Effects of the partial replacement of La by M (M=Ce, Ca and Sr) in La(2-x)M(x)CuO(4) perovskites on catalysis of the water-gas shift reaction

The performance of La(2-x)M(x)CuO(4) perovskites (where M = Ce, Ca or Sr) as catalysts for the water-gas shift reaction was investigated at 290 degrees C and 360 degrees C. The catalysts were characterized by EDS, XRD, N(2) adsorption-desorption, XPS and XANES. The XRD results showed that all the perovskites exhibited a single phase (the presence of perovskite structure), suggesting the incorporation of metals in the perovskite structure. The XPS and XANES results showed the presence of Cu(2+) on the surface. The perovskites that exhibited the best catalytic performance were La(2-x)Ce(x)CuO(4) perovslcites, with CO conversions of 85%-90%. Moreover, these perovskites have higher surface areas and larger amounts of Cu on the surface. And Ce has a higher filled energy level than the other metals, increasing the energy of the valence band of Ce and providing more electrons for the reaction. Besides, the La(1.80)Ca(0.20)CuO(4) perovskite showed a good catalytic performance.

CuO and CuO-ZnO catalysts supported on CeO(2) and CeO(2)-LaO(3) for low temperature water-gas shift reaction

This paper describes an investigation on CuO and CuO-ZnO catalysts supported on CeO(2) and CeO(2)-La(2)O(3) oxides, which were designed for the low temperature water-gas shift reaction (WGSR). Bulk catalysts were prepared by co-precipitation of metal nitrates and characterized by energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD), surface area (by the BET method), X-ray photoelectron spectroscopy (XPS), and in situ X-ray absorption near edge structure (XANES). The catalysts` activities were tested in the forward WGSR, and the CuO/CeO(2) catalyst presented the best catalytic performance. The reasons for this are twofold: (1) the presence of Zn inhibits the interaction between Cu and Ce ions, and (2) lanthanum oxide forms a solid solution with cerium oxide, which will cause a decrease in the surface area of the catalysts. Also the CuO/CeO(2) catalyst presented the highest Cu content on the surface, which could influence its catalytic behavior. Additionally, the Cu and Cu(1+) species could influence the catalytic activity via a reduction-oxidation mechanism, corroborating to the best catalytic performance of the Cu/Ce catalyst. (c) 2010 Elsevier B.V. All rights reserved.

Quantitative ester analysis in cachaca and distilled spirits by gas chromatography-mass spectrometry (GC-MS)

An analytical procedure for the separation and quantification of ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl lactate, ethyl octanoate, ethyl nonanoate, ethyl decanoate, isoamyl octanoate, and ethyl laurate in cachaca, rum, and whisky by direct injection gas chromatography-mass spectrometry was developed. The analytical method is simple, selective, and appropriated for the determination of esters in distilled spirits. The limit of detection ranged from 29 (ethyl hexanoate) to 530 (ethyl acetate) mu g L-1, whereas the standard deviation for repeatability was between 0.774% (ethyl hexanoate) and 5.05% (isoamyl octanoate). Relative standard deviation values for accuracy vary from 90.3 to 98.5% for ethyl butyrate and ethyl acetate, respectively. Ethyl acetate was shown to be the major ester in cachaca (median content of 22.6 mg 100 mL(-1) anhydrous alcohol), followed by ethyl lactate (median content of 8.32 mg 100 mL(-1) anhydrous alcohol). Cachaca produced in copper and hybrid alembic present a higher content of ethyl acetate and ethyl lactate than those produced in a stainless-steel column, whereas cachaca produced by distillation in a stainless-steel column present a higher content of ethyl octanoate, ethyl decanoate, and ethyl laurate. As expected, ethyl acetate is the major ester in whiskey and rum, followed by ethyl lactate for samples of rum. Nevertheless, whiskey samples exhibit ethyl lactate at contents lower or at the same order of magnitude of the fatty esters.

Determination of fluoxetine in plasma by gas chromatography-mass spectrometry using stir bar sorptive extraction

This article presents a method employing stir bar sorptive extraction (SBSE) with in situ derivatization, in combination with either thermal or liquid desorption on-line coupled to gas chromatography-mass spectrometry for the analysis of fluoxetine in plasma samples. Ethyl chloroformate was employed as derivatizing agent producing symmetrical peaks. Parameters such as solvent polarity, time for analyte desorption, and extraction time, were evaluated. During the validation process, the developed method presented specificity, linearity (R-2 > 0.99), precision (R.S.D. < 15%), and limits of quantification (LOQ) of 30 and 1.37 pg mL(-1), when liquid and thermal desorption were employed, respectively. This simple and highly sensitive method showed to be adequate for the measurement-of fluoxetine in typical and trace concentration levels. (c) 2008 Elsevier B.V. All rights reserved.

