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 out...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.展开更多
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 whi...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.展开更多
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 ef...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).展开更多
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 practical...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.展开更多
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 proce...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.展开更多
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...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.展开更多
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.R...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.展开更多
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 consi...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.展开更多
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 cur...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.展开更多
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 ...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.展开更多
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...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.展开更多
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 a...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.展开更多
The atomic structure of the active sites in Cu/CeO2 catalysts is intimately associated with the copper-ceria interaction. Both the shape of ceria and the loading of copper affect the chemical bonding of copper species...The atomic structure of the active sites in Cu/CeO2 catalysts is intimately associated with the copper-ceria interaction. Both the shape of ceria and the loading of copper affect the chemical bonding of copper species on ceria surfaces and the electronic and geometric character of the relevant interfaces. Nanostructured ceria, including particles(polyhedra), rods, and cubes, provides anchoring sites for the copper species. The atomic arrangements and chemical properties of the(111),(110) and(100) facets, preferentially exposed depending on the shape of ceria, govern the copper-ceria interactions and in turn determine their catalytic properties. Also, the metal loading significantly influences the dispersion of copper species on ceria with a specific shape, forming copper layers, clusters, and nanoparticles. Lower copper contents result in copper monolayers and/or bilayers while higher copper loadings lead to multi-layered clusters and faceted particles. The active sites are usually generated via interactions between the copper atoms in the metal species and the oxygen vacancies on ceria, which is closely linked to the number and density of surface oxygen vacancies dominated by the shape of ceria.展开更多
In this paper, oxidation activity of CuO/γ-A12O3 catalysts and the addition of CeO2 on CuO/γ-A12O3 catalysts for oxidation reaction of n-hexane (n-C6H14 ) and carbon monoxide (CO ) were studied by means of the flow ...In this paper, oxidation activity of CuO/γ-A12O3 catalysts and the addition of CeO2 on CuO/γ-A12O3 catalysts for oxidation reaction of n-hexane (n-C6H14 ) and carbon monoxide (CO ) were studied by means of the flow method techniques, XRD and TPD-MS. Experimental results indicated that (1) the addition of CeO2 improving disperse degree of CuO on CuO/γ-Al2O3 catalysts which caused a large increase in activity; (2) the addition of CeO2 may increase oxygen supplying ability and oxygen recovery ability of catalyst surface.展开更多
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...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.[展开更多
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 surfac...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.展开更多
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%. T...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.展开更多
The solid structures and thermostabilities of Cu-Fe-O and Cu-Fe-Ce-O supported on alumina were studied by XRD, ESR, Mossbauer and TPR techniques. The studies indicate that there are Fe2CuO4, CuO and alpha-Fe2O3 phases...The solid structures and thermostabilities of Cu-Fe-O and Cu-Fe-Ce-O supported on alumina were studied by XRD, ESR, Mossbauer and TPR techniques. The studies indicate that there are Fe2CuO4, CuO and alpha-Fe2O3 phases in Cu-Fe-O with the granula of less than 13 nm. With the catalyst pretreatment temperature rising, the crystallite of Fe2CuO4 in the catalysts grows up and that of CuO disappears gradually. The presence of Ce leads to the increase of Cu2+ concentration, inhibits the crystal growth of CuO and Fe2CuO4 in the catalyst except that of Fe2O3, and eliminates the difference for reductive reaction of oxygen in Fe-O and Cu-O. At 800 degrees C, the crystal growth of Fe2O3 in Cu-Fe-Ce-O is slower than that in Cu-Fe-O, i.e., CeO2 in Cu-Fe-Ce-O inhibits the growth of Fe2O3 phase effectively, and enhances the thermostability of catalysts so as to avoid the sintering of active elements in catalysts. CeO2 promotes the reducibility of catalysts at lower temperature.展开更多
Copper-based composites strengthened by ceria nanoparticles were processed by conventional powder metallurgy: mixing (30 min and 46 rpm), compaction (cold, uniaxial, 1080 MPa for 10 s) and sintering (800°C for 6 ...Copper-based composites strengthened by ceria nanoparticles were processed by conventional powder metallurgy: mixing (30 min and 46 rpm), compaction (cold, uniaxial, 1080 MPa for 10 s) and sintering (800°C for 6 h in vacuum atmosphere of 10−5 torr). It was studied the microstructure (optical microscopy, scanning electron microscopy), X-ray diffraction with Rietveld refinement and some properties (electrical conductivity, Vickers hardness and fracture analysis) of the compositions 92 wt% Cu - 8 wt% CeO2 and 80 wt% Cu - 20 wt% CeO2. The results showed uniform phase distribution, low porosity and ceria disperse inside copper grain. In despite of properties, the composites had electrical conductivity of 38% IACS and 15% IACS and hardness of 69 and 88 HV5, respectively. The results of 92 wt% Cu - 8 wt% CeO2 composites were promising, and they are in according with actual literature.展开更多
基金Project(2012BAE06B05)supported by the National Science and Technology Support Plan of China
文摘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.
基金Project(51234009)supported by the National Natural Science Foundation of ChinaProject(2014DFA90520)supported by International Cooperation Program of Ministry of Science of ChinaProject(2013A100003)supported by the Production,Teaching and Research Program of Guangdong Province,China
文摘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.
