Biomass Gasification - Process analysis and dimensioning aspects for downdraft units and gas cleaning lines

In such territories where food production is mostly scattered in several small / medium size or even domestic farms, a lot of heterogeneous residues are produced yearly, since farmers usually carry out different activities in their properties. The amount and composition of farm residues, therefore, widely change during year, according to the single production process periodically achieved. Coupling high efficiency micro-cogeneration energy units with easy handling biomass conversion equipments, suitable to treat different materials, would provide many important advantages to the farmers and to the community as well, so that the increase in feedstock flexibility of gasification units is nowadays seen as a further paramount step towards their wide spreading in rural areas and as a real necessity for their utilization at small scale. Two main research topics were thought to be of main concern at this purpose, and they were therefore discussed in this work: the investigation of fuels properties impact on gasification process development and the technical feasibility of small scale gasification units integration with cogeneration systems. According to these two main aspects, the present work was thus divided in two main parts. The first one is focused on the biomass gasification process, that was investigated in its theoretical aspects and then analytically modelled in order to simulate thermo-chemical conversion of different biomass fuels, such as wood (park waste wood and softwood), wheat straw, sewage sludge and refuse derived fuels. The main idea is to correlate the results of reactor design procedures with the physical properties of biomasses and the corresponding working conditions of gasifiers (temperature profile, above all), in order to point out the main differences which prevent the use of the same conversion unit for different materials. At this scope, a gasification kinetic free model was initially developed in Excel sheets, considering different values of air to biomass ratio and the downdraft gasification technology as particular examined application. The differences in syngas production and working conditions (process temperatures, above all) among the considered fuels were tried to be connected to some biomass properties, such elementary composition, ash and water contents. The novelty of this analytical approach was the use of kinetic constants ratio in order to determine oxygen distribution among the different oxidation reactions (regarding volatile matter only) while equilibrium of water gas shift reaction was considered in gasification zone, by which the energy and mass balances involved in the process algorithm were linked together, as well. Moreover, the main advantage of this analytical tool is the easiness by which the input data corresponding to the particular biomass materials can be inserted into the model, so that a rapid evaluation on their own thermo-chemical conversion properties is possible to be obtained, mainly based on their chemical composition A good conformity of the model results with the other literature and experimental data was detected for almost all the considered materials (except for refuse derived fuels, because of their unfitting chemical composition with the model assumptions). Successively, a dimensioning procedure for open core downdraft gasifiers was set up, by the analysis on the fundamental thermo-physical and thermo-chemical mechanisms which are supposed to regulate the main solid conversion steps involved in the gasification process. Gasification units were schematically subdivided in four reaction zones, respectively corresponding to biomass heating, solids drying, pyrolysis and char gasification processes, and the time required for the full development of each of these steps was correlated to the kinetics rates (for pyrolysis and char gasification processes only) and to the heat and mass transfer phenomena from gas to solid phase. On the basis of this analysis and according to the kinetic free model results and biomass physical properties (particles size, above all) it was achieved that for all the considered materials char gasification step is kinetically limited and therefore temperature is the main working parameter controlling this step. Solids drying is mainly regulated by heat transfer from bulk gas to the inner layers of particles and the corresponding time especially depends on particle size. Biomass heating is almost totally achieved by the radiative heat transfer from the hot walls of reactor to the bed of material. For pyrolysis, instead, working temperature, particles size and the same nature of biomass (through its own pyrolysis heat) have all comparable weights on the process development, so that the corresponding time can be differently depending on one of these factors according to the particular fuel is gasified and the particular conditions are established inside the gasifier. The same analysis also led to the estimation of reaction zone volumes for each biomass fuel, so as a comparison among the dimensions of the differently fed gasification units was finally accomplished. Each biomass material showed a different volumes distribution, so that any dimensioned gasification unit does not seem to be suitable for more than one biomass species. Nevertheless, since reactors diameters were found out quite similar for all the examined materials, it could be envisaged to design a single units for all of them by adopting the largest diameter and by combining together the maximum heights of each reaction zone, as they were calculated for the different biomasses. A total height of gasifier as around 2400mm