Recovery of materials from waste printed circuit boards by vacuum pyrolysis and vacuum centrifugal separation

In this research, a two-step process consisting of vacuum pyrolysis and vacuum centrifugal separation was employed to treat waste printed circuit boards (WPCBs). Firstly, WPCBs were pyrolysed under vacuum condition at 600 °C for 30 min in a lab-scale reactor. Then, the obtained pyrolysis residue was heated under vacuum until the solder was melted, and then the molten solder was separated from the pyrolysis residue by the centrifugal force. The results of vacuum pyrolysis showed that the type-A of WPCBs (the base plates of which was made from cellulose paper reinforced phenolic resin) pyrolysed to form an average of 67.97 wt.% residue, 27.73 wt.% oil, and 4.30 wt.% gas; and pyrolysis of the type-B of WPCBs (the base plates of which was made from glass fiber reinforced epoxy resin) led to an average mass balance of 72.20 wt.% residue, 21.45 wt.% oil, and 6.35 wt.% gas. The results of vacuum centrifugal separation showed that the separation of solder was complete when the pyrolysis residue was heated at 400 °C, and the rotating drum was rotated at 1200 rpm for 10 min. The pyrolysis oil and gas can be used as fuel or chemical feedstock after treatment. The pyrolysis residue after solder separation contained various metals, glass fibers and other inorganic materials, which could be recycled for further processing. The recovered solder can be reused directly and it can also be a good resource of lead and tin for refining.     

Treatment of waste printed circuit board by green solvent using ionic liquid

Recycling of waste printed circuit boards (WPCBs) is an important subject not only for the protection of environment but also for the recovery of valuable materials. A feasibility study was conducted to dissolve bromine epoxy resins of WPCBs using ionic liquid (IL) of 1-ethyl-3-methylimizadolium tetrafluoroborate [EMIM(+)][BF(4)(-)] (nonaqueous green solvent) for recovering copper foils and glass fibers. Experimental results indicated that the initial delamination had seen from the cross-section of the WPCBs by mean of metallographic microscope and digital camera when WPCBs were heated in [EMIM(+)][BF(4)(-)] at 240°C for a duration of 30min. When temperature was increased to 260°C for a duration of 10min, the bromine epoxy resins of WPCBs were throughout dissolved into [EMIM(+)][BF(4)(-)] and the separations of copper foils and glass fibers from WPCBs were completed. This clean and non-polluting technology offers a new way to recycle valuable materials from WPCBs and prevent the environmental pollution of WPCBs effectively.     

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.     

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.     

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.     

Influence factors of determining optimal organic solvents for swelling cured brominated epoxy resins to delaminate waste printed circuit boards

Journal of Material Cycles and Waste Management - In the previous study, organic solvent dimethyl sulfoxide (DMSO) could effectively delaminate waste printed circuit boards (WPCBs) by swelling...     

Recovery of residual metals from − 0.5 mm non-metallic fractions in WPCBs using electrostatic separation enhanced by air classification

Journal of Material Cycles and Waste Management - Electrostatic separation is a cleaning physical method to recover metals from waste printed circuit boards (WPCBs), but it has poor separation...     

Qualitative and quantitative determination of heavy metals in waste cellular phones

Twenty four waste cellular phones, manufactured between 2002 and 2011, were selected in order to determine the total heavy metal content in each of their parts (printed circuit boards (PCBs), plastic housing (PH) and liquid crystal display monitors (LCDs)) and compare the results with the permissible limits set by the 2003 Directive on Restriction of Hazardous Substances (RoHS). All the selected samples were pulverized and digested with strong acids. Inductively coupled plasma-mass spectrometry was used to measure the heavy metal content in each sample. The results revealed that concentration levels of the examined heavy metals were higher in PCBs, followed by PH and LCD in that particular order (PCB > PH > LCD). With the exception of Pb and Cr present in PCBs of mobile phones released before the year 2006, all the other metal concentrations were according to the Directive. Concentration levels of Cd, Hg were lower than the permissible limits set by the EU, either before or after the validity of the 2003 RoHS Directive. Considering their significant heavy metal content, coupled with their large quantities produced worldwide in an annual rate, waste cellular phones need to be treated under an environmentally sound management scheme, prioritizing recycling and at the same time eliminating the possibility of any harm.     

