Surface ozonation of polyvinyl chloride for its separation from waste plastic mixture by froth floatation

Selective surface modification of polyvinyl chloride (PVC) by ozonation was evaluated to facilitate the separation of PVC from other heavy plastics with almost the same density as PVC, especially polyethylene terephthalate (PET), by the froth flotation process. The optimum froth flotation conditions were investigated, and it was found that at 40°C, 90% of PVC and PET plastics floated. The bubble size became larger and the area covered with bubbles on the plastic surface was reduced with increasing temperature. Optimum PVC separation was achieved with the flotation solution at 40°C and mixing at 180–200 rpm, even for sheet samples 10 mm in size. Combined treatment by ozonation and froth flotation is a simple, effective, and inexpensive method for PVC separation from waste plastics.     

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.     

Separation of polycarbonate and acrylonitrile–butadiene–styrene waste plastics by froth flotation combined with ammonia pretreatment

The objective of this research is flotation separation of polycarbonate (PC) and acrylonitrile–butadiene–styrene (ABS) waste plastics combined with ammonia pretreatment. The PC and ABS plastics show similar hydrophobicity, and ammonia treatment changes selectively floatability of PC plastic while ABS is insensitive to ammonia treatment. The contact angle measurement indicates the dropping of flotation recovery of PC is ascribed to a decline of contact angle. X-ray photoelectron spectroscopy demonstrates reactions occur on PC surface, which makes PC surface more hydrophilic. Separation of PC and ABS waste plastics was conducted based on the flotation behavior of single plastic. At different temperatures, PC and ABS mixtures were separated efficiently through froth flotation with ammonia pretreatment for different time (13 min at 23 °C, 18 min at 18 °C and 30 min at 23 °C). For both PC and ABS, the purity and recovery is more than 95.31% and 95.35%, respectively; the purity of PC and ABS is up to 99.72% and 99.23%, respectively. PC and ABS mixtures with different particle sizes were separated effectively, implying that ammonia treatment possesses superior applicability.     

Flame treatment for the selective wetting and separation of PVC and PET

Flame treatment has been used for many years to modify the surface of plastics to allow coatings to be added. The effect of the treatment is to produce hydrophilic species on the surface of the plastic making it water-wettable. The production of hydrophilic plastic surfaces is also required in the selective separation of plastics by froth flotation. For the process to be selective one plastic must be rendered hydrophilic while another remains hydrophobic. In this study the potential for separation of PVC and PET has been investigated. Flame treatment was shown to be very effective in producing a hydrophilic surface on both plastics, although the process was not selective under the conditions investigated. Raising the temperature of the plastics above their softening point produced a hydrophobic recovery. As the softening point of PVC was significantly lower than for PET it was possible to produce a significant difference in hydrophobicity, as judged using contact angle measurement. When immersed in water the contact angle of the PVC was found to be strongly dependent on the pH. Good separation efficiency of the two plastics was achieved by froth flotation from pH 4 to 9. One particular advantage of the technique is that no chemical reagents may be required in the flotation stage. The practicalities of designing a flake treatment system however have to be addressed before considering it to be a viable industrial process.     

Separation of packaging plastics by froth flotation in a continuous pilot plant

The objective of the research was to apply froth flotation to separate post-consumer PET (Polyethylene Terephthalate) from other packaging plastics with similar density, in a continuously operated pilot plant. A representative sample composed of 85% PET, 2.5% PVC (Polyvinyl Chloride) and 11.9% PS (Polystyrene) was subjected to a combination of alkaline treatment and surfactant adsorption followed by froth flotation. A mineral processing pilot plant, owned by a Portuguese mining company, was adapted for this purpose. The experimentation showed that it is possible to produce an almost pure concentrate of PET, containing 83% of the PET in feed, in a single bank of mechanical flotation cells. The concentrate grade attained was 97.2% PET, 1.1% PVC and 1.1% PS. By simulation it was shown that the Portuguese recycling industry specifications can be attained if one cleaning and one scavenger stages are added to the circuit.     

Automotive shredder residue (ASR) characterization for a valuable management

Car fluff is the waste produced after end-of-life-vehicles (ELVs) shredding and metal recovery. It is made of plastics, rubber, glass, textiles and residual metals and it accounts for almost one-third of a vehicle mass. Due to the approaching of Directive 2000/53/EC recycling targets, 85% recycling rate and 95% recovery rate in 2015, the implementation of automotive shredder residue (ASR) sorting and recycling technologies appears strategic. The present work deals with the characterization of the shredder residue coming from an industrial plant, representative of the Italian situation, as for annual fluxes and technologies involved. The aim of this study is to characterize ASR in order to study and develop a cost effective and environmentally sustainable recycling system. Results show that almost half of the residue is made of fines and the remaining part is mainly composed of polymers. Fine fraction is the most contaminated by mineral oils and heavy metals. This fraction produces also up to 40% ashes and its LHV is lower than the plastic-rich one. Foam rubber represents around half of the polymers share in car fluff. Moreover, some chemical–physical parameters exceed the limits of some parameters fixed by law to be considered refuse derived fuel (RDF). As a consequence, ASR needs to be pre-treated in order to follow the energy recovery route.     

