Enhancing mineral liberation of a Canadian rare earth ore with microwave pretreatment

Liberation, as an attribute of mineralogy characteristic, whose impacts on finely disseminated Canadian rare earth ore was studied with microwave pretreatment. Samples of a light rare earth ore along with mostly ankerite and biotite as dominant gangue minerals as well as bastnaesite, strontianite and goethite as dominated minerals were exposed to further comminution by ball mill and microwave pretreatment fragmentation. Mineralogical characteristics were analyzed by using a mineral liberation analyzer (MLA). The results indicated that tight association mutually penetrates among dominated minerals in the range size of ?300 + 212 μm and ?212 + 150 μm and gangue minerals in the form of adjacent type, fine vein type, shell type and packing type. Temperature in the ore samples pre-treated by microwave can rapidly rise to 250 °C with microwave power of 0–1.5 kW and microwave time of 0–2 min. Applying the microwave pretreatment merely reduces the hardness of the ore causing the fracture of rare earth ore, but this does not transform or change the original mineralogy characteristics of the ore samples. On the basis of above study, the liberation value of bastnaesite, strontianite and goethite with microwave pretreatment is greater than with conventional comminution when the liberation class is above 75%. The distribution of particle size of rare earth ore samples is better with microwave pretreatment than with conventional comminution for particle size of 7.4 × 10^?5 m. With microwave pretreatment, the theoretical grade–recovery of bastnaesite, strontianite and goethite in the rare earth ore attains better results than with conventional comminution at a given grade.     

电感耦合等离子质谱法测定离子型稀土原矿中离子相稀土总量

采用电感耦合等离子质谱法(ICP-MS)直接测定离子型稀土原矿中离子相稀土总量,实验对浸取溶液、浸取溶液的浓度及用量、被测元素的同位素、样品酸度、内标元素、仪器的最佳工作参数进行了选择,建立了优化分析条件.单一元素标准加入的回收率为95%~105%,离子相稀土总量回收率为98.4%,相对标准偏差小于5%,测定范围为:0.010%~0.50%.方法准确可靠,操作简单,精密度和准确度都能满足分析要求.     

Anti-swelling mechanism of DMDACC on weathered crust elution-deposited rare earth ore

In order to inhibit the swelling of the clay minerals in the in-situ leaching process of weathered crust elution-deposited rare earth ores (WCE-DREO), diallyl dimethyl ammonium chloride (DMDACC) was introduced as an anti-swelling agent and combined with (NH₄)₂SO₄ as a novel composite leaching agent. It can be found that the novel composite leaching agent exhibits a good anti-swelling performance and leaching capacity of rare earth, and has great potential on the actual exploitation of WCE-DREO. The anti-swelling mechanism of DMDACC was studied by characterization analysis. The results show that DMDACC with positive charges can be adsorbed on the clay particles by the electrostatic attraction and hydrogen bonds, and neutralize the negative charge of the clay particles. The double electrical layers are suppressed and the repulsion force between clay sheets decreases. It causes the clay particles prone to aggregate. Moreover, DMDACC can enter the interlayer and expel out the water molecules in interlayer. The interlayer spacing is decreased and the hydration swelling of the clay particles is weakened. It can provide a theoretical basis for the development of novel anti-swelling agents.     

某含银多金属矿石工艺矿物学研究

对某含银多金属矿石的工艺性质进行了重点研究,包括矿物组成、嵌存状态、粒度分布等。同时,对超出显微镜分辨能力的次显微银采用扫描电镜进行系统研究。测定结果表明:矿石中银矿物主要为含银黝铜矿、辉铜银矿、硫锑铜银矿、银黝铜矿、辉银矿、碲银矿、角银矿、自然银等;银矿物与黝铜矿嵌存关系密切,而黝铜矿主要嵌存在方铅矿中,黝铜矿、方铅矿为银矿物的主要载体矿物。矿石的工艺矿物学研究为选矿工艺流程和条件试验的确定提供可靠数据,使选矿试验获得理想的回收指标。     

MLA自动检测技术在低品位钼矿石工艺矿物学研究中的应用

我国工艺矿物学一直是采用显微镜人工检测,费时费力且往往不能为选矿工艺及时提供信息。以现有的设备和手段,工艺矿物检测速度和精度都难以适应当前矿业发展的需求,已成为阻碍矿业技术进步的"瓶颈"问题。本文针对广东省某低品位钼矿石,采用澳大利亚的MLA自动检测技术,实现对该钼矿的工艺矿物学参数的快速准确检测。     

