Abstract
An important product of biomass carbohydrate conversion is 5-hydroxymethylfurfural as a potential raw material component of a wide range of important chemicals. The aim of the work was to study the conversion of glucose into 5-hydroxymethylfurfural in the presence of modified clinoptilolite and mordenite-clinoptilolite zeolite rocks from Transcarpathia. A number of acid catalysts have been synthesized by liquid-phase ion exchange of native cations with calcium, lanthanum, and ammonium cations, as well as by dealumination with hydrochloric and ethylenediaminetetraacetic acid. Their properties were characterized using XRD and XRF analysis, low-temperature nitrogen adsorption/desorption, and FTIR spectroscopy. The acidity of the samples was determined by reverse n-butylamine titration. Acid treatment of the samples contributed to an increase in the specific surface area of the samples by an order of magnitude. The samples were tested in the conversion of 9% aqueous glucose solution into 5-hydroxymethylfurfural. The composition of the reaction products was analyzed by gas chromatography. The glucose conversions and the yields of 5-hydroxymethylfurfural, levulinic acid, and fructose were calculated. The glucose conversions ranged from 30 to 70 %. The results were analyzed in accordance with the characteristics of the nature of the active sites of the catalysts and the porous structure of the latter. It was found that the samples with the presence of Lewis acid sites in the form of extra-framework aluminum and multiply charged cations are characterized by the highest 5-hydroxymethylfurfural yields. Due to glucose conversion occurs mainly on the outer surface of zeolite crystals and at the entrances to the cavities, the polycationic form of clinoptilolite, despite its low porous characteristics, demonstrates the highest yield of 5-hydroxymethylfurfural.
References
Esteban J., Yustos P., Ladero M. Catalytic processes from biomass-derived hexoses and pentoses: a recent literature overview. Catalysts., 2018, 8, 637–678.
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.
Xu H., Wang Z., Huang J., Jiang Y. Thermal Catalytic Conversion of Biomass-Derived Glucose to Fine Chemicals. Energy Fuels, 2021, 35(10), 8602–8616.
Tomishige K., Yabushita M., Cao J., Nakagawa Y. Hydrodeoxygenation of potential platform chemicals derived from biomass to fuels and chemicals. Green Chem., 2022, 24, 5652–5690.
Choudhary V., Mushrif S.H., Ho C., Anderko A., Nikolakis V. et al. 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. Soc., 2013, 135, 3997–4006.
Bhaumik P., Dhepe P.L. Solid Acid Catalyzed Synthesis of Furans from Carbohydrates. Catal. Rev., 2016, 58(1), 36–112.
Li J., Li J., Zhang D., Liu C. Theoretical elucidation of glucose dehydration to 5-hydroxymethylfurfural catalyzed by a SO3H-functionalized ionic liquid. J. Phys. Chem. B, 2015, 119, 13398–13406.
Barbosa S.L., de S. Freitas M., dos Santos W.T.P. et al. Dehydration of d-fructose to 5-hydroxymethyl-2-furfural in DMSO using a hydrophilic sulfonated silica catalyst in a process promoted by microwave irradiation. Sci. Rep., 2021, 11, 1919.
Pande A., Niphadkar P., Pandare K., Bokade V. Acid modified H‑USY zeolite for efficient catalytic transformation of fructose to 5‑hydroxymethylfurfural (biofuel precursor) in methyl isobutyl ketone−water biphasic system. Energy Fuels., 2018, 32(3), 3783–3791.
Levytska S.I. Investigation of glucose isomerization into fructose on MgO-ZrO2 catalyst in flow mode. Catalysis and Petrochemistry, 2017, 26, 46–52. [in Ukrainian].
Huang F., Jiang T., Dai H., Xu X., Jiang S., Xhen L., Fei Z., Dyson P.J. Transformation of glucose to 5-hydroxymethylfurfural over regenerated cellulose supported Nb2O5 center dot nH2O in aqueous solution. Catal. Letters., 2020, 10, 13489–13495.
Wei W.Q., Wu S.B. Experimental and kinetic study of glucose conversion to levulinic acid in aqueous medium over Cr/HZSM-5 catalyst. Fuel, 2018, 225, 311–321.
Patrylak K., Bobonych F., Voloshyna Yu. et al. Ukrainian mordenite-clinoptilolite rocks as a base for linear hexane isomerization catalyst. Appl. Catal. A Gen., 1998, 174(1–2), 187–198.
Patrylak L., Konovalov S., Yakovenko A., Pertko O., Povazhnyi V. et al. Fructose transformation into 5-hydroxymethylfurfural over natural transcarpathian zeolites. Сhem. Chem. Technol., 2022, 16(4), 521–531.
Patrylak L., Konovalov S., Zubenko S., Yakovenko A. Transformation of hexoses on natural and synthetic zeolites. Сhem. Chem. Technol., 2023, 17(2), 287–293.
Vasylechko V., Sydorchuk V., Manko N., Kostiv O., Klyuchivska O., Ilkov O., Bagday S., Zelinskiy A., Gromyko A., Stoika R., Kalychak Ya. Effect of physico-chemical modification of clinoptilolite composites on their antimicrobial activity. Chem. Chem. Technol., 2025, 19(2), 183–195.
Breck D.W. Zeolite molecular sieves: structure, chemistry and use. – John Wiley, New York, 1974.
Ahmed A.M., Jarullah A.T., Hussein H.M., Ahmed A.N. Mordenite-Type Zeolite from Iraq Sand: Synthesis and Characterization. J. Petrol. Research and Studies, 2023, 13(3), 126–142.
Voloshyna Yu., Pertko O., Pavazhnyi V., Yakovenko A. Effect of modifying the clinoptilolite-containing rocks of Transcarpathia on their porous characteristicss and catalytic properties in the conversation of C6-hydrocarbons. Chem. Chem. Technol., 2023, 17(2), 373–385.
Anderson M.W., Klinowski J. Zeolites treated with silicon tetrachloride vapour. Part 1 – Preparation and characterization. J. Chem. Soc., Faraday Trans.1, 1986, 82, 1449–1496.
Mahala S., Arumugam S.M., Kumar S., Devi B., Elumalai S. Tuning of MgO's base characteristics by blending it with amphoteric ZnO facilitating the selective glucose isomerization to fructose for bioenergy development. Nanoscale Adv., 2023, 5(9), 2470–2486.
Khivantsev K., Jaegers N.R., Kovarik L., Derewinski M.A., Kwak J.-H., Szanyi J. On the nature of extra-framework aluminum species and improved catalytic properties in steamed zeolites. Molecules, 2022, 27(7), 2352.
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., 2023, 13(7), 4795–4808.
Patrylak L.K., Pertko O.P., Povazhnyi V.A., Yakovenko A.V., Konovalov S.V. Evaluation of nickel-contaning zeolites in the catalytic transformation of glucose in an aqueous medium. Appl. Nanosci., 2022, 12(4), 869–882.