High temperature water electrolysis in solid oxide cells

Hydrogen production via high temperature steam electrolysis is a promising technology as it involves less electrical energy consumption compared to conventional low temperature water electrolysis, as consequence of the more favourable thermodynamic and electrochemical kinetic conditions for the reaction. This paper reports on the Solid Oxide Electrolyser Cell (SOEC) performance as function of the operating parameters temperature, humidity and current density. Current–voltage measurements are coupled with impedance spectroscopy, in order to identify the different loss terms in the cell behaviour coming from the electrolyte resistance and the electrode processes. Remarkably high electrical-to-hydrogen energy conversion efficiencies are achieved (e.g., cell voltages of 1.0 and 1.25 V at −1 A cm⁻² and 900 and 800 °C, respectively). Results obtained, moreover, show that an important limitation for the electrolysis reaction, at least at moderate absolute humidity values below about 70 vol.% can be the steam diffusion in the hydrogen/steam electrode.     

23,000 h steam electrolysis with an electrolyte supported solid oxide cell

An electrolyte supported solid oxide cell of 45 cm² area was operated in the steam-electrolysis mode during more than 23,000 h before scheduled shutdown, of which 20,000 h with a current density of j = ?0.9 A cm^?2. The cell consisted of a scandia/ceria doped zirconia electrolyte (6Sc1CeSZ), CGO diffusion-barrier/adhesion layers between electrolyte and electrodes, a lanthanum strontium cobaltite ferrite (LSCF) oxygen electrode, and a nickel/gadolinia-doped ceria (Ni/GDC) steam/hydrogen electrode. Voltage degradation in the operation period with j = ?0.9 A cm^?2 was 7.4 mV/1000 h (0.57%/1000 h) and the increase in the area specific resistance 8 mΩ cm²/1000 h. The final cell voltage was 1.33 V (at 851 °C cell temperature). After dismantling, the cell showed no mechanical damage at electrolyte and H₂/H₂O electrode; a small fraction of the oxygen electrode was delaminated. Impedance spectroscopy applied at the steady state DC current density confirmed a degradation dominated by an increasing ohmic term, mainly due to ionic conductivity decay in the electrolyte. In addition, a small non-ohmic and at least partly reversible O₂ electrode contribution to degradation was identified, affected by a pollution from the (compressor) purge air.     

Tribological properties of powder metallurgical tool steels used in powder compaction pressing dies

The tribological properties of two powder metallurgical (PM) tool steels, high and low nitrogen containing, are investigated by means of three different wear tests: ball‐on‐disc, rubber wheel and scratch test. The ball‐on‐disc tests showed two distinct friction curves corresponding to each material. In order to simulate the tribosystem existing in metal powder compaction dies, the rubber wheel and the scratch test were modified. The rubber wheel test was performed using ferrous powder instead of sand, and scratch testing was carried out by sliding a powder compact over the tool steels. The scratch tests indicated a higher steady‐state coefficient of friction for the low nitrogen containing PM steel as compared with the high nitrogen containing alloy. Additionally, the results from the rubber wheel tests were in agreement with industrial experiences, showing the low nitrogen containing tool steel to suffer from severe galling. Copyright © 2011 John Wiley & Sons, Ltd.     

CRYSTAL SIZE GROWTH IN THE LIQUID PHASE METHANOL SYNTHESIS CATALYST

ABSTRACT

The phenomenon of crystal growth in the methanol synthesis catalyst has been studied. Crystallite size distributions in the cuo/ZnO/Al₂O₃ methanol synthesis catalyst have been determined. The effects of temperature, reaction environment and time under reaction conditions have been studied. It is observed that water in the reaction mixture promotes crystal growth.     

A SINGLE-STAGE,LIQUID-PHASE DIMETHYL ETHER SYNTHESIS PROCESS FROM SYNGAS III. DUAL CATALYST CRYSTAL GROWTH,DEACTIVATION, AND ACTIVITY CONSERVATION STUDIES

ABSTRACT

In the liquid phase dimethyl ether (DME) synthesis process, both the methanol synthesis catalyst )composed of CuO, ZnO, and Al₂O₃) and the methanol dehydration catalyst (composed of gamma-alumina) are slurried in the inert oil phase. Various long-term activity checks were conducted on these dual catalysts to characterize the crystal growth and the thermal aging behavior. X-ray powder diffraction, X-ray fluorescence and elemental intensity compositions, and the crystallite size distributions of the aged catalysts were examined. Based on the current investigation, it was established that the crystal growth and the catalyst deactivation problems in the methanol synthesis catalyst are less severe when it is used along with the methanol dehydration catalyst.     

Bottom-up cost evaluation of SOEC systems in the range of 10–100 MW

A detailed bottom-up cost evaluation of SOEC systems in the range of 10–100 MW was carried out based on recent experimental results in the SOEC field. Capital costs of installed SOEC systems were evaluated starting from raw SOEC materials. Two scenarios were defined, assuming different capacities of SOEC units, yearly production capacities of SOEC cells and stacks as well as operating conditions of manufacturing lines. It resulted in installed capital costs of 309–395 €/kW for SOEC units integrated into power-to-methane plants (reference case) and of 380–494 €/kW for stand-alone SOEC units. This highlights the cost reduction potential of the SOEC technology when thermally coupled with a steam source. These costs were compared with previous capital cost estimates for future SOEC, proton exchange membrane (PEM) and alkaline electrolysis systems available in the literature. A sensitivity analysis allowed to identify which parameters have the highest impact on installed system costs. In the least favorable conditions, it was estimated that they could raise up to 494–618 €/kW for SOEC units in the reference case and up to 573–727 €/kW for stand-alone SOEC units.     

