Edited by Klaus-Viktor Peinemann, Suzana Pereira Nunes, and Lidietta Giorno Membrane Technology Related Titles Peinemann, Klaus-Viktor / Pereira Nunes, Suzana (eds.) Sammells, A F., Mundschau, M V (eds.) Volume Set Nonporous Inorganic Membranes for Chemical Processing 2011 2006 ISBN-13: 978-3-527-31479-9 ISBN: 978-3-527-31342-6 Membrane Technology Rijk, Rinus / Veraart, Rob (eds.) Global Legislation for Food Packaging Materials 2010 ISBN: 978-3-527-31912-1P Freeman, B., Yampolskii, Y., Pinnau, I (eds.) Materials Science of Membranes for Gas and Vapor Separation Drioli, Enrico / Giorno, Lidietta (Hrsg.) 2006 Membrane Operations ISBN: 978-0-470-85345-0 Innovative Separations and Transformations Ohlrogge, K., Ebert, K (eds.) 2009 Membranen ISBN-13: 978-3-527-32038-7 Grundlagen, Verfahren und industrielle Anwendungen Heimburg, Thomas 2006 Thermal Biophysics of Membranes ISBN: 978-3-527-30979-5 Tutorials in Biophysics (Band 1) 2007 ISBN-13: 978-3-527-40471-1 Pereira Nunes, S., Peinemann, K.-V (eds.) Membrane Technology in the Chemical Industry 2006 ISBN: 978-3-527-31316-7 Membrane Technology Volume 3: Membranes for Food Applications Edited by Klaus-Viktor Peinemann, Suzana Pereira Nunes, and Lidietta Giorno The Editors Dr Klaus-Viktor Peinemann KAUST Membranes Research Center Bldg.2, 3rd Floor,Room 3216-W9 4700 King Abdullah Univ 23955-6900 Thuwal Saudi Arabia Dr Suzana Pereira Nunes KAUST Membranes Research Center Bldg.2, 3rd Floor,Room 3216-W9 4700 King Abdullah Univ 23955-6900 Thuwal Saudi Arabia Prof Lidietta Giorno University of Calabria Institute on Membrane Technology Via P Bucci 17/C 87036 Rende (CS) Italia All books published by Wiley-VCH are carefully produced Nevertheless, authors, editors, and publisher not warrant the information contained in these books, including this book, to be free of errors Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate Library of Congress Card No.: applied for British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at http://dnb.d-nb.de # 2010 WILEY-VCH Verlag GmbH & Co KGaA, Boschstr 12, 69469 Weinheim All rights reserved (including those of translation into other languages) No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers Registered names, trademarks, etc used in this book, even when not specifically marked as such, are not to be considered unprotected by law Cover Design Adam Design, Weinheim Typesetting Thomson Digital, Noida, India Printing and Binding betz-druck GmbH, Darmstadt Printed in the Federal Republic of Germany Printed on acid-free paper ISBN: 978-3-527-31482-9 V Contents Preface XI List of Contributors 1.1 1.2 1.2.1 1.2.2 1.2.2.1 1.2.2.2 1.2.2.3 1.2.2.4 1.2.2.5 1.3 1.3.1 1.3.1.1 1.3.1.2 1.3.1.3 1.3.2 1.3.2.1 1.3.2.2 1.3.2.3 1.3.2.4 1.3.3 1.3.3.1 1.4 1.4.1 1.4.2 1.5 XIII Cross-Flow Membrane Applications in the Food Industry Frank Lipnizki Introduction Dairy Industry Dairy Industry Overview Key Membrane Applications Removal of Bacteria and Spores from Milk, Whey and Cheese Brine Milk Protein Standardization, Concentration and Fractionation Whey Protein Concentration and Fractionation Whey Demineralization Cheese Manufacturing Fermented Food Products Beer Beer from Tank Bottoms/Recovery of Surplus Yeast Beer Clarification 11 Beer Dealcoholization 11 Wine 12 Must Correction 13 Clarification of Wine 13 Rejuvenation of Old Wine (Lifting) 13 Alcohol Removal 14 Vinegar 14 Clarification of Vinegar 15 Fruit Juices 15 Fruit-Juice Clarification 16 Fruit-Juice Concentration 17 Other Membrane Applications in the Food Industry 17 VI Contents 1.5.1 1.5.2 1.6 1.6.1 1.6.2 1.6.2.1 1.6.2.2 1.6.2.3 1.6.3 Membrane Processes as Production Step 18 Membrane Processes for Water and Wastewater 18 Future Trends 18 New Applications of Membrane Processes 20 New Membrane Processes 20 Pervaporation 21 Electrodialysis 21 Membrane Contactors – Osmotic Distillation 22 Integrated Process Solutions: Synergies and Hybrid Processes References 23 Membrane Processes for Dairy Fractionation 25 Karin Schroën, Anna M.C van Dinther, Solomon Bogale, Martijntje Vollebregt, Gerben Brans, and Remko M Boom Introduction 25 Membrane Separation of Components 27 Removal of Milk Fat from Whole Milk 27 Removal of Bacteria and Spores from Skim Milk (Cold Pasteurization) 27 Concentration of Casein Micelles in Skim Milk 28 Recovery of Serum Proteins from Cheese Whey 30 Methods to Enhance Membrane Separation 30 Critical Flux Concept 31 Uniform Low Transmembrane Pressure Concept (UTP) 32 Turbulence Promotion 32 Backpulsing and Flow Reversal 33 Other Methods 33 Use of Models for Membrane Separation 34 How to Get from Separation to Fractionation 35 Membranes with Uniform Pore Size 36 Simulation of Particle Behavior 37 Membrane Modification 37 Outlook 38 References 39 2.1 2.2 2.2.1 2.2.2 2.2.3 2.2.4 2.3 2.3.1 2.3.2 2.3.3 2.3.4 2.3.5 2.4 2.5 2.5.1 2.5.2 2.5.3 2.6 3.1 3.1.1 3.1.1.1 3.1.1.2 3.2 3.2.1 3.2.1.1 23 Milk and Dairy Effluents Processing: Comparison of Cross-Flow and Dynamic Filtrations 45 Michel Y Jaffrin, Valentina S Espina, and Matthieu Frappart Introduction 45 Properties and Applications of Various Proteins 45 Caseins 45 Whey