Recovery of vanadium from vanadium slag by composite roasting with CaO/MgO and leaching

A novel process of composite roasting with CaO/MgO and subsequent acid leaching was proposed to improve the recovery rate of vanadium from Linz–Donawiz (LD) converter vanadium slag. The effects of the MgO/(CaO+MgO) molar ratio and the roasting and leaching parameters on the recovery of vanadium were studied. The results showed that the leaching efficiency of vanadium decreased from 88% to 81% when CaO was replaced completely by MgO; however, it could be improved by roasting with the composite of CaO/MgO. The maximum vanadium leaching efficiency of 94% was achieved under the optimum MgO/(CaO+MgO) mole ratio of 0.5:1. The results from X-ray diffractometry (XRD) and scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM−EDS) confirm that the formation rate of acid-soluble vanadates can be enhanced during roasting with the composite of CaO/MgO and that the leaching kinetics can be accelerated owing to the suppression of calcium sulfate precipitation.     

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。     

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.     

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。     

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。     

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。     

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 extendingapplication.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.     

低钒转炉钢渣提钒湿法工艺的动力学研究

为了提高湿法浸出低钒钢渣中钒的浸出效率,并对湿法浸出低钒钢渣中钒提供理论依据,从动力学角度分析整个浸出过程。考察温度、液固比、硫酸质量分数和搅拌速率对浸出过程的影响。研究结果表明:在90℃、液固比为10?1以及硫酸浓度6.0mol/L时,浸取9h,低钒钢渣中钒的浸出率可达到95.3%。通过正交实验和动力学推导,得到描述浸出过程的经验方程,低钒钢渣湿法浸出钒的动力学模型为收缩核动力学模型,浸出过程的表观活化能为12.794kJ/mol,该模型表明浸出过程中的控制步骤取决于固膜扩散速率。提高温度、液固比和硫酸质量分数,均可加速钒的浸出速度,提高钒的浸出率。     

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%。     

Cyclic metallurgical process for extracting V and Cr from vanadium slag: Part I. Separation and recovery of V from chromium-containing vanadate solution

The separation and recovery of V from chromium-containing vanadate solution were investigated by a cyclic metallurgical process including selective precipitation of vanadium, vanadium leaching and preparation of vanadium pentoxide. By adding Ca(OH)₂ and ball milling, not only the V in the solution can be selectively precipitated, but also the leaching kinetics of the precipitate is significantly improved. The precipitation efficiency of V is 99.59% by adding Ca(OH)₂ according to Ca/V molar ratio of 1.75:1 into chromium-containing vanadate solution and ball milling for 60 min at room temperature, while the content of Cr in the precipitate is 0.04%. The leaching rate of V reaches 99.35% by adding NaHCO₃ into water according to NaHCO₃/V molar ratio of 2.74:1 to leach V from the precipitate with L/S ratio of 4:1 mL/g and stirring for 60 min at room temperature. The crystals of NH₄VO₃ are obtained by adjusting the leaching solution pH to be 8.0 with CO₂ and then adding NH₄HCO₃ according to NH₄HCO₃/NaVO₃ molar ratio of 1:1 and stirring for 8 h at room temperature. After filtration, the crystallized solution containing ammonia is reused to leach the precipitate of calcium vanadates, and the leaching efficiency of V is >99% after stirring for 1 h at room temperature. Finally, the product of V₂O₅ with purity of 99.6% is obtained by calcining the crystals at 560 °C for 2 h.     

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.     

Recycling of waste carbon residue from spent lithium-ion batteries via constant-pressure acid leaching

Waste carbon residue (WCR) was efficiently detoxicated and regenerated to high-purity graphite (PGC) used in lithium-ion batteries through the constant-pressure acid leaching technique. The leaching conditions were optimized by the combination of orthogonal and single-factor experiments. Results show that PGC with 99.5% purity is regenerated at temperature of 60 °C, initial acid concentration of 12%, leaching time of 180 min, and liquid-to-solid ratio of 25:1, satisfying the requirements of commercial graphite. Meanwhile, the sodium hydroxide precipitation process was designed to recover valuable components from leachate efficiently. Ni, Co, Mn, and Al recoveries reach 96.92%, 87.5%, 97.83%, and 92.17%, respectively, at pH=11. Moreover, the co-product NaF can be recovered with purity over 99% via evaporative crystallization. The loss rate of fluorine is less than 0.5%, thereby eliminating the pollution risk of fluorine to the environment. The proposed process shows considerable environmental and economic benefits.     

