Experimental determination of some physical properties of gasoline,ethanol and ETBE ternary blends

The addition of oxygenated renewable fuels, such as ethanol or ethyl tert-butyl ether (ETBE) to standard gasoline may be necessary to comply with some environmental directives but could also prevent compliance with some fuel regulations and could also seriously change engine performance. From this point of view, the Reid Vapour Pressure (RVP), the distillation curve, the oxygen content and the density belong to the group of the most relevant parameters. This study evaluates the influence of the simultaneous addition of ethanol and ETBE on some physical properties of engine gasoline. The main conclusion is that the simultaneous addition of ETBE and ethanol changes the RVP, the distillation curve and the density in a way that can affect engine operation and the mandatory EN 228 and ASTM D4814 standards. Some opposite properties of both oxygenates could help to increase the renewable energy content without preventing compliance with these regulations.

Behind the scenes of functional brain imaging: A historical and physiological perspective

At the forefront of cognitive neuroscience research in normal humans are the new techniques of functional brain imaging: positron emission tomography and magnetic resonance imaging. The signal used by positron emission tomography is based on the fact that changes in the cellular activity of the brain of normal, awake humans and laboratory animals are accompanied almost invariably by changes in local blood flow. This robust, empirical relationship has fascinated scientists for well over a hundred years. Because the changes in blood flow are accompanied by lesser changes in oxygen consumption, local changes in brain oxygen content occur at the sites of activation and provide the basis for the signal used by magnetic resonance imaging. The biological basis for these signals is now an area of intense research stimulated by the interest in these tools for cognitive neuroscience research.

Estudo da cristalinidade de filmes finos de nitreto de índio e simulado pelo pacote de programas Wien2k

Neste trabalho, foi utilizado o método de deposição assistida por feixe de íons (IBAD na sigla em inglês) para produção de filmes finos de nitreto de índio em substratos de silício (111) e Safira-C. Variando as condições de deposição e utlilizando a técnica de difração de raios-X, investigou-se com o intuito de obter os parâmetros que resultam em filmes finos com melhor grau de cristalinidade. Os filmes produzidos a 380C apresentaram alta cristalinidade, superior àqueles a 250C. Temperaturas muito superiores a 380C não ocasionam a formação de filme cristalino de InN, como foi observado ao utilizar a temperatura de 480C; o mesmo se observa ao utilizar temperatura ambiente. Na temperatura considerada adequada ,de 380C, obteve-se que a utilização de Ra, ou seja, a razão de fluxo de partículas entre o nitrogênio e índio, em torno de 2,3 permite obter um melhor grau de cristalinização, o qual decresce conforme se diverge desse valor. A comparação entre difratogramas de amostras produzidas com e sem a evaporação prévia de titânio, o qual é possível observar um deslocamento dos picos do InN, indicam que o efeito Gettering permite a redução de impurezas no filme, principalmente de oxigênio. Utilizou-se a técnica de Retroespalhamento de Rutherford para obtenção da composição dos elementos e o perfil de profundidade. Notou-se uma forte mistura dos elementos do substrato de silício e safira com o nitreto de índio mesmo próximos a superfície. A presença indesejável de impurezas, principalmente o oxigênio, durante a deposição de filmes finos é praticamente inevitável. Desta forma, cálculos ab initio baseados na Teoria do Funcional da Densidade (DFT) foram realizados para investigar defeitos isolados e complexos de oxigênio no nitreto de índio e a sua influência nas propriedades óticas. Considerou-se diferentes concentrações de oxigênio (x=2,76, 8,32, 11,11 e 22,22%) aplicando-se o método PBEsolGGA e TB-mBJ para o tratamento da energia e potencial de troca e correlação. Obteve-se que é energeticamente favorável o oxigênio existir principalmente como defeito carregado e isolado. Os resultados utilizando a aproximação de TB-mBJ indicam um estreitamento do bandgap conforme a concentração de oxigênio aumenta. Entretanto, a alta contribuição do efeito de Moss-Burstein resulta num efetivo alargamento do band gap, gerando valores de band gap ótico maiores que no do bulk de nitreto de índio.

