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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Lewis acid catalyst design for the transesterification of lower quality feedstock for biodiesel production

Chuck, Christopher J. January 2007 (has links)
No description available.
2

Biodegradation and Dewatering of an Industrial Waste Oil

McInnis, Jeffrey A. 01 May 2003 (has links)
Waste oil generated from industrial operations at a diesel locomotive maintenance facility was investigated to establish its treatability and potential volume reduction. The waste oil and water mixture separated into four distinct layers; free oil, emulsified oil, weathered oil, and wastewater. The research was conducted in a series of three batch experiments and focused on the emulsified and weathered oils. The waste oil was aerobically treated in nutrient amended, 55 gallon (208 L) drums for 38 to 42 days in 10 and 20 % mixtures with sufficient air for mixing and oxygen. Biodegradation, and the role of a synthetic surfactant in promoting biodegradation, was measured using chemical oxygen demand (COD), fluorescein diacetate (FDA), and gas chromatography (GC) analyses with extractable material. Dewatering of biodegraded oil was measured using capillary suction test (CST), time to filter (TTF), and percent cake solids. Batch 1 examined the role of bioaugmentation by comparing a 10% waste oil mixture that was augmented with a mixture of hydrocarbon degraders to a 10 % mixture of waste oil with no bioaugmentation. Final COD reductions were 59 (± 9) and 38 (±3) % for the bioaugmented and non-bioaugmented reactors, respectively. Chromatographs showed significant reduction in the abundance of peaks by the end of the experiment for both reactors. Overall results suggested that there was no significant difference in biodegradation capabilities between the amended and native microorganisms. Batch 2 was conducted to determine if a synthetic surfactant (Tween-80) could enhance biodegradation of a 10 % waste oil mixture. The surfactant-amended reactor showed COD reduction 3 days before the non-surfactant-amended reactor. Chromatographs showed similar results for both reactors with the non-surfactant-amended reactor showing slightly better degradation by the end of the experiment. The total COD reduction by the end of the experiment was the same in both (R1: 85 ± 20%, R2: 84 ± 16 %), suggesting that exogenous surfactant addition did not have a long-term impact in the biodegradation of the waste oil. Batch 3 examined the effect of different oil phases and concentrations on biodegradation and the dewatering characteristics of post-biodegraded waste oil. The 20 % weathered and emulsified waste oil mixture showed a clear delay in COD reduction (no notable reduction until day 24) compared to the 10 % weathered waste oil mixture. The final COD reductions were the same (R1: 48 ± 13%, R2: 49, ± 23 %). Chromatographs showed similar results for both reactors and indicated that degradation of the waste oil occurred in both reactors. The data suggest that the 20 % waste oil mixture can be degraded to the same extent as the 10 % mixture in 38 days. Dewatering characteristics, as measured by CST, were poor for the 20 % post-biodegraded combined waste oil mixture without conditioning. Conditioning with alum or ferric chloride substantially improved dewatering of the waste oil for the 20 % mixture but was of limited benefit for the 10 % mixture. Percent cake solids for conditioned 10 % post-biodegraded waste oil mixture was 44 (± 0.3) to 50 (± 1.7) % and 34 (± 0.3) to 50 (± 1.8) % for the 20 % mixture. The cake solids for the unconditioned 10 % mixture was 50 to 65 % and 54 to 68 % for the 20 % mixture. The higher percent cake solids for the unconditioned 20 % mixture was countered by the very high TTF (up to 30 min. to filter 50 mL) and the inability to dewater the sludge during the last five sampling events. Conditioning appeared to have a limited effect on the dewatering properties of the 10 % mixture. / Master of Science
3

Produção de esteres etilicos (biodiesel) a partir da transesterização basica de oleo residual / Productions of ethyl esters (biodesel) from the transesterification core residual oil

