8

Membrane Separation Technology in Processing Bioactive Components

Ashwani Kumar
National Research Council of Canada

CONTENTS
8.1 8.2 8.3 Introduction ..................................................................................................193 Membrane Basics.........................................................................................194 Applications .................................................................................................195 8.3.1 Preconcentration...............................................................................196 8.3.2 Fractionation.....................................................................................197 8.3.3 Hybrid Processes..............................................................................199 8.3.4 New Membrane Processes ...............................................................201 8.3.5 Cleaning Chemical and Solvent Recycling .....................................203 8.4 Summary ......................................................................................................204 Acknowledgments..................................................................................................205 References..............................................................................................................205

8.1 INTRODUCTION
In recent years there has been a lot of interest in functional foods and nutraceuticals, particularly their impact on human health and prevention of certain diseases. Manufacturers have responded to this sudden demand by releasing a large number of products. However, there is a lot of scope of research and development in making safe, reliable, and effective products from complex matrices of natural products. In addition to growing good-quality natural products, there are challenges in harvesting, postharvest treatment, extraction, rening, analysis of active ingredients, and safety before an effective and reliable product is made. Although all of the above activities

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play an important role in making a good product, special attention needs to be focused on separation and purication mainly due to the fact that 40% to 80% of the cost of production is assigned to separation and purication unit operations in making functional foods and nutraceuticals. Therefore, a lot of research effort has gone into developing efcient extraction and separation schemes. This chapter will mainly focus on rening and purication of bioactive compounds from natural products using membrane-based separation schemes. Membrane-based processes are usually more energy efcient than distillation, adsorption, and chromatography. Furthermore, membranes have the advantage of compatibility with a wide range of solvents and chemical products, ability to process thermally sensitive compounds, easy amenability to automation, smaller footprint, and seamless scale up. These advantages open up several possibilities of membrane application in the production of bioactive compounds in the areas of energy efcient preconcentration of dilute solutions, fractionation of diverse classes of compounds from a complex mixture, recovery of intermediates, and recycling of solvents. However, it is also important to be aware of the challenges posed by membranebased separation schemes, such as limited selectivity, fouling leading to performance decline, cleaning, and higher capital costs in certain installations. This chapter is divided in to three sections dealing with membrane basics, applications, and nal remarks.

8.2 MEMBRANE BASICS

Membranes could be described as barriers that provide selective and controlled passage of one component over the other from a multicomponent mixture. Membranes have been classied by pore sizes, materials, driving forces and devices, even specic applications. The basic denitions and principles of operation have been described in textbooks.1,2,3 The membranes are usually made of polymeric, ceramic, and metallic materials and are semipermeable to mixture components. These can be in at sheet, spirals, hollow bers, and tubular form and can be housed in specially designed housing or modules for applications. Membranes are often used in cross-ow ltration mode and permeation or rejection of a particular component mainly depends on the pore size, morphology, and interactions of feed components with membrane materials. A membranes ability to reject a solute is often expressed in molecular weight cutoff, which is determined by sieving experiments with standard solutes of varying molecular weights. A brief summary of the main types of membranes and their characteristics is given in Table 8.1 for those processes that are most relevant for functional foods and nutraceutical applications. In processing complex matrices of natural products, the extracts usually contain many dissolved and suspended species with varying physical and chemical properties. The separation and purication steps are complex. Considering that a variety of membrane-based processes that operate on different principles are available (Table 8.1), one can envision that these processes could have an effective role in separation schemes. Based on the knowledge of the characteristics of extracts and species of interest, one can select a suitable membrane process. The process development generally involves screening of commercially available membranes under different

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TABLE 8.1 Membrane Processes and Their Characteristics

Membrane Process Pervaporation Reverse Osmosis Nanoltration Driving Force Vacuum Pressure Pressure Molecular Pore Sizes, Weight Cutoff, nm Dalton <1 <1 110 Low 1001000 Species Retained Nonvolatile or afnity basis Ions, large molecules Multivalent ions, large molecules Macromolecules, pathogens Large macromolecules, some pathogens Non-ionic solutes Nonvolatile solute Nonextractable species Species Permeated Volatile or afnity basis Water, alcohol Monovalent ions, water, alcohol Ions, water, alcohol, small molecules Some macromolecules, ions, water, alcohol Ionic solutes Water Extractable species

Ultraltration

Pressure

10100

1000100,000

Microltration Pressure

10010,000

Electrodialysis Electric current Osmotic Partial pressure distillation difference Membrane Concentration solvent gradient extraction

operating variables such as cross-ow velocities, permeate rate, operating pressure, and temperature. Longer-term process evaluation is also used to establish membrane cleaning schedules for restoring performance. This basic laboratory data is utilized to run pilot-scale experiments to ascertain the overall viability of the process for a particular application. These laboratory experiments and analysis of collected data are well described, particularly for food applications.1,3

8.3 APPLICATIONS
It is obvious from the description given in Section 8.2 that separation characteristics of membranes are dependent not only on the physicochemical properties of the membrane but also on the feed characteristics and operating variables. This observation also provides a broad basis for developing applications of membranes in separation and purication to suit particular requirements of bioactive compounds from a complex mixture. The following sections present a summary of membranebased separation processes.

