Preparation of copper arsenite and its application in purification of copper electrolyte

The preparation of copper arsenite with arsenic trioxide was presented and its application in the purification of copper electrolyte was proposed. The variables of n（OH^-）/n（As）, n（Cu）/n（As）, NaOH concentration, reaction temperature and pH value have some effects on the yield of copper arsenite. The optimum conditions of preparing copper arsenite are that the molar ratio of alkali to arsenic is 2：1, NaOH concentration is 1 mol/L, the molar ratio of copper to arsenic is 2：1, pH value is 6.0 and reaction temperature is 20℃. The yield of copper arsenite is as high as 98.65% under optimum conditions and the molar ratio of Cu to As in the product is about 5：4. The results of the purification experiments show that the removal rate of antimony and bismuth is 53.85% and 53.33% respectively after 20g/L copper arsenite is added. The purification of copper electrolyte with copper arsenite has the advantages of simple technique, good purification performance and low cost.     

铜电解液净化中铜砷的分离与回收(英文)

经二氧化硫还原、蒸发结晶,使铜电解液中铜、砷、锑和铋得到有效去除。结晶产物经过溶解、氧化、中和、沉淀、过滤和蒸发结晶,得到三氧化二砷和硫酸铜。当采用SO2将铜电解液中As(Ⅴ)充分还原为As(Ⅲ),并加热蒸发浓缩铜电解液中硫酸浓度至645g/L时,铜电解液中铜、砷、锑和铋的去除率分别为87.1 %,83.9 %,21.0 %和84.7%。在温度30℃,将65g结晶产物溶于200mL自来水时,砷的去除率为92.81%。将所得滤液在如下条件下净化:n(Fe):n(As)为1.2,双氧水为理论用量的19倍,氧化温度为45℃,氧化时间为40min,终点pH为3.7,净化后蒸发浓缩结晶,所得硫酸铜溶液中硫酸铜含量达到98.8%。     

Purification mechanism of copper electrolyte by As（Ⅲ）

A new kind of precipitate, antimony arsantimonate, was found during the precipitation reactions in acidic solution containing As（Ⅲ）, Sb（Ⅲ） and Sb（ Ⅴ ） by means of chemical analysis, SEM, XRD and IR spectrometry. The results show that the As content in antimony arsantimonate increases with the increase of n（As（Ⅲ）/n（Sb） in solution and the content of component Sb（Ⅲ） and Sb（Ⅴ） remains almost constant with the variation of n（Sb（Ⅲ））/n（Sb（Ⅴ）） in solution. The antimony arsantimonate is a kind of floccules with size of 1-5 μm. The crystal performance of the compound gets better with the decrease of n（As（Ⅲ））/n（Sb）, the cell parameter of which is near to 10.33×10^-10m under different n（As（Ⅲ））/n（Sb） and As atom locates on the surface, not in the inner of the grain. The chemical bonds of As--OH, Sb---OH, As---O--Sb, Sb--O---Sb and O---H of the precipitate are included in the precipitate. The chemical structure of precipitate is described as Sb（OH）2---O--[Sb（OH）3--（O---As（OH）--O---Sb（OH）3）3]----O--- Sb（OH）2·xH2O. The structure analysis shows that the copper electrolyte can be purified by As（Ⅲ） because the antimony arsantimonate precipitate forms.     

Sb在铜电解液净化中的应用

介绍了Sb在铜电解液净化中的应用。铜阳极泥分银渣 (含Sb 2 1.35 %)以及由Sb2 O3 和BaSO4 合成的吸附剂能选择性吸附电解液中的As,Sb ,Bi。在确保电解液主要成分不变的情况下 ,不论是分银渣还是合成吸附剂都能从铜电解液中吸附 90 %Bi,80 %Sb及部分As。在讨论吸附机理的同时 ,还研究了阳极铜含Sb对电解过程杂质在阳极泥和电解液之间的分配比例的影响。发现提高Sb在阳极铜里的相对含量可增大电解过程As,Sb ,Bi进入阳极泥的比例 ,从而为铜电解净液寻找了一条方便经济的途径。     

铜电解液中砷的还原及脱除(英文)

