理效果,探讨颗粒的结构稳定性及改性麦饭石对颗粒结构稳定、生物活性的影响,初步分析颗粒的适用性及可行性。结果表明,颗粒能满足对一般酸度较低ACMD的稳定性要求,有麦饭石颗粒的结构膨胀、基质外泄情况及SO42-去除效果优于无麦饭石颗粒,说明麦饭石对颗粒的结构稳定性、生物活性有一定的积极影响。