Francesco Vegliò

Thiosulphate leaching for gold hydrometallurgy

Thiosulphate leaching of precious metals has been developed as an alternative and non-toxic technique to the conventional cyanidation. This process has advantages over cyanide in a decreased interference from foreign cations and a lower environmental impact. Ammoniacal thiosulphate solution allows the solubilization of gold as stable anionic complex. Leaching of gold occurs at appreciable dissolution rates. The aim of this work is devoted to a preliminary evaluation of the feasibility of thiosulphate leaching for the extraction of gold from precious metals ores on a laboratory scale. The experimental work has allowed the authors to point out the influence of temperature, thiosulphate concentration, ammonia concentration and copper sulphate concentration on the gold dissolution from an ore (51.6 g/t Au) that originated from the Dominican Republic. Gold was recovered from the leach liquors by adsorption onto activated carbon or by electrowinning. With the optimisation of the process parameters about 80% gold recovery has been attained, as in the case of conventional cyanidation.

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.

Study on the influence of various factors in the hydrometallurgical processing of waste printed circuit boards for copper and gold recovery

The present lab-scale experimental study presents the process of leaching waste printed circuit boards (WPCBs) in order to recover gold by thioureation. Preliminary tests have shown that copper adversely affects gold extraction; therefore an oxidative leaching pre-treatment was performed in order to remove base metals. The effects of sulfuric acid concentration, hydrogen peroxide volume and temperature on the metal extraction yield were studied by analysis of variance (ANOVA). The highest copper extraction yields were 76.12% for sample A and 18.29% for sample D, after leaching with 2M H2SO4, 20 ml of 30% H2O2 at 30°C for 3h. In order to improve Cu removal, a second leaching was performed only on sample A, resulting in a Cu extraction yield of 90%. Other experiments have shown the negative effect of the stirring rate on copper dissolution. The conditions used for the process of gold extraction by thiourea were: 20 g/L thiourea, 6g/L ferric ion, 10 g/L sulfuric acid, 600 rpm stirring rate. To study the influence of temperature and particle size, this process was tested on pins manually removed from computer central processing units (CPUs) and on waste CPU for 3½ h. A gold extraction yield of 69% was obtained after 75% of Cu was removed by a double oxidative leaching treatment of WPCBs with particle sizes smaller than 2 mm.

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 10V% 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 5M. 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 30min 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 5M HCl, 1V% H2O2, 10V% NaClO at 336K for 3h with a solid/liquid ratio of 1/10. 100% of Pd and Au of what was in the chloride leachate were precipitated by using 2g/L SBH. Finally, a process flow sheet for the recovery of Cu, Ag, Au and Pd from PCB was proposed.

Olive mill solid residues as heavy metal sorbent material: a preliminary study.

Biosorption of heavy metals is an innovative and alternative technology to remove these pollutants from aqueous solutions using inactive and dead biomasses such as agricultural and industrial wastes, algae and bacteria. In this study olive mill solid residue was used as heavy metal adsorbent material for its wide availability as agricultural waste and also for its cellulosic matrix, rich of potential metal binding active sites. Preliminary studies concerned with the removal of different heavy metals (Hg, Pb, Cu, Zn and Cd), the effect of pre-treatments by water and n-hexane and the regeneration possibility. Olive mill solid residue resulted able to remove heavy metals from aqueous solutions with an affinity series reflecting the hydrolytic properties of the metallic ions, but also a particular affinity for copper. It can be supposed that biosorption phenomenon occur by a general ion exchange mechanism combined with a specific complexation reaction for copper ions. Water pre-treatment is sufficient to reduce COD release in the effluent according to the law limit, while n-hexane pre-treatment strongly reduces also the adsorption properties of this material. Experimental isotherms obtained under different operating conditions were fitted using a non linear regression method for the estimation of the Langmuir parameters. Moreover a simple Scatchard plot analysis was performed for a preliminary investigation of the active sites, showing the presence of two different site affinities depending on the metal concentration, according to the previous hypothesis of two kinds of uptake mechanisms for copper biosorption. Regeneration tests gave good results in terms of yield of regeneration and also concentration ratios.