Lima, Danilo Ribeiro de 09 August 2008 (has links)
Orientador: Maria Regina Wolf Maciel / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-11T20:12:49Z (GMT). No. of bitstreams: 1 Lima_DaniloRibeirode_M.pdf: 2097787 bytes, checksum: 174055436552208f0eeb28c29f157213 (MD5) Previous issue date: 2008 / Resumo: Biodiesel (ésteres alquílicos) é um combustível limpo derivado de fontes renováveis como óleo vegetal e gordura animal. O biodiesel é biodegradável, possui elevado ponto de fulgor, não-tóxico e produz menos COx e resíduos aromáticos do que o diesel de petróleo. Atualmente, devido ao elevado preço do óleo de soja e de canola, a produção de biodiesel a partir de matérias-primas de baixo custo como óleo residual pode aumentar a competitividade econômica do biodiesel frente ao diesel de petróleo, além de ser uma maneira de reciclar resíduos. A etanólise do óleo residual coletado em restaurante comercial foi estudada utilizando os catalisadores hidróxido de sódio e de potássio. Com teor de acidez superior a 3,8%, a transesterificação do óleo residual apresentou problemas comuns a esse tipo de matéria-prima, como formação de sabão e dificuldade de separação de fases. Assim, os planejamentos experimentais foram realizados em condições específicas de modo a resolver estes problemas. O óleo residual foi caracterizado pelo teor de acidez, umidade, composição de ácidos graxos, índice de iodo, viscosidade cinemática e massa específica. Primeiramente, foi realizado um planejamento fatorial fracionário para determinação das variáveis (temperatura, razão molar etanol:óleo, tipo e quantidade de catalisador e tempo de reação) de maior influência na conversão. O hidróxido de sódio formou uma mistura pastosa e homogênea após a destilação do etanol e, por isso, foi escolhido o catalisador hidróxido de potássio para os próximos planejamentos. A temperatura de reação de 30ºC também se mostrou a mais adequada. Além disso, os modelos estatísticos apresentaram curvatura, sendo necessária a adição de pontos axiais nos próximos planejamentos. Posteriormente, foram realizados planejamentos do tipo composto central com as variáveis mais significativas obtidas em planejamentos anteriores, visando não somente a obtenção da maior conversão, mas também bons índices de rendimento de ésteres. Os resultados mostraram que uma quantidade de KOH de 1,3%, temperatura de 30°C, razão molar etanol:óleo residual de 8:1, tempo de 50 minutos foram adequados para uma maior conversão e rendimento de ésteres obtidos. As curvas de contorno e superfícies de resposta mostraram as melhores condições de reação de cada planejamento de experimentos. Por fim, as melhores condições de operação foram tomadas para a obtenção dos dados cinéticos (energia de ativação e constantes da taxa) / Abstract: Biodiesel (alkyl esters) is a clean burning fuel derived from a renewable lipid feedstock such as vegetable oil or animal fat. It is biodegradable, non-inflammable, nontoxic and produce much lesser COx, sulfur dioxide and unburned hydrocarbons than petroleum-based diesel. Nowadays, due to the price of virgin oil such as soybean and canola oils, the use of low-cost feedstock such as waste frying oils in a base-catalyzed process should help make biodiesel competitive in price with petroleum diesel, beyond being a suitable way to reuse waste materials. Waste frying oil ethanolysis was studied using sodium hydroxide and potassium hydroxide as catalysts. The waste oil was collected in restaurant boxes. The waste oil showed free fatty acids content up to 3.8% and typical problems related to this condition as soap formation and phase separation interference were observed. Then, experimental designs were carried out in specific conditions to solve such problems. The properties of waste oil studied were acid value, water content, fatty acids composition, iodine value, kinematic viscosity and density. At first, a fractional factorial experimental design was chosen to analyze the most significant factors (temperature, ethanol to oil molar ratio, type and amount of catalyst and time) on the conversion oil to biodiesel. The use of sodium hydroxide as catalyst resulted in a dense and homogeneous phase after ethanol distillation, then potassium hydroxide was chosen to the subsequent experimental designs. The temperature of 30ºC was found more suitable as well. Moreover, curvature was detected in the fractional factorial experimental designs studied and star points were included in the following ones. Afterwards, central composite designs were carried out with the most significant factors obtained in previous designs not only looking for the higher conversion rate but also good ester yield. The reaction was optimized using 1.3% KOH, 30°C, ethanol to oil molar ratio of 8:1 and 50 minutes of stirring. The surface response methodology was used to study the best conditions related to each design. At last, a computer-aided tool of this system was used to model the kinetic of biodiesel production in order to calculate kinetic parameters such as reaction rate constants and the activation energy / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química
4

