A New Process for Maleic Anhydride Synthesis from a Renewable Building Block: The Gas-Phase Oxidehydration of Bio-1-butanol.

We investigated the synthesis of maleic anhydride by oxidehydration of a bio-alcohol, 1-butanol, as a possible alternative to the classical process of n-butane oxidation. A vanadyl pyrophosphate catalyst was used to explore the one-pot reaction, which involved two sequential steps: 1) 1-butanol dehydration to 1-butene, catalysed by acid sites, and 2) the oxidation of butenes to maleic anhydride, catalysed by redox sites. A non-negligible amount of phthalic anhydride was also formed. The effect of different experimental parameters was investigated with chemically sourced 1-butanol, and the results were then confirmed by using genuinely bio-sourced 1-butanol. In the case of bio-1-butanol, however, the purity of the product remarkably affected the yield of maleic anhydride. It was found that the reaction mechanism includes the oxidation of butenes to crotonaldehyde and the oxidation of the latter to either furan or maleic acid, both of which are transformed to produce maleic anhydride.

[1]  Johan P.M. Sanders,et al.  Bulk chemicals from biomass , 2008 .

[2]  Sadao Suzuki,et al.  Oxidation Activity and Acidity of V2O5–P2O5 Catalyst , 1974 .

[3]  D. Golden,et al.  Iodine-Catalyzed Isomerization of Olefins. I. Thermodynamic Data from Equilibrium Studies of Positional and Geometrical Isomerization of 1-Butene and 2-Butene , 1964 .

[4]  Zerihun T. Dame,et al.  3-Methoxy-2-methyl-carbazole-1,4-quinone, carbazomycins D and F from Streptomyces sp. CMU-JT005. , 2011, FEMS microbiology letters.

[5]  G. Centi,et al.  Catalytic conversion of C4 hydrocarbons on vanadium-phosphorus oxides: factors influencing the selectivity in 1-butene oxidation , 1985 .

[6]  James H. Clark,et al.  Green chemistry for the second generation biorefinery—sustainable chemical manufacturing based on biomass , 2007 .

[7]  Yuriy Román‐Leshkov,et al.  Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates , 2007, Nature.

[8]  G. Huber,et al.  Liquid-phase catalytic processing of biomass-derived oxygenated hydrocarbons to fuels and chemicals. , 2007, Angewandte Chemie.

[9]  G. Centi,et al.  THE CHEMISTRY OF CATALYSTS BASED ON VANADIUM-PHOSPHORUS OXIDES. PART IV. CATALYTIC BEHAVIOR OF CATALYSTS PREPARED IN ORGANIC MEDIUM IN OXIDATION OF C4 FRACTION , 1984 .

[10]  Y. Taufiq-Yap,et al.  A study of the kinetics and mechanism of the adsorption and anaerobic partial oxidation of n-butane over a vanadyl pyrophosphate catalyst , 2000 .

[11]  A. Youssef,et al.  Structural and surface properties of SnO2–AlPO4 catalysts in relation to their dehydration activities , 1998 .

[12]  F. Cavani,et al.  Influence of the oxidation state of vanadium on the reactivity of V/P/O, catalyst for the oxidation of n-pentane to maleic and phthalic anhydrides , 2006 .

[13]  H. Hattori.  Solid base catalysts: generation of basic sites and application to organic synthesis , 2001 .

[14]  S. Ordóñez,et al.  Consequences of the iron–aluminium exchange on the performance of hydrotalcite-derived mixed oxides for ethanol condensation , 2011 .

[15]  M. Neurock,et al.  Mechanistic consequences of composition in acid catalysis by polyoxometalate keggin clusters. , 2008, Journal of the American Chemical Society.

[16]  F. Cavani,et al.  VPO catalyst for n-butane oxidation to maleic anhydride: A goal achieved, or a still open challenge? , 2006 .

[17]  G. Hutchings,et al.  Structural evolution and catalytic performance of DuPont V-P-O/SiO2 materials designed for fluidized bed applications , 2010 .

[18]  G. Centi,et al.  Functionalization of paraffinic hydrocarbons by heterogeneous oxidation. I. Control of selectivity in n-butane conversion to maleic anhydride , 1987 .

[19]  F. Cavani,et al.  Surface dynamics of a vanadyl pyrophosphate catalyst for n-butane oxidation to maleic anhydride: an in situ raman and reactivity study of the effect of the P/V atomic ratio. , 2010, Chemistry.

[20]  J. Moffat,et al.  Cation/proton interactions and acid strengths in salts of 12-tungstophosphoric acid prepared from 1A, 1B and 3B monovalent cations , 1997 .

