Orientador: Maria Alvina Krähenbühl / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-17T04:16:54Z (GMT). No. of bitstreams: 1 Silva_LucianaYumiAkisawa_D.pdf: 1464377 bytes, checksum: 8980b0b6666145c777fdc5a801fdf850 (MD5) Previous issue date: 2010 / Resumo: O biodiesel e um combustível biodegradável, renovável e com menor emissão de gases poluentes do que o petrodiesel. Ele e composto por ésteres alquilícos de ácidos graxos obtidos pela transesterificação de óleos ou gorduras com um álcool de cadeia curta como o metanol ou o etanol. Os ésteres etílicos resultantes da transesterificação com o etanol ainda são pouco caracterizados. Dados de suas propriedades termofísicas e de equilíbrio de fases; que são muito importantes para o projeto, modelagem, simulação e otimização do processo de produção do biodiesel, são escassos na literatura. Neste trabalho determinaram-se dados de pressão de vapor dos ésteres laurato de etila, miristato de etila, palmitato de etila, estearato de etila, oleato de etila e linoleato de etila, e dados de equilíbrio líquido-vapor dos sistemas palmitato de etila + estearato de etila a 40 mmHg, palmitato de etila + oleato de etila a 40 e 70 mmHg e palmitato de etila + linoleato de etila a 70 mmHg. Para a determinação experimental propôs-se a utilização de uma técnica não convencional: a calorimetria exploratória diferencial ("Differential Scanning Calorimetry" - DSC). Nas analises foram utilizadas de 2-5 mg de amostra a uma taxa de aquecimento de 25 oC/min. As amostras foram colocadas em cadinhos herméticos de alumínio com um pequeno orifício na tampa ("pinhole") de 0,25 mm de diâmetro, para garantir a pressão interna constante. Para a determinação de dados de pressão de vapor, o DSC revelou-se ser uma técnica adequada e suas principais vantagens em relação as técnicas convencionais são: utilização de pequena quantidade de amostra e menor tempo de analise. Os dados de equilíbrio líquido-vapor medidos pelo DSC foram satisfatórios. Esta técnica mostrou-se restrita, não sendo adequada para a determinação do equilíbrio liquidovapor de sistemas cujos componentes apresentam grande diferença de volatilidade / Abstract: Biodiesel is a biodegradable, renewable fuel with lower greenhouse gas emissions. It consists of the alkyl esters of fatty acids, obtained by the transesterification of fats and oils with a short chain alcohol such as methanol or ethanol. Ethyl esters resulting from transesterification with ethanol are poorly characterized. The thermophysical properties and phase equilibrium data involving the fatty acid ethyl esters are very important in the design, modeling, simulation, and the optimization of the production of biodiesel, are scarce in the literature. In this work was determined vapor pressure data of the esters ethyl laurate, ethyl myristate, ethyl palmitate, ethyl stearate, ethyl oleate and ethyl linoleate; and vapor-liquid equilibrium data of systems ethyl pamitate + ethyl stearate at 40 mmHg, ethyl palmitate + ethyl oleate at 40 and 70 mmHg and ethyl palmitate + ethyl linoleate ant 70 mmHg. For the experimental determination proposed the use of a non-conventional technique: differential scanning calorimetry (DSC). Samples of 2 to 5 mg were used in the analysis, with heating rate of 25 ?C/min. The samples were placed in hermetic aluminum crucibles with a small hole in the lid ("pinhole") of 0.25 mm diameter, which maintain a constant internal pressure. The technique of differential scanning calorimetry was shown to be appropriate to determining the vapor pressure of ethyl esters. This technique showed advantages over conventional techniques: the use of a small sample size and shorter analysis time. The vapor-liquid equilibrium data measured by DSC were satisfactory. This technique proved to be restricted and it is not suitable for determining the vapor-liquid equilibrium data of systems whose components have large difference in volatility / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química

