熔盐氯化法选择性提取废旧荧光粉中稀土元素

废旧稀土荧光粉的回收利用对我国稀土资源的可持续发展和环境保护具有重要的意义.本文以AlCl3-KCl熔盐为氯化剂,对废旧荧光粉中的稀土元素进行氯化提取.在热力学分析的基础上,考察了氯化焙烧条件和碱熔处理对稀土氯化提取率的影响,并采用X射线衍射仪(XRD)和扫描电子显微镜-X射线能谱仪(SEM-EDS)对反应前后废旧荧光...     

废旧稀土金属钕铁硼回收技术研究现状与展望

稀土是重要的战略资源,也是世界强国资源争夺的核心。磁性材料尤其钕铁硼永磁体在生产制备和使役过程中产生大量废料,我国废旧钕铁硼产量逐年增多,形成了稀土“城市矿山”。研究废旧钕铁硼的回收利用技术,对我国稀土绿色和可持续发展具有重要意义。本文总结了国内外废旧稀土金属钕铁硼各种回收方法,综述了近年来稀土磁性废料回收技术研究进展,并面向保护环境和节约资源及低成本的发展趋势,对废旧稀土金属回收技术进行了展望。     

草酸盐沉淀法回收钕铁硼废料中稀土元素的研究

钕铁硼因其优异的磁性能而得到广泛的应用,在生产加工过程中会产生40%左右的废料,其中氧化严重的废料需用化学方法来回收价格高昂的稀土元素。利用稀土草酸盐和草酸亚铁在水中溶解度的巨大差异,向钕铁硼废料酸溶液中滴加草酸直接得到稀土草酸盐,使稀土元素和杂质元素分离。通过研究草酸的用量、溶液的p H值及反应温度对草酸盐沉淀实验结果的影响,得到的产物通过热重分析(TGA)研究其分解过程,确定其完全分解的条件。最后用X射线衍射仪(XRD)检测产物的物相,用X射线荧光光谱仪(XRF)分析产物的元素种类及含量。实验结果表明,在80℃,p H 1.5~2.0,草酸用量比1.5,沉淀效果最佳,得到的稀土草酸盐经过烘干在800℃下灼烧得到混合稀土氧化物,Nd和Pr的混合稀土氧化物达99.27%。在钕铁硼废料的回收中应用草酸盐沉淀法可以高效地分离稀土元素和铁元素,提高废料的回收利用率,促进资源循环。     

硫化沉淀法从废旧钕铁硼回收稀土的余液中提取钴

用药剂1作还原剂,药剂2作中和剂,药剂3作沉淀剂,在常压下,探索了药剂1和药剂3用量、平衡pH值、反应温度及反应时间等因素对硫化沉淀法回收钴的影响.实验表明,当药剂1加入量大于等于料液中9?量,药剂3加入量为理论量1.4～1.6倍,平衡pH值5.0～5.5,在80～100℃下反应2～3h,回收精矿中有价金属钴的品位可达12%以上,钴的回收率大于97%.     

从废旧电子元件中提取钯工艺的研究

研究了从废旧电子元件中回收钯的方法：硝酸溶解－－盐酸除银－氧化剂加氯化铵沉淀钯。精制后,可获得纯度为９９．９５％的海绵钯,钯的回收率不低于９５％。通过与其它两种工艺比较,证明了此工艺的优越性     

从钕铁硼废料中提取稀土工艺研究

采用氧化焙烧-盐酸分解法,研究从钕铁硼废料中提取稀土的工艺条件,探讨了焙烧温度和时间对铁的氧化率的影响,在浸出过程中考察了盐酸浓度、反应时间、反应温度以及液固比对稀土浸出率的影响,并分析了pH值和陈化时间对浸出液除杂效果的影响.结果表明:在700℃焙烧1.5 h,铁的氧化率最高,铁基本完全氧化成三价铁,在最佳浸出条件下稀土浸出率高达到99.33%,浸出液中和除杂时,调节pH值为3.5,陈化时间大于2 h,料液中非稀土杂质含量低,特别是铁仅为0.0014 g/L,浸出液完全达到稀土萃取的要求.      

