Pipeline natural gas is the primary fuel of choice for distributed fuel cell-based applications. The concentration of sulfur in odorized natural gas is about 30 ppm, with acceptable levels being <1 ppm for catalyst stability in such applications. Packed bed technology for desulfurization suffers from several disadvantages including high pressure drop and slow regeneration rates that require large unit sizes. We describe a novel Rapid Temperature Swing Adsorption (RTSA) system utilizing hollow fibers with polymer 'binder', impregnated with high loadings of sulfur selective sorbent 'fillers'. Steam and cooling water can be utilized to thermally swing the sorbent during the regeneration cycles. An impermeable, thin polymer barrier layer on the outside of fiber sorbents allows only thermal interactions with the regeneration media, thereby promoting consistent sorption capacity over repeated cycles. A simplified flow pattern minimizes pressure drop, porous core morphology maximizes sorption efficiencies, while small fiber dimensions allows for rapid thermal cycles.

The entire thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file; a non-technical public abstract appears in the public.pdf file. Title from PDF of title page (University of Missouri--Columbia, viewed on January 26, 2010). Thesis advisor: Dr. Wyatt Thompson. Includes bibliographical references.

Thesis (M.S.) -- Mississippi State University. Department of Chemical Engineering. / Title from title screen. Includes bibliographical references.

Solid oxide fuel cells (SOFCs) are electrochemical energy conversion devices that directly transform the chemical energy of fuel into electrical energy. They generate electricity far more efficiently and with fewer emissions per megawatt-hour compared to any combustion-based power generation system. More remarkably, SOFCs can directly use hydrocarbon fuels without requiring external fuel reforming, employing low-cost Ni catalyst instead of noble-metal catalysts used for low-temperature fuel cells. However, the conventional SOFCs using Ni-based anodes fed with carbon-containing fuels have one pitfall; the carbon produced by hydrocarbon cracking is deposited on the Ni surface, thereby precluding the surface of the Ni-based anodes from being available for further fuel oxidation and consequently impeding SOFC operation. This dissertation focuses on overcoming this critical drawback to allow for the simultaneous use of Ni-based anodes and hydrocarbon fuels. Further work focuses on improving SOFC performance to provide the highest efficiencies possible. To boost the power densities of SOFCs, a novel, facile approach to modify the surface structure of anode powders and thereby enlarge the three-phase boundary (TPB) regions of anodes is presented. One such powder preparation method based on the electric charge variation of oxides depending upon the pH of the solution results in significantly extended TPB regions and thus a remarkable increase in power densities of SOFCs. Another method involves the formation of Ce₁₋[subscript x]Gd₁₋[subscript y]Ni[subscript x+y]VO₄₋[subscript delta] at the phase boundaries between NiO and Ce₀.₈Gd₀.₂O₁.₉ (GDC) by V⁵⁺-incorporation onto NiO surface; this method improves the microstructure of Ni-GDC-based anodes and considerably lowers GDC electrolyte sintering temperature, thereby enhancing the SOFC performance. With these high performance anodes, natural gas-fueled SOFCs are studied through two strategies to alleviate coking: incorporation of catalytic materials onto the Ni surface and the introduction of catalytic functional layers (CFLs) to the outer surface of an anode-supported single cell. Hydrogen tungsten bronze and hydroxylated Sn formed on the Ni surface provide hydroxyls for the deposited solid carbon, removing it from the anodes as CO₂. Moreover, the use of hydrophilic Sn or Sb-incorporated Ni-GDC CFLs prevents the anode from being exposed directly to hydrocarbon fuels and controls the solid carbon accumulation similarly to the former strategy. / text

