Consequences associated to the boiling liquid expanding vapour explosion for liquid hydrogen tanks: assessment and mitigation

Nowadays the urgency to address climate change and global warming is growing rapidly: the industry and the energy sector must be decarbonized. Hydrogen can play a key role in the energy transition: it is expected to progressively replace fossil fuels, penetrating economies and gaining interest from the public. However, this new possible energy scenario requires further investigation on safety aspects, which currently represent a challenge. The present study aims at making a little contribution to this field. The focus is on the analysis and modeling of hazardous scenarios concerning liquid hydrogen. The investigation of BLEVEs (Boiling Liquid Expanding Vapor Explosion) consequences lies at the core of this research: among various consequences (overpressure, radiation), the interest is on the generation and projection of fragments. The goal is to investigate whether the models developed for conventional fuels and tanks give good predictions also when handling hydrogen. The experimental data from the SH2IFT - Safe Hydrogen Fuel Handling and Use for Efficient Implementation project are used to validate those models. This project’s objective was to increase competence within safety of hydrogen technology, especially focusing on consequences of handling large amounts of this substance.

Calculation of the eigenfunctions of the two-group neutron diffusion equation and application to modal decomposition of BWR instabilities

In this thesis, numerical methods aiming at determining the eigenfunctions, their adjoint and the corresponding eigenvalues of the two-group neutron diffusion equations representing any heterogeneous system are investigated. First, the classical power iteration method is modified so that the calculation of modes higher than the fundamental mode is possible. Thereafter, the Explicitly-Restarted Arnoldi method, belonging to the class of Krylov subspace methods, is touched upon. Although the modified power iteration method is a computationally-expensive algorithm, its main advantage is its robustness, i.e. the method always converges to the desired eigenfunctions without any need from the user to set up any parameter in the algorithm. On the other hand, the Arnoldi method, which requires some parameters to be defined by the user, is a very efficient method for calculating eigenfunctions of large sparse system of equations with a minimum computational effort. These methods are thereafter used for off-line analysis of the stability of Boiling Water Reactors. Since several oscillation modes are usually excited (global and regional oscillations) when unstable conditions are encountered, the characterization of the stability of the reactor using for instance the Decay Ratio as a stability indicator might be difficult if the contribution from each of the modes are not separated from each other. Such a modal decomposition is applied to a stability test performed at the Swedish Ringhals-1 unit in September 2002, after the use of the Arnoldi method for pre-calculating the different eigenmodes of the neutron flux throughout the reactor. The modal decomposition clearly demonstrates the excitation of both the global and regional oscillations. Furthermore, such oscillations are found to be intermittent with a time-varying phase shift between the first and second azimuthal modes.

Comparative study of the different models for the calculation of BLEVEs overpressure effects

The BLEVE, acronym for Boiling Liquid Expanding Vapour Explosion, is one of the most dangerous accidents that can occur in pressure vessels. It can be defined as an explosion resulting from the failure of a vessel containing a pressure liquefied gas stored at a temperature significantly above its boiling point at atmospheric pressure. This phenomenon frequently appears when a vessel is engulfed by a fire: the heat causes the internal pressure to raise and the mechanical proprieties of the wall to decrease, with the consequent rupture of the tank and the instantaneous release of its whole content. After the breakage, the vapour outflows and expands and the liquid phase starts boiling due to the pressure drop. The formation and propagation of a distructive schock wave may occur, together with the ejection of fragments, the generation of a fireball if the stored fluid is flammable and immediately ignited or the atmospheric dispersion of a toxic cloud if the fluid contained inside the vessel is toxic. Despite the presence of many studies on the BLEVE mechanism, the exact causes and conditions of its occurrence are still elusive. In order to better understand this phenomenon, in the present study first of all the concept and definition of BLEVE are investigated. A historical analysis of the major events that have occurred over the past 60 years is described. A research of the principal causes of this event, including the analysis of the substances most frequently involved, is presented too. Afterwards a description of the main effects of BLEVEs is reported, focusing especially on the overpressure. Though the major aim of the present thesis is to contribute, with a comparative analysis, to the validation of the main models present in the literature for the calculation and prediction of the overpressure caused by BLEVEs. In line with this purpose, after a short overview of the available approaches, their ability to reproduce the trend of the overpressure is investigated. The overpressure calculated with the different models is compared with values deriving from events happened in the past and ad-hoc experiments, focusing the attention especially on medium and large scale phenomena. The ability of the models to consider different filling levels of the reservoir and different substances is analyzed too. The results of these calculations are extensively discussed. Finally some conclusive remarks are reported.

Analisi costi-benefici della coibentazione antincendio di autobotti per il trasporto di GPL

Il GPL, a causa della sua infiammabilità, può dare luogo a scenari d’incendio e di esplosione. Particolarmente pericoloso è lo scenario del BLEVE – Boiling Liquid Expanding Vapor Explosion, seguito da un incendio del tipo fireball. Una strategia per la riduzione del rischio imputabile a tale scenario è rappresentato dall’applicazione di protezioni passive antincendio. Le misure di protezione passive antincendio sono costituite dall’applicazione al recipiente di GPL di una coibentazione termica, che ritardi il tempo di cedimento dell’apparecchiatura nel caso di esposizione al fuoco e quindi riduce la frequenza del BLEVE e della conseguente fireball, fornendo un lasso di tempo sufficiente per consentire l'avvio di azioni di mitigazione. Nel presente lavoro di tesi si è effettuata l’analisi costi-benefici dell’applicazione di protezioni passive alle autobotti per il trasporto stradale di GPL. Si è applicato un metodo semplificato per l’analisi sopracitata, considerando l’influenza delle incertezze sul risultato finale In particolare sono state considerate le incertezze derivanti dal modello d‘irraggiamento, dal modello di danno e dalle assunzioni in merito alla descrizione della popolazione nell’area di impatto dell’incidente. Il lavoro di tesi è così strutturato. Nel capitolo 1, di carattere introduttivo, sono riportate informazioni sul GPL, sugli scenari incidentali a cui dà origine e sulle protezioni passive antincendio. Nel capitolo 2 vengono descritti i modelli matematici per la simulazione della fireball, considerando sia i modelli per la stima dell’irraggiamento che quelli per il calcolo della probabilità di morte. Il capitolo 3 contiene la descrizione del modello semplificato di analisi costi-benefici ed il calcolo dell’area di impatto equivalente della fireball. Il capitolo 4 contiene l’applicazione del modello di analisi costi-benefici ad alcuni casi di studio reali. Il capitolo 5, infine, contiene le considerazioni conclusive.

Applicazioni degli acciai inossidabili in sistemi per la produzione di energia.

Questo elaborato ha lo scopo di esporre quelli che sono i vantaggi derivanti dall' utilizzo degli acciai inossidabili, specificando il tipo di componente e le ragioni della scelta, nei sistemi per la produzione di energia: dalle turbine, agli impianti nucleari, fino agli impianti che sfruttano le energie alternative (solare, eolica, geotermica, biogas). Inizialmente viene fornito un quadro generale sui differenti tipi di acciai inox (martensitici, ferritici, austenitici e duplex, con le relative proprietà, sottolineandone vantaggi e svantaggi), descrivendone anche i sistemi di designazione, con particolare attenzione alla norma AISI (American Iron and Steel Institute). Una volta messe in risalto queste caratteristiche, vengono esaminati e descritti diversi sistemi di produzione di energia in cui gli acciai inox trovano applicazione: si parte dalle turbine (idraulica, a vapore e a gas), spiegando i benefici nell'utilizzo di particolari categorie di acciai inox nella realizzazione di alcuni dei componenti per questi impianti. Vengono quindi esaminati gli impianti nucleari, partendo da quelli che utilizzano come moderatore e fluido refrigerante acqua naturale, ("PWR", Pressurized Water Reactor) e ("BWR", Boiling Water Reactor), fino a quelli che utilizzano invece acqua pesante ("CANDU", Canadian Deuterium Uranium Reactor), nonchè i reattori veloci ("FBR", Fast Breeding Reactor). Infine, vengono esaminate le applicazioni degli acciai inox, nei sistemi per la produzione di energia che, sfruttano fonti alternative (elencate in precedenza).

Validazione di modelli per la simulazione del film di combustibile liquido a parete in motori ad accensione comandata

Le normative antinquinamento sempre più stringenti in termini di emissioni prodotte da un MCI hanno reso necessario lo studio e lo sviluppo di modelli predittivi in grado quindi di simulare tutto ciò che avviene all’interno della camera di combustione; allo scopo di ottimizzare quello che è un prodotto industriale e che pertanto va venduto. Il presente elaborato di tesi si è quindi incentrato sull’impatto che uno spray di combustibile, iniettato ad alta pressione, ha su pareti calde e fredde, analizzando tutto ciò che concerne l’eventuale sviluppo di wall-film prodotto come la relativa massa, area, spessore e raffreddamento della parete per via della propria interazione con il film a parete. Sono stati prima di tutto studiati i fenomeni fisici in atto e successivamente analizzati i modelli implementati nel codice di calcolo commerciale utilizzato STAR-CD, in particolare il modello di boiling, il modulo 1D-CHT ed il modello di impatto Bai-ONERA; il tutto facendo riferimento a esperimenti, già condotti, presenti in letteratura.

Calibrazione e validazione di modelli per la simulazione CFD di impatto a parete di spray di combustibili

Il seguente lavoro è uno studio di iniezione (strategia, timing, spray pattern) svolto con la simulazione numerica, alle quali oggi si richiede dettaglio e accuratezza. Il lavoro si concentra sullo studio di spray multi componente, tramite la scrittura di una UDF (user define function) proprietaria, valutazione sensibilità dell'impatto a parete, film boiling a parametri modellistici influenzati dal multicomponente e scrittura di un codice per l'elaborazione delle immagini sia sperimentali che numeriche per rendere più esteso il confronto tra CFD e sperimentale, per migliorare le tarature e i modelli e comprendere meglio la fenomenologia.

Determinazione gascromatografica di composti organici volatili e semi-volatili (VOCs e SVOCs) in poliolefine ed effetti delle condizioni di lavorazione

A relevant problem of polyolefins processing is the presence of volatile and semi-volatile compounds (VOCs and SVOCs) such as linear chains alkanes found out in final products. These VOCs can be detected by customers from the unpleasant smelt and can be an environmental issue, at the same time they can cause negative side effects during process. Since no previously standardized analytical techniques for polymeric matrix are available in bibliography, we have implemented different VOCs extraction methods and gaschromatographic analysis for quali-quantitative studies of such compounds. In literature different procedures can be found including microwave extraction (MAE) and thermo desorption (TDS) used with different purposes. TDS coupled with GC-MS are necessary for the identification of different compounds in the polymer matrix. Although the quantitative determination is complex, the results obtained from TDS/GC-MS show that by-products are mainly linear chains oligomers with even number of carbon in a C8-C22 range (for HDPE). In order to quantify these linear alkanes by-products, a more accurate GC-FID determination with internal standard has been run on MAE extracts. Regardless the type of extruder used, it is difficult to distinguish the effect of the various processes, which in any case entails having a lower-boiling substance content, lower than the corresponding virgin polymer. The two HDPEs studied can be distinguished on the basis of the quantity of analytes found, therefore the production process is mainly responsible for the amount of VOCs and SVOCs observed. The extruder technology used by Sacmi SC allows to obtain a significant reduction in VOCs compared to the conventional screw system. Thus, the result is significantly important as a lower quantity of volatile substances certainly leads to a lower migration of such materials, especially when used for food packaging.

Mineral paragenesis and fluid inclusion constraints on the Torre di Rio skarn, Island of Elba

The historical iron ore deposits of eastern Elba held great importance for the region and were its primary source of iron. The Torre di Rio skarn, despite its easily accessible outcrop and vicinity to the larger Rio Marina deposit, was never properly characterized. The results of petrographic and microthermometric study presented in this work provide new constraints on the Torre di Rio skarn. Mineral assemblage of ilvaite, calcite, quartz, iron oxides and sulphides combined with textural evidence indicate that Torre di Rio skarn does not fit into classical skarn model. The complex paragenetic sequence and overlapping of skarn and ore mineralogy is result of fast formation at relatively low temperatures evidenced by the silicon enrichment and pervasive nature of limonite alteration. Hematite-magnetite textural relationship points to boundary conditions of the ore fluid in terms of oxygen fugacity. Eutectic temperatures range from -16 to -33 °C indicating complex fluids. Calculated salinities range from 1.4 to 17.4 wt% NaCleq suggesting multiple fluids of different compositions. Total homogenization temperatures vary from 330 °C to 150 °C with both homogeneously and heterogeneously trapped FIAs. Ore deposition is concentrated where skarn formation was controlled primarily by phase separation during boiling. Calculated fluid pressure at boiling suggest shallow formation depth of a few hundred meters and constrains maximum temperature of ore deposition to c. 260 °C. This work suggest that relatively low salinities of fluid inclusions could indicate dominant marine origin of the hydrothermal fluids that were activated by the Porto Azzurro pluton emplacement and that scavenged Fe from sedimentary host rocks. During boiling at shallow depths and decreasing iron solubility, these fluids started precipitating Fe-minerals at Torre di Rio mineralization. Mixing with batches of more saline fluids at around 236 °C increased salinity abruptly and marked the end of ore deposition.