University of Groningen
Enantioselective liquid-liquid extraction in microreactors
Susanti, Susanti
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2018
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Susanti, S. (2018). Enantioselective liquid-liquid extraction in microreactors. University of Groningen.
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Enantioselective
liquid-liquid extraction
in microreactors
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 clus-ter, 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
Contents
Chapter 1 Introduction 1
1.1. Background 3
1.2. Chirality and its implication for life 3
1.3. Chiral separation techniques 5
1.4. Chiral separation by ELLE 6
1.4.1. Principles of ELLE 6
1.4.2. Extractants/hosts for ELLE 7
1.4.3. Equipment for ELLE 12
U and W-Tube devices 12
Configurations for larger scale operation 13
Centrifugal contactor separators 15
1.5. Microdevices for liquid-liquid extraction 16
1.5.1. Microscale liquid-liquid extractions 16
1.5.2. ELLE in microdevices 20
1.6. Aim of this thesis and thesis outline 20
References 22 Chapter 2 Lactic acid extraction and mass transfer characteristics in
slug flow capillary microreactor 31
Abstract 32 2.1. Introduction 33 2.2. Experimental details 35 2.2.1. Materials 35 2.2.1. Experimental setup 35 2.2.2. Experimental procedures 36 2.2.3.1. Physical extraction 37 2.2.3.2. Reactive extraction 38
2.2.3.3. Slug flow pattern visualization 38
2.2.3.4. Analytical procedures 39
2.3. Results and discussion 39
2.3.1. Mass transfer in physical extraction 39
2.3.2. Mass transfer in reactive extraction 48
2.4. Conclusions 56
References 57 Appendices 60
Appendix 2A. Extraction efficiency as a function of the residence time in
physical extraction 60
Appendix 2B. Dissociation of lactic acid in the aqueous phase 61
Appendix 2C. Extraction efficiency as a function of the residence time and
inlet lactic acid concentration in reactive extraction 62
Appendix 2D. (Kova)Chem as a function of the residence time and inlet lactic
Chapter 3 Proof of concept for continuous enantioselective liquid– liquid extraction in capillary microreactors using 1-octanol as a
sustainable solvent 65
Abstract 66
3.1. Introduction 67
3.2. Materials and methods 69
3.2.1. Materials 69
3.2.2. Experimental setup 69
3.2.3. Experimental procedures 70
3.2.3.1. ELLE experiments in the capillary microreactors 70
3.2.3.2. ELLE experiments with DNB-(R,S)-Leu and CA3 in a batch set-up 71
3.2.3.3. Analytical procedures 71
3.3. Theory and definitions 72
3.4. Results and discussions 74
3.4.1. Equilibrium experiments in batch with 1,2-DCE and 1-octanol 74
3.4.2. Experiments in the continuous microreactor set-up 74
3.4.2.1. Continuous experiments in 1,2-DCE 74
3.4.2.2. Continuous experiments in 1-octanol 77
3.5. Conclusions 80
References 81 Appendices 84 Chapter 4 Modelling studies on enantioselective extraction of an amino
acid derivative in slug flow capillary microreactors 89
Abstract 90
4.1. Introduction 91
4.2. Experimental method 92
4.2.1. Materials 92
4.2.2. ELLE in capillary microreactors 93
4.2.3. Determination of ELLE equilibrium constants in batch reactors 94
4.2.4. Analytical procedures 94
4.3. Model development 95
4.3.1. Calculation of the molar fluxes 96
4.3.2. Bulk phase concentrations 98
4.3.3. Physico-chemical parameters 99
Interfacial area 99
Overall mass transfer coefficient 99
Enhancement factor 100
Activity coefficient 101
Physical properties of the system 101
4.3.4. Numerical solution method 102
4.4. Results and discussions 103
4.4.1. Equilibrium extractions 103
4.4.2.1. Model I: instantaneous complexation rate for both the (S)- and
(R)-enantiomers 104
4.4.2.2. Model II: instantaneous complexation rate for the (S)-enantiomer
and finite complexation rate for the (R)-enantiomer 106
4.4.3. Process simulation for multi-stage ELLE operation 109
4.5. Conclusions 114
Nomenclature 115 References 116 Appendices 120 Appendix 4A. Extraction performance as a function of the residence time 120 Appendix 4B. Enhancement factor in the aqueous phase in the presence of
dissociation reaction 121
Appendix 4C. Number of segments along the microreactor and its effect on
the model convergence 123
Chapter 5 Enantioselective liquid-liquid extraction studies on
(D,L)-tryptophan using a cationic Pd-XylBINAP complex as chiral host
in 1-octanol 125
Abstract 126
5.1. Introduction 127
5.2. Experimental section 128
5.2.1. Materials 128
In situ preparation of Pd(PF6)2((S)-XylBINAP) 128
5.2.2. Enantioselective liquid-liquid extraction of DL-Tryptophan with
Pd(PF6)2((S)-XylBINAP) 129
5.2.2.1. Extraction set-up 129
5.2.2.2. Experimental procedures 129
5.2.3. Analytical procedures 130
5.3. Theory and definitions 130
5.4. Results and discussions 131
ELLE of racemic Trp using different concentrations of the
Pd(PF6)2((S)-XylBINAP) complex. 133
Reactive extraction of enantiopure tryptophan 134
5.5. Conclusions 137 References 138 Appendix 5A 140 Summary 143 Samenvatting 147 Acknowledgement 151 List of publications 154
