Pd-Bi nanoparticles on anionic-exchange resins for oxidation of polyols

1. Pd-Binanoparticles on anionic-exchangeresinsforoxidationofpolyols Joint Slovak-Hungarian Laboratory forDevelopment of Catalyzed ChemicalProcesses of Biomass Utilization Ing. Stanislav Vajíček Doc. Ing. Magdaléna Štolcová PhD.

2. Oxidationofglycerol N. Dimitratos, J. A. Lopez, D. Lennon, F. Porta, L. Prati, A. Villa, Cat. Letters, 108 (2006) 147-154

3. Oxidation products - utilization Glyceric acid1 • coolant in the form of quaternary ammonium salts • preparation of surfactants • production of synthetic analogues of phospholipids • preparation of polymers Dihydroxyacetone1 • production of self-tanning agents • treatment of sen wine quality Glycolic Acid2 • water softening, solvent • cosmetics - products for hair and skin • textile and leather industries – coloring Tartronic acid2 • trap of dissolved oxygen in alkaline water • protection of metal surfaces against corrosion β-hydroxypyruvic acid3 • preparation of L-serine - production of biologically active peptides • cosmetics - creams, face masks • essential amino acids 1H. Habe, T. Fukuoka, D. Kitamoto, K. Sakaki, Applied Microbiological Biotechnology, 84 (2009) 445-452. 2P. M. Bizot, B. R. Bailey, P. D. Hicks, US Patent No.: 5,750,037 (1998) 3A. Abbadi, H. van Bekkum, Applied Catalysis A: General, 148 (1996) 113-122.

4. Oxidationofprimaryalcoholgroupsofglycerol • alkaliregion – oxidationofprimaryalcoholgroups • mono- and dicarboxylicacids • catalystsbased on Pd, Pd-Bi, Au, Au-Pd, Pt • support: activecarbon, graphit, metal oxides* (TiO2, CeO2, Al2O3, SiO2) • metal particlesize * I. Sobczak, K. Jagodzinska, M. Ziolek, Catal. Today, 158, (2010), 121-129

5. Garcia (1995) • cat. 5 wt.% Pd/C – impregnationofcharcoalwith PdCl42- • pH = 11, 60°C • max. yieldof GLYA 60% at 90% conversionof GLY Bianchi (2005) • cat. 1 wt.% Pd/C • impregnation by PVA, precursorreduction - NaBH4 • metal particlesize 2-4 nm • oxygenpressure 300 kPa, 30 - 50˚C, NaOH/glycerol = 4

6. Alardin (2001) Bi-promotedPdcatalysts – oxidationofpolyols greatactivity and selectivityofPd-Bi/C catalysts in oxidationreactionofpolyols (spec. glyoxalacid) Karski (2003) cat. 5 wt.%Bi - 5 wt.%Pd/C highactivity and selectivityforoxidationofglucose strongsynergiceffectbetweenPd and Bi selectivity to gluconicacid 90% at 80% conversion Prati (2007) Catalystpreparation: Au/C: imobilizationfrom PVA solution + reductionwith 0,1M NaBH4 Au-Pd/C: imobilization Au/C with Na2PdCl4solution in pres. of PVA metal particlesize 3 - 4 nm oxygenpressure 300 kPa, 50˚C, NaOH/GLY = 4 Selectivity to GLYA 80% at 50% conversionof GLY

7. Oxidationofsecondaryalcoholgroupsofglycerol • dihydroxyacetone • acidregion, pH = 1,5-3 • catalystsbased on Pt, Pt-Bi, Pt-Au • support: activecarbon • P. Gallezot, Catalysis Today, 37 (1997) 414-416. • H. Kimura, Applied Catalysis A: General, 105 (1993) 147-158. • D. Liang, S. Cui, J. Gao, J. Wang, P. Chen, Z. Hou, Journal of catalysis, 32 (2011) 1831-1837

8. Kimura (1993) cat. 1 wt.%Bi–5 wt.%Pt/C – yieldof DHA 20% at 30% conversionof GLY cat. 0,6 wt.%Bi–3 wt.%Pt/C – yieldof DHA 30% atconversionof GLY 40% Batch and fixed-bedreactor Gallezot (1997) cat. 1 wt.%Bi-5 wt.%Pt/C yieldof DHA 37%, conversionof GLY 80% batchreactor W. B. Hu (2010) cat. 3 wt.% Pt-0.6 wt.% Bi supported on activatedcarbon 80°C, 3 bar and at an initial pH of 2 selectivity to DHA of 60% at 80% glycerol conversion low glycerol oxidation rate (TOF=370 h-1) Rodrigues (2011) cat. 1 wt.Au/MWCNT 60°C, 3 bar and at an initial pH of 2 selectivity to DHA of 60% at 93% glycerol conversion glycerol oxidation rate (TOF) = 4240 h-1

9. Aimofwork • Preparation of catalysts based on palladium loaded on different type ofpolymericsupport • Modification of catalysts by promoters, especially bismuth • Study reactionconditions –effecton the catalytic activity • Physico-chemicalcharacterisationofcatalysts • Study theperformanceof the catalystsin different types of reactors • Optimization of reaction conditions with regard to maximizing the yield of the desiredproductsof mono-and dicarboxylic acids and DHA • Study thecatalyticperformanceofthecatalysts fortheoxidation ofvariouspolyols

10. Experimental Catalyst preparation • microporous gel-type resin • macroporous ion-exchange resin • metallated by ion exchange method • reduced with sodium borohydride or H2 Analysisofreactionmixture HPLC: • column - Alltech OA-1000 • detectors: • SPD 10AVp • RID-10A

11. semi-batch glass reactor jacketed tubular glass

12. Thepreliminaryresults

13. Influenceofsupport type • The Pd-Bi particles supported onto microporous gel-type resin showed better catalytic performance than those supported onto macroporous resins

14. Influenceof metal content in batchreactor • Higher content of metal in molar ratio Pd:Bi of 3:1 increased conversion of GLY • No significant differences between reduction with NaBH4 and H2 was observed

15. Influenceof metal content in fixed-bedreactor • Molar ratio and content of metals loaded on support strongly influenced the activity and selectivity of the catalysts in both batch and fixed bed reactors

16. Thankyouforyourattention This work was supported by the Slovak Research and Development Agency under the contract No. APVV-0133-11 and ERDF under the contract No. HUSK/1101/1.2.1/0318