Activated Carbons Impregnated with Na2S and H2SO4: Texture, Surface Chemistry and Application to Mercury Removal from Aqueous Solutions

The effects of treatment of an activated carbon with Sulphur precursors on its textural properties and on the ability of the complex synthesized for mercury removal in aqueous solutions are studied. To this end, a commercial activated carbon has been modified by treatments with aqueous solutions of Na2S and H2SO4 at two temperatures (25 and 140 °C) to introduce sulphur species on its surface. The prepared adsorbents have been characterized by N2 (-196 °C) and CO2 (0 °C) adsorption, thermogravimetric analysis, temperature-programmed decomposition and X-ray photoelectron spectroscopy, and their adsorption capacities to remove Hg(II) ions in aqueous solutions have been determined. It has been shown that the impregnation treatments slightly modified the textural properties of the samples, with a small increase in the textural parameters (BET surface area and mesopore volumes). By contrast, surface oxygen content was increased when impregnation was carried out with Na2S, but it decreased when H2SO4 was used. However, the main effect of the impregnation treatments was the formation of surface sulphur complexes of thiol type, which was only achieved when the impregnation treatments were carried out at low temperature (25 °C). The presence of surface sulphur enhances the adsorption behaviour of these samples in the removal of Hg(II) cations in aqueous solutions at pH 2. In fact, complete Hg(II) removal is only obtained with the sulphur-containing activated carbons.

(Table 1) Ooze/chalk cycles: frequency of occurrence at DSDP Leg 74 Sites

Shallow- to deep-water environments are represented by the sediments and rocks recovered from the Walvis Ridge- Angola Basin transect. These calcareous oozes, chalks, limestones, and volcaniclastic sedimentary rocks are used to define and correlate four lithostratigraphic units. The sediments were deposited in cycles which represent recurring tectonic or Oceanographic events and may be related to climatic fluctuations and orbital perturbations. Turbidites are the most common and easily identified sedimentary cycle. They are Late Cretaceous to Paleocene in age and are repeated in intervals ranging from thousands to tens of thousands of years. They are also found interbedded between basalt layers. Turbidites are easily distinguished from the other cycles present by their sedimentary structures, mineral composition, alteration products, and physical properties (GRAPE) data. Large-scale turbidites, debris, or slump breccias are found at or just above the Cretaceous/Tertiary boundary and indicate an event of considerable energy possibly related to intense tectonic activity. Diagenetic cycles, interpreted as small-scale dissolution cycles or sequences produced by biogenic activity, occur in early Paleocene chalks. The recurrence intervals average -20,000 y. but have a wide range of values. Variations in CaCO3 content, color, gradational boundaries, and trace fossil content characterize these sediments. These cycles reflect bottom-water conditions. Ooze-chalk cycles occur in upper Oligocene to upper Paleocene sediments and represent conditions that once existed at the sediment/water interface where they obtained their diagenetic potential. These oscillations are repeated over tens of thousands of years and may have no modern analogs. Color variations in sediments at the Cretaceous/Tertiary boundary indicate local fluctuations in oxygen content within the sediments or the water column. This situation lasted for several hundred thousand years and is not repeated elsewhere in the sequence. Large dissolution cycles are recorded in the sediments at Site 527 that are of middle Miocene and early Oligocene to middle Eocene age. During this time the seafloor at this site appears to have been located at or subsided to a depth occupied by a fluctuating CCD and lysocline.

Chemical observations in the Red Sea and the inner Gulf of Aden during the International Indian Ocean Expedition 1964/65

