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

XIX Polish Conference of Chemical and Process Engineering 2/23 Outline Motivation & Objectives Methodology Case studies Conclusion Future work…

XIX Polish Conference of Chemical and Process Engineering 3/25 Motivation Objectives Methodology Case study 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.

XIX Polish Conference of Chemical and Process Engineering 4/25 Motivation Objectives Methodology Case study 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

XIX Polish Conference of Chemical and Process Engineering 5/25 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 study Conclusion Future work Develop systematic computer aided methods & tools for design & analysis of a wide range of hybrid processes

XIX Polish Conference of Chemical and Process Engineering 6/25 Methodology: Design Algorithm Introduction Objectives Methodology Case study Conclusion Future work

XIX Polish Conference of Chemical and Process Engineering 7/25 Methodology: Design Algorithm Introduction Objectives Methodology Case study Conclusion Future work

XIX Polish Conference of Chemical and Process Engineering 8/25 Methodology: Generic Model Introduction Objectives Methodology Case study Conclusion Future work

XIX Polish Conference of Chemical and Process Engineering 9/25 Case study: Reaction - Separation Introduction Objectives Methodology Case study 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), 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

XIX Polish Conference of Chemical and Process Engineering 10/25 Case study: Process scenarios  Hybrid processes various rates of addition of components various component fluxes and A m various operational parameters in membranes Introduction Objectives Methodology Case study Conclusion Future work  Batch operation different initial conditions

XIX Polish Conference of Chemical and Process Engineering 11/25 Case study: Model Step 4: Hybrid process model Process 1: Reaction Process 2: Pervaporation m cat Introduction Objectives Methodology Case study Conclusion Future work

XIX Polish Conference of Chemical and Process Engineering 12/25  Constitutive equations: where :  Mol balance: Case study: Model DAE model: 4 ODEs and AEs 52 ;No. of variables: Modified UNIFAC (Lyngby) Introduction Objectives Methodology Case study Conclusion Future work

XIX Polish Conference of Chemical and Process Engineering 13/25 Step 4: Feasible design: Hybrid process polyvinyl alcohol membrane (PERVAP1001, GFT) A m = m 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 study Conclusion Future work

XIX Polish Conference of Chemical and Process Engineering 14/25 Case study Step 4: Influence of addition of the catalyst on the batch time Introduction Objectives Methodology Case study Conclusion Future work

XIX Polish Conference of Chemical and Process Engineering 15/25 Case study Step 4: Influence of t switch at overall process performance in t batch = 5h 25w% Introduction Objectives Methodology Case study Conclusion Future work

XIX Polish Conference of Chemical and Process Engineering 16/25 Introduction Objectives Methodology Case study 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

XIX Polish Conference of Chemical and Process Engineering 17/25 Introduction Objectives Methodology Case study Conclusion Future work Case study: Separation-Separation Step 1a: Separation of equimolar mixture of acetic acid (HAc) and water 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

XIX Polish Conference of Chemical and Process Engineering 18/25 Introduction Objectives Methodology Case study Conclusion Future work Case study: Separation-Separation Step 4: Identification of sequence of processes - Driving Force approach mol% H2O80mol% H2O 99.5 mol%HAc 99.5 mol% H2O 99.5 mol% HAc 100 mol

XIX Polish Conference of Chemical and Process Engineering 19/25 Introduction Objectives Methodology Case study Conclusion Future work Case study: Separation-Separation Step 4: Feasible design: Heat requirement in terms of membrane module characteristic selectivity cut  = 50  = 2.25

XIX Polish Conference of Chemical and Process Engineering 20/25 Introduction Objectives Methodology Case study 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

XIX Polish Conference of Chemical and Process Engineering 21/25 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 study Conclusions Future work

XIX Polish Conference of Chemical and Process Engineering 22/25 Future work Introduction Objectives Methodology Case study Conclusion Future work Investigation of other hybrid processes - 4 case studies done Further development of membrane database

XIX Polish Conference of Chemical and Process Engineering 23/23 Thank you for your attention ! Questions are welcome ! Supervisors: Prof. G. Jonsson, Prof. R. Gani PRISM - 6th Framework EU project CAPEC co-workers Acknowledgement: