Submitted by Marilene Donadel (marilene.donadel@unioeste.br) on 2017-08-18T19:11:56Z No. of bitstreams: 1 Viviane Manozzo 2016.pdf: 3333567 bytes, checksum: ebe7b9726675839238cfd3ee3c4ed3ca (MD5) / Made available in DSpace on 2017-08-18T19:11:56Z (GMT). No. of bitstreams: 1 Viviane Manozzo 2016.pdf: 3333567 bytes, checksum: ebe7b9726675839238cfd3ee3c4ed3ca (MD5) Previous issue date: 2016-08-29 / The whole world is experiencing an energy crisis, though a lot of potential is wasted because it is necessary to develop technologies for the utilization of biomass as a raw material capable of producing energy. Municipal waste, wood waste, agricultural crop residues, plants and algae, breeding animal waste, food processing and organic waste are considered the main sources of production and biomass and boost research in the energy sector in search responses to the crises faced. The objective of this study was to obtain experimental data of thermal decomposition of biomass Pistia stratiotes and Eichhornia crassipes to determine the kinetic parameters through the pyrolysis process. Thus, laboratory studies were conducted in order to determine the chemical and physical properties: particle size, moisture, volatile matter, ash, cellulose, lignin and superior calorific value (PCS), to obtain the thermal decomposition curve by thermogravimetric analysis for biomasses studied ; and determine the kinetic parameters during pyrolysis of biomass decomposition methods using non-isothermal differential. The thermogravimetric analysis was performed under an inert nitrogen atmosphere at temperatures ranging from 60ºC to 990ºC for four heating rates of 5, 10, 15 and 20 °C / min. Results as 10.83 MJ / kg and 12, 96 MJ / kg were found for PCS of biomasses Pistia stratiotes and Eichhornia crassipes respectively. The determination of the kinetic parameters we used the methods: Flyn Wall Osawa, Kissinger and Friedman. The mass loss of biomass Pistia stratiots presented in the temperature range 244-823 ° C. The Eichhornia crassipes in the range 241-991°C. To Pistia stratiotes the activation energy calculated by the FWO method foinde 178.60 kJ / mol - 332.79 kJ / mol. Kissinger 155.89 kJ / mol. Friedman in the range of 153.75 kJ / mol - 369.09 kJ / mol. For Eichhornia crassipes the activation energy calculated by the method presented FWO in the range of 156.59 kJ / mol - 531 80 kJ / mol. Kissinger 130.46 kJ / mol. Friedman in the range of 156.53 kJ / mol - 349.47 kJ / mol. The results obtained were of the same order of magnitude. The kinetic data confirm that the molecular structures are represented by different mechanisms thermal decomposition reaction rate and the decomposition rate with the temperature in the pyrolysis showing that this technique is a powerful tool for transforming biomass into products which contribute to generation of energy. / O mundo todo vive uma crise energética, no entanto um grande potencial é desperdiçado, pois é preciso que se desenvolvam tecnologias para o aproveitamento de biomassas como matéria prima capaz de produzir energia. Os resíduos urbanos, restos de madeira, resíduos de culturas agrícolas, plantas e algas, resíduos de criadouros de animais, de processamento de alimentos e de resíduos orgânicos se apresentam como as principais fontes de produção e biomassa e impulsionam as pesquisas no setor energético em busca de respostas para as crises enfrentadas. Assim, o objetivo deste estudo foi obter dados experimentais de decomposição térmica das biomassas Pistia stratiotes e Eichhornia crassipes visando determinar os parâmetros cinéticos por meio do processo de pirólise. Desta forma, estudo laboratoriais foram desenvolvidos visando determinar as propriedades químicas e físicas: granulometria, umidade, material volátil, cinzas, celulose, lignina e poder calorífico superior (PCS), obter as curvas de decomposição térmica através de análises termogravimétricas para as biomassas em estudo; e determinar os parâmetros cinéticos durante a pirólise de decomposição das biomassas utilizando métodos não isotérmicos diferenciais. A termogravimetria foi realizada em atmosfera inerte de nitrogênio, com temperaturas variando de 60ºC a 990ºC, para quatro taxas de aquecimento: 5, 10, 15 e 20ºC / min. Resultados como 10,83 MJ/kg e 12, 96 MJ/kg foram encontradas para o PCS das biomassas Pistia stratiotes e Eichhornia crassipes respectivamente. A determinação dos parâmetros cinéticos utilizou–se dos métodos: Flyn Wall Osawa, Kissinger e o Friedman. A perda de massa da biomassa Pistia stratiotes apresentou na faixa de temperatura de 244 – 823 °C. A Eichhornia crassipes na faixa de 241 – 991 °C. Para Pistia stratiotes a energia de ativação calculada pelo método FWO foi de 178,60 kJ / mol – 332,79 kJ / mol. Por Kissinger 155,89 kJ / mol. Por Friedman na faixa de 153,75 KJ / mol – 369,09 kJ / mol. Para Eichhornia crassipes a energia de ativação calculada pelo método FWO apresentou na faixa de 156,59 kJ / mol – 531, 80 kJ / mol. Por Kissinger 130,46 kJ / mol. Por Friedman na faixa de 156,53 kJ / mol – 349,47 kJ / mol. Os resultados obtidos foram da mesma ordem de grandeza. Os dados cinéticos obtidos confirmam que as estruturas moleculares são representadas por diferentes mecanismos de decomposição térmica, taxas de reação e taxa de decomposição com a temperatura no processo de pirólise comprovando que a técnica é uma poderosa ferramenta para transformar biomassas em produtos que contribuem para geração de energia.

