萃取色谱分离稀土元素进展

评述了近年来我国学者对萃取色谱分离稀土元素各种体系的研究及其在高纯稀土分离方面的应用，并对高纯稀土制备的发展方向进行了展望。     

稀土萃取分离工艺研究新进展

综述了近年来我们实验室在稀土萃取分离工艺研究方面取得的一些新进展。主要有:(1)稀土萃取分离工艺的计算机一步放大;(2)回流启动技术;(3)三出口新工艺;(4)稀土料液浓缩新方法;(5)稀土与非稀土元素的分离;(6)专家系统技术在稀土萃取分离工艺控制中的应用。     

酸性磷类萃取剂MANPP分离稀土元素的研究

报道一种在盐酸体系中,对稀土的萃取平衡常数及对若干稀土的分离因数均大于P507的新型酸性磷类萃取剂及其萃取分离稀土的机理。     

轻稀土萃取分离工艺技术经济评价

在传统、三出口、组合联动轻稀土萃取分离工艺研究分析的基础上,设计开发了带模糊分离和置换萃取等技术的组合联动轻稀土萃取分离新工艺流程,并与传统工艺进行了技术经济比较。经比较证明,组合联动轻稀土分离新工艺先进合理,充槽投资更省,生产成本更低,生产废水排放更少。     

P538纸上萃取色层法分离稀土元素及萃取机理的研究

研究了以P538为固定相,用不同浓度的无机酸或无机酸与其盐的混合溶液作展开剂进行反相纸层析时对稀土R_F值的影响。实验表明,所得的R_F值对稀土元素的原子序数作图时,有明显的四分组效应。根据同一元素在不同酸中的R_F值的顺序,可知在不同的无机酸中,P538对稀土的萃取能力顺序为:HCl>HNO_3>H_2SO_4。稀土元素与P538反应时的摩尔比及释放出的氢离子数分别为1和3。萃取温度对稀土元素的R_F值无显著影响;重稀土组的分离系数(β_Z~(Z 1))比轻稀土组大,因而P538纸层析可将重稀土(Ho～Lu)相互分离。     

三元稀土萃取分离工艺中有效分离系数的研究

本文通过计算机模拟计算,对恒定混合萃取比的三元稀土萃取分离工艺中有效分离系数的变化规律进行了研究,并在串级萃取理论的基础上提出了一种采用有效分离系数确定三元稀土萃取分离工艺参数的方法。     

石油亚砜萃取色谱法分离钪和稀土

提出以石油亚砜为固定相,硫氰酸铵和盐酸为流动相的萃取色谱法分离钪和稀土。研究了影响钪和稀土分离的条件,本体系中钪和钕的分离系数达到1.3×10~4。该方法可用于混合稀土中小量钪的分离,提取和分析。     

石油亚砜萃取分离稀土和钪

本文研究了稀土和钪在 PSO-HCl、PSO-HNO_3、PSO-NH_4SCN-HCl 体系中萃取行为、其中 PSO-NH_4SCN-HCl 体系的β_(Nd)~(Sc)高达5×10~3。应用于大量稀土中小量钪的分离和测定。     

稀土萃取分离流程的优化选择

溶剂萃取分离法是稀土分离的主要方法。稀土萃取分离的工艺包括溶剂萃取体系、工艺参数的优化选择[1-2]和分离流程的优化选择[3]。优化目的是减少消耗,降低成本。1　选择稀土分离流程的判别式用Ａ、Ｂ、Ｃ分别表示单一稀土元素或多个稀土元素的组合,萃取次序为Ａ-Ｂ-Ｃ,其摩尔分数分别为ｆＡ、ｆＢ、ｆＣ。βＡＢ为Ａ/Ｂ切割的分离系数,βＢＣ为Ｂ/Ｃ切割的分离系数。分离ＡＢＣ混合稀土的二出口流程有以下两种:流程Ｉ　　　　　　　流程ＩＩ选择Ａ/ＢＣ切割即选择流程Ｉ,选择ＡＢ/Ｃ切割即选择流程ＩＩ。显然,分离流程的优化选择实质上…     

