Series Preface ............................................... xiii
Preface ........................................................ xv
List of Contributors ......................................... xvii
1 An Overview of Biorefinery Technology ........................ 1
Mahmoud A. Sharara, Edgar C. Clausen and Danielle Julie
Carrier
1.1 Introduction ............................................ 1
1.2 Feedstock ............................................... 2
1.3 Thermochemical Conversion of Biomass .................... 4
1.3.1 Fast Pyrolysis and Hydrothermal Liquefaction ..... 4
1.3.2 Gasification ..................................... 6
1.4 Biochemical Conversion ................................. 10
1.4.1 Pretreatment .................................... 11
1.4.2 Enzymatic Hydrolysis ............................ 12
1.4.3 Fermentation .................................... 13
1.4.4 Pre-Pretreatment ................................ 14
1.5 Conclusion ............................................. 15
Acknowledgements ............................................ 15
References .................................................. 16
2 Overview of the Chemistry of Primary and Secondary Plant
Metabolites ................................................. 19
Chantal Bergeron
2.1 Introduction ........................................... 19
2.2 Primary Metabolites .................................... 20
2.2.1 Saccharides (Sugars) ............................ 20
2.2.2 Lignin .......................................... 22
2.2.3 Amino Acids, Peptides, and Proteins ............. 22
2.2.4 Fatty Acids, Lipids ............................. 23
2.2.5 Organic Acids ................................... 23
2.3 Secondary Metabolites .................................. 23
2.3.1 Simple Phenols and Phenolic Acids ............... 24
2.3.2 Polyphenols ..................................... 24
2.3.3 Terpenes ........................................ 31
2.3.4 Alkaloids ....................................... 34
2.4 Stability of Isolated Compounds ........................ 35
2.5 Conclusion ............................................. 35
References .................................................. 35
3 Separation and Purification of Phytochemicals as
Co-Products in Biorefineries ................................ 37
Hua-Jiang Huang and Shri Ramaswamy
3.1 Introduction ........................................... 37
3.2 Conventional Separation Approaches ..................... 39
3.2.1 Steam Distillation .............................. 39
3.2.2 Conventional Solid-Liquid Extraction ............ 40
3.2.3 Ultrasound-Assisted Extraction .................. 42
3.2.4 Microwave-Assisted Extraction ................... 43
3.2.5 Pressurized Subcritical Liquid Extraction ....... 44
3.3 Supercritical Fluid Extraction ......................... 45
3.4 Separation and Purification of Phytochemicals from
Plant Extracts and Dilute Solution in Biorefineries .... 46
3.4.1 Liquid-Liquid Extraction ........................ 46
3.4.2 Membrane Separation ............................. 48
3.4.3 Molecular Distillation .......................... 48
3.5 Summary ................................................ 49
References .................................................. 51
4 Phytochemicals from Corn: a Processing Perspective .......... 55
Kent Rausch
4.1 Introduction: Corn Processes ........................... 55
4.1.1 Dry Milling ..................................... 56
4.1.2 Wet Milling ..................................... 57
4.1.3 Alternative Wet Milling Processes ............... 57
4.1.4 Dry Grind ....................................... 59
4.1.5 Alternative Dry Grind Processes ................. 61
4.1.6 Nixtamalization ................................. 62
4.2 Phytochemicals Found in Corn ........................... 63
4.2.1 Introduction .................................... 63
4.2.2 Phytosterols .................................... 65
4.2.3 Carotenoids ..................................... 67
4.2.4 Polyamine Conjugates ............................ 67
4.3 Corn Processing Effects on Phytochemical Recovery ...... 71
4.3.1 Research with Corn Fiber Obtained from Wet
Milling and Dry-Grind-Based Processes ........... 72
4.3.2 Research on Phytochemicals and the
Nixtamalization Process ......................... 82
4.4 Conclusions ............................................ 86
References .................................................. 87
5 Co-Products from Cereal and Oilseed Biorefinery Systems ..... 93
Nurhan Turgut Dunford
5.1 Introduction ........................................... 93
5.2 Cereals ................................................ 95
5.2.1 Wheat ........................................... 95
5.2.2 Barley ......................................... 100
