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.

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.

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.

Assessment of selective sequential extraction procedure for determining arsenic partitioning in copper slag

An optimized selective sequential extraction(SSE)procedure was developed to assess the arsenic(As)partitioning in copper slag.The potential As species in copper slag are partitioned into the readily soluble As,dissolvable arsenates,sparingly soluble arsenates,As residing in sulfides,arsenopyrite and metal As,as well as As incorporated into glassy silicates.The inductively coupled plasma atomic emission spectrometry(ICP-AES),scanning electronic microscopy(SEM),transmission electron microscope(TEM),X-ray diffractometry(XRD)and Fourier transform infrared spectroscopy(FTIR)were used to characterize the leachates and residues produced from the operation scheme.The selectivity and recovery of extractants were evaluated through single-phase extraction procedures.Partitioning data of As in slag samples show good agreement with the reported works and the total As recovery of each operation is over 90%.This suggests that the optimized SEE scheme can be reliably employed for As partitioning in As-bearing byproducts from copper smelting.

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.

Arsenic trioxide encapsulated liposomes prepared via copper acetate gradient loading method and its antitumor efficiency

In this study, arsenic trioxide(ATO) was encapsulated in liposomes via copper acetate(Cu(OAc)2) gradients and high entrapment efficiency of over 80% was obtained. The average particle size and the zeta-potential of the liposomes were detected to be 115.1 ± 29.1 nm and-21.97 ± 0.6 m V, respectively. The TEM images showed rod-like precipitates in the inner aqueous phase, which was supposed be due to the formation of insoluble ATO–Cu complex.The in vitro drug release of ATO–Cu liposomes exhibited a sustained release over 72 h, and the release rates decreased with the increase of the p H of release media. Pharmacokinetic and tissue distribution studies of ATO liposomes showed significantly reduced plasma clearance rate, increased AUC0–12h and T1/2, and improved tumor distribution of As compared to iv administration of ATO solution. The anti-tumor effect of ATO loaded liposomes to S180 tumor-bearing mice was significantly improved with a tumor inhibition rate of 61.2%,meanwhile the toxicity of encapsulated ATO was greatly decreased. In conclusion, ATO can be effectively encapsulated into liposomes by remote loading method via Cu(OAc)2 gradients;the co-administration of ATO and Cu(Ⅱ) via liposomal formulation may find wide applications in the treatment of various tumors.

Pyrometallurgical Removal of Arsenic from Electrostatic Precipitators Dusts of Copper Smelting

This work describes the experimental results of pyrometallurgical removing of arsenic from the dust collected in the electrostatic copper precipitators within the gas cleaning system of a Copper Flash Smelting Furnace. The generation of dust in the copper smelting worldwide ranges from 2 - 15 wt% per ton of a copper concentrate. In Chile, copper smelters produce approximately 110 kt/y of dust with a concentration of arsenic between 1 and 15 wt%. The dust is a complex of metals oxides and sulfurs with copper concentrations greater than 10 wt% and relatively high silver concentrations. Since its high arsenic concentration, it is difficult to recover valuable metals through hydrometallurgical processes or by direct recirculation of the dust in a smelting furnace. Thus, the development of pyrometallurgical processes aimed at reducing the concentration of arsenic in the dust (<0.5 wt%) is the main objective of this study, giving particular attention to the production of a suitable material to be recirculated in operations of copper smelting. The work provides a detailed characterization of the dust including the Quantitative Evaluation of Minerals by Scanning Electron Microscopy (QEMSCAN), Scanning Electron Microscope-Energy Dispersive X-ray Analysis (SEM/EDS), X-Ray Diffraction (XRD), the elemental chemical analysis using Atomic Adsorption (AAS), and X-Ray Fluorescence (X-RF). By considering that arsenic volatilization requires a process of sulfidation-decomposition-oxidation, this work seeks to explore the roasting of mixtures of copper concentrate/dust, sulfur/dust, and pyrrhotite/dust. By the elemental chemical analysis of the mixture after and before the roasting process, the degree of arsenic volatilization was determined. The results indicated the effects of parameters such as roasting temperature, gas flow, gas composition, and the ratio of mixtures (concentrate/dust, sulfur/dust, or pyrrhotite/dust) on the volatilization of arsenic. According to the findings, the concentration of arsenic in the roasted Flash Smelting dust can be reduced to a relatively low level (<0.5 wt%), which allows its recirculation into an smelting process.