Proteins 45 Applications of Membrane Cross-Flow Filtration to Milk Processing Milk Microfiltration 46 Bacteria and Spore Removal 46 46 Contents 3.2.1.2 3.2.2 3.2.2.1 3.2.2.2 3.2.3 3.2.3.1 3.2.3.2 3.3 3.3.1 3.3.2 3.3.3 3.3.3.1 3.3.3.2 3.3.3.3 3.3.3.4 3.3.4 3.4 Casein Micelles Separation from Whey Proteins 47 Milk Ultrafiltration (UF) 48 Total Proteins Concentration 48 Whey-Protein Fractionation 49 Applications of Milk Nanofiltration (NF) and Reverse Osmosis (RO) 50 Treatment of Cheese Whey and Fabrication of Yogurts 50 Treatment of Dairy Effluents 51 Dynamic Filtration 51 Principle and Advantages of Dynamic (Shear-Enhanced) Filtration 51 Industrial Dynamic Filtration Systems 52 Application of Dynamic Filtration to Skim-Milk Processing 55 Casein Separation from Whey Proteins by MF 55 Dynamic Ultrafiltration of Skim Milk 60 Total Protein Concentration by UF for Cheese Manufacturing 63 a-La and b-Lg Protein Fractionation by UF 64 Treatment of Dairy-Process Waters by Dynamic NF and RO 66 Conclusion 69 References 70 Electrodialysis in the Food Industry 75 Jamie Hestekin, Thang Ho, and Thomas Potts Introduction 75 Technology Overview 76 Principle of the Electrodialysis Process 76 System Design 79 Concentration Polarization, Limiting Current Density, Current Utilization, and Power Consumption 79 System Design and Cost Analysis 80 Electrodialysis Applications in the Food Industry 82 Wine Industry 83 Juice and Sugar Industry 85 Dairy Industry 88 Protein Fractions 94 Hybrid Technologies 96 Electrodeionization 96 Electrochemical Coagulation 97 Electroreduction 98 Conclusion and Future Innovations 98 References 101 4.1 4.2 4.2.1 4.2.2 4.2.2.1 4.2.2.2 4.3 4.3.1 4.3.2 4.3.3 4.3.4 4.4 4.4.1 4.4.2 4.4.3 4.5 5.1 5.2 5.3 Membrane Processes in Must and Wine Industries 105 Maria Norberta De Pinho Introduction 105 Wine Clarification by Microfiltration and Ultrafiltration 106 Wine Tartaric Stabilization by Electrodialysis 111 VII VIII Contents 5.4 5.5 6.1 6.1.1 6.1.2 6.2 6.2.1 6.2.2 6.3 6.4 7.1 7.1.1 7.1.2 7.1.3 7.1.4 7.1.5 7.2 7.2.1 7.2.2 7.2.3 7.3 7.3.1 7.3.1.1 7.3.1.2 7.3.2 7.3.2.1 7.3.2.2 7.3.3 7.3.3.1 7.3.3.2 7.4 7.4.1 Influence of MF/UF Polysaccharide Removal on Wine Tartaric Stability 113 Nanofiltration of Grape Must for Sugar/Organic Acids Fractionation 115 References 117 New Applications for Membrane Technologies in Enology 119 Martine Mietton Peuchot Reduction of Alcohol Content 119 Reduction of Must Sugars to Obtain a Lower Alcohol Content in Wines 119 Reduction of Alcohol Content in Wine 121 Reduction of Malic Acid in Grape Musts or Volatile Acidity in Wines 123 Reduction of Malic Acid in Musts 123 Reduction of Volatile Acidity 123 Acidification of Musts and Wines 125 Other Potential Applications 126 References 127 Membrane Emulsification for Food Applications 129 Henelyta S Ribeiro, Jo J M Janssen, Isao Kobayashi, and Mitsutoshi Nakajima Introduction 129 Cross-Flow Membrane Emulsification (XME) 130 Dead-End Membrane Emulsification (PME) 131 Rotating Membrane Emulsification (RME) 131 Vibrating Membrane Emulsification (VME) 132 Microchannel Emulsification 133 Understanding of the Process at the Pore Level 134 XME 134 PME 137 MCE 138 Production of Structured Systems for Food Applications 140 O/W Emulsions 140 Membrane Emulsification 140 Microchannel Emulsification 141 W/O Emulsions 144 Membrane Emulsification 144 Microchannel Emulsification 145 W/O/W Emulsions 147 Membrane Emulsification 147 Microchannel Emulsification 149 Encapsulation of Active Molecules 149 Membrane Emulsification 149 10.3 Membranes as Devices for Active Food Packaging delivery is controlled by a combination of diffusion and biodegradation (matrix system); (c) the drug is released using the osmotic pressure developed by diffusion of water across a semipermeable membrane into a salt solution that pushes it out (osmotic system) These concepts have also been extended to other areas of interest to control the delivery of agrochemicals (pesticides), household products (fragrances) and active agents for food-packaging applications (antimicrobials, antioxidants, aroma compounds) Active packaging has been defined as a system in which the product, the package, and the environment interact in a positive way to extend shelf life or to achieve some characteristics [25] A new challenge in the food industry is the current trend in consumer demands for minimally processed, easily prepared and ready-to-eat fresh products Traditional preservation of such products, in which the preservative is added directly to the food, has limited benefits In fact, the active substances are neutralized on contact or diffuse rapidly from the surface, where contamination primarily occurs, into the food mass [26] Moreover, the addition of large amounts of antimicrobials directly to ready-to-eat products can influence the taste, while low amounts result in a short shelf life The controlled release of agents obtained by an active food-packaging system can be generally considered the solution to preserve the quality and increase the storage time for ready-to-eat perishable foods [27] All the active packaging technologies involve