Thermochemical Conversion of Lignocellulosic Materials

Theory, Design, and Applications for the Future

1st Edition - January 22, 2025
Editors: Manuel Garcia-Perez, Farid Chejne-Janna
Language: English
Paperback ISBN:
9 7 8 - 0 - 3 2 3 - 9 5 5 5 1 - 5
eBook ISBN:
9 7 8 - 0 - 3 2 3 - 9 5 5 5 2 - 2

Thermochemical Conversion of Lignocellulosic Materials: Theory, Design, and Applications for the Future proposes a generalized methodology for the design and study of thermoche… Read more

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Thermochemical Conversion of Lignocellulosic Materials: Theory, Design, and Applications for the Future proposes a generalized methodology for the design and study of thermochemical conversion reactors independent of the feedstock used and the technology analyzed. Sections cover essential theory, including biomass thermochemical conversion, biomass supply chains, and thermochemical reactors. The book then examines other important aspects of the thermochemical conversion reaction, presenting modeling and analysis options. Finally, it investigates potential uses and applications for these techniques. Including clear objectives and practical exercises to cement understanding, this book will equip students and researchers with the skills to design and model selective reactors.

Thermochemical Conversion of Lignocellulosic Materials
Cover image
Title page
Table of Contents
Copyright
Contributors
Preface
Chapter 1 The role of biomass to address global energy and environmental challenges
Abstract
Keywords
1.1 Population growth, energy, and socioeconomic development
1.2 Energy production and greenhouse gas emissions
1.3 Energy intensity
1.4 Social progress index
1.5 National energy balance/energy matrix
1.6 Historic evolution of energy consumption
1.7 Bioenergy in national energy matrixes
1.8 The unique role of biomass in the global C cycle
1.9 Accounting for the environmental services of renewable energy
1.10 Measuring performance through carbon abatement cost
1.11 Questions
References
Chapter 2 Biomass resources and supply chains
Abstract
Keywords
2.1 Introduction
2.2 Biomass inventories
2.3 Supply chain
2.3.1 Biomass collection
2.3.2 Grasses and agricultural residues
2.3.3 Forest residues
2.3.4 Urban wood waste
2.3.5 Oilseeds
2.4 Transport
2.5 Depot and depot sitting
2.6 Biomass storage/processing center location
2.6.1 Storage warehouse location using the weighted factors method
2.6.2 Storage warehouse location using the Brown-Gibson method
2.6.3 Storage warehouse location with the center of gravity method
2.6.4 Storage warehouse location with the Break-Even method
2.6.5 Location of a storage warehouse with the northwest corner method
2.6.6 Exhaustive search exact algorithm method
2.7 Questions
References
Chapter 3 Introduction to thermochemical reactors
Abstract
Keywords
3.1 Biomass conversion technologies
3.2 Camp fire experience
3.3 Thermochemical reactions
3.4 Thermochemical reactors
3.5 Equivalence ratio
3.6 Dry thermochemical conversion technologies
3.6.1 Torrefaction
3.6.2 Carbonization
3.6.3 Fast pyrolysis
3.6.4 Gasification with O2
3.6.5 Steam gasification
3.6.6 Combustion
3.7 Wet thermochemical conversion technology
3.7.1 Hydrothermal liquefaction
3.7.2 Organic solvent liquefaction (solvolysis)
3.7.3 Hydrothermal gasification
3.7.4 Wet oxidation
3.8 Questions
References
Chapter 4 Lignocellulosic materials
Abstract
Keywords
4.1 Introduction
4.2 Multiscale structure of lignocellulosic materials
4.3 Cellulose
4.4 Hemicellulose
4.5 Lignin
4.6 Extractives
4.6.1 Types of extractives
4.6.2 Extraction and characterization methods
4.7 Quantifying the content of cellulose, hemicellulose, and lignin
4.8 Mineral composition
4.8.1 Inductively coupled plasma spectroscopy (ICP)
4.8.2 Atomic absorption spectroscopy (AAS)
4.8.3 Laser-induced breakdown spectroscopy (LIBS)
4.8.4 X-ray fluorescence (XRF)
4.8.5 Energy dispersive X-ray (EDX)
4.9 Questions
References
Chapter 5 Drying, particle size reduction, and densification of lignocellulosic materials
Abstract
Keywords
5.1 Biomass particles
5.1.1 Particle shape
5.1.2 Particle size
5.1.3 Particle size distribution
5.1.4 Mechanical properties
5.1.5 Other properties of lignocellulosic powders
5.2 Biomass particle size reduction process
5.3 Grinding of lignocellulosic materials
5.4 Factors affecting size reduction mechanical operations
5.5 Grinding energy calculations
5.6 Biomass feeding in thermochemical reactors
5.7 Biomass drying
5.7.1 Biomass dryers
5.8 Biomass densification
5.9 Biomass particles compression experiments
5.10 Questions and problems
References
Chapter 6 Experimental techniques to study thermochemical reactions
Abstract
Keywords
6.1 Thermochemical reactions
6.2 The role of parametric studies
