Made available in DSpace on 2014-12-17T14:08:53Z (GMT). No. of bitstreams: 1 JussyaraDMA_DISSERT_PARCIAL.pdf: 4692370 bytes, checksum: 475e965cf0951180f8df9ac44768b423 (MD5) Previous issue date: 2012-12-14 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The growing world demand for energy supplied by fossil fuels, a major contributor to the emission of pollutants into the atmosphere and causing environmental problems, has been encouraging governments and international organizations to reflect and encourage the use of alternative renewable sources. Among these new possibilities deserves attention biodiesel, fuel cleaner and easy to reproduce. The study of new technologies involving that source is necessary. From this context, the paper aims at analyzing the thermal stability by thermogravimetric analysis, of the waste generated from atmospheric distillation of mixtures with ratios of 5, 10, 15 and 20% palm biodiesel in diesel with and without addition of BHT antioxidant. It was synthesized biodiesel through palm oil, via homogeneous catalysis in the presence of KOH, with and without the use of BHT and subsequently added to the diesel common indoor type (S1800) from a gas station BR. The diesel was already added with 5% biodiesel, and thus the proportions used for these blends were subtracted from the existing ratio in diesel fuel, resulting in the following proportions palm oil biodiesel: 0% (B5), 5% (B10), 10 % (B15) and 15% (B20). From atmospheric distillation analysis, performed in mixtures with and without BHT were collected residue generated by each sample and performed a thermal study from the thermogravimetric analysis at a heating rate of 10 ?C.min-1, nitrogen atmosphere and heating to 600 ? C. According to the specifications of Resolution No. 7/2008 for biodiesel, it was found that the material was synthesized in accordance with the specifications. For mixtures, it was noted that the samples were in accordance with the ANP Resolution No. 42/2009. Given the TG / DTG curves of the samples of waste mixtures with and without BHT antioxidant was able to observe that they showed a single stage of thermal decomposition attributed to decomposition of heavy hydrocarbons and esters and other heavier constituents of the waste sample weighed. The thermal behavior of residues from atmospheric distillation of mixtures of diesel / biodiesel is very important to understand how this affects the proper functioning of the engine. A large amount of waste can generate a high content of particulate material, coke formation and carbonaceous deposits in engine valves, compromising their performance / A crescente demanda mundial por energia fornecida pelos combust?veis f?sseis, um dos principais respons?veis pela emiss?o de poluentes ? atmosfera e causadores de problemas ambientais, vem estimulando governos e Organismos internacionais a refletir e incentivar o uso de fontes alternativas renov?veis. Dentre essas novas possibilidades merece destaque o biodiesel, combust?vel menos poluente e de f?cil reprodutibilidade. O estudo de novas tecnologias envolvendo essa fonte faz-se necess?rio. Partindo desse contexto, o trabalho tem como objetivo principal analisar a estabilidade t?rmica, por meio da An?lise Termogravim?trica, dos res?duos gerados da destila??o atmosf?rica das misturas com propor??es de 5, 10, 15 e 20 % de biodiesel de dend? no diesel com e sem a adi??o de antioxidante BHT. Sintetizou-se o biodiesel atrav?s do ?leo de dend?, via cat?lise homog?nea na presen?a de KOH, com e sem o uso de BHT, e posteriormente, adicionou-se ao diesel comum do tipo interior (S1800) proveniente de um posto de gasolina BR. Este diesel j? estava aditivado com 5 % de biodiesel, sendo assim, as propor??es utilizadas para estas misturas foram subtra?das da propor??o existente no diesel, resultando nas seguintes propor??es de biodiesel de dend?: 0% (B5), 5% (B10), 10% (B15) e 15% (B20). Da an?lise de Destila??o Atmosf?rica, realizada nas misturas com e sem BHT, foram coletados o res?duo gerado por cada amostra e efetuado um estudo t?rmico, a partir da An?lise Termogravim?trica, na raz?o de aquecimento de 10 ?C.min-1, atmosfera de nitrog?nio e aquecimento at? 600 ?C. De acordo com as especifica??es da Resolu??o N? 7/2008 para o biodiesel, foi constatado que o material sintetizado estava em conformidade com as especifica??es. No tocante ?s misturas, notou-se que as amostras estavam de acordo com a Resolu??o da ANP N? 42/2009. Diante das curvas TG/DTG das amostras de res?duos das misturas com e sem antioxidante BHT, p?de observar que estas apresentaram uma ?nica etapa de decomposi??o t?rmica atribu?da ? decomposi??o dos hidrocarbonetos pesados e dos ?steres met?licos pesados e outros constituintes pesados da amostra de res?duo. O estudo do comportamento t?rmico do res?duo gerado da destila??o atmosf?rica das misturas de ?leo diesel/biodiesel ? de grande relev?ncia para entendermos o qu?o este interfere no bom funcionamento do motor. Uma grande quantidade de res?duos pode gerar um alto teor de material particulado, forma??o de coque e dep?sitos carbon?ceos nas v?lvulas do motor, comprometendo seu desempenho

