Post-combustion CO2 adsorption on activated carbons with different textural properties

Fixed bed CO2 adsorption tests were carried out in model flue-gas streams onto two commercial activated carbons, namely Filtrasorb 400 and Nuchar RGC30, at 303 K, 323 K and 353 K. Thermodynamic adsorption results highlighted that the presence of a narrower micropore size distribution with a prevailing contribution of very small pore diameters, observed for Filtrasorb 400, is a key factor in determining a higher CO2 capture capacity, mostly at low temperature. These experimental evidences were also corroborated by the higher value of the isosteric heat derived for Filtrasorb 400, testifying stronger interactions with CO2 molecules with respect to Nuchar RGC30. Dynamic adsorption results on the investigated sorbents highlighted the important role played by both a greater contribution of mesopores and the presence of wider micropores for Nuchar RGC30 in establishing faster capture kinetics with respect to Filtrasorb 400, in particular at 303 K. Furthermore, the modeling analysis of 15% CO2 breakthrough curves allowed identifying intraparticle diffusion as the rate-determining step of the process.

Active oxygen by Ce–Pr mixed oxide nanoparticles outperform diesel soot combustion Pt catalysts

A Ce0.5Pr0.5O2 mixed oxide has been prepared with the highest surface area and smallest particle size ever reported (125 m2/g and 7 nm, respectively), also being the most active diesel soot combustion catalyst ever tested under realistic conditions if catalysts forming highly volatile species are ruled out. This Ce–Pr mixed oxide is even more active than a reference platinum-based commercial catalyst. This study provides an example of the efficient participation of oxygen species released by a ceria catalyst in a heterogeneous catalysis reaction where both the catalyst and one of the reactants (soot) are solids. It has been concluded that both the ceria-based catalyst composition (nature and amount of dopant) and the particle size play key roles in the combustion of soot through the active oxygen-based mechanism. The composition determines the production of active oxygen and the particle size the transfer of such active oxygen species from catalyst to soot.

Effect of the CeZrNd mixed oxide synthesis method in the catalytic combustion of soot

Ce0.64Zr0.27Nd0.09Oδ mixed oxides have been prepared by three different methods (nitrates calcination, coprecipitation and microemulsion), characterized by N2 adsorption, XRD, H2-TPR, Raman spectroscopy and XPS, and tested for soot combustion in NOx/O2. The catalyst prepared by microemulsion method is the most active one, which is related to its high surface area (147 m2/g) and low crystallite size (6 nm), and the lowest activity was obtained with the catalyst prepared by coprecipitation (74 m2/g; 9 nm). The catalyst prepared by nitrates precursors calcination is slightly less active to that prepared by microemulsion, but the synthesis procedure is very straightforward and surfactants or other chemicals are not required, being very convenient for scaling up and practical utilization. The high activity of the catalyst prepared by nitrates calcination can be attributed to the better introduction of Nd cations into the parent ceria framework than on catalysts prepared by coprecipitation and microemulsion, which promotes the creation of more oxygen vacancies.

Opportunities for ceria-based mixed oxides versus commercial platinum-based catalysts in the soot combustion reaction. Mechanistic implications

The aim of this paper is to study the activities of ceria–zirconia and copper/ceria–zirconia catalysts, comparing with a commercial platinum/alumina catalyst, for soot combustion reaction under different gas atmospheres and loose contact mode (simulating diesel exhaust conditions), in order to analyse the kinetics and to deduce mechanistic implications. Activity tests were performed under isothermal and TPR conditions. The NO oxidation to NO2 was studied as well. It was checked that mass transfer limitations were not influencing the rate measurements. Global activation energies for the catalysed and non-catalysed soot combustion were calculated and properly discussed. The results reveal that ceria-based catalysts greatly enhance their activities under NOx/O2 between 425 °C and 450 °C, due to the “active oxygen”-assisted soot combustion. Remarkably, copper/ceria–zirconia shows a slightly higher soot combustion rate than the Pt-based catalyst (under NOx/O2, at 450 °C).

Mixing, Chemical Reactions, and Combustion in Supersonic Flows

Experiments were conducted at the GALCIT supersonic shear-layer facility to investigate aspects of reacting transverse jets in supersonic crossflow using chemiluminescence and schlieren image-correlation velocimetry. In particular, experiments were designed to examine mixing-delay length dependencies on jet-fluid molar mass, jet diameter, and jet inclination.

