Kinetics of the Decomposition of Fructose Catalyzed by Hydrochloric Acid in Subcritical Water: Formation of 5-Hydroxymethylfurfural, Levulinic, and Formic Acids

This paper deals with the dehydration of fructose (F) to 5-hydroxymethylfurfural (HMF) and the rehydration of HMF to levulinic acid (LA) along with formic acid (FA) in subcritical water (sub-CW) in the presence of HCl as catalyst. The experimental conditions were 483-543 K, 4-15 MPa, and residence times of 0.5-300 s. The pressure (in the range of 4-15 MPa) did not affect the decomposition reactions. This differed from other operating variables. The main products were found to be HMF, 2-furaldehyde (2FA), LA, FA, and soluble polymers. The HMF, LA, and FA were also individually subjected for decomposition at the same condition. We found that, during the sub-CW reaction, byproducts (soluble polymers) were produced not only from F but also from HMF. However, we distinguished between two different polymers (i.e., produced from the decomposition of F or HMF) in a proposed reaction model. The kinetics of the sub-CW reaction was developed by considering not only F, HMF, LA, and FA but also soluble polymers. The kinetic constants obtained from the proposed reaction pathway showed good agreement with experimental results.

[1]  H. Yoshida,et al.  Conversion of scallop viscera wastes to valuable compounds using sub-critical water , 2006 .

[2]  H. Yoshida,et al.  Dehydration of fructose to 5-hydroxymethylfurfural in sub-critical water over heterogeneous zirconium phosphate catalysts. , 2006, Carbohydrate research.

[3]  Leon P.B.M. Janssen,et al.  Green Chemicals: A Kinetic Study on the Conversion of Glucose to Levulinic Acid , 2006 .

[4]  Yu Yang,et al.  Phenanthrene degradation in subcritical water , 2006 .

[5]  H. Vogel,et al.  Catalytical conversion of carbohydrates in subcritical water: A new chemical process for lactic acid production , 2005 .

[6]  Ryuichi Matsuno,et al.  Degradation kinetics of monosaccharides in subcritical water , 2005 .

[7]  Ryuichi Matsuno,et al.  Kinetics on sucrose decomposition in subcritical water , 2005 .

[8]  H. Yoshida,et al.  Effective recovery of harmful metal ions from squid wastes using subcritical and supercritical water treatments. , 2005, Environmental science & technology.

[9]  A. Galkin,et al.  Subcritical and Supercritical Water: A Universal Medium for Chemical Reactions , 2005 .

[10]  S. Adachi,et al.  Decomposition Kinetics of Maltose in Subcritical Water , 2004, Bioscience, biotechnology, and biochemistry.

[11]  J. Lewkowski.  Synthesis, chemistry and applications of 5-hydroxymethyl-furfural and its derivatives , 2003 .

[12]  Sang do Park,et al.  Kinetics of cellobiose decomposition under subcritical and supercritical water in continuous flow system , 2002 .

[13]  M. Hanna,et al.  Levulinic acid production based on extrusion and pressurized batch reaction , 2002 .

[14]  Kunio Arai,et al.  Cellulose hydrolysis in subcritical and supercritical water , 1998 .

[15]  B. M. Kabyemela,et al.  Mechanism and Kinetics of Cellobiose Decomposition in Sub- and Supercritical Water , 1998 .

[16]  B. M. Kabyemela,et al.  Rapid and Selective Conversion of Glucose to Erythrose in Supercritical Water , 1997 .

[17]  Kunio Arai,et al.  Kinetics of glucose epimerization and decomposition in subcritical and supercritical water , 1997 .

[18]  B. Kuster,et al.  The influence of the initial and catalyst concentrations on the dehydration of d-fructose , 1977 .

[19]  B. Kuster,et al.  Analytical Procedures for Studying the Dehydration of D-Fructose☆ , 1977 .

[20]  H. Rase,et al.  Levulinic Acid from Sucrose Using Acidic Ion-Exchange Resins , 1975 .

[21]  L. Manzer,et al.  Biomass derivatives : A sustainable source of chemicals , 2006 .

[22]  James O. Wilkes,et al.  DATA ANALYSIS MADE EASY WITH DATAFIT , 2005 .

[23]  A. Gawlik,et al.  Biomass Conversion in Water at 330−410 °C and 30−50 MPa. Identification of Key Compounds for Indicating Different Chemical Reaction Pathways , 2003 .

[24]  B. Kuznetsov,et al.  Kinetics of levulinic acid formation from carbohydrates at moderate temperatures , 2002 .

[25]  Hiroyuki Yoshida,et al.  Production of Organic Acids and Amino Acids from Fish Meat by Sub‐Critical Water Hydrolysis , 1999, Biotechnology progress.

[26]  J. Horvat,et al.  Mechanism of levulinic acid formation , 1985 .

[27]  R. Montgomery,et al.  The effect of heat on aqueous solutions of sucrose and other carbohydrates , 1947 .