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Catalytic t ransformation of p olyols to c arbonates

Slovak University of Technology , Bratislava Faculty of Chemical and Food Technology Dep. of Organic Technology Joint Slovak-Hungarian Laboratory for Development of Catalyzed Chemical Processes of Biomass Utilization *. Catalytic t ransformation of p olyols to c arbonates.

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Catalytic t ransformation of p olyols to c arbonates

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  1. Slovak UniversityofTechnology, Bratislava FacultyofChemical and FoodTechnology Dep. ofOrganicTechnology Joint Slovak-Hungarian Laboratory for Development of Catalyzed Chemical Processes of Biomass Utilization* Catalytic transformation of polyols to carbonates *Founded by financial support of project No. HUSK/1101/1.2.1/0318 “Chemical Processes of Biomass Utilization in the Slovak-Hungarian Frontier Region” László Seemann, Alexander Kaszonyi, 17th October, 2012, Bratislava

  2. Glycerol carbonate

  3. Preparationofglycerolcarbonate • TRANSESTERIFICATION OF EC WITH GLY • 80°C, 90 min • Catalyst: TBA-MCM41 (X = 94%,S = 84%) H.J. Choat al., J. ofIndust. and EngineeringChem. 16, 2006, 679-683 • 40°C, 10-13 MPa, 90 min in SC-CO2 • Cat.: Amberlist26 (Y = 4,7%), Purosiv (Y = 32%) C. Vievelleat al., Catal. Letters 56, 1998, 245-247

  4. Preparationofglycerolcarbonate • TRANSESTERIFICATION OF DMC WITH GLY • 75-90°C, 50~90 min • DMC/GLY = 3,5 (mol/mol) • KAT/GLY = 0,06-0,08 (mol/mol) • Azeotropic agent: benzene (1,5×MeOH) • Cat.: CaO, CaCO3 (ht, b; Y=~91%, X>91%) • KOH, K2CO3 (hm, b; Y, X = 100%) • 78°C, 50 min • DMC/GLY 1 (mol/mol) • KAT/GLY 4 (w/w) • Cat.: KF/HAP, KF.2H2O (ht, b; Y, X >99%) • 75°C, 90 min • DMC/GLY = 1:5 (mol/mol) • KAT/GLY = 0,1 (w/w) • Cat.: MAZ-311 (Y, X ~95%) J.R. Oucha-Gómezat al., App. Catal. A: Gen. 366, 2009, 315-324, J. Liat al., Chem. Engineering and Proc. 49, 2010, 530-535, F.S. HubertsonSimanjuntakat al., App. Cat. A: Gen. 401, 2011, 220-225, R. Baiat al., J. ofIndust. And EngineeringChem. 17, 2011, 777-781, M. Malyaadriat al., App. Catal. A: Gen. 401, 2011, 153-157

  5. Preparationofglycerolcarbonate • OXIDATIVE CARBONYLATION OF GLY • 140°C, PCO = 2 MPa, PO2 = 1 MPa, 2 h, • Pd(phen)/KI (X = 92%, S = 99%) • GLY/Pd = 400 (mol/mol) J. Hu at al., App. Catal. A: Gen. 386, 2010, 188-193 • 20°C, 0,1 MPa • K2CO3(5 eq.), GLY (5 eq.), Se(1 eq.), (Y = 84%), DMF solvent T. Mizunoat al., HeteroatomChem., 2010

  6. Preparation of glycerol carbonate • DIRECT CARBOXYLATION OF GLY • 180°C, 5 MPa, 6-15 h • Snbasedcat. (max X = 7%) M. Aresta a kol., J. of Mol. Catal. A: Chem. 257, 2006, 149-153 • withoutcat., 40°C,10 MPa, 3 h, • in SC-CO2, Y = 0ofGC C. Vievelleat al., Catal. Letters 56, 1998, 245-247

  7. Preparation of glycerol carbonate • GLYCEROLYSIS OF UREA 140°C, 20 Pa, 3 h GLY/U = 1 (mol/mol) KAT/U = 100% (w/w) Cat.: g-ZrP (X = 76%) 140°C, 3 kPa, 1 h GLY/U = 2 (mol/mol) KAT/GLY = 0,22% (w/w) Cat.: La2O3(Y = 89%, X = 99%) P = atm., N2, 4 h (X = 60%, Y = 3%) 145°C, 4 kPa, 5 h GLY/U = 1 (mol/mol), KAT/GLY = 5% (w/w) Cat.: HTc-Zn (Y = 72, X = 82%) M. Arestaat al., J. ofCatal. 268, 2009, 106-114, L. Wangat al., Catal. Communications 12, 2011, 1458-1462, M.J. Climentat al., J. ofCatal. 269, 2010, 140-149, J.L. Duboisat al., EP2174937A1, 2010, J.L. Duboisat al., WO2010/040786A2, 2010

  8. Overview of our studies • Differenttypesofhomogeneouscatalysts (ZnCl2, ZnO, Zn(NO3)2, MgCl2, MgO, Alumina, alsoreactionwithoutcatalyst) • Optimizationofcatalystcomposition and reactionconditions(G/C, T, G/U) • Heterogenizationofthebesthomogeneouscatalysts(ZnO/Alumina, ZnCl2/Silica, etc.)

  9. Overview of our studiesProduct analysis final product by GCcolumn: Optima-Wax 0.53 mm Program: 100°C for 1 min 10°C/min to 220°C FID: 250°C Inj.: 220°C

  10. Preliminary results

  11. Preliminary results

  12. Aim of studies • Preparation of stable heterogenized catalyst • Catalyst characterization • Rate of GC formation and decomposition at different reaction conditions • Purification of GC

  13. Thank you for your attention This work was supported by the Slovak Research and Development Agencyunder the contract No. APVV-0133-11

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