Chapter 10 Dense ceramic membranes for oxygen separation

doi:10.1016/S0927-5193(96)80013-1

Membrane Science and Technology

Volume 4, 1996, Pages 435-528

https://doi.org/10.1016/S0927-5193(96)80013-1 Get rights and content

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This chapter reviews the recent developments in the area of mixed ionic-electronic conducting membranes for oxygen separation, in which the membrane material is made dense—that is, free of cracks and connected-through porosity, being susceptible only for oxygen ionic and electronic transport. Emphasis is on the defect chemistry, mass transport, and the associated surface exchange kinetics. The basic elements of mixed ionic and electronic transport through dense ceramic membranes are focused. The chapter discusses mixed-conducting acceptor-doped perovskite and perovskite-related oxides and gives examples to illustrate the fundamental factors determining the oxygen fluxes through dense ceramic membranes. A key factor in the possible application of oxygen ion conducting ceramics is that, for use as solid electrolyte in fuel cells, batteries, oxygen pumps or sensors, their electronic transport number should be as low as possible. Stimulated by the search for candidate materials for electrodes in solid oxide fuel cells (SOFC) and oxygen separation membranes, researchers have explored the possibility of introducing electronic conductivity in oxygen-ion conducting fluorite-type matrices by doping with multi-valent dopants.

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The main goal of this research in the first step is to present a new power generation and cooling system with zero emissions for ships. The presented system is a combination of oxygen separator membrane, Oxy-fuel cycle, lithium bromide-water (LiBr-H₂O) double-effect absorption refrigeration cycle, and carbon dioxide (CO₂) liquefaction cycle. The fuel of the system is liquefied natural gas (LNG). In the second step, the presented system is evaluated from energy, exergy, exergy-economic and environmental exergy viewpoints. In the third step, multi-objective optimization is used to pinpoint the optimal state of the presented scheme based on economic, performance, and environmental impacts (EI). The results revealed that in the reference state the energetic efficiency is 95% and exergetic efficiency is 38%. The net power per kilogram of produced oxygen and liquefied carbon dioxide is equal to 1194 kW and 47.42 kW, respectively. The levelized cost per exergy unit (LCPEU) of the gross power of the supercritical CO₂ (SCO₂) cycle turbine, nitrogen turbine, the produced cold water, and total products (cooling and power) are equal to 26.75 $/GJ, 270 $/GJ, and 63.05 $/GJ, respectively. The multi-objective optimization outcomes demonstrated that the exergetic efficiency of the system and the cost per exergy unit (CPEU) of all products can be improved up to 18 % and 13 %, respectively. Moreover, the environmental impact per exergy unit (EIPEU) of all products can be improved by up to 6 %.
Oxygen permeability and surface kinetics of composite oxygen transport membranes based on stabilized δ-Bi<inf>2</inf>O<inf>3</inf>
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Composite ceramic membranes based on the ionic conducting Tm-stabilized δ-Bi₂O₃ (BTM) and the electronic conducting (La_0.8Sr_0.2)_0.99MnO_3-δ (LSM) exhibit among the highest oxygen flux values reported for Bi₂O₃-based membranes. Here, we use pulse-response isotope exchange (PIE) and oxygen flux measurements to elaborate on limiting factors for the oxygen permeation in BTM - 40-70 vol% LSM composites. Once both phases percolate, between 30 and 50 vol% BTM, the flux is essentially independent of the BTM/LSM volume ratio. The oxygen permeability is under mixed diffusion- and surface control, gradually becoming more bulk-limited with increasing temperature. The oxygen exchange coefficients of BTM-LSM are significantly higher than its constituent phases, revealing that a cooperative surface exchange mechanism enhances the kinetics. Some of the Tm was substituted with Pr to introduce electronic conductivity in BTM. (Bi_0.8Tm_0.15Pr_0.05)₂O_3-δ (BTP) exhibits higher surface exchange coefficients compared to BTM, but the oxygen flux remains one order of magnitude lower than that of percolating BTM-LSM composites.
Microstructure coarsening in Ba<inf>0.5</inf>Sr<inf>0.5</inf>Co<inf>0.8</inf>Fe<inf>0.2</inf>O<inf>3-δ</inf> during reactive air brazing
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Reactive air brazing of the ceramic oxygen transport membrane material BSCF causes microstructural modifications. The trend towards minimizing of membrane thicknesses requires a physical understanding of these modifications since they may influence both oxygen permeation and mechanical properties. To this purpose, wetting samples with variations in the Ag-xCuO braze alloy (1 < x < 25 at.-%) and the brazing time (0 < t < 120 min) were characterized by quantitative image analysis. We found that the pore size in reactive air brazed BSCF increases with increased brazing time as well as CuO-content in the braze. A local porosity minimum is always observed at the end of the reaction zone close to the unaffected bulk BSCF. Additionally, a zone with unidirectionally elongated grains at the end of which silver residues were found is observed. The observed coarsening effects are explained by liquid melt film penetration along the grain boundaries which increases the grain boundary mobility. Phase field simulations qualitatively confirmed the experimentally observed elongated grain structure.
Simultaneous synthesis of H<inf>2</inf>, O<inf>2</inf>, and N<inf>2</inf> via an innovatory energy system in Coronavirus pandemic time: Design, techno-economic assessment, and optimization approaches
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In this work, an innovative integrated system that is incorporated from solid oxide electrolysis cells and an oxygen separator membrane is assessed and optimized from the techno-economic aspects to respond to oxygen, hydrogen, and nitrogen demands for hospitals and other health care applications. Besides, a parametric comparison is conducted to apprehend the weights of parameters changes on the performance of criteria. Relying on the assessments, from the hydrogen production of 1 kg/s, 23.19 kg/s of oxygen, and 50.22 kg/s of nitrogen are produced. The parametric study shows that by raising the working temperature of the electrolyzer, the cell voltage variation has descending trend and the power consumption of the system is decreased by 19%. Finally, the results of multi-criteria optimization on the Pareto front reveal that in the optimal case, the system payback period is attained at about 5.32 years and the exergy efficiency of 92.47%, which are improved 16.6% and 16.2% compared to the base case, sequentially. Consequently, this system is proposed to consider as a cost-effective and reliable option towards its vital and valuable productions, in the pandemic period and after's.
High-flux CO<inf>2</inf>-stable oxygen transport hollow fiber membranes through surface engineering
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The influences of bulk diffusion and surface exchange on oxygen transport of (La_0.6Ca_0.4)(Co_0.8Fe_0.2)O_3-δ (LCCF) hollow fiber membranes were investigated. As an outcome, two strategies for increasing the oxygen permeation were pursued. First, porous LCCF hollow fibers as support were coated with a 22 μm dense LCCF separation layer through dip coating and co-sintering. The oxygen permeation of the porous fiber with dense layer reached up to 5.10 mL min⁻¹ cm^-2 at 1000 °C in a 50 % CO₂ atmosphere. Second, surface etching of dense LCCF hollow fibers with H₂SO₄ was applied. The surface etching of both inner and outer surfaces leads to a permeation improvement up to 86.0 %. This finding implies that the surface exchange reaction plays a key role in oxygen transport through LCCF hollow fibers. A good long-term (>250 h) stability of the asymmetric hollow fiber in a 50 % CO₂ atmosphere was found at 900 °C.
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Asymmetric oxygen transport membranes have been extensively studied revealing the importance of the support porosity. In this study, asymmetric membranes with vertically channelled pores were prepared from Ba_0.5Sr_0.5(Co_0.8Fe_0.2)_0.97Zr_0.03O_3-δ (BSCF-Z) by phase inversion tape casting. The rate-limiting effects of the membrane layer thickness, the support structure, and the activation layers were thoroughly analysed. This entails comparing the permeation rate of the samples with the membrane layer on different sides of the channelled supports. Pore tortuosity and computed permeability were evaluated from 3D-X-ray computed tomography and compared to previously reported asymmetric membranes prepared by tape-casting and freeze-drying. Due to a lower pore tortuosity, the channelled supports have an advantage in gas transport over the tape cast and freeze cast supports. However, this is compensated by a thicker membrane layer (∼54 μm) resulting in similar performance compared to the thinner membrane layers (∼20 μm) with freeze cast and tape cast supports.

