Modeling Preparative Chromatographic Separation of Heavy Rare Earth Elements and Optimization of Thulium Purification

Rare Earth Elements are in growing demand globally. This paper presents a case study of applied mathematical modeling and multi objective optimization to optimize the separation of heavy Rare Earth Elements, Terbium-Lutetium, by means of preparative solid phase extraction chromatography, which means that an extraction ligand, HDEHP, is immobilized on a C18 silica phase, and nitric acid is used as an eluent. An ICP-MS was used for online detection of the Rare Earths. A methodology for calibration and optimization is presented, and applied to an industrially relevant mixture. Results show that Thulium is produced at 99% purity, with a productivity of 0.2 - 0.5 kg Tm per m3 stationary phase and second, with Yields from 74% to 99%.

Kinetics of nitric acid leaching of low-grade rare earth elements from phosphogypsum

Phosphogypsum(PG)is a potential resource for rare earth elements(REEs).Several studies have been carried out on REE leaching from PG.However,few in-depth studies have investigated the kinetics of this leaching process.In this study,the leaching kinetics of REEs from PG in nitric acid at different temperatures were explored in depth.The experiments show that the maximum leaching recovery for ΣREE was 58.5%,75.9%and 83.4%at 30,60 and 80℃,respectively.Additionally,among La,Ce,Y and Nd,Y had the highest leaching rate.A new shrinking core model(SCM)based on the dissolution reaction of a cylindrical solid particle with interfacial transfer and diffusion across the product layer as the rate-controlling step was deduced and could well fit the leaching process of REEs from PG.The activation energies for the leaching of La,Ce,Y and Nd were determined on the basis of the new cylindrical SCM.In summary,the cylindrical SCM was a more suitable fitting model than the spherical SCM,and the interfacial transfer and diffusion across the product layer were the rate-controlling step for REE leaching from the PG sample.

Dissolution of Rare Earth Elements from Coal Fly Ash Particles in a Dilute H₂SO₄Solvent

Recently, the worldwide supply of rare earth element (REE) resources will be severely restricted. On the other hand, coal fly ash particles emitted from coal-fired electric power plants contain relatively high concentrations of REEs. The contents of REEs in coal fly ash are regularly several hundreds of ppmw. In order to extract and recover REEs from coal fly ash particles, as a first step, we have investigated their dissolution behavior in a dilute H2SO4 solvent. The REE content of coal fly ash specimens has been precisely determined, and their presence in the ash component of the original coal and their enrichment in coal fly ash particles during coal combustion have been suggested. REEs in coal fly ash dissolve gradually in H2SO4 over time, and this implies two types of occurrences of the REEs in coal fly ash particles. By applying the unreacted core model to the dissolution behavior of REEs in a H2SO4 solvent, we can explain both types of occurrences.

Geochemical Characteristics of Rare Earth Elements in Guposhan Granite Complex and Their Petrogenetic Implication

In this paper the geochemical characteristics of rare earth elements in Guposhan granite complex in Nanling Area,South China,is systematically studied,and the balance of REE distribution in rock-forming minerals, which contain only 21.47～29.71 wt% of total REE in granites,is calculated.The petrogenetic relationship be- tween three different stages of the granites in the complex is discussed,and a geochemical model is suggested for the formation of granitic magma in early stage by partial melting of the crustal basement rocks containing more REE than that in the late stage.It shows that a ion-adsorption type of REE deposit could ocuur in the weath- ering crust on the early stage granite.Rb-Sr isotope isochron dating of the first stage medium-coarse-grained K-feldspar granite shows that its age is 146.5 Ma and initial ^(87)Sr/^(86)Sr ratio is 0.71198.

Effect of rare earth (RE) on diffusion of aluminum atoms in aluminizing

The RE-aluminized coating and pure aluminized coating on 20 carbons steel were prepared by hot dip aluminizing method at 740℃. After diffusion treatment at 850℃for 4 h, the distribution of aluminum and lanthanum elements in the coating was analyzed with energy disperse spectroscopy(EDS) and electron probe microanalyses(EPMA), and the lattice parameter ofα-Fe in the matrix of the coating was measured precisely by X-ray diffractometer(XRD). The results show that RE permeates into the aluminized coating, leads to lattice disturbance and increases the depth of the aluminized coating. On the basis of the results, the expression of the diffusion coefficient of Al atoms is derived from the diffusion flow, and the effect of the high vacancy concentration and high concentration gradient of vacancies on the diffusion of Al atoms was analyzed by establishing the kinetics model of the vacancy mechanism of diffusion. The results show that the high vacancy concentration and high concentration gradient of vacancies in the RE-aluminized processes are the main reason why the diffusion coefficient of Al atoms in RE-aluminizing is bigger than that in pure aluminizing.