Orientador: Caio Glauco Sanchez / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-10T13:46:01Z (GMT). No. of bitstreams: 1 Silva_GiovaniltonFerreirada_D.pdf: 2151460 bytes, checksum: b4f7aed8eddbf42f0d871e6e526ef9b0 (MD5) Previous issue date: 2006 / Resumo: Objetivo deste trabalho foi obter os parâmetros cinéticos do poliéster insaturado com fibra de vidro em balança termogravimétrica e a aplicação do leito fluidizado como reator de pirólise. Primeiramente foi feito um estudo para escolher o modelo cinético a partir dos dados obtidos na balança termogravimétrica. O resultado apontou o modelo de primeira ordem como o mais adequado. Foi feito um planejamento fatorial 22 a fim de avaliar a influência que as variáveis, taxa de aquecimento e diâmetro da partícula, tiveram nos parâmetros cinéticos. Os resultados do planejamento fatorial mostraram que a taxa de aquecimento foi o fator mais importante seguido do diâmetro da partícula, e não houve interação entre os fatores. A energia de ativação foi inversamente proporcional com a taxa de aquecimento e diretamente proporcional com o diâmetro da partícula. A taxa de 10°C/min foi a taxa que forneceu os melhores parâmetros cinéticos. Para leito fluidizado foi proposto um planejamento fatorial 23 para avaliar a influência das variáveis, temperatura, velocidade de fluidização e altura do leito fluidizado, tiveram no rendimento da fração liquida, gasosa e sólida. Os resultados mostraram que a temperatura foi a variável que mais influenciou o processo de pirólise em leito / Abstract: The aim of this work was to find out the kinetic parameters of unsatured polyester with fiberglass using thermogravimetric analysis, and to apply a fluidized bed like pyrolysis reactor. Firstly, it was selected a kinetic model most suitable to use with obtained data from thermogravimetric analysis. The results pointed the first order model like most suitable. It was performed a factorial analysis 22 in order to analyze the system. The experimental variables have varied simultaneously and systematically (heating rate and particle diameter). The responsevariables were used to evaluate the kinetic parameters. The experimental results of the factorial design showed that heating rate was the effect more significant and there were not interactions between the studied variables. The results showed that activity energy decreased when the heating rate increased and, it increased with increasing particle diameter. The heating rate of 10°C/min achieved the best kinetic parameters. Statistical method was applied to fluidized bed followed a 23 factorial design to evaluate the influence of variables: temperature, fluidized rate and height of fluidized bed. Response variables were yield of oil, yield of gas and, yield of solid. The results showed that temperature was the variable most significant for the pirolysis process at fluidized bed. / Doutorado / Termica e Fluidos / Doutor em Engenharia Mecânica

