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.     

Thiourea leaching gold and silver from the printed circuit boards of waste mobile phones

The present communication deals with the leaching of gold and silver from the printed circuit boards (PCBs) of waste mobile phones using an effective and less hazardous system, i.e., a thiourea leaching process as an alternative to the conventional and toxic cyanide leaching of gold. The influence of particle size, thiourea and Fe(3+) concentrations and temperature on the leaching of gold and silver from waste mobile phones was investigated. Gold extraction was found to be enhanced in a PCBs particle size of 100 mesh with the solutions containing 24 g/L thiourea and Fe(3+) concentration of 0.6% under the room temperature. In this case, about 90% of gold and 50% of silver were leached by the reaction of 2h. The obtained data will be useful for the development of processes for the recycling of gold and silver from the PCBs of waste mobile phones.     

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%。     

Influence of treatment techniques on Cu leaching and different organic fractions in MSWI bottom ash leachate

The leaching of heavy metals, such as copper, from municipal solid waste incinerator (MSWI) bottom ash is of concern in many countries and may inhibit the beneficial reuse of this secondary material. Previous studies have focused on the role of dissolved organic carbon (DOC) on the leaching of copper. Recently, a study of the Energy Research Centre of The Netherlands (ECN) showed fulvic acid-type components to exist in the MSWI bottom ash leachates and to be likely responsible for the generally observed enhanced copper leaching. These findings were verified for a MSWI bottom ash (slashed circle 0.1-2 mm) fraction from an incinerator in Flanders. The filtered leachates were subjected to the IHSS fractionation procedure to identify and quantify the fractions of humic acid (HA), fulvic acid (FA) and hydrophilic organic carbon (Hi). The possible complexation of fulvic acid with other heavy metals (e.g., lead) was also investigated. The identified role of fulvic acids in the leaching of copper and other heavy metals can be used in the development of techniques to improve the environmental quality of MSWI bottom ash. Thermal treatment and extraction with a 0.2 M ammonium-citrate solution were optimized to reduce the leaching of copper and other heavy metals. The effect of these techniques on the different fractions of organic matter (HA, FA, Hi) was studied. However, due to the obvious drawbacks of the two techniques, research is focused on finding other (new) techniques to treat MSWI bottom ash. In view of this, particle size-based separation was performed to evaluate its effect on heavy metal leaching and on HA, FA and Hi in MSWI bottom ash leachates.     

Enhanced bioleaching efficiency of copper from waste printed circuit boards (PCBs) by dissolved oxygen-shifted strategy in <Emphasis Type="Italic">Acidithiobacillus ferrooxidans</Emphasis>

Acidithiobacillus ferrooxidans, as chemolithotrophic aerobic bacterium, can obtain energy by oxidation of ferrous ions (Fe²⁺) to ferric ions (Fe³⁺) and use molecular oxygen (O₂) as terminal electron acceptor. In this study, the effects of dissolved oxygen (DO) levels in culture medium on cell growth and copper extraction from waste printed circuit boards (PCBs) were investigated in A. ferrooxidans. The whole culture period was divided into two stages of cell growth and copper extraction. At the former stage, relatively lower DO level was adopted to satisfy bacterial growth while avoiding excessive Fe²⁺ oxidation. At the later stage, higher DO was used to promote copper extraction. Moreover, shift time of DO from lower to higher level was determined via simulating Gauss function. By controlling DO at 10 % for initial 64 h and switching to 20 % afterwards and with 18 g/l PCBs addition at 64 h, final copper recovery reached 94.1 %, increased by 37.6 and 48.3 % compared to constant DO of 10 and 20 % operations. More importantly, copper leaching periods were shortened from 108 to 60 h. It was suggested that application of DO-shifted strategy to enhancing copper extraction from PCBs with reduced leaching periods is being feasible.     

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%。     

废硅电池片表面银的回收

采用氨-肼联合还原法回收废硅电池片上的银,优化了回收的工艺条件。实验得到的最佳回收工艺条件为：室温下采用硝酸2次浸取废硅电池片上的银,其中硝酸质量分数30%,硝酸浸取时间6 min;氯化银粉体用氨水和水合肼还原,n（Ag）∶n（N₂H₄）=0.5,水合肼还原反应温度50 ℃。回收的银粉纯度很高,结晶性较好,无需提纯。     

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.     

