Sequential removal of selenium and tellurium from copper anode slime with high nickel content

A process using soda roasting-alkaline leaching-acid leaching to remove selenium, tellurium and copper sequentially from the copper anode slime with high content of Ni was tested. The mechanism of this process was outlined based on thermodynamic analysis and the change in the XRD patterns of different intermediate products. During soda roasting, copper which occurs as Cu4SeTe in the slime was oxidized to CuO and Cu3TeO6, while selenium and tellurium were oxidized to Ag2SeO4 and Cu3TeO6, respectively. Ag2SeO4 in the calcine is easily leached in the subsequent alkaline leaching, but CuTeO3 resulted from the decomposition of CCu3TeO6 remains inactive in this process through which selenium is leached out in preference to tellurium. The CuTeO3 and Cu O in the alkaline leaching residue can be leached in the following sulfuric acid leaching process. More than 97% of selenium was leached with little tellurium leached under the optimal condition. Then, more than 96% of copper and almost all the tellurium were leached out in the following acid leaching process.

Optimization on selenium and arsenic conversion from copper anode slime by low-temperature alkali fusion process

A process was proposed to convert and separate selenium and arsenic in copper anode slime(CAS) by low-temperature alkali fusion process.Central composite design was employed to optimize the effective parameters,in which Na OH/CAS mass ratio,fusion temperature and fusion time were selected as variables,and the conversion ratio of selenium and arsenic as responses.Second-order polynomial models of high significance and 3D response surface plots were constructed to show the relationship between the responses and the variables.Optimum area of >90% selenium conversion ratio and >90% arsenic conversion ratio was obtained by the overlaid contours at Na OH/CAS mass ratio of 0.65-0.75,fusion temperature of 803-823 K and fusion time of 20-30 min.The models are validated by experiments in the optimum area,and the results demonstrate that these models are reliable and accurate in predicting the fusion process.

Intensification of pretreatment and pressure leaching of copper anode slime by microwave radiation

The application of microwave irradiation for pretreatment of copper anode slime with high nickel content prior to pressure sulfuric acid leaching has been proposed.The microwave-assisted pretreatment is a rapid and efficient process.Through the technology of microwave assisted pretreatment-pressure leaching of copper anode slime,copper,tellurium,selenium and nickel are almost completely recovered.Under optimal conditions,the leaching efficiencies of copper,tellurium,selenium and nickel are 97.12%,95.97%,95.37% and 93.90%,respectively.The effect of microwave radiation on the temperature of copper anode slime and leaching solution is investigated.It is suggested that the enhancement on the recoveries of copper,tellurium and selenium can be attributed to the temperature gradient which is caused by shallow microwave penetration depth and super heating occurring at the solid–liquid interface.The kinetic study shows that the pressure leaching of copper anode slime,with and without microwave assisted pretreatment,are both controlled by chemical reactions on the surfaces of particles.It is found that the activation energy calculated for microwave-assisted pretreatment-pressure leaching(49.47 kJ/mol) is lower than that for pressure leaching which is without microwave assisted pretreatment(60.57 kJ/mol).

Leaching kinetics of selenium from copper anode slimes by nitric acid-sulfuric acid mixture

The leaching kinetics of selenium from copper anode slimes was studied in a nitric acid?sulfuric acid mixture.The effects of main parameters on selenium leaching showed that the leaching rate of selenium was practically independent of stirring speed,while dependent on temperature and the concentrations of HNO3and H2SO4.The leaching of selenium includes two stages.The activation energy in the first stage is103.5kJ/mol,and the chemical reaction is the rate controlling step.It was almost independent of H2SO4concentration and dependent on HNO3concentration since the empirical reaction order with respect to HNO3concentration is0.5613.In the second stage,the activation energy is30.6kJ/mol,and the process is controlled by a mixture of diffusion and chemical reaction.The leaching of selenium was almost independent of HNO3concentration.

Ultra fast microwave-assisted leaching for the recovery of copper and tellurium from copper anode slime

The decomposition of copper anode slime heated by microwave energy in a sulfuric acid medium was investigated. Leaching experiments were carried out in a multi-mode cavity with microwave assistance. The leaching process parameters were optimized using response surface methodology（RSM）. Under the optimized conditions, the leaching efficiencies of copper and tellurium were 99.56% ± 0.16% and 98.68% ± 0.12%, respectively. Meanwhile, a conventional leaching experiment was performed in order to evaluate the influence of microwave radiation. The mechanism of microwave-assisted leaching of copper anode slime was also investigated. In the results, the microwave technology is demonstrated to have a great potential to improve the leaching efficiency and reduce the leaching time. The enhanced recoveries of copper and tellurium are believed to result from the presence of a temperature gradient due to the shallow microwave penetration depth and the superheating at the solid-liquid interface.

