30 research outputs found

    Numerical simulations of ion transport membrane oxy-fuel reactors for CO₂ capture applications

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    Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Mechanical Engineering, 2013.Cataloged from PDF version of thesis.Includes bibliographical references (p. 185-190).Numerical simulations were performed to investigate the key features of oxygen permeation and hydrocarbon conversion in ion transport membrane (ITM) reactors. ITM reactors have been suggested as a novel technology to enable air separation and fuel conversion to take place simultaneously in a single unit. Possessing the mixed ionic and electronic conductivity, perovskite membranes or ion transport membranes permeate selectively oxygen ions from the air (feed) side to the sweep gas or reactive gas (permeate) side of the membrane, driven by the oxygen chemical potential gradient across the membrane at elevated temperature. When a fuel such as methane is introduced into the permeate side as a sweep gas, hydrocarbon oxidation reactions occur by reacting the fuel with the permeated oxygen. The fuel can be partially reformed, completely oxidized or converted to produce higher hydrocarbons. To utilize this technology more effectively, it is necessary to develop a better understanding of oxygen transport and hydrocarbon conversion in the immediate vicinity of the membrane or on its surface. In this thesis, a planar, finite-gap stagnation flow configuration was used to model and examine these processes. A spatially resolved physical model was formulated and used to parameterize an oxygen permeation flux expression in terms of the oxygen concentrations at the membrane surface given data on the bulk concentration. The parameterization of the permeation flux expression is necessary for cases when mass transfer limitations on the permeate side are important and for reactive flow modeling. At the conditions relevant for ITM reactor operation, the local thermodynamic state should be taken into account when the oxygen permeation rate is examined, which has been neglected. To elucidate this, the dependency of oxygen transport and fuel conversion on the geometry and flow parameters including the membrane temperature, air and sweep gas flow rates, oxygen concentration in the feed air and fuel concentration in the sweep gas was discussed. The reaction environment on the sweep side of an ITM was characterized. The spatially resolved physical model was used to predict homogeneous-phase fuel conversion processes and to capture the important features (e.g., the location, temperature, thickness and structure of a flame) of laminar oxy-fuel diffusion flames stabilized on the sweep side. The nature of oxygen permeation does not enable pre-mixing of fuel and oxidizer (i.e., sweep gas and permeated oxygen), establishing non-premixed flames. In oxy-fuel combustion applications, the sweep side is fuel-diluted with CO₂ or/and H₂O, and the entire unit is preheated to achieve a high oxygen permeation flux. This study focused on the flame structure under these conditions and specifically on the chemical effect of CO₂ dilution. The interactions between oxygen permeation and homogeneous-phase fuel oxidation reactions on the sweep side of an ITM were examined. Within ITM reactors, the oxidizer flow rate, i.e., the oxygen permeation flux, is not a pre-determined quantity, since it depends on the oxygen partial pressures on the air and sweep sides and the membrane temperature. Instead, it is influenced by the hydrocarbon oxidation reactions that are also dependent on the oxygen permeation rate, the initial conditions of the sweep gas, i.e., the fuel concentration, flow rate and temperature, and the diluent. A parametric study with respect to key operating conditions, which include the fuel concentration in the sweep gas, its flow rate and temperature and the geometry, was conducted to investigate their interactions. The catalytic kinetics of heterogeneous oxygen surface exchange and fuel oxidation for a perovskite membrane in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface was investigated. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. However, a description of their catalytic surface reactions is still required. The kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions were inferred, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. It is shown that the local thermodynamic state at the membrane surface should be accounted for when constructing and examining membrane permeation and heterogeneous chemistry. The significance of modeling both homogeneous and heterogeneous chemistry and their coupling when examining the results was discussed.by Jongsup Hong.Ph.D

    Techno-economic analysis of pressurized oxy-fuel combustion power cycle for CO₂ capture

