Flux-Reducing Tendency of Pd-Based Membranes Employed in Butane Dehydrogenation Processes

We report on the effect of butane and butylene on hydrogen permeation through thin state-of-the-art Pd–Ag alloy membranes. A wide range of operating conditions, such as temperature (200–450 °C) and H2/butylene (or butane) ratio (0.5–3), on the flux-reducing tendency were investigated. In addition, the behavior of membrane performance during prolonged exposure to butylene was evaluated. In the presence of butane, the flux-reducing tendency was found to be limited up to the maximum temperature investigated, 450 °C. Compared to butane, the flux-reducing tendency in the presence of butylene was severe. At 400 °C and 20% butylene, the flux decreases by ~85% after 3 h of exposure but depends on temperature and the H2/butylene ratio. In terms of operating temperature, an optimal performance was found at 250–300 °C with respect to obtaining the highest absolute hydrogen flux in the presence of butylene. At lower temperatures, the competitive adsorption of butylene over hydrogen accounts for a large initial flux penalty.publishedVersio

High-purity H2 production with CO2 capture based on coal gasification

A novel hybrid concept is proposed, combining Pd-alloy membrane and low temperature separation technology, to produce pure H2 from gasified coal and capture the main part of the generated CO2. 75% of the H2 produced from gasification and water-gas shift is separated from the shifted syngas through H2-selective Pd-alloy membranes. After water removal, the H2-depleted, CO2-rich retentate stream is compressed and cooled, after which CO2 is condensed out at a purity level of ∼99%. The “waste” volatiles from the low-temperature CO2 separation constitute a low heating value syngas that is burnt in a gas turbine. The gas turbine with a steam bottoming cycle generates a surplus of electricity that could be employed for H2 liquefaction. Altogether, the concept has the potential to be developed into a stand-alone high-purity H2 production unit with CO2 capture, suitable e.g. for remote areas from where H2 and possibly also CO2 must be transported by ship. However, the investigations of three different process alternatives, as well as three membrane separator parameters, illustrate that there are many degrees of freedom in the proposed concept that require further analysis, both individually and how they interact, in order to establish an optimized and purposeful stand-alone H2 production concept.acceptedVersio

Influence of Ce3+ polarons on grain boundary space-charge in proton conducting Y-doped BaCeO3

Defect segregation and space-charge formation were investigated for a (0 2 1)[1 0 0] symmetric tilt grain boundary in Y-doped BaCeO3. Density functional theory calculations according to the PBE+U formalism were used to calculate segregation energies for protons, oxygen vacancies and Y-acceptor dopants from the bulk to the grain boundary core. Defect concentration and potential profiles across the grain boundary were obtained from thermodynamic space-charge models. Oxygen vacancies were found to exhibit a particularly exothermic segregation energy of up to −1.66 eV while protons exhibited segregation energies in the range of −0.47 eV to −0.93 eV. The grain boundary was determined to be predominated by protons below 800 K in 3% H2O and the corresponding space-charge potential was 0.4–0.7 V under the Mott–Schottky approximation. The role of electronic defects in the space-charge properties was evaluated, and it was substantiated that electron conduction along the grain boundary could become evident under reducing conditions.publishedVersio

Proton segregation and space-charge at the BaZrO3 (0 0 1)/MgO (0 0 1) heterointerface

Y-doped BaZrO3 (BZY) can be deposited epitaxially on MgO (0 0 1) and the considered interface serves as a model system for studying heterointerface properties of protonic conductors. In this study, the defect chemistry of the interface between ZrO2-terminated BaZrO3 (0 0 1) and MgO (0 0 1) was investigated by first-principles calculations and space-charge theory. Segregation energies from the BZY bulk to the interface ZrO2 and MgO layers were calculated for effectively charged protons, oxygen vacancies, Y-acceptors as well as cation vacancies. Protons were found to exhibit a strong tendency for segregating to the interface, particularly to an oxide ion in the MgO layer, rendering a net positive charge of the interface. According to the applied thermodynamic space-charge models, the interface potential could reach more than 1 V under the Mott-Schottky approximation, with depletion regions extending up to 2 nm into BZY. With fully equilibrated Y-segregation profiles, the interface potential was significantly diminished to about 0.2 V at 573 K and 0.025 bar H2O. While the interface was found to be close to saturated by protons under most condition, it was concluded that proton conduction along the interface could not contribute significantly to the in-plane conductivity of BZY films deposited on MgO substrate.acceptedVersio

Adsorption of CO2 and Facile Carbonate Formation on BaZrO3 Surfaces

The adsorption of CO2 and CO on BaZrO3 (0 0 1) was investigated by first-principles calculations with a focus on the BaO termination. CO2 was found to strongly chemisorb on the surface by formation of carbonate species with an adsorption enthalpy of up to −2.25 eV at low coverage and −1.05 eV for a full monolayer. An adsorption entropy of −8.8 × 10–4 eV K–1 was obtained from the vibrational properties of the adsorbates. Surface coverages were evaluated as a function of temperature and CO2 partial pressure, and the obtained coverage under 1 bar CO2 was more than 0.8 at 1000 K (conditions relevant for steam methane reforming). The fully saturated surface was stable up to about 400 K under ambient atmosphere, i.e., 400 ppm of CO2. The initial stage of BaCO3 formation was evaluated according to migration of barium to the carbonate overlayer, which was found to result in a significant stabilization of the system. The barium migration was found to be essentially unobstructed with a barrier of only ∼5 meV. In light of the stability of carbonate adsorbates at the surface, the prospect of bulk dissolution of carbonate species was evaluated but ultimately found to be negligible in acceptor-doped BaZrO3.acceptedVersio