某铜矿石浮选尾矿工艺矿物学研究

为更好地查清某铜矿石选别过程中铜流失的主要原因,借助先进的扫描电镜、能谱仪及BPMA分析系统等分析手段,测定铜尾矿中的矿物组成、解离度、连生程度、嵌布关系等工艺矿物学参数。结果表明:铜尾矿中铜矿物主要为黄铜矿和铜蓝,铜分布率分别为89. 01%和10. 99%;铜矿物粒度较细,黄铜矿和铜蓝粒径均小于38μm,呈微细粒分布;黄铜矿单体解离度较低,与脉石矿物连生较为密切,铜蓝多以单体形式存在。工艺矿物学研究结果可为该铜矿石生产工艺优化改造,提高铜回收率提供理论依据。     

电感耦合等离子体质谱法测定离子吸附型稀土矿中全相稀土总量

采用硝酸-氢氟酸-高氯酸混酸溶解试样,以电感耦合等离子体质谱法(ICP-MS)对试样溶解液进行测定,提出了以ICP-MS测定离子吸附型稀土矿中全相稀土总量的方法。对氢氟酸用量和测定液中硝酸的含量进行了考察,最终确定氢氟酸用量为5.0mL,测定液介质为体积分数为2%的硝酸。在优化的仪器条件下,15种单一稀土元素校准曲线的线性相关系数均大于0.9999,方法检出限为2.4μg/g。采用实验方法对稀土矿石国家标准物质GBW07158、GBW07160、GBW07161(用于标样制定的样品均采自江西省龙南离子吸附型稀土矿区)中的稀土总量进行测定,测定结果与认定值基本一致。将实验方法应用于稀土矿石国家标准物质GBW07159、GBW07160与离子吸附型稀土矿实际试样中稀土总量的测定,测得结果的相对标准偏差(RSD,n=11)为1.7%~3.1%。     

超声波强化浸取离子型稀土矿中稀土

利用超声波的空化作用可有效强化南方离子型稀土矿中稀土的浸出,从而提高稀土浸出率并缩短矿物中稀土总量的分析时间。在20 g/L的硫酸铵浸矿液中超声浸矿30 min,可使离子型稀土的浸出率达99%以上,而传统搅拌法需4 h,甚至浸取过夜。超声法与搅拌法对干扰杂质铁、铝的浸出率相近,加入乙酰丙酮及磺基水杨酸等掩蔽剂后不影响EDTA滴定稀土时的终点判断,且测定结果与电感耦合等离子体发射光谱法测定结果一致性好。     

Optimization of rare earth carbonate reactive-crystallization process based on response surface method

Rare earth carbonate precipitation is mainly amorphous,of large volume and difficult to filter.To prepare crystalline rare earth carbonate,mother liquor of heavy rare earth was taken as research object,and the experimental scheme was designed based on the response surface central composite design(CCD)method.The concentration of mother liquor,aging time and seed crystal dosage were taken as independent variables,and the particle size of rare earth carbonate was taken as the response value to establish a quadratic polynomial numerical model to optimize the reactive-crystallization process of rare earth carbonate.The results show that these three factors have significant effect on the particle size of rare earth carbonate,and the influence order is mother liquid concentration aging time seed crystal dosage.Moreover,the interaction between mother liquor concentration and seed crystal dosage has a significant effect on the size of rare earth carbonate particles.The optimal parameters predicted by the model are as follows:the concentration of mother liquid is 1.75 g/L,seed crystal dosage is 13.56 wt%,and aging time is 8 h.Under these conditions,the predicted particle size is 28.74 μm,and the experiment particle size is 28.23 μm,between both,the relative error is 0.73%,which indicates that the established response surface model has a good prediction effect and a certain practical significance to guide the reactive-crystallization process of rare earth carbonate.The obtained rare earth carbonate has a crystallinity of 97.82%,uniform particles size,and low-hydrated crystals with a tengerite structure.     

电感耦合等离子体质谱法测定离子型稀土矿中离子相稀土总量及分量

采用硫酸铵溶液提取离子型稀土原矿试样中离子相稀土,以硫酸铵溶液为基体配制校准系列溶液,建立了电感耦合等离子体质谱法(ICP-MS)测定样品溶液中离子相稀土总量及分量的方法。实验表明:对于10.00 g离子型稀土矿试样,加入100 mL 50 g/L硫酸铵溶液振荡15 min后放置30 min可有效提取出离子相稀土;采用5.0 g/L硫酸铵溶液进行校准系列溶液的基体匹配,选择¹⁰³Rh-¹⁸⁵Re双内标可有效校正硫酸铵的基体效应及仪器信号的漂移影响;选择合适的同位素消除了可能存在的质谱干扰。在最佳条件下进行测定,15个稀土元素的校准曲线在10.0~100.0 μg/L范围内线性相关系数均大于0.999 91,方法检出限在0.10~0.66 μg/g之间。方法应用于不同离子型稀土矿区中离子相稀土总量及分量的测定,结果与电感耦合等离子体原子发射光谱法(ICP-AES)一致,相对标准偏差(RSD,n=11)在1.0%~5.2%之间,回收率在98%~104%之间。     

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%.     

