Catalytic epoxidation of olefins in the presence of a vanadyl porphyrin complex

It was found that vanadyl porphyrin complexes synthesized from petroleum metal porphyrin concentrates stimulated epoxidation during the olefin oxygenation process. The yields of obtained oxiranes turned out to be 38–75%, depending on the olefin structure. An epoxidation mechanism that suggests the formation of a protonated dioxygen adduct as an intermediate during oxygenation of olefins in the presence of vanadyl porphyrin complexes was proposed. An analogy is drawn between the epoxide formation reaction upon the catalytic oxygenation of olefins and the Prilezhaev reaction.     

Poly(Styrene‐Divinylbenzene) Based Media for Liquid Chromatography

The latest developments and in particular important synthetic aspects for the preparation of modern poly(styrene‐divinylbenzene) (PS‐DVB) based liquid chromatography (LC) supports are reviewed. In this context, the chemistry of particular porous and nonporous, functionalized, monolithic, coated silica and more specialized mixed organic PS‐DVB media is covered. Special consideration is given to modern approaches such as micro‐(μ)‐HPLC and coating techniques and their most important applications. Synthetic particularities relevant to the corresponding applications are outlined.     

Separating n-alkane mixtures by exploiting differences in the adsorption capacity within cages of CHA, AFX and ERI zeolites

The saturation capacity of n-alkanes in CHA, AFX and ERI zeolites, that consist of cages separated by windows, decreases with increasing carbon number. The major aim of the present communication is to demonstrate the possibility of separating n-alkane mixtures relying on differences in saturation capacities. To investigate this possibility, Configurational-Bias Monte Carlo simulations for adsorption of C3–nC6, nC4–nC6, and nC5–nC6 mixtures in CHA, AFX and ERI were carried out for equimolar bulk fluid phase. These mixture simulations show that for operation at fluid phase fugacities below about 1 MPa, the adsorbed phase in equilibrium with the bulk vapor phase is predominantly the alkane with the longer chain length, i.e. nC6. However, for operation at pressures in excess of 1 MPa, the adsorbed phase in equilibrium with the bulk liquid phase is richer in the component with the smaller chain length. In some cases, the nC6 is practically excluded from the zeolite.     

Betriebsmittelbezogene Lastmodellierung in Verteilungsnetzen

Übersicht Der Betriebszustand eines Verteilungsnetzes wird durch die Strombelastung aller Betriebsmittel beschrieben. Mit Hilfe einer statischen Estimationsmethode werden aus einzelnen Messungen und der Kenntnis der Verbrauchsdaten typische Verbraucherkurven (TVK) berechnet, die das elektrische Verhalten verschiedener Verbrauchergruppen widerspiegeln. Auf dieser Basis ist eine betriebsmittelbezogene Lastmodellierung an beliebigen Betriebsmitteln in Abhängigkeit der Verbraucherzusammensetzung unter Berücksichtigung externer Einflüsse wie der Temperatur möglich. Die so gewonnenen Belastungsverläufe erlauben eine Beschreibung des Netzzustands in den Verteilungsnetzen.

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Bus load modelling in distribution systems

Contents The operating state of a distribution system is determined by the bus load current. Based on individual substation measurements and the load composition typical load curves are calculated using statistical estimation theory. These typical load curves describe the electrical behaviour of the different load types (e.g. household, storage heating, commerce etc.). As soon as the typical load curves are determined it is possible to calculate the bus load current in any substation taking external influences such as temperature into consideration. The bus load current serve as load models which completely describe the operating state of the distribution system.