5.2.3 Sorghum ........................................ 101
5.3 Oilseed Biorefineries ................................. 102
5.3.1 Oil- and Oilseed-Based Products ................ 104
5.3.2 Industrial Products ............................ 106
5.4 Conclusions ........................................... 108
References ................................................. 109
6 Bioactive Soy Co-Products .................................. 117
Arvind Kannan, Srinivas Rayaprolu and Navam Hettiarachchy
6.1 Introduction .......................................... 117
6.1.1 Industrial Agricultural Biomass ................ 118
6.1.2 Processing of Co-and Byproducts ................ 119
6.1.3 Value Addition and Sustainability .............. 119
6.2 Co-Products Obtained from Industrial Biorefineries .... 119
6.2.1 Cereal-and Legume-Based Industrial
Co-Products .................................... 119
6.2.2 Legume Co-Products - Soy ....................... 119
6.3 Technologies Used to Extract Co-Products .............. 122
6.3.1 Extractive Distillation ........................ 122
6.3.2 Adsorption ..................................... 122
6.3.3 Membrane Separation ............................ 123
6.3.4 Supercritical and Subcritical Fluid
Extractions .................................... 123
6.4 Bioactivities and Nutritional Value in Biorefinery
Co-Products ........................................... 123
6.4.1 Anti-Disease Properties ........................ 124
6.4.2 Food Products .................................. 125
6.4.3 Alternative Medicine ........................... 126
6.5 Modern Technologies for Efficient Delivery -
Nanoencapsulation ..................................... 126
6.5.1 Issues - Stability, Bioavailability and
Toxicity ....................................... 126
6.6 Conclusion and Future Prospects ....................... 127
References ................................................. 128
7 Production of Valuable Compounds by Supercritical
Technology Using Residues from Sugarcane Processing ........ 133
Juliana M. Prado and M. Angela A. Meireles
7.1 Introduction .......................................... 133
7.2 Supercritical Fluid Extraction of Filter Cake ......... 135
7.2.1 Supercritical Fluid Extraction ................. 135
7.2.2 Extraction of Long-Chain Fatty Alcohols from
Filter Cake .................................... 135
7.3 Process Simulation for Estimating Manufacturing Cost
of Extracts ........................................... 138
7.3.1 Process Simulation ............................. 138
7.3.2 Manufacturing Cost ............................. 139
7.3.3 Manufacturing Cost Estimation of Sugarcane
Wax ............................................ 139
7.4 Hydrolysis of Bagasse with Sub/Supercritical Fluids ... 143
7.4.1 Biomass Conversion ............................. 143
7.4.2 Polysaccharide Hydrolysis ...................... 144
7.4.3 Hydrothermolysis ............................... 144
7.4.4 Hydrothermolysis of Sugarcane Bagasse .......... 147
7.5 Conclusions ........................................... 148
Acknowledgements ........................................... 148
References ................................................. 148
8 Potential Value-Added Co-products from Citrus Fruit
Processing ................................................. 153
John A. Manthey
8.1 Introduction .......................................... 153
8.2 Fruit Processing and Byproduct Streams ................ 154
8.2.1 Polysaccharide Compositions of Dried Peel
Pellets and Peel Molasses ...................... 156
8.2.2 Phytochemical Compositions of Dried Peel
Pellets and Peel Molasses ...................... 156
8.3 Polysaccharides as Value-Added Products ............... 163
8.3.1 Dietary Fiber .................................. 163
8.3.2 Peel Hydrolysis and Ethanol Production ......... 164
8.3.3 Speciality Pectins ............................. 164
8.4 Phytonutrients as Value-Added Products ................ 165
8.4.1 Flavonoid Glycosides ........................... 165
8.4.2 Polymethoxylated Flavones (PMFs) ............... 166
8.4.3 Hydroxycinnamates .............................. 169
8.5 Fermentation and Production of Enhanced Byproducts .... 170
8.6 Conclusion ............................................ 171
References ................................................. 171
9 Recovery of Leaf Protein for Animal Feed and High-Value
Uses ....................................................... 179
Bryan D. Bals, Bruce E. Dale and Venkatesh Balan
9.1 Introduction .......................................... 179
9.2 Methods of Separating Protein ......................... 181
9.2.1 Mechanical Pressing ............................ 181
9.2.2 Aqueous Extraction ............................. 182
