Conversão catalítica de clorometano em hidrocarbonetos

Amorphous silica-alumina and modified by incipient impregnation of iron, nickel, zinc and chromium were synthetized in oxide and metal state and evaluated as catalysts for the chloromethane conversion reaction. With known techniques their textural properties were determined and dynamics techniques in programmed temperature were used to find the acid properties of the materials. A thermodynamic model was used to determine the adsorption and desorption capacity of chloromethane. Two types of reactions were studied. Firstly the chloromethane was catalytically converted to hydrocarbons (T = 300 450 oC e m = 300 mg) in a fixed bed reactor with controlled pressure and flow. Secondly the deactivation of the unmodified support was studied (at 300 °C and m=250 g) in a micro-adsorver provided of gravimetric monitoring. The metal content (2,5%) and the chloromethane percent of the reagent mixture (10% chloromethane in nitrogen) were fixed for all the tests. From the results the chloromethane conversion and selectivity of the gaseous products (H2, CH4, C3 and C4) were determined as well as the energy of desorption (75,2 KJ/mol for Ni/Al2O3-SiO2 to 684 KJ/mol for the Zn/Al2O3-SiO2 catalyst) considering the desorption rate as a temperature function. The presence of a metal on the support showed to have an important significance in the chloromethane condensation. The oxide class catalyst presented a better performance toward the production of hydrocarbons. Especial mention to the ZnO/Al2O3-SiO2 that, in a gas phase basis, produced C3 83 % max. and C4 63% max., respectively, in the temperature of 450 oC and 20 hours on stream. Hydrogen was produced exclusively in the FeO/Al2O3-SiO2 catalysts (15 % max., T = 550 oC and 5,6 h on stream) and Ni/SiO2-Al2O3 (75 % max., T = 400 oC and 21,6 h on stream). All the catalysts produced methane (10 à 92 %), except for Ni/Al2O3-SiO2 and CrO/Al2O3-SiO2. In the deactivation study two models were proposed: The parallel model, where the product production competes with coke formation; and the sequential model, where the coke formation competes with the product desorption dessorption step. With the mass balance equations and the mechanism proposed six parameters were determined. Two kinetic parameters: the hydrocarbon formation constant, 8,46 10-4 min-1, the coke formation, 1,46 10-1 min-1; three thermodynamic constants (the global, 0,003, the chloromethane adsorption 0,417 bar-1, the hydrocarbon adsorption 2,266 bar-1), and the activity exponent of the coke formation (1,516). The model was reasonable well fitted and presented a satisfactory behavior in relation with the proposed mechanism

Reflux synthesis and hydrothermal processing of ZrO2 nanopowders at low temperature

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Modelling thermodynamic properties of banana waste by analytical derivation of desorption isotherms

Banana is an agricultural product of great economic importance for various developing countries. The relationship between moisture content and water activity provides useful information for the processing and storage of banana waste. The water activity and moisture content of three banana (Mussa spp. Haploid AAB cv. Nanica) waste items were analyzed to determine the desorption isotherms at six different temperatures (20, 30, 40, 50, 60 and 70°C). The desorption isotherms of the peel, pedicel and pulp of overripe bananas were determined in wide ranges of moisture content (0.001-6.360 kg kg-1 d.b.) and water activity (0.02-0.907). The theoretical GAB model was used for modelling the desorption isotherms. An analytical solution of the Clausius-Clapeyron equation was proposed to compute the isosteric heat of sorption, the differential entropy and Gibbs' free energy by way of the GAB model when the effect of temperature on the hygroscopic equilibrium was considered. © 2012 de Gruyter. All rights reserved.

Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry Characterization of Primary Amine End-Functionalized Polystyrene and Poly(methyl methacrylate) Synthesized by Living Anionic Polymerization Techniques

The reaction of living anionic polymers with 2,2,5,5-tetramethyl-1-(3-bromopropyl)-1-aza-2,5- disilacyclopentane (1) was investigated using coupled thin layer chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Structures of byproducts as well as the major product were determined. The anionic initiator having a protected primary amine functional group, 2,2,5,5-tetramethyl- 1-(3-lithiopropyl)-1-aza-2,5-disilacyclopentane (2), was synthesized using all-glass high-vacuum techniques, which allows the long-term stability of this initiator to be maintained. The use of 2 in the preparation of well-defined aliphatic primary amine R-end-functionalized polystyrene and poly(methyl methacrylate) was investigated. Primary amino R-end-functionalized poly(methyl methacrylate) can be obtained near-quantitatively by reacting 2 with 1,1-diphenylethylene in tetrahydrofuran at room temperature prior to polymerizing methyl methacrylate at -78 °C. When 2 is used to initiate styrene at room temperature in benzene, an additive such as N,N,N',N'- tetramethylethylenediamine is necessary to activate the polymerization. However, although the resulting polymers have narrow molecular weight distributions and well-controlled molecular weights, our mass spectra data suggest that the yield of primary amine α-end-functionalized polystyrene from these syntheses is very low. The majority of the products are methyl α-end-functionalized polystyrene.