废旧荧光粉中稀土元素回收利用技术研究现状

稀土具有的独特物理化学性质使其在发光材料、催化剂、永磁体、新能源汽车、风力发电等领域被广泛应用,随着对稀土需求的日益增长,不可再生的稀土资源逐渐匮乏。然而,大量的二次资源中含有丰富的稀土资源,回收循环利用其中稀土是稀土资源可持续开发利用的保障。废旧荧光灯在日常生活中十分常见,其中荧光粉含有大量稀土,回收利用废旧荧光粉中稀土不仅能减少对环境的污染,还能显著提高稀土资源循环利用率。文章综述了废旧荧光粉中稀土回收技术现状,对比分析了磁选法、浮选法、介质分选和超临界CO₂萃取等物理法的应用情况,并对其存在的优势和不足进行了总结概括。同时详细阐述了酸浸、碱熔、化学沉淀、萃取等化学法在工业应用的现状和存在的问题,并且介绍了机械化学活化、微生物浸出在回收废旧荧光粉中稀土的机制和当前研究应用现状。在此基础上,展望了未来废旧荧光粉中稀土回收利用技术的发展方向,为中国早日实现二次资源中稀土的循环利用工业链提供借鉴。     

含铋铅锑银阳极泥中有价金属提取工艺研究

含铋、铅、锑、银阳极泥,采取湿法综合回收其中的有价金属的具体方法研究。     

废旧催化剂中多金属综合回收工艺研究

采用二段逆流浸出—沉钒—氨溶重结晶—再提纯的工艺流程从废旧催化剂中综合回收有价金属钨、钼、钒。结果表明,控制浸出温度70℃,时间3.5h,碳酸钠浓度350g/L,液固比3∶1,钨、钼、钒浸出率均在95%以上,综合回收率可以达到90%以上。     

废旧锂离子电池中有价金属的回收技术进展

随着锂离子电池在电动汽车和储能领域的大量使用,废旧锂离子电池所面临的环境和资源问题日益突出。为了更好地资源利用和环境保护,世界各国对废旧锂离子电池中有价金属的回收和利用,及无危害处理相当重视。文中综述了国内外对废旧锂离子电池回收技术的研究现状,比较了不同回收途径的优缺点,讨论了回收技术的发展方向。本文中归纳的废旧锂离子电池回收方法,在目前回收领域中得到了广泛地研究,并且起到了显著效果,但是大多集中在对锂、钴、镍、锰、铜、铝等有价金属的回收利用上,对废旧锂离子电池中的导电碳、石墨以及电解质的回收和处理方面的研究较少,对工艺过程中产生的污染和安全性问题也缺乏系统的研究。另外,随着锂离子电池生产技术的发展,新的电极材料将会出现并取代过渡金属氧化物,比如单质硫、导电聚合物等;同时也需要相应的电解液与之匹配,如新型的有机电解液、聚合物电解质等,这将向废旧锂离子电池回收技术提出了新的要求。今后废旧锂离子电池资源化回收技术的研究方向是降低成本,减少污染和实现回收物质的多元化以及提高回收率。     

Evaluating organic acids as alternative leaching reagents for rare earth elements recovery from NdFeB magnets

