High-chromium vanadium-titanium magnetite all-pellet integrated burden optimization and softening-melting behavior based on flux pellets

High-chromium vanadium-titanium magnetite(HVTM)is a crucial polymetallic-associated resource to be developed.The allpellet operation is a blast furnace trend that aims to reduce carbon dioxide emissions in the future.By referencing the production data of vanadium-titanium magnetite blast furnaces,this study explored the softening-melting behavior of high-chromium vanadium-titanium magnetite and obtained the optimal integrated burden based on flux pellets.The results show that the burden with a composition of 70wt%flux pellets and 30wt%acid pellets exhibits the best softening-melting properties.In comparison to that of the single burden,the softening-melting characteristic temperature of this burden composition was higher.The melting interval first increased from 307 to 362℃and then decreased to 282℃.The maximum pressure drop(ΔPmax)decreased from 26.76 to 19.01 kPa.The permeability index(S)dropped from 4643.5 to 2446.8 kPa·℃.The softening-melting properties of the integrated burden were apparently improved.The acid pellets played a role in withstanding load during the softening process.The flux pellets in the integrated burden exhibited a higher slag melting point,which increased the melting temperature during the melting process.The slag homogeneity and the TiC produced by over-reduction led to the gas permeability deterioration of the single burden.The segregation of the flux and acid pellets in the HVTM proportion and basicity mainly led to the better softening-melting properties of the integrated burden.

Effect of basicity on sintering behavior of low-titanium vanadium-titanium magnetite

Basicity has an important effect on the sinter quality, especially for low-titanium vanadium-titanium sinter. The effect of basieity on sintering behavior of low-titanium vanadium-titanium mixture, and the transference and distribution of element in sintering process were researched by sinter pot test, mineralogical analysis, scanning electron microscopy （SEM） and energy dispersive spectroscopy （EDS） analysis. The results show that CaO preferentially reacts with TiO2, generating pervoskite, so that the total liquid phase content of the sinter is low. There is an increase in the perovskite concentration of the sinter with the basicity ranging from 1.9：1 to 2.7：1. With increasing the basicity, the calcium ferrite content increases slightly and then rises rapidly, while the silicate content decreases and the metallurgical property of the sinter is improved. As for the distribution of these elements in the sinter, Ti occurs mainly in perovskite, V occurs mainly in silicate, and Fe occurs mainly in magnetite and hematite. The most abundant occurrence of Ca and Si occurs in silicate and perovskite. With increasing the basicity, the contents of A1 and Mg increase in calcium ferrite, while they decrease in other minerals.

Solid-state reduction kinetics and mechanism of pre-oxidized vanadium-titanium magnetite concentrate

The solid-state reduction kinetics of pre-oxidized vanadium-titanium magnetite concentrate was studied. The phase and microstructure of the reduction product were characterized by XRD, SEM and EDS methods, based on which the mechanism of the solid-state reduction was investigated. The results showed that using coal as reductant at 950-1100 °C, the solid-state reduction of the pre-oxidized vanadium-titanium magnetite concentrate was controlled by interface chemical reaction and the apparent activation energy was 67.719 k J/mol. The mineral phase transformation during the reduction process can be described as follows： pre-oxidized vanadium-titanium magnetite concentrate → ulvospinel → ilmenite → Fe Ti2O5 →（FenTi1-n）Ti2O5. M3O5-type（M can be Fe, Ti, Mg, Mn, etc） solid solutions would be formed during the reduction process of the pre-oxidized vanadium-titanium magnetite concentrate at 1050 °C for 60 min. The poor reducibility of iron in M3O5 solid solutions is the main reason to limit the reduction property of pre-oxidized vanadium-titanium magnetite concentrate.

