织金含稀土磷矿酸法浸出性能及预处理优化工艺试验

硫酸、盐酸、磷酸和硝酸对原生织金磷矿的稀土组分浸出效率不理想,总稀土浸出效率不到36%。采用焙烧活化—硝酸氨水混合预浸出处理织金磷矿,最适宜条件下,CaO和MgO的浸出率分别为24.55%和19.75%,相应的P_2O_5和稀土元素(Y、La、Nd、Ce)损失率为11.25%和3.61%。所得精矿中,Y、La、Nd、Ce和P_2O_5实现了不同程度的富集。预处理精矿的浸出性能较原矿显著改善,硝酸体系下P_2O_5和稀土元素(Y、La、Nd、Ce)浸出效率提高了近40个百分点。     

电感耦合等离子体原子发射光谱法测定镝铁电解粉尘中15种稀土元素

用硝酸和氢氟酸溶解试样,高氯酸冒烟除氟,在硝酸介质中用电感耦合等离子体原子发射光谱法(ICP-AES)测定了镝铁电解粉尘中La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y 15种稀土元素。为了提高高含量元素的测定准确度,在测定基体元素Dy时,采用铟作内标;为了消除基体效应对稀土杂质元素测定的影响,采用基体匹配的校准曲线。镝铁电解粉尘中铁含量很低(铁的质量分数不超过1%),对测定没有影响。实验方法测定了一镝铁电解粉尘样品,结果表明,La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Ho、Er、Tm、Yb、Lu和Y 14个稀土杂质元素测定值与ICP-MS的测定值基本一致,镝和14个稀土元素的合量与重量法测得的稀土总量吻合。     

Geochemical Implication of Rare Earth Elements in Process of Soil Development

Ｗｉｔｈｓｉｍｉｌａｒｃｈｅｍｉｃａｌｐｒｏｐｅｒｔｉｅｓ ,ｒａｒｅｅａｒｔｈｅｌｅｍｅｎｔｓａｒｅａｌｗａｙｓｐａｒａｇｅｎｅｔｉｃｉｎｎａｔｕ ｒａｌｅｎｖｉｒｏｎｍｅｎｔ.Ｈｏｗｅｖｅｒ ,ＲＥＥｍａｙｂｅｆｒａｃ ｔｉｏｎａｔｅｄｉｎｖａｒｉｏｕｓｇｅｏｃｈｅｍｉｃａｌｃｏｎｄｉｔｉｏｎｓｏｗ ｉｎｇｔｏｔｈｅｍｉｎｕｔｅｄｉｓｃｒｅｐａｎｃｙａｍｏｎｇａｔｏｍｉｃｓｔｒｕｃｔｕｒｅｓａｎｄｃｈｅｍｉｃａｌｐｒｏｐｅｒｔｉｅｓｏｆＲＥＥ .Ｆｕｒｔｈｅｒｍｏｒｅ ,ｄｉｓｔｒｉｂｕｔｉｏｎｓｔａｔ…     

The accumulation of the rare earth elements and of scandium in successive needle age classes of Norway spruce

The endogenous concentrations of Sc, La, Ce, Sm, Eu, Tb, Yb, and Lu were determined by neutron activation analysis in up to five successive needle age classes of Norway spruce (Picea abies). Trees from nine sites over different bedrocks were sampled individually. Concentration values found are generally much lower than those reported in the literature. This is attributed to the careful removal of any aerosols or soil particles from the needle surface prior to analysis. The concentration of each element increases linearly with the needle age class, i.e., the accumulation can be characterized by just one parameter, the yearly increment. This pattern is followed at small as well as at large concentrations. The accumulation behavior of the investigated elements is identical to that of Si. The relative concentrations of the rare earth elements (REE) in the needles are similar to those in the earth crust. There are significant correlations between the individual REE and between Sc and La.     

Selective dissolution of rare-earth element carbonates in deep eutectic solvents

Dissolution in choline-chloride based deep eutectic solvents(DES) of rare earth elements(REE) from high-purity single carbonate salts of Y, La, Ce, Nd and Sm and from their multicomponent mixtures and also bastn€asite mineral was assessed with a prospect to gain an understanding on the leaching behavior of bastn€asite ores as REE source from DES suspensions. Urea, malonic acid and citric acid were used in different proportions with choline chloride in order to form deep eutectic solvents with desired viscosity and functionality. The results obtained prove promising for use insolvato-metallurgical processes in terms of selective dissolution of the higher-atomic-number(Z) rare earth elements at the expense of the lower-ZREEs and the gangue-originating metal impurities, thus initiating separation among the different REE members from the early hydrometallurgical steps.     

