Developments in an industry-led R&D program for recycling PVC products in Japan

To facilitate recycling, not only R&D but also the creation of efficient recycling systems—collection and processing of recyclates as well as finding appropriate end-uses—is essentially important. PVC has a particular advantage in regards to mechanical recycling when compared to other major plastics. However, there is no one-size-fits-all approach to a solution. Specific situations of used or off-cut products and their applications need to be well studied. Vinyl industry in Japan has devoted itself for many years to the promotion of recycling of vinyl products. It started an R&D support program in 2007 and seven projects have been completed since then. Some of the new developments include mechanical recycling for products like wall covering and tarpaulin which were considered difficult to recycle in the past. Progress in chemical recycling has been made with a technology for the removal of chlorine from shredder dusts. Recovery of chlorine is a challenge for the future. Collaboration among the various players involved in the recycling of a specific product is essential for obtaining a successful result.     

Effect of heating rate on the pyrolysis of high-impact polystyrene containing brominated flame retardants: fate of brominated flame retardants

In the case of plastics containing brominated flame retardants, various brominated organic compounds, including polybrominated dibenzodioxins and dibenzofurans, are yielded when they are degraded. In order to reduce the hazard that might be generated during after-live treatment, the behaviour of flame retarded high-impact polystyrene containing decabromo diphenylether and antimony oxide (Sb₂O₃), was investigated using several heating programs. It was found that the separation of the thermal process into two steps divided at 330?°C makes it possible to obtain an oil fraction rich in brominated compounds at low temperatures and an oil fraction depleted in brominated compounds at high temperatures. The low temperature oil contained a high concentration of SbBr₃ and dibromodibenzofurans. Various brominated compounds with a low volatility and 1-bromo-1-phenylethane from the reaction of HBr with styrene were among the substances in the high temperature oil. The concentration of brominated compounds was reduced from 6?wt% for degradation in a single step to below 1?wt% in the high temperature oil in the two step process.     

Removal of chloride from ethylene glycol solution using alumina/zeolite membrane as a physical boundary between the organic and aqueous phases

The permeation of Cl^? ions from a NaCl/ethylene glycol (EG) solution during electrodialysis was investigated using alumina and alumina/zeolite membranes. Voltage changes had very little effect on Cl^? permeation through the alumina membrane, suggesting that the driving force for the permeation was concentration-gradient-induced diffusion, and not the electric field. Solvation of the Na⁺ ions by EG resulted in EG migration through the membrane. Replacement of the deionized water (electrolyte) in the anodic cell with NaOH resulted in increased Cl^? permeation, although a greater amount of EG migrated into the NaOH solution as well. No notable difference was observed in Cl^? permeation through the alumina and alumina/zeolite membranes, but EG migration decreased when using the latter membrane, suggesting that EG migration was prevented by the zeolite layer. The proposed alumina/zeolite membrane is, hence, useful for solvent recovery by electrodialysis, but its mechanical stability must be improved for industrial applications.     

Validation of diffusive mini-samplers for aldehyde and VOC and its feasibility for measuring the exposure levels of elementary school children

Exposure to various chemicals can cause adverse effects to health, such as asthma and allergies, especially in children. Data on personal exposure levels in children are scarce, thus small lightweight diffusive mini-samplers for aldehydes and volatile organic compounds (VOCs) were designed to measure the exposure level of children to these chemicals. The aim of the study was to validate and examine the applicability of these mini-samplers for measuring daily chemical exposure. The diffusive mini-samplers are 20 mm in length, 11 mm in diameter, and 1.67 g in weight. The devices are cylindrically shaped with polytetrafluoroethylene membrane filters placed at each end. To measure aldehydes and acetone, 20 mg of 2,4-dinitrophenylhydrazine was used as an absorbent. To measure VOCs, a carbon molecular sieve was used. The sampling rate for each chemical was determined by parallel sampling with active samplers in a closed exposure bag. The blank levels of the chemicals and the storage stability of the device were tested. The mini-samplers were compared to commercially available diffusive samplers. To examine the applicability of the samplers, 65 elementary school children carried them for 24 h. The sampling rates for formaldehyde, acetaldehyde, and acetone were 20.9, 22.9, and 19.7 mL min(-1), respectively. The limits of quantification (LOQ) for the 24-hour sampling by high-performance liquid chromatography/ultraviolet (HPLC/UV) analysis were 8.3, 7.6, and 8.8 μg m(-3) for formaldehyde, acetaldehyde, and acetone, respectively. The sampling rates for the 11 VOCs were determined and ranged from 3.3 mL min(-1) for styrene and 2-ethyl-1-hexanol to 11.7 mL min(-1) for benzene. The LOQ for the 24-hour sampling by gas chromatography-mass spectrometry (GC-MS) analysis ranged from 5.9-105.2 μg m(-3), 1.1-24.7 parts per billion. The storage stability after 5 days ranged from 94.8 to 118.2%. Formaldehyde, acetone, benzene, and toluene were detected above the LOQ in more than 90% of the children, and the median concentrations were 21.7, 20.9, 10.1, and 21.5 μg m(-3), respectively. This study shows that the diffusive samplers developed were suitable for children to carry and were capable of measuring the children's daily chemical exposure.     

