Renewable Resources Robert-Jan van Putten,†,‡ Jan C. van der Waal,† Ed de Jong,*,† Carolus B. Rasrendra,‡,⊥ Hero J. Heeres,*,‡ and Johannes G. de Vries* †Avantium Chemicals, Zekeringstraat 29, 1014 BV Amsterdam, the Netherlands ‡Department of Chemical Engineering, University of Groningen, Nijenborgh 4, 9747 AG Groningen, the Netherlands Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, the Netherlands DSM Innovative Synthesis BV, P.O. Box 18, 6160 MD Geleen, the Netherlands Department of Chemical Engineering, Institut Teknologi Bandung, Ganesha 10, Bandung 40132, Indonesia

Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources

Hydrothermal technologies are broadly defined as chemical and physical transformations in high-temperature (200–600 °C), high-pressure (5–40 MPa) liquid or supercritical water. This thermochemical means of reforming biomass may have energetic advantages, since, when water is heated at high pressures a phase change to steam is avoided which avoids large enthalpic energy penalties. Biological chemicals undergo a range of reactions, including dehydration and decarboxylation reactions, which are influenced by the temperature, pressure, concentration, and presence of homogeneous or heterogeneous catalysts. Several biomass hydrothermal conversion processes are in development or demonstration. Liquefaction processes are generally lower temperature (200–400 °C) reactions which produce liquid products, often called “bio-oil” or “bio-crude”. Gasification processes generally take place at higher temperatures (400–700 °C) and can produce methane or hydrogen gases in high yields.

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Thermochemical biofuel production in hydrothermal media: A review of sub- and supercritical water technologies

Mechanism of formation of 5-(hydroxymethyl)-2-furaldehyde from d-fructose and sucrose

The degradation of biomass is studied in the ranges of 330−410 °C and 30−50 MPa and at 15 min of reaction time. To characterize the chemistry of biomass degradation, key compounds which are interme...

Biomass Conversion in Water at 330−410 °C and 30−50 MPa. Identification of Key Compounds for Indicating Different Chemical Reaction Pathways

Dehydration of fructose to 5-hydroxymethylfurfural was performed in a batch mode in the presence of a series of dealuminated H-form mordenites as catalysts, at 165°C, and in a solvent mixture consisting of water and methyl isobutyl ketone (1:5 by volume). Under the operating conditions used, the reaction was not controlled by external or internal diffusional limitations. Fructose conversion and selectivity to 5-hydroxymethylfurfural were found to depend on acidic and structural properties of the catalysts used as well as on the micropore vs. mesopore volume distribution of those catalysts. A maximum in the rate of conversion of fructose was observed for the H-mordenite with a Si/Al ratio of 11. A maximum in the selectivity to 5-hydroxymethylfurfural was observed only for H-mordenites with a low mesoporous volume. The high selectivity obtained (>90%) was correlated with the shape selectivity properties of H-mordenites (bidimensional structure), and particularly with the absence of cavities within the structure allowing further formation of secondary products. The influence of the microporosity vs. mesoporosity on the selectivity to 5-hydroxymethylfurfural was also studied, the formation of mesopores upon dealumination procedures being damaging to obtain a high selectivity. A significant increase in the selectivity (10%) was also obtained by simultaneous extraction of 5-hydroxymethylfurfural with methyl isobutyl ketone circulating in a countercurrent manner in a continuous catalytic heterogeneous pulsed column reactor. Finally, taking into account the most recent results reported in the literature and our own results, it is possible to revise the mechanism of the dehydration of fructose.

David G.B. Boocock

Papers

Rapid hydrothermolysis of cellulose and related carbohydrates