Recycling of WEEE: characterization of spent printed circuit boards from mobile phones and computers

This paper presents a comparison between printed circuit boards from computers and mobile phones. Since printed circuits boards are becoming more complex and smaller, the amount of materials is constantly changing. The main objective of this work was to characterize spent printed circuit boards from computers and mobile phones applying mineral processing technique to separate the metal, ceramic, and polymer fractions. The processing was performed by comminution in a hammer mill, followed by particle size analysis, and by magnetic and electrostatic separation. Aqua regia leaching, loss-on-ignition and chemical analysis (inductively coupled plasma atomic emission spectroscopy - ICP-OES) were carried out to determine the composition of printed circuit boards and the metal rich fraction. The composition of the studied mobile phones printed circuit boards (PCB-MP) was 63 wt.% metals; 24 wt.% ceramics and 13 wt.% polymers; and of the printed circuit boards from studied personal computers (PCB-PC) was 45 wt.% metals; 27 wt.% polymers and ceramics 28 wt.% ceramics. The chemical analysis showed that copper concentration in printed circuit boards from personal computers was 20 wt.% and in printed circuit boards from mobile phones was 34.5 wt.%. According to the characteristics of each type of printed circuit board, the recovery of precious metals may be the main goal of the recycling process of printed circuit boards from personal computers and the recovery of copper should be the main goal of the recycling process of printed circuit boards from mobile phones. Hence, these printed circuit boards would not be mixed prior treatment. The results of this paper show that copper concentration is increasing in mobile phones and remaining constant in personal computers.     

Techniques to separate metal from waste printed circuit boards from discarded personal computers

Waste printed circuit boards contain valuable metals such as Au, Pd, Ag, and Cu that can be reutilized and harmful elements such as Pb, Br, and Cr that must be removed from the viewpoint of environmental conservation. In this research, we examined a method that separates the materials from printed circuit boards contained in discarded personal computers. After cutting the printed circuit boards to a size of 20 × 20 mm, they were heated at 873 K under an Ar atmosphere to remove organic resins containing elements such as C, H, and N. After heat treatment, the printed circuit boards were crushed using a planetary ball mill and the pulverized powders were filtered. The fraction with a granularity of greater than 250 μm was separated into magnetic and nonmagnetic materials by a magnetic field. Because the fraction with a granularity of less than 250 μm contained 39 mass% of C, it was heated at 1273 K in an atmosphere of 95% Ar and 5% O₂ to allow carbon combustion to take place, followed by metal reduction processing at the same temperature in an atmosphere of 97% Ar and 3% H₂. The basicity of the resulting powder was adjusted and the powder was heated at 1773 K under an Ar atmosphere. The proposed method separated the slag and metal, and 80% of the valuable metals contained in printed circuit boards could be collected.     

Enrichment of the metallic components from waste printed circuit boards by a mechanical separation process using a stamp mill

Printed circuit boards incorporated in most electrical and electronic equipment contain valuable metals such as Cu, Ni, Au, Ag, Pd, Fe, Sn, and Pb. In order to employ a hydrometallurgical route for the recycling of valuable metals from printed circuit boards, a mechanical pre-treatment step is needed. In this study, the metallic components from waste printed circuit boards have been enriched using a mechanical separation process. Waste printed circuit boards shredded to <10mm were milled using a stamp mill to liberate the various metallic components, and then the milled printed circuit boards were classified into fractions of <0.6, 0.6-1.2, 1.2-2.5, 2.5-5.0, and >5.0mm. The fractions of milled printed circuit boards of size <5.0mm were separated into a light fraction of mostly non-metallic components and a heavy fraction of the metallic components by gravity separation using a zig-zag classifier. The >5.0mm fraction and the heavy fraction were subjected to two-step magnetic separation. Through the first magnetic separation at 700 Gauss, 83% of the nickel and iron, based on the whole printed circuit boards, was recovered in the magnetic fraction, and 92% of the copper was recovered in the non-magnetic fraction. The cumulative recovery of nickel-iron concentrate was increased by a second magnetic separation at 3000 Gauss, but the grade of the concentrate decreased remarkably from 76% to 56%. The cumulative recovery of copper concentrate decreased, but the grade increased slightly from 71.6% to 75.4%. This study has demonstrated the feasibility of the mechanical separation process consisting of milling/size classification/gravity separation/two-step magnetic separation for enriching metallic components such as Cu, Ni, Al, and Fe from waste printed circuit boards.     

