Green Extraction of Natural Products

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.

• Preface XIIIList of Contributors XV1 Green Extraction: From Concepts to Research, Education, and Economical Opportunities 1Farid Chemat, Natacha Rombaut, Anne-Sylvie Fabiano-Tixier, Jean T. Pierson, and Antoine Bily1.1 Introduction 11.2 Orange Fruit is not Limited to Produce Only Juice? 51.3 Chemistry of Natural Products 91.3.1 Primary Metabolites 91.3.1.1 Glucides 91.3.1.2 Lipids 101.3.1.3 Amino Acids and Proteins 101.3.2 Secondary Metabolites 121.3.2.1 Terpenoids 121.3.2.2 Alkaloids 141.3.2.3 Polyphenols 141.4 From Metabolites to Ingredients 171.5 Green Extraction from Research to Teaching 221.5.1 Principle: Innovation by Selection of Varieties and Use of Renewable Plant Resources 281.5.2 Principle: Use of Alternative Solvents and Agro Solvent 281.5.3 Principle: Production of Coproducts Instead ofWaste to Include Biorefinery 291.5.4 Principle: Prioritizing a Non-denatured and Biodegradable Extract without Contaminant 291.6 Conclusions and Perspective 29References 302 Process Engineering and Product Design for Green Extraction 37Simon Both, Reinhard Ditz, Martin Tegtmeier, Urban Jenelten, and Jochen Strube2.1 Market and Market Development 372.2 Regulatory Framework 382.3 Systematic Apparatus and Process Design 392.3.1 Design of Experiments 402.3.2 Graphical Calculation Methods 402.3.3 Physicochemical Modeling 412.3.4 Approaches for Description of Diffusion 452.3.4.1 Maxwell-Stefan Approach 462.3.4.2 Calculation of Diffusion Coefficients 482.3.4.3 Thermodynamic Factor 492.3.4.4 Determination of Activity Coefficients 492.3.4.5 Proof of Principle 492.4 Model-Based Realization: Apparatus and Process Design 502.4.1 Quantification of Determining Factors 522.4.2 Proof of Principle – Process Optimization 532.4.3 Proof of Principle – Cost-Driven Decision 532.5 Extract Purification 542.5.1 Modeling Approaches 562.5.2 Scale-Up and Mini-plant 562.6 Total Process Development and Design 622.7 Conclusions and Summary 65Acknowledgments 66References 663 Tailor-Made Production of Plants for Green Extraction 71Hansjoerg Hagels3.1 Introduction 713.2 Sustainable Processes 723.2.1 Social Sustainability 733.2.2 Environmental Sustainability 743.2.3 Economic Sustainability 753.3 Production Technology 753.3.1 Choice of Cultivation Location 753.3.2 Crop Rotation 783.3.3 Fertilization 793.3.4 Organic Farming 823.4 Seed and Seed Stock 843.4.1 Breeding 843.4.2 Seed 883.4.3 Vegetative Propagation 883.4.4 Stock Maintenance 893.4.4.1 Diseases 893.4.5 Pests 903.4.5.1 Weed Control 903.4.6 Harvesting Technology 913.4.7 Purification of Harvest 913.4.8 Mechanical Treatment 913.4.9 Thermal Treatment 913.4.9.1 Natural Drying 923.4.9.2 Artificial Drying 923.5 Quality Criteria 923.5.1 Quality Management 923.5.2 Quality Control 95Glossary and Abbreviations 96References 96Further Reading 994 Mass Transfer Enhancement for Solid–Liquid Extractions 101Simon Both, Jochen Strube, and Giancarlo Cravatto4.1 Introduction 1014.2 State of the Art Solid-Liquid Extraction 1024.2.1 Batch Processes 1054.2.2 Continuous Processes 1064.2.3 Hydro- and Steam Distillation 1094.2.4 Alembic Distillation 1114.2.5 Mechanical Expression (Extrusion) 1124.3 Enhancement of Solid–Liquid Extraction Processes 1154.3.1 Microwave-Assisted Extraction (MAE) 1154.3.2 Ultrasound-Assisted Extraction (UAE) 1184.3.3 Turbo Extraction 1194.4 Example Processes for Solid–Liquid Extraction Enhancement 1224.4.1 Extraction of Polyphenols from Black Tea – Conventional and Ultrasound-Assisted