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.

The chemical binders used to make sand molds and cores thermally decompose and release gas when subjected to the high temperature conditions in sand casting processes. Computational models that predict the evolution of the binder gas are being introduced into casting simulations in order to better predict and eliminate gas defects in metal castings. These models require knowledge of the evolved binder gas mass and molecular weight as a function of temperature, but available gas evolution data are limited. In the present study, the mass and molecular weight of gas evolved from PUNB bonded sand are measured as a function of temperature for use with binder gas models. Thermogravimetric analysis of bonded sand is employed to measure the binder gas mass evolution as a function of temperature for heating rates experienced in molds and cores during casting. The volume and pressure of gas evolved from bonded sand are measured as a function of temperature in a specially designed quartz manometer during heating and cooling in a furnace. The results from these experiments are combined with the ideal gas law to determine the binder gas molecular weight as a function of temperature. Thermogravimetric analysis reveals that the PUNB binder significantly decomposes when heated to elevated temperatures, and the PUNB binder gas mass evolution is not strongly influenced by heating rate. During heating of PUNB bonded sand at a rate of 2°C/min, the binder gas molecular weight rapidly decreases from 375 g/mol at 115°C to 99.8 g/mol at 200°C. The molecular weight is relatively constant until 270°C, after which it decreases to 47.7 g/mol at 550°C. The molecular weight then steeply decreases to 30.3 g/mol at 585°C and then steeply increases to 47.2 g/mol at 630°C, where it remains constant until 750°C. Above 750°C, the binder gas molecular weight gradually decreases to 33.3 g/mol at 898°C. The present measurements are consistent with the molecular weights calculated using the binder gas composition data from previous studies. The binder gas is composed of incondensable gases above 709°C, and the binder gas partially condenses during cooling at 165°C if the bonded sand is previously heated below 507°C.

Uncoated defects in hot dip metal-coated steel products result from non-wetting of the steel surface by the molten alloy. The occurrence of uncoated defects is highly detrimental to product quality and production efficiency; uncoated defects compromise the appearance and anti-corrosion performance of hot dip metal-coated steel products and causes time delays in the application of subsequent surface treatments. Although many studies have been directed towards evaluating the effect of steel pre-heat temperature and oxidation on the formation of uncoated defects, fewer investigations have analysed how oil-derived residues remaining on steel surface following the cold rolling and furnace cleaning processes impact upon hot dip metallic coating quality. Furthermore, although a considerable amount of research has focussed on the process of deposit formation in lubricants used in other applications, the composition of oily residues remaining after the continuous annealing process, and the origins of these residues in the original rolling oil formulation, are poorly understood. The primary focus of the present work has been to gain an improved understanding of relationships between cold rolling oil composition, oil residue-formation characteristics and the occurrence of uncoated defects in 55Al-43.4Zn-1.6Si hot dip metallic coatings. Several key classes of rolling oil ingredients which decompose to leave high levels of thermally-stable residue have been identified. The thermal decomposition processes undergone by a variety ingredients within these classes have been studied under both oxidising and reducing conditions using Thermogravimetric Analysis (TGA) and Pressure Differential Scanning Calorimetry (PDSC) techniques, with chemical characterisation of the decomposition process and the resultant thermally-stable residue by infrared spectroscopy. Model blends of each ingredient in a typical cold rolling oil base ester have also been evaluated by TGA and PDSC to identify the impact of ingredient concentration and chemical structure on the amount of oily residue formed. The results of these investigations have been related to the impact of the ingredients on 55Al-43.4Zn-1.6Si hot dip metallic coating quality through the performance of industrial-scale hot dipping trials and hot dip simulation studies. In order to translate these results into a context more closely aligned with industrial conditions, the effect of processing variables, including furnace atmosphere and the availability/concentration of iron in contact with the rolling oil at the steel surface, on the decomposition process of a fully-formulated commercial cold rolling oil has also been investigated. The information gained can potentially be used to tailor operating conditions within the cold rolling/continuous hot dip metallic coating processes to enhance steel surface cleanliness. Finally, the deposit-forming tendencies of an array of different commercial cold rolling oils have been evaluated, leading to the development of a thermal analysis-based test for screening cold rolling oils with respect to their likely impact upon 55Al-43.4Zn-1.6Si hot dip metallic coating quality. This test, together with the understanding obtained on the effect of different rolling oil ingredients on hot dip metallic coating quality, can be used within the industry to formulate improved cold rolling oils.

