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.

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.

Conceptual design of the integral measurement system of the radiation dose of the fuel elements for the ALFRED reactor.

Conceptual design of the integral measurement system of the radiation dose of the fuel elements for the ALFRED reactor.

Characterization Of Single Use Reactor Used For The Manufacturing Of Formulated Products Within The Pharmaceutical Industry

Mixing is a fundamental unit operation in the pharmaceutical industry to ensure consistent product quality across different batches. It is usually carried out in mechanically stirred tanks, with a large variety of designs according to the process requirements. A key aspect of pharmaceutical manufacturing is the extensive and meticulous cleaning of the vessels between runs to prevent the risk of contamination. Single-use reactors represent an increasing trend in the industry since they do not require cleaning and sterilization, reducing the need for utilities such as steam to sterilize equipment and the time between production batches. In contrast to traditional stainless steel vessels, single-use reactors consist of a plastic bag used as a vessel and disposed of after use. This thesis aims to characterize the fluid dynamics features and the mixing performance of a commercially available single-use reactor. The characterization employs a combination of various experimental techniques. The analysis starts with the visual observation of the liquid behavior inside the vessel, focusing on the vortex shape evolution at different impeller speeds. The power consumption is then measured using a torque meter to quantify the power number. Particle Image Velocimetry (PIV) is employed to investigate local fluid dynamics properties such as mean flow field and mean and rms velocity profiles. The same experimental setup of PIV is exploited for another optical measurement technique, the Planar Laser-Induced Fluorescence (PLIF). The PLIF measurements complete the characterization of the reactor with the qualitative visualization of the turbulent flow and the quantitative assessment of the system performance through the mixing time. The results confirm good mixing performances for the single-use reactor over the investigated impeller speeds and reveal that the filling volume plays a significant role in the fluid dynamics of the system.

Verification of rupture disc sizing of Acrylic Reactor

The primary goal of this thesis is to verify the rupture disc sizing of the acrylic reactor. Primarily the test to check the sizing was divided into several stages. It went on to examine ideas to explain the concern and ethical ways, as well as remedies and suggestions to solve the issues and difficulties that were discovered. This thesis will highlight the gathering and arranging of reaction data (recipe composition, enthalpies, reaction temperature, and catalyst feeding times) of the products to be chosen, in accordance with pre-established criteria. To collaborate with the research and development team in the lab to carry out calorimetric testing for the important recipes that have been identified. The verification of the currently installed Rupture Discs in the plant based on the calorimetric test findings is the final stage. This thesis used two separate calorimetry techniques: Phi-TEC II adiabatic calorimetry and differential scanning calorimetry (DSC). The target of the experiment is to check and confirm the correct size of the reactor rupture disc. Arkema (Boretto/Coatex) plant (Emilia romagna) provided a recipe and a scenario following multiple meetings and discussions. The purpose of this technical paper is to describe the outcomes of adiabatic calorimetry performed at the lab scale so that the computation of the vents for a particular recipe and scenario can be verified.