A 16×16×5.6 in. scaled, three-dimensional, physical model of a quarter of a 9-spot pattern was constructed to study the application of two processes designed to improve the efficiency of steam injection. The first process to be tested is the use of propane as a steam additive with the purpose of increasing recovery and accelerating oil production. The second process involves the use of a novel production configuration that makes use of a vertical injector and a smart horizontal producer in an attempt to mitigate the effects of steam override. The experimental model was scaled using the conditions in the San Ardo field in California and crude oil from the same field was used for the tests. Superheated steam at 190 – 200ºC was injected at 48 cm3/min (cold water equivalent) while maintaining the flowing pressures in the production wells at 50 psig. Liquid samples from each producer in the model were collected and treated to break emulsion and analyzed to determine water and oil volumes. Two different production configurations were tested: (1) a vertical well system with a vertical injector and three vertical producers and (2) a vertical injector-smart horizontal well system that consisted of a vertical injector and a smart horizontal producer divided into three sections. Runs were conducted using pure steam injection and steam-propane injection in the two well configurations. Experimental results indicated the following. First, for the vertical configuration, the addition of propane accelerated oil production by 53% and increased ultimate recovery by an additional 7% of the original oil in place when compared to pure steam injection. Second, the implementation of the smart horizontal system increased ultimate oil recovery when compared to the recovery obtained by employing the conventional vertical well system (49% versus 42% of the OOIP).

The past decade has witnessed dramatic changes in the oil and gas industry with the drilling and production extending into progressively deeper waters and higher operating pressures, therefore making it essential to gain a better understanding of the behaviour of gas hydrate at high pressure conditions. New experimental 3-phase H−LW−V (Hydrate−Liquid Water−Vapour) equilibrium data for nitrogen and H−LW−V (Hydrate−Liquid Water−Vapour) and H−LW−LHC (Hydrate−Liquid Water−Liquid Hydrocarbon) data for ethane and propane simple clathrate hydrates were generated by a reliable fixed-volume, isochoric, step-heating technique. The accuracy and reliability of the experimental measurements are demonstrated by comparing measurements with reliable literature data from different researchers. Additional experimental data up to high pressure (200 MPa when available) for CH4, C2H6, C3H8, i-C4H10, N2, Ar, Kr, Xe, H2S, O2, CO and CO2 clathrates have been gathered from literature. The Valderrama modification of the Patel-Teja (VPT) equation of state combined with non-density-dependent (NDD) mixing rules is used to model the fluid phases with previously reported binary interaction parameters. The hydrate-forming conditions are modelled by the solid solution theory of van der Waals and Platteeuw. Langmuir constants have been calculated by both Kihara potential as well as direct techniques. Model predictions are validated against independent experimental data and a good agreement between predictions and experimental data is observed, supporting the reliability of the developed model.

An experimental investigation of condensation of hydrocarbons and hydrocarbon/refrigerant mixtures in horizontal tubes was conducted. Heat transfer coefficients and frictional pressure drops during condensation of a zeotropic binary mixture of R245fa and n-pentane in a 7.75 mm internal diameter round tube were measured across the entire vapor-liquid dome, for mass fluxes ranging from 150 to 600 kg m-2 s-1, and reduced pressures ranging from 0.06 to 0.23. Condensation experiments were conducted for the mixture, as well as its pure constituents over a similar range of conditions. In addition, condensing flow of the hydrocarbon propane was documented visually using high-speed video recordings. Results from these experiments were used to establish the two-phase flow regimes, void fractions, and liquid film thicknesses during condensation of propane flowing through horizontal tubes with internal diameters of 7 and 15 mm. These measurements were made over mass fluxes ranging from 75 to 450 kg m-2 s-1, operating pressures ranging from 952 to 1218 kPa, and vapor qualities ranging from 0.05 to 0.95. Liquid film thickness and void fraction data were subsequently be used to assist the development of heat transfer and pressure drop models. In particular, the heat transfer coefficients and pressure drops observed in the mixture were compared with the corresponding values for the pure constituents. Models for heat transfer and pressure drop in the pure components as well as the mixtures were developed based on the data from the present study. This work extends the available literature on two-phase flow regimes for air-water mixtures, steam, and refrigerants to include hydrocarbons. Additionally, the limited information on condensation in multi-constituent hydrocarbon-hydrocarbon and refrigerant-refrigerant mixtures was extended to include hydrocarbon-refrigerant mixtures. The findings of this study are expected to benefit applications such as refrigeration, low-grade heat-driven power generation, and the development of heat exchangers for the chemical and process industries.

