Extraction processes are essential steps in numerous industrial applications from perfume over pharmaceutical to fine chemical industry. Nowadays, there are three key aspects in industrial extraction processes: economy and quality, as well as environmental considerations. This book presents a complete picture of current knowledge on green extraction in terms of innovative processes, original methods, alternative solvents and safe products, and provides the necessary theoretical background as well as industrial application examples and environmental impacts. Each chapter is written by experts in the field and the strong focus on green chemistry throughout the book makes this book a unique reference source. This book is intended to be a first step towards a future cooperation in a new extraction of natural products, built to improve both fundamental and green parameters of the techniques and to increase the amount of extracts obtained from renewable resources with a minimum consumption of energy and solvents, and the maximum safety for operators and the environment.
Table of Contents:
Preface XIII
List of Contributors XV
1 Green Extraction: From Concepts to Research, Education, and Economical Opportunities 1
Farid Chemat, Natacha Rombaut, Anne-Sylvie Fabiano-Tixier, Jean T. Pierson, and Antoine Bily
1.1 Introduction 1
1.2 Orange Fruit is not Limited to Produce Only Juice? 5
1.3 Chemistry of Natural Products 9
1.3.1 Primary Metabolites 9
1.3.1.1 Glucides 9
1.3.1.2 Lipids 10
1.3.1.3 Amino Acids and Proteins 10
1.3.2 Secondary Metabolites 12
1.3.2.1 Terpenoids 12
1.3.2.2 Alkaloids 14
1.3.2.3 Polyphenols 14
1.4 From Metabolites to Ingredients 17
1.5 Green Extraction from Research to Teaching 22
1.5.1 Principle: Innovation by Selection of Varieties and Use of Renewable Plant Resources 28
1.5.2 Principle: Use of Alternative Solvents and Agro Solvent 28
1.5.3 Principle: Production of Coproducts Instead ofWaste to Include Biorefinery 29
1.5.4 Principle: Prioritizing a Non-denatured and Biodegradable Extract without Contaminant 29
1.6 Conclusions and Perspective 29
References 30
2 Process Engineering and Product Design for Green Extraction 37
Simon Both, Reinhard Ditz, Martin Tegtmeier, Urban Jenelten, and Jochen Strube
2.1 Market and Market Development 37
2.2 Regulatory Framework 38
2.3 Systematic Apparatus and Process Design 39
2.3.1 Design of Experiments 40
2.3.2 Graphical Calculation Methods 40
2.3.3 Physicochemical Modeling 41
2.3.4 Approaches for Description of Diffusion 45
2.3.4.1 Maxwell-Stefan Approach 46
2.3.4.2 Calculation of Diffusion Coefficients 48
2.3.4.3 Thermodynamic Factor 49
2.3.4.4 Determination of Activity Coefficients 49
2.3.4.5 Proof of Principle 49
2.4 Model-Based Realization: Apparatus and Process Design 50
2.4.1 Quantification of Determining Factors 52
2.4.2 Proof of Principle – Process Optimization 53
2.4.3 Proof of Principle – Cost-Driven Decision 53
2.5 Extract Purification 54
2.5.1 Modeling Approaches 56
2.5.2 Scale-Up and Mini-plant 56
2.6 Total Process Development and Design 62
2.7 Conclusions and Summary 65
Acknowledgments 66
References 66
3 Tailor-Made Production of Plants for Green Extraction 71
Hansjoerg Hagels
3.1 Introduction 71
3.2 Sustainable Processes 72
3.2.1 Social Sustainability 73
3.2.2 Environmental Sustainability 74
3.2.3 Economic Sustainability 75
3.3 Production Technology 75
3.3.1 Choice of Cultivation Location 75
3.3.2 Crop Rotation 78
3.3.3 Fertilization 79
3.3.4 Organic Farming 82
3.4 Seed and Seed Stock 84
3.4.1 Breeding 84
3.4.2 Seed 88
3.4.3 Vegetative Propagation 88
3.4.4 Stock Maintenance 89
3.4.4.1 Diseases 89
3.4.5 Pests 90
