Study on a novel flat renewal supported liquid membrane with D2EHPA and hydrogen nitrate for neodymium extraction

The Nd(III) extraction in flat renewal supported liquid membrane(FRSLM),with polyvinylidene fluoride membrane and renewal solution including HNO3 solution as the stripping solution and di(2-ethylhexyl) phosphoric acid(D2EHPA) dissolved in kerosene as the membrane solution,was investigated.The effects of pH in the feed phase,volume ratio of membrane solution to stripping solution,concentra-tion of HNO3 solution and concentration of carrier in the renewal phase on extraction of Nd(III) were also studied,respectively.As a result,the optimum extraction conditions of Nd(III) were obtained when concentration of HNO3 solution was 4.00 mol/L,concentration of D2EHPA was 0.100 mol/L,and volume ratio of membrane solution to stripping solution was 1.00 in the renewal phase,and pH was 4.60 in the feed phase.When initial concentration of Nd(III) was 2.00×10-4 mol/L,the extraction percentage of Nd(III) was up to 92.9% in 75 min.     

Synergistic extraction of rare earth by mixtures of 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester and di-(2-ethylhexyl) phosphoric acid from sulfuric acid medium?

The extraction of Nd3 and Sm3 , including the extraction and stripping capability as well as the separation effect of Nd3 or Sm3 , from a sulfuric acid medium, by mixtures of di-(2-ethylhexyl) phosphoric acid (HDEHP, H2A2(0)) and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester (HEH/EHP, H2L2(0)) were studied. The distribution ratios and synergistic coefficients of Nd3 and Sm3 in different acidities were also determined. A synergistic extractive effect was found when HDEHP and HEH/EHP were used as mixed extractants for Sm3 or Nd3 . The chemical compositions of the extracted complex were determined as Nd·(HA2)2·HL2 and Sm·(HA2)2·HL2. The extraction equilibrium constants, enthalpy change, and entropy change of the extraction reaction were also determined.     

Relation between Neodymium and Calcium in Rape under Ca-Deficiency

Rareearthelements (REEs)areofcertainphysi ologicalactivity .Theycanimprovetheproductivityandqualityofcropsiftheyareusedaptly[1] .Howev er ,thebasicltheoriesneedtobeexploreddeeplythatREESwereapplicated .inagriculture .SomeREEsaresimilartoCainchemicalproper ties ,andtheyhavebeendescribedasCaanalogs[2 ] .Forexample ,thecrystalradiusoflanthanidecationsisin 96 1 1 5 pm ,whichissimilartothatoftherangeofCa2 (99pm) ,especiallythecrystalradiusofNd3 (99.5pm )isclosesttothatofCa2 .REEsoften…     

Study on Transfer and Interfacial Kinetics of Neodymium and Samarium in Membrane Based Extraction

Ｔｈｅｅｘｔｒａｃｔｉｏｎｔｅｃｈｎｏｌｏｇｙｏｆｈｏｌｌｏｗｆｉｂｂｅｒｍｅｍｂｒａｎｅ (ＨＦＭ ) ,ｗｈｉｃｈｗａｓｄｅｖｅｌｏｐｅｄｉｎｅａｒｌｙ 1 980ｓ ,ｉｓａｎｅｗｋｉｎｄｏｆｓｅｐａｒａｔｉｏｎｍｅｔｈｏｄｃｏｍｂｉｎｅｄｐｒｏｃｅｓｓｅｓｏｆｌｉｑｕｉｄ -ｌｉｑｕｉｄａｎｄｍｅｍｂｒａｎｅｅｘｔｒａｃｔｉｏｎ .Ｔｈｉｓｍｅｔｈｏｄｃａｎｏｆ ｆｅｒｓｅｖｅｒａｌａｄｖａｎｔａｇｅｓｃｏｍｐａｒｅｄｗｉｔｈｃｏｎｖｅｎ ｔｉｏｎａｌｅｘｔｒａｃｔｏｒｓ[1～ 2 ] .Ｉｔｃａｎａｌｓｏｐｒｏｖ…     

