mechanistic models on enzymatic hydrolysis and anaerobic digestion

206 Pages·2016·3.6 MB·English

MMiicchhiiggaann TTeecchhnnoollooggiiccaall UUnniivveerrssiittyy
DDiiggiittaall CCoommmmoonnss @@ MMiicchhiiggaann TTeecchh
Dissertations, Master's Theses and Master's Reports
2015
MMEECCHHAANNIISSTTIICC MMOODDEELLSS OONN EENNZZYYMMAATTIICC HHYYDDRROOLLYYSSIISS AANNDD
AANNAAEERROOBBIICC DDIIGGEESSTTIIOONN
Yang Zhang
Michigan Technological University, [email protected]
Copyright 2015 Yang Zhang
RReeccoommmmeennddeedd CCiittaattiioonn
Zhang, Yang, "MECHANISTIC MODELS ON ENZYMATIC HYDROLYSIS AND ANAEROBIC DIGESTION", Open
Access Dissertation, Michigan Technological University, 2015.
https://doi.org/10.37099/mtu.dc.etdr/63
Follow this and additional works at: https://digitalcommons.mtu.edu/etdr
Part of the Biochemical and Biomolecular Engineering Commons
MECHANISTIC MODELS ON ENZYMATIC HYDROLYSIS AND ANAEROBIC
DIGESTION

By
Yang Zhang

A DISSERTATION
Submitted in partial fulfillment of the requirements for the degree of
DOCTOR OF PHILOSOPHY
In Chemical Engineering

MICHIGAN TECHNOLOGICAL UNIVERSITY
2015
© 2015 Yang Zhang

This dissertation has been approved in partial fulfillment of the requirements for the
Degree of DOCTOR OF PHILOSOPHY in Chemical Engineering

Department of Chemical Engineering

Dissertation Advisor: Wen Zhou
Committee Member: Susan T. Bagley
Committee Member: Tony N. Rogers
Committee Member: David R. Shonnard
Department Chair: S. Komar Kawatra