6.2.1 Effect of temperature
6.2.2 Heating rate effect
6.2.3 Effect of external pressure
6.2.4 Particle size effect
6.2.5 Effect of biomass loading (interparticle secondary reactions)
6.2.6 Effect of vapors’ residence time
6.3 Thermal analysis
6.4 Thermogravimetric analysis
6.4.1 Heating layouts and commercial oven types
6.4.2 Sampling and sample containers
6.4.3 Pressure and reaction environment
6.4.4 Temperature measurement
6.4.5 Calibration
6.4.6 Analysis of the data
6.4.7 Challenges in the use of thermogravimetric analysis to study primary reactions
6.4.8 Proximate composition
6.5 Evolved gas analysis-EGA (TG-MS, TG-FTIR)
6.5.1 TG- mass spectrometry (MS)
6.5.2 TG-FTIR
6.6 Differential thermal analysis and differential scanning calorimetry
6.6.1 Differential thermal analysis (DTA)
6.6.2 Calorimetric DTA
6.6.3 Differential scanning calorimetry (DSC)
6.6.4 Power compensated DSC (Fig. 6.29)
6.6.5 Modulated temperature differential scanning calorimetry (MTDSC)
6.6.6 Quantitative aspects of DTA and DSC curves
6.7 Py-MS and Py-GC/MS
6.7.1 Pyrolysis gas chromatography–mass spectrometry (Py-GC/MS)
6.8 Py-DART-MS
6.9 Spoon reactors
6.10 Fluidized bed reactors
6.11 Wire mesh reactors
6.12 Pulse-heated analysis of solid reactions (PHASR)
6.13 Hot rod reactor
6.14 Entrained flow reactor
6.15 Laser pyrolysis and laser ionization spectrometry (REMPI-TOFMS)
6.16 Isothermal pyrolysis tube
6.17 Reactors to study secondary homogeneous reactions
6.18 Reactors to study secondary heterogeneous reactions
6.19 Elemental analysis
6.20 Adiabatic bomb calorimeter (Fig. 6.51)
6.21 Questions
References
Chapter 7 Introduction to thermochemical reactions
Abstract
Keywords
7.1 Introduction to thermochemical reactions
7.2 Pyrolysis of cellulose
7.2.1 Global mechanisms
7.2.2 Elementary reactions
7.2.3 Cellulose depolymerization reactions
7.2.4 Cellulose dehydration reactions
7.2.5 Cellulose fragmentation reactions
7.2.6 Aromatization and poly-condensation reactions
7.2.7 Removal mechanisms of volatile products
7.2.8 Effect of additives
7.3 Pyrolysis of lignin
7.3.1 Other elementary reactions responsible for the formation of CO, CO2 and CH4
7.3.2 Lignin demethylation reactions
7.3.3 Lignin char formation reactions
7.3.4 Lignin complex thermochemical reactions network
7.3.5 Removal mechanisms of volatile products
7.3.6 Aromatization/polycondensation
7.4 Biochar gasification
7.5 Questions
References
Chapter 8 Fundamentals of kinetic analysis on pyrolysis and gasification reactions
Abstract
Keywords
8.1 Introduction to kinetic analysis
8.1.1 Classification of reactions
8.1.2 Definition of conversion
8.1.3 Ideal reactors
8.1.4 Kinetic analysis methods
8.2 Biomass pyrolysis kinetic analysis with experimental data obtained in non-isothermic conditions (representation as a single pseudo-reaction)
8.2.1 Differential Method (Friedman Method)
8.2.2 Other expressions to describe f(α)
8.3 Kinetic analysis of complex reaction systems
8.4 Estimation of kinetic parameters of complex series parallel reactions
8.5 Estimation of product yields from stoichiometric and kinetic information
8.6 Secondary reactions in gas phase
8.7 Char oxidation reactions
8.7.1 Nonisothermal conditions
8.8 Questions
References
Chapter 9 Single particle models
Abstract
Keywords
9.1 Experimental determination of total conversion time
9.2 General methodology for the development of single particle models
9.3 State of the art of biomass pyrolysis single particle models
9.4 Estimation of effective conductivity in biomass and char particles
9.4.1 Effective conductivity perpendicular to the fibers
9.4.2 Siau model
9.4.3 Saastamoinen and Richard model
9.4.4 Effective thermal conductivity along the fibers
9.5 Particle-scale models for biomass pyrolysis
9.6 Analytical solutions for limit cases
9.7 Simplified Bamford’s pyrolysis single particle model
9.8 Single particle models in gasification
9.9 Effective diffusivity
9.10 Single particle model for gasification
9.11 Dimensionless local balance equations
9.12 Solutions of the local mass balance equation under limit conditions
9.13 Advanced gasification models
9.13.1 Solutions of the local mass balance equation under limit conditions for the biochar gasification reaction
9.14 Effect of particle size distribution and flow pattern
9.15 Questions
References
Chapter 10 Estimation of thermodynamic properties
Abstract
Keywords
10.1 Introduction
10.2 Boiling point
10.3 Critical properties
10.4 Heat capacity
10.5 Hansen solubility parameters
10.6 Gas enthalpy of formation
10.7 Gas standard Gibbs free energy
References
Chapter 11 Mass balances in thermochemical processes
Abstract
Keywords
Acknowledgments
11.1 Generalities of thermochemical reactions
11.2 Concentration expression based on aggregate states
