Recovery of copper and cobalt from ancient slag.

About 2.5 million tonnes of copper smelter slag are available in Küre, northern part of Turkey. This slag contains large amounts of metallic values such as copper and cobalt. A representative slag sample containing 0.98% Cu, 0.49% Co and 51.47% Fe was used in the experimental studies. Two different methods, direct acid leaching and acid baking followed by hot water leaching were used for recovering Cu and Co from the slag. The effects of leaching time, temperature and acid concentration on Cu- and Co-dissolving efficiencies were investigated in the direct acid leaching tests. The optimum leaching conditions were found to be a leaching time of 2 h, acid concentration of 120 g L(-1), and temperature of 60 degrees C. Under these conditions, 78% Cu and 90% Co were extracted. In the acid baking + hot water leaching tests, 74% Co was dissolved after 1 h of roasting at 200 degrees C using a 3:1 acid:slag ratio, whereas the Cu-dissolving efficiency was 79% and the total slag weight loss was approximately 50%.     

草酸钴废料协同浸出水钴矿中的钴和铜

利用草酸钴废料协同浸出水钴矿中的钴和铜，考察了工艺条件对浸出率的影响，并推荐了一种二段浸出及后续生产草酸钴的工艺流程。实验结果表明，在草酸钴废料与水钴矿的质量比为20%、反应时间为120 min、反应温度为85 ℃、初始H2SO4浓度为1.00 mol/L、液固比为4 mL/g的最佳工艺条件下，钴和铜的浸出率分别达到98.82%和96.24%。该工艺应用于水钴矿的还原浸出，在回收利用草酸钴废料的同时，降低了还原剂的消耗，且对浸出液后续处理工艺无影响。     

Production of brown and black pigments by using flotation waste from copper slag.

One of the major problems in copper-producing countries is the treatment of the large amount of copper slag or copper flotation waste generated from copper slag which contains significant amounts of heavy metals such as Cu, Zn, Pb and Co. Dumping or disposal of such large quantities of flotation waste from copper slag causes environmental and space problems. In this study, the treatment of flotation waste from copper slag by a thermal method and its use as an iron source in the production of inorganic brown and black pigments that are used in the ceramic industry were investigated. The pigments were produced by calcining different amounts of flotation waste and chromite, Cr2O3, ZnO and CoO mixtures. The pigments obtained were added to transparent ceramic glazes and porcelainized tile bodies. Their colours were defined by L*a*b* measurements with a spectrophotometer. The results showed that flotation waste from copper slag could be used as an iron source to produce brown and black pigments in both ceramic body and glazes.     

Immobilization of copper flotation waste using red mud and clinoptilolite

The flash smelting process has been used in the copper industry for a number of years and has replaced most of the reverberatory applications, known as conventional copper smelting processes. Copper smelters produce large amounts of copper slag or copper flotation waste and the dumping of these quantities of copper slag causes economic, environmental and space problems. The aim of this study was to perform a laboratory investigation to assess the feasibility of immobilizing the heavy metals contained in copper flotation waste. For this purpose, samples of copper flotation waste were immobilized with relatively small proportions of red mud and large proportions of clinoptilolite. The results of laboratory leaching demonstrate that addition of red mud and clinoptilolite to the copper flotation waste drastically reduced the heavy metal content in the effluent and the red mud performed better than clinoptilolite. This study also compared the leaching behaviour of metals in copper flotation waste by short-time extraction tests such as the toxicity characteristic leaching procedure (TCLP), deionized water (DI) and field leach test (FLT). The results of leach tests showed that the results of the FLT and DI methods were close and generally lower than those of the TCLP methods.     

