Impact of small promoter amounts on coke structure in dry reforming of methane over Ni/ ZrO2

Coke deposition is one of the main challenges in the commercialisation of dry reforming of methane over supported Ni catalysts. Besides the coke quantity, the structure of the deposits is also essential for the catalyst lifetime. Accordingly, in this study, we analysed the effect of Na, K, and Cs promoters on both these variables over Ni/ ZrO2 catalysts. Besides blocking the most active coke-forming sites already at low loading, the promoting effect of the alkali metals is also contributed by their coke gasification activity. To evaluate the additional impact of the latter, the behaviour of alkali-doped catalysts was compared to that for Mn-doped catalysts, exclusively featuring the site-blocking promotion mechanism. While the conversion is barely affected by the type of promoter, it has a profound effect on the amount and the composition of carbon deposits formed during the reaction. Promoting with K or Mn reduces the coke content to a similar degree but with less carbon fibres observed in the case of K. The promotion by Cs and Na results in the lowest coke content. The superior performance of Cs and Na-doped Ni/ZrO2 catalysts is attributed to the enhanced coke gasification via carbonate species on top of the site blocking effects.

[1]  Rahman Doost-Mohammady,et al.  Renew , 2022, GetMobile: Mobile Computing and Communications.

[2]  J. Lercher,et al.  Impact of Alkali and Alkali‐Earth Cations on Ni‐Catalyzed Dimerization of Butene , 2020, ChemCatChem.

[3]  E. Hensen,et al.  Ceria–zirconia encapsulated Ni nanoparticles for CO2 methanation , 2019, Catalysis Science & Technology.

[4]  K. Polychronopoulou,et al.  The Relationship between Reaction Temperature and Carbon Deposition on Nickel Catalysts Based on Al2O3, ZrO2 or SiO2 Supports during the Biogas Dry Reforming Reaction , 2019, Catalysts.

[5]  M. Zhang,et al.  Efficient Base-Metal NiMn/TiO2 Catalyst for CO2 Methanation , 2019, ACS Catalysis.

[6]  Aaas News,et al.  Book Reviews , 1893, Buffalo Medical and Surgical Journal.

[7]  D. Vine,et al.  Capturing the Genesis of an Active Fischer-Tropsch Synthesis Catalyst with Operando X-ray Nanospectroscopy. , 2018, Angewandte Chemie.

[8]  A. Veen,et al.  Dry Reforming of Methane at High Pressure in a Fixed-Bed Reactor with Axial Temperature Profile Determination , 2018, Catalysis Letters.

[9]  H. Arellano‐Garcia,et al.  Chemical CO2 recycling via dry and bi reforming of methane using Ni-Sn/Al2O3 and Ni-Sn/CeO2-Al2O3 catalysts , 2018 .

[10]  Joseph Zeaiter,et al.  Catalyst design for dry reforming of methane: Analysis review , 2018 .

[11]  I. Sajó,et al.  Na-promoted Ni/ZrO2 dry reforming catalyst with high efficiency: details of Na2O–ZrO2–Ni interaction controlling activity and coke formation , 2017 .

[12]  J. Lercher,et al.  Enhanced Activity in Methane Dry Reforming by Carbon Dioxide Induced Metal‐Oxide Interface Restructuring of Nickel/Zirconia , 2017 .

[13]  J. Hazemann,et al.  In-operando elucidation of bimetallic CoNi nanoparticles during high-temperature CH 4 /CO 2 reaction , 2017 .

[14]  G. Rupprechter,et al.  Methane dry reforming over ceria-zirconia supported Ni catalysts , 2016 .

[15]  R. Prasad,et al.  An overview on dry reforming of methane: strategies to reduce carbonaceous deactivation of catalysts , 2016 .

[16]  A. Urakawa,et al.  High-pressure advantages in stoichiometric hydrogenation of carbon dioxide to methanol , 2016 .

[17]  Z. Iqbal,et al.  Energy efficient methane tri-reforming for synthesis gas production over highly coke resistant nanocrystalline Ni–ZrO2 catalyst , 2016 .

[18]  Jeffrey T. Miller,et al.  Differences in the Nature of Active Sites for Methane Dry Reforming and Methane Steam Reforming over Nickel Aluminate Catalysts , 2016 .

[19]  K. Lee,et al.  Citrate Sol-Gel Method for the Preparation of Sodium Zirconate for High-Temperature CO2 Sorption , 2016 .

