Ketonization and deoxygenation of alkanoic acids and conversion of levulinic acid to hydrocarbons using a Red Mud bauxite mining waste as the catalyst

Abstract Red Mud bauxite mining waste which consists of a highly alkaline mixture of Fe 2 O 3 (typically >60%, w/w), TiO 2 and several complex sodium alumino-silicates is a viable, but non-selective catalyst for the ketonization of carboxylic acids. The active catalyst consists of reduced iron oxide, silicate, aluminate and carbide phases that have to be formed either by pre-reduction of the Red Mud with a blend of formic and acetic acids or in situ by reduction with H 2 (g) at T  > 350 °C. Under H 2 (g) this catalyst can convert biomass derived levulinic acid into a blend of C9 alkenes and alkanes in up to 76% (w/w) yield. The reduced Red Mud is a non-alkaline magnetic solid that was analyzed by various techniques (XRD, Mossbauer, EA, Raman, TGA). It can be reused as a catalyst without loss of activity.

[1]  Anja Oasmaa,et al.  Characterization of biomass-based flash pyrolysis oils , 1998 .

[2]  V. Batra,et al.  Catalytic applications of red mud, an aluminium industry waste: A review , 2008 .

[3]  Z. Qi,et al.  Review of biomass pyrolysis oil properties and upgrading research , 2007 .

[4]  Jean-Paul Lange,et al.  Valeric biofuels: a platform of cellulosic transportation fuels. , 2010, Angewandte Chemie.

[5]  J. Wagner,et al.  Water Gas Shift Catalysis , 2009 .

[6]  K. Parida,et al.  Catalytic Ketonization of Acetic Acid on Zn/Al Layered Double Hydroxides , 2000 .

[7]  E. R. Squibb IMPROVEMENT IN THE MANUFACTURE OF ACETONE.1 , 1895 .

[8]  Maurizia Seggiani,et al.  Catalytic upgrading of pyrolytic oils over HZSM-5 zeolite : behaviour of the catalyst when used in repeated upgrading-regenerating cycles , 2001 .

[9]  Bankim Chandra Ray,et al.  Removal of hydrogen sulfide using red mud at ambient conditions , 2011 .

[10]  Ryōji Takahashi,et al.  Ketonization of carboxylic acids over CeO2-based composite oxides , 2005 .

[11]  Craig Klauber,et al.  Bauxite residue issues: I. Current management, disposal and storage practices , 2011 .

[12]  Riichiro Saito,et al.  Characterizing carbon nanotube samples with resonance Raman scattering , 2003 .

[13]  Dong Wang,et al.  Catalytic upgrading of levulinic acid to 5-nonanone , 2010 .

[14]  S. Kycia,et al.  Thermal Decomposition of Acetic and Formic Acid Catalyzed by Red Mud—Implications for the Potential Use of Red Mud as a Pyrolysis Bio-Oil Upgrading Catalyst§§Dedicated to Prof. Ulf Schuchardt on the occasion of his retirement. , 2010 .

[15]  M. Balakrishnan,et al.  Waste materials – catalytic opportunities: an overview of the application of large scale waste materials as resources for catalytic applications , 2011 .

[16]  I. Marco,et al.  Catalytic pyrolysis of plastic wastes with two different types of catalysts: ZSM-5 zeolite and Red Mud , 2011 .

[17]  Jean-Paul Lange,et al.  Towards 'bio-based' Nylon: conversion of gamma-valerolactone to methyl pentenoate under catalytic distillation conditions. , 2007, Chemical communications.

[18]  K. Parida,et al.  Catalytic ketonization of monocar☐ylic acids over Indian Ocean manganese nodules , 1998 .

[19]  Fraser D. Waldie,et al.  Stainless Steel As a Catalyst for the Total Deoxygenation of Glycerol and Levulinic Acid in Aqueous Acidic Medium , 2011 .

[20]  M. Gliński,et al.  Catalytic Ketonization over Oxide Catalysts, Part IV. Cycloketonization of Diethyl Hexanodiate , 2000 .

[21]  R. Lago,et al.  Production of nanostructured magnetic composites based on Fe0 nuclei coated with carbon nanofibers and nanotubes from red mud waste and ethanol. , 2011 .

[22]  N. Bakhshi,et al.  Catalytic upgrading of pyrolysis oil , 1993 .

[23]  G. Power,et al.  Bauxite residue issues: III. Alkalinity and associated chemistry , 2011 .

