CHEMICAL BEHAVIOR OF CERIUM ELEMENT IN ROCK WEATHERING SYSTEM

１ＩＮＴＲＯＤＵＣＴＩＯＮＴｈｅｅｌｅｃｔｒｏｎｉｃｓｔｒｕｃｔｕｒｅｏｆｇｒｏｕｎｄｓｔａｔｅａｔｏｍｃｅｒｉｕｍｉｓＸｅ４ｆ１５ｄ１６ｓ２,ａｎｄｔｈｅｅｌｅｃｔｒｏｎｉｃｓｔｒｕｃｔｕｒｅｏｆｔｒｉｖａｌｅｎｔｏｘｉｄｉｚｉｎｇｓｔａｔｅｉｓＸ...     

Technology development for rare earth cleaner hydrometallurgy in China

China is the global leader in rare earth(RE)production using hydrometallurgical processes. Advantageous extraction techniques of rare earths from Baotou mixed rare earth minerals, bastnaesite, and ion-adsorption clays of rare earth deposits have been developed in China.The separation and purification technologies have also achieved rapid development. The industrial application processes for rare earth hydrometallurgy were summarized in the present paper. With the large demands and rapid development of rare earths, the issues of resources and environment are more prominent. This review gives an overview of the main processes that were developed in the past toward greener hydrometallurgy of rare earths in China. Based on the development of the rare earth industry,comprehensive utilization and cleaner production should still be focused on in the future, to support the sustainable development.     

Processing of rare earth concentrates

The paper describes process details for extraction of rare earths from an intermediate grade concentrate of Madhya Pradesh region in India and a South African slag. The xenodme concentrate obtained from the former place was an intermediate grade （47%） rare earth phosphate containing both monazite and xenotime. The South African slag was a low-grade waste product typically containing only 4% of rare earths. The rare earth resource concentrates have been treated individually by different methods such as alkali fusion and alkali leaching to convert them into their mixed oxides. Both types of materials have been processed and greater than 98% solubilization of metal values has been achieved in the intermediate grade xenotime and 80% from the South African slag. The residue of xenotime hydroxide has been washed thoroughly to collect the sodium phosphate, as by-product and the slurry pH have been adjusted to separate rare earths from thorium effectively. Other impurities such as uranium and iron have been removed by precipitation of rare earths by oxalic acid. It has been possible to recover 〉95% yttrium along with other rare earth oxides.     

Recovery of rare earth elements from phosphorites in the USSR

Data on the main rare earth compositions in the USSR are presented, showing that the most promising sources are phosphorites and apatites. The rate earth oxide content in the above ore concentrates reaches 1%. Technological schemes for recovering the total and individual rare earth oxides as byproducts have been developed. Extraction methods are used for recovering rare earths from nitrate solutions, with individual oxides more than 99.9% pure being obtained. Apatites are decomposed by nitric acid, yielding apart from fertilizers, strontium carbonate, sodium fluorosilicate, chalk and oxides of rare earth elements.     

TUNGSTEN ELECTRODES CONTAINING THREE TYPES OF RARE EARTH OXIDES

ＩＮＴＲＯＤＵＣＴＩＯＮＷｉｔｈｉｎｃｒｅａｓｉｎｇｄｅｍａｎｄｓｔｏｔｈｅｐｒｏｐｅｒｔｙｏｆｗｅｌｄｉｎｇｅｌｅｃｔｒｏｄｅａｎｄｂｅｔｅｒｋｎｏｗｌｅｄｇｅｏｆＴｈＷｅｌｅｃｔｒｏｄｅｍａｔｅｒｉａｌ’ｓｒａｄｉｏａｃｔｉｖｉｔｙ,ｓｏｍｅｓ...     

EFFECTS OF Y2O3 AND CeO2 ON PROCESSING AND CHARACTERISTICS OF TUNGSTEN ELECTRODES

１ＩＮＴＲＯＤＵＣＴＩＯＮＩｎｒｅｃｅｎｔｙｅａｒｓ,ｔｕｎｇｓｔｅｎｅｌｅｃｔｒｏｄｅｍａｔｅｒｉａｌｓｃｏｎｔａｉｎｉｎｇｏｎｅｋｉｎｄｏｆｒａｒｅｅａｒｔｈｍｅｔａｌｏｘｉｄｅａｓＬａ２Ｏ３,ＣｅＯ２ａｎｄＹ２Ｏ３,ｈａｖｅｂｅｅｎｄｅｖｅｌ...     

