Dessulfurização oxidativa do dibenzotiofeno catalisada por V2O5 suportado

A necessidade de redução da emissão de poluentes, visando diminuir os sérios problemas de poluição atmosférica enfrentados atualmente, é hoje uma das principais preocupações mundiais, provocando o surgimento de leis mais rígidas, que restringem o teor de enxofre na gasolina e no diesel. Assim, o desenvolvimento de tecnologias mais eficazes na remoção de enxofre nestes combustíveis tem recebido atenção crescente. Estas tecnologias incluem a extração física com solvente, a adsorção seletiva, processos de redução/oxidação microbiológicos e a dessulfurização oxidativa (ODS). A dessulfurização oxidativa converte os compostos de enxofre em sulfonas que podem ser facilmente separadas por processos físicos. Portanto, a ODS apresenta grande potencial para tornar-se um processo complementar a processo de hidrodessulfurização tradicional na produção de combustíveis altamente dessulfurizados. Neste contexto, este trabalho visou o estudo do desempenho de catalisadores de V2O5 suportados em alumina, sílica e sílica-alumina frente à reação de ODS do dibenzotiofeno em presença do peróxido de hidrogênio, como oxidante, e da acetonitrila, como solvente polar aprótico. Os catalisadores foram preparados por impregnação ao ponto úmido e caracterizados por difração de raios-X (DRX), análise textural, redução à temperatura programada (TPR-H2), dessorção de amônia à temperatura programa (TPD-NH3) e espectroscopia Raman. O efeito de parâmetros reacionais como quantidade de solvente, relação O/S e concentração de catalisador foram investigados, utilizando a alumina como suporte, visando estabelecer as condições reacionais que levassem a maiores valores de conversão do dibenzotiofeno (DBT). Uma vez estabelecidas estas condições, foi analisado o efeito do teor de V2O5 presente no catalisador e, posteriormente, o efeito do suporte catalítico. Os resultados obtidos mostraram a 70 C razão molar H2O2/Sde 16,6, razão carga/solvente igual a 1:1 e 100 mg do catalisador 15 % V2O5/SiO2, a conversão obtida foi de 95%

Effects of ethanol on vehicle energy efficiency and implications on ethanol life-cycle greenhouse gas analysis.

Bioethanol is the world's largest-produced alternative to petroleum-derived transportation fuels due to its compatibility within existing spark-ignition engines and its relatively mature production technology. Despite its success, questions remain over the greenhouse gas (GHG) implications of fuel ethanol use with many studies showing significant impacts of differences in land use, feedstock, and refinery operation. While most efforts to quantify life-cycle GHG impacts have focused on the production stage, a few recent studies have acknowledged the effect of ethanol on engine performance and incorporated these effects into the fuel life cycle. These studies have broadly asserted that vehicle efficiency increases with ethanol use to justify reducing the GHG impact of ethanol. These results seem to conflict with the general notion that ethanol decreases the fuel efficiency (or increases the fuel consumption) of vehicles due to the lower volumetric energy content of ethanol when compared to gasoline. Here we argue that due to the increased emphasis on alternative fuels with drastically differing energy densities, vehicle efficiency should be evaluated based on energy rather than volume. When done so, we show that efficiency of existing vehicles can be affected by ethanol content, but these impacts can serve to have both positive and negative effects and are highly uncertain (ranging from -15% to +24%). As a result, uncertainties in the net GHG effect of ethanol, particularly when used in a low-level blend with gasoline, are considerably larger than previously estimated (standard deviations increase by >10% and >200% when used in high and low blends, respectively). Technical options exist to improve vehicle efficiency through smarter use of ethanol though changes to the vehicle fleets and fuel infrastructure would be required. Future biofuel policies should promote synergies between the vehicle and fuel industries in order to maximize the society-wise benefits or minimize the risks of adverse impacts of ethanol.

