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。     

Kinetics analysis of decomposition of vanadium slag by KOH sub-molten salt method

A novel process was developed for the decomposition of vanadium slag using KOH sub-molten salt under ambient pressure, and the effects of reaction temperature, alkali-to-ore mass ratios, particle size, and stirring speed on vanadium and chromium extraction were studied. The results suggest that the reaction temperature and KOH-to-ore mass ratio are more influential factors for the extraction of vanadium and chromium. Under the optimal reaction conditions (temperature 180 °C, initial KOH-to-ore mass ratio 4:1, stirring speed 700 r/min, gas flow 1 L/min, and reaction time 300 min), vanadium and chromium extraction rates can reach up to 95% and 90%, respectively. Kinetics analysis results show that the decomposing process of vanadium slag in KOH sub-molten salt can be well interpreted by the shrinking core model under internal diffusion control. The apparent activation energies for vanadium and chromium are 40.54 and 50.27 kJ/mol, respectively.     

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。     

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。     

石煤提钒过程中钒氧化和转化对钒浸出的影响

采用H2SO4、HF浸出石煤原矿和石煤焙烧料中钒,通过浸出对比实验,考察了钒氧化和转化对钒浸出的影响。结果表明：含钒矿物晶体结构未被破坏时,V（Ⅲ）无法浸出;石煤原矿在3.5 mol/L HF中于60℃浸出8 h后,含钒矿物的晶体结构完全被破坏,钒浸出率可达到97.91%;通过焙烧或在浸出过程中添加NaClO3,可使V（Ⅲ）氧化为V（Ⅳ）或V（Ⅴ）。     

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...     

铬铁矿熔盐液相氧化新反应系统的热力学分析

利用自编的热力学计算软件对铬铁矿熔盐液相氧化过程进行了热力学计算与分析，通过与传统铬盐生产方法中的碳酸钠高温氧化焙烧过程的比较表明，在较低温度下，液相氧化新过程具有很强的反应趋势，大的放热量及极宽的反应条件，大大优于现行铬盐生产的传统焙烧过程。     

Post-mortem analysis of high alumina brick attacked by vanadium and titanium bearing slag after service in torpedo ladle

Abstract

High alumina brick after service in a torpedo ladle was analysed by means of atomic emission spectroscopy, X-ray diffraction, electron probe microanalysis and themochemical analysis in order to determine the corrosion mechanism during industrial application in a steel works. The results showed that slag containing vanadium and titanium oxide is more corrosive than common silica slags, and that this facilitates corrosion and penetration into the high alumina brick. Mineralogical observation confirmed that V₂O₅, TiO₂, MnO and FeO and MgO in the slag reacted with native phases presented in high alumina brick to form complex spinel, corundum and anorthite solid solution, etc. The dissolved content of V₂O₅ in the spinel decreased from 6·08 to 2·78 wt-% from the working face to the inner area. However, the FeO and MnO content in the spinel varied little with a slight increase in the TiO₂ content. The expansion coefficient mismatch between the penetrated zone and cold face zones, which results in densification spalling and increased porosity, play a key role in the failure of the high alumina brick.     

Iron extraction from lead slag by bath smelting

A new bath smelting process was proposed to recover iron for solid wastes reduction. 99.79% of iron metallization, 99.61% of iron recovery, pig iron with 93.58% Fe, 0.021% S, 0.11% P, 1.38% C, 0.22% Si, 0.01% Pb and 0.031% Zn were achieved after the wastes were smelted at 1575 °C for 20 min under C/Fe molar ratio of 1.6 and basicity of 1.2. The produced pig iron could be used in steel-making. This study provides a way for recycling iron from smelting slag and hydrometallurgical residue.     

Pure metal extraction from molten oxide slag by short-circuit galvanic cell

The oxygen-ion-permeable membrane galvanic short-circuit method has been developed, in which pure metal was directly extracted from the molten oxide slag, and no external voltage is applied. The galvanic cell employed in the experiment was as follows: graphite rod|[O]_(Fe C saturation)[ZrO_2(MgO)|(FeO)_(slag))|Fe rod. The reduction current in the galvanic cell consisted of an external short-circuit current and an interior short-circuit current in the oxygen-ion-permeable membrane. The real-time variation of external circuit reduction ratio of the molten slag could be obtained from the curve of the external circuit current to the time.     

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.     

