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Utilisation of natural gas (mainly methane, CH[subscript]4), a clean and abundant resource, is of great importance. Conventional method, steam reforming, though still dominant, requires a considerately high capital investment and an intensive energy input. Reforming natural gas by partial oxidation, potentially one of the most attractive alternatives, has been investigated vigorously for decades, mainly focusing on looking for suitable catalyst and understanding of the mechanisms of methane partial oxidation. This work focuses on the feasibility of methane partial oxidation reforming from gas phase reaction under fuel-rich conditions.Firstly, a detailed thermodynamic analysis has been conducted, which covers a broad range of operation conditions of temperature up to 2073 K, pressure up to 100 atm and initial O(subscript)2/CH(subscript)4 ratio of 0 to 2.5. It has been found that high syn-gas (H(subscript)2 and CO) yields can be achieved when the temperature is above 1073 K and the initial O(subscript)2/CH(subscript)4 ratio close to 0.5. High pressure is not favoured. However, high temperatures can suppress the effect of high pressures.Carbon deposition, a crucially important factor in methane partial oxidation, is mainly examined by means of thermodynamic analysis. Solid carbon was identified the major carbon deposition form, which could severely happen if the initial O(subscript)2/CH(subscript)4 ratio is less than 0.5. This feature was also indirectly proven during the experimental tests.Secondly, a series of CHEMKIN simulations were performed using various CH(subscript)4 oxidation reaction mechanisms. The general trend of the CH(subscript)4 partial oxidation reforming was revealed by simulations using the GRI, NIST and Konnov mechanisms. A new concept characterising CH(subscript)4 partial oxidation was conceived. i.e., a fast oxidation zone and a slow conversion ++ / zone, the reaction is under chemical control that requests high operating temperatures, and the reaction can be accelerated by using relatively high initial 0(subscript)2/CH(subscript)4 ratios.Experimental tests were performed to verify the findings obtained in thermodynamic and kinetic studies, and to identify appropriate reaction schemes for further analysis. Prediction from the NIST mechanisms has shown to be in good agreement with experimental observation when the temperature is less than 1273 K. For higher temperatures the NIST under-predicts the H(subscript)2 yield caused by the lack of carbon formation mechanisms. Two other mechanisms (Konnov and GRI) predicted similar trends but the reaction predicted commenced earlier. Therefore, the NIST was identified to be the best.NO(subscript)x catalytic effect on CH4 oxidation at fuel-rich conditions was confirmed experimentally. However, this effect only exists where the oxygen is available. Therefore, employing NO(subscript)x cannot help the CH(subscript)4 partial oxidation in the second reaction zone. Solely relying on NO(subscript)x to speed up the process or lower the operating temperature is not possible. However, employing NO(subscript)x to initiate the reaction at lower temperatures is viable. The possibility of taking the advantage of NOx catalytic effect for direct synthesis of CH3OH (methanol) has been shown feasible and, more attractively, the operating temperatures required are much lower than that for syn-gas production.Among three reaction schemes, i.e., the Glarborg, Bromly and Dagaut, which are able to account for the NO(subscript)x catalytic effect, the Glarborg mechanism proved to be the best in reproducing experimental measurements for syn-gas production tests. However, none available mechanisms can predict similar magnitude of the direct synthesis of CH(subscript)3OH. To understand the mechanisms ++ / of NO(subscript)x catalytic effect, a reaction scheme, Partial Oxidation Mechanisms (POM), has been composed successfully adding five additional reactions into the NIST. The POM can reveal the major catalytic reaction pathways and it is suitable for CH(subscript)4 partial oxidations both with and without NO(subscript)x addition.Finally, a series of simulations were conducted to conservatively estimate the feasibility of CH(subscript)4 partial oxidation using POM. High syn-gas yield is achievable within a reasonable residence time using adiabatic reactor. The variables significantly affecting the syn-gas yield, are preheating temperature, operating pressure, inert dilution, initial ratio of O(subscript)2/CH(subscript)4 and residence time. If NO(subscript)x is used as a catalyst, the preheating temperature can be further reduced.

The first part of this two-part thesis examines the reverse-flow operation of auto-thermal methane reforming in a microreactor. A theoretical study is undertaken to explain the physical origins of the experimentally observed improvements in the performance of the reverse-flow operation compared to the unidirectional operation. First, a scaling analysis is presented to understand the effect of various time scales existing within the microreactor, and to obtain guidelines for the optimal reverse-flow operation. Then, the effect of kinetic parameters, transport properties, reactor design and operating conditions on the reactor operation is parametrically studied through numerical simulations. The reverse-flow operation is shown to be more robust than the unidirectional operation with respect to both optimal operating conditions as well as variations in hydrogen throughput requirements. A rational scheme for improved catalyst placement in the microreactor, which exploits the spatial temperature profiles in the reactor, is also presented. Finally, a design modification of the microreactor called "opposed-flow" reactor, which retains the performance benefits of the reverse-flow operation without requiring the input / output port switching, is suggested. In the second part of this thesis, a novel simulation-based Approximate Dynamic Programming (ADP) framework is presented for optimal control of switching between multiple metabolic states in a microbial bioreactor. The cybernetic modeling framework is used to capture these cellular metabolic switches. Model Predictive Control, one of the most popular advanced control methods, is able to drive the reactor to the desired steady state. However, the nonlinearity and switching nature of the system cause computational and performance problems with MPC. The proposed ADP has an advantage over MPC, as the closed-loop optimal policy is computed offline in the form of so-called value or cost-to-go function. Through the use of an approximation of the value function, the infinite horizon problem is converted into an equivalent single-stage problem, which can be solved online. Various issues in implementation of ADP are also addressed.

