Dephosphorisation of high phosphorus oolitic hematite by carbon composite pre-reduction and fast melting separation

High phosphorus oolitic hematite deposit is a kind of refractory iron ore resource of huge amount. At present, it is difficult to be utilised by traditional physical and chemical technology efficiently and economically. A novel process for utilisation of the high phosphorus oolitic hematite based on carbon composite pre-reduction and fast melting separation has been put forward in the paper. High grade pig iron nugget of low phosphorus could be obtained in the present research. The influence of experimental conditions, such as pre-reduction temperature, C/O (molar ratio) and basicity, on the dephosphorisation behaviours was studied in detail. The thermodynamic basis and reduction and melting separation process were also analysed. The phosphorus content in the iron nugget decreased with the increasing of basicity and increased with the increasing of C/O. The optimum parameters were pre-reduction temperature of 1200°C for 30?min, C/O of 0.95 and basicity of 1.7. After melting separation of molten iron and slag at 1400°C for 10?min, the iron nugget containing 0.02?wt-% [P] would be obtained. The dephosphorisation degree and iron yield in the form of iron nugget were 97.5% and 96.9% respectively. The iron nugget may be directly used as the raw materials of steelmaking from the view point of its high grade.     

Innovative Method for Separating Phosphorus and Iron from High-Phosphorus Oolitic Hematite by Iron Nugget Process

This study puts forward a new method to separate phosphorus and iron from high-phosphorus oolitic hematite through iron nuggets process. Firstly, the physical, chemical, and microscopic characteristics of high-phosphorus oolitic hematite are investigated. Then, the reaction mechanisms of high-phosphorus hematite together with feasibility to separating phosphorus and iron by iron nugget process are discussed. Meanwhile, the experiments of high-phosphorus hematite used in rotary hearth furnace iron nugget processes are studied as well. The results indicate that the iron nugget process is a feasible and efficient method for iron and phosphorus separation of high-phosphorus oolitic hematite. The phosphorus content in iron nuggets is relatively low. Through the optimization of process parameters, the lowest of phosphorus in iron nuggets is 0.22  pct, the dephosphorization rate is above 86  pct, and the recovery of Fe is above 85  pct by the iron nugget process. This study aims to provide a theoretical and technical basis for economical and rational use of high-phosphorus oolitic hematite.     

高磷鲕状赤铁矿磷的存在形态及脱磷机理

 针对高磷鲕状赤铁矿石矿物结构复杂导致的脱磷困难现状,为实现深度脱磷的目的,探索矿物还原过程中磷的形态及微观脱磷过程。以铁品位为44.78%、磷的质量分数为0.92%的高磷鲕状赤铁矿为研究对象,根据其面扫描电镜及矿相结构图可知,矿物之间嵌布紧密、逐层形成鲕状结构,石英、鲕绿泥石与赤铁矿等互相包裹,磷元素集中分布在鲕粒内部的氟磷灰石中。通过对焙烧产物做扫描电镜(SEM)及能谱分析(EDS),对高磷鲕状赤铁矿脱磷机理进行研究。研究结果表明,当YM-1脱磷剂质量分数为16%,还原过程中鲕状结构被破坏,金属铁逐渐从鲕粒中析出聚集,脉石与铁颗粒分离明显,磷化为不同形态被脱除。磁选后尾矿、铁分离完全,磷元素几乎全部进入尾矿,添加复合脱磷剂YM-1焙烧磁选后铁精矿的铁品位为90.16%,铁回收率为91.25%,磷质量分数为0.056%,脱磷率为93.91%。铁精粉各项指标满足工业冶炼要求。     

高磷鲕状赤铁矿直接还原法脱磷技术的试验研究

为了经济、合理地利用高磷赤铁矿资源,在掌握试验用高磷鲕状赤铁矿理化特性和微观特性的基础上,采用直接还原法进行了固态直接还原+高强度磁选和直接生产珠铁2种工艺的试验研究。试验结果表明,高温度、低碱度以及高配碳量有利于铁矿石中磷灰石还原进入铁水中,不利于磷的脱除;通过工艺参数的优化,采用固态还原焙烧-磁选工艺,高磷赤铁矿脱磷率能达到60%以上,而采用珠铁工艺,其脱磷率能够达到80%以上。为合理高效地处理高磷鲕状赤铁矿奠定理论基础和技术依据。     

Study on Phosphorus Removal of High-Phosphorus Oolitic Hematite by Coal-Based Direct Reduction and Magnetic Separation