Investigation of thermal treatment on selective separation of post consumer plastics prior to froth flotation

Plastics have become the widely used materials because of their advantages, such as cheapness, endurance, lightness, and hygiene. However, they cause waste and soil pollution and they do not easily decompose. Many promising technologies are being investigated for separating mixed thermoplastics, but they are still uneconomical and unreliable. Depending on their surface characteristics, these plastics can be separated from each other by flotation method which is useful mineral processing technique with its low cost and simplicity.The main objective of this study is to investigate the flotation characteristics of PET and PVC and determine the effect of plasticizer reagents on efficient plastic separation. For that purpose, various parameters such as pH, plasticizer concentration, plasticizer type, conditioning temperature and thermal conditioning were investigated. As a result, PET particles were floated with 95.1% purity and 65.3% efficiency while PVC particles were obtained with 98.1% purity and 65.3% efficiency.     

Improving the quality of waste-derived char by removing ash

This study characterized and removed ash from waste-derived char to improve the quality of char as fuel. Municipal solid waste (MSW) and automobile shredder residue (ASR) were carbonized at 450 degrees C and at 500 degrees C, respectively, in a rotary kiln with a nitrogen atmosphere for 1h. MSW and ASR char were subjected to sieving and pulverization-sieving to screen incombustibles and the ash-rich fraction, after which float-sink separation, froth floatation, and oil agglomeration were applied to remove ash from the char. The established target quality was (1) less than 30% ash content and (2) more than 20,000 kJ/kg heating value. However, the rate of combustibles recovery had to be lowered to produce a good quality of char along with a high heating value. MSW char attained the targeted quality level using froth floatation or oil agglomeration, whereas, neither separation method was able to make ASR-derived char satisfy the target. Based on the assumption that particle properties of char are determined by the weight ratio of combustibles and ash, the densities of combustibles and ash in char were estimated using the results of float-sink separation, X-ray diffraction (XRD) analysis, and elemental content. To verify the above assumption, an energy dispersive X-ray/scanning electron microscope (EDX/SEM) analyzer was used to observe char particles.     

Dynamic flow analysis of current and future end-of-life vehicles generation and lead content in automobile shredder residue

Since end-of-life vehicles (ELVs) contain toxic substances, they have to be treated properly. The purpose of this study was to obtain useful information for ELV management from the viewpoint of toxicity. We focused on lead as a representative toxic substance contained in vehicles and investigated the dynamic substance flow of lead contained in ELVs and its content in automobile shredder residue (ASR). A population balance model was used to estimate the number of ELVs generated between FYs (fiscal year) 1990–2020, employing a Weibull distribution for the lifespan distribution. Sixteen lead-containing components of the vehicle were considered. It was estimated that the annual number of ELVs generated would be 2.9 million as of FY2020. The results implied that it is hard to remove Pb completely. This is because 5,000–11,000 t-Pb will still remain in vehicles in use in FY2020 even though most components in new model vehicles could be replaced by lead-free alternatives. As of FY2010, the substance flow showed that Pb contained in ELVs amounted to 4,600–5,700 t-Pb. Of this, 13.2–14.0 % was contained in ASR. The Pb content in ASR could be dramatically decreased by FY2020, but it will continue to contain 240–420 mg-Pb/kg if the treatment system is not improved.     

Boiling treatment of ABS and PS plastics for flotation separation

A new physical method, namely boiling treatment, was developed to aid flotation separation of acrylonitrile–butadiene–styrene (ABS) and polystyrene (PS) plastics. Boiling treatment was shown to be effective in producing a hydrophilic surface on ABS plastic. Fourier Transform Infrared analysis was conducted to investigate the mechanism of boiling treatment of ABS. Surface rearrangement of polymer may be responsible for surface change of boiling treated ABS, and the selective influence of boiling treatment on the floatability of boiling treated plastics may be attributed to the difference in the molecular mobility of polymer chains. The effects of flotation time, frother concentration and particle size on flotation behavior of simple plastic were investigated. Based on flotation behavior of simple plastic, flotation separation of boiling treatment ABS and PS with different particle sizes was achieved efficiently. The purity of ABS and PS was up to 99.78% and 95.80%, respectively; the recovery of ABS and PS was up to 95.81% and 99.82%, respectively. Boiling treatment promotes the industrial application of plastics flotation and facilitates plastic recycling.     

