Development of Membrane Reactor Coupling Hydrogen and Syngas Production.

Simultaneous syngas and pure hydrogen production through partial oxidation of methane and water splitting, respectively, were demonstrated by using mixed ionic-electronic conductors. Tubular ceramic membranes prepared from La0.5Sr0.5FeO3 perovskite were successfully utilized in a 10 M lab scale reactor by applying a radial arrangement. The supply of methane to the middle area of the reaction zone was shown to provide a uniform distribution of the chemical load along the tubes' length. A steady flow of steam feeding the inner part of the membranes was used as oxidative media. A described configuration was found to be favorable to maintaining oxygen permeability values exceeding 1.1 mL∙cm-2∙min-1 and long-term stability of related functional characteristics. Methane's partial oxidation reaction assisted by 10%Ni@Al2O3 catalyst proceeded with selectivity values above 90% and conversion of almost 100%. The transition from a laboratory model of a reactor operating on one tubular membrane to a ten-tube one resulted in no losses in the specific performance. The optimized supply of gaseous fuel opens up the possibility of scaling up the reaction zone and creating a promising prototype of a multitubular reaction zone with a simplified sealing procedure.

Structural Features and Defect Equilibrium in Cubic PrBa1-xSrxFe2O6-δ.

The structure, oxygen non-stoichiometry, and defect equilibrium in perovskite-type PrBa1-xSrxFe2O6-δ (x = 0, 0.25, 0.50) synthesized at 1350 °C were studied. For all compositions, X-ray diffraction testifies to the formation of a cubic structure (S.G. Pm3¯m), but an electron diffraction study reveals additional diffuse satellites around each Bragg spot, indicating the primary incommensurate modulation with wave vectors about ±0.43a*. The results were interpreted as a sign of the short-order in both A-cation and anion sublattices in the areas of a few nanometers in size, and of an intermediate state before the formation of an ordered superstructure. An increase in oxygen deficiency was found to promote the ordering, whereas partial substitution of barium by strontium caused the opposite effect. The oxygen content in oxides as a function of oxygen partial pressure and temperature was measured by coulometric titration, and the data were used for the modeling of defect equilibrium in oxides. The simulation results implied oxygen vacancy ordering in PrBa1-xSrxFe2O6-δ that is in agreement with the electron diffraction study. Besides oxidation and charge disproportionation reactions, the reactions of oxygen vacancy distribution between non-equivalent anion positions, and their trapping in clusters with Pr3+ ions were taken into account by the model. It was demonstrated that an increase in the strontium content in Pr0.5Ba0.5-xSrxFeO3-δ suppressed ordering of oxygen vacancies, increased the binding energy of oxygen ions in the oxides, and resulted in an increase in the concentration of p-type carriers.

Impact of oxygen content on preferred localization of p- and n-type carriers in La0.5Sr0.5Fe1-xMnxO3-δ.

The oxygen content in La0.5Sr0.5Fe1-xMnxO3-δ, measured by coulometric titration in a wide range of oxygen partial pressure at various temperatures, was used for defect chemistry analysis. The obtained data were well approximated by a model assuming defect formation in La0.5Sr0.5Fe1-xMnxO3-δvia Fe3+ and Mn3+ oxidation reactions and charge disproportionation on Fe3+ and Mn3+ ions. The partial molar enthalpy and entropy of oxygen in La0.5Sr0.5Fe1-xMnxO3-δ obtained by statistical thermodynamic calculations were found to be in satisfactory agreement with those obtained using the Gibbs-Helmholtz equations, thus further confirming the adequacy of the model. The impact of manganese substitution on defect equilibrium in La0.5Sr0.5Fe1-xMnxO3-δ was shown to be attributed to a lower enthalpy of Mn3+ oxidation reaction (vs. for the oxidation of Fe3+) and the charge disproportionation reaction on Mn3+ (vs. for that on Fe3+). The former makes Mn4+ ions more resistant to reduction than Fe4+. The latter favors the presence of Mn2+, Mn3+, and Mn4+ ions in oxides in comparable concentrations. The distribution of charge carriers over iron and manganese ions was determined as a function of oxygen content in La0.5Sr0.5Fe1-xMnxO3-δ.

Impact of A-Site Cation Deficiency on Charge Transport in La0.5-xSr0.5FeO3-δ.

The electrical conductivity of La0.5-xSr0.5FeO3-δ, investigated as a function of the nominal cation deficiency in the A-sublattice, x, varying from 0 to 0.02, has demonstrated a nonlinear dependence. An increase in the x value from 0 to 0.01 resulted in a considerable increase in electrical conductivity, which was shown to be attributed mainly to an increase in the mobility of the charge carriers. A combined analysis of the defect equilibrium and the charge transport in La0.5-xSr0.5FeO3-δ revealed the increase in the mobility of oxygen ions, electrons, and holes by factors of ~1.5, 1.3, and 1.7, respectively. The observed effect is assumed to be conditioned by a variation in the oxide structure under the action of the cationic vacancy formation. It was found that the cation deficiency limit in La0.5-xSr0.5FeO3-δ did not exceed 0.01. A small overstep of this limit was shown to result in the formation of (Sr,La)Fe12O19 impurity, which even in undetectable amounts reduced the conductivity of the material. The presence of (Sr,La)Fe12O19 impurity was revealed by X-ray diffraction on the ceramic surface after heat treatment at 1300 °C. It is most likely that the formation of traces of the liquid phase under these conditions is responsible for the impurity migration to the ceramic surface. The introduction of a cation deficiency of 0.01 into the A-sublattice of La0.5-xSr0.5FeO3-δ can be recommended as an effective means to enhance both the oxygen ion and the electron conductivity and improve ceramic sinterability.

Non-uniform electron conduction in weakly ordered SrFe1-xMoxO3-δ.

The electrical conductivity of SrFe1-xMoxO3-δ (0.07, 0.15, 0.25) was measured in the range of oxygen partial pressure of 10-16-0.5 atm and at temperatures 800-950 °C by a four-probe dc technique. Experimental results were satisfactorily simulated with a model suggesting that oxygen ions and electronic charge carriers of n- and p-types were involved in conduction. The mobility of charge carriers was calculated using partial conductivities and earlier published oxygen nonstoichiometry data. The mobility of p-type charge carriers was found to decrease in response to a decreasing oxygen content or an increasing molybdenum content in the oxide. The mobility of n-type carriers was found to be unaffected by the oxygen content, but exhibited an accelerating increase upon increasing the molybdenum content. Such behavior of the electron mobility was interpreted in view of the tendency of iron and molybdenum cations to undergo ordering based on the supposition that two different mechanisms of electron transport were involved in these oxides. It was assumed that nanoscale ordered areas with fast electron transport dispersed in the disordered perovskite matrix played the role of a high-conductivity filler in a composite consisting of two components with different conductivities. The behavior of the effective electron mobility was approximated well using the percolation theory. The molybdenum content x = 0.327 was calculated to be the percolation threshold in SrFe1-xMoxO3-δ.