Assessing boost-assist options for turbocharged engines using 1-D engine simulation and model predictive control

Delivering acceptable low end torque and good transient response is a significant challenge for all turbocharged engines. As downsized gasoline engines and Diesel engines make up a larger and larger proportion of the light-duty engines entering the market, the issue takes on greater significance. Several schemes have been proposed to improve torque response in highly boosted engines, including the use of electrical assist turbochargers and compressed air assist. In this paper we examine these methods with respect to their effectiveness in improving transient response and their relative performance along with some of the practical considerations for real world application. Results shown in this paper are from 1-D simulations using the Ricardo WAVE software package. The simulation model is based on a production light-duty Diesel engine modified to allow the introduction of compressed air at various points in the air-path as well as direct torque application to the turbocharger shaft (such as might be available from an electrical assist turbocharger). Whilst the 1-D simulation software provides a suitable environment for investigating the various boost assistance options, the overall air path performance also depends upon the control system. The introduction of boost assistance complicates the control in two significant ways: the system may run into constraints (such as compressor surge) that are not encountered in normal operation and the assistance introduces an additional control input. Production engine controllers are usually based on gain-scheduled PID control and extensive calibration. For this study, the non-linear nature of the engine together with the multiple configurations considered and the slower than real-time execution of 1-D models makes such an approach time consuming. Moreover, an ad-hoc approach would leave some doubt as to the fairness of comparisons between the different boost-assist options. Model Predictive Control has been shown to offer a convenient approach to controlling the 1-D simulations in a close to optimal manner for a typical Diesel VGT-EGR air path configuration. We show that the same technique can be applied to all the considered assistance methods with only modest calibration effort required. Copyright © 2012 SAE International.

Impact of lubricant composition on low-speed pre-ignition

One of the limits on the maximum fuel efficiency benefit to be gained from turbocharged, downsized gasoline engines is the occurrence of pre-ignitions at low engine speed. These pre-ignitions may lead to high pressures and extreme knock (megaknock or superknock) which can cause severe engine damage. Though the mechanism leading to megaknock is not completely resolved, pre-ignitions are thought to arise from local autoignition of areas in the cylinder which are rich in low ignition delay "contaminants" such as engine oil and/or heavy ends of gasoline. These contaminants are introduced to the combustion chamber at various points in the engine cycle (e.g. entering from the top land crevice during blow-down or washed from the cylinder walls during DI wall impingement). This paper presents results from tests in which model "contaminants", consisting of engine lubricant base stocks, base stocks mixed with fuel and base stocks mixed with one or more additives were injected directly into a test engine to determine their propensity to ignite. The ignition tendency was found to be lower for less reactive base stocks and for base stocks mixed with certain additives. Further, when small amounts of fuel were mixed with relatively non-ignitive lubricant base stocks the ignition tendency was found to increase significantly. These results may guide development of new lubricants which could be used to reduce megaknock in downsized engines. Copyright © 2014 SAE International.

Environmental threats to children's health in Southeast Asia and the Western Pacific

The Southeast Asia and Western Pacific regions contain half of the world's children and are among the most rapidly industrializing regions of the globe. Environmental threats to children's health are widespread and are multiplying as nations in the area undergo industrial development and pass through the epidemiologic transition. These environmental hazards range from traditional threats such as bacterial contamination of drinking water and wood smoke in poorly ventilated dwellings to more recently introduced chemical threats such as asbestos construction materials; arsenic in groundwater; methyl isocyanate in Bhopal, India; untreated manufacturing wastes released to landfills; chlorinated hydrocarbon and organophosphorous pesticides; and atmospheric lead emissions from the combustion of leaded gasoline. To address these problems, pediatricians, environmental health scientists, and public health workers throughout Southeast Asia and the Western Pacific have begun to build local and national research and prevention programs in children's environmental health. Successes have been achieved as a result of these efforts: A cost-effective system for producing safe drinking water at the village level has been devised in India; many nations have launched aggressive antismoking campaigns; and Thailand, the Philippines, India, and Pakistan have all begun to reduce their use of lead in gasoline, with resultant declines in children's blood lead levels. The International Conference on Environmental Threats to the Health of Children, held in Bangkok, Thailand, in March 2002, brought together more than 300 representatives from 35 countries and organizations to increase awareness on environmental health hazards affecting children in these regions and throughout the world. The conference, a direct result of the Environmental Threats to the Health of Children meeting held in Manila in April 2000, provided participants with the latest scientific data on children's vulnerability to environmental hazards and models for future policy and public health discussions on ways to improve children's health. The Bangkok Statement, a pledge resulting from the conference proceedings, is an important first step in creating a global alliance committed to developing active and innovative national and international networks to promote and protect children's environmental health.