     

Pressure release of containments during severe accidents in Switzerland

As required by the Swiss Federal Nuclear Safety Inspectorate (HSK) all Switzerland's five nuclear power plants have to install a containment filtered venting system. The integrity of the containment (the last barrier for radioactive releases to the environment) can be threatened by overpressure due to inadequate heat removal. Design requirements have been provided for a specific class of severe accident scenarios. In general the capacity of the system is considered sufficient if it is able to vent the steam production corresponding to a decay heat level of 1% of the thermal reactor power. The mitigation capacity for the reduction of released radioactive material is specified by a retention factor of 1000 for aerosols to prevent or limit a long term ground contamination and a factor of 100 for elementary iodine for prevention or limiting of thyroid doses and to avoid short term evacuation. Besides existing requirements for design, maintenance and operation, additional claims such as passivity and operability at any pressure conditions inside the containment have to be met. Passivity implies that the system can be initiated after a severe accident without any operator action. The system also has to allow early manual venting. Various filtered venting systems are presently available. The nuclear power plants of Beznau, Gosgen, Leibstadt and Muhleberg have already selected such systems and already implemented them or are going to install them step by step. Beznau selected the Sulzer-EWI system which is using a water pool with nozzles-baffle plates and mixing elements to achieve the required filtration of the aerosols. In both Beznau units, the systems are installed and in standby mode. Gosgen, a pressurized water reactor as well as Beznau, is going to implement a filter system developed by Siemens-KWU, known as sliding pressure venting process, combining a venturi scrubber in a water pool and a mesh filter. The boiling water reactor of Leibstadt also selected the same system as Beznau while Müheberg choose the ABB system but not in the common design. The venturi pipes are thereby integrated in the water pool of the outer torus. The system in all five nuclear power plants is fully operable and in standby mode since December 1993.     

Measurement of the dielectric constant of highly absorbing polar liquids at microwave frequencies

Nomograms are given for claculating the dielectric constant and dielectric loss of polar liquids by measuring the standing wave ratio for an infinitely thick layer of fluid and the layer thickness at which wave reflection is minimum. Translated from Izmeritel'naya Tekhnika, No. 2, pp. 46–47, February, 1996.     

On the hypoelastic-idealplastic constitutive model

Summary Recently, the hypoelastic-idealplastic solid under simple shear has been studied. As an unexpected result, the slope of the stress-strain curve at the beginning of the plastic range turned out to be negative. While all other assumptions remained the same, this effect was recognized for all objective stress rates, which have been used for the hypoelastic constitutive law.The main objective of this paper is an interpretation of this remarkable result, where this interpretation should be given in an acceptable and rational form. To this end, we apply the constitutive assumption of the elastic-idealplastic body for comparison.With 1 Figures     

Synthesis and characterization of acidic properties of Al-SBA-15 materials with varying Si/Al ratios

Al-SBA-15 of varying Si/Al ratios in the range 11.4–78.4 was synthesized using tri-block copolymer P123. The calcined materials were examined by XRD, pore size distribution, surface area, ²⁷Al NMR spectroscopy. The acidity and acid strength distribution were studied using microcalorimetric adsorption of NH₃. The acidic properties were also examined by cumene cracking reaction as a function of Si/Al ratios. Systematic variation of acidity and activity was observed as a function of Si/Al ratio. The initial heats of NH₃ adsorption correlated well with activity indicate that acid sites with ΔH > 100 kJ/mole is responsible for cumene cracking activity. Linear correlations were obtained with total acidity and cumene cracking activities. The tetrahedral aluminum was found to be responsible for the observed acidities and catalytic activities.     

Prediction of the effects on dynamic response due to distributed structural modification with additional degrees of freedom

The aim of this study is to investigate means of efficiently assessing the effects of distributed structural modification on the dynamic properties of a complex structure. The dynamic properties of the modified structure can be determined by experimental testing or numerical simulation, both of which are complex, expensive and time-consuming. Assuming that the original dynamic characteristics are already established and that the modification is a relatively simple attachment, the modified dynamic properties may be determined numerically without solving the equations of motion of the full-modified structure. The frequency response functions (FRFs) of the modified structure can be computed by coupling the original FRFs and a delta dynamic stiffness matrix for the modification introduced. The validity of this approach is investigated by applying it to a cantilever beam to which a smaller beam is attached as modification. The original FRFs were obtained experimentally as well as numerically. The delta dynamic stiffness matrix was determined numerically by modeling the attachment and part of the original structure including the attachment points. The FRFs of the modified beam were then computed. Good agreement is obtained by comparing the results to the FRFs of the modified beam determined experimentally as well as by numerical modeling of the complete modified structure.