Correlation Evaluation of Ion Adsorption-Based Rare Earth Leaching Performance Based on Zeta Potential Drop Leaching

Rare earth elements are indispensable raw materials for advanced aero-engines, special optical materials, and high-performance electronic products. With the development of the social economy, the global demand for rare earth resources is increasing, and rare earths have become a key metal for the development of new industries and frontier technologies that are highly valued both at home and abroad. Ion-adsorbed rare earth ores are an important source of rare earths, so the efficient green leaching of ion-adsorbed rare earths is important. Researchers found that the selection of an efficient green leaching agent for ion-adsorbed rare earths is based on the zeta potential of tailing clay minerals in addition to leaching efficiency, and both zeta potential and leaching ion concentration are related to mineral acidity and alkalinity, and the pH of tailing water suspension is a direct indicator of environmental water quality requirements. Therefore, the efficiency of the leaching process is closely integrated with the environmental evaluation, and the characteristics and correlation of the changes in zeta potential, pH, conductivity and pollutant concentration of the pulp of clay mineral content during the leaching process of ore leaching and tailings aqueous electrolyte solution leaching are studied by evaluating the leaching system, and a set of correlation leaching efficiency and environmental impact evaluation method is established based on the results of the above analysis, which is of scientific development of ion adsorption rare earth resources. It has important theoretical significance and practical application value.

Study on Adsorption Behavior of Rare Earth Complexes on Nanometer-Size Titanium Dioxide with ICP-AES

A new method of using nanometer TiO 2 as solid phase extractant coupled with ICP AES was proposed for speciation of rare earth elements. The adsorption behavior of rare earth complexes on nanometer TiO 2 was investigated. Effect of pH value, contact time, elution solution and interfering ions on the recovery of the rare earth complexes were studied. A quantitative recovery (>90%) was found in the pH range of 4～9.0 for Eu citric, 4.5～9.0 for Eu oxine and Eu HIBA, and 6.5～9.0 for Eu 3+ . Eu EDTA can not be adsorbed in the pH range studied. There is large difference in the adsorption behavior on nanometer TiO 2 between rare earth element and its complexes. The possibility of application of nanometer TiO 2 on the speciation of rare earth element was explored.

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.

Novel Approach to Characterization of Rare Earth Complexation with 1, 5-Bis(2-Hydroxy-5-Chlorphenyl)-3-Cyanoformazan in Presence of Cetyltrimethylammonium Bromide

The ternary interaction of 1, 5 bis(2 hydroxy 5 chlorphenyl) 3 cyanoformazan (HCPCF) with cetyltrimethylammonium bromide (CTAB) and rare earths (RE: Yb, Dy, Er and Eu) was investigated at pH 9.84 by the microsurface adsorption spectral correction technique (MSASC). The aggregation of HCPCF on CTAB obeys the Langmuir isothermal adsorption and the interaction of RE with the HCPCF CTAB aggregate was first found to accord with the monolayer binding. The effects of temperature and ionic strength of solution on the aggregations were made. The binary aggregate and the ternary complex were characterized.

SPECTRAL VARIATION AND CHARACTERISTICS OF LOW VALENCY RARE EARTH IONS IN COMPLEX OXIDESⅢ.EFFECT OF THE CRYSTAL ENVIRONMENT AND CHEMICAL FACTORS ON LUMINESCENCE PROPERTIES OF EUROPIUM (Ⅱ) ION

In this paper,the influence of crystal-field on the Luminescence properties of Eu^(2+) in complex oxides are studied theoretically by using purely electrostatic model,the dependence of the 4f^65d levels on Eu-O bond distance is given.Quantum chemistry calculation shows that the splitting extent of 4f^65d energy band in cubic or in octahedral fields will be inversely proportional to R^5,where R is the distance of Eu^(2+) to oxygen ligand.The value of R affects slightly the location of the centre of 4f^65d energy band.According to the exper- imental spectrum data,we have discussed the influence of the host chemical composition,the replaced sites of Eu^(2+) and degree of covalency of Eu-O bond on luminescence properties of Eu^(2+).Some regularity of fluorescence spectrum was observed. In alkali-alkaline earth-phosphates,the splitting extent of 4f^65d band (△E) becomes smaller as the Eu-O bond distance (R) increases.In Na_(3-x)(PO_4)_(1-x)(SO_4)_x and Na_(2-x)CaSi_(1-x)P_xO_4 hosts,d-d emission peak of Eu^(2+) will shift to shorter wavelength with the increase of x's value. The crystal structure data show that Eu^(2+) in K_2Mg_2(SO_4)_3 is affected more strongly by crystal-field and covalancy than in KMgF_3,so K_2Mg_2(SO_4)_3:Eu^(2+) emits blue light (E_(em)~m=400nm) and KMgF_3:Eu^(2+) produces ultraviolet fluorescence.