Plasma methods for the clean-up of organic liquid waste

Prantsidou, Maria January 2014 (has links)
This thesis has studied the low-temperature atmospheric pressure plasma as a potential technological application for the degradation of waste oils. The study has been approached initially by investigating the degradation of oil in gas phase only, in order to understand the gas chemistry and elucidate the plasma-chemical degradation mechanism. Gaseous odourless kerosene and dodecane have been used as simulants to waste oil and their plasma-chemical degradation has been studied using a BaTiO3 packed bed plasma reactor and a gliding arc discharge reactor. Kerosene showed similar degradation behaviour to dodecane and the latter one was chosen as a surrogate to allow quantitative analysis. The dodecane plasma degradation efficiency and the distribution of end-gaseous products have been studied under these two reactors in different gas compositions. Optical emission spectroscopy was used to identify intermediate excited species and calculate the rotational and vibrational temperature profiles. Differences in the dodecane degradation gas chemistry between the packed bed and the gliding arc plasma are discussed and postulated mechanisms are presented for each condition. Gliding arc discharge demonstrates higher degradation efficiency and it will be used mainly for the plasma-liquid treatment. The plasma-liquid dodecane treatment is firstly studied using argon dielectric barrier discharge. The effect of different reactor configuration, humidity and temperature to the discharge characteristics and degradation efficiency will be discussed. The study of the liquid dodecane degradation is extended by using the gliding arc discharge. Using N2 and Ar in both dry and humid conditions for the batch treatment of dodecane, the degradation efficiency, gas chemistry and liquid chemistry are discussed and correlated to the gas chemistry observed during the plasma treatment of gaseous dodecane under the same conditions, in order to gain an overall understanding of the plasma-liquid clean-up process. Finally, the gliding arc plasma treatment of liquid dodecane is studied using the recycling method and shows a significant improvement to the degradation efficiency.
5

Study of Hydrocarbon Waste Biodegradation and the Role of Biosurfactants in the Process

Fallon, Agata M. 18 September 1998 (has links)
Two types of oily waste sludges generated by a railroad maintenance facility were studied to reduce the volume of hydrocarbon waste. The specific goals of this laboratory study were to evaluate rate and extent of microbial degradation, benefits of organism addition, role of biosurfactant, and dewatering properties. The oily waste sludges differed in characteristics and contained a mixture of water, motor oil, lubricating oil, and other petroleum products. Degradation was measured using COD, suspended solids, GC measurements of extractable material, and nonextractable material concentration. Biosurfactant production was characterized using surface tension and polysaccharide measurements. Degradation of ten percent waste oil showed that the removal in a 91 day experiment was 75 percent for COD and suspended solids, 98 percent for extractable oil, and negligible for non-extractable material. It was concluded that methylene chloride extraction could be used to estimate degradation potential of a hydrocarbon waste. Addition of organisms increased the rate and extent of degradation over 22 days, but did not provide any benefits over 91 days. Data suggested that microorganisms degraded simple compounds first, then produced biosurfactants. It was thought that the biosurfactants remained attached to the organism membrane and increased solubility, stimulating the degradation of difficult to degrade waste oil. After oil was degraded the biosurfactants became ineffective. The dewatering properties of 10 percent oily sludge deteriorated with the production of biosurfactant and improved after the surfactant was degraded due to changes in oil solubility. / Master of Science
6

Study of enzymatic production of biodiesel using residual oil and ethanol / Estudo da produÃÃo enzimÃtica de biodiesel utilizando Ãleo residual e etanol