共沉淀分离-电感耦合等离子体原子发射光谱法测定含难熔金属岩石中12种稀土元素

准确测定稀土元素含量,对是否开采含难熔金属岩石的矿山中稀土元素具有重要指导意义。实验采用Na₂O₂在750℃马弗炉中熔融样品,熔融体冷却后用盐酸(1+4)转入烧杯中,往溶液中加入氨水,以样品做载体,共沉淀分离除去钠盐及能与氨水形成络氨离子的金属元素,沉淀物用稀氨水洗涤、热稀盐酸溶解,以电感耦合等离子体原子发射光谱法(ICP-AES)测定试液中La、Ce、Sm、Eu、Gd、Tb、Ho、Er、Dy、Tm、Yb、Y,建立了含难熔金属岩石中12种稀土元素的测定方法。各元素校准曲线的线性范围为0.10~25μg/mL,方法的检出限0.20~1.0μg/g。按照实验方法测定含难熔金属岩石物料中La、Ce、Sm、Eu、Gd、Tb、Ho、Er、Dy、Tm、Yb、Y等12种稀土元素,结果的相对标准偏差(RSD,n=9)为3.2%~6.2%,加标回收率为90%~110%。实验方法可用于含难溶金属岩石中稀土元素含量为0.001%~0.50%(质量分数)的测定。     

风化成土过程中稀土元素地球化学特征

探讨了稀土元素在风化成土过程中轻、重稀土分异、富集、迁移规律以及 Ce、Eu异常特征。分别讨论了成土母质、气候条件、水化学性质、氧化还原条件及其它因素对稀土元素地球化学行为的影响。并提出了当前风化成土过程中稀土元素研究中存在的一些问题。     

共沉淀分离-电感耦合等离子体原子发射光谱法测定含难熔金属岩石中12种稀土元素

准确测定稀土元素含量,对是否开采含难熔金属岩石的矿山中稀土元素具有重要指导意义。实验采用Na₂O₂在750℃马弗炉中熔融样品,熔融体冷却后用盐酸(1+4)转入烧杯中,往溶液中加入氨水,以样品做载体,共沉淀分离除去钠盐及能与氨水形成络氨离子的金属元素,沉淀物用稀氨水洗涤、热稀盐酸溶解,以电感耦合等离子体原子发射光谱法(ICP-AES)测定试液中La、Ce、Sm、Eu、Gd、Tb、Ho、Er、Dy、Tm、Yb、Y,建立了含难熔金属岩石中12种稀土元素的测定方法。各元素校准曲线的线性范围为0.10~25μg/mL,方法的检出限0.20~1.0μg/g。按照实验方法测定含难熔金属岩石物料中La、Ce、Sm、Eu、Gd、Tb、Ho、Er、Dy、Tm、Yb、Y等12种稀土元素,结果的相对标准偏差(RSD,n=9)为3.2%~6.2%,加标回收率为90%~110%。实验方法可用于含难溶金属岩石中稀土元素含量为0.001%~0.50%(质量分数)的测定。     

HCl leaching behaviour of a bastnasite ore in terms of thorium and rare earth elements

Today, nuclear energy is considered as one of the most important energy sources. Thorium (Th) is also very important for nuclear energy because it can exist in nature spontaneously just as uranium (U) without depending on presence of another radioactive element. As plutonium and other trans-uranium elements are produced in lesser amounts compared to U in Th fuel cycle, Th is considered as the cleanest nuclear plant fuel. Bastnasite is one of the minerals which Th can be economically obtained. Bastnasite (Ce, La)FCO3, which is a rare earth fluorocarbonate, contains approximately 0.2–0.3% Th and 75% rare earth oxides. Within the scope of this study, dissolution behaviour of Th and rare earth element (REE) contents present in the bastnasite ores which is obtained from Eskisehir region of Turkey, with HCl leaching method was examined. In this context, the effects of different leaching parameters such as leaching time, HCl concentration and pulp temperature on Th and REE (Ce, Nd, La) dissolution efficiency and the best results have been obtained in the conditions of 5.48 M of HCl dosage, 220 min. of leach time and 70°C pulp temperature. In these optimum conditions, Th, Ce, Nd and La were obtained with dissolution efficiencies of 80.12, 77.12, 70.12 and 71.13%, respectively.     