The experimental results show that mixing-delay length depends on jet Reynolds number, when appropriately normalized, up to a jet Reynolds number of 500,000. Jet inclination increases the mixing-delay length, but causes less disturbance to the crossflow when compared to normal jet injection. This can be explained, in part, in terms of a control-volume analysis that relates jet inclination to flow conditions downstream of injection.

In the second part of this thesis, a combustion-modeling framework is proposed and developed that is tailored to large-eddy simulations of turbulent combustion in high-speed flows. Scaling arguments place supersonic hydrocarbon combustion in a regime of autoignition-dominated distributed reaction zones (DRZ). The proposed evolution-variable manifold (EVM) framework incorporates an ignition-delay data-driven induction model with a post-ignition manifold that uses a Lagrangian convected 'balloon' reactor model for chemistry tabulation. A large-eddy simulation incorporating the EVM framework captures several important reacting-flow features of a transverse hydrogen jet in heated-air crossflow experiment.

MODELING OF TRANSFER PATH FOR DETERMINATION OF COMBUSTION AND NOISE METRICS ON DIESEL ENGINES

Determination of combustion metrics for a diesel engine has the potential of providing feedback for closed-loop combustion phasing control to meet current and upcoming emission and fuel consumption regulations. This thesis focused on the estimation of combustion metrics including start of combustion (SOC), crank angle location of 50% cumulative heat release (CA50), peak pressure crank angle location (PPCL), and peak pressure amplitude (PPA), peak apparent heat release rate crank angle location (PACL), mean absolute pressure error (MAPE), and peak apparent heat release rate amplitude (PAA). In-cylinder pressure has been used in the laboratory as the primary mechanism for characterization of combustion rates and more recently in-cylinder pressure has been used in series production vehicles for feedback control. However, the intrusive measurement with the in-cylinder pressure sensor is expensive and requires special mounting process and engine structure modification. As an alternative method, this work investigated block mounted accelerometers to estimate combustion metrics in a 9L I6 diesel engine. So the transfer path between the accelerometer signal and the in-cylinder pressure signal needs to be modeled. Depending on the transfer path, the in-cylinder pressure signal and the combustion metrics can be accurately estimated - recovered from accelerometer signals. The method and applicability for determining the transfer path is critical in utilizing an accelerometer(s) for feedback. Single-input single-output (SISO) frequency response function (FRF) is the most common transfer path model; however, it is shown here to have low robustness for varying engine operating conditions. This thesis examines mechanisms to improve the robustness of FRF for combustion metrics estimation. First, an adaptation process based on the particle swarm optimization algorithm was developed and added to the single-input single-output model. Second, a multiple-input single-output (MISO) FRF model coupled with principal component analysis and an offset compensation process was investigated and applied. Improvement of the FRF robustness was achieved based on these two approaches. Furthermore a neural network as a nonlinear model of the transfer path between the accelerometer signal and the apparent heat release rate was also investigated. Transfer path between the acoustical emissions and the in-cylinder pressure signal was also investigated in this dissertation on a high pressure common rail (HPCR) 1.9L TDI diesel engine. The acoustical emissions are an important factor in the powertrain development process. In this part of the research a transfer path was developed between the two and then used to predict the engine noise level with the measured in-cylinder pressure as the input. Three methods for transfer path modeling were applied and the method based on the cepstral smoothing technique led to the most accurate results with averaged estimation errors of 2 dBA and a root mean square error of 1.5dBA. Finally, a linear model for engine noise level estimation was proposed with the in-cylinder pressure signal and the engine speed as components.

Emergence and fate of siloxanes in waste streams: Release mechanisms, partitioning and persistence in three environmental compartments