Elemental analysis of printed circuit boards considering the ROHS regulations

The EU RoHS Directive (2002/95/EC of the European Parliament and of the Council) bans the placing of new electrical and electronic equipment containing more than agreed levels of lead, cadmium, mercury, hexavalent chromium, polybrominated biphenyl (PBB) and polybrominated diphenyl ether (PBDE) flame retardants on the EU market. It necessitates methods for the evaluation of RoHS compliance of assembled electronic equipment. In this study mounted printed circuit boards from personal computers were analyzed on their content of the three elements Cd, Pb and Hg which were limited by the EU RoHS directive. Main focus of the investigations was the influence of sample pre-treatment on the precision and reproducibility of the results. The sample preparation steps used were based on the guidelines given in EN 62321. Five different types of dissolution procedures were tested on different subsequent steps of sample treatment like cutting and milling. Elemental analysis was carried out using ICP-OES, XRF and CV-AFS (Hg). The results obtained showed that for decision-making with respect to RoHS compliance a size reduction of the material to be analyzed to particles ?1.5 mm can already be sufficient. However, to ensure analytical results with relative standard deviations of less than 20%, as recommended by the EN 62321, a much larger effort for sample processing towards smaller particle sizes might be required which strongly depends on the mass fraction of the element under investigation.     

Feedstock recycling from plastic and thermoset fractions of used computers (I): pyrolysis

The increasing production of computers, the progress in their performance, and the shorter time between innovation and production has led to increasing numbers of obsolete products. It has thus become necessary to recover some materials from old computers and to protect the environment from a new type of pollution. Such recycling is difficult because of the diversity of polymeric materials used, e.g., thermoplastics (polystyrene or acrylonitrile-butadiene-styrene) and thermosets (epoxy resins), and the relatively high levels of flame retardants (halogen- and nitrogen-containing compounds) added during production. Pyrolysis seems to be a suitable way to recover materials and energy from such waste without component separation if an efficient method for reducing toxic compounds can be applied. In this study, the pyrolysis of plastic and thermoset fractions (keyboards, casings, printed circuit boards, and mixtures thereof) of used computers was studied by thermogravimetry and batch reactor pyrolysis. The degradation products were separated into three fractions, solid, liquid, and gaseous, each of them being characterized by suitable methods such as gas chromatography (GC-MSD, gas chromatography-mass spectrometry detection; GC-AED, gas chromatography-atomic emission detection), infrared (FT-IR) and 1H-NMR (nuclear magnetic resonanace) spectroscopy, and elemental analysis. It has been established that most of the halogens, nitrogen, and sulfur is concentrated in the residue. However, the elimination of hazardous toxic compounds, mainly those containing bromine, is necessary before being able to safely use the pyrolysis oils as fuels or in refinery or petrochemical industry flows.     

Status quo of e-waste management in mainland China

In China, the use and obsolescence of both electronic and electrical equipment have increased rapidly in recent years. China has also begun to take measures to cope with this problem since it began experiencing a rapid process of industrialization and urbanization in the 1990s. In this paper, the profile of the electrical and electronic waste (e-waste) problem in China is depicted from such aspects as domestic e-waste and imported e-waste, along with their recycling systems, policies, and regulations. Based on statistics of the consumption of major household appliances and personal computers, a forecast is made of the numbers of obsolete major household appliances and personal computers. The results show that currently the number of electrical and electronic products in use in China is tremendous. An investigation on household appliances and personal computers in Beijing was made to assess the use and obsolescence of these products. Also, the legal issues relating to e-waste in China are summarized, and these will be the juristic foundation for the solution of e-waste problems.     

Pulverization of waste printed circuit boards

A new pulverization method to reduce the volume of waste printed circuit boards is reported. About 50% of printed circuit boards with integrate circuits (ICs) could be pulverized by our method in one 20-min batch, but boards without ICs could not be pulverized. By repeating the process three times, about 95% of printed circuit boards with ICs could be made into a fine powder with particles less than 106µm. A weight-drop test was also performed to examine the strength of the printed circuit boards and clarify the mechanism of pulverization. When a weight was dropped on the solder-welding side of the board ruptures occurred more easily than when the weight was dropped on the IC-mounted side. With a heavy weight, the IC was fractured more easily when the potential energy was low. Where the stress was concentrated, two types of rupture location were found on printed circuit boards with ICs. One was where the IC was connected to the printed circuit board. The other was where the surface had undulations. It also became clear that the fracture of printed circuit boards depends on the impacting weight rather than on the potential energy.     