This study proposes an advanced leaching method using organic acids to recover rare earth elements (REEs) from NdFeB permanent magnets from end-of-life computers hard disk drives (HDDs). The end-of-life HDDs were first dismantled in order to recover NdFeB magnets, which were then thermally demagnetized at 350 °C during 30 min before crushing in a ball mill under inert atmosphere. Scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS) analyses performed on the NdFeB magnets show the heterogeneous structure containing the major matric phase Nd₂Fe₁₄B and the REEs-rich phase containing Nd and Pr oxides. Additionally, X-ray diffraction (XRD) and Mössbauer spectroscopy (MS) analyses on the ground NdFeB magnet show that grinding NdFeB magnets under inert atmosphere helps to minimize its oxidation. Chemical analysis shows that the composition of the ground sample is Nd: 22.8 wt%, Pr: 3.3 wt%, Dy: 1.2 wt%, Fe: 62.6 wt%, Co: 1.5 wt%, B: 0.9 wt%, Ni: 0.6 wt%. Diagrams of speciation and equilibrium phases (E_h vs. pH) were calculated to determine the predominance of the formed species in the REEs–organic acids systems. The influence of the organic acid type (acetic acid, formic acid, citric acid and tartaric acid), the acid concentration (10 vol%, up to saturation), and the solid/liquid (S/L) ratio (0.5%–10%) on NdFeB magnets leaching was investigated employing an optimal experimental design conceived by the statistical software JMP. Acetic acid (CH₃COOH) shows the highest leaching performance of REEs, allowing leaching yields over 90% for Nd, Dy and Pr in the acid concentration range of 1.6–10 mol/L and the S/L ratio range of 0.5%–5% at a temperature of 60 °C. The results presented in this investigation suggest that REEs can be recovered from magnets of end-of-life HDDs using an eco-friendly method assisted by organic acids.     

High-efficiency simultaneous extraction of rare earth elements and iron from NdFeB waste by oxalic acid leaching

Iron can not be recovered at high value because only rare earth elements are effectively recovered from NdFeB waste via oxidation roasting-hydrochloric acid leaching process.In this study,a new method for leaching NdFeB waste with oxalic acid was developed.The high-efficiency,simultaneous and high-value recovery of rare earth elements and iron was realized to simplify the process and improve the economic benefit.Results of the oxalic acid leaching experiments show that under the optimum leaching conditions at 90℃ for 6 h in the aqueous solution of oxalic acid(2 mol/L) with a liquid-solid ratio of60 mL/g,the iron leaching efficiency and precipitation rate of rare earth oxalate reach 93.89% and 93.17%,respectively.Rare earth oxalate and Fe(C₂O₄)3^3- were left in the residue and the leaching solution,respectively.The leaching mechanism was further analyzed by characterising the leach residues obtained through X-ray powder diffraction(XRD) and scanning electron microscopy-energy dispersive X-ray spectroscopy(SEM-EDS).Results of the leaching kinetics study indicate that the process of oxalic acid leaching follows the shrinking nucleus model,and the leaching kinetics model is controlled by the mixed factors of diffusion and chemical reaction.The leaching residue was calcined at 850℃ for 3 h and then decomposed into rare earth oxide,which can be directly used to prepare rare earth alloy via molten salt electrolysis.For the leaching solution,ferric oxalate solution was reduced using Fe powder to prepare the ferrous oxalate(FeC₂O₄-2H₂O).     

Extraction of rare earth elements from a South American ionic clay

Ionic clays,formed by the natural weathering of REE-bearing minerals and the adsorption of the resulting liberated REE ions onto the clay surface,are an important resource for critical rare earth elements(REEs).Here,a two-step desorption process using ammonium sulfate with active pH adjustment using sulfuric acid was developed to extract REEs from a South American clay.The desorption process was optimized using response surface methodology approach and the optimum operating conditions were deter...     

Extraction and back-extraction behaviors of 14 rare earth elements from sulfuric acid medium by TODGA

