Migration behavior,separation and recycling of rare earth during thermal decomposition of Zhijin phosphorus ore

Zhijin phosphorus ore is a moderate and low-grade phosphorus rare-earth ore contained in mines. The separation and extraction of associated rare earth are important research topics. In this study,the migration behavior of rare earth during the thermal decomposition of Zhijin phosphorus ore and the separation and extraction of rare earth in phosphorus slag are discussed systematically. During the thermal decomposition process of phosphorus ore, almost all of the associated rare earth enters into the phosphorus slag phase but does not enter into the ferrophosphorus or gas phases. Amorphous calcium metasilicate and calcium fluosilicate are major components of phosphorus slag, and rare earth mainly exists as a calsil solid solution. Hydrochloric acid was used for acidolysis of the phosphorous slag.Under the following conditions, 96% of the rare earth in the phosphorous slag can be dissolved in the acidolysis solution: acid excess coefficient of 1.5, reaction time of 50 min and reaction temperature of 50℃. The rare earth in the acidolysis solution was separated and recycled using oxalic acid as a precipitator and NaOH as a pH modifier. At pH of 1.7, rare-earth-enriched matter with rare-earth content of 2.1 wt% was obtained, and the recovery of the rare earth was 88%.     

Slag/metal Separation Process of Gas-reduced Oolitic High-phosphorus Iron Ore Fines

Slag/metal separation process of the highly reduced oolitic high-phosphorus iron ore fines was investigated. Samples were prepared using the reduced ore fines （metallization rate： 88%） and powder additives of CaO and Na2CO3. Slag/metal separation behavior tests were conducted using a quenching method and the obtained metal parts were subjected to direct observation as well as microstructure examination with SEM and EDS; iron recovery and phosphorus distribution tests were conducted using a Si-Mo high temperature furnace and the obtained metal parts were examined by ICP-AES analysis and mass measurement. Thermodynamic calculation using coexistence theory of slag structure was also performed. Results show that temperature for slag/metal separation must be higher than 1823 K and a satisfying slag/metal separation of the highly reduced ore fines needs at least 4 min; phosphorus con- tent of hot metal is mainly determined by thermodynamics; temperature of 1823-1873 K and Na2CO3 mixing ratio of about 3 % are adequate for controlling phosphorus content to be less than 0.3 mass% in hot metal; temperature, time and Na2CO3 mixing ratio do not have significant effect on iron recovery, and iron recovery rate could be higher than 80% as long as a good slag/metal separation result is obtained.     

Direct Reduction of High-phosphorus Oolitic Hematite Ore Based on Biomass Pyrolysis

Direct reduction of high-phosphorus oolitic hematite ore based on biomass pyrolysis gases(CO,H_2,and CH_4),tar,and char was conducted to investigate the effects of reduction temperature,iron ore-biomass mass ratio,and reduction time on the metallization rate.In addition,the effect of particle size on the dephosphorization and iron recovery rate was studied by magnetic separation.It was determined that the metallization rate of the hematite ore could reach 99.35% at iron ore-biomass mass ratio of 1∶0.6,reduction temperature of 1 100℃,and reduction time of 55 min.The metallization rate and the aggregation degree of iron particles increase with the increase of reduction temperature.The particle size of direct reduced iron(DRI) has a great influence on the quality of the iron concentrate during magnetic separation.The separation degree of slag and iron was improved by the addition of 15 mass% sodium carbonate.DRI with iron grade of 89.11%,iron recovery rate of 83.47%,and phosphorus content of 0.28% can be obtained when ore fines with particle size of-10 μm account for 78.15%.     

