Abstract
Supported Pt catalysts are synthesized, characterized and are used in the liquid phase air oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA). Under the optimum reaction conditions of a stepwise increase in the reaction temperature (75 and 140 °C for 12 h each), we achieved as high as 96 % FDCA yield in presence of 1 bar oxygen pressure over Pt/γ-Al2O3. It is shown that as the oxygen pressure increases (1–10 bar), the FDCA yields decrease, since at higher partial pressure of oxygen, overoxidation reactions of substrate and product(s) are possible. It is interesting to note that even with air as an oxidant, we obtained similar yields of FDCA as that with oxygen. Moreover, the effects of base (weak or strong), its concentration (equimolar or excess) were studied in detail. It is important to increase the reaction temperature in a stepwise manner to achieve higher yields of FDCA since at higher temperatures HMF undergoes self-degradation and thus the yields of FDCA decrease. The self-degradation of HMF is also proved by undertaking the reaction under nitrogen environment. The study on the effect of substrate-to-catalyst ratio is done to improve up on the economics of overall process. The effect of supports (reducible and non-reducible) and their oxygen storage capacity is discussed and is proposed to be one of the factors to change the course of reaction. Furthermore, we have shown that FDCA formed in the reaction can be successfully isolated (91 %, isolated yield) in the pure form and its purity is confirmed by NMR, melting point, and elemental analysis. The catalysts were characterized with X-ray powder diffraction, transmission electron microscopy and inductively coupled plasma-optical emission spectroscopy techniques.
Similar content being viewed by others
References
Maki-Arvela P, Holmbom B, Salmi T, Murzin DY (2007) Catal Rev 49:197
Corma A, Iborra S, Velty A (2007) Chem Rev 107:2411
Bozell JJ, Petersen GR (2010) Green Chem 12:539
Sillion B (1999) High Perform Poly 11:417
Roman-Leshkov Y, Barret CJ, Liu ZY, Dumesic JA (2007) Nature 447:982
Chheda JN, Roman-Leshkov Y, Dumesic JA (2007) Green Chem 9:342
Yang F, Liu Q, Bai X, Du Y (2011) Bioresour Technol 102:3424
Tong X, Ma Y, Li Y (2010) Appl Catal 385:1
Werpy T, Petersen G, 2004 Top Value Added Chemicals From Biomass, Available electronically at http://wwwl.eere.energy.gov/biomass/pdfs/35523.pdf
Gandini A, Silvestre AJD, Neto CP, Sousa AF, Gomes M (2008) Polym J Sci 47:295
Benecke HP, Kawczak AW, Garbark DB, (2008) US 207847
King JL, Kawczak AW, Benecke HP, Mitchell KP, Clingerman M.C, (2008) US 81883
Moreau C, Belgacem MN, Gandini A (2004) Top Catal 27:11
Verdeguer P, Merat N, Gaset A (1993) J Mol Catal 85:327
Yuan JP, Chen F (1998) Food Chem 64:42
Besson M, Gallezot P (2000) Catal Today 57:127
Kluytmans JHJ, Markuse AP, Kuster BFM, Marin GB, Schouten JC (2000) Catal Today 57:143
Mallat T, Baiker A (1994) Catal Today 19:247
Fittig R, Heinzelmann H (1876) Chem Ber 9:1198
Toshinari M, Hirokazu K, Takenobu K, Hirohide M, (2007) US 232815
Miura T, Kakinuma H, Kawano T, (2008) US 7411078B2
Partenheimer W, Grushin VV (2001) Adv Synth Catal 343:102
Liga MA, Hallen T, Hu J, White JF, Gray MJ, (2008) PUB. No: US 2008/0103318A1
Ribeiro ML, Schuchardt U (2003) Catal Commun 4:83
Vinke P, Poel WVD, Bekkum HV (1991) Stud Surf Sci Catal 59:385
Vinke P, Dam HEV, Bekkum HV, Centi G (1990) New developments in selective oxidation. Elsevier, New York 147
Kroger M, Prube U, Vorlop KD (2000) Top Catal 13:237
Casanova O, Iborra S, Corma A (2009) ChemSusChem 2:1138
Gorbanev YY, Klitgaard SK, Woodley JM, Christensen CH, Riisager A (2009) ChemSusChem 2:672
Gupta NK, Nishimura S, Takagakib A, Ebitani K (2011) Green Chem 13:824
Taarning E, Nielsen IS, Egeblad K, Madsen R, Christensen CH (2008) ChemSusChem 1:75
Xia BY, Wang JN, Wang XX (2009) J Phys Chem C 113:18115
Grace AN, Pandian K (2007) J Phys Chem Solids 68:2278
Davis SE, Houkb LR, Tamargoa EC, Datyeb AK, Davis RJ (2011) Catal Today 160:55
Baranenko VI, Falkovskii LN, Kirov VS, Kurnyk LN, Musienko AN, Piontkovskii AI (1990) Atomnayannergiya 68:291
Ishida T, Kinoshita N, Okatsu H, Akita T, Takei T, Haruta M (2008) Angew Chem Int Ed 47:9265
Kaspar J, Fornasiero P, Graniani M (1999) Catal Today 50:285
Yao MH, Baird RJ, Kunz FW, Hoost TE (1997) J Catal 166:67
Passos FB, Oliveira ER, Rego CEL, Mattos LV, Noronha FB (2003) Fuel Chem Div 48:325
Reddy BM, Khan A (2005) Catal Surv Asia 9:155
Despande PA, Madras G (2010) AIChE J 56:2662
Siel’niko VV, Tolkachev NN, Stakheev AY (2005) Kinet Catal 46:550
Mattos LV, Noronha FB (2005) J Power Source 145:10
Acknowledgments
Authors thank Dr. D. Srinivas for valuable suggestions and the Council of Scientific and Industrial Research (CSIR) Delhi, for a research fellowship to RS.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Sahu, R., Dhepe, P.L. Synthesis of 2,5-furandicarboxylic acid by the aerobic oxidation of 5-hydroxymethyl furfural over supported metal catalysts. Reac Kinet Mech Cat 112, 173–187 (2014). https://doi.org/10.1007/s11144-014-0689-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11144-014-0689-z