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.     

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.     

Printed wiring boards for mobile phones: characterization and recycling of copper

The popularization of mobile phones, combined with a technological evolution, means a large number of scrap and obsolete equipment are discarded every year, thereby causing economic losses and environmental pollution. In the present study, the printed wiring boards scrap of mobile phones were characterized in order to recycle some of the device components, using techniques of mechanical processing, hydrometallurgy and electrometallurgy. The use of the techniques of mechanical processing (milling, particle size classification, magnetic and electrostatic separation) was an efficient alternative to obtain a concentrated fraction (mainly iron in the magnetic fraction and copper in the conductive fraction) and another fraction containing polymers and ceramics. At the end of mechanical processing, a concentrated fraction of metals could be obtained with an average concentration of 60% copper. This concentrated fraction in metals was dissolved in aqua regia and sent to electrowinning to recover 92% of the dissolved copper. The obtained cathodes have a copper content above 95%, which demonstrates the technical feasibility of recovery of copper using the techniques of mechanical processing, hydrometallurgy and electrometallurgy.     

Present status of the recycling of waste electrical and electronic equipment in Korea

In Korea due to rapid economical growth followed by urbanisation, breakage of large traditional families into small nuclear families, continuous changes in equipment features and capabilities causes tremendous increase in sale of new electrical and electronic equipment (EEE) and decrease in sale of used EEE. Subsequently, the ever-increasing quantity of waste electrical and electronic equipment (WEEE) has become a serious social problem and threat to the environment. Therefore, the gradual increase in the generation of WEEE intensifies the interest for recycling to conserve the resources and protect the environment. In view of the above, a review has been made related to the present status of the recycling of waste electrical and electronic equipment in Korea. This paper describes the present status of generation and recycling of waste electrical and electronic equipment, namely TVs, refrigerators, washing machines, air conditioners, personal computers and mobile phones in Korea. The commercial processes and the status of developing new technologies for the recycling of metallic values from waste printed circuit boards (PCBs) is also described briefly. Since 1998, three recycling centers are in full operation to recycle WEEE such as refrigerators, washing machines and air conditioners, having the total capacity of 880,000 units/year. All waste TVs are recently recycled on commission basis by several private recycling plants. The recycling of waste personal computers and mobile phones is insignificant in comparison with the amount of estimated obsolete those. Korea has adopted and enforced the extended producer responsibility (EPR) system. Korea is making consistent efforts to improve the recycling rate to the standards indicated in the EU directives for WEEE. Especially environmentally friendly and energy-saving technologies are being developed to recycle metal values from PCBs of WEEE.     

废弃印刷线路板熔融盐气化特性:Ⅱ气化反应动力学模型

为评价不同气化方案对印刷线路板熔融盐气化的影响,针对印刷线路板的熔融盐气化反应过程建立了反应动力学模型.模型计算结果表明,气化反应体系首先发生CO、H2和焦炭的氧化反应.生成较大量的CO2和H2O2,此后反应体系内CO2和HO2与焦炭进行氧化还原反应而逐渐减少,在参加反应的焦炭被消耗完全后,反应体系随着水气变换可逆反应的平衡而达到平衡.     

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.     

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.     

废印刷电路板的静电分选实验研究

金属与非金属材料的分离是回收利用废印刷电路板的关键环节。对废印刷电路板物料的静电分选进行了实验研究。实验以电压、辊筒转速、电晕电极与辊筒之间的距离、静电极位置、电晕电极位置、电晕电极数量等为考察因素,研究各因素对电选效果的影响规律。结果表明,影响金属与非金属材料分离的主要因素是电压、辊筒转速和电晕电极与辊筒之间的距离,对于-0.9 0.45mm的破碎物料,当电压为24kV,辊筒转速为15Hz(54.6r/min),电晕电极与辊筒之间的距离为5.2cm时,得到最大静电分选综合效率67.37%。     

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.     

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.