Reduction leaching of rare earth from ion-adsorption type rare earths ore with ferrous sulfate

The practice of in-situ leaching of the ion-adsorption type rare earths ore with ammonium sulfate could only leach most of rare earth in ion-exchangeable phase,but not the colloidal sediment phase.Therefore,the reduction leaching of rare earth from the ion-adsorption type rare earths ore with ferrous sulfate was innovatively put forward.The soak leaching process and the column leaching process were investigated in the present study.It was determined that ion-exchangeable phase could be released,and part of colloidal sediment phase rare earth could be reduction leached by the cations with reduction properties.The mechanism of reduction leaching was discussed with the Eh-pH diagram of cerium.Moreover,the stronger reduction of reductive ions,the greater acidity of leaching agent solution,and the higher reductive ion concentration,could result in the higher rare earth efficiency and the bigger cerium partition in the leaching liquor.In the ferrous sulfate column leaching process,the rare earth leaching rate and the rare earth efficiency were a little higher than with(NH_4)_2SO_4 agent,and the rare earth efficiency and the partitioning of cerium in leaching liquor could be about 102% and 5.31%,respectively.However,the ferrous sulfate leaching process revealed some problems,so compound leaching with magnesium sulfate and a small amount of ferrous sulfate was proposed to an excellent alternative leaching agent for further studies,which may realize efficiency extraction and be environment-friendly.     

Mineral properties and leaching characteristics of volcanic weathered crust elution-deposited rare earth ore

Weathered crust elution-deposited rare earth ore is an important resource of rare earths, including grantic weathered crust elution-deposited rare earth ore and volcanic weathered crust elution-deposited rare earth ore. The development condition of the weathered crust, weathering degree and mineral composition of these ores will be different because of the differences between their parent rocks and weathered crust causes of mineralogy path. Therefore, mineral properties and leaching characteristics of volcanic weathered crust elution-deposited rare earth ore from Chongzuo(CZ), Guangxi province were investigated. It was found that the CZ rare earth ore was a typical mid-yttrium and rich-europium ore, with the overall rare earth(REE) grade in ion-exchangeable phase of 0.15%. Partide size classification showed that finer particle had a higher REE grade. Column leaching tests showed that the leaching efficiency of REE was above 94% with leaching agent concentration of 0.20 mol/L, liquid-solid ratio of 4:3, flow rate of 0.60 mL/min, and initial pH value around 5.67. Compared to ammonium sulfate leaching, magnesium sulfate leaching was advantaged by nearly zero ammonia nitrogen emission while their REE leaching was almost equivalent.     

羧酸盐复合浸取剂对中重稀土浸出强化研究

以缅甸稀土矿与福建稀土矿为研究对象,采用柱浸工艺方法,研究风化壳淋积型稀土矿的矿石性质,分析乙酸铵添加浓度对风化壳淋积型稀土矿轻、中重稀土浸出的影响。结果表明,缅甸和福建稀土矿分别属于中钇型中重稀土选择型稀土矿和富铕轻稀土选择型稀土矿,并且均存在铈负异常和铕负异常现象。乙酸铵最佳添加浓度为0.04mol/L,稀土浸出可达到浸出平衡,浸出率提升到95%,同时乙酸铵主要通过增强钇元素的浸出,使缅甸稀土矿轻/中重稀土比值从1.04下降到0.98,福建稀土矿轻/中重稀土比值从1.65下降到1.47,表明乙酸铵能够明显提高中重稀土的浸出。     

黑色风化物的物理化学性质及稀土配分研究

某稀土矿产生的黑色风化物，是一种稀土以胶态相赋存的新稀土资源。黑色风化物主要由锰、铁，稀土和铅组成，形成锰铁氧化物非晶质的高聚合度无机高分子。黑色风化物强烈地选择铈族轻稀土，与矿区产的矿石和氟碳铈矿稀土配分相近，但黑色风化物含中重稀土最高，矿石次之，氟碳铈矿最低。     

