The oxidation activity and acid-base properties of SnO2-based binary catalysts: II. The SnO2MoO3 and SnO2P2O5 systems

The vapor-phase oxidation of 1-butene, butadiene, and acetic acid, the isomerization of 1-butene, and the dehydration and dehydrogenation of isopropyl alcohol (IPA) were carried out, in the presence of an excess of air, over two series of catalysts, SnO₂MoO₃, and SnO₂P₂O₅, and the relationship between the catalytic behavior and the acid-base properties of the catalysts was investigated. The acidity and the basicity of the SnO₂MoO₃ catalysts were measured by studying the adsorption of basic and acidic molecules, respectively, in the gas phase, using both the static and pulse methods. The acidities of the SnO₂MoO₃ catalysts are dramatically high at the Mo content of 30–60 atom%, though those of the SnO₂-rich (Mo < 20 atom%) and MoO₃-rich (Mo > 80 atom%) catalysts are fairly low. The basicity is remarkably enhanced by the introduction of a small amount of MoO₃ (Mo < 5 atom%). It can be said that the catalysts are basic in the MoO₃-poor composition. In the case of the SnO₂P₂O₅ catalysts, the acidity and basicity were evaluated from the catalytic activity for the dehydration of IPA to propylene and the (dehydrogenation rate for IPA)/(dehydration rate for IPA) ratio, respectively. The introduction of P₂O₅ increases the acidity and decreases the basicity, to a very small extent, so it cannot cause a remarkable modification in the catalytic behavior; that is, the SnO₂P₂O₅ catalysts are rather basic.     

Interaction of tocored with unsaturated fatty esters

Tocored, an oxidation product of tocopherol and its model, 2,2,7,8-tetramethyl-5,6-chromanquinone reacted with methyl linoleate at an elevated temperature to form an adduct with isomerized linoleate. Oxidation of tocored in fatty esters produced a variety of products, depending on the degree of unsaturation of the esters. With methyl palmitate no addition product was detected but tocopurple and tocoreddimer were identified as minor products irrespective of the degree of saturation. A mechanism involving the interaction of tocored with lipid radicals to yield an adduct as the consequence of antioxidative action of tocored is postulated.     

Experimental study on two-phase natural circulation and flow termination in a loop

In order to study the two-phase natural circulation and flow termination during a small break loss of coolant accident in LWR, a hot leg U-bend simulation loop has been built based on the two-phase flow scaling criteria developed under this program. The nitrogen-water system has been used to isolate the key hydrodynamic phenomena from heat transfer problems. Various tests were carried out to establish the basic mechanism of the flow termination and reestablishment as well as to obtain essential information on scale effects of various parameters such as the loop frictional resistance, thermal center, U-bend curvature, and inlet geometry. It was found that the permanent termination of the natural circulation was related to the head balance between the hot and cold legs. The local flow condition at the inverted U-bend could produce intermittent flow, however was not related to the permanent flow termination. The void distribution in a hot leg, flow regime, and natural circulation rate have been measured in detail for various conditions. Significant effects of the inlet geometry on these were observed. Near the flow termination condition, large amplitude flow oscillations occurred. The occurrence of this type of flow instability is important for safety analyses, because it may lead to loop-to-loop oscillations or flow excursions in a prototype system which has a multi-loop configuration.     

A neurofuzzy methodology for impedance-based multiphase flow identification

A neurofuzzy methodology for flow identification based on signals obtained from an impedance void meter is presented. The methodology combines the filtering and interpolative capabilities of neural networks with the representational advantages of fuzzy systems for the purpose of mapping idiosyncratic area-averaged impedance measurements to multiphase flow regimes. It has been shown that electrical signals representing the conductance of the intervening medium can be used to infer crucial flow parameters, and that area-averaged signals contain sufficient information about flow regime and the structure of its two-phase constituents. The neurofuzzy approach is a promising means for reconstructing the visual imagery of flow in a process, analogous to tomography, and holds considerable promise for multiphase flow diagnostic and measurement applications in the nuclear as well as in the petroleum, biomedical, and food-processing industries.     

Sensitivity analysis of bubble size and probe geometry on the measurements of interfacial area concentration in gas-liquid two-phase flow

Interfacial area concentration measurement is quite important in gas-liquid two-phase flow. To determine the accuracy of measurement of the interfacial area using electrical resistivity probes, numerical simulations of a passing bubble through sensors are carried out. The two-sensors method, the four-sensors method and the correlative method are tested and the effects of sensor spacing, bubble diameter and hitting angle of the bubbles on the accuracy of each measurement method are investigated. The results indicated that the two-sensors method is insensitive to the ratio between sensor spacing and bubble diameter, and hitting angle. It overestimates the interfacial area for small hitting angles while it gives a reasonable accuracy for smaller bubbles and large hitting angles. The four-sensors method gives accurate interfacial area measurements particularly for the larger bubble diameters and smaller hitting angles, while for smaller bubbles and larger hitting angles, the escape probability of bubbles through the sensors becomes large and the accuracy becomes worse. The correlative method gives an overall accuracy for interfacial area measurement. Particularly, it gives accurate measurements for larger bubbles and larger hitting angles while for smaller hitting angles, the spatial dependence of the correlation functions affects the accuracy.     

