To date, an estimated 70% of energy consumed comes from fossil fuels, such as coal, oil and natural gas. The major source of sulfur dioxide (SO2) emissions comes from combustion of these fossil fuels. Sulfur dioxide is a significant pollutant, because it and its higher oxidation product (SO3) react with moisture in the atmosphere to produce sulfuric acid. This results in acid rain, which comes back to earth and affects people, animals, and vegetation. Therefore, the governments of Canada, US and European countries are issuing stricter and stricter regulation to control SO2 emissions. In conventional SO2 removal processes, lime or limestone scrubbers are used, but they require large amounts of water and enough landfill sites to deal with the solid wastes. Previous attempts were made in our laboratory to recover SO2 adsorbed on activated carbon to produce sulfuric acid using non-aqueous solvents. Unfortunately, in this adsorption/distillation process, the SO2 recovery was low, as was the quality of sulfuric acid, that could not be marketable. The topic of this thesis was then conceived as an attempt to first recover SO2 via SO3 formation using supercritical carbon dioxide instead of water or non-aqueous flushing agents (desorption step) and then to use the recovered SO3 to produce linear alkylbenzene sulfonates (LAS), the main component of detergent. In the adsorption and oxidation experiments of this project, charcoal activated carbon (AC) was used to adsorb SO2 and to catalyze SO2 oxidation. The process started with a simulated flue gas, 3500 ppm SO2, 5% O2, balanced with N2. When the simulated flue gas passed through the activated carbon bed reactor, more than 95% of SO2 was oxidized to SO3. In the desorption process, SO3 contacted with the AC bed was removed using supercritical carbon dioxide (SCCO2) and 95% sulfur removal was achieved at appropriate operating conditions, for example, for a carbon bed preheated at 250??C for 6 h, and flushed by recycled SCCO2. The LAS production experiments consisted in reacting liquid linear alkylbenzene (LAB) with the recovered SO3 in an absorption column. Ceramic filters and glass beads were used in the absorption columns to break up the gas bubbles and increase the contact time between the gas and the liquid absorbent. When staged pressure columns were used and when LAB was heated to 40??C, nearly 95% of SO3 reacted with LAB to produce LAS.

Efficient use of renewable feedstocks for production of chemicals and intermediates is necessary to reduce dependence upon petroleum. A large portion of these chemicals could be produced using lipids from renewable feedstocks such as vegetable oils, animal fats, and bacterial lipids. For example, many lipid sources contain unsaturated fatty acids, which can be oxidized to form a variety of products such as diacids and epoxides. These chemicals are used to formulate herbicides, detergents, plasticizers, lubricants, paints, and other useful products. One of the most common unsaturated fatty acids is oleic acid, and it can be oxidized with an ozone/oxygen mixture to produce azelaic acid and pelargonic acid. Since the ozone/oxygen mixture is a gas and oleic acid is a liquid under reaction conditions, mass transfer limitations exist. However, a reduction of the mass-transfer limitations can be achieved if the reactants coexist in a single phase. When supercritical carbon dioxide (SC-CO2) is used as the reaction medium, it is possible for both oleic acid and the ozone/oxygen mixture to both exist in the same phase at the same time. Use of supercritical carbon dioxide also provides the possibility of product fractionation, depending upon the solubility of the products in SC-CO2. The overall goal of this research was to determine if any advantages could be realized by conducting the oleic acid oxidation in a supercritical fluid medium. First, the solubility of azelaic acid and pelargonic acid in supercritical carbon dioxide was determined over a range of temperatures and pressures. Pelargonic acid was found to have a significantly higher solubility than azelaic acid, which indicated the potential for product separation with supercritical carbon dioxide. Second, the impact of the solvent medium on reaction kinetics and product formation was determined using two oxidizers: ozone and potassium permanganate. Due to experimental limitations, no reaction was observed in the case of ozone in supercritical carbon dioxide. However, oxidation of oleic acid with potassium permanganate in supercritical carbon dioxide resulted in higher oleic acid conversion and increased yields of azelaic acid and pelargonic acid compared to the oxidation without SC-CO2.

