There has always been a desire to develop industrial processes that minimize the resources they use, and the wastes they generate. The problem is when new guidelines are forced upon long established processes, such as solvent based coating operations. This means instead of integrating an emission reduction technology into the original design of the process, it is added on after the fact. This significantly increases the costs associated with treating emissions. In this work the ultimate goal is the design of an “add-on” abatement system to treat emissions from solvent based coating processes with high destruction efficiency, and lower costs than systems in current use. Since emissions from processes that utilize solvent based coatings are primarily comprised of volatile organic compounds (VOCs), the treatment of these compounds will be the focus. VOCs themselves contain a significant amount of energy. If these compounds could be destroyed by simultaneously extracting the energy they release, operational costs could be substantially reduced. This thesis examines the use of model-based design to develop and optimize a VOC abatement technology that uses a Solid Oxide Fuel Cell (SOFC) for energy recovery. The model was built using existing HYSYS unit operation models, and was able to provide a detailed thermodynamic and parametric analysis of this technology. The model was validated by comparison to published literature results and through the use of several Design of Experiment factorial analyses. The model itself illustrated that this type of system could achieve 95% destruction efficiency with performance that was superior to that of Thermal Oxidation, Biological Oxidation, or Adsorption VOC abatement technologies. This was based upon design criteria that included ten year lifecycle costs and operational flexibility, as well as the constraint of meeting (or exceeding) current regulatory thresholds.

The Solid Oxide Fuel Cell (SOFC) is a promising technology for electricity generation. It converts the chemical energy of the fuel gas directly to electricity energy and therefore, very high electrical efficiencies can be achieved. The high operating temperature of the SOFC also provides excellent possibilities for cogeneration applications. In addition to producing power very efficiently, the SOFC has the potential to concentrate CO₂ with a minimum of an overall efficiency loss. Concentration of CO₂ is a desirable feature of a power generation process so that the CO₂ may be subsequently sequestered thus preventing its contribution to global warming. The primary purpose of this research project was to investigate the role of the SOFC technology in power generation processes and explore its potential for CO₂ capture in power plants. <br /><br /> This thesis introduces an AspenPlus^TM SOFC stack model based on the natural gas feed tubular internal reforming SOFC technology. It was developed utilizing existing AspenPlus^TM functions and unit operation models. This SOFC model is able to provide detailed thermodynamic and parametric analysis of the SOFC operation and can easily be extended to study the entire process consisting of the SOFC stack and balance of plant. <br /><br /> Various SOFC-based power generation cycles were studied in this thesis. Various options for concentrating CO₂ in these power generation systems were also investigated and discussed in detail. All the processes simulations were implemented in AspenPlus^TM extending from the developed natural gas feed tubular SOFC stack model. The study shows that the SOFC technology has a promising future not only in generating electricity in high efficiency but also in facilitating CO₂ concentration, but the cost of the proposed processes still need be reduced so SOFCs can become a technical as well as economic feasible solution for power generation.

There has always been a desire to develop industrial processes that minimize the resources they use, and the wastes they generate. The problem is when new guidelines are forced upon long established processes, such as solvent based coating operations. This means instead of integrating an emission reduction technology into the original design of the process, it is added on after the fact. This significantly increases the costs associated with treating emissions. In this work the ultimate goal is the design of an “add-on” abatement system to treat emissions from solvent based coating processes with high destruction efficiency, and lower costs than systems in current use. Since emissions from processes that utilize solvent based coatings are primarily comprised of volatile organic compounds (VOCs), the treatment of these compounds will be the focus. VOCs themselves contain a significant amount of energy. If these compounds could be destroyed by simultaneously extracting the energy they release, operational costs could be substantially reduced. This thesis examines the use of model-based design to develop and optimize a VOC abatement technology that uses a Solid Oxide Fuel Cell (SOFC) for energy recovery. The model was built using existing HYSYS unit operation models, and was able to provide a detailed thermodynamic and parametric analysis of this technology. The model was validated by comparison to published literature results and through the use of several Design of Experiment factorial analyses. The model itself illustrated that this type of system could achieve 95% destruction efficiency with performance that was superior to that of Thermal Oxidation, Biological Oxidation, or Adsorption VOC abatement technologies. This was based upon design criteria that included ten year lifecycle costs and operational flexibility, as well as the constraint of meeting (or exceeding) current regulatory thresholds.