Extraction 1224.4.1.1 Material and Methods 1234.4.1.2 Equipment Concepts 1264.4.1.3 Equilibrium Line by Multistage Maceration and Total Extraction 1274.4.1.4 Mass Transport Kinetics 1304.4.1.5 Particle Size Distribution 1314.4.1.6 SEM Measurements – Cell Disruption 1324.4.1.7 Conclusions 1324.4.2 Pilot Scale UAE of Clove Buds in Batch and Flow Reactors 1344.4.2.1 Experimental Methods and Reactors 1354.4.2.2 Results and Discussion 1374.4.2.3 Conclusions 1394.4.3 UAE and MAE of Lipids from Microalgae 1394.4.3.1 Experimental Methods and Equipments 1394.4.3.2 Conclusions 1414.5 Conclusion 141Symbols 142References 1425 Fundamentals of Process-Intensification Strategy for Green Extraction Operations 145Tamara Allaf and Karim Allaf5.1 Process-Intensification Strategy PI-S from High Capacity to High Controlled Quality Industrial Manufacturing 1455.2 What Does “Intensified Industrial Manufacturing” Mean? 1455.2.1 Unit Operation Performance 1465.2.2 Final Product Quality 1465.2.3 Equipment Reliability 1475.3 Intensification Strategy as a Pluridimensional Approach 1485.3.1 Objectives of Intensification Strategy 1485.3.2 Specific Case of Food Industry 1485.3.3 PI-S as a Continual Progressing-Development Strategy 1485.4 Fundamentals for Starting Basis Analyses 1495.4.1 Intensification Procedure 1495.4.1.1 Intensification Cycle 1495.4.1.2 Multi-cycle Intensification Procedure 1505.4.1.3 Intensification Charter 1505.4.2 Specificities of Instant Controlled Pressure DIC Drop in Process Intensification Strategy PI-S 1515.4.2.1 Introduction 1515.4.2.2 Transfer Phenomena in Instantaneous Controlled Pressure Drop DIC Treatment 1525.4.2.3 DIC – Texturing 1555.4.3 Mass Transfer by Permeability 1565.5 Processes of Extraction 1585.5.1 Extraction of Volatile Compounds 1585.5.1.1 Kinetics 1595.5.1.2 Intensification of Essential Oil Extraction 1615.5.2 Case of Solvent extraction 1625.5.2.1 Introduction 1625.5.2.2 Extraction Process Issues 1625.5.2.3 Kinetic Modeling 1665.5.3 Conclusion: Process Intensification Strategy: How to Use PI-S Solvent Extraction Processes? 1685.6 Conclusion 170References 1706 Panorama of Sustainable Solvents for Green Extraction Processes 173Iraj Koudous,Werner Kunz, and Jochen Strube6.1 Introduction 1736.2 Thermodynamic Models of Mixing and Dissolving 1766.2.1 UNIFAC and Modified UNIFAC 1766.2.2 The Hansen Solubility Parameters 1786.2.3 COSMO and COSMO-RS 1806.2.3.1 Example 1: Mutual Solubility of Acetone with Benzene, Chloroform, and Carbon disulfide 1836.2.3.2 Example 2: Solubility Screening for Indigo 1846.3 Solvent Selection for Green Solid–Liquid Extraction 1876.3.1 General Green Solvent Ranking with COSMO-RS 1886.3.2 Concrete Example: Solid–Liquid Extraction of Carnesol and Carnosic Acid from Sage 1886.3.3 Experimental Validation of COSMO-RS Solvent Ranking 1926.3.4 Conclusion 1926.4 Alternative Solvents for Green Extraction 1946.4.1 Ionic Liquids 1946.4.2 Low-Transition-Temperature Mixtures and Deep Eutectic Solvents 1966.4.3 Ionic Liquids Screening with COSMO-RS 1976.5 Purification Strategies of Natural Products 1996.5.1 Databased and Calculated Physicochemical Properties 2046.5.2 Feed Characterization 2136.5.2.1 Conceptual Process Design 2166.5.2.2 Modeling Depths and Feed Characterization Approach 2196.5.2.3 System 1: Vanillin 2236.5.2.4 Potential Unit Operations for Product Purification 2236.5.2.5 Data Evaluation 2256.5.2.6 Model-Based Process Design and Calculation of Separation Costs 2256.5.2.7 Separation Cost Estimation 2286.5.2.8 System 2: Tea Aroma 2286.5.2.9 Data for Potential Unit