Selective CO oxidation in the presence of hydrogen over supported Pt catalysts promoted with transition metals

Selective CO oxidation in the presence of excess hydrogen was studied over supported Pt catalysts promoted with various transition metal compounds such as Cr, Mn, Fe, Co, Ni, Cu, Zn, and Zr. CO chemisorption, XRD, TPR, and TPO were conducted to characterize active catalysts. Among them, Pt-Ni/γ-Al₂O₃ showed high CO conversions over wide reaction temperatures. For supported Pt-Ni catalysts, Alumina was superior to TiO₂ and ZrO₂ as a support. The catalytic activity at low temperatures increased with increasing the molar ratio of Ni/Pt. This accompanied the TPR peak shift to lower temperatures. The optimum molar ratio between Ni and Pt was determined to be 5. This Pt-Ni/γ A1₂O₃ showed no decrease in CO conversion and CO₂ selectivity for the selective CO oxidation in the presence of 2 vol% H₂O and 20 vol% CO₂. The bimetallic phase of Pt-Ni seems to give rise to stable activity with high CO₂ selectivity in selective oxidation of CO in H₂-rich stream.     

The removal of hydrogen sulfide with manganic sorbent in a high-temperature fluidized-bed reactor

The removal of hydrogen sulfide (H₂S) from simulated gas was carried out in a batch type fluidized-bed reactor using natural manganese ore (NMO), which consists of several metal oxides (MnO_x: 51.85%, FeO_y: 3.86%, CaO: 0.11%). The H₂S breakthrough curves were obtained by changing temperature, gas velocity, initial H₂S concentration, and aspect ratio. Moreover, the effects of the particle size and the particle-mixing fraction on H₂S removal were investigated in a binary system of different particle size. From this study, H₂S removal efficiency increased with increasing temperature but decreased with increasing excess gas velocity. The breakthrough time for H₂S decreased as the gas velocity increased, which leads to reducing gas-solid contacting due to gas bypassing in a fluidized bed reactor. Improvement of H₂S removal efficiency in continuous process can be expected from the results of the binary particle system with different size in a batch experiment. The NMO could be considered as a potential sorbent in H₂S removal.     

Preparation and characterization of modified starch‐based plastic film reinforced with short pulp fiber. II. Mechanical properties

Native corn starch‐ and hydroxypropylated starch (HPS‐) based plastic films were prepared using the short pulp fiber as the reinforcement and the glycerol as the plasticizer. The results of tensile test showed that the strain and stress at break and elastic modulus increased with pulp content. With glycerol content, the strain at break increased considerably, but the breaking stress and elastic modulus decreased. And the stress–strain curves showed that the brittleness problem of films was overcome by the pulp, glycerol, and water content. The hydroxypropyl starch films showed results similar to those of the native starch films. The results of the three‐point bending test showed that maximum deflection, flexural strength, and specific work increased with pulp content, but the flexural modulus was the highest at a pulp content of 20%. And with the glycerol content, the maximum deflection and specific work of rupture increased, but the bending elastic modulus decreased. The hydroxypropyl starch films showed results similar to those of native starch films as far as the maximum deflection and flexural strength were concerned, but the bending elastic modulus and specific work of the hydroxypropyl starch films were considerably lower than those of starch films. So it was concluded that the flexibility of films was improved by the hydroxypropylation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2108–2117, 2003     

Crystal shape monitoring and supersaturation measurement in cooling crystallization with quartz crystal oscillator

A crystallization monitoring system using a quartz crystal oscillator was utilized to predict different shapes of crystal formation by measuring crystal growth rate and to measure supersaturation. Applying different rates of cooling, crystal formation of different shapes was induced, and the frequency variation of the oscillator and the crystal shape observed with an SEM were compared to determine how the frequency variation can be interpreted for the prediction of produced crystal shape. The experimental results obtained from the crystallization of potassium nitrate and cupric sulfate solutions showed that the proposed frequency measurement technique could be applied in the prediction of crystal shape of cooling crystallization processes. In addition, supersaturation was determined from the measurements of solution and coolant temperatures.     

Properties of chitosan‐based biopolymer films with various degrees of deacetylation and molecular weights

An increase in the depolymerization of chitosan was found with an increased concentration of sodium perborate. Acetic anhydride was added to reacetylated chitosan in a molar ratio per gulcosamine unit, and the amide I band of IR spectra changed with the addition of acetic anhydride. Sixteen chitosans with various molecular weights (MWs) and degrees of deacetylation (DODs) were prepared. X‐ray diffraction patterns indicated their amorphous and partially crystalline states. Increases in the chitosan MW and DOD increased the tensile strength (TS). TS of the chitosan films ranged from 22 to 61 MPa. However, the elongation (E) of chitosan films did not show any difference with MW. TS of chitosan films decreased with the reacetylation process. However, E of chitosan films was not dependent on DOD. The water vapor permeabilities (WVPs) of the chitosan films without a plasticizer were between 0.155 and 0.214 ng m/m² s Pa. As the chitosan MW increased, the chitosan film WVP increased, but the values were not significantly different. Moreover, the WVP values were not different from low DOD to high DOD. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3476–3484, 2003     

High catalytic activity of PdOx/MnO2 for CO oxidation and importance of oxidation state of Mn

