Recycling of organic materials and solder from waste printed circuit boards by vacuum pyrolysis-centrifugation coupling technology

Here, we focused on the recycling of waste printed circuit boards (WPCBs) using vacuum pyrolysis-centrifugation coupling technology (VPCT) aiming to obtain valuable feedstock and resolve environmental pollution. The two types of WPCBs were pyrolysed at 600°C for 30 min under vacuum condition. During the pyrolysis process, the solder of WPCBs was separated and recovered when the temperature range was 400-600°C, and the rotating drum was rotated at 1000 rpm for 10 min. The type-A of WPCBs pyrolysed to form an average of 67.91 wt.% residue, 27.84 wt.% oil, and 4.25 wt.% gas; and pyrolysis of the type-B of WPCBs led to an average mass balance of 72.22 wt.% residue, 21.57 wt.% oil, and 6.21 wt.% gas. The GC-MS and FT-IR analyses showed that the two pyrolysis oils consisted mainly of phenols and substituted phenols. The pyrolysis oil can be used for fuel or chemical feedstock for further processing. The recovered solder can be recycled directly and it can also be a good resource of lead and tin for refining. The pyrolysis residues contained various metals, glass fibers and other inorganic materials, which could be recovered after further treatment. The pyrolysis gases consisted mainly of CO, CO(2), CH(4), and H(2), which could be collected and recycled.     

我国废铅蓄电池产生量与再生铅产能的讨论

废铅蓄电池是再生铅主要原料,铅蓄电池产量、进出口量、社会消费保有量,以及铅蓄电池消费使用领域与废铅蓄电池产生量有关。预测2015年废铅蓄电池产生量,并讨论我国再生铅产能规模,供再生铅产业结构调整与区域布局调整作参考。     

热解技术处理废弃电路板的研究进展

介绍了回收废弃电路板的热分离方法,综述了热解技术在废弃电路板处理中的研究现状及其所具有的优势。阐述了废弃电路板热解产物的资源价值及热解油的分离与提纯的研究现状,讨论了热解技术处理废弃电路板过程中消除剧毒有机溴化合物及HBr回收的研究进展,同时简介了真空热解技术的研究概况,并指出真空热解技术是今后处理废弃电路板的研究方向之一,有广阔的应用前景。     

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.     

Auto shredder residue recycling: Mechanical separation and pyrolysis

Directive 2000/53/EC sets a goal of 85% material recycling from end-of-life vehicles (ELVs) by the end of 2015. The current ELV recycling rate is around 80%, while the remaining waste is called automotive shredder residue (ASR), or car fluff. In Europe, this is mainly landfilled because it is extremely heterogeneous and often polluted with car fluids. Despite technical difficulties, in the coming years it will be necessary to recover materials from car fluff in order to meet the ELV Directive requirement. This study deals with ASR pretreatment and pyrolysis, and aims to determine whether the ELV material recycling target may be achieved by car fluff mechanical separation followed by pyrolysis with a bench scale reactor. Results show that flotation followed by pyrolysis of the light, organic fraction may be a suitable ASR recycling technique if the oil can be further refined and used as a chemical. Moreover, metals are liberated during thermal cracking and can be easily separated from the pyrolysis char, amounting to roughly 5% in mass. Lastly, pyrolysis can be a good starting point from a "waste-to-chemicals" perspective, but further research should be done with a focus on oil and gas refining, in order both to make products suitable for the chemical industry and to render the whole recycling process economically feasible.     

Selective separation of virgin and post-consumer polymers (PET and PVC) by flotation method

More and more polymer wastes are generated by industry and householders today. Recycling is an important process to reduce the amount of waste resulting from human activities. Currently, recycling technologies use relatively homogeneous polymers because hand-sorting waste is costly. Many promising technologies are being investigated for separating mixed thermoplastics, but they are still uneconomical and unreliable. At present, most waste polymers cause serious environmental problems. Burning polymers for recycling is not practiced since poisonous gases are released during the burning process. Particularly, polyvinyl chloride (PVC) materials among waste polymers generate hazardous HCl gas, dioxins containing Cl, etc., which lead to air pollution and shorten the life of the incinerator. In addition, they make other polymers difficult to recycle.Both polyethylene terephthalate (PET) and PVC have densities of 1.30–1.35 g/cm³ and cannot be separated using conventional gravity separation techniques. For this reason, polymer recycling needs new techniques. Among these techniques, froth flotation, which is also used in mineral processing, can be useful because of its low cost and simplicity.The main objective of this research is to recycle PET and PVC selectively from post-consumer polymer wastes and virgin polymers by using froth flotation. According to the results, all PVC particles were floated with 98.8% efficiency in virgin polymer separation while PET particles were obtained with 99.7% purity and 57.0% efficiency in post-consumer polymer separation.     

