Dechlorination of PCBs by electrochemical reduction with aromatic radical anion as mediator

Mediated electrochemical reduction was applied to the dechlorination of polychlorinated biphenyls (PCBs) in tetra-n-butylammonium perchlorate/dimethylformamide solution. Rapid and complete dechlorination was possible with biphenyl or naphthalene as the mediator, whereas the reaction was much slower with anthracene or 9,10-diphenylanthracene. The reaction rate was so high with naphthalene or biphenyl radical anion that differences in reactivity could not be observed between congeners. Side reactions, other than biphenyl formation, could occur depending upon the mediators and the substrates, but contributed less than 10% of the total products in the case of naphthalene-mediated dechlorination. Almost all chloride ion formed in the dechlorination remained in the cathode solution. The order of the reaction was determined to be 0.5 for the substrate and 1 for the mediator (naphthalene) in the dechlorination of 2-chlorobiphenyl; identical to results for the mediated dechlorination of 1-chloronaphthalene. The reaction rate in practical PCB dechlorination could be estimated with the use of the initial concentration of the mediator and chlorine content of the solution provided that the problem of the deactivation of the electrode surface could be solved.     

Investigation of the self-heating and spontaneous ignition of refuse-derived fuel (RDF) during storage

Refuse-derived fuel (RDF)—RDF-5 according to ASTM guidelines—derived from municipal solid waste and other waste materials, has been prepared as a fuel source for power plants in Japan. RDF has been known as a stable and safe solid-fuel. However, some spontaneous ignition incidents occurred during storage of RDF in certain facilities. In the present study, the storage conditions, which might induce the spontaneous ignition in RDF samples, was investigated to understand and prevent this phenomenon. When the initial temperature of RDF sample was consistent, higher water content and shorter induction times was observed (e.g., the induction times of select RDF samples with 5.8% and 16.7% water content, was 446 and 270 min, respectively). Also, the induction time was affected by the size of a RDF sample. No relationship between bacterial fermentation and spontaneous ignition was observed. The linear relationship between the induction time and the inverse of the initial temperature of the RDF sample was obtained in the Arrhenius equation.     

Polyfluorinated telomers in indoor air of Japanese houses

The fluorotelomer alcohols (FTOHs) have been detected in various environmental compartments, including indoor and outdoor air, in North America and Europe. In our previous studies, FTOHs were detected at a relative higher concentration in outdoor air in the Keihan (Kyoto–Osaka, one of the major industrial zones) area, Japan compared to reported data. The exposure level of FTOHs in indoor air in the Keihan area remains unclear. In the present study, indoor air FTOH concentrations were investigated using a passive air sampler containing activated carbon felts. The indoor air sampling was conducted in 49 households of the Keihan area, during winter and summer 2008. Most samples contained 6:2 FTOH, 8:2 FTOH, 10:2 FTOH and 8:2 FTOAc. The median concentration of 8:2 FTOH (5.84 ng m^?3) was highest among fluorotelomers, followed by those of 10:2 FTOH (1.12 ng m^?3), 6:2 FTOH (0.29 ng m^?3), and others. Significant correlations among fluorotelomers were observed in collected samples. The association between housing conditions and 8:2 FTOH concentrations showed that samples collected from bed rooms have higher 8:2 FTOH concentrations than those collected from other locations. In addition, samples collected in winter showed lower levels of 8:2 FTOH than those collected in summer. These findings suggest that 8:2 FTOH is the predominant component among fluorotelomers in indoor air, and that there are emission sources of fluorotelomers in indoor environments of the Keihan area. Further investigations into the origins of fluorotelomers are needed to evaluate indoor contamination with fluorotelomers.     

Improved preparation of recycled polymers in chemical recycling of fiber-reinforced plastics and molding of test product using recycled polymers

We examined an improved preparation method of recycled unsaturated polyester resin from recovered monomeric materials obtained from the depolymerization of fiber-reinforced plastics (FRPs). The formation of unsaturated polyester progressed smoothly in the presence of catalytic amounts of Ca(OAc)₂ and Ti(OBu)₄. The quality of the resin was estimated by the durometer hardness test. The strength test of FRP board prepared from recycled resin showed sufficient hardness for practical use (about 94% of the tensile strength of new resin). We examined the recycled resin by using it to mold successfully an actual test product.     

Relation between odor and odorous components in solid swine manure

Odor similarity of the synthetically prepared solutions and the extract from solid swine manure showed that the main components for odor of solid swine manure are carboxylic acids and sulfides and that p-cresol increases the malodor and skatole modifies the nature of the malodor.     

Efficient chemical recycling of waste fiber-reinforced plastics: use of reduced amounts of dimethylaminopyridine and activated charcoal for the purification of recovered monomer

We have achieved major improvements in the efficient chemical recycling of waste fiber-reinforced plastics (FRPs). The effects of reduction in the amounts of dimethylaminopyridine (DMAP) used for depolymerization were examined. The treatment of waste FRP in the presence of 1 or 2 wt% DMAP resulted in the successful recovery of monomeric materials that could be employed in the polymerization process to produce recycled plastic. The separation of linker units from glass fiber, however, was unsuccessful. The purity of the recovered monomeric material, when treated with activated charcoal, was improved to about 70%. This resulted in effective decoloration of the recovered monomer. Finally, the purified material, after undergoing repolymerization, provided high-quality recycled plastic comparable to new plastics produced from new monomers.     

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     

Gas phase equilibria for dibenzo‐p‐dioxin,dibenzo‐p‐furan and biphenyl in the C‐H‐O system

The gas phase equilibrium calculation for the C‐H‐O system at atmospheric pressure and temperature from 773 to 1773 K at intervals of 250 K was performed to understand the generation and decomposition behavior of dibenzo‐p‐dioxin (DD), dibenzo‐p‐furan (DF) and biphenyl (BP) in relation to the existing oxygen potential. It is possible to categorize these results into three regions from the viewpoint of this potential: region (A), region (B) and region (C) are that of the higher, modest and lower oxygen potential, respectively. In region (A), the equilibrium amounts of DD, DF and BP are nearly zero. In region (B), they increase once and then decrease with rise in temperature. In the most characteristic region (C), they increase uniformly with rise in temperature.     

High performance liquid chromatographic determination of pesticides in soluble phase and suspended phase in river water

A high performance liquid chromatographic method has been developed to determine pesticides in river water as both dissolved phase and suspended phase. The target pesticides were eight herbicides, asulam, diuron, flazasulfuron, linuron, MCPB, mecoprop, pyrazosulfuron‐ethyl and siduron, and two fungicides, oxine‐copper and thiram. The pesticides in filtered river water were extracted with styrene‐divinylbenzene copolymer and were eluted with acetonitrile. The pesticides on suspended solids were extracted ultrasonically with acetonitrile. Each eluate was concentrated and analyzed by HPLC with multiwavelength detector. Recoveries of the pesticides in the overall procedure of this method were 78–114% for filtered river water and 75–107% for suspended solids. The limits of detection in water and suspended solids ranged from 0.1 to 0.9 μg/L and 1 to 7 μg/g, respectively. Pesticide distribution between soluble phase and suspended phase in river water was measured by this method.