3.4.5.1 Weed Control 90
3.4.6 Harvesting Technology 91
3.4.7 Purification of Harvest 91
3.4.8 Mechanical Treatment 91
3.4.9 Thermal Treatment 91
3.4.9.1 Natural Drying 92
3.4.9.2 Artificial Drying 92
3.5 Quality Criteria 92
3.5.1 Quality Management 92
3.5.2 Quality Control 95
Glossary and Abbreviations 96
References 96
Further Reading 99
4 Mass Transfer Enhancement for Solid–Liquid Extractions 101
Simon Both, Jochen Strube, and Giancarlo Cravatto
4.1 Introduction 101
4.2 State of the Art Solid-Liquid Extraction 102
4.2.1 Batch Processes 105
4.2.2 Continuous Processes 106
4.2.3 Hydro- and Steam Distillation 109
4.2.4 Alembic Distillation 111
4.2.5 Mechanical Expression (Extrusion) 112
4.3 Enhancement of Solid–Liquid Extraction Processes 115
4.3.1 Microwave-Assisted Extraction (MAE) 115
4.3.2 Ultrasound-Assisted Extraction (UAE) 118
4.3.3 Turbo Extraction 119
4.4 Example Processes for Solid–Liquid Extraction Enhancement 122
4.4.1 Extraction of Polyphenols from Black Tea – Conventional and Ultrasound-Assisted Extraction 122
4.4.1.1 Material and Methods 123
4.4.1.2 Equipment Concepts 126
4.4.1.3 Equilibrium Line by Multistage Maceration and Total Extraction 127
4.4.1.4 Mass Transport Kinetics 130
4.4.1.5 Particle Size Distribution 131
4.4.1.6 SEM Measurements – Cell Disruption 132
4.4.1.7 Conclusions 132
4.4.2 Pilot Scale UAE of Clove Buds in Batch and Flow Reactors 134
4.4.2.1 Experimental Methods and Reactors 135
4.4.2.2 Results and Discussion 137
4.4.2.3 Conclusions 139
4.4.3 UAE and MAE of Lipids from Microalgae 139
4.4.3.1 Experimental Methods and Equipments 139
4.4.3.2 Conclusions 141
4.5 Conclusion 141
Symbols 142
References 142
5 Fundamentals of Process-Intensification Strategy for Green Extraction Operations 145
Tamara Allaf and Karim Allaf
5.1 Process-Intensification Strategy PI-S from High Capacity to High Controlled Quality Industrial Manufacturing 145
5.2 What Does “Intensified Industrial Manufacturing” Mean? 145
5.2.1 Unit Operation Performance 146
5.2.2 Final Product Quality 146
5.2.3 Equipment Reliability 147
5.3 Intensification Strategy as a Pluridimensional Approach 148
5.3.1 Objectives of Intensification Strategy 148
5.3.2 Specific Case of Food Industry 148
5.3.3 PI-S as a Continual Progressing-Development Strategy 148
5.4 Fundamentals for Starting Basis Analyses 149
5.4.1 Intensification Procedure 149
5.4.1.1 Intensification Cycle 149
5.4.1.2 Multi-cycle Intensification Procedure 150
5.4.1.3 Intensification Charter 150
5.4.2 Specificities of Instant Controlled Pressure DIC Drop in Process Intensification Strategy PI-S 151
5.4.2.1 Introduction 151
5.4.2.2 Transfer Phenomena in Instantaneous Controlled Pressure Drop DIC Treatment 152
5.4.2.3 DIC – Texturing 155
5.4.3 Mass Transfer by Permeability 156
5.5 Processes of Extraction 158
5.5.1 Extraction of Volatile Compounds 158
5.5.1.1 Kinetics 159
5.5.1.2 Intensification of Essential Oil Extraction 161
5.5.2 Case of Solvent extraction 162
5.5.2.1 Introduction 162
5.5.2.2 Extraction Process Issues 162
5.5.2.3 Kinetic Modeling 166
5.5.3 Conclusion: Process Intensification Strategy: How to Use PI-S Solvent Extraction Processes? 168
5.6 Conclusion 170
References 170
6 Panorama of Sustainable Solvents for Green Extraction Processes 173
Iraj Koudous,Werner Kunz, and Jochen Strube
6.1 Introduction 173
6.2 Thermodynamic Models of Mixing and Dissolving 176
6.2.1 UNIFAC and Modified UNIFAC 176
6.2.2 The Hansen Solubility Parameters 178
6.2.3 COSMO and COSMO-RS 180
6.2.3.1 Example 1: Mutual Solubility of Acetone with Benzene, Chloroform, and Carbon disulfide 183
6.2.3.2 Example 2: Solubility Screening for Indigo 184