Development of waste gasification and gas reforming system for municipal solid waste (MSW)

To achieve both high-efficiency power generation and high detoxification performance, advanced-type waste power generation plants such as pyrolysis and gas reforming plants are suggested. Further surveys on actual operational data of these plants are required in terms of reliability of the system when it is introduced to waste disposal sites. To verify the technical effectiveness of advanced-type waste power generation using the pyrolysis and gas reforming method, we evaluated 10?tons/day of municipal solid wastes (MSW) treated in a demonstration plant. A demonstration test was conducted over 100?days including 35?consecutive days of operation treating MSWs. The test results show high recycling performance and harmless nature of the plant which proves it to be an excellent waste recycling system. Major test results are as follows: (1) stabilization of waste treatment is possible with the wastes of various qualities, (2) clean gas is produced from the waste whose energy recovery ratio is approximately 40?%. (3) 99.3?% weight % of dried waste are recovered as valuable materials such as clean gas, char and metal, (4) total amount of dioxin emission to the outside of the plant is very small, down to 0.0051–0.018?μg?TEQ per ton waste.     

Pyrolysis of waste tyres: A review

Approximately 1.5 billion tyres are produced each year which will eventually enter the waste stream representing a major potential waste and environmental problem. However, there is growing interest in pyrolysis as a technology to treat tyres to produce valuable oil, char and gas products. The most common reactors used are fixed-bed (batch), screw kiln, rotary kiln, vacuum and fluidised-bed. The key influence on the product yield, and gas and oil composition, is the type of reactor used which in turn determines the temperature and heating rate. Tyre pyrolysis oil is chemically very complex containing aliphatic, aromatic, hetero-atom and polar fractions. The fuel characteristics of the tyre oil shows that it is similar to a gas oil or light fuel oil and has been successfully combusted in test furnaces and engines. The main gases produced from the pyrolysis of waste tyres are H₂, C₁–C₄ hydrocarbons, CO₂, CO and H₂S. Upgrading tyre pyrolysis products to high value products has concentrated on char upgrading to higher quality carbon black and to activated carbon. The use of catalysts to upgrade the oil to a aromatic-rich chemical feedstock or the production of hydrogen from waste tyres has also been reported. Examples of commercial and semi-commercial scale tyre pyrolysis systems show that small scale batch reactors and continuous rotary kiln reactors have been developed to commercial scale.     

Recycling of non-metallic fractions from waste electrical and electronic equipment (WEEE): A review

The world’s waste electrical and electronic equipment (WEEE) consumption has increased incredibly in recent decades, which have drawn much attention from the public. However, the major economic driving force for recycling of WEEE is the value of the metallic fractions (MFs). The non-metallic fractions (NMFs), which take up a large proportion of E-wastes, were treated by incineration or landfill in the past. NMFs from WEEE contain heavy metals, brominated flame retardant (BFRs) and other toxic and hazardous substances. Combustion as well as landfill may cause serious environmental problems. Therefore, research on resource reutilization and safe disposal of the NMFs from WEEE has a great significance from the viewpoint of environmental protection. Among the enormous variety of NMFs from WEEE, some of them are quite easy to recycle while others are difficult, such as plastics, glass and NMFs from waste printed circuit boards (WPCBs). In this paper, we mainly focus on the intractable NMFs from WEEE. Methods and technologies of recycling the two types of NMFs from WEEE, plastics, glass are reviewed in this paper. For WEEE plastics, the pyrolysis technology has the lowest energy consumption and the pyrolysis oil could be obtained, but the containing of BFRs makes the pyrolysis recycling process problematic. Supercritical fluids (SCF) and gasification technology have a potentially smaller environmental impact than pyrolysis process, but the energy consumption is higher. With regard to WEEE glass, lead removing is requisite before the reutilization of the cathode ray tube (CRT) funnel glass, and the recycling of liquid crystal display (LCD) glass is economically viable for the containing of precious metals (indium and tin). However, the environmental assessment of the recycling process is essential and important before the industrialized production stage. For example, noise and dust should be evaluated during the glass cutting process. This study could contribute significantly to understanding the recycling methods of NMFs from WEEE and serve as guidance for the future technology research and development.     

