Hidehiro Kumazawa

CO2, N2 gas sorption and permeation behavior of chitosan membrane

The sorption equilibria for CO2 and N2 in dry chitosan membrane at 20 and 30 ‡C were measured by a pressure decay method. The steady-state permeation rates for CO2 and N2 in dry and wet (swollen with water vapor) chitosan membranes at 20 and 30 ‡C were measured by a variable volume method. The sorption equilibrium for N2 obeyed Henry’s law, whereas that for CO2 was described apparently by a dual-mode sorption model. This non-linear sorption equilibrium for CO2 could be interpreted by the interaction of sorbed CO2 with the chitosan matrix expressed as a reversible reaction. The logarithm of the mean permeability coefficient for CO2 in dry chitosan membrane increased linearly with upstream gas pressure. A linear increase of the logarithmic mean permeability coefficient for CO2 with the pressure could be interpreted in terms of a modified free-volume model. The mean per-meability coefficient for N2 in dry chitosan membrane only slightly increased with upstream gas pressure. The per-meabilities for CO2 and N2 in wet chitosan membrane increased by 15 to 17 times and 11 to 15 times, respectively, as compared to those in the dry membrane.

PYROLYSIS OF POLYSTYRENE IN A BATCH-TYPE STIRRED VESSEL

Isothermal pyrolysis of PS was investigated in the relatively low temperature range of 370 to 400 °C, using a stirred tank of batch-type with respect to the liquid phase; the gas phase was operated in an open system. To maintain an isothermal condition, the stirring speed was 80 rpm. At the initial stage of pyrolysis at each temperature, the first-order kinetic law was found to be operative. The activation energy was evaluated to be 224 kJ/mol a value close to the previously reported one. The main liquid products were single and double aromatic ring species: styrene, α-methylstyrene, toluene and 1,3-diphenylpropane, 1,3-diphenylbutene. The yield of styrene was much larger than any other product and amounted to ca. 70 % by weight. The present reactor, operated in an open system with respect to the gas phase, tends to suppress the scission of volatile diphenyl radicals because of short residence times of these radicals.

Degradation of polystyrene in supercritical n-Hexane

Degradation of polystyrene was carried out in supercritical n-hexane under reaction temperature ranging from 330 °C to 390 °C, pressure ranging from 30 bar to 70 bar and reaction duration of 90 min. The conversion of polystyrene increased with rising temperature and pressure. The degradation performance was influenced by the temperature rather than applied pressure. Polystyrene rapidly degraded in 30 min after reaching a prescribed temperature ranging from 350 °C to 390 °C. At a prescribed temperature of 390 °C, the degree of degradation was higher than 90%. The degradation reaction was examined experimentally at a relatively low temperature of 330 °C. The degradation of polystyrene by using supercritical n-hexane has been found to be more effective compared to general pyrolysis (thermal degradation). Among the selectivity of liquid products, that of a single aromatic ring group like styrene at 390 °C increased up to 65% in 90 min. It was found from the analysis by a gel permeation Chromatograph (GPC), that high molecular-weight compounds decreased but oligomers increased with rising temperature.

Transport phenomena in gas permeation through glassy polymer membranes with concentration-dependent sorption and diffusion parameters

The modified dual-mode mobility model for permeation of a gas in glassy polymer membranes was combined with the extended dual-mode sorption model to take account of the plasticization effect of sorbed gas molecules on both sorption and diffusion processes. The combined model was further simplified by the introduction of a concentration of the mobile gas species. However, the observed pressure dependence of mean permeability coefficients of carbon dioxide in methylmethacrylate-n-butyl acrylate copolymer and polymethylmethacrylate films at 30°c and also that of oxygen in a polycarbonate film at 50°C and 60°C showed that a plasticization action of sorbed gas species has an influence on the diffusion process rather than on the sorption process, that is, were simulated by the modified dual-mode mobility model combined with the conventional dual-mode sorption model.

