酸浸—萃取—沉淀法回收废锂离子电池中的钴

采用酸浸—萃取—沉淀法回收废锂离子电池中的钴。实验结果表明:废锂离子电池在600℃下煅烧5 h可将正极材料上的有机黏结剂与正极活性物质分离;正极活性物质在Na OH溶液浓度为2.0 mol/L、n(Na OH)∶n(铝)=2.5、碱浸温度为20℃的条件下碱浸反应1 h后,铝浸出率达99.7%;已除铝的正极活性物质在硫酸浓度为2.5 mol/L、H_2O_2质量浓度为7.25 g/L、液固比为10、酸浸温度为85℃的条件下酸浸反应120 min,钴浸出率高达98.0%;酸浸液在p H为3.5、萃取剂P507与Cyanex272体积比为1∶1的条件下,经2级萃取,钴萃取率为95.5%;采用H_2SO_4溶液反萃后在硫化钠质量浓度为8 g/L、反萃液p H为4的条件下沉淀反应10 min,钴沉淀率达99.9%。     

离子液体对废旧印刷线路板中铜、锌、铅的浸出规律

以离子液体1-丁基磺酸-3-甲基咪唑三氟甲烷磺酸盐([BSO_3HMIm]OTf)为浸出剂,初步研究了WPCBs浸铜过程中锌和铅浸出率的影响因素。实验结果表明:铜、锌的浸出率随着WPCBs粒径的减小、H_2O_2溶液加入量的增大而增大,铜的浸出率随浸出温度的升高先增大后减小,锌的浸出率受浸出温度影响不大;铅的浸出率受5种因素影响不大,且总体处于较低水平。在WPCBs粒径为0.100~0.250 mm、离子液体加入量为60.0%(φ)、H_2O_2溶液加入量为7.5%(φ)、固液比为1∶15、浸出温度为50℃的条件下,铜、锌、铅的浸出率分别为99.84%,93.25%,22.46%。     

镀锌钢板废料中锌的碱浸过程影响因素分析

以强碱(NaOH)溶液为浸取剂,采用碱浸法回收镀锌钢板废料中的锌,考察了不同因素(反应温度、反应时间、碱浓度、添加剂)对锌浸出效果的影响,并对添加剂的作用机理进行了分析。实验结果表明:在NaOH质量浓度为250 g/L、反应温度为90℃、反应时间为300 min的最佳工艺条件下,锌的浸出率高达97.89%;添加NaNO_3可提高锌在碱液中的腐蚀电位和腐蚀电流,从而加快镀锌钢板废料中锌的溶解,缩短反应时间;添加KMnO_4对反应速率基本无影响。     

废锌锰电池中金属离子浸出行为研究

研究了废锌锰电池在硫酸体系中,温度和硫酸浓度对金属离子浸出行为的影响。通过实验找到了最佳工艺条件:硫酸浓度为10%,温度为40℃,固液比为1:10,催化剂为1mL,反应时间为2h,搅拌强度为40~80r/min。在此条件下,有用金属浸出率:Zn达到99%以上,Mn达到80%,Fe达到50%,而其他有害金属浸出率低。为进一步分离有害金属和利用废锌锰电池生产鳌合微肥提供理论依据。     

空气—双氧水联合氧化工艺选择性浸出废磷酸铁锂材料中的锂

采用空气—双氧水联合氧化工艺选择性浸出废磷酸铁锂材料(废磷酸铁锂电池正极材料粉末)中的锂,经沉锂后以碳酸锂的形式回收。实验结果表明,在液固比为4 mL/g、H₂SO₄与Li的摩尔比为0.5、搅拌转速为250r/min、反应温度为50℃的条件下空气曝气300 min,再于相同反应温度和搅拌转速下滴加H₂O₂(H₂O₂与Li的摩尔比为0.29)反应120 min,锂、铁和磷的浸出率分别为93.47%、17.26%和19.83%。该工艺较单独双氧水氧化工艺可减少75%以上的双氧水用量,大幅降低了回收成本。溶解氧浓度对浸出体系中Fe³⁺的存在方式有重要影响：在较高浓度(通空气)下以磷酸铁为主;在较低浓度(未通空气但接触空气)下以氢氧化铁为主。     