Characterization and recycling of cadmium from waste nickel–cadmium batteries

A severe threat was posed due to improper and inefficient recycling of waste batteries in China. The present work considered the fundamental aspects of the recycling of cadmium from waste nickel–cadmium batteries by means of vacuum metallurgy separation in scale-up. In the first stage of this work, the characterization of waste nickel–cadmium batteries was carried out. Five types of batteries from different brands and models were selected and their components were characterized in relation to their elemental chemical composition and main phase. In the second stage of this work, the parameters affecting the recycling of cadmium by means of vacuum metallurgy separation were investigated and a L₁₆ (4⁴) orthogonal design was applied to optimize the parameters. With the thermodynamics theory and numerical analysis, it can be seen that the orthogonal design is an effective tool for investigating the parameters affecting the recycling of cadmium. The optimum operating parameters for the recycling of cadmium obtained by orthogonal design and verification test were 1073 K (temperature), 2.5 h (heating time), 2 wt.% (the addition of carbon powder), and 30 mm (the loaded height), respectively, with recycling efficiency approaching 99.98%. The XRD and ICP-AES analyzed results show that the condensed product was characterized as metallic cadmium, and cadmium purity was 99.99% under the optimum condition.     

利用废旧铅膏制备负极板的性能研究

源自铅酸电池回收的再生铅已成为世界铅产量的主要来源,铅酸电池生产也占据了世界铅消耗的80％以上,促进废旧铅膏的处理并直接用于电池的制作研究.采用“湿法脱硫-煅烧”的技术路线处理负极铅膏得到氧化铅.考察了回收铅粉的理化特性,并依据其固有特性,优化了负极板的和膏、固化、化成工艺.得到的样品电池展现出与传统球磨铅粉同样优异的性能.     

Studies on the dechlorination and oil-production technology of waste plastics

 Recycle technology for waste plastics containing polyvinyl chloride (PVC) has been developed in the Hokkaido National Industrial Research Institute for the production of solid and liquid fuel, and has established a recycling process which includes a dechlorination process for PVC plastics, and a two-stage catalytic pyrolysis process for plastics using zeolite catalysts. The dechlorination equipment consists of a two-axis screw extruder with a heating element, which can remove chlorine up to 99.9 wt. % from PVC containing plastics as hydrogen chloride. The product had about 44 000 kJ/kg calorific value and was fed into the next oil production process, although it could also be used as a solid fuel. Natural and synthetic zeolite were used as catalysts for the two-stage catalytic process, which produced a light oil with a boiling point which was between those of kerosene and gasoline. The yield of this oil reached 82 wt. %. The chemical type was analyzed using liquid chromatography, and was found to have many aromatic compounds. These technologies make it possible to produce a nonpolluting, high-calorie solid fuel and a liquid fuel very efficiently. Received: July 19, 2000 / Accepted: September 21, 2000     

Recycling and recovery routes of plastic solid waste (PSW): A review

Plastic solid waste (PSW) presents challenges and opportunities to societies regardless of their sustainability awareness and technological advances. In this paper, recent progress in the recycling and recovery of PSW is reviewed. A special emphasis is paid on waste generated from polyolefinic sources, which makes up a great percentage of our daily single-life cycle plastic products. The four routes of PSW treatment are detailed and discussed covering primary (re-extrusion), secondary (mechanical), tertiary (chemical) and quaternary (energy recovery) schemes and technologies. Primary recycling, which involves the re-introduction of clean scrap of single polymer to the extrusion cycle in order to produce products of the similar material, is commonly applied in the processing line itself but rarely applied among recyclers, as recycling materials rarely possess the required quality. The various waste products, consisting of either end-of-life or production (scrap) waste, are the feedstock of secondary techniques, thereby generally reduced in size to a more desirable shape and form, such as pellets, flakes or powders, depending on the source, shape and usability. Tertiary treatment schemes have contributed greatly to the recycling status of PSW in recent years. Advanced thermo-chemical treatment methods cover a wide range of technologies and produce either fuels or petrochemical feedstock. Nowadays, non-catalytic thermal cracking (thermolysis) is receiving renewed attention, due to the fact of added value on a crude oil barrel and its very valuable yielded products. But a fact remains that advanced thermo-chemical recycling of PSW (namely polyolefins) still lacks the proper design and kinetic background to target certain desired products and/or chemicals. Energy recovery was found to be an attainable solution to PSW in general and municipal solid waste (MSW) in particular. The amount of energy produced in kilns and reactors applied in this route is sufficiently investigated up to the point of operation, but not in terms of integration with either petrochemical or converting plants. Although primary and secondary recycling schemes are well established and widely applied, it is concluded that many of the PSW tertiary and quaternary treatment schemes appear to be robust and worthy of additional investigation.     