This thesis investigates the laminar flame speed of C₁-C₃ alkanes and their binary mixtures at conditions of interest in natural gas based gas turbines viz. high temperature, pressure and dilution. Laminar flame speed has been found useful not only for validating chemical kinetics mechanisms but also for developing empirical scaling laws for practical combustion systems. The thesis addresses the lack of laminar flame speed data of C₁-C₃ alkanes at preheat (300-650 K), pressure (1-10 atm) and significant oxidizer dilution (15-21 vol% O₂). Over 400 measurements are reported over a wide range of conditions along with comparison to predictions from leading chemical mechanisms. Unstretched flame speed measurements were performed using a modified Bunsen flame technique based on reaction zone area from chemiluminescence imaging, whereas the strain sensitivity measurements were performed using a bluff-body stabilized stagnation flame with high resolution PIV. These measurements are used to: (i) discern the uncertainties associated with the measurements, (ii) understand the effect of fuel mixture and vitiation on flame speed, and (iii) validate the performance of the leading chemical kinetics mechanisms. Extensive testing shows the unstretched flame speed measurements from the modified Bunsen technique are reasonably accurate. Vitiation studies for methane and propane flames at high preheat show the reduction in flame speed results primarily from the thermal effect of the diluent and that the relative change in flame speed from the undiluted mixture is well correlated to the fractional change in the adiabatic flame temperature over a range of conditions. Significant difference in the measured and predicted flame speeds were observed for rich, atmospheric pressure, propane and lean, high pressure, methane/ethane mixtures with dilution. This highlights possible avenues for improvements in the chemical kinetics mechanisms. Systematic errors were also identified in the Bunsen flame measurements at certain conditions, such as for rich flames with dilution, indicating a need for better understanding of the Bunsen flame technique at these conditions. The difference in the measured and predicted flame speed does not show any clear correlation with the flame height or the strain sensitivity of the mixture. Finally previously proposed mixing rules for estimating flame speed of fuel mixtures from pure fuel components are shown to be reasonably accurate over a range of pressure, reactant temperature and dilution conditions.

Olefin/paraffin separation is a large potential market for membrane applications. Carbon molecular sieve membranes (CMS) are promising for this application due to the intrinsically high separation performance and the viability for practical scale-up. Intrinsically high separation performance of CMS membranes for olefin/paraffin separations was demonstrated. The translation of intrinsic CMS transport properties into the hollow fiber configuration is considered in detail. Substructure collapse of asymmetric hollow fibers was found during Matrimidﾮ CMS hollow fiber formation. To overcome the permeance loss due to the increased separation layer thickness, 6FDA-DAM and 6FDA/BPDA-DAM polyimides with higher rigidity were employed as alternative precursors, and significant improvement has been achieved. Besides the macroscopic morphology control of asymmetric hollow fibers, the micro-structure was tuned by optimizing pyrolysis temperature protocol and pyrolysis atmosphere. In addition, unexpected physical aging was observed in CMS membranes, which is analogous to the aging phenomenon in glassy polymers. For performance evaluation, multiple "proof-of-concept" tests validated the viability of CMS membranes under realistic conditions. The scope of this work was expanded from binary ethylene/ethane and propylene/propane separations for the debottlenecking purpose to mixed carbon number hydrocarbon processing. CMS membranes were found to be olefins-selective over corresponding paraffins; moreover, CMS membranes are able to effectively fractionate the complex cracked gas stream in a preferable way. Reconfiguration of the hydrocarbon processing in ethylene plants is possible based on the unique CMS membranes.

