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.     

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.     

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.     

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.