Recovery of benzene-rich oil from the degradation of metal- and metal oxide-containing poly(ethylene terephthalate) composites

Pure poly(ethylene terephthalate) (PET) resin and metal-/metal oxide-containing PET composites were thermally decomposed in the presence of Ca(OH)₂ using a tube reactor. The effects of batch and continuous processing, the presence of Ca(OH)₂, and PET size on benzene production were investigated. A maximum benzene yield and purity of 82.9 % and 78.8 wt%, respectively, were obtained at 700 °C in the presence of Ca(OH)₂ when using small PET particles; further, a continuous feed reactor was favored over a batch reactor. Effective contact between PET and Ca(OH)₂ was important in the PET degradation, which promoted hydrolysis of PET and decarboxylation of terephthalic acid, whereas pyrolysis was suppressed. Furthermore, the results of thermal decomposition of PET-based waste—PET-based X-ray films, magnetic tape, and prepaid cards—indicated that the metal and metal oxides contained in the waste had no significant catalytic effect on PET degradation or on the recovery of benzene-rich oil in the presence of Ca(OH)₂.     

Solubility parameters for determining optimal solvents for separating PVC from PVC-coated PET fibers

Poly(vinyl chloride) (PVC) in PVC-coated poly(ethylene terephthalate) (PET) fabrics can be separated through dissolution in a suitable solvent, leaving only the PET fibers. We investigated the solubility of PVC in 30 solvents using swelling tests. The results were compared with those obtained using the Hansen, Gutmann, Swain, E _T(30), and Kamlet–Taft parameters. For this purpose, Gaussian plots of the PVC swellability versus solubility parameter were used to decide the applicability of the solubility parameter system. Only Gutmann’s electron acceptor–donor parameter (AN + DN) and the Kamlet–Taft parameters β and π* could describe the PVC-solvent system satisfactorily. Tetrahydrofuran (THF), methyl ethyl ketone (MEK), N,N-dimethylformamide (DMF), cyclohexanone, and cyclopentanone were tested for separating PVC from PET at different temperatures. THF dissolved PVC at 20 °C, while cyclohexanone and cyclopentanone did so at 40 °C. Traces of PVC remained on the PET fibers when DMF was used. Complete dissolution of PVC was not achieved at any temperature with MEK. The present work shows that solubility parameters are a helpful tool for the search for suitable solvents. It shows also that solubility parameters have to be selected carefully, since their usefulness depends strongly on the polymer properties.     

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.     

Efficient dehalogenation of automobile shredder residue in NaOH/ethylene glycol using a ball mill

We investigated the effectiveness of sodium hydroxide/ethylene glycol (NaOH/EG) for dehalogenation of automobile shredder residue (ASR) using a ball mill. Efficient dehalogenation was achieved at atmospheric pressure by combining the use of EG (196 degrees C b.p.) as a replacement solvent for NaOH with ball milling, which improved contact between ASR and OH(-) in solution. Moderate NaOH concentrations and increased ball mill rotation speeds produced high dechlorination that was not significantly affected by the weight ratio of ASR to EG. NaOH/EG dechlorination increased with temperature with an apparent activation energy of 50 kJ mol(-1) confirming that the reaction proceeded under chemical reaction control. The modified shrinking-core model was appropriate to explain the dechlorination process. Low chloro levels in our NaOH/EG-treated ASR suggested that this material could be used for feedstock recycling and the wet process may be applicable for dehalogenation of other important waste streams.     

Cost-effectiveness Analysis of Reducing the Emission of Nitrogen Oxides in Asia

The purpose of this study is to evaluate cost-effective reduction strategies for nitrogen oxides (NO _x ) in the Asian region. The source-receptor relationships of the Lagrangian “puff” model of long-range transportation, ATMOS-N, were used to calculate the wet/dry deposition of the nitrogen (N) in Asia. Critical loads of N deposition in Asia were calculated from the relationships between the critical load of sulfur (S) and balance of N in and out using the data of S critical load of RAINS-ASIA. The cost functions of N reduction of Asian countries were derived by the regression analysis with the data of cost functions of European countries used in RAINS. In order to assess the environmental impact, the gaps between N deposition and critical load of N were calculated. The emission of NO _x was reduced in some cases of this model, and the changes of gaps between N deposition and critical load were observed as well as the changes of the reduction cost. It is shown that a uniform reduction of NO _x emissions by countries in Asia is not cost-effective strategy.     

Isomer distribution of nitrotriphenylenes in airborne particles, diesel exhaust particles, and the products of gas-phase radical-initiated nitration of triphenylene

The formation of mutagenic nitro-polycyclic aromatic hydrocarbons (NPAHs) 1- and 2-nitrotriphenylene (1- and 2-NTP) via gas-phase OH or NO₃ radical-initiated reactions of triphenylene was demonstrated for the first time using a flow reaction system. In contrast with the results of conventional electrophilic nitration, 2-NTP was formed in larger yield than 1-NTP, but this is consistent with the mechanism proposed for gas-phase radical-initiated nitration of PAH. In diesel exhaust particle (DEP) samples, both 1- and 2-NTP were identified and their concentrations determined, as well as 1-nitropyrene (1-NP), which is a representative combustion-derived NPAH: the mean concentrations of 1-NTP, 2-NTP, and 1-NP were 4.7, 1.9, and 32 pmol mg_DEP^–1, respectively. The mean 2-NTP/1-NTP, 1-NTP/1-NP, and 2-NTP/1-NP ratios in samples of airborne particles collected in a residential area in Osaka, Japan, were>1.55,<0.25, and 0.37, respectively; these values are much higher than those of the DEP samples. This finding indicates that there is another source for airborne NTPs, especially 2-NTP, apart from diesel exhaust. These results strongly suggest that airborne NTPs originate from atmospheric processes such as radical-initiated reactions of triphenylene, and this has a significant influence on the atmospheric occurrence of NTPs.     

Association of the mutagenicity of airborne particles with the direct emission from combustion processes investigated in Osaka, Japan

The association of the direct-acting mutagenicity of soluble organic fraction of airborne particles toward Salmonella typhimurium YG1024 strain with the direct emission was investigated at a roadside and at a residential area in Osaka, Japan. The direct-acting mutagenicity was evaluated as mutagenic activity per unit volume of ambient air (rev m⁻³) and/or that per airborne particulate weight collected on a filter (rev mg⁻¹). The annual or diurnal changes of the mutagenicity of airborne particles at the residential site showed similar patterns to those of some gaseous pollutants such as NO₂ and SO₂, which were emitted from combustion processes. This result indicates that the mutagenicity is mainly attributable to the primary emissions. From the analysis of the relationship between the wind sector and the mutagenic intensity, rev m⁻³ and rev mg⁻¹ values were strongly affected by the emissions from the fixed sources and from the mobile sources, respectively. The rev m⁻³ value and concentration of 1-nitropyrene (1-NP) in unit per m³ at the roadside were a factor of 2.6 and 2.8 higher than those at the residential site, respectively, but the rev mg⁻¹ value and concentration of 1-NP in unit per mg at the roadside were substantially comparable to those at the residential area. These observations suggest that the characteristics of the airborne particles can be attributed to the automotive emissions even at the suburban area.     

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.