A thermodynamic cycle simulation of the four-stroke spark-ignition engine was used to determine the effects of variations in engine design and operating parameters on engine performance and emission characteristics. The overall objective was to use the engine cycle simulation to determine the difference between a propane-fuelled and an iso-octane-fuelled engine for the same operating conditions and engine specifications. A comprehensive parametric investigation was conducted to examine the effects of variations in load, speed, combustion duration, spark timing, equivalence ratio, exhaust gas recycle, and compression ratio for a 3.3 liter, Chrysler Minivan, V 6 engine operating on propane. Parameters were selected for the analysis. Variations in the brake specific fuel consumption, brake specific NOx emissions, and mean exhaust temperature were determined for both the propane-fuelled and the iso-octane-fuelled engines. Brake specific fuel consumption and mean exhaust temperature values for the propane-fuelled engine were consistently lower (3 to 5 %) than the corresponding values for the iso-octane-fuelled engine. Fuel structure did not have a significant effect on brake specific nitric oxide emissions. Predictions made from the simulation were compared with some of the available experimental results. Predicted brake torque and brake power showed acceptable quantitative agreement (less than 10 % variation) in the low engine speed range (1,000 to 3,000 rpm) and similar trends with the available experimental data.

The development of an auxiliary power unit (APU) capable of providing climate control and electricity in long haul trucks is of significant interest due to the expected economic and environmental benefits. A potentially efficient and environmentally friendly APU design is one based on the use of an autothermal fuel reformer that converts on-board truck fuel to a hydrogen rich gas that directly fuels a solid oxide fuel cell unit. To assist in the development of such a unit a numerical study of the autothermal reforming of iso-octane in a compact tubular reactor has been undertaken. This was done to determine the reactor performance and the factors that potentially influence its performance. Variations in the wall thermal conductivity, the catalyst thermal conductivity, the catalyst porosity, the conditions of the inlet reactant gas, and the effectiveness factor of the chemical reaction mechanism have been studied to determine their effects on the performance of the reformer. It has been found that higher thermal conductivities of the outer wall and in the catalyst region gave increased dry hydrogen yield and fuel conversion. The study of the effects of inlet species concentration ratios indicated that maximum hydrogen yield was obtained with an oxygen-to-fuel ratio between 1.0 and 1.15 and a steam-to-fuel ratio of approximately 3.0. Results obtained with various inlet species temperatures and bed porosities showed only small changes in the reformer performance. While the results obtained here do provide useful information about the performance of the autothermal reformer, the model used has been re-assessed and it is recommended that an improved model be used in future work. In particular, the assumed effectiveness factors for all of the chemical reactions occurring in the catalyst region need to be improved. This was highlighted by the fact that a brief study indicated a very strong dependence of the reformer product gas composition on the effectiveness factor. This indicates that while the present model is able to predict trends in the reformer performance, it is limited in its accuracy due to the fact that the effectiveness factor used is only approximately known. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2007-08-31 13:22:27.466

Le toluène (TOL), le n-hexane (HEX), le cyclohexane (CHX) et l'isooctane (ISO) sont des composés organiques volatils (COVs) omniprésents dans les milieux industriels et résidentiels. L'exposition aux mélanges soulève de nombreuses interrogations en regard des possibilités d'interaction. L'inhibition métabolique étant le mécanisme d'interaction le plus plausible, pourrait aboutir à une augmentation de leur concentration interne et donc de leur toxicité. L'objectif de cette étude était de caractériser les interactions métaboliques entre le TOL, l'HEX, le CHX et l'ISO, en utilisant les préparations microsomiales de foie de rat. Nous avons donc étudié le potentiel d'inhibition du métabolisme du TOL par HEX, CHX et ISO, aussi bien que l'inhibition du métabolisme du HEX par TOL, CHX et ISO. Initialement, la mesure du coefficient de partage milieu : air (pm : air) a aussi été faite pour permettre une estimation des concentrations des inhibiteurs et des substrats dans le milieu d'incubation (CHX : 0,23 ISO : 0,21 TOL : 2,35 et HEX : 0,04). Aussi en mesurant le taux de disparition des substrats par chromatographie en phase gazeuse après des incubations de 45 min. pour TOL et de 4 min. pour HEX, le taux de métabolisme a été déterminé pour ces 2 composés incubés individuellement ou en présences des autres COVs. Les résultats suggèrent que le métabolisme du TOL est inhibé de façon compétitive par HEX et de façon incompétitive par CHX et ISO (Ki égale respectivement 0,49, 1,84 et 1,798 μM). L'inhibition de HEX par TOI est de type mixte (Ki = 4,5339 μM), alors que le CHX et l'ISO agissent sur le métabolisme de l'HEX par inhibition compétitive (Ki respectif de 0,75 et 1,54 μM). Ces données in vitro sur les interactions métaboliques pourront être intégrées dans un modèle pharmacocinétique à base physiologique (PBPK) pour prédire la dose interne résultant d'une exposition à ces mélanges chimiques. ______________________________________________________________________________ MOTS-CLÉS DE L’AUTEUR : toluène, hexane, cyclohexane, isooctane, métabolisme in vitro