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.     

Recovery of metals from waste printed circuit boards by supercritical water pre-treatment combined with acid leaching process

Waste printed circuit boards (PCBs) contain a large number of metals such as Cu, Sn, Pb, Cd, Cr, Zn, and Mn. In this work, an efficient and environmentally friendly process for metals recovery from waste PCBs by supercritical water (SCW) pre-treatment combined with acid leaching was developed. In the proposed process, waste PCBs were pre-treated by SCW, then the separated solid phase product with concentrated metals was subjected to an acid leaching process for metals recovery. The effect of SCW pre-treatment on the recovery of different metals from waste PCBs was investigated. Two methods of SCW pre-treatment were studied: supercritical water oxidation (SCWO) and supercritical water depolymerization (SCWD). Experimental results indicated that SCWO and SCWD pre-treatment had significant effect on the recovery of different metals. SCWO pre-treatment was highly efficient for enhancing the recovery of Cu and Pb, and the recovery efficiency increased significantly with increasing pre-treatment temperature. The recovery efficiency of Cu and Pb for SCWO pre-treatment at 420 °C was 99.8% and 80%, respectively, whereas most of the Sn and Cr were immobilized in the residue. The recovery of all studied metals was enhanced by SCWD pre-treatment and increased along with pre-treatment temperature. Up to 90% of Sn, Zn, Cr, Cd, and Mn could be recovered for SCWD pre-treatment at 440 °C.     

Evaluation of a recycling process for printed circuit board by physical separation and heat treatment

Printed circuit boards (PCBs) from discarded personal computer (PC) and hard disk drive were crushed by explosion in water or mechanical comminution in order to disintegrate the attached parts. More parts were stripped from PCB of PC, composed of epoxy resin; than from PCB of household appliance, composed of phenol resin.In an attempt to raise the copper grade of PCB by removing other components, a carbonization treatment was investigated. The crushed PCB without surface-mounted parts was carbonized under a nitrogen atmosphere at 873–1073 K. After screening, the char was classified by size into oversized pieces, undersized pieces and powder. The copper foil and glass fiber pieces were liberated and collected in undersized fraction. The copper foil was liberated easily from glass fiber by stamping treatment.As one of the mounted parts, the multi-layered ceramic capacitors (MLCCs), which contain nickel, were carbonized at 873 K. The magnetic separation is carried out at a lower magnetic field strength of 0.1 T and then at 0.8 T. In the +0.5 mm size fraction the nickel grade in magnetic product was increased from 0.16% to 6.7% and the nickel recovery is 74%.The other useful mounted parts are tantalum capacitors. The tantalum capacitors were collected from mounted parts. The tantalum-sintered bodies were separated from molded resins by heat treatment at 723–773 K in air atmosphere and screening of 0.5 mm. Silica was removed and 70% of tantalum grade was obtained after more than 823 K heating and separation.Next, the evaluation of Cu recycling in PCB is estimated. Energy consumption of new process increased and the treatment cost becomes 3 times higher comparing the conventional process, while the environmental burden of new process decreased comparing conventional process.The nickel recovery process in fine ground particles increased energy and energy cost comparing those of the conventional process. However, the environmental burden decreased than the conventional one.The process for recovering tantalum used more heat for the treatment and therefore the energy consumption increased by 50%, when comparing with conventional process. However, the market price for tantalum is very large; the profit for tantalum recovery is added. Also the environmental burden decreased by the recycling of tantalum recovery. Therefore, the tantalum recovery is very important step in the PCB recycling. If there is no tantalum, the consumed energy and treatment cost increase in the new process, though the environmental burden decreases.     

