Hemicellulose Biorefinery: A Sustainable Solution for Value Addition to Bio-Based Products and Bioenergy

Preface
About This Book
Contents
About the Editor
1: Hemicelluloses Role in Biorefinery Systems of Cellulosic Bioethanol, Particleboard, and Pulp and Paper Industries
	1.1 Introduction
	1.2 Hemicelluloses Valorization in the Cellulosic Bioethanol Production
		1.2.1 Hemicelluloses Recovery in 2G Bioethanol Process
	1.3 Hemicelluloses Valorization in the Pulp and Paper Industry
	1.4 Hemicelluloses Valorization in Particleboard Fabrication
	1.5 Challenges of Biological Aspects of Pentoses Fermentation of Lignocellulosic Hydrolysates Using Saccharomyces cerevisiae
		1.5.1 Yeast Engineering For Second Generation Bioethanol
			1.5.1.1 Xylose Fermentation
			1.5.1.2 Arabinose Fermentation
			1.5.1.3 Engineering Pentose Transports in S. cerevisiae Strains
	1.6 Yield Loss Through the Formation of Inhibitors During the Hydrolysis of Lignocellulose Materials
		1.6.1 Genetic Advances to Improve Yeast Tolerance to Lignocellulosic Hydrolysates
	1.7 Concluding Remarks
	References
2: Sustainable Biorefinery Processing for Hemicellulose Fractionation and Bio-based Products in a Circular Bioeconomy
	2.1 Introduction
	2.2 Processing and Fractionation of Biomass: Hydrothermal-High Pressure Pretreatment
	2.3 High Added Value Products from Hemicellulosic Fraction
		2.3.1 Films and Coatings
		2.3.2 Xylitol
		2.3.3 Xylooligosaccharides: Production and Market Potential
		2.3.4 Furfural and Its Derivatives
		2.3.5 Ethanol from Hemicelluloses: Fermentation of Hexoses and Pentoses
	2.4 Conclusion and Final Remarks
	References
3: Production of Hemicellulosic Sugars from Residual Lignocellulosic Biomass in an Integrated Small-Scale Biorefinery: Techno-...
	3.1 Introduction
	3.2 Heuristic Analysis
		3.2.1 Feedstock
		3.2.2 Biorefinery Design
		3.2.3 Preliminary Assessments
		3.2.4 Process Scale Selection
		3.2.5 Process Technologies Choice
		3.2.6 Evaluation of Product Competitors
		3.2.7 Process Modelling
		3.2.8 Application of the Heuristic Approach to the Case-Study
			3.2.8.1 Available Feedstock
			3.2.8.2 Biorefinery Design
			3.2.8.3 Technology Matureness Level
			3.2.8.4 Preliminary Assessments
			3.2.8.5 Process Scale and Scenario Selection
	3.3 Detailed Process Design and Simulation
		3.3.1 Process Modelling
			3.3.1.1 Drying and Milling
			3.3.1.2 Pre-treatment
			3.3.1.3 Enzymatic Hydrolysis
			3.3.1.4 Fermentation
			3.3.1.5 Ethanol Distillation and Dehydration
			3.3.1.6 Xylo-Oligosaccharides Purification
			3.3.1.7 Wastewater Treatment
			3.3.1.8 Anaerobic Digestion
			3.3.1.9 Combined Heat and Power Generation
		3.3.2 LCB Only
		3.3.3 Results
	3.4 Techno-Economic Assessment
		3.4.1 Methodology
		3.4.2 Results
	3.5 Life Cycle Assessment
		3.5.1 Goal and Scope
		3.5.2 Life Cycle Inventory
		3.5.3 Environmental Characterization
		3.5.4 Effect of the Use of Swine Manure (Wet Biomass)
	3.6 Legal Framework and Implementation Potential for Rural Areas
	3.7 Conclusions
	References
4: Composition and Chemical Structure of Hemicelluloses and Polysaccharides with Capability of Gel Formation
	4.1 Introduction
	4.2 Hemicelluloses
		4.2.1 Supramolecular Structure
		4.2.2 Xylans
		4.2.3 Glucomannans
		4.2.4 Hemicellulose-Lignin Complex