焙烧氟碳铈矿硫酸浸出稀土的动力学(英文)

研究了硫酸浸出德昌稀土与天青石共伴生矿的焙烧矿过程。考查粒度、搅拌速度、硫酸浓度和温度对稀土浸出率的影响,并对稀土的浸出动力学进行分析。在选定的浸出条件下:粒径0.074～0.100mm、硫酸浓度1.5mol/L、液固比8:1、搅拌速度500r/min,稀土浸出反应受内扩散控制,表观活化能为9.977kJ/mol。     

Preparation of Phosphors MAl_2O_4∶Eu~(2 )(M=Ca,Sr,Ba) by Microwave Heating Technique and Their Phosphorescence

1 ＩｎｔｒｏｄｕｃｔｉｏｎＭＡｌ2 Ｏ4∶Ｅｕ2 (Ｍ =Ｃａ ,Ｓｒ ,Ｂａ )ｈａｖｅｂｅｅｎｋｎｏｗｎａｓｅｘｃｅｌｌｅｎｔｐｈｏｓｐｈｏｒｓｗｉｔｈｅｍｉｓｓｉｏｎｃｏｌｏｒｓｆｒｏｍｂｌｕｅｔｏｇｒｅｅｎｕｎ ｄｅｒｕｌｔｒａｖｉｏｌｅｔａｎｄｃａｔｈｏｄｅ ｒａｙｅｘｃｉｔａ ｔｉｏｎ[1～ 3].Ｓｔｕｄｉｅｓｏｎｐｈｏｓｐｈｏｒｓｗｅｒｅｍｏｓｔｌｙｐｅｒｆｏｒｍｅｄｉｎ 1 960ｓ′ａｎｄｅａｒｌｙ 1 970ｓ′ｍａｉｎｌｙｆｏｒｌａｍｐａｎｄｃａｔｈｏｄｅ ｒａｙｔｕｂｅａｐ ｐｌｉｃａｔｉｏｎ .Ｉｎ 1 990…     

稀土氧化物对贮氢合金电极电化学性能的影响

研究了稀土氧化物La_2O3_,CeO_2,Nd_2O_3和Y_2O_3对AB_5型贮氢电极电化学性能的影响。研究表明,除Y2_O3_外,其余的稀土氧化物可提高贮氢电极的1C放电容量和放电电压,延长贮氢电极的循环寿命,且对贮氢电极性能有利的顺序为:La2_O3_>CeO2_>Nd2_O3_;稀土氧化物添加量越多,贮氢电极的循环稳定性越好,但对贮氢电极的1C放电容量和放电电压的影响存在最佳值。造成这些结果的原因是:稀土氧化物增大贮氢合金颗粒间的接触电阻;稀土氧化物的催化作用;稀土氧化物对镍催化剂的稳定作用及抑制贮氢合金进一步氧化的作用。     

Leaching process of rare earths from weathered crust elution-deposited rare earth ore

In order to strengthen the leaching procedure, the chemical processes of leaching rare earths (RE) from the weathered crust elution-deposited rare earth ore were investigated frow the viewpoints of kinetics, hydrodynamic and mass transfer. The results show that the leaching hydrodynamics follows the Darcy law. The leaching kinetics can be described by the shrinking core model; the leaching process is controlled by diffusion of porous solid layer; and the mass transfer can be described with Van Deemter equation. This provides a theoretic basis and a scientific approach with high efficiency and optimized extraction conditions in industrial practice.     

