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.     

Recovery of yttrium from fluorescent powder of cathode ray tube,CRT: Zn removal by sulphide precipitation

This work is focused on the recovery of yttrium and zinc from fluorescent powder of cathode ray tube (CRT). Metals are extracted by sulphuric acid in the presence of hydrogen peroxide. Leaching tests are carried out according to a 2² full factorial plan and the highest extraction yields for yttrium and zinc equal to 100% are observed under the following conditions: 3 M of sulphuric acid, 10% v/v of H₂O₂ concentrated solution at 30% v/v, 10% w/w pulp density, 70 °C and 3 h of reaction.Two series of precipitation tests for zinc are carried out: a 2² full factorial design and a completely randomized factorial design. In these series the factors investigated are pH of solution during the precipitation and the amount of sodium sulphide added to precipitate zinc sulphide. The data of these tests are used to describe two empirical mathematical models for zinc and yttrium precipitation yields by regression analysis. The highest precipitation yields for zinc are obtained under the following conditions: pH equal to 2–2.5% and 10–12% v/v of Na₂S concentrated solution at 10% w/v. In these conditions the coprecipitation of yttrium is of 15–20%.Finally further yttrium precipitation experiments by oxalic acid on the residual solutions, after removing of zinc, show that yttrium could be recovered and calcined to obtain the final product as yttrium oxide. The achieved results allow to propose a CRT recycling process based on leaching of fluorescent powder from cathode ray tube and recovery of yttrium oxide after removing of zinc by precipitation. The final recovery of yttrium is 75–80%.     

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 2 M H₂SO₄, 20 ml of 30% H₂O₂ at 30 °C for 3 h. 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, 6 g/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.     

Simultaneous recovery of vanadium and nickel from power plant fly-ash: Optimization of parameters using response surface methodology

Simultaneous recovery of vanadium (V) and nickel (Ni), which are classified as two of the most hazardous metal species from power plant heavy fuel fly-ash, was studied using a hydrometallurgical process consisting of acid leaching using sulfuric acid. Leaching parameters were investigated and optimized in order to maximize the recovery of both vanadium and nickel. The independent leaching parameters investigated were liquid to solid ratio (S/L) (5–12.5 wt.%), temperature (45–80 °C), sulfuric acid concentration (5–25 v/v%) and leaching time (1–5 h). Response surface methodology (RSM) was used to optimize the process parameters. The most effective parameter on the recovery of both elements was found to be temperature and the least effective was time for V and acid concentration for Ni. Based on the results, optimum condition for metals recovery (actual recovery of ca.94% for V and 81% for Ni) was determined to be solid to liquid ratio of 9.15 wt.%, temperature of 80 °C, sulfuric acid concentration of 19.47 v/v% and leaching time of 2 h. The maximum V and Ni predicted recovery of 91.34% and 80.26% was achieved.     

Recovery of lithium and cobalt from waste lithium ion batteries of mobile phone

In view of the stringent environmental regulations, availability of limited natural resources and ever increasing need of alternative energy critical elements, an environmental eco-friendly leaching process is reported for the recovery of lithium and cobalt from the cathode active materials of spent lithium-ion batteries of mobile phones. The experiments were carried out to optimize the process parameters for the recovery of lithium and cobalt by varying the concentration of leachant, pulp density, reductant volume and temperature. Leaching with 2 M sulfuric acid with the addition of 5% H₂O₂ (v/v) at a pulp density of 100 g/L and 75 °C resulted in the recovery of 99.1% lithium and 70.0% cobalt in 60 min. H₂O₂ in sulfuric acid solution acts as an effective reducing agent, which enhance the percentage leaching of metals. Leaching kinetics of lithium in sulfuric acid fitted well to the chemical controlled reaction model i.e. 1 ? (1 ? X)^1/3 = k_ct. Leaching kinetics of cobalt fitted well to the model ‘ash diffusion control dense constant sizes spherical particles’ i.e. 1 ? 3(1 ? X)^2/3 + 2(1 ? X) = k_ct. Metals could subsequently be separated selectively from the leach liquor by solvent extraction process to produce their salts by crystallization process from the purified solution.     