从废甲醇合成催化剂中回收铜锌

将废RK-05甲醇合成催化剂经过煅烧、浸取、精制等工序回收其中的铜和锌。经正交实验得到煅烧废催化剂的最优工艺参数为:废催化剂筛目100目,煅烧温度950℃,煅烧时间60 min。最佳浸取工艺条件为:废催化剂加入量约4 g/L,浸取温度75℃,浸取剂用量与理论用量体积比2.0~3.0,浸取剂浓度4.0 mol/L,浸取时间10min。精制工序制备CuO的最佳工艺条件为:锌粒与滤渣质量比为1.00,反应时间3 h,煅烧温度450℃,煅烧时间4 h。制备ZnO的最佳工艺条件为:煅烧温度800℃,煅烧时间60 min。回收的产品CuO纯度为99.1%,满足GB/T674—2003《化学试剂粉状氧化铜》中优级品的标准。回收的产品ZnO纯度为99.6%,满足GB/T3185—1992《氧化锌(间接法)》中一级品的标准。     

Preparation of aluminium-magnesium alloys and some valuable salts from used beverage cans

The purpose of this work is to recover standard aluminium-magnesium alloy(s) and some valuable salts from used beverage cans (UBCs). The suggested method updated the current recycling technology by augmenting removal of the coating paint, decreasing magnesium loss during melting process and improving hydrochloric acid leaching of the formed slag. Iron impurity present in the leaching solution, was removed by oxidation using oxygen gas or hydrogen peroxide and filtered as goethite. Results obtained revealed that a mixture of methyl ethyl ketone/dimethyl formamide entirely removes the paint coating at room temperature. The process compares favorably to the current methods involving firing or swell peeling. The coating decomposes to titanium dioxide by heating at 750 degrees C for 30 min. Standard compositions of Al-Mg alloys are formulated using secondary magnesium. The extent of recovery (R) of these alloy(s) is a function of the melting time and temperature and type of the flux. The maximum (R) value amounts to 94.4%. Sodium borate/chloride mix decreases magnesium loss to a minimum. The extent of leaching valuable salts from the slag increases with increasing the molarity, stoichiometric ratio and leaching temperature of the acid used. Removal of iron is a function of the potential of the oxidation process. Stannous chloride has been recovered from the recovered and dried salts by distillation at 700-750 degrees C.     

Ammoniacal leaching and recovery of copper from alloyed low-grade e-waste

The paper concerns a hydrometallurgical method for selective recovery of copper from low-grade electric and electronic wastes. The following consecutive stages were proposed: smelting of the scraps to produce Cu–Zn–Ag alloy, leaching of the alloy in ammoniacal solution, and selective copper electrowinning. Cu–Zn–Ag alloy was a polymetallic and five-phase system. It was leached in chloride, carbonate, sulfate and thiosulfate solutions. This resulted in the separation of the metals, wherein metallic tin and silver as well as lead salts remained in the slimes, while copper and zinc were transferred to the electrolyte. Copper was selectively recovered from the ammoniacal solutions by the electrolysis, leaving zinc ions in the electrolyte. The best conditions of the alloy treatment were obtained in the ammonia–carbonate system, where the final product was copper of high purity (99.9 %) at the current efficiency of 60 %. Thiosulfate solution was not applicable for the leaching of the copper alloy due to secondary reactions of the formation of copper(I) thiosulfate complexes and precipitation of copper(I) sulfide, both inhibiting dissolution of the metallic material.     

Processing of copper converter slag for metals reclamation: Part II: mineralogical study.

Chemical and mineralogical characterizations of a copper converter slag, and its products obtained by curing with strong sulphuric acid and leaching with hot water, were carried out using ore microscopy, scanning electronic microscopy with energy dispersive spectrometry, wave-length dispersive X-ray fluorescence spectrometry, X-ray diffractometry and chemical phase analysis, which provided necessary information to develop a new process for treating such slag and further understanding of the chemical and mineralogical changes in the process.     

Physicochemical properties of slags produced at various amounts of iron addition in lead smelting

In the process of lead production from lead-bearing materials generated in copper metallurgy, a large amount of hazardous waste in the form of slag is produced. To assess the effect of the slag on the environment, its physicochemical properties were determined. In this study, the following methods were used: wavelength dispersive X-ray fluorescence (WD XRF), X-ray diffraction (XRD), and Bunte-Baum-Reerink method to determine softening and melting points, as well as viscosity examination and leaching tests. The measurements were performed on the slag produced with two different amounts of iron addition to the lead smelting process. The resulting slags, an oxide rich phase slag and a sulfide rich phase slag have different compositions and physicochemical properties. It was found that the increase in iron addition causes an increase in the softening melting point of the oxide rich phase slag by about 100 °C, and a twofold increase in the viscosity of both slag phases. The increase in iron addition also results in the decrease in As leachability and increase in Zn, Fe, and Cu leachability from the slags. Slag produced with increased iron addition has a greater impact on the environment.