Thermodynamic investigation on properties of gasohol

The heat capacities (C-p) of three types of gasohol (which consisted of 20 wt % ethanol and 80 wt % unleaded gasoline 93(#) (system S1), 30 wt % ethanol and 70 wt % unleaded gasoline 931 (system S2), 40 wt % ethanol and 60 wt % unleaded gasoline 930 (system S3), where "93(#)" denotes the octane number) were measured by adiabatic calorimetry in the temperature range of 80320 K. A glass transition was observed at 94.24, 95.15, and 95.44 K for system S1, S2, and S3, respectively. A solid-solid phase transition and solid-liquid phase transition were observed at 135.18 and 151.30 K for system S1, 131.82 and 152.10 K for system S2, and 121.29 and 155.09 K for S3, respectively. The polynomial equations for C, with respect to the thermodynamic temperature (T), and with respect to the content of ethanol (x), were established through the least-squares fitting. The thermodynamic functions and the excess thermodynamic functions of the three samples were derived using these thermodynamic relationships and equations.

The experimental research for production of hydrogen from n-octane through partially oxidizing and steam reforming method

The reaction of producing hydrogen for fuel cell which used normal octane as gasoline or diesel oil reactant through catalytic partial oxidizing and steam reforming method has been researched in the fixed-bed reactor. A series of catalysts that mainly used nickel supported on Al2O3 have been studied. It showed that the activity of the catalyst was increased with the content of nickel by using only nickel supported on Al2O3. However, its activity was not obviously increased when the content of nickel was over 5 wt%. The conversion ratio of normal octane and hydrogen selectivity were higher at higher reaction temperature. The single noble catalyst of palladium had better stability compared with that of platinum catalyst although their activity and selectivity were similar during the experimental reaction temperature. The prepared bimetallic catalyst consisted mainly of nickel and little noble metal of palladium supported on Al2O3. It showed that this catalyst had higher activity and selectivity, especially at lower or higher reaction temperatures compared with single nickel or palladium catalyst, and better stability. ((C) 2001 International Association for Hydrogen Energy. Published by Elsevier Science Ltd. All rights reserved.