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.

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.

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.

Detrimental effect of arsenic on hot ductility of copper-bearing steel

The effect of As content on the hot ductility of steel with 0.17 wt.%Cu was investigated at 700-1100℃using a Gleeble-3800 thermal-mechanical simulator.The results showed that increasing the As content from 0 to 0.15 wt.%obviously widened the hot ductility trough and pushed the trough into the high-temperature regime.Meanwhile,when the As content exceeded 0.10 wt.%,significant hot ductility deterioration was found.In the ferrite+austenite two-phase regions of 700-800℃,the fracture appearance changed from dimple ductile to intergranular ductile or from intergranular ductile to intergranular decohesion with increasing As content.The inhibition formation of proeutectoid ferrite and austenite grain coarsening were responsible for the slight hot ductility deterioration by As in the two-phase region.In the austenite single-phase region above 850℃,the fracture appearance changed from dimple ductile to intergranular decohesion with increasing As content,especially at 850-950℃.Suppression of dynamic recrystallization and grain boundary segregation of As resulted in serious damage of the hot ductility and widened the ductility trough in the single-phase region.

Heavy Metal Accumulation in Maize (<i>Zea mays</i>L.) Grown on Chromated Copper Arsenate (CCA) Contaminated Soil Amended with Treated Composted Sewage Biosolid

A pot experiment was conducted to investigate the heavy metal accumulation in maize (Zea mays L.) plant grown in chromated copper arsenate (CCA) soil amended with treated composted sewage biosolid. The initial concentrations of chromium, copper, arsenate in the CCA soil and sewage biosolid were determined by atomic absorption spectrophotometer. These were found to be, in CCA soil: 365.8 ± 6.18, 109.22 ± 14.04, 28.22 ± 3.8 and in sewage biosolid: 35 ± 1.06, 1.0 ± 0.02, 0 mg·kg-1 respectively. The concentration of Cr, Cu and As determined in both the roots and shoots generally decreased with increase in percentage amendment concentration and number of days (20 and 40 days after planting). At 20 days, the total metal concentration ranges in roots were As (5.54 ± 0.03 - 6.69 ± 1.14), Cr (9.59 ± 0.02 - 13.22 ± 0.03), Cu (2.28 ± 0.06 - 4.53 ± 0.37) mg·kg-1 while at 40 days the values were As (5.60 ± 0.19 - 6.08 ± 0.01), Cr (9.47 ± 0.04 - 10.95 ± 0.09), Cu (3.94 ± 0.19 - 4.64 ± 0.07) mg·kg-1. For the shoot system, the concentrations of the metals at 20 days were As (5.28 ± 0.03 - 5.90 ± 0.13), Cr (9.30 ± 0.05 - 10.07 ± 0.06), Cu (3.64 ± 0.12 - 4.72 ± 0.15) mg/kg while at 40 days the values obtained were As (5.28 ± 0.03 - 5.9 ± 0.13), Cr (9.69 ± 0.14 - 10.07 ± 0.03), Cu (2.94 ± 0.72 - 4.53 ± 0.03) mg·kg-1. The roots accumulated the three heavy metals more than the shoot system at all treatments used. Concentration of arsenic, chromium and copper in the plants decreased with increasing percentage amendments. The results suggest relatively low bioavailability of the three metals in CCA soil treated with high percentages of sewage biosolid as an amendment.

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 20 g/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.

An Exploratory Analysis of the Market Perspective on Reclaiming Chromated Copper Arsenate (CCA) from Decommissioned Preservative-Treated Wood Utility Poles

In the area of recycling of spent chromated copper arsenate (CCA)-treated wood, most studies to date have focused on methods of removing/extracting the residual preservative from the wood matrix. It is well recognized that exposure of CCA-treated wood to an acid solution can reverse the CCA fixation process thereby converting the CCA elements into their water-soluble form. The economic viability of the process is enhanced because it can be integrated with other technologies and products (e.g., “green” spray foam insulation, etc.). The market for the “green” CCA is the same as for traditional CCA-the wood treating industry, principally utility poles and pilings. A market research study was conducted to determine the suitability of spent CCA-treated wood as a source for recycled, “green” CCA for manufacturing “green” spray-foam insulation. Specifically, we wanted to discern the attitudes and overall perspectives of buyers/sellers (i.e., utilities and wood treating companies) of CCA preservatives and treated wood products, disposal methods and costs for decommissioned CCA-treated wood, and understand perceptions of and willingness-to-pay for “green” CCA preservatives extracted from the technologies used in this research. Results show that 60% of wood preservative treating respondents and 60% of electric utility company respondents are somewhat or greatly interested in using out-of-service utility poles as feedstock for “green insulation” as part of a new potential business venture.

