Separation of Rare Earths by Solvent Extraction

Abstract

Solvent extraction technology for the separation of rare earths is a recent one. This is mainly due to the low separation factors between the adjacent rare earths for any type of extractants that have been investigated so far. In spite of this inherent weakness arising due to the gradual small changes in basicity in the series of rare earths few extractants have been used on commercial scale for the separation of high purity rare earths. In this paper the mechanisms involved in the extraction of rare earths using different types of extractants like tributylphosphate, di (2-ethylhexyl) phosphoric acid, 2-ethylhexyl 2-ethylhexyl phosphonic acid and quaternary ammonium salts have been discussed. The development of suitable mathematical models of the extraction behaviour of rare earths, particularly for the liquid cation exchangers, and their suitability for the development of the processes for the separation of rare earths is highlighted. Various process parameters that have been optimised using the computer programs developed by incorporating the mathematical models have been used in the purification of rare earths. The flow sheets designed for the separation of various rare earths are also given.     

阳离子交换纤维分离重稀土工艺方法的研究

介绍了离子交换纤维分离重稀土元素的方法，提出了小口径多端同时出口的分离方案，这对缩短分离时间，富集次要成分。提高分离效率及收率，不失为一种多效分离措施。以EDTA作为淋洗剂，同时采用NH4^＋作排代剂，达到了用Cu^2＋作为延缓离子分离重稀土元素的目的。作为溶剂萃取法一个补充手段，本法不失其应急之需，可作为小批量生产提供分析用基准试剂，科研息需高纯重稀土等需求之用。同时验证了阳离子交换纤维分离重稀土是完全可行的。     

Separation and recovery of associated rare earths from the Zhijin phosphorite using hydrochloric acid

The separation and extraction of associated rare earths from the Zhijin phosphorite mine is of great interest. Based on previous studies, the hydrolysis of phosphate ore using hydrochloric acid was systematically studied through extensive testing. Experiments were conducted to separate and recover the rare earths from the hydrolysis solution. Kinetic studies on the acidolysis of phosphorite using hydrochloric acid show that the use of hydrochloric acid in the acidolysis of phosphorite is mainly controlled by a chemical reaction and is also a diffusion-controlled reaction. When 210 L of HCL per 100 kg of phosphorite was used at 30 ℃ for 360 min, 96.1% of the P_2 O_5 and 95.0% of the rare earths are leached from the phosphorite. After defluorination and purification, the pH of the phosphate-acid solution is adjusted to 2.1 using sodium hydroxide, and a rare earth concentrate with rare earth content of 1.76 wt%is obtained; i.e., 90.1% of the rare earths are recovered. The rare earth content is increased to more than5 wt% through multiple enrichment processes, with a total yield of 59.5%.     

MATLAB simulation of preparation of Sm-loaded extractant directly from HEH（EHP）

Computer simulation of the preparation process loading rare earth(RE)directly from acidic extractant and RE chloride was established using MATLAB software.The mechanism of the extraction reaction was assumed,and then an experiment was conducted to confirm the mechanism and the apparent equilibrium constant of the reaction was determined as well.Owing to the involvement of H+ ion in the reaction between acidic extractant and RE chloride,the computer simulation of the process was more complicated than that of the extraction only between different rare earths.In the present work,MATLAB software was therefore introduced to handle the resolution of the complicated processing equation,and the simulation was performed by varying some key parameters including feed composition and phase ratio,etc.Consequently this work presented a simple method to simulate the H+ ion involved countercurrent extraction process of rare earths and also provided the practical references for the relative process designing.     

新型萃取剂Cyanex272在溶剂萃取稀土中的应用

通过新型萃取剂Ｃｙａｎｅｘ２７２同Ｐ２０４和Ｐ５０７的对比预示了Ｃｙａｎｅｘ２７２分离稀土的景，并介绍了近期Ｃｙａｎｅｘ２７２溶剂萃取分离稀土的研究动态，在此基础上提出几点建议。     

Studies on Expert System for Extraction of Rare Earths

An expert system has been developed,using LISP,for extraction of rare earths.The expert system was de-signed to mimic the deduction of chemists for rare earth separation.The knowledge base consists mainly of threeparts:(1)the extractant solvents common use and the separations of the individual rare earths;(2)the recom-mendation of process for the separation of mixed rare earths with extraetant P507;(3)the evaluation of econo-my for planning to build a rare earth factory The knowledge base of this system was organized as files includingframe files and rules.In addition,removing of the rules can be carried out in the file compiling window under theLISP environment.Both the forward-chaining and the reverse chaining were used simultaneously as the infer-ence strategies.The machine used was a microcomputer IBM PC-XT.     

