Esterification of biomass pyrolysis model acids over sulfonic acid-functionalized mesoporous silicas

Esterification of acetic acid with methanol, which was used as a model reaction in the stabilization of bio-oil, was tested over propylsulfonic acid-functionalized SBA-15 materials. Due to the significant amount of water content in bio-oil, the water tolerance properties of the materials were also investigated in detail. The results showed that the functionalized mesoporous materials demonstrated a comparable site activity to H2SO4 in acetic acid esterification proving its potential for application. The effect of propylsulfonic acid loading showed that the intrinsic per site activity increased with the number of acid sites, which suggested the presence of acidic site cooperativity. Water tolerance experiments showed that SO3H-SBA-15 exhibited less reaction inhibition due to water than did H2SO4, which was at least partially ascribed to the hydrophobic propyl groups bonded to sulfonic acid groups. Further functionalization of SO3H-SBA-15 with hydrophobic propyl groups further increased the water tolerance property of the catalyst in the esterification reaction. The reusability of the catalyst was also investigated and showed multiple cycle stability for acetic acid esterification without significant loss of activity.

[1]  V. S. Lin,et al.  Organosulfonic acid-functionalized mesoporous silicas for the esterification of fatty acid , 2003 .

[2]  A. Kienle,et al.  Miniaturized Systems for Homogeneously and Heterogeneously Catalyzed Liquid-Phase Esterification Reaction , 2007 .

[3]  D. Vos,et al.  Sulfonic acid functionalised ordered mesoporous materials as catalysts for condensation and esterification reactions , 1998 .

[4]  J. Clark,et al.  Environmentally friendly chemistry using supported reagent catalysts : Chemically-modified mesoporous solid catalysts , 1997 .

[5]  K. Schwarz,et al.  INTERACTION OF WATER AND METHANOL WITH A ZEOLITE AT HIGH COVERAGES , 1996 .

[6]  A. Corma,et al.  The Influence of Textural and Compositional Characteristics of Nafion/Silica Composites on Isobutane/2-Butene Alkylation , 1999 .

[7]  T. Pinnavaia,et al.  A new nonionic surfactant pathway to mesoporous molecular sieve silicas with long range framework order , 1999 .

[8]  B. Shanks,et al.  Conversion of oils and fats using advanced mesoporous heterogeneous catalysts , 2006 .

[9]  A. Corma,et al.  Organic reactions catalyzed over solid acids , 1997 .

[10]  J. Clark,et al.  Solid acids and their use as environmentally friendly catalysts in organic synthesis , 2000 .

[11]  a Dan Fǎrcaşiu,et al.  Strength of Solid Acids and Acids in Solution. Enhancement of Acidity of Centers on Solid Surfaces by Anion Stabilizing Solvents and Its Consequence for Catalysis , 1997 .

[12]  R. Augusti,et al.  Investigation on the Esterification of Fatty Acids Catalyzed by the H3PW12O40 heteropolyacid , 2008 .

[13]  C. Márquez-Álvarez,et al.  Combined Alkyl and Sulfonic Acid Functionalization of MCM-41-Type Silica: Part 1. Synthesis and Characterization , 2000 .

[14]  E. Arnett,et al.  Thermochemical comparisons of homogeneous and heterogeneous acids and bases. 1. Sulfonic acid solutions and resins as prototype Broensted acids , 1986 .

[15]  W. K. Musker,et al.  Fluorine-19 NMR study of the reaction of p-fluorobenzenethiol and disulfide with periodate and other selected oxidizing agents , 1990 .

[16]  Yijun Liu,et al.  A Novel Sulfonated Carbon Composite Solid Acid Catalyst for Biodiesel Synthesis , 2008 .

[17]  Xueguang Wang,et al.  Propylsulfonic Acid-Functionalized Mesoporous Silica Synthesized by in Situ Oxidation of Thiol Groups under Template-Free Condition , 2007 .

[18]  A. C. Dimian,et al.  Fatty acid esterification by reactive distillation: Part 2—kinetics-based design for sulphated zirconia catalysts , 2003 .

[19]  Xiangguang Yang,et al.  Vapor phase esterification catalyzed by immobilized dodecatungstosilicic acid (SiW12) on activated carbon , 1996 .

[20]  Yijun Liu,et al.  A comparison of the esterification of acetic acid with methanol using heterogeneous versus homogeneous acid catalysis , 2006 .

[21]  T. Okuhara,et al.  Liquid phase esterification of acrylic acid with 1-butanol catalyzed by solid acid catalysts , 1999 .

[22]  Brent H. Shanks,et al.  Design of multifunctionalized mesoporous silicas for esterification of fatty acid , 2005 .

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

[24]  Yijun Liu,et al.  Effect of water on sulfuric acid catalyzed esterification , 2006 .

[25]  T. Okuhara Water-tolerant solid acid catalysts. , 2002, Chemical reviews.

[26]  Daniel C. Harris,et al.  Quantitative Chemical Analysis , 1968, Nature.

[27]  B. R. Jermy,et al.  Catalytic application of Al-MCM-41 in the esterification of acetic acid with various alcohols , 2005 .

[28]  Bradley F. Chmelka,et al.  Direct Syntheses of Ordered SBA-15 Mesoporous Silica Containing Sulfonic Acid Groups , 2000 .

[29]  Anthony V. Bridgwater,et al.  Fast pyrolysis of biomass : a handbook , 1999 .

[30]  G. Morales,et al.  Advances in the synthesis and catalytic applications of organosulfonic-functionalized mesostructured materials. , 2006, Chemical reviews.

[31]  J. Juan,et al.  Efficient Esterification of Fatty Acids with Alcohols Catalyzed by Zr(SO4)2 · 4H2O Under Solvent-Free Condition , 2008 .

[32]  E. Santacesaria,et al.  Vapor-phase esterification catalyzed by decationized Y zeolites , 1983 .

[33]  A. Bridgwater,et al.  Overview of Applications of Biomass Fast Pyrolysis Oil , 2004 .

[34]  Atsushi Takagaki,et al.  Green chemistry: Biodiesel made with sugar catalyst , 2005, Nature.