Adsorption of Rare Earth Ion La(Ⅲ) on Yunnan Bowl Tea Surface from Aqueous Solution

The adsorption characteristics of rare earth ion La(Ⅲ) on Yunnan bowl tea surface from aqueous solution and effects of various surfactants on the adsorption were studied. It was found that Yunnan bowl tea can adsorb strongly La(Ⅲ) and pH may affect drastically the adsorption amount of La(Ⅲ). The adsorption law of La(Ⅲ) on Yunnan bowl tea surface follows the Langmuir equation. The maximum adsorption amount of La(Ⅲ) can reach 15 mg·g (-1). A comprehensive adsorption model is suggested according to the experimental results.

Study on Electronic Structure of Rare Earth Complex with Dioxygen

The electronic structure and chemical bonding of[Ce(CO_3)_3O_2]_2^(8-) have been studied by INDO (Intermediate Neglect of Differentiated Overlap)method in this paper.The results obtained show that the HOMO of[Ce(CO_3)_3O_2]_2^(8-) is mainly composed of the anti-bonding π orbitals of the pcroxide ion(O_2^(2-)) and the LUMO is mainly composed of the 4f orbitals of the Ce(Ⅳ).The peroxide ion coordinates to ceric ion by means of σ and π dative bonds.After coordination the O-O bond of the peroxide ions is strengthened.By comparison with cerous complexes,the contribution of the 4f orbitals to bonding increases in the ceric com- plex.

Trace Determination of Scandium Using Adsorption Voltammetry of Mix-Polynuclear Complex of Scandium-Calcium-Alizarin Red S at Carbon Paste Electrode

A novel method was described for the determination of ultra trace amount of scandium based on the cathodic adsorptive voltammetry of the mix-polynuclear complex of scandium-calcium-alizarin red S at a carbon paste electrode (CPE). The 2nd-order derivative linear scan voltammograms of the adsorbed complex were recorded by model JP-303 polarographic analyzer from 0.0 to -1.0 V (vs. SCE). The experimental conditions of the working procedure were optimized. The results show that the complex can be adsorbed on the surface of the CPE, yielding one peak at -0.61 V, corresponding to the reduction of the alizarin red S in the mix-polynuclear complex at the electrode. The detection limit of Sc^(3+) is 1.0×10^(-10) mol·L^(-1) for 3 min of accumulation time. The procedure was successfully applied to the determination of trace amount of scandium in the sample ores.

Enhancing leaching efficiency of ion adsorption rare earths by ameliorating mass transfer effect of rare earth ions by applying an electric field

Improving the seepage of leaching solution in the ore body and strengthening the mass transfer process of rare earth ions during in-situ leaching are two critical methods to improve the leaching efficiency of rare earth.In this study,2 wt%MgSO_(4)solution was used for the indoor simulated column leaching experiment on rare earth samples and an electric field was applied at both ends of the samples.Then the effects of different intensities,initial application time and duration of the electric field on the rare earth leaching system and its mechanism were investigated.The results show that compared with the single MgSO_(4)solution leaching,applying an electric field with a strength of 6 V/cm can save the leaching time of 30 min and increase the flow velocity of the rare earth leachate by 26.98%.Under the optimal conditions of applying an electric field with a strength of 6 V/cm for 20 min to the leaching system after10 min of the rare earth leachate flowing out,the leaching efficiency of sample increases from 81.20% to 86.05% with the increase of 4.85%.The mechanism analysis shows that when a direct current electric field is applied to the rare earth leaching system,rare earth ions rapidly change from disorderly movement with the seepage into faster and directional movement.In addition,the seepage of the leaching solution is also improved due to the increase of the cross-sectional area of the seepage channel,the polarized water molecules migrate directionally by force from the negative pole,and the movement of the hydrogen is generated by the electrolytic water.More impo rtantly,based on the principle of in-situ leaching process,the layout of injection holes and deflector holes in this process provides a natural site for the electrode layout of the electric field.With the simple equipme nt and the ope ration,the rare earth leaching process with the applied electric field has high feasibility in industrial application.