Effects of basicity and temperature on mineralogy and reduction behaviors of high-chromium vanadium-titanium magnetite sinters

The effects of basicity and temperature on the reduction process of Hongge high-chromium vanadium-titanium magnetite(HCVTM)sinter were investigated in this work.The main characterization methods of X-ray fluorescence(XRF),X-ray diffraction(XRD),scanning electron microscope(SEM),and metallographic microscope were employed in this study.In this work,the reduction of HCVTM sinter with different temperature and basicity were experimented.The Fe,FeO,and TiO in reductive samples increase with increasing basicity and temperatures.The increase of basicity and temperature is favorable to the reduction of HCVTM sinter.The Fe phase has out-migration tendency to the surface of sinter while the perovskite and silicate phases have in-migration tendency to the inside of sinter.The reduction degradation index(RDI)decreases while the reduction index(RI)increases with increasing basicity.The RI increases from 67.14%to 82.09%with increasing temperature from 1073 K to 1373 K.

Influence of Coke Content on Sintering Process of Chromium-containing Vanadium-titanium Magnetite

The sintering of chromium-containing vanadium-titanium magnetite using different coke contents was studied through the sintering pot tests, X-ray diffraction analysis and mineralogical phase analysis. Results showed that, as the coke content increased from 3.2% to 4.4%, the liquid phase and combustion zone thickness increased while the vertical sintering rate and ratio of sintered product decreased. In addition, the combustion ratio of exhaust gas also increased with increasing the coke content, indicating that combustion zone temperature also increased, and the excessive the coke content in the sintering process of vanadiumtitanium magnetite is harmful. As the coke content increased, the magnetite, silicates, and perovskite contents of the sintered ore increased while the contents of hematite and calcium ferrite of sintered ore decreased; drum strength decreased, and reduction degradation properties increased while reduction ability decreased. We found that the appropriate coke content for the sintering process is 3.6 wt%.

Wettability and corrosion behavior between alkaline slag from sodium smelting of vanadium-titanium magnetite and refractory substrates

The sodium smelting of vanadium-titanium magnetite can achieve the comprehensive utilization of Fe,V,and Ti.However,the generation of alkaline slag during this process may cause damage to refractory materials.The wettability and corrosion behavior of alkaline slag on three types of refractory(MgO-C,SiC,and high alumina refractory)substrates were investigated at temperatures up to 1200℃.The effects of duration on the wettability of molten slag on SiC substrates were also investigated.Results showed that the high alumina refractory exhibited better wettability with the molten slag than the others,and thus,it is easier to be corroded.The results of scanning electron microscopy coupled with energy dispersive spectroscopy showed that MgO-C and high alumina refractory substrates were severely eroded.There was a visible and regular interfacial reaction layer between the slag and SiC refractory substrate,which was produced by the redox reaction between the metal oxides in the slag and the SiC refractory substrate.With the increase in holding time,the interface layer expands and silico-ferrite phases are generated at the interface.The redox reaction between Fe_(2)O_(3) and SiC substrate is the main reason for the corrosion.By comparing the differences in wettability and corrosion behavior between the alkaline slag from sodium smelting of vanadium-titanium magnetite and MgO-C,SiC and high alumina refractories,it is concluded that SiC refractory has good corrosion resistance to the slag.Iron oxides in the slag accelerate the oxidation rate of SiC refractory.

Enrichment and reconfiguration of titanium-bearing phase in vortex smelting reduction process of vanadium-titanium magnetite

To comprehensively utilize the low-iron high-vanadium-titanium magnetite,a new method of vortex smelting reduction of vanadium-titanium magnetite was proposed,and the enrichment and reconstitution regularity of Ti-bearing phases in the slag was investigated through X-ray fluorescence spectrometry,X-ray photoelectron spectroscopy,X-ray diffraction analysis,and optical microscopy.The phase diagram revealed that the preferential crystallization of MgTi_(2)O_(5) can be achieved by adjusting the CaO,MgO,and TiO_(2) contents of slag.The predominant Ti-bearing phases in the slag obtained from the reduction process are MgxTi_(3_x)O_(5)(0≤x≤1)and CaTiO_(3).FeTiO_(3) is present at carbon-iron ratio(CR)=1.3,while MgTi_(2)O4 and TiC are formed at CR=1.3.The enrichment of TiO_(2) in the slag increases first and then decreases as the CR increases,and at CR=1.1,the enrichment of TiO_(2) in the slag reaches 51.3 wt.%.Additionally,the concentrations of MgxTi_(3_x)O_(5)(0≤x≤1)and CaTiO_(3) in the slag,along with the grain width of MgxTi_(3_x)O_(5)(0≤x≤1),decrease with the increase in CR.

