The quantitative analysis of complex gas mixtures, such as the hydrazines and their air oxidation products, is of paramount importance in closed cycle systems used, for example, in submarines. A laser optoacoustic (photoacoustic) spectrometer which is capable of detecting these species at parts per billion levels has been developed and a system for field use is described. Laser optoacoustic measurements have been made on a range of other species which absorb in the CO2 laser region of 9 - 11.3~m, including many atmospheric pollutants such as the chlorofluorocarbons, perfluorocarbons, and some of the new 'ozone friendly' propellant and refrigerant species. Absorption coefficient data and limits of detection have been established for many gaseous molecules, and a series of optoacoustic cells has been designed, together with a novel method for the generation of gaseous species at low concentrations. A CO2 laser based optoacoustic spectrometer is compared favourably with a range of other current methods used to detect low levels of atmospheric contaminants, and has been shown to be a most suitable technique for the quantitative detection of a wide range of substances at the parts per billion level.

CO2 injection has demonstrated significant potential for enhanced oil recovery techniques in unconventional reservoirs, but there exists many challenges in optimizing its operations due to the limited understanding of CO2-oil transport mechanisms in these systems. This dissertation addresses these challenges using molecular dynamics (MD) simulations by investigating the gas and oil transport behaviors and properties within single nanopores under reservoir conditions. The first study examines the exchange dynamics of decane with CO2 and CH4 in a 4 nm-wide calcite nanopore. It is shown that both gases form distinct adsorbed and free molecular populations upon entering the pores, leading to different extraction dynamics. Notably, CO2-decane exchange is initially driven by adsorbed populations, with a transition to free populations later; whereas CH4 -decane exchange follows the opposite pattern. Despite these differences, the transport of both gases apparently follows the same diffusive behavior, with CH4 exhibiting higher effective diffusivities. By calculating self-diffusivities at various relevant compositions, it is found they do not always align well with their effective diffusivities. The second study therefore focuses on Maxwell-Stefan (M-S) diffusivities as a more comprehensive framework to describe the diffusion of CO2-decane mixtures in the first study. It is found that D12 (CO2-decane interactions) remains relatively constant across compositions, unlike bulk mixtures, while D1,s (CO2-wall interactions) increases sharply with CO2 loading. In contrast, D2,s (decane-wall interactions) shows a nonmonotonic trend and, unexpectedly, becomes negative under certain compositions. These phenomena are linked to the strong adsorption of CO2, causing significant density heterogeneity and reduced mobility. Using a multi-task Gaussian process regression model, the M−S diffusivities can be predicted with a relative root mean square error below 10%, significantly reducing computational demand for their practical usage. The third study examines concentration gradient driven diffusio-osmosis of oil-CO2 mixtures within silica and calcite nanopores. Despite higher CO2 enrichment near calcite walls, diffusio-osmotic is only marginally stronger than in silica pores, which is attributed to the variations in interfacial fluid structures and hydrodynamic properties in different pores. Continuum simulations suggest that diffusio-osmosis becomes increasingly significant compared to Poiseuille flow as pore width decreases. The fourth study investigates the oil mixture (C10+C19) recovery from a 4 nm-wide calcite dead-end pore with and without CO2 injection. It was found that CO2 accelerates oil recovery and reduces selectivity for lighter components (e.g., C10) compared to the recovery without CO2. Such improvements are influenced by interfacial and bulk phenomena, including adsorption competition and solubilization effects. Together, these studies provide quantitative insights into CO2-oil transport mechanisms and properties in nanopores. Such insights can help develop better reservoir simulators to guide the optimization of CO2 injection-based enhanced oil recovery in unconventional reservoirs. / Doctor of Philosophy / Recovering oil from unconventional reservoirs—types of underground rock formations that trap oil in extremely tiny pores, much smaller than the thickness of a strand of hair—is one of the biggest challenges in the petroleum industry. The narrow pore size greatly increases the fraction of the oil flow, and many pores are not even connected, which stops oil to flow out on its own, making it much harder to extract from these reservoirs. Injecting gases into the reservoirs, like carbon dioxide (CO2), has become a promising solution. This method not only helps to push the oil out but also allows part of the injected CO2 to be stored underground, reducing its impact on the atmosphere. To make this process work better, we need in depth understandings of how oil and gas move in these tiny rock spaces. Four studies have been conducted to elucidate the transport phenomena in CO2 injection-based enhanced oil recovery. The first study finds that the exchange between trapped oil and CO2 is significantly influenced by how oil and CO2 stick to the walls of these tiny pores. However, it is observed that commonly used characterization methods do not always work well in the prediction of recovery behavior, indicating the need for a better framework to describe this process. To address this problem, we have brought up a new framework in the second study, which considers both the interactions between oil and CO2 and the interactions with the pore wall. Given the high computational costs, a machine learning model is trained with the data collected to make future predictions faster and cheaper. The third study quantifies the strength of a new type of flow. This flow can be comparable in magnitude to pressure difference-driven flow in tiny pores. Lastly, the recovery of an oil mixture composed of light and heavy hydrocarbons is explored. It was discovered that gas injection not only increases the overall oil recovery rate but also decreases the selectivity toward lighter hydrocarbons. These discoveries pave the way for improved models and strategies to optimize the gas injection process to recover oil from these challenging reservoirs, ultimately meeting the energy needs while supporting efforts to reduce atmospheric CO2 levels.

