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1.
N-(Methylphenylmethylidenyl) chitosan (MPMC) polymer was synthesized by chemical modification of chitosan. The chemical structure of the modified polymer was characterized by IR, 1H NMR and elemental analysis. Thermogravimetric reveals that the thermal stability of chitosan polymer is greater than MPMC polymer. The activation energies of thermal degradation of chitosan and MPMC polymers determined using Arrhenius relationship. Thermal degradation of MPMC polymer was studied and the products of degradation were identified by GC–MS technique. It seems that the mechanism of degradation of MPMC polymer is characterized by elimination of low-molecular weight radicals. Combination or recombination of H· or OH with these radicals and random scission mechanism along the backbone chain are the main source of the degradation products.  相似文献   

2.
Hydrolytic depolymerization of polyamide waste in water was studied using 0.5 L high pressure autoclave at temperatures of 235, 240, 245, 250 °C and at autogenious pressure 480, 500, 520, and 600 psi (pound per square inch).The reaction rate constant, energy of activation, enthalpy of activation, entropy of activation and equilibrium constant were calculated from the experimental data obtained. The maximum depolymerization (59.2%) of polyamide waste into monomer caprolactum was obtained at 250 °C and 600 psi pressure. The reaction rate constant was obtained on basis of measurement of amine value and residual weight. The depolymerization reaction was found to be pseudo first order with reaction rate constant of the order of 10−3 min−1. The enthalpy, entropy and free energy of activation were recorded as 85.75, −0.1354 and 156.59 kJ mol−1 respectively at the experimental conditions for maximum depolymerization of polyamide waste. The thermodynamic equilibrium constant for this hydrolysis reaction was found to be 2.3 × 10−16.  相似文献   

3.
Chemical recycling of polyamide waste in water was studied using 0.5 L high pressure autoclave at temperatures of 150, 200, 210, 220,230 and 240 °C and at various pressures of 100, 200, 300, 400, 500, 600 and 700 psi (pound per square inch). Viscosity average molecular weight of the polyamide waste sample was determined by Ostwald method and recorded as 1.928 × 103. The reaction was found to be first order with velocity constant in order of 10−2 min−1. The velocity constant and percent conversion of depolymerization reaction at 240 °C and 700 psi pressure were recorded as 2.936 × 10−2 min−1 and 99.99% respectively. The velocity constant was obtained on the basis of measurement of amine value. Kinetic and thermodynamic parameters such as energy of activation, frequency factor, enthalpy of activation were found to be 10.6 kJ mole−1, 0.3719 min−1 and 6.3 kJ mole−1 respectively, at the optimum conditions for maximum depolymerization of polyamide waste.  相似文献   

4.
Linseed oil-based polymers have been synthesized via cationic and thermal polymerization and characterized through various techniques, such as SEM, DMA, DSC and TGA. The morphology of the polymer samples after extraction reveals the smooth structure of the polymer matrix. With an increase in oil content, the morphology is observed to be more loosely bound. With an increase in linseed oil content in the samples, the room temperature storage modulus (E′) varies from 10.4 × 107 to 1.8 × 107 Pa. The glass transition temperatures measured through DMA of the cationic samples ranges from 70 to −6 °C and the crosslink densities range from 18.4 × 103 to 3.4 × 103 mol/m3. The glass transition temperatures of the thermal samples range from 106 to −4 °C and the crosslink densities range from 7.7 × 103 to 2.4 × 103 mol/m3. The TGA results show three stages of degradation of the polymer samples and it is also revealed that these polymers are stable up to 200 °C, showing negligible decomposition.  相似文献   

