Highly dispersed palladium nanoparticles on ultra-porous silica mesocellular foam for the catalytic decarboxylation of stearic acid

Abstract The synthesis, characterization, and application of well-dispersed palladium nanoparticles supported on a mesocellular silica support in the catalytic decarboxylation of stearic acid are reported. Ultra-large pore volume silica mesocellular foam is synthesized as the catalyst support, with amorphous cell-and-window pore diameters of 37 nm and 17 nm, respectively. Silane surface functionalization is employed to ensure thorough metal distribution by providing binding sites for loading of palladium precursor salts. After calcination and reduction, chemisorption and microscopy results indicate ∼2 nm palladium particles are distributed throughout the silica support at 5 wt.% metal loading. The catalysts are active in the batch decarboxylation of stearic acid in nitrogen atmosphere at 300 °C, reaching conversions of 85–90% after 6 h with complete selectivity to the decarboxylation product n -heptadecane. Lower conversions ( n -heptadecane, and 13% as the intermediate stearic acid.

[1]  J. Theo Kloprogge,et al.  A review of the synthesis and characterisation of pillared clays and related porous materials for cracking of vegetable oils to produce biofuels , 2005 .

[2]  Paolo Bondioli,et al.  The Preparation of Fatty Acid Esters by Means of Catalytic Reactions , 2004 .

[3]  Bernard Delmon,et al.  Study of the Hydrodeoxygenation of Carbonyl, Carboxylic and Guaiacyl Groups Over Sulfided Como/gamma-al2o3 and Nimo/gamma-al2o3 Catalyst .2. Influence of Water, Ammonia and Hydrogen-sulfide , 1994 .

[4]  Irina Simakova,et al.  Synthesis of Biodiesel via Deoxygenation of Stearic Acid over Supported Pd/C Catalyst , 2008 .

[5]  Dora E. López,et al.  Synthesis of Biodiesel via Acid Catalysis , 2005 .

[6]  Dmitry Yu. Murzin,et al.  Catalytic Deoxygenation of Fatty Acids and Their Derivatives , 2007 .

[7]  Bradley F. Chmelka,et al.  MESOCELLULAR SILICEOUS FOAMS WITH UNIFORMLY SIZED CELLS AND WINDOWS , 1999 .

[8]  M. Haas,et al.  Simple, high-efficiency synthesis of fatty acid methyl esters from soapstock , 2000 .

[9]  Kari Eränen,et al.  Catalytic deoxygenation of unsaturated renewable feedstocks for production of diesel fuel hydrocarbons , 2008 .

[10]  J. Marchetti,et al.  Possible methods for biodiesel production , 2007 .

[11]  L. C. Meher,et al.  Technical aspects of biodiesel production by transesterification—a review , 2006 .

[12]  F. Twaiq,et al.  Catalytic Conversion of Palm Oil to Hydrocarbons: Performance of Various Zeolite Catalysts , 1999 .

[13]  Daniel E. Resasco,et al.  Catalytic Deoxygenation of Methyl-Octanoate and Methyl-Stearate on Pt/Al2O3 , 2009 .

[14]  D. Murzin,et al.  Production of diesel fuel from renewable feeds: Kinetics of ethyl stearate decarboxylation , 2007 .

[15]  Dmitry Yu. Murzin,et al.  Hydrocarbons for diesel fuel via decarboxylation of vegetable oils , 2005 .

[16]  D. Leung,et al.  Transesterification of neat and used frying oil : Optimization for biodiesel production , 2006 .

[17]  Bernard Delmon,et al.  Influence of the Support of CoMo Sulfide Catalysts and of the Addition of Potassium and Platinum on the Catalytic Performances for the Hydrodeoxygenation of Carbonyl, Carboxyl, and Guaiacol-Type Molecules , 1995 .

[18]  M. J. Hutzler,et al.  Emissions of greenhouse gases in the United States , 1995 .

[19]  A. Krause,et al.  Hydrodeoxygenation of methyl esters on sulphided NiMo/γ-Al2O3 and CoMo/γ-Al2O3 catalysts , 2005 .

[20]  A. Demirbas Effect of Alkali on Liquid Yields from the Pyrolysis of Olive Oil , 2008 .

[21]  B. Singh,et al.  Advancements in development and characterization of biodiesel: A review , 2008 .

[22]  Subhash Bhatia,et al.  Liquid hydrocarbon fuels from palm oil by catalytic cracking over aluminosilicate mesoporous catalysts with various Si/Al ratios , 2003 .

[23]  Rafael Hernandez,et al.  Heterogeneous Cracking of an Unsaturated Fatty Acid and Reaction Intermediates on H+ZSM‐5 Catalyst , 2008 .

[24]  K. Wilson,et al.  Catalysts in Production of Biodiesel: A Review , 2007 .

[25]  D. Tilman,et al.  Carbon-Negative Biofuels from Low-Input High-Diversity Grassland Biomass , 2006, Science.

[26]  Dmitry Yu. Murzin,et al.  Heterogeneous Catalytic Deoxygenation of Stearic Acid for Production of Biodiesel , 2006 .

[27]  Daniel E. Resasco,et al.  Deoxygenation of methylesters over CsNaX , 2008 .

[28]  Bernard Delmon,et al.  Study of the Hydrodeoxygenation of Carbonyl, Carboxylic and Guaiacyl Groups Over Sulfided Como/gamma-al2o3 and Nimo/gamma-al2o3 Catalysts .1. Catalytic Reaction Schemes , 1994 .

[29]  D. Zhao,et al.  Evaluating Pore Sizes in Mesoporous Materials: A Simplified Standard Adsorption Method and a Simplified Broekhoff−de Boer Method , 1999 .

[30]  Somchai Osuwan,et al.  Conversion of methylesters to hydrocarbons over an H-ZSM5 zeolite catalyst , 2009 .

[31]  S. Polasky,et al.  Land Clearing and the Biofuel Carbon Debt , 2008, Science.

[32]  Ayhan Demirbas,et al.  The influence of temperature on the yields of compounds existing in bio-oils obtained from biomass samples via pyrolysis , 2007 .

[33]  Gérald Djéga-Mariadassou,et al.  Utilization of vegetable oils as an alternative source for diesel-type fuel: hydrocracking on reduced Ni/SiO2 and sulphided Ni-Mo/γ-Al2O3 , 1989 .

[34]  Toru Iida,et al.  Decomposition of a long chain saturated fatty acid with some additives in hot compressed water , 2006 .