Effect of Rare Earth on Microstructure of γ-TiAl Intermetallics

The rare earth (RE) elements (Ce, La) were added to binary Ti-47% Al alloys (atomic fraction) by Induction Skull Melting. The element Ce of 1.0 atomic percent was added individually, and La of 0.2 atomic percent was added individually. This article studied the influences of rare earth metal (Ce, La) on microstructure of as-cast TiA1 based alloy by XRD, SEM, EMPA and TEM measurement methodology. The results show that most of rare earth-rich phases (AlCe, Al-La) are uniformly distributed in grain boundary in the shape of discontinuous network, and some particles of rare earthrich phases within the grains are mainly ellipsoids. In addition, rare earth element can obviously refine the grain size and the lamellar thickness of as-cast TiAl based alloy samples. The grain size of Ti-47Al-1.0Ce-0.2La alloy reaches about 30～80μm, and the lameUar thickness of its γ phase and α2 phase are less than 200 and 20nm, respectively.     

有机次膦酸在硝酸体系下提取稀土研究

本文采用溶剂萃取法,用有机次磷酸萃取剂从富含稀土元素镧(La）、钕(Nd）、钇(Y)、铈(Ce）的硝酸溶液中提取稀土。选择盐酸为反萃剂。考察了酸度、萃取剂浓度、相比和萃取时间对萃取率和反萃率的影响,结果表明,二异丁基膦酸萃取稀土的最佳条件为：室温,酸度0.2mol/l,萃取剂浓度40%,A/O比1:5,萃取时间15min,镧（La）、钕（Nd）,铈（Ce）和钇（Y）分别为41.68%、81.30%、81.29%和100%。当利用盐酸作为反萃实验的反萃剂时其最佳条件为：室温,初始水相稀土溶液为0.3 mol/L,反萃剂盐酸为6 mol/L,负载有机相与反萃剂盐酸溶液的体积比为1:6,将反萃的震荡时间改变为5min,应用上述条件的镧(La）、钕(Nd）、铈(Ce）、钇(Y)的反萃率分别为92.45%、94.88%、95.76%、93.34%。有机次膦酸对稀土元素（La）、钕（Nd）、铈（Ce）和钇（Y）的萃取效率不同。钇的提取率高于镧、钕和铈。它是一种有机次膦酸,对轻稀土元素亲和力低,对重稀土元素亲和力强。     

风化壳淋积型稀土矿的基础研究

文章评述了40年来风化壳淋积型稀土矿的基础研究,包括矿床的成因及特征、稀土矿物的组成及性质,稀土与黏土矿物的关系、稀土在黏土矿物中的吸附及迁移理论,论述了风化壳淋积型稀土矿的稀土元素配分的特征及四大效应,并探讨了稀土浸出机理和风化壳淋积型稀土矿稀土浸取的三代工艺,提出了风化壳淋积型稀土矿基础研究和浸出工艺的发展方向及亟待解决的问题.      

铈与YG6硬质合金制备过程中富钙相的交互作用

在硬质合金的原材料仲钨酸铵(APT)粉末中添加Ca和稀土Ce元素,探讨稀土Ce元素与硬质合金制备过程中富钙相的交互作用。材料的物相组成、显微结构及成分分别通过X射线衍射仪、扫描电子显微镜及能谱进行检测与分析。结果表明:氧化钨还原过程中会产生CaWO_4和Ca_(4.26)W_(10)O_(30)两种富钙相,分布在钨颗粒内部和周围,使钨颗粒的棱角钝化,碳化后富钙相转变为Ca_(4.26)W_(10)O_(30)和CaC_2相,富钙相可急剧降低YG6硬质合金的性能;添加适量稀土Ce可降低富钙相对钨粉的影响,钨粉颗粒的棱角变得明显,颗粒尺寸变小且分布均匀,稀土Ce与富钙相发生反应生成Ce_(0.9)Ca_(0.1)O_(1.9)三元相;稀土Ce与富钙相的交互作用效果显著,与1%Ca-YG6硬质合金相比,1%Ce+1%Ca-YG6硬质合金的致密度、硬度和断裂韧性分别提高了7.8%,34.3%和67.8%。     