would be obtained in this case. Besides, by arranging air injecting nozzles at different levels along the reactor, gasification zone could be properly set up according to the particular material is in turn gasified. Finally, since gasification and pyrolysis times were found to considerably change according to even short temperature variations, it could be also envisaged to regulate air feeding rate for each gasified material (which process temperatures depend on), so as the available reactor volumes would be suitable for the complete development of solid conversion in each case, without even changing fluid dynamics behaviour of the unit as well as air/biomass ratio in noticeable measure. The second part of this work dealt with the gas cleaning systems to be adopted downstream the gasifiers in order to run high efficiency CHP units (i.e. internal engines and micro-turbines). Especially in the case multi–fuel gasifiers are assumed to be used, weightier gas cleaning lines need to be envisaged in order to reach the standard gas quality degree required to fuel cogeneration units. Indeed, as the more heterogeneous feed to the gasification unit, several contaminant species can simultaneously be present in the exit gas stream and, as a consequence, suitable gas cleaning systems have to be designed. In this work, an overall study on gas cleaning lines assessment is carried out. Differently from the other research efforts carried out in the same field, the main scope is to define general arrangements for gas cleaning lines suitable to remove several contaminants from the gas stream, independently on the feedstock material and the energy plant size The gas contaminant species taken into account in this analysis were: particulate, tars, sulphur (in H2S form), alkali metals, nitrogen (in NH3 form) and acid gases (in HCl form). For each of these species, alternative cleaning devices were designed according to three different plant sizes, respectively corresponding with 8Nm3/h, 125Nm3/h and 350Nm3/h gas flows. Their performances were examined on the basis of their optimal working conditions (efficiency, temperature and pressure drops, above all) and their own consumption of energy and materials. Successively, the designed units were combined together in different overall gas cleaning line arrangements, paths, by following some technical constraints which were mainly determined from the same performance analysis on the cleaning units and from the presumable synergic effects by contaminants on the right working of some of them (filters clogging, catalysts deactivation, etc.). One of the main issues to be stated in paths design accomplishment was the tars removal from the gas stream, preventing filters plugging and/or line pipes clogging At this scope, a catalytic tars cracking unit was envisaged as the only solution to be adopted, and, therefore, a catalytic material which is able to work at relatively low temperatures was chosen. Nevertheless, a rapid drop in tars cracking efficiency was also estimated for this same material, so that an high frequency of catalysts regeneration and a consequent relevant air consumption for this operation were calculated in all of the cases. Other difficulties had to be overcome in the abatement of alkali metals, which condense at temperatures lower than tars, but they also need to be removed in the first sections of gas cleaning line in order to avoid corrosion of materials. In this case a dry scrubber technology was envisaged, by using the same fine particles filter units and by choosing for them corrosion resistant materials, like ceramic ones. Besides these two solutions which seem to be unavoidable in gas cleaning line design, high temperature gas cleaning lines were not possible to be achieved for the two larger plant sizes, as well. Indeed, as the use of temperature control devices was precluded in the adopted design procedure, ammonia partial oxidation units (as the only considered methods for the abatement of ammonia at high temperature) were not suitable for the large scale units, because of the high increase of reactors temperature by the exothermic reactions involved in the process. In spite of these limitations, yet, overall arrangements for each considered plant size were finally designed, so that the possibility to clean the gas up to the required standard degree was technically demonstrated, even in the case several contaminants are simultaneously present in the gas stream. Moreover, all the possible paths defined for the different plant sizes were compared each others on the basis of some defined operational parameters, among which total pressure drops, total energy losses, number of units and secondary materials consumption. On the basis of this analysis, dry gas cleaning methods proved preferable to the ones including water scrubber technology in al of the cases, especially because of the high water consumption provided by water scrubber units in ammonia adsorption process. This result is yet connected to the possibility to use activated carbon units for ammonia removal and Nahcolite adsorber for chloride acid. The very high efficiency of this latter material is also remarkable. Finally, as an estimation of the overall energy loss pertaining the gas cleaning process, the total enthalpy losses estimated for the three plant sizes were compared with the respective gas streams energy contents, these latter obtained on the basis of low heating value of gas only. This overall study on gas cleaning systems is thus proposed as an analytical tool by which different gas cleaning line configurations can be evaluated, according to the particular practical application they are adopted for and the size of cogeneration unit they are connected to.