The unique physical and chemical properties of rare earth elements lay the foundation for their extensive application. N,N,N',N' Tetra-octyl-3-oxopentanediamide(TODGA) is excellent in its ability of extracting rare earth elements and it is favored for green initiative. In this paper, the extraction and back-extraction of14 rare earth elements by TODGA were studied. Experiments show that in conditions of 6 mol/L sulfuric acid, the extraction temperature of 25 ℃,the phase ratio of 1:1 and 0.04 mol/LTODGA(aviation kerosene as the diluent), the extraction rates of 14 rare earth elements including lanthanum, cerium, praseodymium,neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and yttrium were 99.00%-99.73%. Mixed with hydrochloric acid and nitric acid(HCl 3.5 mol/L, HNO_30.5 mol/L), the recoveries of the 14 rare earth elements are 91.52%-99.91% when the extraction temperature is 25 ℃ and the ratio is 1:1. The following application is based on the optimum conditions above with practical samples(from the roasting production line of China North Rare Earth High-tech Company Limited) for extraction and back-extraction experiments. Experiments show that TODGA has excellent enrichment effect on 14 rare earth elements, the extraction rates are 91.36%-99.80%, the back-extraction rates are 87.29%-99.64% and the total recoveries are 81.19%-99.44%.     

Rare earth passivation and corrosion resistance of zinc coated NdFeB magnets

Rare earth passivation was conducted on Zn coated NdFeB magnets by chemical reaction to enhance the corrosion resistance performance.Morphologies,micro structures and compositions of different passivated coatings were studied by X-ray diffraction,field emission scanning electron microscopy,and X-ray photoelectron spectroscopy,respectively.The corrosion behavior was evaluated by electrochemical measurement and neutral salt spray test.The results show that the rare earth passivation can enhance the corrosion resistance of Zn coated NdFeB magnets.When the concentration of cerium nitrate is 5 g/L,the passivated specimens can achieve the longest NSS time of 360 h,which is 144 h longer than that of the pristine Zn/NdFeB magnets.The passivation layer on the Zn coating surface contributes to the enhancement of the magnets’corrosion resistance.     

NdFeB稀土永磁材料的研究现状

NdFeB稀土永磁材料由于具有优异的磁性能而受到人们的广泛关注.系统地介绍了Nd-FeB的微观结构、矫顽力机制、腐蚀机理及其防护、高性能磁体的制备新工艺等,提出了今后的研究和发展方向.     

注射成形制备NdFeB粘结磁体

为了制备出高性价比的粘结NdFeB注射磁体，本文系统的研究了粘结剂、添加剂的含罱以及磁粉装载量对注射磁体的加工性能、磁性能等的影响规律，并从微观上揭示了其机理。本文采用低成本的陶广：快淬钕铁硼磁粉和国产尼龙6粘结剂制备出了磁性能Br为0．5158T、Heb为321kA／m、Hcj为730kA／m和（BH）max为40kl／m^3的注射磁体，其性能与日本Mate公司的RNI-50产品性能相当，而价格却低得多.     

Separation of rare earth elements from sulfate leach liquor by heterocyclic nitrogen compound

Separation of rare earth dements by solvent extraction has actually been widely used in various fields from analytical chemistry to hydrometallurgy. A representative ore sample obtained from Kadabora Batholiths-Eastern Desert of Egypt, containing the multiple oxides rare earth minerals： Samarskite, Fergusonite, Betafite, and Pyrochlore, was subjected to sulfuric acid leaching. Different sets of equilibrium loading experiments were carded out on a bench scale for the extraction of rare earths （cerium and yttrium） from the sulfate leach liquor using 8,9-dihydro[1,2,4]triazolo[1,5-a]quinazolin-6（TH）-one {TQ} dissolved in methylene chloride. Stripping was carded out by 20% sodium hydroxide. A rare earth cake was produced by oxalic acid precipitation. Its purity reached 87.3%.     

硫酸浸出磷石膏中稀土的动力学研究

针对磷石膏中稀土元素的浸出,已有很多研究报道,但对于浸出动力学研究却很少。文章以硫酸为浸取剂深入研究了磷石膏中稀土浸出的动力学。研究表明:浸出温度和时间的增加均可提高稀土的浸出率,浸出温度80 ℃时,稀土总浸出率最大可达55.8%,其中Y的浸出率最大,为63.9%;稀土的浸出与二水硫酸钙的溶解具有很强的线性相关性;动力学模型拟合表明:磷石膏中稀土浸出反应是受扩散和界面传质混合控制的,浸出反应的表观活化能E_a=9.10 kJ/mol。