Hydrogen from biogas: Catalytic tri-reforming process with Ni/LaCeO mixed oxides

Abstract A series of Ni catalysts supported on La Ce O mixed oxides with different Ni content (Ce1−3xLa2xNixO2−δ, x = 0.10; 0.20 and 0.25) prepared by combustion synthesis, was tested in tri-reforming reaction of simulated biogas. The influence of O2/CH4, CH4/CO2 molar ratios in the reaction stream has been evaluated caring out the reaction at 800 °C, under a fixed gas hourly space velocity (GHSV = 31,000 h−1). The highest catalytic activity was obtained with the Ce0.70La0.20Ni0.10O2−δ sample that showed high stability (CH4, CO2 conversion rates and the H2/CO molar ratio in the reformed gas were 1.56 mmol/s gNi, 0.56 mmol/s gNi and 1.57, respectively) under an average biogas composition (CH4/CO2 = 1.5). No carbon deposition was detected after 150 h of reaction. The characterizations of the samples have highlighted that Ni and La ions were partially incorporated into CeO2 framework, cubic fluorite structure of CeO2 support was retained also at high level of doping. Ni metal phase in close contact with La2O3–CeO2 matrix coupled with Ni2+ with high cationic character appeared to be responsible of the catalytic activity and stability of the catalysts.

[1]  A. Bhattacharya,et al.  Surface segregation of lanthanum and cerium ions in ceria/lanthana solid solutions: comparison between experimental results and a statistical–mechanical model , 2003 .

[2]  Hong Wang,et al.  Nickel-grafted TUD-1 mesoporous catalysts for carbon dioxide reforming of methane , 2010 .

[3]  M. Morris,et al.  The complex synthesis and solid state chemistry of ceria–lanthana solid solutions prepared via a hexamethylenetetramine precipitation , 2011 .

[4]  K. Al Chemistry of nanocrystalline oxide materials , 2013 .

[5]  Ta-Jen Huang,et al.  Effect of steam and carbon dioxide pretreatments on methane decomposition and carbon gasification over doped-ceria supported nickel catalyst , 2005 .

[6]  A. Cao,et al.  Highly stable, mesoporous mixed lanthanum–cerium oxides with tailored structure and reducibility , 2011 .

[7]  E. Moroz,et al.  Nanostructured, Gd-doped ceria promoted by Pt or Pd: investigation of the electronic and surface structures and relations to chemical properties. , 2005, The journal of physical chemistry. B.

[8]  H. Yamatera,et al.  X-ray photoelectron spectroscopy of rare-earth compounds , 1984 .

[9]  J. Assaf,et al.  The advantages of air addition on the methane steam reforming over Ni/γ-Al2O3 , 2004 .

[10]  Xiyuan Sun,et al.  A DFT study on small M-doped titanium (M = V, Fe, Ni) clusters: structures, chemical bonds and magnetic properties , 2009 .

[11]  C. H. Bartholomew Carbon Deposition in Steam Reforming and Methanation , 1982 .

[12]  Young-Soon Baek,et al.  Tri-reforming of CH4 using CO2 for production of synthesis gas to dimethyl ether , 2003 .

[13]  Dong Ju Moon,et al.  Nickel-based tri-reforming catalyst for the production of synthesis gas , 2007 .

[14]  D. L Trimm,et al.  Catalysts for the control of coking during steam reforming , 1999 .

[15]  B. Zhang,et al.  Catalytic performance of La–Ce–O mixed oxide for combustion of methane , 2010 .

[16]  Liyi Shi,et al.  Morphology Dependence of Catalytic Properties of Ni/CeO2 Nanostructures for Carbon Dioxide Reforming of Methane , 2012 .

[17]  K. Schierbaum,et al.  The electronic structure of stoichiometric and reduced CeO2 surfaces: an XPS, UPS and HREELS study , 1994 .

[18]  S. Orlik,et al.  Tri-reforming of methane on structured Ni-containing catalysts , 2012, Theoretical and Experimental Chemistry.

[19]  Aldo Steinfeld,et al.  Thermoneutral tri-reforming of flue gases from coal- and gas-fired power stations , 2006 .

[20]  S. Nikolaev,et al.  Synergistic and size effects in selective hydrogenation of alkynes on gold nanocomposites , 2009 .

[21]  W. D. Collins,et al.  The Use of Hydrogenated Oils in the Manufacture of Tin Plate , 1920 .