Leaching behavior of copper from waste printed circuit boards with Brønsted acidic ionic liquid

In this work, a Brønsted acidic ionic liquid, 1-butyl-3-methyl-imidazolium hydrogen sulfate ([bmim]HSO₄), was used to leach copper from waste printed circuit boards (WPCBs, mounted with electronic components) for the first time, and the leaching behavior of copper was discussed in detail. The results showed that after the pre-treatment, the metal distributions were different with the particle size: Cu, Zn and Al increased with the increasing particle size; while Ni, Sn and Pb were in the contrary. And the particle size has significant influence on copper leaching rate. Copper leaching rate was higher than 99%, almost 100%, when 1 g WPCBs powder was leached under the optimum conditions: particle size of 0.1–0.25 mm, 25 mL 80% (v/v) ionic liquid, 10 mL 30% hydrogen peroxide, solid/liquid ratio of 1/25, 70 °C and 2 h. Copper leaching by [bmim]HSO₄ can be modeled with the shrinking core model, controlled by diffusion through a solid product layer, and the kinetic apparent activation energy has been calculated to be 25.36 kJ/mol.     

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.     

A novel process for recycling and resynthesizing LiNi1/3Co1/3Mn1/3O2 from the cathode scraps intended for lithium-ion batteries

To solve the recycling challenge for aqueous binder based lithium-ion batteries (LIBs), a novel process for recycling and resynthesizing LiNi_1/3Co_1/3Mn_1/3O₂ from the cathode scraps generated during manufacturing process is proposed in this study. Trifluoroacetic acid (TFA) is employed to separate the cathode material from the aluminum foil. The effects of TFA concentration, liquid/solid (L/S) ratio, reaction temperature and time on the separation efficiencies of the cathode material and aluminum foil are investigated systematically. The cathode material can be separated completely under the optimal experimental condition of 15 vol.% TFA solution, L/S ratio of 8.0 mL g^?1, reacting at 40 °C for 180 min along with appropriate agitation. LiNi_1/3Co_1/3Mn_1/3O₂ is successfully resynthesized from the separated cathode material by solid state reaction method. Several kinds of characterizations are performed to verify the typical properties of the resynthesized LiNi_1/3Co_1/3Mn_1/3O₂ powder. Electrochemical tests show that the initial charge and discharge capacities of the resynthesized LiNi_1/3Co_1/3Mn_1/3O₂ are 201 mAh g^?1 and 155.4 mAh g^?1 (2.8–4.5 V, 0.1 C), respectively. The discharge capacity remains at 129 mAh g^?1 even after 30 cycles with a capacity retention ratio of 83.01%.     

Study concerning the recovery of zinc and manganese from spent batteries by hydrometallurgical processes

Used batteries contain numerous metals in high concentrations and if not disposed of with proper care, they can negatively affect our environment. These metals represent 83% of all spent batteries and therefore it is important to recover metals such as Zn and Mn, and reuse them for the production of new batteries. The recovery of Zn and Mn from used batteries, in particular from Zn–C and alkaline ones has been researched using hydrometallurgical methods. After comminution and classification of elemental components, the electrode paste resulting from these processes was treated by chemical leaching. Prior to the leaching process the electrode paste has been subjected to two washing steps, in order to remove the potassium, which is an inconvenient element in this type of processes. To simultaneously extract Zn and Mn from this paste, the leaching method in alkaline medium (NaOH solution) and acid medium (sulphuric acid solution) was used. Also, to determine the efficiency of extraction of Zn and Mn from used batteries, the following variables were studied: reagents concentration, S/L ratio, temperature, time. The best results for extraction yield of Zn and Mn were obtained under acid leaching conditions (2 M H₂SO₄, 1 h, 80 °C).     