Orientador: Roberta Ceriani / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-25T00:34:06Z (GMT). No. of bitstreams: 1 Damaceno_DanieladaSilva_M.pdf: 3241692 bytes, checksum: 461c874bf1a0705ce436bee9c205a2a1 (MD5) Previous issue date: 2014 / Resumo: Óleos e gorduras são uma fonte nutricional relevante de energia, de ácidos graxos essenciais, de vitaminas e de antioxidantes naturais, além da demanda recente como matéria-prima para produção de biodiesel. Em sua grande maioria, passam por algum tipo de processamento antes de ser destinado ao consumo humano. Além disso, derivados de óleos vegetais como ácidos graxos, ésteres graxos, triacilgliceróis, diacilgliceróis e monoacilgliceróis são importantes produtos oleoquímicos, de aplicação nas indústrias de alimentos e química. Neste contexto, o conhecimento e a descrição do comportamento de propriedades termofísicas de compostos graxos em função das diferentes variáveis de processamento podem ser de grande utilidade prática. No entanto, dados experimentais dessas propriedades na literatura aberta são bastante escassos. No caso da temperatura de ebulição de acilgliceróis parciais (mono- e diacilgliceróis), o banco de dados experimentais é formado por apenas seis valores para seis diferentes monoacilgliceróis a 0,13 kPa. Já para os tocoferóis, a literatura aberta apresenta um gráfico monolog da pressão de vapor (0,004 kPa a 0,5 kPa) em função da temperatura (453 K a 533 K). Nenhum dado pode ser encontrado para os diferentes tocoferóis (?-, ?-, ?- e ?-) Assim, nesse trabalho foram determinadas as temperaturas de ebulição de quatro acilgliceróis parciais, monocaprilina, monocaprina, dicaprilina e dicaprina a baixas pressões (1,0 kPa a 13,2 kPa) e dos tocoferóis ?-, ?-, ?- e ?- a 1,1 kPa, utilizando a técnica de calorimetria diferencial exploratória, que é bastante adequada para compostos susceptíveis à degradação térmica e oxidativa, e de custo bastante elevado (amostras na ordem de miligramas). Para os acilgliceróis parciais, parâmetros das equações de Clapeyron, Antoine e DIPPR (Design Institute for Physical Properties) foram ajustados. No caso da equação DIPPR, foram incluídos na regressão valores estimados pelo método de contribuição de grupos de Marrero e Gani para temperatura normal de ebulição e ponto crítico. A entalpia de vaporização foi estimada utilizando a relação de Clausius-Clayperon com a inclusão de um termo de correção para desvios a pressões mais elevadas. Já para a classe dos tocoferóis, uma equação DIPPR foi ajustada para a pressão de vapor e derivada para a entalpia de vaporização / Abstract: Oils and fats are an important source of energy, essential fatty acids, vitamins and nutritional source of natural antioxidants, plus the recent demand for feedstock for biodiesel production. Overwhelmingly, undergo some type of processing before being used for human consumption. Moreover, derived from vegetable oils such as fatty acids, fatty esters, trigacylglycerols, diacylglycerols and monoacylglycerols are important oleochemicals, application in the food and chemical industries. In this context, knowledge and description of the behavior of thermophysical properties of fatty due to different processing variables compounds may be of great practical utility. However, experimental data for these properties in the open literature are scarce. In the case of the boiling temperature of partial acylglcerols (mono- and diacylglycerols), the database of experimental data consists of only six values for six different monoacylglycerols at 0.13 kPa. As for the tocopherols, an open literature monolog shows a graph of vapor pressure (0.004 kPa up to 0.5 kPa) versus temperature (453 K up to 533 K). No data could be found for the different tocopherols (?-, ?-, ?- and ?-). Thus, in this work we determine the boiling temperatures four partial acylglycerols, monocaprin, monocaprylin, dicaprin and dicaprylin at low pressures (1.0 kPa up to 13.2 kPa) and ?-, ?-, ?- and ?- tocopherols 1.1 kPa, using the technique of differential scanning calorimetry, which is very suitable for compounds that are susceptible to thermal and oxidative degradation, and quite expensive (samples in the order of milligrams). For partial acylglycerols, parameters of Clapeyron, Antoine and DIPPR (Design Institute for Physical Properties) equations were adjusted. In the case of DIPPR equation, were included in the regression values estimated by the group contribution method of Marrero and Gani to the normal boiling point and critical point. The enthalpy of vaporization was estimated using the Clausius-Clapeyron relation with the inclusion of a correction term for deviations at higher pressures. As for the class of tocopherols a DIPPR equation was adjusted for vapor pressure and derived for the enthalpy vaporization / Mestrado / Desenvolvimento de Processos Químicos / Mestra em Engenharia Química