9.2.3 Leaf/Stem Separation ........................... 183
9.2.4 Post-Fermentation Recovery ..................... 184
9.3 Protein Concentration ................................. 185
9.3.1 Steam Injection ................................ 185
9.3.2 Acid Precipitation ............................. 186
9.3.3 Ultrafiltration ................................ 186
9.3.4 Spray Drying ................................... 187
9.4 Uses for Leaf Protein ................................. 187
9.4.1 Leaf Protein as Animal Feed .................... 187
9.4.2 Leaf Protein for Human Consumption ............. 188
9.4.3 Leaf Protein for Enzyme Production ............. 188
9.4.4 Leaf Protein for Bio-Based Chemicals ........... 189
9.5 Integration with Biofuel Production ................... 189
9.5.1 Advantages of Biofuel Integration .............. 189
9.5.2 Analysis of Integration Economics .............. 190
9.6 Conclusions ........................................... 192
References ................................................. 192
10 Phytochemicals from Algae .................................. 199
Liam Brennan, Anika Mostaert, Cormac Murphy and Philip
Owende
10.1 Introduction .......................................... 199
10.1.1 Phytochemical Recovery from Biofuel-Destined
Algal Biomass .................................. 200
10.1.2 Algae Biomass Utilisation ...................... 202
10.2 Commercial Applications of Algal Phytochemicals ....... 203
10.2.1 Proteins ....................................... 205
10.2.2 Lipids (i.e. Polyunsaturated Fatty Acids) ...... 205
10.2.3 Vitamins ....................................... 208
10.2.4 Carotenoids .................................... 209
10.2.5 Phycobiliproteins .............................. 211
10.2.6 Phycocolloids .................................. 212
10.2.7 Phycosupplements ............................... 213
10.3 Production Techniques for Algal Phytochemicals ....... 213
10.3.1 Microalgae Biomass Production .................. 213
10.3.2 Macroalgae Biomass Production .................. 216
10.3.3 Phytochemical-Directed Algae Production
Techniques ..................................... 218
10.3.4 Biorefmery Concept ............................. 219
10.4 Extraction Techniques for Algal Phytochemicals ........ 220
10.4.1 Pre-Treatment Processes ........................ 220
10.4.2 Solvent Extraction ............................. 221
10.4.3 Supercritical Fluid Extraction ................. 221
10.4.4 Expanded Bed Adsorption Chromatography ......... 221
10.4.5 Pressurised Liquid Extraction .................. 222
10.4.6 Unit Process in Commercial Phytochemical
Extraction ..................................... 222
10.5 Metabolic Engineering for Synthesis of Algae-
Derived Compounds ..................................... 224
10.5.1 Manipulation of Culture Conditions ............. 224
10.5.2 Nuclear and Chloroplast Transformation ......... 225
10.5.3 Expression of Recombinant Proteins ............. 226
10.5.4 Augmented Fatty Acid Biosynthesis .............. 226
10.5.5 Trophic Conversion of Microalgae ............... 227
10.5.6 Re-Engineering Light-Harvesting Antenna
Complexes ...................................... 227
10.6 Phytochemical Market Evolution ........................ 228
10.7 Conclusions ........................................... 228
Acknowledgement ............................................ 230
References ................................................. 230
11 New Bioactive Natural Products from Canadian Boreal
Forest ..................................................... 241
François Simard, André Pichette and Jean Legault
11.1 Introduction .......................................... 241
11.2 Identification of New Bioactive Natural Products
from Canadian Boreal Forest ........................... 243
11.2.1 Selection of Plant Species and Bio Guided
Isolation Process .............................. 243
11.2.2 Diarylheptanoids from the Inner Bark Betula
Papyrifera ..................................... 244
11.2.3 Labdane Diterpenes from Larix Laricina ......... 245
11.2.4 Phenolic Compounds from Populus Tremuloïdes
Buds ........................................... 246
11.2.5 Sesquiterpenes from Abies Balsamea ............. 248
11.3 Chemical Modification of Bioactive Natural Products
from the Canadian Boreal Forest ....................... 250
11.3.1 Glycosidation of Triterpenoids from Outer
Bark of B. papyrifera .......................... 251
11.4 Conclusion ............................................ 253
References ................................................. 254
12 Pressurized Fluid Extraction and Analysis of Bioactive
Compounds in Birch Bark .................................... 259
Michelle Co and Charlotta Turner
