Thesis (Ph. D.)--University of Wyoming, 2006. / Title from PDF title page (viewed on Dec. 21, 2007). Includes bibliographical references (p. 199-216).

L'apparition des efflorescences sur une construction cimentaire est un phénomène naturel. Il s'agit de la formation d'un dépôt blanc de carbonate de calcium à la surface du matériau, suite à son exposition à des conditions climatiques particulières. Ce phénomène conduit uniquement à une détérioration esthétique qui peut néanmoins engendrer des problèmes économiques importants, car source de litiges client-fournisseur.<br />Cette étude se propose de mieux comprendre ce phénomène, afin de l'atténuer. Pour ce faire, un protocole d'apparition contrôlée des efflorescences primaires a été mis au point, et a été associé à une méthode de quantification des efflorescences.<br />L'atténuation des efflorescences par la substitution d'une partie du ciment par un produit pouzzolanique a été étudiée. L'utilisation de produits très différents a permis d'identifier, à travers de nombreuses caractérisations, les propriétés de ces pouzzolanes qui leur permettent d'atténuer le plus efficacement les efflorescences.

The fact that many of the giant hydrocarbon reservoirs, such as the Ghawar field in Saudi Arabia and the Grosmont formation in Alberta, are formed from carbonates make these rocks important research topics. Compressional and shear wave velocities (at 1 MHz) and the quasi-static strains of thirty seven carbonate rock samples were measured as functions of saturating fluid and confining pressure. Furthermore, P- and S-wave velocities of the saturated samples were measured at constant differential pressure of 15 MPa. The quasi-static strains of the samples under jacketed and unjacketed conditions were also simultaneously acquired. The lithology, mineralogy, porosity and pore type and size distribution of each sample were obtained using a combination of thinsection and scanning electron microscopy, helium porosimetry and mercury intrusion porosimetry. Due to the lack of closing microcracks and compliant pores in low porosity samples, the travel times show slight changes with the confining pressure. Whereas the high porosity samples show remarkable reduction of travel time with the increase of confining pressure in both P- and S-wave. The samples show no changes in travel time with increasing confining pressure under constant differential pressure, and this behavior is taken to be representative of full saturation of the sample and hence used as a measure of quality control. The comparisons of Biot, Gassmann, squirt-Biot and squirt-Gassmann model predictions with the measured water saturated velocities show that the squirt mechanism is not active on all the studied samples. Biot mechanism is likely to be the principle dispersion mechanism in these samples. For S-wave velocities, Gassmanns model consistently over-predict the saturated at low pressure and closely fit the measured velocities at high pressure, whereas, Biot model over-predicts the saturated velocities in most of the studied samples. The strains over the horizontal axis are higher than the vertical axis suggesting that the majority of the compliant pores and crack-like pores are oriented almost in direction parallel to the length of the sample. The static bulk modulus is always lower than dynamic one for all measured samples. The measured grain bulk modulus is reasonably close to the bulk modulus of the constituent mineral. / Geophysics

Since the industrial revolution, CO sub 2 has increased in the atmosphere and about 40% of the increase has been taken up by the ocean. An artifact of increasing CO sub 2 in the ocean is ocean acidification; it changes the calcium carbonate saturation state, which in turn alters the calcification rate of shelled organisms. The purpose of this dissertation is to estimate the changes in the carbonate system in the oceans, and whether these changes are due to natural (biological activity, chemical transformation or mixing of water masses) or anthropogenic (human activities) perturbations. The first hypothesis states that the presence of boric acid (B(OH) sub 3) in seawater changes the thermodynamic constants of CO sub 2, pK sup * sup 1 and pKsup * sup 2. Due to experimental limitations, the solubility of B(OH) sub 3 was determined in electrolyte solutions (LiCl, NaCl, KCl, RbCl and CsCl) instead of real or artificial seawater. The results can be used to estimate the B(OH) sub 3 activity coefficients gamma sub B and solubility [B] in natural mixed electrolyte solutions. The second hypothesis states that filtering seawater sampled in the open ocean is necessary for the determination of total alkalinity (TA). Measurement of 180 samples of surface, oxygen minimum, and deep waters in the Pacific and Indian oceans revealed that the at- sea measured TA of filtered and unfiltered samples were not statistically different. Finally, a synthesis and analysis of the carbonate parameters in the Atlantic and Indian oceans is undertaken. Results from repeat hydrographic cruises in these oceans were used for this task. Parameters TA and total CO sub 2 (TCO sub 2) are predicted using hydrographic properties and a multi-linear regression method to obtain a more homogenous dataset. The results of the predicted TA prove to be successful, which is not the case for TCO sub 2 at the surface of the ocean. Finally, it is found that the increase in anthropogenic CO sub 2 signal remineralization and mixing of water masses increase the acidity of the ocean at the surface and in deep waters, respectively. This causes the aragonite saturation horizon to shoal. Recommendations for further studies are provided in the "Summary and conclusion" chapter.