The Red Sea has a special place among the adjacent seas of the world. High evaporation, exclusion of its deep water from contact with the Indian Ocean proper and complete absence of continental drainage may result special conditions of the chemistry of the Red Sea. This paper aims to describe and explain the peculiarity of the hydrochemical situation. The influence of the topography, of the inflow and outflow through the straights of Bab el Mandeb, of the evaporation, of the stability of the water layers, and of the circulation will be studied. An attempt is made to estimate the apparent oxygen ultilisation in order to obtain an indication of the biological activity. A further attempt is made toward the quantitative estimation of the circulation of the nutrients and also to obtain some information about transport, dissolution, and precipitation of calcium carbonate. The basis of these investigations are mainly observations of R. V. "Meteor" during the International Indian Ocean Expedition 1964/65. The determination of dissolved oxygen, dissolved inorganic phosphate, nitrate, nitrite, ammonia, pH, alkalinity, silicate as well as salinity and temperature forms the necessary basis for such an investigation of the chemical conditions. In the first chapter the methods and some modifications for the determination of the chemical properties as applied during the I.I.O.E. cruise of R. V. "Meteor" are described. The new methods, as worked out and tested under sea going conditions during several years by the author, are described in more detail. These are the methods for nitrate, silicate, the automatic determination of dissolved inorganic phosphate and silicate, the automated determination of total phosphorus, the in situ recording of the oxygen tension, and the modification for the determination of ammonia, calcium, and dissolved oxygen. With these revised methods more than 18,000 determinations have been carried out during the Indian Ocean cruise. The complete working up of the chemical data of the Indian Ocean Expedition of R. V. "Meteor" is devided into four sections: Contributions 1) to the Chemistry of the Red Sea and the Inner Gulf of Aden, 2) to the Gulf of Aden and the Somali Coast Region, 3) to the Western Indian Coast Region, and 4) to the Persian Gulf and the Straits of Oman. This paper presents the first contribution. The special hydrographical conditions are discussed. It can be shown, that the increase of salinity in the surface waters from the south to the north of the Red Sea is only to about 30 % due to evaporation. The remaining increase is presumed to be due to the admixture of deep water to the surface layers. A special rate for the consumption of oxygen (0.114 ml/ l/a) is derived for the deep water of the Red Sea at 1500 m. Based upon the distribution of the dissolved oxygen along the axii of the Red Sea, a chematic model for the longitudinal circulation of the Red Sea is constructed. This model should be considered as a first approximation and may explain the special distribution of phosphate, nitrate, and silicate. Based upon the evaluation of the residence time of the deep water a dissolution rate for silicate is estimated as 1 mygat/a. It seems possible to calculate residence times of water masses outside the Red Sea from the silicate content. The increase of silicate and the consumption of oxygen lead to residence times of the water below the thermocine of 30 to 48 years. The distribution of oxygen in the Straits of Bab el Mandeb is described and discussed. The rate of consumption of the oxygen in the outflowing Red Sea water is estimated to 8.5 ml/ l/a. This rather high rate is explained with reference to the special conditions in the outflowing water. The Red Sea water is characterized initially by a relative high content of oxygen and a low content of nutrients. The increase in nutrients and the decrease in the oxygen content is a secondary process of the Red Sea water on its way to the Arabian Sea. Based upon the vertical distribution of the dissolved inorganic phosphate vertical exchange coefficients of 1 - 4 g/cm/sec and vertical current speeds of 10**-5 to 10**-4 cm/sec are calculated for some stations in the Red Sea. The distribution of phosphate, silicate, nitrate, nitrite and ammonia for the Red Sea and the Straits of Bab el Mandeb are discussed. The special circulation is evaluated and the balance of the nutrients is estimated by means of the brutto transport. The nutrient deficit is assumed to be balanced by sporadic inflow of intermediate water from the Gulf of Aden. An example for such an inflow has been observed and is demonstrated. The silicate-salinity relationships are a suitable way for characterizing water masses in the Red Sea. Equations for the calculation of the different components from the carbonate system, the ion activities, and the calcium carbonate saturation are evaluated. The influence of temperature and pressure is taken into account. The carbonate saturation is calculated from the determined concentrations of calcium, alkalinity, and the hydrogen ion activity. Saturation values of 320 % are found for the surface layer and of 100% ± 1 for the deep water. The extraordinary equilibrium conditions may explain the constant Ca/Cl ratio and also the sedimentation of undissolved carbonate skelecons even in greater depths. A main sedimentation rate of 2 * 10**-3cm/year is evaluated from a total sedimentation of 10 * 106 to/a of calcium carbonate in the Red Sea. The appendix contains those data, which are not published in the data volume of the I.I.O.E. expedition of R. V. "Meteor".