Physical separation,mechanical enrichment and recycling-oriented characterization of spent NiMH batteries

Nickel–metal hydride (NiMH) batteries contain high amount of industrial metals, especially iron, nickel, cobalt and rare earth elements. Although the battery waste is a considerable secondary source for metal and chemical industries, a recycling process requires a suitable pretreatment method before proceeding with recovery step to reclaim all valuable elements. In this study, AA- and AAA-type spent NiMH batteries were ground and then sieved for size measurement and classification. Chemical composition of the ground battery black mass and sorted six different size fractions were determined by an analytical technique. Crystal structures of the samples were analyzed by X-ray diffraction. Results show that after mechanical treatment, almost 87 wt% of the spent NiMH batteries are suitable for further recycling steps. Size classification by sieving enriched the iron content of the samples in the coarse fraction which is bigger than 0.25 mm. On the other hand, the amounts of nickel and rare earth elements increased by decreasing sample size, and concentrated in the finer fractions. Anode and cathode active materials that are hydrogen storage alloy and nickel hydroxide were mainly collected in finer size fraction of the battery black mass.     

Cryo-comminution of plastic waste

Recycling of plastics is a big issue in terms of environmental sustainability and of waste management. The development of proper technologies for plastic recycling is recognised as a priority. To achieve this aim, the technologies applied in mineral processing can be adapted to recycling systems. In particular, the improvement of comminution technologies is one of the main actions to improve the quality of recycled plastics. The aim of this work is to point out suitable comminution processes for different types of plastic waste. Laboratory comminution tests have been carried out under different conditions of temperature and sample pre-conditioning adopting as refrigerant agents CO2 and liquid nitrogen. The temperature has been monitored by thermocouples placed in the milling chamber. Also different internal mill screens have been adopted. A proper procedure has been set up in order to obtain a selective comminution and a size reduction suitable for further separation treatment. Tests have been performed on plastics coming from medical plastic waste and from a plant for spent lead batteries recycling. Results coming from different mill devices have been compared taking into consideration different indexes for representative size distributions. The results of the performed tests show as cryo-comminution improves the effectiveness of size reduction of plastics, promotes liberation of constituents and increases specific surface size of comminuted particles in comparison to a comminution process carried out at room temperature.     

Life cycle impact assessment of various waste conversion technologies

Advanced thermal treatment technologies utilizing pyrolysis or gasification, as well as a combined approach, are introduced as sustainable methods to treat wastes in Singapore. Eight different technologies are evaluated: pyrolysis–gasification of MSW; pyrolysis of MSW; thermal cracking gasification of granulated MSW; combined pyrolysis, gasification and oxidation of MSW; steam gasification of wood; circulating fluidized bed (CFB) gasification of organic wastes; gasification of RDF; and the gasification of tyres.Life cycle assessment is carried out to determine the environmental impacts of the various waste conversion systems including global warming potential, acidification potential, terrestrial eutrophication and ozone photochemical formation. The normalization and weighting results, calculated according to Singapore national emission inventories, showed that the two highest impacts are from thermal cracking gasification of granulated MSW and the gasification of RDF; and the least are from the steam gasification of wood and the pyrolysis–gasification of MSW.A simplified life cycle cost comparison showed that the two most costs-effective waste conversion systems are the CFB gasification of organic waste and the combined pyrolysis, gasification and oxidation of MSW. The least favorable – highest environmental impact as well as highest costs – are the thermal cracking gasification of granulated MSW and the gasification of tyres.     

