Synergies among safety and security in the prevention of major accidents related to dangerous substances

Historical evidence shows that chemical, process, and Oil&Gas facilities where dangerous substances are stored or handled are target of deliberate malicious attacks (security attacks) aiming at interfering with normal operations. Physical attacks and cyber-attacks may generate events with consequences on people, property, and the surrounding environment that are comparable to those of major accidents caused by safety-related causes. The security aspects of these facilities are commonly addressed using Security Vulnerability/Risk Assessment (SVA/SRA) methodologies. Most of these methodologies are semi-quantitative and non-systematic approaches that strongly rely on expert judgment, leading to security assessments that are not reproducible. Moreover, they do not consider the synergies with the safety domain. The present 3-year research is aimed at filling the gap outlined by providing knowledge on security attacks, as well as rigorous and systematic methods supporting existing SVA/SRA studies suitable for the chemical, process, and Oil&Gas industry. The different nature of cyber and physical attacks resulted in the development of different methods for the two domains. The first part of the research was devoted to the development and statistical analysis of security databases that allowed to develop new knowledge and lessons learnt on security threats. Based on the obtained background, a Bow-Tie based procedure and two reverse-HazOp based methodologies were developed as hazard identification approaches for physical and cyber threats respectively. To support the quantitative estimation of the security risk, a quantitative procedure based on the Bayesian Network was developed allowing to calculate the probability of success of physical security attacks. All the developed methods have been applied to case studies addressing chemical, process and Oil&Gas facilities (offshore and onshore) proving the quality of the results that can be achieved in improving site security. Furthermore, the outcomes achieved allow to step forward in developing synergies and promoting integration among safety and security management.

Innovation in conceptual design of chemical processes

Nowadays, the chemical industry has reached significant goals to produce essential components for human being. The growing competitiveness of the market caused an important acceleration in R&D activities, introducing new opportunities and procedures for the definition of process improvement and optimization. In this dynamicity, sustainability is becoming one of the key aspects for the technological progress encompassing economic, environmental protection and safety aspects. With respect to the conceptual definition of sustainability, literature reports an extensive discussion of the strategies, as well as sets of specific principles and guidelines. However, literature procedures are not completely suitable and applicable to process design activities. Therefore, the development and introduction of sustainability-oriented methodologies is a necessary step to enhance process and plant design. The definition of key drivers as support system is a focal point for early process design decisions or implementation of process modifications. In this context, three different methodologies are developed to support design activities providing criteria and guidelines in a sustainable perspective. In this framework, a set of key Performance Indicators is selected and adopted to characterize the environmental, safety, economic and energetic aspects of a reference process. The methodologies are based on heat and material balances and the level of detailed for input data are compatible with available information of the specific application. Multiple case-studies are defined to prove the effectiveness of the methodologies. The principal application is the polyolefin productive lifecycle chain with particular focus on polymerization technologies. In this context, different design phases are investigated spanning from early process feasibility study to operative and improvements assessment. This flexibility allows to apply the methodologies at any level of design, providing supporting guidelines for design activities, compare alternative solutions, monitor operating process and identify potential for improvements.

Le terme pubbliche nella Grecia tardoantica. Architettura, funzioni e trasformazioni dello spazio sociale

Il presente lavoro si propone di concentrare la propria attenzione sulle terme pubbliche di età tardoantica – considerando l’insieme della letteratura scientifica disponibile e la necessità di un aggiornamento metodologico – comprese nelle provinciae dell’Hellas e di Creta, secondo i confini che possono essere tracciati sulla base del Synekdemos di Hierocles (§ 1). Il territorio di queste provinciae tardoantiche corrisponde all’incirca alle moderne regioni amministrative della Grecia Occidentale, della Grecia Centrale, dell’Attica e del Peloponneso per l’Ellade e dell’isola di Creta. In aggiunta all’indagine sulle caratteristiche architettoniche degli impianti, si è tentato di porre in rilievo le trasformazioni funzionali verificatesi in esse durante e dopo il loro utilizzo primario (§ 2). Oltre che sui singoli edifici (§ 2.1), l’indagine si è rivolta al contesto topografico di appartenenza. Le osservazioni raccolte sull’insieme del territorio descritto sono state inoltre messe a confronto con alcuni casi di studio rappresentati dalle città di Salonicco, Atene, Patrasso, Corinto e Gortina (§ 3). Si è cercato infine di sintetizzare i risultati emersi dalla ricerca, per contestualizzare il fenomeno termale tardoantico nell’ambito del suo sviluppo architettonico, dei mutamenti politici e urbanistici, dell’influenza del processo di cristianizzazione sulla società del periodo (§ 4).