Three-liquid-phase extraction and separation of V(V) and Cr(VI) from acidic leach solutions of high-chromium vanadium–titanium magnetite

A new method by liquid-liquid-liquid three phase system, consisting of acidified primary amine N1923 （abbreviated as A-N1923）, poly（ethylene glycol） （PEG） and （NH4）2S04 aqueous solution, was suggested for the separation and simultaneous extraction of Ⅴ（Ⅴ） and Cr（Ⅵ） from the acidic leach solutions of high- chromium vanadium-titanium magnetite. Experimental results indicated that Ⅴ（Ⅴ） and Cr（Ⅵ） could be selectively enriched into the A-N1923 organic top phase and PEG-rich middle phase, respectively, while AI（Ⅲ） and other co-existing impurity ions, such as Si（Ⅳ）, Fe（Ⅲ）, Ti（Ⅳ）, Mg（Ⅱ） and Ca（Ⅱ） in acidic leach solutions, could be enriched in the （NH4）2SO4 bottom aqueous phase. During the process for extraction and separation of Ⅴ（Ⅴ） and Cr（Ⅵ）, almost all of impurity ions could be removed. The separation factors between Ⅴ （Ⅴ） and Cr（Ⅵ） could reach 630 and 908, respectively in the organic top phase and PEG middle phase, and yields of recovered Ⅴ（Ⅴ） and Cr（Ⅵ） in the top phase and middle phase respectively were all above 90%. Various effects including aqueous pH, A-N1923 concentration, PEG added amount and （NH4）2SO4 concentration on three-phase partitioning of Ⅴ（Ⅴ） and Cr（Ⅵ） were discussed. It was found that the partition of Cr（Ⅵ） into the PEG-rich middle phase was driven by hydrophobic interaction, while extraction of Ⅴ（Ⅴ） by A-N1923 resulted of anion exchange between NO; and H2V10O4-28. Stripping of Ⅴ（Ⅴ） and Cr（Ⅵ） from the top organic phase and the middle PEG-rich phase were achieved by mixing respectively with NANO3 aqueous solutions and NaOH-（NH4）2SO4 solutions. The present work highlights a new approach for the extraction and purification of V and Cr from the complex multi-metal co-existing acidic leach solutions of high-chromium vanadium-titanium magnetite.

攀西太和钒钛磁铁矿中钴的分布规律及赋存状态

这是一篇工艺矿物学领域的论文。钴是重要的战略金属,主要以共-伴生元素的形式分布于金属矿床中。攀西地区的钒钛磁铁矿矿床是我国最大的钒钛铁资源基地,其矿床中伴生了大量的钴资源,但富钴矿石中钴在矿物相之间的分布规律及微观的赋存状态还未被查明。本文选择攀西地区太和钒钛磁铁矿矿床作为研究对象,利用化学分析、光学显微镜、扫描电镜(SEM-BSE)、X射线衍射分析(XRD)、高级矿物鉴定和表征系统(AMICS)、电子探针(EPMA)等分析技术对矿床中典型的富钴矿石进行了化学成分、矿物组成以及Co元素在不同矿物间分布规律及赋存状态进行了研究,研究结果表明富钴样品矿物中硫化物具有较高的钴含量,而铁钛氧化物中钴含量较低,其他矿物中几乎不含有钴,钴的分布规律表明其主要分布于硫化物中,少量分布于铁钛氧化物以及脉石矿物中。样品中钴元素具有独立矿物-硫钴镍矿和类质同象两种赋存状态。研究结果为该地区钴资源的综合利用提供矿物学依据。

攀西地区钒钛磁铁矿中硫含量测定方法优化

硫是钒钛磁铁矿中重要的质量和环保指标,准确测定其含量对后续工艺控制和污染评价具有重要意义。攀西地区钒钛磁铁矿中硫赋存形态多样且含量范围宽,采用高频燃烧红外吸收法测定硫时,部分矿区样品易出现积分延迟、低硫精密度差的问题。本文结合扫描电镜技术及红外碳硫仪的程序升温功能,通过大量实验,得出钒钛磁铁矿中硫化物形态及含量的差异是造成上述问题的主要原因,并通过优化仪器分析功率、助熔剂及添加顺序、样品质量等分析条件,实现高频燃烧红外吸收法对攀西地区钒钛磁铁矿中0.0004%~1.52%硫的测定。优化后的实验条件如下:样品质量0.30g、助熔剂为0.30g铁粒、0.20g铜粒和1.0g钨粒,助熔剂和样品的添加顺序为铁粒—铜粒—样品—钨粒,分析功率95%。采用不同硫含量的钒钛磁铁矿标准物质建立标准曲线,硫的质量分数为0.0004%~0.200%时(低硫),标准曲线线性方程为y=1.0028x−1.35×10^(−6)(r=0.9998);硫的质量分数为0.201%~1.52%时(高硫),标准曲线线性方程为y=1.0062x−1.49×10^(−6)(r=0.9998),方法检出限为0.0004%。采用本方法对标准物质及攀西地区钒钛磁铁矿实际样品进行测定,标准物质硫含量测定值在标准值的允许范围内,相对标准偏差(RSD)为0.72%~1.40%;实际样品硫含量测定值的RSD为0.40%~0.67%。

攀西钒钛磁铁矿伴生硫资源综合利用及其低碳发展意义

这是一篇矿业工程领域的论文。以攀西钒钛磁铁矿伴生硫资源为研究对象,阐述了其综合利用路径及其低碳发展意义。硫是攀西钒钛磁铁矿典型的伴生元素之一,也是双碳时代粮食-资源-能源的新兴产业链端口元素。本文基于攀西钒钛磁铁矿伴生资源禀赋条件、硫矿物赋存状态,分析伴生硫资源的现状和特点,以钒钛磁铁矿采选产业链探讨硫在综合利用过程可能产生的环境影响。从矿产品需求和综合利用成熟度风险评价两方面探讨综合利用潜力分析。在伴生硫资源面临绿色低碳发展挑战的情况下,本文从规划顶层设计、技术攻关、产线推广等三方面,提出综合利用建议,旨在促进以绿色低碳的原则指导硫产业的发展,重点推广通过源头选硫产线介入方式进行降碳减污。本文研究能为钒钛磁铁矿伴生硫资源综合利用、环境规划及低碳发展提供新的思路及具体建议。

攀西钒钛磁铁矿尾矿中战略性矿产及其综合利用

这是一篇矿物加工工程领域的论文。攀西地区是我国最大的钒钛磁铁矿资源基地,伴随着钒钛磁铁矿的开采和选冶,产生了巨量的尾矿。攀西钒钛磁铁矿尾矿中钒、钛、铁、铜、钴、镍、磷、钪等战略性元素的含量较高,具有潜在的回收价值,但尚未开展系统的选矿回收实验。通过对攀西地区红格矿区尾矿工艺矿物学的研究,拟定了尾矿中战略性元素综合利用技术路线,并开展了系统的选矿回收实验。以浮选选硫—弱磁选铁—强磁浮选选钛—强磁尾矿浮选磷为技术路线,获得了钴品位为0.175%的硫钴精矿、TFe品位56.57%的铁精矿、TiO_(2)品位45.97%的钛精矿、P_(2)O_(5)品位31.73%的磷精矿。研究表明,通过系统的选矿回收实验,能够减少尾矿排放量21.3%,并且,回收这些战略性矿产能获得年产值7134.89万元。因此,回收攀西地区钒钛磁铁矿尾矿的战略性矿产,具有良好的经济效益和社会效益。

Optimization of BF Slag for High Cr_2O_3 Vanadium-titanium Magnetite

In order to clarify the slag system of high Cr2O3 vanadium-titanium magnetite smelting in BF （blast furnace）, the melting properties of slag samples prepared by analytically pure reagents were measured. By means of orthogonal test synthetic weighted score method, the optimal slag for high Cr2O3 vanadium-titanium magnetite was obtained, which contained 10% MgO, 8% TiO2 and 15% Al2O3, with the binary basicity being 1.15. In addition, the effects of basicity, MgO, TiO2 and A12 03 on slag melting properties were investigated by single factor test, and the results showed that, with increasing the basicity or TiO2 content, melting temperature （Tin） increased, whereas initial vis- cosity （r/0） and high temperature viscosity （r/h） decreased. With increasing the MgO content, Tm decreased firstly and then increased. With increasing the Al2 O3 content, Tm increased, and η0 and r/h decreased firstly and then increased.

