Yttria stabilized zirconia membranes

Similarly, impervious yttria-stabilized zirconia membranes doped with titania have been prepared by the electrochemical vapor deposition method [Hazbun, 1988]. Zirconium, yttrium and titanium chlorides in vapor form react with oxygen on the heated surface of a porous support tube in a reaction chamber at 1,100 to 1,300 C under controlled conditions. Membranes with a thickness of 2 to 60 pm have been made this way. The dopant, titania, is added to increase electron How of the resultant membrane and can be tailored to achieve the desired balance between ionic and electronic conductivity. Brinkman and Burggraaf [1995] also used electrochemical vapor deposition to grow thin, dense layers of zirconia/yttria/terbia membranes on porous ceramic supports. Depending on the deposition temperature, the growth of the membrane layer is limited by the bulk electrochemical transport or pore diffusion. 

The use of Pd-based membrane reactors can increase the hydrogenation rates of several olefins by more than 10 times higher than those in conventional premixed fixed>bed reactors. Furthermore, it has been pointed out that the type and state of the oxygen used to carry out partial oxidation of methane can significantly affect the conversion and selectivity of the reaction. The use of a solid oxide membrane (e.g., a yttria-stabilized zirconia membrane) not only can achieve an industrially acceptable C2 hydrocarbon yield but also may eliminate undesirable gas-phase reactions of oxygen with methane or its intermediates because oxygen first reaches the catalyst through the solid oxide wall [Eng and Stoukides, 1991]. 

Methane can be catalytically oxidized in the fuel cell mode to simultaneously generate electricity and C2 hydrocarbons by dimerization of methane using a yttria-stabilized zirconia membrane. A catalyst, used as the anode, is deposited on the side of the membrane that is exposed to methane and the cathode is coated on the other side of the membrane. When the catalyst Ag>Bi2C>3 is used as the anode for the reaction at 750> 900X and atmospheric total pressure, the selectivity to ethane and ethylene exceeds 90%. But this high selectivity is at the expense of low power output and low overall methane conversion (less than about 2%). 

Figure 9.3 Conversion of thermal decomposition of carbon dioxide in a dense yttria-stabilized zirconia membrane reactor as a function of membrane thickness when a sweep gas is used (top) and when vacuum is applied (bottom) [Itoh et al., 1993]...

Dense palladium-based membranes. Shown in Table 10.1 are modeling studies of packed-bed dense membrane shell-and-tube reactors. All utilized Pd or Pd-alloy membranes except one [Itoh et al., 19931 which used yttria-stabilized zirconia membranes. As mentioned earlier, the permeation term used in Ihe governing equations for the tube and shell sides of the membrane is expressed by Equation (10-51b) with n equal to 0.5 [c.g., Itoh, 1987] or 0.76 [e.g., Uemiya et al., 1991]. 

Figure 10.6 compares the model and experimental results of direct thermal decomposition of CO2 using a dense yttria-stabilized zirconia membrane shell-and-tube reactor [Itoh et. al., 1993]. The agreement for the reactor conversion is very good. At a CO2 feed rate of less than 20 cm /min and with a membrane thickness of 2,(XX) pm the conversion is significantly enhanced by the use of a permselective membrane for oxygen. Beyond a feed rate of 20 cm /min., however, the difference in conversion between a membrane and a conventional reactor. 

First of all, the space time defined in Eq. (11-5) or (11-6) depends on the volume of the reactor and the total volumetric feed rate. Thus, for a given reactor volume, space time is inversely proportional to the total feed rate. Itoh et al. [1993] studied the use of a dense yttria-stabilized zirconia membrane reactor for thermal decomposition of carbon dioxide. The reactor temperature was not kept constant everywhere in the reactor but varying with the reactor length instead. The resulting temperature profile is parabolic with the maximum temperature at the midpoint of the reactor length. This nonisothermal... 

With data on the activity of hydrogen ion in the standard solution available from model estimations, relatiorrships between the pH and cell potential, and hence a practical pH scale, for supercritical systems was developed. The potential of the cell comprising a pH sensor (yttria stabilized zirconia membrane) and a reference electrode (silver/silver chloride external pressure balanced electrode) (Emeas) can be written in the following form "... 

Figure 29. Conductivity of some intermediate-temperature proton conductors, compared to the conductivity of Nafion and the oxide ion conductivity of YSZ (yttria-stabilized zirconia), the standard electrolyte materials for low- and high-temperature fuel cells, proton exchange membrane fuel cells (PEMFCs), and solid oxide fuel cells (SOFCs).

For the purposes of review. Figure 1 illustrates the basic function of the cathode in a solid oxide fuel cell. Whether acting alone or as part of a stack of cells, each cell consist of a free-standing or supported membrane of an oxygen-ion-conducting electrolyte, often yttria-stabilized zirconia (YSZ). Oxygen, which is fed (usually as air) to one side of the membrane, is reduced by the cathode to oxygen ions via the overall half-cell reaction... 

Mixed ion and electronic conducting ceramic membranes (e.g. yttria-stabilized zirconia doped with titania or ceria) can be slip cast into a tubular form from the pastes containing the constituent oxides in an appropriate proportion and other ingredients and the cast tubes are then subject to sintering at 1,200 to 1,500X to render them gas impervious [Hazbun, 1988]. 

Kusakabe et al.83 proposed selective CO oxidation membrane concept to facilitate SMR reaction. Yttria-stabilized zirconia (YSZ) membrane was deposited on the surface of a porous alumina support tube by sol-gel procedure. This again was impregnated with Pt and Rh aqueous solution to produce a Pt- or Rh-loaded YSZ membrane. With addition of 02 in the feed, oxidation of CO can bring CO concentration to the level appropriate for PEMFC (<30ppm). 

A Type-I membrane containing Ce (13%) on the surface was tested at 1023 K. The results showed it to be a good catalyst for the total oxidation of methane. On the other hand, the type-II membrane, in which the support was calcia-stabilized zirconia (CSZ) and magnesia-stabilized zirconia (MSZ) showed lower activity than yttria-stabilized zirconia (YSZ). The activation energy of the last membrane (non porous) for the formation... 

The present work was focused on the synthesis of nanocrystalline components for electrochemical cells via the cellulose-precursor technique. This method was used to prepare nanostructured intermediate-temperature (IT) SOFC anodes made of a series of cermets comprising gadolinia-doped ceria (CGO), yttria-stabilized zirconia (YSZ), Gdi.86Cao.i4Ti207.5 (GCTO) pyrochlore, metallic nickel and copper. Perovskite-type SrFcojAlo.sOs.s (SFA) powder, also obtained via the cellulose precursor, was applied onto membranes of the same composition to enhance specific surface area and electrocatalytic activity in the reactors for methane conversion [3]. 

An ideal membrane must have high electronic and protonic conductivities it should be fairly thin (1-10 pm), and chemically stable for prolonged periods of time under the presence of various gases such as CO2, H2O and H2S etc. The low electronic conductivity limits the H2 flux of the protonceramic membranes. Under pure H2 atmosphere at 900 "C, the protonic conductivities of SCYb and BCNd are about 0.7 x 10 2 and 2.2 x 10 2 S cm , respectively. These values are sh tly lower than the oxygen ionic conductivity of yttria stabilized zirconia (YSZ) or lanthanum strontium cobaltite (LSC) perovskite-type ceramics in air at the same temperature, so that there is room for further improvement in protonic conductivity. 

---