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Το κύριο θέμα της εργασίας είναι η μοντελοποίηση και η αριθμητική επίλυση μη- μόνιμων και μεταβατικών φαινομένων ροής σε αγωγούς μεταφοράς και δίκτυα διανομής φυσικού αερίου. Το φυσικό αέριο είναι ένα σύγχρονο καύσιμο το οποίο έχει μεγάλες ενεργειακές εφαρμογές καλύπτοντας σε μεγάλο ποσοστό το ενεργειακό ισοζύγιο μιας χώρας. Είναι ένα αέριο και φυσικό καύσιμο για τη μεταφορά του οποίου από τα σημεία άντλησης του, έχει δημιουργηθεί ένα πολύπλοκο διεθνές δίκτυο. Το δίκτυο αυτό συνδέεται με τα εθνικά τοπικά δίκτυα που το διανέμουν στους καταναλωτές. Τα πολύπλοκα αυτά δίκτυα αν και σχεδιάζονται για λειτουργία σε μόνιμη ροή στην πραγματικότητα λειτουργούν υπό μη-μόνιμες συνθήκες. Οι μεταβολές και οι αιχμές στις καταναλώσεις κατά τη διάρκεια μια μέρας, η εκκίνηση ή το κλείσιμο των συμπιεστών ή των σταθμών ρύθμισης της ροής, η αστοχία συσκευών του δικτύου ή και αγωγών είναι μερικοί από τους παράγοντες οι οποίοι προκαλούν σημαντικές μεταβολές στη ροϊκή συμπεριφορά αυτών των συστημάτων. Η υπολογιστική προσομοίωση και η ακριβής πρόβλεψη αυτών των ακραίων ροϊκών καταστάσεων είναι πολύ σημαντική για τη σωστή και οικονομική λειτουργία αυτών των δικτύων. Για την ανάλυση αυτών των φαινομένων η παρούσα εργασία διαρθρώθηκε σε οκτώ κεφάλαια. Στο κεφάλαιο 1 γίνεται ο ορισμός του προβλήματος και η περιγραφή των ροϊκών συνθηκών που διέπουν τα δίκτυα φυσικού αερίου. Στο κεφάλαιο 2 γίνεται εκτεταμένη διερεύνηση στην πρότερη ερευνητική προσπάθεια πάνω σε αυτό το θέμα. Στο κεφάλαιο 3 καταστρώθηκε το μαθηματικό μοντέλο το οποίο προσομοιώνει με επιτυχία τέτοιες ροϊκές καταστάσεις. Εν συνεχεία στα κεφάλαια 4 και 5 αναπτύσσονται αριθμητικές μέθοδοι κατάλληλες για την επίλυση αυτού του μοντέλου. Είναι μέθοδοι κατάλληλες για τον αρχικό σχεδιασμό των αγωγών μεταφοράς (κεφάλαιο 4) όσο και ανώτερης τάξης για πιο ακριβείς υπολογισμούς (κεφάλαιο 5). Στο κεφάλαιο 6 γίνεται η παρουσίαση του αλγόριθμου, για την επέκταση των μεθόδων που αναπτύχθηκαν στα κεφάλαια 4 και 5 για την επίλυση δικτύων πολλών αγωγών και κόμβων. Εν συνεχεία στο κεφάλαιο 7 γίνεται πειραματική διερεύνηση σε εργαστηριακές εγκαταστάσεις αγωγών αερίου που προσομοιώνουν μεταβατικά φαινόμενα ροής. Στο κεφάλαιο 8 γίνεται μια εκτεταμένη επισκόπηση και συγκεντρώνονται τα βασικά συμπεράσματα που προέκυψαν από το σύνολο της ερευνητικής εργασίας. Τέλος γίνονται προτάσεις για την περαιτέρω συνέχιση του ερευνητικού έργου πάνω στο συγκεκριμένο γνωστικό αντικείμενο. / The main subject of the present study is the modelling and the numerical simulation of unsteady and transient flow phenomena in natural gas transmission pipelines and distribution networks. Natural gas is a modern fuel which has serious energy applications covering in big percentage the energy balance of many countries. It is a gas and natural fuel for the transport of which from his points of pumping, has been created a complicated international network. This network is connected with the national local networks that distribute it to local consumers. These complicated networks even if they are designed for operation in steady flow conditions actually work under unsteady conditions. The changes and the peaks of the demand at the duration of a day, the start or the sudden stop of compressors or regulation stations, the failure of network appliances are few of the factors which cause important changes in the flow behaviour of these systems. The simulation and the precise forecast of these extreme flow situations are very important for safe, reliable and economic operation of these networks. For the analysis of these phenomena the present work was structured in eight chapters. In chapter 1 become the definition of problem and the description of flow conditions that rule the natural gas networks. In chapter 2 becomes extensive investigation in the previous research effort on this subject. In chapter 3, the mathematic model which simulates with success such flow situations is defined. Further more in chapters 4 and 5 numerical methods suitable for the numerical solution of this model were developed. These methods are suitable for the initial design of pipelines (chapter 4) as much for more precise calculations (chapter 5). In chapter 6 an improved algorithm for the simulation if complicated networks with many pipes and nodes is presented. The numerical solution of the transient network conditions based on the methodology that developed in previous chapters. In chapter 7 experimental investigations of transient flow phenomena in pipe networks was carried out in laboratory installations. In chapter 8 an extensive review of the basic conclusions was presented, combined with proposals for further research.

The inhibitor and steam injection methods have been examined using a laboratory-prepared methane hydrate bearing sediment. New experimental apparatuses have been designed and constructed. In the case of inhibitor injection, the measurement of gas production vs. time suggested that the inhibitor increased dissociation rate. Core temperature decreased upon the inhibitor injection, in contrast to that in the case of pure water injection. The observed pressure differentials between the inlet and outlet of the core sample suggest that the inhibitor effectively prevented the hydrate reformation within the dissociating core sample. In the case of steam injection coupled with depressurization, it can be seen that the effect of steam (or hot water) injection was clear in the later stage of dissociation, compared with that in the case of depressurization alone. The inner (core) temperature change indicates that the coupling of depressurization and steam injection induces MH dissociation from upstream and downstream to the center of the sample. However, it starts from an upstream region and continues downstream steadily in the case of steam (hot water) injection alone.

