Relating catalyst structure and composition to the water–gas shift activity of Cu–Zn-based mixed-oxide catalysts

In order to investigate the effect of cerium oxide on Cu–Zn-based mixed-oxide catalysts four catalyst samples were characterized by means of XRD, in situ XANES and thermogravimetric analysis. The activity of the catalyst samples was tested for the forward water–gas shift reaction. Cerium oxide was found to increase the crystallinity of the ZnO phase indicating a segregation of the Cu and ZnO phases. The TOF of the water–gas shift reaction based on chemisorption data was found to be independent of composition and preparation conditions of the four catalyst samples. In contrast, the catalyst stability depends on composition and preparation conditions. Cerium oxide impregnated before calcination of the hydrotalcite-based Cu–Zn precursors leads to a more stable water–gas shift catalyst.     

Separate assessment of porosity and uncombined carbon in cemented carbides

Porosity and uncombined carbon in cemented carbides are traditionally assessed by comparison to standardized microstructure charts, such as those in ISO 4505-1978. To improve the accuracy in the characterization a fully automatic image analysis procedure has been developed. The analysis is performed using light optical microscopy on unetched polished specimens. The implemented algorithm separates uncombined carbon, C-defects, from pores, A- and B-defects. Pores are approximately distributed in a random way in the structure. Uncombined carbon is on the other hand precipitated into clusters of carbon particles. This difference is together with defect size used as a base for the separation. Small defects situated close together are classified as C-defects, small isolated defects as A-pores and large defects as B-pores. Pores are found to be more round than the somewhat elongated C-defects. The difference in shape is significant and can also be used as a separation criterion.

Image analysis is used to quantitatively characterise the ISO 4505-1978 standard charts with respect to volume fraction, number density and size distribution of defects. The results are compared to measured distributions for true microstructures.     

Expert performance: Its structure and acquisition.

Counter to the common belief that expert performance reflects innate abilities and capacities, recent research in different domains of expertise has shown that expert performance is predominantly mediated by acquired complex skills and physiological adaptations. For elite performers, supervised practice starts at very young ages and is maintained at high daily levels for more than a decade. The effects of extended deliberate practice are more far-reaching than is commonly believed. Performers can acquire skills that circumvent basic limits on working memory capacity and sequential processing. Deliberate practice can also lead to anatomical changes resulting from adaptations to intense physical activity. The study of expert performance has important implications for our understanding of the structure and limits of human adaptation and optimal learning. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

A detailed analysis of ambipolar diffusion in nanostructured metal oxide films

In this paper a transport equation is derived which describes the behaviour of the nanostructured metal oxide films in a photoelectrochemical cell. It is shown that a detailed analysis of the charge compensation mechanism necessarily leads to a transport equation with characteristics similar to but logically distinct from the pure diffusion equation. The studied phenomenon was named ambipolar diffusion in the early 1950s. It takes into account the fact that the diffusion processes of ions and electrons occur at different speeds. A weak electric field therefore couples the processes together to preserve charge neutrality. The electric field in turn affects the transport resulting in a deviation from purely diffusive behaviour. However, this has not been widely recognised in the literature for nanostructured semiconductor films until very recently. In this paper a detailed analysis is presented. It is based on the assumption that the current density is solenoidal. It is shown that application of the ambipolar diffusion model to a photoelectrochemical cell based on a nanostructured metal oxide film leads to an additional term in the transport equation, rather than only a new diffusion coefficient as in earlier work. It is also shown that the boundary conditions interact closely with the equation to form a transport model.     

Existence of discrete-time LQG-controllers

Existence results for the LQG-controller are investigated. An infimal Riccati equation based controller may potentially give closed loop eigenvalues on the unit circle. Assuming left and right invertibility it is shown that there exists an optimal controller if and only if the Riccati equation based controller stabilizes the closed loop system after removal of all its unobservable and uncontrollable modes. Furthermore this reduced controller is the optimal controller, and its transfer function is unique. This existence condition is a considerable simplification of the more general geometric condition recently derived by Trentelman and Stoorvogel.     