Degradation of high density polyethylene, polypropylene and their mixtures in supercritical acetone

The degradation of high density polyethylene (HDPE), polypropylene (PP) and their mixtures was carried out in supercritical acetone under the reaction temperature ranging from 450 ‡C to 470 ‡C, pressure ranging from 60 atm to 100 atm and reaction duration time as 60 min. The yields of gas, oil and wax components and the compositions and distributions of liquid-like products were measured by means of gas chromatography and gas chromatography/mass spectrometer. In every run, the reaction was completed in 30 min after reaching the prescribed temperature. The yields of oil and gas degraded from PP were not greatly influenced by the temperature, whereas in HDPE, the yields of oil decreased and that of gas increased, respectively, with rising temperature. The yields of oil from HDPE and PP increased with increasing pressure up to 7 atm and the values under higher pressure remained almost constant, i.e., 88% for HDPE and 96% for PP. Correspondingly, the yields of wax from HDPE and PP decreased with increasing pressure below 75 atm and above the value they remained almost constant, especially zero with PP. Generally, the degradation performance was influenced by the temperature rather than applied pressure. For the degradation of mixtures of HDPE and PP, with increasing PP composition, the yield of oil increased, whereas that of wax decreased, and above 80% of PP composition, it decreased to zero. For example, the yields of oil, wax and gas from a 52 wt% HDPE-48 wt% PP mixture, amounted to 90 wt%, 1 wt% and 9 wt%, respectively. The yield of wax decreased with increasing PP percentage.

Plasticization of chitosan membrane for pervaporation of aqueous ethanol solution

The process of pervaporation in which two components diffuse through a nonporous polymer membrane was modelled when one of the penetrants can exert a plasticization action to the membrane material. Thereat a phenomenological model was employed for describing the plasticization effect on the diffusivities for penetrants in the membrane. The sorption equilibria and permeation fluxes for aqueous ethanol solutions in a chitosan membrane were measured, and the permeation fluxes for water were compared with those predicted by the proposed model. The concentration of sorbed water was linear with its weight fraction (x4) in the feed solution, whereas the permeation flux of water was. affected by the plasticization action of sorbed water to the polymer. This plasticization effect on the diffusion process can be simulated in terms of the proposed phenomenological model.

Transport of oxygen and carbon dioxide through polycarbonate membrane

Sorption equilibria and permeation rates for oxygen and carbon dioxide in polycarbonate membrane were measured at different temperature between 30 and 60°C and at pressures up to 2.5 MPa. The pressure dependence of mean permeability coefficient to oxygen obeyed the conventional dual-mode mobility model, whereas that to carbon dioxide followed a modified dual-mode mobility model with concentration-dependent diffusivities, as that of polystyrene to the same gas did.

Gas permeation through glassy polymer membranes with relatively low glass-transition temperature

When the glass-transition temperature of the polymer is not so much higher than the experimental temperature, the pressure dependence of the mean permeability coefficient of the poly-mer membrane to a gas is apt to deviate from the prediction by the conventional dual-mode mobility model, and to obey a similar model with concentration-dependent diffusivities because of the plasticization action of sorbed gas in the polymer membrane. In this work, sorption and permeation for oxygen and carbon dioxide in a membrane of polystyrene whose glass-transition temperature is 95°C, were measured to discuss the mechanism of gas diffusion in glassy polymer membranes with relatively low glass-transition temperature at 30, 40 and 50°C respectively.

Preparation of Anthracene Fine Particles by Rapid Expansion of a Supercritical Solution Process Utilizing Supercritical CO 2

The rapid expansion of a supercritical solution (RESS) process is an attractive technology for the production of small, uniform and solvent-free particles of low vapor pressure solutes. The RESS containing a nonvolatile solute leads to loss of solvent power by the fast expansion of the supercritical solution through an adequate nozzle, which can cause solute precipitation. A dynamic flow apparatus was used to perform RESS studies for the preparation of fine anthracene particles in pure carbon dioxide over a pressure range of 150–250 bar, an extraction temperature range of 50–70 °C, and a pre-expansion temperature range of 70–300 °C. To obtain fine particles, 100, 200 and 300 μm nozzles were used to disperse the solution inside of the crystallizer. Both average particle size and particle size distribution (PSD) were dependent on the extraction pressure and the pre-expansion temperature, whereas extractor temperature did not exert any significant effect. Smaller particles were produced with increasing extraction pressure and preexpansion temperature. In addition, the smaller the nozzle diameter, the smaller the particles and the narrower the PSD obtained.