基金Project(2012BAE06B05)supported by the National Science and Technology Support Program of ChinaProject(N130602004)supported by the Fundamental Research Funds for the Central Universities of China
文摘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).
基金Projects(51374066,U1608254) supported by the National Natural Science Foundation of ChinaProject(2014BAC03B07) supported by the National Key Technology R&D Program of ChinaProjects(2012223002,2014020037) supported by Industrial Research Projects in Liaoning Province,China
文摘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.
基金financially supported by the National Science and Technology Support Program of China during the 12th Five-Year Plan Period (No. 2012BAE06B05)the Fundamental Research Funds for the Central Universities of China (No. N130602004)
文摘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.
文摘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.
基金Project(51574135)supported by the National Natural Science Foundation of ChinaProject(KKPT201563022)supported by the Collaborative Innovation Center of Kunming University of Science and Technology,China
文摘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.
基金the International Center for Science, High Technology & Environmental Sciences for financial support of this work (No. 1.213)
文摘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.
基金Project(200501045) supported by Innovation Fund of Guangdong Province of China
文摘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.
文摘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.
基金Project supported by the Postdoctoral Foundation of Central South University and Minerals Processing and Bioengineering, China
文摘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.
基金supported by the National Natural Science Foundation of China(NSFC,Nos.22269013,22263009)the Natural Science Foundation of Jiangxi Province(Nos.20224ACB213001,20202ACB202004,20213BCJ22024,20212BBE53051)the Key Laboratory of Jiangxi Province for Environment and Energy Catalysis(No.20181BCD40004).
文摘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.
文摘The atomic structure of the active sites in Cu/CeO2 catalysts is intimately associated with the copper-ceria interaction. Both the shape of ceria and the loading of copper affect the chemical bonding of copper species on ceria surfaces and the electronic and geometric character of the relevant interfaces. Nanostructured ceria, including particles(polyhedra), rods, and cubes, provides anchoring sites for the copper species. The atomic arrangements and chemical properties of the(111),(110) and(100) facets, preferentially exposed depending on the shape of ceria, govern the copper-ceria interactions and in turn determine their catalytic properties. Also, the metal loading significantly influences the dispersion of copper species on ceria with a specific shape, forming copper layers, clusters, and nanoparticles. Lower copper contents result in copper monolayers and/or bilayers while higher copper loadings lead to multi-layered clusters and faceted particles. The active sites are usually generated via interactions between the copper atoms in the metal species and the oxygen vacancies on ceria, which is closely linked to the number and density of surface oxygen vacancies dominated by the shape of ceria.
文摘In this paper, oxidation activity of CuO/γ-A12O3 catalysts and the addition of CeO2 on CuO/γ-A12O3 catalysts for oxidation reaction of n-hexane (n-C6H14 ) and carbon monoxide (CO ) were studied by means of the flow method techniques, XRD and TPD-MS. Experimental results indicated that (1) the addition of CeO2 improving disperse degree of CuO on CuO/γ-Al2O3 catalysts which caused a large increase in activity; (2) the addition of CeO2 may increase oxygen supplying ability and oxygen recovery ability of catalyst surface.
文摘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.[
文摘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.
文摘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.
文摘The solid structures and thermostabilities of Cu-Fe-O and Cu-Fe-Ce-O supported on alumina were studied by XRD, ESR, Mossbauer and TPR techniques. The studies indicate that there are Fe2CuO4, CuO and alpha-Fe2O3 phases in Cu-Fe-O with the granula of less than 13 nm. With the catalyst pretreatment temperature rising, the crystallite of Fe2CuO4 in the catalysts grows up and that of CuO disappears gradually. The presence of Ce leads to the increase of Cu2+ concentration, inhibits the crystal growth of CuO and Fe2CuO4 in the catalyst except that of Fe2O3, and eliminates the difference for reductive reaction of oxygen in Fe-O and Cu-O. At 800 degrees C, the crystal growth of Fe2O3 in Cu-Fe-Ce-O is slower than that in Cu-Fe-O, i.e., CeO2 in Cu-Fe-Ce-O inhibits the growth of Fe2O3 phase effectively, and enhances the thermostability of catalysts so as to avoid the sintering of active elements in catalysts. CeO2 promotes the reducibility of catalysts at lower temperature.
文摘Copper-based composites strengthened by ceria nanoparticles were processed by conventional powder metallurgy: mixing (30 min and 46 rpm), compaction (cold, uniaxial, 1080 MPa for 10 s) and sintering (800°C for 6 h in vacuum atmosphere of 10−5 torr). It was studied the microstructure (optical microscopy, scanning electron microscopy), X-ray diffraction with Rietveld refinement and some properties (electrical conductivity, Vickers hardness and fracture analysis) of the compositions 92 wt% Cu - 8 wt% CeO2 and 80 wt% Cu - 20 wt% CeO2. The results showed uniform phase distribution, low porosity and ceria disperse inside copper grain. In despite of properties, the composites had electrical conductivity of 38% IACS and 15% IACS and hardness of 69 and 88 HV5, respectively. The results of 92 wt% Cu - 8 wt% CeO2 composites were promising, and they are in according with actual literature.