Perspective of membrane technology in dairy industry: a review
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Transcript of Perspective of membrane technology in dairy industry: a review
For Peer Review
Perspective of membrane technology in dairy industry: A
review
Journal: International Journal of Dairy Technology
Manuscript ID: IJDT-0114-12
Manuscript Type: Review
Date Submitted by the Author: 06-Jul-2012
Complete List of Authors: KUMAR, PAVAN; Sher-e-Kashmir University of Agricultural Sciences & Technology of Jammu, R.S.Pura, Jammu, (J & K), 1Division of Livestock Product and Technology SHARMA, NEELESH; Jeju National University, 2Department of Animal Biotechnology RANJAN, RAJEEV; LLRUVAS, 4Department of Veterinary Pharmacology &
Toxicology KUMAR, SUNIL; Sher-e-Kashmir University of Agricultural Sciences & Technology of Jammu, R.S.Pura, Jammu, (J & K), 1Division of Livestock Product and Technology BHAT, Z.F.; Sher-e-Kashmir University of Agricultural Sciences & Technology of Jammu, R.S.Pura, Jammu, (J & K), 1Division of Livestock Product and Technology Jeong, Dong Kee; Jeju National University, Department of Animal Biotechnology
Keywords: Membrane processes, Microfiltration
International Journal of Dairy Technology
International Journal of Dairy Technology
For Peer Review
Perspective of membrane technology in dairy industry: A review 1
2
PAVAN KUMAR1, NEELESH SHARMA
2, 3, RAJEEV RANJAN
4, SUNIL 3
KUMAR1, Z.F. BHAT
1 and DONG-KEE JEONG
2* 4
1Division of Livestock Product and Technology, Faculty of Veterinary Science & 5
Animal Husbandry, Sher-e-Kashmir University of Agricultural Sciences & 6
Technology of Jammu, R.S.Pura, Jammu, (J & K), India. 7
2Department of Animal Biotechnology, Faculty of Biotechnology, Jeju National 8
University, Jeju, South Korea. 9
3Department of Veterinary Medicine, Faculty of Veterinary Science & Animal 10
Husbandry, Sher-e-Kashmir University of Agricultural Sciences & Technology of 11
Jammu, R.S.Pura, Jammu, (J & K), India. 12
4Department of Veterinary Pharmacology & Toxicology, College of Veterinary 13
Science, LLRUVAS, Hissar, Haryana- 125001, India. 14
15
* Corresponding author: 16
Dong Kee Jeong, 17
Department of Animal Biotechnology 18
Faculty of Biotechnology, Jeju National University, 19
Ara-1 Dong, Jeju-city, Jeju-Do 690-756,South Korea 20
Email: [email protected] 21
Tel : 82-64-754-3331, Fax : 82-64-725-2403 22
23
Running headline: Perspective of membrane technology. 24
25
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Membrane technology has revolutionized the dairy sector. The various types 26
of membranes are used in extending the shelf life of milk without exposure to heat 27
treatment, standardization of the major components of milk for tailoring new products 28
as well increasing yield and quality of the dairy products and concentrating, 29
fractionation and purification of valuable milk components especially valuable milk 30
protein in their natural state. In cheese industry, membranes increase the yield and 31
quality of cheese and control the whey volume, by concentrating the cheese milk. All 32
these makes the membranes as a vital part of dairy industry. With the advancement of 33
newer technology in membrane process, it is possible to recover growth factor from 34
whey. With the introduction of superior membranes as well as newer technology, the 35
major limitation of membranes, fouling or blockage has been overcome to a greater 36
extent. 37
38
Key words: Membrane filtration, demineralization, standardization, concentrating, 39
fractionation, milk purification, 40
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INTRODUCTION 51
The term “membrane technology” is used to collectively represent the 52
separation processes by using specific semi-permeable membrane filters to 53
concentrate or fractionate a liquid into two liquids of different compositions (Winston 54
and Sirkar 1992) by selectively allowing some compounds to pass while encumbering 55
the others. The liquid that is able to pass the membrane is known as “permeates” and 56
retained liquid is known as “retentate” or “concentrate”. In simple term, membranes 57
are typically ‘cross-flow’, where two streams are produced - a ‘permeate’ and a 58
concentrated ‘retentate’ (Fig. 1). The efficiency of membranes is largely governed by 59
the hydrostatic pressure gradients (also known as “transmembrane pressure”) across 60
the membrane and concentration gradient of the liquids. In few cases, electric 61
potential has important role (Winston and Sirkar 1992; Jelen 1992; Klein et al. 1987; 62
Porter 1990). 63
The milk is considered as the best, ideal and a complete food and has an 64
important place in human diet especially in vegetarian diet (Shekhar and Kumar 2011; 65
Shekhar et al. 2010; Kumar et al. 2011b; Kumar and Rai 2010). The milk is an ideal 66
liquid for membrane filtration due to its composition. Membrane technology has been 67
applied in the dairy industry since the early 1960s., but this technology has seen a 68
tremendous growth ever then and now comes the second behind the water treatment 69
technology. Starting in the late sixties, membrane processes gradually have found 70
their way into industrial applications and serve as viable alternatives for more 71
traditional processes like distillation, evaporation or extraction. Based on the main 72
driving force, which is applied to accomplish the separation, many membrane 73
processes can be distinguished (Timmer 2001). The food industry represents 20 to 74
30% of the current 250 million turnovers of membranes used in the manufacturing 75
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industry worldwide. The growth in this market is around 7.5% per year. Several 76
hundreds of thousand square meters of membrane (UF: 400,000; NF: 300,000; RO: 77
100,000; MF: 50,000) are currently operating (Saxena et al. 2009). The largest 78
membrane area is installed in the dairy industry. It has been estimated 2,000,000 m2 79
membrane area were installed for the fractionation of milk and whey. About 2/3 of the 80
membrane area installed in the dairy industry is used for the treatment of whey and 81
about 1/3 for milk (Saxena et al. 2009). The simultaneous development of new base 82
materials for membranes production such as cellulose acetate, polyamides, 83
polysulphons as well as introduction of newer concepts such as reverse osmosis, 84
diafiltration (DF), nanofiltration in membranes resulted their increasingly use in dairy 85
process. Current research and development efforts are directed toward drastic 86
improvements in selectivity while maintaining the inherent high-throughput 87
characteristics of membranes. Although, essentially all membrane processes are used 88
for bioseparation, but greatest interests have been shown in the pressure-driven 89
technologies such as MF or UF (Saxena et al. 2009) (Fig. 2). In the present scenario, 90
various types of membrane separation technologies are available in the market and are 91
commonly using in dairy industry like micro-filtration, ultra-filtration (Balannec et al. 92
2005), nano-filtration (Vourch et al. 2005) and reverse osmosis (Vourch et al. 2005; 93
Balannec et al. 2005). 94
MF is a membrane separation process similar to UF but with even larger 95
membrane pore size allowing particles in the range of 0.2 to 2 micrometers to pass 96
through. The pressure used is generally lower than that of UF process.In the dairy 97
industry, microfiltration is widely used for bacteria reduction and fat removal in milk 98
and whey as well as for protein and casein standardization - especially of cheese milk. 99
MF membranes are especially well suited for the separation of fine particles in the 100
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size range of 0.1–10.0 µm. While UF membranes with 1–100 nm pore size were 101
designed to provide high retention of proteins and other macromolecules (Van Reis 102
and Zydney 2007). UF is a variety of membrane filtration in which hydrostatic 103
pressure forces a liquid against a semipermeable membrane. Suspended solids and 104
solutes of high molecular weight are retained, while water and low molecular weight 105
solutes pass through the membrane. It is a separation/ fractionation process using a 106
10,000 MW cutoff, 40 psig, and temperatures of 50-60°C with polysulfone 107
membranes. It is a medium pressure-driven membrane filtration process. UF in the 108
dairy industry, is used for a wide range of applications such as protein standardization 109
of cheese, milk, powders, fresh cheese production, protein concentration and 110
decalcification of permeates as well as lactose reduction of milk. UF is used to 111
produce the whey protein concentrate, and the permeate is fed directly to RO, which 112
produces water suitable for reuse. NF is a medium to high pressure-driven membrane 113
filtration process. Generally speaking, nanofiltration is another type of reverse 114
osmosis where the membrane has a slightly more open structure allowing monovalent 115
ions to pass through the membrane. Divalent ions are - to a large extent - rejected by 116
the membrane. In the dairy industry, nanofiltration is mainly used for special 117
applications such as partial demineralisation of whey, lactose-free milk or volume 118
reduction of whey. Traditionally, this technology is mainly applied in whey treatment 119
which was later applied in other aspects of dairy processing (Sienkiewicz and Riedel 120
1990). RO is a high pressure-driven membrane filtration process which is based on a 121
very dense membrane. With RO, the membrane pore size is very small allowing only 122
small amounts of very low molecular weight solutes to pass through the membranes. 123
In principle, only water passes through the membrane layer. It is a concentration 124
process using a 100 MW cutoff, 700 psig, temperatures less than 40°C with cellulose 125
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acetate membranes and 70-80°C with composite membranes. In the dairy industry, 126
reverse osmosis is normally used for concentration or volume reduction of milk and 127
whey, milk solids recovery and water reclamation. Some dairy processing plants use 128
RO to polish evaporator condensate. Diafiltration is a specialized type of 129
ultrafiltration process in which the retentate is diluted with water and re-ultrafiltered, 130
to reduce the concentration of soluble permeate components and increase further the 131
concentration of retained components. 132
To get the desired effect, it is sometimes necessary to use a combination of 133
membranes rather than single membrane (Vourch et al. 2005; Balannec et al. 2005). 134
A combination of different membrane processes gives interesting benefits, which 135
cannot be achieve by single membrane operation. The possibility of redesigning 136
overall industrial production by the integration of various already developed 137
membrane operations is becoming of particular interest (Saxena et al. 2009). The use 138
of membrane filtration technology offers a wide range of advantages for the consumer 139
as well as for the producers. 140
1. The membrane technology is a novel non thermal technology that minimizes 141
the adverse effect such as change in phase, denaturation of proteins and 142
change in sensory attributes of temperature rise in the product during filtration. 143
2. They remove unwanted components viz. microorganisms, dregs or sediments 144
that have a negative impact on product quality, making the final product more 145
attractive in texture and increasing its shelf life. 146
3. This is an environment friendly, greener technology due to the low 147
consumption of energy in filtration in comparison to traditional condenser and 148
evaporators. With the ever increasing cost of fossil fuel, membrane technology 149
is full of possibilities of future. 150
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4. The selectivity of membranes is very high due to the unique mechanisms of 151
action such as ion exchange, solution diffusion etc. 152
5. The membranes are suitable to different types of plant design and expansion 153
due to their compact design and need very low maintenance. 154
6. The operations of the membranes are very simple, competitive and do not 155
required any specialized knowledge to handle or operate them. 156
7. During this technology, there is no need to add any extraneous matter for the 157
proper functioning of membrane. 158
However, membranes are having some limitations such as fouling of 159
membranes due to blockage of membrane pores, adsorption of particles on the pores, 160
cake formation and depth fouling (James et al. 2003; Bowen et al. 2002). This is 161
caused by the accumulation of particles or bacteria and sediments present in milk 162
leading the remarkable loss in the efficiency of membranes. Any additional factors 163
such as the presence of bacterial biofilms (Kumar and Anand 1998; Tang et al. 2009) 164
would further aggravate the membrane fouling process resulting in premature 165
membrane replacements having financial consequences. 166
The fouling of membrane remains the major concern in dairy industry 167
(Makardij et al. 1999; Gesan et al. 1995). This major issue of fouling in membranes 168
can be trounce by regular cleaning of membranes at appropriate timer intervals, use of 169
low fouling membranes, membrane modules with suitable channel heights, by 170
