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 ℃, the operation temperatures of these new processes drop to 200-400 ℃. 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.

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.

Oxidation process of low-grade vanadium slag in presence of Na_(2)CO_3

The oxidation process of low-grade vanadium slag in the presence of Na2CO3 was investigated by XRD,SEM/EDS and TG-DSC techniques.The results show that the vanadium slag is oxidized in a temperature range from 273 to 700 °C.Olivine phases and spinel phases are completely decomposed at 500 and 600 °C,respectively.Most of water-soluble sodium vanadates are formed between 500 and 600 °C.When roasting temperature reaches above 700 °C,the vanadium-rich phases of sodium vanadates can be obviously observed.However,at temperature above 800 °C,the samples are sintered.Most of the vanadium is enwrapped by glassy phase compounds which lead to the decrease of the leaching rate of vanadium.At the same time,the effect of roasting temperature on extraction of vanadium and characterization of leach residues were discussed.

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.

A novel method for extracting vanadium by low temperature sodium roasting from converter vanadium slag

Long-term high temperature in conventional vanadium extraction process would cause particles to be sintered and wrapped, thus reducing extraction efficiency of vanadium. Based on the purpose of directional conversion and process intensification, this work proposed a combination of low temperature sodium roasting and high efficiency selective oxidation leaching in vanadium extraction. The investigation of the reaction mechanism suggested that the structure of vanadium slag was changed by roasting, which also caused the fracture of spinel.The addition of MnO2 promoted the directional oxidation of low-valent vanadium into high valence. It also found that Na2S2O8 could oxidize low-valent vanadium effectively in leaching. The leaching efficiency of vanadium reached 87.74% under the optimum conditions, including a roasting temperature of 650 ℃, a roasting time of 2.0 h, a molar ratio of sodium-to-vanadium of 0.6, a MnO2(roasting additive) dosage of 5 wt% and a Na2S2O8(leaching oxidant) dosage of 5 wt%. This percentage is 7.18% higher than that of direct roasting-andleaching under the same conditions.

Microemulsion leaching of vanadium from sodium-roasted vanadium slag by fusion of leaching and extraction processes

The fusion of the leaching and purification processes was realized by directly using microemulsion as the leaching agent.The bis-(2-ethyhexyl)phosphoric acid(DEHPA)/n-heptane/NaOH microemulsion system was established to directly leach vanadates from sodium-roasted vanadium slag.The effect of the leaching agent on the leaching efficiency was investigated,in addition to the molar ratio of H_(2)O/NaDEHP(W),DEHPA concentration,solid/liquid ratio,stirring time,and leaching temperature.In optimal situations,the vanadium leaching efficiency reaches 79.57%.The X-ray diffraction characterization of the leaching residue and the Raman spectrum of the microemulsion before and after leaching demonstrate the successful entry of vanadates from the sodium-roasted vanadium slag into the microemulsion.The proposed method successfully realizes the leaching and purification of vanadates in one step,thereby greatly reducing production costs and environmental pollution.It also offers a new way to achieve the green recovery of valuable metals from solid resources.

Recovery and separation of Fe and Mn from simulated chlorinated vanadium slag by molten salt electrolysis

Tailings from the vanadium extraction process are discarded each year as waste,which contain approximately 30 wt%of Fe.In our previous work,we extracted Fe and Mn from vanadium slag,and Fe and Mn existed in the form of FeCl_(2) and MnCl_(2) after chlorination by NH_(4) Cl to achieve effective and green usage of waste containing Fe and Mn.In this work,square wave voltammetry(SWV)and cyclic voltammetry(CV)were applied to investigate the electrochemical behaviors of Fe^(2+)and Mn^(2+)in Na Cl-KCl melt at 800℃.The reduction processes of Fe^(2+)and Mn^(2+)were found to involve one step.The diffusion coefficients of FeCl_(2) and Mn Cl_(2) in molten salt of eutectic mixtures Na Cl-KCl molten salt were measured.The electrodeposition of Fe and Mn were performed using two electrodes at a constant cell voltage.The Mn/Fe mass ratio of the electrodeposited product in Na Cl-KCl-2.13 wt%FeCl_(2)-1.07 wt%Mn Cl_(2) was 0.0625 at 2.3 V.After the electrolysis of NaCl-KCl-2.13 wt%Fe Cl_(2)-1.07 wt%MnCl_(2) melted at 2.3 V,the electrolysis was again started under 3.0 V and the Mn/Fe mass ratio of the electrodeposited product was 36.4.This process provides a novel method to effectively separate Fe and Mn from simulated chlorinated vanadium slag.

