화학공학소재연구정보센터
Chemical Engineering Science, Vol.173, 455-464, 2017
Experimental and kinetic analysis of the liquid phase hydrodeoxygenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran over carbon-supported nickel catalysts
2,5-Dimethylfuran (DMF) is an attractive biofuel being stable, insoluble in water and an alternative to gasoline. DMF is accessible via hydrodeoxygenation of the cellulosic bio-based platform chemical 5-hydroxymethylfurfural (HMF). Efficient transformations of HMF to DMF have been reported to date; however, the kinetics of the reaction and a comprehensive analysis of the reaction network have not been addressed yet. In the present work, a plausible reaction network based on kinetic study of the hydrodeoxygenation of HMF over a carbon-supported nickel catalyst is proposed. The study of the reaction network showed the reaction indeed proceeds via the hydrogenation of the aldehyde group of HMF to form 2,5-bishydroxymethylfuran (BHMF) and subsequent conversion of BHMF to 5-methylfurfurylalcohol (MFA) followed by hydrogenolysis of MFA to DMF. Side reactions include the formation of 2,5-dihydroxymethyltetrahydrofuran (DHMTHF) and 2,5-dimethyltetrahydrofuran (DMTHF). A suitable kinetic model enabled estimating the kinetic parameters in the reaction temperatures range of 150-190 degrees C. Kinetics analysis revealed the hydrogenation of HMF to BHMF as ratedetermining step, while subsequent deoxygenation to DMF proceeds faster. Interestingly, most undesired reactions were kinetically hindered under selected reaction conditions allowing high selectivity to the target product DMF. (C) 2017 Elsevier Ltd. All rights reserved.