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.

铝粉还原污酸中砷新工艺研究

由于硫化精矿中砷含量越来越高,致使烟气处理过程产生的污酸中砷含量也越来越高,同时污酸中含有铜、铁等有价金属。目前污酸除砷方法多以除砷为目的,形成的含砷渣属于危废,还需要二次处理。本研究研发了还原除砷新工艺,首先向污酸中加入硫化砷渣进行脱铜预处理并回收铜,然后用铝粉还原脱铜后液中的砷回收砷,最后向脱砷液中加入硫酸钾回收铝,还原后液回收还原剂后采用两段中和法处理。试验研究结果表明,在加入铜离子摩尔量1.1倍的硫化砷渣、反应温度85℃、反应时间3 h的条件下,污酸中的铜含量由2000 mg/L降至196 mg/L,硫化铜渣返熔炼配料系统;在还原温度70℃、还原时间2 h,还原剂用量1.8倍的条件下,砷的还原率大于96%,还原后液中的砷含量低于300 mg/L,得到的砷渣品位大于95%,可用于后续制备高品位单质砷;在硫酸钾用量1.1倍、反应温度常温、反应时间2 h的条件下,溶液含铝3.6 g/L,得到的明矾可达到《工业硫酸铝钾》(HG/T2565—2007)一等品标准。该方法除砷效果好,且能将污酸中的砷转变为具有经济价值的砷产品,还不会产生硫化氢气体,具有应用推广价值。

硫酸亚铁焙烧-水浸工艺分离黑铜泥中铜和砷

采用硫酸亚铁焙烧-水浸工艺实现黑铜泥中铜、砷一步分离。考察了铁砷摩尔比(Fe/As)、焙烧温度、焙烧时间、水浸初始pH等对试验效果的影响。较优工艺条件为:焙烧温度400℃、Fe/As=0.3、焙烧时间120 min、水浸温度80℃、水浸时间60 min、水浸液固比7 mL/g、水浸初始pH=4.5,沉砷率高达99%以上,铜浸出率高达96%以上。经XRD分析,沉砷渣主要成分为臭葱石和氧化铁,实现了砷的安全固化处置。

含砷铜渣中砷的分离与固化

砷是锌冶炼过程中的有害杂质元素,不仅制约着锌冶炼的顺利和安全生产,同时也影响企业的经济效益。云南某锌冶炼企业采用“SO_(2)还原浸出—铁粉沉铜”工艺处理锌冶炼浸出渣后所得铜砷渣砷含量高,为降低铜砷渣中砷的含量和提高铜渣的计价系数,采用“SO_(2)还原浸出—铁粉沉铜”工艺铁粉沉铜后的溶液为浸出剂,将含砷铜渣与含有一定浓度H_(2)SO_(4)及Fe^(2+)的铁粉沉铜后溶液以一定的液固比混合,用氧压浸出工艺进行处理,开展砷的分离与固化,深入研究关键技术参数对含砷铜渣中铜、砷浸出率,砷固化率以及固砷渣品质的影响规律。结果表明:含砷铜渣在初始硫酸浓度50 g/L、液固比5∶1、氧分压0.4 MPa、反应温度120℃、反应时间3 h的工艺条件下,可实现含砷铜渣中99%以上的铜和砷被浸出;含砷铜渣在铁砷质量比2.0、初始pH值1.0、液固比5∶1、氧分压0.4 MPa、反应温度120℃、反应时间3 h的固砷工艺条件下进行固砷处理,有价金属损失小,砷以稳定的臭葱石晶体固化,砷固化率98.23%,且臭葱石晶体结构良好、晶粒清晰、表面光滑、边缘整齐;固砷后的溶液经过锌粉置换沉铜,可产出含铜质量分数在70%以上的富铜渣,铜渣中铜的计价系数较除砷前提升13%,既实现了含砷铜渣中砷的分离与固化,降低了砷对环境的污染,又实现了企业的经济效益。研究结果可为锌冶炼含砷铜渣的高值化利用和砷的环境污染防治及环境风险防控提供参考。