A note on the min-max formulation of stiffness optimization including non-zero prescribed displacements

The present theoretical note shows how a natural objective function in stiffness optimization, including both prescribed forces and non-zero prescribed displacements, is the equilibrium potential energy. It also shows how the resulting problem has a saddle point character that may be utilized when calculating sensitivities.     

Continuous production of structured phospholipids in a packed bed reactor with lipase from <Emphasis Type="Italic">Thermomyces lanuginosa</Emphasis>

The possibilities of producing structured phospholipids between soybean phospholipids and caprylic acid by lipase-catalyzed acidolysis were examined in continuous packedbed enzyme reactors. Acidolysis reactions were performed in both a solvent system and a solvent-free system with the commercially immobilized lipase from Thermomyces lanuginosa (Lipozyme TL IM) as catalyst. In the packed bed reactors, different parameters for the lipase-catalyzed acidolysis were elucidated, such as solvent ratio (solvent system), temperature, substrate ratio, residence time, water content, and operation stability. The water content was observed to be very crucial for the acidolysis reaction in packed bed reactors. If no water was added to the substrate during reactions under the solvent-free system, very low incorporation corporation of caprylic acid was observed. In both solvent and solvent-free systems, acyl incorporation was favored by a high substrate ratio between acyl donor and phospholipids, a longer residence time, and a higher reaction temperature. Under certain conditions, the incorporation of around 30% caprylic acid can be obtained in continuous operation with hexane as the solvent. Presented at the 95th American Oil Chemists' Society Annual Meeting and Expo in Cincinnati, Ohio, May 10, 2004.     

A computational investigation of non-isothermal gas-solid flow in a U-bend

The non-isothermal gas-solid flow through a U-bend of a pneumatic conveying dryer system is calculated using the commercial CFD program Fluent 6.1. Steady-state, incompressible and non-isothermal gas-solid flows are employed to simulate the cases. Variables studied include: particle diameter, particle density, solid loading ratio, feed gas temperature, heat flux through the wall, gas velocity and bend radius ratio on heat transfer phenomena between gas and solid particles. Validation is done by comparing calculation results with the available experimental data provided by Baughn et al. [J.W. Baughn, H. Iacovides, D.C. Jackson, B.E. Launder, Local heat transfer measurements in turbulent flow around a 180° pipe bend, Journal of Heat Transfer 109 (1) (1987) 43-48] and Depew and Farbar [C.A. Depew, L. Farbar, Heat transfer to pneumatically conveyed glass particles of fixed size, Journal of Heat Transfer 85 (1963) 164-172].In general, data validations of both cases show good agreement. The gas temperature decreases and the solid temperature increases along the axial direction of the pipe due to transfer of heat from the gas phase to the solid phase. The gas temperature decreases significantly at the outer bend wall due to an accumulation of particles, which causes much more energy to be transferred from the gas to solid phases. At the inner bend wall, the gas temperature decreases slightly but the solid temperature increases significantly due to a low concentration of particles. A U-bend significantly increases the local and area average Nu numbers, but not the mass average Nu number. The slip velocity and particle distribution are the major factors influencing the value of the mass average Nu number.     

Propene and 1-Octene Hydroformylation with Silica-Supported, Ionic Liquid-Phase (SILP) Rh-Phosphine Catalysts in Continuous Fixed-Bed Mode

Supported ionic liquid-phase (SILP) catalysts were made by immobilizing Rh-monophosphine complexes of bis(m-phenylguanidinium)phenylphosphine 1 and NORBOS 2 ligands in 1-n-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF₆], on a silica support. The catalysts were active in continuous gas- and liquid-phase hydroformylation of propene and 1-octene, exhibiting TOFs up to 88 h^-1 for SILP Rh-2 catalysts, while only low selectivities up to 74% n-aldehyde (n/iso ratio of 2.8) were obtained. This is the first example of continuous fixed-bed liquid-phase hydroformylation using SILP catalysts.