采用焙烧-水浸法从报废锂离子动力电池中回收金属

锂离子动力电池在新能源汽车中已获得广泛应用,其报废后Li、Ni、Co、Mn等金属清洁高效回收对促进有色金属循环利用具有重要意义.从LiNi_0.5Co_0.2Mn_0.3O₂为正极材料的锂离子动力电池中回收Li、Ni、Co、Mn,并采用TG-DSC、XRD、ICP-OES、XPS、热力学分析等研究了回收过程物相演变规律及影响金属回收率的主要因素.结果表明:由LiNi_0.5Co_0.2Mn_0.3O₂与NaHSO₄·H₂O组成的混合物,经过焙烧后Li、Ni、Co、Mn元素的赋存状态发生改变,从不溶于水的复杂金属氧化物形式,转化为可溶于水的金属硫酸盐形式.焙烧产物在一定条件下用水浸出后,Li、Ni、Co、Mn元素以金属离子的形式转移到水溶液中获得回收.混合物的组成、焙烧温度对Li、Ni、Co、Mn元素在焙烧产物中的赋存形式呈现制约关系,也是影响Li、Ni、Co、Mn金属回收率的主要因素.     

白云鄂博稀土尾矿的工艺矿物学研究

采用X射线衍射、扫描电子显微镜、矿物解离分析仪(MLA)、电子探针,以及化学分析等分析手段对白云鄂博稀土尾矿的化学组成、矿物组成、矿物嵌布特征进行研究.结果表明:尾矿的矿物组成非常复杂,嵌布粒度很细.尾矿中稀土矿物为氟碳铈矿和独居石,铁元素主要赋存于赤铁矿中,氟元素主要赋存在萤石中,这三种矿物解离度较高,分别为87.28%,89.15%,96.70%.尾矿中铌元素主要赋存在烧绿石、铌铁矿、铌铁金红石、钛铁金红石等铌矿物中;钪元素主要分散在硅酸盐矿物中,钍元素主要以类质同象的形式赋存于稀土矿物中.此研究结果对白云鄂博稀土尾矿的高效综合利用具有一定的指导意义.     

两段焙烧强化含铼低品位钼精矿的氧化分离

针对氧化焙烧法处理低品位钼精矿中存在的钼氧化不完全、铼难挥发分离、有价元素(钼和铼)回收率较低等问题,采用焙烧试验、热重、物相和显微结构分析等研究两段焙烧强化氧化含铼低品位钼精矿中钼、铼的工艺及原理。研究结果表明:两段焙烧是实现钼、铼充分氧化的有效处理工艺。该工艺通过调节两段的温度和气流方向,改善气固对流条件,减小氧化焙烧过程的氧化差异,促进含钼和含铼矿物的深度氧化。在最佳工艺条件下(Ⅰ段焙烧温度675℃,焙烧时间1 h,气流由下至上;Ⅱ段焙烧温度625℃,焙烧时间2 h,气流由上至下),最终焙烧过程铼挥发率可达77.21%,焙烧产物中可溶钼质量分数提高到83.98%。相较于一段焙烧,两段焙烧各层产物的物相组成及微观结构一致,不存在未氧化的辉钼矿(MoS2)和氧化不完全的低价钼氧化物(MoO2),钼主要以MoO3形式存在。     

FeS2改性及其非均相Fenton研究进展

黄铁矿(FeS₂)因其资源丰富、价格低廉和具有可作为潜在的非均质Fenton试剂受到广泛关注。但FeS₂具有比表面积小、Fe(Ⅱ)/Fe(Ⅲ)循环途径较少、循环使用次数低等缺陷,无法进一步满足实际应用的要求。本文综述了常见的改性FeS₂非均相类Fenton优化技术,主要包括引入外场、改变催化剂载体、非均相Fenton反应过程中引入其他物质等三大方向并分析了它们的优缺点,以及FeS₂非均相Fenton的机理和应用,展望了改性FeS2非均相Fenton反应未来的重点研究方向,为进一步完善改性FeS₂非均相类Fenton技术优化方案,开发出低成本、高性能的非均相Fenton水处理方向提供新的思路。     

洞庭湖“四水”的水动力条件对比分析

河流沉积物元素组成是源区岩石、风化作用、河流水动力分选等各种自然过程的结果.其中,水动力条件因控制沉积物的搬运形式、粒度特征、矿物组成等而对河流沉积物元素组成有极重要的控制作用.本研究对“四水”(即湘江、资江、沅江、澧水)入湖河床沉积物的矿物组成、元素富集特征进行分析,并选取合适的特征元素计算水动力分选指数(WI)来反演“四水”河流水动力条件.结果显示,Al₂O₃、TiO₂、Zr等元素是指示沉积物水动力条件的主要特征元素,“四水”的河流水动力条件为澧水>沅江>湘江>资江,WI(Zr/Al₂O₃)为本研究中描述“四水”水动力条件的最适宜指标.     

含铅锌赤褐铁矿氧化焙烧脱硫性能和机理

针对含铅锌赤褐铁矿中主要以铅、锌、铁等金属硫化物形式存在的杂质硫,在还原焙烧过程中不能被有效脱除而影响铁精矿质量的问题,采用氧化焙烧方式研究含铅锌赤褐铁矿中硫的脱除效果和脱硫机理。通过脱硫率、焙烧前后产物的矿相分析、显微观察鉴定以及拉曼光谱测试等表征方法,研究焙烧温度、焙烧时间对含铅锌赤褐铁矿脱硫效果的影响,探讨含铅锌赤褐铁矿的脱硫机理及金属硫化物的转化过程。研究结果表明：含铅锌赤褐铁矿中硫、铅、锌的质量分数分别为3.34%、1.50%和1.25%,在焙烧温度为600～1 050℃和焙烧时间为5～120 min的条件下,氧化焙烧对脱硫过程有不同程度的影响,且随着氧化焙烧温度的提高和焙烧时间的延长,脱硫效果提高。在焙烧温度为1 050℃、焙烧时间为60 min的条件下,硫质量分数降至0.25%,总脱硫率可达92.51%,对低价硫的脱硫率达98.64%。随着氧化焙烧温度的提高,焙烧产物中逐渐呈现多孔微小固熔体形貌和表面高温釉质层。脱硫过程主要为FeS₂、PbS、ZnS等金属硫化物在高温下发生不同的氧化反应,且铅锌等金属含量无明显变化,说明含硫杂质被氧化为SO_...     

稠油硫酸盐热化学还原生成H2S实验研究

为了研究稠油注汽热采过程中生成H₂S机理，以Na₂SO₄，CaSO₄，MgSO₄，Fe₂（SO₄）₃，Al₂（SO₄）₃与稠油硫酸盐热化学还原（TSR）实验为基础，探究稠油TSR生成H₂S机理。实验表明，不同硫酸盐与稠油反应生成H₂S不尽相同，硫酸盐的阳离子所带电荷数决定TSR反应程度的难易，电荷数越多越容易进行反应，且H₂S生成量顺序为Al₂（SO₄）₃>Fe₂（SO₄）₃ > MgSO₄ > CaSO₄ > Na₂SO₄，但生成的烃量顺序为Fe₂（SO₄）₃ > Al₂（SO₄）₃ > MgSO₄ > CaSO₄ > Na₂SO₄。与其他硫酸盐不同的是，由于Fe₂（SO₄）₃的氧化性，Fe³⁺可能与生成的H₂S进一步反应。通过傅里叶红外变换光谱（FT-IR）对固相检测发现，不仅存在金属氧化物（CaO，MgO，Fe₂O₃，Al₂O₃）还存在FeS₂。最后，通过对MgSO₄油相硫含量的检测发现，反应后硫含量高于原油硫含量，证明了无机硫向有机硫的转化。     

含钼铜精矿氧化焙烧-浸出分离钼研究

四川攀西地区的含钼铜精矿中,由于钼、铜矿物组成复杂,共生关系紧密,提出了氧化焙烧-浸出工艺进一步分离钼。将试样置入焙烧炉中进行氧化焙烧,使硫化物转化为CuO、MoO3、Fe2O3等氧化物后;添加NaOH、H2O与MoO3反应生成可溶性Na2MoO4,浸出渣作为铜精矿产品。研究结果表明:铜、钼等以氧化物形式赋存于焙烧矿中,氧化焙烧矿中的硫含量较低为0.53%,硫以SO2气相形式挥发;在焙烧温度650℃、焙烧时间120 min、氢氧化钠用量为30%、浸出温度60℃、浸出时间120min、浸出液固比2∶1的综合条件下,钼的浸出率为94.24%,铜精矿(浸出渣)中铜的质量分数为24.27%,钼分离效果明显。     

Fe2O3修饰CaSO4/Ben载氧体化学链燃烧反应特性

分别采用间歇式流化床反应器和热重分析仪进行多次循环实验及反应性能测试,研究了Fe2O3在化学链燃烧过程中对CaSO₄/Ben(膨润土)载氧体的催化作用,并对比Fe₂O₃不同添加量(质量分数)时CaSO₄/Ben载氧体与CO的反应活化能。结果表明,添加Fe₂O₃后CaSO₄/Ben载氧体的比表面积和孔容增加,还原反应速率提高,并使系统内维持较高浓度的CO₂;添加Fe₂O₃可抑制CaSO₄生成CaO和含硫气体的反应,提高CaSO₄/Ben载氧体循环反应的稳定性;Fe₂O₃的最佳添加量为w=15.0%,该添加量下CaSO₄/Ben载氧体与CO反应的活化能由88.72 kJ/mol降低至43.08 kJ/mol,反应活性显著提高。     

NaOH-Ca(OH)2分解独居石精矿的研究

为降低独居石分解工艺的加碱量,并提高独居石分解率,本研究在NaOH-Ca(OH)₂体系中对独居石精矿进行焙烧分解,采用XRD对焙烧产物进行物相分析,并结合焙烧矿中稀土元素在盐酸中的浸出率判断独居石分解效果.实验分别研究了NaOH添加量、Ca(OH)₂添加量、焙烧温度以及焙烧时间对独居石精矿分解的影响.结果表明,在NaOH-Ca(OH)₂体系中,独居石精矿分解的最佳工艺条件:NaOH添加量为25%,Ca(OH)₂添加量为20%,焙烧温度为800℃,焙烧时间为1.5h.该焙烧条件下独居石全部分解为稀土氧化物,浓盐酸对稀土浸出率可达到98%左右.与现有工业生产工艺相比,本研究工艺中碱添加量降低55%左右,独居石分解率提高2%左右.     

FeO的制备及其室温下稳定性研究

采用草酸亚铁在高纯Ar气条件下加热分解制备FeO,借助于XRD图谱探讨保护气氛对FeO制备的影响以及FeO在常温下存放的稳定性。结果表明,Ar气保护流量低于400mL/min时,产物相除FeO相外,还分别含有Fe3O4、Fe相,甚至有Fe2O3相杂质;较佳的Ar气保护流量为400mL/min,此时制备的FeO纯度高,其他杂质较少。新制备的FeO样品在干燥、潮湿和室内自然环境中保存,90d内未发生明显相的变化。     

A ternary FeS_2/Fe_7S_8@nitrogen-sulfur co-doping reduced graphene oxide hybrid towards superior-performance lithium storage

Iron sulfides are promising anode materials for lithium ion batteries(LIBs) owe to their high theoretical capacity and low cost. However, unsatisfactory electronic conductivity, dissolution of polysulfides, and severe agglomeration during the cycling process limit their applications. To solve these issues, a ternary FeS₂/Fe₇S₈@nitrogensulfur co-doping reduced graphene oxide hybrid(FeS₂/Fe₇S₈@NSG) was designed and synthesized throu...     

Extraction of vanadium from high calcium vanadium slag using direct roasting and soda leaching

The extraction of vanadium from high calcium vanadium slag was attempted by direct roasting and soda leaching. The oxidation process of the vanadium slag at different temperatures was investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). The effects of roasting temperature, roasting time, Na₂CO₃ concentration, leaching temperature, leaching time, and liquid to solid ratio on the extraction of vanadium were studied. The results showed that olivine phases and spinel phases in the vanadium slag were completely decomposed at 500 and 800℃, respectively. Vanadium-rich phases were formed at above 850℃. The leaching rate of vanadium reached above 90% under the optimum conditions:roasting temperature of 850℃, roasting time of 60 min, Na₂CO₃ concentration of 160 g/L, leaching temperature of 95℃, leaching time of 150 min, and liquid to solid ratio of 10:1 mL/g. The main impurities were Si and P in the leach liquor.     

Upgrading and dephosphorization of Western Australian iron ore using reduction roasting by adding sodium carbonate

The technology of direct reduction by adding sodium carbonate (Na₂CO₃) and magnetic separation was developed to treat Western Australian high phosphorus iron ore. The iron ore and reduced product were investigated by optical microscopy and scanning electron microscopy. It is found that phosphorus exists within limonite in the form of solid solution, which cannot be removed through traditional ways. During reduction roasting, Na₂CO₃ reacts with gangue minerals (SiO₂ and Al₂O₃), forming aluminum silicate-containing phosphorus and damaging the ore structure, which promotes the separation between iron and phosphorus during magnetic separation. Meanwhile, Na₂CO₃ also improves the growth of iron grains, increasing the iron grade and iron recovery. The iron concentrate, assaying 94.12wt% Fe and 0.07wt% P at the iron recovery of 96.83% and the dephosphorization rate of 74.08%, is obtained under the optimum conditions. The final product (metal iron powder) after briquetting can be used as the burden for steelmaking by an electric arc furnace to replace scrap steel.     

Occurrence mechanism of silicate and aluminosilicate minerals in Sarcheshmeh copper flotation concentrate

The Sarcheshmeh copper flotation circuit is producing 5×104 t copper concentrate per month with an averaging grade of 28% Cu in rougher, cleaner and recleaner stages. In recent years, with the increase in the open pit depth, the content of aluminosilicate minerals increased in plant feed and subsequently in flotation concentrate. It can motivate some problems, such as unwanted consumption of reagents, decreasing of the copper concentrate grade, increasing of Al₂O₃ and SiO₂ in the copper concentrate, and needing a higher temperature in the smelting process. The evaluation of the composite samples related to the most critical working period of the plant shows that quartz, illite, biotite, chlorite, orthoclase, albeit, muscovite, and kaolinite are the major Al₂O₃ and SiO₂ beating minerals that accompany chalcopyrite, chalcocite, and covellite minerals in the plant feed. The severe alteration to clay minerals was a general rule in all thin sections that were prepared from the plant feed. Sieve analysis of the flotation concentrate shows that Al₂O₃ and SiO₂ bearing minerals in the flotation concentrate can be decreased by promoting the size reduction from 53 to 38 μm. Interlocking of the Al₂O₃ and SiO₂ bearing minerals with chalcopyrite and chalcocite is the occurrence mechanism of silicate and aluminosilicate minerals in the flotation concentrate. The dispersed form of interlocking is predominant.     

Mineralogy and carbothermal reduction behaviour of vanadium-bearing titaniferous magnetite ore in Eastern India

