Catalytic deoxygenation of unsaturated renewable feedstocks for production of diesel fuel hydrocarbons

Abstract The liquid-phase deoxygenation reaction of unsaturated renewables has been investigated in a semi-batch reactor. The reactants examined were the monounsaturated fatty acid, oleic acid, the diunsaturated fatty acid, linoleic acid and the monounsaturated fatty acid ester, methyl oleate. The reactions were carried out over a Pd/C catalyst under constant pressure and temperature in the following domain, 15–27 bar and 300–360 °C, respectively. The influence of carrier gas was additionally investigated. The impact as solvent (mesitylene) was studied as well and reaction pathways were proposed. Furthermore, continuous deoxygenation experiments were conducted, facilitating understanding of the catalyst stability and catalyst deactivation. The deoxygenation catalyst was characterized by physisorption, temperature programmed desorption (TPD), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM).

[1]  Dmitry Yu. Murzin,et al.  Continuous Deoxygenation of Ethyl Stearate: A Model Reaction for Production of Diesel Fuel Hydrocarbons , 2006 .

[2]  D. Murzin,et al.  Kinetics of mesitylene hydrogenation on Ni/Al2O3 , 1999 .

[3]  R. Sun,et al.  A tentative chemical structure of wheat straw lignin , 1997 .

[4]  J. Fierro,et al.  Liquid-Phase Hydrodechlorination of CCl4 to CHCl3 on Pd/Carbon Catalysts: Nature and Role of Pd Active Species , 2002 .

[5]  A. Ivaska,et al.  Cyclic voltammetry as a tool for characterization of supported VIII group metal catalysts , 2006 .

[6]  Sanjib Kumar Karmee,et al.  Preparation of biodiesel from crude oil of Pongamia pinnata. , 2005, Bioresource technology.

[7]  Evripidis Lois,et al.  Tobacco seed oil as an alternative diesel fuel: physical and chemical properties , 2002 .

[8]  M. Sharma,et al.  Prospects of biodiesel production from vegetable oils in India , 2005 .

[9]  T. Vaara,et al.  Rh/C catalysts for methanol hydrocarbonylation: I. Catalyst characterisation , 2001 .

[10]  H. Harwood Reactions of the Hydrocarbon Chain of Fatty Acids. , 1962 .

[11]  T. Salmi,et al.  Barium promoted palladium catalysts for the emission control of natural gas driven vehicles and biofuel combustion systems , 2002 .

[12]  A. Chuvilin,et al.  On the nature of the interaction of H2PdCl4 with the surface of graphite-like carbon materials , 1997 .

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

[14]  R. Idem,et al.  Catalytic conversion of canola oil to fuels and chemicals: roles of catalyst acidity, basicity and shape selectivity on product distribution , 1997 .

[15]  Doraiswami Ramkrishna,et al.  Mathematics in Chemical Engineering: A 50 Year Introspection (Journal Review) , 2004 .

[16]  D. Murzin,et al.  A new heterogeneously catalytic pathway for isomerization of linoleic acid over Ru/C and Ni/H-MCM-41 catalysts , 2002 .

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

[18]  J. Casas,et al.  Effects of Support Surface Composition on the Activity and Selectivity of Pd/C Catalysts in Aqueous-Phase Hydrodechlorination Reactions , 2005 .

[19]  M. Schmal,et al.  Characterization of carbon supported palladium catalysts: inference of electronic and particle size effects using reaction probes , 2004 .

[20]  M. Trabi,et al.  Exploitation of the tropical oil seed plant Jatropha curcas L. , 1999 .

[21]  K. C. Mundim,et al.  Diesel-like fuel obtained by pyrolysis of vegetable oils , 2004 .

[22]  T. Foglia,et al.  Decarbonylation dehydration of fatty acids to alkenes in the presence of transition metal complexes , 1976 .

[23]  Robert L. McCormick,et al.  Combustion of fat and vegetable oil derived fuels in diesel engines , 1998 .

[24]  Paul von Ragué Schleyer,et al.  Hydrogenolysis, IV. Gas phase decarboxylation of carboxylic acids , 1982 .

[25]  A. Corma,et al.  Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering. , 2006, Chemical reviews.

[26]  E. Auer,et al.  Carbons as supports for industrial precious metal catalysts , 1998 .

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

[28]  H. Raheman,et al.  Biodiesel production from mahua (Madhuca indica) oil having high free fatty acids , 2005 .

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