[20]  Yuehua Wu,et al.  Effect of support on the performance of Ni-based catalyst in methane dry reforming , 2015 .

[21]  V. Galvita,et al.  Enhanced Carbon-Resistant Dry Reforming Fe-Ni Catalyst: Role of Fe , 2015 .

[22]  R. Schomäcker,et al.  Ni0.05Mn0.95O catalysts for the dry reforming of methane , 2015 .

[23]  N. Ogawa,et al.  A monomeric [Zr(CO3)4](4-) complex in an ammonium zirconium carbonate aqueous solution studied by extended X-ray absorption fine structure, Raman and nuclear magnetic resonance spectroscopy. , 2015, Dalton transactions.

[24]  P. A. Jensen,et al.  Stability and resistance of nickel catalysts for hydrodeoxygenation: carbon deposition and effects of sulfur, potassium, and chlorine in the feed , 2014 .

[25]  Yuhan Sun,et al.  The Properties of Individual Carbon Residuals and Their Influence on The Deactivation of Ni–CaO–ZrO2 Catalysts in CH4 Dry Reforming , 2014 .

[26]  M. Muhler,et al.  The role of carbonaceous deposits in the activity and stability of Ni-based catalysts applied in the dry reforming of methane , 2022 .

[27]  A. Lyngfelt,et al.  Investigation of different manganese ores as oxygen carriers in chemical-looping combustion (CLC) for solid fuels , 2014 .

[28]  Stephan Andreas Schunk,et al.  Methane Dry Reforming at High Temperature and Elevated Pressure: Impact of Gas-Phase Reactions , 2013 .

[29]  T. Mattisson,et al.  Mechanisms of Solid Fuel Conversion by Chemical‐Looping Combustion (CLC) using Manganese Ore: Catalytic Gasification by Potassium Compounds , 2013 .

[30]  F. Kapteijn,et al.  Oxidative dehydrogenation of ethylbenzene to styrene over alumina: effect of calcination , 2013 .

[31]  W. Marsden.  I and J , 2012 .

[32]  H. Pfeiffer,et al.  Analysis of the CO2 capture in sodium zirconate (Na2ZrO3). Effect of the water vapor addition , 2011 .

[33]  F. Mauri,et al.  Structural properties of carbon nanotubes derived from (13)C NMR , 2011 .

[34]  G. Henkelman,et al.  Mechanism for the water–gas shift reaction on monofunctional platinum and cause of catalyst deactivation , 2011 .

[35]  R. Gläser,et al.  Nickel‐Loaded Zirconia Catalysts with Large Specific Surface Area for High‐Temperature Catalytic Applications , 2011 .

[36]  E. Taglauer.  Surface Chemical Composition , 2008 .

[37]  N. Besley,et al.  NMR chemical shifts of molecules encapsulated in single walled carbon nanotubes. , 2008, The Journal of chemical physics.

[38]  A. Dalai,et al.  Development of stable bimetallic catalysts for carbon dioxide reforming of methane , 2007 .

[39]  A. Ferrari,et al.  Raman spectroscopy of graphene and graphite: Disorder, electron phonon coupling, doping and nonadiabatic effects , 2007 .

[40]  B. Weckhuysen,et al.  X-ray absorption spectroscopy of Mn/Co/TiO2 Fischer-Tropsch catalysts: relationships between preparation method, molecular structure, and catalyst performance. , 2006, The journal of physical chemistry. B.

[41]  M. Illán-Gómez,et al.  Effect of potassium content in the activity of K-promoted Ni/Al2O3 catalysts for the dry reforming of methane , 2006 .

[42]  Z. Xiaoming,et al.  Production of Synthesis Gas via Methane Reforming with CO2 on Ni/SiO2 Catalysts Promoted by Alkali and Alkaline Earth Metals , 2005 .

[43]  H. Lasa,et al.  Coke Formation over a Nickel Catalyst under Methane Dry Reforming Conditions: Thermodynamic and Kinetic Models , 2005 .

[44]  Jae-Woo Kim,et al.  Carbon dioxide reforming of methane over Ni incorporated into Ce–ZrO2 catalysts , 2004 .

[45]  T. Yashima,et al.  Surface properties of a coke-free Sn doped nickel catalyst for the CO2 reforming of methane , 2004 .

[46]  F. Kapteijn,et al.  Catalyst performance testing: bed dilution revisited , 2002 .

[47]  J. Nørskov,et al.  Steam Reforming and Graphite Formation on Ni Catalysts , 2002 .