The seasonal pattern of the carbon isotope content (delta C-13) of atmospheric CO2 depends on local and nonlocal land-atmosphere exchange and atmospheric transport. Previous studies suggested that the delta C-13 of the net land-atmosphere CO2 flux (delta(source)) varies seasonally as stomatal conductance of plants responds to vapor pressure deficit of air (VPD). We studied the variation of (source) at seven sites across the United States representing forests, grasslands, and an urban center. Using a two-part mixing model, we calculated the seasonal delta(source) for each site after removing background influence and, when possible, removing delta C-13 variation of nonlocal sources. Compared to previous analyses, we found a reduced seasonal (March-September) variation in delta(source) at the forest sites (0.5 parts per thousand variation). We did not find a consistent seasonal relationship between VPD and delta(source) across forest (or other) sites, providing evidence that stomatal response to VPD was not the cause of the global, coherent seasonal pattern in (source). In contrast to the forest sites, grassland and urban sites had a larger seasonal variation in (source) (5) dominated by seasonal transitions in C-3/C-4 grass productivity and in fossil fuel emissions, respectively. Our findings were sensitive to the location used to account for atmospheric background variation within the mixing model method that determined (source). Special consideration should be given to background location depending on whether the intent is to understand site level dynamics or regional scale impacts of land-atmosphere exchange. The seasonal amplitude in delta C-13 of land-atmosphere CO2 exchange (delta(source)) varied across land cover types and was not driven by seasonal changes in vapor pressure deficit. The largest seasonal amplitudes of delta(source) were at grassland and urban sites, driven by changes in C-3/C-4 grass productivity and fossil fuel emissions, respectively. Mixing model approaches may incorrectly calculate delta(source) when background atmospheric observations are remote and/or prone to anthropogenic influence.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第16852号 / 工博第3573号 / 新制||工||1540(附属図書館) / 29527 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 田中 功, 教授 乾 晴行, 准教授 宇田 哲也 / 学位規則第4条第1項該当

Abstract The production of liquid transportation fuels such as bioethanol and more recently also biobutanol from renewable resources has received considerable attention. In the production of bio-based alcohols, the separation steps are expensive as the mixtures to be separated are dilute. As an energy-efficient separation technology, pervaporation is considered to be a potential process in biofuel purification. One of the main constraints in the commercialization of pervaporation has been low membrane fluxes, and the consequent high costs due to the high membrane area needed. In order to obtain high fluxes, the membranes should be as thin as possible. In this thesis, the performance of ultra-thin zeolite membranes in pervaporation was investigated. Binary ethanol/water and n-butanol/water mixtures were studied using both hydrophobic and hydrophilic zeolite membranes for alcohol concentration, as well as dehydration. The development of pervaporation membranes and processes has been mainly empirical. Process modeling, however, is an indispensable tool in process design. In this work, the pervaporation performance of the studied membranes was evaluated on the basis of experimental results in combination with mathematical modeling. Due to the low film thickness of the studied membranes, the fluxes were generally higher than reported earlier. Nevertheless, the evaluation in this work showed that the pervaporation performance of the ultra-thin membranes decreased due to flux limitation by membrane support. In this work, pervaporation was modeled by applying both a semi-empirical and a detailed Maxwell-Stefan based mass transfer model. The latter model considers explicitly both adsorption and diffusion, i.e. the phenomena involved in separation by pervaporation. The description of the support behavior was included in the models. Maxwell-Stefan formalism was applied in unary pervaporation for