In this article, mineralogical phase changes and structural changes of iron oxides and phosphorus-bearing minerals during the direct reduction roasting process were investigated by X-ray diffraction (XRD) and scanning electron microscope (SEM). It has been found that the reduction of hematite follows the following general pathway: Fe₂O₃ → Fe₃O₄ → FeO → Fe. The last step of the reduction process contains two side reactions: either FeO → Fe₂SiO₄ → Fe or FeO → FeAl₂O₄ → Fe depending on the micro mineralogical makeup of the ore. In the reduction process of FeO → Fe, oolitic structure was destroyed completely and fluorapatite was diffused into gangue while metallic phase is coarsening at temperatures below 1200°C. Therefore, the separation of phosphorus-bearing gangue and metallic iron can be achieved by wet grinding and magnetic separation, and low phosphorus content metallic iron powder can be obtained. However, when the temperature reached 1250°C and beyond, some of the fluorapatite was reduced to elemental P and diffused into the metallic iron phase, making the P content higher in the metallic iron powder.     

恩施高磷鲕状赤铁矿煤基直接还原的试验

 为最大限度地利用恩施黑石板地区的铁矿资源,先通过XRD、扫描电镜、金相显微镜等手段研究了它的矿相组成和结构,得知其主要成分是赤铁矿和石英,矿的显微结构以鲕粒群簇为主,鲕粒中赤铁矿与磷灰石呈环带状分布。矿相结构决定了用一般的选矿方法分离铁、磷非常困难,为此用实验室煤基直接还原法研究了还原温度、还原时间、煤种、添加剂、磁选工艺等对精矿中铁品位和铁回收率的影响规律,得到了提高还原率的合理工艺参数：以哈密煤为还原剂,焙烧还原温度1573K,还原时间40min,一段磨矿时间15min,磁场强度280kA/m。采用此工艺可使精矿产率、铁品位、铁回收率分别达到43.21%、 95.77%和92.18%,磷品位由0.76%降至0.097%。该研究为该地区高磷鲕状赤铁矿工业化的开发利用提供了依据。     

隐晶质鲕状赤铁矿磁化焙烧过程中铁物相转变规律

摘要：鲕状赤铁矿具有含磷高、易泥化,铁与脉石矿物呈鲕状嵌布结构等特点,常规的重选和浮选等工艺难以取得较好的选矿指标。磁化焙烧-磁选工艺是利用高磷鲕状赤铁矿最有效的手段之一。X射线衍射（XRD）分析结果表明,在750℃的条件下,焙烧矿中磁铁矿的相对质量分数最大。焙烧温度高于800℃会发生过还原现象,生成富氏体,不利于焙烧矿的弱磁选。光学显微镜分析表明磁化焙烧过程不会破坏鲕状赤铁矿的鲕粒结构,只发生铁物相的转变。赤铁矿到磁铁矿的晶型转变由表及里,但是多数鲕状赤铁矿颗粒不会完全磁化,磁化焙烧效果与粒度有关。全铁品位为43.74%的矿样,在焙烧温度750℃、焙烧时间60min的条件下,弱磁选可得到全铁品位为55.42%,铁回收率为85.66%的人工磁铁矿,磁铁矿转化率在90%以上。     

Phosphorus Removal and Iron Recovery from High-Phosphorus Hematite Using Direct Reduction Followed by Melting Separation

To efficiently utilize high-phosphorus oolitic hematite resources, a method using direct reduction followed by melting separation was proposed. In this study, direct reduction behavior of the ore–char briquette and the melting separation behavior of the reduced briquette were investigated. Direct reduction test results show that under investigated conditions, the briquette reached a metallization rate of 80%–88% and a residual carbon value of 0.11–4.85 wt%,and apatite layers were fragmented into tiny particles, some of which were embedded in metallic iron phase. Melting separation test results show that residual carbon can significantly influence the iron recovery rate. For metallic briquettes with the abovementioned qualities, the iron recovery rate ranged from 75% to 98%. To control the phosphorus content in molten iron to be nearly 0.4 wt%, an iron recovery rate of 80% was shown to be adequate.     

Effect of Microwave Treatment Upon Processing Oolitic High Phosphorus Iron Ore for Phosphorus Removal

Influence of microwave treatment on the previously proposed phosphorus removal process of oolitic high phosphorus iron ore (gaseous reduction followed by melting separation) has been studied. Microwave treatment was carried out using a high-temperature microwave reactor (Model: MS-WH). Untreated ore fines and microwaved ore fines were then characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and thermogravimetric analysis (TGA). Thereafter, experiments on the proposed phosphorus removal process were conducted to examine the effect of microwave treatment. Results show that microwave treatment could change the microstructure of the ore fines and has an intensification effect on its gaseous reduction by reducing gas internal resistance, increasing chemical reaction rate and postponing the occurrence of sintering. Results of gaseous reduction tests using tubular furnace indicate both microwave treatment and high reduction temperature high as 1273 K (1000 °C) are needed to totally break down the dense oolite and metallization rate of the ore fines treated using microwave power of 450 W could reach 90 pct under 1273 K (1000 °C) and for 2 hours. Results of melting separation tests of the reduced ore fines with a metallization rate of 90 pct show that, in addition to the melting conditions in our previous studies, introducing 3 pct Na₂CO₃ to the highly reduced ore fines is necessary, and metal recovery rate and phosphorus content of metal could reach 83 pct and 0.31 mass pct, respectively.     