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。     

一种从废旧电路板中回收铜的新工艺

介绍了一种从废旧电路板中分离提取铜并产出超细铜粉的新工艺。首先采用物理分选法分离出含铜的重密度组分,之后采用氧化氨浸—溶剂萃取工艺获得CuSO4溶液,最后以次亚磷酸钠为还原剂,以PVP为保护剂和分散剂,采用二次还原法,获得粒度1.5μm左右的抗氧化铜粉。浸出阶段优化条件为:温度35℃,时间2h,氨水和硫酸铵起始浓度均为2mol/L,空气流量8m3/h,固液质量体积比1∶10。铜萃取及反萃阶段优化条件为:萃取剂Lix84,萃取剂体积分数50%,相比1∶1,TBP浓度0.1mol/L,常温,以500次/min的速度震荡3min;反萃取剂硫酸,浓度0.2mol/L。在优化条件下,浸出、萃取及反萃取阶段的铜提取率分别为96.67%、98.87%及93.34%,效果良好。     

采用HBL101从锌置换渣高酸浸出液中萃取锗

针对现行的湿法炼锌渣中提取锗的研究现状,采用新型萃取剂HBL101从锌置换渣的高酸浸出液中直接萃取锗,考察了料液酸度、萃取剂体积分数、萃取温度、萃取时间和相比对萃取的影响以及氢氧化钠质量浓度、反萃温度、反萃时间和反萃相比对反萃的影响,并对萃取剂转型条件进行了研究.实验表明:有机相组成为30%HBL101+70%磺化煤油(体积分数)作为萃取剂,料液酸度为113.2 g·L-1H₂SO₄,其最佳萃取条件为萃取温度25℃,萃取时间20 min,相比O/A=1∶4.经过五级逆流萃取,锗萃取率达到98.57%.负载有机相用150 g·L-1NaOH溶液可选择性反萃锗得到高纯度锗酸钠溶液,其最佳反萃条件为反萃温度25℃,反萃时间25 min,相比O/A=4∶1.经过五级逆流反萃,反萃率可达到98.1%.反萃锗后负载有机相再用200 g·L-1硫酸溶液反萃共萃的铜并转型,控制反萃温度25℃,反萃时间20 min,O/A=2∶1.经过五级逆流反萃,铜反萃率可达到99.5%并完成转型,萃取剂返回使用.      

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。     

DIBK-TBP萃取分离锆铪的热力学研究

对二异丁基甲酮(DIBK)和TBP从HSCN介质中协同萃取锆铪的性能及热力学进行研究,采用对数函数外推法求得DIBK-TBP体系萃取反应的热力学平衡常数分别为log(K12,Zr)=4.73和log(K12,Hf)=-5.09,锆铪与SCN-形成配合物Zr(SCN)3+和Hf(SCN)3+的稳定性常数分别为1×109.86和1×10-0.80,而铪的分配比在硫氰酸盐存在时要大于锆的分配比,说明过渡金属离子锆和铪在硫氰酸盐存在时与一般金属离子与配位体形成的配合物的稳定性常数愈大,金属离子的分配比愈大的规律相矛盾,并计算出萃取反应的焓变分别为ΔHZr=-11.43 kJ.mol-1和ΔHHf=-7.80 kJ.mol-1,说明对锆铪的萃取反应为放热反应,升高温度不利于萃取反应的进行,常温下自由能变分别为ΔGZr=-26.54 kJ.mol-1和ΔGHf=28.57 kJ.mol-1,熵变分别为ΔSZr=51.54 J.(K.mol)-1和ΔSHf=-124.07 J.(K.mol)-1,说明铪离子比锆离子更易与SCN-形成配位键,从而生成中性分子Hf(SCN)4与有机相发生溶剂化作用而进入有机相中。     

Stability of Rare Earth Ion-N, N′-bis（2′-Pyridine）methyl-1,10-Phenanthroline-2,9-Dimethanmine Binary Complexes

1 ,10 Phenanthrolinehasbeenextensivelyusedasanazaheterocyclicchelateligandinbothanalyticalandpreparativecoordinationchemistry[1] .Asanim portantligand ,1,10 phenanthrolineunitplaysanim portantroleforthedevelopmentofthesupramolecularchemistry .Manynovelsupramolecularcompoundsin clude 1,10 phenanthrolineunit[2～ 4 ] .Furthermore ,consideringtheuniquecombinationofchemicalstabil ities ,redoxproperties ,luminescenceemissionandex citedstatelifetime ,derivativesof 1,10 phenanthrolinehaveplayedama…     

