Dehydrogenation of Light Alkanes Over Rhenium Catalysts on Conventional and Mesoporous MFI Supports

Recently, Re/HZSM-5 (Si/Al = 15) was shown to be an efficient catalyst for ethane dehydrogenation and aromatization at 823 K and atmospheric pressure. In this reaction, the major initial products were benzene, toluene and xylene (BTX), but increasing amounts of ethene were produced with time on stream due to deactivation of the catalyst. We show that by use of rhenium impregnated MFI supports with very few or no acidic sites (Si/Al > 500), highly selective ethane dehydrogenation catalysts are obtained with ethene selectivities of 98%. By use of mesoporous MFI supports (Si/Al >500) the lifetime of the catalyst appears to be slightly improved compared to conventional MFI crystals. The beneficial effect of a mesoporous MFI support is convincingly demonstrated in propane dehydrogenation, where both conversion and selectivities on the mesoporous MFI (Si/Al > 500) impregnated with Re are significantly higher than on Re supported on a comparable conventional MFI support.     

Mandibular gland secretions of the male beewolvesPhilanthus crabroniformis,P. barbatus,andP. pulcher (Hymenoptera: Sphecidae)

The composition of the territorial marking pheromones from mandibular glands of males of the beewolvesPhilanthus crabroniformis, P. barbatus, andP. pulcher have been determined. The structures of the components were elucidated by gas chromatography-mass spectrometry and gas chromatography-Fourier transform infrared spectroscopy. The major compound ofP. crabroniformis is isopropyl tetradecanoate, with somewhat lesser amounts of 2-tridecanone, 3-methyl-3-butenyl tetradecanoate, and 928 (Z)(E)-11-eicosen-1-ol. The major compounds ofP. barbatus are ethyl tetradecanoate and hexadecanal, which are present in approximately a 6040 ratio. These two compounds comprise over 95% of the neutral lipids. Also present in lesser amounts are ethyl dodecanoate, tetradecanal, hexadecan-1-ol, a ^x -octadecen-1-ol, and octadecan-1-ol. The major compounds ofP. pulcher are ethyl (Z)-7-hexadecenoate and geranylgeraniol acetate, which comprise nearly 90% of the neutral lipid fraction, with smaller amounts of tetradecanal, pentadecanal, and ethyl hexadecanoate; trace amounts of ^x hexadecenal, hexadecanal, and octadecanal are also present.     

Heterogeneously assisted oxidation of adsorbates from carbonmonoxide, methanol and ethanol by hydrogen peroxide solutions on platinum electrodes in sulphuric acid

The influence of hydrogen peroxide on the adsorption and oxidation of carbon monoxide, methanol and ethanol adlayers on porous Pt electrodes were studied in 2 M sulphuric acid solution by means of cyclic voltammetry and differential electrochemical mass spectrometry (DEMS). The oxidation of adsorbed species is observed at electrode potentials far less negative than those required for electrochemical adsorbate oxidation. The oxidation by H₂O₂ is dependent on its concentration in solution, as well as on the adsorbates and their coverages. In all cases the isolated adlayers are oxidised by dissolved H₂O₂. However, the presence of H₂O₂ during adsorption partially inhibits adlayer formation from CH₃OH and C₂H₅OH, but avoids almost completely the adsorption of carbon monoxide. The removal of the residues from the surface by dissolved hydrogen peroxide probably occurs through O_ad species formed during the heterogeneous decomposition reaction of H₂O₂ on Pt.     

Solubility of Propane in Sulpholane at Elevated Pressures

The solubility of propane in sulpholane has been determined at temperatures in the range 298‐403 K at pressures up to 17.6 MPa. The experimental results were correlated by the Peng‐Robinson equation of state, and binary interaction parameters have been obtained for this system. The parameters in the Krichevsky‐Ilinskaya equation were calculated from these interaction parameters.     

Compatibilization of polymer blends from poly(styrene‐co‐acrylonitrile) and polycarbonate by oxazoline modification of poly(styrene‐co‐acrylonitrile) in the melt

A good way of achieving compatibility in polymer blends of poly(styrene‐co‐acrylonitrile) (S/AN) and bisphenol A polycarbonate (PC) is the chemical modification of S/AN in the melt. A catalyzed reaction of the nitrile groups with a substituted 2‐amino alcohol or 2‐amino phenol resulted in a conversion of nitrile groups of 55–75% in 60 min. The introduced heterocyclic structures were ethyl hydroxymethyl oxazoline (EHMOXA) and benzoxazole (BenzOXA), respectively. The use of dibutyltin oxide as a catalyst led to the highest efficiency. The modified polymer was characterized by Fourier transform infrared and NMR spectroscopy, elemental analysis, and reactions with organic acids and anhydrides. The modified S/AN showed good technical compatibility (single glass‐transition temperature) with PC in blends made from solution and from the melt. All blends were characterized with oscillating rheometry and differential scanning calorimetry. Rheological measurements showed that EHMOXA–S/AN reacted with PC and had crosslinked structures, whereas BenzOXA–S/AN showed compatibilization without any (crosslinking) reaction. The melt blends of BenzOXA–S/AN and PC showed a downward shift in the complex viscosity due to the influence of the BenzOXA group. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2322–2332, 2003     

