Synthesis of Carbon Nanomaterials through Up-Cycling Agricultural and Municipal Solid Wastes

This work addresses the synthesis of carbon nanomaterials (CNMs) by up-cycling common solid wastes. These feedstocks could supersede the use of costly and often toxic or highly flammable chemicals, such as hydrocarbon gases, carbon monoxide, and hydrogen, which are commonly used as feedstocks in current nanomanufacturing processes for CNMs. Agricultural sugar cane bagasse and corn residues, scrap tire chips, and postconsumer polyethylene (PE) and polyethylene terephthalate (PET) bottle shreddings were either thermally treated by sole pyrolysis or by sequential pyrolysis and partial oxidation. The resulting gaseous carbon-bearing effluents were then channeled into a heated reactor. CNMs, including carbon nanotubes, were catalytically synthesized therein on stainless steel meshes. This work revealed that the structure of the resulting CNMs is determined by the feedstock type, through the disparate mixtures of carbon-bearing gases generated when different feedstocks are pyrolyzed. CNM characterization was conducted by scanning and transmission electron microscopy as well as by Raman spectroscopy and by thermogravimetric analysis. Gas chromatography was used to characterize the gases in the synthesis chamber. This work demonstrated an alternative method for efficient manufacturing of CNMs using both biodegradable and nonbiodegradable agricultural and municipal carbonaceous wastes.

Development of an Autonomous Robot for Gas Storage Spheres Inspection

Inspection for corrosion of gas storage spheres at the welding seam lines must be done periodically. Until now this inspection is being done manually and has a high cost associated to it and a high risk of inspection personel injuries. The Brazilian Petroleum Company, Petrobras, is seeking cost reduction and personel safety by the use of autonomous robot technology. This paper presents the development of a robot capable of autonomously follow a welding line and transporting corrosion measurement sensors. The robot uses a pair of sensors each composed of a laser source and a video camera that allows the estimation of the center of the welding line. The mechanical robot uses four magnetic wheels to adhere to the sphere's surface and was constructed in a way that always three wheels are in contact with the sphere's metallic surface which guarantees enough magnetic atraction to hold the robot in the sphere's surface all the time. Additionally, an independently actuated table for attaching the corrosion inspection sensors was included for small position corrections. Tests were conducted at the laboratory and in a real sphere showing the validity of the proposed approach and implementation.

Properties of gas and dark matter in X-ray galaxy clusters with Sunyaev Zel'dovich measurements

I have studied entropy profiles obtained in a sample of 24 X-ray objects at high redshift retrieved from the Chandra archive. I have discussed the scaling properties of the entropy S, the correlation between metallicity Z and S, the profiles of the temperature of the gas, Tgas, and performed a comparison between the dark matter 'temperature' and Tgas in order to constrain the non-gravitational processes which affect the thermal history of the gas. Furthermore I have studied the scaling relations between the X-ray quantities and Sunyaev Zel'dovich measurements. I have observed that X-ray laws are steeper than the relations predicted from the adiabatic model. These deviations from expectations based on self-similarity are usually interpreted in terms of feedback processes leading to non-gravitational gas heating, and suggesting a scenario in which the ICM at higher redshift has lower both X-ray luminosity and pressure in the central regions than the expectations from self-similar model. I have also investigated a Bayesian X-ray and Sunyaev Zel'dovich analysis, which allows to study the external regions of the clusters well beyond the volumes resolved with X-ray observations (1/3-1/2 of the virial radius), to measure the deprojected physical cluster properties, like temperature, density, entropy, gas mass and total mass up to the virial radius.

Structural changes and dynamic behaviour of vanadium oxide-based catalysts for gas-phase selective oxidations