基于模糊层次分析的稀土资源储备矿种选择

选择离子吸附型稀土矿A 类（富镧少钇型离子矿）、矿种B 类（中钇富铕型离子矿）、矿种C 类（高钇型离子矿）、包头混合型矿种和氟碳铈矿5 类矿种,运用模糊层次分析方法,从稀土资源主要矿种的生产、消费趋势、主要矿种的功能性、前景性、稀缺性、开采的环境危害以及环境治理难度等方面分析了影响选择储备稀土矿种的因素,构建了储备矿种选择的定性和定量指标体系.将定性指标等级分为5 个级别,通过专家打分,进行定性和定量分析后,计算了资源地封存矿种的评价分值.根据评价分值由高到低的顺序,确定资源封存储备矿种的先后顺序为:矿种C 类（高钇型离子矿）、矿种B 类（中钇富铕型离子矿）、矿种A 类（富镧少钇型离子矿）、氟碳铈矿和包头混合型矿种.该模拟计算可为国家决策部门选择储备稀土矿种提供理论依据.      

Recovery of rare earths from ion-absorbed rare earths ore with MgSO4-ascorbic acid compound leaching agent

The magnesium sulfate leaching technology for the ion-absorbed rare earths ore can solve the ammonia pollution problem existing in ammonium sulfate leaching process. However, the leaching capacity of magnesium sulfate is slightly weaker than that of ammonium sulfate, resulting in a bigger consumption of magnesium sulfate. In this paper, the MgSO_4-ascorbic acid compound leaching agent had been demonstrated to deal with the ion-absorbed rare earths ore. The ascorbic acid could form a stable coordination with rare earth ions, so that it can strengthen the leaching of ion-exchangeable phase.Moreover, ascorbic acid has a strong reductive property, it can leach the colloidal sediment phase rare earth as well. The present study investigates the effect of the initial pH and the composition of leaching agent on the rare earth leaching. It is determined that the rare earth leaching efficiency is 107.5% under the condition of pH 2.00,0.15 mol/L magnesium sulfate and 1.0 g/L ascorbic acid in leaching agent. In this case, the content of the ion-exchangeable phase and colloidal sediment phase rare earth in the leaching residues are both only 0.02‰. The leaching efficiency of colloid sediment phase rare earth can be 85.7%,so that the Ce partition in the leaching liquor increases to be 5.77%. The magnesium-ascorbic acid compound leaching agent is proposed to be a promising choice to deal with the ion-absorbed rare earths ore, which can realize the efficient leaching, low consumption of MgSO_4 and environmentally friendly leaching.     

Modification Behavior of Trace Rare Earth on Impurity Phases in Commercial Purity Aluminum

Modifying effect and mechanism of trace rare earth on Fe(Si)-rich impurity phases in commercial purity aluminum were studied with the aids of SEM, EDAX, TEM, etc. It is found that Ce-rich mixed rare earth (RE) is an effective modifying agent, which makes the coarse Fe-rich impurity phases transform into complex compounds of tiny, sphere/short stick form, thus improving mechanical properties of this material; its modifying mechanism is in that RE gathering in front of solid/liquid interface enters into the impurity phases, forming complex (A1FeSiRE) compounds; or is adsorbed in the impurity phases surface, impeding the growth of impurity phases; however, excessive RE will result in the increasing of RE compounds (secondary phases), and plasticity reduction of this material. Therefore, its addition amount should be less than 0.07% (mass fraction).     

A two-parameter model for ion exchange process of ion-adsorption type rare earth ores

The establishment of a mathematical model for the ion exchange process is key to creating a theoretical basis for the mining of ion-adsorption type rare earth ores. Ore samples from Xinfeng, Xunwu and Anyuan were used as the test ore samples in the present study and equilibrium batch tests of ore sample leaching using various ammonium sulfate concentrations were performed. The results show that, after leaching, there is a negative exponential relationship between the ratio of the solid-phase rare earth ion concentration to the aqueous-phase rare earth ion concentration and the initial ammonium ion concentration. However, there is a linear relationship between the natural logarithm of the ratio of the solid-phase ammonium ion concentration to the aqueous-phase ammonium ion concentration and the initial ammonium ion concentration. Based on the above two functional relationships, a two-parameter model for the equilibrium ion exchange process of ion-adsorption type rare earth ores was established. Using the established model to analyze the test data the model error for the Xunwu ore sample is found to be less than 5%. The proposed model is more accurate compared with the Kerr model. The two-parameter model proposed in this study provides theoretical support for the numerical simulation of column leaching (in-situ leaching) of ion-adsorption type rare earth ores.     

