Preparation of high-purity vanadium by magnesium reduction of vanadium dichloride

High-purity vanadium was made by magnesium reduction of vanadium dichloride. Procedures used included 1) the preparation of vanadium tetrachloride by chlorination of partially reduced vanadium oxide-carbon briquets, 2) rechlorination of crude vanadium tetrachloride containing oxychloride compounds, 3) thermal decomposition of vanadium tetrachloride to vanadium trichloride, 4) hydrogen reduction or thermal disproportionation of vanadium trichloride to vanadium dichloride, 5) magnesium reduction of vanadium dichloride to vanadium sponge, and 6) consolidation of vanadium sponge to metal by arc-melting. This work showed that higher yields of high-quality vanadium metal can be prepared by reduction of vanadium dichloride than can be prepared from trichloride. Metal of >99.8 pct purity was prepared by magnesium reduction of vanadium dichloride with reaction efficiencies approaching 98 pct. Only minor losses of vanadium are experienced because of the high efficiencies of the individual process steps and because of the potential for recycling process streams. F. E. BLOCK, formerly with Albany Metallurgy Research Center, Albany, Oregon     

过氧化氢分光光度法测定湿法提钒工艺中钒

为了提高湿法提钒工艺过程控制效率,采用以过氧钒离子(VO(O₂)⁺)显色特性为基础的过氧化氢分光光度法测定钒含量,实现了样品中钒含量的现场快速测定。首先通过在试样溶液中加入适量氢氧化钠溶液,调整溶液pH值至9～10,然后加入过氧化氢将低价态钒全部氧化至钒(V),再加入硫酸调整溶液至酸性,钒(V)与过氧化氢在室温下形成稳定的红棕色过氧钒离子(VO(O₂)⁺),于450 nm处测定吸光度。钒质量浓度在2.0~400 mg/L内与吸光度值符合比尔定律。采用实验方法测定3种湿法冶金提钒液体试样(包括钒浸取溶液、钒盐沉淀后溶液以及废水等)中钒,结果的相对标准偏差(RSD,n=10)分别为0.38%、3.5%和7.6%;与高锰酸钾氧化-硫酸亚铁铵滴定法结果相一致。     

高氯酸氧化-硫酸亚铁滴定法测定钒铁及含钒钢样中钒

钒通常以高锰酸钾或过硫酸铵作氧化剂 ,并以亚铁标准溶液进行氧化还原滴定法测定。本文以高氯酸作氧化剂 ,即用硫酸和磷酸的混合酸溶解试样 ,加硝酸破坏碳化物并加热至刚冒硫酸烟 ,滴入一定量的高氯酸 ,加热使钒、铬等氧化成高价 ,并保持一段时间强热 ,此时被氧化成Ｃｒ 又转变成Ｃｒ ,但Ｖ 并不被还原 ,因而消除了铬的干扰 ;随后再用亚硝酸钠还原锰 ,过量亚硝酸钠用尿素分解 ,用硫酸亚铁铵滴定测钒。本法适用于钒铁中钒的测定 ,同时也适用于含钒钢样中钒的测定 ,方法简便、易掌握、分析快捷、结果可靠。1　实验部分1 1　主要试剂钒标准…     

还原焙烧- 氧化浸出对石煤钒浸出率的影响

以湖北某地石煤钒矿为研究对象,此石煤钒矿中的钒大部分存在于钒云母中,其次为炭质包裹钒和游离态钒。为了更好地研究还原焙烧对钒云母中钒浸出率的影响,首先通过TG- DSC分析结合盐酸酸浸探究了提取石煤中游离态钒和碳质包裹钒的试验条件,然后研究了还原焙烧的焙烧温度、还原剂添加量以及氧化浸出过程中添加氧化剂对钒云母中钒浸出率的影响。结果表明,氧化浸出过程中加入氧化剂KMnO4对钒云母中钒的浸出率几乎没有影响,但在还原焙烧过程中加入还原剂铝可显著提高钒云母中钒的浸出率。     

X射线荧光光谱法测定钒渣、钒渣熟料和提钒尾渣中主次组分

以四硼酸锂-碳酸锂为熔剂,碘化铵做脱模剂,熔融法制备样品,建立了X射线荧光光谱法(XRF)测定钒渣、钒渣熟料、提钒尾渣中二氧化硅、三氧化二铝、氧化钙、氧化镁、氧化锰、五氧化二钒、氧化铬、磷、二氧化钛和全铁的分析方法。试验表明,在试样量为0.25 g、稀释比(m_样品∶m_熔剂)为1∶20、脱模剂用量为20 mg时熔样效果最佳。采用经验系数法对基体效应进行校正及谱线重叠干扰校正,测定钒渣样品各组分的相对标准偏差(RSD,n=10)在0.10%~1.9%之间,检出限在35~460 μg/g之间。用标准物质和实际样品验证,测定结果与标准物质认定值和实际样品湿法测定值相符,能够满足日常分析的要求。     

