1. UploadedinJune2014 Supportedmetalcatalystsinthe conversionofHMFintoFDCA PareshL.DhepeandRamakantaSahu NationalChemicalLaboratory, Pune,India 14th December2011 Caution:DONOTCIRCULATE!! Reac Kinet Mech Cat (2014) 112:173187 DOI 10.1007/s11144-014-0689-z Paresh Dhepe

2. DOE report: FDCA is amongst 12 top most value added chemicals derived Oxidation of HMF into FDCA: Challenge because both CHO and OH group have to be oxidised value added chemicals derived from renewable material Conventionally: oxidations are carried out using stoichiometric reagents (alkyl hydroperoxides, hypochlorite or Supported Au and Pt have shown highly efficient catalytic activity for aqueous phase oxidation of alcohols and hydroperoxides, hypochlorite or iodosylbenzene, perbenzoic acid, permanganate etc.) oxidation of alcohols and aldehydes Drawbacks: Hazardous, loads of waste generation, low active oxygen Preferable: Use of molecular oxygen or air and Heterogeneous catalyst Reac Kinet Mech Cat (2014) 112:173187 DOI 10.1007/s11144-014-0689-z Paresh Dhepe 3. HMF, Catalyst, Solvent, Temperature (75-140C), O2 / Air pressure (1-10 bar), Time (1-48h) Uses Starting compound for polyamide, polyester polyurethane Pharmacology: antibacterial agents medicines to remove kidney stones utilized in artificial veins Pharmacology: antibacterial agents medicines to remove kidney stones, utilized in artificial veins for transplantation etc Fragrance, agrochemicals, and insecticides industries Reac Kinet Mech Cat (2014) 112:173187 DOI 10.1007/s11144-014-0689-z Paresh Dhepe 4. Water (5 g)Water(5g) KMnO4 (0.37g) NaOH (0.96g) 40oC HMF(0.13g) FDCA(~85%yield) 40oC 1h Reac Kinet Mech Cat (2014) 112:173187 DOI 10.1007/s11144-014-0689-z Paresh Dhepe 5. 2g Support + 10 mL water Stirring at RT Add dropwise 10 mL of aqueous Tetraamineplatinum (II) nitrate (0.07g) solution Stirring at RT for 16 hg Dried for 6h Calcination : O2, 400C, 2h, flow = 20 mL/min R d ti H 400C 2h fl 20 L/ iReduction: H2, 400C, 2h, flow = 20 mL/min Pt (3.5 wt%)/Support was obtained (grey colour) Pt on CeO2, AC, TiO2, ZrO2 are also prepared Au (2 wt%)/Al2O3 was also prepared Reac Kinet Mech Cat (2014) 112:173187 DOI 10.1007/s11144-014-0689-z Paresh Dhepe 6. (111) (311) (220) (200) (111) Au (2%)/-Al2 O3 (220)(200)Pt (3.5%)/-Al2 O3 (a.u.) (111) (311) ntensity -Al2 O3 In 10 20 30 40 50 60 70 80 90 2 (degree) Pt peaks at 2 = 39.7 (111), 46.2 (200), 67.0 (220), 81.3(311) Face-centered cubic (fcc) lattice Au peaks at 2 38.1(111), 44.4 (200), 65 (220), 77.7 (311) Reac Kinet Mech Cat (2014) 112:173187 DOI 10.1007/s11144-014-0689-z Paresh Dhepe 7. Catalyst ( % Surface Area ICP XRD Crystal TEM Particle (Pt, 3.5wt%; Au, 2wt%) of Supports (m2/g) Analysis (wt%) Size (nm) Size (nm) Pt/Al2O3 225 3.7 13 15 Pt/AC 552 3.5 14 13 Pt/CeO2 23 3.8 29 - Pt/TiO2 36 3.5 28 - Pt/ZrO 87 3 4 16Pt/ZrO2 87 3.4 16 Au/Al2O3 225 2.0 13 11 Reac Kinet Mech Cat (2014) 112:173187 DOI 10.1007/s11144-014-0689-z Paresh Dhepe 8. O H H OO H Diformyl Furan (DFF) O HO H O HO OH O OO HO Furan Dicarboxylic Acid (FDCA)5-Hydroxymethyl Furfural (HMF) O HO OH O H OH O OO HO OH H OH Formyl Furan Carboxylic Acid (FFCA) Hydroxymethyl Furfural Carboxylic Acid (HMFC) ( )Carboxylic Acid (HMFC) Reac Kinet Mech Cat (2014) 112:173187 DOI 10.1007/s11144-014-0689-z Paresh Dhepe 9. Catalyst Amount Solvent Time (min) Temp. (C) FDCA Ref.y Sub: cat ( ) p ( ) % Yield SiO2-gel 10:1 W+MIBK 240 80 0 [1]Co(acac)3 10:1 W+MIBK 240 88 19 Co-gel 10:1 W+MIBK 240 88 16 W MIBKBlank 0 W+MIBK 240 80 14 Pt-Bi/C 0.66 mmol/ gcat W+MIBK 4200 80 75 (total oxidation [2] ( products) 1wt% Au/TiO2 100: 1 W+MIBK 1080 30 71 [3] 5wt% Au/CeO2 150 water 480 65 99 [4] 5wt% Pt/ZrO2 30 water 1380 100 100% Conv. [5] 1. M. Kroger, U. Prube, K. D. Vorlop, Top. Catal. 