Institutional Complexity and Technology Transfer: A Theoretical and Empirical Analysis

This Doctoral Thesis unfolds into a collection of three distinct papers that share an interest in institutional theory and technology transfer. Taking into account that organizations are increasingly exposed to a multiplicity of demands and pressures, we aim to analyze what renders this situation of institutional complexity more or less difficult to manage for organizations, and what makes organizations more or less successful in responding to it. The three studies offer a novel contribution both theoretically and empirically. In particular, the first paper “The dimensions of organizational fields for understanding institutional complexity: A theoretical framework” is a theoretical contribution that tries to better understand the relationship between institutional complexity and fields by providing a framework. The second article “Beyond institutional complexity: The case of different organizational successes in confronting multiple institutional logics” is an empirical study which aims to explore the strategies that allow organizations facing multiple logics to respond more successfully to them. The third work “ How external support may mitigate the barriers to university-industry collaboration” is oriented towards practitioners and presents a case study about technology transfer in Italy.

Judges and Mass Litigation - a (Behavioural) Law and Economics Perspective

Judicial duties have for decades extended far beyond the scope of traditional adjudication, judges being progressively called upon to occupy the role of social engineers. Meanwhile, contexts in which judges evolve have transformed: mass damage nowadays tends to multiply and create new challenges not only for legal actors, but also for society at large. In spring 2011, the replies received by the European Commission to its public consultation on collective redress indicated European stakeholders’ strong interest in seeing judiciaries play prominent and leading roles in the supervision and monitoring of procedures which enable groups of claimants to seek together compensation for damage caused by mass events. Judges are thus expected to be neutral and robust agents while assuming heavy responsibilities under a considerable burden. Insights from social sciences however invite us to revisit policymakers expectations and may shed new light on current debates about mass litigation.

Structure, Dynamics and Reactivity in the Organic Solid State: Anthracene Derivatives and Charge Transfer Crystals

The work presented in this thesis tackles some important points concerning the collective properties of two typical categories of molecular crystals, i.e., anthracene derivatives and charge transfer crystals. Anthracene derivatives have constituted the class of materials from which systematical investigations of crystal-to-crystal photodimerization reactions started, developed and have been the subject of a new awakening in the recent years. In this work some of these compounds, namely, 9-cyanoanthacene, 9-anthacenecarboxylic acid and 9-methylanthracene, have been selected as model systems for a phenomenological approach to some key properties of the solid state, investigated by spectroscopic methods. The present results show that, on the basis of the solid state organization and the chemical nature of each compound, photo-reaction dynamics and kinetics display distinctive behaviors, which allows for a classification of the various processes in topochemical, non topochemical, reversible or topophysical. The second part of the thesis was focused on charge transfer crystals, binary systems formed by stoichiometric combinations of the charge donating perylene (D) and the charge accepting tetracyano-quinodimethane (A), this latter also in its fluorinated derivatives. The work was focused on the growth of single crystals, some of which not yet reported in the literature, by PVT technique. Structural and spectroscopic characterizations have been performed, with the aim of determining the degree of charge transfer between donor and acceptor in the co-crystals. An interesting outcome of the systematic search performed in this work is the definition of the experimental conditions which drive the crystal growth of the binary systems either towards the low (1:1) or the high ratio (3:1 or 3:2) stoichiometries.

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.

Novel membranes for hemodialysis application

The present work is focused on the synthesis and characterization of novel materials for hemodialysis applications. Cellulose acetate was chosen as base polymer for the preparation of porous Mixed Matrix Membrane adsorbers (MMMAs) and for the synthesis of hybrid ultrafiltration membranes. Hemodialysis is a renal replacement therapy used to eliminate,the waste products and excess fluids accumulating in the blood of people affected by an end stage renal disease. The main environmental drawback associated to it is the large water consumption. The MMMAs were prepared with the porpoise of eliminating waste metabolites (uremic toxins) from the spent dialysate solution, with the prospective limiting the consumption of water related to the process. Batch tests of MMMAs showed that the removal of uric acid is almost complete while the one of urea and creatinine is limited to a 20/30 %. The thinking behind the concept of MMMAs was aimed to develop a small a lab scale chromatographic cartridge to continuously remove uremic toxins from an aqueous feed solution. The cartridge was packed with MMMAs and tested with a mixture of toxins. Experiments results shown a promising removal capability of the system even if the necessity of a higher surface area to achieve better efficiency is denoted. The other important issue related to hemodialysis is the assessment of an overall mass transfer rates in hemodialyzers. The mass transfer correlations proposed in literature do not take into account the effect of permeation and are developed for turbulent flow regime. Therefore, hybrid cellulose acetate/Silica ultrafiltration membranes were prepared to characterize a surrogate system of an artificial kidney (AK) in terms of fluid mechanics and mass transfer. The effect of surface roughness and suction on the velocity profiles was determined and a new dimensionless mass transfer correlation accounting for permeation was developed.

