Efficient isomerization of glucose to fructose over zeolites in consecutive reactions in alcohol and aqueous media.

Isomerization reactions of glucose were catalyzed by different types of commercial zeolites in methanol and water in two reaction steps. The most active catalyst was zeolite Y, which was found to be more active than the zeolites beta, ZSM-5, and mordenite. The novel reaction pathway involves glucose isomerization to fructose and subsequent reaction with methanol to form methyl fructoside (step 1), followed by hydrolysis to re-form fructose after water addition (step 2). NMR analysis with (13)C-labeled sugars confirmed this reaction pathway. Conversion of glucose for 1 h at 120 °C with H-USY (Si/Al = 6) gave a remarkable 55% yield of fructose after the second reaction step. A main advantage of applying alcohol media and a catalyst that combines Brønsted and Lewis acid sites is that glucose is isomerized to fructose at low temperatures, while direct conversion to industrially important chemicals like alkyl levulinates is viable at higher temperatures.

[1]  Ceri Hammond,et al.  Simple and scalable preparation of highly active Lewis acidic Sn-β. , 2012, Angewandte Chemie.

[2]  R. L. D. Souza,et al.  Glucose–fructose isomerisation promoted by basic hybrid catalysts , 2012 .

[3]  W. Fan,et al.  Rapid Synthesis of Sn-Beta for the Isomerization of Cellulosic Sugars , 2012 .

[4]  D. Vlachos,et al.  Carbohydrate dehydration using porous catalysts , 2012 .

[5]  Rajeev S. Assary,et al.  Metalloenzyme-like catalyzed isomerizations of sugars by Lewis acid zeolites , 2012, Proceedings of the National Academy of Sciences.

[6]  Ru Sun,et al.  Combination use of ultrasound irradiation and ionic liquid in enzymatic isomerization of glucose to fructose , 2012 .

[7]  M. Tsapatsis,et al.  Tin-containing zeolite for the isomerization of cellulosic sugars , 2012 .

[8]  Michael Tsapatsis,et al.  One-Pot Synthesis of 5-(Ethoxymethyl)furfural from Glucose using Sn-BEA and Amberlyst Catalysts , 2012 .

[9]  Anders Riisager,et al.  Solid acid catalysed formation of ethyl levulinate and ethyl glucopyranoside from mono- and disaccharides , 2012 .

[10]  Y. Pagán-Torres,et al.  Sn-Beta catalysed conversion of hemicellulosic sugars , 2012 .

[11]  Anders Riisager,et al.  Conversion of mono- and disaccharides to ethyl levulinate and ethyl pyranoside with sulfonic acid-functionalized ionic liquids. , 2011, ChemSusChem.

[12]  Manuel Moliner,et al.  "One-pot" synthesis of 5-(Hydroxymethyl)furfural from carbohydrates using tin-Beta zeolite , 2011 .

[13]  Manuel Moliner,et al.  Mechanism of glucose isomerization using a solid Lewis acid catalyst in water. , 2010, Angewandte Chemie.

[14]  Manuel Moliner,et al.  Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water , 2010, Proceedings of the National Academy of Sciences.

[15]  Claus H. Christensen,et al.  Zeolite H-USY for the production of lactic acid and methyl lactate from C3-sugars , 2010 .

[16]  P. Brandão,et al.  Isomerization of d-glucose to d-fructose over metallosilicate solid bases , 2008 .

[17]  Claude Moreau,et al.  Isomerization of glucose into fructose in the presence of cation-exchanged zeolites and hydrotalcites ☆ , 2000 .

[18]  Avelino Corma,et al.  Inorganic Solid Acids and Their Use in Acid-Catalyzed Hydrocarbon Reactions , 1995 .

[19]  Joop A. Peters,et al.  Methyl α-D-fructofuranoside: Synthesis and conversion into carboxylates , 1994 .