Phase stability and magnetic properties of SrFe18O27 W-type hexagonal ferrite

W-type ferrite is a member of the hexagonal ferrite family and a potential permanent magnet material. However, its synthesis conditions are not fully understood yet. Samples were sintered either at 1400°C in air and quenched, or at 1300°C at reduced oxygen partial pressure. The precise stability conditions of this W-type ferrite were investigated in the temperature range of 1200°C-1400°C using thermogravimetry, XRD, and electron microscopy. At 1300°C, the ferrite is stable at oxygen partial pressures of . At more oxidizing conditions, the ferrite decomposes into M-type ferrite and hematite, while at more reducing atmospheres Sr₄Fe₆O₁₃ and magnetite are formed. The nonstoichiometry δ of SrFe_18−δO₂₇ was derived from thermal analysis data at 1300°C as function of oxygen partial pressure and was found to be mainly due to cation vacancies. Magnetization measurements show that this W-type ferrite exhibits M_s = 103 emu/g at T = 4 K, which agrees well with a ferrimagnetic spin arrangement according to Gorter's model. As alternative, Zn-substituted W-ferrite was found to be stable in air at 1200°C with a large M_s = 123 emu/g at 4 K.     

Small-angle neutron scattering from branched epoxide resins

Small-angle neutron scattering experiments in the range of q² from 0.01 to 25 nm⁻² have been carried out on branched epoxide resins based on bisphenol-A at the Institute Laue—Langevin (I.L.L) in Grenoble (q=(4π/λ) sin(θ/2)). Measurements were made with six samples in the range of M_W from 1500 to 19 000 and four concentrations between 1.3 and 10% (w/w) in deuterated diglyme. The results are as follows: (i) The mean square radius of gyration follows a relationship S²_z=4.69×10⁻⁴M^1.20_W (nm²). (ii) In all cases fairly large second virial coefficients A₂ are obtained which, however, decrease strongly with molecular weight. Above M_W=2500, the virial coefficient follows the relationship A₂=1.6M^−0.85_W (mol cm³g⁻²). (ii) The reciprocal particle scattering factor as a function of q² exhibits only a slight upturn and otherwise shows the behaviour of a randomly branched polycondensate. The slight upturn is discussed as being caused by the finite volume of the monomeric unit. Possible reasons for the high exponent in the S²_z versus M_W dependence are briefly discussed.     

Stretching and deformation vibrations of CH2, C(CH3) and O(CH3) groups of poly(methyl methacrylate)

Infrared and Raman spectra of atactic PMMA and infrared spectra of stereoregular PMMA and of its four deuterated derivatives

, were measured. They were used to assign the bands of stretching and deformation vibrations of CH₂, CCH₃ and OCH₃ groups in the infrared and Raman spectra and to discuss the effect of stereoregularity on these bands in the infrared spectra.     

Detailed Molecular Structure Modeling – A Path Forward to Designing Application Properties of ldPE

Summary: This paper describes a step on the ambitious aim to “design” application properties of ldPE by first simulating the detailed molecular structure of a high‐pressure tubular reactor product. The reactor of a certain configuration produces under well‐defined operating conditions. The next step is to correlate the structure with the application properties. Finally, the sequence will be reversed in order to deduce the operating conditions, which lead to the desired product quality. Two‐dimensional distributions, in molecular weight and branching frequency, as well a two compartment models with a core and a shell stream were simulated and compared with experimental results. Therefore, CFD simulations were carried out to discretize the reaction medium. Samples were taken from both pilot and commercial plants. The TREF‐SEC analytical method was successfully applied in order to measure the microscopic structure of the material. The tremendous numerical problems were solved with the help of the software PREDICI .

Detailed MWD for a pilot scale reactor product.     

Iron(II)‐based catalysts for ethene oligomerization

The synthesis of iron(II) complexes with various tridentate di(imino)pyridine ligands and their potential as ethene oligomerization catalysts are described. The ligands are characterized by ¹H‐ and ¹³C‐NMR spectroscopy and the complexes only by mass spectrometry due to their paramagnetism. After activation either with methylalumoxane (MAO) or with a heterogeneous cocatalyst consisting of partially hydrolyzed trimethylaluminum and silica gel, the prepared complexes proved to be good catalysts for the oligomerization of ethene. 1‐Octene, 1‐hexene, and 1‐decene were the major products, formed in very high isomeric purity (99.9 %). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 476–482, 2003