Solid oxide fuel cells (SOFCs) conventionally operate between 800 and 1000°C. The barriers for full-scale commercialization of SOFCs are the high cost and relatively poor long-term stability due to the high temperatures used in current state-of-the-art SOFCs. One solution is to decrease the operating temperature, e.g. to 550-750°C but this requires developing new electrolytes and electrode materials. Also, to increase efficiency and practicality, the anode should be able to internally reform hydrocarbon fuels especially methane because it is the most common hydrocarbon in natural gas. The overall goal of this research is to develop a coke-tolerant Ni1-x-yCuxMgyO-SDC anode for methane fuelled IT-SOFCs. The Ni-Cu-Mg-O-SDC anode has been chosen based on the premises that doped-ceria is suitable for intermediate operating temperatures (550-800°C), Ni is known as an active metal and good electronic conductor, Cu increases resistance to coking, MgO helps prevent agglomeration of Ni during reduction, and finally SDC improves oxide ion transport to the cell at this intermediate temperature range. In this work, these materials were characterized in three primary ways: material physical and chemical properties, methane steam reforming activity and electrochemical performance. Two different methods have been used to add Cu to Ni1-yMgyO: a one-step co-precipitation method and a two-step co-precipitation/impregnation method. For the first method, Ni1-x-yCuxMgyO was synthesized via co-precipitation of Ni, Mg and Cu. In the two-step method, Ni0.9Mg0.1O was first prepared by co-precipitation, followed by addition of copper to Ni0.9Mg0.1O by impregnation. However, co-precipitation of all metal in one step limits the sintering temperature of the anode in the cell fabrication due to the low boiling point of CuO. Therefore, co-precipitation of Cu is not a practical method and only Cu impregnation should be considered for practical SOFC applications. It was found that the addition of Mg (Ni0.9Mg0.1O) lowers the reducibility of NiO. Addition of Cu to Ni0.9Mg0.1O up to 5% shows similar reducibility as Ni0.9Mg0.1O. The reducibility of Ni1-x-yCuxMgyO becomes lower when the Cu content is increased to 10%. Nonetheless, all materials are fully reduced at 750ºC. The XRD patterns of pure NiO, Ni0.9Mg0.1O, and the Cu-containing material when Cu is less than 10 mol% are similar. The lower reducibility of Ni-Mg-O and Ni-Cu-Mg-O compared to NiO indicates that they form a solid solution with NiO as the matrix. Solid oxide fuel cells (SOFCs) conventionally operate between 800 and 1000°C. The barriers for full-scale commercialization of SOFCs are the high cost and relatively poor long-term stability due to the high temperatures used in current state-of-the-art SOFCs. One solution is to decrease the operating temperature, e.g. to 550-750°C but this requires developing new electrolytes and electrode materials. Also, to increase efficiency and practicality, the anode should be able to internally reform hydrocarbon fuels especially methane because it is the most common hydrocarbon in natural gas. The overall goal of this research is to develop a coke-tolerant Ni1-x-yCuxMgyO-SDC anode for methane fuelled IT-SOFCs. The Ni-Cu-Mg-O-SDC anode has been chosen based on the premises that doped-ceria is suitable for intermediate operating temperatures (550-800°C), Ni is known as an active metal and good electronic conductor, Cu increases resistance to coking, MgO helps prevent agglomeration of Ni during reduction, and finally SDC improves oxide ion transport to the cell at this intermediate temperature range. In this work, these materials were characterized in three primary ways: material physical and chemical properties, methane steam reforming activity and electrochemical performance. Two different methods have been used to add Cu to Ni1-yMgyO: a one-step co-precipitation method and a two-step co-precipitation/impregnation method. For the first method, Ni1-x-yCuxMgyO was synthesized via co-precipitation of Ni, Mg and Cu. In the two-step method, Ni0.9Mg0.1O was first prepared by co-precipitation, followed by addition of copper to Ni0.9Mg0.1O by impregnation. However, co-precipitation of all metal in one step limits the sintering temperature of the anode in the cell fabrication due to the low boiling point of CuO. Therefore, co-precipitation of Cu is