Evaluating the fractionation of ion-adsorption rare earths for in-situ leaching and metallogenic mechanism

The fractionation of ion adsorption rare earths (IAREs) along the depth in a shaft of a deposit at Dajishan, Jiangxi, China was comparatively evaluated using the partition values (PVs) and relative fractionation values (RFVs) of the leached rare earths (REs). It is found that both PVs and RFVs can objectively reflect the migration and fractionation of REs, but RE content and abrasion pH could not. However, the RFVs can provide more information to quantitatively evaluating the migration and fractionation characteristics of REs along the selected direction and region than PVs could, which is of significance for designing the optimal procedures of in-situ leaching based on the determined flow direction of injecting solution. It is demonstrated that the migration of Ce, Pr, and Nd along the depth direction is inert, and that of REs post Sm and Y is active. Meanwhile, the migration of La shows region characteristics which is active in the upper and inert in lower region. More interesting, the dependence of RFVs on atomic number of REs displays a tetrad group variation trend. However, the fractionation of REs among clay minerals with different particle sizes is not evident, especially for the clay in the bottom region. These results indicate that the migration and fractionation of REs not only are dominated by the adsorption of their hydrated ions, but also rely on their hydrolysis tendency, which provide information for understanding the metallogenic mechanism of IAREs.     

Separation of trivalent rare earths from nitrate medium using solvent extraction with a novel extractant 2-ethylhexyl ((2-ethylhexylamino)methyl) phosphonic acid

By introducing the amine group into the structure of P227, a novel extractant 2-ethylhexyl ((2-ethylhexylamino)methyl) phosphonic acid (EEAMPA, abbreviated as HA) was synthesized for the extraction and separation of trivalent rare earths (REs) from nitrate medium. The influence factors including extractant concentration, equilibrium time, HNO₃ concentration, separation factors, cycle regeneration, stripping acidity, and actual leach liquor of metal ions, were studied systematically. The results show that the extraction ability of EEAMPA for REs decreases with increasing acidity. A possible extraction mechanism is proposed and the extracted species as REHA₃(NO₃) are confirmed by the slope analysis method. The extraction equilibrium can reach faster than P227. It shows good chemical stability and cycling regeneration. Stripping studies show that HCl is an excellent stripping agent and REs can be effectively stripped from the organic phase.     

Non-ammonia enrichment of rare earth by magnesium oxide from rare earth leaching liquor in magnesium salt system

In order to solve the problem of ammonia-nitrogen pollution in the enrichment process of the ionadsorption type rare earth ore,the technology of non-ammonia precipitation with magnesium oxide precipitant was carried out.It is determined that the rare earth precipitation efficiency is 99.6% and the purity of rare earth concentrates is only 85.89 wt%under the optimum precipitation conditions.And the contents of MgO,SO_3 and Al_2O_3 in the rare earth concentrates are 5.12 wt%,6.77 wt%and 1.78 wt%,respectively.Furthermore,the thermo-decomposition process of precipitates was investigated by TGDSC,XRD and FI-IR.The thermal decomposition process consists of two stages:the dehydration of rare earth hydroxide and alkaline rare earth sulfate within 900 ℃ and the thermal decomposition of RE_2O_2SO_4 at 900-1300 ℃.Therefore,a high-temperature calcinations method for removing SO_3 from precipitates is proposed.When the precipitates are calcined at 1300 ℃ for 2 h,the rare earth concentrates with a purity of 92.03 wt%can be acquired.Moreover,the content of SO_3 in the concentrate is only 0.46 wt%.In the MgO precipitation and high-temperature calcinations process,the raw material cost is low and the quality of rare earth concentrates is acceptable.It could have great significance for nonammonia enrichment of rare earth from the rare earth leaching liquor,and finally solve the problem of ammonia nitrogen in the extraction process of the ion-adsorption type rare earth ore within magnesium salt system.     

含稀土高岭土精矿回收离子相稀土工艺研究

高岭土精矿具有粒度细、黏度大、渗透性能差、固液分离难、含铝高等特点,南方高岭土常伴有稀土,怎样从精矿中提取合格的稀土,目前国内外还没有一套成熟的工艺技术应用于工业生产上。依据高岭土矿中的稀土赋存特点,通过实验室小试、扩试和工业试验,探索出了一套成熟的工艺技术流程,把浸矿液与高岭土精矿加入到捣浆池中进行搅拌浸取,将矿浆通过板框压滤机压滤,得到的滤饼即是提取稀土后的高岭土精矿,滤液经后续处理即得到稀土产品。同时建成了生产线,已生产稀土10余t,为回收高岭土精矿中的离子型稀土提供了有效工艺。     

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...     

