Separation of halogens and recovery of heavy metals from secondary copper smelting dust

The separation of halogens and recovery of heavy metals from secondary copper smelting(SCS)dust using a sulfating roasting−water leaching process were investigated.The thermodynamic analysis results confirm the feasibility of the phase transformation to metal sulfates and to gaseous HF and HCl.Under the sulfating roasting conditions of the roasting temperature of 250℃ and the sulfuric acid excess coefficient of 1.8,over 74 wt.%of F and 98 wt.%of Cl were volatilized into flue gas.Approximately 98.6 wt.%of Zn and 96.5 wt.%of Cu in the roasting product were dissolved into the leaching solution after the water leaching process,while the leaching efficiencies of Pb and Sn were only 0.12%and 0.22%,respectively.The mechanism studies indicate the pivotal effect of roasting temperature on the sulphation reactions from various metal species to metal sulfates and the salting out reactions from various metal halides to gaseous hydrogen halides.

Cascade sulfidation and separation of copper and arsenic from acidic wastewater via gas-liquid reaction

Copper and arsenic in acidic wastewater were separated by cascade sulfidation followed by replacement of arsenic in theprecipitates by copper in the solution which was realized by recycling precipitates obtained in the first stage into the initial solution.The effects of reaction time,temperature and H2S dosage on copper and arsenic removal efficiencies as well as the effects of solid-toliquidratio,time and temperature on the replacement of arsenic by copper were investigated.With20mmol/L H2S at50°C within0.5min,more than80%copper and nearly20%arsenic were precipitated.The separation efficiencies of copper and arsenic werehigher than99%by the replacement reaction between arsenic and copper ions when solid-to-liquid ratio was more than10%at20°Cwithin10min.CuS was the main phases in precipitate in which copper content was63.38%in mass fraction.

Formation of arsenic−copper-containing particles and their sulfation decomposition mechanism in copper smelting flue gas

The heat recovery steam generator(HRSG)of copper smelting generates a large number of arsenic−coppercontaining particles,and the in-situ separation of arsenic and copper is of importance for cutting off environmental risk and realizing resource recovery.The formation of arsenic−copper-containing particles was simulated,the method of in-situ decomposition of arsenic−copper-containing particles by pyrite was proposed,and the decomposition mechanism was confirmed.It was found that particles with high arsenic content were formed in the simulated HRSG,and copper arsenate was liable for the high arsenic content.Pyrite promoted the sulfation of copper,leading to the in-situ decomposition of copper arsenate.In this process,gaseous arsenic was released,and thus the separation of arsenic and copper was realized.

Separation and recovery of Cu and As during purification of copper electrolyte

Cu, As, Sb and Bi in copper electrolyte could be efficiently removed by reducing with SO2 followed by evaporative crystallization. As2O3 and CuSO4·5H2O were obtained after crystallized product was treated by dissolution, oxidation, neutralization, sedimentation, filtration and evaporative crystallization. The removal rates of Cu, As, Sb and Bi are 87.1%, 83.9%, 21.0% and 84.7%, respectively, when As （Ⅴ） in copper electrolyte is fully reduced to As （Ⅲ） by SO2, and the H2SO4 in concentrated copper electrolyte is 645 g/L. The removal rate of As is 92.81% when 65 g crystallized product is dissolved in 200 mL water at 30 ℃. The CuSO4·5H2O content is 98.8% when the filtrate is purified under the conditions that n（Fe）：n（As） is 1.2, the dosage of H2O2 is 19 times the stoichiometric needed, temperature is 45 ℃, time is 40 min, pH is 3.7, and then is evaporation crystallized.

Separation and recovery of Cu and As from copper electrolyte through electrowinning and SO_2 reduction

Cu and As were separated and recovered from copper electrolyte by multiple stage electrowinning, reduction with SO2and 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.

