Continuous flame oxidation in supercritical water

Abstract

Continuous flames have been observed in Supercritical water oxidation (scWO) of isopropyl alcohol (IPA), using a vertical continuous reactor with sapphire windows and a mixing nozzle. Two types of continuous flame were confirmed: the one was long pale blue colored and the other was red short cone shaped, changing blue to red at around air ratio 2.0. The flame was strongly influenced by IPA concentration, air ratio and design of the mixing nozzle. Results for decomposition of PA are presented for IPA concentrations ranging from 600 up to 28260 ppm as TOC and initial reactor temperatures, were mostly around 490°C, at 25 MPa. Decomposition rate at steady state was over 99.9%. Experimentally measured CO₂ and O₂ concentrations at the flue gas were in good agreement with theoretically calculated values. Even for low air ratio as 1.1, high decomposition rate without CO, NO, NO₂ was achieved.     

Wave propagation in saturated ground using the volume fractions

The purpose of this paper is to study the dynamic behavior of soft ground including a porous layer by considering the porosity change. In order to take the porosity change into account, the concept of the volume fraction, which has been proposed in continuum mechanics, is introduced. The constitutive equations presented by Bowen are applied to the analysis of the porous media. According to Bowen's theory, the porosity is considered as a variable called the volume fraction and has its own constitutive equation. The constitutive equation of the volume fraction has thermoelastic equation coefficients and is determined by the strains of the solid and the fluid. This means that the compressibilities of the solid and the fluid are considered. When the special condition is assumed, Bowen's theory can contain Biots's theory, which has been applied in earthquake engineering. The wave propagation in the ground including a porous layer, modeled by Bowen's theory, is studied and compared with that of Biot's theory. One-dimensional attenuation and surface amplitude are calculated. The effect of the volume fraction is discussed with respect to the compressibilities of the solid and the fluid.     

Numerical analysis of turbulent flow separation in a rectangular duct with a sharp 180‐degree turn by algebraic Reynolds stress model

Turbulent flow in a rectangular duct with a sharp 180‐degree turn is difficult to predict numerically because the flow behavior is influenced by several types of forces, including centrifugal force, pressure‐driven force, and shear stress generated by anisotropic turbulence. In particular, this type of flow is characterized by a large‐scale separated flow, and it is difficult to predict the reattachment point of a separated flow. Numerical analysis has been performed for a turbulent flow in a rectangular duct with a sharp 180‐degree turn using the algebraic Reynolds stress model. A boundary‐fitted coordinate system is introduced as a method for coordinate transformation to set the boundary conditions next to complicated shapes. The calculated results are compared with the experimental data, as measured by a laser‐Doppler anemometer, in order to examine the validity of the proposed numerical method and turbulent model. In addition, the possibility of improving the wall function method in the separated flow region is examined by replacing the log‐law velocity profile for a smooth wall with that for a rough wall. The analysis results indicated that the proposed algebraic Reynolds stress model can be used to reasonably predict the turbulent flow in a rectangular duct with a sharp 180‐degree turn. In particular, the calculated reattachment point of a separated flow, which is difficult to predict in a turbulent flow, agrees well with the experimental results. In addition, the calculation results suggest that the wall function method using the log‐law velocity profile for a rough wall over a separated flow region has some potential for improving the prediction accuracy. Copyright © 2007 John Wiley & Sons, Ltd.     

A regiocontrolled synthesis of substituted indoles by palladium-catalyzed coupling of 2-bromonitrobenzenes and 2-bromoacetanilides

The palladium-catalyzed cross-coupling reaction of 2-bromonitrobenzenes or 2-bromoacetanilides with ethylene has been used to produce a variety of substituted indoles. The mild reaction conditions and selectivity inherent in the coupling reaction have been utilized to produce regiochemically pure 4-, 5-, 6-, and 7-substituted indoles.     

Non-steady state solidification of the Nd-123 superconducting oxides

Crystal growth of the melt-textured bulk Nd_1+xBa_2−xCu₃O_6+d (Nd123) superconducting oxides was investigated by employing isothermal undercooling solidification with hot-seeding in air. From the relationship between growth length and holding time, the Nd123 crystal was found to have almost stopped growing after a certain growth period, while the growth length increased proportionally to the holding time at an early stage of the crystal growth. As a result of quantitative analysis for the Nd123 crystal of which solidification was terminated, the distribution of the Nd/Ba substitution was observed to decrease in the Nd123 single crystal matrix from the seed crystal to the edge of the Nd123 crystals. Also, the substitution content at the edge of the Nd123 crystal, which corresponds to that at the final stage of the crystal growth, was found to be in good agreement with the minimum substitution of the Nd123 solid solution phase in the equilibrium phase diagram at this process temperature. These compositional changes could be explained using the equilibrium phase diagram as associated with the solid solution formation, which is responsible for the non-steady state solidification of the Nd123 crystals even for the isothermal undercooling processing.     

Adsorption behavior of VII group elements on tertiary pyridine resin in hydrochloric acid solution

We investigated the adsorption behaviors of technetium and rhenium on tertiary pyridine resin in hydrochloric acid solution. Technetium has a little larger distribution coefficient in higher concentration of hydrochloric acid region than rhenium. However, the tendency of adsorption behavior of technetium and rhenium is similar. We concluded that the rhenium can be used as the substitute for technetium. Adsorption behaviors of platinum group elements were also investigated. The separation of technetium from platinum group elements is discussed.     

Effect of the chemical species of arsenic on sensitivity in graphite furnace atomic absorption spectrometry.

The sensitivity of graphite furnace atomic absorption spectrometry (GFAAS) to arsenobetaine (AB) was 1.3-times higher than to inorganic As. In order to understand the mechanism underlying this observation, the atomization processes for both chemical species were investigated in terms of the enthalpy change (DeltaH) during the atomization process in GFAAS. The enthalpy change of AB was slightly lower than that of inorganic As, which suggested that AB was atomized more efficiently than was inorganic As. Moreover, it was observed that some co-existing organic materials enhanced the analytical sensitivity of inorganic As. The sensitivity difference between inorganic As and AB depended upon the mechanisms of their atomization processes.     

Reactions of lithium tributyl heteroaryl borates with allylic bromides in the presence of copper(I) cyanide

The reaction of various lithium tributylheteroarylborates with allylic bromides in the presence of copper(I) cyanide furnished the regioselective allylation at the heteroaryl ring.     

An application of fragment interaction analysis based on local MP2

We have developed a method named ‘fragment interaction analysis based on local MP2’ (abbreviated as FILM). This method enables us to decompose the interaction energy associated with dispersion interactions into contributions of localized occupied orbitals. In this study, the basis set dependence of the results derived from FILM was examined. The results suggested that the individual ratio of pair correlation energies of selected orbital pairs to the total dispersion interaction was almost independent of the basis set size. As an illustrative example, detailed analysis was performed on the human immunodeficiency virus type 1 protease complexed with lopinavir molecule.