Study of the solubility and stability of polystyrene wastes in a dissolution recycling process

Dissolution with suitable solvents is one of the cheapest and more efficient processes for polystyrene waste management. In this work the solubility of polystyrene foams in several solvents benzene, toluene, xylene, tetrahydrofuran, chloroform, 1,3-butanediol, 2-butanol, linalool, geraniol, d-limonene, p-cymene, terpinene, phellandrene, terpineol, menthol, eucalyptol, cinnamaldheyde, nitrobenzene, N,N-dimethylformamide and water has been determined.Experimental results have shown that to develop a “green process” the constituents of essential oils, d-limonene, p-cymene, terpinene, phellandrene, are the most appropriate solvents. The action of these solvent does not produce any degradation of polymer chains. The solubility of the polymer in the mentioned solvents at different temperatures has been investigated. The solvent can be easily recycled by distillation.     

Recycling of extruded polystyrene wastes by dissolution and supercritical CO2 technology

Polystyrene (PS) is currently used as packaging, insulating and storing material in various industrial or domestic fields. As a result, a large quantity of PS wastes is produced. Plastic wastes are not usually biodegradable, so it is necessary to suggest a technology to recycle them. Landfills and incineration are reasonably cheap methods but are not environmentally acceptable, therefore, alternative methods for polymer recycling are required. The general purpose of PS foam recycling is to recover a more compact polymeric material without degradation. Dissolution with terpenic solvents is presented here as an efficient and cheap alternative that is developed at room temperature; among the oils studied, limonene was selected because of its intermediate solubility and its abundance. The solvent removal is possible thanks to supercritical technology that provides a high solubility in limonene and almost a complete PS insolubility at moderated pressures (77?bar) and low temperatures (30?°C). Thus, based on the results of thermogravimetric and chromatographic analysis, we propose that.supercritical antisolvent precipitation is an ideal technique for carrying out the separation of PS and limonene, providing a recycled polymer with a reduced volume, almost completely free of solvent and without degradation of the polymeric chains.     

Toward maximizing the recycling rate in a Sapporo waste plastics liquefaction plant

Sapporo Plastics Recycling Co., Ltd., (SPR) started its commercial operation of waste plastics liquefaction in 2000. At first only hydrocarbon oil was reclaimed, this being derived from the waste plastics liquefaction process under the Japanese Containers and Packaging Recycling Law. Presently, thermal degradation residue and hydrochloric acid are being produced as by-products in addition to the hydrocarbon oil. As a result, the SPR plastics liquefaction plant has achieved a high reclamation rate of 96%, and 93% of the recycled products have been reused in Hokkaido, where SPR is located. The technical problems caused by corrosion and clogging have been solved. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

Formation of recycled plastics from depolymerized monomers derived from waste fiber-reinforced plastics

To develop a new method for the chemical recycling of plastics, we examined the formation of recycled polymers from the recovered monomeric materials of solubilized waste fiber-reinforced plastics (FRP) under supercritical alcoholic conditions. Treatment of waste FRP with supercritical MeOH resulted in the formation of monomeric organic compounds that mainly contained dimethyl phthalate (DMP) and propylene glycol. The presence of these materials was confirmed by gas chromatography and nuclear magnetic resonance analyses and they were mixed with new DMP and glycols in various ratios to form unsaturated polyesters. The polymerization progressed successfully for all mixing ratios of the recovered and new DMP. Hardness tests on these recycled polymers indicated that the polymer made from a 1:1 mixture of recovered and new dimethyl phthalate had almost the same level of hardness as the polymers made from new materials. We also examined the formation of recycled FRP by using glass fibers and monomeric materials recovered through the present depolymerization method. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

Influence of the recycled material percentage on the rheological behaviour of HDPE for injection moulding process