Cylinder cyclone (LARCODEMS) density media separation of plastic wastes

Cylindrical cyclone media separators using a suspended calcite separation media simulating industrial scale operations are demonstrated to effectively separate a wide variety of forms and a greater range of particle sizes of plastics by density than presently recycled. Purities of plastic products and recoveries obtained from mixed plastic wastes are comparable to those reported for established separations. Products of ≈100% purity with recoveries of >99% were obtained for high density fractions and >98% purities and recoveries for the low density fractions. Cyclonic centrifugal forces and/or the fine particle size of the separation media appear to minimize hydroscopic and particle shape effects.A mathematical model is proposed for defining plastic waste feed rates and treatable particle size ranges for the LARCODEMS media separator.Waste plastic separations yielded Ecart probable (Ep) values ?0.024 for a water only separation media. The Ep for 1.1 g cm^?3 separation medias was <0.032 with minimal to no variation in values for 1–8 mm particle sizes. Variation in the quality of separations is shown to be minimal with <72 μm, <45 μm and <2 μm media particle sizes. Media density offset created varied according to particle size.     

Metal toxicity assessment of mobile phone parts using Milli Q water

Environmentally safe disposal of end-of-life (EoL) or discarded mobile phone is a serious problem on account of their ever increasing number and toxic metals contents. In the present work, metal toxicity of mobile phone plastics, printed wire boards (PWBs) and batteries were assessed through dynamic batch leaching using Milli Q (MQ) water. Phone plastics failed Toxicity Characterization Leaching Procedure (TCLP) and Waste Extraction Test (WET) for Pb as the cumulative amount of Pb leached from plastics (5.33 mg/l) exceeded the regulatory limits (5.0 mg/l) used in characterizing a waste as hazardous. Similarly, the average cumulative amount (21.83 mg/l) of Ni leached from PWBs exceeded the regulatory limit of 20 mg/l and thus PWBs failed WET. Metals leached from batteries in small amounts (Cr: 0.40 mg/l and Ni: 0.15 mg/l). The presence of Fe in the batteries and its precipitation as oxides/hydroxides in the leaching solution hindered the leaching of other metals in MQ water. Both plastics and PWBs should be treated as hazardous waste and should not be disposed in open landfills. Further, MQ water leaching could provide good simulation of metals leaching from the mobile phones disposed at landfill sites.     

Composition and production rate of medical waste from a small producer in Greece

The objective of this work was to determine the composition and production rate of medical waste from the health care facility of social insurance institute, a small waste producer in Xanthi, Greece. Specifically, produced medical waste from the clinical pathology (medical microbiology) laboratory, the X-ray laboratory and the surgery and injection therapy departments of the health facility was monitored for six working weeks. A total of 240 kg medical solid waste was manually separated and weighed and 330 L of liquid medical waste was measured and classified. The hazardous waste fraction (%w/w) of the medical solid waste was 91.6% for the clinical pathology laboratory, 12.9% for the X-ray laboratory, 24.2% for the surgery departments and 17.6% for the injection therapy department. The infectious waste fraction (%w/w) of the hazardous medical solid waste was 75.6% for the clinical pathology laboratory, 0% for the X-ray laboratory, 100% for the surgery departments and 75.6% for the injection therapy department. The total hazardous medical solid waste production rate was 64 ± 15 g/patient/d for the clinical pathology laboratory, 7.2 ± 1.6 g/patient/d for the X-ray laboratory, 8.3 ± 5.1 g/patient/d for the surgery departments and 24 ± 9 g/patient/d for the injection therapy department. Liquid waste was produced by the clinical pathology laboratory (infectious-and-toxic) and the X-ray laboratory (toxic). The production rate for the clinical pathology laboratory was 0.03 ± 0.003 L/patient/d and for the X-ray laboratory was 0.06 ± 0.006 L/patient/d. Due to the small amount produced, it was suggested that the most suitable management scheme would be to transport the hazardous medical waste, after source-separation, to the Prefectural Hospital of Xanthi to be treated with the hospital waste. Assuming this data is representative of other small medical facilities, medical waste production can be estimated for such facilities distributed around Greece.     

