New type of tin support for hydroprocessing catalyst

TiN supported molybdenum sulfide catalysts showed much higher activity for cleavage of C-C bonds than oxide supported molybdenum sulfide catalysts, indicating the possibility of a new generation of supports for hydroprocessing catalysts.     

Chaos in parametric resonance flow at water-mercury interface

In the electrochemical system with liquid-liquid interface, intense local convections by the resonance with potential pulses take place. Therefore, with laser beam scattering, temporal movement of the water-mercury interface was observed. As a result, the scattering efficiency showed non-linear oscillation.

Such non-linear response could be controlled by potential pulse height. As the potential height was increased, new scattering peaks in the oscillation emerged, which was expected of a kind of bifurcation phenomenon. From these results, phase portrait, Poincarè section, correlation dimension of the strange attractor and the largest Lyapunov exponent of the trajectories were obtained. Consequently, it was concluded that all the parameters indicate chaotic behavior of the resonance flow.     

Ketones from carboxylic acids over supported magnesium oxide and related catalysts

Silica-supported alkaline earth oxides revealed excellent activity to convert acetic acid selectively into acetone in a vapor-phase fixed-bed flow system. Acetone was obtained through the cyclic formation of alkaline earth acetate followed by decomposition. Magnesium oxide should be supported on the silica surface without formation of magnesium silicate, which was inactive for the present reaction. Attempted syntheses of benzophenone and acetophenone are also described.     

Effect of SiC on Interfacial Reaction and Sintering Mechanism of TiB2

Compacts of TiB₂ with densities approaching 100% are difficult to obtain using pressureless sintering. The addition of SiC was very effective in improving the sinterability of TiB₂. The oxygen content of the raw TiB₂ powder used in this research was 1.5 wt%. X-ray photoelectron spectroscopy showed that the powder surface consisted mainly of TiO₂ and B₂O₃. Using vacuum sintering at 1700°C under 13–0.013 Pa, TiB₂ samples containing 2.5 wt% SiC achieved 96% of their theoretical density, and a density of 99% was achieved by HIPing. TEM observations revealed that SiC reacts to form an amorphous phase. TEM-EELS analysis indicated that the amorphous phase includes Si, O, and Ti, and X-ray diffraction showed the reaction to be TiO₂+ SiC → SiO₂+ TiC. Therefore, the improved sinterability of TiB₂ resulted from the SiO₂ liquid phase that was formed during sintering when the raw TiB₂ powder had 1.5 wt% oxygen.     

Low-temperature selective reduction of NO with propene over alkaline-exchanged mordenites

Partially protonated alkaline mordenites showed higher activity per acid amount below 573 K than acidic zeolites for the selective reduction of NO with C₃H₆ in the presence of O₂, which can be related to a high concentration of NO₃ ^- species in the zeolite channels. This revised version was published online in July 2006 with corrections to the Cover Date.     

Depolymerization of fluoroalkyl methacrylate polymers as studied with thermogravimetry

Thermal behaviors of a few kinds of poly(fluoroalkyl methacrylate) prepared by γ-or UV-ray polymerization were investigated by using thermogravimetric measurements with the intermittent analysis of the gaseous products. The degradation of fluoroalkyl methacrylate polymers, monomeric units of which were CH₂=C(CH₃)COOCH₂(CF₂CF₂)_nH, n = 1, 2, and 3, proceeded according to the depolymerization mechanism reproducing the pristine monomer exclusively, but the thermogram in inert atmosphere showed the features of a two-step reaction. Two species of polymer differing in the heat stability were supposed to exist in the polymeric substance produced by γ- or UV-ray irradiation, and the fraction of polymer having lower heat stability increased with the increasing length of the fluoroalkyl ester group. In air, however, the thermogram of poly(fluoroalkyl methacrylate) showed no such a stepwise weight decrease as was observed in inert atomsphere with the elevating temperature, and the temperatures at which the depolymerization was introduced shifted to a much higher region. The results were ascribed to the reaction of initiating polymer radicals produced on polymer having lower stability with oxygen to form hydroperoxide, which once stabilized the polymer radicals and obstructed the initiaition of the unzipping reaction till higher temperature.     