Effect of chemical composition on the element distribution,phase composition and calcification roasting process of vanadium slag

The chemical composition of vanadium slag significantly affects its element distribution and phase composition,which affect the subsequent calcification roasting process and vanadium recovery.In this work,seven kinds of vanadium slags derived from different regions in China were used as the raw materials to study the effects of different components on the vanadium slag’s elements distribution,phase composition,calcification roasting,and leaching rate of major elements using scanning electron microscope,X-ray diffraction analysis,and inductively coupled plasma-optical emission spectroscopy.The results show that the spinel phase is wrapped with silicate phase in all vanadium slag samples.The main elements in the spinel phase are Cr,V,and Ti from the interior to the exterior.The size of spinel phase in low chromium vanadium slag is larger than the other vanadium slags with higher chromium contents.The spinel phase of high-calcium and high-phosphorus vanadium slag is more dispersed.The strongest diffraction peak of vanadium spinel phase in the vanadium slag migrates to a higher diffraction angle,and(Fe_(0.6)Cr_(0.4))_(2)O_(3)is formed after calcification roasting as the chromium content increased.A large amount of Ca_(2)SiO_(4)is produced because excess Ca reacts with Si in high-calcium and high-phosphorus vanadium slag.The vanadium leaching rate reaches 88%in some vanadium slags.The chromium leaching rate is less than 5%in all vanadium slags.The silicon leaching rate of high-calcium and high-phosphorus vanadium slag is much higher than that of the other slags.The leaching rate of manganese is higher than 10%,and the leaching rates of iron and titanium are negligible.

A novel process for comprehensive utilization of vanadium slag

Traditional processes for treating vanadium slag generate a huge volume of solid residue and a large amount of harmful gas,which cause serious environmental problems.In this study,a new process for the comprehensive utilization of vanadium slag was proposed,wherein zeolite A and a V2O5/TiO2 system were synthesized.The structural properties of the as-synthesized zeolite A and the V2O5/TiO2system were characterized using various experimental techniques,including X-ray diffraction,X-ray fluorescence,scanning electron microscopy,and infrared spectroscopy.The results reveal that zeolite A and the V2O5/TiO2 system are successfully obtained with high purity.The results of gas adsorption measurements indicate that the prepared zeolite A exhibits high selectivity for CO2 over N2 and is a candidate material for CO2 capture from flue-gas streams.

Roasting and leaching behaviors of vanadium and chromium in calcification roasting–acid leaching of high-chromium vanadium slag

Calcification roasting–acid leaching of high-chromium vanadium slag(HCVS)was conducted to elucidate the roasting and leaching behaviors of vanadium and chromium.The effects of the purity of Ca O,molar ratio between Ca O and V_2O_5(n(Ca O)/n(V_2O_5)),roasting temperature,holding time,and the heating rate used in the oxidation–calcification processes were investigated.The roasting process and mechanism were analyzed by X-ray diffraction(XRD),scanning electron microscopy(SEM),and thermogravimetry–differential scanning calorimetry(TG–DSC).The results show that most of vanadium reacted with Ca O to generate calcium vanadates and transferred into the leaching liquid,whereas almost all of the chromium remained in the leaching residue in the form of(Fe_(0.6)Cr_(0.4))_2O_3.Variation trends of the vanadium and chromium leaching ratios were always opposite because of the competitive reactions of oxidation and calcification between vanadium and chromium with Ca O.Moreover,Ca O was more likely to combine with vanadium,as further confirmed by thermodynamic analysis.When the HCVS with Ca O added in an n(Ca O)/n(V_2O_5)ratio of 0.5 was roasted in an air atmosphere at a heating rate of 10°C/min from room temperature to 950°C and maintained at this temperature for 60 min,the leaching ratios of vanadium and chromium reached91.14%and 0.49%,respectively;thus,efficient extraction of vanadium from HCVS was achieved and the leaching residue could be used as a new raw material for the extraction of chromium.Furthermore,the oxidation and calcification reactions of the spinel phases occurred at 592and 630°C for n(Ca O)/n(V_2O_5)ratios of 0.5 and 5,respectively.