This study investigated the adsorptive capacity and isotherm of HgCl2 onto spherical activated carbons (SAC) via thermogravimetric analysis (TGA). Activated carbon injection (ACI) is thought as the best available control technology (BACT) for mercury removal from flue gas. There are two major forms of vapor-phase mercury, Hgo and Hg2+, of which HgCl2 accounts for 60-95% of total mercury. Mercury emitted from the incineration of municipal solid wastes (MSW) could cause severely adverse effects on human health and ecosystem since it exists mainly in vapor phase due to high vapor pressure. Although the adsorptive capacity of HgCl2 onto activated carbon has been studied in previous adsorption column tests, only a few studies have thoroughly investigated the adsorption isotherms of HgCl2 onto SAC. Equilibrium and kinetic studies are important towards obtaining a better understanding of mercury adsorption. Many investigations have addressed the relationship between sorption kinetics and equilibrium for different adsorbent/adsorbate combinations. For the removal of vapor-phase mercury, several bench-pilot, and full-scale tests have be proceeded to examine the influence of carbon types, carbon structures, carbon surface characteristics, injection methods (dry or wet), amount of carbon injected, and flue gas temperature on mercury removal. In addition, the dynamics of spherical activated carbons (SAC) adsorbers for the uptake of gas-phase mercury was evaluated as a function of temperature, influent concentration of mercury, and empty-bed residence time. However, only a few studies investigated the adsorption isotherms of HgCl2 onto activated carbons. In this study, TGA was applied to obtain the adsorptive capacity of HgCl2 onto SAC with adsorption temperature (30~150oC) and influent HgCl2 concentration (50~1,000£gg/m3). Experimental results indicated that the adsorptive capacity of HgCl2 onto SAC was 0.67and 0.20 mg/gC at 30¡B70 and 150oC, respectively. This study investigated the adsorptive capacity of HgCl2 vapor onto SAC via TGA analysis. Experimental results indicated that the adsorptive capacity of SAC decreased with the increase of the adsorption temperature. Furthermore, the results suggested that that the adsorption of SAC on HgCl2 vapor was favorable equilibrium at 30 and 70¢J and unfavorable equilibrium at 150¢J. In comparison of the experimental data with isotherm equations, Freundlich isotherm fitted the experimental results better than Langmuir isotherm. The model simulations were found to fit very well to the high concentration experimental kinetic data for both adsorption and desorptionusing two adjust parameter, effective diffusivity, and the Freundlich isothermexponent.¡@The extracted model parameter, effective diffusivity and n, were then used to predict the experimental kinetic data for the same combination at other concentrations.