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8.3.1 PRECONCENTRATION
Most of the process streams in the functional food and nutraceutical industries have very small amounts of dissolved solids of interest. Irrespective of the extracting solvent, a preconcentration step is essential prior to drying and making the nal products. In traditional processes this step is usually thermal in nature, which is accomplished by thermal evaporation or distillation. Energy consumption for removing 1 kg of water from dilute solutions is listed in Table 8.2. It is obvious that a membrane-based preconcentration is very energy efcient. Furthermore, membranebased processing is suitable for thermally sensitive nutraceuticals and functional foods and helps in maintaining the natural taste of the nal product by avoiding the heat-induced taste prole changes. In a U.S. Department of Energy study, it was clearly pointed out that current usage of membrane-based separation schemes in the food processing industry will expand and have a signicant impact on reducing energy consumption.4 Concentration of several food products, such as fruit juices, maple sap, seafood cooker water, and corn light steep water, using reverse osmosis membranes have been reported.5,6,7 However, it should be noted that these applications are limited by the osmotic pressure of the dissolved species and fouling of membranes. Concentration applications are implemented more effectively using membrane-based separation as part of the overall process. Similar applications in nutraceuticals and functional foods are possible; however, published reports are scant. Ekanayake et al.8 patented a process describing the concentration of green tea extract with nanoltration. These inventors claimed superior quality of the membrane-concentrated product in masking the taste of articial sweeteners in beverages. Gugger and Grabiel9 utilized temperature-dependent solubilities of soy isoavones for concentration by ultraltration membranes. The target compound in the feed stream was rst adsorbed on a resin. The eluted isoavone fractions were treated with either reverse osmosis or ultraltration to remove solvent and achieve a higher isoavone concentration in the retentate, which was spray dried to make the nal product. Recently, a similar approach for concentration of isoavones from soybean process waste and extract of red clover owers has been reported by Xu et al.10,11 In these studies concentration by membranes played an important role in making the nal product.

TABLE 8.2 Energy Consumption in Preconcentration of Dilute Solutions by Different Unit Operations (Kumar et al. 1999)
Unit Operation Thermal evaporation Mechanical vapor recompression (MVR) Membranes Energy Consumption, kJ/kg Water Removed 2100 350 90

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8.3.2 FRACTIONATION
Considering that most nutraceuticals and functional foods are produced from complex matrices such as grains, botanicals, and fermentation broths, isolation and purication of the desired active components is very important for product efcacy. A membrane-based separation scheme has vast potential to make an impact in this area, particularly where compounds of interest are of comparable molecular weight, have similar chemical makeup, and impurities are signicantly different from the target compounds. Several studies utilizing membranes in fractionation of food products from grains, meat, and poultry have been described.3,4 Recently the separation of individual whey proteins (alpha-lactalbumin and betalactoglobulin) for use as nutraceuticals was reported. This laboratory study utilized both cellulosic and polyethersulfone membranes and reported the optimal ltration conditions, showing that a dialtration process yielded beta-lactoglobulin as the retentate product with a purication factor of 100 and recovery of 90%. Alphalactoalbumin was recovered in the ltrate with a purication factor of more than 10 and nearly 99% yield.12 A product made from oat extract in water/alcohol mixture and fractionated by membranes to get the active ingredient avenanthramides in reasonably high concentration for skin-care products was patented by Redmond and Fielder.13 The reported process claimed the use of ultraltration membranes for separating the active ingredients from crude extract and reverse osmosis membranes for concentration before making the nal product. Singh14 has reported a process for making high soy protein concentrate (> 70%) with reasonably high concentration of isoavones and saponins while the polysaccharide concentration was reduced. Fractionation of the protein was accomplished by adjusting the pH and using a 10 to 30 kDa ultraltration membrane. Yamaguchi et al.15 reported the use of ultraltration for isolating nicotianamine from water extracts of soybeans. Chou16 has patented a process to make antioxidant-rich compositions prepared from sugar cane and beet juices. A relatively high concentration of polyphenolics and avonoids present in the juices were fractionated by various methods including ultraltration to get a retentate that showed very high oxygen radical absorbance capacity (ORAC) even at 50% recovery of thin juice. Mulligan and Gibbs17 reported using ultraltration for purifying glycolipids; however, only 77% of the product was retained. Buchholz et al.18 improved this process by adjusting the pH of the feed to retain 99% of the product. They have optimized the operation by using ultraltration in regular as well as dialtration mode. Frangi et al.19 reported a procedure to extract procynidol from crude vegetable extract of Vitis vinifera using ultraltration membranes. Though the reported product was free from monomers, the procedure required longer processing time and chlorinated solvents, which are not desirable due to environmental and health concerns. NasiMovaghar et al.20 patented a process that used only blends of polar solvent and water for extraction and employed ultraltration for separating proanthocynadins from the rest of the large molecular weight compounds while nal extract was concentrated by reverse osmosis. Their ow sheet also included steps to recycle solvents. Nwuha21 screened a series of ultraltration membranes for separating green tea catechins and