A Novel Stochastic Game Via the Quantitative μ-calculus

The quantitative μ-calculus qMμ extends the applicability of Kozen's standard μ-calculus [D. Kozen, Results on the propositional μ-calculus, Theoretical Computer Science 27 (1983) 333–354] to probabilistic systems. Subsequent to its introduction [C. Morgan, and A. McIver, A probabilistic temporal calculus based on expectations, in: L. Groves and S. Reeves, editors, Proc. Formal Methods Pacific '97 (1997), available at [PSG, Probabilistic Systems Group: Collected reports, http://web.comlab.ox.ac.uk/oucl/research/areas/probs/bibliography.html]; also appears at [A. McIver, and C. Morgan, “Abstraction, Refinement and Proof for Probabilistic Systems,” Technical Monographs in Computer Science, Springer, New York, 2005, Chap. 9], M. Huth, and M. Kwiatkowska, Quantitative analysis and model checking, in: Proceedings of 12th annual IEEE Symposium on Logic in Computer Science, 1997] it has been developed by us [A. McIver, and C. Morgan, Games, probability and the quantitative μ-calculus qMu, in: Proc. LPAR, LNAI 2514 (2002), pp. 292–310, revised and expanded at [A. McIver, and C. Morgan, Results on the quantitative μ-calculus qMμ (2005), to appear in ACM TOCL]; also appears at [A. McIver, and C. Morgan, “Abstraction, Refinement and Proof for Probabilistic Systems,” Technical Monographs in Computer Science, Springer, New York, 2005, Chap. 11], A. McIver, and C. Morgan, “Abstraction, Refinement and Proof for Probabilistic Systems,” Technical Monographs in Computer Science, Springer, New York, 2005, A. McIver, and C. Morgan, Results on the quantitative μ-calculus qMμ (2005), to appear in ACM TOCL] and by others [L. de Alfaro, and R. Majumdar, Quantitative solution of omega-regular games, Journal of Computer and System Sciences 68 (2004) 374–397]. Beyond its natural application to define probabilistic temporal logic [C. Morgan, and A. McIver, An expectation-based model for probabilistic temporal logic, Logic Journal of the IGPL 7 (1999), pp. 779–804, also appears at [A. McIver, and C. Morgan, “Abstraction, Refinement and Proof for Probabilistic Systems,” Technical Monographs in Computer Science, Springer, New York, 2005, Chap.10]], there are a number of other areas that benefit from its use.One application is stochastic two-player games, and the contribution of this paper is to depart from the usual notion of “absolute winning conditions” and to introduce a novel game in which players can “draw”.The extension is motivated by examples based on economic games: we propose an extension to qMμ so that they can be specified; we show that the extension can be expressed via a reduction to the original logic; and, via that reduction, we prove that the players can play optimally in the extended game using memoryless strategies.     

Distribution of extractives in Sitka spruce (Picea sitchensis) grown in the northern UK

The distribution of acetone soluble extractives in Sitka spruce (Picea sitchensis) grown in Northern Britain was determined. Neither yield class, latitude, longitude nor thinning were found to have an impact on the total amount of acetone soluble extractives. More extractives were present in heartwood compared to sapwood but there were no significant differences in extractive content with stem height. A spectroscopic method capable of medium to high throughput of samples was developed to assess the relative amounts of aliphatic, carbonyl and aromatic functional groups in wood extractives. Heartwood contained a higher relative amount of aromatics than sapwood. Again no significant influence of site factors or stem height was found in terms of extractive composition. The low and stable extractive content of Sitka spruce contributes to its outstanding pulping properties and makes the wood ideally suited for applications like interior cladding or shavings for animal bedding where volatile extractives are of concern.     

Contact‐Killing Polyelectrolyte Microcapsules Based on Chitosan Derivatives

Polyelectrolyte‐multilayer microcapsules are made by layer‐by‐layer (LbL) assembly of oppositely charged polyelectrolytes onto sacrificial colloidal particles, followed by core removal. In this paper, contact‐killing polyelectrolyte microcapsules are prepared based solely on polysaccharides. To this end, water‐soluble quaternized chitosan (QCHI) with varying degrees of substitution (DS) and hyaluronic acid (HA) are assembled into thin films. The quaternary ammonium groups are selectively grafted on the primary amine group of chitosan by exploiting its reaction with glycidyltrimethylammonium chloride (GTMAC) under homogeneous aqueous acidic conditions. The morphology of the capsules is closely dependent on the DS of the quaternized chitosan derivatives, which suggests differences in their complexation with HA. The DS is also a key parameter to control the antibacterial activity of QCHI against Escherichia Coli (E. coli). Thus, capsules containing the QCHI derivative with the highest DS are shown to be the most efficient to kill E. coli while retaining their biocompatibility toward myoblast cells, which suggests their potential as drug carriers able to combat bacterial infections.