Organic geochemistry at DSDP Leg 80 Holes

The four sites drilled on the Irish continental margin (Goban Spur) yielded sediments ranging in age from Holocene to Barremian. Most of the sediments were deposited in well oxygenated waters, and the small amounts of organic matter they contain are highly oxidized. During a few time intervals from the Cenomanian to earliest Turonian, however, the oxygen content of the bottom waters reached very low levels, resulting in the deposition of homogeneous or laminated black sediments containing from 0.5 to 11% total organic carbon (TOC). The original organic matter was of mixed marine and terrestrial origin. The oxidizing-reducing cycles represented by interbedded black and light sediments are probably a result of changes in both circulation and productivity. The black sediments at Sites 550, 551, and 549 were probably deposited near the lower end, middle, and upper end, respectively, of an expanded oxygen-minimum layer. The oil and gas source potential of the laminated black sediments is very good to excellent. The organic-carbon-lean sediments deposited under oxidizing conditions have no oil or gas source potential. The thermal maturity of all sediments is low.

The treatment of domestic wastewater using small-scale vermicompost filter beds

The aim of this study is to quantity the effect of filter bed depth and solid waste inputs on the performance of small-scale vermicompost filter beds that treat the soluble contaminants within domestic wastewater. The study also aims to identify environmental conditions within the filters by quantifying the oxygen content and pH of wastewater held within it. Vermicompost is being utilised within commercially available on-site domestic waste treatment systems however, there are few reported studies that have examined this medium for the purpose of wastewater treatment. Three replicate small-scale reactors were designed to enable wastewater sampling at five reactor depths in 10-cm intervals. The surface of each reactor received household solid organic waste and 1301 m(-2) per day of raw domestic wastewater. The solid waste at the filter bed surface leached oxygen demand into the wastewater flowing through it. The oxygen demand was subsequently removed in lower reactor sections. Both nitrification and denitrification occurred in the bed. The extent of denitrification was a function of BOD leached from the solid waste. The environmental conditions measured within the bed were found to be suitable for earthworms living within them. The study identified factors that will affect the performance and application of the vermicompost filtration technology. (C) 2004 Elsevier B.V. All rights reserved.

Stale flavour volatiles in Australian commercial UHT milk during storage

Methyl ketones, aldehydes and free saturated fatty acids were measured in the headspace of samples of two indirectly processed and two directly processed Australian commercial UHT milks during room temperature storage for 16 weeks. The analytes were isolated using headspace solid phase microextraction and analysed by gas chromatography coupled with flame ionisation detection. All methyl ketones and aldehydes increased during storage, With free saturated fatty acids exhibiting little change. On average, the total methyl ketone and aldehyde concentrations in the indirectly processed UHT milks were higher than those in the directly processed samples. A strong correlation was found between the concentration of methyl ketones and various heat indices (furosine, lactulose and undenatured whey proteins) in the milk samples.

Comparison of the effect of pre-treatment and catalysts on liquid quality from fast pyrolysis of biomass

The overall objective of this work was to compare the effect of pre-treatment and catalysts on the quality of liquid products from fast pyrolysis of biomass. This study investigated the upgrading of bio-oil in terms of its quality as a bio-fuel and/or source of chemicals. Bio-oil used directly as a biofuel for heat or power needs to be improved particularly in terms of temperature sensitivity, oxygen content, chemical instability, solid content, and heating values. Chemicals produced from bio-oil need to be able to meet product specifications for market acceptability. There were two main objectives in this research. The first was to examine the influence of pre-treatment of biomass on the fast pyrolysis process and liquid quality. The relationship between the method of pre-treatment of biomass feedstock to fast pyrolysis oil quality was studied. The thermal decomposition behaviour of untreated and pretreated feedstocks was studied by using a TGA (thermogravimetric analysis) and a Py-GC/MS (pyroprobe-gas chromatography/mass spectrometry). Laboratory scale reactors (100g/h, 300g/h, 1kg/h) were used to process untreated and pretreated feedstocks by fast pyrolysis. The second objective was to study the influence of numerous catalysts on fast pyrolysis liquids from wheat straw. The first step applied analytical pyrolysis (Py-GC/MS) to determine which catalysts had an effect on fast pyrolysis liquid, in order to select catalysts for further laboratory fast pyrolysis. The effect of activation, temperature, and biomass pre-treatment on catalysts were also investigated. Laboratory experiments were also conducted using the existing 300g/h fluidised bed reactor system with a secondary catalytic fixed bed reactor. The screening of catalysts showed that CoMo was a highly active catalyst, which particularly reduced the higher molecular weight products of fast pyrolysis. From these screening tests, CoMo catalyst was selected for larger scale laboratory experiments. With reference to the effect of pre-treatment work on fast pyrolysis process, a significant effect occurred on the thermal decomposition of biomass, as well as the pyrolysis products composition, and the proportion of key components in bio-oil. Torrefaction proved to have a mild influence on pyrolysis products, when compared to aquathermolysis and steam pre-treatment.