La recapture du dioxyde de carbone est aujourd'hui un défi mondial majeur pour minimiser son impact sur le réchauffement climatique. La capture par adsorption physique pourrait être un procédé viable si le bon adsorbant est trouvé, mais cette capture dans les fumées de combustion impose des contraintes comme les faibles concentrations en CO2 (< 20%), la faible pression totale (1 bar) et la présence éventuelle d'eau. Cette thèse avait pour but l'évaluation de l'impact de la vapeur d'eau lors d'adsorption de CO2 sur des matériaux poreux hybrides, les Metal Organic Frameworks. En premier lieu, ce travail a consisté à étudier l'adsorption de CO2 et de vapeur d'eau séparément sur un grand nombre de MOFs. Une sélection de MOFs, prenant en compte des critères de stabilité et de capacité d'adsorption, a ensuite été effectuée afin d'évaluer l'effet de la vapeur d'eau lors d'adsorption du CO2 sur ces derniers. Un dispositif expérimental a été développé où sont obtenues simultanément des enthalpies d'adsorption et des courbes de percées. Dans nos travaux, nous avons pu établir trois types de comportements en présence de vapeur d'eau :- Négatif/Préjudiciable sur l'adsorption du CO2 : dû à un empoisonnement ou à l'instabilité des matériaux en présence d'eau (cas du HKUST-1). - Neutre : quantités de CO2 captées constantes (cas de l'UiO-66).- Positif : amélioration (cas du MIL-101(Cr)) ou remarquable accroissement d'adsorption de CO2 suite à la pré-adsorption de vapeur d'eau (MIL-100(Fe) & MIL-127(Fe)).Ce travail s'inscrit dans le cadre du 7ieme projet européen Macademia "MOFs as Adsorbents and Catalysts: Discovery and Engineering of Materials for Industrial Applications". / The elimination of carbon dioxide has become a worldwide challenge to minimize its impact on global warming. Capture using physical adsorption is viable as long as the right adsorbent is found. CO2 capture from flue gases poses a number of problems in terms of low CO2 concentration (below 20%), low total pressure, and the eventual presence of water. This study focuses on the impact of water vapour during CO2 adsorption on different porous materials. An experimental device has been developed to assess the impact of water vapour during CO2 adsorption: both the heats of adsorption and the breakthrough curves were obtained. The uptakes of CO2 at 0.2 bar have been studied in porous materials after having been pre-equilibrated under different relative humidity's (3 and 40%). The enthalpies allow a better understanding of the phenomena involved. Several MOFs, like HKUST-1(Cu), UiO-66(Zr), MIL-100(Fe), MIL-101(Cr), MIL-127(Fe) have been compared to a zeolite NaX and an activated carbon Takeda-5A.Three different behaviours are shown: - Where water has a negative impact on CO2 adsorption. This can be due to poisoning or the poor stability of the materials like HKUST-1. - Where water seems to have little effect on CO2 adsorption like case of UiO66. - Where water has a positive effect on CO2 uptake. Slight improvement for MIL-101(Cr) and remarkable enhancement of CO2 uptake through pre-adsorption of water vapor has been highlighted here in two cases: the mesoporous MIL-100(Fe) and the bifunctional MIL-127(Fe).This work is part of the European project FP7 Macademia "MOFs as Adsorbents and Catalysts: Discovery and Engineering of Materials for Industrial Applications".

Stárnutí teplonosných kapalin na organické bázi je dlouhodobým problémem, který je znám od počátku jejich používání. První část této disertační práce je tak věnována případové studii funkčního experimentálního systému, který byl jako nový naplněn teplonosnou kapalinou na bázi propan-1,2-diol a pozorován po období 7 let. Pro analýzu stárnutí kapaliny v tomto systému byly sledovány základní provozní vlastnosti kapaliny jako jsou hustota, viskozita, teplota tuhnutí, pH a obsah kovů. Skrze tyto vlastnosti tak bylo sledováno stárnutí kapaliny nepřímo. Přímé sledování stárnutí bylo posléze provedeno analýzou degradačních produktů, jako jsou organické kyseliny a změny ve složení směsi pomocí izotachoforézy a hmotnostní spektrometrie. Pro srovnání byly taktéž analyzovány vybrané vzorky z několik dalších systémů plněných identickou kapalinou s prokazatelně pokročilou formou degradace. V druhé části práce jsou představeny základní fyzikálně-chemické vlastnosti směsí propan-1,3-diolu s vodou a jejich analytické hodnocení a matematické modelování pro universální použití jakožto nového základu pro nemrznoucí teplonosné kapaliny. Na základě dostupných informací je pak hodnocena použitelnost této směsi. Výhoda propan-1,3-diolu je spatřována především ve výrobě z obnovitelných zdrojů a v některých fyzikálních a chemických vlastnostech, které dle dosavadních poznatků předčívají doposud používané glykolové směsi.