Characterization of pyrolysis and oxidation processes of biomaterials, biomasses and biofuels

The urgent need for alternative solutions mitigating the impacts of human activities on the environment has strongly opened new challenges and opportunities in view of the energy transition. Indeed, the automotive industry is going through a revolutionary moment in its quest to reduce its carbon footprint, with biofuels being one of the viable alternatives. The use of different classes of biofuels as fuel additives/standalone components has attracted the attention of many researchers. Despite their beneficial effects, biofuel’s combustion can also result in the production of undesirable pollutants, requiring complete characterization of the phenomena occurring during their production and consumption. Industrial scale-up of biomass conversion is challenging owing to the complexity of its chemistry and transport phenomena involved in the process. In this view, the role of solid-phase and gas-phase chemistry is paramount. Thus, this study is devoted to detailed analysis of physical-chemical phenomena characterizing biomass pyrolysis and biofuel oxidation. The pyrolysis mechanism has been represented by 20 reactions whereas, the gas-phase kinetic models; manually upgraded model (KiBo_MU) and automated model (KiBo_AG), comprises 141 species and 453 reactions, and 631 species and 28329 reactions, respectively. The accuracy of the kinetic models was tested against experimental data and the models captured experimental trends very well. While the development and validation of detailed kinetic mechanisms is the main deliverable of this project, the realized procedure integrating schematic classifications with methodologies for the identification of common decomposition pathways and intermediates represents an additional source of novelty. Besides, the fundamentally oriented nature of the adopted method allows the identification of most relevant reactions and species under the operating conditions different industrial applications, paving the way for reduced kinetic mechanisms. Ultimately, the resulting detailed mechanisms can be used to integrate with more complex fluid dynamics model to accurately reproduce the behavior of real systems and reactors.

Deep and near space tracking stations in support of lunar and planetary exploration missions

The aim of this dissertation is to describe the methodologies required to design, operate, and validate the performance of ground stations dedicated to near and deep space tracking, as well as the models developed to process the signals acquired, from raw data to the output parameters of the orbit determination of spacecraft. This work is framed in the context of lunar and planetary exploration missions by addressing the challenges in receiving and processing radiometric data for radio science investigations and navigation purposes. These challenges include the designing of an appropriate back-end to read, convert and store the antenna voltages, the definition of appropriate methodologies for pre-processing, calibration, and estimation of radiometric data for the extraction of information on the spacecraft state, and the definition and integration of accurate models of the spacecraft dynamics to evaluate the goodness of the recorded signals. Additionally, the experimental design of acquisition strategies to perform direct comparison between ground stations is described and discussed. In particular, the evaluation of the differential performance between stations requires the designing of a dedicated tracking campaign to maximize the overlap of the recorded datasets at the receivers, making it possible to correlate the received signals and isolate the contribution of the ground segment to the noise in the single link. Finally, in support of the methodologies and models presented, results from the validation and design work performed on the Deep Space Network (DSN) affiliated nodes DSS-69 and DSS-17 will also be reported.

Navigation design and flight dynamics operations of the ArgoMoon cis-lunar CubeSat.

