1. Catalytic transformation of polyols to carbonates László Seemann, Alexander Kaszonyi, 17 th October, 2012, Bratislava 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* *Founded by financial support of project No. HUSK/1101/1.2.1/0318 “Chemical Processes of Biomass Utilization in the Slovak-Hungarian Frontier Region”

2. Glycerol carbonate Properties High boiling point Low toxicity Biodegradability Uses Cosmetics, medicines, polycarbonates and polyurethanes Replacement for hazardous and volatile organic solvents Other uses...

3. Preparation of glycerol carbonate  TRANSESTERIFICATION OF EC WITH GLY  80°C, 90 min  Catalyst: TBA-MCM41 (X = 94%,S = 84%) H.J. Cho at al., J. of Indust. and Engineering Chem. 16, 2006, 679-683  40°C, 10-13 MPa, 90 min in SC-CO 2  Cat.: Amberlist26 (Y = 4,7%), Purosiv (Y = 32%) C. Vievelle at al., Catal. Letters 56, 1998, 245-247

4. Preparation of glycerol carbonate  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, CaCO 3 (ht, b; Y=~91%, X>91%) KOH, K 2 CO 3 (hm, b; Y, X = 100%) 78°C, 50 min DMC/GLY 1 (mol/mol) KAT/GLY 4 (w/w) Cat.: KF/HAP, KF.2H 2 O (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-Gómez at al., App. Catal. A: Gen. 366, 2009, 315-324, J. Li at al., Chem. Engineering and Proc. 49, 2010, 530-535, F.S. Hubertson Simanjuntak at al., App. Cat. A: Gen. 401, 2011, 220-225, R. Bai at al., J. of Indust. And Engineering Chem. 17, 2011, 777-781, M. Malyaadri at al., App. Catal. A: Gen. 401, 2011, 153-157

5. Preparation of glycerol carbonate  OXIDATIVE CARBONYLATION OF GLY  140°C, P CO = 2 MPa, P O 2 = 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  K 2 CO 3 (5 eq.), GLY (5 eq.), Se (1 eq.), (Y = 84%), DMF solvent T. Mizuno at al., Heteroatom Chem., 2010

6.  DIRECT CARBOXYLATION OF GLY  180°C, 5 MPa, 6-15 h  Sn based cat. (max X = 7%) M. Aresta a kol., J. of Mol. Catal. A: Chem. 257, 2006, 149-153  without cat., 40°C,10 MPa, 3 h,  in SC-CO 2, Y = 0 of GC C. Vievelle at al., Catal. Letters 56, 1998, 245-247 Preparation of glycerol carbonate

7.  GLYCEROLYSIS OF UREA 140°C, 20 Pa, 3 h GLY/U = 1 (mol/mol) KAT/U = 100% (w/w) Cat.:  -ZrP (X = 76%) 140°C, 3 kPa, 1 h GLY/U = 2 (mol/mol) KAT/GLY = 0,22% (w/w) Cat.: La 2 O 3 (Y = 89%, X = 99%) P = atm., N 2, 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. Aresta at al., J. of Catal. 268, 2009, 106-114, L. Wang at al., Catal. Communications 12, 2011, 1458-1462, M.J. Climent at al., J. of Catal. 269, 2010, 140-149, J.L. Dubois at al., EP2174937A1, 2010, J.L. Dubois at al., WO2010/040786A2, 2010

8. Overview of our studies  Different types of homogeneous catalysts (ZnCl 2, ZnO, Zn(NO 3 ) 2, MgCl 2, MgO, Alumina, also reaction without catalyst)  Optimization of catalyst composition and reaction conditions(G/C, T, G/U)  Heterogenization of the best homogeneous catalysts (ZnO/Alumina, ZnCl 2 /Silica, etc.)

9. Overview of our studies Product analysis final product by GC column: 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

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 Agency under the contract No. APVV-0133-11