Reduction and deposition of arsenic in copper electrolyte

The influences of temperature, H2SO4 concentration, CuSO4 concentration, reaction time and SO2 flow rate on the reduction of arsenic（V） with SO2 were studied and the deposition behavior of arsenic （III） under the effect of concentration and co-crystallization was investigated in copper electrolyte. The results indicate that reduction rate of arsenic （V） decreases with increasing temperature and H2SO4 concentration, but increases with increasing SO2 flow rate and reaction time, and it can reach 92% under appropriate conditions that reaction temperature is 65 °C, H2SO4 concentration is 203 g/L, CuSO4 concentration is 80 g/L, reaction time is 2 h and SO2 gas flow rate is 200 mL/min. To remove arsenic in the copper electrolyte, arsenic （V） is reduced to trivalence under the appropriate conditions, the copper electrolyte is concentrated till H2SO4 concentration reaches 645 g/L, and then the removal rates of As, Cu, Sb and Bi reach 83.9%, 87.1%, 21.0% and 84.7%. The XRD analysis shows that crystallized product obtained contains As2O3 and CuSO4·5H2O.

Pressure leaching technique of smelter dust with high-copper and high-arsenic

The application of pressure leaching technology in the treatment of high-copper and high-arsenic dust was studied.The pressure leaching technique was determined as follows:the liquid to solid ratio(mL/g)of 5:1,the leaching temperature of 453 K,the retention time of 2 h,the initial sulfuric acid concentration of 0.74 mol/L,the oxygen partial pressure of 0.7 MPa,and the agitation speed of 500 r/min.Under these conditions,95%of copper and 99%of zinc and only 6%of iron in the dust were leached,while about 20%of arsenic was also leached.The leaching technique was optimized further to restrain the leaching of arsenic by adding a small quantity of ferrous iron into the leaching system(c(Fe2 +)=0.036 mol/L).Copper and zinc can be effectively separated from arsenic and iron in the leach.The optimal pressure leaching technique of high-copper and high-arsenic smelter dust is proved to be effective.

Role of trivalent antimony in the removal of As, Sb, and Bi impurities from copper electrolytes

The role of trivalent antimony was investigated in removing As, Sb, and Bi impurities from a copper electrolyte. Puri- fication experiments were carried out by adding a various concentrations of Sb（III） ions in a synthetic electrolyte containing 185 g/L sulfuric acid, 45 g/L Cu2＋, 10 g/L As, and 0.5 g/L Bi under stirring at 65℃ for 2 h. The electrolyte was filtered, and the structure, morphology and composition of the precipitate were analyzed by means of chemical analysis, scanning electron mi- croscopy （SEM）, X-ray diffraction （XRD）, transmission electron microscopy （TEM）, and IR spectroscopy. The precipitate is composed of irregular lumps which are agglomerated by fine dendritic and floccus particles, and it mainly consists of As, Sb, Bi, and O elements. Characteristic bands in the IR spectra of the precipitate are As-OX （X=As, Sb, Bi）, Sb-OY （Y=Sb, Bi）, O-As-O1 As-OH, Sb-OH, and O-H. The precipitate is a mixture of microcrystalline SbAsQ, （Sb,As）203, and amorphous phases. As, Sb, and Bi impurities are effectively removed from the copper electrolyte by Sb（III） ions attributing to these pre- cipitates.

Copper and arsenic substance flow analysis of pyrometallurgical process for copper production

The metabolism of copper and arsenic in a copper pyrometallurgy process was studied through substance flow analysis method.The mass balance accounts and substance flow charts of copper and arsenic were established,indicators including direct recovery,waste recycle ratio,and resource efficiency were used to evaluate the metabolism efficiency of the system.The results showed that,the resource efficiency of copper was 97.58%,the direct recovery of copper in smelting,converting,and refining processes was 91.96%,97.13%and 99.47%,respectively.Meanwhile,for producing 1 t of copper,10 kg of arsenic was carried into the system,with the generation of 1.07 kg of arsenic in flotation tailing,8.50 kg of arsenic in arsenic waste residue,and 0.05 kg of arsenic in waste water.The distribution and transformation behaviors of arsenic in the smelting,converting,and refining processes were also analyzed,and some recommendations for improving copper resource efficiency and pollution control were proposed based on substance flow analysis.

