Characterization of highly active silver catalyst for NOx reduction in lean-burning engine exhaust

A new Ag/Al₂O₃ catalyst for removing NOx in lean exhaust gas was developed. Oxidized Ag/Al₂O₃ catalyst is highly active for reduction of NOx with ethanol and propene, whereas reduced Ag/Al₂O₃ catalyst is less active for these reactions. Selectivity to N₂ is also high on the oxidized Ag/Al₂O₃ compared to that on the reduced Ag/Al₂O₃. XRD and SEM studies of these two types of Ag catalysts suggest that oxidation induces an interaction between Ag and the support, where the particles are grown in large size. In contrast, the metallic Ag particles are finely dispersed by the reduction process. Although dispersion of Ag particles is decreased by the oxidation process, the catalytic activity is increased. This suggests that the Ag-alumina sites created in the high temperature oxidizing environment are active in catalytic reduction of NOx. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structural study of hexane-soluble products from hydroliquefaction of three Yallourn brown coal lithotypes over molten salt catalysts

The hexane-soluble fractions of hydroliquefied products from three Yallourn brown coal lithotypes have been separated into five fractions by combined silica-alumina packed column chromatography. Analyses of various fractions by g.c.-m.s. permitted the identification of ≈50 components in the saturate fraction and 40 components in the diaromatic fraction, together with 30 components in the monoaromatics. The components identified were quite similar among hexane-soluble portions of all three lithotypes. A marked predominance of even carbon number alkane (C₂₃-C₂₉) was observed in the hydrocarbon fractions from pale lithotype over $\text{ZnCl}{}_2\text{KCl}$, and medium light lithotype over both pure ZnCl₂ and $\text{ZnCl}{}_2\text{KCl}$. However, medium dark lithotype over both melt catalysts produced a saturate fraction with an odd carbon number(C₂₂-C₂₈) preference. Based on spectral methods, Soxhlet extracts obtained from untreated lithotypes (hexane and benzene solubles) were characterized as complex mixtures of higher molecular weight(300–1000) aliphatic hydrocarbons, which were supposed to be a precursor of the saturates produced from the corresponding lithotype in the catalytic hydroliquefaction.     

E.s.r. study of annealing and melting effects on the molecular motion of spin trapped chain-end radicals located on the polyethylene surface

E.s.r. spectra of chain-end spin labels on the surface of polyethylene powder were obtained for high and low density polyethylene samples at various stages of heat treatment process. The subsequent crystalline structures of the samples were examined with wide angle and small angle X-ray diffraction spectra. The effects of annealing on the motion of the labels were dependent on annealing temperature and the type of the samples. Higher temperature annealing decreased the rotational correlation times (τ_c) and their activation energy in high density polyethylene but did not affect those of low density polyethylene. Melting decreases the values of τ_c and ΔE for both high an low density polyethylene samples. The cause of these decreases were attributed to the changing of the sites of the chain-end labels. The motion of the labels appeared to be influenced by the local segmental motion of the polymer main chains.     

Decomposition of timed automata for solving scheduling problems

A decomposition algorithm for scheduling problems based on timed automata (TA) model is proposed. The problem is represented as an optimal state transition problem for TA. The model comprises of the parallel composition of submodels such as jobs and resources. The procedure of the proposed methodology can be divided into two steps. The first step is to decompose the TA model into several submodels by using decomposable condition. The second step is to combine individual solution of subproblems for the decomposed submodels by the penalty function method. A feasible solution for the entire model is derived through the iterated computation of solving the subproblem for each submodel. The proposed methodology is applied to solve flowshop and jobshop scheduling problems. Computational experiments demonstrate the effectiveness of the proposed algorithm compared with a conventional TA scheduling algorithm without decomposition.     

Relationship between oxidative stability of vitamin E and production of fatty acids in oils during microwave heating

Effects of microwave heating on the oxidative stability ofd-tocopherols were studied in relation to the production of fatty acids in oils. During microwave heating, the stability of tocopherols decreased in the orderδ>β>γ>α. This order did not depend on the types of ethyl esters of fatty acids or oils present. But, the shorter the chainlength and the lower the degree of unsaturation of the fatty acid ethyl esters, the greater was the reduction in amount of individual tocopherols. A similar tendency was observed when tocopherol-stripped vegetable oils, with equimolar mixtures of tocopherols added, were treated under the same conditions. The reduction in tocopherols became greater with increasing levels of free fatty acids.     

