Behavior of vanadium during reduction and smelting of vanadium titanomagnetite metallized pellets

The effects of CaO content, MgO content and smelting temperature on the vanadium behavior during the smelting of vanadium titanomagnetite metallized pellets were investigated. The thermodynamics of reduction and distribution of vanadium was analyzed and the high-temperature smelting experiments were carried out. The thermodynamic calculations show that the distribution ratio of vanadium between the slag and the hot metal decreases with the increments of CaO and MgO content in the slag as well as the increase of the smelting temperature. The smelting experiments demonstrate that the vanadium content in iron and the recovery rate of vanadium in pig iron increase as the CaO content, MgO content and smelting temperature increase, whereas the vanadium distribution ratio between the slag and iron tends to decrease. Moreover, the recovery rate of vanadium in pig iron has a rising trend with increasing the optical basicity of the slag. The addition of MgO in the slag to increase the slag optical basicity can not only improve the vanadium reduction but also promote the formation of magnesium-containing anosovite, which is beneficial to following titanium extraction.     

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.     

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。     

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。     

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。     

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.     

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。     

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.     

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℃。     

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.     

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。     

钒渣提钒和铬循环冶金工艺:(Ⅰ)含铬钒酸盐溶液分离回收钒

研究含铬钒酸盐溶液分离回收钒的循环冶金工艺,工艺过程包括溶液中钒的选择性沉淀、沉淀物中钒的浸出及五氧化二钒的制备.在含铬钒酸盐溶液中加入Ca(OH)2进行球磨,不仅可以使其中的钒选择性沉淀析出,而且沉淀物的浸出动力学性能得到显著改善.在含铬钒酸盐溶液中按Ca/V摩尔比1.75:1加入Ca(OH)2,室温球磨60 min...     

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。     

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。     

钒渣提钒和铬循环冶金工艺:(II)沉钒后液分离回收铬

研究通过用PbCO3沉淀并用Na2CO3溶液浸出从钒沉淀溶液中分离和回收铬的循环冶金工艺.沉钒后液pH调至3.0后,按Pb/Cr摩尔比2.5加入PbCO3,在30℃搅拌180 min,铬浓度从2.360 g/L降到0.001 g/L.过滤后,沉铬富集渣用热Na2CO3溶液浸出得到含有Na2CrO4的浸出液和含有PbCO...     

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.     

从镍钼矿中提取镍钼的工艺

针对现行镍钼矿处理工艺存在的钼镍需要分别提取的缺陷,提出镍钼矿加钙氧化焙烧-低温硫酸化焙烧-水浸提取镍钼的新工艺。以贵州遵义镍钼矿为原料,对CaO加入量、氧化焙烧温度、氧化焙烧时间、硫酸加入量、硫酸化焙烧温度、硫酸化焙烧时间以及焙砂水浸工艺参数对镍钼浸出率的影响进行研究。结果表明:在最佳工艺条件下,钼的浸出率为97.33%,镍的浸出率为93.16%,且最佳工艺参数为100 g镍钼矿加入35 g CaO,700℃氧化焙烧2 h,得到的焙砂加入70 mL浓硫酸,再经250℃硫酸化焙烧2 h;硫酸化焙烧得到的焙砂按液固比2:1加水搅拌,经98℃浸出2 h。加入CaO不仅能有效减少镍钼矿氧化焙烧烟气对环境造成的污染,而且能显著提高镍的浸出率。     

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。     

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.