从废旧锂离子电池中分离回收钴镍锰

提出一种新型的从废旧锂离子电池中分离回收钴镍锰的工艺.该工艺采用物理擦洗-稀酸搅拌浸出的方法分离集流体与活性物质,采用H2SO4+H2O2为浸出剂对活性物质进行浸出,然后采用黄钠铁矾法去除浸出液中的铁,再采用N902萃取分离铜,通过水解沉淀法除铝,最后采用碳酸盐共沉淀法制备镍钴锰碳酸盐前躯体.结果表明:最优浸出条件为液固比10:1、H2SO4浓度2.5 mol/L、H2O2加入量2.0 mL/g(粉料)、温度85℃、浸出时间120 min;在此条件下,钴、镍和锰的浸出率分别达到97%、98%和96%;除去浸出液中的铁、铜和铝后,钴、镍和锰的损失率分别为1.5%、0.57%和4.56%;总体来说,废旧锂离子电池中钴、镍和锰的回收率均可以达到95%.     

报废动力电池镍钴锰酸锂三元正极材料高温氢还原-湿法冶金联用回收有价金属

通过高温氢还原和湿法冶金联用的方法回收报废动力电池镍钴锰酸锂三元正极材料中的镍、钴、锰以及锂金属,并对其回收机理及工艺进行研究。结果表明:报废三元正极材料经过高温氢气还原后,在层状镍钴锰酸锂结构中的锂迁移到表面,变成LiOH、LiOH?H_2O和少量的Li2_CO_3;镍钴锰由之前的Co~(2+)、Ni~(3+)和Mn~(4+)分别还原成了Co~0、Ni~0和MnO,其在还原水洗后物料的表面相分别为Ni(OH)_2和Co(OH)_2及MnO;还原后的LiOH、LiOH?H_2O和少量的Li_2CO_3经过水浸、酸洗、沉淀后,可得纯度为99.5%的Li_2CO_3,实现了锂与镍、钴、锰的分离;还原后的镍、钴和MnO经过硫酸酸浸后,镍、钴和锰浸出率分别为96.88%、97.23%和99.78%。浸出后溶液经氧化沉淀及萃取分离,锰沉淀分离率为98.46%,萃取分离后氯化钴和氯化镍溶液杂质含量低于10 mg/L。     

还原酸浸法从低品位水钴矿中提取铜和钴

以Na2SO3为还原剂从水钴矿还原酸浸液中提取铜和钴,研究了还原剂种类及用量、浸出温度、硫酸浓度等因素对水钴矿还原酸浸过程中有价金属铜和钴浸出率的影响。结果表明,Na2SO3是较适宜的还原剂;在还原剂用量为水钴矿原矿质量的10%、硫酸浓度为3 mol/L、浸出温度为60℃、液固比为2-1、浸出时间为60 min的条件下,铜和钴的浸出率分别达99.06%和98.87%。并提出了"M5640萃铜→黄钠铁矾法除铁→碳酸钠除铝→氟化钠除钙、镁→蒸发结晶得钴产品"的后续分离净化流程,能有望应用于水钴矿及类似物料中有价金属的提取与分离的工业生产。     

利用广西大厂锡矿制备铁酸锌光催化粉体

以广西大厂92号锡矿为主要原料,采用溶胶-凝胶法合成了铁酸锌光催化粉体.工艺过程为:原料粉碎球磨,用浓盐酸浸出铁,在浸出液中加入双氧水,将Fe2 氧化成Fe3 ,用浓氨水调节pH值,使Fe3 全部沉淀.用浓硝酸溶解氢氧化铁沉淀与适量的氧化锌,然后加入柠檬酸的醇溶液,混合溶液于70℃加热得到前驱体溶胶,凝胶经不同温度焙烧制得纳米铁酸锌粉体,通过对甲基橙溶液的光催化降解考察其光催化活性.利用化学全分析法、XRD、紫外-可见漫反射光谱、紫外-可见分光光度法进行表征.结果表明:通过控制适宜的酸浸工艺条件,铁的浸出率达到45.62%;经过600℃热处理3 b的铁酸锌粉体对甲基橙溶液的光催化降解效果最好.     

利用低冰镍制备铁酸镍前躯体

以低冰镍为原料,采用草酸盐共沉淀法合成颗粒细小的铁酸镍前躯体 NiFe2(C2O4)3·6H2O。NiCl2?FeCl2?(NH4)2C2O4?H2O体系的热力学研究表明：Ni2+和Fe2+的理论最佳共沉淀pH值为2,2?24C O 对Ni2+、Fe2+离子具有较强的络合作用。在理论研究的基础上,考察沉淀参数对沉淀率和前躯体粒度的影响。结果表明：最佳共沉淀条件为溶液pH=2,反应温度为45°C,(NH4)2C2O4加入量为理论值的1.2倍,PEG400加入量为3%。在此条件下,Ni2+和Fe2+的沉淀率达99.8%,所得前躯体的粒径为1~2 um。XRD和TG?DTA分析表明：所得前躯体为单相置换固溶体,反应过程中镍、铁原子相互取代。     

Co-Ni-Fe-Mn配合-沉淀体系的平衡热力学

根据质量守恒和同时平衡原理,以Me(Co、Ni、Fe、Mn)为金属元素,建立Me-OH-、Me-OH--CO32-、Me-OH--S2-、Me-OH--NH3和Me-OH--NH3-CO32-等多个配合-沉淀体系的热力学平衡模型。结果表明:Fe3+可以在Me-OH-、Me-OH--NH3体系中通过调节pH=3预先沉淀分离,而Co、Ni、Mn仅在Me-OH--NH3-CO32-体系中有分离效果。Me-OH--NH3-CO32-体系热力学计算表明:Co、Ni、Mn在溶液中的行为受pH值、配合剂、沉淀剂浓度共同影响,碳酸根初始总浓度[C]增大和氨初始总浓度[N]减小有利于Co、Ni、Mn形成沉淀。当[C]=1 mol/L、[N]=2 mol/L、pH值为9～10时,大部分Ni以高级氨配离子[Ni(NH3)42+]、[Ni(NH3)52+]、[Ni(NH3)62+]的形式保留在溶液中,而Co、Mn以MnCO3、CoCO3的形式沉淀出来。Co可在Me-OH--S2-体系中通过调节pH<6从溶液中与Mn分离。研究结果可为钴镍二次资源综合回收钴镍、制备钴镍产品提供理论指导。     

钨渣回收制备四氧化三锰新工艺

研究从钨渣中回收锰的新工艺,通过钨渣的低温硫酸化焙烧、烧结块浸出、浸出液除杂、溶液中水解沉锰及氢氧化锰氧化获得Mn3O4粉末,采用SEM和XRD对产品粉末进行分析。结果表明:在浓硫酸过量150%、焙烧时间90 min、浸出温度98℃、浸出时间120 min的条件下,Mn浸出率达到88.9%。浸出液可以通过硫化物沉淀除重金属、硫酸复盐沉淀法深度净化除杂、中和水解除Fe,水解沉锰也有一定的净化作用,溶液pH值为6.56时,除铁率达到99.91%。净化液经水解沉锰后采用10%H2O2氧化,在氢氧化锰氧化过程中,溶液pH值对产物物相的影响较大;溶液pH值为8时在50℃沉锰,并以过量150%的H2O2氧化反应20min,获得粒度小于0.1μm的Mn3O4粉末。     

采用TOPS-99和Cyanex 272钠盐从镍红土矿细菌浸出液中萃取锌、锰、钴和镍（英文）

在煤油中采用TOPS-99和Cyanex 272钠盐从镍红土矿细菌浸出液中提取与分离锌、锰、钴和镍。采用沉淀法去除不需要的金属离子,使用溶剂萃取提取/分离锌、锰、钴和镍。生物浸出铬铁矿表土样品得到的镍红土矿浸出液中含有3.72 g/L Fe,2.08 g/L Al,0.44 g/L Ni,0.02 g/L Co,0.13 g/L Mn,0.14 g/L Zn和0.22 g/L Cr。在p H 4时采用CaCO_3沉积去除100% Fe,96.98%Al和70.42%Cr,随后在pH 5.4时采用50%氨沉积,溶液中剩有Al和Cr。沉积后,采用0.1 mol/L TOPS-99从无铁、铝和铬的浸出液中提取锌,随后采用0.04 mol/L Na TOPS-99提取锰。锌和锰的产率分别是97.77%和95.63%。提取锰后,再采用0.0125 mol/L Na Cyanex 272从浸取液去除钴,最后采用0.12 mol/L NaTOPS-99提取镍,其产率达99.84%。采用稀硫酸去除浸出液中的有机相。     

冶炼硫酸铜氧化法除铁砷实验研究

本文采用氧化法除铁砷以冶炼硫酸铜为原料制备得到电镀级硫酸铜。在冶炼硫酸铜溶液中氧化除杂,所得样品硫酸铜中砷铁杂质随氧化剂用量增加而减少,双氧水适宜用量为理论用量的26倍,氯酸钠适宜为理论用量的6.5倍,NaClO3氧化可降低成本。氧化除杂的适宜条件是固液比为20:80(g:mL),氯酸钠为理论用量的6.5倍,每58.8g冶炼硫酸铜加入浓度为10%硫酸铁溶液2mL,氧化温度为50℃,pH值为3.5。在此适宜条件下,CuSO4.5H2O含量从90.79%增加到98.63%,硫酸铜质量达到电镀级一等品标准。     

季铵盐对钴(Ⅱ)和锰(Ⅱ)的萃取分离

研究了用季铵盐从含氯化钠接近饱和的溶液中萃取分离二价金属离子钴、铁、锰的方法。实验结果表明 ,以含少量异辛醇改性剂的季铵氯化物的煤油溶液为萃取剂 ,萃取时尽管有 15 %～ 2 0 %的二价锰和钴一起被萃取 ,但通过两级洗涤可将负荷有机相中的锰降低到 0 .0 2 g/L以下 ,经三级洗涤除锰即可达到钴、锰分离。钴的回收率可达 98% ,负荷有机相中钴锰含量比大于 30 0。     

Effects of Post-weld Heat Treatment on Microstructure,Mechanical Properties and the Role of Weld Reinforcement in 2219 Aluminum Alloy TIG-Welded Joints

In as-welded state, each region of 2219 aluminum alloy TIG-welded joint shows diff erent microstructure and microhardness due to the diff erent welding heat cycles and the resulting evolution of second phases. After the post-weld heat treatment, both the amount and the size of the eutectic structure or θ phases decreased. Correspondingly, both the Cu content in α-Al matrix and the microhardness increased to a similar level in each region of the joint, and the tensile strength of the entire joint was greatly improved. Post-weld heat treatment played the role of solid solution strengthening and aging strengthening. After the post-weld heat treatment, the weld performance became similar to other regions, but weld reinforcements lost their reinforcing eff ect on the weld and their existence was more of an adverse eff ect. The joint without weld reinforcements after the post-weld heat treatment had the optimal tensile properties, and the specimens randomly crack in the weld zone.     

The First Phase of the SRIF Industrialized Base in ＂West Area＂ Has Been Put into Operation

After nearly two years＇ tense construction, the first phase of industrialized base of Shenyang Research Institute of Foundry （SRIF）, located at the Tiexi Casting and Forging Industrial Park in the west of Tiexi District, has now been completed and formally put into operation.     

