Oxidation and pyrolysis of methane and methyl formate in a plug flow reactor: computational and experimenal studies

Biodiesel represents a possible substitute to the fossil fuels; for this reason a good comprehension of the kinetics involved is important. Due to the complexity of the biodiesel mixture a common practice is the use of surrogate molecules to study its reactivity. In this work are presented the experimental and computational results obtained for the oxidation and pyrolysis of methane and methyl formate conducted in a plug flow reactor. The work was divided into two parts: the first one was the setup assembly whilst, in the second one, was realized a comparison between the experimental and model results; these last was obtained using models available in literature. It was started studying the methane since, a validate model was available, in this way was possible to verify the reliability of the experimental results. After this first study the attention was focused on the methyl formate investigation. All the analysis were conducted at different temperatures, pressures and, for the oxidation, at different equivalence ratios. The results shown that, a good comprehension of the kinetics is reach but efforts are necessary to better evaluate kinetics parameters such as activation energy. The results even point out that the realized setup is adapt to study the oxidation and pyrolysis and, for this reason, it will be employed to study a longer chain esters with the aim to better understand the kinetic of the molecules that are part of the biodiesel mixture.

Experimental and computational study of methane and methyl formate pyrolysis and oxidation in a flow reactor

A study of the pyrolysis and oxidation (phi 0.5-1-2) of methane and methyl formate (phi 0.5) in a laboratory flow reactor (Length = 50 cm, inner diameter = 2.5 cm) has been carried out at 1-4 atm and 300-1300 K temperature range. Exhaust gaseous species analysis was realized using a gas chromatographic system, Varian CP-4900 PRO Mirco-GC, with a TCD detector and using helium as carrier for a Molecular Sieve 5Å column and nitrogen for a COX column, whose temperatures and pressures were respectively of 65°C and 150kPa. Model simulations using NTUA [1], Fisher et al. [12], Grana [13] and Dooley [14] kinetic mechanisms have been performed with CHEMKIN. The work provides a basis for further development and optimization of existing detailed chemical kinetic schemes.

Industrial accidents triggered by lightning: causes and consequences

Natural hazards affecting industrial installations could directly or indirectly cause an accident or series of accidents with serious consequences for the environment and for human health. Accidents initiated by a natural hazard or disaster which result in the release of hazardous materials are commonly referred to as Natech (Natural Hazard Triggering a Technological Disaster) accidents. The conditions brought about by these kinds of events are particularly problematic, the presence of the natural event increases the probability of exposition and causes consequences more serious than standard technological accidents. Despite a growing body of research and more stringent regulations for the design and operation of industrial activities, Natech accidents remain a threat. This is partly due to the absence of data and dedicated risk-assessment methodologies and tools. Even the Seveso Directives for the control of risks due to major accident hazards do not include any specific impositions regarding the management of Natech risks in the process industries. Among the few available tools there is the European Standard EN 62305, which addresses generic industrial sites, requiring to take into account the possibility of lightning and to select the appropriate protection measures. Since it is intended for generic industrial installations, this tool set the requirements for the design, the construction and the modification of structures, and is thus mainly oriented towards conventional civil building. A first purpose of this project is to study the effects and the consequences on industrial sites of lightning, which is the most common adverse natural phenomenon in Europe. Lightning is the cause of several industrial accidents initiated by natural causes. The industrial sectors most susceptible to accidents triggered by lightning is the petrochemical one, due to the presence of atmospheric tanks (especially floating roof tanks) containing flammable vapors which could be easily ignited by a lightning strike or by lightning secondary effects (as electrostatic and electromagnetic pulses or ground currents). A second purpose of this work is to implement the procedure proposed by the European Standard on a specific kind of industrial plant, i.e. on a chemical factory, in order to highlight the critical aspects of this implementation. A case-study plant handling flammable liquids was selected. The application of the European Standard allowed to estimate the incidence of lightning activity on the total value of the default release frequency suggested by guidelines for atmospheric storage tanks. Though it has become evident that the European Standard does not introduce any parameters explicitly pointing out the amount of dangerous substances which could be ignited or released. Furthermore the parameters that are proposed to describe the characteristics of the structures potentially subjected to lightning strikes are insufficient to take into account the specific features of different chemical equipment commonly present in chemical plants.

Development and application of a thermo-hydraulic model supporting the design and the deterministic safety analysis in a sodium cooled fast reactor

Il CP-ESFR è un progetto integrato di cooperazione europeo sui reattori a sodio SFR realizzato sotto il programma quadro EURATOM 7, che unisce il contributo di venticinque partner europei. Il CP-ESFR ha l'ambizione di contribuire all'istituzione di una "solida base scientifica e tecnica per il reattore veloce refrigerato a sodio, al fine di accelerare gli sviluppi pratici per la gestione sicura dei rifiuti radioattivi a lunga vita, per migliorare le prestazioni di sicurezza, l'efficienza delle risorse e il costo-efficacia di energia nucleare al fine di garantire un sistema solido e socialmente accettabile di protezione della popolazione e dell'ambiente contro gli effetti delle radiazioni ionizzanti. " La presente tesi di laurea è un contributo allo sviluppo di modelli e metodi, basati sull’uso di codici termo-idraulici di sistema, per l’ analisi di sicurezza di reattori di IV Generazione refrigerati a metallo liquido. L'attività è stata svolta nell'ambito del progetto FP-7 PELGRIMM ed in sinergia con l’Accordo di Programma MSE-ENEA(PAR-2013). Il progetto FP7 PELGRIMM ha come obbiettivo lo sviluppo di combustibili contenenti attinidi minori 1. attraverso lo studio di due diverse forme: pellet (oggetto della presente tesi) e spherepac 2. valutandone l’impatto sul progetto del reattore CP-ESFR. La tesi propone lo sviluppo di un modello termoidraulico di sistema dei circuiti primario e intermedio del reattore con il codice RELAP5-3D© (INL, US). Tale codice, qualificato per il licenziamento dei reattori nucleari ad acqua, è stato utilizzato per valutare come variano i parametri del core del reattore rilevanti per la sicurezza (es. temperatura di camicia e di centro combustibile, temperatura del fluido refrigerante, etc.), quando il combustibile venga impiegato per “bruciare” gli attinidi minori (isotopi radioattivi a lunga vita contenuti nelle scorie nucleari). Questo ha comportato, una fase di training sul codice, sui suoi modelli e sulle sue capacità. Successivamente, lo sviluppo della nodalizzazione dell’impianto CP-ESFR, la sua qualifica, e l’analisi dei risultati ottenuti al variare della configurazione del core, del bruciamento e del tipo di combustibile impiegato (i.e. diverso arricchimento di attinidi minori). Il testo è suddiviso in sei sezioni. La prima fornisce un’introduzione allo sviluppo tecnologico dei reattori veloci, evidenzia l’ambito in cui è stata svolta questa tesi e ne definisce obbiettivi e struttura. Nella seconda sezione, viene descritto l’impianto del CP-ESFR con attenzione alla configurazione del nocciolo e al sistema primario. La terza sezione introduce il codice di sistema termico-idraulico utilizzato per le analisi e il modello sviluppato per riprodurre l’impianto. Nella sezione quattro vengono descritti: i test e le verifiche effettuate per valutare le prestazioni del modello, la qualifica della nodalizzazione, i principali modelli e le correlazioni più rilevanti per la simulazione e le configurazioni del core considerate per l’analisi dei risultati. I risultati ottenuti relativamente ai parametri di sicurezza del nocciolo in condizioni di normale funzionamento e per un transitorio selezionato sono descritti nella quinta sezione. Infine, sono riportate le conclusioni dell’attività.

Emergency response to railroad accidents involving hazardous materials

The chemical industry has to face safety problems linked to the hazards of chemicals and the risks posed by the plants where they are handled. However, their transport may cause significant risk values too: it’s not totally possible to avoid the occurrence of accidents. This work is focused on the emergency response to railway accidents involving hazardous materials, that is what has to be done once they happen to limit their consequences. A first effort has been devoted to understand the role given to this theme within legislations: it has been found out that often it’s not even taken into account. Exceptionally a few countries adopt guidelines suggesting how to plan the response, who is appointed to intervene and which actions should be taken first. An investigation has been made to define the tools available for the responders, with attention on the availability of chemical-specific safety distances. It has emerged that the ERG book adopted by some American countries has suggestions and the Belgian legislation too establishes criteria to evaluate these distances. An analysis has been conducted then on the most recent accidents occurred worldwide, to understand how the response was performed and which safety distances were adopted. These values were compared with the numbers reported by the ERG book and the results of two devoted software tools for consequence analysis of accidental spills scenarios. This comparison has shown that there are differences between them and that a more standardized approach is necessary. This is why further developments of the topic should focus on promoting uniform procedures for emergency response planning and on a worldwide adoption of a guidebook with suggestions about actions to reduce consequences and about safety distances, determined following finer researches. For this aim, the development of a detailed database of hazardous materials transportation accidents could be useful.