Element migration and phase distribution characteristics during crystallization of rare earth phase in rare earth slag

The crystallization experiment of molten rare earth (RE) slag under different cooling rates was carried out. The characteristics of element migration and phase distribution during RE phase crystallization were studied by using different equipment. The experimental results show that there are two RE phases in the RE slag, namely (Ca, Ce, La)₅(SiO₄)₆F and (Ca,Ce,La,Mg)₃(Ti,Al,Nb)₂O₇. During the cooling crystallization process of molten RE slag, Ca and P elements in the RE phase of (Ca,Ce,La)₅(SiO₄)₆F migrate from inside to outside, and finally gather at the outer edge of the phase to form phase Ca₃(PO₄)₂. The RE phase (Ca,Ce,La)₅(SiO₄)₆F is distributed inside the furnace-cooled slag, and the RE phase (Ca,Ce,La,Mg)₃(Ti,Al,Nb)₂O₇ is distributed in the surface layer of the furnace-cooled slag. And based on the phase distribution characteristics, the central hollowing method is proposed to realize the preliminary enrichment of valuable elements Ti, Nb and RE in RE slag.     

Research progress of rare earth separation methods and technologies

Strategical elements,such as rare earth elements,play a crucial role in the industry,especially in producing high-tech materials.Major global industries have developed a strong dependence on rare earth materials.Every year,there are innovations in industries such as modern technology,green energy,or communications technology,which need more strategic metals to improve investment profitability.This article reviews advances in rare earth separation methods and techniques to guide and recommend the...     

Dissolved rare earth elements estimation of ion-absorption rare earth ores using reflectance spectroscopy in south Jiangxi province,China

Ion-absorption rare earth ores are an important mineral resource in China. Nowadays, the unauthorized mining has become a serious problem, resulting in severe water pollution and the wastage of rare earth elements (REEs). Being able to estimate the concentration of dissolved REEs in water bodies near mines is essential for tackling this environmental problem. Conventionally, quantitative analyses of the contents of dissolved REEs are performed using laboratory-based techniques, which can be time consuming and costly. Spectral reflectance is a rapid and cost-effective means of characterizing the chemical compositions of light-absorbing materials. In this study, reflectance spectroscopy was performed on dissolved REEs, and the correlation between their reflectance characteristics and REE content was determined. A total of 50 aqueous media samples collected in south Jiangxi Province and 25 laboratory-produced aqueous media samples were tested, and their reflectance spectra and REE contents were measured using reflectance spectroscopy and inductively coupled plasma mass spectrometry, respectively. Next, the reflectance, differential reflectance, and absorption depth were analysed based on the REE content. Six diagnostic absorption features related to REEs are recognised in the visible and near-infrared wavelength regions, along with several smaller peaks. It indicates that the results of the absorption depth analysis are in accordance with the absorption spectra characteristics of the REEs, with the R² value being higher than 0.97. The intensity of each of the six absorption bands exhibits a linear correlation to the total REE content. Therefore, linear regression models can be derived for estimating the total concentration of REEs in aqueous media samples. What's more, the detection limit for REEs is determined to be about 30 μg/L. Thus, it can be concluded that reflectance spectroscopy is a suitable technique for estimating the concentration of dissolved REEs.     

熔融制样-X射线荧光光谱法测定轻稀土矿石中8种主量稀土氧化物

稀土矿种类繁多,矿物组成复杂,常富含Ca、P、Fe、Ba、Si、S、Mn、Pb等元素,而采用熔融法制样时,富含Fe、Mn、Pb等单质元素的稀土矿样会腐蚀Pt-Au坩埚。试验将稀土矿石与混合熔剂[m(Li₂B₄O₇)∶m(LiBO₂)=33∶67]以质量比1∶14(稀释比)混合,再加入1mL 500g/L NH₄NO₃溶液为氧化剂、0.2mL 100g/L LiBr溶液为脱模剂,在1050℃下熔融制成均匀玻璃片,使用波长色散X射线荧光光谱法(WDXRF)测定轻稀土矿石中La₂O₃、CeO₂、Pr₆O₁₁、Nd₂O₃、Sm₂O₃、Eu₂O₃、Gd₂O₃、Y₂O₃等8种主量稀土氧化物。方法中稀土氧化物的检出限为5~159μg/g。实验方法用于测定两个稀土矿石标准物质GSB04-3549-2019(稀土总量为4.44%)和GSB04-3309-2016(稀土总量为29.09%)中8种稀土氧化物,低品位稀土矿石标准物质(GSB04-3549-2019)中稀土氧化物测定结果的相对标准偏差(RSD,n=7)小于13%,高品位稀土矿石标准物质(GSB04-3309-2016)中稀土氧化物测定结果的相对标准偏差(RSD,n=7)小于2%。选取2个轻稀土矿石样品(稀土总量分别为2.55%和24.64%),按照实验方法进行稀土总量的加标回收试验,回收率为96%~100%。选取2个稀土矿石标准物质GSB04-3550-2019和GSB04-3311-2016以及2个轻稀土矿石样品,按照实验方法测定La₂O₃、CeO₂、Pr₆O₁₁、Nd₂O₃、Sm₂O₃、Eu₂O₃、Gd₂O₃、Y₂O₃,测定值与标准值或电感耦合等离子体原子发射光谱法(ICP-AES)测定值相吻合。实验方法具有较广的适应性,能满足复杂矿物组成轻稀土矿石中主量稀土氧化物的检测。     