	4.3 Polysaccharides Capable of Forming Gels
		4.3.1 Pectic Substances and Pectin
			4.3.1.1 Pectin Structure
			4.3.1.2 Chemical Characteristics and Their Effects on Emulsifying Pectin Capacity
			4.3.1.3 Sources of Pectin and Extraction Method
		4.3.2 Xyloglucan
		4.3.3 Carrageenan
			4.3.3.1 Structure
	4.4 Conclusion
	References
Analytical Techniques Applied to Hemicellulose Structure and Functional Characterization
	5.1 Introduction
		5.1.1 Composition of Hemicelluloses
	5.2 Physical-Chemical Analytical Methods of Hemicelluloses
		5.2.1 Chemical Characterization
		5.2.2 High-Performance Liquid Chromatography (HPLC)
			5.2.2.1 Liquid-Solid or Adsorption Chromatography
			5.2.2.2 Liquid-Liquid or Partition Chromatography
			5.2.2.3 Liquid Chromatography with Chemically Bound Phase
			5.2.2.4 Ion-Exchange Chromatography
			5.2.2.5 Bio-affinity Chromatography
			5.2.2.6 Chiral Chromatography
			5.2.2.7 Exclusion Chromatography
		5.2.3 High-Performance Anion Exchange Chromatography (HPAEC)
		5.2.4 Infrared Spectroscopy
		5.2.5 X-Ray Techniques
		5.2.6 Nuclear Magnetic Resonance (NMR)
	5.3 Hemicellulose Bioactivity
	5.4 Concluding Remarks
	References
6: Chemical Modification Strategies for Developing Functionalized Hemicellulose: Advanced Applications of Modified Hemicellulo...
	6.1 Introduction
	6.2 Solubilization of Hemicellulose
		6.2.1 Solubilization of Hemicellulose in the Form of High and Low DP
			6.2.1.1 Alkaline Treatment Method
			6.2.1.2 Liquid Hot Water Treatment Method
			6.2.1.3 Organic Solvent Treatment Method
			6.2.1.4 Enzymatic Solubilization Process
		6.2.2 Solubilization of Hemicellulose in the Form of Monosaccharides
			6.2.2.1 Acid hydrolysis Method
			6.2.2.2 Steam Explosion Method
	6.3 Chemical Modifications of Hemicellulose
		6.3.1 Hemicellulose Esterification
			6.3.1.1 Acetylation
			6.3.1.2 Oleoylation
			6.3.1.3 Lauroylation
			6.3.1.4 Fluorination
			6.3.1.5 Crosslinking/Graft Copolymerization
		6.3.2 Etherification of Hemicellulose
			6.3.2.1 Methylation
			6.3.2.2 Carboxymethylation
			6.3.2.3 Benzylation
	6.4 Concluding Remarks
	References
Enzymatic Approach on the Hemicellulose Chain Structural Modification and the Main Enzymes Production and Purification
	7.1 Introduction
	7.2 Hemicellulose and Other Components in Biomass
	7.3 Hemicellulose Bioproducts
	7.4 Enzymatic Modifications of Xylan
	7.5 Xylanases Production from Fungi and Bacteria
	7.6 Improvement of Xylanase Production and Purification
	7.7 Biosynthesis of Xylan
	7.8 Concluding Remarks
	References
8: Hemicellulose Application for the Production of Bioplastics and Biomaterials
	8.1 Introduction
	8.2 Plastic
		8.2.1 Origin of Plastics and Their Importance for Society
		8.2.2 Negative Impacts Caused by an Irregular Plastics Disposal
	8.3 Bioplastics
		8.3.1 Origin of Bioplastics
		8.3.2 Bioplastic Composition and Structure
		8.3.3 The Bioplastics Market
		8.3.4 Emerging Technologies for Bioplastics Produced with Hemicellulose
			8.3.4.1 Importance of Plasticizer for Hemicellulose Films
			8.3.4.2 Development of Biomolecule Blends
				8.3.4.2.1 Compatibility and Miscibility
			8.3.4.3 Crosslinking Agents in Polymeric Chains
			8.3.4.4 Functional Biopackages
			8.3.4.5 Other Applications of Hemicellulose as a Biomaterial
	8.4 Concluding Remarks
	References