Finished leather waste chromium acid extraction and anaerobic biodegradation of the products

Due to the amounts of chromium in the leachate resulting from leather leaching tests, chromium sulfate tanned leather wastes are very often considered hazardous wastes. To overcome this problem, one option could be recovering the chromium and, consequently, lowering its content in the leather scrap. With this objective, chromium leather scrap was leached with sulfuric acid solutions at low temperature also aiming at maximizing chromium removal with minimum attack of the leather matrix. The effects of leather scrap dimension, sulfuric acid and sodium sulfate concentration in the solutions, as well as extraction time and temperature on chromium recovery were studied, and, additionally, organic matrix degradation was evaluated. The best conditions found for chromium recovery were leather scrap conditioning using 25 mL of concentrated H₂SO₄/L solution at 293 or 313 K during 3 or 6 days. Under such conditions, 30–60 ± 5% of chromium was recovered and as low as 3–6 ± 1% of the leather total organic carbon (TOC) was dissolved. Using such treatment, the leather scrap area and volume are reduced and the residue is a more brittle material showing enhanced anaerobic biodegradability. Although good recovery results were achieved, due to the fact that the amount of chromium in eluate exceeded the threshold value this waste was still hazardous. Thus, it needs to be methodically washed in order to remove all the chromium de-linked from collagen.     

Energy-efficient modification of reduction-melting for lead recovery from cathode ray tube funnel glass

Lead can be recovered from funnel glass of waste cathode ray tubes via reduction melting. While low-temperature melting is necessary for reduced energy consumption, previously proposed methods required high melting temperatures (1400 °C) for the reduction melting. In this study, the reduction melting of the funnel glass was performed at 900–1000 °C using a lab-scale reactor with varying concentrations of Na₂CO₃ at different melting temperatures and melting times. The optimum Na₂CO₃ dosage and melting temperature for efficient lead recovery was 0.5 g per 1 g of the funnel glass and 1000 °C respectively. By the reduction melting with the mentioned conditions, 92% of the lead in the funnel glass was recovered in 60 min. However, further lead recovery was difficult because the rate of the lead recovery decreased as with the recovery of increasing quantity of the lead from the glass. Thus, the lead remaining in the glass after the reduction melting was extracted with 1 M HCl, and the lead recovery improved to 98%.     

Evaluation of gold and silver leaching from printed circuit board of cellphones

Electronic waste has been increasing proportionally with the technology. So, nowadays, it is necessary to consider the useful life, recycling, and final disposal of these equipment. Metals, such as Au, Ag, Cu, Sn and Ni can be found in the printed circuit boards (PCB). According to this, the aims of this work is to characterize the PCBs of mobile phones with aqua regia; obtaining “reference” values of leaching, to gold and silver, with cyanide and nitric acid, respectively; and study the process of leaching of these metals in alternative leaching with sodium thiosulfate and ammonium thiosulfate. The metals were characterized by digesting the sample with aqua regia for 1 and 2 h at 60 °C and 80 °C. The leaching of Au with a commercial reagent (cyanide) and the Ag with HNO₃were made. The leaching of Au and Ag with alternative reagents: Na₂S₂O_3, and (NH₄)₂S₂O₃ in 0.1 M concentration with the addition of CuSO₄, NH₄OH, and H₂O₂, was also studied. The results show that the digestion with aqua regia was efficient to characterize the metals present in the PCBs of mobile phones. However, the best method to solubilize silver was by digesting the sample with nitric acid. The leaching process using sodium thiosulfate was more efficient when an additional concentration of 0.015 and 0.030 M of the CuSO₄ was added.     

Aluminium recovery vs. hydrogen production as resource recovery options for fine MSWI bottom ash fraction

Waste incineration bottom ash fine fraction contains a significant amount of aluminium, but previous works have shown that current recovery options based on standard on-step Eddy Current Separation (ECS) have limited efficiency. In this paper, we evaluated the improvement in the efficiency of ECS by using an additional step of crushing and sieving. The efficiency of metallic Al recovery was quantified by measuring hydrogen gas production. The ash samples were also tested for total aluminium content with X-ray fluorescence spectroscopy (XRF). As an alternative to material recovery, we also investigated the possibility to convert residual metallic Al into useful energy, promoting H₂ gas production by reacting metallic Al with water at high pH. The results show that the total aluminium concentration in the <4 mm bottom ash fraction is on average 8% of the weight of the dry ash, with less than 15% of it being present in the metallic form. Of this latter, only 21% can be potentially recovered with ECS combined with crushing and sieving stages and subsequently recycled. For hydrogen production, using 10 M NaOH at 1 L/S ratio results in the release of 6–11 l of H₂ gas for each kilogram of fine dry ash, equivalent to an energy potential of 118 kJ.     