Selective extraction of gold(Ⅲ) from hydrochloric acid-chlorine gas leach solutions of copper anode slime by tri-butyl phosphate(TBP)

The oxidative leaching causes to dissolve various impurities such as Fe, Cu, Pd, Se in copper anode slime. Organicextractant tri-butyl phosphate (TBP) was used to purify leach solution. Several parameters, such as TBP, HCl and chloride inorganicsalt concentrations were chosen in order to determine efficient state for impurities separation. Standard solvent extraction tests forextraction and separation of Au, Pd, Pt, Fe, Cu and Se were conducted with equal volume of aqueous and organic phases in batchexperiments. The effect of hydrochloric acid, organic phase and metals initial concentration were examined at ambient temperature. Itwas found that 0.25 mol/L TBP in the presence of 2.5 mol/L hydrochloric acid can cause high extraction of gold. Meanwhile, in theseconditions the extraction of other impurities is negligible. After extraction, pregnant organic phase was scrubbed by distilled waterand some impurities were removed. Finally, gold was stripped by sodium thiosulfate solution. The stripping solution does not haveany impurities. By adding H2SO4 to stripping solution containing Na2S2O2, SO2 gas is released and Au3+ ions could be reduced.

Effect of additives on anode passivation in direct electrolysis process of copper–nickel based alloy scraps

Effects of nickel component,thiourea,glue and chloride ions and their interactions on the passivation of copper–nickel based alloy scrap anodes were investigated by combining conventional electrochemical techniques.Results obtained from chronopotentiometry and linear voltammetry curves showed that the Ni component made electrochemical stability of the anode strong and difficult to be corroded,caused by the adsorption of generated Cu2O,NiO or copper powder to the anode surface.The Ni2+reducing Cu2+to Cu+or copper powder aggravated the anode passivation.In a certain range of the glue concentration≤8×10–6 or thiourea concentration≤4×10–6,the increase of glue or thiourea concentration increases the anode passivation time.Over this range,glue and thiourea played an adverse effect.The increase of chloride ions concentration led to the increase in passivation time.

Ag recovery from copper anode slime by acid leaching at atmospheric pressure to synthesize silver nanoparticles

In this paper, recovery of silver from anode slime of Sarcheshmeh copper complex in lran and subsequent synthesis of silver nanoparticles from leaching solution is investigated. Sarcheshmeh anode slime is mainly consisted ofCu, Ag, Pb and Se. Amount of Ag in the considered anode slime was 5.4% （by weight）. The goal was to recover as much as possible Ag from anode slime at atmospheric pressure to synthesize Ag nanoparticles. Therefore, acid leaching was used for this purpose. The anode slime was leached with sulfuric and nitric acid from room to 90 ~C at different acid concentrations and the run which yielded the most recovery of Ag was selected for Ag nanoparticles synthesis. At this condition, Cu, Pb and Se are lea- ched as well as Ag. To separate Ag from leach solution HCI was added and silver was precipitated as AgCl which were then dissolved by ammonia solution. The Ag nanoparticles are synthesized from this solution by chemical reduction method by aid of sodium borohydride in the presence of PVP and PEG as stabilizers. The synthesized Ag nanoparticles showed a peak of 394 nm in UV-vis spectrum and TEM images showed a rather uniform Ag nanoparticles of 12 nm.

Anode oxidation of HCHO in THPED-containing electroless copper plating solution

The electrochemical mechanism of anode oxidation of HCHO in electroless copper plating solution with N, N, N′, N′-tetrakis(2-hydroxypropyl)ethylenediamine (THPED) was investigated by measuring cyclic voltammetry curves and anodic polarization curves. Three different oxidation peaks occur at the potentials of -0.62 V (Peak 1), -0.40 V (Peak 2) and -0.17 V (Peak 3) in the anode oxidation process of THPED-containing solution. The reaction at Peak 1, a main oxidation reaction, is the irreversible reaction of adsorbed HCHO with hydrogen evolution. The reaction at Peak 2, a secondary oxidation reaction, is the quasi-reversible reaction of adsorbed HCHO without hydrogen evolution. The reaction at Peak 3 is the irreversible oxidation of anode copper. The current density of Peak 1 increases gradually, that of Peak 2 remains constant and that of Peak 3 decreases with the increase of HCHO concentration. The current density of Peak 3 increases with the increase of THPED concentration and the complexation of THPED promotes the dissolution of anode copper.