纳滤膜对稀土离子的动态吸附行为及截留特性

采用经碳纳米管改性的亲水化纳滤膜浓缩提取稀土浸出液中的稀土离子,探究纳滤膜表面对La3+、Nd3+、Pr3+、Ce3+和Y3+5种稀土离子吸附动力学行为,考察稀土离子半径的大小对纳滤膜吸附性能和截留性能的影响.结果表明,Freundlich吸附方程比Langmuir方程能更好地描述稀土离子在纳滤膜表面上的动态吸附行为,用Freundlich吸附方程拟合后的结果相关度系数R2能达到0.999以上;在初始浓度为5×105 μg/L,温度为25 ℃,运行压力为0.6 MPa的实验条件下,纳滤膜对稀土离子的浓缩提取过程中,初始阶段的截留机理取决于纳滤膜表面的吸附作用和膜孔的机械筛分效应,膜面吸附达到平衡后以膜孔的机械筛分效应为主,此时La3+、Nd3+、Pr3+、Ce3+和Y3+的截留率分别为94.21 %、81.25 %、85.80 %、89.90 %和81.18 %,表明经碳纳米管改性的亲水化纳滤膜能高效浓缩截留稀土浸出液中的稀土离子.      

Rare earth double sulfates from pre-concentrated bastnasite

A mixture of rare earth double sulfates was produced from a Turkish bastnasite-containing pre-concentrate (low grade concentrate) by sulfuric acid baking, subsequent water leaching and precipitation with sodium sulfate. The results of acid baking and leaching indicated that recoveries of rare earth elements up to 90% were readily obtained and the recovery of hydrofluoric acid as a by-product was also possible. Reasonable decontamination of the rare earth double sulfate salt from impurities such as Th, Fe, Al and Mg was possible by rapid precipitation at 50 °C using 1.25 times the stoichiometric amount of Na₂SO_4. The total rare earth double sulfate content (TREDS) was > 90% and analysed 17.3% La, 15.6% Ce, 3.2% Nd, 1.1% Pr, 0.3% Sm, 0.03% Eu, 0.01% Yb and 0.02% Y together with about 0.7% Ca, Fe, Al and other impurities.     

Rare earth element（REE） geochemistry of phosphorites of the Sonrai area of Paleoproterozoic Bijawar basin,Uttar Pradesh,India

The rare earth element(REE) data from the Paleoproterozoic Bijawar basin,Sonrai phosphorites were used to interpret the depositional conditions of the phosphorites.The post archean Australian shales(PAAS) normalized REE patterns of the Sonrai phosphorites were characterized by negative Ce and positive Eu anomalies.Middle rare earth elements(MREE)-enrichment was a characteristic feature.Phosphorites showing the diagenetic effects on the REE patterns were limited.The observed Eu anomaly was indicative of an anoxic(or sulphate reducing) diagenetic environment of phosphate formation.Mixing of sea water and upwelling during the Paleoproterozoic was responsible for the recording of positive Eu and negative Ce anomalies in the Sonrai phosphorites.     

Accumulation of Rare Earth Elements in Various Microorganisms

The removal of rare earth elements （REEs） from solution in various microorganisms was examined. Seventy-six strains from 69 species （22 bacteria, 20 actinomycetes, 18 fungi, and 16 yeasts） were tested. Initially, Sm was used to test the removal capabilities of the various organisms. Gram-positive bacteria, such as Bacillus licheniformis, B. subtilis, Brevibacterium helovolum, and Rhodococcus elythropolis, exhibited a particularly high capacity for accumulating Sm. In particular, the B. lichemiformis cells accumulated approximately 316 μmol Sm per gram dry wt. of microbial cells. A full suite of screenings was then conducted to compare the abilities of the organisms to remove Se, Y, La, Er, and, Lu from solution. Tests were done with solutions containing one REE at a time. Accumulation was nearly identical for the various metals and organisms. However, when solutions with equimolar amounts of two REEs were used, preferential removal from solution was observed. When an Eu/Gd solution was used, gram-positive bacteria removed more Eu and Gd as compared to actinomycetes. When Eu/Sm combination was used, gram-positive bacteria removed equal mounts of both metals and some actinomycetes removed more Eu. The selective removal was quantified by calculating separation factors （S. F.）, which indicated that Streptomyces levoris cells accumulated the greatest proportion of Eu. The removal of REEs from a solution containing five metals （Y, La, Sm, Er, and Lu） was then examined. Mucorjavanicus preferentially accumulated Sm and S. flavoviridis preferentially accumulated Lu. The effects of pH and Sm concentration on the accumulation of Sm by B. licheniformis were also examined. Accumulation increased at higher pH and at greater solution concentrations.     