Selective oxidation is one of the simplest functionalization methods and essentially all monomers used in manufacturing artificial fibers and plastics are obtained by catalytic oxidation processes. Formally, oxidation is considered as an increase in the oxidation number of the carbon atoms, then reactions such as dehydrogenation, ammoxidation, cyclization or chlorination are all oxidation reactions. In this field, most of processes for the synthesis of important chemicals used vanadium oxide-based catalysts. These catalytic systems are used either in the form of multicomponent mixed oxides and oxysalts, e.g., in the oxidation of n-butane (V/P/O) and of benzene (supported V/Mo/O) to maleic anhydride, or in the form of supported metal oxide, e.g., in the manufacture of phthalic anhydride by o-xylene oxidation, of sulphuric acid by oxidation of SO2, in the reduction of NOx with ammonia and in the ammoxidation of alkyl aromatics. In addition, supported vanadia catalysts have also been investigated for the oxidative dehydrogenation of alkanes to olefins , oxidation of pentane to maleic anhydride and the selective oxidation of methanol to formaldehyde or methyl formate [1]. During my PhD I focused my work on two gas phase selective oxidation reactions. The work was done at the Department of Industrial Chemistry and Materials (University of Bologna) in collaboration with Polynt SpA. Polynt is a leader company in the development, production and marketing of catalysts for gas-phase oxidation. In particular, I studied the catalytic system for n-butane oxidation to maleic anhydride (fluid bed technology) and for o-xylene oxidation to phthalic anhydride. Both reactions are catalyzed by systems based on vanadium, but catalysts are completely different. Part A is dedicated to the study of V/P/O catalyst for n-butane selective oxidation, while in the Part B the results of an investigation on TiO2-supported V2O5, catalyst for o-xylene oxidation are showed. In Part A, a general introduction about the importance of maleic anhydride, its uses, the industrial processes and the catalytic system are reported. The reaction is the only industrial direct oxidation of paraffins to a chemical intermediate. It is produced by n-butane oxidation either using fixed bed and fluid bed technology; in both cases the catalyst is the vanadyl pyrophosphate (VPP). Notwithstanding the good performances, the yield value didn’t exceed 60% and the system is continuously studied to improve activity and selectivity. The main open problem is the understanding of the real active phase working under reaction conditions. Several articles deal with the role of different crystalline and/or amorphous vanadium/phosphorous (VPO) compounds. In all cases, bulk VPP is assumed to constitute the core of the active phase, while two different hypotheses have been formulated concerning the catalytic surface. In one case the development of surface amorphous layers that play a direct role in the reaction is described, in the second case specific planes of crystalline VPP are assumed to contribute to the reaction pattern, and the redox process occurs reversibly between VPP and VOPO4. Both hypotheses are supported also by in-situ characterization techniques, but the experiments were performed with different catalysts and probably under slightly different working conditions. Due to complexity of the system, these differences could be the cause of the contradictions present in literature. Supposing that a key role could be played by P/V ratio, I prepared, characterized and tested two samples with different P/V ratio. Transformation occurring on catalytic surfaces under different conditions of temperature and gas-phase composition were studied by means of in-situ Raman spectroscopy, trying to investigate the changes that VPP undergoes during reaction. The goal is to understand which kind of compound constituting the catalyst surface is the most active and selective for butane oxidation reaction, and also which features the catalyst should possess to ensure the development of this surface (e.g. catalyst composition). On the basis of results from this study, it could be possible to project a new catalyst more active and selective with respect to the present ones. In fact, the second topic investigated is the possibility to reproduce the surface active layer of VPP onto a support. In general, supportation is a way to improve mechanical features of the catalysts and to overcome problems such as possible development of local hot spot temperatures, which could cause a decrease of selectivity at high conversion, and high costs of catalyst. In literature it is possible to find different works dealing with the development of supported catalysts, but in general intrinsic characteristics of VPP are worsened due to the chemical interaction between active phase and support. Moreover all these works deal with the supportation of VPP; on the contrary, my work is an attempt to build-up a V/P/O active layer on the surface of a zirconia support by thermal treatment of a precursor obtained by impregnation of a V5+ salt and of H3PO4. In-situ Raman analysis during the thermal treatment, as well as reactivity tests are used to investigate the parameters that may influence the generation of the active phase. Part B is devoted to the study of o-xylene oxidation of phthalic anhydride; industrially, the reaction is carried out in gas-phase using as catalysts a supported system formed by V2O5 on TiO2. The V/Ti/O system is quite complex; different vanadium species could be present on the titania surface, as a function of the vanadium content and of the titania surface area: (i) V species which is chemically bound to the support via oxo bridges (isolated V in octahedral or tetrahedral coordination, depending on the hydration degree), (ii) a polymeric species spread over titania, and (iii) bulk vanadium oxide, either amorphous or crystalline. The different species could have different catalytic properties therefore changing the relative amount of V species can be a way to optimize the catalytic performances of the system. For this reason, samples containing increasing amount of vanadium were prepared and tested in the oxidation of o-xylene, with the aim of find a correlations between V/Ti/O catalytic activity and the amount of the different vanadium species. The second part deals with the role of a gas-phase promoter. Catalytic surface can change under working conditions; the high temperatures and a different gas-phase composition could have an effect also on the formation of different V species. Furthermore, in the industrial practice, the vanadium oxide-based catalysts need the addition of gas-phase promoters in the feed stream, that although do not have a direct role in the reaction stoichiometry, when present leads to considerable improvement of catalytic performance. Starting point of my investigation is the possibility that steam, a component always present in oxidation reactions environment, could cause changes in the nature of catalytic surface under reaction conditions. For this reason, the dynamic phenomena occurring at the surface of a 7wt% V2O5 on TiO2 catalyst in the presence of steam is investigated by means of Raman spectroscopy. Moreover a correlation between the amount of the different vanadium species and catalytic performances have been searched. Finally, the role of dopants has been studied. The industrial V/Ti/O system contains several dopants; the nature and the relative amount of promoters may vary depending on catalyst supplier and on the technology employed for the process, either a single-bed or a multi-layer catalytic fixed-bed. Promoters have a quite remarkable effect on both activity and selectivity to phthalic anhydride. Their role is crucial, and the proper control of the relative amount of each component is fundamental for the process performance. Furthermore, it can not be excluded that the same promoter may play different role depending on reaction conditions (T, composition of gas phase..). The reaction network of phthalic anhydride formation is very complex and includes several parallel and consecutive reactions; for this reason a proper understanding of the role of each dopant cannot be separated from the analysis of the reaction scheme. One of the most important promoters at industrial level, which is always present in the catalytic formulations is Cs. It is known that Cs plays an important role on selectivity to phthalic anhydride, but the reasons of this phenomenon are not really clear. Therefore the effect of Cs on the reaction scheme has been investigated at two different temperature with the aim of evidencing in which step of the reaction network this promoter plays its role.