PdO_x/MnO₂ has been examined as a catalyst for CO oxidation using a conventional flow reactor at reaction temperatures between 50 and 150°C. In the reaction conditions of GHSV (gashourlyspacevelocity) of 1.22 × 10⁵/h and CO concentration of 2000 ppm, PdO_x/MnO₂ showed higher catalytic activity compared with PdO_x/Mn₂O₃, which had been previously reported as an effective catalyst due to the cooperative action of Pd and Mn₂O₃ for this reaction. The reason for higher activity of PdO_x/MnO₂ than PdO_x/Mn₂O₃ has been investigated using TPR (temperatureprogrammed reduction) and XPS studies. TPR showed that PdO_x/MnO₂ could be reduced by CO at much lower temperature than PdO_x/Mn₂O₃. During the experiment of reduction and oxidation, XPS showed that the valence of Mn in the PdO_x/MnO₂ was between 4+ and 3+, which is higher than that of Mn in the PdO_x/Mn₂O₃ catalyst of which the valence has been reported to be between 3+ and 2+. It is known that in this catalyst system the support supplies oxygen onto Pd, where the oxidation occurs with adsorbed CO, and the ability of the support to provide oxygen improves the performance of the catalyst. Therefore, it was concluded that the readiness of MnO₂ to be reduced with maintaining a higher oxidation state showed higher CO oxidation activity than Mn₂O₃ as support for PdO_x.     

Absorption of NO x in packed column (I)

A mathematical model for an absorption of nitrogen oxides into water in packed column was developed based on the mass-transfer coefficient in packed column and the chemical reaction accompanying NO _x absorption produces HNO₃ and HNO₂ in the liquid phase. The subsequent dissociation of HNO₂ in the liquid-phase results in the formation of HNO₃ and NO gas, and then this NO gas follows to be oxidized by O₂ in air. The important factors influenced on the absorption of NO _x are the oxidation state of NO gas and the partial pressure of nitrogen oxides in the gas. The efficiency of NO _x absorption increases with the increase of the partial pressure of NO _x . The most critical value for using the model is the constant of .The selection of 11×10⁻⁴kg·mol/atm·m²·sec for resonable for this model.     

Influence of mixing cycle on the degree of mixing of calcite‐filled polyethylene upon stretching

The mixing cycle‐dependent degree of dispersion and degree of mixing of a calcite (calcium carbonate) agglomerate in high‐density polyethylene (HDPE), low‐density polyethylene (LDPE), and linear low‐density polyethylene (LLDPE) matrices upon stretching was investigated using three different techniques: mechanical property, morphological behavior, and image analyzer analyses. The mechanical properties analyzed in terms of the tensile strength and maximum elongation resulted in that the second mixing was the best for giving a better property for all systems except the LDPE system, which exhibited no significant difference between the second and third mixings. The morphological behavior of the three compounds were different, but no distinctive difference was observed to differentiate the degree of mixing from system to system. The number‐, weight‐, and z + 1‐average diameters of the air hole and the aspect ratio upon the stretching and mixing cycle were calculated to analyze the degree of mixing of the calcite‐filled composites. As a consequence, no difference in the average diameter of the air hole was obtained among the three systems, but the aspect ratios of the air hole varied significantly. Thus, the degree of dispersion and the degree of mixing may be influenced by the average calcite agglomerate size, the average diameter of the air hole, and the aspect ratio upon stretching and mixing cycles. Those factors would be formed by the difference in chemical characteristics upon various microstructures of polyethylene and its molecular weight and molecular weight distribution. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 311–321, 2003     

Measurement of minimum angle of resolution (MAR) in the stereoscopic display using the optotype of stereoscopic stimuli

In stereoscopic images, the crossing point of the viewing directions of the two eyes determines the perceived depth. Assuming that accommodation is affected by the positions of the crossing point, the effect of crossing point on minimum angle of resolution (MAR) was investigated. For 40 participants, MAR was measured by two‐alternative forced choice where Snellen optotype E of up and down directions were used as two kinds of stimuli. As the crossing point of the viewing direction of the left and right eyes moves farther from the sample display, the ability to identify the direction of letter E decreases at the optotype of the same line thickness. The change of MAR shows linear trends with respect to the optical power change that are the reciprocal of the distance from the participant to the crossing points located out of screen and on screen.     

Reactivity,chemical structure,and molecular mobility of urea–formaldehyde adhesives synthesized under different conditions using FTIR and solid‐state 13C CP/MAS NMR spectroscopy

This study was conducted to investigate the effects of reaction pH condition and hardener type on the reactivity, chemical structure, and molecular mobility of urea–formaldehyde (UF) resins. Three different reaction pH conditions, such as alkaline (7.5), weak acid (4.5), and strong acid (1.0), were used to synthesize UF resins, which were cured by adding four different hardeners (ammonium chloride, ammonium sulfate, ammonium citrate, and zinc nitrate) to measure gel time as the reactivity. FTIR and ¹³C‐NMR spectroscopies were used to study the chemical structure of the resin prepared under three different reaction pH conditions. The gel time of UF resins decreased with an increase in the amount of ammonium chloride, ammonium sulfate, and ammonium citrate added in the resins, whereas the gel time increased when zinc nitrate was added. Both FTIR and ¹³C‐NMR spectroscopies showed that the strong reaction pH condition produced uronic structures in UF resin, whereas both alkaline and weak‐acid conditions produced quite similar chemical species in the resins. The proton rotating‐frame spin–lattice relaxation time (T_1ρH) decreased with a decrease in the reaction pH of UF resin. This result indicates that the molecular mobility of UF resin increases with a decrease in the reaction pH used during its synthesis. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2677–2687, 2003