Investigating the Nature of Noble Gas-Copper Bonds by the Quantum Theory of Atoms in Molecules

We investigated noble gas copper bonds in linear complexes represented by the NgCuX general formula in which Ng and X stand for a noble gas (neon, argon, krypton, or xenon) and a halogen (fluorine, chlorine or bromine), respectively, by coupled cluster methods and modified cc-pVQZ basis sets. The quantum theory of atoms in molecules (QTAIM) shows a linear relation between the dissociation energy or noble gas-copper bonds and the amount of electronic charge transferred mainly from the noble gas to copper during complexation. Large changes in the QTAIM quadrupole moments of copper and noble gases resulting from this bonding and a comparison between NgCuX and NgNaCl systems indicate that these noble gas-copper bonds should be better interpreted as predominantly covalent. Finally, QTAIM atomic dipoles of noble gases in NgNaCl systems agree satisfactorily with atomic dipoles given by a simple model for these NgNa van der Waals bonds.

Evaluation of the QuEChERS Method and Gas Chromatography-Mass Spectrometry for the Analysis Pesticide Residues in Water and Sediment

A method for the determination of pesticide residues in water and sediment was developed using the QuEChERS method followed by gas chromatography - mass spectrometry. The method was validated in terms of accuracy, specificity, linearity, detection and quantification limits. The recovery percentages obtained for the pesticides in water at different concentrations ranged from 63 to 116%, with relative standard deviations below 12%. The corresponding results from the sediment ranged from 48 to 115% with relative standard deviations below 16%. The limits of detection for the pesticides in water and sediment were below 0.003 mg L(-1) and 0.02 mg kg(-1), respectively.

Movements and mechanical stresses in gas-filled flat plate solar collectors

Sealed gas filled flat plate solar collectors will have stresses in the material since volume and pressure varies in the gas when the temperature changes. Several geometries were analyzed and it could be seen that it is possible reducing the stresses and improve the safety factor of the weakest point in the construction by using larger area and/or reducing the distance between glass and absorber and/or change width and height relationship so the tubes are getting longer. Further it could be shown that the safety factor won't always get improved with reinforcements. It is so because when an already strong part of the collector gets reinforced it will expose weaker parts for higher stresses. The finite element method was used for finding out the stresses.

Design of gas filled solar collectors

With a suitable gas filling used between cover glass and absorber in a flat plate solar collector, it is possible achieving better thermal performance at the same time as the distance betweenabsorber and glass can be reduced. Though, even if there is no vacuum inside the box, there will be potential risks for exhaustion due to stresses depending on the gas volume varies as the temperature varies. This study found out that it is possible build such a collector with less material in the absorber and the tubes and still getting better performance, without risks for exhaustion.

Gas-filled, flat plate solar collectors

This work treats the thermal and mechanical performances of gas-filled, flat plate solar collectors in order to achieve a better performance than that of air filled collectors. The gases examined are argon, krypton and xenon which all have lower thermal conductivity than air. The absorber is formed as a tray connected to the glass. The pressure of the gas inside is near to the ambient and since the gas volume will vary as the temperature changes, there are potential risks for fatigue in the material. One heat transfer model and one mechanical model were built. The mechanical model gave stresses and information on the movements. The factors of safety were calculated from the stresses, and the movements were used as input for the heat transfer model where the thermal performance was calculated. It is shown that gas-filled, flat plate solar collectors can be designed to achieve good thermal performance at a competitive cost. The best yield is achieved with a xenon gas filling together with a normal thick absorber, where normal thick means a 0.25 mm copper absorber. However, a great deal of energy is needed to produce the xenon gas, and if this aspect is taken into account, the krypton filling is better. Good thermal performance can also be achieved using less material; a collector with a 0.1 mm thick copper absorber and the third best gas, which is argon, still gives a better operating performance than a common, commercially produced, air filled collector with a 0.25 mm absorber. When manufacturing gas-filled flat plate solar collectors, one way of decreasing the total material costs significantly, is by changing absorber material from copper to aluminium. Best yield per monetary outlay is given by a thin (0.3 mm) alu-minium absorber with an argon filling. A high factor of safety is achieved with thin absorbers, large absorber areas, rectangular constructions with long tubes and short distances between glass and absorber. The latter will also give a thin layer of gas which gives good thermal performance. The only doubtii ful construction is an argon filled collector with a normal thick (> 0.50 mm) aluminium absorber. In general, an assessment of the stresses for the proposed construction together with appropriate tests are recommended before manufacturing, since it is hard to predict the factor of safety; if one part is reinforced, some other parts can experience more stress and the factor of safety actually drops.