The development of a diagnostic and monitoring system for vibrating pipe branches

This paper deals with a diagnostic and monitoring system for assessing the integrity of pipe branches, during the operation of the nuclear power plant. This system have been developed under the concept of “easy to use without any sophisticated analysis” and “portable”. The accuracy of the diagnosis is based on the model optimization subsystem, which automatically modifies the numerical vibration model so as to fit its natural frequency to the actual natural frequency. The information obtained by this system may be reflected to a maintenance program of the plant to assure more reliable operation of the plant.     

Precision die-casting of optical MU/SC conversion sleeve

The performance of MU/SC conversion sleeve produced by bulk metallic glass (Zr₅₅Al₁₀Ni₅Cu₃₀) was examined. A precision die-casting method was applied to improve size accuracy. The size accuracy of the conversion sleeve produced by the precision die-casting method was ±1 μm, and optical insertion loss (Li) was less than 0.3 dB for a standard value. The wear resistance of metallic glass is improved by surface oxidation treatment in air at 673 K. The MU/SC conversion sleeve produced from bulk metallic glass has superior characteristics for optical parts.     

NMR study on reaction processes from aluminum chloride hydroxides to alpha alumina powders

Starting from gelatinous aluminum chloride hydroxide, the transformation process toward α-Al₂O₃ was examined using ²⁷Al NMR, both in the liquid and solid states, as a main analytical tool. By increasing the hydrolysis ratio (h, defined as [OH⁻]/[Al³⁺]) of the starting aqueous precursor up to h = 2.5, the transition temperature to the final product, α-Al₂O₃, decreased to as low as 500°C. In this case, the structural change from amorphous alumina to α-Al₂O₃ took place without intermediate transition Al₂O₃ phases. Examining the process of networking during the transition from aqueous sol–through the state of xerogel–to final anhydrous oxide by nuclear magnetic resonance (NMR) revealed the presence of highly polymeric species mainly ascribed to δ-[Al₂O₈Al₂₈(OH)₅₆(H₂O)₂₄]¹⁸⁺ (δ-Al₃₀). δ-Al₃₀ species were found in the solution phase and became predominant after drying. We conclude that the lower temperature synthesis of α-Al₂O₃ became possible due to preformation of polymerized AlO₆ construction units in the precursor, reducing the energy barrier for the nucleation of the final α-Al₂O₃ phase.     

Construction of Cellulose Binding Domain Fusion FMN-Dependent NADH-Azoreductase and Glucose 1-Dehydrogenase for the Development of Flow Injection Analysis with Fusion Enzymes Immobilized on Cellulose

The cellulose binding domain (CBD) of cellulosome-integrating protein A from Clostridium thermocellum NBRC 103400 was genetically fused to FMN-dependent NADH-azoreductase (AZR) and glucose 1-dehydrogenase (GDH) from Bacillus subtilis. The fusion enzymes, AZR-CBD and CBD-GDH, were expressed in Escherichia coli Rosetta-gami B (DE3). The enzymes were purified from cell-free extracts, and the specific activity of AZR-CBD was 15.1 U/mg and that of CBD-GDH was 22.6 U/mg. AZR-CBD and CBD-GDH bound strongly to 0.5 % swollen cellulose at approximately 95 and 98 % of the initial protein amounts, respectively. After immobilization onto the swollen cellulose, AZR-CBD and CBD-GDH retained their catalytic activity. Both enzymes bound weakly to 0.5 % microcrystalline cellulose, but the addition of a high concentration of microcrystalline cellulose (10 %) improved the binding rate of both enzymes. A reactor for flow injection analysis was filled with microcrystalline cellulose-immobilized AZR-CBD and CBD-GDH. This flow injection analysis system was successfully applied for the determination of glucose, and a linear calibration curve was observed in the range of approximately 0.16–2.5 mM glucose, with a correlation coefficient, r, of 0.998.     

A design and simulation tool for ground source heat pump system using energy piles with large diameter

Calculation of the underground temperature resulting from heat injection/extraction into/from ground heat exchangers (GHEXs) with hourly variation is one of the most noteworthy challenges to address when simulating and designing a ground source heat pump (GSHP). In order to overcome this challenge, the authors introduce a method to calculate the underground temperature, by considering heat injection/extraction into/from GHEXs with hourly variation. The method applies the superposition of the infinite cylindrical source (ICS) solution and the infinite line source (ILS) solution to calculate the temperature change due to heat injection/extraction into/from the considered GHEX and other neighboring GHEXs, respectively. The calculation method also considers heat injection/extraction from GHEXs with different heat injection/extraction rates and is able to accommodate GHEXs with large diameters such as energy piles. The calculation method was evaluated by applying it to calculate the temperature variation of the heat carrier fluid in a GSHP system with energy piles.