Cashew nut and coconut shells are two potential renewable and environmentally friendly energy sources that are commonly found as agro-industrial wastes in tropical countries. Despite this fact, they are not yet widely studied as such. Given this lack of specific technical and reliable data, technologies for their conversion into energy cannot be designed with confidence as it happens with other commonly studied biomass feedstock. Thus, the need to generate these data guided this research in order to provide technical information for the designing of appropriate thermochemical conversion technologies for energy generation, particularly, in remote areas, where electricity grid is neither a feasible nor an affordable solution.Among thermochemical processes, pyrolysis plays a key role as it is found in both combustion and gasification at their earlier stages. In both technologies, pyrolysis products are generated and later submitted to further transformations according to the process in use.Hence, pyrolysis was selected for thermal characterisation of cashew nut and coconut shells. The main characteristics envisaged are i) pyrolysis profiles; ii) global, semi-global and individual kinetics; iii) pyrolysis global and individual yields; iv) modelled pyrolysis yields at high heating rates; and, v)char combustion kinetics and reactivity. The main technique used for experimental data generation is thermogravimetry and FTIR spectroscopy. Data experimentally generated from TG and TG-FTIR experiments were processed through different methods and codes, such as the Coats and Redfern model-fitting method, the modelfree methods of Ozawa-Flynn-Wall, Friedman and ASTM E698, for semi-global and global kinetics; DAEM and FG-Biomass were used for pyrolysis individual kinetics and yields determination. Proximate and ultimate analyses were performed as well.The study revealed peculiar characteristics compared to the commonly known lignocellulosic biomass. The volatiles content was above 66%w/w; hemicelluloses DTG peak did not overlap with the cellulose peak; the global pyrolysis activation energies were around 200 and 120 kJ/mol for coconut and cashew nut shells, respectively. Hemicelluloses and cellulose showed varying activation energies as 130-216 and 155-208 kJ/mol, respectively. Char combustion showed two steps with activation energies of 135 and 121 kJ/mol (cashew nut shells); 105 and 190kJ/mol (coconut shells). Individual yields and kinetics were determined for 17 compounds, including tars. These data are of key importance for modelling and the consequent data generation for the designing of appropriate thermochemical energy for these biomasses. / QC 20100914

In recent years, the application of thermal analysis to study the combustion and pyrolysis behavior of fossil fuels has gained a wide acceptance because of its significance for industry and economy. In this thesis, the thermal and kinetic analysis of different origin crude oil samples are performed by two well-known thermal analysis techniques: Differential Scanning Calorimetry (DSC) and Thermogravimetry (TG/DTG). The investigation of combustion and pyrolysis behaviors, kinetic analysis of oil samples and the determination of heating rate effect are the main objectives of this study. Six different crude oils from the Southeastern region of Turkey are analyzed throughout the study. All experiments are performed at different heating rates (5, 10 and 15&ordm / C/min) and air is used for combustion and nitrogen for pyrolysis experiments. In combustion experiments, TGA and DSC techniques indicate that the combustion process of crude oils studied is composed of two main reaction regions. These are low-temperature (LTO) and high-temperature oxidation (HTO) regions. In LTO, huge mass loss occurs (from 69 to 87 %) due to high amount of free moisture and volatile hydrocarbons contained in oil samples. Combustion reactions continue up to 900 K. On DSC curves, two exothermic regions of oxidation regimes are detected. Comparing TG/DTG and DSC curves, it can be understood that the mass loss under combustion is accompanied by exothermic peaks