This research reports on an experimental and theoretical study of soil heating/air stripping and steam injection/vacuum extraction for remediation of MTBE and Diesel Contaminated Soils. Two one-dimensional mass transfer models were using to simulate the process of remediaction. Contaminant kinds(MTBE and Diesel)¡A contaminant concentration (152~13,912 mg/kg soil)¡Asoil temperature(38~120¢J)¡Asteam injection pressure(0.5~1.0 atm)¡A and the mass of steam used(0.379~0.730 kg/h)were employed as the experimental factors in this study. In soil heating/air stripping study, rising soil temperature will enhance the MTBE removed efficiency¡A it was shown in the concentration of effluent gas. Further, the flow rate at outlet of column was higher than that at inlet of column, it revealed MTBE transfers from liquid phase to gas phase and was removed by gas flow. The concentration of effluent gas curve in low initial MTBE concentration test was similar with high concentration test, but the mechanisms was quiet different¡Ait need advanced adsorption test to find the reasons. In medium initial MTBE concentration test¡Athe concentration of effluent gas curve showed linear shape. When using steam injection/vacuum extraction treating MTBE contaminated soil, it showed 90¢Mefficiency can be reached in one hour. In steam injection/vacuum extraction study, it showed higher initial diesel contaminant concentration¡Ahigher initial concentration of effluent gas. Further, in high initial diesel concentration test (13.912 g diesel/kg soil test and about 5g/ kg soil tests)¡Athe concentration of effluent gas curves had a dominant drop at early time in remediation, it revealed the injection steam flow was quiet large, so diesel didn¡¦t has enough time to transfer to gas phase, that the gas couldn¡¦t been saturation at outlet of column. But in low initial diesel concentration test (about 1 g diesel/kg soil tests), the concentration of effluent gas curves showed the typical NAPL remediation curve. The different with in high and low initial concentrations might from the complex composition of diesel. Because at the early time in remediaction of high initial diesel concentration, the low carbon numbers diesel could abundantly evaporate, it caused the high concentration of effluent gas. With the remediation time go by, the low carbon numbers diesel exhaust. So the main composition of effluent gas transfer to high carbon numbers diesel, that the concentration of effluent gas curve showed the slowly decline. For high initial diesel concentration test (13.912 g diesel/kg soil)¡A the efficiency was the highest (73.7¢M). For low initial diesel concentration test (about 1 g diesel/kg soil), the efficiency was the lost (about 20¢M). Further, the remediation of diesel contaminated soil exited a rapid removed period. Under the conditions of this study, the rapid removed period could remove more than 95¢Mcontaminant of diesel removed at hold remediation time. The experiment results also showed that larger the mass of steam injection, shorter the rapid removed period, and larger the steam injection pressure, longer the rapid removed period. When using soil heating/air stripping treating diesel contaminated soil, the removed efficiency was worse 10-20¢Mthan the same initial diesel contaminated concentration. In simulating remediation process, the prediction with the MTBE measured concentration yielded good agreement in NAPL model. But to get the better fit of diesel in NAPL model, it might set the ¡§could removed mass¡¨ to initial condition of model. In non-NAPL model, MTBE also showed good agreement with model, and the model enabled the prediction of the initial contaminant level in the soil.

Following an introduction, the author describes Texas A&M University and its utilities system. After that, the author presents how to construct simulation models for chilled water and heating hot water distribution systems. The simulation model was used in a $2.3 million Ross Street chilled water pipe replacement project at Texas A&M University. A second project conducted at the University of Texas at San Antonio was used as an example to demonstrate how to identify and design an optimal distribution system by using a simulation model. The author found that the minor losses of these closed loop thermal distribution systems are significantly higher than potable water distribution systems. In the second part of the report, the author presents the latest development of software called the Plant Optimization Program, which can simulate cogeneration plant operation, estimate its operation cost and provide optimized operation suggestions. The author also developed detailed simulation models for a gas turbine and heat recovery steam generator and identified significant potential savings. Finally, the author also used a steam turbine as an example to present a multi-regression method on constructing simulation models by using basic statistics and optimization algorithms. This report presents a survey of the author??s working experience at the Energy Systems Laboratory (ESL) at Texas A&M University during the period of January 2002 through March 2004. The purpose of the above work was to allow the author to become familiar with the practice of engineering. The result is that the author knows how to complete a project from start to finish and understands how both technical and nontechnical aspects of a project need to be considered in order to ensure a quality deliverable and bring a project to successful completion. This report concludes that the objectives of the internship were successfully accomplished and that the requirements for the degree of Degree of Engineering have been satisfied.