Iron recovery and rare earths enrichment from Bayan Obo tailings using Coal-Ca(O H)2-NaO H roasting followed by magnetic separation

The recovery of iron and enrichment of rare earths from Bayan Obo tailings were investigated using CoalCa(OH)_2-NaOH roasting followed by magnetic separation.The influences of roasting temperature,roasting time,coal content,milling time,Ca(OH)_2 dosage and NaOH dosage on the iron and rare earths recovery were explored.The results showed that the magnetic concentrate containing 70.01 wt.% Fe with the iron recovery of 94.34% and the tailings of magnetic separation containing 11.46 wt.%rare earth oxides(REO)with the REO recovery of 98.19% were obtained under the optimum conditions(i.e.,roasting temperature of 650°C,roasting time of 60 min,coal content of 2.0%,milling time of 5 min,and NaOH dosage of 2.0%).The Ca(OH)_2 dosage had no effect on the separation of iron and rare earths.According to the mineralogical and morphologic analysis,the iron and rare earths of Bayan Obo tailings could be utilized in subsequent ironmaking process and hydrometallurgy process.     

重量法测定镧镍合金中稀土总量

准确测定镧镍合金中稀土总量,对于有效控制镧镍合金的生产技术和产品质量具有重要意义。因镧镍合金中镍含量在50%(质量分数,下同)以上,其他共存元素中钴约10%、锰约5%,故很难通过单一分离方式彻底分离共存元素。实验依次采用氟化分离、氨水分离、草酸沉淀方式分离共存元素,进而对镧镍合金中稀土总量的测定进行探讨。试样经盐酸和硝酸溶解,采用氢氟酸、氨水、草酸沉淀稀土,逐一分离去除干扰元素,在pH值为1.8~2.0条件下,稀土元素沉淀为草酸稀土,950℃灼烧草酸稀土生成稀土氧化物(不含氧化钍),再以镧对氧化镧换算成金属稀土总量。盐酸-硝酸能够完全平稳溶解试样,且测定结果(30.42%)与参考值(30.43%)相符;采用氟化分离、氨水分离、草酸沉淀的分离方式很好地去除了镍、钴、锰、铝、铜、铁等非稀土杂质;按照实验方法测定镧镍合金样品中稀土总量,结果的相对标准偏差(RSD,n=11)均小于0.50%;加标回收率为 99%~101%。按照实验方法选取两家实验室对镧镍合金中稀土总量进行测定数据比对,结果基本一致并与参考值相符。     

离子型稀土矿浸出过程优化与分析

针对赣南不同性质离子型稀土矿浸出率不同等问题,为确定不同性质离子型稀土矿浸出最佳工艺匹配参数,进行了两种不同性质离子型稀土矿的浸出试验研究,并对其进行了工艺优化和浸出过程分析.结果表明,不同性质的离子型稀土矿浸出的工艺条件应有所不同,同时各工艺条件中的影响因素的大小关系也不一样,应根据稀土矿石性质确定浸出工艺条件.      

重量法测定镧镍合金中稀土总量

准确测定镧镍合金中稀土总量,对于有效控制镧镍合金的生产技术和产品质量具有重要意义。因镧镍合金中镍含量在50%(质量分数,下同)以上,其他共存元素中钴约10%、锰约5%,故很难通过单一分离方式彻底分离共存元素。实验依次采用氟化分离、氨水分离、草酸沉淀方式分离共存元素,进而对镧镍合金中稀土总量的测定进行探讨。试样经盐酸和硝酸溶解,采用氢氟酸、氨水、草酸沉淀稀土,逐一分离去除干扰元素,在pH值为1.8~2.0条件下,稀土元素沉淀为草酸稀土,950℃灼烧草酸稀土生成稀土氧化物(不含氧化钍),再以镧对氧化镧换算成金属稀土总量。盐酸-硝酸能够完全平稳溶解试样,且测定结果(30.42%)与参考值(30.43%)相符;采用氟化分离、氨水分离、草酸沉淀的分离方式很好地去除了镍、钴、锰、铝、铜、铁等非稀土杂质;按照实验方法测定镧镍合金样品中稀土总量,结果的相对标准偏差(RSD,n=11)均小于0.50%;加标回收率为 99%~101%。按照实验方法选取两家实验室对镧镍合金中稀土总量进行测定数据比对,结果基本一致并与参考值相符。     

Comparison of Economical and Technical Indices on Rare Earth Separation Processes of Bastnasite by Solvent Extraction

ＴｈｅｂａｓｔｎａｓｉｔｅｉｎＢａｉｙｕｎ′ｅｂｏｏｆＩｎｎｅｒＭｏｎｇｏｌｉａｉｓｍｏｒｅｔｈａｎ７０％ｏｆｔｈｅｐｒｏｖｅｎｒａｒｅｅａｒｔｈｒｅｓｏｕｒｃｅｓａｌｏｖｅｒｔｈｅｗｏｒｌｄ．Ｔｈｅｓｉｍｉｌａｒｏｒｅｓｗｅｒｅｄｉｓｃｏｖｅｒｅｄ...     