Vanadium-bearing titaniferous magnetite bands hosted by Precambrian gabbro-norite-anorthositic rocks or their metamorphic equivalents were discovered in some parts of Eastern Indian Shield, containing 48%–49% Fe (total), 10%–25% TiO₂, and 0.3%–2.20% V₂O₅ by mass. Mineralogical and petrological study, composition, and characterization of the vanadium-bearing titaniferous magnetite ore were carried out by scanning electron microscopy-energy dispersive X-ray (SEM-EDX), wave length X-ray florescence (WDXRF), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), X-ray diffraction (XRD), etc. Chemical beneficiation for valuable metals, such as Fe, Ti, and V, was performed by reduction roasting. The direct and indirect reduction were investigated by mixing the lump ore with solid activated charcoal in a closed reactor and purging the reducing gas mixture in standard reducibility index apparatus at different temperatures and time intervals. The reduction roasting parameters were optimized. Finally, the reduced samples were crushed and upgraded by magnetic separation. The results show that, the maximum mass fractions of magnetic and nonmagnetic parts achieved are 69.36% and 30.64%, respectively, which contain 10.6% TiO₂ and 0.84% V₂O₅ in the magnetic part and 36.5% TiO₂ and 0.22% V₂O₅ in the nonmagnetic part.     

Investigation of the deterioration of passive films in H<Subscript>2</Subscript>S-containing solutions

The effect of H₂S on the corrosion behavior of 316L stainless steel was investigated using electrochemical methods by changing the gas condition from CO₂ to H₂S and then back to CO₂. The presence of H₂S showed an acceleration effect on the corrosion of 316L stainless steel in comparison with CO₂. The acceleration effect remained even after the complete removal of H₂S by CO₂, indicating that the passive film was irreversibly damaged. X-ray photoelectron spectroscopy (XPS) analysis indicated that the passive film was composed of Cr₂O₃, Fe₂O₃, and FeS₂ after being immersed in H₂S-containing solutions. The semiconducting property of the passive film was then investigated by using the Mott-Schottky approach. The presence of sulfides resulted in higher acceptor and donor densities and thus was responsible for the deterioration of passive films.     

Geochronology and geochemistry of the Fangcheng Neoproterozoic alkali-syenites in East Qinling orogen and its geodynamic implications

Finding of Neoproterozoic syenites at Fangcheng in the northern Qinling region of the East Qinling orogen provides an important constraint on timing of tectonic transformation to extensional regime. The alkaline pluton consists mainly of nepheline syenite, aegirine syenite, and alkali-feldspar syenite. The syenites are of intermediate （SiO2 = 54%-62%）, rich in alkali （K2O＋Na2O = 12%-15%）, aluminum （Al2O3= 16.81%-23.26%） and large ion lithophile elements （LILE）, without any obvious Nb, Ta, Zr, and Hf anomalies. The Fangcheng syenites are geochemically characterized by relative enrichment of LREE, minor differentiation of HREE, significant negative Eu anomalies （Eu = 0.13-0.23）, less negative εNd（t） values of -1.37 to-3.90, young Nd model ages of 1364 to 1569 Ma, and high zircon saturation temperatures of 915 to 1044℃. The syenitic magmas probably originated from small proportion melting of upper mantle in an extensional regime of intraplate-anorogenic tectonic setting, and have been slightly contaminated by crustal materials during ascending and/or emplacement. LA-ICP-MS zircon U-Pb dating yields ages of 844.3±1.6 Ma （MSWD=0.86）, suggesting that the Fangcheng alkaline syenites formed in the early Neoproterozoic. They are the oldest Neoproterozoic alkaline rocks ever recognized in the Qinling orogen as well as in South China. This implies that the tectonic regime of the Qinling region would have transformed from post-collisional stretch to intraplate-anorogenic extension no later than 844 Ma.     

Molybdenite alkali fusion and leaching: reactions and mechanism

The production of MoO₃ from Sarcheshmeh molybdenite concentrate via a pyro-hydrometallurgical process was studied. The molybdenite concentrate and sodium carbonate were premixed and fused under air atmosphere. Then the fused products were leached in water and the dissolved molybdenum was recovered as ammonium molybdate. The ammonium molybdate was then calcined to produce molybdic oxide. At the fusion stage, the effect of the mass ratio of carbonate to sulfide on the reaction products and the solubility of the products was investigated. The results show that during the fusion, sodium molybdate and sodium sulfate are the final reaction products and sodium sulfide is detected as an intermediate reaction product. By melting at 850℃ with 5wt% excess carbonate, the maximum solubility of the products is obtained. The molybdenum is recovered from the solutions as ammonium molybdate.