[24]  W. Hodek,et al.  Catalytic hydroliquefaction of biomass with red mud and CoOMoO3 catalysts , 1990 .

[25]  H. K. Mishra,et al.  Catalytic ketonisation of acetic acid over modified zirconia: 1. Effect of alkali-metal cations as promoter , 1999 .

[26]  S. Halawy Unpromoted and K2O-Promoted Cobalt Molybdate as Catalysts for the Decomposition of Acetic Acid , 2003 .

[27]  G. V. D. Laan,et al.  Kinetics and Selectivity of the Fischer–Tropsch Synthesis: A Literature Review , 1999 .

[28]  Yong Wang,et al.  Production of levulinic acid and use as a platform chemical for derived products , 2000 .

[29]  Maurizia Seggiani,et al.  Catalytic upgrading of pyrolytic oils to fuel over different zeolites , 1999 .

[30]  Wenping Ma,et al.  Fischer–Tropsch synthesis: Attempt to tune FTS and WGS by alkali promoting of iron catalysts , 2010 .

[31]  V. Batra,et al.  CHARACTERIZATION OF INDIAN RED MUD FOR CATALYTIC APPLICATIONS , 2011 .

[32]  Jean-Paul Lange,et al.  Conversion of furfuryl alcohol into ethyl levulinate using solid acid catalysts. , 2009, ChemSusChem.

[33]  J. Kijeński,et al.  Decarboxylative coupling of heptanoic acid. Manganese, cerium and zirconium oxides as catalysts , 2000 .

[34]  Johnathan E. Holladay,et al.  Top Value Added Chemicals From Biomass. Volume 1 - Results of Screening for Potential Candidates From Sugars and Synthesis Gas , 2004 .

[35]  Akshay D. Patel,et al.  Techno-economic analysis of 5-nonanone production from levulinic acid. , 2010 .

[36]  T. Tidwell The first century of ketenes (1905-2005): the birth of a versatile family of reactive intermediates. , 2005, Angewandte Chemie.

[37]  G. Power,et al.  Bauxite residue issues: II. options for residue utilization , 2011 .

[38]  R. Lago,et al.  Controlled reduction of red mud waste to produce active systems for environmental applications: heterogeneous Fenton reaction and reduction of Cr(VI). , 2010, Chemosphere.

[39]  M. Balakrishnan,et al.  Hydrogen production from methane in the presence of red mud –making mud magnetic , 2009 .

[40]  D. E. Willis,et al.  Calculation of Flame Ionization Detector Relative Response Factors Using the Effective Carbon Number Concept , 1985 .

[41]  Markus Gräfe,et al.  Bauxite residue issues: IV. Old obstacles and new pathways for in situ residue bioremediation , 2011 .

[42]  N. Bakhshi,et al.  Production of hydrocarbons by catalytic upgrading of a fast pyrolysis bio-oil. Part II: Comparative catalyst performance and reaction pathways , 1995 .

[43]  Suping Zhang,et al.  Upgrading of liquid fuel from the pyrolysis of biomass. , 2005, Bioresource technology.

[44]  V. Ponec,et al.  The formation of ketones and aldehydes from carboxylic acids, structure-activity relationship for two competitive reactions , 1995 .

[45]  C. Briens,et al.  Red Mud as a Catalyst for the Upgrading of Hemp-Seed Pyrolysis Bio-oil , 2010 .

[46]  A. Jakubowski,et al.  Ketones from monocarboxylic acids: Catalytic ketonization over oxide systems , 1995 .

[47]  M. A. Hasan,et al.  Oxide-catalyzed conversion of acetic acid into acetone: an FTIR spectroscopic investigation , 2003 .

[48]  H. Teterycz,et al.  Ketonization of fatty methyl esters over Sn−Ce−Rh−O catalyst , 2001 .

[49]  J. Criado,et al.  Catalytic Decomposition of Formic Acid on Metal Oxides , 1972 .

[50]  A. Heuer,et al.  Carbide precipitation in austenitic stainless steel carburized at low temperature , 2007 .

[51]  Jie Chang,et al.  Upgrading Bio-oil over Different Solid Catalysts , 2006 .

[52]  Johan E. Hustad,et al.  In situ catalytic upgrading of biomass derived fast pyrolysis vapours in a fixed bed reactor using mesoporous materials , 2006 .

[53]  B. Weckhuysen,et al.  The renaissance of iron-based Fischer-Tropsch synthesis: on the multifaceted catalyst deactivation behaviour. , 2008, Chemical Society reviews.