Characterization of air emissions and residual ash from open burning of electronic wastes during simulated rudimentary recycling operations

Air emissions and residual ash samples were collected and analyzed during experiments of open, uncontrolled combustion of electronic waste (e-waste), simulating practices associated with rudimentary e-waste recycling operations. Circuit boards and insulated wires were handled separately to simulate processes associated with metal recovery. The average emissions of polychlorinated dibenzodioxins and dibenzofurans (PCDD/PCDFs) were 92 ng toxic equivalency (TEQ)/kg [n = 2, relative standard deviation (RSD) = 98%] and 11 900 ng TEQ/kg (n = 3, RSD = 50%) of the initial mass of the circuit boards and insulated wire, respectively. The value for the insulated wire is about 100 times higher than that for backyard barrel burning of domestic waste. The emission concentrations of polybrominated dibenzodioxins and dibenzofurans (PBDD/PBDFs) from the combustion of circuit boards were 100 times higher than for their polychlorinated counterparts. Particulate matter (PM) sampling of the fly ash emissions indicated PM emission factors of approximately 15 and 17 g/kg of the initial mass for the circuit boards and insulated wire, respectively. Fly ash samples from both types of e-waste contained considerable amounts of several metallic elements and halogens; lead concentrations were more than 200 times the United States regulatory limits for municipal waste combustors and 20 times those for secondary lead smelters. Leaching tests of the residual bottom ash showed that lead concentrations exceeded U.S. Environmental Protection Agency landfill limits, designating this ash as a hazardous waste.     

废旧电路板上残留焊锡剥离液的研制

以硝酸-磺酸型退锡剂为基础配方,研制了一种脱除废旧电路板表面残留焊锡的剥离液.该剥离液以硝酸为氧化剂,氨基磺酸为稳定剂,苯并三氮唑为铜的缓蚀剂.实验结果表明:剥离液的最佳配比为硝酸浓度3 mol/L,氨基磺酸浓度0.4 mol/L,苯并三氮唑浓度0.08 mol/L;每升剥离液可处理3.5 kg废旧电路板,处理后电路板中的铅离子含量降至100 mg/kg以下.该剥离液处理后的电路板表面的铜箔保持完好,基本没有被剥离液浸蚀.     

Characterization of shredded television scrap and implications for materials recovery

Characterization of TV scrap was carried out by using a variety of methods, such as chemical analysis, particle size and shape analysis, liberation degree analysis, thermogravimetric analysis, sink-float test, and IR spectrometry. A comparison of TV scrap, personal computer scrap, and printed circuit board scrap shows that the content of non-ferrous metals and precious metals in TV scrap is much lower than that in personal computer scrap or printed circuit board scrap. It is expected that recycling of TV scrap will not be cost-effective by utilizing conventional manual disassembly. The result of particle shape analysis indicates that the non-ferrous metal particles in TV scrap formed as a variety of shapes; it is much more heterogeneous than that of plastics and printed circuit boards. Furthermore, the separability of TV scrap using density-based techniques was evaluated by the sink-float test. The result demonstrates that a high recovery of copper could be obtained by using an effective gravity separation process. Identification of plastics shows that the major plastic in TV scrap is high impact polystyrene. Gravity separation of plastics may encounter some challenges in separation of plastics from TV scrap because of specific density variations.     

A preliminary categorization of end-of-life electrical and electronic equipment as secondary metal resources

End-of-life electrical and electronic equipment (EEE) has recently received attention as a secondary source of metals. This study examined characteristics of end-of-life EEE as secondary metal resources to consider efficient collection and metal recovery systems according to the specific metals and types of EEE. We constructed an analogy between natural resource development and metal recovery from end-of-life EEE and found that metal content and total annual amount of metal contained in each type of end-of-life EEE should be considered in secondary resource development, as well as the collectability of the end-of-life products. We then categorized 21 EEE types into five groups and discussed their potential as secondary metal resources. Refrigerators, washing machines, air conditioners, and CRT TVs were evaluated as the most important sources of common metals, and personal computers, mobile phones, and video games were evaluated as the most important sources of precious metals. Several types of small digital equipment were also identified as important sources of precious metals; however, mid-size information and communication technology (ICT) equipment (e.g., printers and fax machines) and audio/video equipment were shown to be more important as a source of a variety of less common metals. The physical collectability of each type of EEE was roughly characterized by unit size and number of end-of-life products generated annually. Current collection systems in Japan were examined and potentially appropriate collection methods were suggested for equipment types that currently have no specific collection systems in Japan, particularly for video games, notebook computers, and mid-size ICT and audio/video equipment.     