探讨了反应温度、H2SO4浓度、CuSO4浓度、反应时间、SO2气流量等因素对SO2还原铜电解液中As(Ⅴ)的影响,并对浓缩共晶作用下铜电解液中As(III)的脱除行为进行了研究。研究表明:As(V)还原率随着反应温度和H2SO4浓度的升高而降低,随着SO2气流量的增大及反应时间的延长而升高。当反应温度为65°C,H2SO4浓度为203g/L,CuSO4浓度为80g/L,SO2流量为200mL/min,反应时间为2h时,铜电解液中As(Ⅴ)还原率为92%;铜电解液中的As(V)还原后,将铜电解液浓缩至H2SO4浓度为645g/L时,As、Cu、Sb、Bi脱除率分别达到83.9%,87.1%,21%,84.7%.XRD分析结果表明:结晶产物中含有As2O3和CuSO4·5H2O等物相。     

Separation and recovery of Cu and As from copper electrolyte through electrowinning and SO2 reduction

Cu and As were separated and recovered from copper electrolyte by multiple stage electrowinning, reduction with SO₂ and evaporative crystallization. Experimental results showed that when the current density was 200 A/m², the electrolyte temperature was 55 °C, the electrolyte circulation rate was about 10 mL/min and the final Cu concentration was higher than 25.88 g/L, the pure copper cathode was recovered. By adjusting the current density to 100 A/m² and the electrolyte temperature to 65 °C, the removal rate of As was 18.25% when the Cu concentration decreased from 24.69 g/L to 0.42 g/L. After As(V) in Cu-depleted electrolyte was fully reduced to As(III) by SO₂, the resultant solution was subjected to evaporative crystallization, then As₂O₃ was produced, and the recovery rate of As was 59.76%. The cathodic polarization curves demonstrated that both Cu²⁺ concentration and As(V) affect the limiting current of Cu²⁺ deposition.     

铜电解液碳酸钡脱铋新工艺

对铜电解液碳酸钡脱铋工艺进行研究,提出机械活化盐酸催化的铜电解液碳酸钡脱铋新工艺,其工艺过程为:将碳酸钡粉末加水调和研磨制浆后,再加入适量盐酸到碳酸钡浆料中作催化剂,待铜电解液预热到80℃左右加入碳酸钡料浆,搅拌1 h后过滤。实验结果表明,采用碳酸钡脱铋新工艺,1 m3铜电解液加入10 kg碳酸钡,用0.1 L盐酸(HCl 27%)作催化剂,Bi的脱除率可达70%,脱铋渣含Bi量大于4%。与传统碳酸钡脱铋工艺相比较,新工艺净化1 m3铜电解液节省碳酸钡40 kg,脱铋渣中Bi含量增加3倍。     

Deep removal of copper from cobalt sulfate electrolyte by ion-exchange

SP-C was applied for the removal of Cu²⁺ from simulated cobalt sulfate electrolyte containing Co²⁺ 50 g/L and Cu²⁺ 0.5–2.0 g/L. Experimental conditions included pH of 2–4, temperature of 20–60 °C and contact time of 10–40 min. The investigation demonstrated that SP-C had recommendable efficiency in adsorbing Cu²⁺ from the electrolyte with 25- to 100-fold of Co²⁺. The optimal adsorption conditions of SP-C were pH of 4, contact time of 30 min and ambient temperature. The study also showed that the loaded resin could be effectively eluted with 2.0 mol/L H₂SO₄ solution at a contact time of 40 min; the peak concentration of Cu²⁺ in the eluate was about 35 g/L. The sorption characteristics of Cu²⁺ by SP-C could be described by Langmuir isotherm and the pseudo second-order kinetic equation. Infrared spectra showed that nitrogen atoms in the functional group coordinated with Cu²⁺ to form coordination bands.     

高温高压法合成人造金刚石的电解提纯工艺研究

研究了一种提纯金刚石的电解液,详细阐明了电解液各组分和工艺条件对阴极增重量的影响及机制。实验结果表明:所得电解液的最佳配比和工艺条件是氯化铵15g/L,硼酸30g/L,柠檬酸25g/L,氯化钠15g/L,糖精钠10g/L,电流密度8A/dm2,pH值5。使用该电解液能有效降低电解成本,提高电解提纯效率。     

五价锑在脱除铜电解液中砷、锑、铋杂质中的作用(英文)