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.

Modeling, design and experimental characterization of Micro-Electro-Mechanical-Systems for gas chromatographic applications

Design parameters, process flows, electro-thermal-fluidic simulations and experimental characterizations of Micro-Electro-Mechanical-Systems (MEMS) suited for gas-chromatographic (GC) applications are presented and thoroughly described in this thesis, whose topic belongs to the research activities the Institute for Microelectronics and Microsystems (IMM)-Bologna is involved since several years, i.e. the development of micro-systems for chemical analysis, based on silicon micro-machining techniques and able to perform analysis of complex gaseous mixtures, especially in the field of environmental monitoring. In this regard, attention has been focused on the development of micro-fabricated devices to be employed in a portable mini-GC system for the analysis of aromatic Volatile Organic Compounds (VOC) like Benzene, Toluene, Ethyl-benzene and Xylene (BTEX), i.e. chemical compounds which can significantly affect environment and human health because of their demonstrated carcinogenicity (benzene) or toxicity (toluene, xylene) even at parts per billion (ppb) concentrations. The most significant results achieved through the laboratory functional characterization of the mini-GC system have been reported, together with in-field analysis results carried out in a station of the Bologna air monitoring network and compared with those provided by a commercial GC system. The development of more advanced prototypes of micro-fabricated devices specifically suited for FAST-GC have been also presented (silicon capillary columns, Ultra-Low-Power (ULP) Metal OXide (MOX) sensor, Thermal Conductivity Detector (TCD)), together with the technological processes for their fabrication. The experimentally demonstrated very high sensitivity of ULP-MOX sensors to VOCs, coupled with the extremely low power consumption, makes the developed ULP-MOX sensor the most performing metal oxide sensor reported up to now in literature, while preliminary test results proved that the developed silicon capillary columns are capable of performances comparable to those of the best fused silica capillary columns. Finally, the development and the validation of a coupled electro-thermal Finite Element Model suited for both steady-state and transient analysis of the micro-devices has been described, and subsequently implemented with a fluidic part to investigate devices behaviour in presence of a gas flowing with certain volumetric flow rates.

The bursting behavior of gas slugs: laboratory and analytical insights into Strombolian volcanic eruptions.

