A mechanistic kinetic model for the hydrocracking of paraffins based on the single-event kinetics approach has been studied. Several elements of the model have been improved and the parameters of the model have been estimated from experimental data on n-hexadecane hydrocracking. A detailed reaction network of elementary steps has been generated based on the carbenium ion chemistry using the Boolean relation matrices. A total of 49,636 elementary steps are involved in the hydrocracking of n-hexadecane. The rate coefficients of these elementary steps are expressed in terms of a limited number of single event rate coefficients. By virtue of the single event concept, the single event rate coefficients of a given type of elementary steps are independent of the structure of reactant and product. Given their fundamental nature they are also independent of the feedstock composition and the reactor configuration. There is no lumping of components involved in the generation of the reaction network. Partial lumping is introduced only at a later stage of the model development and the lumping is strictly based on the criterion that the individual components in any lump will be in thermodynamic equilibrium. This definition of lumping requires a total of 49 pure components/lumps in the kinetic model for the hydrocracking of n-hexadecane. The "global" rate of reaction of a lump to another lump is expressed using lumping coefficients which account for the transformation of all the components of one lump into the components of another lump through to a given type of elementary steps. The rate expressions thus formulated are inserted into a one-dimensional, three-phase plug flow reactor model. Experimental data have been collected for the hydrocracking of n-hexadecane. The model parameters are estimated by constrained optimization using sequential quadratic programming by minimizing the sum of squares of residuals between experimental and model predicted product profiles. The optimized parameters are finally used for the reactor simulation to study the effect of different process variables on the conversion and product distribution of n-hexadecane hydrocracking. The model is also used to predict the product distribution for the hydrocracking of a heavy paraffinic mixture consisting of C9 to C33 normal paraffins.

Orientador: Rahoma Sadeg Mohamed. / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-07-25T07:15:41Z (GMT). No. of bitstreams: 1 Oliveira_AlexandreParkerde_M.pdf: 11817583 bytes, checksum: eb5c95965e5d6dea4c4ee13a0b0c8983 (MD5) Previous issue date: 1998 / Resumo: A precipitação de parafinas é um sério problema enfrentado pela industria do petróleo ao longo de toda a sua cadeia produtiva gerando custo elevado para sua prevenção e tratamento. Este trabalho tem por objetivos contribuir aos estudos do comportamento de fases de misturas binárias, temárias e multicomponentes de n-parafinas, na faixa de n-'C IND. 23¿¿H IND. 48¿ a n-'C IND. 50¿H IND. 102¿. Temperaturas de Precipitação de Parafinas (TPP) foram levantadas experimentalmente utilizando-se a Calorimetria de Varredura Diferencial (DSC). Resultados experimentais apresentaram três principais comportamentos de fases: precipitação de parafinas como solução sólida, precipitação com componentes parcialmente miscíveis na fase sólida e precipitação dos componentes separadamente. Quando um ou mais componentes intermediários são adicionados a misturas binárias que cristalizam separadamente ou com solubilidade parcial surge uma tendência de solubilização. Foi testada a capacidade de alguns modelos termodinâmicos (misturas ideais, soluções regulares, fase multisólida, CDLP e composição local) na predição do comportamento de fases de misturas de n-parafinas. Conforme esperado, os modelos de soluções regulares, CDLP e composição local se mostraram mais adequados a misturas que formam soluções sólidas. O modelo da fase multisólida demonstrou boa capacidade preditiva para sistemas que cristalizam separadamente ou com solubilidade parcial. Este trabalho também apresenta dados importantes sobre misturas temárias e multicomponentes de n-parafinas, ainda pouco tratadas na literatura / Abstract: Wax Precipitation is a very serious problem faced in the petroleum industry through all phases of production and processing, due to the large costs involved in prevention and treatment. This work is focused on the study of phase behavior of binary, temary and multicomponent mixtures of n-paraffins in the range of n-'C IND. 23¿¿H IND. 48¿ a n-'C IND. 50¿H IND. 102¿. CSOH1o2.Wax Precipitation Temperatures (WPT) were experimentally obtained using Differential Scanning Calorimetry (DSC). Experimental results can be c1assified in three different categories in accordance to the phase behavior obtained: precipitation as solid solutions, precipitation as eutectic mixtures and precipitation wherein the components exhibited limited solid solubility. A tendency for solubilization appears when one or more n-alkanes, with intermediate molecular weight, are introduced in eutectic or with limited solid solubility mixtures. Some thermodynamic models (ideal mixture, regular solution, multisolid phase, CDLP and local composition) were tested for predictions of the phase behavior of those mixtures. As expected, regular solution, CDLP and local composition models provided good predictions for systems that exhibit solid solution behavior while the multisolid phase model provided best description for systems with limited solid solubility and eutectic behaviors. This work also displays important aspects about temary and multicomponent mixtures no much attended in the literature / Mestrado / Mestre em Engenharia de Petróleo