11.2.1 Forms to express concentration in solids
11.2.2 Forms to express the concentration in liquids
11.2.3 Forms to express gas concentration
11.3 Yield and flow rate calculation in a mixture
11.4 Systems and flow diagram in mass balance
11.5 General approach to solving mass balances
11.5.1 Mass balance equation
11.5.2 Mass balance of a combustion reaction using stoichiometry
11.5.3 Mass balance closure
11.6 Application of mass balances in thermochemical processes
11.6.1 Discontinuous batch reactor application
11.6.2 Continuous and discontinuous semibatch reactor application
11.6.3 Continuous reactor application
11.7 Product quantification in thermochemical processes
11.7.1 Mass balances based on product yields
11.8 Questions
References
Chapter 12 Energy balances in thermochemical processes
Abstract
Keywords
Acknowledgments
12.1 Thermodynamic fundamentals energy of balances
12.2 Energy balance and first principle of thermodynamic
12.3 Balance of enthalpy and its properties
12.4 Heating value, enthalpy of combustion, and apparent enthalpy of formation
12.5 Effect of temperature on enthalpy and adiabatic flame temperature
12.6 Application of energy balances to thermochemical processes
12.6.1 Energy assessment of thermochemical processes
12.6.2 Energy balances of thermochemical processes
12.7 Other considerations
12.7.1 Effect of biomass drying
12.7.2 Effect of the introduction of inert gas
12.7.3 Estimation of heat losses
12.8 Questions
References
Chapter 13 Chemical equilibrium in thermochemical processes
Abstract
Keywords
Acknowledgments
13.1 Chemical equilibrium and Gibbs free energy
13.2 Stoichiometric equilibrium models
13.3 Non-stoichiometric equilibrium models
13.4 Resolution of mass and energy balances considering equilibrium calculation
13.4.1 Simulation of the gasification of biomass with stoichiometric equilibrium models
13.4.2 Simulation of the gasification of biomass with non-stoichiometric equilibrium models
13.4.3 Maximum char yield from cellulose pyrolysis
13.4.4 Adiabatic flame temperature with dissociation
13.5 Carbon deposition boundary during oxygen and steam gasification
13.5.1 Carbon deposition boundary
13.5.2 Adiabatic equilibrium calculations for woody biomass air gasification
13.5.3 Adiabatic equilibrium calculations for woody biomass steam gasification
13.6 Questions
References
Chapter 14 Phase equilibrium in thermochemical systems
Abstract
Keywords
14.1 Introduction
14.2 Vapor liquid phase equilibria modeling
14.3 Thermophysical properties
14.4 Design of surrogate mixtures for VLE
14.5 Published VLE models
14.6 Questions
References
Chapter 15 Hydrodynamics and thermochemical reactors design
Abstract
Keywords
15.1 Fluidization regimes
15.2 Packet beds
15.3 Fluidized bed
15.3.1 Geldart particle fluidization classification
15.3.2 Minimum fluidization velocity
15.4 Circulating bed
15.5 Spouted beds
15.6 Rotary kilns
15.7 Auger reactors
15.8 Sizing thermochemical reactors
15.9 Questions
References
Chapter 16 Biomass thermo-chemical products
Abstract
Keywords
16.1 Characterization of solid product (char)
16.1.1 Elemental analysis
16.1.2 Fourier transform infrared spectroscopy (FTIR)
16.1.3 X-ray diffraction (XRD)
16.1.4 13C NMR
16.1.5 High-resolution mass spectroscopy (HRMS)
16.1.6 Py-GC/MS
16.1.7 Raman spectroscopy
16.1.8 Benzene polycarboxylic acids (BPCA)
16.1.9 Scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS)
16.1.10 Transmission electron microscopy (TEM)
16.1.11 Extended X-ray absorption fine structure (EXAFS)
16.1.12 Electron spin resonance spectroscopy (ESR)
16.1.13 Surface area analysis
16.1.14 Mercury intrusion porosimetry (MIP)
16.1.15 Small-angle X-ray scattering (SAXS)
16.1.16 Inductively coupled plasma spectroscopy (ICP)
16.1.17 X-ray photoelectron spectroscopy (XPS)
16.2 Characterization of liquid products
16.2.1 Water content
16.2.2 Quantification of independent compounds
16.2.3 Elemental analysis
16.2.4 Hydrolysable sugars
16.2.5 Total carbohydrates
16.2.6 Pyrolytic lignin
16.2.7 Gel permeation chromatography
16.2.8 Quantification of functional groups
16.2.9 Weak acids and phenols
16.2.10 Total phenols
16.2.11 Measurement of functional groups using spectroscopic methods
16.2.12 Nuclear magnetic resonance spectroscopy
16.2.13 Fourier transform infrared
16.2.14 UV-fluorescence
16.2.15 Gas chromatography—Mass spectroscopy
16.3 Characterization of gases
16.3.1 Gas chromatography
16.4 Questions
References
Chapter 17 Thermochemical biorefineries
Abstract
Keywords
17.1 Thermochemical products platforms
17.1.1 Syngas platform
17.1.2 Biochar platform
17.1.3 Bio-oil platform
17.2 Existing infrastructure
17.3 Synthesis and technology integration
17.3.1 Synthesis of bio-refineries
17.4 Questions
References
Index