The aim of this thesis is to study how explosive behavior and geophysical signals in a volcanic conduit are related to the development of overpressure in slug-driven eruptions. A first suite of laboratory experiments of gas slugs ascending in analogue conduits was performed. Slugs ascended into a range of analogue liquids and conduit diameters to allow proper scaling to the natural volcanoes. The geometrical variation of the slug in response to the explored variables was parameterised. Volume of gas slug and rheology of the liquid phase revealed the key parameters in controlling slug overpressure at bursting. Founded on these results, a theoretical model to calculate burst overpressure for slug-driven eruptions was developed. The dimensionless approach adopted allowed to apply the model to predict bursting pressure of slugs at Stromboli. Comparison of predicted values with measured data from Stromboli volcano showed that the model can explain the entire spectrum of observed eruptive styles at Stromboli – from low-energy puffing, through normal Strombolian eruptions, up to paroxysmal explosions – as manifestations of a single underlying physical process. Finally, another suite of laboratory experiments was performed to observe oscillatory pressure and forces variations generated during the expansion and bursting of gas slugs ascending in a conduit. Two end-member boundary conditions were imposed at the base of the pipe, simulating slug ascent in closed base (zero magma flux) and open base (constant flux) conduit. At the top of the pipe, a range of boundary conditions that are relevant at a volcanic vent were imposed, going from open to plugged vent. The results obtained illustrate that a change in boundary conditions in the conduit concur to affect the dynamic of slug expansion and burst: an upward flux at the base of the conduit attenuates the magnitude of the pressure transients, while a rheological stiffening in the top-most region of conduit changes dramatically the magnitude of the observed pressure transients, favoring a sudden, and more energetic pressure release into the overlying atmosphere. Finally, a discussion on the implication of changing boundary on the oscillatory processes generated at the volcanic scale is also given.

Origin of cold gas and dust in massive elliptical galaxies

The recent availability of multi-wavelength data revealed the presence of large reservoirs of warm and cold gas and dust in the innermost regions of the majority of massive elliptical galaxies. To prove an internal origin of cold and warm gas, the investigation of the spatially distributed cooling process which occurs because of non-linear density perturbations and subsequent thermal instabilities is of crucial importance. The first goal of this work of thesis is to investigate the internal origin of warm and cold phases. Numerical simulations are the powerful tool of analysis. The way in which a spatially distributed cooling process originates has been examined and the off-centre amount of gas mass which cools when different and differently characterized AGN feedback mechanisms operate has been quantified. This thesis demonstrates that the aforementioned non-linear density perturbations originate and develop from AGN feedback mechanisms in a natural fashion. An internal origin of the warm phase from the once hot gas is shown to be possible. Computed velocity dispersions of ionized and hot gas are similar. The cold gas as well can originate from the cooling process: indeed, it has been estimated that the surrounding stellar radiation, which is one of the most feasible sources of ionization of the warm gas, does not manage to keep ionized all the gas at 10^4 K. Therefore, cooled gas does undergo a further cooling which can lead the warm phase to lower temperatures. However, the gas which has cooled from the hot phase is expected to be dustless; nonetheless, a large fraction of early type galaxies has detectable dust in their cores, both concentrated in filamentary and disky structures and spread over larger regions. Therefore a regularly rotating disk of cold and dusty gas has been included in the simulations. A new quantitative investigation of the spatially distributed cooling process has therefore been essential: the contribution of the included amount of dust which is embedded in the cold gas does have a role in promoting and enhancing the cooling. The fate of dust which was at first embedded in cold gas has been investigated. The role of AGN feedback mechanisms in dragging (if able) cold and dusty gas from the core of massive ellipticals up to large radii has been studied.

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.