A crescente necessidade de se obter fontes de energia e materiais mais sustentáveis tem aumentado o interesse em processos baseados na conversão de biomassa. Microalgas são particularmente interessantes por não competirem com alimentos e serem facilmente adaptáveis ao meio de crescimento. Além disso, microalgas podem ser processadas termicamente para geração tanto de biocombustíveis quanto de produtos químicos úteis. Estudos de conversão térmica de microalgas tem aparecido apenas em anos recentes, endereçando principalmente temperaturas entre 350 e 500 ºC. Neste estudo, a pirólise em temperaturas entre 500 e 900 ºC foi avaliada pelo interesse em se obter biocombustíveis e produtos químicos úteis. As classes de compostos obtidos a partir da pirólise isotérmica da microalga da espécie Chlorella vulgaris foram investigadas através de um sistema composto por um pirolisador conectado a um CG/MS. Dentre as classes identificadas, houve uma predominância de compostos aromáticos e nitrogenados, principalmente derivados de proteínas. Além disso, a maioria dos compostos identificados na corrente de produtos voláteis está presente em todas as temperaturas de reação estudadas. Os parâmetros cinéticos de energia de ativação aparente, constante de reação e ordem de reação foram determinados através de três modelos cinéticos conhecidos como K-A-S, Osawa e Freeman-Carroll, a partir de dados termogravimétricos. A energia de ativação determinada para Chlorella apresentou valores entre 60 e 206 kJ/mol, enquanto a ordem de reação teve como resultado valores entre segunda e décima ordem, de acordo com o modelo cinético. / The increasing need to obtain more sustainable sources of energy and raw materials has attracted attention to processes based on biomass conversion. Microalgae are particularly interesting because they do not compete with human food and they are easily adaptable to the growth medium. Besides, microalgae can be thermally processed to produce both biofuels and useful chemicals. Studies on thermal conversion of microalgae have appeared only in recent years, addressing mainly reaction temperatures between 350 and 500 °C. In this study, pyrolysis in temperatures ranging from 500 to 900 ºC have been investigated considering the interest in producing biofuels and useful chemical compounds. The classes of products obtained by isothermal pyrolysis of the Chlorella vulgaris microalgae have been investigated using a pyrolyzer directly connected to a GC/MS system. Among the classes identified, there was a predominance of aromatic and nitrogenous compounds, mainly protein derived compounds. In addition, most products identified in the volatile products stream are present in all reaction temperatures investigated. The kinetic parameters of apparent activation energy, reaction constant and order of reaction were determined through three kinetic models known as K-A-S, Osawa and Freeman-Carroll, calculated from thermogravimetric data. The activation energy for Chlorella presented values within the range of 60 and 206 kJ/mole, while the order of reaction resulted in values between second and tenth order, from the different methods.

M. Tech (Department of Chemistry, Faculty of Applied and Computer Sciences) Vaal University of Technology. / Persisting challenges associated with remediation of heavy metals from aqueous media have stirred the need for enhancement of current technologies. Cellulosic agro waste materials (AWM) as well as ion-imprinted polymers (IIP) have received ardent attention from researchers. These materials are often employed in the following industries: water and wastewater treatment, medical, pharmaceutical and packaging. Applications in water and wastewater treatment have gained significant interest due to desirable features they possess. In the case of AWM, these features include a tuneable surface area and poor porosity, basic surface functional groups and chemical stability. Some desired features in IIP include adsorption sites compatible for the ion imprint obtained after leaching with suitable reagents, rigidity and reusability. The efficacy of employing AWM and IIP for the remediation of toxic chromium from aqueous solution was explored. The current study is made up of part A and B. In part A, Macadamia nutshell powder was treated using HNO3, NaOH, as well as Fenton’s reagent. The three materials underwent a new modification which involved reacting treated adsorbents with cetyltrimethylammonium chloride (CTAC), followed by immobilization of 1,5' diphenylcarbazide (DPC) ligand. The adsorbents were ultimately washed, dried and stored for Cr(VI) batch adsorption experiments. Part B involved a synthesis of IIP and their non-imprinted polymer counterpart (NIP) for Cr(VI) sequestration in aqueous solution. This was done by precipitation polymerization of functional monomers, crosslinker and DPC-Cr(VI) complex as a template. Non-imprinted polymers were fashioned in a manner like that of IIP but with the exclusion of Cr(VI) ion template. Characterizations of the adsorbents were done using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray fluorescence (XRF), and carbon, hydrogen, nitrogen and sulphur (CHNS) analyzer. Batch adsorption experiments were done and parameters such as solution pH, adsorbent dosage, initial Cr(VI) concentration and contact time were optimized. Working solutions were analyzed using ultraviolet-visible (UV-Vis) and atomic absorption (AA) spectroscopy. Adsorption parameters found to be optimum for DPC immobilized cellulosic adsorbents were pH 1.4, adsorbent mass of 0.1 g, 100 mg/L initial concentration and 125 minutes of contact time. The adsorption parameters determined to be optimum for IIP and NIP were pH 2.6, 0.2 g adsorbent mass, 80 mg/L initial concentration and 240 minutes of contact time. Reusability studies demonstrated the potential of adsorbents to remove Cr(VI) ions from aqueous media after successive adsorption-desorption cycles. Selectivity studies indicated that DPC immobilized adsorbents as well as IIP were able to selectively adsorb Cr(VI) ions from aqueous media in the presence of Zn(II), Cu(II), Co(II) and NI(II) ions. Kinetic models revealed that DPC immobilized cellulosic adsorbents and synthetic IIP were most fitting for pseudo-second order and pseudo first order, respectively. On the other hand, adsorption isotherm studies demonstrated that DPC immobilized cellulosic adsorbents and synthetic polymers were best fit for Freundlich and Langmuir adsorption isotherm, respectively.