Gas adsorption and desorption effects on cylinders and their importance for long-term gas records

It is well known that gases adsorb on many surfaces, in particular metal surfaces. There are two main forms responsible for these effects (i) physisorption and (ii) chemisorption. Physisorption is associated with lower binding energies in the order of 1–10 kJ mol−¹, compared to chemisorption which ranges from 100 to 1000 kJ mol−¹. Furthermore, chemisorption only forms monolayers, contrasting physisorption that can form multilayer adsorption. The reverse process is called desorption and follows similar mathematical laws; however, it can be influenced by hysteresis effects. In the present experiment, we investigated the adsorption/desorption phenomena on three steel and three aluminium cylinders containing compressed air in our laboratory and under controlled conditions in a climate chamber, respectively. Our observations from completely decanting one steel and two aluminium cylinders are in agreement with the pressure dependence of physisorption for CO₂, CH₄, and H₂O. The CO₂ results for both cylinder types are in excellent agreement with the pressure dependence of a monolayer adsorption model. However, mole fraction changes due to adsorption on aluminium (< 0.05 and 0 ppm for CO₂ and H₂O) were significantly lower than on steel (< 0.41 ppm and about < 2.5 ppm, respectively). The CO₂ amount adsorbed (5.8 × 1019 CO₂ molecules) corresponds to about the fivefold monolayer adsorption, indicating that the effective surface exposed for adsorption is significantly larger than the geometric surface area. Adsorption/desorption effects were minimal for CH₄ and for CO but require further attention since they were only studied on one aluminium cylinder with a very low mole fraction. In the climate chamber, the cylinders were exposed to temperatures between −10 and +50 °C to determine the corresponding temperature coefficients of adsorption. Again, we found distinctly different values for CO₂, ranging from 0.0014 to 0.0184 ppm °C−¹ for steel cylinders and −0.0002 to −0.0003 ppm °C−¹ for aluminium cylinders. The reversed temperature dependence for aluminium cylinders points to significantly lower desorption energies than for steel cylinders and due to the small values, they might at least partly be influenced by temperature, permeation from/to sealing materials, and gas-consumption-induced pressure changes. Temperature coefficients for CH₄, CO, and H₂O adsorption were, within their error bands, insignificant. These results do indicate the need for careful selection and usage of gas cylinders for high-precision calibration purposes such as requested in trace gas applications.

Use of light intensity, temperature, and humidity to verify exposure location

Research studies on the association between exposures to air contaminants and disease frequently use worn dosimeters to measure the concentration of the contaminant of interest. But investigation of exposure determinants requires additional knowledge beyond concentration, i.e., knowledge about personal activity such as whether the exposure occurred in a building or outdoors. Current studies frequently depend upon manual activity logging to record location. This study's purpose was to evaluate the use of a worn data logger recording three environmental parameters—temperature, humidity, and light intensity—as well as time of day, to determine indoor or outdoor location, with an ultimate aim of eliminating the need to manually log location or at least providing a method to verify such logs. For this study, data collection was limited to a single geographical area (Houston, Texas metropolitan area) during a single season (winter) using a HOBO H8 four-channel data logger. Data for development of a Location Model were collected using the logger for deliberate sampling of programmed activities in outdoor, building, and vehicle locations at various times of day. The Model was developed by analyzing the distributions of environmental parameters by location and time to establish a prioritized set of cut points for assessing locations. The final Model consisted of four "processors" that varied these priorities and cut points. Data to evaluate the Model were collected by wearing the logger during "typical days" while maintaining a location log. The Model was tested by feeding the typical day data into each processor and generating assessed locations for each record. These assessed locations were then compared with true locations recorded in the manual log to determine accurate versus erroneous assessments. The utility of each processor was evaluated by calculating overall error rates across all times of day, and calculating individual error rates by time of day. Unfortunately, the error rates were large, such that there would be no benefit in using the Model. Another analysis in which assessed locations were classified as either indoor (including both building and vehicle) or outdoor yielded slightly lower error rates that still precluded any benefit of the Model's use.^

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Uncalibrated temperature measurement during R/V Maria S. Merian cruise MSM21/1b

GEOMAR's autonomous underwater vehicle (AUV Abyss REMUS 6000) was deployed within the framework of a multi-platform experiment in June 2012 with R/V Maria S. Merian cruise MSM21/1b at about 180 km downstream of Denmark Strait. The scientific payload included a pumped Seabird 49 FastCAT CTD system, a paroscientific pressure sensor, and shear and temperature microstructure profiler from Rockland Scientific Inc.. In total, six of eight AUV dives were carried out successfully. Aborts on three dives were caused by strong counter currents the AUV experienced in the Denmark Strait Overflow plume, which made the AUV fail to reach its waypoints on schedule. During all missions the AUV was programmed to dive at constant depth levels along? straight legs approximately parallel to chosen isobaths with a constant speed of 1.6 m s-1 through the water.