Mechanical treatment of automobile shredder residue for its application as a fuel

Enforcement of the Automobile Recycling Law in Japan requires utilization of automobile shredder residue (ASR). However, the high contents of copper (∼5%) and chlorine (∼1%) in ASR stand in the way of practical application. We studied methods for the removal of copper and chlorine from ASR so that it could be utilized as a fuel. By compression of the ASR for solidification with an extruder, the polyvinylchloride (PVC) that covered electrical cables was softened and stripped from the copper wire. The solidified ASR was comminuted with cutter mills and classified by dry density separation. The copper content of the obtained light products was 0.2%–0.5%. Furthermore, we studied the possibility of dechlorination of the ASR by mechanochemical (MC) activation. The light product of the ASR was milled with CaO or CaCO₃. The chlorine content decreased to about one-tenth of the original value after MC activation over 8 h. Therefore, the combined processing of softening–stripping and comminution liberated the PVC-covered cables and decreased the copper content of the ASR. In addition, dechlorination of the ASR was also possible by MC activation with the addition of calcium compounds.     

End-of-Life Vehicles management: Italian material and energy recovery efficiency

Each European Member State must comply with Directive 2000/53/EC recycling and recovery targets by 2015, set to 85% and 95%, respectively. This paper reports a shredder campaign trial developed and performed in Italy at the beginning of 2008. It turns out to be the first assessment about the critical aspects belonging to the Italian End-of-Life Vehicles (ELVs) reverse supply chain involving 18 dismantling plants, a shredder plant and 630 ELV representatives of different categories of vehicles treated in Italy during 2006. This trial aims at improving the experimental knowledge related to ELVs added waste, pre-treatment, part reuse, recycling and final metal separation and car fluff disposal. Finally, the study also focuses on the calculation of the effective Italian ELV recycling rate, which results equal to 80.8%, and auto shredder residue (ASR) characterization. According to the results obtained in this work, ASR still contains up to 8% of metals and 40% of polymers that could be recovered. Moreover, physical-chemical analysis showed a Lower Heat Value of almost 20,000 kJ/kg and revealed the presence of pollutants such as heavy metals, mineral oils, PCBs and hydrocarbons.     

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.     

End-of-life vehicle recycling and automobile shredder residue management in Japan

The Japanese Government introduced the Law on Recycling of End-of-Life Vehicles (ELV Recycling Law) in 2002. This law requires manufacturers to retrieve chlorofluorocarbons (CFCs), airbags, and automobile shredder residue (ASR) from ELVs and to properly recycle the remaining materials. This framework is compared with European ELV directives. Pilot-scale incineration plant testing has revealed a greater formation of by-product persistent organic pollutants (POPs) during the primary combustion of ASR compared to normal municipal solid waste. This may be attributed to the abundance of chlorine, Cu, and Fe in ASR, as Cu and Fe have been found to catalyze the formation of POPs under certain conditions. However, most by-product POPs were destroyed by the secondary combustion, and almost all were removed after flue gas treatment. The direct melting system is a shaft-type gasification and melting technology that has proved effective in many municipal solid waste applications. This system can be applied to ASR recycling for effective decomposition of brominated flame retardants and polybrominated dioxins.     

Application of dissolved air flotation on separation of waste plastics ABS and PS

The aim of this research was to separate waste plastics acrylonitrile butadiene styrene (ABS) and polystyrene (PS) by dissolved air flotation in a self-designed dissolved air flotation apparatus. The effects of wetting agents, frother, conditioning time and flotation time on flotation behavior of waste plastics ABS (w-ABS) and PS (w-PS) were investigated and the optimized separation conditions were obtained. The results showed that when using 25 mgL(-1) tannic acid, 5 mgL(-1) terpineol, 15 min conditioning time and 15 min flotation time, mixtures of w-ABS and w-PS were separated successfully by dissolved air flotation in two stages, the results revealed that the purity and recovery rate of w-PS in the floated products were 90.12% and 97.45%, respectively, and the purity and recovery rate of w-ABS in the depressed products were 97.24% and 89.38%, respectively. Based on the studies of wetting mechanism of plastic flotation, it is found that the electrostatic force and hydrophobic attraction cannot be the main factor of the interaction between wetting agent molecules and plastic particles, which can be completed through water molecules as a mesophase, and a hydrogen bonding adsorption model with hydration shell as a mesophase was proposed.     