Correlation analysis on partition of rare earth in ion-exchangeable phase from weathered crust ores

1Introduction Weathered crust ores which are widely deposited in Jiangxi,Fujian,Guangdong,Hunan,Yunnan and Guangxi provinces in the south of China[1?3]are the main resources of mid-heavy RE.Their development and utilization have solved the shortage proble…     

Commercial production of rare earth metals by fused salt electrolysis

The commercial production of rare earth metals by fused salt electrolytic methods is described. These methods are used to make mischmetal, cerium, lanthanum, and didymium (Nd + Pr). The feed materials consist essentially of anhydrous chlorides of the metal to be produced, augmented by additions of nonrare earth salts to yield an electrolyte with satisfactory properties for reduction. The rare earths are derived either from monazite or from bastnasite ores. The anhydrous chlorides are manufactured from the hydrated chlorides by methods which minimize oxidation or hydrolysis. Alternatively, anhydrous chlorides may be used which result from the direct chlorination of rare earth ores by the Gold-schmidt process. These are particularly suitable for electrolysis due to their very low oxychloride content. Fluorides and oxides of the rare earths are produced by wet chemical methods to provide the relatively small quantities of these compounds now used for commercial fused salt electrolysis. Reduction cells in use today are constructed mainly from a) ceramics, b) graphite, or c) iron. The advantages and disadvantages of these types of cells are described together with the typical products which result from their use. Primary attention is given to production of mischmetal (mixed rare earth metal), which is the rare earth metal produced on the largest scale today. Brief reference is made also to production of cerium, lanthanum, and didymium (Nd + Pr) metal. Finally, a resume of the current uses of these metals is presented with reference to recent trends in the industrial applications of the rare earth metals.     

熔炼时间对稀土单晶合金坩埚界面反应的影响

为了实现稀土单晶高温合金中稀土含量的稳定控制,明确稀土元素在熔炼过程中参与的坩埚界面反应机理,研究了熔炼时间对含Y高温合金CMSX-4与Al2O3陶瓷坩埚在真空感应熔炼过程中的界面反应和稀土Y收得率的影响。实验结果表明：随着熔炼时间的延长界面反应加剧,熔炼过程中Y首先与Al2O3陶瓷基体发生反应生成Y2O3,生成的Y2O3会继续与Al2O3发生反应生成Y、Al原子比不同的铝酸钇反应层,最终坩埚表面形成的界面反应产物由外层的YAlO3、内层的Y3Al5O12(Y3Al2(AlO4)3) 以及附着的高温合金组成。熔炼10~30min时合金中稀土Y收得量为41.023、4.566和5.368ppm。     

Reaction process of monazite and bastnaesite mixed rare earth minerals calcined by CaO-NaCl-CaCl2

The decomposition reactions of monazite and bastnaesite mixed rare earth minerals calcined by CaO-NaCl-CaCl2 were studied by means of TG-DTA and XRD. The results show that the process of the minerals decomposed by CaO involves two steps. The first step occurs in the temperature range of 425-540 ℃, and the main reactions are bastnaesite decomposition, i.e. REOF reacts with CaO to produce RE2O3 and CaF2, and Ce2O3 is oxidized to CeO2. During this step, CaCO3 is formed at about 500 ℃. The second step takes place in the temperature range of 610-700 ℃, and the reactions are monazite decomposition into RE2O3, Ca5F（PO4）3 and Ca3（PO4）2 by CaO and CaF2. In this process, the decomposition ability is improved because CaO from CaCO3 decomposing has high chemical activity. In calcining process, the new formed Ca5F（PO4）3 restrains fluorine that can escape in form of gaseous compound. The decomposition ratio of the mixed rare earth minerals reaches 90.8% at 700 ℃.     

稀土银合金显微组织观察与分析

对稀土银合金材料进行了金相观察和电子探针扫描分析以及显微硬度测定。实验结果表明,添加两种性质差交大的稀土元素可以充分发挥互补作用,改善银合金的组织与性能。含有稀土钇的银合金有较强的加工硬化效果和较好的抗高温氧化作用。稀土钇与轻稀土元素组合添加将有助于改善银合金的综合性能。     

Effect of CeO2 and Y2O3 as Catalysts on Hydrogen Desorption Properties of NaAlH4

主要研究氩气气氛下通过机械球磨方法制备的掺杂两种稀土氧化物(由0~5mol%CeO2和 Y2O3)对NaAlH4放氢性能的影响。PCT测试结果显示,在相同的条件下,两种稀土氧化物引起 NaAlH4的最大放氢量和平均放氢速率的规律相似,都随着掺量的增加先增大至某一值后又开始减小。相对于 Y2O3,CeO2对NaAlH4的催化效果影响更为突出,达到相同的放氢量 4.8wt%时,1mol%CeO2-NaAlH4的放氢速率明显比1mol% Y2O3-NaAlH4要高。SEM分析结果显示,随着催化剂含量的增加,粉体颗粒更加均匀,继而团聚成絮状。同时研究发现,球磨后呈分散结构的颗粒可能比絮状结构颗粒反应接触面积大,且经过加热放氢后的试样有很多类似于蜂窝状的气孔存在。     

