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 for the production of vanadium from stone coal.     

循环流态化焙烧加压浸出从极难浸石煤中提取钒

以广西某极难浸石煤钒矿为研究对象,研究循环流态化焙烧试样在加压浸出条件下的钒浸出率。结果表明:在相同酸浸条件下,循环流态化空白焙烧试样的钒浸出率高于钠化焙烧的钒浸出率。系统的焙烧浸出工艺对比研究表明:该石煤钒矿只有在循环流态化焙烧并加压高浓度酸浸作用下才能获得最高的钒浸出率,应属于极难浸石煤钒矿。在V(H2SO4):V(HF)=1:1和MnO2添加量(质量分数)为3%的条件下,循环流态化空白焙烧矿的最佳酸浸条件为液固比1:1、浸出温度150℃、浸出时间6 h,钒浸出率可达98.11%。同时,研究循环流态化空白焙烧矿加压浸出的动力学模型、浸出控制步骤及表观活化能。循环流态化空白焙烧能避免钠化焙烧产生的Cl2及HCl等有害气体的排放问题。从焙烧反应设备的创新应用着手,探索试验工艺条件,为极难浸石煤钒矿的工业化利用提供参考和依据。     

高碳石煤流态化氧化焙烧提高钒的浸出率

采用流态化氧化焙烧方式预处理广西某难浸高碳石煤以提高钒的浸出率,对氧化焙烧过程的热力学和钒的氧化动力学进行了分析,并考察了流态化焙烧对钒浸出率的影响。结果表明:石煤在氧化焙烧过程中,碳、黄铁矿的氧化反应在热力学上比V(Ⅲ)氧化反应更易进行,它们的存在对钒氧化具有抑制作用。钒的氧化反应受扩散动力学控制,其表观活化能为347.00 kJ/mol。钒浸出率随焙烧温度的增加先增加后减小,当焙烧温度为700℃和750℃时,钒浸出率随焙烧时间的延长而增加;当焙烧温度为800℃,焙烧时间0.5 h时,钒浸出率最高,达97.51%,延长焙烧时间反而不利于钒浸出。与传统的钠化氧化焙烧法相比,浸出率高,环境污染少。     

石煤钒矿硫酸活化常压浸出提钒工艺

研究石煤钒矿的硫酸活化提钒方法。分别考察矿石粒度、硫酸浓度、活化剂用量、催化剂用量、反应温度、反应时间和浸出液固比等因素对钒浸出率的影响。结果表明:石煤提钒的优化条件为矿石粒度小于74μm的占80%、硫酸浓度150 g/L、活化剂CaF2用量(相对于矿石)60 kg/t、催化剂R用量20 g/L、反应温度90℃、反应时间6 h、液固比(体积/质量,mL/g)2:1,在此优化条件下,钒浸出率可达94%以上;在优化条件下,采用两段逆流浸出,可有效减少活化剂CaF2以及浸出剂硫酸的消耗量;经过两段逆流浸出萃取反萃氧化水解工艺,全流程钒资源总回收率可达86.9%;V2O5产品纯度高于99.5%。     

机械活化强化钒渣钙化提钒工艺

针对转炉钒渣钙化焙烧酸浸工艺中存在的钒转浸率低的问题,采用高能球磨对钒渣进行活化预处理,以期强化其提钒效果。采用激光粒度分析仪、BET比表面积测定仪和XRD对活化前后钒渣进行了粒度、比表面积及物相结构分析;采用浸出实验研究了机械活化对钙化焙烧和浸出的影响规律。结果表明:机械活化法增大了钒渣的比表面积,增加了晶格畸变与微观应力,使含钒物相充分解离,由此可改善钒渣钙化焙烧的动力学条件。在浸出20 min条件下,机械活化80 min可将钒浸出率提高10%,最佳焙烧温度降低100℃。     