[21]  Z. Xue,et al.  Transient FTIR Studies of the Reaction Pathway forn-Butane Selective Oxidiation over Vanadyl Pyrophosphate , 1999 .

[22]  B O Palsson,et al.  Biomass as a source of chemical feedstocks: an economic evaluation. , 1981, Science.

[23]  G. Hutchings,et al.  Vanadium Phosphate Materials as Selective Oxidation Catalysts , 2011 .

[24]  John M. Woodley,et al.  Next‐Generation Catalysis for Renewables: Combining Enzymatic with Inorganic Heterogeneous Catalysis for Bulk Chemical Production , 2010 .

[25]  A. Dean,et al.  Kinetic Analysis of C4 Alkane and Alkene Pyrolysis: Implications for SOFC Operation , 2008 .

[26]  J. Rasko,et al.  FT-IR and mass spectrometric studies on the interaction of acetaldehyde with TiO2-supported noble metal catalysts , 2005 .

[27]  Jeppe Rass-Hansen,et al.  The renewable chemicals industry. , 2008, ChemSusChem.

[28]  V. Guliants,et al.  Probing polyfunctional nature of vanadyl pyrophosphate catalysts: oxidation of 16 C4 molecules , 2001 .

[29]  J. Fierro,et al.  Butyraldehyde production by butanol oxidation over Ru and Cu catalysts supported on ZrO2, TiO2 and CeO2 , 2010 .

[30]  G. Schrader,et al.  In situ FTIR spectroscopy of 1-butene and 1,3-butadiene selective oxidation to maleic anhydride on V - P - O catalysts , 1987 .

[31]  B. K. Hodnett.  Vanadium-phosphorus Oxide Catalysts for the Selective Oxidation of C-4 Hydrocarbons To Maleic-anhydride , 1985 .

[32]  E. Iglesia,et al.  Structure and Surface and Catalytic Properties of Mg-Al Basic Oxides , 1998 .

[33]  Weichao Zhang,et al.  One-Step Synthesis of n-Butanol from Ethanol Condensation over Alumina-Supported Metal Catalysts , 2004 .

[34]  Siglinda Perathoner,et al.  Analysis of the alternative routes in the catalytic transformation of lignocellulosic materials , 2011 .

[35]  G. Centi,et al.  A dynamic approach to selectivity in heterogeneous partial oxidation , 1987 .

[36]  G. Centi,et al.  Oxidation of 1-butene and butadiene to maleic anhydride. 1. Role of oxygen partial pressure , 1983 .

[37]  J. Rasko,et al.  Adsorption and surface reactions of acetaldehyde on TiO2, CeO2 and Al2O3 , 2005 .

[38]  Benjamin G. Harvey,et al.  The role of butanol in the development of sustainable fuel technologies , 2011 .

[39]  S. Sundaresan,et al.  The oxidation of C4 molecules on vanadyl pyrophosphate catalysts , 1996 .

[40]  F. Cavani,et al.  Transient reactivity of vanadyl pyrophosphate, the catalyst for n-butane oxidation to maleic anhydride, in response to in-situ treatments , 2010 .

[41]  G. Schrader,et al.  In situ Fourier transform infrared study of crotyl alcohol, maleic acid, crotonic acid, and maleic anhydride oxidation on a V-P-O industrial catalyst , 1987 .

[42]  B. Delmon,et al.  1-Butanol dehydration on AlPO4 and modified AlPO4: catalytic behaviour and deactivation , 1995 .

[43]  E. Gobbi,et al.  Role of surface properties of the vanadyl pyrophosphate in the formation of maleic and phthalic anhydrides by n-pentane oxidation , 1996 .

[44]  R. Palkovits,et al.  Cellulose-based sustainable polymers: state of the art and future trends. , 2011, Macromolecular rapid communications.

[45]  P. Grange,et al.  Butan-1-ol and butan-2-ol dehydration on nitrided alurninophosphates: influence of nitridation on reaction pathways (vol 259, pg 269, 2004) , 2004 .

[46]  R. Klimkiewicz,et al.  High thermodynamic stability of La-deficient rhombohedral form of lanthanum manganite phase as decisive factor in effective ketonization reaction of 1-butanol , 2008 .

[47]  R. Klimkiewicz,et al.  Double perovskite Pr2-xBixSr2O6 (x = 0.533) in ketonization of 1-butanol: Effect of water vapor addition , 2009 .

[48]  Mark Mascal,et al.  Chemicals from biobutanol: technologies and markets , 2012 .

[49]  A. Gil,et al.  Effect of the Si/Al ratio on the structure and surface properties of silica-alumina-pillared clays , 2005 .