Treatment of exhaust fluorescent lamps to recover yttrium: Experimental and process analyses

The paper deals with recovery of yttrium from fluorescent powder coming from dismantling of spent fluorescent tubes. Metals are leached by using different acids (nitric, hydrochloric and sulphuric) and ammonia in different leaching tests. These tests show that ammonia is not suitable to recover yttrium, whereas HNO(3) produces toxic vapours. A full factorial design is carried out with HCl and H(2)SO(4) to evaluate the influence of operating factors. HCl and H(2)SO(4) leaching systems give similar results in terms of yttrium extraction yield, but the last one allows to reduce calcium extraction with subsequent advantage during recovery of yttrium compounds in the downstream. The greatest extraction of yttrium is obtained by 20% w/v S/L ratio, 4N H(2)SO(4) concentration and 90°C. Yttrium and calcium yields are nearly 85% and 5%, respectively. The analysis of variance shows that acid concentration alone and interaction between acid and pulp density have a significant positive effect on yttrium solubilization for both HCl and H(2)SO(4) medium. Two models are empirically developed to estimate yttrium and calcium concentration during leaching. Precipitation tests demonstrate that at least the stoichiometric amount of oxalic acid is necessary to recover yttrium efficiently and a pure yttrium oxalate n-hydrate can be produced (99% grade). The process is economically feasible if other components of the fluorescent lamps (glass, ferrous and non-ferrous scraps) are recovered after the equipment dismantling and valorized, besides the cost that is usually paid to recycling companies for collection, treatment or final disposal of such fluorescent powders.

Fenton treatment of complex industrial wastewater: optimization of process conditions by surface response method.

Remediation of industrial wastewaters represents a stringent problem in modern society, which requires particular understanding and ad hoc solutions. In this work, we performed extensive experimental study of chemical Fenton oxidation in order to understand the optimal operative conditions to be applied in real industrial wastewaters treatment. We analyzed the effectiveness of chemical oxygen demand (COD) removal from different wastewaters within a wide range of initial COD content. We observed a maximum COD % removal of about 80%, assessing the efficiency of the process. In order to understand the role of different reagents in the final yield, we performed a factorial experimental approach on the Fentons reagents (H(2)O(2) and Fe(2+)) and analyzed the results developing an analytical second-order model. The model depends on three variables, namely: the initial [COD(i)] of the sample, the [COD(i)]/[H(2)O(2)] ratio and [H(2)O(2)]/[Fe(2+)] ratio. We obtained an accurate description of the COD % removal in different initial conditions, with a R(2)=0.85. In particular, we observed that optimal quantities of Fentons reagents are a function of the initial COD of the treated wastes.

Metal recovery from spent refinery catalysts by means of biotechnological strategies.

A bioleaching study aimed at recovering metals from hazardous spent hydroprocessing catalysts was carried out. The exhaust catalyst was rich in nickel (4.5 mg/g), vanadium (9.4 mg/g) and molybdenum (4.4 mg/g). Involved microorganisms were iron/sulphur oxidizing bacteria. Investigated factors were elemental sulphur addition, ferrous iron addition and actions contrasting a possible metal toxicity (either adding powdered activated charcoal or simulating a cross current process by means of periodical filtration). Ferrous iron resulted to be essential for metal extraction: nickel and vanadium extraction yields were 83% and 90%, respectively, while about 50% with no iron. The observed values for molybdenum extraction yields were not as high as Ni and V ones (the highest values were around 30-40%). The investigated actions aimed at contrasting a possible metal toxicity resulted not to be effective; in contrast, sequential filtration of the liquor leach had a significant negative effect on metals extraction. Nickel and vanadium dissolution kinetics resulted to be significantly faster than molybdenum dissolution ones. Furthermore, a simple first order kinetic model was successfully fitted to experimental data. All the observed results supported the important role of the indirect mechanism in bioleaching of LC-Finer catalysts.

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. 2M H2SO4 (98% w/v), 5% H2O2, 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, 6g/L of Fe(3+), 0.5M 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.

Environmental Impact Assessment of Hydrometallurgical Processes for Metal Recovery from WEEE Residues Using a Portable Prototype Plant

Life cycle assessment (LCA) was applied to hydrometallurgical treatments carried out using a new portable prototype plant for the recovery of valuable metals from waste electrical and electronic equipment (WEEE). The plant was fed with the WEEE residues from physical processes for the recycling of fluorescent lamps, cathode ray tubes (CRTs), Li-ion accumulators and printed circuit boards (PCBs). Leaching with sulfuric acid was carried out, followed by metal recovery by selective precipitation. A final step of wastewater treatment with lime was performed. The recovered metals included yttrium, zinc, cobalt, lithium, copper, gold, and silver. The category of global warming potential was the most critical one considering the specifications for southern European territories, with 13.3 kg CO(2)/kg recovered metal from the powders/residues from fluorescent lamps, 19.2 kg CO(2)/kg from CRTs, 27.0 kg CO(2)/kg from Li-ion accumulators and 25.9 kg CO(2)/kg from PCBs. Data also show that metal extraction steps have the highest load for the environment. In general, these processes appear beneficial for the environment in terms of CO(2) emissions, especially for metal recovery from WEEE residues from fluorescent lamps and CRTs.