5.
In the present work the photo-degradation of polychloroprene (PCP) in toluene solution catalyzed by FeCl3·6H2O and polychromatic light was investigated based on FTIR and 13C NMR spectroscopies, on conductivity measurements and DSC technique. The band in the 1700–1790 cm−1 range in the FTIR spectrum characterized the presence of carbonyl products due to the degradation of the PCP on the solution exposed to polychromatic light. The formation of carbonyl on degraded PCP was confirmed by the presence of signal on 13C NMR at δ 203.5. Products of PCP degradation, such as acid chlorides, generated in the toluene solution migrate to the aqueous phase (in contact with toluene phase) and the conductivity of aqueous phase increased as the time is elapsed. The area related to the PCP melting-peak on the DSC (film casted after the PCP-FeCl3·6H2O toluene solution has been exposed to polychromatic light) significantly decreased in comparison to that in the DSC of the raw PCP cast film.  相似文献   

6.
Emission inventory of deca-brominated diphenyl ether (DBDE) in Japan   总被引:1,自引:0,他引:1  
Atmospheric emissions of deca-brominated diphenyl ether (DBDE) in Japan were estimated based on the material flow of DBDE products and their emission factors. In 2002, the demand for DBDE in Japan was 2200 ton/year and the stock level was about 60 000 ton. The DBDE flow into the waste stream was estimated to be about 6000 ton/year and the flow out through second-hand product exports was more than 700 ton/year. Home appliance recycling facilities dismantle and crush domestic wastes containing about 600 ton of DBDE annually. Material recycling of crushed plastics is not commonly practiced as yet. Emission factors from plastics processing (2 × 10−9–1 × 10−7), textile processing (9 × 10−7), home appliance recycling (8 × 10−9–5 × 10−6), and waste incineration (1 × 10−7–2 × 10−6) were estimated using field measurement data. The DBDE emission rate through house dust during the service life of final products (2 × 10−7–9 × 10−7 per year) was estimated using the DBDE concentration in dust and the amount of dust in used televisions. Emission factors from previous studies were also used. The estimated total DBDE emission was 170–1800 kg/year. These results suggest the necessity of characterizing emissions during the service life of products, which is essential information for formulating an appropriate e-waste recycling strategy.  相似文献   

7.
Solidification of sewage sludge has been actively investigated in Japan and Europe since the 1970s. Most previous studies have focused on only the mechanical aspects of potential alternative cover soil made using sewage. Most solidification processes, however, suffer from severe odor problems because of the high alkalinity of the material. The objectives of this study are to develop a cost-effective solidifying agent for conversion of sewage sludge in order to reduce the odor generation, as an alternative to the conventional cement lime-based solidifying agent, and to demonstrate its applicability in the field experimentally. Field test results showed compressive strength well above the 1.0 kg/cm2 criterion for landfill cover soil in Korea. Also, the permeability coefficient was far below the 5 × 10−5 cm/s design criterion for landfill cover soil. Even in harsh weather conditions, such as in winter and summer, the compressive strength was increased. In addition, the permeability was decreased from 3.45 × 10−6 cm/s to 4.78 × 10−7 cm/s, and from 2.27 × 10−6 cm/s to 3.62 × 10−7 cm/s, at 7 days after placement in January and August, respectively. It can therefore be postulated that the proposed solidification process is an appropriate alternative for production of daily landfill cover material. Concerning the odor problem, 5 min of mixing of sewage with TS103, one of the proprietary agents used in this work, was sufficient to suppress the concentration of ammonia emitted to below 10 ppm. Considering all of these experimental field test results, it is expected that the proposed method could be a competitive approach for manufacture of alternative landfill cover material.  相似文献   