Separation of arsenic and antimony from dust with high content of arsenic by a selective sulfidation roasting process using sulfur

The separation of arsenic and antimony from dust with high content of arsenic was conducted via a selective sulfidation roasting process.The factors such as roasting temperature,roasting time,sulfur content and nitrogen flow rate were investigated using XRD,EPMA and SEM-EDS.In a certain range,the sulfur addition has an active effect on the arsenic volatilization because the solid solution phase（（Sb,As）2O3）in the dust can be destroyed after the Sb component in it being vulcanized to Sb2S3 and this generated As2O3 continues to volatile.In addition,an amorphization reaction between As2O（3 ）and Sb2O（3 ）is hindered through the sulfidation of Sb2O3,which is also beneficial to increasing arsenic volatilization rate.The results show that volatilization rates of arsenic and antimony reach 95.36%and only 9.07%,respectively,under the optimum condition of roasting temperature of 350℃,roasting time of 90 min,sulfur content of 22%and N2 flow rate of 70 m L/min.In addition,the antimony in the residues can be reclaimed through a reverberatory process.

Solvent extraction and separation of copper from base metals using bifunctional ionic liquid from sulfate medium

A novel solvent extraction process for extraction and separation of copper from other base metal ions using a bifunctional ionic liquid (IL) (trioctylmethylammonium/2,4,4-trimethylpentyl phosphinate, [A336/Cy272]) in kerosene was reported. This IL was found to extract copper more efficiently than the individual extractants Aliquat 336 or Cyanex 272. Formation of an octahedral copper-IL complex was characterized by UV-Visible spectra and metal ligand interaction was confirmed by FTIR spectra. The loading capacity of 0.1 mol/L [A336/Cy272] was found to be 1.71 g/L. Stripping studies reported that 0.298 g/L copper ions were efficiently stripped using 0.1 mol/L sulfuric acid from 0.05 mol/L loaded IL. The selectivity of copper against nickel, cadmium and iron was investigated from their equimolar binary mixtures using 0.05 mol/L [A336/Cy272] in kerosene. The highest separation factorβCu/Cd=8.41 was obtained at pH 3.56. Copper can be effectively separated from nickel over the pH range studied. The IL extracts preferentially iron over copper and the highest separation factorβFe/Cuwas 3246 at pH 2.4. The extraction rate of metal ions from a synthetic solution containing copper with other metal impurities was in the order of Fe>Zn>Cu>Cd>Co>Ni.

Recovery of iron from copper tailings via low-temperature direct reduction and magnetic separation: process optimization and mineralogical study

Currently, the majority of copper tailings are not effectively developed. Worldwide, large amounts of copper tailings generated from copper production are continuously dumped, posing a potential environmental threat. Herein, the recovery of iron from copper tailings via low-temperature direct reduction and magnetic separation was conducted; process optimization was carried out, and the corresponding mineralogy was investigated. The reduction time, reduction temperature, reducing agent (coal), calcium chloride additive, grinding time, and magnetic field intensity were examined for process optimization. Mineralogical analyses of the sample, reduced pellets, and magnetic concentrate under various conditions were performed by X-ray diffraction, optical microscopy, and scanning electron microscopy-energy-dispersive X-ray spectrometry to elucidate the iron reduction and growth mechanisms. The results indicated that the optimum parameters of iron recovery include a reduction temperature of 1150A degrees C, a reduction time of 120 min, a coal dosage of 25%, a calcium chloride dosage of 2.5%, a magnetic field intensity of 100 mT, and a grinding time of 1 min. Under these conditions, the iron grade in the magnetic concentrate was greater than 90%, with an iron recovery ratio greater than 95%.

Separation of As and Bi and enrichment of As,Cu,and Zn from copper dust using an oxidation-leaching approach

Copper dust with high arsenic content is a hazardous waste that should be treated properly.Herein,the copper dust is oxidized,leached,and separated at room temperature and atmospheric pressure.To separate As and Bi,part of As(Ⅲ)in copper dust is oxidized to As(V),so that most of the As,Cu,and Zn elements enter the solution and the Bi remains in the leaching residue.Also,the influence of several factors,such as H_(2)SO_(4) dosage,H_(2)O_(2) dosage,liquid-solid ratio,leaching temperature and leaching time,on the leaching percentage of As,Bi,Cu,and Zn is systematically investigated.The optimal conditions are obtained as follows:liquid-solid ratio of 3:1,H_(2)O_(2) dosage of 10 ml/50 g(dust),H_(2)SO_(4) dosage of 4.5 ml/50 g(dust),leaching temperature of 85 C,and leaching time of 3 h.Under these conditions,the leaching percentage of As,Cu,Zn,and Bi is found to be 97.39%,96.11%,97.32%,and 2.40%,respectively.For further recovery of As from the leaching solution,the one-step recycle leaching of the leaching solution is performed to increase the concentration of As in the recycled leaching solution.The concentration of arsenic in the recycling leaching solution is found to be 79.63 g·L^(-1),which is beneficial for the study on further recovery of As_(2)O_(3).