Leaching hydrodynamics of weathered elution-deposited rare earth ore with ammonium salts solution

In order to reveal the permeability rule of leaching agent solution and the effects of anions in the leaching process of weathered crust elution-deposited rare earth(RE) ores, the effects of ammonium concentration, temperature, particle size and porosity on the permeability were discussed in detail with(NH_4)2_SO_4, NH_4Cl and NH_4NO_3 as the leaching agent. It was found that the permeation velocity of ammonium salts increased linearly with the increase of hydraulic gradient. The seepage of ammonium salts solution in the RE ores followed Darcy's law and displayed a laminar flow. The properties of the leaching agent solution and RE ores were the main factors that affect the permeability of RE ores. With the decrease of ammonium concentration and increase of temperature, the viscosity of solution decreased and the permeability coefficients of RE ores increased. And the effects of temperature on the viscosity and permeability were larger than ammonium concentration. The permeability of RE ores became worse with the decrease of particle size and porosity, and the particle size played a more important role compared with porosity. The permeability coefficient of RE ores increased and the viscosity of ammonium salts solution decreased in the order of(NH_4)_2SO_4, NH_4Cl and NH_4NO_3, implying that the penetrating power of anions increased in the order of SO_4~(2-), Cl~- and NO_3~-. The results may play a vital role in improving the permeability of weathered crust elution-deposited RE ores.     

Thermodynamics of rare earths in steelmaking

The standard free energies of formation of the oxides, sulfides and oxysulfides of cerium and lanthanum under steelmaking conditions have been calculated and used to predict the behavior of rare earths in steelmaking. Deoxidation and desulfurization constants, expressed in terms of Henrian activities, have been used to construct a precipitation diagram which indicates the sequence of rare earth inclusion formation. An enrichment of lanthanum in (RE)-oxysulfide and cerium in (RE)-sulfide is predicted. It is also predicted that rare earths should be able to reduce the soluble oxygen and sulfur contents of liquid steel well below the contents presently found in most industrial and laboratory practices. A simple method of calculating steelmaking additions for complete rare earth control of inclusion composition is presented. Formerly a Research Engineer at McMaster University     

不同孔隙比下风化壳淋积型稀土矿强度特性

风化壳淋积型稀土开采过程中,孔隙比为影响浸矿效果和矿体稳定性的关键因素.为探索不同孔隙比下风化壳淋积型稀土矿强度特性变化,选取6组重配比的稀土矿样,对不同孔隙比矿样进行了直接剪切实验,探讨孔隙演化对矿体抗剪强度的作用规律,揭示孔隙比对黏聚力和内摩擦角的影响机制.研究表明:不同孔隙比非饱和稀土矿对应着不同的剪切强度,基于试验数据发现剪应力与剪位移呈"类抛物线"变化,并建立了孔隙比与抗剪强度指标的关系模型.机制分析认为,随着孔隙比的增大,结合水膜效应逐渐弱化,粒间接触点数目也随之减少,使矿体抗剪强度减小.      

电感耦合等离子体质谱法测定金属矿中稀土和稀散元素

金属矿中稀土和稀散元素的测定对其综合利用具有重要意义。难溶元素Nb、Ta、Zr、Hf采用酸溶法处理时较难溶解完全,Nb、Ta采用碱熔法处理后再用王水浸取存在不稳定的问题。实验采用偏硼酸锂熔融样品,酒石酸体系浸取,解决了上述Nb、Ta等元素测定中遇到的难题。通过选择待测同位素和干扰校正方法在线校正,以10 μg/L¹⁸⁵Re和10 μg/L¹⁰³Rh为混合内标,采用电感耦合等离子体质谱法(ICP-MS)对浸取液进行测定,实现了对金属矿中La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y共15种稀土元素,及Nb、Ta、Zr、Hf、Ga、Rb、Cd、Cs、In、Tl共10种稀散元素的测定。方法校准曲线的线性相关系数均大于0.999 7,方法检出限为0.03～0.85 μg/g,定量限为0.09～2.55 μg/g。将实验方法应用于铅矿石、钨矿石、钽矿石和锆矿石标准物质中稀土和稀散元素的测定,结果的相对误差(RE)为-5.33%～6.67%,相对标准偏差(RSD,n=12)不大于9.8%。采用实验方法对洛宁铅锌多金属矿区的样品进行测定,结果的相对标准偏差(n=5)不大于9.3%。     