Alcohols and other oxygenates in automotive fuels

The aim of this research was to assess the effect of oxygenated hydrocarbons on the knocking characteristics of an engine when blended with low-leaded gasoline. Alcohols, ethers, esters and ketones were tested individually and in various combinations up to an oxygen content of 4% wt/wt in a blend with Series F-7 gasoline of 90, 92, 94 and 96 RON. Tests were carried out at wide open throttle, constant speed and standard timing setting. Engine speed was varied using a dynamometer and knock was detected by two piezoelectric transducers, one on the cylinder head monitoring all four cylinders and one monitoring the cylinder most prone to knock. The engine speeds associated with trace and light knock of a continuous nature were noted. Curves were produced for each oxygenate blend of base RON used against engine speed for the two knock conditions which were compared with those produced using pure Series F-7 fuels. From this a suggested RON of the blend was derived. RON increase was less when using a higher RON base fuel in the blend. Most individual oxygenates showed similar effects in similar concentrations when their oxygen content was comparable. Blends containing more than one oxygenate showed some variation with methanol/MTBE/3 methylbutan-2-one and methanol/MTBE/4 methyl pentan-2-one knocking less than expected and methanol/MTBE/TBA also showing good knock resistance. Further tests to optimise initial findings suggested a blend of methanol and MTBE to be superior although partial replacement of MTBE by 4 methyl pentan-2-one resulted in a fuel of comparable performance. Exhaust emissions were tested for a number of oxygenated blends in 2-star gasoline. 2-star and 4-star fuels were also tested for reference. All oxygenate blends reduced carbon monoxide emissions as expected and hydrocarbon emissions were also reduced. The largest reduction in carbon monoxide occurred using a 14.5 % (1 : 1 : 1) methanol/MTBE/4 methyl pentan-2-one blend. Hydrocarbon emissions were most markedly reduced by a blend containing 25.5 % 4 methyl pentan-2-one. Power output was tested for the blends and indicated a maximum increase of about 5 % at low engine speeds. The most advantageous blends were methanol/4 methyl pentan-2-one (6 : 5) 11% in 2-star and methanol/MTBE/4 methyl pentan-2-one (6 : 3 : 2) 11% in 2-star. In conclusion methanol/MTBE (6 : 5) and (5 : 5), and various combinations of methanol/MTBE/4 methyl pentan-2-one, notably (6 : 3 : 2) gave good results in all tests conducted. CFR testing of these blends showed them to increase both RON and MON substantially.