Effects of wood species and retention levels on removal of copper,chromium,and arsenic from CCA-treated wood using sodium hypochlorite

Chemical extraction, bioremediation, and electrodialytic processes have been extensively studied for removal of copper, chromium, and arsenic from wood treated with chromated copper arsenate （CCA）. However, one problem has not been addressed： the effects of wood species and retention levels on remediation efficiency. The objectives of this study were to investigate the effects of wood species and retention levels on removal of copper, chromium, and arsenic from CCA-treated wood samples using sodium hypochlorite. Our results showed that sodium hypochlorite （NaOC1） was very effective for removal of copper, chromium, and arsenic from CCA-C treated milled wood samples for all three species used in this study. The Cu, Cr, and As extraction efficiencies for red pine were 95 % Cu, 97 % Cr and 94 % As, for maple were 95 % Cu, 97 % Cr, and 98 % As at 4.0 kg m-3 retention levels, and for aspen were 95 % Cu, 92% Cr, and 91% As at 9.6 kg m-3 retention level, respectively. However, the results showed that wood species and initial retention levels of CCA-treated wood products played very impor- tant roles in terms of removal of Cu, Cr, and As.

Selective separation of copper by membrane-electro-winning and its application in etchant recycling

A close-looped process based on the membrane separation and electrolysis is proposed to regenerate the copper etchant in-situ, recover copper on-site and reuse it. It is characterized by selective separation of copper from the spent etchant, which is accomplished by the ion exchange membrane-electrowinning, and at the same time the other components useful for etching are reclaimed. The experiments show that at least 90 % of electricity efficiency for copper removal can be maintained and the optimum condition for membrane-electrowinning is: cell voltage 2 -2.5 V, operating temperature 40 - 50 ℃ and current density 500 - 1 500 A/m2. The regenerated etchant can be suc cessfully reused to etch copper after adjusting its composition to the normal range, and its recycling property is as good as that of the fresh etchant after 50 times of use-disposal-regeneration cycles.

A practical strategy to subcutaneous administered in-situ gelling co-delivery system of arsenic and retinoic acid for the treatment of acute promyelocytic leukemia

Arsenic trioxide(ATO) combined with all trans retinoic acid(ATRA) is the first choice for the treatment of low and medium risk acute promyelocytic leukemia(APL). Clinical studies reported that the combination of ATO and ATRA could achieve a significant curative effect. However, the retinoic acid syndrome, serious drug resistance and the short half-life in vivo which lead to frequent and large dose administration limit the application of ATRA. In addition, the preparations of arsenic are conventional injections and tablets in clinic, which has poor patients’ compliance caused by frequent long-term administration and serious side effects. In order to overcome the above limitations, a phospholipid phase separation gel(PPSG) loaded with ATO and ATRA was developed. ATO + ATRA-PPSG(AAP), as a biodegradable sustained-release delivery system, was the first achievement of co-delivery of hydrophilic ATO and lipophilic ATRA with high drug loading which is the main problem in the application of nano preparation. The prepared PPSG displayed high safety and biocompatibility. The drug in PPSG was released slowly and continuously in vivo and in vitro for up to 10 d, which could reduce the side effects caused by the fluctuation of blood drug concentration and solve the problem of the long treatment cycle and frequent administration. In vivo pharmacokinetics depicted that PPSG could improve the bioavailability, decrease the peak concentration, and prolong the t 1/2 of ATO and ATRA. Particularly, AAP significantly inhibited the tumor volume, extended the survival period of tumor-bearing mice, and promoted the differentiation of APL cells into normal cells. Therefore, ATO + ATRA-PPSG not only could co-load hydrophilic ATO and lipophilic ATRA according to the clinical dosage, but also possessed the sustained-release and long-acting treatment effect which was expected to reduce administration time and ameliorate compliance of patients. Thus, it had great potential for clinical transformation and application.