State of the art aircraft afterburners employ spray bars to inject fuel and flameholders to stabilize the combustion process. Such afterburner designs significantly increase the length (and thus weight), pressure losses, and observability of the engine. This thesis presents a feasibility study of a compact prime and trigger (PAT) afterburner concept that eliminates the fuel spray bars and flameholders and, thus, eliminates the above-mentioned problems. In this concept, afterburner fuel is injected just upstream or in between the turbine stages. Downstream of the turbine stages, a low power pilot, or trigger , can be used to control the combustion process. The envisioned trigger for the PAT concept is a jet of product gas from ultra-rich hydrocarbon/air combustion that is injected through the afterburner liner. This partial oxidation (POx) gas, which consists mostly of H2, CO, and diluents, rapidly produces radicals and heat that accelerate the autoignition of the primed mixture and, thus, provide an anchor point for the afterburner combustion process. The objective of this research was to demonstrate the feasibility of the PAT concept by showing that (1) combustion of fuel injected within or upstream of turbine stages can occur only downstream of the turbine stages, and (2) the combustion zone is compact, stable and efficient. This was accomplished using two experimental facilities, a developed theoretical model, and Chemkin simulations. The first facility, termed the Afterburner Facility (AF), simulated the bulk flow temperature, velocity and O2 content through a turbojet combustor, turbine stage and afterburner. The second facility, termed the Propane Autoignition Combustor (PAC), was essentially a scaled-down, simplified version of the AF. The developed model was used to predict and interpret the AF results and to study the feasibility of the PAT concept at pressures outside the AF operating range. Finally, the Chemkin simulations were used to study the effect of several POx gas compositions on the afterburner combustion process.

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<p> The homogeneous partial oxidation of ortho-xylene vapour by air in a 316 s.s. flow reactor was studied in this work, which was conducted in connection with, and preceding an investigation of the kinetics of catalytic vapour-phase partial oxidation of a-xylene. The main purpose of the present work was to make an exploratory study of the contribution of the homogeneous reaction, if any, in as much as it would affect the catalytic oxidation to be studied on the same experimental set-up. This would permit the correction for the rate of homogeneous reaction during the catalytic reaction under a range of experimental conditions, or, reveal conditions under which the catalytic reaction could be conducted with minimum contribution by the homogeneous reaction. </p> <p> The three variables studied and the range of conditions for each are as follows : 1. Air: o-xylene molar ratio: ,124 to J78 2. Residence time: 0.443 sec. to 0.539 sec. 3. Temperature: 430° C to 490° c </p> <p>The reaction product stream was analyzed mainly by Gas Chromatography, both qualitatively and quantitatively. Qualitative analyses of liquid samples of the reactor condensate were also conducted using a Nuclear Magnetic Resonance Spectrometer, Mass Spectrometer, Infrared Spectrophotometer and also by conventional chemical techniques. </p> <p> Product analysis indicated a-xylene oxide as the reaction product at the lmv conversions studied. An empirical correlation obtained by statistical analysis of the experimental data, relating the conversions obtained and the variables studied, has been proposed to calculate the extent of the homogeneous reaction under the conditions of a catalytic reaction study. The results obtained in this work are consistent with the suggested kinetics and mechanism for this reaction. </p> / Thesis / Master of Engineering (MEngr)

<p> The partial, catalytic oxidation of ortho-xylene was investigated in a transported-bed reactor in which the vanadium pentoxide catalyst in the form of extremely small particles (average particle size of 45 microns) was conveyed upward by the reacting gases.</p> <p> The reaction was studied at a contact time of about 0.2 seconds, at air-to-o-xylene molar ratios of 42 to 86, at catalyst-to-gas ratios of 8 to 23, and at a reaction temperature of 750°F (400°C).</p> <p> Reaction products were analyzed by Gas Chromatography and Nuclear Magnetic Resonance Spectroscopy.</p> <p> Product analysis indicated a high yield of o-tolualdehyde, small yields of other oxidation products, but only trace amounts of phthalic anhydride. These results are consistent with proposed mechanisms for this reaction.</p> / Thesis / Master of Engineering (MEngr)