Fluid flow mechanisms in a large naturally fractured heterogeneous carbonate reservoir were investigated in this manuscript. A very thin layer with high permeability that produces the majority of production from specific wells and is deemed the Super-K Zone was investigated. It is known that these zones are connected to naturally occurring fractures. Fluid flow in naturally fractured reservoirs is a very difficult mechanism to understand. To accomplish this mission, the Super-K Zone and fractures were treated as two systems. Reservoir management practices and decisions should be very carefully reviewed and executed in this dual continuum reservoir based on the results of this work. Studying this dual media flow behavior is vital for better future completion strategies and for enhanced reservoir management decisions. The reservoir geology, Super-K identification and natural fractures literature were reviewed. To understand how fluid flows in such a dual continuum reservoir, a dual permeability simulation model has been studied. Some geological and production iv data were used; however, due to unavailability of some critical values of the natural fractures, the model was assumed hypothetical. A reasonable history match was achieved and was set as a basis of the reservoir model. Several sensitivity studies were run to understand fluid flow behavior and prediction runs were executed to help make completion recommendations for future wells based on the results obtained. Conclusions and recommended completions were highlighted at the end of this research. It was realized that the natural fractures are the main source of premature water breakthrough, and the Super-K acts as a secondary cause of water channeling to the wellbore.

This study deals with the thermodynamic analysis of a molten carbonate fuel cell (MCFC) hybrid system to determine its efficiencies, irreversibilities and performance.The analysis includes a performance investigation of a typical molten carbonate fuel cell stack, an industrial MCFC hybrid system, and an MCFC hybrid system deployed by Enbridge. A parametric study is performed to examine the effects of varying operating conditions on the performance of the system. Furthermore, thermodynamic irreversibilities in each component are determined and an optimization of the fuel cell is conducted. Finally, a simplified and novel method is used for the cost analysis of the Enbridge MCFC hybrid system.An exergy analysis of the hybrid MCFC systems demonstrates that overall efficiencies of up to 60 % are achievable. The maximum exergy destruction was found in components in which chemical reactions occur. In addition, the turboexpander is one of the major contributors to the overall exergy destruction of the system. The cost analysis of the Enbridge system illustrates that by merging the importance of “green” energy and rising costs of carbon offsets, this new technology could be a promising solution and substitute for future energy supply. / UOIT

Understanding the controls on fluid migration in reservoir rocks is becoming evermore important within the petroleum industry as significant hydrocarbon discoveries become less frequent and more emphasis is placed on enhanced oil recovery methods. To fully understand the factors controlling fluid migration in the subsurface, pore scale information is necessary. In this study, synchrotron-based X-ray computed microtomography (CMT) is being utilized to extract physically realistic images of carbonate rock cores for the evaluation of porosity and mineralogy in the Mississippian Midale beds of the Weyburn Oilfield in southeastern Saskatchewan. Non-destructive in-situ imaging by CMT is unique as it provides a detailed and novel approach for the description of pore space geometry, while preserving connectivity and spatial variation of pore-body and pore-throat sizes. Here, three-dimensional micron to sub-micron (0.3ìm-100ìm) resolution of CMT is coupled with, and compared against, conventional laboratory-based methods (liquid and gas permeametry, mercury injection porosimetry, electrical resistivity, backscattered electron (BSE) from electron probe micro-analysis (EPMA) and transmitted light microscopy). Petrophysical and mineralogical information obtained from both CMT and conventional methods will have direct implications for understanding the petrophysical mechanisms that control fluid movement in the subsurface of the Weyburn Oilfield.<p>At Weyburn, CO2 gas is being injected into producing horizons to enhance oil recovery and permanently sequester CO2 gas. Fundamental questions exist regarding: (1) The significance of pore geometry and connectivity to the movement of CO2 and other fluids in the subsurface, (2) the nature of the interactions between CO¬2 and pore lining minerals and their impact on petrophysical properties, and (3) the distribution and mineralogy of finely disseminated silicate and carbonate minerals adjacent to pore spaces as interaction among these phases and CO2 may result in permanent sequestration of CO2. <p>The two producing horizons within the Weyburn Reservoir, the Midale Marly and Midale Vuggy units, have variable porosities and permeabilities. Porosity in the Marly unit ranges from 16% to 38% while permeability ranges from 1mD to greater than 150 mD across the field. For the Vuggy unit, porosity ranges from 8% to 21% with permeability ranging from 0.3mD to 500mD. Using CMT, pore space is critically examined to highlight the controlling factors on permeability. Digital processing of CMT data indicates that pore space in the Marly unit is dominated by intercrystalline pores having diameters of approximately 4 ìm. From here, it is noted that the pore-throat radii are approximately ½ the radii of the pore-bodies, having profound implications to current oil recovery methods. Tortuosity values from CMT are also observed to have similar values in three orthogonal directions indicating an isotropic pore space distribution within the Marly unit. Alternatively, the Vuggy unit is found to possess greater pore-body and pore-throat sizes that are heterogeneous in distribution. Based on this, permeability in the Vuggy unit is strongly dependant on pore-length scales that vary drastically between localities.