The Department of Energy and the Idaho National Laboratory are developing a Next Generation Nuclear Plant (NGNP) to serve as a demonstration of state-of-the-art nuclear technology. The purpose of the demonstration is two fold: 1) efficient low cost energy generation and 2) hydrogen production. Although a next generation plant could be developed as a single-purpose facility, early designs are expected to be dual-purpose. While hydrogen production and advanced energy cycles are still in their early stages of development, research towards coupling a high temperature reactor, electrical generation and hydrogen production is under way. Many aspects of the NGNP must be researched and developed to make recommendations on the final design of the plant. Parameters such as working conditions, cycle components, working fluids, and power conversion unit configurations must be understood. Three configurations of the power conversion unit were modeled using the process code HYSYS; a three-shaft design with 3 turbines and 4 compressors, a combined cycle with a Brayton top cycle and a Rankine bottoming cycle, and a reheated cycle with 3 stages of reheat were investigated. A high temperature steam electrolysis hydrogen production plant was coupled to the reactor and power conversion unit by means of an intermediate heat transport loop. Helium, CO2, and an 80% nitrogen, 20% helium mixture (by weight) were studied to determine the best working fluid in terms cycle efficiency and development cost. In each of these configurations the relative heat exchanger size and turbomachinery work were estimated for the different working fluids. Parametric studies away from the baseline values of the three-shaft and combined cycles were performed to determine the effect of varying conditions in the cycle. Recommendations on the optimal working fluid for each configuration were made. The helium working fluid produced the highest overall plant efficiency for the three-shaft and reheat cycle; however, the nitrogen-helium mixture produced similar efficiency with smaller component sizes. The CO2 working fluid is recommend in the combined cycle configuration.

Die in diesem Bericht vorgestellten Experimente betreffen die Kondensation von Dampf in horizontalen bzw. leicht geneigten Rohren bei hohen auftretenden Temperaturdifferenzen bis zu über 200 K. Weitere Besonderheiten sind die detaillierte Untersuchung des transienten Verhaltens eines nichtkondensierbaren Gases mit einer neuartigen Messtechnik sowie die Ermittlung des Einflusses des Gases auf den Kondensationsvorgang. Beim Experiment wurden schnelle Übergangsvorgänge ausgelöst, indem ein in einer Kühlwanne liegendes, leicht geneigtes Wärmeübertragerrohr plötzlich mit dem Dampfraum eines unter Druck stehenden Kessels verbunden wurde. Dabei wurden im Rohr unterschiedliche Anfangsbedingungen hinsichtlich der Vorlage von nichtkondensierbaren Gasen (in diesem Falle Luft) eingestellt. Es wurden Versuche mit Atmosphärendruck, mit erhöhtem Druck, aber auch mit vorheriger Evakuierung des Versuchsrohrs durchgeführt. Durch eine Instrumentierung mit neuartigen Nadelsonden, die eine Phasendetektion kombiniert mit einer schnellen lokalen Temperaturmessung ermöglichen, konnte die Umverteilung von Dampf, Kondensat und nichtkondensierbarem Gas als Funktion der Zeit beobachtet werden. Damit bieten die erhaltenen Daten die Möglichkeit, insbesondere die in den Thermohydraulikprogrammen vorhandenen Optionen zur Berechnung der Ausbreitung von nichtkondensierbaren Gasen unter transienten Bedingungen zu validieren.

