Selective conversion of glycerol to hydroxyacetone in gas phase over La2CuO4 catalyst

Abstract The gas phase dehydration of glycerol to hydroxyacetone was investigated over La 2 CuO 4 catalyst under inert conditions. The reaction was performed in the temperature range of 260–400 °C. At low temperature (260 and 280 °C) high yields of hydroxyacetone can be achieved: 76% while at higher temperatures carbon deposition occurred. We showed that the structure of the La 2 CuO 4 catalyst was modified during time on stream: Cu 2+ was partially reduced into Cu 1+ even at 260 °C. The formation of Cu 2 O was revealed by XRD and XPS analysis confirmed that both Cu 2+ and Cu 1+ are present at the surface of the catalyst. After reduction of La 2 CuO 4 into Cu 0 /La 2 O 3 , low catalytic activity was observed proving that metallic copper is not the required species to perform the dehydration of glycerol into hydroxyacetone under our experimental conditions. TGA analysis revealed that only small amount of carbon deposition occurred during time on stream at 260 °C, no catalytic deactivation being observed during 20 h of reaction.

[1]  S. Nakata,et al.  Oxygen storage capacity of delafossite-type CuLnO2 (Ln = La, Y) and their stability under oxidative/reductive atomosphere , 2012 .

[2]  A. Romero,et al.  Conversion of Alcohols (a-Methylated Series) on ALPO 4 Catalysts , 1995 .

[3]  J. Fierro,et al.  Hydrogenolysis of glycerol to propanediols over a Pt/ASA catalyst: The role of acid and metal sites on product selectivity and the reaction mechanism , 2010 .

[4]  A. Neumann,et al.  The thermal transformation from lanthanum hydroxide to lanthanum hydroxide oxide , 2006 .

[5]  Satoshi Sato,et al.  Production of acrolein from glycerol over silica-supported heteropoly acids , 2007 .

[6]  A. Lemonidou,et al.  Ru-based catalysts for glycerol hydrogenolysis—Effect of support and metal precursor , 2009 .

[7]  Arno Behr,et al.  Improved utilisation of renewable resources: New important derivatives of glycerol , 2008 .

[8]  Y. Hwang,et al.  Selective conversion of glycerol to acetol over sodium-doped metal oxide catalysts , 2010 .

[9]  Juan Wang,et al.  Ruthenium Nanoparticles Supported on Carbon Nanotubes for Selective Hydrogenolysis of Glycerol to Glycols , 2009 .

[10]  J. Filho,et al.  Nanocasted oxides for gas phase glycerol conversion , 2011 .

[11]  Satoshi Sato,et al.  Vapor-phase reaction of polyols over copper catalysts , 2008 .

[12]  E. Assaf,et al.  La2−xCexCu1−yZnyO4 perovskites for high temperature water-gas shift reaction , 2009 .

[13]  Fangming Jin,et al.  A Potentially Useful Technology by Mimicking Nature—Rapid Conversion of Biomass and CO2 into Chemicals and Fuels under Hydrothermal Conditions , 2012 .

[14]  G. Szymanski,et al.  Importance of oxygen surface groups in catalytic dehydration and dehydrogenation of butan-2-ol promoted by carbon catalysts , 1991 .

[15]  S. Paul,et al.  Towards the sustainable production of acrolein by glycerol dehydration. , 2009, ChemSusChem.

[16]  T. S. King,et al.  Potassium's promotional effect of unsupported copper catalysts for methanol synthesis , 1989 .

[17]  Jingrun Yuan,et al.  PMMA-templating preparation and catalytic properties of high-surface-area three-dimensional macroporous La2CuO4 for methane combustion , 2011 .

[18]  A. Santamaría,et al.  Gas phase glycerol conversion over lanthanum based catalysts: LaNiO3 and La2O3 , 2013 .

[19]  McGuire,et al.  Structure and properties of the LaCuO3- delta perovskites. , 1993, Physical review. B, Condensed matter.

[20]  J. Dubois,et al.  Glycerol dehydration over calcium phosphate catalysts: Effect of acidic-basic features on catalytic performance , 2012 .

[21]  R. Gläser,et al.  Microwave-assisted synthesis of [Cr]APO-5 , 2006 .

[22]  Hai-Long Wu,et al.  Synthesis of micro-and mesoporous ZSM-5 composites and their catalytic application in glycerol dehydration to acrolein , 2007 .

[23]  J. Fierro,et al.  Defect LaCuO3−δ (δ=0.05−0.45) perovskites , 2000 .

[24]  I. Kozhevnikov,et al.  Gas-phase dehydration of glycerol to acrolein catalysed by caesium heteropoly salt , 2010 .

[25]  L. Hoang,et al.  Aqueous polyol conversions on ruthenium and on sulfur-modified ruthenium , 1991 .

[26]  Galen J. Suppes,et al.  Dehydration of glycerol to acetol via catalytic reactive distillation , 2006 .

[27]  D. C. Frost,et al.  X-ray photoelectron spectroscopy of copper compounds , 1972 .