Competition among rare earth elements on sorption onto six seaweeds

Sorption has been proposed as a promising approach towards a sustainable water decontamination and recently to the recycling of rare earth elements (REE). Although living seaweed have been shown to be capable of removing REE from contaminated solutions, no studies have yet compared the effects of REE competition on sorption onto different groups of seaweed. These effects were analysed in the present study by exposing six living seaweeds (Ulva lactuca, Ulva intestinalis, Fucus spiralis, Fucus vesiculosus, Gracilaria sp. and Osmundea pinnatifida) (3 g/L, fresh weight) to mono-element and multi-element solutions of Y, La, Ce, Pr, Nd, Eu, Gd, Tb and Dy (1 μmol/L). Results show a preference towards light REE in mono-element solutions, which is reduced when in competition with other REE. The competitive effect is less pronounced in heavy REE indicating that these are still able to bind to the macroalgae despite the presence of competing ions. Contrary to water content (%), seaweed specific surface area (cm²/g) shows to be an important factor in the sorption of REE, since larger surface area is associated with higher removal and larger competitive effect.     

有机次膦酸在硝酸体系下提取稀土研究

本文采用溶剂萃取法,用有机次磷酸萃取剂从富含稀土元素镧(La）、钕(Nd）、钇(Y)、铈(Ce）的硝酸溶液中提取稀土。选择盐酸为反萃剂。考察了酸度、萃取剂浓度、相比和萃取时间对萃取率和反萃率的影响,结果表明,二异丁基膦酸萃取稀土的最佳条件为：室温,酸度0.2mol/l,萃取剂浓度40%,A/O比1:5,萃取时间15min,镧（La）、钕（Nd）,铈（Ce）和钇（Y）分别为41.68%、81.30%、81.29%和100%。当利用盐酸作为反萃实验的反萃剂时其最佳条件为：室温,初始水相稀土溶液为0.3 mol/L,反萃剂盐酸为6 mol/L,负载有机相与反萃剂盐酸溶液的体积比为1:6,将反萃的震荡时间改变为5min,应用上述条件的镧(La）、钕(Nd）、铈(Ce）、钇(Y)的反萃率分别为92.45%、94.88%、95.76%、93.34%。有机次膦酸对稀土元素（La）、钕（Nd）、铈（Ce）和钇（Y）的萃取效率不同。钇的提取率高于镧、钕和铈。它是一种有机次膦酸,对轻稀土元素亲和力低,对重稀土元素亲和力强。     

波长与能量色散复合型X射线荧光光谱仪测定海洋沉积物、水系沉积物、岩石和土壤样品中15种稀土元素

单独采用波长色散型X射线荧光光谱仪(WDXRF)或者能量色散型X射线荧光光谱仪(EDXRF)测定稀土元素时不仅存在谱线干扰问题,而且WDXRF分析稀土元素也存在灵敏度低的问题。为解决上述问题,实验采用粉末压片制样,使用最新型研发的波长与能量色散复合式X射线荧光光谱仪(WD-EDXRF)对海洋沉积物、水系沉积物、岩石和土壤样品中La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y 15种稀土元素进行测定。重点研究了波长色散和能量色散各自要分析稀土元素的测量条件。对于Dy、Eu和Tb使用分辨率高的WDXRF分析,其他12种稀土元素使用灵敏度高的EDXRF分析。采用45个海洋沉积物标样、水系沉积物标样、岩石和土壤标样,建立校准曲线。用经验系数法和散射线内标法校正基体效应,并用多元回归扣除稀土元素谱线重叠干扰。采用实验方法测定海洋沉积物、水系沉积物、岩石和土壤样品中稀土元素其检出限在0.01~2.8μg/g之间,较WDXRF降低了约一个数量级。对水系沉积物标样GBW07313进行精密度考察,各稀土元素测定结果的相对标准偏差(RSD,n=5)在0.10%~6.1%之间。对4类样品进行正确度考察,分析结果与认定值符合。     