<p>Pyrolysis of biomass consists of heating solid biomass inthe absence of air to produce solid, liquid and gaseous fuels.In the first part of this thesis rapid pyrolysis of wood(birch) and some agricultural residues (olive waste, sugarcanebagasse and wheat straw in untreated and in pelletized form) athigh temperature (800ºC–1000ºC) is studied ina free fall reactor at pilot scale. These conditions are ofinterest for gasification in fluidized beds. Of main interestare the gas and char yields and compositions as well as thereactivity of the produced char in gasification.</p><p>A higher temperature and smaller particles increase theheating rate resulting in a decreased char yield. The crackingof the hydrocarbons with an increase of the hydrogen content inthe gaseous product is favoured by a higher temperature and byusing smaller particles. Wood gives more volatiles and lesschar than straw and olive waste. The higher ash content inagricultural residues favours the charring reactions. Charsfrom olive waste and straw are more reactive in gasificationthan chars from birch because of the higher ash content. Thecomposition of the biomass influences the product distribution.Birch and bagasse give more volatiles and less char thanquebracho, straw and olive waste. Longer residence time inrapid pyrolysis increase the time for contact between tar andchar which makes the char less reactive. The secondary charproduced from tar not only covers the primary char but alsoprobably encapsulates the ash and hinders the catalytic effectof the ash. High char reactivity is favoured by conditionswherethe volatiles are rapidly removed from the particle, i.e.high heating rate, high temperature and small particles.</p><p>The second part of this thesis deals with slow pyrolysis inpresence of steam for preparation of active carbon. Theinfluence of the type of biomass, the type of reactor and thetreatment conditions, mainly temperature and activation time,on the properties and the yield of active carbons are studied.The precursors used in the experiments are birch (wood) anddifferent types of agricultural residues such as sugarcanebagasse, olive waste, miscanthus pellets and straw in untreatedand pelletized form.</p><p>The results from the pyrolysis of biomass in presence ofsteam are compared with those obtained in inert atmosphere ofnitrogen. The steam contributes to the formation of solidresidues with high surface area and good adsorption capacity.The yield of liquid products increases significantly at theexpense of the gaseous and solid products. Large amount ofsteam result in liquid products consisting predominantly ofwater-soluble polar compounds.</p><p>In comparison to the stationary fixed bed reactor, therotary reactor increases the production of energy-rich gases atthe expense of liquid products.</p><p>The raw materials have strong effect on the yields and theproperties of the pyrolysis products. At equal time oftreatment an increase of the temperature results in a decreaseof the yield of solid residue and improvement of the adsorptioncapacity until the highest surface area is reached. Furtherincrease of the temperature decreases the yield of solidproduct without any improvement in the adsorption capacity. Therate of steam flow influences the product distribution. Theyield of liquid products increases while the gas yielddecreases when the steam flow is increased.</p><p><b>Keywords</b>: rapid pyrolysis, pyrolysis, wood, agriculturalresidues,biomass, char, tar, gas, char reactivity,gasification, steam, active carbon</p>

<p>Vehicles powered by fuel cells are from an environmentalaspect superior to the traditional automobile using internalcombustion of gasoline. Power systems which are based upon fuelcell technology require hydrogen for operation. The ideal fuelcell vehicle would operate on pure hydrogen stored on-board.However, storing hydrogen on-board the vehicle is currently notfeasible for technical reasons. The hydrogen can be generatedon-board using a liquid hydrogen carrier such as methanol andgasoline. The objective of the work presented in this thesiswas to develop a catalytic hydrogen generator for automotiveapplications using methanol as the hydrogen carrier.</p><p>The first part of this work gives an introduction to thefield of methanol reforming and the properties of a fuel cellbased power system. Paper I reviews the catalytic materials andprocesses available for producing hydrogen from methanol.</p><p>The second part of this thesis consists of an experimentalinvestigation of the influence of the catalyst composition,materials and process parameters on the activity andselectivity for the production of hydrogen from methanol. InPapers II-IV the influence of the support, carrier andoperational parameters is studied. In Paper V an investigationof the catalytic properties is performed in an attempt tocorrelate material properties with performance of differentcatalysts.</p><p>In the third part of the thesis an investigation isperformed to elucidate whether it is possible to utilizeoxidation of liquid methanol as a heat source for an automotivereformer. In the study which is presented in Paper VI a largeseries of catalytic materials are tested and we were able tominimize the noble metal content making the system more costefficient.</p><p>In the final part of this thesis the reformer prototypedeveloped in the project is evaluated. The reformer which wasconstructed for serving a 5 kWe fuel cell had a highperformance with near 100 % methanol conversion and COconcentrations below 1 vol% in the product stream. The resultsof this part are presented in Paper VII.</p><p><b>Keywords:</b>methanol, fuel cell, vehicle, catalyst,copper, hydrogen, on-board, steam reforming, partial oxidation,combined reforming, oxidative steam reforming, auto-thermalreforming, zinc, zirconium, chromium, aluminium oxide,manganese, characterization, temperature programmed reduction,X-ray diffraction, chemisorption, carbon monoxide, poisoning,reformer.</p>