X射线荧光光谱法在线测定稀土冶炼分离过程中钬铒铥镱

我国稀土冶炼分离过程复杂,但多数稀土企业仍依靠实验室离线分析指导工艺,导致分析结果严重滞后,因此现迫切需要一种高效稳定的稀土在线分析方法。实验应用稀土配分在线分析仪,建立了一种在线测定稀土冶炼分离过程中Ho、Er、Tm、Yb配分含量的方法。将采样管置于串级萃取槽水相分隔室内,在蠕动泵作用下将样品输送至分析区域,通过X射线荧光光谱法(XRF)进行检测和数据记录。实验将XRF测试条件优化为电压40 kV、电流600 μA、测试时间60 s,模拟现场工况条件下优化蠕动泵泵速为250 r/min,并采用基本参数法消除元素间吸收增强效应。样品11次测定结果的相对标准偏差(RSD)小于0.4%,实验室模拟及现场在线测试结果与电感耦合等离子体原子发射光谱法(ICP-AES)的离线分析结果吻合较好,测试结果滞后时间短,完全能够满足稀土冶炼分离过程工艺动态控制的测定需要。     

氮,氮,氮′,氮′-四辛基-3-氧戊二酰胺色谱柱分离-电感耦合等离子体质谱法测定混合稀土氧化物中重稀土

电感耦合等离子体质谱法(ICP-MS)测定稀土元素时,轻稀土元素Ce、Nd、Sm的氧化物等复合离子严重干扰重稀土元素Tb、Dy、Ho、Er的测定,因此对混合稀土中重稀土元素进行测定前一般需要先对其分离富集。实验在样品溶解后,将N,N,N′,N′-四辛基-3-氧戊二酰胺(TODGA)用硅藻土吸附后装柱,以0.1 mol/L HNO₃为样品溶液介质上柱,通过控制洗脱液的种类、酸度以及洗脱液流速,实现了轻稀土元素La、Ce、Pr、Nd与重稀土元素Tb、Dy、Ho、Er、Tm、Yb、Lu的分离和富集,建立了ICP-MS测定混合稀土氧化物中重稀土元素的方法。实验表明:控制洗脱流速为2.0 mL/min,用pH 2.0的HNO₃淋洗至淋洗体积约为500 mL,继续收集洗脱液,并用ICP-MS检测其中Nd₂O₃含量,直至洗脱液中Nd₂O₃的质量浓度小于200 ng/mL,可将轻稀土元素La、Ce、Pr、Nd及少量Y、Sm、Gd洗脱;再改用350 mL 1 mol/L HCl洗脱重稀土元素,可实现重稀土元素与La、Ce、Pr、Nd及部分Y、Sm、Gd的分离;通过选择¹⁵⁹Tb、¹⁶³Dy、¹⁶⁵Ho、¹⁶⁷Er、¹⁶⁹Tm、¹⁷²Yb、¹⁷⁵Lu为测定同位素可消除质谱干扰。将实验方法应用于混合稀土氧化物中重稀土元素的测定,加标回收率在93%～110%之间,相对标准偏差(RSD,n=8)在1.1%～10%之间。     

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 31966—2015中的草酸盐重量法进行方法比对试验,测定结果基本一致。     

海底稀土资源分离富集新工艺研究

研究了新型中重稀土资源,即海底沉积物中稀土分离富集新工艺。根据沉积物中稀土矿物相与脉石矿物相之间的表面物理性质差异以及不同矿物相在酸性溶液中的稳定性差异,研究了两段分离富集的新工艺流程。首先利用选矿方法将大部分脉石与稀土矿物进行初步分离,获得预富集了稀土的精矿,然后对稀土精矿进行二次化学富集,将杂质元素进一步去除,从而获得高品位的稀土中间产品。通过两次分离富集后,海底沉积物中约99%的杂质元素可被分离,稀土在中间产品中的品位可达6.41%,与原矿相比,稀土富集倍数达67倍,有利后续单个稀土的分离,同时中间产物酸耗可降低到原矿的1/12。     