Orientador: Paulo Roberto Ribeiro / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica e Instituto de Geociências / Made available in DSpace on 2018-08-27T14:52:04Z (GMT). No. of bitstreams: 1 Policarpo_NaraAngelica_D.pdf: 9247509 bytes, checksum: a0105ef97dc1f71d6d3fba2c3066be89 (MD5) Previous issue date: 2014 / Resumo: A miscibilidade natural que ocorre em misturas gás/líquido é um processo governado pela transferência de massa. A caracterização desse processo recai na obtenção dos parâmetros solubilidade do gás no líquido e a sua difusividade. Esses parâmetros respondem duas questões determinantes no planejamento de operações que envolvam a explotação de hidrocarbonetos, como a interação de fluidos do reservatório com o de perfuração, completação ou em operações de recuperação avançada de óleo através da injeção de gás. Essas questões dizem respeito a quantidade máxima de gás dissolvido no líquido e em que taxa isso ocorre. Esse trabalho tem por objetivo principal determinar o coeficiente de difusividade dos gases metano e dióxido de carbono em n-parafina. A medição experimental foi feita utilizando-se a técnica do decaimento de pressão através da utilização de uma célula PVT. Para a mistura metano/n-parafina foram medidos dados para frações molares de 7,7% a 92,3%, pressões de 3,5 MPa a 35 MPa e temperaturas de 62oC a 118oC, enquanto que para a mistura dióxido de carbono/n-parafina foram feitos experimentos para 25%, 50% e 75% em mol de gás nas pressões de 4 MPa, 8 MPa e 13 Mpa, a 70oC. Três modelagens matemáticas ¿ Zhang et al. (2000), Civan e Rasmussen (2009) e Sachs (1998) ¿ foram utilizadas no tratamento dos dados experimentais para obtenção dos parâmetros difusivos: as duas primeiras analíticas e, a terceira, numérica. A principal diferença entre elas está na condição de contorno aplicada na interface gás-líquido. Os resultados obtidos para o coeficiente de difusão são similares aos encontrados na literatura e a modelagem de Civan e Rasmussen (2009) foi a que melhor se ajustou aos dados experimentais, mostrando que o uso da condição de contorno de não equilíbrio na interface confirma a existência de uma resistência interfacial à transferência do gás para a fase líquida / Abstract: Natural gas-liquid miscibility is a process governed by mass transfer. The characterization of such process requires the determination of gas-liquid solubility and diffusivity parameters. Those parameters are important in hydrocarbon exploitation activities such as drilling, completion, production and enhanced oil recovery processes. The amount of gas that is dissolved in the liquid phase and the rate at which it occurs are essential issues to be addressed in planning and executing those operations. The pressure decay technique using a PVT cell was applied to measure the diffusivity of methane and carbon dioxide in n-paraffin. The data were obtained for gas mole fractions ranging from 7.7% to 92.3%, pressures from 3.5 MPa to 35 MPa, and temperatures from 62oC to 118oC for the methane/n-paraffin mixture. The measurements with carbon dioxide/n-paraffin mixtures involved 25%, 50% and 75% gas mole fraction, pressures up to 13 MPa, at 70oC. Three mathematical models ¿ Zhang et al. (2000), Civan and Rasmussen (2009) and Sachs (1998) ¿ were applied to fit the experimental data in order to determine the diffusivity parameters. The main differences among them are concerned with the boundary condition at the gas-liquid interface. Diffusion coefficient results agreed satisfactorily with published data and Civan and Rasmussen's (2009) model better represented the experimental data, showing that the non-equilibrium boundary condition confirms a gas-liquid interface resistance / Doutorado / Explotação / Doutora em Ciências e Engenharia de Petróleo