中国大中型气田天然气成藏物理化学模拟研究

Natural gas pays more important role in the society as clean fuel. Natural gas exploration has been enhanced in recent years in many countries. It also has prospective future in our country through "85" and "95" national research. Many big size gas fields have been discovered in different formations in different basins such as lower and upper Paleozoic in Erdos basin, Tertiary system in Kuche depression in Tarim basin, Triassic system in east of Sichuan basin. Because gas bearing basins had been experienced multiple tectogenesis. The characteristics of natural gases usually in one gas field are that they have multiple source rocks and are multiple maturities and formed in different ages. There has most difficult to research on the gas-rock correlation and mechanism of gas formation. Develop advanced techniques and methods and apply them to solve above problems is necessary. The research is focused on the critical techniques of geochemistry and physical simulation of gas-rock correlation and gas formation. The lists in the following are conclusions through research and lots of experiments. I 8 advanced techniques have been developed or improved about gas-rock correlation and gas migration, accumulation and formation. A series of geochemistry techniques has been developed about analyzing inclusion enclave. They are analyzing gas and liquid composition and biomarker and on-line individual carbon isotope composition in inclusion enclave. These techniques combing the inclusion homogeneous temperature can be applied to study on gas-rock correlation directly and gas migration, filling and formation ages. Technique of on-line determination individual gas carbon isotope composition in kerogen and bitumen thermal pyrolysis is developed. It is applied to determine the source of natural is kerogen thermal degradation or oil pyrolysis. Method of on-line determination individual gas carbon isotope composition in rock thermal simulation has being improved. Based on the "95"former research, on-line determination individual gas carbon isotope composition in different type of maceral and rocks thermal pyrolys is has been determined. The conclusion is that carbon isotope composition of benzene and toluene in homogenous texture kerogen thermal degradation is almost same at different maturity. By comparison, that in mixture type kerogen thermal pyrolysis jumps from step to step with the changes of maturity. This conclusion is a good proof of gas-rock dynamic correlation. 3. Biomarker of rock can be determined directly through research. It solves the problems such as long period preparing sample, light composition losing and sample contamination etc. It can be applied to research the character of source rock and mechanism of source rock expulsion and the path of hydrocarbon migration etc. 4. The process of hydrocarbon dynamic generation in source rock can be seen at every stage applying locating observation and thermal simulation of ESEM. The mechanism of hydrocarbon generation and expulsion in source rock is discussed according to the experiments. This technique is advanced in the world. 5. A sample injection system whose character is higher vacuum, lower leaks and lower blank has been built up to analyze inert gas. He,Ar,Kr and Xe can be determined continuously on one instrument and one injection. This is advanced in domestic. 7. Quality and quantity analysis of benzene ring compounds and phenolic compounds and determination of organic acid and aqueous gas analysis are applied to research the relationship between compounds in formation water and gas formation. This is another new idea to study the gas-rock correlation and gas formation. 8. Inclusion analysis data can be used to calculate the Paleo-fluid density, Paleo-geothermal gradient and Paleo-geopressure gradient and then to calculate the Paleo-fluid potential. It's also a new method to research the direction of hydrocarbon migration and accumulation. 9. Equipment of natural gas formation simulation is produced during the research to probe how the physical properties of rock affect the gas migration and accumulation and what efficiency of gas migrate and factors of gas formation and the models of different type of migration are. II study is focused on that if the source rocks of lower Paleozoic generated hydrocarbon and what the source rocks of weathered formation gas pool and the mechanism of gas formation are though many advanced techniques application. There are four conclusions. 1.The maturity of Majiagou formation source rocks is higher in south than that in north. There also have parts of the higher maturity in middle and east. Anomalous thermal pays important role in big size field formation in middle of basin. 2. The amount of gas generation in high-over maturity source rocks in lower Paleozoic is lager than that of most absorption of source rocks. Lower Paleozoic source rocks are effective source rocks. Universal bitumen exists in Ordovician source rocks to prove that Ordovician source rocks had generated hydrocarbon. Bitumen has some attribution to the middle gas pool formation. 3. Comprehensive gas-rock correlation says that natural gases of north, west, south of middle gas field of basin mainly come from lower Paleozoic source rocks. The attribution ratio of lower Paleozoic source rocks is 60%-70%. Natural gases of other areas mainly come from upper Paleozoic. The attribution ratio of upper Paleozoic source rocks is 70%. 4. Paleozoic gases migration phase of Erdos basin are also interesting. The relative abundance of gasoline aromatic is quite low especially toluene that of which is divided by that of methyl-cyclohexane is less than 0.2 in upper Paleozoic gas pool. The migration phase of upper Paleozoic gas may be aqueous phase. By comparison, the relative abundance of gasoline aromatic is higher in lower Paleozoic gas. The distribution character of gasoline gas is similar with that in source rock thermal simulation. The migration phase of it may be free phase. IH Comprehensive gas-rock correlation is also processed in Kuche depression Tarim basin. The mechanism of gas formation is probed and the gas formation model has been built up. Four conclusions list below. 1. Gases in Kuche depression come from Triassic-Jurassic coal-measure source rocks. They are high-over maturity. Comparatively, the highest maturity area is Kelasu, next is Dabei area, Yinan area. 2. Kerogen thermal degradation is main reason of the dry gas in Kuche depression. Small part of dry gas comes from oil pyrolysis. VI 3.The K12 natural gas lays out some of hydro-gas character. Oil dissolved in the gas. Hydro-gas is also a factor making the gas drier and carbon isotope composition heavier. 4. The mechanism and genesis of KL2 gas pool list as below. Overpressure has being existed in Triassic-Jurassic source rocks since Keche period. Natural gases were expulsed by episode style from overpressure source rocks. Hetero-face was main migration style of gas, oil and water at that time. The fluids transferred the pressure of source rocks when they migrated and then separated when they got in reservoir. After that, natural gas migrated up and accumulated and formed with the techno-genesis. Tectonic extrusion made the natural gas overpressure continuously. When the pressure was up to the critical pressure, the C6-C7 composition in natural gas changed. The results were that relative abundance of alkane and aromatic decreased while cycloalkane and isoparaffin increased. There was lots of natural gas filling during every tectonic. The main factors of overpressure of natural gas were tectonic extrusion and fluid transferring pressure of source rocks. Well preservation was also important in the KL2 gas pool formation. The reserves of gas can satisfy the need of pipeline where is from west to east. IV A good idea of natural gas migration and accumulation modeling whose apparent character is real core and formation condition is suggested to model the physical process of gas formation. Following is the modeling results. 1. Modeling results prove that the gas accumulation rule under cap layer and gas fraction on migration path. 2. Natural gas migration as free phase is difficult in dense rock. 3. Natural gases accumulated easily in good physical properties reservoirs where are under the plugging layer. Under the condition of that permeability of rock is more than 1 * 10~(-3)μm~(-1), the more better the physical properties and the more bigger pore of rock, the more easier the gas accumulation in there. On the contrary, natural gas canonly migrate further to accumulate in good physical properties of rock. 4. Natural gas migrate up is different from that down. Under the same situation, the amount of gas migration up is lager than that of gas migration down and the distance of migration up is 3 times as that of migration down. 5. After gas leaks from dense confining layer, the ability of its dynamic plug-back decreased apparently. Gas lost from these arils easily. These confining layer can confine again only after geology condition changes. 6. Water-wetted and capillary-blocking rocks can't block water but gases generally. The result is that water can migrate continuously through blocking rocks but the gases stay under the blocking rocks then form in there. The experiments have proved the formation model of deep basin gas.

