University of Groningen Enantioselective liquid-liquid extraction in microreactors Susanti, Susanti IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please check the document version below. Document Version Publisher's PDF, also known as Version of record Publication date: 2018 Link to publication in University of Groningen/UMCG research database Citation for published version (APA): Susanti, S. (2018). Enantioselective liquid-liquid extraction in microreactors [Groningen]: University of Groningen Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons). Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Download date: 05-11-2018
Enantioselective liquid-liquid extraction in microreactors Susanti
Cover design by Susanti Layout by Susanti and Lovebird design. www.lovebird-design.com Printed by Eikon + The research described in this thesis was carried out in Chemical Engineering cluster, Engineering and Technology institute Groningen (ENTEG), Faculty of Science Enginering, University of Groningen. The work described in this thesis was financially supported by STW, The Netherlands, through project no. 11404 (Chiral Separations by Kinetic Extractive Resolution in Microfluidic Devices). ISBN: 978-94-034-0943-6 (print ) ISBN: 978-94-034-0942-9 (electronic)
Enantioselective liquid-liquid extraction in microreactors PhD thesis to obtain the degree of PhD at the University of Groningen on the authority of the Rector Magnificus Prof. E. Sterken and in accordance with the decision by the College of Deans This thesis will be defended in public on Tuesday 11 September 2018 at 09.00 hours by Susanti born on 12 September 1983 in Solokanjeruk, Indonesia
Supervisor Prof. H.J. Heeres Co-supervisors Dr. Jun Yue Dr. J.G.M. Winkelman Dr. B. Schuur Assessment committee Prof. F. Picchioni Prof. G.F. Versteeg Prof. V. Hessel
~to my family and my teachers~
Contents Chapter 1 Introduction 1.1. Background 1.2. Chirality and its implication for life 1.3. Chiral separation techniques 1.4. Chiral separation by ELLE 1.4.1. Principles of ELLE 1.4.2. Extractants/hosts for ELLE 1.4.3. Equipment for ELLE U and W-Tube devices Configurations for larger scale operation Centrifugal contactor separators 1.5. Microdevices for liquid-liquid extraction 1.5.1. Microscale liquid-liquid extractions 1.5.2. ELLE in microdevices 1.6. Aim of this thesis and thesis outline References Chapter 2 Lactic acid extraction and mass transfer characteristics in slug flow capillary microreactor Abstract 2.1. Introduction 2.2. Experimental details 2.2.1. Materials 2.2.1. Experimental setup 2.2.2. Experimental procedures 2.2.3.1. Physical extraction 2.2.3.2. Reactive extraction 2.2.3.3. Slug flow pattern visualization 2.2.3.4. Analytical procedures 2.3. Results and discussion 2.3.1. Mass transfer in physical extraction 2.3.2. Mass transfer in reactive extraction 2.4. Conclusions References Appendices Appendix 2A. Extraction efficiency as a function of the residence time in physical extraction Appendix 2B. Dissociation of lactic acid in the aqueous phase Appendix 2C. Extraction efficiency as a function of the residence time and inlet lactic acid concentration in reactive extraction Appendix 2D. (Kova)Chem as a function of the residence time and inlet lactic acid concentration in reactive extraction 1 3 3 5 6 6 7 12 12 13 15 16 16 20 20 22 31 32 33 35 35 35 36 37 38 38 39 39 39 48 56 57 60 60 61 62 64
Chapter 3 Proof of concept for continuous enantioselective liquid liquid extraction in capillary microreactors using 1-octanol as a sustainable solvent Abstract 3.1. Introduction 3.2. Materials and methods 3.2.1. Materials 3.2.2. Experimental setup 3.2.3. Experimental procedures 3.2.3.1. ELLE experiments in the capillary microreactors 3.2.3.2. ELLE experiments with DNB-(R,S)-Leu and CA3 in a batch set-up 3.2.3.3. Analytical procedures 3.3. Theory and definitions 3.4. Results and discussions 3.4.1. Equilibrium experiments in batch with 1,2-DCE and 1-octanol 3.4.2. Experiments in the continuous microreactor set-up 3.4.2.1. Continuous experiments in 1,2-DCE 3.4.2.2. Continuous experiments in 1-octanol 3.5. Conclusions References Appendices 65 66 67 69 69 69 70 70 71 71 72 74 74 74 74 77 80 81 84 Chapter 4 Modelling studies on enantioselective extraction of an amino acid derivative in slug flow capillary microreactors Abstract 4.1. Introduction 4.2. Experimental method 4.2.1. Materials 4.2.2. ELLE in capillary microreactors 4.2.3. Determination of ELLE equilibrium constants in batch reactors 4.2.4. Analytical procedures 4.3. Model development 4.3.1. Calculation of the molar fluxes 4.3.2. Bulk phase concentrations 4.3.3. Physico-chemical parameters Interfacial area Overall mass transfer coefficient Enhancement factor Activity coefficient Physical properties of the system 4.3.4. Numerical solution method 4.4. Results and discussions 4.4.1. Equilibrium extractions 4.4.2. Modelling results of ELLE in microreactors 89 90 91 92 92 93 94 94 95 96 98 99 99 99 100 101 101 102 103 103 104
4.4.2.1. Model I: instantaneous complexation rate for both the (S)- and (R)-enantiomers 4.4.2.2. Model II: instantaneous complexation rate for the (S)-enantiomer and finite complexation rate for the (R)-enantiomer 4.4.3. Process simulation for multi-stage ELLE operation 4.5. Conclusions Nomenclature References Appendices Appendix 4A. Extraction performance as a function of the residence time Appendix 4B. Enhancement factor in the aqueous phase in the presence of dissociation reaction Appendix 4C. Number of segments along the microreactor and its effect on the model convergence Chapter 5 Enantioselective liquid-liquid extraction studies on (D,L)-tryptophan using a cationic Pd-XylBINAP complex as chiral host in 1-octanol Abstract 5.1. Introduction 5.2. Experimental section 5.2.1. Materials In situ preparation of Pd(PF6)2((S)-XylBINAP) 5.2.2. Enantioselective liquid-liquid extraction of DL-Tryptophan with Pd(PF6)2((S)-XylBINAP) 5.2.2.1. Extraction set-up 5.2.2.2. Experimental procedures 5.2.3. Analytical procedures 5.3. Theory and definitions 5.4. Results and discussions ELLE of racemic Trp using different concentrations of the Pd(PF6)2((S)-XylBINAP) complex. Reactive extraction of enantiopure tryptophan 5.5. Conclusions References Appendix 5A Summary Samenvatting Acknowledgement List of publications List of attended conferences 104 106 109 114 115 116 120 120 121 123 125 126 127 128 128 128 129 129 129 130 130 131 133 134 137 138 140 143 147 151 154 154