9: Oligosaccharides from Lignocellulosic Biomass and Their Biological and Physicochemical Properties
	9.1 Introduction
	9.2 Chemical Structure and Composition
	9.3 Properties of Oligosaccharides
		9.3.1 Physicochemical Properties
		9.3.2 Biological/Physiological Properties
	9.4 Production of Prebiotic Oligosaccharides
		9.4.1 Chemical Hydrolysis
			9.4.1.1 Dilute Acid Hydrolysis
			9.4.1.2 Autohydrolysis
			9.4.1.3 Alkaline Solubilization
		9.4.2 Enzymatic Hydrolysis
			9.4.2.1 β-Xylanases
			9.4.2.2 β-d-Mannanases
			9.4.2.3 Debranching Enzymes (Accessory Enzymes)
				9.4.2.3.1 α-Arabinofuranosidase
				9.4.2.3.2 α-Glucuronidase
				9.4.2.3.3 Galactosidase
			9.4.2.4 Synergy and Enzymatic Cocktails for the Production of Xylan/Mannan Oligosaccharides
		9.4.3 Industrial Production
	9.5 Conclusions and Future Perspectives
	References
Advances and New Perspectives in Prebiotic, Probiotic and Symbiotic Products for Food Nutrition and Feed
	10.1 Introduction
	10.2 Prebiotics
		10.2.1 Definition and Classification
		10.2.2 Mechanisms of Action
		10.2.3 Main Action Molecules
			10.2.3.1 Fructooligosaccharides
			10.2.3.2 Xylooligosaccharides
			10.2.3.3 Galactooligosaccharides
	10.3 Intestinal Microbiota
		10.3.1 Composition and Colonization of the Microbiota
		10.3.2 Importance of Intestinal Microbiota
		10.3.3 Microbiota and Diseases
	10.4 Probiotics
		10.4.1 Definition and Classification
		10.4.2 Mechanisms of Action
			10.4.2.1 Modulation of the Immune System
			10.4.2.2 Mucosal Barrier
			10.4.2.3 Inhibition of Pathogens
				10.4.2.3.1 Short-Chain Fatty Acids (SCFAs)
				10.4.2.3.2 Bacteriocins
		10.4.3 Probiotic Properties of Bifidobacterium and Lactobacillus
	10.5 Symbiotics
	10.6 Evaluation Models of Prebiotics, Probiotics, and Symbiotics
		10.6.1 Prebiotics
			10.6.1.1 ``In Vitro´´ Tests
			10.6.1.2 ``In Vivo´´ Tests
		10.6.2 Probiotics
			10.6.2.1 ``In Vitro´´ Tests
			10.6.2.2 ``In Vivo´´ Tests
		10.6.3 Symbiotics
			10.6.3.1 ``In Vitro´´ and ``in Vivo´´ Tests
	10.7 Conclusion and Future Perspectives
	References
Hemicellulose Sugar Fermentation: Hydrolysate Challenges, Microorganisms, and Value-Added Products
	11.1 Introduction
	11.2 Value-Added Products from Hemicellulose
	11.3 Biomass Resources of Hemicellulose
	11.4 Pretreatment Methods: Hemicellulose Hydrolysis and Degradation Products Formation
		11.4.1 Hemicellulose Hydrolysate Detoxification Methods
	11.5 Microorganisms Used in Hemicellulose Sugar Fermentation and Xylose Metabolism
	11.6 Improved Xylose-Fermenting Microorganisms by DNA Technology
	11.7 Conclusion
	References
12: Production of Platform Chemicals and High Value Products from Hemicellulose
	12.1 Introduction
	12.2 Furans
		12.2.1 Furfural
		12.2.2 Furfuryl Alcohol
			12.2.2.1 Two-Step Technology
			12.2.2.2 Single-Step One-Pot Process
	12.3 Polyols
		12.3.1 Xylitol
			12.3.1.1 Catalyst Precursor Structure
			12.3.1.2 Noble Metal-Based Catalysts
			12.3.1.3 Bimetallic Catalytic Systems
		12.3.2 Ethylene Glycol and Propylene Glycol
	12.4 Carboxylic Acids
		12.4.1 Levulinic Acid
			12.4.1.1 Xylose Direct Conversion
			12.4.1.2 Furans Conversion
		12.4.2 Lactic Acid
			12.4.2.1 Conversion of Trioses
			12.4.2.2 Pentoses Conversion
	12.5 Summary and Outlook
	References
13: Synthesis of Furan Compounds from Hemicelluloses