because of the oxidative degradation of crude oil components. As in combustion, two distinct reaction regions are revealed under pyrolysis for all samples. The first region indicates distillation and the second one is due to thermal cracking reactions occur at high temperatures and completed up to 840 K. As expected, lighter crude oils have relatively higher amounts of mass loss in distillation region as compared to heavier ones. Besides, residue amount and burn-out temperatures are higher for heavier oils with higher asphaltene content in cracking region. DSC curves for both reactions show endothermic effects. In combustion and pyrolysis experiments, it is noticed that higher heating rates are resulted in higher reaction regions. Distinguishing peaks of samples shift to higher temperatures with an increase in heating rate. Heat of reaction amount under DSC curves is related to asphaltene content and &amp / #730 / API gravity of crude oils. It is deduced that, when &amp / #730 / API gravity of crude oils decreases, the heat value of this reaction increases. The kinetic parameters are evaluated by different kinetic models and mean activation energies (Em) of samples are obtained. At the end, a correlation is established between Em and &amp / #730 / API gravity of oil samples. It is concluded that heavier oils have higher activation energy and Arrhenius constant values for each reaction region. Besides, it is proved that the activation energy is mostly insensitive to the heating rate.

In this thesis, four different crude oil samples and their saturate, aromatic and resin fractions were analyzed by two different thermoanalytical methods, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The experiments were performed at three different heating rates (5, 10 and 15 &deg / C/min) under air atmosphere. Same gas flow rate and same pressure were applied to all samples. The aim is to determine the kinetic analysis and combustion behavior of crude oils and their fractions and also determining the effect of heating rate on all samples. For all samples two main reaction regions were observed in thermogravimetry (TG), differential thermogravimetry (DTG) and DSC curves due to the oxidative degradation of crude oil components. It was deduced that the free moisture, volatile hydrocarbons were evaporated from the crude oils, light hydrocarbons were burned and fuel was formed in the first reaction region. The second reaction region was the main combustion region where the fuel was burned. From the TGA curves, it was detected that the heavier fraction, resins, lost considerable amounts of their initial mass, approximately 35%, while saturates lost only approximately 3% of their initial mass in the second reaction region. DSC curves of the samples were also examined and observed that as the sample got heavier, the heat of the reaction increased. Saturates, lightest part of the crude oil fractions, gave minimum heat of reaction. As the heating rate increased, shift of peak temperatures to high values and higher reaction regions were observed. The kinetic analysis of crude oils and their fractions were also performed using different kinetic methods. Activation energies (E), mean activation energies (Emean) and Arrhenius constants were found for crude oils and fractions. It was deduced that the resins gave the highest activation energy and Arrhenius constant for both reaction regions. Moreover, it was encountered that heating rate has no effect on activation energies.

In this thesis, a new software, THERA-Kinetics was developed for the evaluation of kinetic parameters using non-isothermal data. Different computational methods, available in the software, were applied to a set of experimental and simulated data distributed in the ICTAC (International Confederation for Thermal Analysis and Calorimetry) Kinetics Project. The reliability of the software was verified by comparing the kinetic results, which were in good agreement, with those obtained by the participants of the ICTAC Kinetics Project. It was also within the scope of this study to examine the combustion characteristics and kinetics of three same origin coal samples. A series of thermogravimetry (TG) and differential scanning calorimetry (DSC) measurements were carried out in non-isothermal conditions at heating rates of 5, 10 and 15 K/min. Reaction regions, peak and burn-out temperatures, weight loss percentages and heat of reactions of the samples were determined for each heating rate from TG and DSC curves. A variety of computational methods, available in the software developed, were applied to experimental data for the evaluation of the kinetic parameters of the coal samples. It was observed that there was no general trend in the activation energy values from the point of heating rate.