[22]  Aldo Steinfeld,et al.  Fuel saving, carbon dioxide emission avoidance, and syngas production by tri-reforming of flue gases from coal- and gas-fired power stations, and by the carbothermic reduction of iron oxide , 2006 .

[23]  J. Hanson,et al.  Unusual Physical and Chemical Properties of Ni in Ce1-xNixO2-y Oxides: Structural Characterization and Catalytic Activity for the Water Gas Shift Reaction , 2010 .

[24]  Jurka Batista,et al.  Efficient catalytic abatement of greenhouse gases: Methane reforming with CO2 using a novel and thermally stable Rh–CeO2 catalyst , 2012 .

[25]  M. Balat Potential importance of hydrogen as a future solution to environmental and transportation problems , 2008 .

[26]  Carl-Jochen Winter,et al.  Hydrogen energy — Abundant, efficient, clean: A debate over the energy-system-of-change☆ , 2009 .

[27]  A. M. Alekseev,et al.  Hysteresis of thermogravimetric curves of nickel catalysts for methane conversion in CH4+CO2 mixture , 1984 .

[28]  Antonio J. Martín,et al.  Dry reforming of methane to syngas over La-promoted hydrotalcite clay-derived catalysts , 2012 .

[29]  Jin-Hong Kim,et al.  Effect of metal particle size on coking during CO2 reforming of CH4 over Ni–alumina aerogel catalysts , 2000 .

[30]  M. S. Hegde,et al.  Chemistry of Nanocrystalline Oxide Materials: Combustion Synthesis, Properties and Applications , 2008 .

[31]  Min Guo,et al.  Hydrothermal Preparation and Oxygen Storage Capacity of Nano CeO2-based Materials , 2007 .

[32]  Saija Rasi,et al.  Trace compounds of biogas from different biogas production plants. , 2007 .

[33]  J. Assaf,et al.  Structural features of La1-xCexNiO3 mixed oxides and performance for the dry reforming of methane , 2006 .

[34]  Ali T-Raissi,et al.  Hydrogen production by catalytic processing of renewable methane-rich gases , 2008 .

[35]  L. Schmidt,et al.  Effects of H2O and CO2 addition in catalytic partial oxidation of methane on Rh , 2009 .

[36]  M. Romeo,et al.  Effect of surface treatments, photon and electron impacts on the ceria 3d core level , 1995 .

[37]  Ta-Jen Huang,et al.  Study of carbon dioxide reforming of methane over Ni/yttria-doped ceria and effect of thermal treatments of support on the activity behaviors , 2003 .

[38]  M. G. Cook,et al.  X-ray photoelectron studies on some oxides and hydroxides of cobalt, nickel, and copper , 1975 .

[39]  Min Wang,et al.  Characterization and catalytic performances of La doped Pd/CeO2 catalysts for methanol decomposition , 2004 .

[40]  Xiaoming Zheng,et al.  The deposition of coke from methane on a Ni/MgAl2O4 catalyst , 2007 .

[41]  Wei Chu,et al.  Synthesis, characterization and catalytic performances of Ce-SBA-15 supported nickel catalysts for methane dry reforming to hydrogen and syngas , 2012 .

[42]  W. Dow,et al.  Yttria-stabilized zirconia supported copper oxide catalyst. I. Effect of oxygen vacancy of support on copper oxide reduction , 1996 .

[43]  Chunshan Song,et al.  Tri-reforming of methane: a novel concept for catalytic production of industrially useful synthesis gas with desired H2/CO ratios , 2004 .

[44]  A. Cao,et al.  Au-mixed lanthanum/cerium oxide catalysts for water gas shift , 2010 .

[45]  J. Fierro,et al.  Role of bulk and surface structures of La1−xSrxNiO3 perovskite-type oxides in methane combustion , 2001 .

[46]  B. M. Reddy,et al.  Novel Nanocrystalline Ce1−xLaxO2−δ (x = 0.2) Solid Solutions: Structural Characteristics and Catalytic Performance , 2010 .

[47]  V. Recupero,et al.  Hydrogen production by methane tri-reforming process over Ni–ceria catalysts: Effect of La-doping , 2011 .

[48]  Suttichai Assabumrungrat,et al.  Methane steam reforming over Ni/Ce-ZrO2 catalyst : Influences of Ce-ZrO2 support on reactivity, resistance toward carbon formation, and intrinsic reaction kinetics , 2005 .

[49]  A. Kotani,et al.  Photoemission on 3d core levels of Cerium: An experimental and theoretical investigation of the reduction of cerium dioxide , 1989 .