From large polycyclic aromatic hydrocarbons to extended aromate-rich networks

The common ground of this study is the development of novel synthetic strategies to extended one-, two- and three-dimensional aromate-rich systems for which a number of applications are envisaged. rnThe point of departure is the synthesis and characterization of highly symmetric macrocyclic PAHs (polycyclic aromatic hydrocarbons) for which various aspects of supramolecular chemistry will be investigated. The versatility of the Yamamoto macrocyclization will be demonstrated on the basis of a set of cyclic trimers that exhibit a rich supramolecular chemistry. 1,10-phenanthroline, triphenylene and ortho-terphenyl building blocks have been successfully assembled to the corresponding macrocycles following the newly developed synthetic route. Scanning-tunneling microscopy (STM) and two-dimensional wide-angle X-ray scattering (2D-WAXS) were used to study the two- and three-dimensional self-assembly, respectively.rnSecondly, the development of chemical approaches to highly shape-anisotropic graphene nanoribbons (GNRs) and related nanographene molecules shall be discussed. Aryl-aryl coupling was used for the bottom-up fabrication of dendronized monomers, polymers and model compounds. Subsequently, these structures were converted into the final graphene material using oxidative (Scholl-type) cyclodehydrogenation. The GNRs thus obtained are characterized by an unprecedented length and lateral extension. The relevance of structural tailoring in the field of well-defined graphene materials is discussed in detail as only the chemical approach provides full geometry control. rnLastly, novel pathways towards the synthesis of extended three-dimensional networks that are dominated by nitrogen-rich motifs will be presented. If porous, these materials hold a great potential in the fields of gas and energy storage as well as for applications in catalysis. Hence, poly(aminal) networks based on melamine as crosslinking unit were synthesized and characterized with respect to the applications mentioned above. As set of conjugated poly(azomethine) networks was investigated regarding their use as a novel class of organic semiconductors for photocatalytic water splitting. The network structures described in this chapter can also be subjected to a controlled pyrolysis yielding mesoporous, nitrogen-rich carbon materials that were evaluated as active component for supercapacitors.rn

Design of an indirectly fired gas turbine integrated with an organic rankine cycle unit for combined heat and power production

In the last years, the European countries have paid increasing attention to renewable sources and greenhouse emissions. The Council of the European Union and the European Parliament have established ambitious targets for the next years. In this scenario, biomass plays a prominent role since its life cycle produces a zero net carbon dioxide emission. Additionally, biomass can ensure plant operation continuity thanks to its availability and storage ability. Several conventional systems running on biomass are available at the moment. Most of them are performant either in the large-scale or in the small power range. The absence of an efficient system on the small-middle scale inspired this thesis project. The object is an innovative plant based on a wet indirectly fired gas turbine (WIFGT) integrated with an organic Rankine cycle (ORC) unit for combined heat and power production. The WIFGT is a performant system in the small-middle power range; the ORC cycle is capable of giving value to low-temperature heat sources. Their integration is investigated in this thesis with the aim of carrying out a preliminary design of the components. The targeted plant output is around 200 kW in order not to need a wide cultivation area and to avoid biomass shipping. Existing in-house simulation tools are used: They are adapted to this purpose. Firstly the WIFGT + ORC model is built; Zero-dimensional models of heat exchangers, compressor, turbines, furnace, dryer and pump are used. Different fluids are selected but toluene and benzene turn out to be the most suitable. In the indirectly fired gas turbine a pressure ratio around 4 leads to the highest efficiency. From the thermodynamic analysis the system shows an electric efficiency of 38%, outdoing other conventional plants in the same power range. The combined plant is designed to recover thermal energy: Water is used as coolant in the condenser. It is heated from 60°C up to 90°C, ensuring the possibility of space heating. Mono-dimensional models are used to design the heat exchange equipment. Different types of heat exchangers are chosen depending on the working temperature. A finned-plate heat exchanger is selected for the WIFGT heat transfer equipment due to the high temperature, oxidizing and corrosive environment. A once-through boiler with finned tubes is chosen to vaporize the organic fluid in the ORC. A plate heat exchanger is chosen for the condenser and recuperator. A quasi-monodimensional model for single-stage axial turbine is implemented to design both the WIFGT and the ORC turbine. The system simulation after the components design shows an electric efficiency around 34% with a decrease by 10% compared to the zero-dimensional analysis. The work exhibits the system potentiality compared to the existing plants from both technical and economic point of view.

A gas ion source for radiocarbon measurements at 200 kV

The novel tabletop miniaturized radiocarbon dating system (MICADAS) at ETH Zurich features a hybrid Cs sputter negative ion source for the measurement of solid graphite and gaseous CO2 samples. The source produces stable currents of up to 6 mu A C- out of gaseous samples with an efficiency of 3-6%. A gas feeding system has been set up that enables constant dosing of CO2 into the Cs sputter ion source and ensures stable measuring conditions. The system is based on a syringe in which CO2 gas is mixed with He and then pressed continuously into the ion source at a constant flow rate. Minimized volumes allow feeding samples of 3-30 mu g carbon quantitatively into the ion source. In order to test the performance of the system, several standards and blanks have successfully been measured. The ratios of C-14/C-12 could be repeated within statistical errors to better than 1.0% and the C-13/C-12 ratios to better than 0.2%. The blank was < 1 pMC.