Thesis (M. Sc.)--Carleton University, 2001. / Includes bibliographical references (p. 84-90). Also available in electronic format on the Internet.

Thesis (m.S. Ch. E.)--University of Puerto Rico, Mayagüez Campus, 2004. / Tables. Printout. Includes bibliographical references (leaves 88-91.)

Frente ao cenário de esgotamento das reservas mundiais de petróleo e a demanda mundial por energia renovável, aliado a necessidade de novas tecnologias para produção de biocombustíveis e o potencial energético das palmáceas, o presente trabalho teve por objetivo a síntese de ésteres metílicos, tendo como matéria-prima o óleo da amêndoa de macaúba, a partir da reação de transesterificação empregando o ácido p-toluenossulfônico (95%) como catalisador. Para tanto foi necessário a caracterização do óleo da amêndoa e o estudo e planejamento das variáveis tempo, razão molar óleo:álcool e percentual de catalisador. Em seguida a avaliação do teor de ésteres por termogravimetria dos ensaios de transesterificação, e por fim, com base nestes dados, a obtenção de um modelo matemático que explicasse satisfatoriamente o rendimento em percentual de ésteres em função das variáveis estudadas. Os resultados apontam o ótimo estado de conservação do óleo utilizado bem como sua composição em termos de ácidos graxos, constituída, predominantemente, pelo ácido oleico, composto este, monoinsaturado e formado por uma cadeia carbônica mediana, o que propicia uma boa qualidade ao combustível produzido. Por meio do perfil termogravimétrico e do espectro na região do infravermelho para o óleo da amêndoa de macaúba pôde-se observar a estabilidade térmica do mesmo até cerca de 220ºC, com um único intervalo de volatilização, que ocorreu até a temperatura de 420ºC, bem como bandas características de absorção dos principais grupos funcionais presentes em suas moléculas, que acabaram se deslocando e alterando suas intensidades de absorção para os ésteres transesterificados. Três planejamentos foram realizados para os ensaios de transesterificação, dois fracionários e um terceiro utilizando a metodologia do Delineamento do Composto Central Rotacional com um fatorial 22, que originou o modelo matemático para o sistema. Com base nos dados obtidos dos planejamentos 1, 2 e 3 foi possível concluir que a faixa de tempo reacional ideal para as condições estudadas é de 2 a 4,5 horas. A razão molar óleo:metanol deve ser superior a estequiometria da reação que é de 1:3. O percentual de catalisador deve ser igual ou superior a 11,5 % para que o teor de ésteres atenda ao exigido pela legislação ANP 2014, que é de 96,5%. A melhor condição encontrada para o rendimento em percentual de ésteres metílicos foi processada utilizando 11,5% de catalisador, razão molar óleo:metanol de 1:6, temperatura de 65ºC, 200 rpm de agitação e tempo reacional de 4,25 horas, atingindo um rendimento de 99%. A partir do modelo matemático gerado, foi comprovada a validade deste para as condições experimentais, com um erro percentual médio de 1%. / Against the backdrop of the depletion of world oil reserves and global demand for renewable energy, combined with the need for new technologies for production of biofuels and the energy potential of palm trees, this study aimed to the synthesis of methyl esters, with the matter macaúba the raw almond oil from the transesterification reaction using p-toluenesulfonic acid (95%) as catalyst. Therefore it was necessary to characterize the almond oil and the study and planning between time, molar ratio of oil: alcohol and catalyst percentage. Then, the evaluation of the content by thermogravimetric esters of transesterification trials, and finally, on the basis of these data, obtaining a kinetic model to explain the percentage yield of esters according to the variables. The results show the great oil conservation status used and its composition in terms of fatty acids, consisting predominantly by oleic acid, compound this, monounsaturated and formed by a median carbon chain, which provides a good quality to that produced fuel. By means of thermogravimetric profile and the spectrum in the infrared region for macaúba almond oil could observe the thermal stability of about 220ºC even with a single