Oxidation Kinetics,Structural Changes and Element Migration during Oxidation Process of Vanadium-titanium Magnetite Ore

The oxidation kinetics, structural changes, and elements migration during the oxidation process of the va- nadium-titanium magnetite （VTM） ore were analyzed. Kinetics analysis indicated that the oxidation process was con- trolled by diffusion control and could be divided into interface diffusion and lattice diffusion with apparent activation energy of 99.69 kJ/mol and 144.08 kJ/mol in the range of 800--1000℃, respectively. The surface structure changed with the oxidization temperature as follows： dense surface→nano sized sheets→submicron particles→molten particles. The compact structure changed into porous one because of the elements migration and enrichment. Both Fe and Ti elements migrated in the opposite direction during the oxidation process. The V etement in the raw ore stably existed in the form of V^5＋ state, some vanadium migrated and occupied the tetrahedral sites of the hematite during the oxidation process.

Carbothermic Reduction Mechanism of Vanadium-titanium Magnetite

To achieve the high-efficiency utilization of vanadium-titanium magnetite（ VTM）,reduction experiments were conducted to determine the carbothermic reduction mechanism of VTM. Effects of volatile matter,temperature,time,and carbon ratio（ molar ratio of fixed carbon in coal to oxygen in iron oxides of VTM） on reduction degree were investigated.Results show that reduction degree increases with increasing volatile matter in coal,temperature,time,and carbon ratio.Phase transformation,microstructure,and reduction path were analyzed by X-ray diffraction,scanning electron microscopy,energy-dispersive X-ray spectroscopy,and Fact Sage 6. 0. The thermoravimetry-differential scanning calorimetry-quadrupole mass spectrometer method was used for kinetic analysis of the main reduction process. Results indicate that the kinetic mechanism follows the principle of random nucleation and growth（ n = 4）,and the activation energy values at 600-900 and 900-1 350 ℃ are 88. 7 and 295. 5 kJ / mol,respectively.

Kinetics and mechanism of coal-based direct reduction of highchromium vanadium-titanium magnetite

High-chromium vanadium-titanium magnetite(HCVTM)is a valuable resource containing metal elements such as iron,vanadium,titanium,and chromium.To recycle these elements,direct reduction is an efficient way.The mechanism and reaction kinetic parameters for the direct reduction of HCVTM were studied.Experimental results show that the reduction degree increases obviously when the C/O ratio and temperature increase.Thermodynamic analysis showed a dramatic mass loss in the direct reduction of HCVTM in the temperature range of 985-1160℃.From 1200 to 1350℃,the reduction curves for the isothermal reduction of HCVTM followed the same trend,with a sharp increase in the initial reaction zone and a slight increase in the reduction rate with increasing time,and finally,the isothermal reduction process of HCVTM was divided into several limiting stages with varying degrees,with inconsistent limiting factors for the reaction rate at different stages.The results also show that the activation energy decreases slightly at larger degrees of reduction.Also,the apparent rate constant k(T)increased with increasing reduction temperature,with lnk(T)showing a good linear relationship with temperature.

A promising method to recover spent V_(2)O_(5)-WO_(3)/TiO_(2) catalyst: treatment by vanadium-titanium magnetite sintering process

A large number of spent selective catalytic reduction(SCR)denitration catalysts are produced after the ultra-low emission transformation of coal-fired power plants in China.According to the China’s“Directory of National Hazardous Wastes(Version 2021)”,these spent vanadium-tungsten-titanium catalysts are classified as“HW50”hazardous waste,and their disposal and utilization processes have been strictly controlled.Thus,an effective and low-cost technique was developed to treat and utilize these spent SCR catalysts by the vanadium-titanium magnetite sintering process.Effects of adding spent SCR catalysts on the sintering production process and product quality indexes of sinter were studied.The results showed that adding spent SCR catalysts can improve the sintering granulation and green feed permeability,thereby increasing the productivity and flame front speed.When the addition proportion of spent SCR catalysts is less than 1 wt.%,the performance indexes of the finished sinter are basically equal to those of the finished sinter without adding spent SCR catalysts.Further increasing the proportion of spent SCR catalysts to 2.0 wt.%results in a decrease in product quality indexes,which could be attributed to the increase in perovskite content in the finished sinter.