On-board hydrogen and syngas production is considered as a transition solution from fossil fuel to hydrogen powered vehicles until problems associated with hydrogen infrastructure, distribution and storage are resolved. A hydrogen- or syngas-rich stream, which substitutes part of the main hydrocarbon fuel, can be produced by supplying diesel fuel in a fuel-reforming reactor, integrated within the exhaust pipe of a diesel engine. The primary aim of this project was to investigate the effects of intake air enrichment with product gas on the performance, combustion and emissions of a diesel engine. The novelty of this study was the utilisation of the dilution effect of the reformate, combined with replacement of part of the hydrocarbon fuel in the engine cylinder by either hydrogen or syngas. The experiments were performed using a fully instrumented, prototype 2.0 litre Ford HSDI diesel engine. The engine was tested in four different operating conditions, representative for light- and medium-duty diesel engines. The product gas was simulated by bottled gases, the composition of which resembled that of typical diesel reformer product gas. In each operating condition, the percentage of the bottled gases and the start of diesel injection were varied in order to find the optimum operating points. The results showed that when the intake air was enriched with hydrogen, smoke and CO emissions decreased at the expense of NOx. Supply of nitrogen-rich combustion air into the engine resulted in a reduction in NOx emissions; nevertheless, this technique had a detrimental effect on smoke and CO emissions. Under low-speed low-load operation, enrichment of the intake air with a mixture of hydrogen and nitrogen led to simultaneous reductions in NOx, smoke and CO emissions. Introduction of a mixture of syngas and nitrogen into the engine resulted in simultaneous reductions in NOx and smoke emissions over a wide range of the engine operating window. Admission of bottled gases into the engine had a negative impact on brake thermal efficiency. Although there are many papers in the literature dealing with the effects of intake air enrichment with separate hydrogen, syngas and nitrogen, no studies were found examining how a mixture composed of hydrogen and nitrogen or syngas and nitrogen would affect a diesel engine. Apart from making a significant contribution to existing knowledge, it is 3 believed that this research work will benefit the development of an engine-reformer system since the product gas is mainly composed of either a mixture of hydrogen and nitrogen or a mixture of syngas and nitrogen.

Made available in DSpace on 2014-06-11T19:30:21Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-12-18Bitstream added on 2014-06-13T19:25:46Z : No. of bitstreams: 1 caputo_pd_me_guara.pdf: 1452016 bytes, checksum: bd796f6ea43f3ec75f5c6bf6d5e2078a (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Esta dissertação analisa a possibilidade de utilizar combustíveis gasosos alternativos para reduzir o consumo de gás de coqueria em usinas siderúrgicas integradas. Foram consideradas misturas a) de gás de coqueria com gases de gaseificação e b) de gás natural com gases de gaseificação, para substituir o gás de coqueria puro e misturas do gás de coqueria com gás de alto forno. Os dois parâmetros principais que definem a intercambiabilidade entre os gases foram o Índice de Wobbe e o Índice de Weaver relativo a descolamento de chama. O percentual de economia de gás de coqueria foi calculado para as diversas misturas consideradas. / This dissertation analyzes the possibility of using alternate fuel gases to reduce the consumption of coke oven gas in integrated steel making plants. The following gas mixtures were considered: a) coke oven gas with different gasification gases and b) natural gas with different gasification gases to substitute either pure coke oven gas or mixtures of coke oven gas with blast furnace gas. Eight gasification gases from biomass and coal were selected from the literature as prospective substitutes. The two main parameters that defined the interchangeability were the Wobbe Index and the Weaver Index related to flame blow out. The economy of coke oven gas was calculated for all considered alternate gases.