Extraction of vanadium from vanadium slag by high pressure oxidative acid leaching

To extract vanadium in an environment friendly manner, this study focuses on the process of leaching vanadium from vanadium slag by high pressure oxidative acid leaching. Characterizations of the raw slag, mineralogy transformation, and the form of leach residues were made by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectroscopy. The result shows that the vana-dium slag is composed of major phases of fayalite, titanomagnetite, and spinel. During the high pressure oxidative acid leaching process, the fayalite and spinel phases are gradually decomposed by sulfuric acid, causing the release of vanadium and iron in the solution. Meanwhile, unreacted silicon and titanium are enriched in the leach residues. With the initial concentration of sulfuric acid at 250 g·L^-1, a leaching tem-perature of 140℃, a leaching time of 50 min, a liquid-solid ratio of 10：1 mL·g^-1, and oxygen pressure at 0.2 MPa, the leaching rate of vana-dium reaches 97.69%.

Extraction of vanadium from high calcium vanadium slag using direct roasting and soda leaching

The extraction of vanadium from high calcium vanadium slag was attempted by direct roasting and soda leaching. The oxidation process of the vanadium slag at different temperatures was investigated by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and energy dispersive spectroscopy （EDS）. The effects of roasting temperature, roasting time, Na2CO3 concentration, leaching tem- perature, leaching time, and liquid to solid ratio on the extraction of vanadium were studied. The results showed that olivine phases and spinel phases in the vanadium slag were completely decomposed at 500 and 800℃, respectively. Vanadium-rich phases were formed at above 850℃. The leaching rate of vanadium reached above 90% under the optimum conditions： roasting temperature of 850℃, roasting time of 60 min, Na2CO3 concentration of 160 g/L, leaching temperature of 95℃, leaching time of 150 min, and liquid to solid ratio of 10：1 mL/g. The main impurities were Si and P in the leach liquor.

Microwave-assisted leaching of vanadium from vanadium slag with sulfuric acid

Microwave irradiation was used to investigate vanadium slag in place of traditional heating.Factors associated with vanadium extraction ratio were studied following the concentration of leaching agent,oxidant dosage,microwave power,microwave irradiation time and mass ratio of liquid to solid.Results indicated that leaching ratio based on microwave leaching at atmospheric pressure can get to 68.48% under the conditions following sulfuric acid concentration 30%,mass ratio of liquid to solid ratio 2∶1,mass ratio of vanadium slag to manganese dioxide dosage 25∶1.4,and microwave power 800W for 3.5 h at 95 ℃.While,leaching ratio based on microwave leaching under pressure was up to 45.79% under the conditions following sulfuric acid concentration 20%,mass ratio of liquid to solid ratio 2∶1,mass ratio of vanadium slag to manganese dioxide dosage 25∶0.9,microwave power 800W for 10 min.Results showed leaching based on microwave irradiation under pressure can shorten time 94.44% in comparison with that at atmospheric pressure,and the leaching extraction can improve about 20%.

Recovery of vanadium from vanadium slag by composite additive roasting-acid leaching process