通过向含有45 g/L Cu2+、185 g/L H2SO4、10 g/L As和0.5 g/L Bi的铜电解液中加入Sb(V),研究五价锑对铜电解液中砷、锑、铋杂质脱除作用机理。过滤电解液,采用化学分析、SEM、TEM、EDS、XRD、FTIR等方法对沉淀渣的结构形貌和成分进行表征。结果表明,沉淀渣呈尺寸为50~200μm的不规则块状,其化学成分主要为砷、锑、铋和氧。红外光谱检测表明,沉淀渣主要特征官能团为As—O—As、As—O—Sb、Sb—O—Bi、Sb—O—Sb和Bi—O—Bi。X射线衍射和电子衍射检测结果表明,沉淀渣由AsSbO4、BiSbO4和Bi3SbO7组成。锑酸盐的生成是五价锑脱除铜电解液中砷、锑、铋杂质的主要原因。     

Removal of copper from nickel anode electrolyte through ion exchange

An novel method for removal of copper from nickel anodic electrolyte through ion exchange was studied after cupric deoxidization. Orthogonal design experiments show the optimum conditions of deoxidizing cupric into Cu+ in the nickel electrolyte are the reductive agent dosage is 4.5 times as the theoretic dosage and reaction time is 0.5 h at 40 ℃ and pH 2.0. Ion exchange experiments show that the breakthrough capacity(Y) decreases with the increase of the linear flow rate(X): Y=1.559-0.194X+ 0.006 7X2. Breakthrough capacity increases with the increase of the ratio of height to radius(RRH). The higher the initial copper concentration, the less the breakthrough capacity(BC). SO42- and nickel concentration have no obvious change during the process of sorption, so it is not necessary to worry about the loss of nickel during the sorption process. Desorption experiments show that copper desorption from the resin is made perfectly with NaCl solution added with 4% (volume fraction) H2O2 (30%) and more than 100 g/L CuCl2 solution is achieved.     

硫酸镍铵复盐结晶法分离回收铜电解液中的镍（英文）

研究采用硫酸镍铵复盐结晶从铜电解液中分离回收镍的方法。研究发现,在相同温度的溶液中,硫酸铜的溶解度小于硫酸镍的溶解度,而硫酸铜铵的溶解度大于硫酸镍铵的溶解度。因此,加入(NH₄)₂SO₄可使铜电解液中的镍选择性结晶析出。按(NH₄)₂SO₄/NiSO₄摩尔比≤0.8加入(NH₄)₂SO₄,在-15℃冷冻结晶10 h,可使其中的镍以Ni(NH₄)₂(SO₄)₂·6H₂O的形式结晶析出。将所得结晶物热解,再将热解产物加水溶解,最后将溶解液浓缩结晶得到合格的NiSO₄·6H₂O产品。复盐结晶法是一种清洁环保、经济高效的从铜电解液中分离回收镍的方法。     

The purification of copper refinery electrolyte

The phrase “purification of copper refinery electrolyte” is misleading since typically, impurities are controlled by withdrawing a bleedstream of the circulating electrolyte. However, solvent extraction and ion exchange have also found some application in impurity control. This article describes conventional practice, including treatment of the bleedstream, and other attempts at electrolyte purification. Impurities to be discussed include Sb, Bi, As, Ni, Ca, ammonia, and organic fragments generated from hydrolysis of conventional cathode growth-modifying addition agents. For more information, contact J.E. Hoffmann, James E. Hoffmann & Associates Co., P.O. Box 420545, Houston, TX 77242-0545; (281) 493-9441; fax (713) 780-0761; e-mail jehentp@aol.com.     

Sb(V) removal from copper electrorefining electrolyte: Comparative study by different sorbents

Removal of Sb(V) from copper electrolyte by different sorbents such as activated carbon, bentonite, kaolin, resin, zeolite and white sand was investigated. Adsorption capacity of Sb(V) removal from copper electrolyte was as follows: white sand < anionic resin < zeolite < kaolin < activated carbon < bentonite. Bentonite was characterized using FTIR, XRF, XRD, SEM and BET methods. The results show specific surface area of 95 m²/g and particles size of 175 nm for bentonite. The optimum conditions for the maximum removal of Sb are contact time 10 min, 4 g bentonite and temperature of 40 °C. The adsorption of Sb(V) on bentonite is followed by pseudo-second-order kinetic (R²=0.996 and k=9×10^?5 g/(mg·min)). Thermodynamic results reveal that the adsorption of Sb(V) onto bentonite from copper electrolyte is endothermic and spontaneous process (ΔG^Θ=–4806 kJ/(mol·K). The adsorption data fit both the Freundlich and Langmuir isotherm models. Bentonite has the maximum adsorption capacity of 10000 mg/g for adsorption of Sb(V) in copper electrolyte. The adsorption of Zn, Co, Cu and Bi that present in the copper electrolyte is very low and insignificant.     