This study investigated the adsorptive and desorption capacity of HgCl2 onto powdered activated carbon derived from carbon black of pyrolyzed waste tires (CPBAC) via thermogravimetric analysis (TGA). Due to incomplete classification and recycling of municipal solid wastes (MSW), they still mix with a lot of hazardous materials, which unfortunately can not be removed by incinerators and air pollution control devices(APCDs). Among them, mercury and its pollutants attract more attention by people. Mercury and its pollutants emitted from the incineration of municipal solid wastes could cause severely adverse effects on human health and ecosystem since they exist mainly in vapor phase due to high vapor pressure. If they can not be remove by the air pollution control devices, they will be emitted to the atmosphere and cause serious effects on environmental ecology via various routes. Activated carbon has been widely applied to the treatment of organic compounds and heavy metals in wastewater and waste gas stream. However, the adsorptive capacity of activated carbon decreases with adsorption temperature. The low adsorptive capacity of activated carbon at high temperature (>150 oC) can be overcome by impregnated activated carbons. Previous study reported that sulfur impregnated powdered activated carbons could effectively remove the vapor-phase elemental mercury (Hgo) emitted from MSW incinerators and utility power plants. However, the impregnated typically used is sulfur (S) which is solely applied for the adsorption of elemental mercury (Hgo). Besides, these studies seldom investigate the distribution of impregnated sulfur in the inner pores of activated carbon and its effects on the specific surface area and pore size distribution. Thus, this study was to investigate the fundamental mechanisms for the adsorption/desorption of HgCl2 by/from sulfur impregnated PAC. Experimental results indicated that the sulfur content of sulfur impregnated CBPAC decreased with increasing impregnation temperatures form 400 to 650 oC; while the surface area of sulfur impregnated CBPAC increased with impregnation temperatures. In this study, TGA was applied to obtain the adsorptive capacity of HgCl2 onto CBPAC with adsorption temperature (150oC) and influent HgCl2 concentration (100~500 £gg/m3). Experimental results indicated that the adsorptive capacity of CBPAC increased with the increase of influent HgCl2 concentration and surface area of the activated carbon. This study revealed that the impregnation of sulfur on CBPAC could increase its adsorption capacity at high temperatures. Desorption experimental parameters included desorption temperature (400, 500, and 600 oC), heating rate (10, 15, and 20 oC /min) and regeneration cycle (1~7 cycles). In probing into the regeneration efficiency of CBPAC, experiments were conducted at the desorption times of 60 and 30 min. The results suggested the regeneration efficiency of carbon under 30 min was generally highter than that under 60 min. Because the desorption time was more longer and the sulfur content was lesser. Therefore, the regeneration times was reduce. Experimental results indicated that the mechanism of HgCl2 desorption from the spent CPBAC was strongly affected by desorption temperature. Both the desorption efficiency and the desorption rate of HgCl2 increased dramatically with desorption temperature. The desorption heat of HgCl2 (823 KJ/mole) was much higher than the vaporization heat of HgCl2 (59.2 KJ/mole), indicating that the adsorption of HgCl2 on sulfur impregnated CBPAC was chemical adsorption. Consequently, raising desorption temperature could enhance the desorption of HgCl2 and shorten the duration for HgCl2 desorption. Moreover, the formation of HgS during the desorption of HgCl2 from activated carbons can be proved by the surface characteristics of sulfur impregnated activated carbons. Results obtained from the regeneration of sulfur impregnated activated carbons indicated that the regeneration cycles decreased as the desorption duration increased. It was attributed to the potential desorption of sulfur from actived carbons, which thus decreased the adsorptive capacity and the regeneration cycles.

Biomass fast pyrolysis liquid, also known as bio-oil, is a promising renewable fuel for heat and power generation; however, implementing crude bio-oil in some current combustion systems can degrade combustion performance and emissions. In this study, optimizing fuel properties to improve combustion is considered. Various bio-oils with different fuel properties are tested in a pilot stabilized spray burner under very close flow conditions. Effects of solids, ash and water content of bio-oil as well as ethanol blending were examined. The results show the amount of solids and ash fractions of the fuel were correlated with combustion efficiency. The CO and unburned hydrocarbon emissions decreased with both water and ethanol content. Increasing the fuel’s volatile content by blending in ethanol has been shown to improve flame stability. Also, the organic fraction of particulate matter emissions was found to be a strong function of the thermogravimetric analysis residue of the fuel.

Biomass fast pyrolysis liquid, also known as bio-oil, is a promising renewable fuel for heat and power generation; however, implementing crude bio-oil in some current combustion systems can degrade combustion performance and emissions. In this study, optimizing fuel properties to improve combustion is considered. Various bio-oils with different fuel properties are tested in a pilot stabilized spray burner under very close flow conditions. Effects of solids, ash and water content of bio-oil as well as ethanol blending were examined. The results show the amount of solids and ash fractions of the fuel were correlated with combustion efficiency. The CO and unburned hydrocarbon emissions decreased with both water and ethanol content. Increasing the fuel’s volatile content by blending in ethanol has been shown to improve flame stability. Also, the organic fraction of particulate matter emissions was found to be a strong function of the thermogravimetric analysis residue of the fuel.

