Dehydrocyclization of Alkanes Over Zeolite-Supported Metal Catalysts: Monofunctional or Bifunctional Route

The direct catalytic conversion of alkanes into aromatics has found potentially important industrial applications. Initially only alkanes with 6 and more carbon atoms in the chain were concerned. Supported platinum catalysts were found active for the aromatization of alkanes; the drawbacks of these catalysts were their deactivation with time on stream and the existence of simultaneous parallel reactions. Much discussion has been published on the aromatization of C₆₊ alkanes. A bifunctional mechanism which involves both the metal and the acid sites of the support and a monofunctional mechanism involving only the metallic sites operate over, respectively, Pt supported on acidic support and Pt supported on nonacidic support. In the present review the mechanisms proposed for the aromatization of alkanes are described. Over monofunctional Pt catalysts two possible mechanisms prevail: 1,6 ring closure on the Pt surface involving primary and secondary C-H bond rupture, followed by dehydrogenation of the cycloalkanes into aromatics (1,5 ring closure to a lesser extent also contributes to aromatic production); or dehydrogenation of the alkanes into olefins, dienes, and trienes followed by thermal ring closure. Zeolites were found most suitable as support for preparing catalysts more active and more selective in the alkane aromatization. In addition catalysts based on noble metals supported on zeolite appeared more resistant against deactivation by coke. In this review the aromatization of hexane, heptane, and octane over Pt-zeolite catalysts is discussed in detail. Comparisons between different zeolite structures and different dehydrogenation sites are given. In particular a critical analysis of the results and interpretation concerning Pt-KL catalysts strongly suggests that the exceptional high selectivity towards aromatization of n-hexane exhibited by Pt-KL could not be explained by only the nest or constraint effect exerted by the channel dimension and morphology, not by only the terminal cracking properties, not by only the partial electron transfer from the zeolite support to the Pt particles, and not by only the Pt particle size. Zeolite structure also affects the aromatic product distribution, in particular when the alkane contains more than 7 carbon atoms. It is shown how Pt on medium-pore zeolites such as In-ZSM-5, silicalites will favor the aromatization of C₈ alkane isomers into ethylbenzene-styrene with respect to other C₈ aromatics. Aromatization of light alkanes, C₂-C₅, requires the increase of the hydrocarbon chain length up to 6 carbon atoms and higher, followed by cyclization reaction. Recently new processes to convert C₂-C₅ alkanes into aromatics have been disclosed, M2-forming from Mobil, Cyclar from BP-UOP, and Aroforming from IFP-Saluted. In general these processes use bifunctional catalysts possessing a dehydrogenating and an acid function. The catalysts consist of a metal ion or metal oxide supported on a microporous acid solid. In this review we analyze the results concerning mainly platinum supported on pentasil-type zeolite. It is shown that althoug Pt has better dehydrogenating properties as compared with gallium and zinc, the efficiency of catalysts based on Pt-ZSM-5 for light alkane aromatization is less because undersirable reactions such as hydrogenolysis and ethene (olefins) hydrogenation occur on the platinum surface, resulting in the production of unreactive alkanes, CH₂, C₂H₆. These drawbacks could be partially suppressed by alloying Pt and by increasing the reaction temperature.     

Fractal Characteristics of Fracture Surfaces

Quantitative fractography is often used to study material failure mechanisms. During calculation of surface or profile roughness parameters, the magnification used in obtaining fractographic data is found to influence the value of the parameters. Fractal geometry has been developed into a tool capable of defining surface and profile topography without sensitivity to magnification, and several studies have related fractal dimension ( D _F) to other physical or mechanical properties. In this study, we obtained the fractal dimension of profiled fracture surfaces of one glass and three proprietary dental porcelains. The fracture toughness ( K _1c) of these materials was also measured using the indentation-strength method. Results show the surfaces to be fractal. No quantitative relationship between fractal dimension and toughness was found. Differences in K _1c were demonstrated between some materials. It is postulated that the size range within which fractal dimension can be defined as constant is dependent on the toughening mechanism, and that the relationship between K _Ic and D _F cannot be identical for all materials.     

