Master of Science

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Disertation thesis deals with development of hot dolomite filter for the purposes of cleaning of gas polluted by biomass and waste gasification with ash and tar as well as sulphur and chlorine compounds as main pollutants. Gas is then cleaned so that it can be utilized in cogeneration units with combustion engines. This supports advancement of gasification techniques using decentralized power and heat generation especially for design of small scale units. Concrete aims of this thesis are stated in chapter 2. Experimental fluid gasification stend Biofluid 100 has been in operations at Brno University of Technology (BUT) since 2000 and it helps research of biomass and waste gasification. Development of the filter initially utilized needs and experience with the utility during cooperation of BUT and ATEKO Hradec Králové. Water scrubber was used for gas cleaning, however, this method proved to be ineffective. Alternative solutions were considered. Based on literature search, natural catalysts with limestone basis were opted. First part of the thesis presents literature search of this issue. Historic development and description of gasification process are briefly discussed as well as elementary classification of gasification generators. This part is followed by chapters dealing with gas pollutants. Tar – the most significant pollutant – is discussed in a separate chapter which presents tar formation, its classification, characteristics and methods for its removal. Brief summary of requirements on gas properties with respect to its utilization in various applications (especially in cogeneration units) follows. Other part of the literature search part focuses on methods of removal of tar from gas, especially on catalyst methods. Dolomite characteristics, description of dolomite calcination as well as simplified kinetic model of tar cracking using dolomite are presented. Based on literature search, laboratory and verification equipment was designed for the purposes of dolomite properties testing. Equipment description as well as description of experimental stend Biofluid 100 where the experimental tests were carried out can be found in introduction of the experimental part. This is followed by a complete description of pilot equipment design of hot dolomite filter with general description of experimental work process, brief characteristics of the fuel and catalytic material used. Final part of the work comprises of experiment results that were carried out on the pilot equipment. Focus is on efficiency of tar removal in connection with operation temperature, amount of catalytist and material used. Influence of these parameters on gas composition and energy intensity of the whole process under these conditions is mentioned as well. Possibility of autonomous unit operations without electricity heating is briefly outlined. Summary of the most significant results including the potential of future hot dolomite filter development is stated the final part of the thesis.

Made available in DSpace on 2014-12-17T15:42:08Z (GMT). No. of bitstreams: 1 FranciscoCBS_DISSERT.pdf: 2327685 bytes, checksum: 7ea91ee570c997cb17e15b80242eeaa3 (MD5) Previous issue date: 2013-07-30 / The present work was to carry out a study on the adsorption of hydrogen sulfide (H2S) in arrays synthesized from a commercial clay mineral formed by a mixture of dolomite and quartz. To produce the ion exchange matrix were made using aqueous solutions of salts of cobalt II chloride hexahydrate (CoCl2.6H2O) II cadmium nitrate tetrahydrate (Cd (NO3)2.4H2O) I mercuric chloride (HgCl) nitrate and chromium III pentahydrate (Cr (NO3)3.5H2O). The arrays were subjected to hydrogen sulphide gas passage for one hour. To check the amount of gas adsorbed was used gravimetric process. The best result was in the adsorption matrix doped with cadmium and the solution retained for a longer time than the largest amount of H2S was the cobalt matrix. The matrix unmodified exhibited poor adsorption capacity. The characterization of the matrices were used XRD, XRF and IV. Mother with cadmium showed a high capacity in ion exchange, because the percentage of cadmium increased from 0% to 81.38% by replacing atoms of calcium and silicon which increased from 96.54% to 17.56% and 15, 72% to 0.32%, respectively, but also the best performance in adsorption of H2S adsorbing 11.89507 mg per gram of matrix / O presente trabalho teve como finalidade realizar um estudo sobre a capacidade de adsor??o de g?s sulf?drico(H2S) em matrizes sintetizadas a partir de um argilomineral comercial formado por uma mistura de dolomita e quartzo. Para produzir as matrizes foram feitas trocas i?nicas utilizando as solu??es aquosas dos sais: cloreto de cobalto II hexaidratado(CoCl2.6H2O), nitrato de c?dmio II tetraidratado (Cd(NO3)2.4H2O), cloreto de merc?rio I (HgCl) e nitrato de cromo III pentaidratado(Cr(NO3)3.5H2O). As matrizes foram submetidas a passagem de g?s sulf?drico durante uma hora. Para verificar a quantidade de g?s adsorvido foi utilizado o processo de gravimetria. O melhor resultado na adsor??o foi com a matriz dopada com a solu??o de c?dmio e a que reteve por mais tempo a maior quantidade de H2S, foi a matriz com cobalto. A matriz n?o modificada apresentou uma fraca capacidade de adsor??o. Na caracteriza??o das matrizes foram utilizadas an?lises de DRX, FRX e IV. A matriz com c?dmio apresentou uma alta capacidade na troca i?nica, pois a porcentagem de c?dmio passou de 0% para 81,38%, substituindo ?tomos de c?lcio e de sil?cio que passaram de 96,54% para 17,56% e de 15,72% para 0,32%, respectivamente, como tamb?m, o melhor desempenho na adsor??o, adsorvendo 11,89507mg de H2S por grama de matriz