Polymer nanocomposites have been proposed as lightweight replacements for traditional composite materials in various applications. Montmorillonite (MMT) and carbon nanotubes (CNTs) are two nanofillers which have accrued significant interest in the past 20 years due to their superior mechanical and electrical properties, respectively. However, efficient dispersion of the nanofiller and damage to CNTs prevent widespread utilization of these materials in polymer nanocomposites. Novel methods of nanocomposite generation combining the use of supercritical carbon dioxide (scCO2) with melt compounding have been investigated to overcome these issues. The focus of this work is on developing the scCO2 treatment of nanomaterial for thermoplastic nanocomposite generation. First, the supercritical carbon dioxide aided melt blending method was applied to nanoclay nanocomposites of Nylon 6/ and organoclay where the polymer may interact with the nanoclay surface. Second, the effect of scCO2 processing of CNTs was investigated with special consideration to the processing variables. Finally, a study was carried out to analyze the electrical conductivity of polycarbonate nanocomposites generated using CNTs deagglomerated by scCO2 processing. The initial focus of this dissertation is the use of supercritical carbon dioxide (scCO2) as a processing aid in the generation of nylon 6 nanocomposites in which the nylon 6 may interact with the nanoclay surface. Wide-angle X-ray diffraction, transmission electron microscopy, rheology, and tensile tests were carried out to investigate the effect of processing with scCO2 on the final composite morphology and properties. It was observed that mechanical properties of composites prepared with the scCO2 aided melt blending method were similar to or higher than those reported in the literature for samples prepared with twin screw compounding. At 7.6 wt% nanoclay the modulus value reaches 4.75 +/- 0.194 GPa which is one of the highest increases (1.7 GPa) reported for these materials processed at intermediate concentrations. Beyond 7.6 wt% the improvement due to scCO2 processing matched that of direct blending. The next objective of this work is to develop a method for the deagglomeration of commercially available multi-walled carbon nanotubes (MWCNTs) by manipulating processing variables and observing carbon nanotube aspect ratios after deagglomeration. High levels of deagglomeration of Baytubes C 150 P and Nanocyl NC-7000 MWCNT agglomerates were observed, resulting in 30 fold and 50 fold decreases in bulk density, respectively, with median agglomerate sizes < 8 um in diameter. These results were obtained while retaining the aspect ratio of the as-received nanomaterial, irrespective of the MWCNT agglomerate morphology. It was found that the supercritical temperature and pressure of 40 deg C and 7.86 MPa were the optimal temperature and pressure for maximum deagglomeration without damaging the MWCNTs. The final goal of this work is to apply the scCO2 aided melt blending process to generate polycarbonate/ carbon nanotube (CNT) nanocomposites with enhanced electrical conductivity and improved dispersion while maintaining the aspect ratio of the as-received CNTs. Different degrees of scCO2 processed Baytubes C 150 P CNT were benignly deagglomerated with scCO2 resulting in 5 fold (5X), 10X, and 15X decreases in bulk density from the as-received CNTs. The CNT were melt compounded with polycarbonate using single screw melt extrusion and compression molded into plaques. A surface conductivity of 4.8 x 10-8 +/- 2.0 x 10-9 S was observed for samples prepared with the scCO2 aided melt blending at 15X scCO2 processing. Electrical percolation thresholds as low as 0.83 wt% were observed for composites prepared with 15X CNTs using the scCO2 aided melt blending method, while concentrations as high as 1.5% are required without scCO2 processing. The percolation concentration in nanocomposites prepared with 15X scCO2 processing and single screw extrusion is competitive with values reported for similar nanocomposites generated using twin screw melt compounding in the literature. Optical microscopy, transmission electron microscopy, and rheology were used to investigate the dispersion and mechanical network of CNTs in the nanocomposites. The dispersion of CNTs generally improved with scCO2 processing compared to direct melt blending but was found to be significantly worse than that of twin screw melt compounded nanocomposites from the literature. Because the percolation thresholds are similar with substantially different extents of dispersion, the importance of maintaining longer CNTs during nanocomposite generation is emphasized. / Ph. D.

