Ethane steam reforming over a platinum/alumina catalyst: effect of sulphur poisoning

In this study we have examined the adsorption of hydrogen sulfide and methanethiol over platinum catalysts and examined the effect of these poisons on the steam reforming of ethane. Adsorption of hydrogen sulfide was measured at 293 and 873 K. At 873 K the adsorbed state of hydrogen sulfide in the presence of hydrogen was SH rather than S, even though the Pt:S ratio was unity. The effect of 11.2 ppm hydrogen sulfide or methanethiol on the steam reforming of ethane was studied at 873 K and 20 barg. Both poisons deactivated the catalyst over a number of hours, but methanethiol was found to be more deleterious, reducing the conversion by almost an order of magnitude, possibly due to the co-deposition of sulfur and carbon. Changes in the selectivity revealed that the effect of sulfur was not uniform on the reactions occurring, with the production of methane reduced proportionally more than the other products, due to the surface sensitivity of the hydrogenolysis and methanation reactions. The water-gas shift reaction was affected to a lesser extent. No regeneration was observed when hydrogen sulfide was removed from the feedstream in agreement with adsorption studies. A slight regeneration was observed when methanethiol was removed from the feed, but this was believed to be due to the removal of carbon rather than sulfur. The overall effect of sulfur poisoning was to reduce activity and enhance hydrogen selectivity

Kohlenstoffbildung auf Nickel und Nickel-Kupfer-Legierungskatalysatoren

Equilibrium, kinetic and morphological studies of carbon formation in CH4+H2, CO, and CO+H2 gases on silica supported nickel and nickel-copper catalysts are reviewed. The equilibrium deviates in all cases from graphite equilibrium and more so in CO+CO2 than in CH4+H2. A kinetic model based on information from surface science results with chemisorption of CH4 and possibly also the first dehydrogenation step as rate controlling describes carbon formation on nickel catalyst in CH4+H2 well. The kinetics of carbon formation in CO and CO+H2 gases are in agreement with CO disproportionation as rate determining step. The presence of hydrogen influences strongly the chemisorption of CO. Carbon filaments are formed when hydrogen is present in the gas while encapsulating carbon dominates in pure CO. Small amounts of Cu alloying promotes while larger amounts (Cu : Ni ≥ 0.1) inhibits carbon formation and changes the morphology of the filaments ("octopus" carbon formation). Adsorption induced nickel segregation changes the kinetics of the alloy catalysts at high carbon activities. Modifications suggested in some very recent papers on the basis of new results are also briefly discussed.Center for Surface Reactivity

Thermo-electrochemical production of compressed hydrogen from methane with near-zero energy loss