8.
Mesua ferrea L. seed oil (MFLSO) modified polyurethanes blends with epoxy and melamine formaldehyde (MF) resins have been studied for biodegradation with two techniques, namely microbial degradation (broth culture technique) and natural soil burial degradation. In the former technique, rate of increase in bacterial growth in polymer matrix was monitored for 12 days via a visible spectrophotometer at the wavelength of 600 nm using McFarland turbidity as the standard. The soil burial method was performed using three different soils under ambient conditions over a period of 6 months to correlate with natural degradation. Microorganism attack after the soil burial biodegradation of 180 days was realized by the measurement of loss of weight and mechanical properties. Biodegradation of the films was also evidenced by SEM, TGA and FTIR spectroscopic studies. The loss in intensity of the bands at ca. 1735 cm−1 and ca. 1050 cm−1 for ester linkages indicates biodegradation of the blends through degradation of ester group. Both microbial and soil burial studies showed polyurethane/epoxy blends to be more biodegradable than polyurethane/MF blends. Further almost one step degradation in TG analysis suggests degradation for both the blends to occur by breakage of ester links. The biodegradation of the blends were further confirmed by SEM analyses. The study reveals that the modified MFLSO based polyurethane blends deserve the potential to be applicable as “green binders” for polymer composite and surface coating applications.  相似文献   

9.
The objective of this study was to investigate the feasibility of using a microbial biopolymer produced by Acetobacter xylinum as a carbon source for heterotrophic biological denitrification. The denitrification rate, COD availability and nitrite concentration were response parameters. Under the experimental conditions, a denitrification rate of about 0.74 kg NO3 N/m3d at 6 h retention time was achieved with microbial cellulose (MC). The reactor effluent contained significantly COD concentrations (20–86 mg/L) so it was not carbon limited, and was receiving enough carbon to facilitate the denitrification process. The maximum nitrite concentration in the effluent was found to be 0.4 mg/L. However, decreasing the retention time to 3 h significantly reduced the efficiency. It can be concluded that the MC is a suitable carbon source for nitrate removal in a heterotrophic biological denitrification process.  相似文献   

10.
In municipal solid waste incineration (MSWI), bottom ash, generated at a stoker grate type incinerator, the critical elements were identified in terms of EU regulation. The stabilizing effect of moderate carbonation (pH 8.28 ± 0.03) on critical contaminants was studied through availability and diffusion leaching protocols. Data from the performed tests were evaluated with the goal of reusing MSWI bottom ash as secondary construction material. To investigate the mobilizing effect of CO2, suspended MSWI bottom ash was severely carbonated (pH 6.40 ± 0.07). The effect of CO2 and its interaction with other leaching factors, such as liquid/solid (L/S) ratio, leaching time, pH, ultrasound treatment, and leaching temperature, were examined using a reduced 26-1 experimental design. Contaminants identified as critical were Cr, Cu, Mo, Sb, Cl, and SO4 2−. Although moderate carbonation decreased the release of Cr, Cu, Mo, and Sb from compacted bottom ash, the main disadvantage remains its inability to demobilize Cl and SO4 2−. The hypothesized mobilizing effect of severe carbonation was proven. The treatment enhanced the separation of critical components (α = 0.05) (except for Cl), i.e., about fivefold for Sb and about twofold for Cr, Cu, and S. Nevertheless, the prospect is good that severe carbonation could constitute the deciding key parameter to facilitate the technical feasibility of a future washing process for MSWI bottom ash.  相似文献   

11.
Polylactic acid (PLA) is a hydrolytically degradable aliphatic polyester, and water vapor permeability may have a significant influence on the rate of degradation. A method is devised to use bags prepared from PLA films and filled with molecular sieves to determine the water vapor permeability in the polymer, its copolymers with caprolactone, and blends with polyethylene glycol. The “solution-diffusion” model is used to determine the permeability parameters. These include the solubility coefficient,S, a measure of the equilibrium water concentration available for hydrolysis and the diffusion coefficient,D, which characterizes the rate of water vapor diffusion into the film under specific conditions. Values ofS andD at 50‡C and 90% relative humidity ranged from 400 × 10-6 to 1000 × 10-6 cm3 (STP)/(cm3 Pa) and 0.20 × 10-6 to 1.0 × 10-6 cm2/s, respectively. TheS andD coefficients were also measured at 20 and 40‡C and compared to those of other polymers. The degree of crystallinity was found to have little influence on the measured permeability parameters. The heat of sorption, δHS, and the activation energy of diffusion, ED, were used to show that the permeability process is best described by the “water cluster” model for hydrophobic polymers. Finally, the diffusion coefficient is used to compare the rate of water diffusion to the rate of water consumption by ester hydrolysis. Results indicate that hydrolytic degradation of PLA is reaction-controlled.  相似文献   