some physical, chemical, or biological action for generating interactions between the package, the product, and the package headspace to increase the shelf life of foods In addition, they can be divided into categories of absorber, releasing system and other systems [26] The actual techniques can be summarized as follows: addition of sachets/pads containing volatile agents; incorporation of volatile and nonvolatile agents directly into the polymers; coating or absorbing agents onto polymer surfaces; immobilization of agents to polymers by ion- or covalent linkages; use of polymers that are inherently antimicrobial; multilayer films with active layer In particular, multilayer films are an interesting solution for active packaging and membranes could have a key role in these multilayer structures In monolayer dense film in fact only a part of the preservative is released [28, 29] and higher concentrations of antimicrobial agents than usually needed have to be loaded in these films to preserve the food Moreover, the release rate of the active compounds is not easily controlled The multilayer films presented in the literature are usually produced by coextrusion of dense film or coating of an active thin layer on the polymer surface; the active layer functions both as reservoir and as release control of the active substance [30–32] In the literature, only few works report the preparation of multilayer films, having an outer barrier dense layer, an active agent-containing matrix layer and a release-control layer The control layer is the key layer to control the initial time-lag period and the flux of penetration of the active agents In these multilayer structures the membranes j233 j 10 Membranes for Food Packaging 234 are suitable devices Han et al [33], for example, suggested the use of such multilayer structure for antimicrobial-release packaging systems Another study on multilayer films concerns the controlled release of a volatile antimicrobial compound, the allylisothiocyanate (A.I.T.C) The multilayer film is made of (a) a tie-layer, cyclodextrins containing the A.I.T.C and (b) perforated membrane, within a fine powder of silica gel, which is in contact with the food product [34] Figoli et al introduced the use of the asymmetric porous membrane in controlledrelease food packaging, produced by nonsolvent-induced phase separation (NIPS) technique [35, 36] They reported the development of an antimicrobial food packaging film based on the use of membranes, with modulate porosity, as a controlling release system The multilayer film was made of three layers: an outer dense layer to control the exchange rate of gases between the external and internal environment of the food packaging, an intermediate adhesive tie-layer which has also the function of reservoir of antimicrobials, and the porous membrane layer, made by phase inversion, that controls the release of antimicrobials to the food In particular, its properties (porosity and morphology) can be properly tailored by changing the phase-inversion process conditions In this case, the investigated polymer was the modified polyaryletheretherketone (PEEK-WC), already widely used in membrane preparation [20, 22] However, the proposed process can be extended also to other polymer traditionally employed in food packaging The multilayer films were prepared as shown in Figure 10.6 All separate layers of the multilayer film could be cast subsequently on one another without removing the dense film from the glass substrate The method to produce the three layers is presented, as follows: 1) The dense PEEK-WC/poly-a-pinene (p-a-p) (different ratio, from 100/0 to 50/50) layer, used as substrate for the multilayer film, was prepared by casting solution A dense PEEK-WC/p-a-p film was formed on the clean glass substrate after the solvent was evaporated The addition of p-a-p has the double function to increase the affinity of the dense film with the second layer and to modify the transport properties of the film itself 2) The second layer was made of p-a-p with and without oxalic acid (0.5, 10 and 25 wt%) The starting solution was stirred and cast at 0% RH and 70  C in a climate chamber Immediately after casting, the formed double layer film was removed from the climate chamber and allowed to cool at room temperature Figure 10.6 Schematic representation of the multilayer film casting process developed 10.3 Membranes as Devices for Active Food Packaging 3) A porous PEEK-WC film was then cast on the double-layer film previously prepared The porous membrane layer was prepared by dry-wet phase inversion A casting solution was produced with different concentrations of PEEKWC in N,N diethylacetamide (DMA) (15, 19 and 23 wt%) The films were cast in a climate chamber at 50% RH and 20  C The porosity and morphology of each membrane were varied changing the time of exposure to air before precipitation (45 s/240 s.) and the water-bath temperature (0  C and 40  C) The multilayer film was removed after immersion from the coagulation bath The same PEEKWC membranes have also been prepared by casting the solution directly on the glass