Flammability limit is a significant safety issue for industrial processes. A certain amount of flammability limit data for pure hydrocarbons are available in the literature, but for industrial applications, there are conditions including different combinations of fuels at standard and non-standard conditions, in which the flammability limit data are scarce and sometimes unavailable. This research is two-fold: (i) Performing experimental measurements to estimate the lower flammability limits and upper flammability limits of binary hydrocarbon mixtures, conducting experimental data numerical analysis to quantitatively characterize the flammability limits of these mixtures with parameters, such as component compositions, flammability properties of pure hydrocarbons, and thermo-kinetic values; (ii) Estimating flammability limits of binary hydrocarbon mixtures through CFT-V modeling prediction (calculated flame temperature at constant volume), which is based on a comprehensive consideration of energy conservation. For the experimental part, thermal detection was used in this experiment. The experimental results indicate that the experimental results fit Le Chatelier’s Law within experimental uncertainty at the lower flammability limit condition. At the upper flammability limit condition, Le Chatelier’s Law roughly fits the saturated hydrocarbon mixture data, while with mixtures that contain one or more unsaturated components, a modification of Le Chatelier’s is preferred to fit the experimental data. The easy and efficient way to modify Le Chatelier’s Law is to power the molar percentage concentrations of hydrocarbon components. For modeling prediction part, the CFT-V modeling is an extended modification of CAFT modeling at constant volume and is significantly related to the reaction vessel configuration. This modeling prediction is consistent with experimental observation and Le Chatelier’s Law at the concentrations of lower flammability limits. When the quenching effect is negligible, this model can be simplified by ignoring heat loss from the reaction vessel to the external surroundings. Specifically, when the total mole changes in chemical reactions can be neglected and the quenching effect is small, CFTV modeling can be simplified to CAFT modeling.

Flammability limit is a most significant property of substances to ensure safety of chemical processes and fuel application. Although there are numerous flammability literature data available for pure substances, for fuel mixtures these are not always available. Especially, for fuel mixture storage, operation, and transportation, inert gas inerting and blanketing have been widely applied in chemical process industries while the related date are even more scarce. Lower and upper flammability limits of hydrocarbon mixtures in air with and without additional nitrogen were measured in this research. Typically, the fuel mixture lower flammability limit almost keeps constant at different contents of added nitrogen. The fuel mixture upper flammability limit approximately linearly varies with the added nitrogen except mixtures containing ethylene. The minimum added nitrogen concentration at which lower flammability limit and upper flammability limit merge together is the minimum inerting concentration for nitrogen, roughly falling into the range of 45 plus/minus 10 vol % for all the tested hydrocarbon mixtures. Numerical analysis of inert gas dilution effect on lower flammability limit and upper flammability limit was conducted by introducing the parameter of inert gas dilution coefficient. Fuel mixture flammability limit can be quantitatively characterized using inert gas dilution coefficient plus the original Le Chatelier's law or modified Le Chatelier's law. An extended application of calculated adiabatic flame temperature modeling was proposed to predict fuel mixture flammability limits at different inert gas loading. The modeling lower flammability limit results can represent experimental data well except the flammability nose zone close to minimum inerting concentration. Le Chatelier's law is a well-recognized mixing rule for fuel mixture flammability limit estimation. Its application, unfortunately, is limited to lower flammability limit for accurate purpose. Here, firstly a detailed derivation was conducted on lower flammability limit to shed a light on the inherent principle residing in this rule, and then its application was evaluated at non-ambient conditions, as well as fuel mixture diluted with inert gases and varied oxygen concentrations. Results showed that this law can be extended to all these conditions.

Knowledge of flammability limits is essential in the prevention of fire and explosion. There are two limits of flammability, upper flammability limit (UFL) and lower flammability limit (LFL), which define the flammable region of a combustible gas/vapor. This research focuses on the flammability limits of hydrogen and its binary mixtures with light hydrocarbons (methane, ethane, n-butane, and ethylene) at sub-atmospheric pressures. The flammability limits of hydrogen, light hydrocarbons, and binary mixtures of hydrogen and each hydrocarbon were determined experimentally at room temperature (20ºC) and initial pressures ranging from 1.0 atm to 0.1 atm. The experiments were conducted in a closed cylindrical stainless steel vessel with upward flame propagation. It was found that the flammable region of hydrogen initially widens when the pressure decreases from 1.0 atm to 0.3 atm, then narrows with the further decrease of pressure. In contrast, the flammable regions of the hydrocarbons narrow when the pressure decreases. For hydrogen and the hydrocarbons, pressure has a much greater impact on the UFLs than on the LFLs. For binary mixtures of hydrogen and the hydrocarbons, the flammable regions of all mixtures widen when the fraction of hydrogen in the mixture increases. When the pressure decreases, the flammable regions of all mixtures narrow. The applications of Le Chatelier’s rule and the Calculated Adiabatic Flame Temperature (CAFT) model to the flammability limits of the mixtures were verified. It was found that Le Chatelier’s rule could predict the flammability limits much better than the CAFT model. The adiabatic flame temperatures (AFTs), an important parameter in the risk assessment of fire and explosion, of hydrogen and the hydrocarbons were also calculated. The influence of sub-atmospheric pressures on the AFTs was investigated. A linear relationship between the AFT and the corresponding flammability limit is derived. Furthermore, the consequence of fire relating to hydrogen and the hydrocarbons is discussed based on the AFTs of the chemicals.

