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207 Pages·2015·6.47 MB·English

IMPROVING HMF YIELD USING AN INTEGRATED
MODELING APPROACH

by

T. Dallas Swift

A dissertation submitted to the Faculty of the University of Delaware in partial
fulfillment of the requirements for the degree of Doctor of Philosophy in Chemical
Engineering

Summer 2015

© 2015 T. Dallas Swift
All Rights Reserved
ProQuest Number: 3730230
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IMPROVING HMF YIELD USING AN INTEGRATED
MODELING APPROACH

by

T. Dallas Swift

Approved: __________________________________________________________
Abraham M. Lenhoff, Ph.D.
Chair of the Department of Chemical and Biomolecular Engineering

Approved: __________________________________________________________
Babatunde A. Ogunnaike, Ph.D.
Dean of the College of Engineering

Approved: __________________________________________________________
James G. Richards, Ph.D.
Vice Provost for Graduate and Professional Education
I certify that I have read this dissertation and that in my opinion it meets
the academic and professional standard required by the University as a
dissertation for the degree of Doctor of Philosophy.

Signed: __________________________________________________________
Dionisios G. Vlachos, Ph.D.
Professor in charge of dissertation

I certify that I have read this dissertation and that in my opinion it meets
the academic and professional standard required by the University as a
dissertation for the degree of Doctor of Philosophy.

Signed: __________________________________________________________
Vladimiros Nikolakis, Ph.D.
Member of dissertation committee

I certify that I have read this dissertation and that in my opinion it meets
the academic and professional standard required by the University as a
dissertation for the degree of Doctor of Philosophy.

Signed: __________________________________________________________
Raul F. Lobo, Ph.D.
Member of dissertation committee

I certify that I have read this dissertation and that in my opinion it meets
the academic and professional standard required by the University as a
dissertation for the degree of Doctor of Philosophy.

Signed: __________________________________________________________
Yushan Yan, Ph.D.
Member of dissertation committee
I certify that I have read this dissertation and that in my opinion it meets
the academic and professional standard required by the University as a
dissertation for the degree of Doctor of Philosophy.

Signed: __________________________________________________________
Michael Tsapatsis, Ph.D.
Member of dissertation committee

I certify that I have read this dissertation and that in my opinion it meets
the academic and professional standard required by the University as a
dissertation for the degree of Doctor of Philosophy.