STUDIES ON THE POLAROGRAPHIC ADSORPTIVE COMPLEX WAVE OF ISONUCLEAR COMPLEX OF RARE EARTH ION-COPPER(Ⅱ)-ALIZARIN COMPLEXON (ALC)

In our previous papers, the isonuclear complexes of RE (Ⅲ)-Ni (Ⅱ) (or Co(Ⅱ))-ALC had been studied by single-sweep polarograph. In the present note, the polarographic adsorptive complex wave of RE (Ⅲ)-Cu (Ⅱ)-ALC is reported. The mechanisms of the two are different, the former being the reduced wave of ligand (ALC),

The upstream rare earth resources of Malaysia:Insight into geology,geochemistry,and hydrometallurgical approaches

Peninsular Malaysia is already well known for having rare earth(RE)resources.However,pertinent data and information on upstream RE resources and reserve potential in Malaysia are yet to be established.It is vital to identify opportunities and challenges for value addition to rare earth elements(REEs)deposits in Malaysia.Therefore,this study evaluates the potential of Malaysian geological formations to serve as repositories for RE resources,such as rare earth minerals(REMs)and REEs,by elucidating the geological processes that are considered critical to the formation of the various deposit types.This paper concisely reviews possible REE mineralization in alkaline igneous rocks,pegmatites,placer deposits:monazite and xenotime,marine sediments,river and lake sediments,ion adsorption clays(IAC)deposits,and shale/coal deposits found in Malaysia.Comparisons between Malaysian deposits revealed that these deposits are potentially enriched with RE resources showing geological formations across the world.The paper reviews the methods and flowsheets used for the recovery of REMs and REEs from primary,secondary as well as alternative resources,with special consideration to the hydrometallurgical procedures comprising of leaching with acids and alkalis tailed by ion exchange,solvent extraction,or precipitation.The REEs ecosystem of Malaysia has also been discussed by considering the latest information from the Malaysian Investment Development Authority(MIDA),the REEs processing center,the Academy of Science of Malaysia(ASM),the People’s Republic of China(PRC),Lynas Malaysia Sdn.Bhd.(Lynas),Ministry of Energy and Natural Resources(NRECC),Jabatan Mineral&Geosains(JMG),Ministry of Science,Technology,and Innovation(MOSTI),and the Malaysian Chamber of Mines.The information on upstream RE resources and recent hydrometallurgical approaches provided in this study will contribute to developing and enhancing midstream and downstream RE-based manufacturing and processing operations in Malaysia.

Preparation of CeO_2-TiO_2/SiO_2 and Its Removal Properties for Fluoride Ion

The CeO 2 TiO 2/SiO 2 surface composites were prepared by sol gel method using SiO 2 as substrate and CeO 2 TiO 2 as coating film. The removal capabilities of the composities for fluoride ion and the influences of environment conditions of the preparation on the coating quality and removal capacities of F - were studied by experiments. SEM was used to study the surface morphologies of the films obtained. It is proved that n Ti(OC 4H 9) 4 / n CeCl 3·7H 2O =1, n CH 3COOH / n Ti(OC 4H 9) 4 =4 5, n C 3H 8O 3 / n Ti(OC 4H 9) 4 =0 3, R H=95% and t 110 ℃ are the acceptable conditions to get the surface composite whose adsorbent capacity( q ) and removal ratio( E ) for F - are 21 4 mg/g and 85 6% respectively.