Process optimization and kinetics for leaching of cerium, lanthanum and neodymium elements from iron ore waste's apatite by nitric acid

The leaching of rare earth elements （REEs） including cerium, lanthanum and neodymium from apatite concentrate obtained from iron ore wastes by nitric acid was studied. The effects of nitric acid concentration, solid to liquid ratio and leaching time on the recoveries of Ce, La and Nd were investigated using response surface methodology. The results showed that the acid concentration and solid to liquid ratio have significant effect on the leaching recoveries while the time has a little effect. The maximum REE leaching recoveries of 66.1%, 56.8% and 51.7% for Ce, La and Nd, respectively were achieved at the optimum leaching condition with 18% nitric acid concentration, 0.06 solid to liquid ratio and 38 min leaching time. The kinetics of cerium leaching was investigated using shrinking core model. It was observed that the leaching is composed of two stages. In the first stage a sharp increase in cerium leaching recovery was observed and at the longer time the leaching became slower. It was found that in the first stage the diffusion of reactants from ash layer is the rate controlling mechanism with an apparent activation energy of 6.54 kJ/mol, while in the second stage the mass transfer in the solution is the controlling mechanism.

Errors Involved in the Taylor's Model for the Crustal Composition and Evolution──An Analysis of Their Causers

It is suggested in this paper that the famous Taylor’s model for the compdrition and evolution of the continental crust consists of three closely related key links. These links include an assumption that the surficial environment has no effect on the sedimentary REE patterns and the REE patterns in shales can reflect the composition of their provenancel a discovery about the discrepancy of sedimentary REE patterns between Archean and Proterozoic, and a deduc-tion that there was a global scale K-granitoid event at the end of the Archean. Based on a de-tailed discussion, this paper substantially negates the rationality of the Taylor’s model and ar-gues that its three critical links be three great errors indeed. Moreover, some other deficiencies or problems it confronts are described in this paper. The authors suggest that what led to the errors involved in the Taylor’s model is its wrongly neglecting the effect of the sedimentary en-vironment on the chemical composition of sediments, and that the environment should be an important factor affecting the distribution patterns of trace elements in the sediments.

Direct microwave leaching conditions of rare earth elements in fluorescent wastes

The luminescent phosphor powder in the fluorescent lamp constitutes 2%of the lamp’s weight.It can be mentioned that fluorescent wastes are a crucial raw material to produce rare earth oxides.In the present study,microwave leaching process was conducted to dissolve rare earth elements yttrium(Y),europium(Eu),and remaining rare earth elements(REEs)present in the phosphor powder of the fluorescent lamp.and the yields were compared.In the microwave leaching process,the effects of the temperature(80-160℃),acid type(hydrochloric acid(HCl),nitric acid(HNO_(3)),sulphuric acid(H_(2)SO_(4))),acid concentration(0.5-6 mol/L),solid to liquid ratio(0.1:10-0.5:10)and reaction time(5-90 min)parameters on leaching efficiencies of varying rare earth elements and calcium were investigated.The highest yield was obtained in the direct microwave leaching of fluorescent waste with the experimental conditions of 6 mol/L HCl,160℃,0.1:10 solid-to-liquid ratio(S:L),and 90 min.Activation energy calculations were made,and kinetic models of the reactions were obtained,and it is observed that Y and Eu dissolution is diffusion-controlled,on the other hand,lanthanum(La),cerium(Ce),and terbium(Tb)were examined to be chemical reaction controlled.Moreover,calcium(Ca)and gadolinium(Gd)seem coherent with the mixed model.Concurrently,mathematical models of all experimental studies are created with the response surface Box-Behnken method and the correlation coefficients of all the models are over 90%.

Solvent extraction kinetics of Sm(Ⅲ),Eu(Ⅲ) and Gd(Ⅲ) with 2-ethylhexyl phosphoric acid-2-ethylhexyl ester

Solvent extraction kinetics of Sm（Ⅲ）, Eu（Ⅲ） and Gd（Ⅲ） from hydrochloric acid have been focused on using 2-ethylhexyl phosphoric acid-2-ethylhexyl ester （P507） with Anordning for Kontinuerlig Undersokning av Fordelningsfaktore rid Vatske Extraction （AKUFVE）. Compared with the conventional set-up, some advantages emerge obviously, for example, fast phase separation, easy operation and convenience of kinetic data acquisition. First of all, the extraction mechanism was discussed based on the dimeric model of P507. Secondly, the effects of stirring speed were investigated and 420 r-min-1 was determined of the following experiments. The effects of pH, concentration of rare earth elements （REEs） and P507 on the extraction rate were analyzed. The results indicated that the extraction mechanism changed with the increasing concentration of P507. Then, the experiments with different temperature were carried out. It turned out that the values of apparent activation energy （Ea） for Sm（Ⅲ）, Eu（Ⅲ） and Gd（Ⅲ） extracted by P507 were 26.80 kJ-mol-1, 13.40 kJ.mol-1 and 1.10 kJ- mol- 1 respectively, the resistance of the entire process was limited by diffusion or both of diffusion and reaction. Finally, the correlation equations were obtained, and the theoretical results fit with the experimental data well, most relative error was within ± 30%.