A numerical study was carried out to improve the design of an autothermal reformer for the onboard production of hydrogen to be used in fuel-cell- powered auxiliary power units (APU) to provide heating and electricity in long haul trucks when they are at rest. The development of these auxiliary power units is based upon the use of power generated by solid oxide fuel cell (SOFC) system, instead of from a conventional gasoline engine. The present work was undertaken to improve the design of a prototype autothermal fuel reformer that had been developed by the Fuel Cell Research Centre (FCRC) at Queen’s University to convert liquid hydrocarbon truck fuel to a hydrogen rich product gas. In this development work and in the previous work iso-octane (C8H18) has been used as a surrogate fuel. Using this surrogate of gasoline, the reformer was simulated using various inlet steam/carbon (H2O/C), oxygen/carbon (O/C) molar ratios and gas-hourly-space-velocity (GHSV). In the reformer considered the reforming process is carried out in a compact tubular reactor with a centerline thermocouple tube using a 2% Pt-ZrCe based catalyst with a local porosity of 0.6. During the initial simulations, it was observed that near the start of the catalyst region there were large temperature gradients due to an exothermic partial oxidation reaction. In order to reduce the temperature gradients and facilitate heat transfer by conduction along the reformer, the central thermocouple tube was replaced with a central solid rod. The effects of variations in the thermal conductivity of central solid rod, of the reactor wall, of the catalyst bed, of the inert porous material near the inlet and the outlet of the catalyst bed, of the gas hourly space velocity, of the effectiveness factor of the chemical reaction mechanism on the performance of the reactor were studied. The results so obtained were analyzed to determine potential design improvements that would increase the hydrogen output. The results were compared with the previous numerical and experimental results obtained in the previous studies of the reformer and found to be in good agreement with the general trends of the temperature profiles as well as the outlet molar concentrations of product species. After the analysis and evaluation of all the results, it was found that by replacement of central thermocouple tube with central solid rod made of high conductivity material and by using material for inert porous region at the outlet that had a thermal conductivity equal to that of the catalyst bed led to more even temperature profiles within the catalyst region. It was also found that the hydrogen molar percentage output could be increased by approximately more than 25% and that the length of the reactor could be reduced by 20mm by incorporating these changes in the reformer design. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2009-03-09 12:14:27.627

Separation of aromatic/aliphatic hydrocarbon mixtures by pervaporation has been of increasing interest in recent decades. Dozens of polymer materials have been reported for separations of benzene/cyclohexane and toluene/iso-ocatne mixtures. However, fundamental understanding of material structure and transport relations is not adequate to generalize guidelines for materials screening. The goals of this study are to tailor the structure of the polyimide materials, correlate the structure and transport relations, and establish guidelines for future materials. The 3, 5-Diaminobenzoic acid (DABA) containing polyimides were synthesized by both chemical and thermal solution imidization. The synthesized polyimides were formed into dense films by solution casting. The physical properties of the polyimides synthesized with monomers: 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 4, 6-trimethyl-1, 3-phenylendiamine (DAM) and DABA, were characterized by DSC, WAXD, GPC and density. The chemical structures were assessed by FTIR and NMR. The pervaporation and sorption of the synthesized polyimide membranes were tested in toluene/iso-octane mixtures at 100°C. The structure- transport property relations were established for the 6FDA-DAM/DABA membranes. The 6FDA-DAM/DABA polyimides were crosslinked by ethylene glycol. The pervaporation and sorption of the crosslinked membranes were tested in toluene/iso-octane mixtures at 100°C. Thermal imidization was found to give a higher imidization degree than chemical imidization. As a result, the polyimides made by chemical imidization contain a higher percentage of carboxylic acid groups than those made by thermal imidization. Chemical imidization gives higher film density, glass transition temperature and lower flux and higher selectivity for the toluene/iso-octane pervaporation than the thermally imidized membranes because of the higher carboxylic acid concentration. The chemically imidized membranes are slightly brittle after the crosslinking. Only the thermal imidization membranes have good flexibility and its pervaporation selectivity improves significantly after the crosslinking. Solubility selectivity and diffusivity selectivity of the 6FDA-DAM/DABA membranes were correlated with solubility parameters and fractional free volume, respectively. The structure-mass transport relations show that for the 6FDA-DAM/DABA membranes, both solubility selectivity and diffusivity selectivity contribute to the pervaporation selectivity. For the chemically imidized membranes, increased DABA concentration has a positive effect on solubility selectivity and diffusivity selectivity. For the thermally imidized membranes, increased DABA concentration has a significant effect on diffusivity selectivity only. / text