A comprehensive comparison of fuel options for fuel cell vehicles in China

Fuel cell vehicles (FCVs) offer the potential of ultra-low emissions combined with high efficiency. Proton exchange membrane (PEM) fuel cells being developed for vehicles require hydrogen as a fuel. Due to the various pathways of hydrogen generation, both onboard and off-board, the question about which fuel option is the most competitive for fuel cell vehicles is of great current interest. In this paper, a life-cycle assessment (LCA) model was made to conduct a comprehensive study of the energy, environmental, and economic (3E) impacts of FCVs from well to wheel (WTW). In view of the special energy structure of China and the timeframe, 10 vehicle/fuel systems are chosen as the study projects. The results show that methanol is the most suitable fuel to serve as the ideal hydrogen source for fuel cell vehicles in the timeframe and geographic regions of this study. On the other hand, gasoline and pure hydrogen can also play a role in short-term and regional applications, especially for local demonstrations of FCV fleets. (c) 2004 Elsevier B.V All rights reserved.

Synthesis and catalytic reactivity of MCM-22/ZSM-35 composites for olefin aromatization

A series of MCM-22/ZSM-35 composites has been hydrothermally synthesized and characterized by XRD, SEM, particle size distribution analysis, N-2 adsorption and NH3-TPD techniques. Pulse and continuous flow reactions were carried out to evaluate the catalytic performances of these composites in aromatization of olefins, respectively. It was found that MCM-22/ZSM-35 composites could be rapidly crystallized at 174 degrees C with an optimal gel composition of SiO2/Al2O3=25, Na2O/SiO2=0.11, HMI/SiO2=0.35, and H2O/SiO2=45 (molar ratio), of which the weight ratio of ZSM-35 zeolite in the composite relied on the crystallization time. The coexistence of MCM-22 and ZSM-35 in the composite (MCM-22/ZSM-35=45/55 wt/wt) was observed to exert a notable synergistic effect on the aromatization ability for butene conversion and FCC gasoline updating, possibly due to the intergrowth of some MCM-22 and ZSM-35 layers.