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    Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Mechanical Engineering, 2009.Includes bibliographical references (leaves 124-127).Growing concerns over greenhouse gas emissions have driven extensive research into new power generation cycles that enable carbon dioxide capture and sequestration. In this regard, oxy-fuel combustion is a promising new technology for capturing carbon dioxide in power generation systems utilizing hydrocarbon fuels. Combustion of a fuel in an environment of oxygen and recycled combustion gases yields flue gases consisting predominantly of carbon dioxide and water. To capture carbon dioxide, water is condensed, and carbon dioxide is purified and compressed beyond its supercritical state. However, conventional atmospheric oxy-fuel combustion systems require substantial parasitic energy in the compression step within the air separation unit, a flue gas recirculation system and carbon dioxide purification and compression units. Moreover, a large amount of flue gas latent enthalpy, which has high water concentration, is wasted. Both lower the overall cycle efficiency. Alternatively, pressurized oxy-fuel combustion power cycles have been investigated. In this thesis, the analysis of an oxy-fuel combustion power cycle that utilizes a pressurized coal combustor is reported. We show that this approach is beneficial in terms of larger flue gas thermal energy recovery and smaller parasitic power requirements. In addition, we find the pressure dependence of the system performance to determine the optimal combustor operating pressure for this cycle.(cont.) We calculate the energy requirements of each unit and determine the pressure dependence of the water-condensing thermal energy recovery and its relation to the gross power output. Furthermore, a sensitivity analysis is conducted on important operating parameters including combustor temperature, Heat Recovery Steam Generator outlet temperature, oxygen purity and oxygen concentration in the flue gases. A cost analysis of the proposed system is also conducted so as to provide preliminary cost estimates.by Jongsup Hong.S.M

    Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

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    The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry.King Abdullah University of Science and Technology (KAUST) (grant number KSU-I1-010-01)King Fahd University of Petroleum and Minerals (Center for Clean Water and Clean Energy at MIT and KFUPM

    Laminar oxy-fuel diffusion flame supported by an oxygen-permeable-ion-transport membrane

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    A numerical model with detailed gas-phase chemistry and transport was used to predict homogeneous fuel conversion processes and to capture the important features (e.g., the location, temperature, thickness and structure of a flame) of laminar oxy-fuel diffusion flames stabilized on the sweep side of an oxygen permeable ion transport membrane (ITM). We assume that the membrane surface is not catalytic to hydrocarbon or syngas oxidation. It has been demonstrated that an ITM can be used for hydrocarbon conversion with enhanced reaction selectivity such as oxy-fuel combustion for carbon capture technologies and syngas production. Within an ITM unit, the oxidizer flow rate, i.e., the oxygen permeation flux, is not a pre-determined quantity, since it depends on the oxygen partial pressures on the feed and sweep sides and the membrane temperature. Instead, it is influenced by the oxidation reactions that are also dependent on the oxygen permeation rate, the initial conditions of the sweep gas, i.e., the fuel concentration, flow rate and temperature, and the diluent. In oxy-fuel combustion applications, the sweep side is fuel-diluted with CO[subscript 2], and the entire unit is preheated to achieve a high oxygen permeation flux. This study focuses on the flame structure under these conditions and specifically on the chemical effect of CO[subscript 2] dilution. Results show that, when the fuel diluent is CO[subscript 2], a diffusion flame with a lower temperature and a larger thickness is established in the vicinity of the membrane, in comparison with the case in which N[subscript 2] is used as a diluent. Enhanced OH-driven reactions and suppressed H radical chemistry result in the formation of products with larger CO and H[subscript 2]O and smaller H[subscript 2] concentrations. Moreover, radical concentrations are reduced due to the high CO[subscript 2] fraction in the sweep gas. CO[subscript 2] dilution reduces CH[subscript 3] formation and slows down the formation of soot precursors, C[subscript 2]H[subscript 2] and C[subscript 2]H[subscript 4]. The flame location impacts the species diffusion and heat transfer from the reaction zone towards the membrane, which affects the oxygen permeation rate and the flame temperature.King Abdullah University of Science and Technology (KAUST) (grant number KSU-I1-010-01)Center for Clean Water and Clean Energy at MIT and KFUPM (Project Number R12-CE-08)King Fahd University of Petroleum and Mineral

    Interactions between oxygen permeation and homogeneous-phase fuel conversion on the sweep side of an ion transport membrane

