Design of fluidized bed photoreactors: Optical properties of photocatalytic composites of titania CVD-coated onto quartz sand

Volumetric optical properties (spectral absorption, scattering and extinction coefficients) of differently expanded narrow-path fluidized beds (FB) of a photocatalyst obtained by plasma-CVD deposition of titania onto quartz sand, relevant for photoreactor design purposes, are determined by using an unidirectional and unidimensional (1DD) model for the solution of the radiative transfer equation (RTE). Two simplified approaches are used: a Kubelka-Munk (KM) type of solution, by which the RTE is transformed into a pair of ordinary differential equations, and a discrete ordinate method (DOM) by which the complete RTE is transformed into an algebraic system that can be solved computationally. The second approach was validated by introducing the obtained optical parameters into a more elaborated bi-directional and two-dimensional (2DD) DOM model. Despite its simplicity, the KM method was able to yield fair order-of-magnitude estimates of the spectral optical properties of these FB.     

Nitrogen dynamics during till and no-till pasture restoration sequences in Rondônia,Brazil

The clearing of tropical rain forest in the Amazon basin has created large areas of cattle pasture that are now declining in productivity. Practices adopted by ranchers to restore productivity to degraded pastures have the potential to alter soil N availability and gaseous N losses from soils. We examined how soil inorganic N pools, net N mineralization and net nitrification rates, nitrification potential and NO and N₂O emissions from soils of a degraded pasture responded to the following restoration treatments: (1) soil tillage followed by replanting of grass and fertilization, (2) no-till application of non-selective herbicide, planting of rice, harvest followed by no-till replanting of grass and fertilization, and (3) the same no-till sequence with soybeans instead of rice. Tillage increased soil NH₄⁺ and NO₃^? pools but NH₄⁺ and NO₃^? pools remained relatively constant in the control and no-till treatments. Cumulative rates of net N mineralization and net nitrification during the first 6 months after treatment varied widely but were hightest in the tilled treatment. Emissions of NO and N₂O fluxes increased with tillage and with N fertilization. There were no clear relationships among rates of N fertilizer application, net N mineralization, net nitrification, NO, N₂O and total N oxide emissions. Our results indicate that pasture restoration sequences involving tilling and fertilizing will increase emissions of N oxides, but the magnitude of the increase is likely to differ based on timing of fertilizer application relative to the presence of plants and the magnitude of plant N demand. Emissions of N oxides appear to be decreased by the use of restoration sequences that minimize reductions in pasture grass cover.     

SELECTIVITY STUDIES IN THE PHOTOCHLORINATION OF METHANE II: EFFECT OF THE RADIATION SOURCE OUTPUT POWER AND OUTPUT SPECTRAL DISTRIBUTION

The effect of the output power and output spectral distribution of the radiation energy fed to a photoreactor upon the reaction yield and selectivities is studied both theoretically and experimentally. The study aims at the analysis of these influences in a series reaction such as the photochlorination of methane where methylene chloride and eventually chloroform are the most valuable products. The computational model employed has been verified for a group of selected conditions by means of bench-sale experiments.

It is found that the chlorine conversion shows the expected square root dependence with respect to the Local Volumetric Rate of Energy Absorption (LVREA). This dependence, in a first approximation, can also be assigned to the effect of the radiation source output power upon yield. It is also found that by manipulating the amount of radiation power fed to the reactor it is possible to ascertain the operating conditions favoring the production of predetermined intermediate products (e.g., methylene chloride or chloroform).

It is concluded that the use of customized lamps especially designed for each particular product on the basis of feasible changes in the characteristics of the existing radiation sources will favor a selective and more economical production of some of the stable intermediates, i.e., lamp design is an important feature in any optimal process design.     

Crystallinity and thermal properties of ethylene-1-decene copolymers

Summary Three copolymers of ethylene and 1-decene, covering a wide range of compositions, have been synthesized with a MgCl₂-supported Ziegler-Natta catalyst. The analysis by DSC and X-ray shows a great degree of heterogeneity in these copolymers and appreciable levels of crystallinity, corresponding to the orthorhombic lattice of polyethylene, are present even for very high 1-decene contents.     

Single-phase gold/palladium catalyst: The nature of synergistic effect

The liquid phase oxidation of glycerol with oxygen has been studied using mono and bimetallic catalysts based on Au and Pd metals supported on activated carbon, in order to study the effect of the metal on the distribution of the products and on activity of catalysts. It was found that by using bimetallic catalysts (Au–Pd) a strong synergistic effect was shown. By using a preformed nucleating centre we were able to obtain a single alloyed phase, which allowed us to address the synergistic effect to the presence of alloyed Au/Pd. The advantage of using this latter catalyst lies not only in the high activity but also in a prolonged catalyst life. Although a partial leaching of palladium and assembling of the particles have been revealed by ICP and HRTEM respectively, activity after 10 re-cycles decreased less than expected (about 10%).     

