University of Groningen
Catalytic transformation of biomass derivatives to value-added chemicals and fuels in microreactors
Hommes, Arne DOI:
10.33612/diss.132909253
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Publication date: 2020
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Hommes, A. (2020). Catalytic transformation of biomass derivatives to value-added chemicals and fuels in microreactors. University of Groningen. https://doi.org/10.33612/diss.132909253
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Catalytic transformation of
biomass derivatives to
value-added chemicals and
fuels in microreactors
Copyright © Arne Hommes, 2020
All rights reserved. Save exceptions stated by the law, no part of this publication may be reproduced, stored in a retrieval system of any nature, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, included a complete or partial transcription, without the prior written permission of the authors, application for which should be addressed to author.
Cover photo: © Gerard Kingma, www.kingma.nu Cover design: Jessi Osorio Velasco
Printed by: Ridderprint BV, www.ridderprint.nl
ISBN: 978-94-6416-107-6
ISBN: 978-94-6416-110-6 (electronic version)
The research described in this dissertation was performed at the Department of Chemical Engineering – Green Chemical Reaction Engineering, Faculty of Science and Engineering, University of Groningen, The Netherlands.
Catalytic transformation of biomass
derivatives to value-added
chemicals and fuels in
microreactors
PhD thesis
to obtain the degree of PhD at the University of Groningen
on the authority of the
Rector Magnificus Prof. C. Wijmenga and in accordance with
the decision by the College of Deans. This thesis will be defended in public on Friday 25 September 2020 at 14.30 hours
by
Arne Hommes
born on 4 May 1989 in Slochteren
Supervisors
Prof. J. Yue Prof. H.J. Heeres
Assessment Committee
Prof. F. Picchioni Prof. D.Y. Murzin Prof. W. de Jong
| 1
Contents
Chapter 1. Catalytic transformation of biomass derivatives to
value‐added chemicals and fuels in continuous flow
microreactors ...
5Abstract ... 6
1.1. Introduction ... 6
1.1.1. Biomass to chemicals and fuels ... 6
1.1.2. Reactor engineering aspects for biomass conversion ... 15
1.1.3. Scope ... 22
1.2. Biomass conversion in microreactors ... 25
1.2.1. Synthesis of furans by sugar dehydration ... 25
1.2.2. Liquid phase oxidation of biomass derivatives ... 42
1.2.3. Hydrogenation of biomass derivatives ... 56
1.2.4. Biodiesel synthesis by the alcoholysis of triglycerides and fatty acids ... 64
1.2.5. Miscellaneous catalytic biomass transformations... 73
1.3. Challenges and future perspectives ... 78
1.3.1. Solid handling ... 78
1.3.2. Incorporation of solid catalysts ... 79
1.3.3. Upscaling of multiphase microreactors ... 81
1.3.4. The “micro-biorefinery” ... 82
1.4. Summarized outlook ... 84
1.5. Aim and scope of research ... 86
References ... 88
Chapter 2.
Aerobic oxidation of benzyl alcohol in a slug flow
microreactor: Influence of liquid film wetting on mass
transfer ...
119Abstract ... 120
2.1. Introduction ... 120
2 |
2.2.1. Chemicals ... 124
2.2.2. Setup ... 124
2.2.3. Reaction test procedure ... 125
2.2.4. Analysis ... 126
2.2.5. Definitions ... 127
2.3. Results and discussion ... 127
2.3.1. Selectivity and oxygen depletion ... 127
2.3.2. Absence of mass transfer limitations at low temperatures .... 128
2.3.3. Wetted and dewetted slug flows ... 130
2.3.4. Determination of kinetic parameters at low temperatures .... 133
2.3.5. Reaction and mass transfer characteristics at high temperatures ... 137
2.4. Conclusions ... 144
Notation ... 144
References ... 146
Supporting Information – Chapter 2 ... 150
Chapter 3.
Mass transfer and reaction characteristics of
homogeneously catalyzed aerobic oxidation of
5-hydroxymethylfurfural in slug flow microreactors ...
165Abstract ... 166
3.1. Introduction ... 166
3.2. Experimental ... 171
3.2.1. Chemicals ... 171
3.2.2. Microreactor setup and procedure ... 172
3.2.3. Analysis ... 174
3.2.4. Definitions ... 175
3.3. Results and discussion ... 176
3.3.1. Reaction profile and mass balance ... 176
3.3.2. Microreactor studies at atmospheric pressure conditions... 178
3.3.3. Microreactor studies at elevated pressure conditions ... 183
3.3.4. Intensification potential in microreactors ... 191
3.3.5. Microreactor optimization strategy ... 195
3.4. Conclusions ... 196
References ... 197
| 3
Chapter 4.
Experimental and modeling studies on the Ru/C
catalyzed levulinic acid hydrogenation to γ–valerolactone in
packed bed microreactors ...
227Abstract ... 228
4.1. Introduction ... 228
4.2. Experimental ... 233
4.2.1. Materials and chemicals ... 233
4.2.2. Setup and procedure ... 233
4.2.3. Analysis ... 235
4.2.4. Definitions ... 236
4.3. Results and discussion ... 236
4.3.1. Mass balance and reaction profile ... 236
4.3.2. Influence of operating variables on the reaction performance 238 4.3.3. Comparison with literature results ... 242
4.3.4. Development of the microreactor model ... 243
4.3.5. Model discussion ... 251
4.4. Microreactor optimization strategy ... 258
4.5. Conclusions ... 260
Notation ... 260
References ... 260
Supporting Information – Chapter 4 ... 269
Chapter 5.
Enzymatic biodiesel synthesis by the biphasic
esterification of oleic acid and 1-butanol in microreactors .
289 Abstract ... 2905.1. Introduction ... 290
5.2. Experimental ... 294
5.2.1. Chemicals ... 294
5.2.2. Microreactor setup and experimental procedure ... 294
5.2.3. Analysis ... 296
5.2.4. Definitions ... 296
5.3. Results and discussion ... 297
5.3.1. Reaction performance in the PTFE microreactor ... 297
5.3.2. Kinetic model validation in the PTFE microreactor ... 303
5.3.3. Biodiesel production optimization: Enzyme turnover number in PTFE and stainless steel microreactors ... 309
5.3.4. Outlook ... 312
4 |
Notation ... 314
References ... 315
Supporting Information – Chapter 5 ... 321