In this thesis a study of the factors affecting virus and virus-sized particle transport in discrete fractured dolomite rocks is presented. Physical and chemical characteristics of two fractured rocks were determined, including fracture aperture distribution, rock matrix porosity, mineral composition, and surface charge. Hydraulic and transport tests were conducted in the fractures with a conservative solute (bromide) and carboxylate-modified latex (CML) microspheres of three sizes (20, 200, and 500 nm in diameter). The earlier arrival of larger microspheres as compared to bromide indicated the effects of pore-size exclusion and preferential flow paths in the fractures. The tailing of the bromide and the smaller microsphere (20 nm) in the breakthrough curves (BTC) indicated the diffusive mass transfer between the mobile water (flowing) and immobile water (stagnant water in the low aperture areas and porous rock matrix). The effects of ionic strength and cation type on the transport of viruses (bacteriophages MS2 and PR772) and virus-sized microspheres (20 and 200 nm) were determined from the transport tests in a fracture at three levels of ionic strength (3, 5, and 12 mM) and composition (containing Na+ and/or Ca2+ ions). Retention of the microspheres and bacteriophages increased with increasing ionic strength. The addition of divalent ions (Ca2+) influenced the retention to a greater extent than monovalent ions (Na+). The effects of the aperture distribution variability, matrix diffusion, and specific discharge on the solute and microsphere transport were determined from the transport tests conducted in two fractures. The higher variability in the aperture distribution contributed to higher solute dispersion, and flow channeling as evident from the breakthrough curves for individual spatially distributed outlets. A three-dimensional model simulation of the bromide transport with varying matrix porosity identified that the porous matrix influenced the solute transport. In the transport tests, retention of the microspheres decreased with increasing specific discharge in both fractures. The results of this research have helped in identifying the important factors and their effects on solute, virus, and virus-sized colloid transport in fractured dolomite rocks, which can be useful in determining the risk of pathogen contamination of water supplies in fractured dolomite rock aquifers.