he feasibility of sequestering supercritical CO2 in depleted gas reservoirs. The experimental runs involved the following steps. First, the 1 ft long by 1 in. diameter carbonate core is inserted into a viton Hassler sleeve and placed inside an aluminum coreholder that is then evacuated. Second, with or without connate water, the carbonate core is saturated with methane. Third, supercritical CO2 is injected into the core with 300 psi overburden pressure. From the volume and composition of the produced gas measured by a wet test meter and a gas chromatograph, the recovery of methane at CO2 breakthrough is determined. The core is scanned three times during an experimental run to determine core porosity and fluid saturation profile: at start of the run, at CO2 breakthrough, and at the end of the run. Runs were made with various temperatures, 20°C (68°F) to 80°C (176°F), while the cell pressure is varied, from 500 psig (3.55 MPa) to 3000 psig (20.79 MPa) for each temperature. An analytical study of the experimental results has been also conducted to determine the dispersion coefficient of CO2 using the convection-dispersion equation. The dispersion coefficient of CO2 in methane is found to be relatively low, 0.01-0.3 cm2/min.. Based on experimental and analytical results, a 3D simulation model of one eighth of a 5-spot pattern was constructed to evaluate injection of supercritical CO2 under typical field conditions. The depleted gas reservoir is repressurized by CO2 injection from 500 psi to its initial pressure 3,045 psi. Simulation results for 400 bbl/d CO2 injection may be summarized as follows. First, a large amount of CO2 is sequestered: (i) about 1.2 million tons in 29 years (0 % initial water saturation) to 0.78 million tons in 19 years (35 % initial water saturation) for 40-acre pattern, (ii) about 4.8 million tons in 112 years (0 % initial water saturation) to 3.1 million tons in 73 years (35 % initial water saturation) for 80-acre pattern. Second, a significant amount of natural gas is also produced: (i) about 1.2 BSCF or 74 % remaining GIP (0 % initial water saturation) to 0.78 BSCF or 66 % remaining GIP (35 % initial water saturation) for 40-acre pattern, (ii) about 4.5 BSCF or 64 % remaining GIP (0 % initial water saturation) to 2.97 BSCF or 62 % remaining GIP (35 % initial water saturation) for 80-acre pattern. This produced gas revenue could help defray the cost of CO2 sequestration. In short, CO2 sequestration in depleted gas reservoirs appears to be a win-win technology.

To date, an estimated 70% of energy consumed comes from fossil fuels, such as coal, oil and natural gas. The major source of sulfur dioxide (SO2) emissions comes from combustion of these fossil fuels. Sulfur dioxide is a significant pollutant, because it and its higher oxidation product (SO3) react with moisture in the atmosphere to produce sulfuric acid. This results in acid rain, which comes back to earth and affects people, animals, and vegetation. Therefore, the governments of Canada, US and European countries are issuing stricter and stricter regulation to control SO2 emissions. In conventional SO2 removal processes, lime or limestone scrubbers are used, but they require large amounts of water and enough landfill sites to deal with the solid wastes. Previous attempts were made in our laboratory to recover SO2 adsorbed on activated carbon to produce sulfuric acid using non-aqueous solvents. Unfortunately, in this adsorption/distillation process, the SO2 recovery was low, as was the quality of sulfuric acid, that could not be marketable. The topic of this thesis was then conceived as an attempt to first recover SO2 via SO3 formation using supercritical carbon dioxide instead of water or non-aqueous flushing agents (desorption step) and then to use the recovered SO3 to produce linear alkylbenzene sulfonates (LAS), the main component of detergent. In the adsorption and oxidation experiments of this project, charcoal activated carbon (AC) was used to adsorb SO2 and to catalyze SO2 oxidation. The process started with a simulated flue gas, 3500 ppm SO2, 5% O2, balanced with N2. When the simulated flue gas passed through the activated carbon bed reactor, more than 95% of SO2 was oxidized to SO3. In the desorption process, SO3 contacted with the AC bed was removed using supercritical carbon dioxide (SCCO2) and 95% sulfur removal was achieved at appropriate operating conditions, for example, for a carbon bed preheated at 250°C for 6 h, and flushed by recycled SCCO2. The LAS production experiments consisted in reacting liquid linear alkylbenzene (LAB) with the recovered SO3 in an absorption column. Ceramic filters and glass beads were used in the absorption columns to break up the gas bubbles and increase the contact time between the gas and the liquid absorbent. When staged pressure columns were used and when LAB was heated to 40°C, nearly 95% of SO3 reacted with LAB to produce LAS.

he feasibility of sequestering supercritical CO2 in depleted gas reservoirs. The experimental runs involved the following steps. First, the 1 ft long by 1 in. diameter carbonate core is inserted into a viton Hassler sleeve and placed inside an aluminum coreholder that is then evacuated. Second, with or without connate water, the carbonate core is saturated with methane. Third, supercritical CO2 is injected into the core with 300 psi overburden pressure. From the volume and composition of the produced gas measured by a wet test meter and a gas chromatograph, the recovery of methane at CO2 breakthrough is determined. The core is scanned three times during an experimental run to determine core porosity and fluid saturation profile: at start of the run, at CO2 breakthrough, and at the end of the run. Runs were made with various temperatures, 20°C (68°F) to 80°C (176°F), while the cell pressure is varied, from 500 psig (3.55 MPa) to 3000 psig (20.79 MPa) for each temperature. An analytical study of the experimental results has been also conducted to determine the dispersion coefficient of CO2 using the convection-dispersion equation. The dispersion coefficient of CO2 in methane is found to be relatively low, 0.01-0.3 cm2/min.. Based on experimental and analytical results, a 3D simulation model of one eighth of a 5-spot pattern was constructed to evaluate injection of supercritical CO2 under typical field conditions. The depleted gas reservoir is repressurized by CO2 injection from 500 psi to its initial pressure 3,045 psi. Simulation results for 400 bbl/d CO2 injection may be summarized as follows. First, a large amount of CO2 is sequestered: (i) about 1.2 million tons in 29 years (0 % initial water saturation) to 0.78 million tons in 19 years (35 % initial water saturation) for 40-acre pattern, (ii) about 4.8 million tons in 112 years (0 % initial water saturation) to 3.1 million tons in 73 years (35 % initial water saturation) for 80-acre pattern. Second, a significant amount of natural gas is also produced: (i) about 1.2 BSCF or 74 % remaining GIP (0 % initial water saturation) to 0.78 BSCF or 66 % remaining GIP (35 % initial water saturation) for 40-acre pattern, (ii) about 4.5 BSCF or 64 % remaining GIP (0 % initial water saturation) to 2.97 BSCF or 62 % remaining GIP (35 % initial water saturation) for 80-acre pattern. This produced gas revenue could help defray the cost of CO2 sequestration. In short, CO2 sequestration in depleted gas reservoirs appears to be a win-win technology.