真空热处理对碳化钒粉末制备的影响

为了制备高纯的碳化钒粉末,对五氧化二钒为原料小批量制备所得碳化钒产物进行了真空热处理。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、LECO碳氧分析仪等测试手段对热处理产物进行了表征,重点研究了热处理温度对碳化钒粉末的影响,并用X射线光电子能谱仪(XPS)测试探讨了热处理对碳化钒纯化的机理。结果表明:在1100℃的热处理温度下,可得到有序的V8C7相,游离碳和氧含量分别为0.18%、0.31%;热处理的过程使得碳化钒中的游离碳和氧的下降是粉末中游离碳和剩余的少量钒氧化物发生了进一步的还原反应和粉末中吸附水的消失造成的。     

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℃。     

Recovering indium with sulfating roasting from copper-smelting ash

A technology for recovering indium from Jinchuan copper-smelting ash was developed. Indium in the ash was first enriched to the leaching-slag in leaching process,and then recovered by sulfating roasting. The method included mixing the leaching-slag with sulfuric acid,making them into particles,roasting the mixture,and then leaching the calcine with hot water. Above 90% of indium in calcine could be dissolved into the leaching solution. The optimized conditions were determined as follows： the mass ratio of sulfuric acid to leaching slag was 0.1,the roasting time was about 1 to 1.5 h in the temperature range of 200-250℃,and the calcine was leached for 1 h with 5：1 of liquid/solid ratio at 60℃. Over 99% of indium in leaching solution was finally enriched by Zn substitution or sulfide precipitation.     

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.     

Extraction of Vanadium from LD Converter Slag by Pressure Leaching Process with Titanium White Waste Acid

研究了以钛白废酸直接加压浸出转炉钒渣提钒的工艺。矿物学研究表明：钒、钛、铁、锰、铬等金属元素形成的尖晶石是转炉钒渣的主要物相。绘制了V-Fe-H2O、V-Ti-H2O、V-Mn-H2O、V-Cr-H2O等三元系150 ℃高温电位-pH图,明确了酸浸提钒过程的热力学：在低酸度浸出提钒条件下,可溶性离子Fe2+、Fe3+、Mn2+、Cr2+、Cr3+等的热力学稳定与可溶性含钒离子的热力学稳定区重合,酸浸过程中与钒共同进入浸出液中。钛白废酸酸浸正交试验结果表明：温度和初始酸浓度是影响酸浸过程的主要因素。基于正交试验结果,进一步考察温度对浸出过程的影响,结果表明,随着酸浸温度由100 ℃升高到160 ℃的过程中,浸出渣中的钛有效富集含量在4.56%至12.0%之间变化,其他离子主要赋存于浸出液中。在较优条件下：温度 140 ℃,液固比10:1,初始酸浓度200 g·L-1,搅拌转速500 r/min,酸浸时间90 min,钒的浸出率为 96.85%     

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。     

废弃SCR脱硝催化剂与废NaCl盐焙烧回收催化剂中的钛、钒、钨（英文）

通过废弃选择性催化还原(SCR)脱硝催化剂与废NaCl盐焙烧,可以将催化剂中的钨和钒与钛分离。在最佳浸出条件下(焙烧温度900℃,焙烧时间3 h,废盐与废催化剂的质量比为0.5,浸出温度80℃,反应时间60 min),钨和钒的浸出率分别达到84.63%和66.42%,同时钛的损失率仅为1.3%。废NaCl盐和焙烧温度可以促进锐钛矿型TiO₂转化为金红石型TiO₂,反应后得到了金红石型TiO₂。金红石型TiO₂中的钛的价态为四价,晶格氧和化学吸附氧分别占57.26%和42.74%。该方法可以同时解决2种废弃物的处置问题。     

Recovery of V<Subscript>2</Subscript>O<Subscript>5</Subscript> from Bayer liquor by ion exchange

A new technology was developed to recover V2O5 from Bayer spent liquor by ion exchange.The experimental results show that in the conditions of 105°C and 0.20-0.25 mass ratios between CaO in lime and Al2O3 in spent liquor, the precipitation rate of vanadium in Bayer liquor is more than 85%.The vanadium-bearing precipitation is leached by NaHCO3 solution.The leaching rate of vanadium can reach 85% in the conditions of 95°C, 40 g·L-1 of NaHCO3 concentration, and ventilating of CO2.The 201 × 7 type of resin has...