Edilson Holanda Costa Filho 09 October 2008 (has links)
Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Biodiesel is a mixture of fatty acid alkyl esters produced by the reaction between vegetable oils and short chain alcohols, like methanol and ethanol, using a catalyst that can be acid, basic or enzymatic. However, the high cost of the raw material when refined vegetable oil is used, have made biodiesel production economically unattractive. Therefore, research with waste oils has increased, showing the technical viability of the production of biodiesel using the residential and industrial residues as raw material. Another variable that has influenced this type of reaction is the type of alcohol. In Brazil, the use of ethanol is interesting because the country has become one of the top worldwide producers of ethanol from vegetables sources, a cheaper and less toxic product than methanol, decreasing our petroleum dependence. The type of catalyst also influences biodiesel production. Alkali is the catalysts that is more often used in industry, but when the vegetable oil has a high acid value, it can not be used because soap is produced, diminishing the esters yield. In this case an acid or an enzyme is used as a catalyst. Based on the previous explanation, the results of this work correspond to the study of enzymatic production of biodiesel using waste oil and ethanol. The immobilized Candida antarctica lipase (Novozym 435) behavior was studied in the oleic acid esterification, studying the effect of the variables that has influence in the process. The variables chosen were: temperature (30 â 50oC), molar ratio acid:alcohol (1:1 â 1:6) and water content (0 â 20%). The reaction were performed in closed reactors with a capacity of 250 mL containing 10 g of oil, a known amount content of alcohol, pre-determined by experimental design and enzyme content of 5% p/p, based on the oil mass. The reaction medium was kept under constant stirring, 200 rpm. Maximum conversion of 88,36% was achieved when high molar ration, the lower temperature and water content values were used. However, by the kinetic study, it can be concluded that it is not necessary to use an alcohol excess to achieve good conversions. After that, the behavior of Candida Antarctica lipase B immobilized in chitosan was studied in acid oleic esterification. A slower initial rate of reaction was observed in comparison to Novozym 435. The behavior of both lipases was also studied in the esterification of waste coconut oil, showing good stability and giving a conversion of about 80% in 60 minutes. Both biocatalyst could be reused 10 times, keeping the same activity. In order to compare the behavior of Novozym 435 in two different mediums, an experimental design was performed with waste cotton oil, which had a low acid value. The same negative influence of the temperature and molar ratio was observed, but with a high reaction time, getting a maximum conversion of 82,66% in 72 hours of reaction. To calculate the conversions, the decreasing of the acid value was used when the raw material had a high acid value, and when the raw material had a low acid value the glycerol production was used. / O biodiesel à uma mistura de Ãsteres alquÃlicos de Ãcidos graxos resultante da reaÃÃo entre Ãleos vegetais e Ãlcoois de cadeia curta, como