Report: recycling of flame-retarded plastics from waste electric and electronic equipment (WEEE).

Shredder residues produced in plants processing waste electric and electronic equipment are excluded from material recycling due to a variety of polymeric materials and the presence of brominated flame retardants (BFR), which might contain banned polybrominated diphenyl ethers or toxic polybrominated dioxins and furans (PBDD/F). Herein we present a technological approach to transfer a significant portion of the shredder residue into recycled polymers. The technological approach consists of a density-based enrichment of styrenics, which are subjected to a solvolysis process (CreaSolv process) in a second stage. This stage allows the elimination of non-target polymers and extraction of BFR and PBDD/F. Pilot processing of 11.5 and 50 kg shredder residues indicated a material yield of about 50% in the density stage and 70-80% in the CreaSolv process, and an effective removal of BFR additives. The recycled products were proved to comply with threshold values defined by the European directive on the restriction of hazardous substances (RoHS) and the German Chemikalienverbotsverordnung. Mechanical material properties exhibited high tensile and flexural modules as well as slight impact strength, which qualify the products for applications in new electronic equipment.     

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.     

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.     

Survey of mercury,cadmium and lead content of household batteries

The objective of this work was to provide updated information on the development of the potential impact of heavy metal containing batteries on municipal waste and battery recycling processes following transposition of the new EU Batteries Directive 2006/66/EC. A representative sample of 146 different types of commercially available dry and button cells as well as lithium-ion accumulators for mobile phones were analysed for their mercury (Hg)-, cadmium (Cd)- and lead (Pb)-contents. The methods used for preparing the cells and analysing the heavy metals Hg, Cd, and Pb were either developed during a former study or newly developed. Several batteries contained higher mass fractions of mercury or cadmium than the EU limits. Only half of the batteries with mercury and/or lead fractions above the marking thresholds were labelled. Alkaline–manganese mono-cells and Li-ion accumulators, on average, contained the lowest heavy metal concentrations, while zinc–carbon batteries, on average, contained the highest levels.     

Management of waste electrical and electronic equipment in two EU countries: A comparison

The paper presents some data regarding waste electrical and electronic (WEEE) management in one of the founding countries of the EU, Italy, and in a recent entry into the EU, Romania. The aim of this research was to analyze some problems that countries entering the EU will have to solve with respect to WEEE management. The experiences of Italy and Romania could provide an interesting reference point. The strengths and weaknesses that the two EU countries have encountered can be used in order to give a more rational plan for other countries. In Italy the increase of WEEE collection was achieved in parallel with the increase of the efficiency of selective Municipal Solid Waste collection. In Romania, pilot experiences were useful to increase the awareness of the population. The different interests of the two populations towards recyclable waste led to a different scenario: in Romania all types of WEEE have been collected since its entrance into the EU; in Italy the “interest” in recycling is typically related to large household appliances, with a secondary role of lighting equipment.     

Waste electrical and electronic equipment (WEEE) management in Korea: generation, collection, and recycling systems

In Korea, generation of waste electrical and electronic equipment (WEEE), or electronic waste (e-waste), has rapidly increased in recent years. The management of WEEE has become a major issue of concern for solid waste communities due to the volumes of waste being generated and the potential environmental impacts associated with the toxic chemicals found in most electronic devices. Special attention must be paid when dealing with WEEE because of toxic materials that it contains (e.g., heavy metals, polybrominated diphenyl ethers, phthalates, and polyvinyl chloride). If managed improperly, the disposal of WEEE can adversely affect the environment and human health. Environmental regulatory agencies; electronic equipment manufacturers, retailers, and recyclers; environmental nongovernmental organizations; and many others are much interested in updated statistics with regard to how much WEEE is generated, stored, recycled, and disposed of. In Korea, an extended producer responsibility policy was introduced in 2003 not only to reduce the amount of electronic products requiring disposal, but also to promote resource recovery from WEEE; the policy currently applies to a total of ten electrical and electronic product categories. This article presents an overview of the current recycling practices and management of electrical and electronic waste in Korea. Specifically, the generation rates, recycling systems and processes, and recent regulations of WEEE are discussed. We estimated that 1 263 000 refrigerators, 701 000 washing machines, 1 181 000 televisions, and 109 000 airconditioning units were retired and handled by the WEEE management system in 2006. More than 40% of the products were collected and recycled by producers. Four major producers’ recycling centers and other WEEE recycling facilities are currently in operation, and these process a large faction of WEEE for the recovery of valuable materials. Much attention should still be paid to pollution prevention and resource conservation with respect to WEEE. Several suggestions are made in order to deal with electronic waste management problems effectively and to prevent potential impacts.     