Effect of Modification Treatment for Reduction of Dephosphorization Slag in Hot Metal Bath

To extract the valuable elements from the steel slag, a novel approach has been proposed by modification treatment to provide the stronger driving forces and accelerate the reduction. Three types of dephosphorization steel slags were reduced using carbon-saturated iron bath to extract iron and phosphorus simultaneously. During the process of reduction, slag composition, temperature, and original P2O5 content were investigated respectively. Slag modification treatment, adding either silica or alumina to vary the slag composition, was proven to accelerate the reduction of dephosphorization slag. The equilibrium time can be shortened from 60 to 30 min. Slag modification also allowed the reduction reaction to occur at lower temperature. After slag modification, the original P2O5 content in slag presents a slight difference on reduction process. Almost half of the reduced phosphorus was vaporized within 5 and 20 min. As more and more FeO was reduced, CO gas generation decreased, and evaporation amount of phosphorus therefore decreases.     

Optimization of BF Slag for High Cr2O3 Vanadium-titanium Magnetite简

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.     

Influences of Technological Parameters on Smelting-separation Process for Metallized Pellets of Vanadium-bearing Titanomagnetite Concentrates

The smelting-separation process for metallized pellets of vanadium-bearing titanomagnetite concentrates was studied.The influences of smelting temperature,smelting time,and the basicity of the metallized pellet on vana-dium and iron recovery were investigated.The characteristics of titanium slag were analyzed using X-ray diffraction, energy dispersive spectroscopy,and mineralographic microscopic analysis.The results demonstrate that appropriate increases in smelting temperature and smelting time can improve the vanadium and iron recovery from metallized pel-lets and are beneficial for the slag-iron separation.Although increasing the basicity of the metallized pellet can consid-erably improve the vanadium and iron recovery,the TiO2 grade of titanium slag was decreased.Under the optimal conditions,90·17% of vanadium and 92·98% of iron in the metallized pellet were recovered,and the TiO2 grade of titanium slag was 55·01%.It was found that anosovite,augite,spinel,glassiness,and metallic iron were the main mineral phases of the titanium slag.     

Comprehensive Utilization of Ludwigite Ore Based on Metallizing Reduction and Magnetic Separation

With the aim of high-efficiency utilization of Dandong ludwigite ore, a new process of metallizing reduction and magnetic separation was proposed, and the effects of reduction temperature, reduction time, carbon ratio, ore size and coal size on the efficiency of the process were investigated in details, and relevant mechanisms were elucidated by SEM and EDS. The optimum technological parameters for metallizing reduction and magnetic separation on ludwigite ore were obtained as reduction temperature of 1 250 °C, reduction time of 60 min, carbon ratio of 1.4, ore size of 0.500-2.000 mm, and coal size of 0.50-1.50 mm. After adopting the optimum parameters, the iron content and recovery ratio of iron in magnetic substance are 87.78% and 88.02%, respectively, while the recovery ratios of boron, magnesium and silicon in non-magnetic substance are 88.86%, 94.60% and 98.66%, respectively. After metallizing reduction and magnetic separation, valuable elements of ludwigite ore could be separated and utilized in subsequent steelmaking process and hydrometallurgy process.     

Phosphorous Enrichment in Molten Adjusted Converter Slag：Part II Enrichment Behavior of Phosphorus in CaO-SiO_2-FeO_x-P_2O_5 Molten Slag

 The enrichment behavior of phosphorus in CaO-SiO2-FeOx-P2O5 slag was studied by making an investigation on the distribution of phosphorous content in the CaO-SiO2-FeOx-P2O5 molten slag. The research results showed that the 2CaO·SiO2 solid particles existing in molten slag were the condensation sites for the phosphorus enrichment. The enrichment process of phosphorus in the molten slag can be recognized as three substeps: mass transfer of phosphorus from bulk slag to the surface of 2CaO·SiO2 particle, superficial solid solution reaction of phosphorus around the 2CaO·SiO2 particle, and diffusion of phosphorus through the product layer of 2CaO·SiO2-3CaO·P2O5 solid solution to the inner of 2CaO·SiO2 particle. Moreover, higher temperature is favorable to the phosphorous enrichment from molten bulk slag to the 2CaO·SiO2 particles.     

Process of Re-Resourcing of Converter Slag

 The process of “re-resourcing of converter slag” was put forward based on the analysis of the existing steel slag treatment process. The converter slag obtained from Jinan steel plant was studied. After grinding, the slag contained 33% of iron particles, 5484% of magnetic part (wTFe=20%), and 4184% of non-magnetic part, which could be used for making cement directly. At a temperature below 1000 ℃, the non-magnetic Fe2O3 in the slag could be efficiently reduced to magnetic iron by pure H2 and CO. The slag after precise reduction had high degree of dispersion and did not get sintered, which provided an optimum condition for the separation of iron and impurities. To separate the slag and enrich the iron after reduction, the laboratory-scale device of magnetic separation was designed and made. The process of slag re-resourcing, which included magnetic sorting, precise reduction, magnetic separation, and removal of free calcium oxide (f-CaO), was proposed to obtain iron-rich magnetic materials and cement adulterant materials. Through this process, 33 kg iron particles, 150 kg iron-rich material and 700 kg cement could be obtained in each ton slag. Besides, this process to recycle converter slag had a lower energy and material consumption and no pollutant emission.     

Effect of B_2O_3 on Melting Temperature of CaO-Based Ladle Refining Slag

B2O3 is selected as fluxing agent of CaO-based ladle refining slag to decrease the melting temperature as well as to improve the speed of slag forming and the refining efficiency.The effects of B2O3 on the melting temperature of two series of refining slags including the low basicity slags(the mass ratio of CaO/SiO2 is 3-4)and the high basicity slags(the mass ratio of CaO/SiO2 is 5-8.75)were investigated.The slag melting temperature was measured using the hemisphere method.The results indicate that the fluxing action of B2O3 is better than that of CaF2 and Al2O3.For the CaO-based refining slag with low basicity,the melting temperature is decreased effectively when B2O3 is used to substitute for equal mass of CaF2,Al2O3 and SiO2,respectively.For the CaO-based refining slag with high basicity,when CaF2 is substituted by B2O3,the melting temperature can be decreased remarkably.Especially,when the mass ratios of CaO/Al2O3 and CaO/SiO2 are in the range of 1.1-4.0 and 5.25-8.0,respectively,the slag melting temperature is lower than 1300 ℃.Therefore,the B2O3-containing refining slags with high ratios of CaO/Al2O3 and CaO/SiO2 have ultra low melting temperature.     

二氧化钛改质对含磷转炉渣中磷富集行为的影响

为了有效富集含磷转炉渣中磷,通过TiO₂熔融改质研究了磷富集行为,对TiO₂改质过程进行了热力学探讨,同时对实验炉渣进行磁选分离提取了富磷相.在1623 K条件下,随着渣中TiO₂含量的增加,渣中先期析出的n2CaO·SiO₂-3CaO·P₂O₅（以下简记nC₂S-C₃P）固溶体与TiO₂不断反应析出CaSiTiO₅、CaTiO₃和高磷固溶体（n'C₂S-C₃P,n'2S-C₃P固溶体会随着TiO₂含量的增加而逐渐减少甚至消失,如渣中TiO₂含量进一步增加或过量,前述反应生成的高磷固溶体（n'C₂S-C₃P）继续与TiO₂反应,从而使富磷相中磷含量进一步提高.经350mT磁场强度下磁选后,改性后的渣中收集到的非磁性物较原渣提高了23.84%,P₂O₅分配比由0.96增加到2.92,分离的非磁性物占炉渣总量的65.43%,渣中74.46%的磷进入收集的非磁性物中,实现了绝大部分磷元素的回收利用.      