substrate to evaluate the effect of the polya-pinene substrate, with and without oxalic acid, on the properties (i.e morphology, porosity) of the membrane The different membranes obtained by varying the concentration of oxalic acid and polymer, are illustrated in Figure 10.7 In particular, the increase of the polymer concentration (from 19 to 23 wt%) produces an asymmetric dense membrane The final antimicrobial multilayer films have also been examined by scanning electron microscopy, SEM The individual layers of the film, indicated by the arrows, can clearly be distinguished in the picture (Figure 10.8) The release rates of oxalic acid from the multilayer film was determined by bringing into contact the porous membrane side with distilled water and monitoring the change of pH with time The results proved that the release rate depended strongly on the phase inversion processing conditions and on the compounds used in the preparation of porous membrane layer (air exposure time, water-bath temperature, polymer concentration, oxalic acid concentration) In particular, the oxalic acid release increased with decreasing the coagulation bath temperature (from 40 to  C) and when the operating temperature was increased from to 25  C [35, 36] Figure 10.7 SEM cross-sections of the different membranes (release layer) obtained by changing the concentration of oxalic acid (from to 25 wt.%) and PEEKWC polymer (from 19 to 25 wt.%) j235 j 10 Membranes for Food Packaging 236 Figure 10.8 Cross-section of the multilayer film (SEM magnification of 400Â) Based on these results, a production line for scale production of the multilayer film was proposed as shown in Figure 10.9 The polymer is extruded to produce a dense film with barrier or specific gas or water-vapor properties, then, a commercial tie-layer resin, loaded with a specific antimicrobial, is cast on the dense film Finally, the polymer solution is spread on the adhesive layer and brought into contact with the coagulation bath (i.e water) that will determine the formation of the asymmetric porous membrane Another example reported in the literature is that of Altinkaya et al who presented the incorporation of lysozyme [37] and natural antioxidants [38], such as L-ascorbic acid and L-tyrosine, into cellulose acetate (CA) asymmetric porous structures by phase-inversion technique In order to achieve controlled release of the active compounds studied, the films structure was modified by changing the morphology (from porous to dense) tailoring the composition of the initial casting solution In particular, the films were produced using the dry phase-inversion technique The polymer was dissolved in a mixture of acetone and water and, then, cast on a support and exposed to an air stream Different morphologies were obtained by changing the phase-inversion processing conditions such as evaporation temperature, relative humidity, wet casting thickness as well as the composition of the membrane-forming solution In the case of lysozyme [37], the highest release rate and antimicrobial activity were obtained with the film prepared with 5% CA solution including 1.5% Figure 10.9 Production line suggested for the fabrication of the multilayer film with the asymmetric membrane as the antimicrobial controlled-release system 10.3 Membranes as Devices for Active Food Packaging lysozyme At higher CA concentration (15%) the porosity of the film was reduced with a consequent decrease of the release rate The diffusion of lysozyme in CA, porous and dense, films was 4.17  10À10 (cm2 sÀ1) and 1.50  10À10 (cm2 sÀ1), respectively The mechanical properties of the films were evaluated also in terms of tensile strength, % elongation at break and Young’s modulus The tensile strength, Young’s modulus and elongation at break of the films increased with increasing CA concentration due to reduced pore sizes and porosity of the films The incorporation of lysozyme into the films prepared with 5% and 10% CA solution did not determine any change in the mechanical properties with respect to the films without lysozyme In contrast, the film prepared with 15% of CA loaded with lysozyme showed a significant reduction in tensile strength and elongation at break values Also, in the case of the loading of low molecular weight natural antioxidants [38], such as L-ascorbic acid and L-tyrosine, the diffusion rate through the films was reduced by increasing the CA concentration in the casting solution The use of the porous or dense structure in contact with food environment and the different CA concentration of the made film are the main factors responsible of the release rate of these active compounds The diffusion rate of L-ascorbic acid was 3.33  10À10 (cm2 sÀ1) and 1.67  10À10 (cm2 sÀ1) in porous and dense structures, respectively, while for L-tyrosine was 1.00  10À10 (cm2 sÀ1) and 0.8  10À10 (cm2 sÀ1) in porous and dense structures, respectively Also the mechanical properties of the films increased significantly on increasing the CA concentration, due to the fact that the films produced had a lower porosity, pore size and they were practically dense Figoli et al [39], recently illustrated the advantages of using microencapsulation as a promising technology for protecting the natural active substances from the stresses and damages that can occur during food-package manufacturing and for improving the active-agent distribution Thanks to these effects and according to their structure, the microcapsules could better control the release of the active substances and promote the interaction of the film with the active substances carrier In this work, bio-microcapsules of chitosan have been developed using a system that combines the membrane process concept with the phase-inversion technique using a monoporous polymeric film [40] This technique permitted the formation of monodispersed biopolymer droplets that were then cross-linked with a natural additive adapted for this polymer structure, and that enhanced the water resistance of chitosan itself The capsule size and morphology were adjusted by changing the ingredient parameters such as the cross-linking concentration and tailored with the pore diameter of the monoporous film employed Furthermore, two different types of natural antimicrobial were included in the capsules enabling loading both during their production and after the droplet formation The chemicalphysical analysis of the new chitosan microcapsules was carried out by means of optical microscopy, SEM and EDX The chitosan capsules produced are shown in Figure 10.10 The antimicrobial activity of the microcapsules was assayed by turbidimetric methods against Staphylococcus aureus selected as a pathogen micro-organism, which j237 j 10 Membranes for Food Packaging 238 Figure 10.10 Optical microscope image of chitosan microcapsules without (a) and with (b) antimicrobical compound may be present in fresh food The results showed that the addition of the antimicrobials enhanced the antimicrobial effect of chitosan itself and the growth of Staphylococcus Aureus was totally inhibited 10.4 Conclusion In a period in which consumers are demanding higher-quality foods and changes in retailing practices (such as market globalization resulting in longer distribution of food), or the consumer’s way of life (resulting in less time spent shopping for fresh food at the market and cooking), the major challenge to the food-packaging industry is the development of new packaging concepts that extend shelf life while maintaining and monitoring food safety and quality In this context, membranes can play an important role and, even if their potentialities have not been completely exploited, some promising membrane features in food packaging have been reported and discussed in this chapter Their use has been addressed toward two main perspectives: (a) modulating the gas exchange rate between the inside and outside of the package environment (such as some applications of modified-atmosphere packaging) and (b) actively controlling the release or absorption of specific compounds from the packaged food (active packaging) In particular, the possibility of tailoring the membrane morphology, porosity and properties allows an extension of their use to a broad range of food-packaging purposes Furthermore, the growing environmental awareness coupled with the inexorable rise of pre-packaged disposable meals has directed the research to the development of environmentally friendly packaging materials with biodegradable properties, preferably with components from natural sources rather than from petrochemical materials Even if up to now biopolymers have been slow to reach commercial maturity, due to their high costs and less optimal physical properties than conventional plastics, things are changing, and new large-scale production systems are bringing down the costs of biodegradable polymers, and sophisticated polymerization and blending techniques are improving the material properties In this 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Paik, H.D., and Lee, D.S (2000) Antimicrobial low-density polyethylene film coated with bacteriocins in binder medium Food Sci Biotechnol., 9, 14–20 Han, J.H (2000) Antimicrobial Food Packaging Food Technol., 54 (3), 53–63 34 Oikawa, T., Fukushima, Y., Ishii, K., 35 36 37 38 39 40 Takesue, M., Muto, Y., Fujii, K., and Fukaya, S.,Antimicrobial laminate and bag, container, and shaped cup using same, in United States Patent nr (2000) 6,150,004 Kyodo Printing Co., Ltd (Tokyo, JP): Japan Figoli, A., Drioli, E., Jansen, J.J.M., and Wessling, M.,Film antimicrobico per prolungare la shelf life, ISSN0033-9687, Rassegna dell’Imballaggio, Nov 2004, n.16, Year 25th Jansen, J.J.M (2004) Preparation and Characterisation of a New Antimicrobial Polymer film for food Packaging Application, Master Thesis Faculty of Science and Technology, University of Twente, Enschede (NL) and Institute of Membrane Technology (ITM-CNR), Italy Gemili, S., Yemenicioglu, A., and Altinkaya, S.A (2009) Development of cellulose acetate based antimicrobial food packaging materials for controlled release of lysozyme J Food Eng., 90, 453–462 Gemili, S., Yemenicioglu, A., and Altinkaya, S.A (2010) Development of antioxidant food packaging materials