1. Systematic analysis and design of hybrid processes P. T. Mitkowski, G. Jonsson, R. Gani CAPEC Department of Chemical Engineering Technical University of Denmark

2. European Congress of Chemical Engineering – 6 2/20 Motivation Motivation & Objectives Outline Motivation Objectives Methodology Case studies Conclusion Future work Methodology Case studies Conclusion Future work…  Hybrid process is a combination of at least two processes which influence each other and the optimization of the design must take into account this interdependency.

3. European Congress of Chemical Engineering – 6 3/20 Motivation Objectives Methodology Case studies Conclusion Future work  Hybrid processes are finding increasing use in pharmaceutical and biochemical manufacturing providing better alternatives (sometimes only alternatives) in cases where: reaction(s) kinetically or equilibrium controlled - low process yield difficult separation task - low driving force  Current design/analysis techniques are largely experiment-based, therefore, there is a potential for reducing time & costs for process development through systematic computer-aided techniques

4. European Congress of Chemical Engineering – 6 4/20 Objectives Needs & Issues  Algorithm for design-selection of processes that may be considered in the hybrid process (systems integration)  Generic model of the hybrid process through a computer aided modelling tool (modelling)  Databases of solvents, membranes, reactions and chemicals (use of available knowledge)  Case studies for validation of models, methods & tools (validation) Introduction Objectives Methodology Case studies Conclusion Future work Develop systematic computer aided methods & tools for design & analysis of a wide range of hybrid processes

5. European Congress of Chemical Engineering – 6 5/20 Methodology: Design Algorithm Introduction Objectives Methodology Case studies Conclusion Future work

6. European Congress of Chemical Engineering – 6 6/20 Methodology: Generic Model Introduction Objectives Methodology Case studies Conclusion Future work

7. European Congress of Chemical Engineering – 6 7/20 Case study: Reaction - Separation Introduction Objectives Methodology Case studies Conclusion Future work Step 1a: Esterification of cetyl oleate over Novozym 435 (Canadia anatarctica on acrylic resin) [1]. [1] T. Garcia, A.Coteron, J.Aracil,,Chem. Eng. Science 55,(2000), 1411-1423 Step 2: Increase productivity of cetyl oleate by removing of water. X > 80 mol%. Step 1b: Solvent free system Step 3: Pervaporation with hydrophilic polymeric membranes to remove water

8. European Congress of Chemical Engineering – 6 8/20 Case study: Model Step 4: Hybrid process model Process 1: Reaction Process 2: Pervaporation m cat Introduction Objectives Methodology Case studies Conclusion Future work

9. European Congress of Chemical Engineering – 6 9/20  Constitutive equations: where :  Mol balance: Case study: Model DAE model: 4 ODEs and AEs 52 ;No. of variables: 117 + Modified UNIFAC (Lyngby) Introduction Objectives Methodology Case studies Conclusion Future work ICAS - MoT

10. European Congress of Chemical Engineering – 6 10/20 Step 4: Feasible design: Hybrid process polyvinyl alcohol membrane (PERVAP1001, GFT) A m = 0.0288m 2 t batch = 5h t switch = 0h V = 0.6 dm 3 IC Equimolar C w in = 0.005mol/dm 3 Case study Am Am Introduction Objectives Methodology Case studies Conclusion Future work [min]

11. European Congress of Chemical Engineering – 6 11/20 Case study Step 4: Influence of addition of the catalyst on the batch time Introduction Objectives Methodology Case studies Conclusion Future work

12. European Congress of Chemical Engineering – 6 12/20 Case study Step 4: Influence of t switch at overall process performance in t batch = 5h 25w% Introduction Objectives Methodology Case studies Conclusion Future work

13. European Congress of Chemical Engineering – 6 13/20 Introduction Objectives Methodology Case studies Conclusion Future work Case study: Conclusion Batch reaction combined with pervaporation give promising results. Process conditions: – Amount of catalyst increase up to 30 w% – Start coupled operation within first hour – PERVAP1001, GFT

14. European Congress of Chemical Engineering – 6 14/20 Introduction Objectives Methodology Case studies Conclusion Future work Case study: Separation-Separation Step 1a: Separation of equimolar mixture of acetic acid (HAc) and water (100 kmol/hr) Experimental VLE data fitted to Mod. UNIFAC (Lyngby) Step 2: Two streams with a purity of 99.5 mol% of HAc and water Step 3: Distillation + Pervaporation with hydrophilic polymeric membrane ICAS - TML

15. European Congress of Chemical Engineering – 6 15/20 Introduction Objectives Methodology Case studies Conclusion Future work Case study: Separation-Separation Step 4: Identification of sequence of processes - Driving Force approach. 99.5 mol% H2O80mol% H2O 99.5 mol%HAc 99.5 mol% H2O 99.5 mol% HAc 100 kmol/hr

16. European Congress of Chemical Engineering – 6 16/20 Introduction Objectives Methodology Case studies Conclusion Future work Case study: Separation-Separation Step 4: Feasible design: Heat requirement in terms of membrane module characteristic selectivity cut  = 50  = 2.25 ICAS - MoT ICAS - Sim

17. European Congress of Chemical Engineering – 6 17/20 Introduction Objectives Methodology Case studies Conclusion Future work Case study: Conclusion Distillation combined with pervaporation gives process improvment Distillation followed by pervaporation – required high selective membrane – possible doped pollyaniline membrane Distillation with side pervaporation – can give improvment even with low selective membrane

18. European Congress of Chemical Engineering – 6 18/20 Conclusions  Systematic computer-aided methods and tools for hybrid process analysis & design has been developed and has been presented along with two case studies  The main difficulty is the availability of data and property models  Computer aided tools help to reduce time and resources needed for hybrid process development  Identifies a small set of alternatives where the experimental effort might be concentrated on Introduction Objectives Methodology Case studies Conclusions Future work

19. European Congress of Chemical Engineering – 6 19/20 Future work Introduction Objectives Methodology Case studies Conclusion Future work Investigation of other hybrid processes - 4 case studies done Further development of membrane database

20. European Congress of Chemical Engineering – 6 20/20 Thank you for your attention ! Questions are welcome ! Supervisors: Prof. G. Jonsson, Prof. R. Gani PRISM - 6th Framework EU project CAPEC co-workers Acknowledgement: