Characterization and Iron Removal Treatment of Ion-Adsorption Rare Earth Tailings in Southern China

The ion-adsorption rare earth tailings have become a serious environmental pollution in Southern China, yet the potential of their economical value has not been fully exploited. In this work, the chemical and mineral compositions of the ion-adsorption rare earth tailings were characterized by Mineral Liberation Analyze (MLA) and XRF. The results show that 91.98 wt% of the tailings are composed of kaolinite and quartz, latter of which was removed by the sieving method. The other minor minerals contain feldspar, biotite, muscovite, titanomagnetite and limonite. Amongst these, the iron-bearing minerals are mostly found in the titanomagnetite and limonite which can be mostly removed by using a periodic high-gradient magnetic separator with a magnetic induction of 0.6 Tesla. The Fe2O3 content of the tailings changed from 2.11 wt% to 1.06 wt% after the sorting process, which met the Chinese national standard of TC-3 grade raw materials for ceramic industry applications. The Fe2O3 content in kaolinite was further decreased after Na2S2O4 treatment.

Separation of Kaolinite from Ion-Adsorption Rare Earth Tailings in Southern China and Iron Removal Treatment

Several hundred million tons of ion-adsorption rare earth tailings exist in Ganzhou, Southern China, which is a severe environmental hazard. To reduce and reutilize the tailing, kaolinite has been separated from the tailings by mechanical separation in laboratory scale and pilot scale. The results show that the tailing is mainly composed of fine kaolinite and coarse quart. Quartz and kaolinite can be separated by sieves, shaker, spiral chute or hydrocyclone, which has the similar results in laboratory scale and pilot scale. 30.2% of the tailings can be re-sourced and applied in ceramic industries. 41.7% of kaolinite can be obtained after sorting and iron removal by magnetic separator in pilot scale, which can be applied in ceramic industries according to the Chinese national standard (TC-3). The results give a progressive solution to re-source the tailings economically.

Solvent impregnated resin prepared using task-specific ionic liquids for rare earth separation

A novel bifunctional task-specific ionic liquid(TSIL),i.e.[trialkylmethylammonium][sec-nonylphenoxy acetate]([A336] [CA-100]) was impregnated on intermediate polarized XAD-7 resin,and the prepared solvent impreganated resin(SIR) was studied for rare earth(RE) separation.Adsorption ability of the SIR was indicated to be obviously higher than that prepared by [A336][NO3] because of the functional anion of [A336][CA-100].Adsorption kinetics,adsorption isotherm,separation and desorption of the SIR were also stu...

Recovery of iron from Baotou rare earth tailings by magnetizing roast

The difference of physicochemical properties among minerals in Baotou rare earth tailings is not significant,which leads to a great difficulty in separation of minerals.In this article,the process of magnetizing roast and low-intensity magnetic separation was used to recover iron.Effect of calcination temperature,holding time and carbon/oxygen ratio on roasting efficiency was investigated.The parameters evaluating magnetizing roast efficiency and theoretical value were determined.X-ray diffraction(XRD)analysis was used to investigate the conversion of Fe phase after roasting.The results show that the best magnetizing roast conditions are calcination temperature of 650℃,holding time of 2.5 h,and carbon/oxygen molar ratio of 3.85.The best magnetization rate is 2.36,which is close to the theoretical value of 2.33.Based on experiments of low-intensity magnetic separation under different intensities,the best current intensity is 2.0 A to obtain the best separation results.Under the best condition,the concentrate grade of iron is 45.45% and the recovery of iron is 68.36%.Most of rare earth,fluorine,and phosphorus are enriched in the magnetic separation tailings.The XRD analysis shows that Fe exists in Fe2O3 before roasting and exists in Fe3O4after roasting.

Pore structure characterization and seepage analysis of ionic rare earth orebodies based on computed tomography images

Pore network structure of ore body is a diffusion channel of leaching agent solution that exerts a significant influence on seepage.The ore body structure,pore distribution,pore and throat size,and pore network characteristics of topsoil,weathered,and semiweathered layers of ionic rare earth ore in southern Jiangxi Province were explored in this study.The effect of leaching operation on the pore structure was investigated,and main factors affecting the seepage were analyzed.Results showed that the semiweathered layer presents a dense structure and a small number of unconnected pores.Pores of topsoil and weathered layers are mainly long and narrow column openings with some planar fractures.Even pore distribution and large size span were observed.Compared with the weathered layer,the topsoil layer demonstrates larger voids,smaller average pore volume and equivalent radius,and fewer coordination throats;however,the average equivalent radius of the throat in the topsoil layer is larger and largescale channels exist through ore body vertically.Hence,permeability of the topsoil layer is significantly higher than that of the weathered layer.Colloidal clay minerals migrate easily and the occurrence of silting in the small porosity blocks the throat and significantly decreases the permeability of the ore body in the leaching process.The equivalent radius of the throat is the key to the seepage.Reducing the migration of fine particles is an effective measure to protect the throat and shorten the leaching period.

Study of Transport and Separation of Rare Earth Ions through the Emulsion Liquid Membrane of Bis(2,4,4-trimethylpentyl)phosphinic Acid-Span 80-Toluene

It is indicated from a study of transport of rare earth ions through the emulsion liquid mem- brane of bis(2,4,4-trimethylpentyl)phosphinic acid-Span 80-toluene that transporting rare earth ions com- pletely and rapidly was realized under the optimum experimental conditions:1.0×10^(-3)～3.0×10^(-3)mol/L bis(2,4,4-trimethylpentyl)phosphinic acid and 2%～4%(W/V)Span 80 in toluene solution as membrane phase,0.50～2.0 mol/L HCl as inner phase,rare earth ion solutions with pH 3.5～5.0 as outer phase.Ac- cording to the differences of transport behavior for rare earth ions,it is possible to separate rare earth ions from mixed solutions of rare earth ions by this liquid membrane system.

Magnetizing roast and magnetic separation of iron in rare-earth tailings

Magnetic separation of iron in rare-earth tailings was achieved by magnetizing roast process with coal as reductant. Effects of the temperature, carbon to oxygen ratio, and cooling type on magnetic susceptibility and composition of rare-earth tailings were investigated. The results show that roast conditions with the temperature of 650 °C, carbon to oxygen ratio of 3.85, and holding time of 2.5 h are in favor of reduction of Fe_2O_3 to Fe_3O_4 when the roasted rare-earth tailings is cooled along with furnace. Under these roast conditions, magnetic susceptibility of rare-earth tailings is 2.36 that is very close to theoretical value(2.33). However, magnetic separation results of iron in rare-earth tailings cooled along with furnace are not satisfactory. Through comparing magnetic separation results of iron in rare-earth tailings cooled by different ways, it is found that water cooling is more favored of magnetic separation of iron in the roasted rare-earth tailings than furnace cooling and air cooling. Grade and recovery of iron in concentrate from rare-earth tailings cooled by water are 45.00%-49.00% and 65.00%-77.50%, respectively.

Applications of ionic liquids in electrodeposition of rare earths

The electrodeposition and electrochemical behaviors of rare earths in different ionic liquids are summarized. It is demonstrated that most of the rare earths can be electrodeposited in ionic liquids except cerium. Anion of ionic liquids appears to play a significant role in determining the electrochemical windows, and then deciding whether the corresponding ionic liquids can be used for rare earths electrodeposition. The electrochemical behaviors of the reduction process in ionic liquids are similar to those in high-temperature molten salts. The reduction of RE(III) to RE(II) has different reversibility, but the reaction of rare earths to their zerovalent state is irreversible.

Study on rare earth electrolyte of SDC-LSGM

Ce0.85Sm0.15O1.925 （SDC） and La0.9Sr0.1Ga0.5Mg0.2O2.85 （LSGM） were synthesized using Glycine-Nitrate Process （GNP）, and the composite electrolytes were prepared by mixing SDC and LSGM. An X-ray diffraction pattern indicated that the mixture of SDC and LSGM consisted of their original phases after heating at 1450 ℃ for 10 h. The electronic conductivity of SDC-LSGM composite electrolytes were measured by direct current polarization method using Hebb-Wagner ion blocking cell at 700-800 ℃ in the oxygen partial pressure range of 104-10-20 MPa and compared with the results of SDC. Typical polarization curves, which were theoretically predicted, were observed on all the samples. The slopes of lgσe-lgPo2 plot for all the composite electrolytes agreed with the theoretically predicted value of-1/4 at some intermediate oxygen partial pressures and -1/6 at low oxygen partial pressure. The electronic conductivity of SDC-LSGM composite electrolytes decreased with the increase in LSGM content, whereas the ionic transport number ti of all the samples increased with the increase in LSGM content.

Synthesis,Structure and Ionic Conductivity of La_(2/3-x)Li_(3x)MoO_4

A series of compounds, La 2/3- x Li 3 x MoO 4, were first prepared. Their structures are tetragonal scheelites with the cationic defects. The cell parameters a, c and values of c/a decrease with the increasing of the substitution amount (3 x ) of lithium ion. Cationic vacancies are getting more as Li + concentration is lower. The diffusion of lithium ion is predominant. The concentration of charge carriers increases with increasing the substitution amount (3 x ) of lithium ion, meanwhile, the concentration of cationic vacancies decreases. The conductivity approaches the best when the substitution amount (3 x ) of lithium ion is about 0.3. The conductivity of La 0.567 Li 0.3 MoO 4 is 6.5×10 -6 S·cm -1 at room temperature.

Synthesis and Crystal Structure of a Neodymium Ionic Associate [Nd(dmso)_7Cl][Bph_4]_2

The title compound, [Nd(dmso) 7Cl][Bph 4] 2(dmso=dimethylsulfoxide, Bph 4=tetraphenylboron anion) was synthesized in organic solvent acetone/EtOH and the structure was determined by single crystal X ray diffraction. The crystal is triclinic with space group P 1, and the crystal data are as follows: a =1 2554(1) nm, b = 1 2799(1) nm, c =2 4598(3) nm; α =93 53(1)°, β =104 50(1)°, γ =112 77(1)°, V =3 4722(6) nm 3, Z =2, M r=1365 01, D c=1 306 g·cm -3 . The crystal is composed of a big cation [Nd(dmso) 7Cl] 2+ and two big anions [BPh 4] -. The Nd 3+ is coordinated by a chlorine atom and seven oxygen atoms from seven dimethylsulfoxides forming a distorted square antiprism coordination polyhedron,while the BPh - 4 anion is charge equilibrium ion.

Phytoremediation of Rare Tailings-Contaminated Soil

In order to achieve the goal of circular economy and sustainable development of ecological environment,it is important to separate and recover associated elements from rare mineral resources.Compared with traditional physical and che-mical remediation methods of contaminated soil,phytoremediation is regarded as the most promising green in-situ restoration technology.The purpose of this review is to efctive alleviate the environmental problems caused by rare tailings contaminated soil through phytoremediation and realize the recovery of uranium-thorium,rare earth elements(REEs)and tantalum niobium.This review took rare tailings with uranium-thorium,REEs tantalum-niobium in China as the research object,then the background,significance,mechanisms and applcation strategies of phytoremediation were elaborated.In additon,the cases of spedies with tolerance to uranium thorium,tantalum niobium as well as REEs and their remediation mechanisms were summarized,respectively.Particularly,the typical plants represented by Bras-sica juncea,Sunflower,Phytolacca americana,Dicramopteris dichotoma,Salix SPP,etc,were very efctive in the reme-diation of rare tailings.The infuence factors of phytoremediation eficiency of tailings contaminated soil were discused.Two main factors were the mobility of heavy metals in soil(external cause)and the ennichment ability of species(inter-nal cause).Since the traditional phytoremediation also had some limitations in view of this,the work discussed some auxiliary methods(such as chelaing agents or microbial assisted restoration)to improve the effiency of phytoreme-diation.Finally,the future development of phytoremediation and potential applcation directions were explored.

Recovery of Rare Earth Elements Present in Mining Tails, by Leaching with Nitric and Hydrochloric Solutions

The rare earth elements (REE) include the group of 15 lanthanides, scandium and yttrium and have diverse applications in technological and nuclear areas. The existence of REE in massive solid mining wastes generated in leaching processes of copper minerals in the Atacama region of Chile generates the possibility of creating added value to the treatment of this type of waste and supporting the development of a circular economy, generating a useful by-product in different industries. In order to know the behavior of these elements present in the solid carrier waste, a leaching process was carried out by using two agents separately, corresponding to hydrochloric and nitric acid. The technical feasibility to recover REE from carrier tail was demonstrated, the best leaching agent for these elements being a hydrochloric solution, obtaining a maximum recovery efficiency of 64.5%, for an acid concentration: 3M, temperature: 40°C and (liquid/solid) ratio: 4. Lanthanum and cerium present the best individual recoveries compared to the other REE, with a maximum efficiency for a hydrochloric solution of 75.7% and 70.0%, respectively. The interaction of operational parameters that most influence the REE recovery corresponds to the temperature and the (liquid/solid) ratio. After 4 hours of leaching, REE recovery efficiencies remain practically constant. Acid consumptions correspond to 11 (kg HCl/ton mining tail) and 29 (kg HNO3/ton mining tail). The highest amount recovery ratios of these elements correspond to 0.355 and 0.224 (kg REE/ton mining tail), for hydrochloric and nitric solutions, respectively. These results influence the types of reagents and parameters to be studied in the following stages of the global process.

玢岩型铁矿床尾矿中磷、稀土战略性矿产资源调查与综合利用研究:以安徽凹山矿田为例

玢岩型铁矿床是铁矿石的重要来源,其除了赋存巨量铁矿资源外,还以产出大量磷灰石为特征,伴生大量的磷、稀土、钒等资源。20世纪,矿业开发大多只回收主要矿种铁,对伴生资源的评价和综合利用较少。文章以凹山玢岩型铁矿田尾矿库为研究对象,开展伴生资源调查评价和综合利用示范研究。通过系统钻探采样、矿物组合分析、元素赋存状态和综合利用实验等研究,文章揭示出尾矿库中经济矿物为磷灰石,可综合利用资源为磷和稀土,并估算尾矿库中磷储量超过115万t、稀土5万t,社会和经济效益巨大,可作为范例进一步研究并推广应用。

NH_(3)SO_(3)改性稀土尾矿催化剂NH_(3)-SCR脱硝活性及SO_(2)/H_(2)O耐受性能研究

采用球磨、微波焙烧方法制备了不同质量分数NH_(3)SO_(3)改性稀土尾矿NH_(3)-SCR脱硝催化剂。通过BET、SEM-EDS、XRD、NH_(3)-TPD、H_(2)-TPR分析了催化剂脱硝活性及SO_(2)/H_(2)O耐受性能。结果表明:NH_(3)SO_(3)改性使催化剂脱硝活性得到了显著提高,10%NH_(3)SO_(3)改性催化剂在300~350℃脱硝活性可达90%左右。SO_(2)/H_(2)O共同作用可将10%NH_(3)SO_(3)改性催化剂脱硝活性提高至97%,其促进作用保持了良好的稳定性,且具有可逆性。NH_(3)SO_(3)改性稀土尾矿后,催化剂比表面积、酸性位点及强度增加,表面活性物质分散度更高,弱化了尾矿矿物晶型,提高了催化剂吸附能力和氧化还原能力,从而提高催化脱硝活性,同时具备优良的SO_(2)/H_(2)O耐受性。

Investigations on mineralogical characteristics of rare earth minerals in Bayan Obo tailings during the roasting process

This paper focused on the investigation of the mineralogical characteristics of rare earth minerals from Bayan Obo tailings during the roasting process in the presence of coal,Ca（OH）_2 and NaOH.Roasting experiments and leaching experiments were carried out to study the decomposition of rare earth minerals.The results indicated that bastnaesite and monazite could be completely decomposed at 650 ℃ and the leaching ratio of rare earths could reach 89.78%.The reaction mechanisms of bastnaesite and monazite at 650 ℃were analyzed.For bastnaesite,both the outer layer decomposition and inner core decomposition occurred simultaneously during the roasting.However,monazite was decomposed in a spatial sequence starting from the outer layer and proceeding to the inner core.

Investigating the use of an ionic liquid for rare earth mineral flotation

Common collectors for rare earth mineral(REM) flotation,which include carboxylates and hydroxamates,face problems such as being non-selective and sensitive to impurity ions.A type of ionic liquid(IL),tetraethylammonium mono-(2-ethylhexyl)2-ethylhexyl phosphonate([N_(2222)][EHEHP]),has been investigated previously for rare earth elements(REE) solvent extraction,and was proven to be selective and effective.In this work,[N_(2222)][EHEHP] was evaluated as a collector in bastnasite(a primary REM source for REE production) flotation for the first time.The results were compared with quartz and hematite,two common gangue minerals in REM deposits.Zeta potential measurements and Fouriertransform infrared spectroscopy(FT-IR) were completed to investigate the surface chemical properties involved in the flotation of these minerals using this collector.The findings were compared with microflotation results.FT-IR and zeta potential measurements suggest adsorption of the collector’s phosphonate group onto bastnäsite and hematite,likely through chemisorption;whereas for quartz,the minimum micro flotation recovery is likely due to no adsorption of IL on its surface.Micro flotation re sults show higher collectability of [N_(2222)] [EHEHP] for hematite than bastnasite,the latter only shows appreciable recovery at pH 5 with elevated dosage of IL(500 g/t).To achieve better separation,a two-stage flotation scheme was designed and evaluated by bench scale flotation on a synthetic mineral mixture.The concentrates and tails were analyzed by magnetic separation,and it is found that bastnasite recovery over 90% with maximum upgrade ratio 1.7 can be achieved with elevated collector dosage.