Current thinking on the best propulsion system for a next-generation supersonic cruising (Mach 2 to Mach 4) aircraft is a mixed-flow turbofan engine with afterburner. This study investigates the performance increase of a turbofan engine through the use of isothermal combustion inside the high-pressure turbine (High-Pressure Turburner, HPTB) as an alternative form of thrust augmentation. A cycle analysis computer program is developed for accurate prediction of the engine performance and a supersonic transport cruising at Mach 2 at 60,000 ft is used to demonstrate the merit of using a turburner. When assuming no increase in turbine cooling flow is needed, the engine with HPTB could provide either 7.7% increase in cruise range or a 41% reduction in engine mass flow when compared to a traditional turbofan engine providing the sane thrust. If the required cooling flow in the turbine is almost doubled, the new engine with HPTB could still provide a 4.6% increase in range or 33% reduction in engine mass flow. In fact, the results also show that the degradation of engine performance because of increased cooling flow in a turburner is less than half of the degradation of engine performance because of increased cooling flow in a regular turbine. Therefore, a turbofan engine with HPTB will still easily out-perform a traditional turbofan when even more cooling than currently assumed is introduced. Closer examination of the simulation results in off-design regimes also shows that the new engine not only satisfies the thrust and efficiency requirement at the design cruise point, but also provides enough thrust and comparable or better efficiency in all other flight regimes such as transonic acceleration and take-off. Another finding is that the off-design bypass ratio of the new engine increases slower than a regular turbofan as the aircraft flies higher and faster. This behavior enables the new engine to maintain higher thrust over a larger flight envelope, crucial in developing faster air-breathing aircraft for the future. As a result, an engine with HPTB provides significant benefit both at the design point and in the off-design regimes, allowing smaller and more efficient engines for supersonic aircraft to be realized. / Ph. D.

Resumo: Esta dissertação analisa a possibilidade de utilizar combustíveis gasosos alternativos para reduzir o consumo de gás de coqueria em usinas siderúrgicas integradas. Foram consideradas misturas a) de gás de coqueria com gases de gaseificação e b) de gás natural com gases de gaseificação, para substituir o gás de coqueria puro e misturas do gás de coqueria com gás de alto forno. Os dois parâmetros principais que definem a intercambiabilidade entre os gases foram o Índice de Wobbe e o Índice de Weaver relativo a descolamento de chama. O percentual de economia de gás de coqueria foi calculado para as diversas misturas consideradas. / Abstract: This dissertation analyzes the possibility of using alternate fuel gases to reduce the consumption of coke oven gas in integrated steel making plants. The following gas mixtures were considered: a) coke oven gas with different gasification gases and b) natural gas with different gasification gases to substitute either pure coke oven gas or mixtures of coke oven gas with blast furnace gas. Eight gasification gases from biomass and coal were selected from the literature as prospective substitutes. The two main parameters that defined the interchangeability were the Wobbe Index and the Weaver Index related to flame blow out. The economy of coke oven gas was calculated for all considered alternate gases. / Orientador: João Andrade de Carvalho Junior / Coorientador: Sergio Leite Lopes / Banca: Mauricio Araujo Zanardi / Banca: Marco Aurelio Ferreira / Mestre

The purpose of the research was to design, build, test, and recommend a process to economically separate CO from a gas mixture of CO, CO2, and O2. The general method considered in this research to accomplish the separation was liquid absorption in a packed column. Several experiments were performed to identify the best process solution to use in a prototype. The experiments, based on the COSORB process, consisted of CuCl mixed with a complexing agent (metal tri-chloride) and a solvent (metal tetra-chloride, toluene, ethanol, etc.). The best method consisted of an aqueous solution of CuCl and MgCl2, which has previously been used for CO absorption experiments reported in the literature. The absorption takes place at elevated pressure (30 psig) and ambient temperature, and the stripping occurs at approximately 75 ºC. Using the apparatus at approximate design conditions, the highest removal of CO was 88% with a product composition of 48%. The highest product composition achieved was 84%; in this case CO removal was 66%. Product composition was low because a significant amount of CO2 physically absorbed into solution (which also decreased the pH of the solution to about 4, according to calculation). The removal of CO should increase with a taller column and higher liquid flow through the column; however, this might decrease the product composition. Advantages of this process are that the raw materials used are relatively cheap, heating and cooling requirements are lower than similar processes, and operation is relatively simple.