基于稀土元素示踪技术的库岸崩滑土体堆积特征研究

降雨和库水位变化是库岸崩滑的重要诱发因素。以黄河中游土质库岸为研究对象,在由3°缓坡、40°陡坡和70°急坡组成的概化岸坡上,利用稀土元素(REE)示踪技术,研究降雨和库水位升降作用下库区堆积土体的来源,分析离岸方向上的土体堆积特征。结果表明:在水位下降、水位上升、降雨作用-水位下降和降雨作用-水位上升4种工况下,同一组地形经过5场试验后,库区内来源于缓坡、陡坡、急坡的土量以及堆积土体总量均与堆积土体和库岸之间的距离存在负指数函数关系,且相关性较高;急坡是库区堆积土体的主要来源,其中水位变化条件下尤为明显;在水位上升和水位下降工况下,同一组地形5场试验后来源于急坡的堆积土量平均约占总堆积土量的71%;急坡对库区堆积土体的泥沙贡献率在坡脚处基本达到最高,各组地形5场试验后急坡对临岸堆积体泥沙量的平均贡献率约为66%。因而,在水库蓄水或放水时,需重点做好对急坡的防护。

广州周边地区地表水稀土元素污染特征及来源解析

以广州市周边地区地表水为研究对象,测定地表水中溶解态稀土元素La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb和Lu的浓度,采用单因子评价指数、内梅罗综合污染指数以及潜在生态风险指数对地表水中溶解态稀土元素进行污染和风险评价,通过APCS-MLR受体模型对广州市周边城区地表水中溶解态稀土元素的来源进行定量化解析,探究高度城市化的非矿区地表水中稀土元素的浓度分布特征。结果表明,研究区地表水溶解态稀土元素La、Ce、Nd、Pr、Gd、Dy、Sm、Er、Yb、Ho、Tb、Eu、Tm和Lu的平均浓度分别是背景值的6.97、5.15、4.06、4.58、1.58、1.71、1.14、1.26、1.22、1.67、1.33、0.47、0.83和0.80倍,表明广州市周边地区地表水中稀土元素可能存在富集现象,尤其是La、Ce、Nd和Pr等轻稀土元素。空间分布特征表明,稀土元素浓度较高的区域集中在位于广州市市内的石门山、黄山鲁和白云山,推断轻稀土元素浓度可能会受到城市中剧烈的人为活动影响。单因子污染指数结果表明,研究区地表水主要受轻稀土元素(La、Ce、Pr和Nd)污染;内梅罗综合污染指数分析表明,石门山、罗浮山、白云山和黄山鲁采样区地表水中稀土元素属于重度污染水平。潜在生态风险评价结果表明,轻稀土元素La、Ce、Pr和Nd为主要污染因子,石门山、白云山和黄山鲁采样区地表水中稀土元素污染属于中度风险水平;罗浮山和帽峰山属于低风险水平。皮尔逊相关性分析显示研究区地表水中稀土元素之间存在较强的相关性;由APCS-MLR受体模型分析得出2个主要污染源(源1和源2)和未解析源(源3),源1为自然源,贡献率为80.96%~99.12%,为研究区地表水稀土元素的主要来源;源2为人为源,主要由交通运输、工业活动等引起,其贡献率为0.32%~8.67%,是研究区地表水稀土元素的第二大来源。

铈对微囊藻的生长效应及被富集的动力学研究

研究了稀土元素Ce4+对铜绿微囊藻生长效应及其被铜绿微囊藻富集的动力学过程。结果表明:当Ce4+的添加浓度小于0.2mg/L时,对铜绿微囊藻的生长有促进作用,当Ce4+的添加浓度大于0.2mg/L时铜绿微囊藻的生长受到抑制。Ce4+在铜绿微囊藻中富集的动力学过程可用二级吸附动力学模型表征。

南华砷铊矿床元素地球化学和成矿模式

南华砷铊矿床位于云南省南华县城东南，北距县城55km。矿床产于上林罗统江边组雄黄厂段（Jc），以砷和铊元素组合为特征，属于典型的低温热液改造矿床。通过矿床地质、稀土元素和成矿模式的研究，对矿床成矿作用进行讨论。卤素，尤其氯是铊富集成矿的矿化剂，铊价态变化在富集成矿过程中具有重要作用。成矿流体是具有De和EU负异常的酸性溶液，基本保留了矿源层的稀土分布模式。在成矿过程中亲石元素和亲硫元素均不同程度地参与成矿作用。铊成矿期可分生物化学预富集期、构造活化成矿期和表生贫化期。

镧对微囊藻的生长效应及被富集的动力学研究

研究了稀土元素La3+对微囊藻生长效应及其被微囊藻富集的动力学过程 .结果表明 :当La3+的添加浓度小于 2mg·l- 1 时 ,对微囊藻的生长有促进作用 ,当La3+的添加浓度大于 2mg·l- 1 时 ,微囊藻的生长受到抑制 .

