New catalytic processes for the upgrading of furfural and 5-hydroxymethylfurfural to chemicals and fuels

The demand of energy, fuels and chemicals is increasing due to the strong growth of some countries in the developing world and the development of the world economy. Unfortunately, the general picture derived sparked an exponential increase in crude oil prices with a consequent increase of the chemical, by-products and energy, depleting the global market. Nowadays biomass are the most promising alternative to fossil fuels for the production of chemicals and fuels. In this work, the development of three different catalytic processes for the valorization of biomass-derived has been investigated. 5-hydroxymethylfurfural oxidation was studied under mild reaction condition using gold and gold/copper based catalysts synthetized from pre-formed nanoparticles and supported onto TiO2 and CeO2. The analysis conducted on catalysts showed the formation of alloys gold/copper and a strong synergistic effect between the two metals. For this reason the bimetallic catalysts supported on titania showed a higher catalytic activity respect to the monometallic catalysts. The process for the production of 2,5-bishydroxymethyl furan (BHMF) was also optimized by means the 5-hydroxymethylfurfural hydrogenation using the Shvo complex. Complete conversion of HMF was achieved working at 90 °C and 10 bar of hydrogen. The complex was found to be re-usable for at least three catalytic cycles without suffering any type of deactivation. Finally, the hydrogenation of furfural and HMF was carried out, developing the process of hydrogen transfer by using MgO as a catalyst and methanol as a hydrogen donor. Quantitative yields to alcohols have been achieved in a few hours working in mild condition: 160 °C and at autogenous pressure. The only by-products formed were light products such as CO, CO2 and CH4 (products derived from methanol transformation), easily separable from the reaction solution depressurizing the reactor.

From fossil to sustainable diets: an assessment of farming energy footprint

The dependence of industrial agricolture on fossil fuels has been assessed in two comparative case studies between Italy (Emilia-Romagna and Piemonte)and Missouri. The first is related to dairy farming; 15 different farms were surveyed, divided into three different groups: grain based, pasture based and organic. The second is devoted to rice cropping; 12 holdings were examined divided into two groups: conventional and organic. Energy footprint was determined for structures, machinery, fertilizers, pesticides, fuel, electricity, feed and seeds. Possible scenarios of transition to a more sustainable agricolture based on renewable energy sources were analized in detail for all the farms analized.

Sulla ricerca del minimo dei consumi per vetture sportive

La ricerca oggetto di questa tesi, come si evince dal titolo stesso, è volta alla riduzione dei consumi per vetture a forte carattere sportivo ed elevate prestazioni specifiche. In particolare, tutte le attività descritte fanno riferimento ad un ben definito modello di vettura, ovvero la Maserati Quattroporte. Lo scenario all’interno del quale questo lavoro si inquadra, è quello di una forte spinta alla riduzione dei cosiddetti gas serra, ossia dell’anidride carbonica, in linea con quelle che sono le disposizioni dettate dal protocollo di Kyoto. La necessità di ridurre l’immissione in atmosfera di CO2 sta condizionando tutti i settori della società: dal riscaldamento degli edifici privati a quello degli stabilimenti industriali, dalla generazione di energia ai processi produttivi in senso lato. Nell’ambito di questo panorama, chiaramente, sono chiamati ad uno sforzo considerevole i costruttori di automobili, alle quali è imputata una percentuale considerevole dell’anidride carbonica prodotta ogni giorno e riversata nell’atmosfera. Al delicato problema inquinamento ne va aggiunto uno forse ancor più contingente e diretto, legato a ragioni di carattere economico. I combustibili fossili, come tutti sanno, sono una fonte di energia non rinnovabile, la cui disponibilità è legata a giacimenti situati in opportune zone del pianeta e non inesauribili. Per di più, la situazione socio politica che il medio oriente sta affrontando, unita alla crescente domanda da parte di quei paesi in cui il processo di industrializzazione è partito da poco a ritmi vertiginosi, hanno letteralmente fatto lievitare il prezzo del petrolio. A causa di ciò, avere una vettura efficiente in senso lato e, quindi, a ridotti consumi, è a tutti gli effetti un contenuto di prodotto apprezzato dal punto di vista del marketing, anche per i segmenti vettura più alti. Nell’ambito di questa ricerca il problema dei consumi è stato affrontato come una conseguenza del comportamento globale della vettura in termini di efficienza, valutando il miglior compromesso fra le diverse aree funzionali costituenti il veicolo. Una parte consistente del lavoro è stata dedicata alla messa a punto di un modello di calcolo, attraverso il quale eseguire una serie di analisi di sensibilità sull’influenza dei diversi parametri vettura sul consumo complessivo di carburante. Sulla base di tali indicazioni, è stata proposta una modifica dei rapporti del cambio elettro-attuato con lo scopo di ottimizzare il compromesso tra consumi e prestazioni, senza inficiare considerevolmente queste ultime. La soluzione proposta è stata effettivamente realizzata e provata su vettura, dando la possibilità di verificare i risultati ed operare un’approfondita attività di correlazione del modello di calcolo per i consumi. Il beneficio ottenuto in termini di autonomia è stato decisamente significativo con riferimento sia ai cicli di omologazione europei, che a quelli statunitensi. Sono state inoltre analizzate le ripercussioni dal punto di vista delle prestazioni ed anche in questo caso i numerosi dati rilevati hanno permesso di migliorare il livello di correlazione del modello di simulazione per le prestazioni. La vettura con la nuova rapportatura proposta è stata poi confrontata con un prototipo di Maserati Quattroporte avente cambio automatico e convertitore di coppia. Questa ulteriore attività ha permesso di valutare il differente comportamento tra le due soluzioni, sia in termini di consumo istantaneo, che di consumo complessivo rilevato durante le principali missioni su banco a rulli previste dalle normative. L’ultima sezione del lavoro è stata dedicata alla valutazione dell’efficienza energetica del sistema vettura, intesa come resistenza all’avanzamento incontrata durante il moto ad una determinata velocità. Sono state indagate sperimentalmente le curve di “coast down” della Quattroporte e di alcune concorrenti e sono stati proposti degli interventi volti alla riduzione del coefficiente di penetrazione aerodinamica, pur con il vincolo di non alterare lo stile vettura.

Advanced Waste-To-Energy Cycles

The increase in environmental and healthy concerns, combined with the possibility to exploit waste as a valuable energy resource, has led to explore alternative methods for waste final disposal. In this context, the energy conversion of Municipal Solid Waste (MSW) in Waste-To-Energy (WTE) power plant is increasing throughout Europe, both in terms of plants number and capacity, furthered by legislative directives. Due to the heterogeneous nature of waste, some differences with respect to a conventional fossil fuel power plant have to be considered in the energy conversion process. In fact, as a consequence of the well-known corrosion problems, the thermodynamic efficiency of WTE power plants typically ranging in the interval 25% ÷ 30%. The new Waste Framework Directive 2008/98/EC promotes production of energy from waste introducing an energy efficiency criteria (the so-called “R1 formula”) to evaluate plant recovery status. The aim of the Directive is to drive WTE facilities to maximize energy recovery and utilization of waste heat, in order to substitute energy produced with conventional fossil fuels fired power plants. This calls for novel approaches and possibilities to maximize the conversion of MSW into energy. In particular, the idea of an integrated configuration made up of a WTE and a Gas Turbine (GT) originates, driven by the desire to eliminate or, at least, mitigate limitations affecting the WTE conversion process bounding the thermodynamic efficiency of the cycle. The aim of this Ph.D thesis is to investigate, from a thermodynamic point of view, the integrated WTE-GT system sharing the steam cycle, sharing the flue gas paths or combining both ways. The carried out analysis investigates and defines the logic governing plants match in terms of steam production and steam turbine power output as function of the thermal powers introduced.

Luminophores and Carbon nanostructures: towards new functional materials

In the scenario of depleting fossil fuels, finding new energy technologies and conserving conventional energy resources have become essential to sustain modern civilization. While renewable energies are on the rise, considerable interest has been turned also to reduce energy consumption of conventional devices and appliances, which are often not yet optimized for this purpose. Modern nanotechnology provides a platform to build such devices by using nanomaterials showing exceptional physico-chemical properties. In particular, carbon materials (fullerenes, carbon nanotubes, graphene etc.), which show high thermal and electrical conductivity, aspect ratio, shear strength and chemical/mechanical resistance, are quite promising for a wide range of applications. However, the problem of solubility often hampers their handling and industrial utilization. These limitations can be mitigated by functionalizing carbon nanostructures, either covalently or non covalently, with organic or inorganic compounds. The exo- and endohedral functionalization of carbon nanotubes (CNTs) with organic/inorganic moieties to produce luminescent materials with desired properties are the main focus of this doctoral work. These hybrids have been thoroughly designed and characterized with chemical, microscopic and photophysical analyses. All the materials based on carbon nanostructures described in this thesis are innovative examples of photoactive and luminescent hybrids, and their morphological and photophysical properties help understanding the nature of interactions between the active units. This may prompt the design and fabrication of new functional materials for applications in the fields of optoelectronics and photovoltaics.

Optimization of bioenergy solutions at different farm scales

RAF is a bio-energetic descriptive model integrates with MAD model to support Integrated Farm Management. RAF model aimed to enhancing economical, social and environmental sustainability of farm production in terms of energy via convert energy crops and animal manure to biogas and digestate (bio-fertilizers) by anaerobic digestion technologies, growing and breeding practices. The user defines farm structure in terms of present crops, livestock and market prices and RAF model investigates the possibilities of establish on-farm biogas system (different anaerobic digestion technologies proposed for different scales of farms in terms of energy requirements) according to budget and sustainability constraints to reduce the dependence on fossil fuels. The objective function of RAF (Z) is optimizing the total net income of farm (maximizing income and minimizing costs) for whole period which is considered by the analysis. The main results of this study refers to the possibility of enhancing the exploitation of the available Italian potentials of biogas production from on-farm production of energy crops and livestock manure feedstock by using the developed mathematical model RAF integrates with MAD to presents reliable reconcile between farm size, farm structure and on-farm biogas systems technologies applied to support selection, applying and operating of appropriate biogas technology at any farm under Italian conditions.

Soil organic carbon dynamics under perennial energy crops

The European renewable energy directive 2009/28/EC (E.C. 2009) provides a legislative framework for reducing GHG emissions by 20%, while achieving a 20% share of energy from renewable sources by 2020. Perennial energy crops could significantly contribute to limit GHG emissions through replacing equivalent fossil fuels and by sequestering a considerable amount of carbon into the soil through the large amounts of belowground biomass produced. The objective of this study is to evaluate the effects of land use change that perennial energy crops have on croplands (switchgrass) and marginal grasslands (miscanthus). For that purpose above and belowground biomass, SOC variation and Net Ecosystem Exchange were evaluated after five years of growth. At aboveground level both crops produced high biomass under cropland conditions as well as under marginal soils. At belowground level they also produced large amounts of biomass, but no significant influences on SOC in the upper layer (0-30 cm) were found. This is probably because of the "priming effect" that caused fast carbon substitution. In switchgrass only it was found a significant SOC increase in deeper layers (30-60 cm), while in the whole soil profile (0-60 cm) SOC increased from 42 to 51 ha-1. However, the short experimental periods (for both switchgrass and miscanthus), in which land use change was evaluated, do not permit to determine the real capacity of perennial energy crops to accumulate SOC. In conclusion the large amounts of belowground biomass enhanced the SOC dynamic through the priming effect resulting in increased SOC in cropland but not in marginal grassland.

Alla ricerca della sostenibilità: lo sviluppo dell'agricoltura dall'Unità d'Italia alla Green Economy

L’elaborato finale presentato per la tesi di Dottorato analizza e riconduce a unitarietà, per quanto possibile, alcune delle attività di ricerca da me svolte durante questi tre anni, il cui filo conduttore è l'impatto ambientale delle attività umane e la promozione dello sviluppo sostenibile. Il mio filone di ricerca è stato improntato, dal punto di vista di politica economica, sull'analisi storica dello sviluppo del settore agricolo dall'Unità d'Italia ai giorni nostri e dei cambiamenti avvenuti in contemporanea nel contesto socio-economico e territoriale nazionale, facendo particolare riferimento alle tematiche legate ai consumi e alla dipendenza energetica ed all'impatto ambientale. Parte della mia ricerca è stata, infatti, incentrata sull'analisi dello sviluppo della Green Economy, in particolare per quanto riguarda il settore agroalimentare e la produzione di fonti di energia rinnovabile. Enfasi viene posta sia sulle politiche implementate a livello comunitario e nazionale, sia sul cambiamento dei consumi, in particolare per quanto riguarda gli acquisti di prodotti biologici. La Green Economy è vista come fattore di sviluppo e opportunità per uscire dall'attuale contesto di crisi economico-finanziaria. Crisi, che è strutturale e di carattere duraturo, affiancata da una crescente problematica ambientale dovuta all'attuale modello produttivo, fortemente dipendente dai combustibili fossili. Difatti la necessità di cambiare paradigma produttivo promuovendo la sostenibilità è visto anche in ottica di mitigazione del cambiamento climatico e dei suoi impatti socio-economici particolare dal punto di vista dei disastri ambientali. Questo punto è analizzato anche in termini di sicurezza internazionale e di emergenza umanitaria, con riferimento al possibile utilizzo da parte delle organizzazioni di intervento nei contesti di emergenza di tecnologie alimentate da energia rinnovabile. Dando così una risposta Green ad una problematica esacerbata dall'impatto dello sviluppo delle attività umane.

Copper(I) phenanthroline complexes and supramolecular systems containing fullerenes: Photophysics, photochemistry and potential applications in sustainable energy technologies.

Chemistry can contribute, in many different ways to solve the challenges we are facing to modify our inefficient and fossil-fuel based energy system. The present work was motivated by the search for efficient photoactive materials to be employed in the context of the energy problem: materials to be utilized in energy efficient devices and in the production of renewable electricity and fuels. We presented a new class of copper complexes, that could find application in lighting techhnologies, by serving as luminescent materials in LEC, OLED, WOLED devices. These technologies may provide substantial energy savings in the lighting sector. Moreover, recently, copper complexes have been used as light harvesting compounds in dye sensitized photoelectrochemical solar cells, which offer a viable alternative to silicon-based photovoltaic technologies. We presented also a few supramolecular systems containing fullerene, e.g. dendrimers, dyads and triads.The most complex among these arrays, which contain porphyrin moieties, are presented in the final chapter. They undergo photoinduced energy- and electron transfer processes also with long-lived charge separated states, i.e. the fundamental processes to power artificial photosynthetic systems.

Chemical analysis and reactivity of biomass pyrolysis products. Application to the development of carbon-neutral biofuels and chemicals

In this dissertation the pyrolytic conversion of biomass into chemicals and fuels was investigated from the analytical point of view. The study was focused on the liquid (bio-oil) and solid (char) fractions obtainable from biomass pyrolysis. The drawbacks of Py-GC-MS described so far were partially solved by coupling different analytical configurations (Py-GC-MS, Py-GC-MIP-AED and off-line Py-SPE and Py-SPME-GC-MS with derivatization procedures). The application of different techniques allowed a satisfactory comparative analysis of pyrolysis products of different biomass and a high throughput screening on effect of 33 catalysts on biomass pyrolysis. As the results of the screening showed, the most interesting catalysts were those containing copper (able to reduce the high molecular weight fraction of bio-oil without large yield decrease) and H-ZSM-5 (able to entirely convert the bio-oil into “gasoline like” aromatic products). In order to establish the noxious compounds content of the liquid product, a clean-up step was included in the Py-SPE procedure. This allowed to investigate pollutants (PAHs) generation from pyrolysis and catalytic pyrolysis of biomass. In fact, bio-oil from non-catalytic pyrolysis of biomass showed a moderate PAHs content, while the use of H-ZSM-5 catalyst for bio-oil up-grading determined an astonishing high production of PAHs (if compared to what observed in alkanes cracking), indicating an important concern in the substitution fossil fuel with bio-oil derived from biomass. Moreover, the analytical procedures developed in this thesis were directly applied for the detailed study of the most useful process scheme and up-grading route to chemical intermediates (anhydrosugars), transportation fuels or commodity chemicals (aromatic hydrocarbons). In the applied study, poplar and microalgae biomass were investigated and overall GHGs balance of pyrolysis of agricultural residues in Ravenna province was performed. A special attention was put on the comparison of the effect of bio-char different use (fuel or as soil conditioner) on the soil health and GHGs emissions.

Paleontological studies of Cretaceous vertebrate fossil beds in the Tataouine Basin (southern Tunisia)

The ‘Continental Intercalaire’ deposits of the Tataouine basin of southern Tunisia preserve one of the most diverse Cretaceous vertebrate fauna from Africa. This research project focuses on a detailed revision of the stratigraphic distribution of mid-Cretaceous fossil beds in the Tataouine Basin and includes the description of four, newly discovered vertebrate tracksites. In the Tataouine region, macro- and microvertebrate remains are recovered from three stratigraphic intervals: the lower Douiret Formation (Barremian), the Chenini (rare) and Oum ed Diab members of the Aïn El Guettar Formation (Albian). A detailed, basin-scale revision of the stratigraphic occurrence of fossil-bearing strata indicates 1. lateral facies variability within the context of a low gradient, circalittoral to coastal-plain environment; 2. multiple and diachronous fossil beds which include elasmobranchs, actinopterygians, sarcopterygians, turtles, crocodyliforms, pterosaurs, and non-avian dinosaurs remains. Four vertebrate tracksites have been discovered in the study area: 1. the Middle Jurassic Beni Ghedir site which preserves approximately 130 tridactyl footprints distributed over an area of 200 square meters, representing the oldest evidence of a dinosaur fauna in Tunisia; 2. the late Albian Chenini tracksite, which includes poorly preserved crocodilian tracks and the dinosaur ichnospecies Apulosauripus federicianus; 3. the Cenomanian Ksar Ayaat locality, where footprints assigned to a pleurodiran turtle are exposed, and 4. the upper Cenomanian Jebel Boulouha site which presents almost 100 well-preserved tridactyl tracks referred to small-sized theropods, fossil bird tracks - ichnogenus Koreanaorins – and tracks referred to a mammalian trackmaker, representing the first report of fossil bird and mammal from the Cretaceous of continental Africa and Tunisia respectively. In addition, data collected from the Tunisian tracksites have been compared with coeval tracksites in Italy and Croatia, showing analogies in morphology and paleoenvironment of dinosaur ichnoassociations, supporting the already hypothesized subaerial connection between these areas during the mid-Cretaceous.

Studio del metodo dell'assorbimento diretto della CO2 per l'analisi del radiocarbonio

L’attuale rilevanza rappresentata dalla stretta relazione tra cambiamenti climatici e influenza antropogenica ha da tempo posto l’attenzione sull’effetto serra e sul surriscaldamento planetario così come sull’aumento delle concentrazioni atmosferiche dei gas climaticamente attivi, in primo luogo la CO2. Il radiocarbonio è attualmente il tracciante ambientale per eccellenza in grado di fornire mediante un approccio “top-down” un valido strumento di controllo per discriminare e quantificare il diossido di carbonio presente in atmosfera di provenienza fossile o biogenica. Ecco allora che ai settori applicativi tradizionali del 14C, quali le datazioni archeometriche, si affiancano nuovi ambiti legati da un lato al settore energetico per quanto riguarda le problematiche associate alle emissioni di impianti, ai combustibili, allo stoccaggio geologico della CO2, dall’altro al mercato in forte crescita dei cosiddetti prodotti biobased costituiti da materie prime rinnovabili. Nell’ambito del presente lavoro di tesi è stato quindi esplorato il mondo del radiocarbonio sia dal punto di vista strettamente tecnico e metodologico che dal punto di vista applicativo relativamente ai molteplici e diversificati campi d’indagine. E’ stato realizzato e validato un impianto di analisi basato sul metodo radiometrico mediante assorbimento diretto della CO2 ed analisi in scintillazione liquida apportando miglioramenti tecnologici ed accorgimenti procedurali volti a migliorare le performance del metodo in termini di semplicità, sensibilità e riproducibilità. Il metodo, pur rappresentando generalmente un buon compromesso rispetto alle metodologie tradizionalmente usate per l’analisi del 14C, risulta allo stato attuale ancora inadeguato a quei settori applicativi laddove è richiesta una precisione molto puntuale, ma competitivo per l’analisi di campioni moderni ad elevata concentrazione di 14C. La sperimentazione condotta su alcuni liquidi ionici, seppur preliminare e non conclusiva, apre infine nuove linee di ricerca sulla possibilità di utilizzare questa nuova classe di composti come mezzi per la cattura della CO2 e l’analisi del 14C in LSC.

COSMIC-LAB: Terzan 5 as a fossil remnant of the Galactic bulge formation epoch

The formation and evolution of galaxy bulges is a greatly debated topic in modern astrophysics. An approach to address this issue is to look at the Galactic bulge, the closest to us. According to some theoretical models, our bulge built-up from the merger of substructures formed from the instability and fragmentation of a proto-disk in the early phases of Galactic evolution. We may have discovered the remnant of one of these substructures: the stellar system Terzan 5. Terzan 5 hosts two stellar populations with different iron abundances, thus suggesting it once was far more massive than today. Moreover, its peculiar chemistry resembles that observed only in the Galactic bulge. In this Thesis we perform a detailed photometric and spectroscopic analysis of this cluster to determine its formation and evolutionary histories. Form the photometric point of view we built a high-resolution differential reddening map in Terzan 5 direction and we measured relative proper motions to separate its member population from the contaminating field stars. This information represents the necessary work to measure the absolute ages of Terzan 5 populations via the Turn-off luminosity method. From the spectroscopic point of view we measured abundances for more than 600 stars belonging to Terzan 5 and its surroundings in order to build the largest field-decontaminated metallicity distribution for this system. We find that the metallicity distribution is extremely wide (more than 1 dex) and we discovered a third, metal-poor and alpha-enhanced population with average [Fe/H]=-0.8. The striking similarity between Terzan 5 and the bulge in terms of their chemical formation and evolution revealed by this Thesis suggests that Terzan 5 formed in situ with the bulge itself. In particular its metal-poor populations trace the early stages of the bulge formation, while its most metal-rich component contains crucial information on the bulge more recent evolution.