The oxidation of three different steels used in the construction of petroleum refineryheaters was investigated by using thermogravimetric analysis technique (TGA). C-5,P-11, and P-22 steel samples were tested in two different oxidizing environments / air and CO2+N2+H2O (that simulates the combustion products of natural gas) at two different temperatures / 450oC and 500oC. In air oxidation P-22 had the best oxidation resistance among the three steels at two temperatures. In CO2+N2+H2O environment,C-5 possessed better oxidation resistance than P-22 and P-11. Analyses of oxidation products by using optical microscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM) were carried out to correlate TGA results to oxide composition and morphology. Lower oxidation rate of P-22 in air was explained with reference to the formation of Cr-O phase. Analytical rate equations showed that all the steels obeyed parabolic rate equation during oxidation and no transition was observed

174 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-08-20T15:49:02Z No. of bitstreams: 1 Tese de doutorado - Ingrid - VERSÃO FINAL - UFBA.pdf: 5563445 bytes, checksum: 8345d9745885c1103c219247c69338fc (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-08-20T15:51:20Z (GMT) No. of bitstreams: 1 Tese de doutorado - Ingrid - VERSÃO FINAL - UFBA.pdf: 5563445 bytes, checksum: 8345d9745885c1103c219247c69338fc (MD5) / Made available in DSpace on 2013-08-20T15:51:20Z (GMT). No. of bitstreams: 1 Tese de doutorado - Ingrid - VERSÃO FINAL - UFBA.pdf: 5563445 bytes, checksum: 8345d9745885c1103c219247c69338fc (MD5) Previous issue date: 2012 / O rincoforol (2-metil-5(E)hepteno-4-ol) é o maior constituinte do feromônio de agregação do macho do Rhynchophorus palmarum L. (Coleoptera: Curculionidade), um besouro que ataca diversas espécies de palmeiras e é o principal vetor do nematódeo Bursaphelenchus cocophylus, agente causador da doença do anel vermelho.No Brasil, esse besouro ataca principalmente o coqueiro e o dendezeiro, culturas de grande relevância econômica para o país. Esse feromônio vem sendo utilizado em iscas do tipo eppendorf com um orifício na tampa para controlar a população do besouro. Esse dispositivo facilita a liberação lenta quando comparada à evaporação direta do estado líquido. No entanto, a validade dessas iscas depende da velocidade de evaporação do rincoforol através do dispositivo, que libera quantidade excessiva do feromônio. Com o objetivo de prolongar o tempo de liberação do rincoforol, diferentes zeólitos foram sintetizados, caracterizados e avaliados em relação à sua utilização como adsorvente para o rincoforol. Para isso, a influência de variáveis como: estrutura do zeólito, razão Si/Al, natureza do cátion de compensação, dimensão de poros e acidez foi verificada para o processo de adsorção. Devido à falta de informações referente à estabilidade do rincoforol, foi realizado um estudo termogravimétrico sobre seu comportamento térmico. Estudos de recuperação demonstraram que houve interação entre o rincoforol e os zeólitos ZSM-5 e MCM-22 nas diferentes razões Si/Al, resultando na degradação do feromônio, inviabilizando seu uso como suporte para liberação prolongada. Os materiais silicalita-1, zeólito Y e zeólito L apresentaram bons resultados de recuperação e a liberação do rincoforol a partir desses materiais foi medida em uma termobalança em condição isotérmica. Resultados promissores foram observados quando a velocidade de liberação obtida a partir dos zeólitos foi comparada com o rincoforol comercial. Assim, os estudos realizados nesse trabalho permitiu selecionar zeólitos com grande potencial comercial como dispositivo liberador do rincoforol por um período prolongado. / Salvador