metanol ou etanol, auxiliada por um catalisador, que pode ser Ãcido, bÃsico ou enzimÃtico. Entretanto, o alto custo da matÃria-prima quando se utiliza Ãleo vegetal de grau alimentÃcio tem inviabilizado economicamente a produÃÃo desse biocombustÃvel. Por isso, as pesquisas com Ãleo residual tem aumentado, mostrando a viabilidade tÃcnica da produÃÃo de biodiesel a partir de resÃduos residenciais e industriais. Outro fator que influencia a reaÃÃo de produÃÃo de biodiesel à o tipo de Ãlcool. No Brasil, o uso do etanol à interessante desde que o nosso paÃs se tornou um dos maiores produtores mundiais de etanol vegetal, um produto mais barato e menos tÃxico que o metanol, diminuindo assim a nossa dependÃncia do petrÃleo. O catalisador tambÃm exerce influÃncia nesse tipo de reaÃÃo. Os catalisadores mais usados industrialmente sÃo as bases, mas quando o Ãleo vegetal tem um alto teor de Ãcidos graxos livres, o que acontece, geralmente, com os Ãleos residuais, nÃo à possÃvel usar catalisador bÃsico por favorecer a formaÃÃo de sabÃo e diminuir o rendimento em Ãsteres. Nesse caso, usa-se um catalisador Ãcido ou enzimÃtico. Partindo dessa premissa, os resultados constantes nessa dissertaÃÃo correspondem ao estudo da produÃÃo enzimÃtica de biodiesel utilizando Ãleo residual e etanol. Avaliou-se o comportamento da lipase comercial imobilizada de CÃndida antarctica tipo B (Novozym 435) na esterificaÃÃo do Ãcido olÃico comercial, estudando as variÃveis que influenciam no processo. As variÃveis escolhidas foram: temperatura (30-50o C), razÃo molar Ãcido:Ãlcool (1:1-1:6) e a concentraÃÃo de Ãgua presente no meio (0-20%). As reaÃÃes foram conduzidas em erlenmeyers de 250 mL fechados contendo 10 g de Ãleo e a quantidade de Ãlcool prÃ-determinada pelo planejamento de experimentos, mantendo-se a agitaÃÃo fixa em 200rpm e a concentraÃÃo de enzima em 5% m/m baseada na massa de Ãleo medida, obtendo-se uma conversÃo mÃxima de 88,36% na condiÃÃo de maior razÃo molar, menor temperatura e menor concentraÃÃo de Ãgua. Entretanto, pelo estudo cinÃtico concluÃ-se que nÃo à necessÃrio um excesso de Ãlcool para conseguir boas conversÃes. Em seguida, avaliou-se o comportamento de uma lÃpase do tipo B de CÃndida antarctica imobilizada em quitosana na esterificaÃÃo do Ãcido olÃico, observando um comportamento semelhante ao da Novozym 435 mas com uma taxa inicial de reaÃÃo mais lenta. Avaliou-se tambÃm o comportamento das duas lÃpases na esterificaÃÃo do Ãleo de coco residual Ãcido, observando uma boa estabilidade para ambos os biocatalisadores que forneceram uma conversÃo acima de 80% com 60 minutos de reaÃÃo e puderam ser reutilizados por no mÃnimo 10 vezes consecutivas sem perda considerÃvel de atividade. Para comparar o comportamento da Novozym 435 em dois meios distintos, realizou-se um planejamento experimental fatorial com um Ãleo de algodÃo residual de baixa acidez livre, observando a mesma influÃncia negativa da temperatura e da razÃo molar entre reagentes, mas com um tempo de reaÃÃo maior, pois uma conversÃo mÃxima de 82,66% sà foi atingida com 72 horas de reaÃÃo. Para o cÃlculo da conversÃo, utilizou-se a reduÃÃo do Ãndice de acidez quando a matÃria-prima tinha um alto teor de Ãcidos graxos livres e o mÃtodo do periodato de sÃdio na determinaÃÃo da glicerina quando a matÃria-prima tinha uma baixa acidez livre.
7