Understanding the controls on fluid migration in reservoir rocks is becoming evermore important within the petroleum industry as significant hydrocarbon discoveries become less frequent and more emphasis is placed on enhanced oil recovery methods. To fully understand the factors controlling fluid migration in the subsurface, pore scale information is necessary. In this study, synchrotron-based X-ray computed microtomography (CMT) is being utilized to extract physically realistic images of carbonate rock cores for the evaluation of porosity and mineralogy in the Mississippian Midale beds of the Weyburn Oilfield in southeastern Saskatchewan. Non-destructive in-situ imaging by CMT is unique as it provides a detailed and novel approach for the description of pore space geometry, while preserving connectivity and spatial variation of pore-body and pore-throat sizes. Here, three-dimensional micron to sub-micron (0.3ìm-100ìm) resolution of CMT is coupled with, and compared against, conventional laboratory-based methods (liquid and gas permeametry, mercury injection porosimetry, electrical resistivity, backscattered electron (BSE) from electron probe micro-analysis (EPMA) and transmitted light microscopy). Petrophysical and mineralogical information obtained from both CMT and conventional methods will have direct implications for understanding the petrophysical mechanisms that control fluid movement in the subsurface of the Weyburn Oilfield.<p>At Weyburn, CO2 gas is being injected into producing horizons to enhance oil recovery and permanently sequester CO2 gas. Fundamental questions exist regarding: (1) The significance of pore geometry and connectivity to the movement of CO2 and other fluids in the subsurface, (2) the nature of the interactions between CO¬2 and pore lining minerals and their impact on petrophysical properties, and (3) the distribution and mineralogy of finely disseminated silicate and carbonate minerals adjacent to pore spaces as interaction among these phases and CO2 may result in permanent sequestration of CO2. <p>The two producing horizons within the Weyburn Reservoir, the Midale Marly and Midale Vuggy units, have variable porosities and permeabilities. Porosity in the Marly unit ranges from 16% to 38% while permeability ranges from 1mD to greater than 150 mD across the field. For the Vuggy unit, porosity ranges from 8% to 21% with permeability ranging from 0.3mD to 500mD. Using CMT, pore space is critically examined to highlight the controlling factors on permeability. Digital processing of CMT data indicates that pore space in the Marly unit is dominated by intercrystalline pores having diameters of approximately 4 ìm. From here, it is noted that the pore-throat radii are approximately ½ the radii of the pore-bodies, having profound implications to current oil recovery methods. Tortuosity values from CMT are also observed to have similar values in three orthogonal directions indicating an isotropic pore space distribution within the Marly unit. Alternatively, the Vuggy unit is found to possess greater pore-body and pore-throat sizes that are heterogeneous in distribution. Based on this, permeability in the Vuggy unit is strongly dependant on pore-length scales that vary drastically between localities.

The path of research in the pulp and paper industry is heading towards the elimination of the lime cycle, which requires large amounts of energy, and changing the conventional recovery boiler system to a gasification process that will reduce the possibility of smelt water explosions while meeting future environmental regulations. Research has been carried out on both gasification processes and on causticizing processes that can replace or complement the lime cycle, however very little research has gone into the actual kinetics of causticization using black liquor in gasification processes. This research project fills in some of the missing knowledge in the area of kinetics of autocausticization reactions, which entails the use of borates as the autocausticizing agent. A temperature dependent kinetic model coupled with a mass transfer coefficient has been developed and compared to experimental data.

The synthesis of precipitated calcium carbonate nanoparticles with the use of double water in oil emulsion has been developed. Restricting the mass of calcium ions present in the system makes it possible to predict particle size precipitated. A model was developed to calculate the concentration required to synthesize a desired particle size. This model took into account a coalescence factor. The coalescence factor is described at the probability of two emulsion droplets, with separate nucleation processes within them, colliding and forming one nucleation process. The Ca2+ ions diffused through the oil membrane into the emulsion droplets with (CaCO3)2- ions by concentration gradients and facilitated transport. The size and shape of precipitated calcium carbonate synthesized was confirmed using scanning electron microscope and light scattering. Particles ranging from 100 nm to 1200 nm have been synthesized using mass restriction. The effect of temperature on the crystalline structure of precipitated calcium carbonate was studied. This was done by x-ray diffraction, where it was found that calcite was the dominating crystalline structure.