Aqueous-phase hydrogenation of furfural over supported palladium catalysts: effect of the support on the reaction routes
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The effect of the support nature (different carbons, aluminum oxide, mixed MgAl oxide) on the activity of palladium catalysts and on the reaction routes of aqueous-phase hydrogenation of furfural at a temperature of 423 K and a pressure of 3 MPa was investigated. The carbon-supported catalysts were found to be the most active, and almost complete conversion of furfural is achieved. In the presence of these catalysts, the reaction proceeds predominantly through two parallel water-involved routes depending on the nature of carbon support: catalysts supported on carbon nanoglobules are selective to 4-oxopentanal (selectivity up to about 63%), while catalysts supported on carbon nanotubes give mainly cyclopentanone (selectivity up to 57%). The palladium catalysts based on the oxide supports (γ-Al2O3, MgAlOx) are much less active in the aqueous-phase hydrogenation of furfural compared to carbon-supported catalysts, and complete conversion of furfural does not occur (only up to 55%). In the presence of catalysts prepared using basic support (i.e., MgAl oxide), there are no reactions involving water, and furfuryl alcohol and tetrahydrofurfuryl alcohol are the principal products. According to the results of catalyst characterizations, the revealed differences in performance of palladium catalysts are caused by the effect of the support nature on the formation and dispersion of supported Pd nanoparticles, as well as by the distinctions in the structure and acid–base properties of the supports.
KeywordsPalladium catalysts Support effect Aqueous-phase hydrogenation Furfural
The authors thank Dr. Liudmila Stepanova and Olga Maevskaya for participation in the preparation of catalysts and in the potentiometric measurements, Dr. Rinat Izmailov for the analysis of the synthesized samples by ICP-AES, Sergey Evdokimov for his help with NMR measurements, and Dr. Alexey Arbuzov for providing the FTIR spectra of the supports. Besides, the authors are grateful to Dr. Vyacheslav Yurpalov for useful discussion of the catalytic results. Characterization of catalysts and identification of reaction products were performed using equipment of the Omsk Regional Center of Collective Usage, Siberian Branch of the Russian Academy of Sciences.
The work was supported by the Ministry of Science and Higher Education of the Russian Federation in accordance with the Fundamental Research Program of State Academies of Sciences for 2013‒2020, Subject V.47, Project No. V.47.1.3 (state Registration Number in the EGISU NIOKTR System: AAAA-A17-117021450099-9).
- 1.Alonso DM, Marcotullio G (2018) In: López Granados M, Alonso DM (eds) Furfural: an entry point of lignocellulose in biorefineries to produce renewable chemicals, polymers, and biofuels. World Scientific, HackensackGoogle Scholar
- 2.Dias AS, Lima S, Pillinger M, Valente AA (2010) In: Pignataro B (ed) Ideas in chemistry and molecular sciences: advances in synthetic chemistry. Wiley, WeinheimGoogle Scholar
- 6.Machado G, Leon S, Santos F, Lourega R, Dullius J, Mollmann ME, Eichler P (2016) Nat Resour 7:115–129Google Scholar
- 24.Ohyama J, Satsuma A (2017) In: Fang Z, Smith RL, Li H (eds) Production of biofuels and chemicals with bifunctional catalysts. Springer Nature, SingaporeGoogle Scholar
- 25.Song S, Wu G, Guan N, Li L (2017) In: Fang Z, Smith RL, Li H (eds) Production of biofuels and chemicals with bifunctional catalysts. Springer Nature, SingaporeGoogle Scholar
- 32.Voll M, Kleinschmit P (2012) Ullmann’s encyclopedia of industrial chemistry. Wiley-VCH, WeinheimGoogle Scholar
- 35.Serp P, Machado B (2015) Nanostructured carbon materials for catalysis. The Royal Society of Chemistry, CambridgeGoogle Scholar
- 38.Lycourghiotis A (2009) In: de Jong KP (ed) Synthesis of solid catalysts. Wiley, WeinheimGoogle Scholar
- 39.Marceau E, Carrier X, Che M (2009) In: de Jong KP (ed) Synthesis of solid catalysts. Wiley, WeinheimGoogle Scholar