Carbon dioxide levels in atmosphere are linked with a number of adverse environmental impacts including climate change. CO2 utilization is one of the available technologies to reduce CO2 emissions released into atmosphere by its conversion into value added products. Hydrogenation of CO2 into hydrocarbons (with methanol being an intermediate) can be achieved in a single-pot using bi-functional catalysis system composed of metal/metal-oxide and zeolite. In this study, activated novel indium cobalt (InCo) and zeolite beta samples (BEA) were used for the conversion of CO2 into a hydrocarbon mixture rich of iso-paraffins via methanol in a single pot. The objective was to investigate the effect of zeolite beta acidity (represented by SiO2/Al2O3 ratio) and the configuration of the reactor on the overall performance of the above mentioned bi-functional system. Three samples of zeolite beta with different SiO2/Al2O3 ratios were synthesized in-house (Beta-20, Beta-100 and Beta-300) and used along with commercial beta as methanol to hydrocarbons catalysts. XRD patterns of the synthesized samples showed that all of the obtained samples are zeolite beta with high crystallinity. Adsorption-desorption isotherms of the studied zeolites revealed micro-mesoporosity of the samples. Analysis of SEM images suggests that the particles of the studied samples are of a similar range of size (100-200 nm). Each zeolite sample was used to fill two reactor configurations: dual bed and mixed bed. Samples were tested at a temperature of 300 oC, a pressure of 50 bar and CO2:H2 ratio of 1:4 except for Beta-100 sample which was tested at a CO2:H2 ratio of 1:3. CO2 conversion is a characteristic of the methanol synthesis catalyst (InCo) and it ranged between 15% to 20% for all cases. Dimethyl ether (DME) generation in dual bed configuration was much faster and at much higher rates than in mixed bed configuration for all tested samples, indicating that mixed bed configuration is more stable for this particular system. Heavier hydrocarbons (C6 and C7) are generated in higher amounts over low acidic zeolite beta than over beta of high acidity. More acidic zeolite beta, however, was found to be more stable than beta of less acidity.

Described in many studies as dangerous for the environment and potentially carcinogenic for humans, Chlorinated Paraffins (CPs) are easily widespread due to their substantial production and use in different products. Previous studies reported the presence of CPs in different plastic polymers. However, the impact of recycled content in plastic materials on the CPs levels hasn’t particularly been considered. Recycling plastics is becoming essential but the accumulative potential of pollutants, such as CPs, need investigations. The presence of CPs in both virgin and mixed recycled and virgin plastics was studied. Plastic pellets and plastic pieces from products made of three polymer types:Poly(methyl 2-methylpropenoate) (PMMA), Thermoplastic Rubber (TPR) and Thermoplastic Polyurethane (TPU) were analysed. A solid-liquid extraction assisted by ultrasonication was performed, followed by cleanup using silica. CPs in plastic extracts were analysed by Gas Chromatography Orbitrap High Resolution Mass Spectroscopy (GC-Orbitrap-HRMS). Because of the high volatility characteristic of long chain Chlorinated Paraffins (LCCPs), only short chain and medium chain Chlorinated Paraffins (SCCPs and MCCPs ) have been studied in this project. Interesting variations in the presence of SCCPs and MCCPs have been observed from one polymer type to another. In the results, we show that MCCPs were less frequently detected compared to SCCPs. A higher detection frequency of CPs was observed for samples containing recycled plastics. The results indicate that CPs are present in plastic polymers (TPU, PMMA and TPR) and that the content of recycled material has a direct impact on the levels of SCCPs and MCCPs.