Analysis of spring break-up and its effects on a biomass feedstock supply chain in northern Michigan

Demand for bio-fuels is expected to increase, due to rising prices of fossil fuels and concerns over greenhouse gas emissions and energy security. The overall cost of biomass energy generation is primarily related to biomass harvesting activity, transportation, and storage. With a commercial-scale cellulosic ethanol processing facility in Kinross Township of Chippewa County, Michigan about to be built, models including a simulation model and an optimization model have been developed to provide decision support for the facility. Both models track cost, emissions and energy consumption. While the optimization model provides guidance for a long-term strategic plan, the simulation model aims to present detailed output for specified operational scenarios over an annual period. Most importantly, the simulation model considers the uncertainty of spring break-up timing, i.e., seasonal road restrictions. Spring break-up timing is important because it will impact the feasibility of harvesting activity and the time duration of transportation restrictions, which significantly changes the availability of feedstock for the processing facility. This thesis focuses on the statistical model of spring break-up used in the simulation model. Spring break-up timing depends on various factors, including temperature, road conditions and soil type, as well as individual decision making processes at the county level. The spring break-up model, based on the historical spring break-up data from 27 counties over the period of 2002-2010, starts by specifying the probability distribution of a particular county’s spring break-up start day and end day, and then relates the spring break-up timing of the other counties in the harvesting zone to the first county. In order to estimate the dependence relationship between counties, regression analyses, including standard linear regression and reduced major axis regression, are conducted. Using realizations (scenarios) of spring break-up generated by the statistical spring breakup model, the simulation model is able to probabilistically evaluate different harvesting and transportation plans to help the bio-fuel facility select the most effective strategy. For early spring break-up, which usually indicates a longer than average break-up period, more log storage is required, total cost increases, and the probability of plant closure increases. The risk of plant closure may be partially offset through increased use of rail transportation, which is not subject to spring break-up restrictions. However, rail availability and rail yard storage may then become limiting factors in the supply chain. Rail use will impact total cost, energy consumption, system-wide CO2 emissions, and the reliability of providing feedstock to the bio-fuel processing facility.

The Domestic Natural Gas Shortage in China

This thesis analyzes the domestic shortage in the Chinese natural gas market. Both the domestic supply and demand of natural gas are growing fast in China. However, the supply cannot catch up with the demand. Under the present pricing mechanism, the Chinese natural gas market cannot get the equilibrium by itself. Expensive imports are inadequate to fill the increasing gap between the domestic demand and supply. Therefore, the shortage problem occurs. Since the energy gap can result in the arrested development of economics, the shortage problem need to be solved. This thesis gives three suggestions to solve the problem: the use of Unconventional Gas, Natural Gas Storage and Pricing Reform.

Assessments and Computational Simulations in Support of a Time-Varying Mass Flow Rate Measurement Technique for Pulsatile Gas Flow

This thesis covers the correction, and verification, development, and implementation of a computational fluid dynamics (CFD) model for an orifice plate meter. Past results were corrected and further expanded on with compressibility effects of acoustic waves being taken into account. One dynamic pressure difference transducer measures the time-varying differential pressure across the orifice meter. A dynamic absolute pressure measurement is also taken at the inlet of the orifice meter, along with a suitable temperature measurement of the mean flow gas. Together these three measurements allow for an incompressible CFD simulation (using a well-tested and robust model) for the cross-section independent time-varying mass flow rate through the orifice meter. The mean value of this incompressible mass flow rate is then corrected to match the mean of the measured flow rate( obtained from a Coriolis meter located up stream of the orifice meter). Even with the mean and compressibility corrections, significant differences in the measured mass flow rates at two orifice meters in a common flow stream were observed. This means that the compressibility effects associated with pulsatile gas flows is significant in the measurement of the time-varying mass flow rate. Future work (with the approach and initial runs covered here) will provide an indirect verification of the reported mass flow rate measurements.