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Doctor of Philosophy / Department of Chemical Engineering / Keith L. Hohn / Catalytic partial oxidation (CPO) has received considerable interest recently both as a way to utilize remote natural gas resources and to provide H[subscript]2 for a fuel cell. Studies on the reactions at lower temperatures and transient conditions were performed, which can provide insights on the mechanism of CPO at high reactions, particularly on the role of the chemical and physical state of the noble metal catalyst. In this work, ignition of methane CPO on Pt/Al[subscript]2O[subscript]3 and Rh/Al[subscript]2O[subscript]3 catalysts and methanol CPO on Pt/Al[subscript]2O[subscript]3 catalysts were studied using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The ignition mechanism study of CH4 on Pt/Al[subscript]2O[subscript]3 showed that oxygen mainly covers the surface until ignition. Competition between the two reactants is assumed. The heat of adsorption of oxygen is a key factor for ignition of the methane partial oxidation reaction on Pt/Al[subscript]2O[subscript]3. The ignition mechanism on Rh/Al[subscript]2O[subscript]3 was found to be different from Pt/Al[subscript]2O[subscript]3. The oxidation state of the catalyst changed significantly as the temperature was raised towards the ignition. An oxidized rhodium state, Rh[superscript]n+, progressively formed as the temperature was increased while Rh[superscript]0 decreased. In addition, a greater amount of Rh[supercript]n+ was found when the oxygen concentration in the feed was higher. From these results, it is hypothesized that ignition of methane CPO on Rh/Al[subscript]2O[subscript]3 is related to the accumulation of the Rh[superscript]n+ state. Dissociation adsorption of methanol occurs on both Al2O3 and Pt/Al[subscript]2O[subscript]3. It is suggested that formate was one of the important intermediates in the reaction pathway. Oxygen species play a key role in the formation of formate on the catalysts, and it also affects the product composition. Formate mainly decomposed into CO, which is the dominant source for CO[subscript]2 production in the reactions at higher temperatures.

Perovskita de LaFeO3 sintetizadas pelo método de Pechini foram avaliadas como catalisadores para a reação de oxidação parcial do metano. Foi impregnado níquel por via úmida como fase ativa em concentrações de 15 e 30 %, sobre as perovskitas, 15NLF e 30NLF, respectivamente, e o seu efeito foi avaliado para a mesma reação. Foi realizado análises termogravimétricas (TGA/DTGA) nos precursores da perovskitas, constatando a sua formação a 650 °C. A análise de microscopia de varredura (MEV) foi realizada nas amostras da perovskita pura, sendo que em uma delas foi realizada um banho de ultrassom para diminuir o tamanho de suas partículas e avaliar este efeito na reação de POM. Análises de difração de raio X (DRX) mostraram que todas as amostras apresentam as mesmas propriedades cristalográficas, sendo que, nas amostras contendo níquel, o metal apresentou-se na forma de NiO. O tamanho dos cristais, cálculado através da equação de Scherer, foi na ordem de 20 nm. Este resultado apontou que o níquel impregnado não participa da estrutura perovskita, mas sim está sobreposto a esta. Através da microscopia eletrônica de transmissão (TEM) foi possível visualizar a dispersão da fase ativa na superfície óxida e tamanhos de partículas na ordem de 20 nm. A redução a temperatura programada (TPR) apresentou as temperaturas de redução de espécies níquel e de ferro, presente na perovskita, e permitiu compreender a atuação das espécies Ni+2 e Fe0 na formação de H2 e CO. Os testes catalíticos foram realizados a 700ºC e 750°C, a pressão atmosférica, para uma vazão de alimentação de 200 cm3.min-1. Os testes cataliticos mostraram que a conversão de H2 dobrou para perovskita Ni/LaFeO3 em relação a LaFeO3. O catalisador 15NLF apresentou melhor estabilidade que o catalisador 30NLF para a reação. / LaFeO3 perovskite synthesized by the Pechini method were evaluated for the partial oxidation reaction of methane. Nickel was impregnated as the active phase in concentrations of 15 and 30%, on perovskites, 15NLF and 30NLF, respectively, and its effect was evaluated for the same reaction. Thermogravimetric analyzes (TGA / DTGA) were carried out on the perovskite precursors, confirming their formation at 650 °C. Scanning microscopy (SEM) was performed on pure perovskite samples, in one of them an ultrasonic bath was performed to reduce the size of its particles and to evaluate this effect in the POM reaction. X-ray diffraction (XRD) analyzes showed that all samples had the same crystallographic properties, and in the samples containing nickel, the metal was present as NiO. The size of the crystals, calculated through the Scherer equation, was in the order of 20 nm. This result pointed out that the impregnated nickel does not participate in the perovskite structure. Through transmission electron microscopy (TEM) it was possible to visualize the dispersion of the active phase on the oxide surface and particle sizes in the order of 20 nm. The programmed temperature reduction (TPR) showed the iron and nickel species reduction temperatures present in the perovskite, and allowed to understand the Ni+ 2 and Fe0 species in the H2 and CO formation. The catalytic tests were performed at 700 °C and 750 °C at atmospheric pressure for a flow rate of 200 cm3.min-1. The catalytic tests showed that the conversion of H2 doubled to perovskite Ni/LaFeO3 in relation to LaFeO3. 15NLF catalyst presented better stability than the 30NLF catalyst for the reaction.