Complete Oxidation of Methane at Low Temperature over Pt Catalysts Supported on High Surface Area SnO2

The catalytic activity of Pt catalysts supported on high surface area tin(IV) oxide in the complete oxidation of CH₄ traces under lean conditions at low temperature was studied in the absence and in the presence of water (10 vol.%) or H₂S (100 vol.ppm). Their catalytic properties were compared to those of Pd/Al₂O₃ and Pt/Al₂O₃. In the absence of H₂S in the feed, Pt/SnO₂appears as a very promising catalyst for CH₄ oxidation, being even significantly more active under wet conditions than the best reference catalyst, Pd/Al₂O₃. Catalysts steamed-aged at 873 K were also studied in order to simulate long term ageing in real lean-burn NGV exhaust conditions. To this respect, Pt/SnO₂ is slightly less resistant than Pd/Al₂O₃. In the presence of H₂S, Pt/SnO₂catalysts are rapidly and almost completely poisoned, comparably to Pd/Al₂O₃and the catalytic activity is hardly restored upon oxidising treatment below 773 K. A synergetic effect between Pt and specific surface SnO₂sites active in CH₄oxidation is proposed to explain the superior catalytic behaviour of Pt/SnO₂.     

Adsorption and desorption kinetics of hydrocarbons in FCC catalysts studied using a tapered element oscillating microbalance (TEOM). Part 2: numerical simulations

The factors affecting the adsorption and desorption kinetics in a TEOM are reviewed in detail with particular attention given to the assumptions required to obtain physical transport parameters from the data. Two models are presented to simulate TEOM adsorption data in the case that concentration differences down the catalyst bed can be neglected, as is appropriate when the amount of catalyst used is small, the carrier gas flowrate is large, and/or the adsorbate partial pressure is low. In the first model, the effective diffusion coefficient, D_e, is taken to be constant. In the second model, the effective diffusion coefficient is assumed to obey the Darken equation, D_e=D₀/(1−θ). The TEOM results obtained on n-hexane, n heptane, n-octane, toluene and p-xylene on a commercial FCC catalyst and on pure rare-earth exchanged zeolite Y under non-reacting conditions (373-) are analysed in detail. It is found that intracrystalline diffusion is not the limiting factor affecting the overall rates of adsorption and desorption for the systems studied. Instead, it is the transport of molecules between the adsorbed and vapour phases at the edge of zeolite crystallites that is the limiting transport step affecting the overall kinetics. For the FCC catalyst, the limiting step is the transport of molecules at the zeolite-matrix interface rather than, say, the matrix-vapour interface. Local rate constants for the desorption of the hydrocarbons at the rate-controlling interface have been obtained.     

Parallelised production of fine and calibrated emulsions by coupling flow-focusing technique and partial wetting phenomenon

The capacity of microfluidic technology to fabricate monodisperse emulsion droplets is well established. Parallelisation of droplet production is a prerequisite for using such an approach for making high-quality materials for either fundamental or industrial applications where product quantity matters. Here, we investigate the emulsification efficiency of parallelised drop generators based on a flow-focusing geometry when incorporating the role of partial wetting in order to make emulsion droplets with a diameter below 10 μm. Confinement intrinsically encountered in microsystems intensifies the role played by interfaces between liquids and solids. We thus take advantage of partial wetting to enhance the maximum confinement accessible due to liquid flow focusing. We compare the performances brought by partial wetting to more established routes such as step emulsification. We show that the step configuration and the partial wetting regime are both well suited for being parallelised and thus open the way to the production of fine and calibrated emulsions for further applications. Finally, this new route of emulsification that exploits partial wetting between the fluids and the channel walls opens possibilities to the formation of substantially smaller droplets, as required in many fields of application.     

A second-generation system for unbiased reading frame selection

Reading frame selection of nucleic acids has important implications for protein engineering and genomics. Current methods are limited because selection of the gene of interest inevitably depends on the solubility of its translated product. Here we report the construction of the pInSALect vector, which provides strict reading frame selection without concomitant selection for protein solubility or folding. This plasmid incorporates the cis-splicing VMA intein sequence from Saccharomyces cerevisiae to facilitate the post-translational self-excision of the protein of interest, thereby eliminating potential aggregation problems. Results from two libraries of chimeric glycinamide ribonucleotide formyltransferases confirm the superior performance of pInSALect over existing reading frame selection systems.     