6.3 Solvent Selection for Green Solid–Liquid Extraction 187
6.3.1 General Green Solvent Ranking with COSMO-RS 188
6.3.2 Concrete Example: Solid–Liquid Extraction of Carnesol and Carnosic Acid from Sage 188
6.3.3 Experimental Validation of COSMO-RS Solvent Ranking 192
6.3.4 Conclusion 192
6.4 Alternative Solvents for Green Extraction 194
6.4.1 Ionic Liquids 194
6.4.2 Low-Transition-Temperature Mixtures and Deep Eutectic Solvents 196
6.4.3 Ionic Liquids Screening with COSMO-RS 197
6.5 Purification Strategies of Natural Products 199
6.5.1 Databased and Calculated Physicochemical Properties 204
6.5.2 Feed Characterization 213
6.5.2.1 Conceptual Process Design 216
6.5.2.2 Modeling Depths and Feed Characterization Approach 219
6.5.2.3 System 1: Vanillin 223
6.5.2.4 Potential Unit Operations for Product Purification 223
6.5.2.5 Data Evaluation 225
6.5.2.6 Model-Based Process Design and Calculation of Separation Costs 225
6.5.2.7 Separation Cost Estimation 228
6.5.2.8 System 2: Tea Aroma 228
6.5.2.9 Data for Potential Unit Operation 228
6.5.2.10 Process Design and Cost Estimation 229
6.5.2.11 Discussion and Conclusions 230
Symbols 231
Greek Letters 232
Indices 232
References 232
7 Water as Green Solvent for Extraction of Natural Products 237
Loïc Petigny, Mustafa Zafer Özel, Sandrine Périno, Joël Wajsman, and Farid Chemat
7.1 Introduction 237
7.2 Maceration 239
7.2.1 Principle and Process 239
7.2.2 Applications 240
7.3 Subcritical Water Extraction 243
7.3.1 Principle and Process 243
7.3.2 Applications 245
7.4 Enzymatic Assistance 248
7.4.1 Principles and Process 248
7.4.2 Applications 249
7.5 Micellar Extraction 251
7.5.1 Principle and Process 251
7.5.2 Applications 252
7.6 Hydrotropes 255
7.6.1 Principles and Process 255
7.6.2 Applications 256
7.7 Conclusion 259
References 260
8 Coverage Exploitation of By-Products from the Agrofood Industry 265
Carlos A. Ledesma-Escobar and María D. Luque de Castro
8.1 Introduction 265
8.2 Treatments for Safe Disposal/Exploitation of Agrofood Wastes or Residues 265
8.2.1 Physical Processes 266
8.2.2 Physicochemical Processes 267
8.2.3 Advanced Oxidation Processes 267
8.2.4 Thermal Processes 268
8.2.5 Biological Treatments 270
8.3 Exploitation of By-products from Olive Trees and Olive Oil Production 271
8.3.1 Generalities 271
8.3.2 Exploitation of Alpechín 277
8.3.3 Overall Use of Either Alperujo or Orujo 278
8.3.4 Partial Use of Either Alpechín or Alperujo 279
8.3.5 Olive Leaf Exploitation 280
8.3.6 Foreseeable/Desirable Future Uses of Olive Tree–Olive Oil Wastes 280
8.4 Exploitation of By-products from Vineyards and Wine Production 283
8.4.1 Generalities 283
8.4.2 Types and Characteristics of Vineyard Residues 286
8.4.3 Present and Potential Exploitation of Vineyard Residues 286
8.4.4 Types and Characteristics ofWine Residues 288
8.4.5 Present and Potential Exploitation ofWine Residues: Overall and Partial Exploitation 288
8.5 Exploitation of By-products from the Citrus Juice Industry 291
8.5.1 Generalities 291
8.5.2 Uses and Potential Applications of Bioactive Compounds from Citrus Residues 293
8.5.3 Potential Exploitation of Citrus Residues for Energy Production 296
8.5.4 Other Overall and Partial Uses of Citrus Residues 297
Acknowledgments 297
List of Abbreviations 298
References 298
9 Selective Extraction from Food Plants and Residues by Pulsed Electric Field 307
Eugene Vorobiev and Nikolai Lebovka
9.1 Introduction 307
9.2 Basics of PEF-Assisted Extraction 308
9.3 Application of PEF for Different Food Plants and Residues 310
9.3.1 Sugar Beets 310
9.3.2 Red Beets 313
9.3.3 Chicory Roots 316
9.3.4 Apples 317
9.3.5 Grapes 318