range of volatilization, which occurred until the temperature of 420ºC and characteristic absorption bands of the main functional groups present in the molecules which eventually moving and changing its absorption intensities for the biodiesel produced. Three schedules were performed for transesterification trials, two and a third fraction using the methodology of the Delineation Central Composite Rotational with a factorial 22, which gave the mathematical model for the system. Based on the data obtained from the plans 1, 2 and 3 it was concluded that the range of reaction time ideal for the conditions studied is 2 to 4,5 hours. The molar ratio of oil: methanol must be greater than the stoichiometry of the reaction is 1:3. The catalyst percentage should be equal to or greater than 11,5% for the income as a percentage of esters meets the required legislation by the ANP in 2014, which is 96,5%. The best condition found for the percentage yield of methyl esters was processed using 11,5% catalyst molar ratio of oil: methanol 1:6, 65°C temperature, 200 rpm agitation and reaction time of 4,25 h, reaching a yield of 99%. From the generated mathematical model has been established for the validity of the experimental conditions, with an average percentage error of 1%.

Made available in DSpace on 2014-12-17T14:06:54Z (GMT). No. of bitstreams: 1 FlaviaMA_DISSERT.pdf: 2525916 bytes, checksum: e66ea09a8c50d8b220412e1d5685d5d1 (MD5) Previous issue date: 2010-03-11 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / In this work have been studied the preparation, characterization and kinetic study of decomposition of the polymerizing agent used in the synthesis under non-isothermal condition ceramics PrMO3 of general formula (M = Co and Ni). These materials were obtained starting from the respective metal nitrates, as a cations source, and making use of gelatin as polymerizing agent. The powders were calcined at temperatures of 500?C, 700?C and 900?C and characterized by X-ray Diffraction (XRD), Thermogravimetric Analysis (TG / DTG/ DTA), Infrared Spectroscopy (FTIR), Temperature Programmed Reduction (TPR) and Scanning Electron Microscopy (SEM). The perovskite phase was detected in all the X-rays patterns. In the infrared spectroscopy observed the oxide formation as the calcination temperature increases with the appearance of the band metal - oxygen. The images of SEM revealed uniform distribution for the PrCoO3 and particles agglomerated as consequence of particle size for PrNiO3. From the data of thermal analysis, the kinetics of decomposition of organic matter was employed using the kinetics methods called Model Free Kinetics and Flynn and Wall, in the heating ratios 10, 20 and 30? C.min-1 between room temperature and 700?C. Finally, been obtained the values of activation energy for the region of greatest decomposition of organic matter in samples that were determined by the degree of conversion (α) / Neste trabalho foi realizado a prepara??o, caracteriza??o e um estudo cin?tico da decomposi??o t?rmica do agente polimerizante utilizado na s?ntese sob condi??o n?o isot?rmica de materiais cer?micos de f?rmula geral PrMO3 (M = Co ou Ni). Esses materiais foram obtidos partindo dos respectivos nitratos met?licos, como fonte de c?tions, e fazendo uso da gelatina como agente polimerizante. Os p?s-obtidos foram calcinados a temperaturas de 500?C, 700?C e 900?C e caracterizados pelas t?cnicas de Difra??o de Raios X (DRX), An?lise Termogravim?trica (TG/DTG/DTA), Espectroscopia na regi?o do infravermelho (FTIR), Redu??o ? Temperatura Programada (RTP) e Microscopia Eletr?nica de Varredura (MEV). A fase perovsquita foi evidenciada em todos os difratogramas de raios X para os materiais de PrCoO3 e PrNiO3. Nos espectros de FTIR foi observado a forma??o do ?xido na medida em que a temperatura de calcina??o aumenta com o aparecimento da banda referente ? liga??o Metal Oxig?nio. As imagens do MEV evidenciaram distribui??o uniforme para o PrCoO3 e part?culas aglomeradas em consequ?ncia do tamanho da part?cula para o PrNiO3. Com os dados da an?lise t?rmica, o estudo ci-n?tico da decomposi??o da mat?ria org?nica foi empregado utilizando-se os m?todos cin?ticos denominados Model Free Kinetics e Flynn e Wall, nas raz?es de aquecimento 10, 20 e 30?C.min-1 entre a temperatura ambiente e 700?C. Foram obtidos os valores das energias de ativa??o para a regi?o de maior decomposi??o da mat?ria org?nica nas amostras que foram determinadas como uma fun??o do grau de convers?o (α)