CaO-FeO-SiO2-Al2O3/Na2O/TiO2渣系与碳饱和铁水间磷分配行为

 为了研究Al2O3、Na2O和TiO2作为铁水预处理渣的助熔剂对铁水预处理脱磷的影响,借助FactSage热力学软件绘制了CaO-FeO-SiO2渣系1 573 K液相区。随着Al2O3和Na2O质量分数的增加,该渣系液相区明显扩大,TiO2对渣系液相区影响不大。实验室研究采用纯铁箔替代碳饱和铁水进行热力学平衡试验,间接测定了1 573 K时铁水预处理脱磷渣与碳饱和铁水间的平衡磷分配比。结果表明,渣铁磷分配比随渣中Al2O3和TiO2质量分数的增加而减小,TiO2对磷分配比的影响相对较小;渣铁磷分配比随渣中Na2O质量分数和碱度的增加而增加,Na2O可显著提高渣的脱磷能力;渣铁磷分配比随渣中FeO质量分数的增加先增加后减小,最合适的FeO质量分数为35%～40%。     

渣系碱度对含碳球团渣相组成和渣铁分离的影响

采用煤基直接还原熔分技术和FactSage热力学分析软件以及XRD分析手段,研究了渣系碱度wCaO/wSiO2对高铁铝土矿含碳球团渣相组成和渣铁分离效果的影响。实验结果表明,渣系碱度对含碳球团的渣系组成和渣铁分离效果有重要影响。当碱度为1.0和1.5时,粒铁尺寸最大,渣铁的分离效果最好,粒铁收得率分别为91.55%和91.86%;当碱度为0.5时,粒铁尺寸较小,渣铁分离效果较差,粒铁收得率为65.43%。当碱度为2.0时;粒铁尺寸最小,渣铁分离效果最差,粒铁收得率只有44.53%。XRD分析结果表明,当渣系碱度分别为0.5、1.0、1.5和2.0时,熔分渣的主要组成分别为α-Al2O3-CaAl2Si2O8、α-Al2O3-CaO·6Al2O3-Ca2Al2SiO7、CaO·6Al2O3-Ca2SiO4-Ca2Al2SiO7、Ca2Al2SiO7-Fe2SiO4。FeAl4O7、CaAl4O7以及金属铁在熔分渣中的含量较少。     

环保型高磷铁水预脱磷渣的脱磷性能研究

实验室条件下采用间接测量法,测定了CaF2系和B2O3系脱磷渣的磷分配.即首先测量磷在液态渣和固态铁间的分配比,再通过计算得到磷在液态渣和铁水之间分配比,同时根据渣系成分和光学碱度计算了磷容量.同时采用了扫描电镜、能谱分析与X射线衍射分析技术对脱磷渣进行了研究.实验结果表明,B2O3系预脱磷渣的磷容量远大于CaF2系预脱磷渣的磷容量,因此可以用B2O3全部替代CaF2作为助熔剂进行高磷铁水的预脱磷处理,2种渣系的磷分配均随渣中有效CaO含量的升高而升高.用B2O3作为助熔剂时,B2O3能与渣中高熔点物质2CaO·SiO2和3CaO·P2O5反应生成低熔点物质,从而起到助熔的作用.且w(B2O3)/w(CaO)比值为0.16时,磷分配比为最高值,即该渣脱磷能力最强.     

Effect of CaF2 and SiO2 modification on phosphorus utilisation in P-bearing slag

Abstract

In order to recycle phosphorus in P-bearing converter slag for slag phosphate fertiliser, the effect of CaF₂ and SiO₂ modification on P-bearing steelmaking slag on phosphorus-bearing phases, P₂O₅ solubility and magnetic separation behaviour has been researched. The results show that the phosphorus-rich phase is mainly n2CaO·SiO₂–3CaO·P₂O₅ (nC₂S–C₃P for short) and exists along with fluorapatite phase [Ca₅(PO₄)₃F] after the addition of CaF₂. The fluorapatite cannot be dissolved in 2% citric acid solution, which decreases the P₂O₅ solubility in slag. Although adding CaF₂ can increase the P₂O₅ content of phosphorus-rich phase, it can improve its metallisation and magnetisation of RO phase, increase the amount of recovered magnetic substances, and separate incompletely phosphorus and iron, therefore it is adverse to the phosphorus recovery from P-bearing slag by magnetic separation. P₂O₅ content of phosphorus-rich phase is more than 31% and P₂O₅ solubility of slag is increased to 96% in fluorine-free modified slag, which can meet the requirement of P₂O₅ content and P₂O₅ solubility of the phosphate fertiliser. Meanwhile, 87.1% of the phosphorus in the fluorine-free modified slag is contained in non-magnetic substance, and most of the phosphorus was recycled.     