熔渣法碳化铬涂层的抗氧化性能研究

对熔渣法碳化铬涂层在各种温度下经20h和200h的氧化性能进行了研究，与常用的一些锅炉用钢进行了对比试验，结果表明碳化铬涂层抗氧化性能比15CrMo、102、T91钢好，可以与TP347钢相媲美。     

Distribution behavior of vanadium and phosphorus between slag and molten steel

The correlation of the equilibrium behaviors of phosphorus and vanadium between slag and low carbon molten steel in inert atmosphere was investigated with respect to the experimental variables of slag basicity, the (P₂O₅) and (V₂O₅) content, and the reaction temperature. The distribution ratios of phosphorus and vanadium increased with an increase in the slag basicity. The logarithms of the vanadium distribution ratio were greater by a factor of about two than those of phosphorus in the range of low slag basicity, but the difference diminished with an increase in the slag basicity. The logarithms of the vanadium distribution ratio increased linearly with an increase in the (P₂O₅) and (V₂O₅) content in the slag, while those of phosphorus remained nearly constant. The logarithms of the phosphorus and vanadium distribution ratio decreased with an increase in temperature, and the dependence on temperature was greater for the phosphorus than for the vanadium. For both the maximization of the vanadium yield and the minimization of the rephosphorization of molten steel in the steelmaking process, the ratio of N_(V2O5)/N_(P2O5), the slag basicity, the ratio of f_[P]/f_[V], and the temperature should be maximized, and the (FeO) content in the slag should be minimized.     

Appropriate titanium slag composition during smelting of vanadium titanomagnetite metallized pellets

The suitable titanium slag composition with high titanium content for electric furnace smelting of vanadium titanomagnetite was investigated through thermodynamics and related phase diagram analysis. According to the thermodynamic results, low-melting-point regions and MgTi₂O₅ primary phase area in the phase diagrams, the suggested titanium slag composition for the present vanadium titanomagnetite metallized pellets should consist of 50% TiO₂, 8%–12% MgO and 13% Al₂O₃ (mass fraction) with a binary basicity of 0.8–1.2. Finally, the verified smelting experiments were conducted and successful separation of the molten iron from the titanium slag is obtained. The obtained vanadium-containing molten iron contains 0.681% V and 0.267% Ti, and the obtained titanium slag contains 52.21% TiO₂ (mass fraction), in which MgTi₂O₅ is the primary phase. The titanium resource in the final titanium slag production could be used to produce TiO₂ pigment by acid leaching methods.     

Study of the oxidation kinetics of vanadium carbide

The oxidation of an oxycarbide of vanadium, VO_0.6C_0.7, and of a vanadium carbide, VC_0.98, was studied athermally up to temperatures of 800° C and isothermally between 400 and 580° C at oxygen pressures ranging from 10^–2 to 1 atm. The oxycarbide followed the parabolic rate law below 450° C with V₂O₅ forming as the only reaction product. The activation energy was 49 kcal/mole. VC_0.98 did not form an oxide in this temperature range, but rather dissolved oxygen, the activation energy being 26.6 kcal/mole. No oxygen pressure dependence on the kinetics was found for either sample in this temperature range. Both samples followed the cubic rate law during oxidation in the range of 500–580° C during which V₂O₅ formed. There was a P^1/3 dependence and the activation energy was the same for both materials, 51 kcal/mole. The cubic rate law and the positive pressure dependency (rather than an anticipated negative dependency) were attributed to an electric field associated with oxygen ions chemisorbed on a thin layer of V₂O₅.     

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。     

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.     

熔融氧化镍渣连续冷却过程磁铁矿晶体析出长大行为研究

镍渣中铁元素的高效提取一直是镍渣高效高值化再利用关注的热点。本文利用Factsage软件对熔融氧化镍渣中磁铁矿晶体的形成及优先选择性析出行为进行预测,然后采用高温激光共聚焦显微镜(HT-CLSM)对熔融氧化镍渣连续冷却过程中磁铁矿晶体的析出长大进行原位观察,对比研究了5~50 ℃/min冷却速率下磁铁矿晶体的生长过程,通过SEM-EDS、XRD、ICP手段对观察样品的形貌、物相和成分进行表征。结果表明,熔融氧化镍渣连续冷却过程磁铁矿晶体会从熔体中优先选择性析出,初始析出温度在1430~1450 ℃之间。较低的冷却速率(5~15 ℃/min)下,晶体初始形核析出较慢,晶粒在1200~1400 ℃稳定生长,平均生长速率可达0.141 μm/s,最终晶粒尺寸超过100 μm;较高的冷却速率(25~50 ℃/min)可以促使磁铁矿晶体在生长初期迅速形核并析出,但稳定生长速率较小,最终晶粒尺寸在20~30 μm范围。