Microdosímetros gasosos geralmente empregam uma mistura gasosa equivalente ao tecido humano mole (Tissue-equivalent Gas TEG), composta de um hidrocarboneto, dióxido de carbono e nitrogênio, de forma que o poder de freamento na mistura e no tecido sejam semelhantes. Entretanto, independentemente do hidrocarboneto adotado, dados tanto teóricos como experimentais do primeiro coeficiente de Townsend de ionização (α) nestas misturas são raros, ainda que a primeira TEG, cujo metano é o gás majoritário, tenha sido proposta em 1956 por Rossi e Failla e continue sendo amplamente utilizada. Neste trabalho, dados do parâmetro α em TEGs baseadas no metano (CH4 64,4%, CO2 32,4% e N2 3,2%) e nos isômeros do butano (C4H10 51,4%, CO2 42,3% e N2 6,3%) são apresentados pela primeira vez em geometria planar para a faixa de campo elétrico normalizado pela densidade do gás (E/N) entre 100 290 Td (1 Td = 10-21 V.m2). O método de medidas adotado baseia-se na técnica de Townsend pulsada, onde o primeiro coeficiente de Townsend pode ser determinando comparando a corrente elétrica no regime de avalanche e a corrente de ionização primária gerada pela incidência de um feixe de laser de nitrogênio em um eletrodo metálico (catodo) de uma câmara de geometria planar, sendo o anodo um eletrodo de alta resistividade (ρ=2×1010Ω.m). O aparato experimental, até então operado apenas em pressão atmosférica, foi modificado para também trabalhar em baixa pressão (120 hPa), de modo a aumentar a faixa de E/N investigada. A validação do método e das alterações do sistema de detecção foi realizada utilizando os três gases componentes das TEGs cujos parâmetros de transporte são amplamente estudados: o nitrogênio, o dióxido de carbono e o metano. Observou-se que o parâmetro na TEG com metano assemelha-se com os valores determinados para o metano puro. Na TEG baseada no isobutano, ele é compatível com o primeiro coeficiente de Townsend do dióxido de carbono para campos acima de 170 Td. Já o parâmetro na mistura com n-butano é intermediário entre os valores obtidos para o dióxido de carbono e o nitrogênio. Os resultados experimentais, disponíveis em forma tabular, foram comparados com os simulados utilizando o programa Magboltz 2, evidenciando boa concordância dentro da incerteza experimental. / Gaseous microdosimeters usually employ a Tissue-equivalent Gas (TEG), made of a hydrocarbon, carbon dioxide and nitrogen, in order to make similar the stopping power in this mixture and in the human soft tissue. Notwithstanding, regardless the chosen hydrocarbon, both theoretical and experimental data on the first Townsend ionization coefficient (α) in this mixtures are rare, even though the first TEG, which methane is the most abundant gas, was proposed in 1956 by Rossi and Failla and it has been widely employed since then. In this work, data on the parameter α in TEGs based on methane (CH4 64.4%, CO2 32.4%, and N2 3.2%) and butanes isomers (C4H10 51.4%, CO2 42.3% e N2 6.3%) are presented for the first time in planar geometry in the gas density-normalized electric field (E/N) range between 100 290 Td (1 Td = 10-21 V.m2). The adopted method is based on the Pulsed Townsend Technique, where the first Townsend coefficient can be determined by comparing the electric current in the avalanche mode and the primary ionization current, produced by an nitrogen laser beam incidence in a metallic electrode (cathode) of a parallel plate chamber, which the anode is a resistive electrode (ρ=2×1010Ω.m). The experimental setup, previously operated only at atmospheric pressure, was adapted to work also at low pressure (120 hPa), in order to increase the investigated E/N range. The validation of both method and detection system modifications was made by employing three TEGs components, nitrogen, carbon dioxide and methane, whose transport parameters are extensively studied. The parameter in the methane-based TEG follows the behavior observed in pure methane. In the isobutane-based TEG, it is compatible with the first Townsend coefficient in carbon dioxide for E/N above 170 Td. The parameter in the n-butane-based TEG lies between the obtained values of in carbon dioxide and nitrogen. The experimental results, included in tabular form, agree with those from Magboltz 2 simulations within the experimental uncertainties.