Siloxanes are widely used in personal care and industrial products due to their low surface tension, thermal stability, antimicrobial and hydrophobic properties, among other characteristics. Volatile methyl siloxanes (VMS) have been detected both in landfill gas and biogas from anaerobic digesters at wastewater treatment plants. As a result, they are released to gas phase during waste decomposition and wastewater treatment. During transformation processes of digester or landfill gas to energy, siloxanes are converted to silicon oxides, leaving abrasive deposits on engine components. These deposits cause increased maintenance costs and in some cases complete engine overhauls become necessary. ^ The objectives of this study were to compare the VMS types and levels present in biogas generated in the anaerobic digesters and landfills and evaluate the energetics of siloxane transformations under anaerobic conditions. Siloxane emissions, resulting from disposal of silicone-based materials, are expected to increase by 29% within the next 10 years. Estimated concentrations and the risk factors of exposure to siloxanes were evaluated based on the initial concentrations, partitioning characteristics and persistence. It was determined that D4 has the highest risk factor associated to bioaccumulation in liquid and solid phase, whereas D5 was highest in gas phase. Additionally, as siloxanes are combusted, the particle size range causes them to be potentially hazardous to human health. When inhaled, they may affix onto the alveoli of the lungs and may lead to development of silicosis. Siloxane-based COD-loading was evaluated and determined to be an insignificant factor concerning COD limits in wastewater. ^ Removal of siloxane compounds is recommended prior to land application of biosolids or combustion of biogas. A comparison of estimated costs was made between maintenance practices for removal of siloxane deposits and installation/operation of fixed-bed carbon absorption systems. In the majority of cases, the installation of fixed-bed adsorption systems would not be a feasible option for the sole purpose of siloxane removal. However they may be utilized to remove additional compounds simultaneously.^

Dynamical modeling of biogas production supported by an experimental anaerobic digestion process

This paper presents the development of a combined experimental and numerical approach to study the anaerobic digestion of both the wastes produced in a biorefinery using yeast for biodiesel production and the wastes generated in the preceding microbial biomass production. The experimental results show that it is possible to valorise through anaerobic digestion all the tested residues. In the implementation of the numerical model for anaerobic digestion, a procedure for the identification of its parameters needs to be developed. A hybrid search Genetic Algorithm was used, followed by a direct search method. In order to test the procedure for estimation of parameters, first noise-free data was considered and a critical analysis of the results obtain so far was undertaken. As a demonstration of its application, the procedure was applied to experimental data.

Development and Validation of a Model-Based Combustion Controller for Water Injection Management

This manuscript reports the overall development of a Ph.D. research project during the “Mechanics and advanced engineering sciences” course at the Department of Industrial Engineering of the University of Bologna. The project is focused on the development of a combustion control system for an innovative Spark Ignited engine layout. In details, the controller is oriented to manage a prototypal engine equipped with a Port Water Injection system. The water injection technology allows an increment of combustion efficiency due to the knock mitigation effect that permits to keep the combustion phasing closer to the optimal position with respect to the traditional layout. At the beginning of the project, the effects and the possible benefits achievable by water injection have been investigated by a focused experimental campaign. Then the data obtained by combustion analysis have been processed to design a control-oriented combustion model. The model identifies the correlation between Spark Advance, combustion phasing and injected water mass, and two different strategies are presented, both based on an analytic and semi-empirical approach and therefore compatible with a real-time application. The model has been implemented in a combustion controller that manages water injection to reach the best achievable combustion efficiency while keeping knock levels under a pre-established threshold. Three different versions of the algorithm are described in detail. This controller has been designed and pre-calibrated in a software-in-the-loop environment and later an experimental validation has been performed with a rapid control prototyping approach to highlight the performance of the system on real set-up. To further make the strategy implementable on an onboard application, an estimation algorithm of combustion phasing, necessary for the controller, has been developed during the last phase of the PhD Course, based on accelerometric signals.

Development and testing of innovative methodologies for modelling and control of normal and knocking combustion and implementation of novel rapid prototyping solutions

The thesis work deals with topics that led to the development of innovative control-oriented models and control algorithms for modern gasoline engines. Knock in boosted spark ignition engines is the widest topic discussed in this document because it remains one of the most limiting factors for maximizing combustion efficiency in this kind of engine. First chapter is thus focused on knock and a wide literature review is proposed to summarize the preliminary knowledge that even represents the background and the reference for discussed activities. Most relevant results achieved during PhD course in the field of knock modelling and control are then presented, describing every control-oriented model that led to the development of an adaptive model-based combustion control system. The complete controller has been developed in the context of the collaboration with Ferrari GT and it allowed to completely redefine the knock intensity evaluation as well as the combustion phase control. The second chapter is focused on the activity related to a prototyping Port Water Injection system that has been developed and tested on a turbocharged spark ignition engine, within the collaboration with Magneti Marelli. Such system and the effects of injected water on the combustion process were then modeled in a 1-D simulation environment (GT Power). Third chapter shows the development and validation of a control-oriented model for the real-time calculation of exhaust gas temperature that represents another important limitation to the performance increase in modern boosted engines. Indeed, modelling of exhaust gas temperature and thermocouple behavior are themes that play a key role in the optimization of combustion and catalyst efficiency.