Electrodialysis for NaCl/EG solution using ion-exchange membranes

A new concept for the recycling of poly(vinyl chloride) (PVC) has been introduced, including the dehydrochlorination of PVC in ethylene glycol (EG) with NaOH as a reactant, the subsequent separation of NaCl from EG by electrodialysis, and the recovery of chlorine for the synthesis of new PVC. In this work, the separation of NaCl by electrodialysis was investigated. About 98 % of the salt were recovered from EG, with less than 10 % of the EG permeating the membranes after 5 h.     

Applications of a hydro-biogeochemical model and long-term simulations of the effects of logging in forested watersheds

We simulated hydrological and biogeochemical responses to logging in a forested watershed to determine the vulnerability and/or resiliency of the forest ecosystems in the Lake Shumarinai Basin in northern Hokkaido, Japan. We used a biogeochemical model (PnET-CN) and a rainfall–runoff model (HYCYMODEL) to predict ecosystem responses. The PnET-CN model simulated well the observed NO₃ ⁻ concentrations in streamwater, particularly at high concentrations during snowmelt; however, the model could not simulate small increases in NO₃ ⁻ during the summer. By considering hydrological processes within the watershed and combining the model with the HYCYMODEL (PnET + HYCYMODEL), the seasonality of streamwater NO₃ ⁻ concentrations was better simulated. Using these models, the long-term effects of logging were simulated for coniferous, deciduous, and mixed forests. NO₃ ⁻ concentrations in streamwater increased in response to the logging disturbance in both coniferous and deciduous forests. In the coniferous forest, NO₃ ⁻ concentrations reached a maximum 10 years after logging, and high concentrations persisted for 30 years. In contrast, NO₃ ⁻ concentrations in the deciduous forest reached a maximum within 3–4 years and recovered to pre-disturbance levels after 15 years. We also used the models to determine the effects of different sizes and types (coniferous, deciduous, and mixed forest) of logging areas on Lake Shumarinai. The model results indicated that large areas of cutting require more than 100 years for complete lake recovery. Whereas the annual discharge to the lake minimally increased, the annual NO₃ ⁻ load greatly increased. Our simulation results elucidate the vulnerability and resiliency of forest ecosystems and provide valuable information for ecosystem management.     

Nucleophilic substitution of poly(vinyl chloride) with iminoacetic acid and n-dodecanethiol

The modification of poly(vinyl chloride) was carried out with iminodiacetic acid (IDA, C₄H₇NO₄) and iminodiacetic acid dimethylester (IDADM, C₆H₁₁NO₄), as well as with n-dodecanethiol (DT, C₁₂H₂₆S) in the presence of K₂CO₃. The reaction was carried out at different temperatures below 100 °C with dimethyl formamide (DMF) and cyclohexanone as solvents. IDA did not show any reactivity, probably due to the dipolar character of the molecule. IDADM caused the elimination of HCl, while only substitution ratios of about 3 % were observed. However, the modification of PVC with DT resulted in a substitution rate of 18 % without elimination. DT-PVC showed excellent thermal properties, comparable with those of the unmodified polymer.     

Detecting crucial dispersal pathways using a virtual ecology approach: A case study of the mirid bug <Emphasis Type="Italic">Stenotus rubrovittatus</Emphasis>

Detecting dispersal pathways is important both for understanding species range expansion and for managing nuisance species. However, direct detection is difficult. Here, we propose detecting these crucial pathways using a virtual ecology approach, simulating species dynamics using models, and virtual observations. As a case study, we developed a dispersal model based on cellular automata for the pest insect Stenotus rubrovittatus and simulated its expansion. We tested models for species expansion based on four landscape parameters as candidate pathways; these are river density, road density, area of paddy fields, and area of abandoned farmland, and validated their accuracy. We found that both road density and abandoned area models had prediction accuracy. The simulation requires simple data only to have predictive power, allowing for fast modeling and swift establishment of management plans.     

One-pot wet ball-milling for waste wire-harness recycling

Journal of Material Cycles and Waste Management - In this study, we developed a one-pot wet ball-milling method for the recovery of highly pure copper wire, poly(vinyl chloride) (PVC) coating, and...