Produção e avaliação físico-química, microbiológica e ecotoxicológica de biodiesel metílico de óleo residual de fritura (ORF) / Production and physical, chemical, microbiological, ecotoxicological assessment, of methyl biodiesel from frying residual oil (FRO)

Carrim, Aysha Jussara Ivonilde 27 June 2016 (has links)
Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2016-08-12T11:39:05Z No. of bitstreams: 2 Tese - Aysha Jussara Ivonilde Carrim - 2016.pdf: 3120455 bytes, checksum: 1dc51f3ce478b97db5f111505e62cfa4 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2016-08-12T11:42:23Z (GMT) No. of bitstreams: 2 Tese - Aysha Jussara Ivonilde Carrim - 2016.pdf: 3120455 bytes, checksum: 1dc51f3ce478b97db5f111505e62cfa4 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2016-08-12T11:42:23Z (GMT). No. of bitstreams: 2 Tese - Aysha Jussara Ivonilde Carrim - 2016.pdf: 3120455 bytes, checksum: 1dc51f3ce478b97db5f111505e62cfa4 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2016-06-27 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Biodiesel has been highlighted among biofuels for producing from renewable sources and a wide variety of grease raw materials such as plant and animal origins, including residue and environmental liabilities. Seeking to decrease the costs of biodiesel, the market has been using residual oils and fats, especially frying residual oils, as low-cost grease raw material. Therefore, the objective of this study is to understand the aspects of chemical production as well as the ecotoxicological and microbiological safety of FRO biodiesel. We observed that the physical, chemical quality of the FRO biodiesel production is adequate to most of the parameters analyzed, such as content of ester, mono-, di- and triacylglycerides; however, parameters such as viscosity, acidity index, water content, and oxidative stability had negative effects. In order to improve the oxidative stability, we tested a few natural antioxidants among which L-tryptophan and curcumin provided an induction period of over eight hours, acting synergistically on an oxidative stability increase until 30 hours. Regarding the toxicity of the biodiesel produced, the test organism employed, Artemia salina, indicated low toxicity for the biofuel in saline and brackish aquatic environments. For the microbiological quality, we isolated a bacteria identified as Bacillus licheniformis, which was able to produce biosurfactant (s) and degrade both biodiesel and soil oil as well as oil by-products. Thus, frying oil biodiesel has low toxicity in saline and brackish environments tending to be more easily degraded by a microbiological action, which is positive from the environmental point of view, but negative for storage, requiring mixture with other better quality biodiesel samples to generate commercial biodiesel with specifications that meet the legislation / Dentre os biocombustíveis, o biodiesel tem se destacado por ser produzido a partir de fontes renováveis e grande variedade de matérias-primas graxas, tais como de origem vegetal e animal, incluindo resíduos e passivos ambientais. Na intenção de diminuir os custos do biodiesel, o mercado tem buscado utilizar óleos e gorduras residuais (OGR), em especial óleos residuais de fritura (ORF), como matéria-prima graxa de baixo custo. Assim, este trabalho visa conhecer os aspectos da produção química e de segurança ecotoxicológica e microbiológica do biodiesel de ORF. Em relação à produção de biodiesel de ORF, observou-se que sua qualidade físico-química encontra-se adequada para a maioria dos parâmetros analisados, tais como teor de éster, de mono-, di- e triacilglicerídos, entretanto, parâmetros como viscosidade, índice de acidez, teor de água e estabilidade oxidativa foram negativamente afetados. Para melhorar a estabilidade oxidativa foram testados antioxidantes naturais, dos quais o L-triptofano e a curcumina proporcionaram período de indução acima de 8 horas, atuando sinergisticamente na elevação da estabilidade oxidativa por até 30 horas. No que se refere à toxicidade do biodiesel produzido, o organismo-teste utilizado, Artemia salina, indicou baixa toxicidade para esse biocombustível em ambientes aquáticos salinos e salobros. Em relação à qualidade microbiológica, foi isolada uma bactéria identificada como Bacillus licheniformis, a qual foi capaz de produzir biossurfactante(s) e degradar tanto o biodiesel, quanto o óleo de soja e derivados de petróleo. Assim, o biodiesel de óleo de fritura possui baixa toxicidade em ambientes salino e salobro e tende ser mais facilmente degradado por ação microbiológica, o que é positivo do ponto de vista ambiental, mas negativo do ponto de vista do armazenamento, e necessita ser misturado a outras amostras de biodiesel de melhor qualidade para gerar um biodiesel comercial que apresente especificações dentro do estabelecido na legislação.
8

Opportunities for Industrial Symbiosis BetweenCHP and Waste Treatment Facilities : (Case Study of Fortum and Ragn Sells, Brista)

Arushanyan, Yevgeniya January 2011 (has links)
Pursuing the possibilities of increasing efficiency, saving costs and improving environmental performance more and more companies today are looking into the possibilities of industrial synergies between companies andprocesses. This study is considering the possibilities of industrial symbiosis between combined heat and power plant (Fortum) and a waste sorting facility (Ragn Sells). The paper shows possible scenarios of utilization heat fromCHP for the various processes within the waste treatment facility. The work includes the overview of previous research done in this area as well as theoretical analysisand estimation of the probable economic and environmental effects from the application of industrial symbiosis. The study covers several possibilities for the industrial symbiosis between CHP and waste treatment facility in form of heat application for the waste streams upgrading.The study proposes the heat application for the following processes: composting speed-up, anaerobic digestion, sludge drying, waste oil treatment and concrete upgrading. In the result of the work the conclusions are made concerning the possibility and feasibility of application of the proposed scenarios and their environmentaland economic effects. / Division Industrial Ecologywww.kth.se/itm/indecowww.ima.kth.se
9

