Orientador: Denis Jose Schiozer / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica e Instituto de Geociencias / Made available in DSpace on 2018-08-13T11:18:36Z (GMT). No. of bitstreams: 1 Risso_ValmirFrancisco_D.pdf: 9435021 bytes, checksum: 278e304092ceeb3f841e585ac7a34e55 (MD5) Previous issue date: 2007 / Resumo: O ajuste de histórico de produção tem como principal objetivo calibrar modelos numéricos de campos de petróleo para que os resultados de produção e de pressão da simulação sejam coerentes com o histórico de produção e de pressão observados e que estes modelos ajustados possam ser usados na previsão de produção com maior confiabilidade. Essa técnica apresenta algumas limitações, principalmente no início do desenvolvimento do campo quando há menos dados observados e as incertezas são maiores, o que torna o processo de ajuste do modelo numérico menos confiável. Com o avanço das técnicas de processamento sísmico e com a sísmica 4D, já é possível a obtenção de mapas de saturação do campo e com essa informação adicional, melhorar a qualidade do modelo em estudo possibilitando realizar previsões de comportamento do campo mais confiáveis, principalmente em campos onde a água proveniente de poços injetores ou de aqüíferos ainda não alcançou os poços produtores. O trabalho atual propõe uma metodologia para aumentar a confiabilidade do modelo numérico através da incorporação dos mapas de saturação no processo de ajuste do histórico do campo, combinando estas informações com os dados de produção de óleo, água e gás, de injeção e de pressão. A utilização dos mapas no processo de ajuste aumenta o número de parâmetros a serem analisados no processo de ajuste, aumentando assim o número de simulações necessárias e dificultando a análise dos resultados. Uma alternativa para tentar minimizar esse problema é a metodologia do planejamento estatístico e da superfície de resposta, a qual permite estudar um número maior de variáveis e regiões críticas ao mesmo tempo possibilitando otimizar ou minimizar várias respostas simultaneamente, estruturando melhor as etapas do processo de ajuste evitando-se o processo usual de tentativa e erro. / Abstract: The main objective of history matching is to improve numerical models of oil fields by incorporating observed data, production and pressure, into the characterization process, in order to obtain more reliable production forecasting. This technique presents some limitations mainly in the beginning of the development of oil fields, when less information is available and higher uncertainties are present. With seismic 4D, it is possible to obtain saturation maps allowing the improvement of the numerical model yielding a more reliable production forecasting. The objective of this work is to developed a methodology to improve the numerical model through the incorporation of the saturation maps in the process of history matching. The process requires a higher number of critical parameters to be analyzed in the adjustment process; therefore, it is necessary to increase the number of simulations yielding a more complex procedure. An alternative to minimize this problem is the statistical design and response surface methodologies which allow to study many variables and regions at the same time. It is possible to optimize some answers simultaneously, improving the process by reducing the manual work yielding better results. / Doutorado / Reservatórios e Gestão / Doutor em Ciências e Engenharia de Petróleo

Friction Stir Welding (FSW) is an emerging joining technology in which basic process understanding is still inadequate. Knowledge of FSW parameter relationships is needed to better understand the process and implement proper machine control. This study utilized a 3-factor, 3-level factorial design of experiments to investigate relationships between key process inputs and measured output parameters. All experiments utilized 7075-T7 aluminum and a threaded pin tool with a 25.4 mm shoulder diameter, 4.76 mm pin length, and 7.9 mm pin diameter. Spindle speed, feed rate, and tool depth were varied throughout 54 welds while X, Y, and Z forces, X torque, three tool temperatures, and motor power were measured. Empirical models were developed to relate outputs to inputs. The relationships between inputs and outputs are nonlinear and require, at a minimum, a quadratic equation to reasonably model them. These models were further analyzed to explore possible control schemes. Tool depth was found to be the most fundamental means of controlling weld forces and tool temperatures. This research describes the input/output relationships enumerated above for FSW as well as a discussion of possible control schemes.