An improved prediction result of entropic‐FV model for vapor–liquid equilibria of solvent–polymer systems

In this work, entropic expressions of UNIFAC‐FV and Entropic‐FV models were evaluated by using an extensive database of infinite dilution vapor–liquid equilibrium (VLE) data of athermal systems containing polypropylene, polyethylene, and polyisobutylene. For the infinite dilution athermal systems, performance of the Entropic‐FV model was better than that of the UNIFAC‐FV model. Then, finite concentration VLE data of non‐athermal systems that consisted of 16 polymers and 36 solvents containing a large variety of solvent–polymer systems ranging from nonpolar to polar substances were considered to optimized 46 pairs of group interaction parameters of the Entropic‐FV model. For systems containing polar solvents of three types of solvents studied, revised group interaction parameters gave significant improvements from 17.9 to 13.0% average absolute deviation (AAD) of solvent activities. For overall results, improvements were achieved from 15.1 to 12.4% AAD. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1145–1153, 2005     

Depolymerization of poly(fluoroalkyl methacrylate-co-methyl methacrylate) as studied with thermogravimetry

Thermal behaviors of a few kinds of poly(fluoroalkyl methacrylate-co-methyl methacrylate) prepared by γ-ray copolymerization were investigated by using thermogravimetric measurements together with the intermittent analysis of the gaseous products. The thermal degradation of copolymers composed of one of fluoroalkyl methacrylates of the following structures: CH₂?C(CH₃)COOCH₂(CF₂CF₂)_nH, where n = 1,2, and 3, and methyl methacrylate proceeded according to the depolymerization mechanism reproducing the pristine component comonomers exclusively, but their thermograms in inert atmosphere showed the feature of a two-step reaction. In air, however, thermograms of copolymers did not show such a stepwise decrease in weight with the elevating temperature, and temperatures at which depolymerization was introduced shifted to a much higher region. The overall aspects of depolymerization of copolymers seemed to be much similar to that of fluoroalkyl methacrylate homopolymer previously reported, and the retardation of depolymerization by air was considered to be due mainly to the stabilization of once-formed polymer radicals by oxygen.     

Thermal decomposition of uranium peroxide hydrates

The thermal decomposition of uranium peroxide hydrates, UO₄·4H₂O and UO₄·2H₂O, has been investigated by thermal analyses, X-ray diffraction study and infrared spectroscopy. As a result, it is concluded that the thermal decomposition of uranium peroxide hydrates proceeds in the following sequence: where 3 ≤ x ≤ 3.5.     

Preparation of gelatinous aluminium hydroxide by urea from aqueous solutions containing chloride,nitrate and sulphate of aluminium

The preparation of gelatinous aluminium hydroxide from aqueous solutions containing a mixture of the chloride, nitrate or sulphate of aluminium and urea by heating at 95°C has been investigated under different conditions. The pH value of aqueous solutions, on heating for a given period of time, gradually increases, rises steeply at pH 4.0–7.5 and finally approaches a constant value. The precipitate appears at about pH 7 in the presence of chloride or nitrate ions and about pH 4 in the presence of sulphate ions. Although the gelatinous precipitates in the chloride and nitrate systems are apparently different from the granular, filterable one in the sulphate system, their compositions are not influenced by the species of aluminium salt. The fresh precipitates exist in an amorphous state, and go to pseudoboehmite by ageing. It seems that the amount of pseudoboehmite increases as the concentration of aluminium salt in aqueous solution decreases. However, the transformation from amorphous aluminium hydroxide to pseudoboehmite is reduced in the presence of sulphate ions. Furthermore, it is found that the X-ray diffraction peak for the (200) plane, as an orthorhombic structure, in the pseudoboehmite precipitated from chloride or nitrate solution is more intense than that from sulphate solution.