熔融制样-X射线荧光光谱法测定轻稀土精矿中稀土总量

作为稀土工业的原料,稀土精矿中稀土总量的测定方法步骤多、流程长。实验采用熔融制样-X射线荧光光谱法测定轻稀土精矿中稀土总量,研究了制样和测量条件。准确称取6.000 0g无水四硼酸锂和偏硼酸锂混合熔剂(质量比2∶1)于铂黄坩埚中,以0.500 0g硝酸锂为氧化剂消除试样中还原物质对铂黄坩埚的侵蚀,称取0.600 0g稀土精矿试样,再于试样表面均匀覆盖0.500 0g氧化硼防止试样喷溅,滴加0.5mL 20mg/mL的溴化铵溶液作为脱模剂。将坩埚放进预加热到1 050℃的熔样机内熔融19min制备样片,可消除矿物效应、粒度效应及表面效应。通过各稀土元素X射线荧光谱线的选择减少谱线干扰,以经验系数法校正谱线干扰和基体效应,用稀土精矿标样建立各稀土元素校准曲线。各组分校准曲线的相关系数在0.991~0.999之间,试样重复测量的相对标准偏差(RSD)小于0.5%,稀土总量测定结果与重量法一致。方法的精密度和正确度能够满足生产要求。     

Extraction of rare earths and yttrium with high molecular weight carboxylic acids

The extraction behaviour of trivalent rare earths namely La, Ce, Pr, Nd, Sm, Gd, Dy and Ho including Y (M(III), where M represents rare earths and yttrium ) from chloride medium has been studied with the solutions of high molecular weight carboxylic acids such as cekanoic, naphthenic, neo-heptanoic and Versatic 10 in dodecane. The effects of equilibrium pH, extractant concentration, metal ion concentration etc have been investigated. Using slope analysis technique it has been inferred that the metal ions form monomeric complex of the type [M(HA₂)₃] with carboxylic acids (H₂A₂, the dimer form). The stoichiometry of the species has also been confirmed using non-linear least square regression method. The carboxylic acids show different behaviour for Y extraction, it resembles to that of heavy rare earth (Ho), for sterically hindered acids (neo-heptanoic and Versatic 10) and to that with lighter rare earths (Ce, Pr) for the less sterically hindered acids (cekanoic and napthenic). The extraction order for the rare earths has been found to be the same with the four acids, i.e., La < Ce < Pr < Nd < Sm < Gd < Dy < Ho. The extraction constant (K_ex) of the systems and the separation factor amongst the rare earth pairs have been evaluated.     

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.     

Theoretical elucidation of rare earth extraction and separation by diglycolamides from crystal structures and DFT simulations

Diglycolamides(DGAs) show excellent application prospects for the extraction and separation of rare earth metals from highly radioactive liquid wastes and rare earth ores.The extraction ability of DGAs for rare earth ions in nitrate or chloride media increases with increasing atomic number of the rare earth metal.To understand the origin of this phenomenon,three binuclear crystals [Ln(TEDGA)3][Ln(NO_3)_6] of N,N,N',N'-tetraethyldiglycolamide(TEDGA) with rare earth ions La(Ⅲ),Pr(Ⅲ) and Eu(III) were prepared and characterized crystallographically.The three complexes belong to the triclinic crystal system,P-1 space group.The bond lengths of Ln-O_(amide) are significantly shorter than those of Ln-O_(ether) in the same crystal.The Ln-O_(amide) and Ln-O_(enher) bond lengths gradually decrease with increasing atomic number of the rare earth ion.The dihedral angle formed by TEDGA and metal ions through the tridentate coordination gradually increases with increasing metal ion atomic number,tending toward the formation of sizeable planar coordination structures for the most massive rare earth ions.The structures of the compounds formed by the extractant and metal ion were optimized by means of DFT simulations.We find that the interaction between TEDGA and the rare earth ion is dominated by electrostatic interaction by analyzing binding energy,WBIs,Mulliken charge,natural electron configurations,and molecular orbital interaction.The covalent component of the Ln-O bonds of the complexes increases with increasing metal atomic number.The observed increase in extraction and separation capacity of diglycolamides for rare earth ions with increasing atomic number might be due to the formation of two fivemember rings by one tridentate ligand.The rare earth ions with large atomic numbers tend to form planar structures with large dihedral angles with DGA ligands.     

降低离子型稀土原地浸矿残留稀土的对策探讨

离子吸附型稀土矿是国家战略资源,加强稀土废弃矿资源综合利用、充分回收残留稀土资源是今后稀土研究领域重要研究方向之一.文章在总结离子吸附型稀土矿提取工艺发展演变的基础上,重点分析了离子吸附型稀土废弃矿中残留稀土原因及其赋存状态.研究结果表明,离子吸附型稀土废弃矿中残留稀土的主要因素有浸矿过程的浸矿盲区、毛细现象、风化不完...     