Strong dependence on pressure of the performance of a Co/SiO2 catalyst in Fischer–Tropsch slurry reactor synthesis

A 10 wt% Co/SiO₂ catalyst was prepared by the incipient wet-impregnation method and tested in Fischer–Tropsch synthesis in a slurry reactor under conditions approaching industrial practice. The catalyst precursor was investigated by X-ray diffraction (XRD), temperature-programmed reduction (TPR), transmission electron microscopy (TEM) and photoelectron spectroscopy (XPS). The XPS and XRD techniques revealed the presence of a crystalline Co₃O₄ spinel-type phase, while-in addition-TEM and XPS analyses pointed to the formation of another amorphous Co₃O₄ spinel phase, both species interacting weakly with the silica substrate. The influence of total pressure on the conversion, selectivity and stability of the catalyst was studied. Upon increasing the overall pressure from 20 to 40 bar, not only activity increased but also the catalyst are not deactivating. These results are explained in terms of an increase of gases solubility in the solvent, this increment of CO concentration in the liquid phase favours carbonyl species formation and the cobalt particles segregation that implies an increase in the metal surface area.     

Vessel Inspection: A Micro-Aerial Vehicle-based Approach

Vessel maintenance entails periodic visual inspections of the internal and external parts of the hull in order to detect the typical defective situations affecting metallic structures, such as coating breakdown, corrosion, cracks, etc. The main goal of project MINOAS is the automation of the inspection process, currently undertaken by human surveyors, by means of a fleet of robotic agents. This paper overviews an approach to the inspection problem based on an autonomous Micro Aerial Vehicle (MAV) which, as part of this fleet, is in charge of regularly supplying images that can teleport the surveyor from a base station to the areas of the hull to be inspected. The control software approach adopted for the MAV is fully described, with a special emphasis on the self-localization capabilities of the vehicle. Experimental results showing the suitability of the platform to the application are as well reported and discussed.     

Polymerization by phase transfer catalysis

Poly(amide-carbonate)s and poly(amide-thiocarbonate)s derived from the diphenol-amides N-(2,6-dichloro-4-nitrophenyl)-2,2-bis(hydroxyphenyl)-propylamide (I), N-(2,6-dichloro-4-nitrophenyl)-3,3-bis(hydroxyphenyl)-butylamide (II), and N-(2,6-dichloro-4-nitrophenyl)-4,4-bis(hydroxyphenyl)-pentylamide (III), and phosgene or thiophosgene, have been synthesized under phase transfer conditions using several quaternary ammonium salts as phase transfer catalysts. Benzyltriethylammonium chloride (BTEAC) was effective in practically all cases due the hydrophilicity of this catalysts. Received: 21 February 1997/Revised: 28 April 1997/Accepted: 30 April 1997     

Silphinene Sesquiterpenes as Model Insect Antifeedants

Silphinene sesquiterpenes are established chrysomelid antifeedants. In this work, nine silphinene analogs, 11-acetoxy-5-angeloyloxysilphinen-3-one (1), 11-acetoxy-5-tigloyloxysilphinen-3-one (2), 11-acetoxy-5-iso- butyryloxysilphinen-3-one (3), 11-hydroxy-5-angeloyloxysilphinen-3-one (4), 11,5-dihydroxysilphinen-3-one (5), 11,5-diacetoxysilphinen-3-one (6), 5,11-diisobutyryloxysilphinen-3-one (7), silphinen-3,5,11-trione (8), and O-methyl-5-epicantabrenolic acid methyl ester (10), and a presilphiperfolane sesquiterpene (9) were tested against several divergent insect species, including the lepidopteran Spodoptera littoralis, the chrysomelid Leptinotarsa decemlineata, and five aphid species, and their antifeedant effects were compared with those of picrotoxinin, a GABA-antagonist, and thymol, an allosteric modulator for insect GABA receptors. All insects tested responded to at least one silphinene analog and/or GABA antagonist. Compound 3 and thymol were effective antifeedants against all species tested except S. littoralis, with varying potencies according to their feeding ecologies. The toxicity of these compounds was species-dependent and did not correlate with their antifeedant effect.     

Separation of Triacylglycerol Species from Interesterified Oils by High-Performance Liquid Chromatography

Using a 1,3-regioselective lipase as a catalyst, soybean oil and olive oil were interesterified with the short-chain triacylglycerol tributyrin (1,2,3-tributyrylglycerol) to produce mixtures of structured triacylglycerols (SL-TAG). The SL-TAG were purified by column chromatography and analyzed by both normal-phase (silica column; NP_SIL) and reversed-phase [octadecyl silane (ODS) column] high-performance liquid chromatography (HPLC). Individual SL-TAG molecular species were detected by evaporative light-scattering detection, and characterized by mass spectrometry. NP_SIL HPLC successfully separated the newly synthesized SL-TAG into two groups of TAG: one composed of one butyryl group and two long-chain fatty acyl groups (from soybean or olive oil); the second was composed of two butyryl groups and one long-chain fatty acyl group. The SL-TAG species were further analyzed by reversed-phase HPLC which gave a more detailed separation of the TAG species present in the two SL-TAG.