滇东南建水稀土矿稀土数值特征及研究意义

为查明建水稀土矿的稀土数值特征,在长岭岗岩体风化壳的黏土层、全风化层、半风化层、弱风化层中采集了82件样品,进行全相稀土氧化物、离子相稀土氧化物质量分数分析,包括全相稀土氧化物的质量分数、离子相稀土氧化物的质量分数、全相与离子相稀土氧化物质量分数的相关系数、全相稀土氧化物在各个风化层位中的变化系数、离子相稀土氧化物在各个风化层位中的变化系数、结晶相稀土氧化物的质量分数。经资料整理,黏土层、全风化层、半风化层、弱风化层中的稀土数值有明显差异。造成稀土数值差异的主要原因为:成矿母岩的风化程度,稀土矿物离解程度,离子相稀土氧化物的迁移富集程度。加强稀土数值的研究,有助于深化风化壳离子吸附型稀土矿的成矿机理认识。     

2,4-二氯-6-溴偶氮氟膦与稀土的显色反应及其应用

摘 要：对显色剂2,4-二氯-6-溴偶氮氟膦与稀土元素在微波催化下的显色反应进行了研究。在硝酸及少量吡啶介质中,于40℃的微波水浴中加热催化8 min,试剂与各稀土发生显色反应,形成稳定的蓝色配合物。典型稀土元素La、Ce与显色剂的配合比均为1︰3,各稀土配合物的最大吸收波长位于632～636 nm,表观摩尔吸光系数相近,ε为 0.89～1.15×105 L?mol-1?cm-1。以634 nm作为测定波长,改变混合稀土的配分进行试验,结果表明,La、Ce、Y的比例对稀土总量测定的影响不显著。加入四元混合掩蔽剂,采用本方法对岩石等实际样品中稀土总量进行测定,相对标准偏差（RSD, n=5）为2.0%～2.4%,回收率为 93%～98%。     

风化壳淋积型稀土矿浸出液沉淀浮选溶液化学分析

通过对风化壳淋积型稀土矿浸出液沉淀浮选进行溶液化学研究,探讨了体系pH、沉淀剂及浮选剂对沉淀浮选的影响.结果表明,风化壳淋积型稀土矿浸出液杂质可通过优先沉淀浮选以氢氧化物或焦磷酸盐或聚磷酸沉淀形式全部有效除去,最后将优先沉淀浮选除杂后浸出液中和提高pH值,再用沉淀浮选方法有效提取稀土.     

电感耦合等离子体质谱法测定白云鄂博矿石中15种稀土元素总量及其分量

白云鄂博矿物为典型的晶格型矿物,含有铌、锆、钛等难溶金属的矿物,常规酸溶法处理难以将其溶解完全。采用氢氧化钠和过氧化钠碱熔融分解白云鄂博矿石样品,热水浸取,碱分离后,用盐酸和过氧化氢破坏滤纸和溶解沉淀,以1%盐酸为测定介质,通过控制基体质量浓度不大于0.5 g/L和采用Cs内标进行校正以消除基体效应,建立了电感耦合等离子体质谱法(ICP-MS)测定白云鄂博矿石中包括镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥、钇在内的15种稀土元素含量及其总量的方法。实验表明,各稀土元素在质量浓度为5.00~100.0 ng/mL(以氧化物计,下同)范围内和稀土元素与内标元素的强度比呈良好的线性关系,相关系数均不小于0.999 6。方法检出限为0.010~0.034 ng/mL,定量限为0.030~0.10 ng/mL。按照实验方法对白云鄂博矿石样品中稀土元素总量及其分量进行测定,测定结果与电感耦合等离子体原子发射光谱法或X射线荧光光谱法基本一致;相对标准偏差(RSD,n=6)在1.0%~4.9%之间,加标回收率在95%~105%之间。将实验方法应用于稀土矿石成分分析标准物质中稀土元素总量及其分量的测定,结果与认定值基本一致。