Removal of Phosphorus From High Phosphorus Iron Ores by Selective HCl Leaching Method

  The selective HCl leaching method was used to remove phosphorus from high phosphorus iron ores. The hydroxyapatite in high phosphorus iron ores was converted into soluble phosphate during the process of HCl leaching. The effects of reaction time, particle size, hydrochloric acid concentration, reaction temperature, liquid solid ratio and stirring strength on the dephosphorization ratio were studied. The results showed that the dephosphorization ratio can exceed 98% under the conditions of reaction time 30-45 min, particle size ＜0147 mm, hydrochloric acid concentration 25 mol/L, reaction temperature 25 ℃, liquid solid ratio 5∶1 and stirring strength 502-1276 s-1. After dephosphorization reaction, the content of phosphorus in iron ore complied completely with the requirements of steel production.     

高磷铁矿石脱磷技术研究现状及发展趋势

高磷铁矿石的选矿已成为国内外的一大选矿技术难题,本文总结了当前国内外高磷铁矿脱磷工艺的研究现状及方法,从我国高磷铁矿选矿技术现状和高磷铁矿选铁脱磷工艺存在的问题进行了综述和分析,提出开发高磷铁矿石的提铁降磷工艺的发展方向及趋势.     

SiO2、Na2CO3对预还原烧结过程中气化脱磷的影响

白云鄂博铁精矿磷含量较高为0.08%(质量分数),且磷元素主要以氟磷灰石的形式存在。基于前期白云鄂博矿磷的赋存状态及白云鄂博矿预还原烧结工艺对脱磷影响的研究,同时为了开发利用其他中、高磷铁矿,研究了白云鄂博铁精矿预还原烧结过程中磷的气化脱除机制。利用FactSage热力学软件、XRD、SEM-EDS对比分析不同SiO2、Na2CO3添加量对预还原烧结过程中气化脱磷率、金属化率以及物相转变的影响。结果表明:最佳的SiO2、Na2CO3添加量(质量分数)分别为3%、1%,对应的脱磷率为31%,金属化率为96%,实现了预还原烧结过程中磷的有效脱除,进一步明确预还原烧结脱磷机制,为以后中、高磷铁矿脱磷的研究指明了方向。     

配加高磷铁矿的烧结杯实验

在固定碱度和MgO含量等条件下,进行了配加高磷铁矿的烧结杯实验,研究了烧结过程、烧结矿性能及适宜配碳量,为工业应用高磷铁矿提供参考;通过烧结前后磷的存在形式变化,分析了磷的转化机理,探讨了烧结脱磷的可行性。     

高磷鲕状铁矿酸浸脱磷

研究了酸浸处理高磷铁矿脱磷及其影响因素.实验用鄂西鲕状高磷矿Fe的质量分数为51.7%,P的质量分数约0.5%,S的质量分数为0.34%.通过硫酸浸出,浸出矿中磷的质量分数降低至0.07%左右,而铁损只有0.18%,S的质量分数为0.35%,满足钢铁生产的要求.通过扫描电镜观察和能谱分析表征了高磷矿中磷的脱除,在实验酸度下能明显看出磷灰石溶解,而铁相基本不反应,并得到了热力学计算证明.实验确定了最佳的酸浸条件:浸出时间1 h,液固比100mL:8 g,酸度0.2 mol·L-1,振荡频率150 Hz.通过微波加热预处理,高磷铁矿中产生微裂纹,增加了矿石的比表面积,但是这并没有明显促进酸浸脱磷的进行.通过补酸的方式循环利用酸浸液处理高磷铁矿能得到较好的脱磷效果,脱磷率稳定在80%,能有效减少酸耗、保护环境.      

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%.     

