Keywords
How to Cite
Abstract
Biomass-derived 5-hydroxymethylfurfural (5-HMF) is a potential raw material for the production of a wide range of valuable chemicals and biofuels. Industrial production of 5-HMF from hexoses on solid catalysts is promising nowadays. Acid zeolites have great potential in application as catalysts for the dehydration of sugars. The purpose of this work was to obtain granular zeolite catalysts with optimal acidity and evaluate their effectiveness depending on the nature of the binder used. A zeolite catalyst without binder and samples with 10 wt % of kaolin/alumina were prepared. Their porous characteristics and acidity were studied by means of nitrogen low temperature adsorption/desorption, ammonia thermo-programmed desorption, and pyridine adsorption with IR control. The activity and selectivity of the catalysts for 5-HMF synthesis from glucose in the dimethyl sulfoxide medium at 160 ◦C were studied. The high efficiency of granular samples in glucose transformation into 5-HMF is confirmed. They are not only not inferior to, but even superior to, powdered samples. The component sources of Brønsted and Lewis acidity of the ammonium form of zeolite, which demonstrates acceptable activity (selectivity for 5-HMF is 34 %) despite the small number of Lewis centers, are considered in detail. The highest efficiency is demonstrated by the sample with aluminum oxide, which not only does not significantly deteriorate the microporous characteristics but also improves the mesoporosity of the catalyst. The selectivity towards 5-HMF on it reaches 44%. However, the developed mesoporosity of the sample with aluminum oxide is not critical to its activity. The main influence on the effectiveness of the catalyst in the synthesis of 5-HMF is played by the presence of acid centers of medium strength.
References
Esteban J., Yustos P., Ladero M. Catalytic Processes from Biomass-Derived Hexoses and Pentoses: A Recent Literature Overview. Catalysts, 2018, 8, 637-678.
https://doi.org/10.3390/catal8120637
Chen N., Zhu Z., Ma H., Liao W., Lü H. Catalytic upgrading of biomass-derived 5-hydroxymethylfurfural to biofuel 2,5-dimethylfuran over Beta zeolite supported non-noble Co catalyst. Mol. Catal., 2020, 486, 110882.
https://doi.org/10.1016/j.mcat.2020.110882
Kläusli T. AVA Biochem: commercialising renewable platform chemical 5-HMF. Green Process Synth., 2014, 3, 235-236.
https://doi.org/10.1515/gps-2014-0029
Choudhary V., Mushrif S.H., Ho C., Anderko A., Nikolakis V., Marinkovic N.S., Frenkel A.I., Sandler S.I., Vlachos D.G. Insights into the interplay of Lewis and Brønsted acid catalysts in glucose and fructose conversion to 5-(hydroxymethyl)furfural and levulinic acid in aqueous media. J. Am. Chem. Soc., 2013, 135 (10), 3997-4006.
https://doi.org/10.1021/ja3122763
Li Y., Meng X., Luo R., Zhou H., Lu S., Yu S., Bai P., Guo X., Lyu J. Aluminum/Tin-doped UiO-66 as Lewis acid catalysts for enhanced glucose isomerization to fructose. Appl. Catal. A: Gen., 2022, 632, 118501. https://doi.org/10.1016/j.apcata.2022.118501
https://doi.org/10.1016/j.apcata.2022.118501
Kuster B.F.M. 5-Hydroxymethylfurfural (HMF). A Review Focusing on its Manufacture. Starch - Stärke, 1990, 42, 314-321.
https://doi.org/10.1002/star.19900420808
Weitkamp J., Hunger M. Acid and Base Catalysis on Zeolites. In: Cejka J, Van Bekkum H, Corma A, Schueth F (eds), Introduction to Zeolite Molecular Sieves. 2007. Elsevier, 787-836.
https://doi.org/10.1016/S0167-2991(07)80810-X
Pande A., Niphadkar P., Pandare K., Bokade V. Acid modified H USY zeolite for efficient Catalytic Transformation of Fructose to 5 Hydroxymethyl Furfural (Biofuel Precursor) in Methyl Isobutyl Ketone−Water Biphasic System. Energy Fuels, 2018, 32, 3783-3791.
https://doi.org/10.1021/acs.energyfuels.7b03684
Patrylak L.K., Konovalov S.V., Yakovenko A.V., Pertko O.P., Povazhnyi V.A., Voloshyna Yu.G., Melnychuk O.V., Filonenko M.M. Micro-mesoporous kaolin-based zeolites as catalysts for glucose transformation into 5-hydroxymethylfurfural. Appl. Nanosci., 2022.
https://doi.org/10.1007/s13204-022-02620-5
Patrylak L., Konovalov S., Pertko O., Yakovenko A., Povazhnyi V., Melnychuk O. Obtaining glucose-based 5-hydroxymethylfurfural on large-pore zeolites. Eastern-European Journal of Enterprise Technologies, 2001, 2, N 6 (110), 38-44.
https://doi.org/10.15587/1729-4061.2021.226575
Patrylak L.K., Yakovenko A.V. Alkylation of isobutane with butenes under microcatalytic conditions in pulse regime. Voprosy khimii i khimicheskoi tekhnologii, 2021, 134 (1) 55-61 [in Ukrainian].
https://doi.org/10.32434/0321-4095-2021-134-1-55-61
Rouqerol F., Rouqerol J., Sing K. Adsorption by Powders and Porous Solids: Principles, Methodology and Applications. Academic Press: San Diego, 1999, 201 .
Yakovenko A.V., Patrylak L.K., Manza I.A., Patrylak K.I. Study of the acidity of zeolite alkylation catalysts by temperature programmed ammonia desorption. Theor. Exp. Chem., 2000, 36, 228-230.
https://doi.org/10.1007/BF02522757
Lanzafame P., Barbera K., Papanikolaou G., Perathoner S., Centi G., Migliori M., Catizzone E., Giordano G. Comparison of H+ and NH4+ forms of zeolites as acid catalysts for HMF etherification. Catal. Today, 2018, 304, 97-102.