氧化铝赤泥盐酸浸出稀土元素研究

在用盐酸浸出氧化铝赤泥提取氧化钪的过程中,稀土元素镧,铈,钕也一同浸出,进入到浸出液中。研究了拜耳法赤泥盐酸浸出稀土元素镧,铈,钕的过程。研究了浸出温度、酸度、液固比和浸出时间对稀土元素浸出率的影响。研究结果表明,影响稀土浸出率的因素依次是浸出温度,盐酸浓度,配料液固比,和浸出时间。当接近沸点109℃浸出时,镧、铈、钕浸出率提高最快。盐酸酸度在4～5 mol.L-1时,浸出率升高较快,5～7 mol.L-1时,缓慢提高,当超过7 mol.L-1时,镧、铈、钕的浸出率基本不变化。当液固比为4.0时,镧、铈、钕元素的浸出率较低,仅为60%～75%之间,当液固比提高到5.0时,稀土元素的浸出率升高较快。随着浸出时间的延长,氧化稀土的浸出率从60～180 min时,缓慢提高,在180 min时达到最大值,超过180 min后,变化不大。在温度为沸点(109℃),液固比6.0,时间180 min。盐酸浓度7 mol.L-1的条件下浸出,赤泥中La,Ce,Nd的浸出率能达到95%以上。     

贵州赫章铜厂沟铜矿稀土元素地球化学特征及成矿物源示踪

通过对赫章铜矿化带的野外地质调查、采样、室内显微镜下分析、化学分析、扫描电镜、X衍射成分分析,研究了铜矿的矿物组成、矿石类型特征(初步划分为砂岩型铜矿石和蚀变构造角砾岩型铜矿石),矿石铜品位为3.26%～3.88%。采用ICP-MS方法测定了赫章铜矿两类型矿石、赋矿围岩及峨眉山玄武岩的稀土元素及微量元素组成,并进行了稀土特征值等的对比研究;LREE/HREE比值为9.43～11.12,La/Yb比值为11.86～14.6,显示出各样品轻稀土明显富集;δCe值为0.75～0.84,显示出负异常。除HTC-3的δEu=1.11、显示出很弱正异常外,其余样品的δEu=0.94～1.06,Eu仅显示非常微弱的异常。铜厂沟铜矿岩矿样品微量元素分布模式图表明其分布特征具有同源性。通过研究各样品的稀土元素、微量元素地球化学特征、铜矿化蚀变过程中稀土元素的迁移规律及呈现继承性的特点,结合飞仙关组砂岩的形成环境,得出峨眉山玄武岩为铜矿成矿(矿化)的物质来源结论。     

电感耦合等离子体原子发射光谱法测定磷矿中微量稀土元素

样品经碱熔,溶液提取,沉淀富集后得到只含稀土元素的溶液,采用电感耦合等离子体原子发射光谱(ICP-AES)法测定磷矿中15种稀土元素La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y。主要考察了共存元素间的干扰情况,选择无干扰或干扰量对分析结果可以忽略不计的谱线为最佳分析线,标准曲线法直接测定磷矿中稀土元素。本法测定结果与ICP-MS测定结果相符合,可满足日常分析要求。     

粉末压片-X射线荧光光谱法测定土壤、水系沉积物和岩石样品中15种稀土元素

采用粉末样品压片制样,使用波长色散X射线荧光光谱仪对土壤、水系沉积物和岩石样品中15个稀土元素(La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y)进行测定。重点探讨了15个稀土元素的测量条件,如分析线、分析晶体,基体效应和谱线重叠干扰校正。使用60余个土壤、水系沉积物和岩石标样建立校准曲线,采用经验系数法和散射线内标法校正基体效应,并用多元回归准确扣除稀土元素谱线重叠干扰。重稀土元素的检出限多在0.2 μg/g以下。对土壤标准样品进行精密度考察,15个稀土元素测量结果的相对标准偏差(RSD,n=10)为0.74%～17%。对土壤、水系沉积物和岩石标准样品进行分析,测定值和认定值一致。