Energy-adjusted pseudopotentials for the rare earth elements

Nonrelativistic and quasirelativistic energy-adjusted pseudopotentials and optimized (7s6p5d)/[5s4p3d]-GTO valence basis sets for use in molecular calculations for fixed f-subconfigurations of the rare earth elements, La through Lu, have been generated. Atomic excitation and ionization energies from numerical HF, as well as SCF pseudopotential calculations using the derived basis sets, differ by less than 0.1 eV from numerical HF all-electron results. Corresponding values obtained from CI(SD), CEPA-1, as well as density functional calculations using the quasirelativistic pseudopotentials, are in reasonable agreement with experimental data.     

Optimization of preparative chromatographic separation of multiple rare earth elements

This work presents a method to optimize multi-product chromatographic systems with multiple objective functions. The system studied is a neodymium, samarium, europium, gadolinium mixture separated in an ion exchange chromatography step. A homogeneous Langmuir Mobile Phase Modified model is calibrated to fit the experiments, and then used to perform the optimization task. For the optimization a multi-objective Differential Evolution algorithm was used, with weighting based on relative value of the components to find optimal operation points along the Pareto front. The objectives of the Pareto front are weighted productivity and weighted yield with purity as an equality constraint. A prioritizing scheme based on relative values is applied for determining the pooling order. A simple rule of thumb for pooling strategy selection is presented. The multi-objective optimization gives a Pareto front which shows the rule of thumb, as a gap in one of the objective functions.     

ICP-MS同时测定植物性食品中稀土元素的方法研究

建立了植物性食品中16种稀土杂质(Sc、Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb和Lu)元素的电感耦合等离子体质谱(ICP-MS)的分析方法.考察了基体效应及质谱干扰,应用In内标,有效地补偿基体效应所引起的测量偏差,建立修正公式校正质谱干扰.对照分析了参考标准物质.对所测定元素,校正曲线的相关系数为＞0.9990,方法的检出限低于2.2 pg/g(Sc为95pg/g),回收率为92%～106%,RSD优于3.2%(n=7).     

Reversed-phase thin-layer chromatography of the rare earth elements

Summary Partition chromatographic behaviour of the rare earth elements on C₁₈ bonded silica reversed-phase material has been investigated by thin-layer chromatography in methanol — lactate media. The rare earth lactato complexes are distributed and fractionated on bonded silica layers without ion-interaction reagents. The concentration and pH of lactate solution, methanol concentration and temperature have effects on the migration and resolution of the rare earth elements. The partition system is particularly suited to separate adjacent rare earths of middle atomic weight groups, allowing the separation of gadolinium, terbium, dysprosium, holmium, erbium and thulium to be achieved by development to 18 cm distance.     

Detailed study on simultaneous separation of rare earth elements by capillary electrophoresis

Separation of all rare earth elements (REEs) by capillary zone electrophoresis was investigated in a system of alpha-hydroxyisobutyric acid (HIBA) as a main complex reagent and acetic acid (HAc) as an assistant complex reagent. In the combined system, ligand Ac- plays an important role in improving separation of Eu and Gd, and Y and Dy. The calculated ratio of Ac- to HIB- concentrations was compared and demonstrated that Eu and Gd, and Y and Dy tend to be separated at lower, and higher ratio of the two free ligands, respectively. An operational buffer system was developed for a complete separation of all REE ions.     

离子色谱非梯度洗脱法同时测定7种稀土元素的研究

研究了离子色谱非梯度洗脱法同时测定7种稀土元素的方法,用草酸一元淋洗液,采用非梯度洗脱方式,以PAR为显色荆,在520nm处对7种稀土元素同时进行检测。考察了淋洗液的组成、浓度、pH及流量等因素对被测组分分离和测定的影响,选择了显色剂的浓度、流量和检测波长,并进行了干扰实验,在选定的最佳分离测定条件下,测定了7种稀土元素的线性回归方程、检出限0．04～0．20mg／L,回收率在94．3％～101．5％之间。本方法已用于稀土氧化物的高温氯化产物中稀土元素的测定。     

Investigation of the separation of scandium and rare earth elements from red mud by use of reversed-phase HPLC