     

Assessment of the use of spent copper slag for land reclamation.

The shortage of waste landfill space for waste disposal and the high demand for fill materials for land reclamation projects in Singapore have prompted a study on the feasibility of using spent copper slag as fill material in land reclamation. The physical and geotechnical properties of the spent copper slag were first assessed by laboratory tests, including hydraulic conductivity and shear strength tests. The physical and geotechnical properties were compared with those of conventional fill materials such as sands. The potential environmental impacts associated with the use of the spent copper slag for land reclamation were also evaluated by conducting laboratory tests including pH and Eh measurements, batch-leaching tests, acid neutralization capacity determination, and monitoring of long-term dissolution of the material. The spent copper slag was slightly alkaline, with pH 8.4 at a solid : water ratio of 1 : 1. The batch-leaching test results show that the concentrations of the regulated heavy metals leached from the material at pH 5.0 were significantly lower than the maximum concentrations for their toxicity limits referred by US EPA's Toxicity Characteristic Leaching Procedure (TCLP). It was also found that the material is unlikely to cause significant change in the redox condition of the subsurface environment over a long-term period. In terms of physical and geotechnical properties, the spent copper slag is a good fill material. In general, the spent copper slag is suitable to be used as a fill material for land reclamation.     

离子液体对废旧印刷线路板中铜、锌、铅的浸出规律

以离子液体1-丁基磺酸-3-甲基咪唑三氟甲烷磺酸盐([BSO_3HMIm]OTf)为浸出剂,初步研究了WPCBs浸铜过程中锌和铅浸出率的影响因素。实验结果表明:铜、锌的浸出率随着WPCBs粒径的减小、H_2O_2溶液加入量的增大而增大,铜的浸出率随浸出温度的升高先增大后减小,锌的浸出率受浸出温度影响不大;铅的浸出率受5种因素影响不大,且总体处于较低水平。在WPCBs粒径为0.100~0.250 mm、离子液体加入量为60.0%(φ)、H_2O_2溶液加入量为7.5%(φ)、固液比为1∶15、浸出温度为50℃的条件下,铜、锌、铅的浸出率分别为99.84%,93.25%,22.46%。     

生态修复植物蜈蚣草中砷的回收

采用管式炉高温热解-NaOH-Na₂CO₃混合液碱浸-CuSO₄·5H₂O沉淀的方法回收生态修复植物蜈蚣草中的砷，最终得到产品砷酸铜。该方法的最佳工艺条件为：热解温度600 ℃，热解时间30 min，CaO加入量（CaO与蜈蚣草的质量比）8%； m（NaOH）∶m（Na₂CO₃）=1∶3，碱浸温度70 ℃， 碱浸时间2 h， 固液比1∶10； 沉淀反应pH 5， 沉淀反应温度70 ℃。采用该方法处理生态修复植物蜈蚣草，得到产品砷酸铜的纯度为93%，砷回收率达88%。     

An overview on the production of pigment grade titania from titania-rich slag.

To recover pigment grade TiO2, operating plants all over the world use chemical processes. Slag-based technology is considered to be attractive because of low waste generation and low chemical cost due to high titanium content and is poised to replace the conventional technology. This paper provides a review of the slag-based technology with the specific aim to produce leachable slag and achieving high titania yield from recovered wastes. Leachable oxides of the lower oxidation state, such as TiO and Ti2O3, facilitate the leaching process. However, during smelting these oxides increase the viscosity of the slag. Formation of titanium carbide or carbonitride is also not desirable as it leads to resistance to the leaching of titanium. This report highlights the problems and their possible solutions to obtain leachable slag.     