Well stimulation is the treatment remedy when oil/gas productivity decreases to unacceptable economical limits. Well stimulation can be carried out through either "Matrix Acidizing" or fracturing with both "Hydraulic Fracturing" and "Acid Fracturing" techniques. "Matrix Acidizing" and "Acid Fracturing" applications involve injecting an acid to react with the formation and dissolve some of the minerals present and recover or increase the permeability. The permeability enhancement is achieved by creating conductive channels "wormholes" in case of "Matrix Acidizing" or creating uneven etching pattern in case of "Acid Fracturing" treatments. In both cases, and to design a treatment successfully, it is necessary to determine the distance that the live acid will be able to penetrate inside the formation, which in turn, determines the volume of the acid needed to carry out the treatment. This distance can be obtained through lab experiments, if formation cores are available, or estimated by modeling the treatment. The successful model will depend on several chemical and physical processes that take place including: the acid transport to the surface of the rock, the speed of the reaction of the acid with the rock, which is often referred to as "Reaction Rate", and the acid leak-off. The parameters describing these processes such as acid diffusion coefficient and reaction kinetics have to be determined experimentally to ensure accurate and reliable modeling. Hydrochloric acid and simple organic acids such as acetic and citric acids have been used extensively for stimulation treatments. The diffusion and reaction kinetics of these acids, in a straight form, were investigated thoroughly in literature. However, solely these acids are used in a simple form in the field. Acid systems such as gelled, crosslinked gelled, surfactant-based, foam-based, or emulsified acids are used to either retard the reaction rate or to enhance acid diversion. Literature review shows that additional work is needed to understand the reaction and report the diffusion and kinetics of these systems with carbonate. In addition, a new chelating agent (GLDA) was recently introduced as a stand-alone stimulating fluid. The kinetics and the mass transfer properties of this acid were not studied before. Therefore, the objective of this work is to study the reaction of different acid systems with calcite and dolomite and report the mass transport and kinetic data experimentally. Lactic acid, a chelating agent (GLDA), and in-situ gelled HCl-formic acids were investigated in this study. In some cases, rheology measurements and core flood experiments were conducted. The data were combined with the reaction study to understand the behavior of these acids and examine their efficiency if injected in the formation.

Samples from three well cores in the Pipe Creek Junior Reef (Niagaran-Cayugan) in the' Wabash Formation of northeastern Indiana revealed an indirect and imperfect relationship between dolomite and clay content. A microscopic examination of the larger than two micron fractions of residues that were insoluble in acetic acid, and semi-quantitative X-ray analyses of the smaller than two micron fractions revealed illite to be the only clay mineral present in 91 samples. Illite comprised approximately 50 percent of the insoluble residue and more than 90 percent of the aluminum oxide-containing minerals. No magnesium silicates were found.Illite and dolomite contents were calculated from spectrochemical analyses of Al203 and MgCO3 respectively in 94 reef-influenced samples from three Indiana Geological Survey well cores. The regression and linearity of the dolomite/illite relationship revealed an imperfect correlation in two of the three cores.Nineteen thin sections of textural' varieties, from the core that did not reveal a strong illite/dolomite correlation, and eight thin sections from a portion of interbedded limestones and dolostones in the pipe Creek Junior quarry reef flank revealed the authigenetic origin of dolomite and the probable detrital origin of illite. The concentration of illite and other insolubles by post-micritization microstylolitization occurred along seams of carbonate solution and high permeability which developed selectively within the micritic matrices. Dolomite selectively crystallized in those more permeable sediments following the complete or nearly complete lithification of the reef.Ball State UniversityMuncie, IN 47306

Manito Lake is a large, perennial, Na-SO4 dominated hypersaline lake located in the northern Great Plains of western Canada. Significant water level decrease over the past several decades has lead to reduction in volume and surface area. Today, the lake is 15% of its mid -20th century volume and 46% of its former area. This decrease in water level has exposed large areas of nearshore microbialites. These organosedimentary structures have various external morphologies, vary in mineralogical composition, and show a variety of internal fabrics from finely laminated to massive and clotted. These features range from small, mm-scale, finely laminated encrustations to large, reef-like structures up to 5 m high and over 500 m long. Although there is relatively little consistent lateral variability in terms of morphology, the structures do vary significantly with elevation in the basin. Petrographic evidence confirms a strong biological involvement in the formation of these structures. Nonetheless, inorganic and trapping mechanisms may also play a role. Dolomite, aragonite, and calcite are the most commonly found minerals in these structures, however, monohydrocalcite, magnesian calcite, hydromagnesite, dypingite, and nesquehonite are also present. The calcite is a pseudomorph after ikaite, which forms an open porous dendritic and shrub-like fabric, comprising the interiors of massive shoreline microbialite mounds and pinnacles. These ikaite pseudomorphs are encased in millimeter to centimeter-scale laminated dolomite-aragonite rinds. Radiocarbon dating and stable isotope analysis have indicated microbialite formation began about 2200 yBP in a shallow, productive, saline and cold lake. Over the next 900 years, the microbialites record a transgressing lake in a cool climate, which corresponds to a period not previously documented in this region but is referred to as the Dark Ages Cold Period, which has been documented in other parts of the Northern Hemisphere. This is followed by 500 years of warmer conditions coinciding with the Medieval Climate Anomaly. Starting about 600 years ago the lake experienced a dramatic decrease in level resulting in formation of extensive carbonate pavements, cemented siliciclastics, rinds, and coatings.