Organic–silicate hybrid catalysts based on various defined structures for Knoevenagel condensation

Two types of organic–inorganic hybrid base catalysts are prepared. Organic-functionalized molecular sieves (OFMSs), particularly “amine-immobilized porous silicates”, are designed based on common idea to immobilize catalytic active sites on silicate surface. Silicate–organic composite materials (SOCMs), such as “ordered porous silicate–quaternary ammonium composite materials”, are the precursors of ordered porous silicates obtained during the synthesis. Both the OFMS and the SOCM are used as the catalysts for Knoevenagel condensation. Among the OFMSs, there is clear tendency that the use of molecular sieve with larger pore volume and/or surface area gives the product in higher yield. Aminopropylsilyl (AP)-functionalized mesoporous silicates such as AP-MCM-41 gives the product in high yield under mild conditions. No loss of activity is observed after repeated use for three times. The SOCMs are also active for the same reaction. The precursors of the mesoporous silicates are more active than those of microporous silicates. This material can be repeatedly used without significant loss of activity. High activity is not due to the leached species. The active sites of the SOCM catalysts are considered to be SiO⁻ moieties located on the pore-mouth. Activity of the SOCM increases when the reaction is carried out without solvent, whereas decrease in activity of the OFMS is observed in the solvent-free system.     

Stability of fine water droplet clouds

The rate of evaporation of monodisperse water droplets was first evaluated by solving numerically the modified Maxwell equation, assuming the cellular model for a droplet clouds. The results are discussed in comparison with those for a single isolated droplet, which can be obtained analytically. The critical conditions for the droplet cloud to be stable are then evaluated as a function of droplet number concentration, droplet size and initial conditions of the surrounding air. Secondly, the equilibrated system, where a water droplet cloud is steadily mixed with unsaturated air, was analysed on the basis of enthalpy and material balance of the system to evaluate the total volume change of the droplets. Some of these analyses were verified by experiment, using an ultramicroscopic technique which is useful for droplet size analysis.     

Abnormal metabolism of polyunsaturated fatty acids and phospholipids in diabetic glomeruli

Studies were done on changes in phospholipid content and fatty acid composition of phospholipids and on the role of the acylation pathway in synthesis of phospholipids in the development of abnormal fatty acid composition in the glomeruli of rats 2 and 10 mo after induction of diabetes with streptozotocin. The proportions of individual phospholipids in the glomeruli of rats were not changed 2 mo after induction of diabetes, but the proportion of phosphatidylethanolamine (PE) decreased and that of sphingomyelin increased 10 mo after induction of diabetes. In contrast, in liver the proportion of PE was increased and that of phosphatidylcholine was decreased. These results showed that changes of individual phospholipids in glomeruli were time-dependent and tissue-specific. Two mo after induction of diabetes, the main change in the phospholipid fatty acid composition of diabetic glomeruli was a decrease in arachidonic acid (AA); the main change in serum free fatty acids (FFA) was an increase in linoleic acid (LA) and a decrease in AA. Ten mo after induction of diabetes, the main changes in the phospholipid fatty acid composition of glomeruli were an increase in LA and a decrease in AA; the main change of the serum FFA composition was a decrease in AA. Thus, the fatty acid composition of glomerular phospholipids was not directly correlated to that of the serum in diabetic rats. Acyl-CoA synthetase and acyltransferase activities increased in diabetic glomeruli with either AA or LA as substrate, but activity toward LA increased more at 2 mo after induction of diabetes. Acyl-CoA synthetase activity increased in diabetic glomeruli with LA as substrate, but that did not change with AA as substrate at 10 mo after induction of diabetes. Furthermore, acyltransferase activity decreased in diabetic glomeruli with AA as substrate, although that did not change with LA as substrate at 10 mo after induction of diabetes.     

Graft polymerization of vinyl acetate onto silica

The free‐radical graft polymerization of vinyl acetate onto nonporous silica particles was studied experimentally. The grafting procedure consisted of surface activation with vinyltrimethoxysilane, followed by free‐radical graft polymerization of vinyl acetate in ethyl acetate with 2,2′‐azobis(2,4‐dimethylpentanenitrile) initiator. Initial monomer concentration was varied from 10 to 40% by volume and the reaction was spanned from 50 to 70°C. The resulting grafted polymer, which was stable over a wide range of pH levels, consisted of polymer chains that are terminally and covalently bonded to the silica substrate. The experimental polymerization rate order, with respect to monomer concentration, ranged from 1.61 to 2.00, consistent with the kinetic order for the high polymerization regime. The corresponding rate order for polymer grafting varied from 1.24 to 1.43. The polymer graft yield increased with both initial monomer concentration and reaction temperature, and the polymer‐grafted surface became more hydrophobic with increasing polymer graft yield. The present study suggests that a denser grafted polymer phase of shorter chains was created upon increasing temperature. On the other hand, both polymer chain length and polymer graft density increased with initial monomer concentration. Atomic force microscopy–determined topology of the polymer‐grafted surface revealed a distribution of surface clusters and surface elevations consistent with the expected broad molecular‐weight distribution for free‐radical polymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 300–310, 2003