铝合金表面激光熔覆CeO_2+Ni60A熔覆层的组织及耐磨性

利用激光熔覆技术,在6063铝合金表面制备了添加不同CeO2含量的Ni60A合金熔覆层,分析了CeO2+Ni60A熔覆层的显微组织及硬度,筛选了最佳稀土添加量,并研究了其耐磨性能。结果表明:Ni60A熔覆层中稀土CeO2含量低于2%(质量分数)时易出现气孔,高于2%时易开裂;添加CeO2的含量为2%时,熔覆层的组织缺陷较少,表面硬度较高,微观组织均匀且晶粒细小;熔覆层中稀土的含量不宜超过4%,过量的CeO2对硬度的提高作用不大,而CeO2的含量在0%~2%的范围内随着其含量的增加,硬度升高明显;在相同磨粒磨损条件下,2% CeO2+Ni60A熔覆层的耐磨性是铝合金基体的7.1倍,是Ni60A熔覆层的1.6倍;激光熔覆Ni60A可以显著降低表面摩擦系数,而添加Ce能提高熔覆层的摩擦系数稳定性,从而改善耐磨性能。     

Mechanism of CeMgAl11O19:Tb3+ alkaline fusion with sodium hydroxide

Comprehensive CeMgAl11O19:Tb3+(CTMA)disintegration via alkaline fusion was discussed. The rare earth(RE) elements in CTMA were dissolved by HCl completely after alkaline fusion. Relationships between the alkaline fusion temperature and various properties of the compounds were examined by various techniques to elucidate their roles in the expected CTMA disintegration.X-ray diffraction(XRD) analysis indicates the phase transformation sequence. A scientific hypothesis of crystal structure disintegration presents that sodium ions substitute for the europium and barium ions in the mirror plane and magnesium ions in the spinel block successively, resulting in that more oxygen vacancies and interstitial sodium ions appear. The unit cell [P63/mmc(194)] breaks from the mirror plane. Then it is decomposed into Na Al O2, and magnesium, cerium, and terbium ions combine with free OH-into Mg O, Tb2O3 and CeO2;Tb2O3 and CeO2 change into Ce0.6Tb0.4O2-x. In the end, the rare earth oxide is recycled easily by the acidolysis. The mechanism provides fundamental basis for recycling of REEs from waste phosphors.     

Rare Earth Compounds in Cemented Carbides with Trace Rare Earth Additions

The morphology,structure and distribution of the rare earth compounds in the YG8R.YT5R and YT14Rcemented carbides with additions of trace light rare earths were studied with an analytical electron microscope.The particles of the rare earth compounds in these alloys are all spherical and distribute at interfaces betweenthe Co-cement phase and WC hard phase or(TiW)C solid solution,and in the(TiW)C solid solution.In theYG8R and YTI4R alloys,the rare earth compound is RE_2O_3 with a bcc structure,while in the YT5R alloy.the rare earth compound is RE_2O_2S with a hcp structure.     

稀土Ce对253MA耐热钢凝固组织及夹杂物的影响

采用激光共聚焦显微镜、场发射扫描电镜(SEM)和电子背散射衍射(EBSD)等设备,对含稀土Ce的耐热钢253MA连铸坯的凝固组织及夹杂物的形貌、成分和结构进行表征分析。结果表明:比较两种含稀土Ce耐热钢的凝固组织,稀土Ce有增大凝固组织等轴晶率、细化柱状晶的作用;稀土Ce夹杂物主要相结构为CeO₂和(CeO)₂SO₄,呈细小、近球形弥散分布;对夹杂物进行统计和评级,发现稀土Ce含量的增加有利于D类球形夹杂物增多,有助于提高耐热钢的耐高温、抗氧化性能。