	13.1 Introduction
	13.2 Properties of Furfural
	13.3 Influencing Factors of Furfural Production
		13.3.1 Raw Material
		13.3.2 Solvent System
			13.3.2.1 Monophasic System
			13.3.2.2 Biphasic System
		13.3.3 Catalyst
			13.3.3.1 Homogeneous Catalyst
			13.3.3.2 Heterogenous Catalyst
		13.3.4 Temperature, Time, Heating Method and Additive
	13.4 Furfural Production
		13.4.1 Production of Furfural from Xylose
		13.4.2 Production of Furfural from Hemicellulose
		13.4.3 ``One-Pot´´ Method for Furfural Production from Lignocellulosic Biomass
		13.4.4 Two-Step Method for Furfural Production from Lignocellulosic Biomass
	13.5 The Formation Mechanism of Furfural
		13.5.1 Hydrolysis Mechanism of Hemicellulose
		13.5.2 Dehydration Mechanism of Xylose to Furfural
			13.5.2.1 Cyclic Mechanism for Furfural Formation from Xylose
			13.5.2.2 Acyclic Mechanism for Furfural Formation from Xylose
				13.5.2.2.1 Protonation of Ring Oxygen (O5)
				13.5.2.2.2 Protonation of C2-OH
			13.5.2.3 Mechanism of Furfural Formation from Xylose Catalyzed by Brønsted Acid and Lewis Acid
	13.6 Synthesis of 5-Hydroxymethylfurfural (5-HMF) from Hemicellulose
		13.6.1 Properties of 5-HMF
		13.6.2 Production of 5-HMF from Hemicellulose Derived Sugars
		13.6.3 Formation Mechanism of 5-HMF from Hexose
			13.6.3.1 Formation Mechanism of 5-HMF from Fructose
			13.6.3.2 Formation Mechanism of 5-HMF from Aldose
	References
14: Biomedical and Pharmaceutical Applications of Xylan and Its Derivatives
	14.1 Introduction
		14.1.1 Xylan
			14.1.1.1 Homoxylan
			14.1.1.2 Arabinoxylan
			14.1.1.3 Glucuronoxylan
			14.1.1.4 Glucuronoarabinoxylan or Arabinoglucuronoxylan
	14.2 Extraction of Xylan
	14.3 Xylan-Based Biorefineries
		14.3.1 Hydrolysis of Xylan
			14.3.1.1 Xylooligosaccharides Production by Physicochemical Hydrolysis
			14.3.1.2 Xylooligosaccharides Production by Enzymatic Hydrolysis
		14.3.2 Xylan Derivatives
			14.3.2.1 Xylan Ester
			14.3.2.2 Sulfated Xylan
			14.3.2.3 Xylan-Based Other Biorefinery Products
	14.4 Biomedical and Pharmaceutical Applications of Xylan Derivatives
		14.4.1 Xylan-Based Drug Delivery Systems
			14.4.1.1 Xylan-Based Films for Drug Delivery
		14.4.2 Xylan-Based Hydrogels for Drug Delivery
		14.4.3 Xylan-Based Microparticles and Nanoparticles for Drug Delivery
	14.5 Conclusions
	References
15: Hemicellulose-Based Delivery Systems: Focus on Pharmaceutical and Biomedical Applications
	15.1 Introduction
	15.2 Structure
	15.3 Sources
	15.4 Biodegradability and Biocompatibility of Hemicelluloses
	15.5 Gelation Mechanism of Hemicelluloses
	15.6 Applications
		15.6.1 Pharmaceutical Applications
			15.6.1.1 Hydrogels
				15.6.1.1.1 Hydrogels Using Chemically Modified Hemicellulose
				15.6.1.1.2 Hemicellulose-Containing Interpenetrating Network (IPN) Hydrogels
					Temperature-Responsive Hydrogels
					pH-Responsive Hydrogels
					Magnetic Field Responsive Hydrogels
					Photosensitive Hydrogels
					Electric-Responsive Hydrogels
					Nanoreinforced Hydrogels
					Hemicellulose-Reinforced Nanocellulose Hydrogels
			15.6.1.2 Films
			15.6.1.3 Nanocomposites
			15.6.1.4 Microparticles
		15.6.2 Biomedical Applications
			15.6.2.1 Wound Healing
			15.6.2.2 Tissue Engineering
	15.7 Conclusion and Future Perspectives
	References