Orientador: Celso Eduardo Tuna / Resumo: Com a criação de combustíveis alternativos para a redução de emissões de CO2 no setor aeronáutico, torna-se necessária a determinação de suas propriedades de segurança e, entre elas destacam-se os limites de inflamabilidade. O combustível alternativo aeronáutico, que é utilizado neste trabalho, é o farnesano, fabricado a partir da cana de açúcar, por um processo que transforma açúcar em hidrocarboneto, pela empresa Amyris, localizada em São Paulo, Brasil. O objetivo dessa dissertação é determinar experimentalmente os limites de inflamabilidade, inferior (LII) e superior (LSI) do farnesano, QAV e misturas de 10% (F10) e 50 % (F50) em massa de farnesano com o QAV a pressões reduzidas em ar. Utiliza-se uma bancada experimental, que segue a norma americana ASTM E681, para a determinação dos limites de inflamabilidade, em que se utiliza o critério visual de propagação de chama e um recipiente de vidro borosilicatado de 20,716 L. Primeiramente são determinados os limites de inflamabilidade dos combustíveis para a pressão de 101,3 kPa em temperaturas entre 140 e 220°C, comparando-se os resultados com os valores teóricos disponíveis na literatura para a validação do procedimento experimental. Em segundo lugar, são determinados os limites de inflamabilidade das amostras a pressões reduzidas como 80, 60, 40 e 20 kPa em temperaturas entre 140 e 200°C. Foram realizados, no total 636 testes para determinação dos limites de inflamabilidade, sendo a duração média, para cada teste de 20 minu... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The creation of alternative fuels to reduce CO2 emissions from the aeronautical sector needs determination of their safety properties, among which are flammability limits. farnesane is the alternative aviation fuel used in here, which has been produced from sugar cane through a conversion process known as direct sugar to hydrocarbon (DSHC) created by a company called Amyris, which is located in São Paulo, Brazil. Thereby, it is aimed to experimentally determine the flammability limits, lower (LFL) and upper (UFL) of farnesane, Jet fuel and mixtures of 10% (F10) and 50% (F50) in mass of farnesane at reduced pressures with air. For such a purpose, an experimental bench was built in accordance with American standard ASTM E681 to determine the lower flammability limits, in which flame propagation was analyzed visually through a 20.716 L borosilicate glass flask. The Flammability Limits of the fuels were initially determined at a pressure of 101.3 kPa and temperatures ranging between 140 and 220 ° C, whose results were compared with theoretical values found in literature in order to validate the experimental procedure. Afterwards, the Flammability Limits of samples were determined at reduced pressures, i.e. 80, 60, 40 and 20 kPa, and temperatures ranging between 140 and 200 ° C. 636 tests were performed altogether, the average time of each test was 20 minutes. Finally, prediction equations of flammability limits, were presented as a function of temperature / Mestre