Characterization of residential chimney conditions for flue gas flow measurements

A literature survey and a theoretical study were performed to characterize residential chimney conditions for flue gas flow measurements. The focus is on Pitot-static probes to give sufficient basis for the development and calibration of a velocity pressure averaging probe suitable for the continuous dynamic (i.e. non steady state) measurement of the low flow velocities present in residential chimneys. The flow conditions do not meet the requirements set in ISO 10780 and ISO 3966 for Pitot-static probe measurements, and the methods and their uncertainties are not valid. The flow velocities in residential chimneys from a heating boiler under normal operating condi-tions are shown to be so low that they in some conditions result in voiding the assumptions of non-viscous fluid justifying the use of the quadratic Bernoulli equation. A non-linear Reynolds number dependent calibration coefficient that is correcting for the viscous effects is needed to avoid significant measurement errors. The wide range of flow velocity during normal boiler operation also results in the flow type changing from laminar, across the laminar to turbulent transition region, to fully turbulent flow, resulting in significant changes of the velocity profile during dynamic measurements. In addition, the short duct lengths (and changes of flow direction and duct shape) used in practice are shown to result in that the measurements are done in the hydrodynamic entrance region where the flow velocity profiles most likely are neither symmetrical nor fully developed. A measurement method insensitive to velocity profile changes is thus needed, if the flow velocity profile cannot otherwise be determined or predicted with reasonable accuracy for the whole measurement range. Because of particulate matter and condensing fluids in the flue gas it is beneficial if the probe can be constructed so that it can easily be taken out for cleaning, and equipped with a locking mechanism to always ensure the same alignment in the duct without affecting the calibration. The literature implies that there may be a significant time lag in the measurements of low flow rates due to viscous effects in the internal impact pressure passages of Pitot probes, and the significance in the discussed application should be studied experimentally. The measured differential pressures from Pitot-static probes in residential chimney flows are so low that the calibration and given uncertainties of commercially available pressure transducers are not adequate. The pressure transducers should be calibrated specifically for the application, preferably in combination with the probe, and the significance of all different error sources should be investigated carefully. Care should be taken also with the temperature measurement, e.g. with averaging of several sensors, as significant temperature gradients may be present in flue gas ducts.

Thermal losses in sealed, gas-filled flat plate solar collectors

A sealed space between absorber and cover glass makes it possible reducing the influence of humidity condensate and dust at the same time as the enclosed space can be filled with a suitable gas for lowering the losses. This paper is about the size of the losses in these collectors. A calculating model of a gas-filled flat plate solar collector was built in Matlab with standard heat transfer formulas. It showed that the total loss can be reduced up to 20% when changing to an inert gas. It is also possible using a much shorter distance and still achieve low losses at the same time as the mechanical stresses in the material is reduce.

Modeling and forecasting long-term natural gas (NG) consumption in Iran, using particle swarm optimization (PSO)

The gradual changes in the world development have brought energy issues back into high profile. An ongoing challenge for countries around the world is to balance the development gains against its effects on the environment. The energy management is the key factor of any sustainable development program. All the aspects of development in agriculture, power generation, social welfare and industry in Iran are crucially related to the energy and its revenue. Forecasting end-use natural gas consumption is an important Factor for efficient system operation and a basis for planning decisions. In this thesis, particle swarm optimization (PSO) used to forecast long run natural gas consumption in Iran. Gas consumption data in Iran for the previous 34 years is used to predict the consumption for the coming years. Four linear and nonlinear models proposed and six factors such as Gross Domestic Product (GDP), Population, National Income (NI), Temperature, Consumer Price Index (CPI) and yearly Natural Gas (NG) demand investigated.