Table of Contents
List of Tables .................................................................................................................................. ix
List of Figures ................................................................................................................................. xi
Acknowledgements ........................................................................................................................ xv
Preface ......................................................................................................................................... xvii
List of Publications ....................................................................................................................... xix
Abstract ......................................................................................................................................... xxi
Chapter 1 Introduction and Research Objectives ............................................................................. 1
Chapter 2 On Improved Mechanistic Modeling for Enzymatic Hydrolysis of Cellulose ................ 5
Abstract ........................................................................................................................................ 6
2.1 Introduction ............................................................................................................................ 7
2.2 Materials and Methods ......................................................................................................... 10
2.2.1 Oligomer reactions with beta-glucanases ..................................................................... 10
2.2.2 Inhibition effects ........................................................................................................... 13
2.2.3 Enzymatic thermal deactivation and inactive adsorption .............................................. 15
2.2.4 Model parameters .......................................................................................................... 17
2.3 Results and Discussion ........................................................................................................ 17
2.3.1 Testing cellulosic substrate accessibility ...................................................................... 17
2.3.2 Oligomer reactions ........................................................................................................ 20
2.3.3 Inhibition effects ........................................................................................................... 20
2.3.4 Enzyme decay and the slow-down of enzymatic hydrolysis kinetics ........................... 21
2.4 Conclusions .......................................................................................................................... 23
Nomenclature ............................................................................................................................. 24
Tables ......................................................................................................................................... 27
Figures ....................................................................................................................................... 29
References .................................................................................................................................. 33
Chapter 3 On a Novel Mechanistic Model for Simultaneous Enzymatic Hydrolysis of Cellulose and
Hemicellulose Considering Morphology ....................................................................................... 35
Abstract ...................................................................................................................................... 36
3.1 Introduction .......................................................................................................................... 37
3.2 Methodology ........................................................................................................................ 39
3.2.1 Morphology of substrate containing hemicellulose and cellulose ................................ 39
v
3.2.2 Advanced site concentration formalism ........................................................................ 43
3.2.3 Ablation and oligomer rate equations ........................................................................... 46
3.3 Numerical Simulation Results and Discussion .................................................................... 48
3.3.1 Comparison with experiments in Qing and Wyman (2011b) and investigation of effects
of substrate morphology......................................................................................................... 50
3.3.2 Comparison with experiments in Banerjee et al. (2010a) ............................................. 51
3.3.3 Comparison with Experiments in Kumar and Wyman (2009) ...................................... 52
3.4 Conclusions .......................................................................................................................... 53
Nomenclature ............................................................................................................................. 55
Acknowledgments ...................................................................................................................... 60
Tables ......................................................................................................................................... 61
Figures ....................................................................................................................................... 64
References .................................................................................................................................. 71
Supporting Information (SI) ...................................................................................................... 73
Appendix .................................................................................................................................. 107
Chapter 4 A Mechanistic Design Framework for Optimal Enzyme Usage in Hydrolysis of
Hemicellulose-cellulosic Substrates ............................................................................................ 109
Abstract .................................................................................................................................... 110
4.1 Introduction ........................................................................................................................ 111
4.2 Methods.............................................................................................................................. 113
4.2.1 Morphology of lignocellulosic substrates ................................................................... 113
4.2.2 Reactions of enzyme mixture ...................................................................................... 113
4.2.3 Model parameters and optimization procedure ........................................................... 115
4.3 Results and Discussion ...................................................................................................... 118
4.3.1 Enzyme optimization and adding time effects for Avicel hydrolysis ......................... 118
4.3.2 Enzyme optimization and adding time effects for AFEX-pretreated corn stover
hydrolysis ............................................................................................................................. 120
4.4 Conclusions ........................................................................................................................ 123
Acknowledgments .................................................................................................................... 124
Tables ....................................................................................................................................... 125
Figures ..................................................................................................................................... 127
References ................................................................................................................................ 132
Supporting Information (SI) .................................................................................................... 135
vi
Chapter 5 Improved ADM1 Model for Anaerobic Digestion Process Considering Physico-chemical
Reactions ...................................................................................................................................... 147
Abstract .................................................................................................................................... 148
5.1 Introduction ........................................................................................................................ 149
5.2 Methodology ...................................................................................................................... 152
5.2.1 Bio-chemical framework............................................................................................. 152
5.2.2 Physico-chemical framework ...................................................................................... 153
5.3 Results and Discussion ...................................................................................................... 157
5.3.1 Model validation ......................................................................................................... 157
5.3.2 Effects of inorganic components on anaerobic digestion ........................................... 157
5.4 Conclusions ........................................................................................................................ 161
Nomenclature ........................................................................................................................... 161
Acknowledgments.................................................................................................................... 163
Tables ....................................................................................................................................... 165
Figures ..................................................................................................................................... 169
References ................................................................................................................................ 175
Supporting Information (SI) .................................................................................................... 177
Appendix .................................................................................................................................. 183
vii

List of Tables
Table 2.1 Parameters used in the model ............................................................................27
Table 3.1 Main components of hemicellulose-cellulosic substrates and their specific
enzymes ........................................................................................................61
Table 3.2 Simulation results compared with experimental data from Banerjee et al.
(2010a) ..........................................................................................................62
Table 4.1 Optimal enzyme mass fractions for 72 hours hydrolysis of Avicel ................125
Table 4.2 Optimal enzyme mass fractions for 72 hours hydrolysis of AFEX pretreated
corn stover ...................................................................................................126
Table 5.1 Matrix representation of the rate coefficients and equations for ADM1 bio-
chemical framework part 1: soluble components .......................................165
Table 5.2 Matrix representation of the rate coefficients and equations for ADM1 bio-
chemical framework part 2: particulate components ..................................166
Table 5.3 Matrix representation of the rate coefficients and equations for ADM1
physico-chemical framework part 1: liquid-gas processes .........................167
Table 5.4 Matrix representation of the rate coefficients and equations for ADM1
physico-chemical framework part 2: liquid-liquid processes .....................167
Table 5.5 Matrix representation of the rate coefficients and equations for ADM1
physico-chemical framework part 3: liquid-solid processes .......................168
Table 5.6 Acid-base and precipitation reactions considered in anaerobic digestion ......168
ix