钒渣钙镁复合焙烧-浸出提钒（英文）

为了提高转炉钒渣提钒回收率,提出钙镁复合焙烧-酸浸提钒新工艺,研究MgO/(CaO+MgO)摩尔比、焙烧和浸出工艺参数对钒回收率的影响。结果表明:当焙烧添加剂CaO完全被MgO取代时,钒浸出率降低,由88%降至81%;然而,采用CaO/MgO复合焙烧却能强化钒的浸出。当MgO/(CaO+MgO)的摩尔比为0.5:1时,钒浸出率达到94%。XRD和SEM-EDS结果表明,CaO/MgO复合焙烧添加剂能强化焙烧过程中可溶性钒酸盐的生成,并通过减少硫酸钙沉淀的生成改善浸出过程的动力学条件。     

低品位石煤矿中钒的浮选回收(英文)

用脱泥-浮选方法对低品位石煤矿进行钒的预富集。通过X荧光光谱分析(XRF)、X射线衍射分析(XRD)和扫描电镜(SEM-EDS)方法对该矿进行矿物组成及微观结构分析。结果表明,在酸性条件下,使用醚胺(EA)作为捕收剂可以将石煤中含钒矿物与脉石矿物进行分离。通过脱泥-浮选流程,最终得到的钒精矿中五氧化二钒的品位为1.88%,回收率为76.58%,并且抛除了72.51%的尾矿。对低品位石煤矿进行钒的预富集,可以提高五氧化二钒的品位,降低耗酸物质的含量及冶炼成本。     

Vanadium recovery from clay vanadium mineral using an acid leaching method

A technique including direct acid leaching,vanadium precipitation with alkaline,sodium hydroxide releaching,impurity removing by adjusting pH value,precipitation vanadium with ammonium chloride,and vanadium pentoxide by roasting steps was proposed according to the characteristic of Xichuan clay vanadium mineral.The factors influencing leaching vanadium such as temperature and the concentration of sulfuric acid were investigated and optimized.The experimental results indicate that the extract ratios of V2O5 can reach 94% and 92% at a sodium chlorate ratio of 3% and a manganese dioxide ratio of 3%,respectively.A completely chemical precipitation method was adopted to decontaminate and enrich the vanadium in the acid leaching solution.The X-ray diffraction (XRD) pattern and the purity analysis of vanadium pentoxide indicate that the purity of final vanadium pentoxide can reach 99% and meet the standard specifications.The total recovery can reach about 75%.The technique has the characteristics of simplicity,less investlnent,and more environment safety as compared with the traditional salt roasting method.     

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 °C 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 °C 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.     

Pressure leaching of converter vanadium slag with waste titanium dioxide

The process of pressure leaching the converter vanadium slag with waste titanium dioxide without roasting was studied. Mineralogy analysis indicates that the converter vanadium slag contains mainly three mineral phases: magnetite, titanium magnetite, and silicate phase. Vanadium is in combination with iron, titanium, manganese, aluminum, and silicon. The impacts of leaching temperature, leaching time, stirring speed, liquid-to-solid ratio, and initial leaching agent concentration were investigated on the waste titanium dioxide leaching process. The results indicate that under the optimal conditions, the vanadium and the iron leaching rates are 96.85 % and 93.50 %, respectively, and the content of titanium is 12.6 % in the residue. The main mineral phases for the residues under the optimal operation conditions are quartz, ilmenite, anatase, and silicate phase, and the residues can be reused as the extraction of titanium raw materials for titanium dioxide production technology by the sulfate method.     