Nanomaterials have attracted substantial attention in the area of catalysis due to the unique properties they exhibit such as high surface areas, intricate pore networks and unique morphologies. TiO2 has attracted attention as a catalyst since the discovery of its high photocatalytic activity by Fuishima and Honda in 1972. Given its high thermal stability, low cost, low environmental impact, and versatility, TiO2 is a widely used commercial catalyst and catalyst support. TiO2 is used in many applications such as photocatalysis is also an excellent support material for noble metals in a number of oxidative synthesis and pollution-control reactions. Though TiO2 is a widely used catalyst support, currently available commercial titanias often have low surface area and poor thermal and hydrothermal stability. While several methods reported in literature produce materials of higher surface area and more ideal porosity relative to commercially available titanias, these procedures generally involve inherent drawbacks including time-consuming, complicated, and expensive processes that are not industrially viable. Cost-effective, large-scale preparations of stable, high surface area, mesoporous TiO2 need to be developed. The work in this dissertation focuses on (1) producing high surface area stabilized TiO2 supports of controlled pore diameters and (2) the preparation of well dispersed Pt on these supports using industrially viable processes. The effects of dopants Al, La, Si, and Zr on the stability, surface area, and porosity of anatase TiO2 supports were investigated. Results show that dopants increased the surface area and thermal stability of anatase through structural modifications and grain growth inhibition. Stabilized titanias produced by this method demonstrated equivalent or higher thermal stability and surface area compared with pure anatase and previously reported materials after treatment at 400°C and 700°C including 22 mol% Al-TiO2 calcined at 400°C which had a surface area of 479 ± 39 m2/g, a pore volume of 0.46 ± 0.04 cm3/g, and a pore diameter of 2.9 ± 0.2 nm. Ten synthesis variables were examined and optimized using statistically designed experiments (DOEs). Equations were developed to predict the conditions to obtain the highest surface area and pore volume at the desired pore diameter and predict the pore diameter range that may be obtained for aluminum-modified anatase TiO2. Confirmation trials closely matched predicted surface areas, pore volumes, and pore diameters in all but one trial, demonstrating the power of DOEs in identifying and controlling synthesis variables in relatively few experiments. The structure of Al-modified anatase TiO2 was analyzed to determine the mechanism of Al stabilization. Surface Al stabilized TiO2 by lowering anatase surface energy, stabilizing planes of high surface energy which would otherwise join to achieve stabilization. Al in TiO2 lattice vacancies stabilized TiO2 through increasing lattice strain and limiting mass transport necessary for grain growth. Results demonstrate the importance of structure analysis of doped nanomaterials in the development of stabilized catalysts and catalyst supports. An industrially viable, one-pot synthesis of Pt supported on 22 mol% Al-modified anatase is presented. Pt dispersions as high as 54% (one-pot method) and 59% (DI method) have been obtained. Results show that this one-pot method and the DI method using our Al-modified supports are promising syntheses of highly dispersed Pt catalysts and demonstrate that the alumina-stabilized anatase support is superior to other many available anatase supports.

自Duncan在1956年提出管制圖的經濟設計以來,陸續有許多學者提出各種不同型態管制圖的經濟設計,但是在這些文章中,尚無將描點的連串檢定列入考慮者,然而在管制圖中加入描點的連串檢定實有其必要性,加入描點的連串檢定可增加管制圖的偵測能力,但是這種作法頗為麻煩,因此Jaehn(1987)提出了區域管制圖來取代傳統管制圖加上連串檢定的不便,本研究提出X Bar-S Square 區域管制圖的經濟設計以改善一般經濟管制圖未將描點的連串檢定列入考慮的缺點.我們以製程中各項製程和成本資料為因子,對經濟區域管制圖的最佳設計參數值做敏感度分析,以找出製程中的關鍵參數.另外我們應用Saniga(1989)經濟統計管制圖的觀念設計經濟統計區域管制圖.雖然經濟統計區域管制圖所計算出的成本會比經濟區域管制圖稍大,但是在統計表現上卻符合我們的要求.