Open-cell Metallic Foams for the Electrochemical Conversion of Biomass-derived Compounds

The electrochemical conversion is a sustainable way for the production of added-value products, operating in mild conditions, using in-situ generated hydrogen/oxygen by water and avoiding the use of high H2/O2 pressures. The aim of this work is to investigate the electrocatalytic conversion of 5-hydroxymetilfurfural (HMF) and D-glucose, in alkaline media, using metallic open-cell foams based-catalysts. The electrochemical hydrogenation of HMF to 2,5-bis(hydroxymethyl)furan (BHMF) was performed using nanostructured Ag, deposited by galvanic displacement (GD) or electrodeposition (ED), on Cu foam, obtaining AgCu bimetallic nanoparticles (ED) or dendrites (GD) which enhanced electroactive surface area, charge and mass transfer, than bare foams. In diluted 0.02M HMF solutions, Ag/Cu samples selectively produce BHMF; the large surface area enhanced the productivity, compared to their 2D counterparts. Furthermore, at more concentrated solutions (0.05 – 0.10M) a gradually decrease of selectivity is observed. The performances of the electrodes is stable during the catalytic tests but a Cu-enrichment of particles occurred. The performances of Ni foam-based catalysts, obtained by calcination of Ni foam or by electrodeposition of Ni-hydroxide/Ni and Ni particle/Ni, were firstly investigated for the selective electrochemical oxidation of D-glucose toward gluconic acid (GO) and glucaric acid (GA). Then, the calcined catalyst was chosen to study the influence of the reaction conditions on the reaction mechanism. The GO and GA selectivities increase with the charge passed, while the formation of by-products from C-C cleavage/retro-aldol process is maximum at low charge. The fructose obtained from glucose isomerization favours the formation of by-products. The best glucose/NaOH ratio is between 0.5 and 0.1: higher values suppress the OER, while lower values favour the formation of low molecular weight products. The increases of the potential enhance the GO selectivity, nevertheless higher GA selectivity is observed at 0.6 – 0.7V vs SCE, confirmed by catalytic test performed in gluconate (30-35% GA selectivity).

Fluid dynamic analysis and modelling of industrial chemical equipment

The research is aimed at contributing to the identification of reliable fully predictive Computational Fluid Dynamics (CFD) methods for the numerical simulation of equipment typically adopted in the chemical and process industries. The apparatuses selected for the investigation, specifically membrane modules, stirred vessels and fluidized beds, were characterized by a different and often complex fluid dynamic behaviour and in some cases the momentum transfer phenomena were coupled with mass transfer or multiphase interactions. Firs of all, a novel modelling approach based on CFD for the prediction of the gas separation process in membrane modules for hydrogen purification is developed. The reliability of the gas velocity field calculated numerically is assessed by comparison of the predictions with experimental velocity data collected by Particle Image Velocimetry, while the applicability of the model to properly predict the separation process under a wide range of operating conditions is assessed through a strict comparison with permeation experimental data. Then, the effect of numerical issues on the RANS-based predictions of single phase stirred tanks is analysed. The homogenisation process of a scalar tracer is also investigated and simulation results are compared to original passive tracer homogenisation curves determined with Planar Laser Induced Fluorescence. The capability of a CFD approach based on the solution of RANS equations is also investigated for describing the fluid dynamic characteristics of the dispersion of organics in water. Finally, an Eulerian-Eulerian fluid-dynamic model is used to simulate mono-disperse suspensions of Geldart A Group particles fluidized by a Newtonian incompressible fluid as well as binary segregating fluidized beds of particles differing in size and density. The results obtained under a number of different operating conditions are compared with literature experimental data and the effect of numerical uncertainties on axial segregation is also discussed.

Pyrolysis-Gas Chromatography-Mass Spectometry and Chemometric Analysis for the Characterization of Complex Matrices