云南某高磷鲕状赤铁矿提铁降磷试验研究

云南某鲕状赤铁矿磷含量高达0.87%,铁品位为45.14%。对此矿石进行单一的强磁选及反浮选试验研究,结果表明都不能获得磷品位低于0.2%,铁品位较高的铁精矿。采用强磁-反浮选及脱泥-反浮选均能获得磷品位低于0.2%,铁品位高于52%的铁精矿。脱泥-反浮选具有投资成本低,流程结构简单的优势,推荐采用此流程处理该矿石。该研究对开发此类高磷鲕状赤铁矿具有一定的借鉴意义。     

Coupled reaction kinetics of duplex steelmaking process for high phosphorus hot metal

Abstract

The duplex steelmaking process has been proven to be an effective solution for the utilisation of high phosphorus iron ore, yet systematic analyses of the dephosphorisation rate and mechanism of duplex process for high phosphorus hot metal are seldom reported. Comprehensive exploration and discussion on the kinetics of duplex steelmaking process for high phosphorus hot metal are thus required. First, based on the kinetic model proposed by Robertson et al., a modified coupled reaction kinetic model was formulated and employed to analyse the dephosphorisation process of duplex melting for high phosphorus hot metal. Furthermore, a series of experiments were carried out to validate the accuracy of the established model, and the calculated results showed good agreement with the experimental data. Finally, a parametric study was conducted to perform a further discussion of the mechanism of duplex steelmaking process for high phosphorus hot metal.     

高磷鲕状赤铁矿铁磷分离试验研究

对高磷鲕状赤铁矿进行了显微结构研究,采用添加脱磷剂直接还原焙烧-磁选工艺进行了铁和磷分离试验,研究了焙烧温度、内配碳量、添加剂配比对铁、磷分离主要技术指标的影响。结果表明:磷主要以磷灰石的形态嵌布在鲕状结构中,部分与赤铁矿形成环状间层,层间的厚度变化范围在3~15μm之间;在焙烧温度1 000℃、内配碳量6%、添加剂配比10%的优化工艺条件下,通过球磨-磁选试验可得到含铁品位大于85%、含磷量在0.15%~0.20%之间的优质还原铁粉和含磷为3.5%~4%的富磷渣。     

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The coal- based direct reduction- magnetic separation was adopted to deal with the high phosphorus oolitic hematite after the mineral composition and structure of this ore were identified by XRD and SEM, and the factors which effected the process were studied and analyzed. The results show that the optimum process condition is temperature of 1250??, time of 30min, carbon/oxygen ratio of 1. 8 and basicity of 0. 8, under this condition , the magnetic concentrate yield is 47. 68%, concentrate grade is 86. 51%, recovery rate of iron is 92. 94%, phosphorus content is 0. 18% and metallization rate is 92. 56%, the recovery rate of phosphorus of tailing is 92. 88%.     

Transforming Hematite into Magnetite Using Mechanochemical Approach as a Pretreatment of Oolitic Hematite

Potential transformation of oolitic hematite into magnetite by mixing iron powder using the mechanochemical method has been achieved and discussed in this paper. The phase transition of pure hematite in the preliminary test was identified by X-ray diffractometer (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) techniques. The experimental results have shown that the crystallographic planes of magnetite, (220), (311), (400), and (511) were observed clearly in the Fe/α-Fe₂O₃ mixture after milling for 15 h, indicating that α-Fe₂O₃ had been effectively transformed into Fe₃O₄. The diffraction peaks of magnetite were also observed at d = 0.29605 nm (2θ = 30.163°), 0.25226 nm (2θ = 35.559°), 0.24156 nm (2θ = 37.190°), and 0.20898 nm (2θ = 43.458°) after 13 h milling-time. It suggests that the oolitic hematite is transformed into magnetite successfully by mechanochemical processing. The processing might be applied potentially for the magnetic separation of oolitic hematite.     