Investigation of innovative combustion systems for reduced fuel consumption and increased specific power production

This work resumes a wide variety of research activities carried out with the main objective of increasing the efficiency and reducing the fuel consumption of Gasoline Direct Injection engines, especially under high loads. For this purpose, two main innovative technologies have been studied, Water Injection and Low-Pressure Exhaust Gas Recirculation, which help to reduce the temperature of the gases inside the combustion chamber and thus mitigate knock, being this one of the main limiting factors for the efficiency of modern downsized engines that operate at high specific power. A prototypal Port Water Injection system was developed and extensive experimental work has been carried out, initially to identify the benefits and limitations of this technology. This led to the subsequent development and testing of a combustion controller, which has been implemented on a Rapid Control Prototyping environment, capable of managing water injection to achieve knock mitigation and a more efficient combustion phase. Regarding Low-Pressure Exhaust Gas Recirculation, a commercial engine that was already equipped with this technology was used to carry out experimental work in a similar fashion to that of water injection. Another prototypal water injection system has been mounted to this second engine, to be able to test both technologies, at first separately to compare them on equal conditions, and secondly together in the search of a possible synergy. Additionally, based on experimental data from several engines that have been tested during this study, including both GDI and GCI engines, a real-time model (or virtual sensor) for the estimation of the maximum in-cylinder pressure has been developed and validated. This parameter is of vital importance to determine the speed at which damage occurs on the engine components, and therefore to extract the maximum performance without inducing permanent damages.

Development of a thermochemical/biological process to convert waste biomass into new resources

The increasing attention to environmental issues of recent times encourages us to find new methods for the production of energy from renewable sources, and to improve existing ones, increasing their energy yield. Most of the waste and agricultural residues, with a high content of lignin and non-hydrolysable polymers, cannot be effectively transformed into biofuels with existing technology. The purpose of the study was to develop a new thermochemical/ biological process (named Py-AD) for the valorization of scarcely biodegradable substances. A complete continuous prototype was design built and run for 1 year. This consists into a slow pyrolysis system coupled with two sequential digesters and showed to produce a clean pyrobiogas (a biogas with significant amount of C2-C3 hydrocarbons and residual CO/H2), biochar and bio-oil. Py-AD yielded 31.7% w/w biochar 32.5% w/w oil and 24.8% w/w pyrobiogas. The oil condensate obtained was fractionated in its aqueous and organic fraction (87% and 13% respectively). Subsequently, the anaerobic digestion of aqueous fraction was tested in a UASB reactor, for 180 days, in increasing organic loading rate (OLR). The maximum convertible concentration without undergoing instability phenomena and with complete degradation of pyrogenic chemicals was 1.25 gCOD L digester-1 d-1. The final yield of biomethane was equal to 40% of the theoretical yield and with a noticeable additional production equal to 20% of volatile fatty acids. The final results confirm that anaerobic digestion can be used as a useful tool for cleaning of slow pyrolysis products (both gas and condensable fraction) and the obtaining of relatively clean pyrobiogas that could be directly used in internal combustion engine.

Analisi del ciclo di vita di un processo industriale innovativo per la produzione di syngas da biogas

