Exploring the reaction conditions for Ru/C catalyzed selective hydrogenolysis of xylitol alkaline aqueous solutions to glycols in a trickle-bed reactor

Abstract The hydrogenolysis of an alkaline aqueous solution of xylitol to mainly ethylene- and propylene-glycols was studied over a Ru/C catalyst in a high pressure fixed-bed reactor run in the trickle-bed mode with co-current downflow of liquid feed and hydrogen. The effects of reaction parameters including H2 pressure (40–80 bar), temperature (190–200 °C) and pH values (NaOH/xylitol molar ratio in the range 0.1–0.2, pH 9–12) and residence time have been explored to increase the selectivity of this reaction to the desired ethyleneglycol product. The activity and final products distribution were much influenced by the hydrogen pressure. An optimum to afford a high conversion and a high selectivity to ethyleneglycol at different space times was found at 60 bar. The effects observed are in agreement with the reaction pathways previously proposed and the relative reaction rates of the dehydrogenation/hydrogenation and base-catalyzed reactions of the intermediates are affected by the hydrogen pressure and the concentration of the alkaline promoter.

[1]  R. Palkovits,et al.  Hydrogenolysis goes bio: from carbohydrates and sugar alcohols to platform chemicals. , 2012, Angewandte Chemie.

[2]  Tao Zhang,et al.  Direct catalytic conversion of cellulose into ethylene glycol using nickel-promoted tungsten carbide catalysts. , 2008, Angewandte Chemie.

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

[4]  George W. Huber,et al.  Aqueous-phase hydrodeoxygenation of sorbitol with Pt/SiO2―Al2O3: Identification of reaction intermediates , 2010 .

[5]  E. Tronconi,et al.  A mathematical model for the catalytic hydrogenolysis of carbohydrates , 1992 .

[6]  A. Corma,et al.  Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering. , 2006, Chemical reviews.

[7]  J. Barbier,et al.  Polyol Conversion by Liquid Phase Heterogeneous Catalysis Over Metals , 1988 .

[8]  Alain Perrard,et al.  Glucose Hydrogenation on Ruthenium Catalysts in a Trickle-Bed Reactor , 1998 .

[9]  I. T. Clark.  Hydrogenolysis of Sorbitol , 1958 .

[10]  J. Wisniak,et al.  Hydrogenation of Xylose over Platinum Group Catalysts , 1974 .

[11]  J. Barbier,et al.  Catalytic hydrogenolysis of sorbitol , 1983 .

[12]  Brent H. Shanks,et al.  Effect of sulfur and temperature on ruthenium-catalyzed glycerol hydrogenolysis to glycols , 2005 .

[13]  Catherine Pinel,et al.  Conversion of biomass into chemicals over metal catalysts. , 2014, Chemical reviews.

[14]  B. Shanks,et al.  Probing the ruthenium-catalyzed higher polyol hydrogenolysis reaction through the use of stereoisomers , 2012 .

[15]  Haiqiang Lin,et al.  Improved performance of magnetically recoverable Ce-promoted Ni/Al2O3 catalysts for aqueous-phase hydrogenolysis of sorbitol to glycols , 2012 .

[16]  Tao Zhang,et al.  One-pot conversion of cellulose to ethylene glycol with multifunctional tungsten-based catalysts. , 2013, Accounts of chemical research.

[17]  Xinggui Zhou,et al.  Hydrogenolysis of sorbitol to glycols over carbon nanofiber supported ruthenium catalyst , 2010 .

[18]  Tapio Salmi,et al.  Deactivation kinetics of Mo-supported Raney Ni catalyst in the hydrogenation of xylose to xylitol , 2000 .

[19]  Tapio Salmi,et al.  Xylose hydrogenation: kinetic and NMR studies of the reaction mechanisms , 1999 .

[20]  Jiying Sun,et al.  Selective hydrogenolysis of biomass-derived xylitol to ethylene glycol and propylene glycol on supported Ru catalysts , 2011 .

[21]  W. Yuan,et al.  Carbon nanofiber/graphite-felt composite supported Ru catalysts for hydrogenolysis of sorbitol , 2009 .

[22]  M. Hawley,et al.  Mechanism Study of Sugar and Sugar Alcohol Hydrogenolysis Using 1,3-Diol Model Compounds , 1995 .

[23]  K. Weissermel,et al.  Industrial Organic Chemistry , 1978 .

[24]  P. Gallezot,et al.  Conversion of biomass to selected chemical products. , 2012, Chemical Society reviews.

[25]  P. Venuvanalingam,et al.  Hydrogenolysis of sorbitol over Ni and Pt loaded on NaY , 2011 .

[26]  Yue Liu,et al.  Tungsten trioxide promoted selective conversion of cellulose into propylene glycol and ethylene glycol on a ruthenium catalyst. , 2012, Angewandte Chemie.

[27]  G. Lu,et al.  Chemoselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals. , 2008, Chemical Society reviews.

[28]  D. Murzin,et al.  Recent Progress in Synthesis of Fine and Specialty Chemicals from Wood and Other Biomass by Heterogeneous Catalytic Processes , 2007 .

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