赣南峰山离子型稀土矿床成矿机理探讨

以赣南大埠岩体西部峰山钻孔风化壳剖面为研究对象,在风化壳剖面各层地质特征研究的基础上,对风化壳剖面各层中含稀土矿物开展了扫描电镜和电子探针分析,探讨了风化壳剖面各层主、微量(包括稀土)元素和离子相稀土元素特征。研究表明,风化壳中稀土元素呈“弓背式”分布,矿体位于风化壳剖面2~9 m,w(REE)平均为516.8×10^(-6),离子相稀土元素浸出率为51%~84%,离子相与全项稀土元素总量分布特征一致。风化壳中稀土元素主要以离子吸附态形式和独立矿物(次生方铈矿和风化残余的磷钇矿、褐钇铌矿)形式存在,以离子吸附态形式为主。峰山风化壳离子吸附型稀土矿为轻、重稀土元素共生型稀土矿,以重稀土元素占主导,矿体上部相对富集轻稀土元素,下部相对富集重稀土元素。风化壳剖面中稀土元素的富集分异主要受轻重稀土元素地球化学行为的差异性、风化程度和黏土矿物含量联合控制。

赣南稀土尾矿山土体硝态氮累积特征研究

稀土开采会造成大量浸矿剂(硫酸铵)残留在土壤中,高浓度铵态氮(NH_(4)^(+)-N)可能在生物化学作用下转化为硝态氮(NO_(3)^(-)-N)。为探明NO_(3)^(-)-N在稀土尾矿山土体内的含量及影响因素,明确硝酸盐污染程度,本研究选择赣南地区一个离子型稀土原地浸矿尾矿山,由表土分层采样至基岩面,并分析土壤NO_(3)^(-)-N及相关的理化性质。研究结果表明,尾矿山土体NO_(3)^(-)-N含量变异范围非常大(2.80~193.99 mg·kg^(–1)),其平均值为46.30±55.16 mg·kg^(–1),表层土壤NO_(3)^(-)-N含量范围为2.89~6.75 mg·kg^(–1),与自然土壤相近;表层以下土壤NO_(3)^(-)-N含量明显高于自然土壤。尾矿山土体深部含矿层土壤NO_(3)^(-)-N含量明显高于表层,NO_(3)^(-)-N含量随深度的分布规律与自然土壤相反,这是矿体部分残留大量浸矿剂造成的。土壤NH_(4)^(+)-N含量主导了NO_(3)^(-)-N的产生量,但NO_(3)^(-)-N在土体不同深度、山体不同部位的累积量还受降雨淋溶及NO_(3)^(-)-N迁移过程的控制。开采结束4年后,尾矿山内累积的NO_(3)^(-)-N仍不断向环境中释放。长期来看,尾矿山土壤中富集的NH_(4)^(+)-N将不断转化为NO_(3)^(-)-N并随水迁移,持续威胁生态环境及人类健康。本研究可为稀土原地浸矿场地土壤及下游水体污染的评价和治理提供理论基础与科学支撑。

氮添加对稀土尾砂地猴樟幼苗根系生长、生物量分配及非结构性碳水化合物的影响

为探究氮添加对稀土矿尾砂地猴樟(Cinnamomun bodinieri)幼苗生长及非结构性碳水化合物(NSC)含量的影响,以1年生猴樟扦插苗为研究对象,选用硝酸铵钙作为氮肥(含N 15%),设置3种氮肥水平(CK(0)、N1(1.8 g·株^(-1))、N2(3.6 g·株^(-1))),分析不同氮添加水平下猴樟幼苗根系生长、生物量分配和NSC等指标的差异,探讨稀土尾砂地猴樟对氮添加的响应。结果发现:稀土尾砂地氮添加均增加了猴樟幼苗不同组织的生物量积累,其中N1处理下叶生物量、冠层生物量分别较N2处理下显著提升了44.75%、57.43%(P<0.05);N2处理下叶比重分别较CK、N1处理显著提升了123.53%、15.85%(P<0.05)。不论是粗根(直径>2 mm),还是细根(直径≤2 mm),氮添加均显著增加了植物的根长和根表面积(P<0.05),其中N1处理的促进效果最显著(P<0.05);N2处理下的比根长、比表面积均高于CK与N1,且与CK显著差异(P<0.05)。对NSC来说,N1处理提升了叶、茎中的可溶性糖质量分数,而N2处理下细根NSC质量分数分别比CK、N1显著降低了46.49%、28.61%。综上,在稀土矿尾砂地植被恢复过程中,宜选用1.8 g·株^(-1)硝酸铵钙氮肥对猴樟幼苗进行施肥管理。