Made available in DSpace on 2014-06-11T19:35:06Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-02-22Bitstream added on 2014-06-13T19:24:24Z : No. of bitstreams: 1 carvalho_ct_dr_araiq.pdf: 783523 bytes, checksum: 845f90e2b52f8926bba04e0f2219f870 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Sintetizou-se o ácido 2-metoxicinamalpirúvico (2-MeO-HCP), através da reação de condensação aldólica do 2-metoxicinamaldeído (CH3O-C6H4-(CH)2-CHO), 96 % de pureza com o piruvato de sódio, (Na-2-MeO-CP), 99% puro, ambos da Aldrich. A pureza do ácido 2-metoxicinamalpirúvico sintetizado foi determinada por DSC através do pico de fusão em 125 ºC. O ácido 2-metoxicinamalpirúvico foi convertido a uma solução de aproximadamente 0,15 mol L-1 de 2-metoxicinamalpiruvato de sódio (pH~7,5). Com esse sal foram sintetizados os compostos no estado sólido (Ln-2-MeO-CP.nH2O), sendo que Ln representa os lantanídeos trivalentes e Y(III), 2-MeO-CP o ligante 2-metoxicinamalpiruvato e n o número de moléculas de água com n = 1,5 para o composto de túlio e itérbio e para os demais compostos n = 1. Os Ln-2-MeO-CP.nH2O foram obtidos no estado sólido por adição lenta do ligante aos respectivos cloretos metálicos ou nitratos sob agitação contínua até a total precipitação dos íons metálicos. Os precipitados foram filtrados em papel de filtro Whatman n 42 lavando-se os mesmos com água destilada até a obtenção de teste negativo para cloretos com AgNO3 em meio nítrico e difenilamina para nitratos. Posteriormente os precipitados foram secos em temperatura ambiente e armazenados em dessecador contendo cloreto de cálcio. Técnicas instrumentais utilizadas no estudo dos compostos: Termogravimetria e Análise Térmica Diferencial Simultânea (TG-DTA) e Calorimetria Exploratória Diferencial (DSC) e Complexometria com EDTA (padrão de 1,000 x 10-2 mol L-1 ) forneceu informações sobre grau de hidratação, comportamento térmico e estequiometria; Difratometria de Raios X pelo método do pó, informações da cristalinidade e Espectroscopia de Absorção na Região do Infravermelho sugeriu a forma de coordenação dos compostos sintetizados. Na caracterização do ácido... / The 2-methoxycinnamylidenepyruvic acid (2-MeO-HCP) was synthesized through the reaction of aldolic condensation of 2-methoxycinnamaldehyde (CH3O-C6H4-(CH) 2-CHO), 96% purity, with sodium pyruvate, (Na-2 - MeO-CP) 99% pure, both from Aldrich. The purity of 2-methoxycinnamylidenepyruvic synthesized was determined by DSC through the melting peak at 125 ºC. The 2-methoxycinnamylidenepyruvic acid was converted to a solution of about 0.15 mol L-1 of the sodium 2-methoxycinnamylidenepyruvate (pH ~ 7.5). With this salt were synthesized the solid compounds (Ln-2-MeO-CP.nH2O), where Ln represents trivalent lanthanides and Y (III), 2-MeO-CP is the methoxycinnamylidenepyruvate ligand and n the number of water molecules with n = 1.5 for the compound thulium, ytterbium and for the other compounds, n = 1. The Ln-2-MeO-CP.nH2O were obtained in the solid state by slow addition of the ligand to the respective metal chlorides or nitrates on continuous stirring until total precipitation of metal ions. The precipitates were filtered through filter paper Whatman number 42, washing them with distilled water to obtain a negative test for chloride with AgNO3 in nitric acid and diphenylamine to nitrates. Subsequently the precipitates were dried at room temperature and stored in a desiccator containing calcium chloride. Instrumental techniques used in the study of compounds: Thermogravimetry and differential thermal analysis (TG-DTA), Differential Scanning Calorimetry (DSC) and Complexometry with EDTA (standard padrão de 1,000 x 10-2 mol L-1 ) provided information on degree of hydration, thermal behavior and stoichiometry; X-ray Diffractometry by the method of powder provided information about crystallinity, and Absorption Spectroscopy in the Infrared Region suggested the form of coordination of the compounds synthesized. In the characterization of 2-methoxycinnamylidenepyruvic, apart from the DSC... (Complete abstract click electronic access below)