Purification of brines by chemical precipitation and ion‐exchange processes for obtaining battery‐grade lithium compounds

Lithium salts are very important in the production of lithium batteries since they are used as precursors for the fabrication of cathode materials that require very low level of impurities (battery grade). Usually, the lithium extraction process from brine first yields lithium carbonate, which is then used as raw material for the production of other lithium compounds. However, it implies an increase in investment costs, considering more equipment and process stages. To remove the impurities and produce battery‐grade lithium compounds directly from brines, a laboratory‐scale process was developed using the methods of ion exchange and chemical precipitation. Thus, impurity‐free brine ready to be used in an industrial membrane electrolysis process is obtained. Different sequences and operating conditions were investigated for the purification of lithium‐concentrated brines, removing the main impurities of the natural brines: calcium, magnesium, and sulfate. For the characterization of solutions, crystals, and ion‐exchange resins, atomic absorption spectrophotometry, scanning electron microscopy, and X‐ray scattering spectroscopy were used. The results indicate that during the chemical precipitation process, lithium‐concentrated brine reacted with some additives (precipitating agents) at different stages in the batch reactors. Subsequently, the pulp obtained was sedimented and filtered, eliminating or reducing the impurities of the lithium brine. Thus, the most efficient precipitation sequence was evaluated as a function of the removal percentage of the species. The removal efficiencies obtained for Ca⁺², Mg⁺², and SO₄^?2 were of 98.93%, 99.93%, and 97.14%, respectively. Thereafter, the use of the ion‐exchange resins reduced the concentration of Ca⁺² and Mg⁺² to the values below 1 ppm. The combined use of both processes provided promising results that could be applied in the industry.     

Al-Er-Zr合金的热变形行为及动态析出

通过对Al-0.04Er-0.08Zr合金进行200°C 到450°C 范围内的热压缩测试对该合金的热变形行为进行了研究，在这个过程中利用Arrhenius-type方程进行线性拟合从而分析应力-应变曲线，之后通过透射电镜来观察研究变形组织。结果表明对于固溶态以及时效态合金来讲，在热压缩过程中动态回复是使合金软化的一个主要机制。高温以及低应变速率的热变形会诱导固溶态合金快速析出。动态析出会明显增加固溶态合金在热压缩过程中其表面的流变应力，但是却不能有效提高变形合金的硬度。动态析出还会导致应力-应变曲线拟合出现Arrhenius型偏差。     

白云鄂博矿焙烧浸出-萃取沉淀分离稀土及钍的试验研究

采用焙烧浸出-萃取沉淀法从白云鄂博稀土精矿中分离稀土和钍,得到最佳焙烧浸出条件为: 矿酸比1∶1.5、焙烧时间1 h、焙烧温度200 ℃、水浸液固比8∶1、水浸时间4 h、水浸温度50 ℃,最佳条件下CeO₂、La₂O₃、Nd₂O₃、Pr₆O₁₁、Sm₂O₃和ThO₂浸出率分别为80.77%、69.24%、95.71%、76.82%、93.31% 和98.13%。采用羧酸类萃取-沉淀剂从浸液中萃取分离稀土和钍,在萃取-沉淀剂皂化度70%、料液pH=3.1、萃取-沉淀剂和钍的摩尔比4∶1的最佳条件下,稀土和钍萃取-沉淀率分别为19%和90%,实现了稀土和钍的有效分离。     

卷取温度对超低碳T-3CA第二相析出的影响

 为研究卷取温度对超低碳T-3 CA中第二相粒子析出行为的影响，采用金相、TEM等检测手段，分析了580、630、680 ℃ 3个典型卷取温度下超低碳T 3 CA中第二相粒子的析出特性，结果发现卷取温度越高，热轧形成的TiC粒子尺寸越粗大，分布越稀疏。结合相关动力学计算分析了卷取温度对TiC粒子沉淀析出时临界晶核尺寸、相对形核率、相对沉淀析出时间的影响。结果表明，随着卷取温度由580提高到680 ℃，TiC粒子沉淀析出时临界晶核尺寸增大约1.0 nm，相对形核率降低约1.0个数量级，相对沉淀析出孕育时间增大约0.8个数量级。     

面向不均衡数据集的过抽样算法

合成少数类过抽样技术（SMOTE）中的噪声样本可能参与合成新样本，所以难以保证新样本的合理性。针对这个问题，结合聚类算法提出了改进算法CSMOTE。该算法抛弃了SMOTE在最近邻间线性插值的思想，使用少数类的簇心与其对应簇中的样本进行线性插值合成新样本，并且对参与合成的样本进行了筛选，降低了噪声样本参与合成的可能。在六个实际数据集上，将CSMOTE算法与四个SMOTE的改进算法以及两种欠抽样算法进行了多次的对比实验，CSMOTE算法在所有数据集上均获得了最高的AUC值。实验结果表明，CSMOTE算法具有更高的分类性能，可以有效解决数据集中样本分布不均衡的问题。     