Manito Lake is a large, perennial, Na-SO4 dominated hypersaline lake located in the northern Great Plains of western Canada. Significant water level decrease over the past several decades has lead to reduction in volume and surface area. Today, the lake is 15% of its mid -20th century volume and 46% of its former area. This decrease in water level has exposed large areas of nearshore microbialites. These organosedimentary structures have various external morphologies, vary in mineralogical composition, and show a variety of internal fabrics from finely laminated to massive and clotted. These features range from small, mm-scale, finely laminated encrustations to large, reef-like structures up to 5 m high and over 500 m long. Although there is relatively little consistent lateral variability in terms of morphology, the structures do vary significantly with elevation in the basin. Petrographic evidence confirms a strong biological involvement in the formation of these structures. Nonetheless, inorganic and trapping mechanisms may also play a role. Dolomite, aragonite, and calcite are the most commonly found minerals in these structures, however, monohydrocalcite, magnesian calcite, hydromagnesite, dypingite, and nesquehonite are also present. The calcite is a pseudomorph after ikaite, which forms an open porous dendritic and shrub-like fabric, comprising the interiors of massive shoreline microbialite mounds and pinnacles. These ikaite pseudomorphs are encased in millimeter to centimeter-scale laminated dolomite-aragonite rinds. Radiocarbon dating and stable isotope analysis have indicated microbialite formation began about 2200 yBP in a shallow, productive, saline and cold lake. Over the next 900 years, the microbialites record a transgressing lake in a cool climate, which corresponds to a period not previously documented in this region but is referred to as the Dark Ages Cold Period, which has been documented in other parts of the Northern Hemisphere. This is followed by 500 years of warmer conditions coinciding with the Medieval Climate Anomaly. Starting about 600 years ago the lake experienced a dramatic decrease in level resulting in formation of extensive carbonate pavements, cemented siliciclastics, rinds, and coatings.

In this thesis a study of the factors affecting virus and virus-sized particle transport in discrete fractured dolomite rocks is presented. Physical and chemical characteristics of two fractured rocks were determined, including fracture aperture distribution, rock matrix porosity, mineral composition, and surface charge. Hydraulic and transport tests were conducted in the fractures with a conservative solute (bromide) and carboxylate-modified latex (CML) microspheres of three sizes (20, 200, and 500 nm in diameter). The earlier arrival of larger microspheres as compared to bromide indicated the effects of pore-size exclusion and preferential flow paths in the fractures. The tailing of the bromide and the smaller microsphere (20 nm) in the breakthrough curves (BTC) indicated the diffusive mass transfer between the mobile water (flowing) and immobile water (stagnant water in the low aperture areas and porous rock matrix). The effects of ionic strength and cation type on the transport of viruses (bacteriophages MS2 and PR772) and virus-sized microspheres (20 and 200 nm) were determined from the transport tests in a fracture at three levels of ionic strength (3, 5, and 12 mM) and composition (containing Na+ and/or Ca2+ ions). Retention of the microspheres and bacteriophages increased with increasing ionic strength. The addition of divalent ions (Ca2+) influenced the retention to a greater extent than monovalent ions (Na+). The effects of the aperture distribution variability, matrix diffusion, and specific discharge on the solute and microsphere transport were determined from the transport tests conducted in two fractures. The higher variability in the aperture distribution contributed to higher solute dispersion, and flow channeling as evident from the breakthrough curves for individual spatially distributed outlets. A three-dimensional model simulation of the bromide transport with varying matrix porosity identified that the porous matrix influenced the solute transport. In the transport tests, retention of the microspheres decreased with increasing specific discharge in both fractures. The results of this research have helped in identifying the important factors and their effects on solute, virus, and virus-sized colloid transport in fractured dolomite rocks, which can be useful in determining the risk of pathogen contamination of water supplies in fractured dolomite rock aquifers.