Determination of total chlorine and bromine in solid wastes by sintering and inductively coupled plasma-sector field mass spectrometry

A sample preparation method based on sintering, followed by analysis by inductively coupled plasma-sector field mass spectrometry (ICP-SFMS) for the simultaneous determination of chloride and bromide in diverse and mixed solid wastes, has been evaluated. Samples and reference materials of known composition were mixed with a sintering agent containing Na₂CO₃ and ZnO and placed in an oven at 560 °C for 1 h. After cooling, the residues were leached with water prior to a cation-exchange assisted clean-up. Alternatively, a simple microwave-assisted digestion using only nitric acid was applied for comparison. Thereafter the samples were prepared for quantitative analysis by ICP-SFMS. The sintering method was evaluated by analysis of certified reference materials (CRMs) and by comparison with US EPA Method 5050 and ion chromatography with good agreement. Median RSDs for the sintering method were determined to 10% for both chlorine and bromine, and median recovery to 96% and 97%, respectively. Limits of detection (LODs) were 200 mg/kg for chlorine and 20 mg/kg for bromine. It was concluded that the sintering method is suitable for chlorine and bromine determination in several matrices like sewage sludge, plastics, and edible waste, as well as for waste mixtures. The sintering method was also applied for determination of other elements present in anionic forms, such as sulfur, arsenic, selenium and iodine.     

Analysis of potential RDF resources from solid waste and their energy values in the largest industrial city of Korea

The production potential of refuse derived fuel (RDF) in the largest industrial city of Korea is discussed. The purpose of this study is to evaluate the energy potential of the RDF obtained from utilizing combustible solid waste as a fuel resource. The total amount of generated solid waste in the industrial city was more than 3.3 million tonnes, which is equivalent to 3.0 tonnes per capita in a single year. The highest amount of solid waste was generated in the city district with the largest population and the biggest petrochemical industrial complex (IC) in Korea. Industrial waste accounted for 89% of the total amount of the solid waste in the city. Potential RDF resources based on combustible solid wastes including wastepaper, wood, rubber, plastic, synthetic resins and industrial sludge were identified. The amount of combustible solid waste that can be used to produce RDF was 635,552 tonnes/yr, consisting of three types of RDF: 116,083 tonnes/yr of RDF-MS (RDF from municipal solid waste); 146,621 tonnes/yr of RDF-IMC (RDF from industrial, municipal and construction wastes); and 372,848 tonnes/yr of RDF-IS (RDF from industrial sludge). The total obtainable energy value from the RDF resources in the industrial city was more than 2,240,000 × 10⁶ kcal/yr, with the following proportions: RDF-MS of 25.6%, RDF-IMC of 43.5%, and RDF-IS of 30.9%. If 50% or 100% of the RDF resources are utilized as fuel resources, the industrial city can save approximately 17.6% and 35.2%, respectively, of the current total disposal costs.     