A review of the recycling of rare earth metals

Although rare earth metals are more abundant than their name would indicate, disruptions of their supplychain have occurred recently, and it is no surprise thatthe US Department of Energy (DOE) and the European Union (EU) Commission have listed several of them as critical for their role as materials essential for a clean society. This paper briefly reviews the major uses for rare earth metals and identifies the potential sources of scrap for recycling. The paper then describes the various processes developed to recycle rare earth-containing scraps, such as spent Ni-metal hydride (MH) batteries, magnets, catalysts, polishing powders and phosphors, with case studies taken from industrial practice and research work. The success of recycling efforts depends not only on adequate technical advancements but also requires the overcoming of non-technical challenges comprising, among others, logistics (collection, transportation), and an appropriate political and legal framework.     

Insight into leaching of rare earth and aluminum from ion adsorption type rare earth ore: Adsorption and desorption

Clay minerals are inferred to be the primary host materials for ion-exchangeable rare earth in ion adsorption type rare earth ore(IAREO).During the rare earth leaching process,the adsorption and desorption reactions of the cations controlling the leaching process continue to occur at the clay minerals-leaching agent solution interface.In order to understand the leaching mechanism and behavior of rare earth and co-leached aluminum,adsorption,competitive adsorption,and desorption experiments were ...     

EDTA滴定法测定稀土矿石中氧化钙

根据稀土矿石的特性,以氢氧化钠、过氧化钠、碳酸钠熔融分解试样,经过强碱分离铝、硅、氟、磷等杂质元素,氨水分离铁等元素后,用EDTA滴定法测定稀土矿石中氧化钙含量。试验发现经过强碱分离后硅、氟、磷等元素不影响钙的测定结果。讨论了少量铝、钡、锰元素的干扰情况及其干扰消除方法：用三乙醇胺和硫酸钾掩蔽剩余少量Al、Ba等干扰元素,盐酸羟铵掩蔽锰的干扰,加入硫酸镁来改善滴定终点的颜色变化;并实验得出空白值对不同称样量的贡献值也不一样,因为必须做空白实验。在pH>13的氢氧化钾介质中,以钙指示剂为指示剂,EDTA标准溶液滴定稀土矿石中氧化钙,测定值与ICP AES法值相一致,RSD在08%～43%之间。     

Multi-component assembly of luminescent rare earth hybrid materials

This review focuses on the recent research progress in the multi-component assembly of luminescent rare earth hybrid materials, which is based on the luminescent rare earth compounds and two or more other building units, including the other photoactive species. It covers the multi-component luminescent rare earth hybrids which was assembled with different (a) organic-inorganic polymeric units, (b) nanoporous units, (c) nanoparticle composites or (d) other developing special units. Finally, future challenges and opportunities in this field are discussed. Herein it mainly focuses on the work of Yan's group in recent years.     

Kinetics model for leaching of ion-adsorption type rare earth ores

This paper aims to establish a mathematical model that can analyze the whole leaching kinetics process of ion-adsorption type rare earth ores. This leaching process is composed of three steps: (1) ammonium ions arrive at the ore particle surface through the diffusion layer; (2) ammonium ions exchange with rare earth ions; and (3) rare earth ions enter into the external solution through the diffusion layer. In the leaching process, it is hypothesized that the ore particle size remains constant. The process of ammonium ions and rare earth ions passing through the diffusion layer was described by the Fick law, and the reversible ion exchange process between ammonium ions and rare earth ions was described by the Kerr model. A leaching kinetics model of rare earth ions by ammonium ions was constructed. Accuracy of this kinetics model was verified with laboratory tests. It is found that the correlation coefficients of all data are greater than 0.9000. The proposed kinetics model is therefore feasible for kinetics analysis throughout the leaching process.