从银铅锌废渣中回收硝酸银的研究

介绍了用灼烧、浸取、沉淀、溶转和离子交换等方法,从银铅锌废渣中直接回收硝酸银,收率可达80.12%,AgNO3纯度为99.9%。考察了试料粒度、FeCl3质量浓度、溶液酸度、固液比,反应温度及浸取时间对银浸出率的影响。     

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。     

Two-stage Sequential Electrochemical Treatment of Nitrate Brine Wastes

Nitrates in concentrated brines can be electrochemically reduced in the cathodic chamber of a split-cell electrochemical reactor with formation of ammonium (and small amounts of nitrite). Fortunately, ammonium may be electrochemically oxidized to nitrogen gas in the anodic reaction chamber if a coupled sequential process is used. The presence of chloride in the brine waste is an important consideration in oxidative electrochemical processes, however, because it cycles through oxidized and reduced states at the electrode surfaces and in the bulk solution. Electrochemical oxidation converts chloride ions to “active chlorine” species with additional oxidizing capability (chlorine, hypochlorous acid and hypochlorite – essentially bleach), as well as to chlorates, depending on the reaction conditions. The production of these active species improves treatment performance in the ammonium oxidation phase since oxidation is no longer limited to the electrode surface. However, the process must be engineered to minimize loss of process efficiency due to parasitic side reactions (chloramines and chlorate). In this study, two-stage batch electrolysis was conducted using a three-electrode (copper anode, platinum-coated titanium cathode, silver/silver chloride reference) electrochemical cell, with the anodic and cathodic chambers separated by a Nafion 117 membrane. Treatment of nitrate and ammonium was tested with and without the presence of chloride in the waste. No significant difference was observed in cathodic nitrate reduction with chloride present or absent. However, the presence of chloride in the solution favored overall soluble nitrogen elimination upon oxidation. Increasing applied current increased production of undesirable byproducts (especially chlorate).     

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.     

Long-term leaching test of incinerator bottom ash: evaluation of Cu partition

Two types of leaching tests were performed on the bottom ash from municipal solid waste incinerators. A short-term batch test specified by the America Nuclear Society (ANS) and long-term column tests with acetic acid (pH 5.2) as leaching solution were used to evaluate copper leachability. The Cu leaching after the 5-d ANS test is about 1% of the original Cu content of 5300 mg/kg. Upon addition of a stabilizing agent, the Cu leaching quantity is reduced; the extent of reduction depends on the type of chemical used (phosphate, carbonate and sulfide). The 1.6% Na(2)S addition showed negligible Cu leaching, and Na(2)S was, therefore, used in subsequent column tests. The 30-d column test indicates a steady increase of Cu leaching amount with time and reaches about 1.5% of the original Cu content after 30 d. A 180-d column test further increased the Cu leaching to about 5.1% of the original Cu content, whereas no appreciable Cu leaching was found with the addition of 1.6% Na(2)S. A sequential extraction was conducted on the raw ash, ash with the addition of Na(2)S and the residue ash after 30 d of operation to characterize Cu affinity for different solid fractions. The data were used to evaluate the fate of Cu through these interactions.     

粉煤灰制聚合氯化铝铁和白碳黑新工艺

采用粉煤灰制备聚合氯化铝铁和白碳黑.该法共分一次酸浸、碱溶、焙烧、二次酸浸4个阶段.实验确定的最佳工艺条件为:一次酸浸阶段酸溶温度100℃,碱溶阶段m(氢氧化钠):m(活化高硅渣)=0.6,二次酸浸阶段m(碳酸钠):m(灰渣A)=0.8、盐酸质量分数20%.在此条件下Fe~(3+)和Al~(3+)的总浸出率分别为96.54%和86.67%.主要产品聚合氯化铝铁的质量符合GB15892-2003<水处理剂聚氯化铝>的标准;产品白碳黑的质量符合GBl0517-89<沉淀二氧化硅>的标准.     

