1. Laboratory for Chemical Technology, Ghent University http://www.lct.UGent.be Experimental and kinetic study of the Transesterification of Ethyl acetate and Methanol over Gel and Macroporous acidic ion – exchange resins Evelien Van de Steene 1

2. Transesterification 2 Transesterification: Biodiesel production Transesterification: Model reaction PhD symposium, Ghent, 5 th December 2012

3. Ion exchange resin as catalyst 3 Ecofriendly Noncorrosive Reusable 3 Gel-type resins (K1221) Macroporous resins (K2629, K2640, Amberlyst 15) No permanent pore structure Micropores Swelling ! Permanent pore structure Macro- & Micropores 4 – 10 % DVB10 – 20 % DVB PhD symposium, Ghent, 5 th December 2012

4. Ion exchange resin swells ! 4 25 mL MeOH 10 mL dry K2649 16 mL wet K2649 25 mL MeOH 18 % DVB 10 mL dry K1221 > 25 mL wet K1221 25 mL MeOH 4 % DVB Higher DVB content => less swelling PhD symposium, Ghent, 5 th December 2012

5. The swelling influences the reaction rate 5 18 % 20 % 4 % total active sites = for all resins % DVB determines the conversion PhD symposium, Ghent, 5 th December 2012 Temperature : 333 K Pressure : 0.1 Mpa MeOH:EtOAc molar ratio: 10:1 Mass of catalyst: 0.5 kg

6. 6 Eley-Rideal reaction mechanism MeOH EtOAc EtOH MeOAc * * ** * * * * * * * * *** * * * ** Reaction Mechanism & kinetic model Total swelling => MeOAc* + MeOH MeOH* + MeOAc Resulting kinetic model PhD symposium, Ghent, 5 th December 2012 MeOH* + EtOAc EtOAc* + MeOH * + MeOH MeOH* MeOH + EtOAc* EtOH + MeOAc* Active (acid) site

7. Good agreement: model calculations vs. experimental data E A = 49 kJ mol -1 irrespective the catalyst used k SR (gel) = 3 à 4-fold k SR (macroporous) k SR ~ available active sites ~ swelling => affinity of ester is the same for all resin 7 Kinetic modeling results ResinKinetic parameters Ion-exchange equilibrium coefficient Statistical evaluation (10 -6 m 3 kg cat -1 mol -1 s -1 ) (kJ mol -1 ) Total number of experimental data RSSQF K1221 52.7 ± 0.348.7 ± 0.9 1.15 ± 0.14 4.87 ± 0.38 12822471 000 K2640 14.5 ± 4.142.9 ± 5.61.86 ± 0.676.26 ± 1.90 233218 000 K2629 9.2 ± 1.049.7 ± 2.0 2.54 ± 0.359.04 ± 2.03 7022125 000 Amberlyst 1510.3 ± 7.552.3 ± 6.61.36 ± 0.990.90 ± 6.04129635 000 PhD symposium, Ghent, 5 th December 2012

8. Thank you for your kind attention 8 PhD symposium, Ghent, 5 th December 2012