卤素法电镀锡阳极泥中锡的碱浸回收及动力学分析

以NaOH溶液为浸出剂,采用碱浸法回收卤素法电镀锡阳极泥中的锡,考察了浸出效果的影响因素,并对浸出过程的动力学进行了研究。实验结果表明:在NaOH质量浓度200 g/L、反应温度90℃、液固比6、反应时间240 min的最佳工艺条件下,锡的浸出率约为98%;最佳工艺条件下,浸出液中的氟离子对后续锌粉置换回收锡没有影响;在303.15~363.15 K范围内,该浸出过程主要受内扩散控制,反应活化能为9.725 k J/mol。     

用含锌废催化剂制备纳米氧化锌

以含锌废催化剂为原料,经酸浸、除杂、锌粉置换、合成等工艺制得碱式碳酸锌,再经过滤、洗涤、干燥、煅烧制备纳米氧化锌。考察了酸浸工艺硫酸溶液含量和液固比（硫酸与含锌废催化剂的质量比）对锌浸出率的影响,以及煅烧温度对纳米氧化锌质量的影响。实验结果表明：在硫酸质量分数为30%、液固比为5的最佳酸浸工艺条件下,锌浸出率为92%;在最佳煅烧温度为400 ℃的条件下,氧化锌质量分数大于95%,比表面积大于50 m²/g;纳米氧化锌颗粒大小均匀,平均粒径小于50 nm。     

用含锌废催化剂制备纳米氧化锌

以含锌废催化剂为原料,经酸浸、除杂、锌粉置换、合成等工艺制得碱式碳酸锌,再经过滤、洗涤、干燥、煅烧制备纳米氧化锌。考察了酸浸工艺硫酸溶液含量和液固比(硫酸与含锌废催化剂的质量比)对锌浸出率的影响,以及煅烧温度对纳米氧化锌质量的影响。实验结果表明:在硫酸质量分数为30%、液固比为5的最佳酸浸工艺条件下,锌浸出率为92%;在最佳煅烧温度为400℃的条件下,氧化锌质量分数大于95%,比表面积大于50 m2/g;纳米氧化锌颗粒大小均匀,平均粒径小于50 nm。     

酸浸出法回收冶金污泥中的有价金属

采用二次酸浸出的方法回收镍钴湿法冶金工业污泥中的有价金属。先采用水和硫酸作为浸出剂浸出Mg和Na,最佳工艺条件为浸出液的pH 7.5、浸出时间5 min、浸出剂体积与干污泥质量的比(ω)为10 mL/g。再采用硫酸作为浸出剂、焦亚硫酸钠作为还原剂进行二次酸浸,在硫酸与污泥质量比为1.3、焦亚硫酸钠与污泥质量比为0.3、ω为5 mL/g、浸出温度85℃、浸出时间20 min的最佳工艺条件下,Co、Ni、Cu、Mn和Zn的浸出率分别达92.45%、93.48%、89.52%、97.78%和94.79%。经XRD表征,浸出后污泥中未见原污泥中的矿物相,说明原污泥中的矿物几乎全部被溶解。     

用含硫化砷废渣制备砷酸铜

以湖北省某化工企业含砷废水处理过程中产生的含硫化砷废渣为研究对象,采用氧化碱浸—沉淀工艺制备砷酸铜。考察了沉淀反应液pH、沉淀反应温度、搅拌转速对砷沉淀效果的影响。采用XRD和SEM技术对砷酸铜的物相及形貌进行了表征。实验结果表明：废渣在氧化碱浸过程的砷浸出率为96.53%;沉淀反应时间为30 min时,沉淀步骤的最佳工艺条件为沉淀反应液pH 5.0、搅拌转速500 r/min、沉淀反应温度50 ℃。验证实验结果表明,在该工艺条件下,砷沉淀率均达93.96%以上。SEM表征结果显示,砷酸铜产品为颗粒状,粒径约为500 nm。XRD表征结果显示,砷酸铜产品中主要含有Cu₃As₂O₈,Cu₄O（AsO₄）₂,Cu₄（As₂O₇）O₂。该方法工艺简单、无二次污染,为废渣的综合利用提供了一种新的技术路线。     