Operation 2286.5.2.10 Process Design and Cost Estimation 2296.5.2.11 Discussion and Conclusions 230Symbols 231Greek Letters 232Indices 232References 2327 Water as Green Solvent for Extraction of Natural Products 237Loïc Petigny, Mustafa Zafer Özel, Sandrine Périno, Joël Wajsman, and Farid Chemat7.1 Introduction 2377.2 Maceration 2397.2.1 Principle and Process 2397.2.2 Applications 2407.3 Subcritical Water Extraction 2437.3.1 Principle and Process 2437.3.2 Applications 2457.4 Enzymatic Assistance 2487.4.1 Principles and Process 2487.4.2 Applications 2497.5 Micellar Extraction 2517.5.1 Principle and Process 2517.5.2 Applications 2527.6 Hydrotropes 2557.6.1 Principles and Process 2557.6.2 Applications 2567.7 Conclusion 259References 2608 Coverage Exploitation of By-Products from the Agrofood Industry 265Carlos A. Ledesma-Escobar and María D. Luque de Castro8.1 Introduction 2658.2 Treatments for Safe Disposal/Exploitation of Agrofood Wastes or Residues 2658.2.1 Physical Processes 2668.2.2 Physicochemical Processes 2678.2.3 Advanced Oxidation Processes 2678.2.4 Thermal Processes 2688.2.5 Biological Treatments 2708.3 Exploitation of By-products from Olive Trees and Olive Oil Production 2718.3.1 Generalities 2718.3.2 Exploitation of Alpechín 2778.3.3 Overall Use of Either Alperujo or Orujo 2788.3.4 Partial Use of Either Alpechín or Alperujo 2798.3.5 Olive Leaf Exploitation 2808.3.6 Foreseeable/Desirable Future Uses of Olive Tree–Olive Oil Wastes 2808.4 Exploitation of By-products from Vineyards and Wine Production 2838.4.1 Generalities 2838.4.2 Types and Characteristics of Vineyard Residues 2868.4.3 Present and Potential Exploitation of Vineyard Residues 2868.4.4 Types and Characteristics ofWine Residues 2888.4.5 Present and Potential Exploitation ofWine Residues: Overall and Partial Exploitation 2888.5 Exploitation of By-products from the Citrus Juice Industry 2918.5.1 Generalities 2918.5.2 Uses and Potential Applications of Bioactive Compounds from Citrus Residues 2938.5.3 Potential Exploitation of Citrus Residues for Energy Production 2968.5.4 Other Overall and Partial Uses of Citrus Residues 297Acknowledgments 297List of Abbreviations 298References 2989 Selective Extraction from Food Plants and Residues by Pulsed Electric Field 307Eugene Vorobiev and Nikolai Lebovka9.1 Introduction 3079.2 Basics of PEF-Assisted Extraction 3089.3 Application of PEF for Different Food Plants and Residues 3109.3.1 Sugar Beets 3109.3.2 Red Beets 3139.3.3 Chicory Roots 3169.3.4 Apples 3179.3.5 Grapes 3189.3.6 Other Fruits and Vegetables 3199.3.7 Egg Yolk 3209.3.8 Bio-suspensions and Yeasts 3209.3.9 Microalgae 3219.3.10 Rhizomes 3239.3.11 Bones 3239.3.12 Eggshell 3249.3.13 Leaves 3249.3.14 Herbs 3249.3.15 Ginseng 3259.3.16 Peels 3259.3.17 Mushrooms 3259.3.18 Juices and Juice-Based Beverages 3269.4 Conclusions 327Acknowledgments 327References 32710 Green Extraction of Artemisinin fromArtemisia annua L 333Alexei A. Lapkin10.1 Introduction 33310.2 Extraction Technologies for Isolation of Artemisinin from A. annua 33310.2.1 Industrial Extraction Processes 33610.2.2 Cleaner and Intensified Processes for Extraction of Artemisinin 33910.2.2.1 Innovative Process Conditions for Extraction 33910.2.2.2 Alternative Solvents for Extraction of Artemisinin 34010.3 Innovation in Artemisinin Purification 34610.3.1 Hybrid Adsorption–Crystallization Separation 34610.3.2 Column and HPLC Chromatography 34710.3.3 Countercurrent Chromatography 34810.4 Analysis of Artemisinin and Co-metabolites 34810.5 Conclusions and Outlook 350References 351Index 357