The present PhD thesis was focused on the development and application of chemical methodology (Py-GC-MS) and data-processing method by multivariate data analysis (chemometrics). The chromatographic and mass spectrometric data obtained with this technique are particularly suitable to be interpreted by chemometric methods such as PCA (Principal Component Analysis) as regards data exploration and SIMCA (Soft Independent Models of Class Analogy) for the classification. As a first approach, some issues related to the field of cultural heritage were discussed with a particular attention to the differentiation of binders used in pictorial field. A marker of egg tempera the phosphoric acid esterified, a pyrolysis product of lecithin, was determined using HMDS (hexamethyldisilazane) rather than the TMAH (tetramethylammonium hydroxide) as a derivatizing reagent. The validity of analytical pyrolysis as tool to characterize and classify different types of bacteria was verified. The FAMEs chromatographic profiles represent an important tool for the bacterial identification. Because of the complexity of the chromatograms, it was possible to characterize the bacteria only according to their genus, while the differentiation at the species level has been achieved by means of chemometric analysis. To perform this study, normalized areas peaks relevant to fatty acids were taken into account. Chemometric methods were applied to experimental datasets. The obtained results demonstrate the effectiveness of analytical pyrolysis and chemometric analysis for the rapid characterization of bacterial species. Application to a samples of bacterial (Pseudomonas Mendocina), fungal (Pleorotus ostreatus) and mixed- biofilms was also performed. A comparison with the chromatographic profiles established the possibility to: • Differentiate the bacterial and fungal biofilms according to the (FAMEs) profile. • Characterize the fungal biofilm by means the typical pattern of pyrolytic fragments derived from saccharides present in the cell wall. • Individuate the markers of bacterial and fungal biofilm in the same mixed-biofilm sample.

Chemical and kinematical properties of Blue Straggler stars in Galactic globular clusters

Blue straggler stars (BSSs) are brighter and bluer (hotter) than the main-sequence (MS) turnoff and they are known to be more massive than MS stars.Two main scenarios for their formation have been proposed:collision-induced stellar mergers (COL-BSSs),or mass-transfer in binary systems (MT-BSSs).Depleted surface abundances of C and O are expected for MT-BSSs,whereas no chemical anomalies are predicted for COL-BSSs.Both MT- and COL-BSSs should rotate fast, but braking mechanisms may intervene with efficiencies and time-scales not well known yet,thus preventing a clear prediction of the expected rotational velocities.Within this context,an extensive survey is ongoing by using the multi-object spectrograph FLAMES@VLT,with the aim to obtain abundance patterns and rotational velocities for representative samples of BSSs in several Galactic GCs.A sub-population of CO-depleted BSSs has been identified in 47 Tuc,with only one fast rotating star detected.For this PhD Thesis work I analyzed FLAMES spectra of more than 130 BSSs in four GCs:M4,NGC 6397,M30 and ω Centauri.This is the largest sample of BSSs spectroscopically investigated so far.Hints of CO depletion have been observed in only 4-5 cases (in M30 and ω Centauri),suggesting either that the majority of BSSs have a collisional origin,or that the CO-depletion is a transient phenomenon.Unfortunately,no conclusions in terms of formation mechanism could be drawn in a large number of cases,because of the effects of radiative levitation. Remarkably,however,this is the first time that evidence of radiative levitation is found in BSSs hotter than 8200 K.Finally, we also discovered the largest fractions of fast rotating BSSs ever observed in any GCs:40% in M4 and 30% in ω Centauri.While not solving the problem of BSS formation,these results provide invaluable information about the BSS physical properties,which is crucial to build realistic models of their evolution.

Analysis and modelling of the performance of technologies for flue gas treatment in Waste-to-Energy processes

Waste management represents an important issue in our society and Waste-to-Energy incineration plants have been playing a significant role in the last decades, showing an increased importance in Europe. One of the main issues posed by waste combustion is the generation of air contaminants. Particular concern is present about acid gases, mainly hydrogen chloride and sulfur oxides, due to their potential impact on the environment and on human health. Therefore, in the present study the main available technological options for flue gas treatment were analyzed, focusing on dry treatment systems, which are increasingly applied in Municipal Solid Wastes (MSW) incinerators. An operational model was proposed to describe and optimize acid gas removal process. It was applied to an existing MSW incineration plant, where acid gases are neutralized in a two-stage dry treatment system. This process is based on the injection of powdered calcium hydroxide and sodium bicarbonate in reactors followed by fabric filters. HCl and SO2 conversions were expressed as a function of reactants flow rates, calculating model parameters from literature and plant data. The implementation in a software for process simulation allowed the identification of optimal operating conditions, taking into account the reactant feed rates, the amount of solid products and the recycle of the sorbent. Alternative configurations of the reference plant were also assessed. The applicability of the operational model was extended developing also a fundamental approach to the issue. A predictive model was developed, describing mass transfer and kinetic phenomena governing the acid gas neutralization with solid sorbents. The rate controlling steps were identified through the reproduction of literature data, allowing the description of acid gas removal in the case study analyzed. A laboratory device was also designed and started up to assess the required model parameters.