<p>The polychlorinated biphenyls (PCBs) comprise a group of 209 congeners varying in the number of chlorine atoms and substitution patterns. These compounds tend to be biomagnified in foodwebs and have been shown to induce an array of effects in exposed organisms. The structural characteristics of the PCBs influence their potency as well as mechanism of action. In order to assess the biological potency of these compounds a multi-step quantitative structure-activity relationship (QSAR) procedure was used in the project described in this thesis.</p><p>The ultraviolet absorption (UV) spectra were measured for all 209 PCBs, and digitised for use as physico-chemical descriptors. Interpretations of the spectra using principal component analysis (PCA) showed the number of ortho chlorine atoms and para-para substitution patterns to be significant. Additional physico-chemical descriptors were derived from semi-empirical calculations. These included various molecular energies, the ionisation potential, electron affinity, dipole moments, and the internal barrier of rotation. The internal barrier of rotation was especially useful for describing the conformation of the PCBs on a continuous scale.</p><p>In total 52 physico-chemical descriptors were compiled and analysed by PCA for the tetra- to hepta-chlorinated congeners. The structural variation within these compounds was condensed into four principal properties derived from a PCA for use as design variables in a statistical design to select congeners representative for these homologue-groups. The 20 selected PCBs have been applied to study structure-specific biochemical responses in a number of bioassays, and to study the biomagnification of the PCBs in various fish species.</p><p>QSARs were established using partial least squares projections to latent structures (PLS) for the PCBs potency to inhibit intercellular communication, activate respiratory burst, inhibit dopamine uptake in synaptic vesicles, compete with estradiol for binding to estrogen receptors, and induce cytochrome P4501A (CYP1A) related activities. By the systematic use of the designed set of PCBs the biological potency was screened over the chemical domain of the class of compounds. Further, sub-regions of highly potent PCBs were identified for each response measured. For risk assessment of the PCBs potency to induce dioxin-like activities the predicted induction potencies (PIPs) were calculated. In addition, two sets of PCBs were presented that specifically represent congeners of environmental relevance in combination with predicted potency to induce estrogenic and CYP1A related activities.</p>

The polychlorinated biphenyls (PCBs) comprise a group of 209 congeners varying in the number of chlorine atoms and substitution patterns. These compounds tend to be biomagnified in foodwebs and have been shown to induce an array of effects in exposed organisms. The structural characteristics of the PCBs influence their potency as well as mechanism of action. In order to assess the biological potency of these compounds a multi-step quantitative structure-activity relationship (QSAR) procedure was used in the project described in this thesis. The ultraviolet absorption (UV) spectra were measured for all 209 PCBs, and digitised for use as physico-chemical descriptors. Interpretations of the spectra using principal component analysis (PCA) showed the number of ortho chlorine atoms and para-para substitution patterns to be significant. Additional physico-chemical descriptors were derived from semi-empirical calculations. These included various molecular energies, the ionisation potential, electron affinity, dipole moments, and the internal barrier of rotation. The internal barrier of rotation was especially useful for describing the conformation of the PCBs on a continuous scale. In total 52 physico-chemical descriptors were compiled and analysed by PCA for the tetra- to hepta-chlorinated congeners. The structural variation within these compounds was condensed into four principal properties derived from a PCA for use as design variables in a statistical design to select congeners representative for these homologue-groups. The 20 selected PCBs have been applied to study structure-specific biochemical responses in a number of bioassays, and to study the biomagnification of the PCBs in various fish species. QSARs were established using partial least squares projections to latent structures (PLS) for the PCBs potency to inhibit intercellular communication, activate respiratory burst, inhibit dopamine uptake in synaptic vesicles, compete with estradiol for binding to estrogen receptors, and induce cytochrome P4501A (CYP1A) related activities. By the systematic use of the designed set of PCBs the biological potency was screened over the chemical domain of the class of compounds. Further, sub-regions of highly potent PCBs were identified for each response measured. For risk assessment of the PCBs potency to induce dioxin-like activities the predicted induction potencies (PIPs) were calculated. In addition, two sets of PCBs were presented that specifically represent congeners of environmental relevance in combination with predicted potency to induce estrogenic and CYP1A related activities.