Extraction of rare earth elements from their oxides using organophosphorus reagent complexes with HNO3 and H2O in supercritical CO2

Direct extraction of metals from solids with complexing agents in supercritical CO2(SC-CO2) has recently attracted interests in separation,purification,recovery,and analysis of metals.In the present study,the static/dynamic extraction of rare earth elements(Nd,Ce) from their oxides(Nd2O3,CeO2) with organophosphorus complexes with HNO3 and H2O in SC-CO2 was investigated.The static extraction efficiency of Nd from Nd2O3 with the tri-n-butylphosphate(TBP)-HNO3 complex could reach 95% under optimized experiment...     

Extraction of selected rare earth elements from anthracite acid mine drainage using supercritical CO_2 via coagulation and complexation

Rare earth elements(REEs) are valuable raw materials which are in great demand in modern high technology industries.Developing methods to produce/recover REEs from waste is significant to the national security of any developed country.This study was focused on investigating the use of supercritical CO2(sCO_2) to extract REEs from anthracite acid mine drainage(AMD).Four different mine drainage water source locations at Blaschak Coal Corp.in Pennsylvania,USA were selected for sample collection.An extraction process was developed and demonstrated for two of those water sources containing the highest concentration of REEs.A method involving metal ion coagulation,their dissolution from the sludge into a concentrated aqueous HNO_3 solution,complexation with organic ligands and sCO_2 extraction was developed to recover REEs from AMD.Specifically,sodium aluminate(NaAlO_2) was used as the coagulant to concentrate REEs from the AMD into a solid precipitate.Consequently,over 99%of the REEs in AMD is concentrated in the remaining sludge.During the coagulation process,the effects of pH and NaAlO_2 concentration on REE precipitation were investigated.Fuming nitric acid(HNO_3) was used to digest the pre-concentrated sludge and tributyl phosphate(TBP) was used to form REE/TBP/HNO_3,a non-polar complex with selected REEs,specifically,cerium(Ce),lanthanum(La) and neodymium(Nd).HNO_3 concentration and organic/aqueous phase ratio were considered as the variables to improve complexation efficiency.Dynamic extraction experiments using sCO_2 and REE/TBP/HNO_3 solutions were then conducted at optimal conditions of 60℃ and 20 MPa.The overall REE extraction efficiencies are found to increase with the atomic number of the REE.As a result,the average overall REE extraction efficiencies of 41.8%,40.1% and 58.2% for Ce,La and Nd,respectively,are obtained.The potential improvements in the overall extraction efficiency are also discussed.     

Enhanced separation of praseodymium and neodymium by kinetic“push and pull”system of[A336][NO_3]-DTPA in a column extractor

A new approach was suggested in present work for improving the separation between Pr(Ⅲ) and Nd(Ⅲ)by a so-called kinetic "push and pull" system consisting of [A336][NO_3] and DTPA in a column extractor.It is revealed that,when organic extractant [A336][NO_3] is continuously pumped into the column extractor in the form of dispersed oil droplets and at the same time DTPA was injected into the aqueous feed solution whet the extraction was just started,the separatiot factor of Pr(Ⅲ) to Nd(Ⅲ),βPr/Nd,increased obviously with the time,and could even achieve 21.7.Such an amazing increase in β_(Pr)/Nd value might be due to the extraction rate of Pr(Ⅲ) by [A336][NO_3] oil droplets being faster than that of Nd(Ⅲ),while the complexing rate of Nd(Ⅲ) with DTPA in the aqueous solutions being faster than that of Pr(III).The opposite order of the two rates for Pr(Ⅲ) and Nd(Ⅲ) result in their kinetic "push and pull" separation.In contrast,the β_(Pr)/Nd value in traditional thermodynamic separation reported in previous literatures is only around 5 or even less,even though using the same extractant [A336][NO3] and DTPA but by previously adding DTPA into the aqueous feed solutions for pre-complexing of Pr(Ⅲ) and Nd(Ⅲ).Various effects from the pH and addition amount of DTPA aqueous solutions,LiNO_3 concentrations in initial aqueous feed solutions,the initial concentration ratios of Pr(Ⅲ) to Nd(Ⅲ) ions,the initial pH of aqueous feed solutions,and the concentrations of [A336][NO_3] in organic phases,on the kinetic separatiot of Pr(Ⅲ) and Nd(Ⅲ) are discussed.The present work highlights a promising approach for separation of rare earths or other targets with extreme similarity in physicochemical properties.     