[EN] Conventional production of hydrogen requires large industrial plants to minimize energy losses and capital costs associated with steam reforming, water-gas shift, product separation and compression. Here we present a protonic membrane reformer (PMR) that produces high-purity hydrogen from steam methane reforming in a single-stage process with near-zero energy loss. We use a BaZrO3-based proton-conducting electrolyte deposited as a dense film on a porous Ni composite electrode with dual function as a reforming catalyst. At 800 degrees C, we achieve full methane conversion by removing 99% of the formed hydrogen, which is simultaneously compressed electrochemically up to 50 bar. A thermally balanced operation regime is achieved by coupling several thermo-chemical processes. Modelling of a small-scale (10 kg H-2 day-1) hydrogen plant reveals an overall energy efficiency of >87%. The results suggest that future declining electricity prices could make PMRs a competitive alternative for industrial-scale hydrogen plants integrating CO2 capture.This work was supported by the Research Council of Norway (grant 256264) and the Spanish Government (SEV-2016-0683 grant).Malerød-Fjeld, H.; Clark, D.; Yuste Tirados, I.; Zanón González, R.; Catalán-Martínez, D.; Beeaff, D.; Hernández Morejudo, S.... (2017). Thermo-electrochemical production of compressed hydrogen from methane with near-zero energy loss. Nature Energy. 2(12):923-931. https://doi.org/10.1038/s41560-017-0029-4S923931212Morejudo, S. H. et al. Direct conversion of methane to aromatics in a catalytic co-ionic membrane reactor. Science 353, 563–566 (2016).Chu, S. & Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature 488, 294–303 (2012).Logan, B. E. & Elimelech, M. Membrane-based processes for sustainable power generation using water. Nature 488, 313–319 (2012).Rostrup-Nielsen, J. R. Catalysis and large-scale conversion of natural gas. Catal. Today 21, 257–267 (1994).Voss, C. Applications of pressure swing adsorption technology. Adsorption 11, 527–529 (2005).Gallucci, F., Fernandez, E., Corengia, P. & van Sint Annaland, M. Recent advances on membranes and membrane reactors for hydrogen production. Chem. Eng. Sci. 92, 40–66 (2013).Boeltken, T., Wunsch, A., Gietzelt, T., Pfeifer, P. & Dittmeyer, R. Ultra-compact microstructured methane steam reformer with integrated Palladium membrane for on-site production of pure hydrogen: Experimental demonstration. Int. J. Hydrogen Energy 39, 18058–18068 (2014).Al-Mufachi, N. A., Rees, N. V. & Steinberger-Wilkens, R. Hydrogen selective membranes: A review of palladium-based dense metal membranes. Renew. Sustainable Energy Rev. 47, 540–551 (2015).Sengodan, S. et al. Layered oxygen-deficient double perovskite as an efficient and stable anode for direct hydrocarbon solid oxide fuel cells. Nat. Mater. 14, 205–209 (2015).Myung, J.-h, Neagu, D., Miller, D. N. & Irvine, J. T. S. Switching on electrocatalytic activity in solid oxide cells. Nature 537, 528–531 (2016).Iwahara, H., Uchida, H., Ono, K. & Ogaki, K. Proton conduction in sintered oxides based on BaCeO3. J. Electrochem. Soc. 135, 529–533 (1988).Hamakawa, S., Hibino, T. & Iwahara, H. Electrochemical methane coupling using proton conductors. J. Electrochem. Soc. 140, 459–462 (1993).Bonanos, N., Knight, K. S. & Ellis, B. Perovskite solid electrolytes: structure, transport properties and fuel cell applications. Solid State Ion. 79, 161–170 (1995).Norby, T. Solid-state protonic conductors: principles, properties, progress and prospects. Solid State Ion. 125, 1–11 (1999).Kreuer, K. D. On the development of proton conducting materials for technological applications. Solid State Ion. 97, 1–15 (1997).Kreuer, K. D. Aspects of the formation and mobility of protonic charge carriers and the stability of perovskite-type oxides. Solid State Ion. 125, 285–302 (1999).Kreuer, K. D. Proton-conducting oxides. Annu. Rev. Mater. Res. 33, 333–359 (2003).Tao, S. W. & Irvine, J. T. S. A stable, easily sintered proton-conducting oxide electrolyte for moderate-temperature fuel cells and electrolyzers. Adv. Mater. 18, 11581-1584 (2006).Wang, H., Peng, R., Wu, X., Hu, J. & Xia, C. Sintering behavior and conductivity study of yttrium-doped BaCeO3–BaZrO3 solid solutions using ZnO additives. J. Am. Ceram. Soc. 92, 2623–2629 (2009).Coors, W. G. in Advances in Ceramics—Synthesis and Characterization, Processing and Specific Applications (Ed. Sikalidis, C.) Ch. 22, 501–520 (InTech, UK, 2011) (2011).Manabe, R. et al. Surface protonics promotes catalysis. Sci. Rep. 6, 38007, (2016).Rohland, B., Eberle, K., Ströbel, R., Scholta, J. & Garche, J. Electrochemical hydrogen compressor. Electrochimica Acta 43, 3841–3846 (1998).Kochetova, N., Animitsa, I., Medvedev, D., Demin, A. & Tsiakaras, P. Recent activity in the development of proton-conducting oxides for high-temperature applications. RSC Adv. 6, 73222–73268 (2016).Yamazaki, Y. et al. Proton trapping in yttrium-doped barium zirconate. Nat. Mater. 12, 647–651 (2013).Kjølseth, C. et al. Space-charge theory applied to the grain boundary impedance of proton conducting BaZr0.9Y0.1O3-δ . Solid State Ion. 181, 268–275 (2010).Coors, W. G A stoichiometric titration method for measuring galvanic hydrogen flux in ceramic hydrogen separation membranes. J. Membr. Sci. 458, 245–253 (2014).Zeppieri, M., Villa, P. L., Verdone, N., Scarsella, M. & De Filippis, P. Kinetic of methane steam reforming reaction over nickel- and rhodium-based catalysts. Appl. Catal. A 387, 147–154 (2010).Wang, B., Zhu, J. & Lin, Z. A theoretical framework for multiphysics modeling of methane fueled solid oxide fuel cell and analysis of low steam methane reforming kinetics. Appl. Energy 176, 1–11 (2016).Overview of Electricity Production and Use in Europe (European Environment Agency, 2016).Edwards, R., Larive, J.-F., Rickeard, D. & Weindorf, W. Well-To-Wheels Analysis of Future Automotive Fuels and Powertrains in the European Context, Well-to-Tank Report Version 4.a, JEC Well-to-Wheels Analysis (Joint Research Centre, 2014).Cho, V. H., Hamilton, B. A. & Kuehn, N. J. Assessment of Hydrogen Production with CO 2 Capture Volume 1: Baseline State-of-the-Art Plants (National Energy Technology Laboratory, 2010).Schjølberg, I. et al. Small-Scale Reformers for On-Site Hydrogen Supply (International Energy Agency-Hydrogen Implementing Agreement, 2012).de Visser, E. et al. Dynamis CO2 quality recommendations. Int. J. Greenhouse Gas Control 2, 478–484 (2008).Bertucciolo, L. et al. Development of Water Electrolysis in the European Union (Fuel Cells and Hydrogen Joint Undertaking, 2014).Edwards, R. et al. Well-To-Wheels Analysis of Future Automotive Fuels and Powertrains in the European Context, Well-to-Wheels Report Version 4.a, JEC Well-to-Wheels Analysis (Joint Research Centre 2014).Huss, A., Maas, H. & Hass, H. Well-to-Wheels Analysis of Future Automotive Fuels and Powertrains in the European Context, Tank-to-Wheels Report Version 4.0, JEC Technical Reports (Joint Research Centre, 2013)