La stabilité des carburants en phase liquide est de premier ordre dans le domaine du transport. Par exemple, les carburants, les lubrifiants ou les additifs doivent être stables de leur production jusqu'à leur utilisation. Cette thèse a pour but de développer et de valider une méthodologie alliant l’acquisition de données expérimentales et le développement de modèles cinétiques pour l'autoxydation en phase liquide.Expérimentalement, une approche complémentaire a été mise en place pour obtenir à la fois des données de réactivité globales via un appareil PetroOxy et des profils d’espèces via un autoclave instrumenté.Numériquement, une méthodologie basée sur un générateur de mécanismes est proposée pour obtenir une chimie détaillée en phase liquide. Les paraffines linéaires et branchées sont étudiées comme des carburants modèles représentatifs de l'autoxidation de carburants réels afin de valider l’approche proposée. Ces familles chimiques sont représentatives de la composition des carburants réels et alternatifs.La réactivité des n-paraffines de C8 à C16 ainsi que d’isomères de l’octane a été étudiée en PetroOxy sur la gamme de température 373-433 K. Puis, des profils d’espèces détaillés de la phase gaz et de la phase liquide ont été obtenus durant l’étude de l’oxydation du n-C8 et du 2-methylheptane dans un autoclave à 383 K et 10 bars. Des mécanismes cinétiques détaillés ont été développé pour toutes les molécules jusqu’à C14. Les mécanismes reproduisent qualitativement la formation des espèces majoritaires lors de l’autoxidation des alcanes ainsi que les tendances observées liées à la longueur de chaîne et la ramification. L’analyse des mécanismes cinétiques a mis en avant le rôle prédominant des radicaux peroxy (ROO) et peroxy-hydroperoxyde (HOOQOO) dans la consommation de carburants modèles.Cette étude a permis d’améliorer la compréhension des processus d’autoxidation des alcanes linéaires et branchés. L’étude de nouveaux systèmes permettra d’améliorer la compréhension globale des processus d’autoxidation et, de réduire l’écart de compréhension existant entre l’autoxidation des carburants réels et des carburants modèles. / Liquid phase stability is a major concern in the transportation and the energy fields. Relevant examples are fuels, lubricants and additives which have to be stable from their production to their application (engine, combustors). This thesis aims to develop and validate a complete methodology combining both experimental data acquisition and the development of kinetic models for liquid phase autoxidation.The experimental methodology is based on a complementary approach to obtain (i) a global reactivity descriptor (Induction Periods) and (ii) detailed species profiles respectively using a PetroOxy device and an instrumented autoclave. Numerically, the presented methodology includes detailed liquid phase mechanisms generation with an automatic mechanism generator (RMG). Normal and iso-paraffins were selected as fuel surrogates for autoxidation to validate the developed methodology. They were selected regarding their large contribution in fuel composition and their growing interest as drop-in fuels.The reactivity of both n-paraffins from C8 to C16 and several C8 iso-paraffins was investigated over a wide temperature range (373-433 K) in the PetroOxy with liquid phase analyses. Then, detailed species profiles from the autoxidation of both n-octane and 2-methylheptane in autoclave were obtained at 383 K and 10 bars. Detailed liquid phase mechanisms were developed for all molecules tested up to C14. Mechanisms qualitatively reproduce the overall phenomenology of the chain length, the branching and the major species profiles observed experimentally. Mechanisms analysis allow to identify the main consumption pathways of alkanes through peroxy (ROO) and peroxy-hydroperoxide radicals (HOOQOO) over the temperature range investigated (373-473 K).This study permitted to increase the comprehension of autoxidation processes involved in normal and branched alkanes. The study of new chemical systems will increase the global comprehension of autoxidation processes and in fine it will reduce the gap between the current autoxidation knowledge and the real fuel autoxidation.

Smart textiles especially Phase Change Materials (PCMs) are getting attention because these materials can provide regulation of wearer’s body climate and provide comfort in the temperature fluctuations during the physical activity like sports. These materials have the advantage of latent heat energy storage that can absorb and release high amount of energy over a narrow temperature range around the human’s body temperature to provide thermal comfort. Phase Change Materials (PCMs) absorb energy during the heating process as phase change takes place and release energy to the surroundings during the reverse cooling process. The types of phase change materials that are suitable for sports applications are hydrated inorganic salts, linear long chain hydrocarbons, Poly Ethylene Glycol (PEG). The concept of thermal comfort and working of PCMs in the textiles garments are important for determining the functionality of PCMs. Phase Change materials are micro capsulated in the shells by “Situ polymerization technique before application to sportswear and garments. The PCMs microcapsules are incorporated in the sportswear and garments by fiber technology, lamination, foaming and coating. The testing of clothing containing micro capsulated PCMs is discussed after the incorporation of PCMs in textiles. Quality parameters that are key for getting good results are mentioned i.e. particle size, thermal conductivity, fire hazard treatment, durability and performance of micro capsulated PCMs and clothing. In the last section findings, suggestions and conclusion are discussed. / Program: Magisterutbildning i Applied Textile Management