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identied the alcohol stable membranes. However, rejection value for catechins and caffeine were not sufciently different to make a caffeine-free catechin product. There has been concern among a section of consumer about the use of aggressive chemicals and solvents in processing nutraceuticals and functional foods. In keeping this in mind, process development for rening compounds of interest from a complex matrix has been attempted using only water extraction. Considering that membranebased processes largely involve inert material, these could be a natural choice for fractionation of such extracts. However, it is also important to note that the choice of extraction procedure plays an important role in downstream processing with membranes. One interesting example is development of a membrane-based process for rening natural sweeteners from stevia leaves extract.22,23 Extraction of glycoside sweeteners was accomplished in lightly packed column at an optimized pH, temperature, and ow rate to extract most of the sweetener and least amount of phenolics and lipids that might cause fouling problem during subsequent processing by membranes. Microltration of the extract removed suspended and colloidal impurities while sweeteners and dissolved compounds permeated through the membrane. Permeate from microltration was ultraltered with a membrane of 2 to 3 kDa molecular weight cutoff , followed by dialtration in a batch mode until all sweeteners were washed out. Values of sweetener concentration in permeate at different dialtration volumes of the original feed and permeate ux are listed in Table 8.3. It is obvious from the table that most of the sweetners are recovered at a dialtration volume of 3 to 4. The permeate from ultraltration was processed at higher than ambient temperatures by a reverse osmosis membrane to concentrate the glycosides and remove lower molecular weight components that are perhaps responsible for bitter aftertaste of the product. It was also found that by raising the processing temperature from 50C to 800C, the amount of impurities removedwas increased from 55% to 89%. A conceptual process ow diagram is given in Figure 8.1. Though the nal product from this process had a very good taste prole, the overall yield was lower than conventional processes based on solvent extraction. In a later study,24 a sequential extraction by solvents such as alcohols and hexane was followed with membrane processing of the extract. This process gave higher yields and good-quality product.

TABLE 8.3 Stevioside Concentration and Permeation Rates for Different Dialtration Volumes in Ultraltration Step
Dialtration Volume 0 2.0 3.0 4.0 ND - not detected Sweetener Concentration, g/l 1.5 0.75 0.25 ND Permeation Rates, l.m2h1 35 47 64 65

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HEX MF Perm DF DF

UF

DF NF

Sweetener concentrate

Water recycle

FIGURE 8.1 Conceptual process ow diagram for producing stevia sweetener concentrate; HEX is heat exchanger; DF, UF, and NF are dialtration, ultraltration, and nanoltration.

One very interesting nding of this study was that prior solvent treatment of stevia leaves was helpful in removing some of the natural products such as lipids, phenolics, and chlorophyll, which are known to foul membranes. Obviously, membrane processing of this extract was relatively easy and the overall yield of the sweeteners was higher than the previous water-based process.23

8.3.3 HYBRID PROCESSES

Efciency of a separation process to some extent depends on the type of material to be separated. In this regard membrane-based separations are no exception. Often, a membrane-based scheme could achieve good results; however, there are theoretical (e.g., osmotic pressure of the dissolved species) and material limitations (e.g., surface characteristics leading to fouling). Considering that functional food and nutraceuticals are present in complex matrices containing a large number of chemically different species, their separation and purication pose additional challenges. In order to develop these challenging applications, so-called hybrid processes are often very effective due to additional controls over the range of operating variables. Basically, a hybrid process combines more than one unit of operations to create overall synergy in the separation scheme. Hybrid processes have been reported1 utilizing pervaporation and distillation; reverse osmosis and multistage ash distillation; pressure swing adsorption and membrane permeation; condensation and vapor permeation; and reverse osmosis and freeze drying. Often the output stream from one process becomes the input stream for the next process. It appears that this hybrid process approach has not been often utilized in separation and purication of functional foods and nutraceuticals. Selected examples from literature are described below:

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In a process reported by Cheryan,25 extraction of two major proteins present in corn meal was done in aqueous alkaline medium and the proteins were separated by centrifugation. The individual proteins zein and glutelin were separated by using a combination of ultraltration and ethanol extraction. The permeate of ultraltration was also recycled using a reverse osmosis membrane. Seafood process cooker water usually contains suspended solids, protein, amino acids, and avoring components. The suspended solids are removed by centrifugation or sieving, and proteins are concentrated by several folds with protein recoveries up to 90%.7,26 Nasi-Movaghar et al.20 patented a process for extraction and rening of proanthocynadins from plant material. Their approach was different from earlier processes19 using a number of solvents, which allowed ultraltration only in the batch process. They used heat and pressure to extract proanthocynadins from plant matter, followed by ultraltration and chromatographic separation. Ethanol eluted proanthocynadins mixture was concentrated by reverse osmosis before drying the concentrate to powder. Borneman et al.27 reported a process for removing polyphenols from apple juice using a specially made ultraltration membrane that utilized adsorptive capabilities of polyvinyl pyrrolidine. A new process for making defatted soymilk with higher isoavone concentration was reported by Xu et al.28 This process used wet grinding and centrifugation at a higher ratio of bean to water and separated fat by centrifugation. However, the protein concentration in the soymilk so produced was lower, which was brought up to 3% by ultraltration. The permeate from a 30 kDa ultraltration membrane was also rich in isoavones. This stream was used to develop another process for recovering soy isoavones (Xu et al.11) by ultraltering the permeate from milk production by a 1 kDa membrane. This lower molecular weight membrane was selected to reject phytates. The amount of isoavones in ultraltration permeate at varying processing conditions is shown in Figure 8.2. It is obvious from this gure that permeate from the high-temperature ultraltration of cooked milk was richest in isoavones. It is mainly due to the dissociation of isoavones from proteins at higher processing temperatures. The permeate was concentrated with a commercial reverse osmosis membrane by 90%. The concentrate was further dried to make a powder that contained 11 mg/g isoavones, which represented 8.4% mass yield of dried beans. Soy-based isoavones are commonly used as nutraceuticals; however, these have been associated with estrogenic activity in a recent publication.29 Red clover owerbased products have high amounts of isoavones and do not show any estrogenic activity. Although there are compositional differences in isoavones extracted from soy beans (aglicones and glycosides) and red clover owers (bichanin A and formononetin), their absorption in humans is similar.30 A process for extraction and rening isoavones from red clover owers was developed31 that involved alkaline extraction, adsorption on polyvinylpolypyrrolidone powder, elution by ethanol, concentration, and nally freeze drying. The nal product contained 20% isoavones, which accounted for more tham 50% of the isoavone content of dried red clover owers. Although the recovery and the concentration of isoavones in the nal product were reasonably high, this process had numerous steps. A simpler process involving extraction by ethanol-water blends followed by processing with ultraltration and reverse osmosis membranes was recently developed.32 The process

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50 Permeate 45 40 Isoavone yield in permeate (%) 35 30 25 20 15 10 5 0 Soymilk

No cooking, UF at 21C

With cooking, UF at 21C

With cooking, UF at 50C

FIGURE 8.2 Yield of isoavones in UF permeate as percentage of total amount in soybeans; results are presented as total amount of isoavones in soybeans; error bars are based on duplicate runs.

utilized the solvation properties of ethanol-water blends and formation of micelles by partial removal of solvents. In this process the overall recovery of isoavones from dried red clover owers was 35% while the concentration of isoavones in the nal product was 9%, which is lower than the earlier process but was suitable for making nutraceutical supplements. Process ow diagrams of these two processes are shown in Figure 8.3. It is obvious that a membrane-based process has a reduced number of process steps with little penalty to overall recovery. Furthermore, this process offers the possibility of recycling the solvents. Obviously, in selecting a proper process, an overall assessment needs to be done.