计算机闭环控制串级萃取稀土分组过程的试验研究──兼论模拟混合澄清槽萃取过程的数学模型

在１０升混合室容积的多级混合澄清槽萃取器上，实施了溶剂萃取稀土分组生产过程的计算机闭环控制。在连续运行的五个月中，水相和有机相两个出口都稳定得到了９９．９９％纯度的产品。试验中发现基于模拟“分液漏斗法”串级萃取过程的数学模型进行的计算机仿真实验结果在萃取过程的动态响应上与混合澄清槽的实际情况有很大的差异，因此作者提出了模拟混合澄清槽萃取过程的数学模型。     

Extraction and separation of yttrium from other rare earths in chloride medium by phosphorylcarboxylic acids

Two phosphorylcarboxylic acids, 3-((bis(2-ethylhexyloxy))phosphoryl)propanoic acid (PPA) and 3-((bis(2-ethylhexyloxy))phosphoryl)-3-phenylpropanoic acid (PPPA), were synthesized for separating yttrium from other rare earths in the chloride feed of ion-adsorption type rare earth concentrate. The effect of the factors such as pH_1/2, temperature, saponification degree and phase modifiers was investigated. The separation efficiencies of PPA and PPPA are obviously better than the typical extractants such as sec-octylphenoxy acetic acid (CA-12) and naphthenic acid (NA). The extraction process of rare earths by PPA and PPPA is a cation exchanging reaction, which is similar to those of CA-12 and NA. The loaded rare earths in both PPA and PPPA systems can be effectively back-extracted by 0.5 mol/L HCl or higher concentration. A cascade extraction process for separating yttrium from other rare earths was developed using PPPA as the extractant. The yttrium product with the purity of 97.20 wt% was obtained by 35 stages of extraction and 12 stages of scrubbing.     

Recovery of Rare Earths, Niobium, and Thorium from the Tailings of Giant Bayan Obo Ore in China

The recovery of rare earths, niobium, and thorium from Bayan Obo??s tailings has been investigated because the Bayan Obo ore is rich in rare earths and rich in niobium and thorium, but it is mined mainly as an iron ore and will be used up soon. By carbochlorination between 823?K (550?°C) and 873?K (600?°C) for 2?hours, 76 to 93?pct of rare earths were recovered from the tailings, which were much higher than those from Bayan Obo??s rare earth concentrate, together with 65 to 78?pct of niobium, 72 to 92?pct of thorium, 84 to 91?pct of iron, and 81 to 94?pct of fluorine. This suggests a cooperative reaction mechanism that carbochlorination of iron minerals (and carbonates) in the tailings enhances that of rare earth minerals, which is supported by a thermodynamic analysis. Subsequently, niobium separation from the low-volatile, ultrahigh iron chloride mixture was achieved efficiently by selective oxidation with Fe₂O₃. This process, combined with the best available technologies for separation of rare earths and thorium from the involatile chloride mixture and for comprehensively using other valuable elements, allows the ore to minimize radioactive waste and to use rare metal resources sustainably in the future.     

Study on preparation and application of novel saponification agent for organic phase of rare earths extraction

In view of the problem of ammonia-nitrogen wastewater pollution in rare earths extraction and separation, the novel saponification agent of organic phase, which is magnesium bicarbonate solution, was prepared with the natural rich and cheap dolomite as raw material through carbonation process. The behavior and purification of main impurities ions in the carbonation process as well as the application effect of the novel saponification agent in the extraction and separation was researched. The results showed that the concentration of Fe, Al, Si impurities ions was less than 5 ppm in the saponification agent through the development of effective removal technology, respectively. When the novel saponification agent was used in the extraction and separation, magnesium utilization rate was more than 95%, and rare earths extraction rate above 99.5% has achieved. Therefore, the technology could replace ammonia-water to saponify the organic phase in rare earth extraction and separation process.     

稀土资源收储专项储备量的确定

文中梳理了定性确定稀土资源储备规模的文献资料,利用现实可提供储备量与预测趋势可提供储备量的波动关系以及储备量模拟模型,定量化计算了稀土资源收储储备量,以2000-2011年的稀土资源产、销、存数据为例,设计了稀土资源可提供储备量波动范围分别为0%、5%和10%的3个方案,模拟计算了3个方案的年最大储备量、最小储备量、专项储备量和绝对储备量,初步确定了2012年中国稀土资源收储的专项储备量.国家储备进行储备决策时,可以根据国家财政状况、国内外经济景气状况和稀土产业发展状况,选择实施高度储备、中度储备还是低度储备,并在不同储备思路指导下动态调节专项储备量.