Assessing the dynamic behavior of wsn motes and rfid semi-passive tags for temperature monitoring.

A notorious advantage of wireless transmission is a significant reduction and simplification in wiring and harness. There are a lot of applications of wireless systems, but in many occasions sensor nodes require a specific housing to protect the electronics from hush environmental conditions. Nowadays the information is scarce and nonspecific on the dynamic behaviour of WSN and RFID. Therefore the purpose of this study is to evaluate the dynamic behaviour of the sensors. A series of trials were designed and performed covering temperature steps between cold room (5 °C), room temperature (23 °C) and heated environment (35 °C). As sensor nodes: three Crossbow motes, a surface mounted Nlaza module (with sensor Sensirion located on the motherboard), an aerial mounted Nlaza where the Sensirion sensor stayed at the end of a cable), and four tags RFID Turbo Tag (T700 model with and without housing), and 702-B (with and without housing). To assess the dynamic behaviour a first order response approach is used and fitted with dedicated optimization tools programmed in Matlab that allow extracting the time response (?) and corresponding determination coefficient (r2) with regard to experimental data. The shorter response time (20.9 s) is found for the uncoated T 700 tag which encapsulated version provides a significantly higher response (107.2 s). The highest ? corresponds to the Crossbow modules (144.4 s), followed by the surface mounted Nlaza module (288.1 s), while the module with aerial mounted sensor gives a response certainly close above to the T700 without coating (42.8 s). As a conclusion, the dynamic response of temperature sensors within wireless and RFID nodes is dramatically influenced by the way they are housed (to protect them from the environment) as well as by the heat released by the node electronics itself; its characterization is basic to allow monitoring of high rate temperature changes and to certify the cold chain. Besides the time to rise and to recover is significantly different being mostly higher for the latter than for the former.

Exploitation of fibre characteristics in temperature sensing and radio-over-fibre applications

The development of sensing devices is one of the instrumentation fields that has grown rapidly in the last decade. Corresponding to the swift advance in the development of microelectronic sensors, optical fibre sensors are widely investigated because of their advantageous properties over the electronics sensors such as their wavelength multiplexing capability and high sensitivity to temperature, pressure, strain, vibration and acoustic emission. Moreover, optical fibre sensors are more attractive than the electronics sensors as they can perform distributed sensing, in terms of covering a reasonably large area using a single piece of fibre. Apart from being a responsive element in the sensing field, optical fibre possesses good assets in generating, distributing, processing and transmitting signals in the future broadband information network. These assets include wide bandwidth, high capacity and low loss that grant mobility and flexibility for wireless access systems. Among these core technologies, the fibre optic signal processing and transmission of optical and radio frequency signals have been the subjects of study in this thesis. Based on the intrinsic properties of single-mode optical fibre, this thesis aims to exploit the fibre characteristics such as thermal sensitivity, birefringence, dispersion and nonlinearity, in the applications of temperature sensing and radio-over-fibre systems. By exploiting the fibre thermal sensitivity, a fully distributed temperature sensing system consisting of an apodised chirped fibre Bragg grating has been implemented. The proposed system has proven to be efficient in characterising grating and providing the information of temperature variation, location and width of the heat source applied in the area under test.To exploit the fibre birefringence, a fibre delay line filter using a single high-birefringence optical fibre structure has been presented. The proposed filter can be reconfigured and programmed by adjusting the input azimuth of launched light, as well as the strength and direction of the applied coupling, to meet the requirements of signal processing for different purposes in microwave photonic and optical filtering applications. To exploit the fibre dispersion and nonlinearity, experimental investigations have been carried out to study their joint effect in high power double-sideband and single-sideband modulated links with the presence of fibre loss. The experimental results have been theoretically verified based on the in-house implementation of the split-step Fourier method applied to the generalised nonlinear Schrödinger equation. Further simulation study on the inter-modulation distortion in two-tone signal transmission has also been presented so as to show the effect of nonlinearity of one channel on the other. In addition to the experimental work, numerical simulations have also been carried out in all the proposed systems, to ensure that all the aspects concerned are comprehensively investigated.

Implementation of an intelligent sensor for measurement and prediction of solar radiation and atmospheric temperature

Dissertação de mestrado, Engenharia Electrónica e Telecomunicações, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2011

A new low temperature synthesis route of fraipontite (Zn,Al)3(Si,Al)2O5(OH)4

A low temperature synthesis method based on the decomposition of urea at 90°C in water has been developed to synthesise fraipontite. This material is characterised by a basal reflection 001 at 7.44 Å. The trioctahedral nature of the fraipontite is shown by the presence of a 06l band around 1.54 Å, while a minor band around 1.51 Å indicates some cation ordering between Zn and Al resulting in Al-rich areas with a more dioctahedral nature. TEM and IR indicate that no separate kaolinite phase is present. An increase in the Al content however, did result in the formation of some SiO2 in the form of quartz. Minor impurities of carbonate salts were observed during the synthesis caused by to the formation of CO32- during the decomposition of urea.