Organic oxalate as leachant and precipitant for the recovery of valuable metals from spent lithium-ion batteries

Spent lithium-ion batteries containing lots of strategic resources such as cobalt and lithium are considered as an attractive secondary resource. In this work, an environmentally compatible process based on vacuum pyrolysis, oxalate leaching and precipitation is applied to recover cobalt and lithium from spent lithium-ion batteries. Oxalate is introduced as leaching reagent meanwhile as precipitant which leaches and precipitates cobalt from LiCoO(2) and CoO directly as CoC(2)O(4)·2H(2)O with 1.0 M oxalate solution at 80°C and solid/liquid ratio of 50 g L(-1) for 120 min. The reaction efficiency of more than 98% of LiCoO(2) can be achieved and cobalt and lithium can also be separated efficiently during the hydrometallurgical process. The combined process is simple and adequate for the recovery of valuable metals from spent lithium-ion batteries.     

Recovery of copper and cobalt from ancient slag.

About 2.5 million tonnes of copper smelter slag are available in Küre, northern part of Turkey. This slag contains large amounts of metallic values such as copper and cobalt. A representative slag sample containing 0.98% Cu, 0.49% Co and 51.47% Fe was used in the experimental studies. Two different methods, direct acid leaching and acid baking followed by hot water leaching were used for recovering Cu and Co from the slag. The effects of leaching time, temperature and acid concentration on Cu- and Co-dissolving efficiencies were investigated in the direct acid leaching tests. The optimum leaching conditions were found to be a leaching time of 2 h, acid concentration of 120 g L(-1), and temperature of 60 degrees C. Under these conditions, 78% Cu and 90% Co were extracted. In the acid baking + hot water leaching tests, 74% Co was dissolved after 1 h of roasting at 200 degrees C using a 3:1 acid:slag ratio, whereas the Cu-dissolving efficiency was 79% and the total slag weight loss was approximately 50%.     

Recovery of nickel, cobalt and some salts from spent Ni-MH batteries

This work provides a method to help recover nickel, cobalt metals and some of their salts having market value from spent nickel-metal hydride batteries (SNiB). The methodology used benefits the solubility of the battery electrode materials in sulfuric or hydrochloric acids. The results obtained showed that sulfuric acid was slightly less powerful in leaching SNiB compared to HCl acid. Despite that, sulfuric acid was extremely applied on economic basis. The highest level of solubility attained 93.5% using 3N sulfuric acid at 90 degrees C for 3h. The addition of hydrogen peroxide to the reacting acid solution improved the level of solubility and enhanced the process in a shorter time. The maximum recovery of nickel and cobalt metals was 99.9% and 99.4%, respectively. Results were explained in the light of a model assuming that solubility was a first order reaction. It involved a multi-step sequence, the first step of which was the rate determining step of the overall solubility. Nickel salts such as hydroxide, chloride, hexamminenickel chloride, hexamminenickel nitrate, oxalate and nickel oleate were prepared. With cobalt, basic carbonate, chloride, nitrate, citrate, oleate and acetate salts were prepared from cobalt hydroxide Cost estimates showed that the prices of the end products were nearly 30% lower compared to the prices of the same chemicals prepared from primary resources.     

生态修复植物蜈蚣草中砷的回收

采用管式炉高温热解-NaOH-Na₂CO₃混合液碱浸-CuSO₄·5H₂O沉淀的方法回收生态修复植物蜈蚣草中的砷,最终得到产品砷酸铜。该方法的最佳工艺条件为：热解温度600 ℃,热解时间30 min,CaO加入量（CaO与蜈蚣草的质量比）8%; m（NaOH）∶m（Na₂CO₃）=1∶3,碱浸温度70 ℃, 碱浸时间2 h, 固液比1∶10; 沉淀反应pH 5, 沉淀反应温度70 ℃。采用该方法处理生态修复植物蜈蚣草,得到产品砷酸铜的纯度为93%,砷回收率达88%。     

Processing of copper converter slag for metal reclamation. Part I: Extraction and recovery of copper and cobalt.