Method to recover and reuse chromated copper arsenate wood preservative from spent treated wood

The volume of chromated copper arsenate (CCA) treated wood products coming out of service is expected to increase dramatically during the next decade. There is a need for an alternative waste management approach to landfilling. This paper investigates the variables affecting extraction of CCA components from wood particles and the potential to oxidize and reuse the recovered chemicals. Most of the CCA components could be extracted by 10% H2O2 at 50 degrees C in 6 h with an average extraction efficiency of 95% for Cr, 94% for Cu and 98% for As. The extract containing Cr(III), Cu(II) and As(V) could be oxidized in several stages by aqueous 2.5% w/w H2O2 in less than 2 h to a condition where it was compatible with CCA treating solutions and could be reused for treating new wood. When the recovered extract was mixed with fresh CCA solution in different ratios, the mixed CCA-C solutions had similar solution stability as freshly prepared CCA-C solution and treated wood had similar leaching properties as wood treated with fresh solution.     

Effects of cement on redistribution of trace metals and dissolution of organics in sewage sludge and its inorganic waste-amended products

The suitability of using cement-stabilized sludge products as artificial soils in earth works was evaluated. The sludge products investigated were cemented sludge, cement-treated clay-amended sludge (SS+MC), and cement-treated copper slag-amended sludge (SS+CS). The leachability of lead (Pb), zinc (Zn), copper (Cu), and chromium (Cr) were assessed using the sequential extraction technique, toxicity characteristic leaching procedure (TCLP), NEN 7341 availability test, and column leaching test. The results indicated that Zn leachability was reduced in all the cement-stabilized sludge products. In contrast, Cu was transferred from the organic fraction to the readily leachable phases in the cement-stabilized sludge products and therefore exhibited increased leachability. The increased Cu leachability could be attributed to dissolution of humic substances in the sludge as a result of elevated pH. Good correlation between dissolved organic carbon (DOC) and heavy metal leaching from the cement-stabilized sludge products was observed in the column leaching experiment. Even with a cement percentage as small as 12.5%, calcium silicate hydrate (C-S-H) was formed in the SS+MC and SS+CS products. Inclusion of the marine clay in the SS+MC products could reduce the leaching potentials of Zn, and this was the great advantage of the marine clay over the copper slag for sludge amendment.     

Treatment of copper industry waste and production of sintered glass-ceramic.

Copper waste is iron-rich hazardous waste containing heavy metals such as Cu, Zn, Co, Pb. The results of leaching tests show that the concentration of these elements exceeds the Turkish and EPA regulatory limits. Consequently, this waste cannot be disposed of in its present form and therefore requires treatment to stabilize it or make it inert prior to disposal. Vitrification was selected as the technology for the treatment of the toxic waste under investigation. During the vitrification process significant amounts of the toxic organic and inorganic chemical compounds could be destroyed, and at the same time, the metal species are immobilized as they become an integral part of the glass matrix. The copper flotation waste samples used in this research were obtained from the Black Sea Copper Works of Samsun, Turkey. The samples were vitrified after being mixed with other inorganic waste and materials. The copper flotation waste and their glass-ceramic products were characterized by X-ray analysis (XRD), scanning electron microscopy and by the toxicity characteristic leaching procedure test. The products showed very good chemical durability. The glass-ceramics fabricated at 850 degrees C/2 h have a large application potential especially as construction and building materials.     

Removal of copper,chromium, and arsenic from CCA-C treated wood by EDTA extraction

Ethylenediaminetetracetic acid (EDTA) is one of the most common chelators used to bind the metal ions in extremely stable complexes in heavy metal contaminated soils and thus to remediate such substrates. EDTA forms water soluble complexes with many metal ions and it is used to release the various metals. In this study, EDTA extraction of copper, chromium, and arsenic from chromated copper arsenate (CCA-C) treated wood was evaluated using batch leaching experiments. CCA-treated wood samples were extracted with eight different concentrations of EDTA for 4, 8, 18, and 24 h at room temperature. Exposing CCA-treated chips and sawdust to EDTA extraction enhanced removal of CCA components compared with extraction by deionized water. Grinding CCA-treated wood chips into 40-mesh sawdust provided greater access to and removal of CCA components. Extraction with 1% EDTA solution for 24 h removed 60% copper, 13% chromium, and 25% arsenic from treated chips. EDTA extraction of treated sawdust samples resulted in 93% copper, 36% chromium, and 38% arsenic removal. CCA leaching from treated wood blocks was also evaluated according to modified AWPA E11-99 standard test method of determining the leachability of wood preservatives. Leaching of CCA components from treated wood blocks with 1% EDTA solution for 14 days caused more copper leaching compared to leaching with deionized water. Leaching with 1% EDTA for 14 days removed 53% copper from the blocks whereas 14% copper was leached from the blocks with deionized water. The results suggest that EDTA extraction removes significant quantities of copper from CCA-treated wood. Thus, EDTA could be important in the remediation of wood waste treated with the newest formulations of organometalic copper compounds and other water-borne wood preservatives containing copper.     