新疆哈密黄山地区铜镍硫化物矿床的稀土元素特征及意义

通过对新疆哈密黄山铜镍矿带典型矿床矿石矿物和含矿岩石的稀土元素地球化学研究,发现产于造山带的铜镍硫化物矿床的容矿镁铁-超镁铁质岩具有富水特征,部分硫化物稀土曲线呈特殊的"三重弯曲"模式,反应出由于多种液相(流体和熔体)共存,硫化物熔体中含有大量热液流体,在主成矿期(岩浆熔离期)后逐渐演化出富含气液的成矿流体。本区矿床稀土特征不同于克拉通边缘的铜镍矿床,造成上述热液流体参与成矿的原因在于含矿岩体本身富水,可能与碰撞后富水洋壳的拆沉熔融有关。

江西宁都葛藤嘴浅变质岩离子吸附型稀土矿成矿模式

江西宁都葛藤嘴离子吸附型稀土矿床是新近发现的新类型稀土矿床，成矿母岩为一套浅变质岩系。本文对矿区内的浅变质岩岩石类型、稀土元素含量及风化壳中稀土分布特征进行了研究，总结了成矿模式。矿区内岩石类型有变质砂岩、变质凝灰岩、千枚岩及片岩类。

稀土元素在土壤中迁移、转化模型的建立及验证

建立了稀土在褐土土壤中迁移、转化模型 ,定量评价稀土在土壤中的迁移、转化过程 .模型包括土壤中稀土化学热力学平衡体系、土壤水分物理形状和土壤剖面的稀土通量 .在中国农业大学内进行了田间实验 ,对模型进行了验证 ,模拟值与实测值能很好的拟合 .

一种大功率稀土纵向振动换能器的研究

本文采用通用有限元软件ANSYS对一种稀土纵向换能器进行了建模,利用软件中提供的机械振动、电磁场和耦合场等功能分析了换能器的电磁特性和机械振动特性,包括几种磁路结构的比较、磁致伸缩效应的建模、换能器的纵向振动模态以及在空气中的阻抗特性。

组合优化设计制备Y^(3+)/Dy^(3+)共掺Bi_2ZnB_2O_7新型荧光粉的发光性质

为获得Bi2ZnB2O7:Y3+/Dy3+新型荧光粉材料的最强黄光发光强度,运用均匀设计和二次通用旋转组合设计相结合法对Y3+/Dy3+最佳离子掺杂浓度进行优化研究,得到Y3+和Dy3+离子的最佳掺杂浓度分别为4.498mol%和6.001mol%.采用高温固相法合成最优样品,对样品结构进行表征,测定其激发光谱和发射光谱对Dy3+离子在Bi2ZnB2O7基质中的发光性质,研究发现:样品在452nm激发下,发射光谱主要由(460~500nm)蓝光发射、(550~610nm)黄光发射、(650~700nm)红光发射组成,分别对应于Dy3+的4F9/2→6H15/2、4F9/2→6H13/2及4F9/2→6H11/2跃迁;Bi2ZnB2O7基质为Dy3+提供了非中心对称的晶格格位;最优样品中Dy3+的荧光寿命为0.427ms,与相同浓度Dy3+单掺杂样品相比较可知引入Y3+在一定程度上提高了发光强度.

超磁致伸缩加速度传感器(英文)

稀土铁超磁致伸缩材料具有磁致伸缩逆效应，以此为基础的加速度传感器具有过载能力强、测量范围广、能在恶劣环境下工作、寿命长等一系列优异性能，在重工业、化学等工业领域的自动化控制系统中有着广泛的应用前景。为了有效地设计和优化超磁致伸缩加速度传感器，该文根据能量变分原理，建立了超磁致伸缩材料Tb-Dv-Fe制作的加速度传感器的磁-机械强耦合模型，应用该模型采用自编有限元软件，计算了传感器空气隙中的磁感应强度和施加加速度的关系，并测试了施加加速度从20—150m／s^2范围内传感器空气隙中的磁感应强度，发现计算结果与实验结果符合较好，相对误差小于9％，满足工程需要。表明建立的超磁致伸缩加速度传感器的磁-机械强耦合有限元模型是有效的，能够反映超磁致伸缩加速度传感器的输入输出关系。