The focus of this study was to determine the effects of pretreatment of wheat straw by superheated steam (SS) alone or in combination with boiling water (BW) on biomass structure and yields of fermentation products (cell mass and fermentation end-products) by Clostridium thermocellum. Different cultivars of wheat straw were ground to a particle size less than 355 µm, and exposed to the following methods of pretreatment: i) 15 min soaking in 119 °C boiling water under absolute pressure of 193 kPa, followed by processing with SS at atmospheric pressure at different temperatures and retention times; ii) 15 min processing with SS at atmospheric pressure; and iii) 15 min soaking in 119 °C boiling water under absolute pressure of 193 kPa. Processing with SS was conducted at a variety of temperatures in the range of 180-220 °C. The severity of pretreatment was expressed through a treatment severity factor as a measure of harshness of treatment. Pretreatment combinations of boiling water with superheated steam at different retention times inside the SS chamber were also investigated. Wheat straw samples were then used as substrates in fermentation reactions with C. thermocellum. The most noticeable effects on biomass structure and fermentation were observed at the highest severity factor of 6.5, corresponding to 15 min pretreatment with boiling water followed by 15 min treatment with SS at 220˚C. This pretreatment provided the maximum increase in percentage of contribution of amorphous cellulose (% CAC), and the highest fermentation yield in terms of hydrogen, carbon dioxide, and ethanol production. / October 2015

This research project was about the combined organic Rankine cycle which extracted energy from the exhaust gas of a diesel engine. There was a study about significant properties of suitable working fluids. The chosen working fluid, R134a, was used to operate at the dry condition when it exited the steam piston engine. Furthermore, R134a is environmentally friendly with low environmental impact. It was also compatible with sealing materials. There were calibrations for the components of the combined Rankine cycle. The efficiency of the heat exchanger converting exhaust heat from the diesel engine to vaporize R134a was 89%. The average efficiency of the generator was 50%. The hydraulic pump used for the combined Rankine cycle showed a transporting problem, as vapor-lock occurred when the pump ran for about 1 minute. The output of the combined Rankine cycle was normalized to compensate for the parasitic losses of a virtual vane pump used in hydraulic systems for the 6 liter diesel engines. There were three different vane pump widths from different pumps to compare frictional loss. The pump with the smallest vane width presented the least frictional mean effective pressure (fmep) (0.26 kPa) when scaled with the displacement of the GMC Sierra 6 liter diesel engine. The power output of the Rankine cycle was scaled to brake mean effective pressure (bmep) to compare with the frictional mean effective pressure. The maximum bmep was at 0.071 kPa when diesel engine had rotational speed at 2190 RPM. The power outputs of the organic Rankine compensated partially the frictional loss of the vane pumps in the 6 liter diesel engine. By using R134a, the condensing pressure was 0.8 MPa; hence, the power outputs from steam engine were limited. Therefore, refrigerants with lower condensing pressure were needed. There were proposal for improvement of the organic Rankine by substituting R134a by R123 (0.1 MPa), R21 (0.2 MPa), and R114 (0.25 MPa) . / text