8.3.4 NEW MEMBRANE PROCESSES

In previous sections, membrane-based processes that are more frequently used in well-established food process industry are described with examples of applications in the nutraceutical and functional food industry. However, there are several new membrane-based processes that are at various stages of development and perhaps have potential for application in the industry. Selected examples of these developing membrane processes are given below. A review of the applications of pervaporation in food processing has been published by Karlsson and Trgrdh.33 Pervaporation of avoring compounds from grape juice34,35 and ester-based avoring compounds36 have been reported. It was observed that in the presence of increasing amounts of ethanol vapors the recovered

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Ground red clover owers Ethanol solution Dried and powdered red clover blossom Dried isoavone concentrate

Extraction

Spent residue

Batch extraction in water at constant temperature and pH

Freeze drying Alkali Liquid isoavone concentrate

Ethanol extract

Washing

Ultraltration

Retentate

Filter on a 50200 mesh sieve

Rejects Condensate

Vacuum evaporation

Permeate

Reverse osmosis Filtrate + PVP and adjust pH PVP adsorbent for reuse Ethanol-eluted isoavones

Permeate

Retentate Ethanol evaporation

Centrifuge

Adsorbent PVP with isoavones

Water washing of adsorbent

Ethanol elution of isoavones

Aqueous solution Supernatant liquid Wash water Refrigeration

Supernatant

Micelles Drying

Isoavone-enriched product

(a)

(b)

FIGURE 8.3 (a) Extraction and polymeric adsorption-based process ow diagram, (b) extraction and membrane-based process ow diagram.

aroma prole was changed signicantly. A very comprehensive study on the screening of numerous commercial membranes for recovering peach avors was also reported.37 A similar approach could be used to recover volatile components such as essential oils present in plant materials. A membrane-based solvent extraction process could overcome many of the problems encountered in a traditional solvent extraction process involving dispersion, coalescence, emulsication, and loading limits. Membrane hollow bers made with hydrophobic material could be used to provide signicantly higher contacting area that would provide very high extraction rates for selective solvent extraction of the desired species present in the aqueous phase across the membrane barrier. Prasad and Sirkar38,39 have reported the use of this techniques for purifying mevinolinic acid and thiazoles using different solvents. The purity of the products was very high and the membranes did not show any deterioration after long-term use. Dahuron and Cussler40 have reported extraction of proteins using polyethyleneglycol containing potassium phosphate. Recently Kertsz et al.41 have reported a simultaneous solvent extraction and stripping process for recovering phenlanaline in n-alkanes

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containing a phosphoric acid derivative. These authors have presented a comprehensive study of mass transfer and kinetics of this system. Reviews of potential food application of electroltration have been published by Vradis and Floros42 and Bazinet et al.43 They have provided the theoretical basis as well as the potential of this technique to overcome some of the fouling problem in regular pressure driven membranes processes, particularly for the charged species in the feed. Pressure ltration of bioactive compounds is dependent on the ionic environment of the feed as it inuences the hydrodynamic radius of species. Hofmann and Posten44 have given a sound basis for enhanced ux in separation of biopolymers and proteins under the inuence of electric eld. Recently, Labb et al.45 have reported feasibility of separating green tea polyphenols by electroltration. These authors reported that up to 50% concentration of epagallocatechin and epagallocatechin gallate could be achieved without signicant migration of caffeine. However, a similar study to recover polyphenols from tobacco extracts encountered serious membrane fouling.46 A feasibility study of separating bioactive peptide from casein isolates has been reported by Bargeman et al.47 These authors reported that active peptide was concentrated from 7.5% to 26%. Obviously, additional studies to develop these techniques for commercial applications are required. Osmotic distillation process uses the vapor pressure difference as the driving force while the feed stream and concentrated osmotic agent stream are separated by a hydrophobic porous membrane. This technique is particularly suitable for heat-sensitive compounds and has largely been used for concentration of fruit juices.48,49 Recently Babu et al.50 reported concentration of lime juice and phycocynin colorant by osmotic membrane distillation. They have studied the effects of various parameters on ux and developed models to predict ux using resistance models. Afnity membrane separation combines afnity chromatography and traditional pressure-driven membrane separation processes. This technique is suitable if the feed stream contains several compounds of comparable molecular weight and characteristics to the compound of interest. A ligand or binding agent that has afnity to the compound of interest is added to the feed solution and separated from other compounds by membranes. The retentate from the process is treated with a proper eluent to dissociate the ligand and the compound of interest is separated by a second membrane ltration step. Matthiasson and Ling51 successfully separated biologically active concavalin A from jack beans using S cerevisia cells as ligands and D-glucose as eluent. Considering that micelles are larger than the dissolved organic solutes, surface active agents also have been used to make micelles with the key component of the feed for easy separation.52 Ruckenstein and Zeng53 reported the development of chitin-silica membranes for separating lysozyme from ovalbumin. These membranes were an order of magnitude superior to the chitin beads for this separation and could be used for larger-scale separation.