Electrowinning of Copper Using Rotating Cylinder Electrode Utilizing Lead Anode

The effect of lead anode, rotating cylinder electrode (RCE), amount of 1,2-dihydroxypropane (12-DHP), temperature and rotation on the electrowinning of copper from low concentration acidified copper sulphate solution has been investigated. Copper powder was electrodeposited onto RCE that made of pure copper. From cyclic voltammetry experiments, an empirical parameter called the departure percent, S, was obtained which may represent the stability of the organic additive in the given medium and under the experimental conditions. The inhibition percentage, P, was 0.00 - 89.91% depending on the experimental variables. P was affected by temperature and mole fraction of 12-DHP, while rotation did not show any influence on it. Values of activation energy of electrodeposition process, Ea, were found to be less than 28 kJ mol-1 indicating diffusion controlled process. The overall mass transfer correlations under the present conditions have been computed using the dimensional analysis method. The data were valid for 90 < Sh < 1098, 737 < Sc < 59284 and 271 < Re < 7046 and the results agreed with the previous studies of mass transfer to rotating cylinders in turbulent flow regimes. The effect of time, content of 12-DHP, temperature and the speed of rotation on the morphological changes of the electrodeposited copper powder as well as deposits composition and crystallite size have been studied. Various crystallite sizes ranged 7.1 nm - 250.6 nm were obtained and characterized by EDS and XRD. Different topographs proved that the rate of copper electrodeposition increased by increasing deposition time, temperature and the speed of rotation. Also, they proved that the deposition rate decreased by adding 12-DHP to the solution. Therefore, the results obtained by SEM supported those achieved by measuring the limiting current density and follow the normal manner when organic solvents were added to the electrodeposition bath.

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.

Uniform lithium deposition induced by copper phthalocyanine additive for durable lithium anode in lithium-sulfur batteries

Copper phthalocyanine(CuPc)is adopted as an electrolyte additive to stabilize lithium anode for lithiumsulfur(Li-S)batteries.CuPc with a planar molecular structure and lithiophilic N-containing group,is likely to be adsorbed on the surface of Li anode to form a coating layer,which can restrict the direct contact between Li anode and solvents,and guide the uniform deposition of Li^(+)ions.The Li||Li symmetric cells demonstrate a stable cycle performance,and Li||Cu cells show high Coulombic efficiencies.In Li-S batteries,the formed stable solid-electrolyte interface(SEI)film containing copper sulfides can protect Li anode from the polysulfide corrosion and side reactions with the electrolyte,leading to the compact and smooth surface morphology of Li anode.Therefore,the Li-S batteries with CuPc additive deliver much higher capacity,better cycle performance and rate capability as compared to the one without CuPc additive.

Unusual anodic peak on negative potential scan for copper in alkaline media

The unusual anodic peak emerging on negative potential scan for copper in concentrated NaOH media was investigated by X ray diffraction, X ray photoelectron spectroscopy techniques, potentiodynamic scan, galvanostatic reduction and fast triangular voltage methods. The results show that CuO is formed on the electrode at potentials above this unusual peak A 2,3 , but also produced at peak A 2,3 when copper has been beforehand anodized at high potentials. Longer pre oxidation time and higher pre oxidation potential are advantageous to the formation of CuO at peak A 2,3 . It is presented that the pent up growth of oxide layer in the high potential region occurs at the interface between metal and oxide by the field assisted migration of O 2- ions to electrode, and when potential negatively shifts to the range of peak A 2,3 , the O 2- (or cation vacancies) accumulated in the film could move towards the solution and combine with Cu 2+ ions at the interface between oxide and solution.[

Effect of equal-channel angular pressing on pitting corrosion resistance of anodized aluminum-copper alloy

The effect of equal-channel angular pressing(ECAP) on the pitting corrosion resistance of anodized Al-Cu alloy was investigated by electrochemical techniques in a solution containing 0.2 mol/L AlCl3 and also by surface analysis.Anodizing was conducted for 20 min at 200 and 400 A/m2 in a solution containing 1.53 mol/L H2SO4 and 0.018 5 mol/L Al2(SO4)3·16H2O at 20 ℃.Anodized Al-Cu alloy was immediately dipped in boiling water for 20 min to seal the micro pores present in anodic oxide films.The time required before initiating pitting corrosion of anodized Al-Cu alloy is longer with ECAP than without,indicating that ECAP process improves the pitting corrosion resistance of anodized Al-Cu alloy.Second phase precipitates such as Si,Al-Cu-Mg and Al-Cu-Si-Fe-Mn intermetallic compounds are present in Al-Cu alloy and the size of these precipitates is greatly decreased by application of ECAP.Al-Cu-Mg intermetallic compounds are dissolved during anodization,whereas the precipitates composed of Si and Al-Cu-Si-Fe-Mn remain in anodic oxide films due to their more noble corrosion potential than Al.FE-SEM and EPMA observation reveal that the pitting corrosion of anodized Al-Cu alloy occurs preferentially around Al-Cu-Si-Fe-Mn intermetallic compounds,since the anodic oxide films are absent at the boundary between the normal oxide films and these impurity precipitates.The improvement of pitting corrosion resistance of anodized Al-Cu alloy processed by ECAP appears to be attributed to a decrease in the size of precipitates,which act as origins of pitting corrosion.