[50]  F. Cavani,et al.  The contribution of homogeneous reactions in catalytic oxidation processes: safety and selectivity aspects , 2005 .

[51]  P. Gallezot,et al.  Process options for converting renewable feedstocks to bioproducts , 2007 .

[52]  M. Králik,et al.  Dehydration of C4 alkanols conjugated with a positional and skeletal isomerisation of the formed C4 alkenes , 2001 .

[53]  W. Green,et al.  Erratum to “Comprehensive reaction mechanism for n-butanol pyrolysis and combustion” [Combust. Flame 158 (2011) 16–41] , 2011 .

[54]  P. Gallezot,et al.  Catalytic routes from renewables to fine chemicals , 2007 .

[55]  F. Gasparini,et al.  The contribution of homogeneous and non-oxidative side reactions in the performance of vanadyl pyrophosphate, catalyst for the oxidation of n-butane to maleic anhydride, under hydrocarbon-rich conditions , 2005 .

[56]  A. Kiennemann,et al.  Reactions of Acetaldehyde on CeO2 and CeO2-Supported Catalysts , 1995 .

[57]  J. Clark,et al.  The integration of green chemistry into future biorefineries. , 2009 .

[58]  C. Cobzaru,et al.  Gas phase aldol condensation of lower aldehydes over clinoptilolite rich natural zeolites , 2008 .

[59]  K. Minachev,et al.  Conversion of butyraldehyde on the oxides of rare-earth elements , 1978 .

[60]  T. Tsuchida,et al.  Direct Synthesis of n-Butanol from Ethanol over Nonstoichiometric Hydroxyapatite , 2006 .

[61]  J. Dumesic,et al.  Catalytic strategies for changing the energy content and achieving C--C coupling in biomass-derived oxygenated hydrocarbons. , 2008, ChemSusChem.

[62]  J. Fierro,et al.  Study by XPS and TPD of the interaction of n-pentane and n-butane with the surface of `non-equilibrated' and `equilibrated' V–P–O catalysts , 1998 .

[63]  A. Ozaki,et al.  Production of Furan by Vapor-phase Oxidation of Crotonaldehyde Using Heteropoly Compounds as Catalysts , 1980 .

[64]  G. Hutchings,et al.  Green Catalysis with Alternative Feedstocks , 2009 .

[65]  B. Kamm,et al.  Production of platform chemicals and synthesis gas from biomass. , 2007, Angewandte Chemie.

[66]  Joseph J. Bozell,et al.  Feedstocks for the Future : Biorefinery Production of Chemicals from Renewable Carbon , 2008 .

[67]  Juben Nemchand Chheda,et al.  Katalytische Flüssigphasenumwandlung oxygenierter Kohlenwasserstoffe aus Biomasse zu Treibstoffen und Rohstoffen für die Chemiewirtschaft , 2007 .

[68]  Chun Yang,et al.  Bimolecular Condensation of Ethanol to 1-Butanol Catalyzed by Alkali Cation Zeolites , 1993 .

[69]  F. Cavani,et al.  The characterization of the surface properties of VPO-based catalysts by probe molecules , 1997 .

[70]  Huajun Guo,et al.  Catalytic Aerobic Oxidation of Renewable Furfural with Phosphomolybdic Acid Catalyst: an Alternative Route to Maleic Acid , 2011 .

[71]  B. Kamm.  Produktion von Plattformchemikalien und Synthesegas aus Biomasse , 2007 .

[72]  A. Corma,et al.  Chemical routes for the transformation of biomass into chemicals. , 2007, Chemical reviews.

[73]  Gabriele Centi,et al.  Mechanistic aspects of maleic anhydride synthesis from C4 hydrocarbons over phosphorus vanadium oxide , 1988 .

[74]  T. Tsuchida,et al.  Reaction of ethanol over hydroxyapatite affected by Ca/P ratio of catalyst , 2008 .

[75]  P. Grange,et al.  Acidic and Catalytic Properties of Sio2-ta2o5 Mixed Oxides Prepared By the Sol-gel Method , 1995 .

[76]  Jiping Ma,et al.  Oxidation of 5-hydroxymethylfurfural to maleic anhydride with molecular oxygen , 2011 .

[77]  P. Čičmanec,et al.  The partial oxidation of crotonaldehyde over V–Mo–O catalyst , 2007 .

[78]  A. S. Ndou,et al.  Dimerisation of ethanol to butanol over solid-base catalysts , 2003 .

[79]  S. Kaliaguine,et al.  Aldol condensation of aldehydes over semicrystalline zeolitic-mesoporous UL-ZSM-5 , 2005 .

[80]  L. Schmidt,et al.  Autothermal partial oxidation of butanol isomers , 2012 .