9.3.6 Other Fruits and Vegetables 319
9.3.7 Egg Yolk 320
9.3.8 Bio-suspensions and Yeasts 320
9.3.9 Microalgae 321
9.3.10 Rhizomes 323
9.3.11 Bones 323
9.3.12 Eggshell 324
9.3.13 Leaves 324
9.3.14 Herbs 324
9.3.15 Ginseng 325
9.3.16 Peels 325
9.3.17 Mushrooms 325
9.3.18 Juices and Juice-Based Beverages 326
9.4 Conclusions 327
Acknowledgments 327
References 327
10 Green Extraction of Artemisinin fromArtemisia annua L 333
Alexei A. Lapkin
10.1 Introduction 333
10.2 Extraction Technologies for Isolation of Artemisinin from A. annua 333
10.2.1 Industrial Extraction Processes 336
10.2.2 Cleaner and Intensified Processes for Extraction of Artemisinin 339
10.2.2.1 Innovative Process Conditions for Extraction 339
10.2.2.2 Alternative Solvents for Extraction of Artemisinin 340
10.3 Innovation in Artemisinin Purification 346
10.3.1 Hybrid Adsorption–Crystallization Separation 346
10.3.2 Column and HPLC Chromatography 347
10.3.3 Countercurrent Chromatography 348
10.4 Analysis of Artemisinin and Co-metabolites 348
10.5 Conclusions and Outlook 350
References 351
Index 357
About the Author :
Farid Chemat is a full Professor of Chemistry at Avignon University (France), Director of GREEN Extraction Team (alternative extraction techniques and solvents), co-director of ORTESA LabCom research unit Naturex-UAPV, and scientific coordinator of "France Eco-Extraction" dealing with dissemination of research and education on green extraction technologies. Born in 1968, he received his PhD degree in process engineering from the Institut National Polytechnique de Toulouse-France in 1994. After periods of postdoctoral research work with Prolabo-Merck (1995-1997), he spent two years (1997-1999) as a senior researcher at the University of Wageningen (The Netherlands). In 1999, he moved to the University of La Réunion (France DOM) as an assistant professor and since 2006 holds the position of Professor at the University of Avignon (France). His main research interests are focused on innovative and sustainable extraction techniques, protocols and solvents (especially microwave, ultrasound and bio-based solvents) for food, pharmaceutical, fine chemistry, biofuel, and cosmetic applications. His research activity is documented by more than 140 scientific peer-reviewed papers, 9 books and 7 patents.
Jochen Strube is a full Professor of Chemical and Biotechnology Engineering and Director of the Institute for Separation and Process Technology at Clausthal University of Technology (Germany). Together with Hansjörg Hagels from Boehringer Ingelheim he currently leads the German working group of industry and academics for "Plant-based Extraktion -- Products and Process" of ProcessNet at Dechema e.V. Frankfurt am Main. Born in 1965, he received his Dr.-Ing. (1992) and Habilitation/"venia legendi" (2000) degree in Chemical Engineering at the University of Dortmund. From 1999 - 2006 he worked for Bayer AG Leverkusen, Germany. Since 2006 he has been Director of the Institute for Separation and Process Technology in Clausthal. His main research interests are focused on predictive model-based design of separation processes for complex mixtures such as plant-based extracts or fermentation broths and validation with mini-plant technology. Under his initiative the institute was re-directed with a fully equipped mini-plant technology under ATEX for industrial applications of higher value products in regulated environments like pharmaceutics, biologics, botanics, cosmetics, flavors, nutrition and nutraceuticals etc. His research activity is summarized by over 130 scientific peer-reviewed papers, 9 books and 6 patents.