MgO和MnO对CaO-SiO2-Fe2O3-P2O5渣的物相影响

转炉渣中的磷主要存在于n2CaO·SiO2-3CaO·P2O5（以下简记为nC2S-C3P）固溶体的富磷相中。为了深入理解转炉渣的物相,便于有效富集钢渣中的磷,研究MgO和MnO含量的变化对CaO-SiO2-Fe2O3-P2O5渣中nC2S-C3P固溶体的磷含量及渣结晶物相的影响,并对其进行热力学分析。结果表明：在CaO-SiO2-Fe2O3-P2O5四元渣系中加入少量MgO或MnO,可以在一定程度上提高nC2S-C3P固溶体中的磷含量;继续提高MgO或MnO含量,固溶体中的磷含量不再发生变化。随着MgO或MnO的加入,富铁相增多,有利于钢渣的磁选分离。     

高铁铝土矿直接还原回收粒铁和氧化铝

 采用煤基直接还原熔分技术和氧化铝溶出的方法,研究了直接还原工艺对粒铁尺寸和粒铁收得率的影响,以及钙铝比[(w(CaO)/w(Al2O3))] 对渣相组成和渣中氧化铝的溶出影响。结果表明,当[(w(CaO)/w(Al2O3))]为1.7、[w(C)/w(O)]为1.4、还原熔分温度为1 450 ℃,还原熔分时间为20 min时,还原熔分过程中的粒铁尺寸最大,粒铁收得率也最高,粒铁尺寸和收得率分别为11.5 mm和93%。当[(w(CaO)/w(Al2O3))]为1.0时,渣相组成主要以钙铝黄长石(Ca2Al(Al,Si)2O7)为主,当[(w(CaO)/w(Al2O3))]为1.5时,渣相组成主要以钙铝黄长石(Ca2Al(Al,Si)2O7)、硅酸二钙(Ca2SiO4)和七铝十二钙(Ca12Al14O33)为主,当[(w(CaO)/w(Al2O3))]为1.7～1.9时,渣相组成主要以七铝十二钙(Ca12Al14O33)和硅酸二钙(Ca2SiO4)为主。当[(w(CaO)/w(Al2O3))]为1.7时,溶出时间为2.0 h时,氧化铝的溶出率最高,溶出率为87.5%,溶出率较0.5 h时提高了9.4%。因此,当渣系组成以七铝十二钙(Ca12Al14O33)和硅酸二钙(Ca2SiO4)为主时,更有利于氧化铝的溶出。     

Phosphorus Capacity of CaO-SiO2-Al2O3-MgO-FexO Slag

The CaO-SiO2-Al2O3-MgO-FexO slag occurs in the production process of Corex ironmaking technology.Most of its metallurgical properties,especially the phosphorus property,are different from the slag produced from blast furnace or converter.In order to explore the dephosphorization ability of CaO-SiO2-Al2O3-MgO-FexO slag,its phosphorus capacity was measured at 1 673 Kby gas-slag-metal equilibrium technique.An iron crucible was used as the reaction vessel,Ag alloy with 0.2% P was used as the metal phase which equilibrated with CaO-SiO2-Al2O3-MgO-FexO slag,and a constant flow of CO-CO2-N2 gas was used to provide oxygen partial pressure in the experiment.The effects of MgO,FexO and basicity on slag phosphorus capacity were investigated by single factor test.The results show that the phosphorus capacity rises firstly and then decreases with increasing MgO content under the condition of basicity 1.3,FexO content of 2% and Al2O3 content of 12%.The phosphorus value reaches maximum as the MgO content is 8%.When the basicity of slag is 1.1,MgO content is 10%,and Al2O3 is 12%,the phosphorus capacity increases with the increase of FexO content.The phosphorus capacity rises linearly when the basicity is increased from 1.1to 1.5.