This thesis illustrates parameter optimization of compressive strength, flexural strength and impact resistance of steel fiber reinforced high strength concrete (SFRHSC) by statistical design and analysis of experiments. Among several factors affecting the compressive strength, flexural strength and impact resistance of SFRHSC, five parameters that maximize all of the responses have been chosen as the most important ones as age of testing, binder type, binder amount, curing type and steel fiber volume fraction. Taguchi and regression analysis techniques have been used to evaluate L27(313) Taguchi&amp / #65533 / s orthogonal array and 3421 full factorial experimental design results. Signal to noise ratio transformation and ANOVA have been applied to the results of experiments in Taguchi analysis. Response surface methodology has been employed to optimize the best regression model selected for all the three responses. In this study Charpy Impact Test, which is a different kind of impact test, have been applied to SFRHSC for the first time. The mean of compressive strength, flexural strength and impact resistance have been observed as around 125 MPa, 14.5 MPa and 9.5 kgf.m respectively which are very close to the desired values. Moreover, this study is unique in the sense that the derived models enable the identification of underlying primary factors and their interactions that influence the modeled responses of steel fiber reinforced high strength concrete.

Orientadores: Saul Barisnik Suslick, Denis Jose Schiozer / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica, Instituto de Geociências / Made available in DSpace on 2018-08-12T08:07:04Z (GMT). No. of bitstreams: 1 Avansi_GuilhermeDaniel_M.pdf: 1362823 bytes, checksum: 732bf257c2ca9c9de80531fdd59770e5 (MD5) Previous issue date: 2008 / Resumo: O processo tradicional de estratégia de produção demanda muitas simulações, devido ao alto número de variáveis e combinações. Devido à impossibilidade de investigar todas as alternativas, processos tradicionais levam a resultados sub-ótimos. Processos automatizados podem resolver em partes esse problema, porém o tempo computacional se eleva devido ao acréscimo do número de simulações geradas no processo. Dentro desta perspectiva, este trabalho propõe uma metodologia de aplicação de metamodelos no processo de estratégia de produção e na avaliação econômica de campos de petróleo, possibilitando um número maior de alternativas e aumentando as chances de melhores decisões na escolha da estratégia de produção de campos de petróleo, sendo que metamodelos já foram utilizados em outras áreas (análise de risco, ajuste de histórico etc.). Os metamodelos estudados e aplicados envolvem: métodos estatísticos; planejamento estatístico; metodologia de superfície de resposta e teste de consistência. Os metamodelos utilizados neste trabalho mostraram que podem ser utilizados para seleção de estratégias de produção, trazendo uma opção adicional ao processo além de encontrar soluções que não são observadas pelos métodos tradicionais, e que permitiu mudar a decisão utilizada no processo de avaliação econômica em um amplo espaço de solução / Abstract: The traditional process of production strategy demands many simulations due to the high number of variables and possibilities. Sub-optimal results can be obtained from manual processes; Automatic processes can mitigate this problem but the computational effort increases as a result of the number of simulations generated in the process. Thus, the objective of this work is an attempt of application of proxy models in the production strategy optimization and in the economic evaluation in petroleum fields, allowing the selection of production strategy evaluating a higher number of alternatives and increasing the chances to find better solutions. Proxies have been used in important applications such as risk analysis, history matching etc. The applied proxy models combine the following components: statistics methods, experimental planning, the response surface methodology and consistency checking. We have shown that proxy models can be used in a definition of production strategy, bringing an additional option in the process. The advantage is to find solutions that are not investigated by the traditional methods; proxy models create new possibilities to change a decision used in an economic evaluation process in a wider solution space / Mestrado / Reservatórios e Gestão / Mestre em Ciências e Engenharia de Petróleo