The amount of polymer material wasted during thermoplastic injection moulding is very high. It comes from both the feed system of the part, and parts necessary to set up the mould, as well as the scrap generated along the process due to quality problems. The residues are managed through polymer recycling that allows reuse of the materials in the manufacturing injection process. Recycling mills convert the parts into small pieces that are used as feed material for injection, by mixing the recycled feedstock in different percentages with raw material. This mixture of both raw and recycled material modifies material properties according to the percentage of recycled material introduced. Some of the properties affected by this modification are those related to rheologic behaviour, which strongly conditions the future injection moulding process. This paper analyzes the rheologic behaviour of material with different percentages of recycled material by means of a capillary rheometer, and evaluates the influence of the corresponding viscosity curves obtained on the injection moulding process, where small variations of parameters related to rheological behaviour, such as pressure or clamping force, can be critical to the viability and cost of the parts manufactured by injection moulding.     

Hydrothermal recycling of waste and performance of the recycled wooden particleboards

Recycling today constitutes the most environmentally friendly method of managing wood waste. A large proportion of the wood waste generated consists of used furniture and other constructed wooden items, which are composed mainly of particleboard, a material which can potentially be reused. In the current research, four different hydrothermal treatments were applied in order to recover wood particles from laboratory particleboards and use them in the production of new (recycled) ones. Quality was evaluated by determining the main properties of the original (control) and the recycled boards. Furthermore, the impact of a second recycling process on the properties of recycled particleboards was studied. With the exception of the modulus of elasticity in static bending, all of the mechanical properties of the recycled boards tested decreased in comparison with the control boards. Furthermore, the recycling process had an adverse effect on their hygroscopic properties and a beneficial effect on the formaldehyde content of the recycled boards. The results indicated that when the 1st and 2nd particleboard recycling processes were compared, it was the 2nd recycling process that caused the strongest deterioration in the quality of the recycled boards. Further research is needed in order to explain the causes of the recycled board quality falloff and also to determine the factors in the recycling process that influence the quality degradation of the recycled boards.     

Photochemical Kinetic Modeling of Degradation of Aqueous Polyvinyl Alcohol in a UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript> Photoreactor

This study presents a photochemical kinetics model to describe the degradation of water-soluble PVA (Polyvinyl Alcohol) polymer in a UV/H₂O₂ batch reactor. Under the effect of UV light, the photolysis of hydrogen peroxide into hydroxyl radicals can generate a series of polymer scission reactions. For a better understanding and analysis of the UV/H₂O₂ process in the cracking of the PVA macromolecules, a chemical reaction mechanism of the degradation process and a relevant photochemical kinetics model are developed to describe the disintegration of the polymer chains. Taking into account the probabilistic fragmentation of the polymer, the statistical moment approach is used to model the molar population balance of live and dead polymer chains. The model predicts the PVA molecular weight reduction, the acidity of the solution, and hydrogen peroxide residual. In addition to previously published data collected in this laboratory, a new set of experiments were conducted using a 500 mg/L PVA aqueous for different hydrogen peroxide/PVA ratios for model validation. Measurements of average molecular weights of the polymer, hydrogen peroxide concentrations and pH of the PVA solution were determinant factors in constructing a reliable photochemical model of the UV/H₂O₂ process. Experimental data showed a decrease in the PVA molecular weight and a buildup of the solution acidity. The experimental data also served to determine the kinetics rate constants of the PVA photochemical degradation and validate the model whose predictions are in good agreement with data. The model can provide a comprehensive understanding of the impact of the design and operational variables.     

Life cycle assessment and energy intensity of CFRP recycling using supercritical N-butanol

Journal of Material Cycles and Waste Management - Recycling carbon fiber reinforced polymer (CFRP) waste is unavoidable for the sustainable manufacturing and cost reduction of CFRP products....     