with controller release properties J Food Eng., 96, 325–332 Figoli, A., Mascheroni, E., Rollini, M., Limbo, S., Talarico, S., Piergiovanni, L., and Drioli, E., bio-microcapsules preparation by membrane process for a controlled release of natural antimicrobials PERMEA 2009, Proceedings Oral presentation, Prague, 7–11 June 2009, p 73 Figoli, A., De Luca, G., Longavita, E., and Drioli, E (2007) PEEKWC capsules prepared by phase inversion technique: A morphological and dimensional study Sep Sci Technol., 42, 2809–2827 j241 Index a c accumulation 30f adsorption 36, 126, 137, 209, 227 aggregation 50, 155 antioxidants 167, 205, 237 – activity 205 – total antioxidant activity (TAA) 180f cake formation 32, 36 carbonation 22 casein micelles – concentration 25, 28f., 35, 45 – rejection 57, 59 – separation 47, 55 – skim milk 28f – transmission 48 cell immobilization 211 centrifugation 25, 27, 50, 66, 81 – wine production 106 CFD (computational fluid dynamics) 35f., 132, 134f., 138 cheese – curding 26 – partial concentration – preconcentration – preservation – processing 8f., 51 – standardized cheese milk – total concentration – whey 30 chromatography – fractionation 48 – ion-exchange membrane 66 Clapeyron’s law 175 clarification – beer 9ff – fruit juice 16f – MF/UF 105ff – vinegar 15 – wine 13, 209 cleaning – chemical 33 – electrodialysis systems 99 – in situ 82 – methods 31 b backtransport models 32, 35 – backpulsing 28, 32f – backwashing 33 bacteria removal – milk 3f., 46 – skim milk 27 beer – clarification 9ff – dealcoholization 9, 11f – maturation 11 – membrane bioreactor 212f – production 10ff bioactive compounds 217f., 224 biocatalyst 201ff – esterases 206 – GRAS (generally regarded as safe) 214 – laccase 205 – lipases 206f biocatalytic membrane reactor, see membrane bioreactor biological oxygen demand (BOD) biologically active compound 167 biotransformation 201 brine 4, 16 – boundary layer 174 – treatment Brownian motion 152 by-product 201f j Index 242 – sequences 1, 110f COD (carbon oxygen demand) – dairy effluent 50f – dairy process water 66ff – dairy wastewater 94 – reduction 52 concentration factor, see wine concentration polarization 36, 52, 60, 79, 175, 186, 189 conductivity – dairy-process water 66f – ionic concentration solutions 88f – wine 113 costs – energy 2, 8, 30, 47, 62, 87, 168f – equipment 8, 63 – membrane replacement 17, 170 – operating 10 – packing 168 – production – shipping 168 – storage 168 – water cross-flow velocity 38 cryoconcentration 168, 194 crystallization – cold 106 – induction time 114f curding 25f current – density 79f – efficiency 87f d dairy effluents 51f Dean vortices 33 deionization degree (DEID) 113f desalination 1, 75, 95f diafiltration (DF) 5, 13 – milk 48 – whey demineralization – whey proteins fractionation 49 – wine 13f diffusion – Brownian 37 – coefficients 37, 175, 227 – rate 237 – selectivity 227 – shear-induced 35, 37 direct osmosis (DO) 194 distillation – applications 177ff – flux 174f – fruit juice concentration 171ff – membrane (MD) 168, 170f., 183ff – membrane osmotic (MOD) 190f – osmotic (OD) 22, 121f., 170ff Donnan exclusion mechanism 22, 75 droplet – break-up 137 – coalescence 130, 152 – force-balance model 135, 137 – formation 134ff – generation unit (DGU) 133, 151f – lipid-coated ice droplet hydration method 147 – -size 131, 134, 139, 143 – -size distribution (DSD) 129, 148, 151ff – stabilization 142ff – torque-balance model 135, 137 e electrodoalysis (ED) 1f., 8, 21f – acidification 125f – applications 82ff – cost analysis 79ff – dairy industry 88ff – deacidification 84f., 168 – demineralization 30, 50, 84, 88ff – electrochemical coagulation 97f – electrodeionization 96f – electroreduction 98f – food industry 75ff – juice industry 85ff – lactic-acid production 90ff – process 76f., 112 – protein fractionation 94ff – reversal (EDR) 75 – stack 78, 81f – sugar industry 85ff – system design 79ff – tartaric stabilization 105f., 111ff – wine 83ff emulsification – coefficient of variation (CV) 132 – cross-flow membrane (XME) 129ff – dead-end membrane (PME) 130f., 134, 137, 144, 150 – dispersed phase 138f., 141, 143, 146f – encapsulation active molecules 149ff – low-shear processing 156f – membrane (ME) 129, 134, 136, 139ff – microchannel (MCE) 129, 133f., 138f., 141ff – rotating membrane (RME) 130ff – vibrating membrane (VME) 132 emulsifier 7, 45, 206 Index – hydrophile–lipophile balance (HLB) 142, 148 – hydrophilic 149 – hydrophobic 146, 149, 151 – proteins 142 – small-molecule 137 emulsion – flocculated networks 155 – monodisperse 133f., 139, 143, 146, 150f – oil-in-water (O/W) 130, 132, 140ff – polydisperse 153, 155 – semiliquid 152 – stability 152ff – water-in-oil (W/O) 130, 144ff – water–oil–water (W/O/W) 147ff – yield stress 154 enological processes 106, 119ff enzyme – dosage 204 – immobilization 209, 213 enzyme membrane reactors (EMRs) 167f enzyme – oxidative 209 – stability 209 enzymatic – activity 208f., 213 – cell-free reactors 212 – coagulation – hydrolyse of starch 203 – pulping 168 – synthesis 206 evaporation 5, 17 – compression 91 – flux 172, 175f – multistage 168 – solvent 143, 230 – thermal 194 – vacuum (VE) 50, 91, 115 extraction – liquid–liquid 23 – mass agent 202 f fermentation – aerobe 15 – beer 9ff – wine 12ff filtration – cross-flow 3, 9f., 21, 38, 45f., 48 – dead-end 4, 9, 28, 106 – diatomaceous-earth 105f – dynamic 45, 51ff – kieselguhr 4, 11, 106 – shear-enhanced 51f – sterile 12, 106 flow – resistance 82 – reversal 33 – -through models 35 – turbulent flux – critical 2, 31f., 35 – decrease 30f – steady-state 36, 188 foaming 6, 22 food packaging – active packaging 224f., 232ff – controlled-release polymers 226, 232ff – films 229ff – food contact materials (FCM) 223 – modified-atmosphere (MAP) 225f., 228ff – multilayer films 233ff – synthetic polymers 223ff – traditional 225 – under-vacuum 226 force – drag 135 – interfacial tension 134f., 137 fouling 1, 26, 30f., 46, 50, 107 – degree 110 – electrodialysis systems 87, 99 – internal 57, 63 – layer 30 fractionation 5, 35f – milk-fat globules 27 – sugar/organic acids 116 – whey proteins 48f., 52 free biocatalysts membrane bioreactor, see membrane bioreactor fruit juice – clarification 16, 167 – concentration 167f., 176 – deacidification 169 – depectinization 167 – integrated processes 167ff – production 16ff – quality 180, 182 – single-strength 168 – stabilization 167 functional food – flavor 201 – ingredients 203 – membrane bioreactors 202ff – nutraceutical 203 – nutrapharmaceutical 208 – odor 201 – prebiotic 203 – probiotic 203 j243 j Index 244 g gas-exchange rate 225 gas separation (GS) 168 gel filtration mode 32 GMP (K-casein-glycomacropeptid) h heat – transfer coefficient 187 – treatment of milk 7, 27 hydrogel coating 173 i ice-cream manufacturing interaction – chip surface–emulsifier molecule – electrostatic 139 – hydrodynamic 135, 155 – nonattractive 139 – particles–liquids 37 – protein–ZrO2 49 interface – liquid/membrane 190 – oil/water 208 – vapor/liquid 171, 183 interfacial – area 170 – rheology 137 – tension 134f., 137f isoelectric point 131 139 l lattice-Boltzmann method 37, 134 Loeb–Sourirajan phase-separation process 226 m macromolecular 106f mass transfer – boundary layer 186 – control 202 – distribution coefficient 22 – gas–liquid 22 – liquid–liquid 22 membrane – anion-exchange 76f., 91, 93 – area 32, 62 – asymmetric 26, 226, 229f., 234, 236 membrane bioreactors – beer processing 212f – biocatalytic membrane reactor (BMR) 201ff – continuous-flow stirred-tank membrane reactor 209 – ethanol production 212f – fat processing 206ff – free biocatalysts membrane bioreactor (MBR) 201ff – fruit-juices production 213 – lactose hydrolysis 215ff – milk processing 214ff – oil processing 206ff – pectin hydrolysis 210f., 213f – protein hydrolysis 215 – starch processing 203ff – stirred-tank reactor 207 – sugar processing 203ff – two-separate phase membrane bioreactor 207 – wine 208ff membrane – bipolar 76f., 87, 90ff – cation-exchange 76f., 79, 87, 91, 93 – ceramic 3f., 26, 29f., 47f., 59, 130, 172f – chemistry 99 – composite 30, 226 membrane controlled-release devices 226, 232f membrane distillation (MD) – applications 187ff – air-gap (AGMD) 184 – direct contact (DCMD) 184, 187ff – operating parameters 186f – sweeping gas (SGMD) 184 – vacuum (VMD) 184, 187, 188ff membrane – flux 29, 226 – hydrophilic 1, 130, 145, 169, 172, 208 – hydrophobic 130, 145, 169, 173, 183, 208 – ion-exchange 1, 22, 30, 50, 75ff – lifetime 82, 170 – liquid 225 – metallic 130 – modification 37 membrane modules – circular polymer 66 – helically wound hollow-fiber 174 – membrane distillation (MD) 185ff – microporous polymer hollow fiber 174ff – osmotic distillation (OD) 172ff – plate-and-frame 10f., 174, 185 – rotating-disk 58ff – shell-and-tube 186 – spiral-wound (SW) 4, 17, 48, 51, 66, 185, 202 – tubular 10, 49, 59, 185, 202 – VSEP 60f., 63f., 66 Index membrane – multichannel 47 – nonporous 21, 225 – nonselective 229f – nuclepore 36 – osmotic distillation (OD) 172ff – performance 31, 34 – permselectivity 227, 229 – polymeric 21, 30, 47f., 75, 185 – porosity 136, 169, 173, 185, 225 membrane processes – applications in food industry 17ff – continuous 10 – ED, see electrodialysis – hybrid 23 – integrated 167ff – MF, see microfiltration – NF, see nanofiltration – PV, see pervaporation – pressure-driven 1f., 186 – RO, see reverse osmosis – three-stage 66 – two-stage 49 – UF, see ultrafiltration membrane – radius 58 – regeneration 110 – SCT 47 – selectivity 32, 65, 121, 202, 226ff – semipermeable 229 membrane separation – models 17, 34f – of components 27ff membrane – SPG (Shirasu-porous-glass) 130f., 140f., 145, 149 – supported-liquid 170, 191ff – surface area 108f – surface morphology 31f – thickness 173, 189 – track-etched 26 – volumetric productivity 32 – zeolite 21 microdispersions 134 microencapsulation 237f microfiltration (MF) 1f., 26 – bacteria removal 3f., 46 – beer clarification 11 – cross-flow 11 – /electrodialysis (ED) 80 – milk 46 – osmotic distillation (OD) 177, 179, 181f – polysaccharide removal 113f – powder milk 56 – productivity 107f – skim milk 58 – spore removal 46 – tangential MF/UF 105f – wine clarification 105ff microsieve 29, 36f – metal 36 – polymeric 36 – silicon 26, 36 microsolute