Manuel Garcia-Perez

Manuel Garcia-Perez got his BSc in Chemical Engineering and his first master in Process Engineering from the Oriente’s University in Cuba. He got his MSc and his PhD from Laval University in Quebec, Canada. After completing his PhD he did two post-doctoral assignments at the University of Georgia in US and at Monash University in Australia. He is currently a full professor and chair of the Biological Systems Engineering department at Washington State University. Dr. Garcia-Perez is associate editor of Biomass and Bioenergy, and reviewer editor of the Journal of Analytical and Applied pyrolysis. He also served for six years at the USDA-DOE Biomass research and development technical advisory committee. Dr. Garcia-Perez has made contributions to advance our understanding of biomass thermochemical reactions, the chemistry of pyrolysis-oils and carbonaceous materials. So far, he has published more than 160 peer reviewed publications.

Affiliations and expertise

Department Chair and Professor, Department of Biological Systems Engineering, Washington State University, Pullman, WA, USA

Farid Chejne-Janna

Farid Chejne-Janna is a Physicist and Mechanical Engineer and Doctor in Engineer, specific area related to Energy System, he is a titular Professor of Universidad Nacional de Colombia, Adjunct Professor of Washington State University in United State, Member of Number of the Academia Colombiana de Ciencias Exactas, Físicas y Naturales. He has several research works related to mathematical modelling at different scales of thermochemical processes (drying, pelletizing, pyrolysis slow and fast, torrefaction, gasification and combustion) and other physical phenomena, several studies related to energy efficiency and with thermal equipment design. His scientific contribution is highlighted by the publication of more than 100 scientific articles in high-impact journals, he has 5 patents, 8 prototypes and around 10 books. His scientific contribution has earned him multiple recognitions in various areas of science and industry, among which stands out the Medal of Merit and Prize for Academic Excellence from the Universidad Nacional of Colombia, Scientific Talent from the Universidad Pontificia Bolivariana and Medellín Research Award in Colombia.

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