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。     

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.     

EDTA滴定法测定稀土铝中间合金中稀土总量

准确测定稀土铝中间合金中稀土总量,对于有效控制稀土铝中间合金的生产技术和产品质量具有重要意义。用400g/L氢氧化钠溶液溶解试样,此时,稀土与氢氧化钠反应生成氢氧化稀土沉淀,而铝与氢氧化钠反应后以偏铝酸根的形式留在了试液中,过滤,实现了铝与稀土元素的分离;用盐酸溶解沉淀,加入氢氟酸,此时稀土和氢氟酸反应生成氟化稀土沉淀,而铁与氢氟酸反应形成络合物留在溶液中,过滤,实现了干扰元素铁与稀土元素的分离;加入盐酸和高氯酸溶解沉淀,用抗坏血酸还原残留铁(Ⅲ),乙酰丙酮溶液掩蔽残留的少量干扰元素铝,控制pH 5.5,以二甲酚橙作指示剂,用EDTA标准溶液滴定至溶液由红紫色变为亮黄色即为终点,建立了EDTA滴定法测定稀土铝中间合金中稀土总量的方法。将实验方法用于稀土铝中间合金(镧铝、钐铝、铒铝、钇铝)试样中稀土总量的测定,并在试样中分别加入不同量的于950℃马弗炉中灼烧过的高纯氧化镧、高纯氧化钐、高纯氧化铒和高纯氧化钇试剂进行加标回收试验,结果的相对标准偏差(RSD,n=11)不大于0.30%,加标回收率为99.6%～100.4%。选取镧铝、钐铝试样,按照实验方法测定其中稀土总量,并采用国标GB/T...     

Progress in green and efficient enrichment of rare earth from leaching liquor of ion adsorption type rare earth ores

Ion adsorption type rare earth ores (IATREOs) are a valuable strategic mineral resource in China, which feature a complete composition of fifteen rare earth elements and are rich in medium and heavy rare earth (RE) elements. In the leaching process for recovering rare earth elements from IATREOs, many impurities will be leached together with rare earth elements and enter the leaching liquor. An impurity removal-precipitation enrichment technique is currently applied to selectively recovery rare earth elements from the leaching liquor with the high content of impurities and low concentration of rare earth elements by using ammonium bicarbonate in the industry. However, a high loss of rare earth elements and severe ammonia nitrogen pollution are caused by this process. Therefore, more beneficial impurities removal technologies, mainly for aluminum, and green enrichment technologies with lower pollution are now urgently needed. For this purpose, this paper analyzed two aspects of research progress in recent decades: the green separation of rare earth elements and aluminum from leaching liquor and the green and efficient enrichment of rare earth elements. Finally, an approach for the high-efficiency and green enrichment of rare earth elements from leaching liquor of the IATREOs is proposed in several aspects, including impurity inhibition leaching, neutralization and impurity removal, alkaline calcium and magnesium salt precipitation enrichment, and centrifugal extraction enrichment.     

Extraction kinetics and kinetic separation of La(III), Gd(III), Ho(III) and Lu(III) from chloride medium by HEHEHP

According to the tetrad-effect, 14 elements of lanthanides can be divided into four groups. In our previous study, a new approach was proposed for the kinetic separation of four rare earth ions La(III), Gd(III), Ho(III) and Lu(III) coming from four groups. In that study, four rare-earth ions were kinetically separated from their coexisting mixed aqueous solutions, by performing liquid-column elution using the aqueous solution containing four lanthanide rare-earth ions as the stationary phase and the dispersed organic oil droplets containing HEHEHP (2-ethyl hexyl phosphonic acid mono 2-ethyl hexyl ester) extractant as the mobile phase. The study of extraction kinetics is very important for understanding the kinetic separation of rare earth ions, which was carried out in this paper. The extraction kinetics of La(III), Gd(III), Ho(III) and Lu(III) by HEHEHP diluted in heptane were investigated using single drop method. The different parameters affecting the extraction rate such as column length, specific interfacial area, rare earth ion concentration, extractant concentration, hydrogen ion concentration and temperature were separately studied and the rate equations are deduced. It is first order with respect to rare earth ion and HEHEHP concentrations, and negative first order with respect to hydrogen ion concentrations. The rate constants at 293.15 K are 10^−6.23, 10^−5.73, 10^−5.58 and 10^−5.43, respectively. The experimental results demonstrate that the extraction rate of La(III), Gd(III), Ho(III) or Lu(III) is diffusion-controlled, and the extraction reaction takes place at the interface rather than in the bulk phase. The extraction model was proposed. Besides, the kinetic separation of rare earth ions by HEHEHP oil drops was discussed.     