Hydrometallurgical treatment of used printed circuit boards after thermal treatment

The hydrometallurgical route of copper and tin extraction from printed circuit boards (PCB) of used personal computers after thermal pretreatment is discussed. The PCB fractions crushed and sorted into −8 + 0, −8 + 3 and −3 + 0 mm were used for the experiments. The samples were thermally pretreated at temperatures of 300, 500, 700 and 900 °C during 15, 30 and 60 min with the presence of air (burning) before the leaching process.The leaching solution of 1 M HCl and temperature of 80 °C was used for the leaching. The original as well as thermally pretreated samples were leached under these conditions.The weight losses within the range from 5% to 35% were achieved by burning depending on the burning temperature. The increase of burning temperature causes the copper extraction into solution up to 98%, while copper extraction into solution from non-burned samples was up to 6%. The opposite effect was observed in the case of the tin leaching, where the highest extraction was achieved when the original sample was leached. The increase of the burning temperature caused the lowering of the copper extraction.     

废弃印刷线路板资源化处理的研究进展

介绍了当前废弃印刷线路板资源化处理的主要方法，包括湿法、火法、机械法、生物法、超临界流体法和等离子体熔炼法等。综述了各种处理方法的侧重点及利弊；提出热解法与机械法联用可较好地解决在破碎过程中所遇到的问题，具有较大优势，可作为未来大量废弃印刷线路板资源化处理工艺研究的重点。     

Assessment of toxic metals in waste personal computers

Considering the enormous production of waste personal computers nowadays, it is obvious that the study of their composition is necessary in order to regulate their management and prevent any environmental contamination caused by their inappropriate disposal. This study aimed at determining the toxic metals content of motherboards (printed circuit boards), monitor glass and monitor plastic housing of two Cathode Ray Tube (CRT) monitors, three Liquid Crystal Display (LCD) monitors, one LCD touch screen monitor and six motherboards, all of which were discarded. In addition, concentrations of chromium (Cr), cadmium (Cd), lead (Pb) and mercury (Hg) were compared with the respective limits set by the RoHS 2002/95/EC Directive, that was recently renewed by the 2012/19/EU recast, in order to verify manufacturers’ compliance with the regulation. The research included disassembly, pulverization, digestion and chemical analyses of all the aforementioned devices. The toxic metals content of all samples was determined using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). The results demonstrated that concentrations of Pb in motherboards and funnel glass of devices with release dates before 2006, that is when the RoHS Directive came into force, exceeded the permissible limit. In general, except from Pb, higher metal concentrations were detected in motherboards in comparison with plastic housing and glass samples. Finally, the results of this work were encouraging, since concentrations of metals referred in the RoHS Directive were found in lower levels than the legislative limits.     

Leaching of heavy metals from E-waste in simulated landfill columns

In recent history the volume of electronic products purchased by consumers has dramatically escalated. As a result this has produced an ever-increasing electronic waste (E-waste) stream, which has generated concerns regarding the E-waste’s potential for adversely impacting the environment. The leaching of toxic substances from obsolete personal computers (PCs) and cathode ray tubes (CRTs) of televisions and monitors, which are the most significant components in E-waste stream, was studied using landfill simulation in columns. Five columns were employed. One column served as a control which was filled with municipal solid waste (MSW), two columns were filled with a mixture of MSW and CRTs, and the other two were filled with MSW and computer components including printed wire boards, hard disc drives, floppy disc drives, CD/DVD drives, and power supply units. The leachate generated from the columns was monitored for toxic materials throughout the two-year duration of the study. Results indicate that lead (Pb) and various other heavy metals that were of environmental and health concern were not detected in the leachate from the simulators. When the samples of the solids were collected from underneath the E-waste in the columns and were analyzed, significant amount of Pb was detected. This indicates that Pb could readily leach from the E-waste, but was absorbed by the solids around the E-waste materials. While Pb was not observed in the leachate in this study, it is likely that the Pb would eventually enter the leachate after a long term transport.     