Phosphate recovery from phosphorus-rich solution obtained from chicken manure incineration ash

The recovery of phosphorus from waste is very important for Japan because Japan has no natural phosphorus resources. In order to recover phosphorus from incineration ash of chicken manure, an acid dissolution–alkali precipitation method was investigated. Phosphorus content in the ash was 8%. The ash was treated with hydrochloric acid to obtain phosphorus-rich solution. Phosphorus could then be recovered as a precipitant by adding sodium hydroxide solution into the phosphorus-rich solution and gradually changing the pH in the solution to 3, 4, and 8. At pH 3, a small amount of phosphorus was precipitated to remove iron, which would cause coloring of subsequent precipitants. At pH 4, 84% of the phosphorus in the original solution could be recovered as CaHPO₄ · 2H₂O with a purity of 92%. At pH 8, 8% of the phosphorus in the phosphorus-rich solution could be recovered as identified hydroxyapatite. A recovery rate of 92% phosphorus as CaHPO₄ · 2H₂O and identified as hydroxyapatite was achieved.     

Chemical and process mineralogical characterizations of spent lithium-ion batteries: An approach by multi-analytical techniques

Mineral processing operation is a critical step in any recycling process to realize liberation, separation and concentration of the target parts. Developing effective recycling methods to recover all the valuable parts from spent lithium-ion batteries is in great necessity. The aim of this study is to carefully undertake chemical and process mineralogical characterizations of spent lithium-ion batteries by coupling several analytical techniques to provide basic information for the researches on effective mechanical crushing and separation methods in recycling process. The results show that the grade of Co, Cu and Al is fairly high in spent lithium ion batteries and up to 17.62 wt.%, 7.17 wt.% and 21.60 wt.%. Spent lithium-ion batteries have good selective crushing property, the crushed products could be divided into three parts, they are Al-enriched fraction (+2 mm), Cu and Al-enriched fraction (?2 + 0.25 mm) and Co and graphite-enriched fraction (?0.25 mm). The mineral phase and chemical state analysis reveal the electrode materials recovered from ?0.25 mm size fraction keep the original crystal forms and chemical states in lithium-ion batteries, but the surface of the powders has been coated by a certain kind of hydrocarbon. Based on these results a flowsheet to recycle spent LiBs is proposed.     

Recycling PC and TV waste glass in clay bricks and roof tiles

Disposal of PC monitors and TV sets is a growing problem, with over 40% of the weight of these systems comprised of waste glasses with high Pb (funnel) or Ba–Sr concentrations (panel), making them unsuitable for recycling and manufacturing new glass. A possible way to re-use these glasses is in the manufacturing of clay bricks and roof tiles. This possibility was appraised by laboratory simulation of the brickmaking process and technological characterization of unfired and fired products. The recycling of both funnel and panel glasses into clay bodies is technologically feasible, resulting in a substantially reduced plasticity behaviour during shaping–drying (implying a reduction of mechanical strength), and a promotion of sintering during firing. No significant release of Pb, Ba, and Sr was observed during the firing and leaching test for the carbonate-poor body; in contrast, some Pb volatilization during firing and Sr leaching were observed for the carbonate-rich body. Additions of 2 wt.% appear to be practicable, while 5 wt.% glass induces unacceptable modifications of technological properties. The recommended amount is within 2 and 4 wt.%, depending on the characteristics of the clay bodies. The main constraint is that the glass must have a particle size below the limit of the pan mills used in brickmaking (<1 mm).     

Recycling and reuse of waste from electricity distribution networks as reinforcement agents in polymeric composites

Of the waste generated from electricity distribution networks, wooden posts treated with chromated copper arsenate (CCA) and ceramic insulators make up the majority of the materials for which no effective recycling scheme has been developed. This study aims to recycle and reuse this waste as reinforcement elements in polymer composites and hybrid composites, promoting an ecologically and economically viable alternative for the disposal of this waste. The CCA wooden posts were cut, crushed and recycled via acid leaching using 0.2 and 0.4 N H₂SO₄ in triplicate at 70 °C and then washed and dried. The ceramic insulators were fragmented in a hydraulic press and separated by particle size using a vibrating sieve. The composites were mixed in a twin-screw extruder and injected into the test specimens, which were subjected to physical, mechanical, thermal and morphological characterization. The results indicate that the acid treatment most effective for removing heavy metals in the wood utilizes 0.4 N H₂SO₄. However, the composites made from wood treated with 0.2 N H₂SO₄ exhibited the highest mechanical properties of the composites, whereas the use of a ceramic insulator produces composites with better thermal stability and impact strength. This study is part of the research and development project of ANEEL (Agência Nacional de Energia Elétrica) and funded by CPFL (Companhia Paulista de Força e Luz).     