This diploma thesis deals with design of air-water heat pump which uses natural refrigerant, propane. In the thesis there are mentioned various types of devices using the source of low-potential heat for heating. The main part of the thesis is the design of the heat pump cooling circuit. In this section, individual components are designed, the calculation and comparison of the heating factor for different operating parameters is performed. Finally, the construction of the coolant circuit and the air exchanger is designed.

This thesis is concerned with the design of a heat pump that does not use a ventilator during operation. In the introductory chapter, the functioning and the basic components of this device and other types of heat pumps are described. Properties of some commonly used refrigerants and oils as well as their classifications are stated. Due to the absence of a ventilator, a special heat exchanger was designed to achieve the required heat power. The choice of components in this refrigeration system takes into consideration the efficiency and functionality of the device.

In heterogeneous catalysis, promoting the activity of the catalytic metals is long known as an important method to make a process more efficient and viable. Noble metals have been promoted classically by a chemical coverage of an ionic solution on the surface of the catalyst or using inert support, e.g., silica or alumina, allowing an increase of the dispersion of the catalyst. Therefore, new methods of promotion needed to be better explored to improve the efficiency of metal and metal oxide catalysts. One way of enhancing the catalyst’s activity is to disperse the noble metal at the nanoscale using an active type of support that is ion-conducting. Not only lattice ions can be exchanged with the surface of the nanoparticles but it can also engage in the oxidation reaction on the surface, resulting in what is known as metal-support interaction (MSI). Another method of improving the catalytic activity is to polarize the catalyst, allowing ions to migrate from a solid electrolyte to the gas-exposed surface, in a phenomenon known as electrochemical promotion of catalysis (EPOC). The change in the ions concentration on the surface would change the adsorption energy of the gaseous reactants and enhance or supress the catalytic rate. In this thesis, the effect of supporting nanoparticles of noble and non-noble metal (oxides) (Pt, Ru, Ir, Ni) was studied for the case of ionic and ionic-electronic conducting supports (CeO2, TiO2, YSZ). The enhancement in their catalytic rate was found and correlated to an electrochemical property, the exchange current density. Then, using isotopically-labeled oxygen, the oxygen exchange ability of the conductive oxides was evaluated when supporting Ir and Ru nanoparticles and correlated with the results from C3H8 isotopic oxidation reaction, which showed the extent of involvement of oxygen from the support as carried by the isotopically-labeled CO2 produced. Following this, electrochemical promotion of catalysis experiments were performed for different reactant/catalyst systems (C2H4 - Pt, Ru; C3H8 - Pt; CH4 - Pd, Ni9Pd). In the first system, the main outcome was the functional equivalence found for the MSI and EPOC effect in promoting the catalysts as experiments were performed at different temperatures, reactants partial pressures and polarization values. In the case of C3H8/Pt, the novel dispersion of Pt on an intermediate supporting layer (LSM/GDC) was found as a feasible method to obtain long stability of the catalyst while electrochemically promoting the rate of reaction. For CH4 oxidation, the polarization of the Pd nanoparticles showed continuous oxidation of the bulk of the catalyst resulting in a continuous increase of the catalytic rate. The Ni9Pd synthesized in a way to form a core/double-shell layer of Ni/Pd resulted in an enhanced catalytic rate and enhanced stability compared to stand-alone Pd. And lastly, to comprehend the ions’ effect in the electrochemical promotion and the non-Faradaic nature of the phenomena, density-functional theory (DFT) modeling was used to demonstrate the increase of the heat of adsorption of reactants depending on their electronegative/positive nature.