Solvent extraction of neodymium（III） from acidic nitrate medium using Cyanex 921 in kerosene

The extraction of neodymium(Ⅲ) from acidic nitrate medium was investigated using Cyanex 921 as extractant in kerosene. The metal concentration in the aqueous phase before and after extraction was determined spectrophotometrically by Arsenazo Ⅲ method. The complete equilibration was achieved in 15 min. The effects of shaking time, nitric acid concentration, nitrate concentration, extractant concentration, and temperature on the extraction were studied. The extraction of Nd(Ⅲ) was found to increase very slowly with increase in concentration of HNO3 in the range of 0.001-0.008 mol/L and then decreased when 0.01 mol/L HNO3 was used. The percentage of extraction was increased with increase in nitrate concentration from 0.01-0.45 mol/L and then decreased when nitrate concentration increased to 0.5 mol/L. Quantitative extraction of Nd(Ⅲ) (98%) was obtained from the aqueous phase containing 0.001 mol/L HNO3 and 0.1 mol/L KNO3 using 0.5 mol/L Cyanex 921. On the basis of slope analysis, the extracted complex in the organic phase was proposed to be Nd(NO3)3.2Cyanex 921. The extraction of Nd(III) was found to increase with increase in concentration of metal ion in the range of 0.001-0.05 mol/L from 0.001 mol/L HNO3 and 0.1 mol/L KNO3 with 0.1 mol/L Cyanex 921. The percentage of extraction of neodymium was found to decrease with increase in temperature. From temperature variation studies, the negative value of △H indicated the extraction reaction to be exothermic and the negative value of △S indicated the formation of a stable complex. Almost 100% Nd(Ⅲ) was recovered from the fully loaded organic phase using 0.002 mol/L H2SO4 and 0.01 mol/L HCl.     

液膜法提取高纯铼

用TBP[（C4H9O）3PO]、异戌醇[（CH3）2CH（CH2）2OH]、L113B、液体石蜡、磺化煤油和NH4NO3水溶液等液膜体系提取（富集）铼。实验结果表明,在选择条件下,铼的提取（富集）率在99.4%以上,提取（富集）的ReO4^-经过处理后,金属铼的纯度在99.9%以上。     

Separation of Eu（III） with supported dispersion liquid membrane system containing D2EHPA as carrier and HNO3 solution as stripping solution

The Eu(III) separation in supported dispersion liquid membrane (SDLM),with polyvinylidene fluoride membrane (PVDF) as the support and dispersion solution containing HNO3 solution as the stripping solution and Di(2-ethylhexyl) phosphoric acid (D2EHPA) dis-solved in kerosene as the membrane solution,was studied.The effects of pH value,initial concentration of Eu(III) and different ionic strengths in the feed phase,volume ratio of membrane solution and stripping solution,concentration of HNO3 solution,concentration of carrier,different stripping agents in the dispersion phase on the separation of Eu(III) were also investigated,respectively.As a result,the optimum separation conditions of Eu(III) were obtained as the concentration of HNO3 solution was 4.00 mol/L,concentration of D2EHPA was 0.160 mol/L,and volume ratio of membrane solution to stripping solution was 30:30 in the dispersion phase,and pH value was 5.00 in the feed phase.Ionic strength had no obvious effect on the separation of Eu(III).Under the optimum conditions studied,when initial concentration of Eu(III) was 1.00×10–4 mol/L,the separation rate of Eu(III) was up to 94.2% during the separation period of 35 min.The kinetic equation was developed in terms of the law of mass diffusion and the theory of interface chemistry.The results were in good agreement with the literature data.     