V2O5碳热还原合成碳化钒粉末的反应过程

为了实现小批量连续化制备碳化钒粉末,以工业级V2O5和纳米炭黑为原料,利用碳热还原法,在常压下碳管炉中得到了V8C7。通过X射线衍射仪(XRD)、扫描电镜(SEM),分析了合成过程。结果表明:在较低的温度下,纳米炭黑将V2O5还原为VO2;随着合成温度的升高,还原为更低价的V2O3,但没有VO生成;接着发生碳化反应,生成VC1-x、V8C7,合成的各阶段相互重叠;在合成过程中,试样的显微组织因物相不同而有所不同,生成的钒氧化物为炭黑附着的颗粒状大团聚体,VC1-x粉末颗粒呈类球形,但大小不均匀;随着温度升高,合成的最终产物V8C7粉末颗粒呈球形或类球形,大小均匀,粒度为1μm左右;还原碳化过程中,产生的气体有CO、CO2。     

溶剂萃取法从含钒浸出液中提钒的研究进展

提钒原料、浸出工艺及浸出条件等将决定浸出液中钒的存在形态及净化方法.溶剂萃取法可有效净化回收浸出液中的钒，具有处理量大、选择性高、可回收利用、产品纯度高等优点，在钒冶金中得到越来越广泛的应用.笔者针对不同提钒原料所得到的含钒浸出液，综述了各类萃取剂以一定萃取机制从中萃取钒的研究现状.讨论了萃取过程中溶液pH值、协萃剂、萃取时间、杂质元素及萃取预处理等因素对钒萃取分离的影响，并介绍了溶剂萃取法从含钒浸出液中提钒新技术，提出了钒溶剂萃取技术的未来发展方向.      

Extraction of vanadium from direct acid leach solution of converter vanadium slag

Direct acid leaching of converter vanadium slag by titanium dioxide waste is eco-friendly and efficient, but with low selectivity. This novel technique can result in a vanadium solution which contains chromium(III), aluminium(III), magnesium(II), manganese(II) and high amount of iron(II) and iron(III). Bis (2-ethylhexyl) phosphoric acid (D2EHPA) and tri-butyl-phosphate (TBP) diluted with sulphonated kerosene were applied for vanadium extraction from the multi-element leach solution. The effects of the initial pH, concentration of D2EHPA, ratio of organic to aqueous phase, and the extraction time on the extraction efficiency of vanadium were investigated in saponification and unsaponifiable systems, respectively. The results showed that the vanadium extraction percentage can be up to 97% and the iron extraction percentage can be less than 10% in a thirteen-stage counter-current simulation test and the separation coefficient between vanadium and iron can reach to 109.8. Furthermore, vanadium(IV) can also be separated from other impurities such as aluminium(III), magnesium(II), manganese(II), chromium(III) efficiently. The loaded organic phase was stripped by 184?g?L^?1 sulphuric acid solution in a three-stage counter-current stripping process and with the total vanadium stripping percentage of greater than 99.5%. In the end, the vanadium pentoxide products with a purity of 99.14% were obtained.     

提钒后钒钛磁铁精矿直接还原研究

首先运用Fact Sage软件从理论上分析了铁氧化物的还原反应在还原温度950~1 100℃下发生的可能性,然后将提钒后钒钛磁铁精矿与无烟煤按比例混匀、压样后进行直接还原实验,研究无烟煤添加量、原料粒度、还原温度、还原时间对还原产物金属化率的影响,并采用X射线衍射分析还原产物的物相变化.结果表明:在本论文还原温度下,还原反应在理论上是可以进行的.当无烟煤添加量(质量分数)为18%、原料粒度75μm、还原温度为1 100℃、还原时间为90 min时,还原产物的金属化率可达99.18%,还原产物的物相主要为金属铁、黑钛石以及硅酸盐.     

Precipitation and fine structure in medium-carbon vanadium and vanadium/niobium microalloyed steels

Hot-rolled and continuously cooled, medium-carbon microalloyed steels containing 0.2 or 0.4 pct C with vanadium (0.15 pct) or vanadium (0.15 pct) plus niobium (0.04 pct) additions were investigated with light and transmission electron microscopy. Energy dispersive spectroscopy in a scanning transmission electron microscope was conducted on precipitates of the 0.4 pct C steel with vanadium and niobium additions. The vanadium steels contained fine interphase precipitates within ferrite, pearlite nodules devoid of interphase precipitates, and fine ferritic transformation twins. The vanadium plus niobium steels contained large Nb-rich precipitates, precipitates which formed in cellular arrays on deformed austenite substructure and contained about equal amounts of niobium and vanadium, and V-rich interphase precipitates. Transformation twins in the ferrite and interphase precipitates in the pearlitic ferrite were not observed in either of the steels containing both microalloying elements. Consistent with the effect of higher C concentrations on driving the microalloying precipitation reactions, substructure precipitation was much more frequently observed in the 0.4C-V-Nb steel than in the 0.2C-V-Nb steel, both in the ferritic and pearlitic regions of the microstructure. Also, superposition of interphase and substructure precipitation was more frequently observed in the high-C-V-Nb steel than in the similar low-C steel.     