Resource-availability scenario analysis for formal and informal recycling of end-of-life electrical and electronic equipment in China

In strategic end-of-life electrical and electronic equipment (EoL EEE) management, it has become important to not only avoid the negative environmental impacts but also enhance the positive effects of secondary resource utilization. This is especially true in emerging countries such as China, where medium- to long-term increases in the amount of EoL EEE generation are projected. This study aims to assess the resource availability potential for EoL EEE recycling based on penetration scenarios for formal and/or informal treatment options in China. We categorized substances contained in EoL television sets and personal computers into environmental, resource, and economic aspects under consideration of product transitions. Barium and copper have a high negative potential impact on human health and/or the ecosystem. Focusing on metals with a high resource potential, the resource availability is assessed under different treatment options using characterization factors identified through a life-cycle impact assessment method, the ReCiPe 2008. The results suggest that copper and lead recycling could alleviate the increase in mining costs of resource utilization. Scenario analysis for penetration of formal and informal recycling options indicated that the difference in the alleviated mining costs between the status quo and short-term transition projections until 2030 corresponds to 2.1–2.4 billion dollars.     

Distribution of copper,silver and gold during thermal treatment with brominated flame retardants

The growing consumption of electric and electronic equipment results in creating an increasing amount of electronic waste. The most economically and environmentally advantageous methods for the treatment and recycling of waste electric and electronic equipment (WEEE) are the thermal techniques such as direct combustion, co-combustion with plastic wastes, pyrolysis and gasification. Nowadays, this kind of waste is mainly thermally treated in incinerators (e.g. rotary kilns) to decompose the plastics present, and to concentrate metals in bottom ash. The concentrated metals (e.g. copper, precious metals) can be supplied as a secondary raw material to metal smelters, while the pyrolysis of plastics allows the recovery of fuel gases, volatilising agents and, eventually, energy. Indeed, WEEE, such as a printed circuit boards (PCBs) usually contains brominated flame retardants (BFRs). From these materials, hydrobromic acid (HBr) is formed as a product of their thermal decomposition.In the present work, the bromination was studied of copper, silver and gold by HBr, originating from BFRs, such as Tetrabromobisphenol A (TBBPA) and Tetrabromobisphenol A-Tetrabromobisophenol A diglycidyl ether (TTDE) polymer; possible volatilization of the bromides formed was monitored using a thermo-gravimetric analyzer (TGA) and a laboratory-scale furnace for treating samples of metals and BFRs under an inert atmosphere and at a wide range of temperatures. The results obtained indicate that up to about 50% of copper and silver can evolve from sample residues in the form of volatile CuBr and AgBr above 600 and 1000 °C, respectively. The reactions occur in the molten resin phase simultaneously with the decomposition of the brominated resin. Gold is resistant to HBr and remains unchanged in the residue.     

The separation of waste printed circuit board by dissolving bromine epoxy resin using organic solvent

Separation of waste printed circuit boards (WPCBs) has been a bottleneck in WPCBs resource processing. In this study, the separation of WPCBs was performed using dimethyl sulfoxide (DMSO) as a solvent. Various parameters, which included solid to liquid ratio, temperature, WPCB sizes, and time, were studied to understand the separation of WPCBs by dissolving bromine epoxy resin using DMSO. Experimental results showed that the concentration of dissolving the bromine epoxy resin increased with increasing various parameters. The optimum condition of complete separation of WPCBs was solid to liquid ratio of 1:7 and WPCB sizes of 16 mm² at 145 °C for 60 min. The used DMSO was vapored under the decompression, which obtained the regenerated DMSO and dissolved bromine epoxy resin. This clean and non-polluting technology offers a new way to separate valuable materials from WPCBs and prevent the environmental pollution of waste printed circuit boards effectively.     

Correction to: An automated assessment method for integrated circuit chip detachment from printed circuit board by multistep binarization and template matching of X-ray transmission images

Given the increase in digital product waste, demand for recycling of printed circuit boards (PCBs) is increasing. Precious and minor metals are often well concentrated in integrated circuit (IC) chips, especially in PCBs; hence, IC chips are primary targets for recycling. The technology for the non-destructive detachment of IC chips from PCBs is increasing in sophistication; however, the effectiveness of IC chip detachment is currently assessed manually and visually. In the present study, an automated IC chip detachment assessment method was developed, which combines multistep binarization and template matching of X-ray transmission images of crushed PCBs. To validate the method, five types of mechanically crushed PCBs from mobile phones were examined, and the developed method successfully assessed the IC chip detachment rate, with an average error rate of only 2.2% compared to visual assessment.

     

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...