Abstract Fertilizer industry often generates phosphorous rich wastewaters containing heavy metals. While phosphorous is a valuable compound for the industry, heavy metals hinder the recovery of phosphorous due to their detrimental effects on human health and the environment. Consequently, heavy metals must be removed from the wastewaters. In this study the use of micellar-enhanced ultrafiltration (MEUF) was evaluated for the removal of cadmium, copper, zinc and nickel from phosphorous rich wastewaters. This study has been conducted following a systematic methodology from single metal synthetic wastewaters to more complex synthetic and real wastewaters. The experimental work was conducted in a laboratory scale stirred cell using 3, 5 and 10 kDa regenerated cellulose membranes and in a cross flow semi-pilot scale equipment using a 10 kDa spiral wound polyethersulphone membrane. Statistical design of experiments was used as the research methodology to evaluate the effect of factors on the MEUF process performance as well as for finding optimal conditions. The factors studied were heavy metal, phosphorous and surfactant feed concentrations, pH, membrane nominal molecular weight limits, transmembrane pressure and cross flow velocity. The membrane performance was characterized by the heavy metal retention/rejection coefficients and the permeate flux. The experimental results showed that the removal of heavy metals from single synthetic wastewaters by MEUF is more efficient for more diluted systems. In complex systems containing phosphorous, simultaneous removal of heavy metals was successfully achieved obtaining rejection coefficients up to 80%. Phosphorous was not retained by the membrane showing the potential applicability of MEUF to purify phosphorous rich wastewaters. The study of metal complex formation and heavy metal competition has been shown to be very important in order to predict the MEUF results. Concentration polarization phenomenon was insignificant in the synthetic wastewaters but it was more severe when applying MEUF to real wastewaters. In addition, with real wastewaters SDS leakage was insignificant. This study has provided new and valuable knowledge regarding the applicability of MEUF to industrial wastewater treatment. / Tiivistelmä Lannoiteteollisuus tuottaa usein jätevesiä, jotka sisältävät huomattavia määriä fosforia, sekä pieniä määriä raskasmetalleja. Vaikka fosfori on tärkeä raaka-aine lannoiteteollisuudelle, jätevesissä olevat raskasmetallit kuitenkin estävät sen hyötykäyttöä fosforin lähteenä. Raskasmetallit ovat haitallisia sekä luonnolle että ihmisten terveydelle, joten niiden erottaminen jätevesistä on tärkeää. Tässä työssä tutkittiin miselliavusteisen ultrasuodatuksen (MEUF) käyttöä kadmiumin, kuparin, sinkin ja nikkelin poistamiseen fosforipitoisista jätevesistä. Väitöskirjatyössä tutkittiin systemaattisesti synteettisiä jätevesiä, jotka sisälsivät joko yhtä tai useita raskasmetalleja, sekä lannoitetehtaalta kerättyjä jätevesiä. Kokeet tehtiin laboratoriomittakaavan sekoituskennolla, jossa käytettiin 3, 5 ja 10 kDa:n regeneroituja selluloosakalvoja, sekä semi-pilot -mittakaavan spiraalielementillä, jonka materiaalina oli 10 kDa:n polyeetterisulfonikalvo. Väitöskirjatyössä hyödynnettiin tilastollista koesuunnittelua, jonka avulla arvioitiin muuttujien vaikutuksia MEUF-prosessin käyttäytymiseen. Koesuunnittelua hyödynnettiin myös optimiolosuhteiden määrittelemisessä. Koesuunnitelmien muuttujina olivat raskasmetallien, fosforin ja pinta-aktiivisen aineen pitoisuudet, pH, suodatuskalvojen katkaisukoot, paine sekä ristikkäisvirtauksen nopeus. Kalvon käyttäytymistä arvioitiin raskasmetallien erotustehokkuuden ja permeaattivuon avulla. Koetulokset osoittivat raskasmetallien erotuksen olevan tehokkainta synteettisistä, yhtä metallia sisältävistä jätevesistä, joiden raskasmetallipitoisuus oli pieni. Fosforia sisältävistä monimetalliliuoksista saavutettiin 80&#160;%:inen raskametallien poistotehokkuus. Kalvoerotuksessa fosforipitoisuus ei muuttunut merkittävästi, mikä osoittaa MEUF:n olevan potentiaalinen menetelmä raskasmetallien poistamiseen fosforipitoisista jätevesistä. Metallikompleksien muodostumisen ja raskasmetallien välisen kilpailun ymmärtäminen osoittautuivat erittäin tärkeiksi MEUF-tuloksien ennustamisessa. Konsentraatiopolarisaatioilmiö ei ollut merkittävä käsiteltäessä synteettisiä jätevesiä, mutta teollisten jätevesien käsittelyssä ilmiöllä oli huomattava vaikutus permeaattivuohon. Kuitenkin teollisen jätevesien käsittelyssä SDS:n vuotaminen kalvon läpi oli merkityksetöntä. Tämä tutkimus on antanut uutta ja merkittävää tietoa MEUF:n soveltuvuudesta teollisten jätevesien käsittelyn.