Μελετήθηκε η αντίδραση αναμόρφωσης της αιθανόλης με ατμό προς παραγωγή υδρογόνου για την τροφοδοσία στοιχείων καυσίμου. Η παραγωγή υδρογόνου από αιθανόλη, αποτελεί ελκυστική διεργασία τόσο από οικονομική, όσο και από περιβαλλοντική άποψη. Το παραγόμενο υδρογόνο μπορεί να χρησιμοποιηθεί σε στοιχεία καυσίμου ως ρεύμα τροφοδοσίας, όπου οξειδώνεται ηλεκτροχημικά παρουσία αέρα αποδίδοντας ηλεκτρική ενέργεια και θερμότητα με μοναδικό προϊόν καύσης το νερό. Η αντίδραση αναμόρφωσης της αιθανόλης με ατμό είναι θερμοδυναμικά εφικτή και η αύξηση της θερμοκρασίας οδηγεί σε αυξημένη απόδοση σε υδρογόνο. Η συνολική διεργασία παραγωγής υδρογόνου από ατμοαναμόρφωση της αιθανόλης έχει υψηλότερη θεωρητική απόδοση από την ατμοαναμόρφωση του μεθανίου, η οποία είναι η κύρια διεργασία παραγωγής υδρογόνου σήμερα. Οι μελέτες της αντίδρασης αναμόρφωσης της αιθανόλης με ατμό σε καταλύτες κοβαλτίου, ευγενών μετάλλων και νικελίου, έδειξαν ότι οι βέλτιστοι καταλύτες της διεργασίας είναι οι 2% Rh/Al2O3, 5% Ru/Al2O3 και 17% Ni/(La2O3/Al2O3). Οι καταλύτες νικελίου εναποτεθειμένοι σε γ-Al2O3, La2O3 και La2O3/Al2O3 μελετήθηκαν προκειμένου να διερευνηθεί το δίκτυο των αντιδράσεων της αιθανόλης με τον ατμό με χρήση δυναμικών τεχνικών και τεχνικών μόνιμης κατάστασης. Προσεγγίστηκε το δίκτυο αντιδράσεων και τιτλοδοτήθηκε ο εναποτεθειμένος άνθρακας. Αναπτύχθηκαν κεραμικοί και μεταλλικοί θερμικά ολοκληρωμένοι αντιδραστήρες αναμόρφωσης της αιθανόλης με ατμό. Η πραγματοποίηση των αντιδράσεων αναμόρφωσης και καύσης στον κεραμικό αντιδραστήρα οδήγησε σε ικανοποιητική απόδοση. Παράλληλα, διεξήχθησαν πειράματα αναμόρφωσης και καύσης της αιθανόλης στο μεταλλικό αντιδραστήρα με χρήση καταλυτικών κλινών. Τα πειράματα αναμόρφωσης - καύσης απέδειξαν τη λειτουργικότητα του συστήματος, ενώ η σχετική θέση των καταλυτικών κλινών διαπιστώθηκε ότι αποτελεί σημαντικό παράγοντα στην απόδοση του αντιδραστήρα. Τέλος, αναπτύχθηκαν καινοτόμοι μέθοδοι εναπόθεσης καταλυτικών στρωμάτων στις επιφάνειες μεταλλικών σωλήνων. Στην εξωτερική επιφάνεια εναποτέθηκε αλούμινα ως υπόστρωμα για τον καταλύτη αναμόρφωσης με ψεκασμό πλάσματος, ενώ στο εσωτερικό του σωλήνα χρησιμοποιήθηκε μέθοδος εναπόθεσης αλουμινίου για τη δημιουργία του απαιτούμενου συγκολλητικού υποστρώματος. Οι καταλύτες που παρήχθησαν είχαν υψηλή αντοχή σε θερμικούς κύκλους και μεγάλη απόδοση στην αντίδραση αναμόρφωσης. / Production of hydrogen from steam reforming of ethanol is examined for application in fuel cells. The production of hydrogen from ethanol is an attractive operation from economical as well as from environmental point of view. The produced hydrogen can be fed to fuel cells, undergoing oxidation and producing electric energy and heat with the only combustion product being water. Steam reforming of ethanol is thermodynamically feasible and high temperatures result in high efficiency towards hydrogen production. The overall thermal efficiency of the operation is calculated and proven to be higher than the respective value of steam reforming of methane, which is the main commercial hydrogen producing operation. Steam reforming of ethanol was studied with catalysts based on Co, noble metals and Ni. The most promising materials were found to be the 2% Rh/Al2O3, 5% Ru/Al2O3 and 17% Ni/(La2O3/Al2O3) catalysts. The reaction network of steam reforming of ethanol, as well as carbon deposition, over nickel catalysts supported on γ-Αl2O3, La2O3 and La2O3/γ-Al2O3 is investigated employing transient and steady state techniques. Ceramic and metallic heat integrated reactors were developed for the reaction of steam reforming of ethanol. Experiments of coupled combustion – reformation in the ceramic reactor resulted in increased efficiency. In addition, experiments of coupled combustion – reformation were carried out in a metallic reactor by use of catalytic beds. The combustion-reformation experiments proved the effectiveness of the reactor, while the relative position of the two catalytic beds plays important role in the efficiency of the reactor. Finally, novel methods of catalyst deposition over metallic tubes were developed. On the outer surface an intermediate film of aluminum oxide was deposited by means of thermal plasma spraying in order to support the catalyst. Over the inner surface of the tube, aluminum powder was deposited and thermally processed to produce the necessary intermediate substrate. The materials produced by the above mentioned methods, were rigid and stable under extreme thermal-cycles, additionally the reforming material exhibited high efficiency.

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.