[48]  Colin W. Park,et al.  Growth of filamentous carbon from the surface of Ni/SiO2 doped with alkali metal bromides. , 2002, Journal of colloid and interface science.

[49]  Riichiro Saito,et al.  Raman spectroscopy on isolated single wall carbon nanotubes , 2002 .

[50]  Kevin Barraclough,et al.  I and i , 2001, BMJ : British Medical Journal.

[51]  Toshiaki Mori,et al.  Role of Potassium in Carbon-Free CO2 Reforming of Methane on K-Promoted Ni/Al2O3 Catalysts , 2001 .

[52]  J. S. Lee,et al.  The role of MnO in Ni/MnO-Al2O3 catalysts for carbon dioxide reforming of methane , 2001 .

[53]  B. Feldman,et al.  13C NMR spectroscopy of amorphous hydrogenated carbon — further evidence of inhomogeneity , 2001 .

[54]  F. Frusteri,et al.  Potassium-enhanced stability of Ni/MgO catalysts in the dry-reforming of methane , 2001 .

[55]  C. H. Bartholomew.  Mechanisms of catalyst deactivation , 2001 .

[56]  Freek Kapteijn,et al.  Catalyst deactivation: is it predictable?: What to do? , 2001 .

[57]  J. Robertson,et al.  Interpretation of Raman spectra of disordered and amorphous carbon , 2000 .

[58]  J. Nørskov,et al.  Chemisorption of Methane on Ni(100) and Ni(111) Surfaces with Preadsorbed Potassium , 1999 .

[59]  Clausen,et al.  Design of a surface alloy catalyst for steam reforming , 1998, Science.

[60]  G. Ertl,et al.  Handbook of Heterogeneous Catalysis , 1997 .

[61]  R. T. Yang,et al.  Unified Mechanism of Alkali and Alkaline Earth Catalyzed Gasification Reactions of Carbon by CO2 and H2O , 1997 .

[62]  D. Acosta,et al.  Characterization of Alkali-Doped Ni/SiO2 Catalysts , 1997 .

[63]  T. Fukui,et al.  Suppression of carbon deposition in the CO2-reforming of CH4 by adding basic metal oxides to a Ni/Al2O3 catalyst , 1996 .

[64]  Yu‐Wen Chen,et al.  Temperature-programmed-reduction studies of nickel oxide/alumina catalysts: effects of the preparation method , 1995 .

[65]  F. Kapteijn,et al.  Isotopic steady-state and step-response study on carbon gasification catalyzed by calcium , 1995 .

[66]  J. Moulijn,et al.  Towards a unified theory of reactions of carbon with oxygen-containing molecules , 1995 .

[67]  D. Stirling,et al.  TPR studies of the effects of preparation conditions on supported nickel catalysts , 1990 .

[68]  F. Chen,et al.  Effect of alkali and alkaline-earth metals on the resistivity to coke formation and sintering of nickel-alumina catalysts , 1990 .

[69]  C. Bennett,et al.  A comparison of activated hydrogen chemisorption on some supported metal catalysts , 1988 .

[70]  F. Topsøe,et al.  Statistical models for ensemble control by alloying and poisoning of catalysts: I. Mathematical assumptions and derivations , 1987 .

[71]  R. Standley,et al.  Determination of bonding in amorphous carbon films: a quantitative comparison of core-electron energy-loss spectroscopy and 13C nuclear magnetic resonance spectroscopy , 1986 .

[72]  F. Kapteijn,et al.  Kinetics of the alkali carbonate catalysed gasification of carbon , 1986 .

[73]  J. E. Lester,et al.  The effect of supports on the chemisorptive properties of catalysts: I. Magnetic studies of nickel catalysts , 1985 .

[74]  Jens R. Rostrup-Nielsen,et al.  SULFUR-PASSIVATED NICKEL CATALYSTS FOR CARBON-FREE STEAM REFORMING OF METHANE , 1984 .

[75]  W. Mross.  Alkali Doping in Heterogeneous Catalysis , 1983 .

[76]  D. Mckee.  Mechanisms of the alkali metal catalysed gasification of carbon , 1983 .

[77]  P. S. Harris,et al.  Formation of carbonaceous deposits from the reaction of methane over nickel , 1975 .

[78]  D. Mckee.  Effect of metallic impurities on the gasification of graphite in water vapor and hydrogen , 1974 .

[79]  B. Borie,et al.  Alkali Metal-Nickel Oxides of the Type MNiO2 , 1954 .