To minimize the vanadium content in the vanadium extraction tailings, composite additive roasting with (CaO + MgO) and subsequent acid leaching process was carried out dealing with vanadium-bearing converter slag. The effect of additive with different MgO/(CaO + MgO) molar ratios on the roasting and leaching behaviours of vanadium slag was investigated, and the optimum process conditions were obtained. The results show that in the roasting experiment, under the conditions of roasting temperature of 850 ℃ and roasting time of 2 h, the main kinds of vanadate transformed from Ca_(2)V_(2)O_(7) to Ca_(5)Mg_(4)V_(6)O_(2)4 and then to Mg_(2)V_(2)O_(7) with the increase in the MgO/(CaO + MgO) molar ratio. In the leaching experiment, under the conditions of particle size less than 75 μm, leaching temperature of 50 ℃, pH of 2.5, liquid–solid ratio of 20:1, and MgO/(CaO + MgO) molar ratio of 1:3, the leaching efficiency of vanadium is increased by about 5%, but the substitution of MgO for most or all of CaO will significantly reduce the leaching efficiency of vanadium. Furthermore, the leaching efficiency of impurities (P and Cr) can also be decreased by a composite addictive (CaO + MgO) roasting process. The X-ray diffraction, scanning electron microscopy, energy dispersive spectrometry, and X-ray photoelectron spectroscopy of the original vanadium slag and solid products of both roasting and leaching processes were also evaluated.

Extraction of vanadium from molten vanadium bearing slag by oxidation with pure oxygen in the presence of CaO

A novel process of vanadium extraction from vanadium slag in its molten state was conducted at the laboratory scale by oxidation with pure oxygen in the presence of CaO. The effect of mass ratio of CaO to V2O5 on the recovery of vanadium was studied. The sintered samples were leached by H2SO4 solution and characterized by XRD, XPS, SEM and EDS techniques. Compared with the roasting process, the energy saving effect of the proposed process was also discussed. The results showed that vanadium-rich phases were formed and vanadium mainly existed in the forms of CaV2O5 and Ca2V2O7. The formation mechanism of calcium vanadates in the molten vanadium bearing slag was explained. The XRD and XPS results implied that there was a limit to the oxidation reaction of V(IV) to V(V) under the high temperatures even though oxygen-supply was sufficient. An increase in the CaO content led to an increase in the formation of Ca2V2O7. About 90%of the vanadium recovery was obtained under optimal experiment conditions (mass ratio of CaO to V2O5 of 0.6, particle size 120 to 150μm, leaching temperature 90 °C, leaching time 2 h, H2SO4 concentration 20%, liquid to solid ratio 5:1 mL/g, stirring speed 500 r/min). The energy of 1.85×106 kJ could be saved in every 1000 kg of vanadium bearing slag using the proposed process from the theoretical calculation results. Recovery of vanadium from the molten vanadium bearing slag and utilisation of its heat energy are important not only for saving metal resources, but also for energy saving and emission reduction.

Effects of Oxides Contents in Vanadium Slag on Corrosion Mechanism of MgO-C Bricks

The influence of V2O3, FeO, TiO2, MnO and MgO in vanadium slag on the corrosion mechanism of MgO-C bricks was studied by stationary immersion tests at vanadium-extracting temperature. Experimental results show that FeO, TiO2, and MnO could enhance the corrosion rate and V2O3 and MgO could decrease it. Microstructure and phase composition of worn samples were investigated by SEM-EDS, revealing the presence of Fe particles, produced by graphite reduction, and (Mg,Fe,Mn)O solid solution at the interface. The formation process of (Mg,Fe,Mn)O solid solution was discussed and the corrosion mechnism of MgO-C bricks was thus proposed.

Leaching behavior and mineralogical evolution of vanadium released from sodium roasted-acid leaching tailing of vanadium slag

The sodium roasted-acid leaching tailing(SRALT)of vanadium slag with a certain amount of vanadium exhibits potential environmental risk.To investigate the leaching behavior of vanadium from the SRALT,neutral batch leaching tests were performed.The evolution of vanadium concentration,pH,redox potential(Eh),dissolved oxygen,and conductivity as a function of time was measured.Pourbaix diagrams of V–H2O system with different vanadium concentrations were obtained to identify the ionic speciation of vanadium in leachate.X-ray diffraction,X-ray photoelectron spectroscopy,field emission-scanning electron microscopy,and thermogravimetry–differential scanning calorimetry analysis were conducted to investigate the mineralogical evolution of the SRALT during the leaching process.It was found that the major minerals of the original SRALT are titanomagnetite,spinel,olivine,and augite.The valence states of V existing in the original SRALT are V^(3+)and V^(5+).The pH and Eh values of the obtained leachates are 10.00–10.58 and(−43)–(+67)mV,respectively.In this pH and Eh region,the released vanadium is mainly present as HVO_(4)^(2−).The FeOOH and CaCO_(3)would form during the leaching process.The HVO_(4)^(2−)would be mainly adsorbed by the FeOOH and slightly incorporated into the CaCO_(3),resulting in the decline in the vanadium concentration.The vanadium concentration above 27 mg L^(−1)and the dissolved oxygen value below 5.0 mg L^(−1)can be obtained after a short leaching period.As a V(V)-releasing and oxygen-depleting substance,the leaching toxicity of the SRALT should not be ignored.