Composition and structure of triacylglycerols in brown adipose tissue of rats fed fish oil

This study examines the incorporation of highly unsaturated n−3 fatty acids (HUFA) into triacylglycerols (TAG) of brown adipose tissue (BAT), and their effect on the positional distribution of saturated (SFA) and of unsaturated (UFA) 16- or 18-carbon fatty acids. To this end, rats were fed a fish oil diet for up to four weeks. The stereospecific analysis of TAG was based on generation ofsn-1,2- andsn-2,3-acylglycerols by Grignard degradation, followed by synthesis of phosphatidic acid and specific hydrolysis with phospholipase A₂. From the end of the first week of fish oil feeding, a steady-state in the fatty acid composition of TAG in BAT was reached. HUFA concentration increased 30-fold, mainly at the expense of n−9 UFA and of SFA. The amount of SFA decreased selectively at position 3, where these fatty acids were progressively replaced by n−3 HUFA. By contrast, the amount of UFA decreased at all positions, and their positional distribution was not affected. About 60% of HUFA was incorporated at position 3. Nearly twice as much 22∶6n−3 was incorporated into TAG than had been previously observed in white adipose tissue (WAT) [Leray, C., Raclot, T., and Groscolas, R. (1993)Lipids 28, 279–284]. At the steady-state, the distribution of HUFA was characterized by high proportions of 22∶6n−3 and 20∶5n−3 in position 3. Moreover, in each position of TAG, a steady level was reached rapidly (within 1 wk). It is concluded that, during fish-oil feeding, fatty acids in TAG of BAT show characteristic time-course changes that lead to a characteristic composition and a tissue-specific positional distribution. This suggests that adipose tissue has its own specificity in controlling the build-up of TAG stores, which is likely to be regulated by the specificity of acylating enzymes as well as molecular rearrangements.     

Determination of solid fat content (SFC) of binary fat blends and use of these data to predict SFC of selected ternary fat blends containing low-erucic rapeseed oil

Several oils and fats often used for the industrial preparation of European shortenings were blended in binary systems. The equilibrium (after 48 h at 15°C) solid fat contents (SFC; determined by pulsed NMR spectroscopy) were measured and plotted against blend composition. SFC of the blends resulted from the SFC of each fat for the considered temperature as well as the type of interaction existing between those fats (namely, ideal behavior, monotectic interaction, eutectic interaction, and so on). The type of relationship fitted was dependent on the kind of interaction: Linear relationships were found for total compatibility between fats, and polynomial-type (order 2) relationships were found for fats exhibiting incompatibility. Some corresponding ternary oils and fats blends were also prepared and analyzed. Selected relationships (regression equations of the fitted curves) obtained for binary blends were combined in order to calculate the SFC of the corresponding ternary blends. Experimental values were generally close to predicted ones. The representation of SFC as a function of composition is interesting as it allows one to determine rapidly and easily the type of molecular interaction between two fats and also to determine equations that can be combined to calculate easily the SFC of corresponding ternary blends crystallized in the same way with a good accuracy. The texture (hardness) of several binary and ternary blends was also measured. The combination of the results obtained for SFC with the results obtained for the hardness of binary blends allows the prediction of the hardness of a corresponding ternary blend under the same conditions.     

Electrochemical behaviour of copper in neutral aerated chloride solution. I. Steady-state investigation

The electrochemical behaviour of a Cu rotating disc electrode in neutral aerated NaCl solution was investigated in the cathodic and anodic ranges and at the corrosion potential. In the cathodic range, where the reduction of oxygen takes place, reduction peaks allow the identification and quantitative evaluation of insoluble corrosion products (CuCl and Cu₂O). In the anodic range Cu is dissolved, most likely as CuCl ₂ ^– . A new mechanism for the anodic dissolution is proposed after comparing our data with previously published mechanisms. Corrosion currents were found to decrease with time and to be a function of the rotation rate of the electrode. Both the mixed kinetics of the anodic partial reaction and diffusion through a porous layer seem to be relevant in controllingl _corr.     

Essential fatty acids in trout serum lipoproteins,vitellogenin and egg lipids

This paper describes evidence of (n−3) and particularly of 22∶6 (n−3) fatty acid enrichment in trout lipoproteins as well as in vitellogenin, egg lipovitellin and oil globule. Among the lipoproteins, HDL and LDL were the main forms of blood lipid transport, whereas phospholipids and cholesteryl esters are the preferential chemical carriers for (n−3) fatty acid transport. However, cholesteryl esters were less important as esterified fatty acid carriers than in man. Taken together with the data obtained in mammals, our results suggest that there may be a relationship between EFA activity and the distribution of the EFA among the lipoprotein lipid fractions in vertebrates, irrespective of the EFA series. Administration of an (n−3) fatty acid deficient diet for three months prior to trout spawning produced a significant increase in egg lipid content, primarily as a result of the increase of the oil globule composed almost exclusively of triacylglycerols. This diet decreased the 22∶6 (n−3), as well as the (n−3) fatty acid contents of lipoproteins, lipovitellin, vitellogenin and the oil globule. In contrast, the (n−3) fatty acid level was always higher in lipoproteins and lipovitellin than in the vitellogenin and the oil globule. Moreover, the relative levels of 22∶6 (n−3) and total (n−3) fatty acids were quite similar in lipoproteins and lipovitellin on the one hand, and in vitellogenin and the oil globule on the other. These findings suggest a direct relationship between the two forms of plasma lipid transport and the two egg compartments. During ovogenesis, dietary lipids seemed to be diverted from the adipose tissue and essentially deposited in the egg.     