12.1 Introduction .......................................... 259
12.2 Qualitative Analysis of Birch Bark .................... 261
12.2.1 Antioxidant Assays ............................. 261
12.2.2 Antimicrobial Activity ......................... 265
12.2.3 Antitumour Activity ............................ 265
12.3 Quantitative Analysis of Bioactive Compounds in
Birch ................................................. 267
12.3.1 Terpenoids ..................................... 267
12.3.2 Carbohydrates .................................. 268
12.3.3 Flavonoids ..................................... 270
12.4 High-Performance Liquid Chromatography with Diode
Array, Electrochemical and Mass Spectrometric
Detection of Antioxidants ............................. 270
12.5 Extraction of Bioactive Compounds ..................... 272
12.5.1 Conventional Solid Liquid Extraction (SLE) ..... 272
12.5.2 Supercritical Fluid Extraction (SFE) ........... 273
12.5.3 Pressurized Fluid Extraction (PFE) ............. 273
12.6 Discussion and Future Perspectives .................... 278
Acknowledgements ........................................... 279
References ................................................. 279
13 Adding Value to the Integrated Forest Biorefinery with
Co-Products from Hemicellulose-Rich Pre-Pulping Extract .... 287
Abigail S. Engelberth and G. Peter van Walsum
13.1 Introduction .......................................... 287
13.1.1 Why Hemicellulose .............................. 288
13.1.2 Increased Revenue .............................. 289
13.1.3 Hemicellulose Possibilities .................... 289
13.2 Hemicellulose Recovery ................................ 289
13.2.1 Integration of Hemicellulose Extraction with
the Current Pulping Process .................... 289
13.2.2 Applications of Hot-Water Extraction ........... 294
13.3 Hemicellulose Conversion .............................. 295
13.3.1 Hydrolysis of Hemicellulose Oligomers .......... 295
13.3.2 Fermentation to Alcohols ....................... 295
13.3.3 Conversion of Extracts to Triacylglycerides
(TAGs) ......................................... 298
13.3.4 Hemicellulose Upgrading Via the Carboxylate
Platform ....................................... 299
13.3.5 Conversion to Tridecane ........................ 303
13.3.6 Fermentation to Commodity Chemicals ............ 304
13.4 Process Economics ..................................... 305
13.4.1 Integrating Extraction into an Existing Mill ... 305
13.4.2 Energy Cost for Extraction ..................... 305
13.5 Conclusion ............................................ 306
References ................................................. 306
14 Pyrolysis Bio-Oils from Temperate Forests: Fuels,
Phytochemicals and Bioproducts ............................. 311
Mamdouh Abou-Zaid and Ian M. Scott
14.1 Introduction .......................................... 311
14.2 Overview of Forest Feedstock .......................... 312
14.2.1 Residues ....................................... 312
14.2.2 Phytochemistry and Distribution of Feedstock ... 313
14.2.3 Bioactivities and Applications in Forestry ..... 313
14.3 Pyrolysis Technology .................................. 317
14.4 Prospects for Fuel Production ......................... 317
14.5 Chemicals in the Bio-Oil .............................. 318
14.6 Valuable Chemical Recovery Process .................... 320
14.6.1 Sugars ......................................... 320
14.6.2 Phenols ........................................ 321
14.7 Selected Phytochemicals from Pyrolysis Bio-Oils ....... 321
14.8 Other Products ........................................ 322
14.9 Future Prospects ...................................... 323
References ................................................. 323
15 Char from Sugarcane Bagasse ................................ 327
K. Thomas Klasson
15.1 Introduction .......................................... 327
15.2 Sugarcane Bagasse Availability ........................ 330
15.3 Thermal Processing in an Inert Atmosphere
(Pyrolysis) ........................................... 331
15.4 Technology for Converting Char to Activated Char ...... 332
15.5 Char and Activated-Char Characterization and
Implications for Use .................................. 333
15.6 Uses of Bagasse Char and Activated Char ............... 343
15.6.1 Fuel ........................................... 343
15.6.2 Soil Conditioning and Carbon Sequestration ..... 343
15.6.3 Environmental and Industrial Applications ...... 343
15.7 Conclusions ........................................... 345
References ................................................. 345
Index ......................................................... 351
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