Biodegradation of Poly(ε-caprolactone) (PCL) Film by <Emphasis Type="Italic">Alcaligenes faecalis</Emphasis>

The biodegradation behavior of PCL film with high molecular weight (80,000 Da) in presence of bacterium Alcaligenes faecalis and the analysis of degraded polymer film have been carried out. Thin Films of PCL were prepared by means of solution casting method and the bacterial degradation behavior was carried in basal medium, in presence of bacteria with time variation after UV treatment. It was observed that after UV treatment the degradation of polymer film was increased and the degradation rate followed a three steps degradation mechanism. The degraded polymer film was analyzed by means of Differential Scanning Calorimeter (DSC), Thermo Gravimetric Analyzer (TGA) and Fourier Transform Infrared Spectroscope (FTIR). DSC results revealed that at the initial stages of the degradation up to 15–20 days, the bacterium preferentially degrades the amorphous parts of the polymer film over the crystalline zone. Thermo gravimetric analysis highlighted the low temperature stability of degraded films with extent of degradation. FTIR results showed the chain scission mechanism of the polymer chains and also supported the preferential degradation of amorphous phase over crystalline phase in the initial stages of the degradation.     

Recent trends in recycling activities and waste management in Japan

Japan's basic approach to municipal solid waste (MSW) is (1) waste reduction, (2) promotion of recycling, (3) volume reduction by intermediate treatment, and (4) environmentally sound final disposal. A brief history of legislative trends in waste management is given as background for current waste management and recycling activities. The material recovery rate for MSW collected by local municipalities was only 5.6% in 1996. More than half of MSW, on a volume basis, consists of containers and packages, while great amounts of landfill space are also taken up by bulky wastes such as electric appliances. Therefore, in order to promote recycling and decrease landfill waste, Japan is targeting containers, packages, and electric appliances. A law promoting separate collection and recycling of containers and packages (Packaging Waste Recycling Law) and a law requiring the recycling of specific home electric appliances into new products (Home Electric Appliance Recycling Law) were introduced in June 1995 and June 1998, respectively. These laws are in line with the OECD policy Extended Producer Responsibility (EPR). Received: September 16, 1998 / Accepted: March 10, 1999     

Molecular Modification and Compatibilization of Collected Polyethylene

The increasing use of plastics in packaging materials leads to growing amounts of plastic waste. Recycling material is generally regarded as advantageous. But in fact very few products are made from plastic waste, partly this can be explained by that little is known about the recycling process and the properties of collected materials. There is a need for injection moulding grades of recycled polyethylene, while large amounts of extrusion grades are available from packaging waste. A controlled way of de-branching or partly degrading PE would be desirable. Peroxides are commonly used to crosslink polyolefins, but under certain conditions a chain scission reaction occur. Another problem encountered with recycling of polyethylene are the poor miscibility of low amounts contaminations, i. e. polypropylene. A compatibilizer can improve properties of such polymer blends, in this work EPDM is used as compatibilzer. Studies of mechanical properties and viscosity measurements show that it is possible to partly degrade PE with peroxide exposing it to high temperature and oxygen. The properties of PE/PP blends were improved with EPDM as compatibilizer.     

A holistic life cycle analysis of waste management scenarios at increasing source segregation intensity: The case of an Italian urban area

Life cycle analysis of several waste management scenarios for an Italian urban area was performed on the basis of different source segregation collection (SS) intensities from 0% up to 52%. Source segregated waste was recycled and or/recovered by composting. Residual waste management options were by landfilling, incineration with energy recovery or solid recovered fuel (SRF) production to substitute for coal. The increase in fuel and materials consumption due to increase in SS had negligible influence on the environmental impact of the system. Recycling operations such as incineration and SRF were always advantageous for impact reduction. There was lower impact for an SS of 52% even though the difference with the SS intensity of 35% was quite limited, about 15%. In all the configurations analyzed, the best environmental performance was achieved for the management system producing SRF by the biodrying process.     