Specific Adsorption of Trivalent La, Ce and Y by Soils and Ferro-manganese Oxides and Its Mechanism

In this paper, the adsorption-desorption variations of trivalent La, Ce, Y and mixed rare earths are discussed. The curves of pH-rare earth element adsorption were very well fitted to the equation: InD =a+b pH. The selectivity of RE (rare earth element) ions by the samples decreased in the following order: Ce> RE> La> Y, but the sequences were: La> Ce> Y on kaolinite and Y> La on amorphous iron oxide. Since the trivalent RE ions existed in the form of RE(OH)2+ in the solutions from pH < 5.45 to 7.0, the ratio of H+ displaced to RE3+ adsorbed in micromole was proposed to be about 2. The specific adsorption mechanism for RE was proposed to be that the RE ions complexed with oxide surface and the ion-surface complex of Ce3+ promoted oxidization on Mn hydroxide.

Types, Characteristics and Formation Mechanisms of Ion-adsorpted RE Deposits

Based on characteristics of unaltered rocks and REE patterns, ion-adsorpted RE deposits can be devided into four types including Y-rich and Eu-poor granites, Y-mid and and Eu low granites, Eu-rich granites, Eu-mid volcanic and subvolcanic rocks. The distribution of REE contents in weathered profiles shows an are-shaped pattern. It indicates that the REE contents are enriched in full weathered and upper parts of sub-weathered zones. The REE patterns-in weathered crusts also demonstrate characteristics essentially inherited from those in unaltered rocks; On the other hand, cerium; has a positive anomaly in soil zone and negative anomalies in full weathered and sub-weathered zones. Gradual decrease in the slopes of the REE pattern curves indicates that HREE contents are more enriched than LREE in lower portion of the pro files. REE abundance in unaltered rocks and appropriate climate are essential conditions for ion adsorpted deposits. According to experiments of the REE adsorption on clay minerals, REE concentrations, pH values and ion strength in solutions significantly affect adsorption contents and partition coefficients. The distribution of the REE in weathered profiles are controlled by percolation and adsorption coupling in groundwater-rock interaction systems.

La^(3+)/NH_(4)^(+)在双电层内交换过程中铵的吸附规律

离子交换反应过程中铵的吸附规律是浸矿剂用量计算的基础。以化学纯高岭土为吸附剂,以镧离子为吸附质,制备高岭土饱和镧矿样,采用不同浓度铵离子浸取矿样中的镧离子。结果表明:当铵离子浓度为1~5 mg/L时,铵只出现物理吸附;当铵离子浓度大于300 mg/L时,铵开始出现化学吸附;离子交换吸附开始时,铵离子吸附量为0.012 mg/g,双电层内ζ电势趋于0,滑动面与扩散层最外层几乎重合。通过铵的解吸实验,得到镧离子交换完全后,物理吸附态、离子交换态和固定态的所占比例分别为30%、65%和5%;铵的总吸附量与镧离子浸出量之间的摩尔比接近5∶1。此结果为高岭土作为主要黏土矿物的离子型稀土矿浸矿剂的用量计算提供理论依据。

一株分离自华南离子吸附型稀土矿的短小芽孢杆菌对稀土元素的吸附行为及机理研究

离子吸附型稀土矿是重要的表生矿床,提供了全球90%以上的重稀土。矿床中活跃的微生物能够通过吸附作用影响稀土元素的富集及分异,然而风化壳中的天然细菌对全配分稀土元素吸附行为及机理的相关研究仍然较为缺乏。本文选用离子吸附型稀土矿风化壳中分离出的短小芽孢杆菌,通过吸附实验研究在不同pH值、吸附时间和细菌浓度条件下,细菌对稀土元素的吸附行为。结果表明,短小芽孢杆菌对稀土元素的吸附容量最大可达41.9 mg/g,且重稀土元素在细菌细胞表面和水体之间的分配系数大于轻稀土元素。TEM图像显示,稀土元素在细菌表面形成沉淀;EDS分析显示,细胞表面大量Na、K、Ca等元素在与稀土元素发生离子交换后被脱除。细胞表面磷与稀土元素的分布一致性指示磷酸基团是稀土元素吸附的重要位点,重稀土元素通过与磷酸基团形成稳定的高配位络合物优先吸附在细菌表面。Zeta电位曲线表明,短小芽孢杆菌等电点为2.8,在高于等电点的pH值条件下,微生物对稀土的吸附存在静电吸引。因此,在表生环境中,微生物能够通过形成微沉淀、离子交换、表面络合和静电作用的多种机制吸附稀土元素,促进稀土元素的富集及分异。另外,短小芽孢杆菌有望作为潜在的生物吸附剂应用于稀土元素提取及回收。