12.
For an effective decomposition and removal of organic halogenated compounds, a packed-bed non-thermal plasma reactor with in situ absorption of the resulting halogenated products by alkaline sorbent incorporated was proposed. In the plasma reactor, α-Al2O3 particles of 1 and 3 mm (mean particle diameter) were packed as solid dielectric medium to enhance the plasma power density in the reactor. Further, alkaline sorbent of Ca(OH)2 was doped onto the surface of α-Al2O3 particles, in order to remove halogenated products by in situ absorption with Ca(OH)2. A high-voltage and high-frequency pulsed power of −15 to 15 kV and 1 kHz was applied to the wire electrode of the plasma reactor by means of a DC power source. In the present study, as the sample of an organic halogenated compound that is most popularly used, we selected dichloromethane (CH2Cl2), and 500 ppm of the initial concentration of CH2Cl2 was fed into the reactor accompanied by air at a fixed flow rate of 500 × 10−6 m3 min−1 at room temperature. As a result, it was recognized that the amount of CH2Cl2 decomposed by non-thermal plasma in an α-Al2O3 particle bed increased with an increase in plasma input power. The ratio of decomposition of CH2Cl2 was almost 100% at 13 kV of electric power and 1 kHz frequency, and CO2, CH3Cl, COCl2, HCl, and Cl2 were observed as the major reaction products. On the other hand, when CH2Cl2 was introduced into the plasma reactor where α-Al2O3 particles doped with Ca(OH)2 were packed, the ratio of decomposition of CH2Cl2 became higher, compared to the case that α-Al2O3 particles were not doped with Ca(OH)2. Moreover, there were no halogenated by-product gases detected in the outlet gas from the reactor. As the solid reaction products, CaClOH and Ca(ClO)2·4H2O were detected on Ca(OH)2 by X-ray diffraction. From these findings, it was recognized that CH2Cl2 was decomposed more effectively without producing unwanted harmful halogenated by-products in the proposed non-thermal plasma reactor where α-Al2O3 particles doped with Ca(OH)2 sorbent were packed.  相似文献   

13.
The kinetic behavior of polyesterification of the alkyd resins synthesized using glycerol and phthalic anhydride modified with oleic acid from the palm oil at temperatures between 120 and 240 °C was studied. Three alkyds having oleic acid contents of 28, 40, and 65% were prepared by employing fatty acid method. The extent of the polyesterification reaction and average degree of polymerization were monitored by determining the acid number of the aliquot of the reaction mixture at various intervals of time and by measuring the volume of water evolved. Kinetic studies revealed that initial reaction rates followed a second-order kinetics up to certain limit and thereafter deviations were observed. The extent of reaction varied from 77.4 to 86.3% before deviation for all the three samples and exhibited a considerable degree of conversion. The second-order rate constants calculated from the linear part were found to be of the order of 10−5 g (mg KOH)−1 min−1. Molecular weight of the alkyd samples was determined by GPC; number average molecular weight of the alkyds ranged from 980 to 2,070.  相似文献   