This thesis deals with the stopping of hydration of alkali activated slag by organic solvents and investigates to what extent the selected organic solvent affects the results of the analyses. The solvents used were acetone, diethyl ether, ethanol, isopropanol and methanol, and this is because these are the most commonly used organic solvents in practice. Thermogravimetric analysis along with differential thermal analysis was used to assess the degree of influence of organic solvents on the alkali activated slag and Portland cement samples. Methanol and acetone affected the samples the most and the longer the sample was stored in the solvent, the more it reacted with the organic solvent. The adverse interaction of organic solvent was greatest for the Portland cement samples. Samples that were rinsed with diethyl ether prior to analysis had lower mass losses than samples that were not rinsed. In the case of alkali activated slag, it was found that the way in which the thermogravimetric results were affected by organic solvents was highly dependent on the activator used, with the smallest effect observed for Na2CO3 activation, while the largest effect was observed for NaOH activation at temperatures below 600 °C, and for higher temperatures for water glass activation.

Tato práce se zabývá studiem termooxidační stability kompozitů polymethylmethakrylátu (PMMA) plněného mikro a nanočásticemi siliky. V připravených vzorcích byly použity různé objemové zlomky a různé velikosti částic siliky. Studium stability bylo prováděno pomocí termogravimetrie, která umožňuje simulovat podmínky termooxidační degradace. Indukční perioda byla stanovena za použití různých rychlostí ohřevu a aplikací izokonverzních metod. Závislosti teplot degradací na rychlostech ohřevu sloužily pro určení parametrů odvozených ze čtyř různých teplotních funkcí, které dovolují předpověď stability materiálu (indukční periody) při zvoleném rozsahu teplot. Zjištěné výsledky ukazují, že větší částice siliky snižuji stabilitu PMMA, zatímco nanočástice v nízkých koncentracích ji nijak neovlivňují.

No description available.

No description available.

For the first time, a novel processing method of co-refining wood and polyolefin (PO) by steam-explosion was scientifically explored for wood-thermoplastic composites without a coupling agent. Traditional studies have addressed the improvement of adhesion between components of wood thermoplastic composites through the use of coupling agents such as maleated PO. The objective of this study was to increase adhesion between wood and PO through reactive processing conditions of steam-explosion. PO characteristics, such as type (polyethylene or polypropylene), form (pellet, fiber, or powder) and melt viscosity were studied along with oxygen gas content of the steam-explosion reactor vessel. Modification of co-processed wood fiber was characterized in four studies: microscopy analysis of dispersion of PO with wood fiber, sorption properties of co-processed material, chemical analysis of fractionated components, and morphological investigation of co-processed material. Two additional studies are listed in the appendices that relate to adsorption of amphiphilic polymers to the cellulose fiber surface, which is one hypothesis of fiber surface modification by co-steam-explosion. Microscopy studies revealed that PO melt viscosity was found to influence the degree of dispersion and uniformity of the steam-exploded material. The hygroscopic nature of the co-processed fiber declined as shown by sorption isotherm data. Furthermore, a water vapor kinetics study found that all co-refined material had increased initial diffusion coefficients compared to the control fiber. Chemical changes in fractionated components were PO-type dependent. Lignin extracted from co-processed wood and polyethylene showed PO enrichment determined from an increase of methylene stretching in the Fourier Transform infrared subtraction spectra, while lignin from co-processed wood and polypropylene did not. Additionally, extracted PO showed indirect signs of oxidation as reflected by fluorescence studies. Solid state nuclear magnetic resonance spectroscopy revealed a number of differences in the co-processed materials such as increased cellulose crystallinity, new covalent linkages and an alternative distribution of components on the nanoscale reflected in the T1Ï relaxation parameter. Steam-explosion was shown to modify wood fiber through the addition of "non-reactive" polyolefins without the need for coupling agents. In light of these findings, co-refining by steam-explosion should be viewed as a new reactive processing method for wood thermoplastic composites. / Ph. D.

