Evelien Van de Steene

1. Experimental and kineticstudy of the Transesterification of Ethyl acetate and Methanol over Gel and Macroporous acidic ion – exchange resins Evelien Van de Steene

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

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

4. PhD symposium, Ghent, 5th December 2012 Ion exchange resinswells ! 16 mL 10 mL dry K2649 > 25 mL 10 mL dry K1221 wet K2649 wet K1221 25 mLMeOH 25 mLMeOH 25 mLMeOH 25 mLMeOH 4 % DVB 18 % DVB lessswelling Higher DVB content =>

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

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

7. PhD symposium, Ghent, 5th December 2012 Kineticmodelingresults • Goodagreement: model calculationsvs. experimental data • EA= 49 kJ mol-1 irrespective the catalystused • kSR (gel) = 3 à 4-fold kSR (macroporous) • kSR~ availableactive sites ~ swelling • => affinity of ester is the samefor all resin

8. PhD symposium, Ghent, 5th December 2012 Thankyouforyour kind attention