Una delle metodologie che negli ultimi tempi viene utilizzata più frequentemente per la valutazione ambientale di prodotti, processi e servizi è detta LCA, Life Cycle Assessment: essa valuta l’impatto ambientale associato ad un processo o ad un prodotto considerando tutto il suo ciclo di vita. Nel presente elaborato di tesi la metodologia è applicata ad un processo chimico industriale in fase di studio su scala di laboratorio presso il Dipartimento di Chimica Industriale dell’Università di Bologna, che prevede la sintesi di syngas a partire da biogas tramite le reazioni di dry reformng (DR) e steam refroming (SR). Tale processo è stato studiato poiché a livello teorico presenta i seguenti vantaggi: l’utilizzo di biogas come materia prima (derivante dalla digestione anaerobica dei rifiuti), lo sfruttamento dell’anidride carbonica presente nel biogas e l’utilizzo di un solo reattore anziché due. Il processo viene analizzato attraverso due diversi confronti: in primo luogo è comparato con processi con tecnologie differenti che producono il medesimo prodotto (syngas); in secondo luogo è paragonato a processi che impiegano la stessa materia prima (biogas), ottenendo prodotti differenti. Nel primo confronto i processi confrontati sono uno scenario di Autothermal reforming (ATR) e uno scenario che prevede DR e SR in due reattori separati; nel secondo confronto i prodotti che si ottengono sono: energia termica ed elettrica attraverso un sistema CHP, biometano con un sistema di upgrading del biogas, energia e biometano (CHP + upgrading) ed infine metanolo prodotto da syngas (generato dal processo studiato). Per il primo confronto è risultato che lo scenario che porta ad un minore impatto ambientale è il processo studiato dall'università di Bologna, seguito dallo Scenario con DR e SR in reattori separati ed infine dal processo di ATR. Per quanto concerne il secondo confronto lo scenario migliore è quello che produce biometano, mentre quello che produce metanolo è al terzo posto.

Catalizzatori strutturati per valorizzazione di biogas a syngas

Il presente lavoro di tesi è stato realizzato all’interno del programma Overseas, per cui è stata realizzata una collaborazione tra il Dipartimento di Chimica Industriale “Toso Montanari” (Chimind) dell’Università di Bologna e l’Instituto de Investigaciones en Catálisis y Petroquímica (Incape) dell’Università del Litoral di Santa Fe. Nel lavoro viene riportato lo studio di catalizzatori strutturati a base di Rh-CeO2, Rh/ZnAl2O4 e Rh/Al2O3, supportati su schiume NiCrAl, dei quali verrà valutata l’attività catalitica rispetto alla reazione di dry reforming del metano. La preparazione dei catalizzatori strutturati è stata eseguita utilizzando due diverse tecniche, dip-coating e elettrodeposizione. L’obbiettivo del lavoro è stato valutare il metodo di sintesi più adatto al supporto utilizzato. Le prove catalitiche sono state eseguite a 750°C, P atmosferica, rapporto CH4:CO2 1:1 con tempo di reazione di 2h. Dai risultati ottenuti dalle prove effettuate i catalizzatori sono risultati attivi, in particolare il supporto di CeO2 risulta già attivo per la reazione, soprattutto per quanto riguarda la conversione del metano. Tuttavia, la presenza di Rh migliora la conversione dei reagenti ed il rapporto H2/CO. La presenza di Zn, sul catalizzatore Rh/ZnAl2O4 va a peggiorare le prestazioni catalitiche, abbassando in particolare la conversione della CO2. In generale i catalizzatori ricoperti mediante elettrodeposizione mostrano attività catalitica più elevata. Dallo studio sulla superficie del catalizzatore Rh-CeO2 ridotto tramite XPS è emersa la presenza di Rh(0). Tuttavia, indifferentemente dalla tecnica di sintesi utilizzata, dall’ossido del supporto e dalla quantità di fase attiva, tutti i catalizzatori hanno sviluppato massicce quantità di carbonio filamentoso di dimensioni nanometriche, che hanno portato alla disgregazione e alla perdita di parte del coating.

Studio del reforming combinato del biogas su nanoparticelle bimetalliche supportate

The study of the combined reforming (CR) process to produce synthesis gas (CO + H2) feeding Clean Biogas (CB, biogas in which the main pollutants have been removed) has been performed on Ni-based bimetallic catalysts promoted by small amounts of Rh or Cu, prepared by incipient wetness impregnation or coprecipitation of different precursors on mixed oxides Mg/Al/O obtained by calcination of hydrotalcite-type (Ht) coprecipitates. It has been observed as the formation of bimetallic particles promoted the catalytic activity and limited the deactivation phenomena, allowing to operate at lower temperature and feeding lower amounts of steam. By this way, it was possible to define the best promoter, to tune its amount and the formation of the bimetallic nanoparticles. Finally, it has been simulated the scale-up of the CR process to industrial level, evaluating the feasibility and economic degree by comparison with the industrially exploited Autothermal reforming (ATR) process, evidencing the possible scalability and the advantages at environmental and energetic level in comparison to the current reforming processes.