Clean processing of copper converter slag to reclaim cobalt and copper could be a challenge. An innovative and environmentally sound approach for recovering valuable metals from such a slag has been developed in the present study. Curing the slag with strong sulphuric acid, without re-smelting or roasting as practiced currently in the industry, render it accessible to leaching, and more than 95% of cobalt and up to 90% of copper was extracted together with iron by water leaching, leaving silica behind in a residue. The copper in the leach liquor was recovered by cementation with iron and the dissolved iron crystallized as ferrous sulphate monohydrate. The cobalt in the mother-liquor rich in iron was recovered by either cementation or sulphide precipitation. Operation variables in the new process were also investigated and optimized.     

Hydrometallurgical recycling of cobalt from zinc plants residue

A large amount of hot filter cake (HFC) is annually generated in Iranian zinc plants. It contains 1% zinc, 16–30% manganese, 5–25% calcium and 1–4.5% cobalt. Usually, zinc is selectively leached by an alkaline medium and its residue is known as alkaline leached HFC (ALHFC). In the present study, the possibility of cobalt extraction from ALHFC was investigated using a creative hydrometallurgical process. At the first stage, zinc and cadmium were selectively removed with sulfuric acid. At the second stage, it was deeply focused on the possibility of selective reductive leaching of cobalt by H₂O₂ as a reductant in the presence of manganese. As results, several differences were found between the mechanism of cobalt and manganese leaching. Accordingly, cobalt leaching was more affected by acid concentration and manganese leaching was more affected by reductant concentration. Consequently, with manipulating these important parameters, it was made possible to selectively separate cobalt from manganese. Based on the obtained results, 90.9% of cobalt and only 10.04% of manganese were leached with 1% of H₂O₂. At the third stage, pregnant cobalt solution was successfully purified through a solvent extraction process with D2EHPA. Finally, cobalt hydroxide as our final product with a purity of more than 99% was precipitated from the pure pregnant solution at 70 °C.     

Tannic acid as a novel and green leaching reagent for cobalt and lithium recycling from spent lithium-ion batteries

Tannic acid–acetic acid is proposed as novel and green chemicals for cobalt and lithium recycling from spent lithium-ion batteries through a leaching process. The synergism of both acids was documented through batch and continuous studies. Tannic acid promotes cobalt dissolution by reducing insoluble Co³⁺ into soluble Co²⁺, while acetic acid is critical to improve the dissolution and stabilize the metals in the pregnant leach solution. Based on batch studies, the optimum conditions for metal recovery at room temperature are acetic acid 1 M, tannic acid 20 g/L, pulp density 20 g/L, and stirring speed 250 rpm (94% cobalt and 99% lithium recovery). The kinetic study shows that increasing temperature to 80 °C improves cobalt and lithium recovery from 65 to 90% (cobalt) and from 80 to 99% (lithium) within 4 h at sub-optimum condition (tannic acid 10 g/L). Kinetic modeling suggests the leaching process was endothermic, and high activation energy indicates a surface chemical process. For other metals, the pattern of manganese and nickel recovery trend follows the cobalt recovery trend. Copper recovery was negatively affected by tannic acid. Iron recovery was limited due to the weak acidic condition of pregnant leach solution, which is beneficial to improve leaching selectivity.

     

氯化铵浸取法回收盐泥中的镁

以盐泥为原料,采用氯化铵浸取回收盐泥中的Mg²⁺,以浸取液和回收的氨反应制取氢氧化镁产品。考察了盐泥浆液固含量、浸取时间、物料比（氯化铵与盐泥中氢氧化镁的摩尔比）等工艺条件对Mg²⁺浸取率的影响,并以比表面积为考察指标进行正交实验,确定氢氧化镁的最佳制备条件。实验结果表明：在盐泥浆液固含量为248 g/L、浸取时间为100 min、物料比为2.3的条件下,Mg²⁺浸取率为75.0%;在n（MgCl₂）:n（NH₄Cl）=0.5、氨水浓度3 mol/L、氨水滴加速率 0.8 mL/min、反应温度 90 ℃的最佳条件下,制备的氢氧化镁的比表面积为17.87 m²/g,粒径约为3 μm。该工艺简单可行,为盐泥的综合利用提供了新的思路。