1. Computer aided design, analysis and experimental investigation of membrane assisted batch reaction P. T. Mitkowski a, C. Buchaly b, P. Kreis b, G. Jonsson a, R. Gani a, A. Górak b a CAPEC, Department of Chemical Engineering, DTU b TVT, Department of Biochemical and Chemical Engineering, University of Dortmund

2. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 2/26 Outline  Motivation  Objective  Methodology  Case study Problem analysis and design Experimental investigation  Conclusion

3. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 3/26 Introduction Equilibrium, reversible reaction (like esterification, etherification, etc) are usually characterized by low process yield, low conversion of limiting component Selective removal of reaction product(s) will move the equilibrium towards product Motivation Objectives Methodology Case study Conclusion

4. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 4/26 Motivation The ultimate solution is to combine reaction and separation process into one operation but we need sufficient understanding of constituent processes (controlling parameters, process limitations) Motivation Objectives Methodology Case study Conclusion

5. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 5/26 Objectives Application of developed systematic computer-aided framework for design and analysis of Reaction – Separation process.  Use computer aided techniques through model-based methodology to find the existence of feasible region and evaluate the performance of design (simulation).  Experimental study of proposed design for synthesis of n-propylpropionate in a batch mode. Motivation Objectives Methodology Case study Conclusion

6. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 6/26 Methodology: Process design Motivation Objectives Methodology Case study Conclusion

7. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 7/26 Framework: Design and Validation Motivation Objectives Methodology Case study Conclusion

8. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 8/26 Case study: Reaction analysis Motivation Objectives Methodology Case study Conclusion Step 1a: Heterogeneous esterification of n-propyl propionate. - preservative in food and feed industry - manufacture propionates used in pharmaceutical, agrochemical, perfume industry Table 1 Binary azeotropes at 1 atm (SMSwin). Problem analysis Experiments CompositionType of azeotrop Molar fraction [%] T b [K] @ 1atm. POHH2OH2OProProPAc POH – H2O – ProProHeterogeneous27.8156.8715.31-359.47 ProPro – H 2 OHeterogeneous-69.3130.69-363.40 H 2 O – PAcHomogeneous-5.85-94.15372.94 H 2 O – POHHomogeneous57.8242.18--361.92 Amberlyst 46 Duarte, C., Buchaly, C., Kreis, P., Loureiro, J.M. (2006), Inżynieria Chemiczna i Procesowa, 27.

9. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 9/26 Problem analysis: Solvent Step 1b: Need of solvent Addition of solvent is not needed in the reaction temperature range (293 – 356) K and reactant ratio 1:1, 2:1, 3:1,…1:3 (propanol : propionic acid) BUT 1) solvent will decrease the ratio of products to reactants activities OR 2) solvent that will remove water and move the reaction equilibrium to the right hand side of the reaction Motivation Objectives Methodology Case study Conclusion Problem analysis Experiments

10. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 10/26 Process goals & Separation technique Step 2: Increase productivity of n-propyl propionate in the batch operation time of 12h. High conversion of PAc (<2 w% ). Simple product purification. Step 3: Pervaporation with hydrophilic polymeric membranes for selective water removal Motivation Objectives Methodology Case study Conclusion Problem analysis Experiments

11. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 11/26 Problem analysis: Modelling Step 4: Process configuration and Model equations Mass balance: where: Constitutive equations: + Modified UNIFAC (Lyngby) Motivation Objectives Methodology Case study Conclusion Problem analysis Experiments

12. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 12/26 Problem analysis: reactants ratio Step 4: Feasible design - molar ratio POH : PAc at T = 353.15K Motivation Objectives Methodology Case study Conclusion Problem analysis Experiments

13. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 13/26 Step 4: Feasible design - Influence of catalyst addition Problem analysis: Catalyst Motivation Objectives Methodology Case study Conclusion Problem analysis Experiments

14. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 14/26 Step 4: Feasible design – Influence of time switch Problem analysis: Switching time Motivation Objectives Methodology Case study Conclusion Problem analysis Experiments

15. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 15/26 Lab-scale Multipurpose Set up @UniDo Membrane separation characteristic Membrane reactor Analytical analysis: Organic compounds: GC-FID Water: Karl Fischer titration Motivation Objectives Methodology Case study Conclusions Problem analysis Experiments

16. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 16/26 Membrane characteristic Pervaporation experiment Objective Membrane separation characteristic of PERVAP ® 2201D (Sulzer) for: - binary mixture (POH/H2O) - quaternary mixture (POH/PAc/ProPro/H2O) Motivation Objectives Methodology Case study Conclusions Problem analysis Experiments

17. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 17/26 Membrane characteristic Very selective membrane towards water Good agremeant with semi-empirical Meyer-Blumenroth model Pervaporation experiment at T = 348.15 K, PP = 10 mbar Pervaporation experiment at T = 323.15 K, P = 10 mbar Components PAc0.08900.00070.0399 0.0000 POH0.74000.00540.0006 0.0000 ProPro0.09310.00010.0011 0.0000 H2O0.07780.99397.43977.4854 Components PAc0.08850.00050.0091 0.0000 POH0.73050.00490.0014 0.0000 ProPro0.09090.00010.0007 0.0000 H2O0.09010.99451.84361.8538 Motivation Objectives Methodology Case study Conclusions Problem analysis Experiments

18. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 18/26 Reaction Experiment Objective Verify reaction kinetics model Motivation Objectives Methodology Case study Conclusions Problem analysis Experiments

19. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 19/26 Reaction experiment: Results T=353.35 K, m CAT /m r = 0.22, POH:PAc = 2:1, m r = 1328.9 g T=341.15 K, m CAT /m r = 0.14, POH:PAc = 2:1, m r = 950 g Motivation Objectives Methodology Case study Conclusions Problem analysis Experiments

20. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 20/26 Membrane Reactor Membrane reactor experiment Objective Influence of process parameters on the overall system performance: - reactants ratio (POH:PAc) - mass ratio of reactants/catalyst - switching time - temperature Motivation Objectives Methodology Case study Conclusions Problem analysis Experiments

21. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 21/26 Membrane Reactor: Results Motivation Objectives Methodology Case study Conclusions Problem analysis Experiments T R = 346.24 K, T M = 343.19 K, m CAT /m r = 0.23, POH:PAc = 2:1, t switch = 60.00 min; (E4) T R = 344.85 K, T M = 343.48 K, m CAT /m r = 0.23, POH:PAc = 2.2:1, t switch = 134.95min; (E3)

22. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 22/26 Membrane Reactor: Results T R = 346.83 K, T M = 347.65 K, m CAT /m r = 0.12, POH:PAc = 2:1, t switch = 75.80 min; (E1) Motivation Objectives Methodology Case study Conclusions Problem analysis Experiments T R = 346.24 K, T M = 343.19 K, m CAT /m r = 0.23, POH:PAc = 2:1, t switch = 60.00 min; (E4)

23. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 23/26 Membrane Reactor: Results T R = 336.21 K, T M = 334.11 K, m CAT /m r = 0.21, POH:PAc = 3:1, t switch = 61.37 min; (E6) T R = 354.11 K, T M = 353.09 K, m CAT /m r = 0.23, POH:PAc = 3:1, t switch = 61.37min; (E5) Motivation Objectives Methodology Case study Conclusions Problem analysis Experiments

24. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 24/26 Membrane Reactor: Results Batch Membrane Reactor vs. Batch Reactor Motivation Objectives Methodology Case study Conclusions Problem analysis Experiments

25. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 25/26 Conclusions Successful application of computer aided framework The reaction kinetic model and trans-membrane solution-diffusion flux model gave good agreement with experimental data Six experiments of membrane assisted batch reaction at different temperature, reactant molar ratio, switching time and amount of catalyst (membrane reactor) Membrane reactor increased product yield by overcoming limitations of equilibrium and kinetically controlled reaction Motivation Objectives Methodology Case study Conclusions Problem analysis Experiments

26. AIChE Annual Meeting, Salt Lake City, 3-7 November, 2007 26/26 Q & A Acknowledgments: Supervisors: Prof. G. Jonsson, Prof. R. Gani Dr.-Ing. P. Kreis, Prof. A. Górak PRISM - 6th Framework EU project TVT (UniDo) and CAPEC (DTU) co-workers Thank you for you attention ! Questions