8.3.5 CLEANING CHEMICAL

AND

SOLVENT RECYCLING

In a membrane-based separation process, various cleaning chemicals are periodically used for restoring membrane performance as well as cleaning and sterilizing the ancillary equipment. These procedures have added importance for the nutraceutical

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and functional food industry for maintaining a higher level of purity and safety of products for human consumption. The cleaning uids are composed of caustic solution, surfactant solution, enzymes, and chemicals, or a combination of these ingredients. With repeated use, these cleaning uids are contaminated with impurities and need to be replaced. This adds to the cost of operation in replacement chemicals as well as disposal fees. A membrane-based recycling of these cleaning uids is attractive as properly selected membranes could remove suspended, colloidal, and dissolved species while water and active cleaning agent could be recycled. Caustic recycling in orange juice and dairy plants is in use and has replaced more energy-extensive evaporation systems.54 By using a multistage membrane separation scheme, other cleaning agents could also be recovered. As discussed in Section 8.3.3, organic solvents are used in extraction and elution of nutraceuticals extensively. A membrane-based approach can recover and concentrate the compound of interest and allow the recycling of solvent. For example, a typical reverse osmosis membrane will permeate water and ethanol while retaining compounds of interest. There are some commercial membranes that are suitable for alcohol and hexane recycling; however, there are very few membranes that are suitable for other solvents such as ketones and esters that are often used in the extraction of functional food and nutraceuticals. There have been several reports of new solvent-resistant nanoltration membranes55,56,57,58 that might be suitable for recovery of compounds in the range of 300 to 900 Da molecular weights, which includes a large number of nutraceuticals.

8.4 SUMMARY
In recent years there has been great interest in using plant-derived functional food and nutraceuticals. These compounds are usually present in low concentrations in a complex matrix; therefore, extraction, separation, and purication is generally very expensive. Opportunities offered by membrane-based processes in concentration, fractionation, and purication of these compounds have been identied in this work. Several examples of processes utilizing a membrane unit operation in combination with other unit operations such as extraction, adsorption, and thermal evaporation are presented. Multistage membrane processes for rening desired compounds are also discussed. Several new membrane processes are briey described that need to be developed further for use in functional food and nutraceutical production. Membrane-based processes for recycling chemicals and solvents used in the functional foods are also highlighted as potential applications. Finally, the challenges for researchers in developing newer products and processes relevant for the functional food and nutraceutical industry are identied. Use of membranes in water purication and wastewater treatment alone or in combination with other unit operations is fairly well established. Membrane-based separation schemes are now making inroads into many other chemical processes, food, and dairy industries. Advantages of the membrane-based approach in nonthermal processing, energy efciency, easy amenability to automation, modular nature, and generally smaller footprint have been clearly exploited. Potential of a

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hybrid-process approach needs to be exploited further even with the presently available technology. Many of the new membrane processes have potential applications in functional food processing; however, these need to be researched further with particular focus on material and process development. Membrane researchers have many challenges to overcome in the areas of membrane materials, morphologies, and surface characteristics that have an impact on compatibility of membrane with feed stream, separation performance, and resistance to fouling. Although many of the specically targeted compounds are extracted from complex matrices using aggressive solvents, often at higher than ambient temperature and extremes of pH, there are very few membranes in the market to process such streams economically and effectively. Therefore, there is a need for developing membranes that are suitable for treating such feeds.

ACKNOWLEDGMENTS
The author is thankful for the support of his colleagues in the Advanced Separation Technology Project.

REFERENCES
1. Ho, W.S.W. and Sirkar, K.K., Membrane Handbook, Chapman and Hall, New York, 1992. 2. Mulder, M., Basic Principles of Membrane Technology, 1st ed., Kluwer Academic Publishers, Dordrecht, 1996. 3. Cheryan, M., Ultraltration and Microltration Handbook, Technomic, Lancaster, PA, 1998. 4. Mohr, C.M., Engelgau, D.E., Leeper, S.A., and Charboneau, B.L., Membrane Applications and Research in Food Processing, Noyes Data Corporation, Park Ridge, NJ, 1989, 15. 5. Williams, M.E., Bhattacharya, Ray, and McCray, in Membrane Handbook, Ho, W.S.W. and Sirkar, K.K, Eds., Chapman and Hall, New York, 1992, 346. 6. Singh, N. and Cheryan, M., Membrane technology in corn rening and bioproductprocessing, Starch - Strke, 50(1), 16, 1998. 7. Kumar, A., Croteau, S., and Kutowy, O., Use of membranes for energy efcient concentration of dilute streams, Appl. Energy, 64, 107, 1999. 8. Ekanayake, A., Bunger, J.R., and Mohlenkamp, M.J., Jr., Green Tea Extract Subjected to Cation Exchange Treatment and Nanoltration to Improve Clarity and Color, U.S. Patent 6,268,009, July 31, 2001. 9. Gugger, E. and Grabiel, R., Production of Isoavone Enriched Fractions from Soy Protein Extracts, U.S. Patent 6,171,638, January, 2001, and U.S. Patent 6,565,912, May 20, 2003. 10. Xu, L., Lamb, K., and Kumar, A., A membrane-based process for recovering isoavones from a waste stream of soy processing, Food Res. Int., 37, 867, 2004. 11. Bhattacharjee, S., Bhattacharjee, C., and Datta, S., Studies on the fractionation of lactoglobulin from casein whey using ultraltration and ion exchange membranes chromatography, J. Membrane Sci., 275, 141, 2006.