Dechlorination of polyvinyl chloride in NaOH/ethylene glycol solution by microwave heating

This study investigated the dehydrochlorination of flexible polyvinyl chloride (PVC) containing 59.2% PVC, 29.7% dioctyl phthalate (DOP), and approximately 12% stabilizers. Flexible PVC was treated with NaOH/ethylene glycol (NaOH/EG) solutions at NaOH concentrations in the range 0.5–4 mol/l and was heated in a microwave heater at a temperature between 100° and 160°C for 0–30 min. All chlorides were completely eliminated by internal heating at 160°C using microwaves for 10 min in a 1 mol/l NaOH/EG solution, and the residue was made up of hydrocarbons. The weight loss rate reached a maximum of 74.7% at a temperature of 160°C. It was discovered that the use of microwaves significantly shortened the reaction time compared to using conventional electric heaters or other external heating systems and also allowed the use of lower concentrations of NaOH. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

Upgrading of poly(vinyl chloride) by chemical modifications using sodium sulfide

The recycling of poly(vinyl chloride) (PVC) is one of the most important issues in the treatment of waste plastics. To improve PVC recycling, it is necessary to develop new recycling techniques, including new techniques for the dechlorination of chlorine-containing polymers. It has been established that wet dechlorination of PVC in NaOH/ethylene glycol solution is more effective than dry dechlorination. In this study, the wet process was used, and the chemical modification of PVC by nucleophilic substitution was considered for upgrading waste PVC. Chlorine was substituted in solution by several nucleophilic reagents, thus changing the properties of PVC. The reaction of PVC in Na2S/ethylene glycol solution at 170°C resulted in the formation of a mixture comprising 32% elimination and 26% substitution products. The scanning electron microscopy/energy dispersive X-ray spectroscopy mappings and elementary analysis of PVC indicated that this chlorine-substitution process led to cross-linking by sulfur.     

Combination of three-stage sink-float method and selective flotation technique for separation of mixed post-consumer plastic waste

The aim of this research was to separate the different plastics of a mixed post-consumer plastic waste by the combination of a three-stage sink-float method and selective flotation. By using the three-stage sink-float method, six mixed-plastic wastes, belonging to the 0.3-0.5 cm size class and including high density polyethylene (HDPE), polypropylene (PP), polyvinylchloride (PVC), polystyrene (PS), polyethylene terephthalate (PET) and acrylonitrile-butadiene-styrene copolymers (ABS) were separated into two groups, i.e., a low density plastic group (HDPE and PP) and a high density plastic group (PET, PVC, PS and ABS) by tap water. Plastic whose density is less than that of the medium solution floats to the surface, while the one whose density is greater than that of the medium solution sinks to the bottom. The experimental results elucidated that complete separation of HDPE from PP was achieved by the three-stage sink-float method with 50% v/v ethyl alcohol. To succeed in the separation of a PS/ABS mixture from a PET/PVC mixture by the three-stage sink-float method, a 30% w/v calcium chloride solution was employed. To further separate post-consumer PET/PVC and PS/ABS based on plastic type, selective flotation was carried out. In order to succeed in selective flotation separation, it is necessary to render hydrophilic the surface of one or more species while the others are kept in a hydrophobic state. In flotation studies, the effects of wetting agent, frother, pH of solution and electrolyte on separation were determined. The selective flotation results showed that when using 500 mg l(-1) calcium lignosulfonate, 0.01 ppm MIBC, and 0.1 mg l(-1) CaCl2 at pH 11, PET could be separated from PVC. To separate ABS from PS, 200 mg l(-1) calcium lignosulfonate and 0.1 mg l(-1) CaCl2 at pH 7 were used as a flotation solution. Wettability of plastic increases when adding CaCl2 and corresponds to a decrease in its contact angles and to a reduction in the recovery of plastic in the floated product.     

Floatability of polymer materials modulated by frothers

Flotation tests of 35 polymer materials were carried out to investigate their floatability modulated by frothers. Results of flotation tests demonstrated that polymer resins and soft PVC showed high floatability, floatability of hard PVC plastics was relatively low and was related to the frothers, and there exists significant difference in the floatability of different post-consumer plastics. Flotation rate of post-consumer plastics varies from 0% to 100%. Furthermore, three-category low-energy surface (LES) was defined based on the hydrophile index of the materials involved in this paper, and an adsorption model was proposed to explain the results of flotation and to discuss the floatability of polymer materials modulated by frothers. Frother molecules are prone to adsorb on the surface of bubble rather than LES at relatively low concentration, bubble adsorbed by frother molecules is prone to approach first-category LES rather than third-category LES, and the structure of liquid film is formed on the first-category LES at large concentration. Floatability of polymer materials modulated by frothers is further discussed: frothers increase the floatability of the first-category LES but decrease the floatability of the third-category LES, while the floatability of the second-category LES is related to the type of frothers.