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.     

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.     

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.     

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.     

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.     

Recycling-oriented characterization of plastic frames and printed circuit boards from mobile phones by electronic and chemical imaging

This study characterizes the composition of plastic frames and printed circuit boards from end-of-life mobile phones. This knowledge may help define an optimal processing strategy for using these items as potential raw materials. Correct handling of such a waste is essential for its further “sustainable” recovery, especially to maximize the extraction of base, rare and precious metals, minimizing the environmental impact of the entire process chain. A combination of electronic and chemical imaging techniques was thus examined, applied and critically evaluated in order to optimize the processing, through the identification and the topological assessment of the materials of interest and their quantitative distribution. To reach this goal, end-of-life mobile phone derived wastes have been systematically characterized adopting both “traditional” (e.g. scanning electronic microscopy combined with microanalysis and Raman spectroscopy) and innovative (e.g. hyperspectral imaging in short wave infrared field) techniques, with reference to frames and printed circuit boards. Results showed as the combination of both the approaches (i.e. traditional and classical) could dramatically improve recycling strategies set up, as well as final products recovery.     

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。     

Chemical composition and liberation characterization of printed circuit board comminution fines for beneficiation investigations

Chemical composition and liberation are critical attributes in characterizing a resource stock for beneficiation investigations. Though end-of-life printed circuit board is recognized as a valuable secondary resource stock, no procedural standard exists for the determination of its chemical composition, nor for the ?75 μm fines generated during its comminution. The effect of the digestion procedure on the final assays in wet spectroscopic analyses was assessed in this work. Liberation was also explored against literature background. Determination of assays of all constituent elements in printed circuit board comminution fines was found to require comparison of data from more than one digestion condition, while composite particles still persist at the fines sizes, though very few. The discussion reflects how these impact the beneficiation investigations.     

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.     

EGSB-CASS-生物滤池工艺处理天然橡胶加工废水

根据某天然橡胶加工企业生产废水的水质特点,采用EGSB-CASS-生物滤池工艺处理天然橡胶加工废水。工程运行结果表明,该工艺对CODCr、氨氮、SS平均去除率分别达到97％,94％,90％,出水水质符合GB8978-1996《污水综合排放标准》一级标准。     

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

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

废弃印刷线路板中材料的资源化回收利用技术

废弃印刷线路板（WPCBs）既有污染环境的一面,又有可资源化回收利用的一面.通过机械物理法、热解、超临界流体氧化和离子液体溶解等方法对其进行分离和回收金属和非金属材料.初步分选的金属需要进一步提纯以实现高附加值.而非金属材料可以用热解法、微波处理、超临界流体技术、等离子技术等技术进行产气和能量回收,也可以通过制备建筑材料或填料和其它功能村料进行物料回收.总之,对WPCBs进行适当地处理不但可以减轻环境压力,还可以变废为宝,实现资源再生利用.     

Utilization of magnetic and electrostatic separation in the recycling of printed circuit boards scrap

The progress of the technology is directly related to the growth of production and consumption of electrical/electronics equipment, especially of personal computers. This type of equipment has a relatively short average lifetime, 2-3 years. The amount of defective or obsolete equipment has been increasing substantially; consequently its disposition and/or recycling should be studied. In this work, printed circuit boards, which are used in personal computers, were studied in order to recover the metals in the circuit boards through mechanical processing, such as crushing, screening, as well as magnetic and electrostatic separation. The results obtained demonstrate the feasibility of using these processes to separate metal fractions from polymers and ceramics, and that it is possible to obtain a fraction concentrated in metals containing more than 50% on average of copper, 24% of tin and 8% of lead.     

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.     

Thermal decomposition of electronic wastes: mobile phone case and other parts

Pyrolysis and combustion runs at 850°C in a horizontal laboratory furnace were carried out on different parts of a mobile phone (printed circuit board, mobile case and a mixture of both materials). The analyses of the carbon oxides, light hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), polychlorodibenzo-p-dioxin, polychlorodibenzofurans (PCDD/Fs), and dioxin-like PCBs are shown. Regarding semivolatile compounds, phenol, styrene, and its derivatives had the highest yields. In nearly all the runs the same PAHs were identified, naphthalene being the most common component obtained. Combustion of the printed circuit board produced the highest emission factor of PCDD/Fs, possibly due to the high copper content.     

从废印制电路板元器件中分离电容器的方法

以典型废印制电路板湿法剥离得到的元器件为研究对象,通过筛分和磁选相结合的物理方法,分离其中的电容器。研究发现,筛分后电容器分布在9.5-19 mm和4.0-9.5 mm范围内,并且50%以上的元器件与电容器得到分离。9.5-19 mm范围内的元器件经过磁选,可以将强磁性的铜线绕阻类元器件分离出来,剩余元器件采用8 mm宽的条形筛进行筛分,筛上物主要为电容器,筛下物主要为芯片和引脚;4.0-9.5 mm范围内的元器件经过磁选,可以将92.93%的电容器分离出来。     

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.     

Quantitative characterization of recyclable resources dismantled from waste liquid crystal display products

Currently only limited materials, such as common metals and plastics, are recovered from waste flat-panel displays, thus necessitating the development of a comprehensive recycling process. This study aims to establish a statistical database about the types and amounts of valuable resources in waste liquid crystal display (LCD) products. To obtain these data, the waste LCD products were disassembled into four components: plastics, printed circuit boards, metals, and other materials, including their panels, and the weight of each component was measured. Overall, the product weight decreased with increasing manufacturing year regardless of the product screen size; however, the decreasing rate varied from 14 to 73%. The metal weight ratios decreased significantly by 24–31%. Meanwhile, regardless of the manufacturing year, the plastic weight ratios remained almost constant at about 20%. On the other hand, the weight ratio of the other components increased by 26–46% with increasing manufacturing year suggesting that rare-earth metal recycling has become more important. These statistical analyses are expected to contribute to the development of an eco-friendly, high-efficiency dismantling/separation process that will enable higher value recycling and minimal waste disposal.     

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.     

The general utilization of scrapped PC board

The traditional burning process is used to recover copper from scrapped PC board (printed circuit board) but it causes serious environmental problems. In this research a new process was developed which not only prevents pollution problems, but also maximizes the utility of all the materials on the waste board. First, the scrapped PC board was crushed and grounded, then placed in the NH₃/NH₅CO₃ solution with aeration in order to dissolve copper. After distilling the copper NH₃/NH₅CO₃ solution and then heating the distilled residue of copper carbonate, pure copper oxide was obtained with particle size of about 0.2 μm and the shape elliptical. The remaining solid residue after copper removal was then leached with 6 N hydrochloric acid to remove tin and lead. The last residue was used as a filler in PVC plastics. The PVC plastics with PC board powder as filling material was found to have the same tensile strength as unfilled plastics, but had higher elastic modulus, higher abrasion resistance, and was cheaper.