the determination of diffusivities in zeolite membranes. The models performed well within the range of experimental data. Additionally, a practical modeling approach was developed in this work to predict the temperature dependency of adsorption on zeolites. The developed approach can be utilized, e.g., in pervaporation modeling. Thus, this thesis provides knowledge of using ultra-thin zeolite membranes in the pervaporation of alcohol/water mixtures, and offers tools for pervaporation modeling. / Tiivistelmä Kiinnostus uusiutuvista raaka-aineista valmistettavia liikennepolttoaineita, kuten bioetanolia ja -butanolia, kohtaan lisääntyy koko ajan. Biopohjaisten alkoholien tuotannossa etenkin erotusvaiheet ovat kalliita, koska erotettavat liuokset ovat laimeita. Pervaporaatio on energiatehokas kalvoerotusmenetelmä ja sen vuoksi potentiaalinen osaprosessi biopolttoaineiden tuotantoon. Pervaporaation kaupallistamisen merkittävimpiä rajoitteita ovat olleet alhaiset ainevuot, jotka johtavat suureen kalvopinta-alan tarpeeseen ja näin ollen korkeisiin kustannuksiin. Korkean ainevuon saavuttamiseksi kalvojen tulisi olla mahdollisimman ohuita. Tässä väitöstyössä tutkittiin hyvin ohuiden zeoliittimembraanien suorituskykyä pervaporaatiossa. Kohteena olivat binääriset etanoli/vesi- ja n-butanoli/vesiseokset, joista väkevöitiin alkoholeja tai poistettiin vettä hydrofobisia ja hydrofiilisiä zeoliittimembraaneja käyttäen. Pervaporaatiossa käytettävien kalvojen ja pervaporaatiota hyödyntävien prosessien kehitystyö on ollut pääasiassa kokeellista. Prosessimallinnus on kuitenkin tärkeä työkalu prosessisuunnittelussa. Tässä työssä membraanien suorituskykyä pervaporaatiossa arvioitiin sekä kokeellisesti että mallinnuksen keinoin. Käytettyjen kalvojen ohuuden ansiosta tässä työssä saavutetut ainevuot olivat yleisesti ottaen korkeampia kuin aiemmin raportoiduilla membraaneilla. Ohuilla kalvoilla tukimateriaalin aiheuttama aineensiirron vastus oli kuitenkin merkittävä, alentaen membraanien suorituskykyä. Tässä työssä pervaporaatiota mallinnettiin käyttäen sekä puoliempiiristä että yksityiskohtaisempaa Maxwell-Stefan -pohjaista mallia. Jälkimmäisessä mallissa adsorptio ja diffuusio, eli ilmiöt joihin erotus pervaporaatiossa perustuu, otetaan eksplisiittisesti huomioon. Myös tukimateriaalin vaikutukset huomioitiin käytetyissä malleissa. Maxwell-Stefan -mallinnusta käytettiin puhtaiden komponenttien pervaporaatiossa zeoliittimembraanin diffuusiokertoimien määrittämiseksi. Käytettyjen mallien suorituskyky kokeellisella alueella oli hyvä. Tässä työssä kehitettiin lisäksi helppokäyttöinen menetelmä aineiden adsorptiokäyttäytymisen ennustamiseen zeoliiteissa eri lämpötiloissa. Kehitettyä menetelmää voidaan hyödyntää esimerkiksi pervaporaation mallinnuksessa. Kokonaisuudessaan väitöstyöstä saadaan tietoa ultraohuiden membraanien käytöstä pervaporaatiossa sekä työkaluja pervaporaation mallinnukseen.

No description available.

A modified dew point method for measuring vapor pressures of condensed phases is applied to solid mixtures of benzene and cyclohexane. From the measured vapor pressures, activity coefficients and excess Gibbs energies are derived. Much less accurate information about excess entropy and excess enthalpy is obtained. A comparison is made with the known properties of liquid mixtures of the same molecules. / Thesis / Master of Science (MSc)

New low volatile formulations of dicamba and 2,4-D are being developed to reduce injury to non-tolerant crops. Experiments were conducted comparing dicamba and 2,4-D volatility as affected by formulation, soil moisture content and soil texture. All formulations were applied to soil contained in greenhouse flats. After application greenhouse flats were then placed between a bio-indicator row of cotton and soybean. An open ended plastic dome covered the treated flats and crops for 48 hours prior to removal. Plant heights and yield of bio-indicator crops were unaffected by 2,4-D and dicamba volatility. Soil texture and moisture content did not significantly affect volatility. The greatest soybean crop injury was observed following application of the dimethylamine salt of dicamba and cotton injury was greatest following application of the ethylhexylester salt of 2,4-D. Volatility was generally reduced with new formulations of dicamba or 2,4-D; however, volatility was not completely eliminated.