三溴偶氮胂分光光度法测定镁合金中稀土总量

采用三溴偶氮胂分光光度法,以盐酸分解含单一或混合轻稀土镧、铈、镨、钕和中稀土钐、钆的镁基合金,25 mL溶液中0.6 g/L显色剂用量为3～8 mL,盐酸浓度为0.5～1.0 mol/L,在640 nm波长下测定了镁基合金中的稀土总量。基体镁对测定无干扰。轻、中稀土总量的质量浓度在0.2～0.8 μg/mL范围内与吸光度呈线性,相关系数R²在0.999以上,表观摩尔吸光系数ε_RE为(1.10～1.19)×10⁵ L·mol^-1·cm^-1。按照实验方法测定各类稀土镁合金样品中稀土总量,结果的相对标准偏差(RSD,n=6)不超过1.6%;并与电感耦合等离子体原子发射光谱法(ICP-AES)测定结果相一致。     

Extraction and mutual separation of rare earths from used polishes by chemical vapor transport

A dry recovery process for rare earths from used polishes has been investigated by using a chemical vapor transport method via the formation of vapor complexes RAl _n Cl_3+3n (R=rare earth). The used polishes were chlorinated with N₂+Cl₂ gas mixture at 1273 K, and the resulting rare earth chlorides were transported chemically with the vapor complexes along the temperature gradient. Most rare earth chlorides, AlCl₃, and FeCl₃ were transported during 82 hours of heating. The rare earth chlorides were mainly condensed over the temperature range of 1220 to 730 K. On the other hand, AlCl₃ and FeCl₃ were deposited at temperatures below 400 K. The highest LaCl₃ and CeCl₃ purity of about 80 pct was obtained in the process.     

石蜡相分光光度法测定稀土的研究

系统研究了稀土 -8 羟基喹啉显色体系在石蜡相中的显色反应。在NH4Cl-NH3·H2 O(pH 9)介质中 ,稀土 -8 羟基喹啉显色络合物可定量被石蜡萃取 ,且固相色阶明显 ,RE2 O3 在 0～ 80 μg/ 5 0mL范围内符合比尔定律 ,从而建立了测量稀土的新的固相分光光度法。大多数干扰离子可通过控制溶液酸度进行萃取分离。方法应用于江西稀土矿中稀土总量的测定 ,结果满意。     

Extraction and back-extraction behaviors of 14 rare earth elements from sulfuric acid medium by TODGA

The unique physical and chemical properties of rare earth elements lay the foundation for their extensive application. N,N,N',N' Tetra-octyl-3-oxopentanediamide(TODGA) is excellent in its ability of extracting rare earth elements and it is favored for green initiative. In this paper, the extraction and back-extraction of14 rare earth elements by TODGA were studied. Experiments show that in conditions of 6 mol/L sulfuric acid, the extraction temperature of 25 ℃,the phase ratio of 1:1 and 0.04 mol/LTODGA(aviation kerosene as the diluent), the extraction rates of 14 rare earth elements including lanthanum, cerium, praseodymium,neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and yttrium were 99.00%-99.73%. Mixed with hydrochloric acid and nitric acid(HCl 3.5 mol/L, HNO_30.5 mol/L), the recoveries of the 14 rare earth elements are 91.52%-99.91% when the extraction temperature is 25 ℃ and the ratio is 1:1. The following application is based on the optimum conditions above with practical samples(from the roasting production line of China North Rare Earth High-tech Company Limited) for extraction and back-extraction experiments. Experiments show that TODGA has excellent enrichment effect on 14 rare earth elements, the extraction rates are 91.36%-99.80%, the back-extraction rates are 87.29%-99.64% and the total recoveries are 81.19%-99.44%.     

Comparative studies on Y(III) and Dy(III) extraction from hydrochloric and nitric acids by Cyanex 572 as a novel extractant

Extraction of Y(III) and Dy(III) from hydrochloric and nitric acids by Cy-572 in kerosene was studied. The factors affecting the extraction were separately investigated. The stoichiometry of the extracted species was deduced on the basis of slope analysis method. Evaluation of extraction equilibrium and stripping investigation was studied as well as saponification effect of Cy-572. The composition of the extracted metal species in the organic phase was found to be $\overline{{[\text{MA}}_3·{\left(\text{HA}\right)}_3]}$ for Y(III) or Dy(III) in both media. 1.0 mol/L HCl is the best stripping agent for each metal ion from the studied acidic media in one step. Saponified Cy-572 does not exhibit any selectivity towards the extraction of Y(III) or Dy(III) from both HCl and HNO₃ solutions. Based on the obtained results, the data were compared and the separation feasibility between lanthanides and Y(III) in the two media was discussed.