Eyjolfsdottir, Ester

Riisager, Anders

Online Research Database In Technology

Aerobic oxidation of HMF to FDA with ruthenium containing ferrite-spinel catalyst

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Downloaded from orbit.dtu.dk on: Dec 19, 2017Aerobic Oxidation of HMF to FDA with Ruthenium containing Ferrite-Spinel CatalystEyjolfsdottir, Ester Inga; Riisager, AndersPublication date:2011Document VersionPublisher's PDF, also known as Version of recordLink back to DTU OrbitCitation (APA):Eyjolfsdottir, E., & Riisager, A. (2011). Aerobic Oxidation of HMF to FDA with Ruthenium containing Ferrite-Spinel Catalyst. Poster session presented at 10th EuropaCat Congress , Glasgow, United Kingdom.Aerobic Oxidation of HMF to FDA withRuthenium containing Ferrite-Spinel CatalystEster Eyjo´lfsdo´ttir, Anders RiisagerCentre for Catalysis and Sustainable Chemistry (CSC),Department of Chemistry, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmarkeieyj@kemi.dtu.dkIntroduction pIn the past years, there has been a rising demand for efficient heterogeneouslycatalyzed oxidation processes for production of both fine and bulk chemicals[1]. In order to avoid waste generation, considerable effort has been put intothe development of aerobic oxidation methods using molecular oxygen as thestoichiometric reagent. Recent studies have shown that ruthenium oxides areactive oxidation catalysts for various functional groups [2].In this work we have used a ferrite-spinel based catalyst,MnFe1.5Ru0.35Cu0.15O4, previously described by Ji et al. [3] to efficientlyoxidize 5-hydroxymethyl furfural (HMF) to 2,5-furandicarboxylic acid (FDA)in water in the presence of molecular oxygen:Why HMF and FDA? HMF can be obtained from biomass via dehydration of hexosemonosaccharides, such as glucose or fructose [4], and is a precursor formany compounds with high industrial potentials, such as FDA, figure 1. FDA has been identified as an important value added chemical by theU.S. Department of Energy biomass program [5]. FDA can replace chemicals derived from fossil fuels in manufacture ofpolyamides, polyesters, and polyurethanes.Figure 1: Reaction network and lifecycle of HMF as a renewable platform molecule.Reaction pathwayFigure 2: Possible reaction pathways for the oxidation of HMF to FDA.The oxidation of HMF to FDA can proceed via two pathways; oxidation of thealcohol group to aldehyde, forming diformyl furan (DFF) or oxidation of thealdehyde group to carboxylic acid, forming 5-hydroxy-2-furancarboxylic acid(HMFCA). Further oxidation of both DFF and HMFCA yields 5-formylfuran-2-carboxylic acid (FFCA) and then, FDA.Experimental and ResultsThe catalyst, MnFe1.5Ru0.35Cu0.15O4 was prepared as described by Ji et al.[3]. All reactions were carried out in a stirred Parr reactor autoclave, andthe degree of conversion and yields of individual products were quantified byHPLC.0 2 4 6 8 1 0 1 2 1 4 1 6 1 8 2 0 2 2 2 402 04 06 08 01 0 0  Yield [%]T i m e  [ H o u r s ] F D A D F F H M F C A Figure 3: Product yields as afunction of reaction time.Reaction conditions: 10 mL2.2 wt% HMF in aqueoussolution, molar ratio ofcatalyst to HMF = 0.55, 10bar O2, 110◦C.Full conversion of HMF wasachieved in all reactions.0 5 1 0 1 5 2 0 2 5 3 002 04 06 08 01 0 0  Yield [%]P r e s s u r e  [ b a r  O 2 ] F D A D F F H M F C A H M FFigure 4: Product and HMFyields and as a function ofoxygen pressure.Reaction conditions: 10 mL2.2 wt% HMF in aqueoussolution, molar ratio ofcatalyst to HMF = 0.55,110◦C, 6 hours.2 0 4 0 6 0 8 0 1 0 0 1 2 002 04 06 08 01 0 0 Yield [%]            	                 Figure 5: Product and HMFyields as a function ofreaction temperature.Reaction conditions: 10 mL2.2 wt% HMF in aqueoussolution, molar ratio ofcatalyst to HMF = 0.55, 10bar O2, 6 hours.Conclusions Quantitative yields of FDA can be achieved at 110◦C and 25 bar O2 in 6hours using 2.2 wt% aqueous solution of HMF and molar ratio of Ru toHMF of 0.19. Increased oxygen pressures and increased reaction temperatures havepositive effect on the reaction rate, although too high temperatures havebeen shown to cause degradation of HMF. Detection of both DFF and HMFCA in post-reaction mixtures suggeststhat the reaction proceeds via both possible reaction pathways shown infigure 2.[1] Franz, G.; Sheldon, R. A. In ”Oxidation”, Ullmann’s Encyclopedia of Industrial Chemistry, electronic release, 6th ed.; Wiley-VCH:Weinheim, 2000; Chapter 2.[2] Arends, I. W. C. E.; Kodama, T.; Sheldon, R. A. In Ruthenium Catalysts and Fine Chemistry; Bruneau, C., Dixneuf, P. H., Eds.;Springer-Verlag, 2004; Vol. 11, Chapter Oxidation using ruthenium catalysts, pp 277–320.[3] Ji, H.-B.; Ebitani, K.; Mizugaki, T.; Kaneda, K. Catalysis Communications 2002, 3, 511 – 517.[4] Corma, A.; Iborra, S.; Velty, A. Chemical Reviews 2007, 107, 2411–2502.[5] Werpy, T.; Petersen, G. Top Value Added Chemicals from Biomass Vol.1, http://www.osti.gov/bridge, 2004, Accessed April 25th2010.This work was supported by the Danish National Advanced Technology Foun-dation and Novozymes A/S.

Aerobic Oxidation of HMF to FDA with Ruthenium containing Ferrite-Spinel Catalyst

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Aerobic Oxidation of HMF to FDA with Ruthenium containing Ferrite-Spinel Catalyst

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