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    The interactions between oxygen permeation and homogeneous fuel oxidation reactions on the sweep side of an ion transport membrane (ITM) are examined using a comprehensive model, which couples the dependency of the oxygen permeation rate on the membrane surface conditions and detailed chemistry and transport in the vicinity of the membrane. We assume that the membrane surface is not catalytic to hydrocarbon or syngas oxidation. Results show that increasing the sweep gas inlet temperature and fuel concentration enhances oxygen permeation substantially. This is accomplished through promoting oxidation reactions (oxygen consumption) and the transport of the products and reaction heat towards the membrane, which lowers the oxygen concentration and increases the gas temperature near the membrane. Faster reactions at higher fuel concentration and higher inlet gas temperature support substantial fuel conversion and lead to a higher oxygen permeation flux without the contribution of surface catalytic activity. Beyond a certain maximum in the fuel concentration, extensive heat loss to the membrane (and feed side) reduces the oxidation kinetic rates and limits oxygen permeation as the reaction front reaches the membrane. The sweep gas flow rate and channel height have moderate impacts on oxygen permeation and fuel conversion due to the residence time requirements for the chemical reactions and the location of the reaction zone relative to the membrane surface.Center for Clean Water and Clean Energy at MIT and KFUPMKing Abdullah University of Science and Technology (Grant KUK-I1-010-01

    Numerical simulation of ion transport membrane reactors: Oxygen permeation and transport and fuel conversion

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    Ion transport membrane (ITM) based reactors have been suggested as a novel technology for several applications including fuel reforming and oxy-fuel combustion, which integrates air separation and fuel conversion while reducing complexity and the associated energy penalty. To utilize this technology more effectively, it is necessary to develop a better understanding of the fundamental processes of oxygen transport and fuel conversion in the immediate vicinity of the membrane. In this paper, a numerical model that spatially resolves the gas flow, transport and reactions is presented. The model incorporates detailed gas phase chemistry and transport. The model is used to express the oxygen permeation flux in terms of the oxygen concentrations at the membrane surface given data on the bulk concentration, which is necessary for cases when mass transfer limitations on the permeate side are important and for reactive flow modeling. The simulation results show the dependence of oxygen transport and fuel conversion on the geometry and flow parameters including the membrane temperature, feed and sweep gas flow, oxygen concentration in the feed and fuel concentration in the sweep gas.King Fahd University of Petroleum and MineralsKing Abdullah University of Science and Technology (KAUST) (grant number KSU-I1-010-01

    Operating pressure dependence of the pressurized oxy-fuel combustion power cycle

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    Oxy-fuel combustion technology is an attractive option for capturing carbon dioxide (CO2) in power generation systems utilizing hydrocarbon fuels. However, conventional atmospheric oxy-fuel combustion systems require substantial parasitic energy in the compression step within the air separation unit (ASU), the flue gas recirculation system and the carbon dioxide purification and compression unit (CPU). Moreover, a large amount of flue gas latent enthalpy, which has high water concentration, is wasted. Both lower the overall cycle efficiency. Pressurized oxy-fuel combustion power cycles have been investigated as alternatives. Our previous study showed the importance of operating pressure for these cycles. In this paper, as the extended work of our previous study, we perform a pressure sensitivity analysis to determine the optimal combustor operating pressure for the pressurized oxy-fuel combustion power cycle. We calculate the energy requirements of the ASU and the CPU, which vary in opposite directions as the combustor operating pressure is increased. We also determine the pressure dependence of the water-condensing thermal energy recovery and its relation to the gross power output. The paper presents a detailed study on the variation of the thermal energy recovery rate, the overall compression power demand, the gross power output and the overall net efficiency.Aspen Technology, Inc.Thermoflow Inc.ENEL (Firm

    Analysis of oxy-fuel combustion power cycle utilizing a pressurized coal combustor