高磷鲕状铁矿直接还原?磁选提铁降磷扩大试验研究

为给回转窑工业试验提供参数,以小型试验最佳结果为基础,进行了高磷鲕状铁矿煤基直接还原?磁选提铁降磷扩大试验。结果表明,在最佳的条件下可获得铁品位94.17%、铁回收率77.47%以及磷质量分数0.08%的粉末还原铁,推荐的回转窑工业试验初始条件为:石灰石用量（质量分数）28%、无烟煤用量（质量分数）16%、还原温度1300 ℃,还原时间3 h。采用XRD以及SEM-EDS研究了无烟煤的作用机理,发现无烟煤用量增加,促进了浮氏体、镁铁尖晶石的还原以及铁颗粒长大,从而提高了铁的回收效果,但过多的无烟煤通过增强还原气氛及其带入的灰分消耗了石灰石,使铁矿物中的磷以及磷灰石还原成单质磷并与铁颗粒形成铁磷合金。      

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%。     

高磷鲕状赤铁矿酸浸脱磷动力学

在HSC6.0计算软件热力学分析的基础上,采用正交实验确定了高磷鲕状赤铁矿酸浸脱磷保铁的最佳工艺,并以最佳工艺为基础进行了酸浸过程中脱磷和铁损反应的动力学研究。热力学分析表明H_2SO_4为最佳酸浸用酸。正交实验得出最佳酸浸条件为:H+浓度为0.5mol/L的H_2SO_4溶液、酸浸时间40min、温度298K、液固比200mL∶14g、搅拌速度100r/min。在该条件下,脱磷率可达98.89%,铁损率仅为0.51%。通过SEM-EDS对酸浸前后高磷鮞状赤铁块矿试样分析表征得出:经H_2SO_4浸出后,磷灰石基本完全溶解,含铁矿相未发生明显反应。动力学分析显示:优化条件下,酸浸脱磷反应在298~328K内符合收缩未反应核模型,浸出过程主要受内扩散控制,表观活化能为11.24kJ/mol;铁损反应在298~328K内遵循收缩未反应核模型,浸出过程主要受化学反应控制,表观活化能为42.24kJ/mol。     

高磷铁矿脱磷技术现状及磷资源化提取新方法

 为了提高磷铁矿作为炼铁原料的使用率,对高磷铁矿中磷元素的降低和脱除技术（选矿法、化学浸出法、生物浸出法、高温脱磷法）的特点及发展现状进行了综合评述,并从磷的资源化利用的角度探讨其提取与利用的可能性。介绍了一种基于湿法酸浸-生物吸附方法提取高磷铁矿或高温脱磷渣中磷资源新工艺技术,对其基本原理、工艺流程与技术特点进行了讨论。该提磷新方法的最大优势在于可以从pH值为1～2的酸浸溶液中直接选择性地吸附脱磷,使酸液得以循环使用,而磷也可解吸成高纯度的磷酸盐得以回收,吸附剂本身则可以多次循环使用。     

Improvement of Sinter Properties With Ultra Fine-Sized Iron Concentrate by HPRG

The experiments were conducted on the changes of sintering performance of one kind of ultra fine-sized iron concentrate with or without being processed by high pressure roll grinding (HPRG). The experimental results indicate that the specific surface area increases from 1723. 0 to 2201. 6 cm²/g when the iron concentrate is processed by HPRG. The permeability of sintering mix increases and the iron concentrate becomes easy to react with CaO reagent at high temperature. The effect gets intensified when iron concentrate and lime are processed together by HPRG. The further studies indicate that compared with the base case, the sinter quality also gets improved, in which the yield of sinter increases from 67.24% to 69. 52% and further to 71. 68%, the tumble index (TD increases from 60. 38% to 62. 13% and further to 64. 45%, and the productivity increases from 1. 42 to 1. 57 t/(m² · h) and further to 1. 62 t/(m² · h) when the iron concentrate is processed by HPRG or is processed with lime together. The metallurgical properties of sinter also get improved when the iron concentrate is pretreated by high pressure roll. The results indicate that it is conducive to the increase of sinter quality and productivity when the iron concentrates are processed by HPRG.     

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.     

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,...     