Estimation of liquid film mass transfer coefficients for columns randomly packed with partially wetted rings

A semitheoretical correlation based on an extension of the random length, random angle statistical model of Davidson (1959) is developed which predicts liquid film mass transfer coefficients in a column packed with partially wetted Raschig rings. The method takes into account the ring size and the mixing which occurs at the packing junctions and allows an estimation of the effective length of a packing piece for a particular liquid viscosity. Predicted values of mass transfer coefficients are in good agreement with the experimental values obtained for the carbon dioxide-water and carbon dioxide-aqueous glycerol systems at 25°C reported by Mangers and Ponter (1980b) and other systems reported by Sherwood and Holloway (1940).     

Die design for rigid PVC—the effect of die land length on extrudate swell

PVC profile extrusion compounds have a unique morphology. While other polymers gradually decrease in extrusion die swell with increasing length/thickness (L/D) ratio, PVC profile extrusion compounds have a low die swell, quite independent of the die's L/D ratio in the range of 5 to 20. The fact that the die land length can be changed without changing the extrudate swell is an important consideration, which makes die design and balancing dies simpler and easier for PVC profile extrusion compounds. While other polymers substantially increase extrudate swell with increased shear rate, the swell of the PVC profile compounds is not much affected by shear or extrusion rate. This unique behavior allows wider processing latitude in profile extrusion and faster extrusion rates than with other polymers. Another unique factor in the rheology of PVC profile extrusion compounds is that extrusion die swell increases with increasing melt temperature, while other polymers have decreasing die swell with increasing melt temperature. The unusual rheology of PVC profile extrusion compounds is attributed to its unique melt morphology, where the melt flow units are 1 um bundles and molecules that have low surface to surface interaction and entanglement at low processing temperatures but increased melting and increased entanglement at higher processing temperatures. Other polymers, unlike PVC, have melt flow at the molecular level.     

Development of optical anisotropy in vitrains during carbonization

The purpose of this work was to examine the possible significance in the formation of metallurgical coke of the anisotropic spherical mesophase exemplified by that found during the carbonization of pitch-like materials, and to ascertain if the various types of optical anisotropy found in coke could form a basis for the characterization of cokes produced from different coals. Vitrains from a wide range of coals were carbonized at temperatures from 370 to 1000 °C and the types and amounts of optical anisotropy in the resulting semi-cokes and cokes were determined from microscopic examination, the anisotropic components being classified according to grain size of the granular mosaics and appearance. The anisotropy developed directly from the isotropic phase, appearing initially as a fine-grained mosaic. With increasing carbonization temperature, this fine-grained mosaic was transformed into progressively coarser-grained anisotropy, the extent of this transformation depending on the rank of the vitrain. It is therefore concluded that the formation, growth and coalescence of anisotropic spherical bodies, such as occurs during the carbonization of pitch, is not a necessary precursor of the mosaic anisotropy in coke. The type and amount of anisotropy developed provide a quantitative means of characterising different cokes.     

The existence of a soluble plasmalogenase in guinea pig tissues

The distribution of plasmalogenase for the hydrolysis of 1-alkenyl-2-acyl-sn-glycero-3-phosphoethanolamine (plasmenylethanolamine) in the subcellular fractions of guinea pig tissues was examined. Plasmalogenase activity was found in high abundance in the cytosolic fractions of the brain and the heart. Assessment of microsomal marker enzyme activities in the cytosolic fraction revealed that plasmalogenase activity in the cytosol was not due to microsomal contaminations. The characteristics of the cytosolic plasmalogenase were very similar to the microsomal enzyme with respect to the pH profile of the reaction, the presence of divalent cations and K_m values for plasmenylethanolamine. However, the cytosolic enzyme was slightly less stable at 55°C than the microsomal enzyme. Cytosolic enzyme activity was eluted as a broad peak in Sepharose 6B chromatography with an average molecular weight of 250,000. Our results demonstrate that most of brain plasmalogenase activity is soluble which makes the brain cytosol an excellent source to initiate the purification of this enzyme.     

Infrared study of nitrogen monoxide adsorption on palladium ion-exchanged ZSM-5 catalysts

The adsorption of NO at room temperature on a H-ZSM-5 catalyst exchanged with Pd(NH₃) ₄ ²⁺ complex and activated in oxygen at 773 K has been examined by FTIR spectroscopy. After the oxidizing treatment, the Pd tetrammine complex decomposed into Pd(II) ions and/or Pd(II) hydroxyl complexes dispersed in the zeolite channels. The subsequent adsorption of NO at room temperature led to the reduction of Pd(II) to Pd(I) entities, resulting in the formation and adsorption of NO₂ on H-ZSM-5. The Pd(I) entities were shown to adsorb NO and form mononitrosyl complexes dispersed in the zeolite porosity and characterized by a single infrared absorption band at 1881 cm^–1. The Pd(I) mononitrosyl complex was shown to reversibly coordinate water and NO₂ molecules. The resulting nitrosyl complex was characterized by a single NO vibration band at 1836 cm^–1.