Building a better methane generation model: Validating models with methane recovery rates from 35 Canadian landfills

The German EPER, TNO, Belgium, LandGEM, and Scholl Canyon models for estimating methane production were compared to methane recovery rates for 35 Canadian landfills, assuming that 20% of emissions were not recovered. Two different fractions of degradable organic carbon (DOC_f) were applied in all models. Most models performed better when the DOC_f was 0.5 compared to 0.77. The Belgium, Scholl Canyon, and LandGEM version 2.01 models produced the best results of the existing models with respective mean absolute errors compared to methane generation rates (recovery rates + 20%) of 91%, 71%, and 89% at 0.50 DOC_f and 171%, 115%, and 81% at 0.77 DOC_f. The Scholl Canyon model typically overestimated methane recovery rates and the LandGEM version 2.01 model, which modifies the Scholl Canyon model by dividing waste by 10, consistently underestimated methane recovery rates; this comparison suggested that modifying the divisor for waste in the Scholl Canyon model between one and ten could improve its accuracy. At 0.50 DOC_f and 0.77 DOC_f the modified model had the lowest absolute mean error when divided by 1.5 yielding 63 ± 45% and 2.3 yielding 57 ± 47%, respectively. These modified models reduced error and variability substantially and both have a strong correlation of r = 0.92.     

Copper stabilization in beneficial use of waterworks sludge and copper-laden electroplating sludge for ceramic materials

A promising strategy for effectively incorporating metal-containing waste materials into a variety of ceramic products was devised in this study. Elemental analysis confirmed that copper was the predominant metal component in the collected electroplating sludge, and aluminum was the predominant constituent of waterworks sludge collected in Hong Kong. The use of waterworks sludge as an aluminum-rich precursor material to facilitate copper stabilization under thermal conditions provides a promising waste-to-resource strategy. When sintering the mixture of copper sludge and the 900 °C calcined waterworks sludge, the CuAl₂O₄ spinel phase was first detected at 650 °C and became the predominant product phase at temperatures higher than 850 °C. Quantification of the XRD pattern using the Rietveld refinement method revealed that the weight of the CuAl₂O₄ spinel phase reached over 50% at 850 °C. The strong signals of the CuAl₂O₄ phase continued until the temperature reached 1150 °C, and further sintering initiated the generation of the other copper-hosting phases (CuAlO₂, Cu₂O, and CuO). The copper stabilization effect was evaluated by the copper leachability of the CuAl₂O₄ and CuO via the prolonged leaching experiments at a pH value of 4.9. The leaching results showed that the CuAl₂O₄ phase was superior to the CuAlO₂ and CuO phases for immobilizing hazardous copper over longer leaching periods. The findings clearly indicate that spinel formation is the most crucial metal stabilization mechanism when sintering multiphase copper sludge with aluminum-rich waterworks sludge, and suggest a promising and reliable technique for reusing both types of sludge waste for ceramic materials.     

Pilot scale evaluation of the BABIU process – Upgrading of landfill gas or biogas with the use of MSWI bottom ash

Biogas or landfill gas can be converted to a high-grade gas rich in methane with the use of municipal solid waste incineration bottom ash as a reactant for fixation of CO₂ and H₂S. In order to verify results previously obtained at a laboratory scale with 65–90 kg of bottom ash (BA), several test runs were performed at a pilot scale, using 500–1000 kg of bottom ash and up to 9.2 N m³/h real landfill gas from a landfill in the Tuscany region (Italy). The input flow rate was altered. The best process performance was observed at a input flow rate of 3.7 N m³/(h t_BA). At this flow rate, the removal efficiencies for H₂S were approximately 99.5–99%.