A presença de sais no petróleo ocasiona grandes problemas operacionais relacionados à corrosão, uma vez que estes acabam formando ácido clorídrico no processo de separação do óleo bruto. Com o intuito de amenizar os efeitos de corrosão ácida, aminas podem ser adicionadas no topo das colunas para agir como neutralizantes. Porém, dependendo das condições operacionais e da quantidade de amina adicionada, pode ocorrer a deposição de cloridratos de aminas, promovendo a corrosão sob depósito. Assim, o conhecimento da pressão de sublimação desses sólidos é de extrema importância para especificar as condições de operação e o melhor desempenho destes aditivos no processo. Dentro desse contexto, o objetivo deste trabalho é determinar as pressões e entalpias de sublimação de cloridratos de aminas com a técnica termogravimétrica. Devido às dificuldades encontradas para obtenção de dados precisos de pressão em baixas temperaturas, uma extensão ao método termogravimétrico foi proposta, tornando possível medir pressões na ordem de 1 0,5 Pa. As substâncias estudadas foram: brometo de amônio, cloreto de amônio, cloridrato de etanolamina, cloridrato de metilamina, cloridrato de piridina, cloridrato de trimetilamina e dicloridrato de n-(1- naftil)etilenodiamina. Resultados de pressão e entalpia de sublimação alcançados com ácido benzoico, brometo de amônio e cloreto de amônio foram validados com dados da literatura Para os demais sólidos estudados, não há muitos dados disponíveis na literatura. No entanto, como a reação de sublimação do cloreto de amônio é análoga à dos demais cloridratos de amina, as entalpias de sublimação puderam ser comparadas e os resultados encontrados foram satisfatórios. Por fim, para uma melhor aplicabilidade dos resultados obtidos, uma equação de Clausius-Clapeyron modificada foi utilizada para correlacionar os dados medidos. Uma ótima correlação foi possível para todos os sais estudados, com coeficiente de correlação sempre superior a 0,97. / The presence of salts in petroleum causes operational problems related to corrosion, due to the fact that they end up forming hydrochloric acid in the crude oil separation process. In order to mitigate the effects of acid corrosion, amines can be added at the top of the columns to act as neutralizers. However, depending on the operational conditions and the amount of amine added, a deposition of amine hydrochlorides may occur, promoting under-deposit corrosion. Thus, the knowledge of the sublimation pressure of these salts has an extreme importance in trying to predict and to optimize the performance of the additives in the process. Within this context, the purpose of this study is to determine pressure and enthalpy of sublimation of amine hydrochlorides with the thermogravimetric technique. Due to the difficulties encountered to obtain precise pressure data at low temperatures, an extension of the thermogravimetric method was proposed, enabling to measure sublimation pressures in the order of 1 0,5 Pa. The substances studied were: ammonium bromide, ammonium chloride, ethanolamine hydrochloride, methylamine hydrochloride, pyridine hydrochloride, trimethylamine hydrochloride and n-(1-naphthyl)ethylenediamine dihydrochloride. Results of pressure and enthalpy of sublimation obtained with benzoic acid, ammonium bromide and ammonium chloride were validated using literature data. For other solids investigated in this study, experimental data is scarce in the literature. However, as the sublimation reaction of ammonium chloride is analogous to the others amine hydrochlorides, enthalpies of sublimation could be compared with the results found. Since similar values were observed, the results were considered satisfactory. Finally, the measured data were correlated using a modified Clausius-Clapeyron equation. A good correlation was possible for all salts studied, with correlation coefficient always higher than 0.97.