A chromatographic method has been developed for separation and determination of scandium (Sc) and rare earth elements (REEs) in samples from a red mud (RM)-utilization process. Reversed-phase high-performance liquid chromatography (RP-HPLC) with post-column derivatization using 4-(2-pyridylazo)-resorcinol (PAR) and UV–visible detection at 520 nm was tested using different gradient elution profiles and pH values to optimize separation and recovery, primarily for Sc but also for yttrium and the individual lanthanides, from iron present in the samples. The separation was performed in less than 20 min by use of a mobile phase gradient. The concentration of -hydroxyisobutyric acid (-HIBA), as eluent, was altered from 0.06 to 0.4 mol L^–1 (pH 3.7) and 0.01 mol L^–1 sodium salt n-octane sulfonic acid (OS) was used as modifier. Very low detection limits in the nanogram range and a good resolution for Sc and REEs except for Y/Dy were achieved. Before application of the method to the red mud samples and to the corresponding bauxites, Sc and REEs were leached from red mud with 0.6 mol L^–1 HNO₃ and mostly separated, as a group, from the main elements by ion exchange/selective elution (6 mol L^–1 HNO₃) in accordance with a pilot-plant process developed in this laboratory. After evaporation of the eluent to dryness the extracted elements were re-dissolved in the mobile phase. By use of this chromatographic method Sc, which is the most expensive of the elements investigated and occurs in economically interesting concentrations in red mud, could be separated not only from co-existing Fe but also from Y/Dy, Yb, Er, Ho, Gd, Eu, Sm, Nd, Pr, Ce and La. All the elements investigated were individually recovered. Their recoveries were found to be nearly quantitative.     

茶叶中稀土元素的萃取分离-ICP-AES法测定

采用1-苯基-3-甲基-4-苯甲酰基-5-吡唑酮(PMBP)苯溶液萃取分离-ICP-AES法同时测定茶叶中15种稀土元素,消除了基体的干扰,并对样品前处理方法、萃取分离条件进行了考查.方法回收率为: 92.3%～112%,相对标准偏差＜2.5%.在最佳工作条件下,测定了茶叶标准物质(GBW07605)中稀土元素,结果与标准值吻合.     

Pseudopotential study of the rare earth monohydrides,monoxides and monofluorides

Nonrelativistic and quasirelativistic energy-adjusted pseudopotentials for fixed 4f subconfigurations of the rare earth elements La through Lu together with corresponding optimized valence basis sets have been used in SCF and CI(SD) calculations to determine the spectroscopic constants for the energetically low lying superconfigurations of the lanthanide monohydrides, monoxides and monofluorides. The experimentally observed trends in dissociation energies, bond lengths and vibrational frequencies for the ground states of the calculated superconfigurations of the monoxides and monofluorides are well reproduced. The results for the monohydrides are mainly predictions.     

Efficient recovery of rare earth elements from coal based resources: a bioleaching approach

Rare earth element (REE) resources in coal-related materials are vast. Assuming a coal production rate of 600 million short tons per year with an average REE content of 200 ppm, the potential REE resource is 120,000 tons per year, which is similar to the annual global production of REEs. Most of those resources that are associated with coal-related materials are found in association with the gangue or ash-based content from the coal ore. Under normal coal plant operation, the REEs often end up in refuse piles or tailings impoundments. In many cases, these REEs can be recovered at low cost using appropriate coal preparation, heap leaching, solvent extraction and/or selective precipitation, followed by subsequent separation and purification of individual REEs. In the present research, the processing approach uses a natural pyrite stream, which was removed during coal cleaning and used to enhance leaching. Bio-oxidation has been used commercially to accelerate leaching, and this approach has been applied to coal-based materials. The ferric ions generated from bio-oxidation oxidize sulfide minerals such as pyrite, which generates acid. Both acid and ferric ions are helpful for leaching REEs, as well as for removing residual sulfides, thereby preventing future acid mine drainage and related liabilities. It can be seen that, recovery of REEs from coal waste materials can enable coal producers to use untapped REEs resources to produce revenue and extend resource life while simultaneously reducing future environmental issues and costs.