13 (2000) 237 2. M. L. Ribeiro, Catal. Commun. 4 (2003) 83 3 Y Y Gorbanev S K Klitgaard J M Woodley C H Christensen A Risager ChemSusChem 2 (2009) 6723. Y. Y. Gorbanev S. K. Klitgaard J. M. Woodley, C. H. Christensen, A. Risager, ChemSusChem 2 (2009) 672 4. O. Casanova, S. Iborra, A. Corma, ChemSusChem 2 (2009)1138 5. M. A. Lilga, R. T. Hallen, J. Hu, J. F. White, M. J. Gray, PUB. No: US 2008/0103318A1 (2008) Reac Kinet Mech Cat (2014) 112:173187 DOI 10.1007/s11144-014-0689-z Paresh Dhepe 10. 100 Conversion % 70 80 90 (%) Conversion,% Intermediate,% FDCAyield,% 50 60 70 on&yield( 20 30 40 Conversi 0 10 HMF, 0.1g; water, 60g; Pt /-Al2O3 0.1g; O2 150 psi @ RT; 100C; 24h Base HMF to FDCA formation required base 1 equivalent of mild base (Na2CO3) showed better activity (-COOH : Na = 1:1) , g; , g; 2 3, g; 2 p @ ; ; Reac Kinet Mech Cat (2014) 112:173187 DOI 10.1007/s11144-014-0689-z Paresh Dhepe 11. (C o n v e rs io n : O 2 ), (In te rm e d ia te : O 2 ), (F D C A : O 2 ) 9 0 1 0 0 (C o n v e rs io n : A ir), (In te rm e d ia te : A ir), (F D C A : A ir) (C o n v e rs io n : N 2 ), (In te rm e d ia te : N 2 ), (F D C A : N 2 ) 6 0 7 0 8 0 eld% 4 0 5 0 6 0 roductsYie 1 0 2 0 3 0 Pr 0 6 1 2 1 8 2 4 3 0 3 6 4 2 4 8 0 1 0 N ff t i HMF: 0.1g; Water: 60g; Pt/Y-Al2O3: 0.1g; O2: 150 psi OR Air: 750 psi; 100C; Na2CO3: 0.0841g T im e (h ) No effect on air or oxygen ~38% FDCA Yield was observed at 100C in 48h reaction time No FDCA was observed in N2 atmosphere Reac Kinet Mech Cat (2014) 112:173187 DOI 10.1007/s11144-014-0689-z Paresh Dhepe 12. (1 0 0 C c o n v e rs io n ), (1 0 0 C in te rm e d ia te ), (1 0 0 F D C A ) 1 0 0 ( ), ( ), ( ) (1 2 0 C c o n v e rs io n ), (1 2 0 C in te rm e d ia te ), (1 2 0 C F D C A ) (1 4 0 C c o n v e rs io n ), (1 4 0 C In te rm e d ia te ), (1 4 0 C F D C A ) 7 0 8 0 9 0 eld(%) 5 0 6 0 ersion&Yie 2 0 3 0 4 0 Conve 0 1 0 2 0 0 3 6 9 1 2 1 5 1 8 2 1 2 4 2 7 3 0 3 3 3 6 3 9 4 2 4 5 4 8 5 1 T im e (h ) HMF: 0.1g; Water: 60g; Pt/Y-Al2O3: 0.1g; O2: 150 psi; Na2CO3: 0.0841g At higher temperature the reaction rate is higher 52% FDCA was observed at 140C in 30h reaction time Reac Kinet Mech Cat (2014) 112:173187 DOI 10.1007/s11144-014-0689-z Paresh Dhepe 13. O Pressure (psi @ O solubility at Time (h) Products Yield (%)O2 Pressure (psi @ room temp.) O2 solubility at 140C (cm3/g) Time (h) Products Yield (%) Intermediate FDCA 150 0.1390%) for FDCA formation from HMF by aerial oxidation at moderate conditions One equivalent mild base gave more oxidation product yield The catalyst is recyclable FDCA i l ti d fi ti t di d i i t h i FDCA isolation and confirmation was studied using various techniques Adsorption of organics may be the cause of deactivation! Reac Kinet Mech Cat (2014) 112:173187 DOI 10.1007/s11144-014-0689-z Paresh Dhepe