鲕状赤铁矿微波加热还原提铁脱磷机制

采用微波加热还原鲕状赤铁矿内配碳球团,考察了还原温度、碱度及添加剂用量对球团含磷组元迁移的影响,对微波碳热还原提铁脱磷机制进行了分析。结果表明,随着还原温度的升高含磷组元逐渐被还原,当还原温度达到1 150℃以上时含磷矿物被大量还原,并且富集到还原铁中造成还原铁粉磷含量过高。在较低还原温度下,通过选择合适的碱度和脱磷剂用量,能有效地抑制含磷组元的还原,促进铁氧化物的还原和聚集。实验采用原矿粒度0.8 mm、碱度0.8、碳氧摩尔比1.0、钠盐添加剂用量20%(质量分数)、还原温度为950℃保温10 min的条件对物料进行还原,将还原物料研磨到0.074 mm在65 mT的场强下进行磁选可得到全铁质量分数82.79%、回收率86.49%、P质量分数0.34%的指标,所得到的还原铁粉杂质较少,而含磷物质主要以磷酸盐的形式存在于磁选渣中。     

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.     

富氧顶吹熔融还原冶炼高磷铁矿与钛铁矿配矿的试验研究

采用模拟HIsmelt的富氧顶吹熔融还原技术冶炼惠民高磷铁矿与勐桥钛铁矿配矿,在温度为1 500K,碱度为1.3,配碳比为1.0的条件下,恒温时间20min(在升温过程中,没有通入惰性气体),恒温过程中通入O2(流量250L/h、纯度为99%)10min。恒温时间结束后,调整氧气流量为5L/h,保持其氧化性气氛至冷却。研究了不同配矿比例对铁回收率、生铁中磷、硫含量以及磷、硫分配比的影响。研究结果表明,在惠民铁矿和勐桥精矿的比例为1∶1时,其冶炼结果比较理想:铁的回收率为95.1%,生铁中磷的质量分数约为0.32%,硫的质量分数为0.054%,钛的质量分数为0.031%。     

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.     

锰矿石脱磷新工艺的研究

研究开发出一种高磷碳酸锰矿的化学脱磷新方法:加氯化钙焙烧—稀盐酸浸出法。实验室试验表明,用此法处理花垣锰矿的两种高磷磁选精矿,最终产品锰品位提高约0.5倍,锰回收率达98％,磷锰比由0.01～0.013降低到0.002—0.0021,脱磷率达80—85％。指标优于其他方法,盐酸用量仅为黑锰矿法的22％。     

酸浸对废旧电池回收磷酸铁中杂质的去除作用

伴随着锂离子电池大规模退役潮的来临,废旧电池对环境的危害逐渐凸显,废旧电池中的有价金属作为“城市矿山”的资源化利用也受到了广泛关注。目前的回收工艺主要集中于提锂,而对提锂后的废渣关注度不够。以废旧磷酸铁锂电池材料提锂后的磷酸铁为研究对象,提出直接酸浸提纯工艺,通过改变浸出液的浓度、浸出时间、浸出次数等工艺参数,获得纯度较高的磷酸铁。结果表明,在原材料球磨处理、高温高压、水热反应等条件下,Al、Cu、Ca、Ni杂质元素的浸出率分别为36%、51.35%、89.48%、90.91%,说明酸浸对废旧电池回收磷酸铁中杂质具有明显的去除作用。试验结果为实现从废旧磷酸铁锂材料中回收碳酸锂和磷酸铁再制备磷酸铁锂的完整再生循环过程提供基础。     

高磷低品位锰矿浓酸熟化脱磷试验研究

提出用拌浓酸熟化的方法对难选贫锰矿进行脱磷正交试验研究,考察了浓酸用量、熟化时间、矿石粒度对脱磷效果的影响。实验表明：浓酸用量和矿石粒度对脱磷效果影响显著。该锰矿拌浓酸熟化处理最优工艺条件：浓硝酸用量100％,时间12h,粒度-0．125＋0．1mm。在最优工艺条件下,锰矿品位从11．56％提至44．23％,P／Mn从0．0126降至0．0056,锰回收率达93．68％,达到,台金用锰矿石标准AMn45Ⅲ的技术指标。