Degradacao termica e catalitica da borra oleosa de Petroleo com materiais nanoestruturados al-mcm-41 e AL-SBA-15

Paulino, Ana Adalgisa Dias 04 November 2012 (has links)
Made available in DSpace on 2014-12-17T14:09:14Z (GMT). No. of bitstreams: 1 AnaADP_TESE.pdf: 2810011 bytes, checksum: 6f11363dfc6e540fe688b7737b77893b (MD5) Previous issue date: 2012-11-04 / Aiming to reduce and reuse waste oil from oily sludge generated in large volumes by the oil industry, types of nanostructured materials Al-MCM-41 and Al-SBA-15, with ratios of Si / Al = 50, were synthesized , and calcined solids used as catalysts in the degradation of oily sludge thermocatalytic oil from oilfield Canto do Amaro, in the state of Rio Grande do Norte. Samples of nanostructured materials were characterized by thermogravimetric analysis (TG / DTG), X-ray diffraction (XRD), scanning electron microscopy (SEM), absorption spectroscopy in the infrared Fourier transform (FT-IR) and adsorption nitrogen (BET). The characterization showed that the synthesized materials resulted in a catalyst nanostructure, and ordered pore diameter and surface area according to existing literature. The oily sludge sample was characterized by determining the API gravity and sulfur content and SARA analysis (saturates, aromatics, resins and asphaltenes). The results showed a material equivalent to the average oil with API gravity of 26.1, a low sulfur content and considerable amount of resins and asphaltenes, presented above in the literature. The thermal and catalytic degradation of the oily sludge oil was performed from room temperature to 870 ? C in the ratios of heating of 5, 10 and 20 ? C min-1. The curves generated by TG / DTG showed a more accelerated degradation of oily sludge when it introduced the nanostructured materials. These results were confirmed by activation energy calculated by the method of Flynn-Wall, in the presence of catalysts reduced energy, in particular in the range of cracking, showing the process efficiency, mainly for extraction of lightweight materials of composition of oily sludge, such as diesel and gasoline / Com o objetivo de reduzir e reutilizar o res?duo de borra oleosa de petr?leo, gerado em grandes volumes pela ind?stria petrol?fera, materiais nanoestruturados dos tipos Al-MCM-41 e Al-SBA-15, com raz?es de Si/Al = 50, foram sintetizados, calcinados e utilizados como s?lidos catal?ticos na degrada??o termocatal?tica da borra oleosa de petr?leo, proveniente do campo petrol?fero Canto do Amaro, no estado do Rio Grande do Norte. As amostras dos materiais nanoestruturados foram caracterizadas por an?lise termogravim?trica (TG/DTG), difra??o de raios X (DRX), microscopia eletr?nica de varredura (MEV), espectroscopia de absor??o na regi?o do infravermelho com transformada de Fourier (FT-IR) e adsor??o de nitrog?nio (BET). A caracteriza??o mostrou que os materiais sintetizados resultaram em um catalisador nanoestruturado, ordenado e com di?metro de poros e ?rea superficial de acordo com a literatura existente. A amostra de borra oleosa foi caracterizada atrav?s da determina??o do grau API e do teor de enxofre e da an?lise do SARA (saturados, arom?ticos, resinas e asfaltenos). Os resultados mostraram um material equivalente ao petr?leo m?dio, com grau API de 26,1, baixo teor de enxofre e com quantidade consider?vel de resinas e asfaltenos, acima da apresentada na literatura. A degrada??o t?rmica e catal?tica da borra oleosa de petr?leo foi realizada da temperatura ambiente at? 870?C, nas raz?es de aquecimento de 5, 10 e 20oC min-1. As curvas geradas pela TG/DTG apresentaram uma degrada??o mais acelerada da borra oleosa quando se introduziram os materiais nanoestruturados. Esses resultados foram ratificados pela energia de ativa??o, calculada atrav?s do m?todo de Flynn-Wall, em que a presen?a dos catalisadores reduziu a energia, em especial na faixa de craqueamento, mostrando a efici?ncia do processo, principalmente para a extra??o de materiais leves da composi??o da borra oleosa, como diesel e gasolina

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