Microdosímetros gasosos geralmente empregam uma mistura gasosa equivalente ao tecido humano mole (Tissue-equivalent Gas TEG), composta de um hidrocarboneto, dióxido de carbono e nitrogênio, de forma que o poder de freamento na mistura e no tecido sejam semelhantes. Entretanto, independentemente do hidrocarboneto adotado, dados tanto teóricos como experimentais do primeiro coeficiente de Townsend de ionização (α) nestas misturas são raros, ainda que a primeira TEG, cujo metano é o gás majoritário, tenha sido proposta em 1956 por Rossi e Failla e continue sendo amplamente utilizada. Neste trabalho, dados do parâmetro α em TEGs baseadas no metano (CH4 64,4%, CO2 32,4% e N2 3,2%) e nos isômeros do butano (C4H10 51,4%, CO2 42,3% e N2 6,3%) são apresentados pela primeira vez em geometria planar para a faixa de campo elétrico normalizado pela densidade do gás (E/N) entre 100 290 Td (1 Td = 10-21 V.m2). O método de medidas adotado baseia-se na técnica de Townsend pulsada, onde o primeiro coeficiente de Townsend pode ser determinando comparando a corrente elétrica no regime de avalanche e a corrente de ionização primária gerada pela incidência de um feixe de laser de nitrogênio em um eletrodo metálico (catodo) de uma câmara de geometria planar, sendo o anodo um eletrodo de alta resistividade (ρ=2×1010Ω.m). O aparato experimental, até então operado apenas em pressão atmosférica, foi modificado para também trabalhar em baixa pressão (120 hPa), de modo a aumentar a faixa de E/N investigada. A validação do método e das alterações do sistema de detecção foi realizada utilizando os três gases componentes das TEGs cujos parâmetros de transporte são amplamente estudados: o nitrogênio, o dióxido de carbono e o metano. Observou-se que o parâmetro na TEG com metano assemelha-se com os valores determinados para o metano puro. Na TEG baseada no isobutano, ele é compatível com o primeiro coeficiente de Townsend do dióxido de carbono para campos acima de 170 Td. Já o parâmetro na mistura com n-butano é intermediário entre os valores obtidos para o dióxido de carbono e o nitrogênio. Os resultados experimentais, disponíveis em forma tabular, foram comparados com os simulados utilizando o programa Magboltz 2, evidenciando boa concordância dentro da incerteza experimental. / Gaseous microdosimeters usually employ a Tissue-equivalent Gas (TEG), made of a hydrocarbon, carbon dioxide and nitrogen, in order to make similar the stopping power in this mixture and in the human soft tissue. Notwithstanding, regardless the chosen hydrocarbon, both theoretical and experimental data on the first Townsend ionization coefficient (α) in this mixtures are rare, even though the first TEG, which methane is the most abundant gas, was proposed in 1956 by Rossi and Failla and it has been widely employed since then. In this work, data on the parameter α in TEGs based on methane (CH4 64.4%, CO2 32.4%, and N2 3.2%) and butanes isomers (C4H10 51.4%, CO2 42.3% e N2 6.3%) are presented for the first time in planar geometry in the gas density-normalized electric field (E/N) range between 100 290 Td (1 Td = 10-21 V.m2). The adopted method is based on the Pulsed Townsend Technique, where the first Townsend coefficient can be determined by comparing the electric current in the avalanche mode and the primary ionization current, produced by an nitrogen laser beam incidence in a metallic electrode (cathode) of a parallel plate chamber, which the anode is a resistive electrode (ρ=2×1010Ω.m). The experimental setup, previously operated only at atmospheric pressure, was adapted to work also at low pressure (120 hPa), in order to increase the investigated E/N range. The validation of both method and detection system modifications was made by employing three TEGs components, nitrogen, carbon dioxide and methane, whose transport parameters are extensively studied. The parameter in the methane-based TEG follows the behavior observed in pure methane. In the isobutane-based TEG, it is compatible with the first Townsend coefficient in carbon dioxide for E/N above 170 Td. The parameter in the n-butane-based TEG lies between the obtained values of in carbon dioxide and nitrogen. The experimental results, included in tabular form, agree with those from Magboltz 2 simulations within the experimental uncertainties.

The goal of this master's thesis was to develop a method for gas chromatography using the Controlled Evaporation Mixer (CEM) for gas mixture sampling. Gas mixture contained chemical substances formed during manufacturing of acrylic acid by two-step oxidation of propylene. The analyzed mixture composed of permanent gases, light hydrocarbons and compounds containing oxygen. During the method development several capillary columns with polar and nonpolar stationary phase were used. After selection of the most suitable column (SPB-1 Sulfur, Supelco, USA) the method was further optimized for the maximal possible separation efficiency. However, it was impossible to separate propane and propene on SPB-1 Sulfur column. These gases were possible to determine on TCD detector and separate on respective columns prior to the detector. For that purpose, the optimization of multiple-port valves switching inside the gas chromatograph was performed. The next step was calibration of gas chromatograph for a purpose of quantitative analysis of selected substances. The calibration solution containing solvent and an analyte was evaporated and diluted with nitrogen by CEM to obtain desired analyte concentration. Formaldehyde and propane had a very low response on detectors, acetaldehyde was undetectable in desired...