Autothermal reforming of palm empty fruit bunch bio-oil: thermodynamic modelling

This work focuses on thermodynamic analysis of the autothermal reforming of palm empty fruit bunch (PEFB) bio-oil for the production of hydrogen and syngas. PEFB bio-oil composition was simulated using bio-oil surrogates generated from a mixture of acetic acid, phenol, levoglucosan, palmitic acid and furfural. A sensitivity analysis revealed that the hydrogen and syngas yields were not sensitive to actual bio-oil composition, but were determined by a good match of molar elemental composition between real bio-oil and surrogate mixture. The maximum hydrogen yield obtained under constant reaction enthalpy and pressure was about 12 wt% at S/C = 1 and increased to about 18 wt% at S/C = 4; both yields occurring at equivalence ratio Φ of 0.31. The possibility of generating syngas with varying H2 and CO content using autothermal reforming was analysed and application of this process to fuel cells and Fischer-Tropsch synthesis is discussed. Using a novel simple modelling methodology, reaction mechanisms were proposed which were able to account for equilibrium product distribution. It was evident that different combinations of reactions could be used to obtain the same equilibrium product concentrations. One proposed reaction mechanism, referred to as the ‘partial oxidation based mechanism’ involved the partial oxidation reaction of the bio-oil to produce hydrogen, with the extent of steam reforming and water gas shift reactions varying depending on the amount of oxygen used. Another proposed mechanism, referred to as the ‘complete oxidation based mechanism’ was represented by thermal decomposition of about 30% of bio-oil and hydrogen production obtained by decomposition, steam reforming, water gas shift and carbon gasification reactions. The importance of these mechanisms in assisting in the eventual choice of catalyst to be used in a real ATR of PEFB bio-oil process was discussed