钒渣与Na2O2焙烧提钒技术的探索

将钒渣与过氧化钠(Na2O2)混和,经压块、焙烧、水浸等处理工艺,将钒富集到V2O5中.研究了焙烧温度、压块压力、焙烧时间、Na2O2加入量、浸出温度等因素对钒浸出率的影响.结果表明,当Na2O2与钒渣中V2O5的摩尔比在0.5∶1～4∶1、焙烧温度在700～1 000℃、压块压力在1～25 MPa范围内变化时,钒浸出...     

钒氧化物矿直接合金化冶炼含钒合金钢工艺的研究

介绍了钒氧化物矿直接合金化冶炼含钒合金钢工艺的研究进展,分析了当前钒氧化物矿直接合金化研究中存在的问题.     

X射线光电子能谱分析钒渣熟料中钒的价态

将转炉钒渣和碳酸钠混合, 在800 ℃下通过控制空气氧化时间制备一系列氧化程度不同的钒渣熟料, 对这些熟料进行水浸试验与X射线衍射(XRD)物相分析, 并使用X射线光电子能谱(XPS)分析法, 对钒渣熟料中钒元素的价态进行了定量研究。试验结果表明, XPS全谱得到的钒渣熟料元素与原始成分基本相符。窄扫图谱拟合过程得到了熟料各价态V 2p_3/2的结合能与半峰高宽的数据, 钒价态拟合结果显示随着氧化时间的增加, 熟料中V和V含量分别增加和减少, V含量先升高后降低, 结果与熟料的水浸结果以及XRD分析结果相符。     

Reexamination of vanadium for allotropy

The possibility of allotropy in vanadium at subambient temperatures has been investigated by measuring electrical resistivity in the [110] direction of a single crystal, by measuring elastic constants, and by X-ray diffractometry. All studies indicated no allotropy.     

含钒废触媒除油制样及五氧化二钒测定方法的研究

废触媒含有大量油渍,粘稠、不易进行分析样品的制备和测定。选用酒精燃烧除油法除去样品中油渍使其成为松散样品,选择样品前处理的最佳温度为500~600℃,对两种测定五氧化二钒方法即直接测定法和两步测定法进行了比较。结果表明,直接测定法测定废触媒中五氧化二钒含量,不需要进行烧失量校正,简化了分析步骤,相对标准偏差为0.18%~0.60%,回收率在98.4%~103.4%之间。分别进行不同实验室之间及ICP-AES法测定结果比较,结果吻合较好,该方法具有较好的适用性和可操作性。     

钒资源现状及有机磷类萃取剂萃钒的研究进展

介绍了全球的钒资源的主要分布、储量情况及其市场供需与应用状况。从中心结构、有效基团与空间效应、离子交换协同萃取三个方面综述了机磷(膦)类萃取剂的萃钒机理及其近年来萃钒的新型磷(膦)类萃取剂的研发与应用进展,指出了新型磷(膦)类型萃取剂的研发、新工艺的应用以及协同萃取是目前磷(膦)类萃取剂萃钒的主要研究方向。分析了酸性磷(膦)类萃取剂萃钒、中性磷类萃取剂萃钒和其他新型磷(膦)类萃取剂萃钒的不同萃取体系的萃钒机制。分析认为有机相的损失,萃取和反萃钒的步骤,萃取和分离时间较长,出现乳化现象等是当前萃取钒体系普遍存在的难点。因此需要不断开发新型高效萃取剂,发展清洁绿色萃取技术,在原萃取剂的基础上利用协同效应,探索新的萃取剂组合方式,更好地推进中国钒工业的发展。      

钒(Ⅴ)-次磷酸钠-偶氮胂Ⅲ体系催化动力学光度法测定痕量钒

基于0.016 mol/L的H2SO4介质中,痕量钒(Ⅴ)对次磷酸钠(NaH2PO2)还原偶氮肿Ⅲ(AsAⅢ)的褪色反应有明显的阻抑作用,建立了测定痕量钒(Ⅳ)的动力学光度法.钒(Ⅴ)质量浓度在0～4.0μg/L范围内服从比尔定律,方法检出限为0.058μg/L.在25 mL溶液中,测定0.1→μg钒(Ⅴ)的相对标准偏差为1.5%(n=11).讨论了酸度、反应物浓度、温度、反应时间、干扰离子等因素的影响,研究了反应的最佳条件,并测定了一些动力学参数,催化反应的表观活化能为46.80 kJ/mol.用于测定人发和茶叶样品中痕量钒(Ⅴ),相对标准偏差为3.0%～4.2%,标准加入回收率为98.2%～101.4%.     

Precipitation of carbides in deformed vanadium

Strain aging measurements on alloys of vanadium with 0.3 at. pct carbon have been carried out over the temperature range 200°C to 500°C. The multiplicity of hardening stages char-acteristic of quench aging in this alloy is not altered by deformation. This behavior is in-terpreted as evidence that carbides nucleate in such profusion through the bulk of the metal that dislocations do not contribute an appreciable fraction of additional nucleation sites (even after 40 pct deformation). Only in the final stages of hardening does deformation in-fluence the kinetics of the process.