Lignin forms an important part of lignocellulosic biomass and is an abundantly available residue. It is a potential renewable source of phenol. Liquefaction of enzymatic hydrolysis lignin as well as catalytical hydrodeoxygenation of the main intermediates in the degradation of lignin, that is, catechol and guaiacol, was studied. The cleavage of the ether bonds, which are abundant in the molecular structure of lignin, can be realised in near-critical water (573 to 673 K, 20 to 30 MPa). Hydrothermal treatment in this context provides high selectivity in respect to hydroxybenzenes, especially catechol. RANEY Nickel was found to be an adequate catalyst for hydrodeoxygenation. Although it does not influence the cleavage of ether bonds, RANEY Nickel favours the production of phenol from both lignin and catechol. The main product from hydrodeoxygenation of guaiacol with RANEY Nickel was cyclohexanol. Reaction mechanism and kinetics of the degradation of guaiacol were explored.
Hydroxymethylfurfural (HMF) has an outstanding position among bio-based platform chemicals, because high-value polymer precursors and fuel additives can be derived from HMF. Unfortunately, the large-scale industrial production of HMF is not yet realized. An open research question is the choice of hexose feedstock material. In this study, we used the highly available disaccharide sucrose for HMF synthesis. The conversion of sucrose was catalyzed by sulfuric acid in water media. Experiments were conducted at temperatures of 180, 200, and 220 • C with reaction times of 2-24 min. A carbon balance showed that the yield of unwanted side products rose strongly with temperature. We also developed a kinetic model for the conversion of sucrose, involving nine first-order reactions, to uncover the kinetics of the main reaction pathways. Within this model, HMF is produced exclusively via the dehydration of fructose. Glucose isomerizes slowly to fructose. Side products arise simultaneously from glucose, fructose, and HMF. A pathway from hexoses to xylose via reverse aldol reaction was also included in the model. We believe that sucrose is the ideal feedstock for large-scale production of HMF because it is more abundant than fructose, and easier to process than sugars obtained from lignocellulosic biomass.
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