钒渣空白焙烧-碳酸氢钠浸出选择性提钒

针对现有钒渣生产氧化钒工艺熟料浸出选择性差、浸出液杂质浓度高的问题,提出钒渣空白焙烧-碳酸氢钠浸出提钒新工艺,重点研究了焙烧温度、焙烧时间、钒渣粒度、碳酸氢钠浓度、浸出温度、浸出时间、熟料粒度、液固比对钒浸出率的影响规律,采用矿物解离分析仪(MLA)、扫描电镜(SEM)、能谱仪(EDS)等表征方法,分析了钒渣焙烧、浸出过程的物相和形貌变化特征。结果表明:钒渣空白焙烧过程中,钒主要与钙、锰结合生成焦钒酸钙锰,呈环状分布在氧化铁、铁板钛矿边缘;在焙烧温度930℃、焙烧时间120 min、碳酸氢钠浓度160 g/L、浸出温度95℃、浸出时间120 min、液固比(mL∶g)2∶1等条件下浸出,钒浸出率为94.03%;浸出液中钒38.83 g/L、硅0.21 g/L、铁0.08 g/L、磷0.08 g/L、钙0.02 g/L,锰、镁、铝、铬均<0.01 g/L,这表明浸出液中杂质浓度低,实现了熟料中钒的选择性浸出。碳酸化浸出液中的钙、锰、镁、铁、铝、磷、铬浓度低且理论上不富集,沉钒后的上层液可直接循环浸出熟料,省去废水处理工艺过程,避免水处理固废产生。

熔融钒渣钙化及酸浸过程动力学研究

针对现有转炉钒渣钙化工艺中存在流程长和能耗高的弊端,直接利用转炉中熔融钒渣的热量,在分离出半钢后,向熔融钒渣中加入氧化钙,使含钒物相发生钙化转型生成易溶于酸的钒酸钙。由Factsage8.1软件计算得到熔融钒渣可能发生的化学反应的热力学结果。研究过程中采用XRF、ICP、XRD和SEM/EDS等技术进行表征。XRD结果表明,随着CaO添加量的增加,熔融钒渣中逐渐形成CaV_(2)O_(5)、Ca_(7)V_(4)O_(17)、CaVO_(3)和Ca_(3)V_(2)O_(8)。当CaO添加过多后,也会形成Ca_(2)SiO_(4)和CaTiO_(3),这些物相会包裹部分钒,降低钒的浸出率。而后对钙化钒渣进行了酸浸提钒试验,考察了钒渣粒度、浸出温度、酸浓度和液固比对钒浸出率的影响,动力学计算结果可知,酸浸过程的表观活化能为11.56 kJ/mol,表明钙化钒渣的酸浸反应为内扩散控制。

镁化焙烧钒渣中钒的酸浸动力学研究

为了促进钒渣镁化焙烧−酸浸提钒法的工业应用,研究钒渣镁化焙烧熟料中钒的酸浸出动力学。结合XRD、XPS和SEM,揭示在浸出初期的10 min内,MgSiO_(3)和大部分钒酸盐急剧地消耗酸,形成SiO2和V(V)的氧钒根离子。通过研究钒浸出效率随浸出时间的变化,建立钒浸出的动力学模型。结果表明,浸出过程分为两个不同的阶段,且两个阶段的动力学均遵循收缩核模型。0~10 min的浸出速率由固体产物层扩散和化学反应共同控制,而10~30 min的浸出速率仅由化学反应控制。因此,浸出初始10 min内加速传质很关键,而后续20 min内精确控温至关重要。