Use of steel fibres recovered from waste tyres as reinforcement in concrete: Pull-out behaviour,compressive and flexural strength

The increasing amount of waste tyres worldwide makes the disposition of tyres a relevant problem to be solved. In the last years over three million tons of waste tyres were generated in the EU states [ETRA, 2006. Tyre Technology International – Trends in Tyre Recycling. http://www.etra-eu.org]; most of them were disposed into landfills. Since the European Union Landfill Directive (EU Landfill, 1999) aims to significantly reduce the landfill disposal of waste tyres, the development of new markets for the tyres becomes fundamental.Recently some research has been devoted to the use of granulated rubber and steel fibres recovered from waste tyres in concrete. In particular, the concrete obtained by adding recycled steel fibres evidenced a satisfactory improvement of the fragile matrix, mostly in terms of toughness and post-cracking behaviour. As a consequence RSFRC (recycled steel fibres reinforced concrete) appears a promising candidate for both structural and non-structural applications.Within this context a research project was undertaken at the University of Salento (Italy) aiming to investigate the mechanical behaviour of concrete reinforced with RSF (recycled steel fibres) recovered from waste tyres by a mechanical process. In the present paper results obtained by the experimental work performed up to now are reported. In order to evaluate the concrete-fibres bond characteristics and to determine the critical fibre length, pull-out tests were initially carried out. Furthermore compressive strength of concrete was evaluated for different volume ratios of added RSF and flexural tests were performed to analyze the post-cracking behaviour of RSFRC. For comparison purposes, samples reinforced with industrial steel fibres (ISF) were also considered.Satisfactory results were obtained regarding the bond between recycled steel fibres and concrete; on the other hand compressive strength of concrete seems unaffected by the presence of fibres despite their irregular geometric properties. Finally, flexural tests furnished in some cases results comparable to those obtained when using ISF as concerns the post-cracking behaviour.     

Comparative environmental assessment of natural and recycled aggregate concrete

Constant and rapid increase in construction and demolition (C&D) waste generation and consumption of natural aggregate for concrete production became one of the biggest environmental problems in the construction industry. Recycling of C&D waste represents one way to convert a waste product into a resource but the environment benefits through energy consumption, emissions and fallouts reductions are not certain. The main purpose of this study is to determine the potentials of recycled aggregate concrete (concrete made with recycled concrete aggregate) for structural applications and to compare the environmental impact of the production of two types of ready-mixed concrete: natural aggregate concrete (NAC) made entirely with river aggregate and recycled aggregate concrete (RAC) made with natural fine and recycled coarse aggregate. Based on the analysis of up-to-date experimental evidence, including own tests results, it is concluded that utilization of RAC for low-to-middle strength structural concrete and non-aggressive exposure conditions is technically feasible. The Life Cycle Assessment (LCA) is performed for raw material extraction and material production part of the concrete life cycle including transport. Assessment is based on local LCI data and on typical conditions in Serbia. Results of this specific case study show that impacts of aggregate and cement production phases are slightly larger for RAC than for NAC but the total environmental impacts depend on the natural and recycled aggregates transport distances and on transport types. Limit natural aggregate transport distances above which the environmental impacts of RAC can be equal or even lower than the impacts of NAC are calculated for the specific case study.     

A Mechanistic Model Describing the Degradation of Polymers

This study examined the cooperative effects of diffusion and reaction on the degradation of a polymer. The work was intended to describe bulk degradation processes, where the polymer volume remains nearly constant. Test coupons made from poly (2-ethyl 2-oxazoline) were immersed in water for controlled durations. The coupons were weighed before and after immersion in the wet and dried condition. The coupons were observed to gain weight for short immersion durations. At longer durations the weight change became negative as the solvent reacted with and dissolved the polymer. An average solvent concentration was found from the weight measurements. Fick’s law was used to express the increase in concentration while a first order reaction law was used to represent the decrease in concentration of the solvent. The competing changes in concentration were combined from which the net solvent concentration at any given time was obtained. The model was compared with the experimental measurements using coupons of various thicknesses. The model was found to describe the observed polymer degradation in water including thickness effects.     