锌冶炼烟气制酸废水中汞的测定

采用冷原子吸收光度法测定经石灰乳和铁盐处理后的锌冶炼烟气制酸废水中汞的浓度时,可按废水中汞浓度与其pH的关系,从试样pH的高低大致估计其汞浓度范围,由此确定其稀释倍数和取样量。试样用KBrO3-KBr消解法消解,用直接法稀释,这样可以减少操作步骤、缩短测定周期、减少样品中汞的损失、提高监测结果的可靠性和准确性,同时可减少人力、物力浪费,降低监测成本。     

Metals, non-metals and PCB in electrical and electronic waste--actual levels in Switzerland

The chemical composition of waste of small electrical and electronic equipment (s-WEEE), a rapidly growing waste stream, was determined for selected metals (Cu, Sb, Hg etc.) and non-metals (Cl, Br, P) and PCBs. During a 3-day experiment, all output products and the s-WEEE input mass flows in a WEEE recycling plant were measured. Only output products were sampled and analyzed. Material balances were established, applying substance flow analysis (SFA). Transfer coefficients for the selected substances were also determined. The results demonstrate the capability of SFA to determine the composition of the highly heterogeneous WEEE for most substances with rather low uncertainty (2 sigma +/- 30%). The results confirm the growing importance of s-WEEE regarding secondary resource metals and potential toxic substances. Nowadays, the thirty times smaller s-WEEE turns over larger flows for many substances, compared to municipal solid waste. Transfer coefficient results serve to evaluate the separation efficiency of the recycling process and confirm--with the exception of PCB and Hg--the limitation of hand-sorting and mechanical processing to separate pollutants (Cd, Pb, etc.) out of reusable fractions. Regularly applied SFA would serve to assess the efficacy of legislative, organizational and technical measures on the WEEE.     

Investigation on the heavy-metal content of zinc-air button cells

Within the framework of a German government project (initiated by the Federal Environment Agency) to check the compliance of commercially available batteries with the German Battery Ordinance concerning their heavy metal contents, 18 different types of commercially available zinc-air button cells were analysed for their cadmium, lead and mercury contents. After microwave assisted dissolution with aqua regia, Cd and Pb were determined using inductively coupled plasma mass spectrometry (ICP-MS), and Hg was determined using inductively coupled plasma optical emission spectrometry (ICP OES) and atomic absorption spectrometry. Cd contents were found to be much lower than the permitted limits; Pb contents were also found to be below the limits. Hg contents were found to be near the limits, and in one case the limit was exceeded.     

New characterisation method of electrical and electronic equipment wastes (WEEE)