On November 16, 2022, the NASA’s Space Launch System (SLS) has been launched for the first time in the context of Artemis-1 mission where, together with the Orion Multi-Purpose Crew Vehicle, a set of 10 CubeSats have been delivered into a translunar trajectory. Among the small satellites deployed during Artemis-1 there is ArgoMoon, a 6U CubeSat built by the Italian company Argotec and coordinated by Italian Space Agency (ASI). The primary goal of ArgoMoon is to capture images of the Interim Cryogenic Propulsion Stage. The ArgoMoon trajectory has been designed as a highly elliptical geocentric orbit, with several encounters with the Moon. In order to successfully fly ArgoMoon along the designed cis-lunar trajectory, a ground-based navigation system has been developed exploiting the guidance techniques also used for regular deep space missions. The navigation process is subdivided into Orbit Determi- nation (OD) and a Flight Path Control (FPC), and it is designed to follow the reference trajectory, prevent impacts with the Earth and the Moon, intensively test the navigation techniques, and guarantee the spacecraft disposal at the end of the mission. The work done in this thesis has accomplished the navigation of ArgoMoon, covering all aspects of the project life, from pre-launch design and analysis to actual operations. Firstly, the designed navigation process and the pre-mission assessment of its performance will be presented. Then, the results of the ArgoMoon navigation operations performed after the launch in November 2022 will be described in detail by discussing the main encountered challenges and the adopted solutions. The results of the operations confirmed the robustness of the designed navigation which allowed to accurately estimate the trajectory of ArgoMoon despite a series of complex events.

Packaging and food waste preventing strategies for sustainable food supply chain networks

The central aim of this dissertation is to introduce innovative methods, models, and tools to enhance the overall performance of supply chains responsible for handling perishable products. This concept of improved performance encompasses several critical dimensions, including enhanced efficiency in supply chain operations, product quality, safety, sustainability, waste generation minimization, and compliance with norms and regulations. The research is structured around three specific research questions that provide a solid foundation for delving into and narrowing down the array of potential solutions. These questions primarily concern enhancing the overall performance of distribution networks for perishable products and optimizing the package hierarchy, extending to unconventional packaging solutions. To address these research questions effectively, a well-defined research framework guides the approach. However, the dissertation adheres to an overarching methodological approach that comprises three fundamental aspects. The first aspect centers on the necessity of systematic data sampling and categorization, including identifying critical points within food supply chains. The data collected in this context must then be organized within a customized data structure designed to feed both cyber-physical and digital twins to quantify and analyze supply chain failures with a preventive perspective.

Development of processes for the valorization of lignocellulosic biomass based on renewable energies

The world grapples with climate change from fossil fuel reliance, prompting Europe to pivot to renewable energy. Among renewables, biomass is a bioenergy and bio-carbon source, used to create high-value biomolecules, replacing fossil-based products. Alkyl levulinates, derived from biomass, hold promise as bio-additives and biofuels, especially via acid solvolysis of hexose sugars, necessitating further exploration. Alkyl levulinate's potential extends to converting into γ-valerolactone (GVL), a bio-solvent produced via hydrogenation with molecular-hydrogen. Hydrogen, a key reagent and energy carrier, aids renewable energy integration. This thesis delves into a biorefinery system study, aligning with sustainability goals, integrating biomass valorization, energy production, and hydrogen generation. It investigates optimizing technologies for butyl levulinate production and subsequent GVL hydrogenation. Sustainability remains pivotal, reflecting the global shift towards renewable and carbon bio-resources. The research initially focuses on experimenting with the optimal technology for producing butyl levulinate from biomass-derived hexose fructose. It examines the solvolysis process, investigating optimal conditions, kinetic modeling, and the impact of solvents on fructose conversion. The subsequent part concentrates on the technological aspect of hydrogenating butyl levulinate into GVL. It includes conceptual design, simulation, and optimization of the fructose-to-GVL process scheme based on process intensification. In the final part, the study applies the process to a real case study in Normandy, France, adapting it to local biomass availability and wind energy. It defines a methodology for designing and integrating the energy-supply system, evaluating different scenarios. Sustainability assessment using economic, environmental, and social indicators culminates in an overall sustainability index, indicating scenarios integrating the GVL biorefinery system with wind power and hydrogen energy storage as promising due to high profitability and reduced environmental impact. Sensitivity analyses validate the methodology's reliability, potentially extending to other technological systems.

Integrating the age factor in designing industrial environments and workstations in the workforce ageing era

As people spend a third of their lives at work and, in most cases, indoors, the work environment assumes crucial importance. The continuous and dynamic interaction between people and the working environment surrounding them produces physiological and psychological effects on operators. Recognizing the substantial impact of comfort and well-being on employee satisfaction and job performance, the literature underscores the need for industries to implement indoor environment control strategies to ensure long-term success and profitability. However, managing physical risks (i.e., ergonomic and microclimate) in industrial environments is often constrained by production and energy requirements. In the food processing industry, for example, the safety of perishable products dictates storage temperatures that do not allow for operator comfort. Conversely, warehouses dedicated to non-perishable products often lack cooling systems to limit energy expenditure, reaching high temperatures in the summer period. Moreover, exceptional events, like the COVID-19 pandemic, introduce new constraints, with recommendations impacting thermal stress and respiratory health. Furthermore, the thesis highlights how workers' variables, particularly the aging process, reduce tolerance to environmental stresses. Consequently, prolonged exposure to environmental stress conditions at work results in cardiovascular disease and musculoskeletal disorders. In response to the global trend of an aging workforce, the thesis bridges a literature gap by proposing methods and models that integrate the age factor into comfort assessment. It aims to present technical and technological solutions to mitigate microclimate risks in industrial environments, ultimately seeking innovative ways to enhance the aging workforce's comfort, performance, experience, and skills. The research outlines a logical-conceptual scheme with three main areas of focus: analyzing factors influencing the work environment, recognizing constraints to worker comfort, and designing solutions. The results significantly contribute to science by laying the foundation for new research in worker health and safety in an ageing working population's extremely current industrial context.

Models and methods for damage and quantitative risk assessment of Natech scenarios

Natural events are a widely recognized hazard for industrial sites where relevant quantities of hazardous substances are handled, due to the possible generation of cascading events resulting in severe technological accidents (Natech scenarios). Natural events may damage storage and process equipment containing hazardous substances, that may be released leading to major accident scenarios called Natech events. The need to assess the risk associated with Natech scenarios is growing and methodologies were developed to allow the quantification of Natech risk, considering both point sources and linear sources as pipelines. A key element of these procedures is the use of vulnerability models providing an estimation of the damage probability of equipment or pipeline segment as a result of the impact of the natural event. Therefore, the first aim of the PhD project was to outline the state of the art of vulnerability models for equipment and pipelines subject to natural events such as floods, earthquakes, and wind. Moreover, the present PhD project also aimed at the development of new vulnerability models in order to fill some gaps in literature. In particular, a vulnerability model for vertical equipment subject to wind and to flood were developed. Finally, in order to improve the calculation of Natech risk for linear sources an original methodology was developed for Natech quantitative risk assessment methodology for pipelines subject to earthquakes. Overall, the results obtained are a step forward in the quantitative risk assessment of Natech accidents. The tools developed open the way to the inclusion of new equipment in the analysis of Natech events, and the methodology for the assessment of linear risk sources as pipelines provides an important tool for a more accurate and comprehensive assessment of Natech risk.

Sostenibilità degli allevamenti di bovini da latte: valutazione degli impatti ambientali di un'azienda emiliana.

Il surriscaldamento globale è un fenomeno preoccupante ed è accertato che le attività umane sono responsabili di questa crisi climatica causata dall’aumento dei gas serra immessi nell’atmosfera. L’agricoltura contribuisce per il 23% delle emissioni planetarie di gas serra, che derivano per quasi l’80% dalla gestione degli allevamenti. L’allevamento è responsabile di diversi impatti ambientali, quali le emissioni enteriche delle bovine, le emissioni dalla fase di gestione delle deiezioni, e quelle che avvengono nella fase di coltivazione dei terreni aziendali, quali le emissioni di protossido di azoto dovute alle fertilizzazioni azotate e le emissioni derivanti dall’uso dei combustibili per le macchine agricole utilizzate per la gestione del bestiame, il consumo idrico, il consumo di energia per la climatizzazione estiva dell’allevamento e la produzione e lo smaltimento dei rifiuti plastici. Il rapporto però tra produzione di bestiame e cambiamento climatico è bilaterale. Infatti, i cambiamenti climatici influiscono negativamente sulla produzione zootecnica, con effetti diretti sulla salute animale e sull'efficienza riproduttiva, ma anche effetti indiretti derivanti dai cambiamenti nella qualità e quantità dei mangimi, disponibilità di acqua, alterazioni dell'ecosistema che portano a cambiamenti nella distribuzione di agenti patogeni e malattie. Proprio alla relazione, biunivoca, tra allevamento del bestiame ed impatto ambientale è dedicata la presente tesi. È stato infatti condotto uno studio con l'obiettivo di valutare gli impatti ambientali degli allevamenti di bovini da latte, sulla base di un modello di valutazione del ciclo di vita (Life Cycle Assessment) per un allevamento campione di un’azienda emiliana. I risultati emersi mostrano la possibilità di identificare gli impatti più rilevanti nell'allevamento bovino nei mangimi, negli imballaggi in plastica, nel consumo di energia e carburante.

Correlazioni tra assetto geologico-strutturale del distretto cinabrifero del M.te Amiata e sue risorse geotermiche-epitermali

I giacimenti di cinabro (±stibina) del M.te Amiata costituiscono un distretto minerario di importanza mondiale, con una produzione storica totale che supera le 117 kt di Hg, prodotte tra il 1850 e il 1982. Nell’area del distretto minerario si trova l’omonimo sistema geotermico, con 6 impianti per la produzione di energia elettrica che producono 121MW equivalenti di energia. Lo scopo di questa tesi è di individuare e di verificare correlazioni esistenti tra la peculiare distribuzione N-S delle mineralizzazioni a cinabro, le manifestazioni geotermiche e l’assetto strutturale che caratterizza il distretto cinabrifero e il sistema geotermico. Le correlazioni sono state individuate attraverso l’applicazione di algoritmi Machine Learning (ML), utilizzando Scikit-learn, ad un dataset bidimensionale, costruito con applicazioni GIS per contenere tutti i dati geologici-giacimentologici reperiti in letteratura riguardo al distretto amiatino. È stato costruito un modello tridimensionale dell’area di studio basato sulla produzione di quattro solidi che raggruppano le formazioni geologiche presenti nell’area sulla base delle loro caratteristiche geoidrologiche. Sulla base dei risultati ottenuti si può affermare che le tecniche di ML si sono dimostrate utili nell’identificare correlazioni tra i diversi fattori geologico-strutturali che caratterizzano il sistema geotermico del M.te Amiata; la peculiare distribuzione spaziale N-S dei giacimenti del distretto dipende dalla combinazione di un sistema di faglie e di pieghe; i modelli di regressione basati su alberi decisionali (CatBoost e Random Forest) sono complessivamente più performanti e geologicamente significativi. Questo lavoro suggerisce che il ML rappresenta uno strumento in grado di suggerire nuove e poco sperimentate relazioni tra elementi geologici-giacimentologici di un’area complessa come un sistema geotermico ed è in grado di guidare eventuali fasi successive di studi geologici complessi.

Produzione di biogas dagli scarti della lavorazione dell’alga ulva lactuca coltivata in mare aperto

Il presente lavoro si pone tre obiettivi: studio dei possibili utilizzi del sottoprodotto algale di Ulva L., a valle di un processo di estrazione dell’azienda South Agro srl che produce biofertilizzanti da alghe; digestione anaerobica del sottoprodotto, presso i laboratori dell’Università di Bologna, per determinarne il BMP; analisi costi-benefici per tre scenari diversi per un impianto a biogas di piccola taglia. Il primo obiettivo, è stato conseguito tramite una panoramica bibliografica delle vie di biovalorizzazione della biomassa Ulva L. Emerge che Ulva L. presenta numerose potenzialità dall’ambito alimentare ai chemicals, dall’ambito energetico a quello dei fertilizzanti. In questo lavoro esploreremo la conversione per valorizzazione energetica. Per il secondo obiettivo, è stato effettuato lo studio del potenziale biochimico del metano del residuo dell’azienda: ha prodotto una quantità di metano inferiore alla quota minima emersa dalle ricerche, che incrociano valutazioni del BMP alle fattibilità economiche di transformazione per la produzione di biometano. Questo suggerisce una possibile digestione anaerobica con un feed costituito da diversi residui algali a disposizione della stessa azienda, dato che tratta tre macroalghe. Considerando un valore di BMP di 180 Nmq / t SV, corrispondente a un feed di 3,3 t/g proveniente da tre alghe diverse, emerge una potenzialità di biometano prodotto economicamente possibile per un impianto a biogas di piccola taglia. Per il terzo obiettivo, è stata effettuata un’analisi costi-benefici tramite MATLAB e fogli Excel, basate su ricerche di impianti a biogas di piccola taglia e applicazione degli incentivi vigenti dalle normative. Il tutto è servito per creare tre scenari diversi (100, 200 e 300 kWel) che avvierebbero diversi benefici a livello territoriale, oltre che per l’azienda in questione: efficientamento energetico, economici, ambientali, simbiosi industriale e anche di avviamento di processi d’economia circolare.

Analisi di una pompa volumetrica ad ingranaggi esterni a basse emissioni acustiche con ruote elicoidali coniugate

Le recenti Normative hanno portato via via all’imposizione di limiti sempre più stringenti circa le emissioni acustiche prodotte da impianti oleodinamici in funzione. In aggiunta a ciò, l’avvento dell’elettrificazione dei motori nel settore dei trasporti e nell’automotive ha reso indispensabile sviluppare nuove soluzioni di pompe più silenziose. Il presente elaborato tratta una nuova tipologia di pompa volumetrica ad ingranaggi esterni sviluppata dall’azienda Marzocchi Pompe S.p.A. con range di cilindrata da 3 a 14 cm3/giro, la quale presenta una coppia di ingranaggi a denti elicoidali con profilo coniugato. A seguito di una descrizione sulla natura delle emissioni sonore all’interno di una pompa ad ingranaggi tradizionale sono state individuate le cause scatenanti del problema. Vengono dunque descritte le procedure e le tecniche costruttive messe in atto per realizzare una soluzione adatta alla riduzione della rumorosità. Al fine di validare tale soluzione, si descrivono i test eseguiti su dedicati banchi di prova. Una volta ottenuti i dati, essi sono stati confrontati con quelli relativi ad altre pompe. Si può dunque concludere che la soluzione proposta garantisce una netta riduzione delle emissioni acustiche avendo efficienze confrontabili con le pompe più tradizionali. Infine, è stato predisposto un metodo sperimentale per valutare, a seguito dello studio di oscillazioni sonore prodotte dalla pompa in questione, se in essa fossero presenti difetti e di quale natura.

Sviluppo di un Intervento di Riqualificazione Energetica per un Edificio ad uso Espositivo

Nel seguente elaborato di tesi si è studiata la riqualificazione energetica di un edificio ad uso espositivo, di notevole volumetria, durante una esperienza di tirocinio svolta presso MoRe Energy s.r.l.. Inizialmente il cliente ha commissionto il lavoro limitandosi al voler sostituire l'attuale impianto ad aria a servizio di una parte dell'immobile ma, in fase di lavoro, si è evidenziato che le notevoli dispersioni in inverno e gli apporti in estate erano tali da non garantire le corrette condizioni di comfort secondo le norme di settore. Si è quindi predisposta una dettagliata analisi dei carichi termici invernali ed estivi, predisponendo degli interventi sull'involucro tali da migliorare il benessere da un punto di vista globale. Per fare questo ci si è avvalsi del software commerciale DesignBuilder, che monta al suo interno EnergyPlus come motore di calcolo, un codice di calcolo dinamico molto performante basato sul metodo Ashrae Heat Balance. Valutati gli interventi sull'involucro si è passati a predisporre una soluzione impiantistica: si è valutato che un impianto ad aria misto con UTA e termoventilanti ad integrazione fosse la soluzione migliore per l'edificio. Infine, si è studiata una possibile canalizzazione dell'aria utilizzando il metodo a perdita di carico unitaria costante.