Enhancement of the recycling of waste Ni-Cd and Ni-MH batteries by mechanical treatment

A serious environmental problem was presented by waste batteries resulting from lack of relevant regulations and effective recycling technologies in China. The present work considered the enhancement of waste Ni-Cd and Ni-MH batteries recycling by mechanical treatment. In the process of characterization, two types of waste batteries (Ni-Cd and Ni-MH batteries) were selected and their components were characterized in relation to their elemental chemical compositions. In the process of mechanical separation and recycling, waste Ni-Cd and Ni-MH batteries were processed by a recycling technology without a negative impact on the environment. The technology contained mechanical crushing, size classification, gravity separation, and magnetic separation. The results obtained demonstrated that: (1) Mechanical crushing was an effective process to strip the metallic parts from separators and pastes. High liberation efficiency of the metallic parts from separators and pastes was attained in the crushing process until the fractions reached particle sizes smaller than 2 mm. (2) The classified materials mainly consisted of the fractions with the size of particles between 0.5 and 2 mm after size classification. (3) The metallic concentrates of the samples were improved from around 75% to 90% by gravity separation. More than 90% of the metallic materials were separated into heavy fractions when the particle sizes were larger than 0.5 mm. (4) The size of particles between 0.5 and 2 mm and the rotational speed of the separator between 30 and 60 rpm were suitable for magnetic separation during industrial application, with the recycling efficiency exceeding 95%.     

Current situation of used household batteries in Iran and appropriate management policies

Used household batteries are considered as hazardous wastes in many countries due to the potential environmental and human health risks associated with the heavy metals present in batteries. This article presents the current situation of waste household batteries and policies in Iran. Iran with more than 70 million people is a developing country where latest technologies like cell phones and laptops are in widespread use and battery consumption increases accordingly. The household battery demand in Iran has rapidly grown since 2001 and it is expected to increase more quickly in next years, due to increasing technological development. Based on the available data, more than 9800 metric tons of household batteries were imported into Iran in recent decade, with the market value of about US$ 42.6 million. At present, there is no program available in Iran regarding to collection, separation, recycling or safe disposal of used batteries. Therefore, almost all of the spent household are discarded into municipal solid waste (MSW) and sent to sanitary landfills. Appropriate policies to meet safe disposal of household batteries in Iran is also discussed in this investigation.     

Life cycle assessment of integrated recycling schemes for plastic containers and packaging with consideration of resin composition

Many life cycle assessment studies have evaluated and compared the environmental performance of various technologies for recycling plastic containers and packaging in Japan and other countries. However, no studies have evaluated the combination of recycling technologies in consideration of the resin composition in terms of the quantity of each recycled product so as to maximize their environmental potential. In this study, 27 scenarios of recycling schemes for household waste plastic containers and packaging are developed through integrating a conventional recycling scheme with additional recycling schemes. The conventional recycling scheme involves municipal curbside collection and either the material recycling or feedstock recycling of waste plastics. The additional recycling schemes are feedstock recycling in steel works of the residue from conventional material recycling processes, and corporate voluntary collection and independent material recycling of specific types of plastic trays. Life cycle assessment based on the modeling of recycling processes considering the resin composition in terms of the quantity of each recycled product is applied to evaluate and compare these scenarios from the viewpoints of fossil resource consumption and CO₂ emission. The results show that the environmental loads are reduced in all scenarios including the additional recycling schemes compared with the conventional recycling scheme. However, the independent plastic tray recycling scheme exhibits lower additional environmental savings when the residue recycling scheme is integrated with the conventional material recycling scheme. This is because both additional recycling schemes aim to utilize polystyrene and polyethylene terephthalate, which would otherwise be incinerated as residue from material recycling processes. The evaluation of the environmental loads of plastic recycling with consideration of the resin composition in terms of the quantity of each recycled product makes it possible to investigate recycling schemes that integrate different technologies to maximize their environmental potential.     

The BATINTREC process for reclaiming used batteries

The Integrated Battery Recycling (BATINTREC) process is an innovative technology for the recycling of used batteries and electronic waste, which combines vacuum metallurgical reprocessing and a ferrite synthesis process. Vacuum metallurgical reprocessing can be used to reclaim the mercury (Hg) in the dry batteries and the cadmium (Cd) in the Ni-Cd batteries. The ferrite synthesis process reclaims the other heavy metals by synthesizing ferrite in a liquid phase. Mixtures of manganese oxide and carbon black are also produced in the ferrite synthesis process. The effluent from the process is recycled, thus significantly minimizing its discharge. The heavy metal contents of the effluent could meet the Integrated Wastewater Discharge Standard of China if the ratio of the crushed battery scrap and powder to FeSO4.7H2O is set at 1:6. This process could not only stabilize the heavy metals, but also recover useful resource from the waste.