Innovative separation and beneficiation techniques of various materials encountered in electrical and electronic equipment wastes (WEEE) is a major improvement for its recycling. Mechanical separation-oriented characterisation of WEEE was conducted in an attempt to evaluate the amenability of mechanical separation processes. Properties such as liberation degree of fractions (plastics, metals ferrous and non-ferrous), which are essential for mechanical separation, are analysed by means of a grain counting approach. Two different samples from different recycling industries were characterised in this work. The first sample is a heterogeneous material containing different types of plastics, metals (ferrous and non-ferrous), printed circuit board (PCB), rubber and wood. The second sample contains a mixture of mainly plastics. It is found for the first sample that all aluminium particles are free (100%) in all investigated size fractions. Between 92% and 95% of plastics are present as free particles; however, 67% in average of ferromagnetic particles are liberated. It can be observed that only 42% of ferromagnetic particles are free in the size fraction larger than 20 mm. Particle shapes were also quantified manually particle by particle. The results show that the particle shapes as a result of shredding, turn out to be heterogeneous, thereby complicating mechanical separation processes. In addition, the separability of various materials was ascertained by a sink–float analysis and eddy current separation. The second sample was separated by automatic sensor sorting in four different products: ABS, PC–ABS, PS and rest product. The fractions were characterised by using the methodology described in this paper. The results show that the grade and liberation degree of the plastic products ABS, PC–ABS and PS are close to 100%. Sink–float separation and infrared plastic identification equipment confirms the high plastic quality. On the basis of these findings, a global separation flow sheet is proposed to improve the plastic separation of WEEE.     

Review of Italian experience on automotive shredder residue characterization and management

Automotive Shredder Residue (ASR) is a special waste that can be classified as either hazardous or non hazardous depending on the amount of hazardous substances and on the features of leachate gathered from EN12457/2 test. However both the strict regulation concerning landfills and the EU targets related to End-of-Life Vehicles (ELVs) recovery and recycling rate to achieve by 2015 (Directive 2000/53/EC), will limit current landfilling practice and will impose an increased efficiency of ELVs valorization. The present paper considers ELVs context in Italy, taking into account ASRs physical–chemical features and current processing practice, focusing on the enhancement of secondary materials recovery. The application in waste-to-energy plants, cement kilns or metallurgical processes is also analyzed, with a particular attention to the possible connected environmental impacts. Pyrolysis and gasification are considered as emerging technologies although the only use of ASR is debatable; its mixing with other waste streams is gradually being applied in commercial processes. The environmental impacts of the processes are acceptable, but more supporting data are needed and the advantage over (co-)incineration remains to be proven.     

Polybrominated diphenyl ethers in e-waste: Level and transfer in a typical e-waste recycling site in Shanghai,Eastern China

Very few data for polybrominated diphenyl ethers (PBDEs) were available in the electronic waste (e-waste) as one of the most PBDEs emission source. This study reported concentrations of PBDEs in e-waste including printer, rice cooker, computer monitor, TV, electric iron and water dispenser, as well as dust from e-waste, e-waste dismantling workshop and surface soil from inside and outside of an e-waste recycling plant in Shanghai, Eastern China. The results showed that PBDEs were detected in the majority of e-waste, and the concentrations of ΣPBDEs ranged from not detected to 175 g/kg, with a mean value of 10.8 g/kg. PBDEs were found in TVs made in China after 1990. The mean concentrations of ΣPBDEs in e-waste made in Korea, Japan, Singapore and China were 1.84 g/kg, 20.5 g/kg, 0.91 g/kg, 4.48 g/kg, respectively. The levels of ΣPBDEs in e-waste made in Japan far exceed the threshold limit of RoHS (1.00 g/kg). BDE-209 dominated in e-waste, accounting for over 93%. The compositional patterns of PBDEs congeners resembled the profile of Saytex 102E, indicating the source of deca-BDE. Among the samples of dust and surface soil from a typical e-waste recycling site, the highest concentrations of Σ₁₈PBDEs and BDE-209 were found in dust in e-waste, ranging from 1960 to 340,710 ng/g and from 910 to 320,400 ng/g, which were 1–2 orders of magnitude higher than other samples. It suggested that PBDEs released from e-waste via dust, and then transferred to surrounding environment.     