Characterization and Pyrometallurgical Removal of Arsenic from Copper Concentrate Roasting Dust

This paper describes the experimental results of removing arsenic from the dust collected in electrostatic precipitators of a fluidized bed roasting furnace (RP dust). The fluidized bed roasting process generates 600 kilotons of copper concentrate per year with 3 - 6 wt% of concentration of arsenic, producing a roasted product with a low content of arsenic below 0.3 wt%. The process generates 27 kilotons of RP dust per year with a concentration of arsenic of the order of 5 wt% and copper concentration of around 20 wt%. Subsequently, the dust collected in the electrostatic precipitators is treated by hydrometallurgical methods allowing the recovery of copper, and the disposition of arsenic as scorodite. This work proposes to use a pyrometallurgy process to the volatilization of arsenic from RP dust. The obtained material can be recirculated in copper smelting furnaces allowing the recovery of valuable metals. The set of experiments carried out in the roasting of the mixture of copper concentrate/RP dust and sulfur/RP dust used different ratios of mixtures, temperatures and roasting times. By different techniques, the characterization of the RP dust determined its size distribution, morphology, and chemical and mineralogical composition. RP dust is a composite material of small particles (<5 μm) in 50 μm agglomerates, mostly amorphous, with a complex chemical composition of sulfoxides. The results of the roasting experiments indicated that for a 75/25 weight ratio of the mixture of the copper concentrate/PR dust under 700℃, 15 minutes of roasting time with injection of air, the volatilization of arsenic reached 96% by weight. The arsenic concentration after the roasting process is less than 0.3% by weight. For a 5/95 mixture of sulfur/RP dust, at 650℃, the volatilization of arsenic reached a promissory result of 67%. Even that this study was carried out for a particular operation, the results have the potential to be extended to dust produced in the roasting of concentrates of nickel, lead-zinc, and gold.

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.

Recovery of iron from copper slag by deep reduction and magnetic beneficiation

Aiming at recovering iron from high-iron-content copper slag, this article introduced a combination technol- ogy of deep reduction and magnetic beneficiation, investigated the iron recovery efficiency and optimized the technical conditions. When coke powder with 86wt% fixed carbon was used as a reductant, iron was successfully extracted from the copper slag. Under the optimized condition of the coke powder content of 14wt%, the calcium-to-silicon mass ratio （Ca/Si） of 0.2, the roasting temperature of 1300℃, the roasting time of 3 h, the grinding time of 20 min, and the magnetic field intensity of 61 kA-m-1, the iron recovery rate of the copper slag can reach 91.82%, and the extracted iron powder has an iron grade of 96.21%. With the characteristics of high iron grade and low impurity content, the extracted iron powder can be used as high-quality raw materials of weathering steel.

Selective separation of Cu(Ⅱ),Zn(Ⅱ),and Cd(Ⅱ)by solvent extraction

An experimental investigation was presented on the separation of Cu（Ⅱ）, Zn（Ⅱ）, and Cd（Ⅱ） from a rich sulfate leachate of zinc slag by solvent extraction. The results of orthogonal experiments indicate that LIX 984N is highly selective and very efficient in the extraction of Cu（Ⅱ）, and the analysis of variance indicates that the sequence of parameters according to their influence on the separation efficiency is phase ratio 〉 LIX 984N concentration 〉 pH value 〉 extraction time. The optimal condition for copper extraction is obtained as 25% of LIX 984N concentration, 7 rain of extraction time, 3：2 of phase ratio O/A, and pH = 1.7. The separation of Zn（Ⅱ） and Cd（Ⅱ） was performed after the copper extraction from the raffinate. Comparative analysis of the separation with di-2-ethylhexyl phosphoric acid （D2EHPA）, D2EHPA-tributyl- phosophate （TBP） synergistic extracting system, and 2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester （HEHEHP） was made at pH = 2.0. It is demonstrated that the extraction efficiency with D2EHPA is improved after being saponified by sodium hydroxide, and D2EHPA-TBP synergistic extracting, as well as HEHEHP, has a superior selectivity to Zn（Ⅱ） over Cd（Ⅱ）.