Inhalation of respirable dust in coal mines is a serious occupational health hazard which can lead to the development of chronic and irreversible lung diseases, such as Coal Worker's Pneumoconiosis (CWP) and Progressive Massive fibrosis (PMF). After the passage of the Federal Coal Mine Health and Safety Act (CMHSA) in the late 1960's the prevalence of CWP among US coal miners decreased. However, since the late 1990's a resurgence of lung diseases has been reported, particularly in central Appalachia. On the other hand, dust monitoring data suggest that concentrations of respirable coal mine dust (RCMD) and crystalline silica have been on a downward trend. This contradiction has prompted keen interest in detailed characterization of RCMD to shed light on dust constituents-and their sources. Such information might help miners understand where and under what conditions specific sources contribute to RCMD, and how dust controls and monitoring could be enhanced to mitigate the exposure to respirable hazards. Respirable dust particles generated in coal mines are generally associated with three primary sources: the coal strata that is mined and generates mostly coal particles that could contribute for lung diseases, the rock strata that is cut along with the coal and generates most of the respirable silica and silicates, and the rock dust products that are the main source of carbonates which could produce respiratory irritations. Thermogravimetric Analysis (TGA) is one of many analytical tools that might be used for dust characterization. Its primary benefit is that it can be used to apportion the total sample mass into three mass fractions (i.e., coal, carbonates, non-carbonates) which should be roughly associated with the primary dust sources (i.e., coal strata, rock dust products, rock strata) in many coal mines. This thesis consists of two main chapters: Chapter 1, outlines the research motivation, recaps the efforts to establish a standard TGA method for RCMD, and shows results of the validation experiments that were performed in the current work to enable application of the TGA method to a large set of RCMD and laboratory-generated dust samples. In Chapter 2, 46 lab-generated samples from primary dust source materials collected in 15 coal mines, and 129 respirable dust samples from 23 US coal mines are analyzed using the TGA method validated in Chapter 1. Results for both sets of samples are presented and the mine samples are interpreted based on sampling location, mining method and region. Additionally, Chapter 3 summarizes recommendations for future work. / Master of Science / The chronic exposure to dust generated in underground coal operations represents a serious health concern among coal miners that can lead to the development of lung diseases such as Coal Workers Pneumoconiosis (CWP or "black lung). Despite of dust compliance monitoring data that have shown that the concentrations of dust have been declining, since the late 1990's the number of US coal miners diagnosed with lung diseases has been increasing, especially in central Appalachia. This contradiction has prompted keen interest in detailed characterization of respirable coal mine dust (RCMD) to shed light on dust constituents-and their sources. Such information might help miners understand where and under what conditions specific sources contribute to RCMD, and how dust controls and monitoring could be enhanced to mitigate the exposure to respirable hazards. Thermogravimetric Analysis (TGA) has been proposed as an alternative approach for dust characterization. Its primary benefit is that it can be used to apportion the total sample mass into three mass fractions (i.e., coal, carbonates, non-carbonates) which should be roughly associated with the primary dust sources (i.e., coal strata, rock dust products, rock strata) in many coal mines. This thesis consists of two main chapters: Chapter 1, outlines the research motivation, recaps the efforts to establish a standard TGA method for RCMD, and shows results of the validation experiments that were performed in the current work to enable application of the TGA method to a large set of RCMD and laboratory-generated dust samples. In Chapter 2, 46 lab-generated samples from primary dust source materials collected in 15 coal mines, and 129 respirable dust samples from 23 US coal mines are analyzed using the TGA method validated in Chapter 1. Results for both sets of samples are presented and the mine samples are interpreted based on sampling location, mining method and region. Additionally, Chapter 3 summarizes recommendations for future work.