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%.     

Leachability of heavy metals from copper blasting grit waste

This investigation presents the results of leaching tests, using the multiple-batch procedure, on cadmium, zinc, copper, lead, and chromium from copper blasting grit waste generated from a shipbuilding and repair company in Bahrain. The leaching test results have demonstrated that the metals tested were generally released in low concentrations except for copper and zinc. Metal leachability appeared to be dependent upon the pH and composition of the leaching medium.     

An advanced study on the hydrometallurgical processing of waste computer printed circuit boards to extract their valuable content of metals

This study refers to two chemical leaching systems for the base and precious metals extraction from waste printed circuit boards (WPCBs); sulfuric acid with hydrogen peroxide have been used for the first group of metals, meantime thiourea with the ferric ion in sulfuric acid medium were employed for the second one. The cementation process with zinc, copper and iron metal powders was attempted for solutions purification. The effects of hydrogen peroxide volume in rapport with sulfuric acid concentration and temperature were evaluated for oxidative leaching process. 2 M H₂SO₄ (98% w/v), 5% H₂O_2, 25 °C, 1/10 S/L ratio and 200 rpm were founded as optimal conditions for Cu extraction. Thiourea acid leaching process, performed on the solid filtrate obtained after three oxidative leaching steps, was carried out with 20 g/L of CS(NH₂)₂, 6 g/L of Fe³⁺, 0.5 M H₂SO₄, The cross-leaching method was applied by reusing of thiourea liquid suspension and immersing 5 g/L of this reagent for each other experiment material of leaching. This procedure has lead to the doubling and, respectively, tripling, of gold and silver concentrations into solution. These results reveal a very efficient, promising and environmental friendly method for WPCBs processing.     

用含硫化砷废渣制备砷酸铜

以湖北省某化工企业含砷废水处理过程中产生的含硫化砷废渣为研究对象,采用氧化碱浸—沉淀工艺制备砷酸铜。考察了沉淀反应液pH、沉淀反应温度、搅拌转速对砷沉淀效果的影响。采用XRD和SEM技术对砷酸铜的物相及形貌进行了表征。实验结果表明：废渣在氧化碱浸过程的砷浸出率为96.53%;沉淀反应时间为30 min时,沉淀步骤的最佳工艺条件为沉淀反应液pH 5.0、搅拌转速500 r/min、沉淀反应温度50 ℃。验证实验结果表明,在该工艺条件下,砷沉淀率均达93.96%以上。SEM表征结果显示,砷酸铜产品为颗粒状,粒径约为500 nm。XRD表征结果显示,砷酸铜产品中主要含有Cu₃As₂O₈,Cu₄O（AsO₄）₂,Cu₄（As₂O₇）O₂。该方法工艺简单、无二次污染,为废渣的综合利用提供了一种新的技术路线。     

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.     

Case study: Using soil washing/leaching for the removal of heavy metal at the twin cities army ammunition plant

COGNIS TERRAMET® soil leaching and Bescorp soil washing systems have been successfully combined to remediate an ammunition test burn area at the Twin Cities Army Ammunition Plant (TCAAP), New Brighton, Minnesota. This cleanup is the first in the country to successfully combine these two technologies, and it offers a permanent solution to heavy metal remediation. Over 20,000 tons of soil were treated in the project. The cleaned soil remained on-site, and the heavy metal contaminants were removed, recovered, and recycled. Eight heavy metals were removed from the contaminated soil achieving the very stringent cleanup criteria of <175 ppm for residual lead and achieving background concentrations for seven other project metals (antimony, cadmium, chromium, copper, mercury, nickel, and silver). Initial contaminant levels were measured as high as 86,000 ppm lead and 100,000 ppm copper, with average concentrations over 1,600 ppm each. In addition, both live and spent ordnance were removed in the soil treatment plant to meet the cleanup criteria. By combining soil washing and leaching, COGNIS and Bescorp were able to assemble a process which effectively treats all the soil fractions so that all soil material can be returned on-site, no wastewater is generated, and the heavy metals are recovered and recycled. No hazardous waste requiring landfill disposal was generated during the entire remedial operation.