硅胶-聚合胺树脂从模拟低品位铜矿浸出液中富集纯化铜

研究SP-C硅胶-聚合胺树脂在模拟低品位铜矿硫酸浸出液中富集纯化铜的工艺,在Cu2 1~2 g/L、Fe3 2~8 g/L范围内,考察该树脂吸附分离铜铁的性能。结果表明:该树脂对铜具有良好的选择性能,对铁的选择性能较差;湿树脂铜的穿漏交换容量及饱和交换容量分别为0.27和0.34 mol/L,解析高峰液Cu2 约30 g/L,铜铁分离系数达到397;最佳工艺条件为:料液pH 1.86,接触时间30 min。     

薄层液膜下直流电场对铜的腐蚀行为、氯离子迁移行为和枝晶生长的影响(英文)

采用动电位极化和表面分析技术(SEM/EDS),研究薄层液膜下直流电场对印刷电路板铜的腐蚀行为、氯离子迁移行为和枝晶生长的影响。结果表明:直流电场使铜的腐蚀减弱;氯离子在直流电场作用下由负极到正极发生定向迁移,并且富集于电场的正极,导致电场正极发生严重的局部腐蚀;枝晶生长于电场的负极,并且其速率和尺寸随着外加电压的增加和暴露时间的延长而分别加快和变大。     

Synthesis of novel silica-supported chelating resin containing tert-butyl 2-picolyamino-N-acetate and its properties for selective adsorption of copper from simulated nickel electrolyte

A novel silica-supported tert-butyl 2-picolyamino-N-acetate chelating resin (Si-AMPY-1) was successfully synthesized and characterized by elemental analysis, FT-IR, SEM and ¹³C CP/MAS NMR. The adsorption behaviors of the Si-AMPY-1 resin for Cu(II) and Ni(II) were studied with batch and column methods. The batch experiments indicated that the Si-AMPY-1 resin adsorbed Ni(II) mainly via physisorption, while adsorbed Cu(II) via chemisorption. The column dynamic breakthrough curves revealed that the Si-AMPY-1 resin can efficiently separate Cu(II) from the simulated nickel electrolyte before the breakthrough point. Moreover, the concentration of Cu(II) in the column effluent was decreased to be less than 3 mg/L within the first 43 BV (bed volumes), and the mass ratio of Cu/Ni was 21:1 in the saturated resin, which completely satisfied the industrial requirements of the nickel electrorefining process. Therefore, it was concluded that the Si-AMPY-1 resin can be a promising candidate for the deep removal of Cu(II) from the nickel electrolyte.     

铜电解液净化工艺的比较与选择

本文对国内外常见的铜电解液净化方法进行阐述,并分别就净化工序的三个部分进行比较,根据各厂的实际情况选择最经济合理的净液方案.     

二段脱铜液还原结晶法脱砷新工艺

对铜电解液脱砷方法进行研究,提出以二段脱铜液为原料,采用SO2还原结晶法脱砷新工艺。在二段脱铜液中通入SO2,将其中的As(Ⅴ)还原成As(Ⅲ),还原后的溶液通过蒸发结晶析出As2O3,达到二段脱铜液脱砷的目的。结果表明:当As(Ⅴ)浓度为12.41 g/L、H2SO4浓度为253.00 g/L、反应温度为60℃时,向二段脱铜液中通入SO290 min后静置90 min,二段脱铜液中As(Ⅴ)的还原率达到94.54%。还原后的溶液进行蒸发结晶,当蒸发前与结晶后的体积比(V0:V1)为3.5时,砷的脱除率达到91.33%,结晶产物为As2O3。与传统脱砷工艺相比,新工艺具有操作简单、成本低廉及砷的脱除效果明显等优势。     

氧气转炉烟气净化回收技术

针对氧气转炉炼钢工艺及其污染物的特点,介绍了氧气转炉炼钢烟气净化回收方法,并对"OG法"和"LT法"两种烟气净化回收系统的系统组成、工艺流程和技术水平进行了比较,提出了"OG法"改造为"LT法"的建议。