Hydrogen Induced Vacancy Clustering and Void Formation Mechanisms at Grain Boundaries in Palladium

Hydrogen has a significant impact on the formation of vacancies, clusters and voids in palladium and other metals. The formation of vacancy-hydrogen complexes in bulk Pd and at Σ3 and Σ5 grain boundaries was investigated using first-principles calculations and thermodynamic models. Equilibrium vacancy and cluster concentrations were evaluated as a function of temperature and hydrogen partial pressure based on the Gibbs energy of formation including vibrational and configurational entropies. Vacancies were found to be significantly stabilized by association with interstitial hydrogen, leading to enhanced concentrations by several orders of magnitude. Vacancy clusters were further stabilized at grain boundaries, with equilibrium concentrations reaching site saturation for clusters comprising up to three vacancies. Nanovoids were investigated based on Wulff constructions from calculated surface energies of the (0 0 1) and (1 1 1) terminations as a function of temperature and coverage of hydrogen adsorbates. The most stable termination changed from (1 1 1) in vacuum to (0 0 1) in H2, and the surface energies were lowered due to hydrogen adsorbates. Consequently, voids were also stabilized in the presence of hydrogen. Coalescing of vacancies into nanovoids was found to be thermodynamically unfavorable due to the loss of configurational entropy. It was therefore concluded that enhanced concentrations of vacancies and clusters does not directly cause the formation of voids. The formation of voids in Pd-based membranes was discussed in terms of microstructural characteristics, and strain due to chemical expansion and plastic deformation.publishedVersio

Formation of hydrogen bubbles in Pd-Ag membranes during H2 permeation

Palladium membranes used for hydrogen separation seemingly develop cavities filled with hydrogen, i.e. hydrogen bubbles, along the grain boundaries. These bubbles may represent initial stages of pinhole formation that lead to unselective leakage and compromise the long-term stability of the membranes. Alloying with Ag improves the permeability of Pd, but whether these H2 bubbles form in Pd-Ag membranes remained unknown. In this work, the microstructure of a Pd77Ag23 membrane was characterized by electron microscopy after H2 permeation testing for 50 days at 15 bar at temperatures up to 450 C. The results show that Ag does not prevent bubbles from emerging along high-angle grain boundaries, but reduces the number of potential nucleation sites for cavity formation by supressing the development of dislocation networks when H-saturated Pd is cycled through the miscibility gap. Both magnetron-sputtered and electroless plated membranes are afflicted by H2 bubbles, thus their formation seems determined by intrinsic properties of the material independent of the fabrication technique. The qualitative discussion enables to point directions for enhancement of membrane stability.publishedVersio

Nanocomposites of few-layer graphene oxide and alumina by density functional theory calculations

The atomistic and electronic structure and oxygen stoichiometry of nanocomposites between alumina and graphene oxide were investigated by density functional theory calculations. The nanocomposite was described as interfaces between α-Al2O3 (0001) surfaces and graphene oxide; the latter was defined with oxygen bound as epoxy groups and a C:O atomic ratio of 4:1. The optimized composite structure with 1–3 layers of graphene oxide in between Al2O3 contains bridging Alsingle bondOsingle bondC bonds at the interface. Reduction of the composite was investigated by removal of oxygen from the interface Alsingle bondOsingle bondC bonds, within the graphene oxide layers and in Al2O3. It was found that removal of oxygen within the graphene oxide layers is essentially independent of the Al2O3 interface, i.e., the same as in pure graphene oxide. Oxygen was, however, more strongly bound in the interface Alsingle bondOsingle bondC bonds by 0.80 eV, and reduction of graphene oxide to graphene is accordingly preferred within the graphene oxide layers rather than at the oxide interface.acceptedVersio

Stability investigation of micro-configured Pd-Ag membrane modules - Effect of operating temperature and pressure

The long-term stability over a period of up to 50 days has been reported for various designs of microstructured Pd77Ag23 membrane modules for H2 production and purification. Even though microchannels provide sufficient mechanical support for moderate trans-membrane pressure difference and temperatures, i.e., 4–5 bars and 400–450 °C, long-term operation under these operating conditions results in a large deformative settling of the Pd77Ag23 film into the microchannel support. This settling leads to microstructural changes and pore formation on the feed surface of the membrane film that ultimately results in membrane failure. For pressures above approximately 5 bars, the application of microchannel-supported modules is thus not feasible, and for that purpose a continuous porous stainless steel support is introduced that allows for a sufficient stabilisation of the thin Pd77Ag23 films. For such a porous stainless steel supported microchannel module, a hydrogen flux of 195.3 mL cm−2 min−1 is obtained at 450 °C and 5 bars feed pressure, corresponding to a permeability of 3.4·10−8 mol m−1 s−1 Pa−0.5. During the complete operation of 1100 h at 450 °C, the module shows a very good stability up to the highest feed pressure applied of 15 bars. The N2 leakage flux has remained below the detection limit of the equipment, 5 μL cm−2 min−1, resulting in a minimum value for the H2/N2 permselectivity of 39.000 applying the pure H2 flux value obtained at 5 bars.acceptedVersio