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Chapter 10 Dense ceramic membranes for oxygen separation

Publisher Summary

Gas Sep. Purif.

J. Membr. Sci.

Appl. Catal. A: General

Solid State Ionics

Catal. Today

Solid State Ionics

Energy Conversion

Mat. Sci. Eng.

Solid State Ionics

Mat. Res. Bull.

Solid State Ionics

Solid State Ionics

Solid State Ionics

Prog. Solid State Chem.

Solid State Ionics

Solid State Ionics

Solid State ionics

J. Chem. Phys.

Solid State Ionics

Solid State Ionics

Solid State Ionics

J. Solid State Chem.

Chem. Rev.

J. Electrochem. Soc

Activation of methane using solid oxide membranes

Catal. Today

Oxide ion transport for selective oxidative coupling of methane with new membrane reactor

AICh. E. J.

Simulation of nonisothermal catalytic membrane reactor for methane partial oxidation to syngas

Failure mechanisms of ceramic membrane reactors in partial oxidation of methane to synthesis gas

Catal. Lett.

Methane to synthesis gas via ceramic membranes

Am. Ceram. Soc. Bull.

Waste reduction and recovery using O2-perme-able membrane reactors

Ind. Eng. Chem. Res.

Inorganic membrane reactors

Cat. Rev.-Sci. Eng.

An operators view on gas membranes

Inorganic membrane reactors to enhance the produc- tivity of chemical processes

Catalytic inorganic membrane reactors: Present experience and future opportunities

Catal. Rev.-Sci. Eng.

Selective permeation of gases through dense sintered alumina

Trans. Br. Ceram. Soc.

Permeability of sintered alumina materials to gases at high temperatures

Trans. Br. Ceram. Soc

Mixed conduction in nonstoichiometric oxides

Development of alternative oxygen production source using a zirconia solid electrolyte membrane

Waste reduction and recovery using O₂-perme-able membrane reactors