Recycling of WEEE plastics: a review

Electric and electronic equipment (EEE) is swiftly growing in volume, level of sophistication, and diversity. Also, it evolves briskly, moved by innovation and technical change, and draws on numerous and at times rare resources. Waste EEE (WEEE) has evolved into an important societal problem. Recycling and treating WEEE implies occupational as well as environmental hazards that are still incompletely documented. Still, second hand EEE has been exported and treated in Africa, China, and India in a precarious informal context. In developed countries, EEE recycling has been sustained by a wide range of initiatives and motives, such as sustainability, creating jobs, and the value of precious or rare metals. Current EU Directives require a steep reduction of WEEE plastics (WEEP) going to landfill. Mechanical, thermal, and feedstock recycling of WEEP are analysed and some options confronted. Plastics recycling should be weighed against the eventual risks related to their hazardous ingredients, mainly legacy brominated fire retardants and heavy metals. Another paper is related to a somewhat similar problem, yet involving a different mix of plastics: recycling plastics from automotive shredder residue.     

Estimation of end of life mobile phones generation: the case study of the Czech Republic

The volume of waste electrical and electronic equipment (WEEE) has been rapidly growing in recent years. In the European Union (EU), legislation promoting the collection and recycling of WEEE has been in force since the year 2003. Yet, both current and recently suggested collection targets for WEEE are completely ineffective when it comes to collection and recycling of small WEEE (s-WEEE), with mobile phones as a typical example. Mobile phones are the most sold EEE and at the same time one of appliances with the lowest collection rate. To improve this situation, it is necessary to assess the amount of generated end of life (EoL) mobile phones as precisely as possible. This paper presents a method of assessment of EoL mobile phones generation based on delay model. Within the scope of this paper, the method has been applied on the Czech Republic data. However, this method can be applied also to other EoL appliances in or outside the Czech Republic. Our results show that the average total lifespan of Czech mobile phones is surprisingly long, exactly 7.99 years. We impute long lifespan particularly to a storage time of EoL mobile phones at households, estimated to be 4.35 years. In the years 1990-2000, only 45 thousands of EoL mobile phones were generated in the Czech Republic, while in the years 2000-2010 the number grew to 6.5 million pieces and it is estimated that in the years 2010-2020 about 26.3 million pieces will be generated. Current European legislation sets targets on collection and recycling of WEEE in general, but no specific collection target for EoL mobile phone exists. In the year 2010 only about 3-6% of Czech EoL mobile phones were collected for recovery and recycling. If we make similar estimation using an estimated average EU value, then within the next 10 years about 1.3 billion of EoL mobile phones would be available for recycling in the EU. This amount contains about 31 tonnes of gold and 325 tonnes of silver. Since Europe is dependent on import of many raw materials, efficient recycling of EoL products could help reduce this dependence. To set a working system of collection, it will be necessary to set new and realistic collection targets.     

Precious Metals in Municipal Solid Waste Incineration Bottom Ash

Municipal solid waste incineration (MSWI) bottom ash contains economically significant levels of silver and gold. Bottom ashes from incinerators at Amsterdam and Ludwigshafen were sampled, processed, and analyzed to determine the composition, size, and mass distribution of the precious metals. In order to establish accurate statistics of the gold particles, a sample of heavy non-ferrous metals produced from 15 tons of wet processed Amsterdam ash was analyzed by a new technology called magnetic density separation (MDS). Amsterdam’s bottom ash contains approximately 10 ppm of silver and 0.4 ppm of gold, which was found in particulate form in all size fractions below 20 mm. The sample from Ludwigshafen was too small to give accurate values on the gold content, but the silver content was found to be identical to the value measured for the Amsterdam ash. Precious metal value in particles smaller than 2 mm seems to derive mainly from waste of electrical and electronic equipment (WEEE), whereas larger precious metal particles are from jewelry and constitute the major part of the economic value. Economical analysis shows that separation of precious metals from the ash may be viable with the presently high prices of non-ferrous metals. In order to recover the precious metals, bottom ash must first be classified into different size fractions. Then, the heavy non-ferrous (HNF) metals should be concentrated by physical separation (eddy current separation, density separation, etc.). Finally, MDS can separate gold from the other HNF metals (copper, zinc). Gold-enriched concentrates can be sold to the precious metal smelter and the copper-zinc fraction to a brass or copper smelter.     

