Biogas steam and oxidative reforming processes for synthesis gas and hydrogen production in conventional and microreactor reaction systems

Abstract In this work, a renewable source, biogas, was used for synthesis gas and hydrogen generation by steam reforming (SR) or oxidative reforming (OR) processes. Several Ni-based catalysts and a bimetallic Rh–Ni catalyst supported on magnesia or alumina modified with oxides like CeO2 and ZrO2 were used. For all the experiments, a synthetic biogas which consisted of 60% CH4 and 40% CO2 (vol.) was fed and tested in a fixed bed reactor system and in a microreactor reaction system at 1073 K and atmospheric pressure. The catalysts which achieved high activity and stability were impregnated in a microreactor to explore the viability of process intensification. For the SR process different steam to carbon ratios, S/C, varied from 1.0 to 3.0 were used. In the case of OR process the O2/CH4 ratio was varied from 0.125 to 0.50. Comparing conventional and microreactor reaction systems, one order of magnitude higher TOF and productivity values were obtained in the microreactors, while for all the tested catalysts a similar activity results were achieved. Physicochemical characterization of catalysts samples by ICP-AES, N2 physisorption, H2 chemisorption, TPR, SEM, XPS and XRD showed differences in chemical state, metal–support interactions, average crystallite sizes and redox properties of nickel and rhodium metal particles, indicating the importance of the morphological and surface properties of metal phases in driving the reforming activity.

[1]  W. Farneth,et al.  Quantitative determination of the number of active surface sites and the turnover frequencies for methanol oxidation over metal oxide catalysts: I. Fundamentals of the methanol chemisorption technique and application to monolayer supported molybdenum oxide catalysts , 2000 .

[2]  X. Verykios,et al.  Reforming of methane with carbon dioxide to synthesis gas over supported Rh catalysts , 1994 .

[3]  S. Moon,et al.  Poisoning effect of nitrogen compounds on the performance of CoMoS/Al2O3 catalyst in the hydrodesulfurization of dibenzothiophene, 4-methyldibenzothiophene, and 4,6-dimethyldibenzothiophene , 2001 .

[4]  Peter Pfeifer,et al.  Reforming of diesel fuel in a micro reactor for APU systems , 2008 .

[5]  Miroslaw L. Wyszynski,et al.  Biogas upgrade to syn-gas (H 2CO) via dry and oxidative reforming , 2011 .

[6]  Volker Hessel,et al.  Chemical micro process engineering , 2003 .

[7]  K. Polychronopoulou,et al.  The phenol steam reforming reaction over MgO-based supported Rh catalysts , 2004 .

[8]  Rajamani Krishna,et al.  Fundamentals and selection of advanced Fischer-Tropsch reactors , 1999 .

[9]  J. Fierro,et al.  Glycerol steam reforming over Ni catalysts supported on ceria and ceria-promoted alumina , 2010 .

[10]  Dieter Deublein,et al.  Comprar Biogas from Waste and Renewable Resources: An Introduction | Dieter Deublein | 9783527318414 | Wiley , 2007 .

[11]  J. Fierro,et al.  Partial oxidation of methane to syngas over Ni/MgO and Ni/La2O3 catalysts , 2005 .

[12]  Martin A. Abraham,et al.  Deactivation due to sulfur poisoning and carbon deposition on Rh-Ni/Al2O3 catalyst during steam reforming of sulfur-doped n-hexadecane , 2009 .

[13]  J. Arraibi,et al.  Hydrogen production from methane and natural gas steam reforming in conventional and microreactor reaction systems , 2012 .

[14]  Adolfo E. Castro Luna,et al.  Carbon dioxide reforming of methane over a metal modified Ni-Al2O3 catalyst , 2008 .

[15]  Richard Chahine,et al.  Challenges for renewable hydrogen production from biomass , 2010 .

[16]  Xenophon E. Verykios,et al.  Mechanistic aspects of the reaction of CO2 reforming of methane over Rh/Al2O3 catalyst , 2003 .

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

[18]  Chunshan Song,et al.  Influence of ceria and nickel addition to alumina-supported Rh catalyst for propane steam reforming at low temperatures , 2009 .

[19]  R. Navarro,et al.  Effect of ZrO2 addition on Ni/Al2O3 catalyst to produce H2 from glycerol , 2012 .

[20]  Takafumi Yoshida,et al.  Steam reforming of a clean model biogas over Ni/Al2O3 in fluidized- and fixed-bed reactors , 2002 .

[21]  K. Tomishige,et al.  Promoting effect of Pt, Pd and Rh noble metals to the Ni0.03Mg0.97O solid solution catalysts for the reforming of CH4 with CO2 , 1997 .

[22]  J. Fierro,et al.  Ethanol steam reforming over Ni/MxOy–Al2O3 (M=Ce, La, Zr and Mg) catalysts: Influence of support on the hydrogen production , 2007 .

[23]  J. Huang,et al.  Particle loading in a catalyst-trap microreactor: Experiment vs. simulation , 2009 .

[24]  H. Hofbauer,et al.  Catalytic steam reforming of model biogas , 2008 .

[25]  M. Chen,et al.  Validation of an inductively coupled plasma mass spectrometry (ICP-MS) method for the determination of cerium, strontium, and titanium in ceramic materials used in radiological dispersal devices (RDDs). , 2007, Analytica chimica acta.

[26]  H. S. Fogler,et al.  Elements of Chemical Reaction Engineering , 1986 .

[27]  S. Assabumrungrat,et al.  Synthesis gas production from dry reforming of methane over CeO2 doped Ni/Al2O3: Influence of the doping ceria on the resistance toward carbon formation , 2005 .

[28]  Mark E. Davis,et al.  Fundamentals of Chemical Reaction Engineering , 2002 .

[29]  A. Boréave,et al.  Catalytic CO2 reforming of methane over Ir/Ce0.9Gd0.1O2−x , 2005 .

[30]  S. Therdthianwong,et al.  Improvement of coke resistance of Ni/Al2O3 catalyst in CH4/CO2 reforming by ZrO2 addition , 2008 .

[31]  Jixiang Chen,et al.  Synthesis gas production from dry reforming of methane over Ce0.75Zr0.25O2-supported Ru catalysts , 2010 .

[32]  Pål Börjesson,et al.  Environmental systems analysis of biogas systems—Part I: Fuel-cycle emissions , 2006 .

[33]  M. Illán-Gómez,et al.  Ni, Co and bimetallic Ni–Co catalysts for the dry reforming of methane , 2009 .

[34]  M. Larrubia,et al.  Nanostructured Pt- and Ni-based catalysts for CO2-reforming of methane , 2010 .

[35]  Gunther Kolb,et al.  Fuel processing in integrated micro-structured heat-exchanger reactors , 2007 .

[36]  K. Kunimori,et al.  Effect of oxygen addition to steam and dry reforming of methane on bed temperature profile over Pt and Ni catalysts , 2004 .