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

Replacing petroleum feedstocks by biomass requires efficient methods to convert carbohydrates to a variety of chemical compounds. We report the catalytic conversion of sugars giving high yield to 5-hydroxymethylfurfural (HMF), a versatile intermediate. Metal halides in 1-alkyl-3-methylimidazolium chloride are catalysts, among which chromium (II) chloride is found to be uniquely effective, leading to the conversion of glucose to HMF with a yield near 70%. A wide range of metal halides is found to catalyze the conversion of fructose to HMF. Only a negligible amount of levulinic acid is formed in these reactions.

Metal Chlorides in Ionic Liquid Solvents Convert Sugars to 5-Hydroxymethylfurfural

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

https://digital.csic.es/bitstream/10261/113789/1/Production_carbon_Sevilla.pdf

The production of carbon materials by hydrothermal carbonization of cellulose

Energy shortage, environmental crisis, and developing customer demands have driven people to find facile, low-cost, environmentally friendly, and nontoxic routes to produce novel functional materials that can be commercialized in the near future. Amongst various techniques, the hydrothermal carbonization (HTC) process of biomass (either of isolated carbohydrates or crude plants) is a promising candidate for the synthesis of novel carbon-based materials with a wide variety of potential applications. In this Review, we will discuss various synthetic routes towards such novel carbon-based materials or composites via the HTC process of biomass. Furthermore, factors that influence the carbonization process will be analyzed and the special chemical/physical properties of the final products will be discussed. Despite the lack of a clear mechanism, these novel carbonaceous materials have already shown promising applications in many fields such as carbon fixation, water purification, fuel cell catalysis, energy storage, CO(2) sequestration, bioimaging, drug delivery, and gas sensors. Some of the most promising examples will also be discussed here, demonstrating that the HTC process can rationally design a rich family of carbonaceous and hybrid functional carbon materials with important applications in a sustainable fashion.

Engineering Carbon Materials from the Hydrothermal Carbonization Process of Biomass

A batch-type subcritical water system was used to perform the decomposition reaction of d-fructose to 5-hydroxymethy furfural (HMF) over a temperature range of 473−593 K. The catalytic effect of various organic and inorganic acids with pH values in the range of 1.5−5 was evaluated. It was found that not only the pH, but also the nature of the acids, had great influence on the decomposition pathway. At lower pH, a rehydration of HMF to levulinic and formic acids occurred, whereas at higher pH, polymerization reactions occurred. Phosphoric acid (pH 2) was determined to give good balance between activity, yield, and byproduct amounts. The optimum condition for the best yield of HMF (65%) was achieved at a temperature of 513 K for a residence time of 120 s. The decomposition reaction of other monosaccharides and disaccharides were also investigated, and it was determined that the ketohexoses give higher yields than aldohexoses. However, all saccharides showed the possibility of the conversion to HMF in subcri...

Acid-catalyzed production of 5-hydroxymethyl furfural from d-fructose in subcritical water

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.

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

Feridoun Salak Asghari

Papers

Acid-catalyzed production of 5-hydroxymethyl furfural from d-fructose in subcritical water

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

Dehydration of fructose to 5-hydroxymethylfurfural in sub-critical water over heterogeneous zirconium phosphate catalysts

Production of phenolic compounds from rice bran biomass under subcritical water conditions

Sub-critical water treatment of rice bran to produce valuable materials