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。     

Recovery of metallic iron from high phosphorus oolitic hematite by carbothermic reduction and magnetic separation

Abstract

This study aims to provide theoretical and technical basis for economical and rational use of high phosphorus oolitic hematite. Following physical, chemical and microscopic characterisation of high phosphorus oolitic hematite ore the feasibility of separation of phosphorus and metallic iron by reduction roasting and magnetic separation process were investigated. The results indicate that such a process is a feasible and efficient method for iron and phosphorus separation of high phosphorus oolitic hematite. The recovery of metallic iron and dephosphorisation rate is relatively low without additives but is significantly improved by appropriate CaO and Na₂CO₃ addition. With 8%CaO and 3%Na₂CO₃ the recovery of metallic iron and dephosphorisation rate reach 95.1 and 94.0% respectively.     

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。     

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。     

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。     

高铝高硫低品位铁矿粉还原熔分制备珠铁

 基于转底炉珠铁工艺,以一种高铝高硫低品位铁矿粉和无烟煤为原料,在实验室条件下进行了还原熔分试验研究,考察了温度、配碳量、碱度和添加剂对高铝铁矿含碳球团还原熔分行为的影响,并分析了碱度和添加剂对珠铁中硫质量分数的影响。试验结果表明,温度为1 350～1 450 ℃时,空白球团熔分效果较差,金属铁渗碳量较低;提高配碳量,金属铁渗碳量略有增加,但熔分效果仍较差;碱度增加会促进球团还原,1 450 ℃时,碱度为0.6、0.8、1.0、1.2的球团可以实现渣铁良好分离,珠铁中硫质量分数逐渐降低,碱度为1.2时降低较明显;Na2CO3配比增加,球团熔分也会逐渐变差,1 450 ℃时球团基本均可以熔分,珠铁中的硫质量分数逐渐降低,但脱硫效果不明显;当碱度为1.2、Na2CO3配加为8%、CaF2配加为4%时,球团可以在1 450 ℃下良好熔分,脱硫效果显著,珠铁中硫质量分数为0.085%,脱硫率达到96.5%,所得珠铁基本满足炼钢要求。     

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%.     

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。     

鲕状高磷赤铁矿熔融还原过程脱磷技术研究

针对"宁乡式"鲕状高磷赤铁矿的矿物学特点,研究用熔融还原法处理"宁乡式"鲕状赤铁矿脱磷的技术。热力学及动力学分析和熔融还原脱磷实验表明,碱度、萤石比例等因素影响脱磷率。鲕状高磷赤铁矿熔融还原过程中配加CaO、CaF2脱磷效果显著,脱磷率最高可达97.3%。合适的二元碱度在1.8~2.2之间,CaF2的合理加入量在6%~9%。     

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%.     

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.     

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.     

微波作用高磷铁矿提铁脱磷的研究

为充分利用高磷铁矿,进行了微波作用高磷鲕状赤铁矿煤基碳热还原提铁脱磷的研究.高磷铁矿经微波作用碳热还原、细磨和磁选,其脱磷率达到87.8%,收铁率达到90%.本文从晶格能、热力学和动力学方面分析了微波强化高磷铁矿提铁脱磷的作用机理,探讨了微波应用于高磷铁矿提铁脱磷的可能性.结果表明:微波可以加快铁矿石碳热还原反应速率,...     

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。     

微波还原-磨矿磁选对鲕状赤铁矿提铁脱磷的影响

摘要：采用微波加热还原 磨选技术研究鲕状赤铁矿的提铁脱磷条件,且探索最佳磨选条件。在原矿粒度小于0.18mm占90%、配碳系数1.0、碱度系数0.8、脱磷剂用量15%（质量分数）的条件下,采用微波加热在950℃下还原30min获得金属化球团,对金属化球团进行破碎、研磨,考察磨矿粒度、磁选强度对铁粉铁品位、回收率、P含量、脱磷率的影响规律,并对还原样品、磁选后的铁粉和非磁性渣进行了扫描电镜、能谱和X射线衍射分析。研究结果表明,金属化球团在研磨粒度小于0.045mm占62.90%、磁选强度65mT条件下,可获得铁粉铁品位87.69%、回收率77.86%、P质量分数0.30%、脱磷率86.37%。     

红土镍矿选择性还原-熔分制备镍铁合金

以硅镁型红土镍矿为原料,采用金属化焙烧-熔分工艺,通过正交试验制备金属化球团,将所得金属化球团在1500℃条件下熔融分离30 min提取镍铁合金,考察影响因素对实验结果的影响.结果表明:在选择性还原制备金属化球团过程中,对金属化率的影响程度从大到小的因素依次是C/O摩尔比、焙烧温度、焙烧时间和碱度;实验可获得镍品位19%的镍铁合金;在碱度为0.8-1.2范围内,S和P分配比随着碱度的升高而增大.利用X射线衍射和扫描电镜对金属化球团及熔融分离出的渣进行微观分析,发现加入的石灰石与复杂矿相反应可释放出简单镍氧化物和铁氧化物,促进还原反应的进行,当石灰石不足时,少量铁以Fe3+的形式存在于铁金属化率70%的金属化球团中.      

Dephosphorisation of ferromanganese alloy using rare earth oxide-containing slags

The phosphates of rare earth (RE) metals are highly stable in natural environment, and RE oxides have higher optical basicity than CaO and BaO. Therefore, the thermodynamic conditions for dephosphorisation using RE oxide-containing slags are expected to be favourable. Factors influencing the efficiency and Mn loss during the dephosphorisation of ferromanganese using RE oxide-containing slags were studied. An increase in the dephosphorisation temperature up to 1673?K (1400°C) is beneficial to the process and decreases Mn loss, and the maximum degree of dephosphorisation for slags containing 6 wt% RE oxides are 47.44 and 50.85%, corresponding to the minimum values of Mn loss are 1.64 and 1.35% at 1673?K (1400°C); further temperature increases would deteriorate the dephosphorisation efficiency and lead to an obvious increase in Mn loss. An increase in the quantity of pre-melted slags, and of their RE oxide content, improves the dephosphorisation efficiency but inevitably leads to a more pronounced Mn loss. It was also found that an increase in Si contents above 0.25 wt% in the ferromanganese alloys not only deteriorates the dephosphorisation efficiency but also increases the Mn loss; and the dephosphorisation efficiency decreases to almost zero when the silicon content increases up to 0.62 wt%.