14.
A simple, low-cost method for suppression of dioxins/furans (hereinafter referred to as dioxins) is required because many middle- and, especially, small-scale incinerators have fallen into disuse or have been dismantled because of the high running and system costs of measures for the suppression of dioxins. Therefore, the purpose of the present study was to develop a simple removal method for dioxins from combustion gas and to evaluate the basic removal rate of dioxins. The removal method for suspended matter in a gas mixture (cold model) and dioxins in exhaust gases (hot model) has been investigated by means of gas injection into water, the mechanism of which is that the suspended matter in the gas gathers at the gas–liquid interface. In the cold model, the removal ratio of fine particles (RP) by gas injection into water was reproduced well by the following equation: RP (%) = 100 × {1−exp(−0.8 · SS · tC)}, where SS (cm2/cm3) is the specific surface area of bubbles and tC (s) is the residence time of bubbles in water. The removal ratio of fine particles increased as the product Ss · tC increased. In a hot model using the exhaust gas from combustion experiments of polyvinyl chloride, the removal ratio of dioxins (RD) by injecting the exhaust gas into water was estimated by the following equation: RD (%) = 100 × {1−exp(−0.8 · SS · tC · CD0 0.07)}, where CD0 [ng/cm3 (at standard temperature and pressure)] is the dioxins concentration in the exhaust gas before injection into water. RD depends greatly on the specific surface area of bubbles and the residence time of the bubbles in water, and only weakly on the dioxins concentration in the exhaust gas. Injection of the exhaust gas into water has been shown to be effective and was evaluated as a simple method for the removal of dioxins from exhaust gas.  相似文献   

15.
Chitosan (0.1–1%, w/w), dissolved in 2% acetic acid solution, was added into 1% methylcellulose (MC)-based formulation containing 0.5% vegetable oil, 0.25% glycerol and 0.025% Tween?80. Films were prepared by casting. Puncture strength (PS), puncture deformation (PD), viscoelasticity coefficient and water vapour permeability (WVP) of the films were measured. The PS value of 312 N/mm was observed for MC-based films containing 0.25% chitosan. Values of PD, viscoelasticity coefficient and WVP of these films were 5.0 mm, 44.1%, and 6.0 g mm/m2 day kPa, respectively. The MC-based films containing 0.25% chitosan were also exposed to gamma radiation (0.5–50 kGy). The PS of the treated films decreased significantly from 312 at 0 kGy to 201 N/mm when treated at a dose of 50 kGy. However, WVP values were not affected by increasing irradiation the dose used. The Fourier Transform Infrared spectroscopy supported the molecular interactions due to addition of chitosan in MC-based films. Thermo gravimetric analysis and differential scanning calorimetric experiments showed that thermal properties of the films were significantly improved by chitosan loading. Surface topography of the films was studied by scanning electron microscopy and found rougher due to chitosan addition.  相似文献   

16.
The formation and decomposition of tetrafluoroborate ions (BF4) in H3BO3-Al3+-F solutions were investigated via experiments and thermodynamic calculations. The concentration of the formed BF4 increased with decreasing pH, raising the total fluoride concentration and lowering the total aluminum ion concentration. Once formed, BF4 was stable under neutral and alkaline conditions. Fluoride in the form of BF4 was converted to fluoroaluminate ions by adding an aluminum compound under acidic conditions. A method for removing fluoride in the form of BF4 is proposed whereby fluoroaluminate ions formed by the reaction of BF4 with aluminum are decomposed with calcium ions. This process was applied to the treatment of wastewater from flue gas desulfurization plants, and resulted in a satisfying level of reduction in the range of the fluoride emission limit of 8 mg/l.  相似文献   

17.
To obtain basic information for evaluating critical levels of O3 under different nitrogen loads for protecting Japanese beech forests, two-year-old seedlings of Fagus crenata Blume were grown in potted andisol supplied with N as NH4NO3 solution at 0, 20 or 50 kg ha−1 year−1 and exposed to charcoal-filtered air or O3 at 1.0, 1.5 and 2.0 times the ambient concentration from 16 April to 22 September 2004. The O3 induced significant reductions in the whole-plant dry mass, net photosynthetic rate at 380 μmol mol−1 CO2 (A 380), carboxylation efficiency (CE) and concentrations of ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) and total soluble protein (TSP) in the leaves. The concentrations of Rubisco and TSP were negatively correlated with the concentration of leaf acidic amino acid, suggesting that O3 enhanced the degradation of protein such as Rubisco. The N supply to the soil did not significantly change the whole-plant dry mass and A 380, whereas it significantly increased the CE and concentrations of Rubisco and total amino acid. No significant interactive effects of O3 and N supply to the soil were detected on the growth, photosynthetic parameters and concentrations of protein and amino acid in the leaves. In conclusion, N supply to the soil at ≤50 kg ha−1 year−1 does not significantly change the sensitivity to O3 of growth and net photosynthesis of Fagus crenata seedlings.  相似文献   