[50]  B. Weckhuysen,et al.  Phase segregation in cerium-lanthanum solid solutions. , 2006, The journal of physical chemistry. B.

[51]  He Fei,et al.  Studies on nickel-based catalysts for carbon dioxide reforming of methane , 2005 .

[52]  Young-Sam Oh,et al.  Methane reforming over Ni/Ce-ZrO2 catalysts: effect of nickel content , 2002 .

[53]  Fabio B. Noronha,et al.  Partial oxidation and autothermal reforming of methane on Pd/CeO2–Al2O3 catalysts , 2008 .

[54]  F. Rossi,et al.  Chemical absorption of H2S for biogas purification , 2004 .

[55]  Dongyan Xu,et al.  A novel process for converting coalmine-drained methane gas to syngas over nickel–magnesia solid solution catalysts , 2005 .

[56]  K. Kunimori,et al.  Performance of NiO–MgO solid solution-supported Pt catalysts in oxidative steam reforming of methane , 2005 .

[57]  X. Verykios,et al.  Carbon dioxide reforming of methane to synthesis gas over supported Ni catalysts , 1994 .

[58]  K. Tomishige Syngas production from methane reforming with CO2/H2O and O2 over NiO–MgO solid solution catalyst in fluidized bed reactors , 2004 .

[59]  P. Sánchez,et al.  Precursor influence and catalytic behaviour of Ni/CeO2 and Ni/SiC catalysts for the tri-reforming process , 2012 .

[60]  Shaobin Wang,et al.  Effects of promoters on catalytic activity and carbon deposition of Ni/γ‐Al2O3 catalysts in CO2 reforming of CH4 , 2000 .

[61]  A. Mitsos,et al.  Optimal design and operation of a natural gas tri-reforming reactor for DME synthesis , 2009 .

[62]  J. Kuhn,et al.  Synthesis gas production to desired hydrogen to carbon monoxide ratios by tri-reforming of methane using Ni–MgO–(Ce,Zr)O2 catalysts , 2012 .

[63]  F. Mondragón,et al.  Carbon dioxide reforming of methane over La2NiO4 as catalyst precursor—Characterization of carbon deposition , 2008 .

[64]  Bingsi Liu,et al.  Preparation of La2NiO4/ZSM-5 catalyst and catalytic performance in CO2/CH4 reforming to syngas , 2005 .

[65]  Shufen Fan,et al.  A comparative study on perovskite-type mixed oxide catalysts A′xA1 − xBO3 − λ (A′ = Ca, Sr, A = La, B = Mn, Fe, Co) for NH3 oxidation , 1989 .

[66]  F. Schäfers,et al.  Relative sub-shell photoionization cross-sections of nickel metal determined by hard X-ray high kinetic energy photoemission , 2013 .

[67]  S. Kawi,et al.  Promotional effect of alkaline earth over Ni–La2O3 catalyst for CO2 reforming of CH4: Role of surface oxygen species on H2 production and carbon suppression , 2011 .

[68]  Shengfu Ji,et al.  Effect of O2 and H2O on the tri-reforming of the simulated biogas to syngas over Ni-based SBA-15 catalysts , 2010 .

[69]  Wenjie Shen,et al.  Reduction property and catalytic activity of Ce1-XNiXO2 mixed oxide catalysts for CH4 oxidation , 2003 .

[70]  Debora Fino,et al.  A novel ZnO-based adsorbent for biogas purification in H2 production systems , 2011 .

[71]  C. Abreu,et al.  Kinetic evaluation of the tri-reforming process of methane for syngas production , 2010 .

[72]  Lucun Guo,et al.  Effect of Sm and Mg co-doping on the properties of ceria-based electrolyte materials for IT-SOFCs , 2009 .

[73]  Huiquan Li,et al.  Preparation of Ni/MgxTi1 − xO catalysts and investigation on their stability in tri-reforming of methane , 2007 .

[74]  V. Recupero,et al.  Catalytic Performance of Ce1−xNixO2 Catalysts for Propane Oxidative Steam Reforming , 2008 .

[75]  K. Sotowa,et al.  Methane steam reforming over Ce–ZrO2-supported noble metal catalysts at low temperature , 2004 .

[76]  R. Gorte,et al.  Steam reforming of n-butane on Pd/ceria , 2001 .

[77]  Amit Kumar,et al.  Luminescence properties of europium-doped cerium oxide nanoparticles: role of vacancy and oxidation states. , 2009, Langmuir : the ACS journal of surfaces and colloids.