Shin-ichiro Kawasaki

Simple and rapid hydrogenation of p-nitrophenol with aqueous formic acid in catalytic flow reactors

Summary The inner surface of a metallic tube (i.d. 0.5 mm) was coated with a palladium (Pd)-based thin metallic layer by flow electroless plating. Simultaneous plating of Pd and silver (Ag) from their electroless-plating solution produced a mixed distributed bimetallic layer. Preferential acid leaching of Ag from the Pd–Ag layer produced a porous Pd surface. Hydrogenation of p-nitrophenol was examined in the presence of formic acid simply by passing the reaction solution through the catalytic tubular reactors. p-Aminophenol was the sole product of hydrogenation. No side reaction occurred. Reaction conversion with respect to p-nitrophenol was dependent on the catalyst layer type, the temperature, pH, amount of formic acid, and the residence time. A porous and oxidized Pd (PdO) surface gave the best reaction conversion among the catalytic reactors examined. p-Nitrophenol was converted quantitatively to p-aminophenol within 15 s of residence time in the porous PdO reactor at 40 °C. Evolution of carbon dioxide (CO2) was observed during the reaction, although hydrogen (H2) was not found in the gas phase. Dehydrogenation of formic acid did not occur to any practical degree in the absence of p-nitrophenol. Consequently, the nitro group was reduced via hydrogen transfer from formic acid to p-nitrophenol and not by hydrogen generated by dehydrogenation of formic acid.

Corrosion Resistance in Highly Concentrated Hydrochloric Acid and Creep Rupture Strength of a Ti-Pd Alloy for a Supercritical Water Oxidation Reactor

Abstract The corrosion resistance and the creep rupture strength of a Ti-Pd alloy were evaluated for the materials application containing a highly concentrated chloride feed in a supercritical wat...

Effect of Temperature on Anisotropic Crystal Growth of Boehmite under Hydrothermal Condition

Temperature effect (200-400 °C) on the anisotropic crystal growth of boehmite under hydrothermal conditions with and without octanoic acid was investigated. The crystallinity and the size of particles increased with increasing the treatment temperature. The crystal growth was facilitated greatly above the critical temperature of water. Although several possible factors could affect the crystal growth behavior, the experimental results were discussed in terms of water properties, such as dielectric constant and viscosity. The crystallization was enhanced when the viscosity and dielectric constant of water were low. The viscosity reduction at higher temperature may enhance diffusion and crystallization, in particular, without octanoic acid. The enhancement of crystallization at lower dielectric constant implies that the formation of particles, which are less polar than precursor ions, favorably proceeds in such media. The crystal growth along c-axis showed less temperature dependence around the critical temperature in the experiments with octanoic acid, which suggests that the modification reaction on the (001) surface was also facilitated because the modification reaction forms less polar products. This is probably the reason why the aspect ratio (a/c) was considerably higher for the products obtained with the treatments above the critical temperature.

Practical development of continuous supercritical fluid process using high pressure and high temperature micromixer

In the synthesis of metal oxide fine particles by continuous supercritical hydrothermal method, the particle characteristics are greatly affected by not only the reaction conditions (temperature, pressure, residence time, concentration, etc.), but also the heating rate from ambient to reaction temperature. Therefore, the heating method by direct mixing of starting solution at room temperature with supercritical water is a key technology for the particle production having smaller size and narrow distribution. In this paper, mixing engineering study through comparison between conventional T-shaped mixers and recently developed swirl mixers was carried out in the hydrothermal synthesis of NiO nanoparticles from Ni(NO3)2 aqueous solution at 400 °C and 30 MPa. Inner diameter in the mixers and total flow rates were varied. Furthermore, the heating rate was calculated by computational fluid dynamics (CFD) simulation. Relationship between the heating rate and the average particle size were discussed. It was clari...