Generation of copper rich metallic phases from waste printed circuit boards

The rapid consumption and obsolescence of electronics have resulted in e-waste being one of the fastest growing waste streams worldwide. Printed circuit boards (PCBs) are among the most complex e-waste, containing significant quantities of hazardous and toxic materials leading to high levels of pollution if landfilled or processed inappropriately. However, PCBs are also an important resource of metals including copper, tin, lead and precious metals; their recycling is appealing especially as the concentration of these metals in PCBs is considerably higher than in their ores. This article is focused on a novel approach to recover copper rich phases from waste PCBs. Crushed PCBs were heat treated at 1150 °C under argon gas flowing at 1 L/min into a horizontal tube furnace. Samples were placed into an alumina crucible and positioned in the cold zone of the furnace for 5 min to avoid thermal shock, and then pushed into the hot zone, with specimens exposed to high temperatures for 10 and 20 min. After treatment, residues were pulled back to the cold zone and kept there for 5 min to avoid thermal cracking and re-oxidation. This process resulted in the generation of a metallic phase in the form of droplets and a carbonaceous residue. The metallic phase was formed of copper-rich red droplets and tin-rich white droplets along with the presence of several precious metals. The carbonaceous residue was found to consist of slag and ～30% carbon. The process conditions led to the segregation of hazardous lead and tin clusters in the metallic phase. The heat treatment temperature was chosen to be above the melting point of copper; molten copper helped to concentrate metallic constituents and their separation from the carbonaceous residue and the slag. Inert atmosphere prevented the re-oxidation of metals and the loss of carbon in the gaseous fraction. Recycling e-waste is expected to lead to enhanced metal recovery, conserving natural resources and providing an environmentally sustainable solution to the management of waste products.     

Separation of polycarbonate and acrylonitrile–butadiene–styrene waste plastics by froth flotation combined with ammonia pretreatment

The objective of this research is flotation separation of polycarbonate (PC) and acrylonitrile–butadiene–styrene (ABS) waste plastics combined with ammonia pretreatment. The PC and ABS plastics show similar hydrophobicity, and ammonia treatment changes selectively floatability of PC plastic while ABS is insensitive to ammonia treatment. The contact angle measurement indicates the dropping of flotation recovery of PC is ascribed to a decline of contact angle. X-ray photoelectron spectroscopy demonstrates reactions occur on PC surface, which makes PC surface more hydrophilic. Separation of PC and ABS waste plastics was conducted based on the flotation behavior of single plastic. At different temperatures, PC and ABS mixtures were separated efficiently through froth flotation with ammonia pretreatment for different time (13 min at 23 °C, 18 min at 18 °C and 30 min at 23 °C). For both PC and ABS, the purity and recovery is more than 95.31% and 95.35%, respectively; the purity of PC and ABS is up to 99.72% and 99.23%, respectively. PC and ABS mixtures with different particle sizes were separated effectively, implying that ammonia treatment possesses superior applicability.     

Occupational hygiene in terms of volatile organic compounds (VOCs) and bioaerosols at two solid waste management plants in Finland

Factors affecting occupational hygiene were measured at the solid waste transferring plant at Hyvinkää and at the optic separation plant in Hämeenlinna. Measurements consisted of volatile organic compounds (VOCs) and bioaerosols including microbes, dust and endotoxins.The most abundant compounds in both of the plants were aliphatic and aromatic hydrocarbons, esters of carboxylic acids, ketones and terpenes. In terms of odour generation, the most important emissions were acetic acid, 2,3-butanedione, ethyl acetate, alpha-pinene and limonene due to their low threshold odour concentrations. At the optic waste separation plant, limonene occurred at the highest concentration of all single compounds of identified VOCs. The concentration of any single volatile organic compound did not exceed the occupational exposure limit (OEL) concentration. However, 2,3-butanedione as a health risk compound is discussed based on recent scientific findings linking it to lung disease.Microbe and dust concentrations were low at the waste transferring plant. Only endotoxin concentrations may cause health problems; the average concentration inside the plant was 425 EU/m³ which clearly exceeded the threshold value of 90 EU/m³. In the wheel loader cabin the endotoxin concentrations were below 1 EU/m³. High microbial and endotoxin concentrations were measured in the processing hall at the optic waste separation plant. The average concentration of endotoxins was found to be 10,980 EU/m³, a concentration which may cause health risks. Concentrations of viable fungi were quite high in few measurements in the control room. The most problematic factor was endotoxins whose average measured concentrations was 4853 EU/m³.     

Recovery of valuable metals from WPCB fines by centrifugal gravity separation and froth flotation

Journal of Material Cycles and Waste Management - This paper reports physical and physicochemical routes for the recycling of gold, silver, and copper from waste printed circuit boards (WPCBs). The...