石煤提钒的浮选工艺及吸附机理

针对传统石煤提钒工艺中钒回收率低、环境污染严重等问题,在工艺矿物学研究的基础上,采用浮选的方法对含钒石煤矿进行条件实验和闭路实验,设计出提钒浮选流程,并利用分子动力学模拟研究捕收剂分子在矿物解理面的吸附过程。结果表明:石煤中主要含钒矿物为钒云母,主要的脉石矿物为石英;通过闭路浮选实验,得到了五氧化二钒品位为3.20%(质量分数)、回收率为74.50%的钒精矿;捕收剂分子容易在钒云母(001)面发生吸附,而在石英(001)面几乎不吸附,从而实现了石煤中钒云母和石英的浮选分离。     

钒钛磁铁矿提钒尾渣浸取钒

采用硫酸氢氟酸次氯酸钠组合浸出体系浸取钒钛磁铁矿提钒尾渣中的钒,研究浸出过程中试剂浓度、浸出液固比、浸出温度、浸出时间、物料粒度对钒浸出率的影响。结果表明:钒的浸出率随试剂浓度、液固比、温度和时间的升高而增大;当矿物粒度小于0.20 mm时,钒浸出率有随矿物粒度变小而减小的趋势。在物料粒度0.15~0.25 mm、初始硫酸浓度150 g/L、初始氢氟酸浓度30 g/L、次氯酸钠加入量为矿量1.5%、矿浆液固比6:1、浸出温度90℃、浸出时间6 h、搅拌速度500 r/min的条件下,钒的浸出率可达85%以上。     

Solvent extraction of vanadium from sulfuric acid solution

The behaviour of vanadium(V) extracted from sulfuric acid solution was investigated using Cyanex 923 as an cxtractant. The effects of the concentration of Cyanex 923 and the pH of the solution were studied. The extraction of vanadium(V) increases with the increase of Cyanex 923 concentration and shaking time. Cyanex 923 can extract vanadium(V) fi'om sulfuric acid solution at low pH conditions, and the best pH conditions for exuaction of vanadium(V) are at pH 1.0-2.0. The species extracted into the organic phase is VO2HSO4 with one molecule of Cyanex 923. Equilibrium studies were used to assess the extraction efficiency of vanadium(V) recovery from the sulfuric acid solution.     

熔融钒渣纯氧氧化钙化提钒(英文)

在实验室条件下对熔融态钒渣直接氧化钙化提钒新工艺进行研究。在反应过程中利用纯氧氧化,CaO作为添加剂,硫酸浸出熟料。采用XRD、XPS、SEM及EDS等手段对钒渣熟料进行分析,考察不同CaO/V2O5质量比与硫酸浓度对熟料中钒浸出的影响,并与现行焙烧工艺在能耗方面进行对比。结果表明:钒渣熟料中形成了钒的富集相,钒渣的氧化钙化产物主要为CaV2O5和Ca2V2O7,并对钒酸钙的形成机理进行了阐释;XRD和XPS分析得出熔渣中钒的氧化反应在供氧充足的情况下存在一定限制,CaO的增加能促进五价钒在熔渣中的稳定;在优化的实验条件下(CaO/V2O5质量比0.6,粒度120~150μm,浸出时间2 h,浸出温度90°C,液固比5:1 mL/g,H2SO4浓度20%,搅拌强度500 r/min),钒的浸出率能达到90%;能耗计算得到每处理1000 kg钒渣,利用新工艺可以节约能量1.85×106 kJ。实验与计算结果验证新工艺是一种节能减排的提钒手段。     

低品位钒渣在碳酸钠存在下的氧化过程

利用XRD,SEM/EDS和TG-DSC等手段对低品位钒渣在Na2CO3存在条件下的氧化过程进行检测。结果表明：钒渣的氧化温度范围为273至700°C,橄榄石相与尖晶石相彻底分解的温度分别是500和600°C,大部分水溶性的钒酸盐在500与600°C之间形成。当温度达到700°C以上时,钒酸盐富集相明显可见,但焙烧温度在800°C以上时,样品发生烧结,并且钒被形成的玻璃相包裹,导致其浸出率下降。同时,研究不同焙烧温度对钒浸出率的影响,并对浸出残渣进行分析。     

Research and prospect on extraction of vanadium from vanadium slag by liquid oxidation technologies