Chlorinated paraffins (CPs) are ubiquitous environmental contaminants. They fulfill all of the criteria (persistent, toxic, and subject to long-range transport) for persistent organic pollutants (POPs) according to the United Nations Economic Commission for Europe (UNECE). CPs are also under consideration for inclusion in the Stockholm Convention on POPs. Their presence has been shown in various environmental matrices in the industrialized parts of the world, as well as in remote regions such as the Arctic. The aim of this thesis was to increase the limited knowledge of the presence of CPs in the environment, their sources to the environment, and the resulting human exposure. An analytical procedure for the determination of CPs in environmental samples based on gas chromatography coupled to electron capture detection (GC-ECD) has been developed. GC-ECD is a relatively inexpensive instrument that is fast and easy to operate. These advantages open up the possibility for a comprehensive screening of the occurrence of CPs in the environment, including developing countries. Furthermore, the occurrence of CPs in ambient air and in indoor air and dust was studied. Elevated CP concentrations in indoor air (<5-210 ng/m3) were observed compared to ambient air (0.7-33 ng/m3), which is indicative of the presence of indoor emission sources. Indoor air and dust concentrations were used to estimate the human exposure to CPs via the indoor environment. Comparison of the estimates to available dietary intake estimates indicated that the indoor exposure pathways are not negligible. CP concentrations in ambient air from urban Stockholm were higher than in rural Aspvreten, Sweden. This indicates the presence of additional (emission) sources in urban areas compared to rural sites. Additionally, a seasonal variation of air concentrations was observed at both locations, suggesting temperature dependent emission sources for CPs. These observations were supported by a substance flow analysis of CPs performed for Stockholm. This study estimated the major emission sources of CPs to the Stockholm environment to be emissions from painted surfaces and in-place sealants. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 3: Manuscript. Paper 4: Manuscript.

京都大学 / 0048 / 新制・課程博士 / 博士(社会健康医学) / 甲第19968号 / 社医博第73号 / 新制||社医||9(附属図書館) / 33064 / 京都大学大学院医学研究科社会健康医学系専攻 / (主査)教授 木原 正博, 教授 松原 和夫, 教授 中山 健夫 / 学位規則第4条第1項該当 / Doctor of Public Health / Kyoto University / DFAM

Rapid economic development has occurred during the past few decades in China with the Yangtze River Delta (YRD) area as one of the most progressive areas. The urbanization, industrialization, agricultural and aquaculture activities result in extensive production and application of chemicals. Organohalogen contaminants (OHCs) have been widely used as i.e. pesticides, flame retardants and plasticizers. They are persistent, bioaccumulative and pose a potential threat to ecosystem and human health. However, limited research has been conducted in the YRD with respect to chemicals environmental exposure. The main objective of this thesis is to investigate the contamination level, distribution pattern and sources of OHCs in the YRD. Wildlife from different habitats are used to indicate the environmental pollution situation, and evaluate selected matrices for use in long term biomonitoring to determine the environmental stress the contamination may cause. In addition, a method is developed for dicofol analysis. Moreover, a specific effort is made to introduce statistic power analysis to assist in optimal sampling design. The thesis results show extensive contamination of OHCs in wildlife in the YRD. The occurrences of high concentrations of chlorinated paraffins (CPs) are reported in wildlife, in particular in terrestrial species, (i.e. short-tailed mamushi snake and peregrine falcon). Impurities and byproducts of pentachlorophenol products, i.e. polychlorinated diphenyl ethers (PCDEs) and hydroxylated polychlorinated diphenyl ethers (OH-PCDEs) are identified and reported for the first time in eggs from black-crowned night heron and whiskered tern. High concentrations of octachlorodibenzo-p-dioxin (OCDD) are determined in these samples. The toxic equivalents (TEQs) of polychlorinated dibenzo-p-dioxin (PCDDs) and polychlorinated dibenzofurans (PCDFs) are at mean levels of 300 and 520 pg TEQ g-1lw (WHO2005 TEQ) in eggs from the two bird species, respectively. This is two orders of magnitude higher than European Union (EU) regulation limit in chicken eggs. Also, a novel pattern of polychlorinated biphenyls (PCBs) with octa- to decaCBs, contributing to as much as 20% of total PCBs therein, are reported in birds. The legacy POPs shows a common characteristic with relatively high level of organochlorine pesticides (i.e. DDT, hexacyclohexanes (HCHs) and Mirex), indicating historic applications. In contrast, rather low concentrations are shown of industrial chemicals such as PCBs and polybrominated diphenyl ethers (PBDEs). A refined and improved analytical method is developed to separate dicofol from its major decomposition compound, 4,4’-dichlorobenzophenone. Hence dicofol is possible to assess as such. Statistic power analysis demonstrates that sampling of sedentary species should be consistently spread over a larger area to monitor temporal trends of contaminants in a robust manner. The results presented in this thesis show high CPs and OCDD concentrations in wildlife. The levels and patterns of OHCs in YRD differ from other well studied areas of the world. This is likely due to the extensive production and use of chemicals in the YRD. The results strongly signal the need of research biomonitoring programs that meet the current situation of the YRD. Such programs will contribute to the management of chemicals and environment in YRD, with the potential to grow into the human health sector, and to expand to China as a whole. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 5: Submitted. Paper 6: Manuscript.</p><p> </p>