Signed: __________________________________________________________
Daniel Hickman, Ph.D.
Member of dissertation committee
ACKNOWLEDGMENTS
I am truly grateful to my advisor Professor Dion Vlachos for his guidance and
support over the last several years. I would also like to thank Dr. Vlad Nikolakis, who I
worked with very closely throughout my graduate career. I have grown immensely since
joining the Vlachos group and I credit both Dion and Vlad for helping guide my
professional development. My experience in graduate school would not have been the
same without them. I would also like to thank Professors Raul Lobo, Yushan Yan, and
Michael Tsapatsis, as well as Dr. Dan Hickman for serving on my thesis committee and
providing valuable feedback on my thesis. I also acknowledge the United States
Department of Energy for funding the Catalysis Center for Energy Innovation, which
support my PhD research.
I would also like to thank my experimental collaborators in the Vlachos and Fan
groups. I had many enlightening conversations with each of them that have helped me
better understand the nuances of my project. Their experimental contributions were
invaluable in my research, and I am deeply grateful for their dedication and hard work.
Christina Bagia’s and George Peklaris’s experimental studies of fructose dehydration
kinetics in HCl were instrumental in developing the kinetic model for fructose
dehydration in Chapter 2. Dr. Vinit Choudhary and Dr. George Tsilomelekis performed
the kinetic isotope effect experiments shown in Chapter 2. I appreciate my conversations
with Paul Dornath, who constructed and tested the reactive adsorber in Chapter 3. I am
also grateful to Dr. Marta León who studied adsorption isotherms on zeolite H-BEA that
were incorporated into the model depicted in Chapter 4. Dr. Jacob Kruger and Zachary
v
Erdman worked together to measure the dehydration kinetics of fructose and HMF in H-
BEA that are shown in Chapter 4. Finally, I’d like to thank Hannah Nguyen, who
measured the kinetics of glucose dehydration and adsorption isotherms in H-BEA used in
Chapter 4 as well as the CrCl experiments shown in Chapter 5.
3
It has been a pleasure to work with my colleagues in the Vlachos research group
and CCEI. In addition to my collaborators, I have had enlightening and educational
conversations with Dr. Nima Nikbin, Dr. Tim Courtney, Professor Samir Mushrif, Dr.
Stavros Caratzoulas, Professor Neeraj Rai, Dr. Glen Jenness, Molly Koehle and Dr. Liu
Yang. I wish you all the best professionally. I would also like to thank Ben, Jenna, Ariel,
Colin, Andrew, Lauren, John, Carly, Trong, and so many others who helped make my
time in Delaware memorable.
I would like to take this opportunity to thank my parents and my sister for their
support. Finally, I would like to thank my wife Lauren Swift, whose support and insight
has helped me grow personally and professionally in more ways than I can count.
v i
TABLE OF CONTENTS
LIST OF TABLES ......................................................................................................... xi
LIST OF FIGURES ..................................................................................................... xii
ABSTRACT .................................................................................................................. xx
Chapter
1 INTRODUCTION .............................................................................................. 1
1.1 Motivation .................................................................................................. 1
1.2 Chemical Reactions for HMF Production from Hexose Sugars ................ 4
1.3 Reactive Separations for HMF Production ................................................ 8
1.4 Intensification of Isomerization and Dehydration ................................... 10
1.5 Thesis Scope and Overview ..................................................................... 11
2 KINETICS OF HOMOGENEOUS BRØNSTED ACID CATALYZED
FRUCTOSE DEHYDRATION AND HMF REHYDRATION: A COMBINED
EXPERIMENTAL AND COMPUTATIONAL STUDY ................................ 15
2.1 Introduction .............................................................................................. 15
2.2 Methods.................................................................................................... 18
2.2.1 Materials ...................................................................................... 18
2.2.2 Reaction Kinetics ......................................................................... 19
2.2.3 Analytical Methods ...................................................................... 19
2.2.4 Experimental Conditions ............................................................. 19
2.2.5 Computational Methods ............................................................... 20
2.3 Reaction Network Development .............................................................. 22
2.3.1 Tautomer Equilibrium .................................................................. 22
2.3.2 Fructose Dehydration Skeleton Model ........................................ 25
2.3.3 Excess Formic Acid Formation ................................................... 28
2.3.4 Reaction Orders ........................................................................... 30
2.3.5 Functional Form of Model ........................................................... 32
2.4 Model Analysis and Discussion ............................................................... 34
2.4.1 Parameter Estimation ................................................................... 34
vi i
2.4.2 Insights into Continuous Flow Reactor Design ........................... 38
2.5 Extension to Mixed-solvent Systems ....................................................... 39
2.5.1 Experimental Conditions and Kinetics ........................................ 41
2.5.2 Fructose Dehydration Kinetics in Mixed Solvents ...................... 42
2.5.3 Temperature Effects ..................................................................... 47
2.5.4 HMF Degradation in Mixed Solvents .......................................... 48
2.6 Conclusions .............................................................................................. 49
2.7 Permissions .............................................................................................. 50
3 REACTIVE ADSORPTION FOR THE SELECTIVE CONVERSION OF
FRUCTOSE TO HMF ...................................................................................... 51
3.1 Introduction .............................................................................................. 51
3.2 Experiments and Data Analysis ............................................................... 54
3.2.1 Reaction Model ............................................................................ 54
3.2.2 Single-component Isotherms ....................................................... 54
3.2.3 Multicomponent Adsorption ........................................................ 56
3.3 Reactive Adsorption Model ..................................................................... 57
3.4 Results and Discussion ............................................................................ 59
3.4.1 Adsorption Isotherms ................................................................... 59
3.4.2 Reactive Adsorption..................................................................... 62
3.4.3 Transport Limitations................................................................... 76
3.5 Conclusions .............................................................................................. 81
3.6 Permissions .............................................................................................. 82
4 TANDEM LEWIS ACID/BRØNSTED ACID-CATALYZED CONVERSION
OF CARBOHYDRATES TO HMF USING ALUMINOSILICATE ZEOLITE
BETA ................................................................................................................ 83
4.1 Introduction .............................................................................................. 83
4.2 Experimental Methods ............................................................................. 85
4.2.1 Materials ...................................................................................... 85
4.2.2 Reaction Kinetics ......................................................................... 85
4.2.3 Adsorption Isotherms ................................................................... 86
4.2.4 Brønsted Site Density Measurements .......................................... 86
4.3 Computational Methods ........................................................................... 87
vi ii
4.3.1 Adsorption.................................................................................... 87
4.3.2 Continuity Equations ................................................................... 88
4.3.3 Homogeneous Reaction Network ................................................ 89
4.3.4 Heterogeneous Reaction Network ............................................... 90
4.3.5 Parameter Estimation Procedure .................................................. 91
4.4 Results and Discussion ............................................................................ 92
4.4.1 Single-component Isotherms ....................................................... 92
4.4.2 Model Assessment ....................................................................... 94
4.4.3 Species Partitioning between Solution and Zeolite Phases and
Contribution of Homogeneous Chemistry ................................... 97
4.4.4 Kinetic Parameters and Comparison to Other Catalysts ............ 101
4.4.5 Sensitivity of Estimated Parameters .......................................... 104
4.4.5.1 Reaction Network Sensitivity ..................................... 104
4.4.5.2 Sensitivity to Solution pH ........................................... 105
4.4.5.3 Evaluation of Transport Limitations ........................... 107
4.4.6 Kinetic Regimes ......................................................................... 109
4.4.7 Optimizing HMF Yield in Single Phase and Biphasic Systems 115
4.4.8 Identification of Key Materials’ Properties ............................... 118
4.5 Conclusions ............................................................................................ 119
5 TANDEM LEWIS/BRONSTED HOMOGENEOUS ACID CATALYSIS:
CONVERSION OF GLUCOSE TO HMF IN AN AQUEOUS CrCl -HCl
3
SOLUTION..................................................................................................... 121
5.1 Introduction ............................................................................................ 121
5.2 Experimental Conditions ....................................................................... 122
5.3 Reaction Network and Kinetic Modeling .............................................. 123
5.4 Kinetic Parameters ................................................................................. 125
5.4.1 Mannose Conversion in HCl ...................................................... 125
5.4.2 HMF Degradation in CrCl ........................................................ 126
3
5.4.3 Sugar Isomerization and Epimerization Reactions in CrCl ...... 127
3
5.4.4 Effects of CrCl Concentration and Temperature on Rate and
3
Yields ......................................................................................... 134
5.5 Optimizing HMF Yield in Tandem Reactions ....................................... 137
5.6 Reactive Extraction ................................................................................ 143
5.7 Conclusions ............................................................................................ 145
ix