Orientadores: Maria Angela de Almeida Meireles Petenate, Diego Tresinari dos Santos / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-27T11:45:25Z (GMT). No. of bitstreams: 1 DelCastilloTorres_RicardoAbel_M.pdf: 4457201 bytes, checksum: 2afa693e20d4497964c4faa4de811759 (MD5) Previous issue date: 2015 / Resumo: Este trabalho apresenta um estudo da aplicação do CO2 supercrítico como antissolvente em contato com a solução de ativos (SA) obtida a partir da extração de compostos de sementes de urucum (Bixa orellana L.) semi desengorduradas a fim de se obter partículas ricas em bixina. Para isso, duas etapas foram desenvolvidas. Na primeira etapa foi aperfeiçoada a técnica de obtenção da SA a partir da extração dos compostos das sementes com etanol, combinando dois equipamentos: Ultra turrax (UTurrax), que produz suspensão operado por recirculação do líquido, e o Ultrassom (USom), que produz cavitação acústica no líquido. Esta é a primeira vez que o UTurrax foi usado para obter compostos ativos das sementes semi desengorduradas de urucum. A mistura etanol e ativos formou a suspensão, denominada de SA. O objetivo nesta etapa foi obter uma SA rica em bixina e pobre em gorduras. Com esse intuito foram feitas extrações variando-se as condições de uso ou não de USom e a razão massa de solvente por massa de matéria-prima (S/F). A composição química dos extratos foi analisada em relação ao teor de bixina e fenólicos por método espectrofotométrico, enquanto que o teor de óleo foi determinado nas sementes pelo método de extração Soxhlet. O uso de USom (800 W) e S/F de 1,6 g CO2/g urucum apresentou menor teor de óleo na SA, isto é, o maior teor de óleo permaneceu nas sementes (0,49 ± 0,08 g/100 g sementes, b.u.). Houve também menor rendimento de extração (X0): 2,6 ± 0,4 g/100 g sementes (b.u.), uma vez que a extração foi mais seletiva, resultando em rendimento de extração de bixina e fenólicos de 0,19 ± 0,06 g/100 g sementes (b.u.) e 0,8 ± 0,1 g/100 g sementes (b.u.), respectivamente. Na segunda etapa, a SA foi alimentada na unidade de precipitação Antissolvente Supercrítico (SAS) com o objetivo de formar partículas e caracterizar a distribuição da bixina e fenólicos nos diversos setores no interior da coluna. Com esse intuito, foi utilizado um planejamento experimental fatorial completo com 3 variáveis (pressão, vazão de CO2 e vazão de SA) em 2 níveis (10 ¿ 12 MPa, 500 ¿ 800 g/h e 0,5 ¿ 1 mL/min, respectivamente) sem repetição, totalizando 8 experimentos. O rendimento de precipitação foi influenciado negativamente pela pressão, sendo maior (80,5 %) a 10 MPa, 500 g/h e 0,5 mL/min. Da análise de distribuição das massas das partículas na coluna de precipitação, concluiu-se que para todos os experimentos maior massa foi depositada na base da coluna (aproximadamente 40%). Da mesma forma, maior concentração de bixina foi determinada na parede da coluna (51 ± 15 g/100 g extrato), com massa de extrato igual a 8,73 g/100 g sementes para 12 MPa, 500 g/h e 1 mL/min. A concentração de fenólicos nas partículas coletadas não foi influenciada pelas variáveis de estudo. A eficiência de precipitação de bixina nesta condição foi de 88,4 %. Porém, acredita-se que a eficiência de precipitação de bixina pode ter sido ainda maior, pois, houve setores da coluna nos quais foi difícil a coleta das partículas. Por último, através do processo de precipitação na unidade SAS, foi possível a obtenção de partículas com concentração de bixina 59 vezes maior do que a concentração inicial de bixina na SA alimentada / Abstract: The following thesis consist of the development of the application of the supercritical CO2 as an anti-solvent in contact with the Active solution obtained from the extraction of semi-defatted Annatto seeds (Bixa orellana L.) to obtain particles rich in bixin. To that objective, the present thesis was developed in two stages. In the first stage it was necessary to perfect the technique for obtaining the Active solution by extracting the compounds from the seeds with ethanol. This was accomplished by combining two pieces of equipment. One of the equipment of production of suspension operated by recirculation of a liquid (Ultra-turrax) and another equipment of production of acoustic cavitations (Ultrasound) inside the liquid. To the best of the author¿s knowledge, this was the first time that the Ultra- turrax was used as a method of extraction; furthermore it was the first time that the equipment was used to obtain Active components from the semi-defatted Annatto seeds. The mixture formed by the ethanol used here as a solvent and the actives formed Suspension which is nominated as Active solution. The objective for this stage was to obtain an Active solution high in bixin with minimum oil content. The extractions were done with that purpose, varying the conditions of use or not of ultrasound and the ratio of S/F (mass of solvent/ mass of raw material). The