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    Growing concerns over greenhouse gas emissions have driven extensive research into new power generation cycles that enable carbon dioxide capture and sequestration. In this regard, oxy-fuel combustion is a promising new technology in which fuels are burned in an environment of oxygen and recycled combustion gases. In this paper, an oxy-fuel combustion power cycle that utilizes a pressurized coal combustor is analyzed. We show that this approach recovers more thermal energy from the flue gases because the elevated flue gas pressure raises the dew point and the available latent enthalpy in the flue gases. The high-pressure water-condensing flue gas thermal energy recovery system reduces steam bleeding which is typically used in conventional steam cycles and enables the cycle to achieve higher efficiency. The pressurized combustion process provides the purification and compression unit with a concentrated carbon dioxide stream. For the purpose of our analysis, a flue gas purification and compression process including de-SO[subscript x], de-NO[subscript x], and low temperature flash unit is examined. We compare a case in which the combustor operates at 1.1 bars with a base case in which the combustor operates at 10 bars. Results show nearly 3% point increase in the net efficiency for the latter case.Aspen Technology, Inc.Thermoflow Inc

    Analysis of Degradation Phenomena of SOC Stacks Operated in Reversible SOFC/SOEC Cycling Mode

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    The reversible SOFC/SOEC operation of solid oxide cell (SOC) stacks promise high overall electricity-to-electricity round-trip efficiencies and low storage costs. Although in recent years the degradation rates of SOFC and SOEC stacks in single mode long-term operation have been steadily decreased, the understanding of degradation mechanisms during reversible SOFC/SOEC operation remains an important and challenging issue. Therefore, the Korean-German project "Solid Oxide Reversible Fuel Cell / Electrolysis Stack" (SORFES) focuses on the development of the core component technology for a 1 kW reversible SOC stack in order to enhance the hydrogen productivity and its utilization. The primary goals are the improvement of the performance and the durability of SOC stacks during reversible SOFC/SOEC operation and the quantification and the qualification of the relevant degradation effects. The paper presents and compares the performance and degradation results of two SOC stacks which were operated mainly in galvanostatic steady-state SOFC mode and in reversible SOFC/SOEC cycling mode. The stacks with ASC cells of Elcogen (Estonia) were fabricated by the industrial project partner E&KOA (Daejeon, Korea). The reversible cycles consist of day/night switches between SOEC and SOFC, thus covering intermittent renewable electricity supply (e.g. of photovoltaics). The stacks were electrochemically characterized by jV-curves and electrochemical impedance spectroscopy (EIS). The first SOC stack with 10 cells was operated during 500 h in SOFC at constant current density followed by 500 h of operation under reversible SOFC/SOEC cycling conditions. The initial performance and homogeneity along the repeat units (RUs) of the stack in SOFC and SOEC at the beginning of operation are presented. In order to better understand the stack degradation, the results between reversible SOFC/SOEC cycling and galvanostatic steady-state SOFC operation are compared. The degradation, especially of the OCV, the power density and the area specific resistance (ASR) of the different RUs are analyzed and discussed. Moreover, the progression of the individual resistances, specifically of the ohmic-, the electrode polarization- and the gas concentration resistances of the RUs are evaluated and presented. The influence of temperature gradients and thermo-mechanical stresses during reversible exothermic (SOFC) and endothermic (SOEC) cycling are outlined and discussed. The results of the first stack test were used to improve the stack components and setup, e.g. the contacting and sealing of the cells in the stack and the protective coating on the interconnects. Moreover, the operating conditions during reversible SOFC/SOEC cycling were optimized. The second improved stack with 6 RUs was operated for 2800 h in galvanostatic steady-state SOFC mode and reversible SOFC/SOEC cycling mode with low degradation rate. The results of the present paper help to understand and improve the long-term stability of SOC stacks during reversible SOFC/SOEC cycling, thus promoting the SOC technology for renewable energy storage applications

    Effect of Tensile Stress on the Oxide Properties of a Nickel-Based Alloy 600 in Simulated PWR Secondary Water

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    The purpose of this work was to examine the effect of tensile stress on the oxide properties of a nickel-based Alloy 600 that was exposed to simulated nuclear steam generator water at 340 °C for 1000 h. The size of the outer oxide particles increased, and the chromium content of the inner oxides decreased under tensile stress. Electrochemical measurements revealed that the charge carrier density increased, and the charge transfer resistance and film resistance were reduced under the tensile stress condition. These changes in the oxide properties are attributed to the formation of short diffusion paths such as line and surface defects due to tensile deformation
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