龙陵县新寨-茅草园稀土矿特征及控矿条件浅析

龙陵新寨-茅草园地区花岗岩风化壳离子吸附型稀土矿床受内生地质和表生地质条件双重控制,主要赋存于白垩纪花岗岩体全风化层中下部及强风化层上部,V 1-1矿体分布面积38.59km 2,单工程控制矿体品位(SREO)0.035%~0.128%,平均0.047%;V 1-2矿体分布面积16.85 km 2,单工程控制矿体品位(SREO)0.035%~0.110%,平均0.048%,达大型远景规模,具有较好的勘查开发前景。

稀土La^(3+)离子在高岭石表面吸附的原位AFM研究

离子吸附型稀土矿是我国优势矿产资源,该类型矿床中,稀土元素主要是以离子的形式吸附在高岭石、埃洛石和铁锰氧化物等次生矿物上。本文主要通过原子力显微镜(AFM)的微观区域的力学测量功能,结合DLVO理论,研究原位水环境下稀土La^(3+)对高岭石不同表面(Si面和Al面)Stern电位的影响,揭示高岭石对La^(3+)的吸附能力随Si面和Al面表面性质不同而变化。实验结果表明:当La^(3+)浓度从0增加至1.0 mmol/L时,高岭石Si面的Stern电位由−46 mV转变为4 mV,表明高岭石Si面对La^(3+)有吸附作用;而Al面的Stern电位(在28~31 mV之间波动)几乎没有变化,表明高岭石Al面对La^(3+)的吸附作用不强。该研究表明在pH=4~6的风化壳条件下,高岭石Si面对La^(3+)的吸附可能占主导作用,Al面的贡献相对较小。本研究从微观角度揭示了稀土元素在高岭石不同表面的吸附特征,明确了高岭石不同表面对稀土元素吸附的贡献,为阐明风化壳中稀土的富集机制提供信息。

含铀钍氯化稀土溶液中离子交换法提铀

提出了一种利用铀酰离子与Cl^(-)的络合,从高稀土低铀的含氯体系浸出液中分离提取铀而将大部分的稀土元素和钍留在浸出液中的离子交换法。研究了离子吸附过程中体系pH和氯离子浓度等对吸附效果的影响。结果表明,在反应pH=0~1、Cl^(-)浓度7 mol/L的优化条件下,饱和树脂对铀的吸附量能够达到43.34 mg/g。后续采用7 mol/L HCl溶液酸洗和去离子水淋洗,回收钍和稀土的同时实现了铀的分离提取。该技术不改变传统稀土提取工艺流程,仅增加铀提取工艺技术单元,可实现铀的分离与浓缩,具有工艺流程短、不影响原有稀土提取工艺和矿产最大化利用的特点。

离子吸附型稀土矿电动开采技术初探

离子吸附型稀土矿是我国的特色资源,为全世界提供了90%以上的中、重稀土。然而,现有的离子吸附型稀土矿中铵盐原地浸出开采工艺存在环境污染严重、资源利用率低、开采周期长和滑坡地质灾害频发等问题,开发新一代高效绿色的离子吸附型稀土矿提取技术是国家稀土战略的紧迫需求。本文介绍了电动开采离子吸附型稀土矿的概念设想,并对电动技术的特点进行了初步探索。通过实验室土柱实验证实了电动开采离子吸附型稀土矿的可行性,结果表明:电动法稀土采收率高,约为同等条件下传统直接浸出方法的2倍。电动开采过程中,电压梯度对稀土回收有重要影响:电压梯度升高,稀土元素浸出速率提高,但同时电解强烈,导致阴极附近稀土元素沉淀含量增加,浸出液中稀土元素含量降低。其次,电动开采过程必须添加提取剂,提取剂起到增加体系导电性和交换解吸风化壳中稀土离子的作用。最后,结合电动过程阳极由于电解产生H^(+)的特点,本文还提出了采用碳酸钙作为复合提取剂成分的设想,起到了有效缓解土壤pH值变化,并释放钙盐的作用。