攀西钒钛磁铁矿硫族元素工艺矿物学研究

对攀西钒钛磁铁矿攀枝花、白马、红格、太和4大矿区和选厂的矿样进行了详细的工艺矿物研究,查明了硫族元素在矿石中的赋存状态和分布规律。钴、镍、铜等可综合利用的黄铜矿、镍黄铁矿、方钴矿等矿物平均粒度小于0.074mm,嵌布粒度微细,但与磁黄铁矿和黄铁矿关系密切,大部分赋存于磁黄铁矿和黄铁矿等矿物中,与钛磁铁矿紧密镶嵌的黄铁矿次之,仅少部份以微细矿物的形式赋存于铁相和硅酸盐相矿物中;在选矿过程中进入铁精矿的硫化物也以磁黄铁矿为主。结合硫族元素的利用现状和对矿石中硫族元素的工艺矿物学研究资料,认为在目前的选矿工艺中,以磁黄铁矿和黄铁矿为选别目标,进一步提高以硫精矿为载体的钴、镍、铜元素的精矿品位和回收率,形成可利用含钴镍铜较高品位的硫精矿是可能的,也是符合生产实际的。

攀西白马岩体的矿物结晶顺序与钒钛磁铁矿成因

距今约260 Ma的白马岩体位于上扬子板块西缘的攀西裂谷中,是一个大型的含钒钛磁铁矿镁铁质-超镁铁质杂岩体,是峨眉山大火成岩省的重要组成部分。含矿岩体主要由磁铁橄长岩和橄榄辉长岩组成,主要工业矿体赋存在下部的橄长岩岩相带中。显微镜下显示橄榄石和角闪石均存在2种不同的结构状态,岩浆具有多次脉动的侵位特点。矿物结构特点及磁铁矿、钛铁矿、橄榄石、角闪石及斜长石等矿物电子探针成分测定显示,矿物的结晶顺序大致为斜长石+橄榄石+辉石→角闪石+磁铁矿+钛铁矿→角闪石。根据角闪石和斜长石成分计算角闪石最低结晶温度为1090℃,斜长石的最高结晶温度是1120℃,推测磁铁矿的结晶温度介于1090~1120℃之间。橄榄石的Fo值由下部的磁铁橄长岩向上部的橄榄辉长岩呈逐渐降低的变化趋势,表明随着岩浆的结晶分异进程,系统的氧逸度是逐步变化的,暗示整个结晶分异过程系统处于封闭状态。磁铁矿中w(V2O3)变化于0.72%~1.37%之间,可近似看成是岩浆演化过程氧逸度较低的量化标志(<FMQ+0.5),这种低氧逸度条件下硅酸盐矿物的结晶,会导致粒间熔体氧逸度逐步升高且成分向着富Fe的方向演化。岩浆的这种成分演化特点,是晚期形成不混溶熔浆及富Fe-Ti矿浆的主要原因。

攀西钒钛磁铁矿高压辊磨粉碎试验

使用高压辊磨机对攀西钒钛磁铁矿进行了粉碎试验,主要包括辊面压力、辊面速度和矿石含水量对辊压中料粒度特性的影响。在辊面压力5.6 N/mm2、辊面速度0.195 m/s、矿石含水量小于7%的条件下,当入料粒度P80为15.5 mm时,辊压中料基本全部通过-5 mm筛孔,-3.2 mm产率为91.05%,-0.074 mm产率为15.29%,P80降低至1.55 mm,破碎比达到10。同时对不同的边料及闭路循环工艺对粉碎物料粒度特性的影响进行了试验。