Influence of Short Central PEO Segment on Hydrolytic and Enzymatic Degradation of Triblock PCL Copolymers

Hydrolytic, enzymatic degradation and composting under controlled conditions of series of triblock PCL/PEO copolymers, PCEC, with central short PEO block (M _n 400 g/mol) are presented and compared with homopolymer (PCL). The PCEC copolymers, synthesized via ring-opening polymerization of ε-caprolactone, were characterized by ¹H NMR, quantitative ¹³C NMR, GPC, DSC and WAXS. The introduction of the PEO central segment (<?2 wt%) in PCL chains significantly affected thermal degradation and crystallization behavior, while the hydrophobicity was slightly reduced as confirmed by water absorption and moisture uptake experiments. Hydrolytic degradation studies in phosphate buffer after 8 weeks indicated a small weight loss, while FTIR analysis detected changes in crystallinity indexes and GPC measurements revealed bulk degradation. Enzymatic degradation tested by cell-free extracts containing Pseudomonas aeruginosa PAO1 confirmed high enzyme activity throughout the surface causing morphological changes detected by optical microscopy and AFM analysis. The changes in roughness of polymer films revealed surface erosion mechanism of enzymatic degradation. Copolymer with the highest content of PEO segment and the lowest molecular weight showed better degradation ability compared to PCL and other copolymers. Furthermore, composting of polymer films in a model compost system at 37 °C resulted in significant degradation of the all synthesized block copolymers.     

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.     

Amino-Modified Halloysite Nanotubes to Reduce Polymer Degradation and Improve the Performance of Mechanically Recycled Poly(lactic acid)

From an environmental point of view, mechanical recycling is, in general, a good end-of-life option for poly(lactic acid) (PLA), one of the most important biobased polymers. However, the degradation of PLA during the service life and, especially, during the mechanical recycling process, leads to a decrease in the properties of PLA, thus reducing the applications of the recycled plastic. The main aim of this work was to study the addition of small amounts of halloysite nanotubes, during the recycling step, as the basis of a cost-effective method for improving the properties of the recycled PLA. Raw halloysite was modified with an aminosilane, and 2% by weight of both raw and modified halloysite were melt compounded with PLA previously subjected to accelerated ageing. The addition of the nanotubes led to recycled materials with improved properties because halloysite reduces the degradation of PLA by blocking the carboxyl groups, generated during the ageing and washing steps, which catalyze the degradation during the recycling process. This effect was more intense in the silanized nanotubes, because the carboxyl groups were effectively blocked by acid–base interactions with the amino groups of the chemical modification. The properties of the recycled plastic with only 2 wt% of silanized halloysite were very close to those of the virgin plastic.     

Feedstock recycling of waste polymeric material

The first International Symposium on Feedstock Recycling of Polymeric Materials (ISFR) was hosted in 1999 in Sendai, Japan. Since then, the ISFR has been held five times in different places in Asia and Europe. Each of these conferences focused on special issues covered by the Journal of Material Cycles and Waste Management. The topics included thermal processes with and without catalysts, wet processes in various solvents, the dehydrochlorination of PVC, mechanical recycling and separation techniques, as well as the treatment of biomaterials. This review is a compilation of the most interesting and important developments discussed at the ISFR during the last decade.     

Degradation of PVC Containing Mixtures in the Presence of HCl Fixators

Degradation of a model polymer mixture (PVC/PS/PE) and a waste polymer mixture in the presence of HCl fixators (Red Mud, precipitated CaCO₃ and dolamite) was studied using thermal gravimetric analysis (TGA) and a cycled-spheres-reactor. The experiments in cycled-spheres reactor model were performed by stepwise pyrolysis. Liquid products and HCl from each step were collected separately. For the model polymer mixture, the precipitated CaCO₃ showed the best effect on the fixation of evolved HCl and the reduction of chlorine content in the liquid products whereas RM yielded the best result for the waste polymer mixture. In addition, using HCl fixator also affected the degradation of both types of polymer mixture, leading to the formation of more gaseous and less residue.