高磷鲕状赤铁矿深度还原过程中磷的迁移规律

 针对鄂西某地高磷鲕状赤铁矿进行了深度还原技术研究,考查了还原温度、还原时间、配碳系数和CaO添加量对磷迁移规律的影响。结果表明：进入铁粉中磷的品位和回收率随着还原温度的升高和还原时间的延长而升高,随着配碳系数的增大先升高后降低,并在配碳系数为2.0时达到最大;而受CaO添加量的影响较小。还原物料的XRD和SEM分析表明大部分磷被还原为单质迁移进入了铁粉中。对高磷鲕状赤铁矿深度还原过程中磷的迁移规律进行了初步探索,为进一步研究高磷鲕状赤铁矿提供了一定的理论基础。     

温度对高磷鲕状赤铁矿含碳球团直接还原影响

对高磷鲕状赤铁矿含碳球团直接还原进行了研究。结果表明,1100℃以下时,提高温度可以显著提高球团金属化率;1100℃以上时,继续提高温度对球团金属化率影响不大。球团金属化率越高,磁选精矿铁品位越高。还原温度不仅显著影响球团的金属化率,还影响金属铁相的长大及磁选效果。因此,控制适宜的温度对高磷鲕状赤铁矿含碳球团直接还原至关重要。     

Enrichment of phosphorus in reduced iron during coal based reduction of high phosphorus-containing oolitic hematite ore

With the objective of phosphorus enrichment in the metallic iron during coal based reduction, high phosphorus oolitic hematite ore was reduced in the presence of coal with the coal/ore molar ratio (C/O, the molar ratio of fixed carbon in coal to oxygen in iron oxides of ore) varying from 1·0 to 2·5 at temperatures ranging from 1473 to 1548 K. The metallic iron was beneficiated from reduction products by magnetic separation. The results showed that the enrichment of phosphorus in the metallic iron improved with increasing temperature and C/O molar ratio. The phosphorus content and the phosphorus enrichment could reach 2·5 and 77·5%, respectively, with a C/O molar ratio of 2·5 at 1548 K and after 60 min reduction. The high phosphorus-containing metallic iron so obtained could then be converted to steel and high phosphorus steelmaking slag that can be used as a phosphate fertiliser. Kinetic analysis demonstrated that the process of phosphorus enrichment in the metallic iron could be divided into two stages, early and late, described by phase boundary controlled reaction and diffusion controlled, respectively. At the early stage, the apparent activation energy and pre-exponential factor of phosphorus enrichment decreased from 182·12 kJ mol^?1 and 9509·06 min^?1 to 132·60 kJ mol^?1 and 395·44 min^?1, respectively, when the C/O molar ratio was increased from 1·0 to 2·5. At the later stage, the apparent activation energy and pre-exponential factor were 245·87 kJ mol^?1 and 172?818·99 min^?1 at a C/O molar ratio of 1·0, respectively, whilst those were reduced to 210·73 kJ mol^?1 and 13?930·28 min^?1 at a C/O molar ratio of 2·5.     

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%.     

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.     

Selective separation of iron and scandium from Bayer Sc-bearing red mud

In this study, we investigated the separation of iron and scandium from Sc-bearing red mud. The red mud object of our study contained 31.11 wt% total iron (TFe), 0.0045 wt% Sc, hematite (Fe₂O₃) and ferrosilite (FeO·SiO₂) as the main Fe-bearing minerals. The Sc-bearing red mud was treated by a novel deep reduction roasting and magnetic separation process that includes the addition of coke and CaO to extract Fe and enriching Sc from the Sc-bearing red mud. The addition of coke and CaO enhances the transformation of hematite (Fe₂O₃) to metallic iron (Fe⁰) and magnetite (Fe₃O₄) as well as the transformation of ferrosilite into metallic iron (Fe⁰). The test results show that utilizing the new process a Fe concentrate with a TFe content of 81.22 wt% and Fe recovery of 92.96% was obtained. Furthermore, magnetic separation tailings with Sc content of 0.0062 wt% and Sc recovery of 98.65% were also obtained. The test results were achieved under the following process conditions: roasting temperature of 1373 K, roasting time of 45 min, calcium oxide dosage of 20 wt%, coke dosage of 25 wt%, grinding fineness of 90% < 0.04 mm, and magnetic field intensity of 0.24 T. The major minerals in the Fe concentrate are metallic iron (Fe⁰) and magnetite (Fe₃O₄). The main minerals in the magnetic separation tailings with a low TFe content of 2.62% are CaO·SiO₂, Na₂O·SiO₂, FeO·SiO₂, Ca₃Fe₂Si₃O₁₂, CaAl₂SiO₆ and CaFe(SiO₃)₂.