chemical composition of extracts was analyzed in relation to percentage of bixin and phenolics using the Spectrophotometry method, while the percentage of oils from the seeds were determine by the Soxhlet extraction method. The use of ultrasound (800 W) and S/F of 1.6 presented a low percentage of oil in the Active solution; which means, the greater the percentage of oil present in the seeds (0.49 ± 0.08 %, b.u.), the lower the efficiency of extraction (X0): 2.64 ± 0.42 % (b.u.) The extraction was more selective, resulting in efficient bixin extraction and phenolics in a solution of extract of 0.19 ± 0.06 % (b.u.) and 0.75 ± 0.10 % (b.u.), respectively. In the second stage, an Active solution was inserted into the precipitation unit-SAS with the purpose of forming particles and to characterize the distribution of bixin and phenolic in diverse sectors of the column. To that objective a complete experimental factorial design with 3 variables were used (pressure, flow of CO2 and flow of Active solution) and 2 levels (10 ¿ 12 MPa, 500 ¿ 800 g/h and 0.5 ¿ 1 mL/min, respectively) without repetition, totalizing 8 experiments. The efficiency of precipitation was negatively influenced by pressure, being greater (80.5 %) to 10 MPa, 500 g CO2/h and 0.5 mL Active solution /min. From the analysis of distribution of the masses of particles in the interior of the column of precipitation, it concluded that for all the experiments, greater amount of mass was deposit in the column¿s base (approximately 40%). Great concentration of bixin was settled in the column¿s walls (51 ± 15 %), where the mass of the extract was of 8.73 % for 12 MPa, 500 g CO2/h and 1 mL Active solution /min. The concentration of phenolics in the particles collected was not influenced by the variables of study. The precipitation efficiency of bixin in this condition was 88.4 %. However, its believe that the efficiency of bixin precipitation it could had been greater, because there were areas of the column that it was impossible to collect precipitated particles. Lastly, through the precipitation process in the SAS-unit, was possible to obtain particles with concentration of bixin 59 times greater than the initial concentration of bixin in Active solution inserted in the SAS-unit / Mestrado / Engenharia de Alimentos / Mestre em Engenharia de Alimentos

No description available.

No / A precipitation process is considered in which completely miscible solution and supercritical antisolvent are passed through premixing and diluting zones of a turbulent flow. The influence of flow velocity on particle size and nuclei concentration is discussed in terms of mixing and precipitation time constants and their supersaturation dependencies. The proposed model allowed the major process parameters such as supersaturation profile, mixed fluid fraction and mean particle size to be calculated and compared with experimental data. For the crystallization system paracetamol/ethanol/CO2 studied, the supersaturation profile becomes established at Re104. The particle size and shape are defined, firstly, by increase of supersaturation and relative volume of mixed (on molecular scale) fluid with increase of flow velocity and, secondly, by decrease of residence time available for nucleation with increase of flow velocity. These competitive processes can result in minimum particle size at a defined flow rate.

The next generation of nuclear power sources, Gen. IV, will include an emphasis on small, modular reactor (SMR) designs, which will allow for standardized, factory-based manufacturing and flexibility in the design of power plants by utilizing one or several modular reactor units in parallel. One of the reactor concepts being investigated is the Molten Salt Reactor concept (MSR), which utilizes a molten salt flow loop to cool the reactor and transfer heat to the power conversion cycle (PCS).Here, the use of a supercritical carbon dioxide (S-CO2) Brayton cycle is assumed for that PCS. The purpose of this thesis is to investigate the heat exchange between these two systems and to determine the suitability of a common heat exchanger concept, the shell-and-tube heat exchanger (STHE). This was accomplished using a code written in Python programming language that optimized the geometry ofa baffled STHE for a range of conditions the reflect MSR power plants currently in the design or concept stages. Star-CCM+ computational fluid dynamics (CFD)software was used to visualize the flow patterns of molten salt and CO2 in these STHE designs, and it was also used to determine heat transfer coefficients and pressure drops. These values were compared to those calculated by the optimizer code in order to validate its results. Finally, modularity analysis was performed for these STHE designs. Trends were generalized from these results that will contribute to judgments about the suitability of STHE’s for use with MSR’s and S-CO2.