Newly Automated System For Integrated Assessment Of The Conditions Of Underwater Gas Pipelines

An underwater gas pipeline is the portion of the pipeline that crosses a river beneath its bottom. Underwater gas pipelines are subject to increasing dangers as time goes by. An accident at an underwater gas pipeline can lead to technological and environmental disaster on the scale of an entire region. Therefore, timely troubleshooting of all underwater gas pipelines in order to prevent any potential accidents will remain a pressing task for the industry. The most important aspect of resolving this challenge is the quality of the automated system in question. Now the industry doesn't have any automated system that fully meets the needs of the experts working in the field maintaining underwater gas pipelines. Principle Aim of this Research: This work aims to develop a new system of automated monitoring which would simplify the process of evaluating the technical condition and decision making on planning and preventive maintenance and repair work on the underwater gas pipeline. Objectives: Creation a shared model for a new, automated system via IDEF3; Development of a new database system which would store all information about underwater gas pipelines; Development a new application that works with database servers, and provides an explanation of the results obtained from the server; Calculation of the values MTBF for specified pipelines based on quantitative data obtained from tests of this system. Conclusion: The new, automated system PodvodGazExpert has been developed for timely and qualitative determination of the physical conditions of underwater gas pipeline; The basis of the mathematical analysis of this new, automated system uses principal component analysis method; The process of determining the physical condition of an underwater gas pipeline with this new, automated system increases the MTBF by a factor of 8.18 above the existing system used today in the industry.

Optimal Rehabilitation Strategy In Water Distribution Systems Considering Reduction In Greenhouse Gas Emissions

Most of water distribution systems (WDS) need rehabilitation due to aging infrastructure leading to decreasing capacity, increasing leakage and consequently low performance of the WDS. However an appropriate strategy including location and time of pipeline rehabilitation in a WDS with respect to a limited budget is the main challenge which has been addressed frequently by researchers and practitioners. On the other hand, selection of appropriate rehabilitation technique and material types is another main issue which has yet to address properly. The latter can affect the environmental impacts of a rehabilitation strategy meeting the challenges of global warming mitigation and consequent climate change. This paper presents a multi-objective optimization model for rehabilitation strategy in WDS addressing the abovementioned criteria mainly focused on greenhouse gas (GHG) emissions either directly from fossil fuel and electricity or indirectly from embodied energy of materials. Thus, the objective functions are to minimise: (1) the total cost of rehabilitation including capital and operational costs; (2) the leakage amount; (3) GHG emissions. The Pareto optimal front containing optimal solutions is determined using Non-dominated Sorting Genetic Algorithm NSGA-II. Decision variables in this optimisation problem are classified into a number of groups as: (1) percentage proportion of each rehabilitation technique each year; (2) material types of new pipeline for rehabilitation each year. Rehabilitation techniques used here includes replacement, rehabilitation and lining, cleaning, pipe duplication. The developed model is demonstrated through its application to a Mahalat WDS located in central part of Iran. The rehabilitation strategy is analysed for a 40 year planning horizon. A number of conventional techniques for selecting pipes for rehabilitation are analysed in this study. The results show that the optimal rehabilitation strategy considering GHG emissions is able to successfully save the total expenses, efficiently decrease the leakage amount from the WDS whilst meeting environmental criteria.

Are real options a real option for real-world finance professionals? case study : the application of real options to evaluate investment projects in the latin american oil and gas field services industry

Brasil e outros mercados emergentes continuarão a apresentar muitas oportunidades de investimento nos próximos anos. Profissionais financeiros que gerenciam os processos de orçamento de capital nas empresas terão grandes desafios a enfrentar. Características específicas destes projetos como preços ligados a commodities (por exemplo: petróleo e gás e projetos agrícolas) e as incertezas habituais relacionadas com os mercados emergentes são desafios adicionais. Neste cenário, ferramentas mais sofisticadas de orçamento de capital como Opções Reais, oferece uma teoria mais robusta para lidar com incerteza, flexibilidade gerencial, e os resultados voláteis embutidas nestas oportunidades. A teoria de Opções Reais assume que o envolvimento dos gestores nos projetos gera valor à medida que potencializam os bons resultados ou reduzem as perdas por abandonar projetos com maus resultados. O objetivo principal desta pesquisa foi aplicar a análise de Opções Reais para um projeto de investimento e discutir o processo e os resultados da metodologia. O estudo de caso analisa retroativamente um projeto de investimento na Colômbia e compara os resultados sob o tradicional VPL e Opções Reais. As técnicas de avaliação foram realizadas como se estivessem sendo aplicadas no momento em que o projeto foi aprovado, e depois comparadas com o desempenho real do projeto. O estudo de caso avaliado possui dois tipos de Opções Reais: primeiro, o efeito de uma opção para cancelar um contrato que é analisado a partir da perspectiva do cliente que pode exercer essa opção, e o segundo, a opção de abandonar e adiar a partir da perspectiva da empresa que irá executar a investimento.