碳化反沉淀法去除硫酸锰浸出液中钙、镁的研究

采用碳化沉锰法去除硫酸锰溶液中的钙、镁离子。以CO₂为碳化剂, 将硫酸锰溶液中的Mn²⁺以碳酸锰沉淀的形式从原溶液中分离出来, 然后用硫酸将沉淀物溶解, 从而达到除杂的目的。考查了CO₂流量、反应温度、pH值及反应时间对钙、镁离子去除效果的影响, 结果表明, 最适宜条件为反应温度45 ℃、溶液pH值7.0、CO₂流量2.7 L/min、反应时间60 min, 此时碳化产物中钙、镁离子含量分别为0.03%和0.01%, 达到了HG/T 2836-2011高纯碳酸锰Ⅰ型品的标准。     

CuSO4对氰化提金贫液中SCN-的沉淀效果以及对共存离子浓度的影响

针对氰化提金贫液循环利用过程SCN^-积累以及外排带来的环境污染问题，以CuSO₄作为沉淀剂处理某高浓度SCN^-贫液，考察了沉淀剂用量、沉淀时间及沉淀温度对SCN^-沉淀效果和对共存离子浓度的影响。结果表明，当在贫液中加入1.6倍化学反应计量的CuSO₄后于室温搅拌60 min，SCN^-的去除率达87.5%以上，体系中T_Cu、S₂O₃ ^2-和SO₃ ^2-浓度也大幅降低，同时得到纯度达97%以上的CuSCN产品。沉SCN^-后的贫液只需石灰中和并沉部分SO₄ ^2-后，其活性得到进一步恢复，可直接返回金精矿浸出工序充分利用其中的CN^-，实现提金贫液的循环利用。     

中国沉淀法白炭黑产业发展现状及展望

沉淀法白炭黑是外观呈白色、多孔性无定形水合二氧化硅粉末,具有化学惰性,且耐高温、不燃、无毒、无味、无嗅。因其电绝缘性高、内表面积大,被广泛应用于橡胶、食品、医药、涂料等国民经济多个领域。梳理了国内沉淀法白炭黑主要厂家的生产能力、企业分布等基本情况,介绍了沉淀法白炭黑进出口情况、消费状况和行业技术进展等现状,并对沉淀法白炭黑应用前景进行展望,以期为沉淀法白炭黑生产企业和从事沉淀法白炭黑技术研究人员提供参考。     

乙醇提取-丙酮沉淀法提取分离茶皂素的工艺研究

以油茶饼粕为原料，采用乙醇提取-丙酮沉淀法对茶皂素进行提取分离。以茶皂素纯度和得率为考察指标，对乙醇体积分数、液料比、提取温度、提取时间、提取次数、提取液浓缩程度和丙酮用量等工艺参数进行了单因素优化。结果表明：体积分数95%的乙醇为提取溶剂，乙醇与预处理过的油茶饼粕液料比为9：1（mL：g），提取温度为70℃，提取时间为4 h，提取次数为2次，提取液浓缩至刚好有固体析出，丙酮用量为4倍浓缩液体积量时提取分离效果较佳，得到的茶皂素纯度为85.17%，得率为9.82%。不同溶剂打浆对产品纯化效果的比较发现：丙酮、乙酸乙酯、无水乙醇、体积分数95%的乙醇作为打浆纯化溶剂用于提高茶皂素纯度效果均不明显。     

Single-phase and binary phase nanogranular ferrites for magnetic hyperthermia application

The study demonstrates the performance of heating efficiency in single-phase and binary phase spinel ferrite nanosystems. Ferrimagnetic cobalt ferrite (CoFe₂O₄) (CFO) and superparamagnetic copper ferrite/copper oxide (CuFe₂O₄/CuO) (CuF) nanosystems of different particle sizes were synthesized through a microwave-assisted coprecipitation method. The heating behavior was observed in range of both field amplitudes (8-24 kA/m at 516 kHz) and frequencies (325-973 kHz at 12 kA/m). The heating efficiency was analyzed and compared by means of particle size, magnetization, effective anisotropy constant, and Néel relaxation mechanism. Indeed, the heating rate was maximized in larger ferrite particles with low effective anisotropy constant. Moreover, though the magnetization and effective anisotropy constant of single-phase CoFe₂O₄ nanoparticles were higher, the binary phase CuFe₂O₄/CuO nanosystems of similar crystallite size (28 nm) exhibited superior heating efficiency (4.21°C/s). For a field amplitude and frequency of 24 kA/m and 516 kHz, the heating rate of CuF and CFO ferrites with different crystallite sizes decreased in the order of 4.21 > 2.14 > 0.58 > 0.52°C/s for 29 nm > 25 nm > 12 nm > 15 nm, respectively. The results emphasize that binary phase ferrite nanoparticles are better thermoseeds than the single-phase ferrites for the magnetic hyperthermia application.