A thermodynamic inhibitor - methanol is used for hydrates control both at gas-gathering pipelines and gas conditioning / treatment field plants of Novatek JSC. Due to severe climate conditions and absence of serious infrastructure high operation costs for hydrate control take place. For reducing inhibitor losses some new technological solutions were proposed including recycling and regeneration of saturated methanol. A small module for producing methanol at field conditions was designed. Technological schemes for methanol injection and recirculation are discussed. These technologies reduce methanol losses. Small methanol-producing plant at Yurkharovskoe gas-condensate field (12.5 million ton methanol per year) integrated with field gas treatment plant is presented. The technology includes producing converted gas (syngas) from natural gas, catalytic process for raw methanol synthesis and rectification of raw methanol at final stage. Some particularities of the integrated technology are as follows. Not needs for preliminary purification of required raw materials (natural gas and water). Dried natural gas after conditioning (without any traces of sulfuric compounds) and pure water from simplified water treatment block are used. Rectification of raw methanol is combined with rectification of saturated methanol from gas treatment plant. Economic estimations show that the integrated methanol-producing technology and optimization of methanol circulation in technological processes essentially reduce capital and operational costs for hydrate control at northern gas and gas-condensate fields.

Natural gas feeds often contain contaminants such as CO₂, H₂S, H₂O, and small hydrocarbons. Carbon dioxide is a major contaminant reducing the heating value of the gas and causing pipeline corrosion, so CO₂ level should be lowered to below 2% to meet the United States pipeline specifications. Membrane separation technology can be advantageous over cryogenic distillation and amine adsorption in terms of cost and efficiency. The key hurdle to overcome in polymeric membrane separation technology is improvement in selectivity, productivity, and durability without introducing significant additional cost. The ultimate goal of this study is to analyze effects due to polymerization conditions and imidization methods on properties of 1,3-propanediol monoesterified crosslinkable polyimide (PDMC). Hillock, Omole, Ward, and Ma did work on PDMC synthesis; however, variability of polymer properties remains a challenge that must be overcome for industrial implementation of PDMC material. First, reaction temperature and reaction time of polymerization prior to imidization were considered as key conditions to affect molecular weight, crosslinkability and transport properties of polymer. Batches with controlled reaction temperature and time were prepared, and properties of each dense film were measured and optimized in terms of permeability, selectivity, and plasticization suppression. Second, imidization methods for PDMC were also studied. There are mainly two kinds of Imidization: chemical Imidization and thermal Imidization. Surprisingly, thermally imidized PDMC showed 70% higher permeability than chemically imidized samples with minimal acrifice in selectivity. At high reaction temperature during the thermal imidization, transamidation can occur. It is believed that the transamidation led to more randomized sequence distribution in the thermally imidized samples. We thus hypothesize that the higher permeability of the thermally imidized PDMC results from greater uniformity of the sequence distribution, as compared to the chemically imidized sample that does not experience high temperature during imidization. XRD, DSC, DMA, and permeation instruments checked and supported this hypothesis. FTIR, TGA, and NMR ruled out the possibility of an alternate hypothesis related to side reaction. Finally, effects of aggressive feed conditions on both chemically imidized PDMC and thermally imidized PDMC dense film were examined. The aggressive feed conditions include high CO₂ partial pressure, operating temperatures, and exposure to high feed pressure. Testing aggressive feed conditions for dense film should be pursued before pursuing hollow fiber applications, to decouple effects on the basic material from those on the more complex asymmetric morphology. This study enables understanding of the disparity between various previous researchers’ selectivity and permeability values. The work shows clearly that polymerization conditions and imidization methods must be specified and controlled to achieve consistently desirable polymer properties. In addition, for batch scale-up and development to a hollow fiber, this fundamental study should enable production of high molecular weight PDMC with good fiber spinnability and defect-free structure.

With increasing concerns about the harmful effects of conventional liquid fossil fuel emissions, natural gas has become a very attractive alternative fuel to power prime movers and stationary energy conversion devices. This research studies the injection and ignition numerically for natural gas (mainly methane) as a fuel applied to diesel engine. Natural gas injector and glow plug ignition enhancement are two of the most technical difficulties for direct injection natural gas engine design. This thesis models the natural gas injector, and studies the characteristics of the internal flow in the injector and natural gas jet in the combustion chamber during the injection process. The poppet valve model and pintle valve model are the first reported models to simulate the natural gas injector to improve the traditional velocity and pressure boundary conditions. This thesis also successfully models the glow plug assisted natural gas ignition and combustion processes by developing a glow plug discretized model and a novel virtual gas sub-layer model. Glow plug discretized model can describe the transient heat transfer, and adequately represents the thin layers of heat penetration and the local temperature difference due to the cold gas jet impingement. The virtual gas sub-layer model considers complicated physical processes, such as chemical reaction, heat conduction, and mass diffusion within the virtual sub-layers without significantly increasing computational time and load. KIVA-3V CFD code was chosen to simulate the fluid flow. Since the KIVA-3V is designed specifically for engine research application with conventional liquid fuels, many modifications have been implemented to facilitate this research.