Fluorinated acrylic polymers: Surface properties and XPS investigations

A series of polymers based on methylmethacrylate, butylacrylate, and ω‐perfluorooctylalkylacrylate were prepared by radical polymerization. By changing both the length of the hydrocarbon spacer, between the fluorinated chain and the ester function of the fluorinated monomer, and its concentration, the surface properties of the resulting terpolymers were greatly influenced. Polymers containing small amounts of fluorinated comonomer units had considerably reduced surface energies compared to the copolymer poly (methylmethacrylate‐co‐butylacrylate) taken as reference. The outermost surface composition has been investigated by the XPS technique, confirming the strong fluorine enrichment. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 821–827, 2006     

Plasma and lipoprotein fatty acid composition in glycogen storage disease type I

Nocturnal intragastric feeding has been shown to be an effective means to improve clinical and biochemical features in glycogen storage disease type I (GSD-I). In this study, we investigated the fatty acid patterns in a whole plasma and in circulating lipoproteins in patients on this therapy. The results demonstrated massive concentration of total fatty acids coupled with higher levels of triglycerides, free cholesterol, cholesterol ester and phospholipids. This hyperlipidemia involved all fatty acids without distinction of carbon or bond numbers. However, the increase was more pronounced for saturated than polyunsaturated fatty acids, as was demonstrated by the ratios of both oleic acid to linoleic acid (1.91±0.40 vs 0.80±0.09 in controls) and of ω3+ω6 to ω9 fatty acid families (0.92±0.11 vs 1.66±0.08 in controls). The fatty acid patterns in very low (VLDL), low (LDL) and high (HDL) density lipoprotein showed substantial differences in composition, reflecting an association between an abnormal lipoprotein pattern and essential fatty acid deficiency. Furthermore, GSD-I patients exhibited a significant increase in VLDL (17±2 vs 47±7 mg/dl) and LDL cholesterol (124±7 vs 206±24 mg/dl), coupled with a decrease in HDL cholesterol (49±4 vs 28±3 mg/dl). These data documenting high LDL cholesterol and low HDL cholesterol associated with an increased concentration and proportion of saturated fatty acids suggest that GSD-I patients on nocturnal intragastric feeding are at high risk for atherosclerosis and its complications.     

A memetic algorithm to solve an unrelated parallel machine scheduling problem with auxiliary resources in semiconductor manufacturing

In this paper, we propose a metaheuristic for solving an original scheduling problem with auxiliary resources in a photolithography workshop of a semiconductor plant. The photolithography workshop is often a bottleneck, and improving scheduling decisions in this workshop can help to improve indicators of the whole plant. Two optimization criteria are separately considered: the weighted flow time (to minimize) and the number of products that are processed (to maximize). After stating the problem and giving some properties on the solution space, we show how these properties help us to efficiently solve the problem with the proposed memetic algorithm, which has been implemented and tested on large generated instances. Numerical experiments show that good solutions are obtained within a reasonable computational time.     

Extracting Microfacet‐based BRDF Parameters from Arbitrary Materials with Power Iterations

We introduce a novel fitting procedure that takes as input an arbitrary material, possibly anisotropic, and automatically converts it to a microfacet BRDF. Our algorithm is based on the property that the distribution of microfacets may be retrieved by solving an eigenvector problem that is built solely from backscattering samples. We show that the eigenvector associated to the largest eigenvalue is always the only solution to this problem, and compute it using the power iteration method. This approach is straightforward to implement, much faster to compute, and considerably more robust than solutions based on nonlinear optimizations. In addition, we provide simple conversion procedures of our fits into both Beckmann and GGX roughness parameters, and discuss the advantages of microfacet slope space to make our fits editable. We apply our method to measured materials from two large databases that include anisotropic materials, and demonstrate the benefits of spatially varying roughness on texture mapped geometric models.