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12. Cheang, B. and Zydney A.L., Separation of alpha-lactalbumin and beta-lactoglobulin using membrane ultraltration, Biotechnol. Bioeng., 83(2), 201, 2003. 13. Redmond, M.J. and Fielder, D.A., Oat Extracts: Rening, Compositions and Methods of Use, U.S. Patent, 6,818,232, November 16, 2004. 14. Singh, N., Soy Protein Concentrate Having High Isoavone Content and Process of Its Manufacture, U.S. Patent 6,818,246, November 16, 2004. 15. Yamaguchi, N. et al., Method for Producing Nicotianamine and Nicotanamine-Containing Matter, Japanese Patent 2003, 231,675A, August 19, 2003. 16. Chou, C. C., Preparation Antioxidants Enriched Functional Food Products from Sugar Cane and Beet, U.S. Patent Application 2003 0,198,694, published October 23, 2003. 17. Mulligan, J. and Gibbs, P., Recovery of biosurfactants by ultraltration, J. Chem. Tech. Biotechnol., 47, 23, 1990. 18. Buchholz, R., Ulrich, F., and Mixich, J., Process for Preparing Puried Glycolipids by Membrane Separation Process, U.S. Patent 5,440,028, August 8, 1995. 19. Frangi, E. et al., Process for Preparing Grape Seed Extracts Enriched in Procynidol Oligomers, U.S. Patent 5,4845,94, January 16, 1996. 20. Nasi-Movaghar, K., Svanoe, T.T., and Seroy, W.A., Method for Extraction of Proanthocynadins from Plant Material, U.S. Patent 5,912,363, June 15, 1999. 21. Nwuha, V., Novel studies on membrane extraction of bioactive components of green tea in organic solvents: part I, J. Food Eng., 44, 4, 233. 22. Zhang, S.Q., Kumar, A., and Kutowy, O., Membrane-based separation scheme for processing sweeteners from stevia leaves, Food Res. Int., 33, 617, 2000. 23. Kutowy, O., Zhang, S.Q., and Kumar, A., Extraction of Sweet Compounds from Stevia Rebaudiana Bertoni, U.S. Patent 5,972,120, October 26, 1999. 24. Kutowy, O. and Kumar, A., Improved Stevia Extraction and Rening, Provisional U.S. Patent led on February 18, 2004, Appl. No. 60/545,167. 25. Cheryan, M., Ultraltration and Microltration Handbook, Technomic, Lancaster, PA, 1998, 418. 26. Cheryan, M., Ultraltration and Microltration Handbook, Technomic, Lancaster, PA, 1998, 427. 27. Borenman, Z., Gokeman, V., and Nijhvis, H.H., Selective removal of polyphenols and brown color in apple juices using PES/PVP membranes in a single ultraltration process, Separ. Puric. Technol., 22, 53, 2001. 28. Xu, L., Kumar, A., and Lamb, K., A laboratory study for developing an aqueous process to make skimmed soymilk, J. Am. Oil Chem. Soc., 81, 91, 2004. 29. Atkinson, C. et al., Red clover-derived isoavones and mammographic breast density: a double-blind, randomized, placebo-controlled trial [ISRCTN42940165], Breast Cancer Res., 6, R170, 2004. 30. Tsunoda, N., Pomeroy, S., and Nestel, P., Absorption in humans of isoavones from soy and red clover is similar, J. Nutr., 132, 2199, 2002. 31. Xu, L. et al., Production of an isoavone concentrate from red clover owers, J. Food Sci., 70, 5558, 2005. 32. Xu, L. et al., Recovery of isoavones from red clover owers by a membrane-based process, Innov. Food Sci. Emerg. Technol., in press, 2006. 33. Karlsson, H.O.E. and Trgrdh, G., Applications of pervaporation in food processing, Trends Food Sci. Technol., 7, 78, 1996. 34. Rajgopalan, N. and Cheryan, M., Pervaporation of grape juice aroma, J.Membrane Sci., 104, 243, 1995. 35. Schafer, T. et al., Recovery of aroma compounds from a wine-must fermentation by organophilic pervaporation, Biotechnol. Bioeng., 62, 412, 2000.