Iso-octane, n-heptane, ethanol and their blends were tested in a constant volume combustion chamber to measure laminar burning velocities. The experimental apparatus was modified from the previous version to an automatically-controlled system. Accuracy and speed of data acquisition were improved by this modification. The laminar burning velocity analysis code was also improved for minimized error and fast calculation. A large database of laminar burning velocities at elevated temperatures and pressures was established using this improved experimental apparatus and analysis code. From this large database of laminar burning velocities, laminar flame speeds were extracted. Laminar flame speeds of iso-octane, n-heptane and blends were investigated and analysed to derive new correlations to predict laminar flame speeds of any blending ratio. Ethanol and ethanol blends with iso-octane and/or n-heptane were also examined to see the role of ethanol in the blends. Generally, the results for iso-octane and n-heptane agree with published data. Additionally, blends of iso-octane and n-heptane exhibited flame speeds that followed linear blending relationships. A new flame speed model was successfully applied to these fuels. Ethanol and ethanol blends with iso-octane and/or n-heptane exhibited a strongly non-linear blending relationship and the new flame speed model was not applied to these fuels. It was shown that the addition of ethanol into iso-octane and/or n-heptane accelerated the flame speeds. / text

Gasoline compression ignition (GCI) engines show promise in meeting stringent new environmental regulations, as they are characterized by high efficiency and low emissions. Simulations using chemical kinetic models provide an important platform for investigating the behaviors of the fuels inside these engines. However, because real fuels are complex, simulations require surrogate mixtures of small numbers of species that can replicate the properties of real fuels. Accordingly, the development of high fidelity, well-validated kinetic models for surrogates is critical in order to accurately replicate the combustion chemistry of different fuels under engine-related conditions. This work focuses on the development of combustion kinetic models to better understand gasoline fuel combustion in GCI engines. An updated iso-octane detailed kinetic model was developed based on new thermodynamic group values and recently evaluated rate coefficients from literature. The model was validated against a wide range of experimental data and conditions. The iso-octane model was further used in 0D simulations for a homogeneous charge compression ignition (HCCI) engine. The results showed that the low-temperature heat release in engines increases with engine boosting when the addition of alky radicals to molecular oxygen is more favored. Ethanol addition was also found to act as a radical sink which inhibits the radical pool formation and results in lower reactivity. Although detailed models provide clarification of the combustion chemistry, their high computational cost impedes their utilization in 3-D engine simulations. Hence, a reduced model for toluene primary reference fuels was developed and validated against ignition delay time and flame speed experiments from literature. The model was then used in numerically investigating the effects of the fuel’s physical properties using hollow-cone and multi-hole injectors in a partially premixed compression ignition (PPCI) engine. It was concluded that the effects of physical properties are evident in multi-hole injection cases, which is attributable to the differences in mixture stratification. Finally, reduced models for multi-components surrogates for three full-blend fuels (light naphtha-Haltermann straight-run naphtha and GCI fuels) were developed. The models were validated against ignition delay time experiments from the literature and tested in 3D engine simulations.

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Carbonaceous deposits accumulate on the majority of the inner surfaces of internal combustion engines. The presence of these deposits is known to cause impaired engine performance. This is manifested as increased knocking, higher fuel consumption, higher emissions and other adverse effects. One of the proposed mechanisms for this behaviour is the adsorption and desorption of fuel components in the pores within the deposit. The porous nature of the deposits promotes this behaviour, altering the fuel composition and reducing the amount of fuel entering the combustion chamber. Previous research in this area was aimed at determining the porous structure of the deposits by combining experimental procedures with molecular simulations to investigate adsorption interactions with fuel components. Using a characterisation procedure regularly applied to activated carbons, a molecular model was developed that was able to provide new insights into the deposit structure. This model enabled predictions to be made for the single-component adsorption of normal heptane and iso-octane, two species commonly used as a gasoline reference fuel. Results showed significant adsorption of both species, and highlighted the impact of adsorption into the internal porous structure of the engine deposits. The aim of this thesis is to further investigate adsorption in engine deposits by expanding the studies to more complex systems. We develop a model to predict the adsorption of normal heptane, iso-octane, toluene and their mixtures in deposits of different origins and under different conditions. The study of multi-component mixtures provides insight into selectivity effects of adsorption under confinement, while at the same time bringing the systems under consideration closer to realistic multi-component mixtures that better represent fuel blends. The study also considers for the first time adsorption of aromatic species, both as a single component and in mixtures, since aromatics have a high presence in gasoline fuel. We explore the influence of molecular structure of adsorbing species, composition of the bulk mixture and temperature on the uptake and selectivity behaviour of the engine deposits. We demonstrate that under equilibrium conditions, deposits can adsorb substantial amounts of hydrocarbon species of all types. However, selectivity behaviour in engine deposits was found to be a subtle and complex property, highly sensitive to both pore size and system pressure.