transmission 52 migration effects 39, 112 milk – composition 26f., 46 – concentration 5, 46 – consistency – cream stability 27 – fat removal 27 – pH adjustment – powder 55 – processing 3f., 46f – protein concentrate (MPC) – protein standardization 5, 45f – skim 3, 5, 27f., 55, 58, 60ff – taste 8, 27 – total solids 5f., – ultra-high temperature (UHT) 55, 57, 61ff molecular – distillation 206 – encapsulation 205f molecular weight cut-offs (MWCOs) 2, 107f., 113, 168, 204f must – acidification 125f – concentrated (CM) 106, 115 – fermentation 105 – rectificated concentrated (RCM) 105f., 115 – reduced acidity 120, 123 – sugar reduction 119f n nanofiltration (NF) 1f – dairy-process water 66f – fruit juice concentration 168 – grape must 115f – milk 50 – rejection coefficients 115 – taste of wine 126 – volatile acidity in wine 124 – whey demineralization neutralization 124f nitrogenation 22 nonsolvent-induced phase separation (NIPS) technique 234 j245 j Index 246 o organoleptic 3, 126, 168 Ostwald ripening 152 p partial condensation 168 pasteurization 15, 28, 48 – cold 27, 46 – ultra- permeability – coefficient 227 – gas 223, 225ff – water-vapor 226 permeate – flow rate 61f – flux 47f., 56 – flux decline 107f – recirculation 47, 51 pervaporation (PV) 1f., 21, 168, 227 – aroma recovery 21 – fruit juice 168, 181 pH – adjustment 80, 86f., 123 – milk processing – wine processing 123f pore size 3f., 26f – distribution 26, 36 – MF membrane 107f – uniform 35ff porosity gradient (GP) 47f precipitation – polysaccharide 113 – selective 50 – tartrate salts 84 – thermocalcic pressure – capillary penetration 173 – critical penetration 169f – Laplace 138, 169 – osmotic 2, 146f., 149, 168 – vapor 171 – -variation cycle 57 proteins – bovine serum albumin (BSA) 30, 45, 142f – denaturation 34 – egg-white 142 – immobilization 211 – immunoglobulins 30 – a-lactalbumin 6, 30, 45 – b-lactalbumin 6, 30, 45, 142, 215 – lactoferrin 30 – repulsion 50 – serum proteins recovery 30 – soybean flour 142 – total concentration 48, 63 – transferrin 30 purification 167, 202 r retentate – concentration factor 47 – microfiltration retention factor 204 reverse osmosis 1f., 81 – fruit juice concentration 177f., 194 – dairy-process water 66 – diafiltration 13f – membrane distillation (MD) 188f – milk 5f., 50 – must 115 – osmotic distillation (OD) 177ff – volatile acidity in wine 124 Reynolds number 186 ripening 9, 26, 152 s saltification balance 125 salting-out effect 95 shelf life – foods 223, 229, 233 – retention 229 simulated ultrafiltrate (SMUF) 28 solute rejection rates 52 solution – brine – diffusion 1, 21 – stripping 170, 176, 190 – surface tension 173, 183 spore removal – milk 3f., 46 – skim milk 27 Stack’s process 95 starter-culture sterilization cold 28, 30 t tartaric stabilization, see electrodialysis temperature polarization 186, 189 total soluble solids (TSS) 175ff transmembrane flux 38, 131, 173, 175 transmembrane pressure (TMP) 3, 5, 26, 32, 57, 61, 64 – MF 107ff – UF 108f – uniform (UTP) 28, 32f., 46f., 52 Index transmembrane temperature gradient 187, 191 turbidity – fruit juice 181 – permeate 47, 55f., 58 turbulence – micro- 33 – promotion 29, 32 u ultrafiltration 1f – cheese production 9, 29, 63 – /electrodialysis (ED) 80 – fruit juice 16, 177ff – membrane distillation (MD) 188 – milk 5f., 8, 48f – osmotic distillation (OD) 177ff – polysaccharide removal 113ff – powder milk 56 – productivity 107f – skim milk 60ff – vinegar 15 – whey demineralization – whey proteins fractionation 52, 64f – wine clarification 105ff UV-light treatment v videomicroscopy 134, 137f vinegar 14f viscosity – emulsion 153, 155 – fruit juice 168, 181 – Krieger-Dougherty (KD) equation 155f – milk volume reduction ratio (VRR) 47, 49f., 56, 61, 64f w water – aroma 121 – dairy-process 66 – deoxygenized 22 – treatment 1, 18 – waste- 1, 8, 18, 20, 94 watering down 121 whey – defatted 6f – demineralization 7f., 30 – processing 6ff whey protein concentrate (WPC) 4f., 66 whey protein isolate (WPI) 4, whey protein transmission 47, 49, 57ff wine – acidification 125f – alcohol content reduction 119ff – clarification 13, 209 – compounds 14 – concentration factor 107ff – dealcoholization 12, 14 – fruitiness 123 – pH adjustment 123f – quality 14, 107, 119, 123 – rejuvenation 13 – stabilization 209 – taste 126, 209 – volatile acidity 123 y yeast – membrane bioreactors 208f., 211 – residues 106 – surplus 10 yoghurt – processing 50 – selective demineralization 50 j247 ... Bacteria and Spore Removal 46 46 Contents 3. 2.1.2 3. 2.2 3. 2.2.1 3. 2.2.2 3. 2 .3 3.2 .3. 1 3. 2 .3. 2 3. 3 3. 3.1 3. 3.2 3. 3 .3 3 .3. 3.1 3. 3 .3. 2 3. 3 .3. 3 3. 3 .3. 4 3. 3.4 3. 4 Casein Micelles Separation from Whey... Modification 37 Outlook 38 References 39 2.1 2.2 2.2.1 2.2.2 2.2 .3 2.2.4 2 .3 2 .3. 1 2 .3. 2 2 .3. 3 2 .3. 4 2 .3. 5 2.4 2.5 2.5.1 2.5.2 2.5 .3 2.6 3. 1 3. 1.1 3. 1.1.1 3. 1.1.2 3. 2 3. 2.1 3. 2.1.1 23 Milk and Dairy... ISBN- 13: 978 -3- 527-40471-1 Pereira Nunes, S., Peinemann, K.-V (eds.) Membrane Technology in the Chemical Industry 2006 ISBN: 978 -3- 527 -31 316-7 Membrane Technology Volume 3: Membranes for Food Applications