废印刷线路板资源化研究进展

从废印刷线路板(WPCBs)层间热固性树脂的角度出发,将WPCBs资源化处理技术归纳为热固性树脂直接回收法、热固性树脂分解法和热固性树脂溶胀法,并对现有资源化技术进行总结,同时对将来研究方向进行了展望,为WPCBs资源化产业化发展提供参考。     

废旧线路板非金属材料综合利用

随着信息时代的到来,废印刷线路板处理技术日益成熟,大量的废线路板非金属粉亟需处理。从环境保护和资源回收的角度,综述了废印刷线路板非金属粉的资源化利用。     

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.     

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.     

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.     

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.     

Prioritizing material recovery for end-of-life printed circuit boards

The increasing growth in generation of electronic waste (e-waste) motivates a variety of waste reduction research. Printed circuit boards (PCBs) are an important sub-set of the overall e-waste stream due to the high value of the materials contained within them and potential toxicity. This work explores several environmental and economic metrics for prioritizing the recovery of materials from end-of-life PCBs. A weighted sum model is used to investigate the trade-offs among economic value, energy saving potentials, and eco-toxicity. Results show that given equal weights for these three sustainability criteria gold has the highest recovery priority, followed by copper, palladium, aluminum, tin, lead, platinum, nickel, zinc, and silver. However, recovery priority will change significantly due to variation in the composition of PCBs, choice of ranking metrics, and weighting factors when scoring multiple metrics. These results can be used by waste management decision-makers to quantify the value and environmental savings potential for recycling technology development and infrastructure. They can also be extended by policy-makers to inform possible penalties for land-filling PCBs or exporting to the informal recycling sector. The importance of weighting factors when examining recovery trade-offs, particularly for policies regarding PCB collection and recycling are explored further.     

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.     

Leaching of metals from printed circuit boards using ionic liquids

Journal of Material Cycles and Waste Management - The rise in the electronics industry has impacted the environment through the large volumes of waste that are improperly disposed of and the...     

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.     

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.     

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.     

废弃印刷线路板中环氧树脂的资源化技术

印刷线路板是电子工业的基础,伴随着电子废弃物的快速增长,废弃印刷线路板的回收已经成为迫切需要研究的领域。对废弃印刷线路板中环氧树脂常用的资源化方法、物理法、热解法、超临界法及化学溶剂法等进行了介绍,并比较了几种方法的优缺点。     

Thermal decomposition of tetrabromobisphenol-A containing printed circuit boards in the presence of calcium hydroxide

Journal of Material Cycles and Waste Management - Recycling of printed circuit boards (PCBs) is complicated by the presence of flame retardants containing halogen and phosphorus, as the degradation...     

Thiourea leaching gold and silver from the printed circuit boards of waste mobile phones

The present communication deals with the leaching of gold and silver from the printed circuit boards (PCBs) of waste mobile phones using an effective and less hazardous system, i.e., a thiourea leaching process as an alternative to the conventional and toxic cyanide leaching of gold. The influence of particle size, thiourea and Fe(3+) concentrations and temperature on the leaching of gold and silver from waste mobile phones was investigated. Gold extraction was found to be enhanced in a PCBs particle size of 100 mesh with the solutions containing 24 g/L thiourea and Fe(3+) concentration of 0.6% under the room temperature. In this case, about 90% of gold and 50% of silver were leached by the reaction of 2h. The obtained data will be useful for the development of processes for the recycling of gold and silver from the PCBs of waste mobile phones.     

Recycling of printed circuit boards: ultrasound-assisted comminution and leaching for metals recovery

Journal of Material Cycles and Waste Management - The increase of electronic equipment consumption associated makes the recycling process crucial worldwide. Use of emerging technologies for...     

A new strain for recovering precious metals from waste printed circuit boards

A new strain, Pseudomonas Chlororaphis (PC), was found for dissolving gold, silver, and copper from the metallic particles of crushed waste printed circuit boards (PCBs). The optimized conditions that greatly improved the ability of producing CN^? (for dissolving metals) were obtained. Dissolving experiments of pure gold, silver, and copper showed that the metals could be changed into Au⁺, Ag⁺, and Cu²⁺. PC cells and their secreta would adsorb metallic ions. Meanwhile, metallic ions destroyed the growth of PC. Dissolving experiments of metallic particles from crushed waste PCBs were performed by PC. The results indicated that 8.2% of the gold, 12.1% silver, and 52.3% copper were dissolved into solution. This paper contributed significance information to recovering precious metals from waste PCBs by bioleaching.     

Combustion and inorganic bromine emission of waste printed circuit boards in a high temperature furnace

High temperature combustion experiments of waste printed circuit boards (PCBs) were conducted using a lab-scale system featuring a continuously-fed drop tube furnace. Combustion efficiency and the occurrence of inorganic bromine (HBr and Br₂) were systematically studied by monitoring the main combustion products continuously. The influence of furnace temperature (T) was studied from 800 to 1400 °C, the excess air factor (EAF) was varied from 1.2 to 1.9 and the residence time in the high temperature zone (RT_HT) was set at 0.25, 0.5, or 0.75 s.Combustion efficiency depends on temperature, EAF and RT_HT; temperature has the most significant effect. Conversion of organic bromine from flame retardants into HBr and Br₂ depends on temperature and EAF. Temperature has crucial influence over the ratio of HBr to Br₂, whereas oxygen partial pressure plays a minor role. The two forms of inorganic bromine seem substantially to reach thermodynamic equilibrium within 0.25 s. High temperature is required to improve the combustion performance: at 1200 °C or higher, an EAF of 1.3 or more, and a RT_HT exceeding 0.75 s, combustion is quite complete, the CO concentration in flue gas and remained carbon in ash are sufficiently low, and organobrominated compounds are successfully decomposed (more than 99.9%).According to these results, incineration of waste PCBs without preliminary separation and without additives would perform very well under certain conditions; the potential precursors for brominated dioxins formation could be destroyed efficiently. Increasing temperature could decrease the volume percentage ratio of Br₂/HBr in flue gas greatly.