Study on selenium extraction from anode slime

Taking a copper anode slime as the raw material, a novel process for selenium extraction was studied. The primary selenium recovery can reach above 88.5% and the quality index of selenium product can be up to 99.5%. The economic benefit resulted is remarkable and environment has been protected.

铜阳极泥中有价元素湿法回收工艺研究进展

我国铜生产量居世界第一,其中80%采用火法冶炼工艺。冶炼过程中产生的铜阳极泥富含Cu、Ag、Au、Se、Te等多种有价元素,具有很高的回收价值。本文分析对比了铜阳极泥的主流处理工艺,其中,湿法工艺作为一种低能耗高效浸出工艺,近些年被广泛地研究。文章系统综述了铜阳极泥湿法处理工艺研究进展,归纳了铜阳极泥氧化浸出、物理强化浸出等预处理方法,总结了铜阳极泥中Cu、Se、Te以及贵金属Ag、Au的回收方法及反应机理。基于当前的研究进展,未来应重点关注湿法工艺的绿色性,开发用于浸出、配合、萃取等过程的绿色试剂,并加强对阳极泥中稀贵金属(Pt、Pd、Rh等)回收的研究,同时需要提升不同元素选择性分离的能力,以获得高纯度产品。

基于MetCal的铜阳极炉精炼过程热力学仿真分析

基于所构建的铜阳极炉精炼过程热力学仿真模型及系统,计算了某典型阳极炉精炼生产工况,验证模型热力学分析的可行性,进而考察气料比(R_(GF))、石英熔剂率(R_(Flux))和精炼温度(t)等工艺参数对产物组成及杂质分配行为的影响。结果表明:提高R_(GF)、R_(Flux),可在一定程度上改变精炼渣组成,改善杂质入渣脱除效果,但因精炼渣量较小,除Co和Cr外其他杂质元素的实际入渣脱除率变化不大;提高温度对产物组分影响不大,但会降低杂质的脱除效果。综合工艺参数对阳极精炼过程的影响规律,得到的较优工艺参数为R_(GF)为22 m^(3)/t,R_(Flux)为0.16%,t为1200℃。在此条件下,铜液的Cu品位、S含量和O含量分别约为99.39%、0.0065%、0.17%。

Ta/Ta_(2)O_(5)/Cu结构制备及应用性能研究

介绍了以Ta/Ta_(2)O_(5)/Cu为结构的平板MIM电容器的制备方法和性能测试,探究金属Cu直接作为钽电解电容器阴极层的可行性。通过阳极氧化法在钽箔表面制备非晶态的Ta_(2)O_(5)薄膜,以化学镀铜、磁控溅射镀铜两种镀铜工艺制备Ta/Ta_(2)O_(5)/Cu结构,并对所得结构进行结构表征和性能测试。实验结果表明:不同镀铜方式制备的Ta/Ta_(2)O_(5)/Cu结构在电学性能测试过程中都没有表现出电容特性,正负极之间的电阻仅有0.7Ω;以金属Cu直接作为钽电容器的阴极层会导致金属铜在测试过程中被氧化成铜离子从而进入Ta_(2)O_(5)介质层中,进而导致Ta_(2)O_(5)的击穿,因此金属铜不适合直接作为钽电容的阴极层。

基于GRNN算法的铜阳极炉精炼还原终点预报模型

针对阳极炉炼铜还原期终点判断依赖人工判断的局限,利用机器学习技术实现智能判断。通过图像去模糊处理优化图像特征,对图像进行灰度差分矩阵运算,将矩阵中提取出的特征值作为神经网络的输入,构建了一种新的铜阳极炉精炼还原期终点判断模型。试验结果显示,在真实生产环境下,采用GRNN算法对还原终点进行预测,有助于消除铜阳极炉精炼过程中不同指标之间的相关性,减少了数据冗余和系统误差,使预测精度提高至96.54%。相较于传统方法,这种新的判断模型有效提高了阳极炉炼铜还原期终点判断的准确性。