A series of innovative green metallurgical processes using novel reaction media including the NaOH/KOH sub-molten salt media and the NaOH–NaNO₃ binary molten salt medium, for the extraction of vanadium and chromium from the vanadium slag have been developed. In comparison with the traditional sodium salt roasting technology, which operates at 850 °C, the operation temperatures of these new processes drop to 200–400 °C. Further, the extraction rates of vanadium and chromium utilizing the new approaches could reach 95% and 90%, respectively, significantly higher than those in the traditional roasting process, which are 75% and approximate zero, respectively. Besides, no hazardous gases and toxic tailings are discharged during the extraction process. Compared with the conventional roasting method, these new technologies show obvious advantages in terms of energy, environments, and the mineral resource utilization efficiency, providing an attractive alternative for the green technology upgrade of the vanadium production industries.     

直接酸浸-溶剂萃取法从废油加氢催化剂中回收钒和镍（英文）

采用直接酸浸-溶剂萃取法从废油加氢催化剂中选择性萃取分离钒和镍。钒(Ⅳ)和镍(Ⅱ)的萃取分离分为两步：钒和镍的酸浸以及溶剂萃取。首先,通过酸浸实现钒和镍的高效浸取,浸出率分别为88.07%和75.58%。其次,逆流萃取实验表明,在酸性环境下以P204作为钒的高效萃取剂进行三段萃取,钒的萃取率为99.21%,而镍和铁则不萃取。钒萃取余液经氨水-硫酸铵脱铝预处理后,在氨介质中以LIX84-Ⅰ作为镍的高效萃取剂进行三段萃取,镍的萃取率为99.79%。这种钒镍回收的工艺流程不仅可以实现钒和镍的分离回收,而且可以实现试剂的循环利用。     

N-辛基吡啶类离子液体对钒渣水浸液中钒的萃取机理

钒是重要的战略资源,目前主要是从钒钛磁铁矿经"高炉冶炼-转炉吹钒"工艺所得钒渣中采用湿法冶金提取,其中萃取方法应用最多。本文研究以N-辛基吡啶类离子液体为萃取剂,正戊醇为稀释剂,采用溶剂萃取法考察萃取分离V(Ⅴ)的影响因素,包括温度、时间以及溶液pH并对其萃取机理进行研究。结果表明:在[OPy]Cl和[OPy][BF₄]萃取V(Ⅴ)最适宜的条件下,即萃取时间分别为60 s和40 s、pH=2.957～8.029、温度为25℃时,两者的V(Ⅴ)萃取率分别达到95.42%和93.52%;结合离子选择性电极法、斜率法、紫外-可见光谱分析、红外光谱分析等方法研究并确定了N-辛基吡啶类离子液体萃取V(Ⅴ)的机理为阴离子交换。     

酸浸粉煤灰提取铝铁工艺研究

粉煤灰中的铝、硅以复杂的玻璃体红柱石形式存在,酸溶性非常差,必须破坏S iO2-A l2O3键,使粉煤灰中的铝活化,提高粉煤灰的酸溶性。研究了以CaF2为助剂焙烧活化粉煤灰和酸溶提取铝铁的条件,考察了粉煤灰焙烧活化和盐酸溶出条件对粉煤灰中铝铁浸出率的影响。实验表明,焙烧活化条件为:CaF2用量为1%、粉煤灰与石灰石的质量比为2.5、焙烧温度为850℃、烧成时间2 h;酸溶的最佳工艺条件为:溶出温度为85℃、溶出时间为2.0h、盐酸浓度为7mol/L、液固比为3.5,粉煤灰中铝铁溶出率高达90.5%。     

从某钌蒸馏渣中回收提纯铂的研究

钌蒸馏渣中贱金属的稀硫酸直接浸出率低,渣中的铂溶解率低,回收困难。采用焙烧研磨、还原预处理后,贱金属易被浸出;富集在硫酸浸出渣中铂易被王水溶解(溶出率99%),物料中的钌在渣中也得到富集;铂溶液经氯化铵沉淀煅烧得到粗铂;粗铂溶解后经多次氧化水解除杂、氯化铵沉淀法精炼,得到99.99%的海绵铂产品,铂回收率98.07%。