A model for estimation of potential generation of waste electrical and electronic equipment in Brazil

Sales of electrical and electronic equipment are increasing dramatically in developing countries. Usually, there are no reliable data about quantities of the waste generated. A new law for solid waste management was enacted in Brazil in 2010, and the infrastructure to treat this waste must be planned, considering the volumes of the different types of electrical and electronic equipment generated.This paper reviews the literature regarding estimation of waste electrical and electronic equipment (WEEE), focusing on developing countries, particularly in Latin America. It briefly describes the current WEEE system in Brazil and presents an updated estimate of generation of WEEE. Considering the limited available data in Brazil, a model for WEEE generation estimation is proposed in which different methods are used for mature and non-mature market products.The results showed that the most important variable is the equipment lifetime, which requires a thorough understanding of consumer behavior to estimate. Since Brazil is a rapidly expanding market, the “boom” in waste generation is still to come. In the near future, better data will provide more reliable estimation of waste generation and a clearer interpretation of the lifetime variable throughout the years.     

Chemical hazards associated with treatment of waste electrical and electronic equipment

This review paper summarizes the existing knowledge on the chemical hazards associated with recycling and other end-of-life treatment options of waste electrical and electronic equipment (e-waste). The hazards arise from the presence of heavy metals (e.g., mercury, cadmium, lead, etc.), flame retardants (e.g., pentabromophenol, polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol-A (TBBPA), etc.) and other potentially harmful substances in e-waste. If improperly managed, the substances may pose significant human and environmental health risks. The review describes the potentially hazardous content of e-waste, examines the existing e-waste management practices and presents scientific data on human exposure to chemicals, workplace and environmental pollution associated with the three major e-waste management options, i.e., recycling, incineration and landfilling. The existing e-waste management practices and associated hazards are reviewed separately for developed and developing countries. Finally, based on this review, the paper identifies gaps in the existing knowledge and makes some recommendations for future research.     

Sources and levels of potentially toxic elements in the biodegradable fraction of autoclaved non-segregated household waste and its compost/digestate

Waste that reflected the average UK composition of household waste was treated by autoclaving at the three set pressure/temperature levels of 2.7 bar/130 degrees C, 6.2 bar/160 degrees C and 15.5 bar/200 degrees C. The biodegradable fraction of the autoclaved household waste (;floc') was manually separated by screening and underwent characterization for its Cd, Cr, Cu, Pb, Hg, Ni, and Zn content. Autoclaving did not guarantee the production of compost/digestate that met the UK specification for compost, BSi PAS100, without restrictions being made on the composition of the waste feedstock. Results indicate that the levels of Zn and Cd associated with floc materials alone could lead to compost limit values being exceeded. For all other potentially toxic elements (PTEs), the estimated excessive (i.e. above levels of compliance) PTEs levels for compost/digestate were mainly due to external (i.e. non-floc) materials, primarily electronic/electrical waste. Batteries may have also contributed to the high levels of Zn and Hg. In this study, for all PTEs examined, with the exception of Cd and Zn, autoclaving had a performance comparable to that of the most effective mechanical biological treatment systems.     

Measurement of odour with focus on sampling techniques

The treatment of waste and many manufacturing processes cause odour emissions. In order to prevent odours, the residents and businesses in the neighbourhood of such plants complain about odour, and it becomes necessary to reduce the emissions. To achieve that, the emissions have to be investigated and evaluated in a representative and reproducible manner. The DIN EN 13725 (2003) [DIN EN 13725. 2003. Luftbeschaffenheit--Bestimmung der Geruchsstoffkonzentration mit dynamischer Olfaktometrie--Air quality--Determination of odour concentration by dynamic olfactometry, Deutsche Fassung EN 13725:2003. Beuth Verlag, Berlin (DE)] provides a European standard for the measurement of odour. Nevertheless, the subject of sampling is not standardised; even though it has a substantial influence on the results of the measurements. In this paper, the odour measurement itself, as well as the different kinds of sampling methods (depending on the specific type of source), will be presented and discussed.     

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.