Thermodynamics Study on the Decomposition of Chromite with KOH

Institute of Process Engineering, Chinese Academy of Sciences, China, has proposed a method for oxidative leaching of chromite with potassium hydroxide. Understanding the mechanism of chromite decomposition, especially in the potassium hydroxide fusion, is important for the optimization of the operating parameters of the oxidative leaching process. A traditional thermodynamic method is proposed and the thermal decomposition and the reaction decomposition during the oxidative leaching of chromite with KOH and oxygen is discussed, which suggests that chromite is mainly destroyed by reactions with KOH and oxygen. Meanwhile, equilibrium of the main reactions of the above process was calculated at different temperatures and oxygen partial pressures. The stable zones of productions, namely, K2CrO4 and Fe2O3, increase with the decrease of temperature, which indicates that higher temperature is not beneficial to thermodynamic reactions. In addition, a comparison of the general alkali methods is carried out, and it is concluded that the KOH leaching process is thermodynamically superior to the conventional chromate production process.     

Influence of Heat Treatment on Damping Behaviour of the Magnesium Wrought Alloy AZ61

The effect of isochronal heat treatments for 1h on variation of damping, hardness and microstructural change of the magnesium wrought alloy AZ61 was investigated. Damping and hardness behaviour could be attributed to the evolution of precipitation process. The influence of precipitation on damping behaviour was explained in the framework of the dislocation string model of Granato and Lücke.     

Effect of Rare Earth Doping on Impedance,Modulus and Conductivity Properties of Multiferroic Composites:0.5(BiLa_xFe_(1-x)O_3)–0.5(PbTiO_3)

The Lanthanum-doped bismuth ferrite–lead titanate compositions of 0.5(Bi LaxFe1-xO3)–0.5(Pb Ti O3)(x = 0.05,0.10,0.15,0.20)(BLxF1-x-PT) were prepared by mixed oxide method.Structural characterization was performed by X-ray diffraction and shows a tetragonal structure at room temperature.The lattice parameter c/a ratio decreases with increasing of La(x = 0.05–0.20) concentration of the composites.The effect of charge carrier/ion hopping mechanism,conductivity,relaxation process and impedance parameters was studied using an impedance analyzer in a wide frequency range(102–106Hz) at different temperatures.The nature of Nyquist plot confirms the presence of bulk effects only,and non-Debye type of relaxation processes occurs in the composites.The electrical modulus exhibits an important role of the hopping mechanism in the electrical transport process of the materials.The ac conductivity and dc conductivity of the materials were studied,and the activation energy found to be 0.81,0.77,0.76 and 0.74 e V for all compositions of x = 0.05–0.20 at different temperatures(200–300 °C).     

Using Finite Element and Contour Method to Evaluate Residual Stress in Thick Ti-6Al-4V Alloy Welded by Electron Beam Welding

This work was to reveal the residual stress profile in electron beam welded Ti-6Al-4V alloy plates(50 mm thick) by using finite element and contour measurement methods.A three-dimensional finite element model of 50-mmthick titanium component was proposed,in which a column–cone combined heat source model was used to simulate the temperature field and a thermo-elastic–plastic model to analyze residual stress in a weld joint based on ABAQUS software.Considering the uncertainty of welding simulation,the computation was calibrated by experimental data of contour measurement method.Both test and simulated results show that residual stresses on the surface and inside the weld zone are significantly different and present a narrow and large gradient feature in the weld joint.The peak tensile stress exceeds the yield strength of base materials inside weld,which are distinctly different from residual stress of the thin Ti-6Al-4V alloy plates presented in references before.     