Studies on the deactivation and reactivation of spent hydroprocessing catalyst

A study is reported on the deactivation of hydroprocessing catalysts and their reactivation by the removal of coke and metal foulants. The literature on hydrotreating catalyst deactivation by coke and metals deposition, the environmental problems associated with spent catalyst disposal, and its reactivation/rejuvenation process were reviewed. Experimental studies on catalyst deactivation involved problem analysis in industrial hydroprocessing operations, through characterization of the spent catalyst, and laboratory coking studies. A comparison was made between the characteristics of spent catalysts from fixed bed and ebullating bed residue hydroprocessing reactor units and the catalyst deactivation pattern in both types of reactor systems was examined. In the laboratory the nature of initial coke deposited on the catalyst surface and its role on catalyst deactivation were studied. The influence of initial coke on catalyst surface area and porosity was significant. Both catalyst acidity and feedstock quality had a remarkable influence on the amount and the nature of the initial coke. The hydroenitrogenation function (HDN) of the catalyst was found to be deactivated more rapidly by the initial coke than the hydrodesulphurization function (HDS). In decoking experiments, special attention was paid to the initial conditions of coke combustion, since the early stages of contact between the coke on the spent catalyst surface and the oxygen are crucial in the decoking process. An increase in initial combustion temperature above 440oC and the oxygen content of the regeneration gas above 5% vanadium led to considerable sintering of the catalyst. At temperatures above 700oC there was a substantial loss of molybdenum from the catalyst, and phase transformations in the alumina support. The preferred leaching route (coked vs decoked form of spent catalyst) and a comparison of different reagents (i.e., oxalic acid and tartaric acid) and promoters (i.e., Hydrogen Peroxide and Ferric Nitrate) for better selectivity in removing the major foulant (vanadium), characterization and performance evaluation of the treated catalysts and modelling of the leaching process were addressed in spent catalyst rejuvenation studies. The surface area and pore volume increased substantially with increasing vanadium extraction from the spent catalyst; the HDS activity showed a parallel increase. The selectivity for leaching of vanadium deposits was better, and activity recovery was higher, for catalyst rejuvenated by metal leaching prior to decoking.

Catalytic pyrolysis of agricultural residues for bio-oil production

Agricultural residues from Thailand, namely stalk and rhizome of cassava plants, were employed as raw materials for bio-oil production via fast pyrolysis technology. There were two main objectives of this project. The first one was to determine the optimum pyrolysis temperature for maximising the organics yield and to investigate the properties of the bio-oils produced. To achieve this objective, pyrolysis experiments were conducted using a bench-scale (150 g/h) reactor system, followed by bio-oil analysis. It was found that the reactor bed temperature that could give the highest organics yield for both materials was 490±15ºC. At all temperatures studied, the rhizome gave about 2-4% higher organics yields than the stalk. The bio-oil derived from the rhizome had lower oxygen content, higher calorific value and better stability, thus indicating better quality than that produced from the stalk. The second objective was to improve the bio-oil properties in terms of heating value, viscosity and storage stability by the incorporation of catalyst into the pyrolysis process. Catalytic pyrolysis was initially performed in a micro-scale reactor to screen a large number of catalysts. Subsequently, seven catalysts were selected for experiments with larger-scale (150 g/h) pyrolysis unit. The catalysts were zeolite and related materials (ZSM-5, Al-MCM-41 and Al-MSU-F), commercial catalysts (Criterion-534 and MI-575), copper chromite and ash. Additionally, the combination of two catalysts in series was investigated. These were Criterion-534/ZSM-5 and Al-MSU-F/ZSM-5. The results showed that all catalysts could improve the bio-oils properties as they enhanced cracking and deoxygenation reactions and in some cases such as ZSM-5, Criterion-534 and Criterion-534/ZSM-5, valuable chemicals like hydrocarbons and light phenols were produced. The highest concentration of these compounds was obtained with Criterion-534/ZSM-5.

Nano-indentation measurement of oxide layers formed in LBE on F/M steels

Ferritic/martensitic (F/M) steels (T91, HT-9, EP 823) are candidate materials for future liquid lead or lead bismuth eutectic (LBE) cooled nuclear reactors. To understand the corrosion of these materials in LBE, samples of each material were exposed at 535 °C for 600 h and 200 h at an oxygen content of 10 wt%. After the corrosion tests, the samples were analyzed using SEM, WDX and nano-indentation in cross section. Multi-layered oxide scales were found on the sample surfaces. The compositions of these oxide layers are not entirely in agreement with the literature. The nano-indentation results showed that the E-modulus and hardness of the oxide layers are significantly lower than the values for dense bulk oxide materials. It is assumed that the low values stem from high porosity in the oxide layers. Comparison with in-air oxidized steels show that the E-modulus decreases with increasing oxide layer thickness. © 2008 Elsevier B.V. All rights reserved.