(600ba) Dehydration of Fructose into Furans over Zeolite Catalyst Using Carbon Black As Adsorbent

Authors: 
Dornath, P., University of Massachusetts Amherst
Fan, W., University of Massachusetts Amherst

Due to increasing demands for transportation fuels and commodity chemicals as well as environmental and political concerns associated with diminishing fossil fuel resources, research efforts have been driven towards the efficient utilization of renewable feedstock, such as naturally abundant lignocellulosic biomass1. Development of economically viable processes for the syntheses of chemical intermediates from biomass-derived carbohydrates has been considered as an important challenge in this area. One major pathway for converting lignocellulosic biomass into fuels and chemicals involves the production of furans, such as 5-hydroxymethylfurfural (HMF) and furfural, from the dehydration of hexose and pentose sugars2-3.

  The key challenge for the selective production of HMF from the dehydration of fructose is the development of selective heterogeneous catalyst and protection of further reaction of the formed HMF. In this study, formation of HMF from the dehydration of fructose over zeolite catalysts in aqueous phase was studied in a reactive adsorption system using carbon black (BP2000) as an adsorbent4-5. The dehydration of fructose over zeolite BEA catalyst in water revealed that selectivity to HMF is largely influenced by the formation of levulinic acid and formic acid from the rehydration of produced HMF as well as subsequent condensation reactions. In order to increase selectivity to HMF, reactive adsorption with carbon adsorbents was used to prevent the further reactions of the produced HMF. It was found that BP2000 carbon black exhibited high selectivity and capacity for the adsorption of HMF and furfural from the aqueous phase. The unique adsorption performance of BP2000 is likely due to the large surface area, hydrophobic nature and micropore structure. With using the carbon adsorbent, furan selectivity (selectivity of HMF and furfural) over zeolite BEA was improved from 27% to 44% with a furan yield of 41%. The furan selectivity and yield obtained in the presence of the carbon adsorbent were similar to those obtained from the aqueous/organic reaction system using methyl isobutyl ketone (MIBK) as an extraction phase.

 References:

1.        Huber, G. W.; Iborra, S.; Corma, A., "Synthesis of transportation fuels from biomass: Chemistry, catalysts, and engineering". Chem. Rev. 2006, 106 (9), 4044-4098.

2.         Chang, C.-C.; Green, S. K.; Williams, C. L.; Dauenhauer, P. J.; Fan, W., "Ultra-selective cycloaddition of dimethylfuran for renewable p-xylene with H-BEA". Green Chem. 2014, 16 (2), 585-588.

3.         Williams, C. L.; Chang, C.-C.; Do, P.; Nikbin, N.; Caratzoulas, S.; Vlachos, D. G.; Lobo, R. F.; Fan, W.; Dauenhauer, P. J., "Cycloaddition of Biomass-Derived Furans for Catalytic Production of Renewable p-Xylene". ACS Catal. 2012, 2 (6), 935-939.

4.         Dornath, P.; Fan, W., "Dehydration of fructose into furans over zeolite catalyst using carbon black as adsorbent". Microporous Mesoporous Mater. 2014, 191 (0), 10-17.

5.         Swift, T. D.; Bagia, C.; Nikolakis, V.; Vlachos, D. G.; Peklaris, G.; Dornath, P.; Fan, W., "Reactive adsorption for the selective dehydration of sugars to furans: Modeling and experiments". AIChE J. 2013, 59 (9), 3378-3390.