not a practical method and only Cu impregnation should be considered for practical SOFC applications. It was found that the addition of Mg (Ni0.9Mg0.1O) lowers the reducibility of NiO. Addition of Cu to Ni0.9Mg0.1O up to 5% shows similar reducibility as Ni0.9Mg0.1O. The reducibility of Ni1-x-yCuxMgyO becomes lower when the Cu content is increased to 10%. Nonetheless, all materials are fully reduced at 750ºC. The XRD patterns of pure NiO, Ni0.9Mg0.1O, and the Cu-containing material when Cu is less than 10 mol% are similar. The lower reducibility of Ni-Mg-O and Ni-Cu-Mg-O compared to NiO indicates that they form a solid solution with NiO as the matrix. Addition of Mg also lowers the BET specific surface area from 11.5 m2/g for NiO:SDC to 10.4 m2/g for Ni0.9Mg0.1O. The surface area is further reduced when Cu is added; for example, at 10% Cu, the surface area is 8.2 m2/g. The activity of 50wt% Ni1-x-yCuxMgyO/50wt% SDC samples for methane steam reforming (SMR) and water-gas-shift reaction (WGS) was evaluated in a fully automated catalytic fixed-bed reactor where the exiting gases were analyzed online by a gas chromatograph (GC). The tests were performed at steam-to-carbon ratios (S/C) of 3, 2 and 1, and at temperatures of 750°C and 650°C for twenty hours. Higher methane conversions were obtained at the higher temperature and higher S/C ratio. Higher methane conversion are obtained using NiO:SDC and Ni0.9Mg0.1O:SDC than Ni-Cu-Mg-O. The conversion decreases with increasing Cu content. Over NiO:SDC and Ni0.9Mg0.1O:SDC the methane conversions are the same; for example 85% at 750°C for S/C of 3. At the same conditions, impregnation of 5%Cu and 10%Cu yields lower conversions: 62% and 48%, respectively. The activity for the WGS reaction was determined by mornitoring CO2/(CO+CO2) ratio. As expected because WGS is a moderately exothermic reaction, this ratio decreases when increasing the temperature. However, the CO2/(CO+CO2) ratio increases with higher S/C. The results indicate that adding Mg does not affect the WGS activity of NiO. The WGS activity of Ni0.9Mg0.1O:SDC is higher when Cu is added. The effect of additional Cu is more pronounced at 650ºC. At 750°C, changing the amount of Cu does not change the WGS activity because the WGS reaction rapidly reaches equilibrium at this high temperature. At 750°C for S/C of 1, carbon filaments were found in all samples. At 650ºC, different types of deposited carbon were observed: carbon fibers and thin graphite layers. Spent NiO:SDC had the longest carbon fibers. Addition of Mg significantly reduced the formation of carbon fibers. Impregnating 5% Cu on Ni0.9Mg0.1O:SDC did not change the type of deposited carbon. Monitoring the amount of deposited carbon on Ni0.9Mg0.1O:SDC, 3%Cu and 5%Cu impregnated on Ni0.9Mg0.1O:SDC for S/C of 0 at 750ºC showed that Cu addition deactivated methane cracking causing a reduction in the amount of carbon deposited. Electrochemical performance in the presence of dry and humidified hydrogen was determined at 600, 650, 700 and 750ºC. Electrolyte-supported cells constructed with four different anodes were tested using polarization curve and electrochemical impedance spectra. The four anodes were NiO:SDC, Ni0.9Mg0.1O:SDC, 3%Cu and 5%Cu on Ni0.9Mg0.1O:SDC. Adding Mg improved the maximum power density from 356 mW.cm-2 with NiO:SDC to 369 mW.cm-2 with Ni0.9Mg0.1O:SDC at 750ºC in dry hydrogen. Addition of Cu, on the other hand, lowered the maximum power density to 325 mW.cm-2 with 3%Cu impregnated and to 303 mW.cm-2 with 5% Cu impregnated. The cell with Ni0.9Mg0.1O:SDC was also tested under dry methane. To minimize methane cracking under this extreme condition, a current density of 0.10 A.cm-2 was always drawn when methane was present in the feed. The voltage decreased during the first hour from 0.8 to 0.5 V, then remained stable for 10 hours, and then started to drop again. Many small cracks were observed on the anode after completion of the electrochemical test, but there was no evidence of much carbon being deposited. In addition to dry methane, tests were also carried out, using the same material, with a H2O/CH4 mixture of 1/6 in order to generate a polarization curve at 750°C. Under these conditions, the maximum power density was 226 mW.cm-2. This is lower than the maximum power density obtained with humidified hydrogen, which was 362 mW.cm-2.

A program of study has been established for the quantitative study of electrode reactions in solid oxide fuel cells. The initial focus of the program is the mixed conducting cathode material strontium-doped lanthanum manganate (LSM). A formalism was established treating reactions taking place at the gas-exposed surface of mixed conducting electrodes. This formalism was incorporated into a phenomenological model for oxygen reduction in LSM, which treats the phenomenon of sheet resistance. Patterned electrodes were designed that reduce the dimensionality of the appropriate model, and these electrodes were successfully fabricated using DC sputtering and photolithography. A new model for the bulk defect equilibrium in LSM was proposed and shown to be a better fit to nonstoichiometry data at low temperatures. The fitting was carried out with a particle swarm optimizer and a rigorous method for identification. It was shown that a model for the interface structure between LSM and yttria-stabilized zirconia (YSZ) that assumes free oxygen vacancies in YSZ does not accord with experimental observations. Cluster variation method (CVM) was adapted for analysis of the problem, and a new analytical method combining CVM and electrical contributions to the free energy was proposed.

For the past few decades, Ni-YSZ (yttria-stabilized zirconia) has been the dominate anode material of high temperature (>1000¢J) solid oxide fuel cells (SOFCs). However, the conductivity of Ni/YSZ is not enough when the operation temperature is in the intermediate rage of 500~700¢J. Instead, Ni/CGO is a good candidate as the anode material of intermediate temperature SOFCs (IT-SOFC), due to its enhanced conductivity. This work was aimed at the preparation of Ni/CGO composite anodes using the electrostatic assisted ultrasonic spray pyrolysis (EAUSP) method. By properly adjusting the deposition parameters, highly porous composite films with desired phases and microstructure rendering low electrode impedances were obtained. The results indicated that deposition temperature and the applied voltage dictated the evolution of film morphology and hence the interface impedance between the electrode and the electrolyte. Therefore, the optimum deposition parameters for the best microstructure and hence minimum interface impedance were 12 kV for the applied voltage, 6 : 4 for the Ni-CGO mole ratio, 450¢J for the deposition temperature. The microstructure thus obtained possessed a cauliflower-like structure with high porosity. The resultant interface impedance at 550¢J was 0.09 Ωcm2, lower than that obtained from the conventional anode preparation routes of dip-casting (0.14 Ωcm2) or mechanical mixing (0.12 Ωcm2).

Fuel cells are direct energy conversion devices to generate electricity. They have the lowest emission level of all forms of electricity generation. Fuel cells require no combustion of the fuel. The thermal energy gained from fuel cells may be utilized in micro turbines (gas turbines). In this work, first and second law analyses are performed on a hybrid system consisting of a solid oxide fuel cell (SOFC) combined with a micro turbine to be able to find an optimum point of pressure and corresponding mass ratio to gain maximum work output. Also another system with same equipments only without a gas turbine is investigated to see the effects of gas turbine. The analyses are performed utilizing a code written in MATLAB for each of the equipments. Fuel used is biomass with a certain concentration. To be able to use biomass in a fuel cell-micro turbine hybrid cycle, it is gasified and converted into a certain calorific value gas, with the use of gasifiers. In this study fluidized bed gasifier is utilized since it has the advantage of good mixing and high heat transfer leading to a uniform bed condition. Desulphuration and gas filter units will be implemented in order to clean the producer gas before being used in hybrid system. For a certain percentage of the fuel that may pass through the fuel cell without being used, a combustor is utilized. Optimum point mass and pressure ratios for system are MR = 0.6411 and Pr = 8. Gas turbine supplies more power and higher efficiency to the system. There are different choices for fuel selection in hybrid systems. The reason why biomass is examined among these is that it decreases the depletion of energy carriers and reduces the environmental impact.

Electrodes in a solid oxide fuel cell (SOFC) must possess both adequate porosity and electronic conductivity to perform their functions in the cell. They must be porous to permit rapid mass transport of reactant and product gases and sufficiently conductive to permit efficient electron transfer. However, it is nearly impossible to simultaneously control porosity and conductivity using conventional design and fabrication techniques. In this dissertation, computational design and performance optimization of microarchitectured SOFCs is first investigated in order to achieve higher power density and thus higher efficiency than currently attainable in state-of-the-art SOFCs. This involves a coupled multiphysics simulation of mass transport, electrochemical charge transfer reaction, and current balance as a function of SOFC microarchitecture. Next, the fabrication of microarchitectured SOFCs consistent with the computational designs is addressed based on anode-supported SOFC button cells using the laser ablation technique. Finally, the performance of a fabricated SOFC unit cell is characterized and compared against the performance predicted by the computational model. The results show that the performance of microarchitectured SOFCs was improved against the baseline structure and measured experimental data were well matched to simulation results.

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

Solid oxide fuel cells are electrochemical energy conversion devices utilizing solid electrolytes transporting O2- that typically operate in the 800 - 1000 °C temperature range due to the large activation barrier for ionic transport. Reducing electrolyte thickness or increasing ionic conductivity can enable lower temperature operation for both stationary and portable applications. This thesis is focused on the fabrication of free standing ultrathin (<100 nm) oxide membranes of prototypical O2- conducting electrolytes, namely Y2O3-doped ZrO2 and Gd2O3-doped CeO2. Fabrication of such membranes requires an understanding of thin plate mechanics coupled with controllable thin film deposition processes. Integration of free standing membranes into proof-of-concept fuel cell devices necessitates ideal electrode assemblies as well as creative processing schemes to experimentally test devices in a high temperature dual environment chamber. We present a simple elastic model to determine stable buckling configurations for free standing oxide membranes. This guides the experimental methodology for Y2O3-doped ZrO2 film processing, which enables tunable internal stress in the films. Using these criteria, we fabricate robust Y2O3-doped ZrO2 membranes on Si and composite polymeric substrates by semiconductor and micro-machining processes, respectively. Fuel cell devices integrating these membranes with metallic electrodes are demonstrated to operate in the 300 - 500 °C range, exhibiting record performance at such temperatures. A model combining physical transport of electronic carriers in an insulating film and electrochemical aspects of transport is developed to determine the limits of performance enhancement expected via electrolyte thickness reduction. Free standing oxide heterostructures, i.e. electrolyte membrane and oxide electrodes, are demonstrated. Lastly, using Y2O3-doped ZrO2 and Gd2O3-doped CeO2, novel electrolyte fabrication schemes are explored to develop oxide alloys and nanoscale compositionally graded membranes that are thermomechanically robust and provide added interfacial functionality. The work in this thesis advances experimental state-of-the-art with respect to solid oxide fuel cell operation temperature, provides fundamental boundaries expected for ultrathin electrolytes, develops the ability to integrate highly dissimilar material (such as oxide-polymer) heterostructures, and introduces nanoscale compositionally graded electrolyte membranes that can lead to monolithic materials having multiple functionalities. / Engineering and Applied Sciences