Submitted by EDWIN SANTIAGO RIOS ESCALANTE null (esre_2808@hotmail.com) on 2016-09-12T20:28:02Z No. of bitstreams: 1 template-feg-2016-VERSÃO FINAL.pdf: 3419531 bytes, checksum: 2e6eca3a01fecef269a3334812ba75d2 (MD5) / Approved for entry into archive by Felipe Augusto Arakaki (arakaki@reitoria.unesp.br) on 2016-09-14T19:40:34Z (GMT) No. of bitstreams: 1 escalante_esr_me_guara.pdf: 3419531 bytes, checksum: 2e6eca3a01fecef269a3334812ba75d2 (MD5) / Made available in DSpace on 2016-09-14T19:40:34Z (GMT). No. of bitstreams: 1 escalante_esr_me_guara.pdf: 3419531 bytes, checksum: 2e6eca3a01fecef269a3334812ba75d2 (MD5) Previous issue date: 2016-07-12 / Agência Nacional de Petróleo, Gás Natural e Biocombustíveis (ANP) / Os limites superior e inferior de inflamabilidade são as concentrações máximas e mínimas de um combustível no ar, respectivamente, na qual uma chama pode se propagar, eles são considerados ferramentas chaves na predição do fogo, avaliando a possibilidade de explosão e projeto de sistemas de proteção. Existe interesse em encontrar os limites de inflamabilidade do etanol misturado com um diluente para pressões reduzidas para o futuro uso desse biocombustível em aplicações aeronáuticas tendo em conta a altitude típica de um avião comercial (<40 000 ft.). Neste trabalho foi desenvolvido experimentalmente a inflamabilidade do combustível líquido: Etanol hidratado e utilizou-se como gás diluente o nitrogênio. A bancada experimental usada, consiste de um recipiente esférico de 20 litros como câmara de aquecimento, uma fonte de ignição por faísca localizada na parte central da câmara. O líquido foi injetado com uma seringa de precisão de 1ml de volume para logo se evaporar no interior da câmara, o nitrogênio e ar foram injetados usando pressões parciais. O método para medir a inflamabilidade foi baseado na ignição elétrica e observação visual da propagação da chama conforme norma ASTM E-681. Primeiro os limites superior e inferior de inflamabilidade foram determinados para elevada temperatura (60℃) e pressão ambiente (101,325 kPa) para comparar os resultados com os dados publicados na literatura científica. Depois procedeu-se trabalhar com pressões reduzidas (80, 60, 40 e 20 kPa) para essa mesma temperatura, finalmente foram realizados testes para uma temperatura maior (110℃) para avaliar a influência da temperatura sobre os limites de inflamabilidade de misturas etanol-ar-diluente, os resultados foram plotados como função da relação e adição de nitrogênio e esses gráficos seguem a mesma tendência de trabalhos publicados na literatura científica. / The upper and lower limits of flammability are the maximum and minimum concentrations of a fuel in the air, respectively, in which the flame can spread; they are considered key tools for predicting fire, evaluating the possibility of explosion and protection system design. There is interest in finding the flammability limits of ethanol mixed with a diluent to reduced pressure for future use this biofuel in aeronautical applications having regard the typical height of a commercial aircraft (<40, 000 ft.). In this experimental work was carried flammability of the liquid fuel: Ethanol hydrate and used as a diluent gas nitrogen. The experimental apparatus consists of a 20 liters spherical vessel as heating chamber, a spark ignition source located in the central part of the chamber. The liquid was injected with a 1 ml syringe precision volume immediately evaporates in the chamber; nitrogen and air were injected using partial pressures. The method for flammability measuring was based in both visual observation electric ignition and flame propagation as defined by ASTM E-681. First, the upper and lower flammability limits were determined to a high temperature (60 ℃) and ambient pressure (101.325 kPa) to compare the results with data published in the scientific literature. After, we proceeded to work at reduced pressures (80, 60, 40 and 20 kPa) to same temperature. Finally, tests were carried out for a higher temperature (110 ℃) to evaluate the influence of temperature on the flammability limits ethanol-air-diluent mixtures, the results were plotted as a function of the relationship and adding nitrogen and these graphs follow the same trend of papers published in scientific literature.

Cette étude s’inscrit dans le cadre de l’évaluation du risque d’accélération de flamme en situation accidentelle. La méthodologie développée dans le cadre de l’évaluation du risque hydrogène dans l’industrie nucléaire a permis de proposer un critère permettant d’évaluer le risque d’accélération des flammes de prémélange hydrogène/air/diluants, sur la base des propriétés du mélange. L’objectif de cette étude est l’acquisition de données fondamentales relatives aux mélanges gaz naturel/air et gaz de synthèse/air puis l’extension de la méthodologie appliquée aux mélanges hydrogène/air à ces mélanges. Ainsi, trois mélanges gazeux ont été choisis et ont fait l’objet de cette étude. Il s’agit du G27 (82%CH4/18%N2), du G222 (77%CH4/23%H2), et du H2/CO (50%H2/50%CO). Au cours de ce travail les limites d’inflammabilités des mélanges ont été déterminées pour une température initiale de 300 K et une pression de 1 et 2 bars. Les vitesses fondamentales de flamme et les longueurs de Markstein ont été mesurées à différentes températures initiales (300, 330 et 360 K) et à deux pressions initiales (1 et 2 bar) pour chacun des mélanges. Une modélisation cinétique de la vitesse de flamme a été réalisée et a permis l’évaluation de l’énergie d’activation globale sur la base du modèle cinétique présentant le meilleur accord avec l’expérience. La propension des mélanges a s’accélérer fortement en présence d’obstacles a ensuite été caractérisée au cours de l’étude de l’accélération de flamme. Cette étude de l’accélération de flamme a permis de mettre en évidence que différents critères d’accélération s’appliquent selon que la flamme soit stable ou pas. Un critère permettant de prédire l’accélération de flamme a été proposée dans les deux cas. / The context of the current study is the assessment of the occurrence of flame acceleration in accidental situations. The methodology developed for the assessment of hydrogen hazard in the nuclear industry led to the definition of a criterion for the prediction of the acceleration potential of a hydrogen/air/dilutant mixture based on its properties. This study aims to extend this methodology to gaseous mixtures that can be encountered in the classical industry. Therefore, three mixtures were chosen: the first two are representatives of a natural gas/air mixture: G27 (82%CH4/18%N2) and G222 (77%CH4/23%H2). The third one is a H2/CO (50%H2/50%CO) mixture and represents the Syngas. During this work, flammability limits were measured at 300 K and two initial pressures (1 and 2 bar) for each mixture. Fundamental flame speeds and Markstein lengths were also measured at three initial temperatures (300, 330, 360 K) and 2 initial pressures (1 and 2 bar) for each mixtures. A kinetic modeling was performed based on three detailed kinetic models and allowed the calculation of the global activation energy on the basis of the kinetic model which showed the best agreement with the experimental data. The acceleration potential for each mixture in presence of obstacles has then been investigated. It was found that different criteria were to be applied depending on whether the flame is stable or not. A predicting criterion was proposed in both case.