Microstructures and Tensile Properties of Ultrafine-Grained Ni–(1–3.5) wt% SiC_(NP) Composites Prepared by a Powder Metallurgy Route

Silicon carbide nanoparticle-reinforced nickel-based composites(Ni–Si CNP),with a Si CNPcontent ranged from1 to 3.5 wt%,were prepared using mechanical alloying and spark plasma sintering.In addition,unreinforced pure nickel samples were also prepared for comparative purposes.To characterize the microstructural properties of both the unreinforced pure nickel and the Ni–Si CNPcomposites transmission electron microscopy(TEM) was used,while their mechanical behavior was investigated using the Vickers pyramid method for hardness measurements and a universal tensile testing machine for tensile tests.TEM results showed an array of dislocation lines decorated in the sintered pure nickel sample,whereas,for the Ni–Si CNPcomposites,the presence of nano-dispersed Si CNPand twinning crystals was observed.These homogeneously distributed Si CNPwere found located either within the matrix,between twins or on grain boundaries.For the Ni–Si CNPcomposites,coerced coarsening of the Si CNPassembly occurred with increasing Si CNPcontent.Furthermore,the grain sizes of the Ni–Si CNPcomposites were much finer than that of the unreinforced pure nickel,which was considered to be due to the composite ball milling process.In all cases,the Ni–Si CNPcomposites showed higher strengths and hardness values than the unreinforced pure nickel,likely due to a combination of dispersion strengthening(Orowan effects) and particle strengthening(Hall–Petch effects).For the Ni–Si CNPcomposites,the strength increased initially and then decreased as a function of Si CNPcontent,whereas their elongation percentages decreased linearly.Compared to all materials tested,the Ni–Si CNPcomposite containing 1.5% Si C was found more superior considering both their strength and plastic properties.     

Directional Growth of Tin Crystals Controlled by Combined Solute Concentration Gradient Field and Static Magnetic Field

A new method was introduced to achieve directional growth of Sn crystals. Microstructures in liquid(Pb)/liquid(Sn) diffusion couples were investigated under various static magnetic fields. Results show that the β-Sn crystals mainly reveal an irregular dendritic morphology without or with a relatively low static magnetic field(B0.3 T). When the magnetic field is increased to 0.5 T, the β-Sn dendrites close to the final stage of growth begin to show some directional character. With a further increase in the magnetic field to a higher level(0.8–5 T), the β-Sn dendrites have an enhanced directional growth character, but the dendrites show a certain deflection. As the magnetic field is increased to 12 T, the directional growth of the β-Sn dendrites in the center of the couple is severely destroyed. The mechanism of the directional growth of the β-Sn crystals and the deflection of the β-Sn crystals with the application of static magnetic field was tentatively discussed.     

Quantitative Analysis of the Crystallographic Orientation Relationship Between the Martensite and Austenite in Quenching–Partitioning–Tempering Steels

The orientation relationships(ORs)between the martensite and the retained austenite in low-and medium-carbon steels after quenching–partitioning–tempering process were studied in this work.The ORs in the studied steels are identified by selected-area electron diffraction(SAED)as either K–S or N–W ORs.Meanwhile,the ORs were also studied based on numerical fitting of electron backscatter diffraction data method suggested by Miyamoto.The simulated K–S and N–W ORs in the low-index directions generally do not well coincide with the experimental pole figure,which may be attributed to both the orientation spread from the ideal variant orientations and high symmetry of the low-index directions.However,the simulated results coincide well with experimental pole figures in the high-index directions{123}_(bcc).A modified method with simplicity based on Miyamoto’s work was proposed.The results indicate that the ORs determined by modified method are similar to those determined by Miyamoto’method,that is,the OR is near K–S OR for the low-carbon Q–P–T steel,and with the increase of carbon content,the OR is closer to N–W OR in medium-carbon Q–P–T steel.     

Growth Kinetics of Single Inclusion Particle in Molten Melts

On the basis of the single-particle framework, a new theory on inclusion growth in metallurgical melts is developed to study the kinetics of inclusion growth on account of reaction and collision. The studies show that the early growth of inclusion depends on reaction growth and Brawnian motion collision, and where the former is decisive, the late growth depends on turbulence collision and Stokes＇ collision, and where the former is dominant; collision growth is very quick during the smelting process, lessened in the refining process, but nearly negligible in the continuous casting process.