>Magister Scientiae - MSc / Millions of tonnes of fly ash are generated worldwide every year to satisfy the large demand for energy. Management of this fly ash has been a concern and various approaches for its beneficial use have been investigated. Over the last two decades, there has been intensive research internationally that has focused on the use of different sources of fly ash for zeolite synthesis.However, most of the studies have concentrated on class C fly ash and very few have reported the use of South African class F fly ash as feedstock for zeolite synthesis.Class F fly ash from South Africa has been confirmed to be a good substrate for zeolite synthesis due to its compositional dominance of aluminosilicate and silicate phases. However, because differences in quartz-mullite/glass proportions of fly ash from different sources produces impure phases or different zeolite mineral phases under the same activation conditions, the present study focused on optimization of synthesis conditions to obtain pure phase zeolite Na-P1 from class F South African coal fly ash. Synthesis variables evaluated in this study were; hydrothermal treatment time (12 - 48 hours), temperature (100 – 160 oC) and addition of varying molar quantities of water during the hydrothermal treatment step (H2O:SiO2 molar ratio ranged between 0 - 0.49).Once the most suitable conditions for the synthesis of pure phase zeolite Na-P1 from fly ash were identified, a statistical approach was adopted to refine the experiments, that was designed to evaluate the interactive effects of some of the most important synthesis variables. In this case, the four synthesis variables; NaOH concentration (NaOH: SiO2 molar ratio ranged between 0.35– 0.71), ageing temperature (35 oC – 55 oC), hydrothermal treatment time (36 - 60 hours) and temperature (130 oC – 150 oC) were studied. The response was determined by evaluating the improvement in the cation exchange capacity of the product zeolite.The starting materials (fly ashes from Arnot, Hendrina and Duvha power stations) and the synthesized zeolite product were characterized chemically, mineralogically and morphologically by X-Ray fluorescence spectrometry, X-ray powder diffraction, scanning electron microscopy, and transmission electron microscopy. Other characterization technique used in the study were Fourier transform infrared spectroscopy to provide structural information and also monitor evolution of crystallinity during synthesis, as well as cation exchange capacity to determine the amount of exchangeable positively charged ions. Nitrogen adsorption was used to determine the surface area and porosity, and inductively coupled mass spectrometry for multi-elemental analysis of the post-synthesis supernatants.The results from the X-ray diffraction spectroscopy showed that the most pure zeolite Na-P1 phase was achieved when the molar regime was 1 SiO2 : 0.36 Al2O3 : 0.59 NaOH : 0.49 H2O and at synthesis conditions such that ageing was done at 47 oC for 48 hours while the hydrothermal treatment time and temperature was held at 48 hours and 140 oC, respectively. Results from statistically designed experiments show that there was a distinct variation of phase purity with synthesis conditions. From the analysis of linear and non linear interactions, it was found that the main effects were ageing temperature and hydrothermal treatment time and temperature, which also showed some interactions. This experimental approach enabled a clearer understanding of the relationship between the synthesis conditions and the purity of the zeolite Na-P1 obtained.The quality of zeolites is a major determinant in the efficiency of toxic element removal from waste water. Preliminary experiments conducted using optimised zeolite Na-P1 obtained in this study with a cation exchange capacity of 4.11 meq/g showed a high percentage removal of Pb,Cd, Ni, Mn, V, As, B, Fe, Se, Mo Sr, Ba and Zn from process brine obtained from Emalahleni water reclamation plant.In summary, a pure phase of zeolite Na-P1 was obtained from South African class F fly ash feedstock at relatively mild temperature. The systematic approach, incorporating statistical design of experiments, developed in this study resulted in a better understanding regarding the relationships of synthesis parameters in the formation of zeolites from fly ash. The zeolite Na-P1 synthesized with a high cation exchange capacity was effective for removal of toxic elements from brine.