Oxidative dehydrogenation of ethylbenzene to styrene over ultra-dispersed diamond and onion-like carbon

The catalytic properties of sp³-hybridized ultra-dispersed diamond and sp²-hybridized onion-like carbon in the oxidative dehydrogenation of ethylbenzene to styrene were investigated, highlighting the structure sensitivity of the reaction. The sp³-carbon led initially to C-C cleavage and benzene formation, while a switchover of the main reaction pathway into the styrene formation occurred with time on stream due to the formation of surface sp² carbon, required for the selective styrene formation. This was confirmed by the behavior and the high stable styrene selectivity shown by onion-like carbons. High temperature oxygen pre-treatment created catalytically active species at the sp² carbon surface, confirming that a high thermal stability carbon-oxygen complex was the active surface site for forming styrene.     

Preparation and characterization of polyacrylamide cryogels produced from a high‐molecular‐weight precursor. I. Influence of the reaction temperature and concentration of the crosslinking agent

A new type of cryogel was prepared through a reaction of high‐molecular‐weight polyacrylamide (viscosity‐average molecular weight ≈ 3 × 10⁶ Da) with glutaraldehyde in a moderately frozen aqueous medium. The influence of the crosslinking agent concentration and temperature of the reaction on the gel fraction yield, swelling characteristics, and morphology of the cryogels was investigated. The dependence of the gel fraction yield on the reaction temperature was bell‐shaped. The recognized regularities of the formation of this new type of polyacrylamide cryogel based on a high‐molecular‐weight precursor were very similar to those observed earlier for polyacrylamide cryogels synthesized through the cryopolymerization of monomeric precursors. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Removing of light hydrocarbons from gas mixtures using polymeric composite membranes based on poly(1-trimethylsilylpropyne)

Usually the methodologies used to analyse the feasibility of water reuse projects are focused on the internal costs. The aim of this paper is to show a methodology to assess the feasibility of a water reuse project taking into account not just the internal impact, but also the external impact (environmental and social, for example) and the opportunity cost derived from the project. Internal benefit is obtained from the difference between internal income and internal costs. Internal income is obtained by multiplying the selling price of reclaimed water and the volume obtained. Internal costs are made up of the sum of investment costs, operating costs, financial costs and taxes. While some of these factors identified can be calculated directly in terms of money, biophysical and social aspects demand the definition of units of measurement. In order to homogenize results, an annual reference is proposed. A monetary value can be obtained from the calculation of each impact. However, there are a series of externalities for which no explicit market exists. In these cases economic valuation methods are used, based on hypothetical scenarios or patterns observed in related markets.     

Supermicroporous alumina–silica zinc oxides

A new family of porous mixed oxides with pores largely in the 8–20 Å range have been prepared. TEOS acts as a solvent and as a source of silica to which aluminum butoxide and transition metal acetates are added. Neutral amines are added as templates and to effect hydrolysis. This paper describes the ZnO–Al₂O₅–SiO₂ system but similar results have been obtained with other transition metal oxides. An interesting feature of the technique is that the larger the amine template the greater is the surface area of the mixed oxide with only a slight increase in the average pore diameter. Both NMR and atomic pair distribution functional methods have been used to prove the homogeneity of the mixed oxide products. This preparative method complements our earlier report in Chemical Communications on mixed oxides prepared with ZrO₂ and TiO₂ incorporating transition metal oxides.     

Planar defect of the nano-structured zinc oxide as the site for stabilization of the copper active species in Cu/ZnO catalysts

The catalytic activity of CuZn catalysts in the synthesis of methanol is related to those reduced Cu species, which originate from the Cu_xZn_1−xO solid solution of wurtzite-like structure. Copper cations in the Cu_xZn_1−xO solid solution are localized in the extended stacking faults of the ZnO lattice. Copper sites could be supposedly described as the product of introducing (OH)Cu(OH) to the planar defects of zinc oxide structure. Hydroxyl groups stabilize the planar defects of ZnO. The process of the samples reduction leads to the formation of flat Cu⁰ particles over the surface of zinc oxide. The planar defects of ZnO structure are preserved in the reduced state. During the reoxidation, copper atoms return back to the extended stacking faults of ZnO as the tape-like clusters of flat-square coordinated copper cations.     

Synthesis of Boron Nitride by Self-Propagating Reactions at High Pressure

Peculiarities of the formation of BN in a self-propagating reaction between LiBF₄ and Li₃N have been studied under a wide range of p,T conditions within the region of thermodynamic stability of cBN. Boron nitride crystallized mainly in the form of highly ordered hBN (1700–2100 K), of mesographitic BN (2200–3000 K), or of turbostratic BN (>3000 K). Cubic boron nitride was obtained with a low yield (up to 14 vol%) as a result of precipitation from the metastable eutectic liquid in the BN-Li₃N system. These results give further evidence for an alternative metastable behavior in the BN phase formation under high pressures.     

Oxidation of methane in a wide range of pressures and effect of inert gases

The analysis of methane oxidation in a wide range of pressures (0.05–10 atm) demonstrates that the efficiency of CH₃ radicals recombination is of great importance for high selectivity of C₂ hydrocarbons formation. The relative efficiency of different “colliders” assisting the stabilization of exited C₂H*₆ molecules increases in the series: solid surface> Ar> He. The increase of the overall reaction rate upon increasing pressure of the inert gases in the case of catalysts having a higher surface area and more developed pore structure is likely due to the contribution of the surface-induced chain reaction in the volume of pores.     

Variation of total phenolic content and individual low-molecular-weight phenolics in foliage of mountain birch trees (Betula pubescens ssp.tortuosa)

We studied seasonal and between-tree variation in the composition and content of total and individual low-molecular-weight phenolics (LMWP) in leaves of mountain birch trees (Betula pubescens ssp.tortuosa). The major phenolic compounds were chlorogenic acid, quercetin-3-O--D-glucuronopyranoside, myricetin-3-O-(5-acetyl)-L-rhamnopyranoside, and 1-O-galloyl--D-(2-O-acetyl)-glucopyranose. The content of total phenolics, as well as the sum of individual LMWP, varied only slightly among trees while variation in contents of individual LMWP was large. Concentrations of almost all phenolics decreased during the growing season but pairwise correlations between individual phenolics remained similar over the whole season indicating tree-specific LMWP profiles over the season. Among flavonoids, the between-tree component of variation was 2.6 times as large as the seasonal component, while for variation of nonflavonoids the between-tree component was larger than the seasonal one. To explain the significant correlations within both flavonoid and nonflavonoid compounds, we discuss the biogenesis of LMWP in birch leaves, as well as their ecological role.     

Inventory pinch based,multiscale models for integrated planning and scheduling‐part II: Gasoline blend scheduling

Integration of planning and scheduling optimizes simultaneous decisions at both levels, thereby leading to more efficient operation. A three‐level discrete‐time algorithm which uses nonlinear models and integrates planning and detailed scheduling is introduced: first level optimizes nonlinear blend models via multiperiod nonlinear programming (NLP), where period boundaries are initially determined by the inventory pinch points; second level uses fixed recipes (from the first level) in a multiperiod mixed‐integer linear program to determine first an optimal production plan and then to optimize an approximate schedule which minimizes the total number of switches in blenders and swing tanks; third level computes detailed schedules that adhere to inventory constraints computed in the approximate schedule. If inventory infeasibilities appear at the second or the third level, the first‐level periods are subdivided and blend recipes are reoptimized. Algorithm finds the same or better solutions and is substantially faster than previously published full‐space continuous‐time model. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2475–2497, 2014