18.
The objective of the study was to develop a low cost and environmentally friendly liner system for a landfill bioreactor to harness energy from waste. The landfill bioreactor test cell was constructed and evaluated for performance under dry tropical conditions of Sri Lanka. The research was carried out from March 2009 to September 2010. The clay-waste polyethylene-clay composite liner system was developed and permeability was tested. The permeability values of the liner under both saturated and unsaturated conditions at the high estimated hydraulic head of 86.2 cm were in between 6.3 × 10−8 and 2.6 × 10−8 cm/s. The permeability of the liner under waste filled condition varied between 2.17 × 10−9 and 8.15 × 10−9 cm/s, which satisfies the standard permeability value. Thus, the results were below the minimum requirement at very high estimated leachate head. After loading the test cell, leachate and permeate characteristics were analyzed for 273 days, from January 2010 to September 2010. The study showed the relationships among various parameters including pH, electrical permeability, chemical oxygen demand, biological oxygen demand, ammonia, nitrate, phosphate, total solids, volatile solids, total suspended solids and volatile suspended solids. The results of the analysis indicated that there are significant differences in the values of leachate and permeate parameters. The permeate parameters had values very much lower than those of leachate. It reveals that the clay-waste polyethylene-clay composite liner system reduced the concentration of these parameters when the leachate passed through the liner. The biofilm formed in waste polyethylene within the liner may have degraded most of organic materials found in the leachate when it passed through the liner. Therefore, the clay-waste polyethylene-clay composite liner system can be applied for full scale landfill bioreactors, particularly for Asian developing countries, due to better performance and more environmentally friendly characteristics.  相似文献   

19.
The kinetics of polyesterification of glycerol, phthalic anhydride and jatropha oil leading to the formation of alkyd resins were studied. A series of alkyd resins having different amount of jatropha oil viz., 40–80% have been prepared by employing two stage alcoholysis-polyesterification process. The extent of reaction and average degree of polymerisation were calculated from the end group analysis of the reaction mixture withdrawn at regular intervals of time. The initial reaction rates followed the second order kinetics and thereafter deviations were observed. An appreciable degree of conversion was noticed from the extent of the reaction which lies in the range of 49.5–62.5%. The average degree of polymerisation calculated in the region of deviation from second order suggested the occurrence of chain branching at relatively shorter intervals along the polymer chain. The second order rate constants were found to be of the order of 10−5 g (mg KOH)−1 min−1.  相似文献   

20.
The electrochemical degradation of chitosan using Ti/Sb–SnO2 electrode was studied in this work. The experimental results showed that as a non-active electrode with high oxygen potential, Ti/Sb–SnO2 electrode had a good efficiency for degrading chitosan. The kinetic behavior of electrochemical degradation of chitosan using Ti/Sb–SnO2 electrode and the function relationship between experimental parameters and degradation rate constant were also investigated. The kinetic analysis revealed that this electrochemical process using Ti/Sb–SnO2 electrode obeyed the zeroth–order reaction kinetics under the experimental conditions examined. The degradation rate constant at Ti/Sb–SnO2 electrode had the linear relationship with 1.13 power of current density, ?1.36 power of initial concentration of chitosan and 0.19 power of concentration of acetic acid, The temperature dependences of the degradation rate constant could be expressed by the Arrhenius equation. The concentration of sodium acetate had a negligible influence on the degradation rate constant.  相似文献   

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