2007 by Taylor & Francis Group, LLC

Membrane Separation Technology in Processing Bioactive Components

207

36. Baudot, A. and Marin, M., Improved recovery of an ester avor compound by pervaporation coupled with ash condensation, Ind. Eng. Chem. Res., 38, 4458, 1999. 37. Song, B., Lee, J.-H., and Choi, Y.-H., A pervaporation technique for peach avors using PDMS and DS-7 membranes, Food Eng. Progress, 6, 133, 2002. 38. Prasad, R. and Sirkar, K.K., Hollow ber solvent extraction of pharmaceutical products, J. Membrane Sci., 47, 235, 1989. 39. Prasad, R. and Sirkar, K.K., Hollow ber solvent extraction: performance and design, J. Membrane Sci., 50, 153, 1990. 40. Dahuron, L. and Cussler, E.L., Protein extraction with hollow bers, Am. Inst. Chem. Eng. J., 34, 130, 1988. and Schlosser, S., Membrane-based solvent extraction and 41. Kertsz, R., Simo, S., stripping of phenylalanine in HF contactors, J. Membrane Sci., 257, 37, 2005. 42. Vradis, I. and Floros, J., Electrically assisted membrane separation processes, in Food Process Design and Evaluation, R.K. Singh, Ed., 1995, CRC Press, Boca Raton, FL. 43. Bazinet, L., Lamrche, F., and Ippersiel, D., Bipolar-membrane electrodialysis: applications of electrodialysis in the food industry, Trends Food Sci. Technol., 9, 107, 1998. 44. Hofmann, R. and Posten C., Improvement of dead-end ltration of biopolymers with pressure electroltration, Chem. Eng. Sci., 58, 3847, 2003. 45. Labb, D. et al., Electromigration feasibility of green tea catechins, J.Membrane Sci., 254, 101, 2005; Matthiasson, B. and Ling, T.G.I., Ultraltration afnity purication: a process for large scale bioseparation process, in Membrane Separations in Biotechnology, McGregor, W.C., Ed., 1986, Marcel-Dekker, New York. 46. Bazinet, L., DeGrandpr, Y., and Porter, A., Enhanced tobacco polyphenol electromigration and impact on membrane integrity, J. Membrane Sci., 254, 111, 2005. 47. Bargeman, G. et al., The development of electro-membrane ltration for the isolation of bioactive peptides: the effect of membrane selection and operating parameters on the transport rate, Desalination, 149, 369, 2002. 48. Cisse, M. et al., The quality of orange juice processed by coupling crossow microltration and osmotic evaporation, Int. J. Food Sci. Technol., 40, 105, 2005. 49. Bui, A.V. and Nguyen, H.M., Scaling up of osmotic distillation from laboratory to pilot plant for concentration of fruit juices, Int. J. Food Eng., 2, 5, 2005. 50. Babu, B.R., Rastogi, N.K., and Raghavarao, K.S.M.S., Mass transfer in osmotic distillation of phycocyanin colorant and sweet-lime juice, J. Membrane Sci., 272, 58, 2006. 51. Matthiasson, B. and Ling, T.G.I., Ultraltration afnity purication: a process for large scale bioseparation process, in Membrane Separations in Biotechnology, McGregor, W.C., Ed., 1986, Marcel-Dekker, New York. 52. Scamehorn, J.F. and Harwell, J.H., An overview of surfactant-based separation processes, Surface Sci. Ser., 26, 341, 1987. 53. Ruckenstein, E. and Zeng, X., Macroporous chitin afnity membranes for lysozyme separation, Biotechnol. Bioeng., 56, 610, 2000. 54. Cheryan, M., Ultraltration and Microltration Handbook, Technomic, Lancaster, PA, 1998, 384. 55. Bhanusali, D. and Bhattacharyya, D., Advances in solvent resistant nanoltration membranes: experimental observations and applications, Annals New York Acad. Sci., 984, 159, 2003. 56. Yang, X.J., Livingston, A.G., and Fretas dos santos, L., Experimental observations of nanoltration with organic solvents, J. Membrane Sci., 190, 45, 2001.

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208

Functional Food Ingredients and Nutraceuticals

57. Musale, D.A. and Kumar, A., Solvent and pH resistance of surface crosslinked chitosan/poly(acrylonitrile) composite nanoltration membranes, J. Appl. Polym. Sci., 1782, 77, 2000. 58. Musale, D.A. and Kumar, A., Effects of surface crosslinking on sieving characteristics of chitosan/poly(acrylonitrile) composite nanoltration membranes, Separ. Purif. Technol., 21, 27, 2000.

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