No description available.

With the increasing research on advanced reactors, molten salt reactors have been recognized for their potential. As with any advanced reactor concept, each component and material must be thoroughly investigated before any reactors of that type are created. One of the most pressing issues in MSR research is that of the salts themselves. Though there are a multitude of salts to choose from when designing such a reactor, many of these salts lack the extensive research required to fully understand them. Across the decades there have been many studies that have investigated select molten salts, but there are a few problems with many of those studies. Those problems are the following: prior papers use obsolete and less reliable methods for their measurements, the papers don't investigate the salts across a wide enough range of temperatures nor at varying compositions, and finally many of the salts that are seen as candidates today were not given as much attention when molten salt reactors were first conceptualized which has resulted in a lack of research on them. Indeed, the research into these salts is lacking in many ways. This study seeks to investigate a collection of promising coolant salts in depth with acknowledgment to those past studies. LiF-NaF-KF (46.5-11.5-42.0 mol%) will be used as a calibration standard and for the purpose of verifying our methodology. Specifically, FLiNaK was used in the development of volume-height curves as calibration for density measurements. NaOH-KOH of four different compositions ( 0.5-0.5mol%, 0.55-0.45mol%, 0.6-0.4mol%, and 0.65-0.35 mol%) will be evaluated for their densities and heat capacities. And finally, BeF2-NaF(43-57mol%) will be evaluated within the question of if the properties are desirable enough that the dangers posed by beryllium are an acceptable risk. BeF2-NaF will have melting point, heat capacity, density, and vapor pressure measurements performed. Additionally, extensive impurity analysis and removal (via an HF gas system) was done to our BeF2-NaF samples. The melting point and heat capacity were evaluated using dynamic scanning calorimetry (DSC), the vapor pressure was evaluated using thermogravimetric analysis (TGA), and the density was measured using a system similar to the Arrhenius method that measures height. / Master of Science / Decades have passed since the discussion of nuclear energy began. Although great progress has been made in the field, the nuclear reactors in use today consist mainly of boiling water reactors (BWRs) or pressurized water reactors (PWRs). As reliable as these reactors have become, one can no longer ignore the fact that there is a multitude of other options for how a reactor can be built and operated. Options that provide greater safety and more energy output. Many reactor concepts of the past were discounted for the extensive research that would be required to make use of them. However, as time has passed and technology has improved, that research has become more and more possible. Many advanced reactors are the result of that attention to the reactor concepts and materials of the past that couldn't be given the attention that they deserve until now. Molten salt reactors (MSRs) are one of those promising concepts. However, before they can be built every part of the reactor, from the structure to the materials, must be entirely understood. One of the most pressing issues in MSR research is the properties of the salts in consideration for use. Though there are a multitude of salts to choose from when designing such a reactor, many of these salts lack the extensive research required to fully understand them. Across the decades there have been many studies that have investigated select molten salts, but there are a few problems with many of those studies. Those problems are the following: the papers are so old that the methods that were used are now obsolete, the papers don't investigate the salts across a wide enough range of temperatures nor at varying compositions, and finally many of the salts that are seen as candidates today were not given as much attention when molten salt reactors were first conceptualized which has resulted in a lack of research on them. Indeed, the research into these salts is lacking in many ways. This study seeks to investigate a collection of promising coolant salts in depth with acknowledgment to those past studies. LiF-NaF-KF will be used as a calibration standard and for the purpose of verifying our methodology. A multitude of different compositions of NaOH-KOH will be evaluated for their densities and heat capacities. And finally, BeF2-NaF will be evaluated within the question of if the properties are desirable enough that the dangers posed by beryllium are an acceptable risk. BeF2-NaF will have melting point, heat capacity, density, and vapor pressure measurements performed. Additionally, extensive impurity analysis and removal was done to our BeF2-NaF samples.