Recovery of valuable metals from electronic and galvanic industrial wastes by leaching and electrowinning

In the present paper, a study on laboratory scale to perform a treatment for valuable metals recovery from electronic and galvanic industrial wastes, is reported. The characterisation of the waste, performed by XRD, SEM, EDX and chemical analysis, showed a high metals content in the sludge, such as Cu, Ni, Mn, Pb, Sn, W. A leaching process, coupled by electrowinning, is then proposed in order to reduce the volume of the waste material and to recover selectively valuable metals, such as Cu and Ni. During the leaching step, carried out by using H(2)SO(4), several factors were investigated (acid concentration, temperature and time of treatment). The leached liquor has been successfully treated with an electrowinning process, to recover copper and nickel. The copper and nickel depositions, were performed in acid and alkaline conditions, respectively. The Faraday yield was of about 95%. The energy consumption was 2.13 and 4.43 kWh per kg of copper and nickel recovered, respectively. At the end of the process, about 94-99% of the initial content of Cu and Ni was recovered at the cathode. The experimental results obtained, showed the technical feasibility of the process.     

Nickel recovery from spent nickel catalyst.

A process for nickel recovery from a spent catalyst of definite composition has been developed using the hydro-metallurgical route. The processing steps includes direct sulphuric acid leaching followed by separation of iron as well as silica and other impurities. For a 152 microm particle size catalyst, extraction of about 98% nickel was achieved at 363 K in 2 h using a sulphuric acid concentration (v/v) of 8% and a pulp density of 10%. The dissolution of nickel followed diffusion-controlled leaching kinetics. Increase in temperature and sulphuric acid concentration resulted in increase in the nickel recovery. The activation energy for nickel dissolution was calculated to be 62.8 kJ mol(-1). Finally, nickel was recovered as value-added products such as sulphide and oxalate with overall recovery of 90 and 88% of nickel, respectively.     

Process development for recovery of copper and precious metals from waste printed circuit boards with emphasize on palladium and gold leaching and precipitation

A novel hydrometallurgical process was proposed for selective recovery of Cu, Ag, Au and Pd from waste printed circuit boards (PCBs). More than 99% of copper content was dissolved by using two consecutive sulfuric acid leaching steps in the presence of H₂O₂ as oxidizing agents. The solid residue of 2nd leaching step was treated by acidic thiourea in the presence of ferric iron as oxidizing agent and 85.76% Au and 71.36% Ag dissolution was achieved. The precipitation of Au and Ag from acidic thiourea leachate was investigated by using different amounts of sodium borohydride (SBH) as a reducing agent. The leaching of Pd and remained gold from the solid reside of 3rd leaching step was performed in NaClO-HCl-H₂O₂ leaching system and the effect of different parameters was investigated. The leaching of Pd and specially Au increased by increasing the NaClO concentration up to 10 V% and any further increasing the NaClO concentration has a negligible effect. The leaching of Pd and Au increased by increasing the HCl concentration from 2.5 to 5 M. The leaching of Pd and Au were endothermic and raising the temperature had a positive effect on leaching efficiency. The kinetics of Pd leaching was quite fast and after 30 min complete leaching of Pd was achieved, while the leaching of Au need a longer contact time. The best conditions for leaching of Pd and Au in NaClO-HCl-H₂O₂ leaching system were determined to be 5 M HCl, 1 V% H₂O₂, 10 V% NaClO at 336 K for 3 h with a solid/liquid ratio of 1/10. 100% of Pd and Au of what was in the chloride leachate were precipitated by using 2 g/L SBH. Finally, a process flow sheet for the recovery of Cu, Ag, Au and Pd from PCB was proposed.