Effect of Neodymium on Physiological Activities in Oilseed Rape during Calcium Starvation

The effects of RE on increasing crop productivity and stress tolerance were reported inpast years[' '2). La ion acts as a calcium-influxinhibitor by displacing Ca2 from cell wallsand occupying Ca2 -binding sites on the plasmalemma, as effective as Ca in the deferral ofsenescence. Besides blocking calcium channels, La has been frequently reported to mimicCa2 effect on plant ion transport. Migliaccioet al. found that both Ca2 and La3 stimulated auxin uptake into pea epicotyl segmentsfr…     

DIBK-P350和DIBK-TOPO负载有机相中铪和锆的反萃

分别以盐酸、硫酸、碳酸氢铵、碳酸铵和碳酸钾的水溶液为反萃剂,对比研究了其对DIBK-P350体系和DIBK-TOPO体系负载有机相中铪和锆的反萃性能。结果表明,盐酸、硫酸、碳酸氢铵和碳酸钾对这两个体系负载有机相中铪和锆的反萃率或分离系数较低,不适合作为该体系的反萃剂,而碳酸铵((NH_4)_2CO_3)较适合作为反萃剂。在室温、油水相比O/A=1/2、(NH_4)_2CO_3浓度1.5~2.0mol/L的优化条件下,DIBK-P350体系负载有机相中(NH_4)_2CO_3对铪的单级反萃率和锆铪的分离系数分别达到91.61%和6.94。对DIBK-TOPO体系负载有机相反萃的优化条件为:室温、油水相比O/A=1/2、(NH_4)_2CO_3浓度2.0 mol/L,(NH_4)_2CO_3对铪的单级反萃率和锆铪的分离系数分别达94.33%和15.30。     

Ethyl-bis-triazinylpyridine (Et-BTP) for the separation of americium(III) from trivalent lanthanides using solvent extraction and supported liquid membrane methods

The present paper deals with the solvent extraction and supported liquid membrane studies on Ln(III)/An(III) separation using ethyl-bis-triazinylpyridine (Et-BTP) as the extractant. The solvent extraction studies involved evaluation of a) diluents, b) phase modifiers, c) stripping agents and d) role of feed acidity. Though reasonably high separation factor values were obtained when Et-BTP was used along with α-bromo carboxylic acids, the mixtures could not be used for liquid membrane studies due to unsatisfactory stripping. On the other hand, a combination of Et-BTP with chlorinated cobalt dicarbollide (CCD) in nitrobenzene resulted in significant Am(III) mass transfer when used in the solvent extraction as well as SLM studies. Improved transport, membrane stability, and decontamination from lanthanides were observed when the organic phase diluent composition was 60% nitrobenzene + 40% n-dodecane. Using 0.02 M Et-BTP along with 0.005 M CCD in 60% nitrobenzene + 40% n-dodecane, the SLM studies on a mixture of ²⁴¹Am, ¹⁵²Eu and ¹⁴⁷Nd in a feed containing 0.1 M HNO₃, indicated quantitative Am³⁺ transport in 3.5 h with co-transport of about 8% Nd³⁺ and 22% Eu³⁺.     

用三烷基氧化膦从氰化浸出液中萃取低浓度金

研究了三烷基氧化膦(TRPO)-磷酸三丁酯(TBP)-煤油萃取体系对氰化浸金液中低浓度金(Ⅰ)的萃取和反萃取能力,结果表明,尽管TRPO体系中添加TBP对金(Ⅰ)的萃取率影响很小,但一定量的TBP能提高体系的反萃效果。考察了料液pH值、硫酸锂浓度等因素对萃取率的影响,探讨了不同的反萃温度、反萃相比对负载有机相中金(Ⅰ)的反萃效果。结果表明,采用TRPO-TBP-煤油组成的有机相,对金(Ⅰ)质量浓度为9.5 mg/L、盐析剂硫酸锂浓度为1.0 mol/L的碱性氰化液在相比A/O=1∶1条件下进行萃取时,金(Ⅰ)的单级萃取率可达95%以上;反萃温度越高,相比(A/O)越大,反萃效果越好,可以将大部分金(Ⅰ)反萃出来。