applying high pressure, application of electric potential, ultrasound waves, 171
microturbulence, ceramic membranes, uniform transmembrane pressure (UTP) 172
vibrating and rotating disc modules and use of turbulent flow of liquids (Sandblom 173
1974; Howell 1995; Saboya and Maubois 2000; Wakeman and Williams 2002; Al-174
Akoum et al. 2002; Engler and Wiesner 2000; Ding et al. 2002; Winzeler and Belfort 175
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1993; Wakemen and Tarleton 1991; Duriyabunleng et al. 2001; Villameil and de Jong 176
2000; Vishwanathan and Ben 1989; Wakeman 1998). An alternative approach was 177
used for high frequency back pulsing to clean the membrane surface (Levesley and 178
Hoare 1999). 179
The efficiency of a membrane largely depends on the concentration of liquids 180
such as filtering the high concentrated liquids (viscous liquids) markedly decrease the 181
efficiency of membranes and need more time to pass it. 182
183
USE OF MEMBRANE IN DAIRY INDUSTRY 184
185
In the modern dairy processing, membranes play a major role in clarification 186
of the milk, increase the concentration of the selected components as well as 187
separation of the specific valuable components from milk or dairy by- products etc. 188
Membrane separation technology seems a logical choice for the fractionation of milk, 189
because many milk components can be separate on size (Fig. 3) (Brans et al. 2004). 190
Membranes are already well established in the processing of whey and are gaining 191
popularity in other dairy applications (Daufin et al. 2001). The membrane technology 192
improves the economics of dairy by reducing the cost of production as well 193
generating new revenue resources (Siebert et al. 2001). The membrane technologies 194
like MF, UF, NF and RO are used for various purposes for instance control bacterial 195
growth, extend shelf life of milk and milk products, pre-concentrate milk and whey 196
proteins, produce whey protein concentrate and valuable by-products, improve cheese 197
yields and product consistency, fractionate whey and lactose intermediates. 198
Membrane technology proves a suitable and economical alternative to many 199
important processing stage of milk in dairy industry such as centrifugation, 200
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bactofugation, evaporation, demineralization of whey etc. (Pouliot 2008). Physical 201
removal of microorganisms from skim milk by MF is becoming increasingly 202
attractive to the dairy industry. The CO2-aided cold MF process has the potential to 203
become economically attractive to the dairy industry, with direct benefits for the 204
quality and shelf life of dairy products (Fristch and Moraru 2008). Although initial 205
reports have indicated that MF will reject fat and microbes while allowing other milk 206
constituents to pass through the membrane, resulting in (theoretically) a fat-free, 207
bacteria-free milk (Piot et al. 1987; Maubois 1991). 208
In the modern cheese industry, the valuable whey protein isolates from whey 209
make a sizeable income from this industry (Sienkiewicz and Riedel 1990). This 210
converted the disposable problem of whey into a profitable opportunity for cheese 211
makers. In dairy, the pressure driven membrane filters such as MF, UF, NF and RO 212
are most commonly used. The membrane area of RO has stabilized around 60,000 m2, 213
mainly for whey concentration. MF is developing due to its capability to retain, partly 214
or totally, particles (microorganisms, casein micelles, fat globules), and while NF is 215
has a large field of applications due to its intermediate selectivity (200–1000 Da) 216
between UF and RO (demineralization, de-ionization, purification) in particular for 217
whey protein valorization (Saxena et al. 2009). Now, it is possible to separate every 218
major component by use of proper membrane technology. In dairy, milk undergoes 219
different of treatment such as heat, enzymes etc and this causes the change in the 220
phase and organoleptic properties of milk. By applying membrane technology, 221
products are made from milk without undergoing such treatments. 222
223
Application of membranes in different fields of dairy technology 224
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Various types of membrane filters with different properties are available in 225
market (Table 1) and commonly using in the dairy industry. Membranes have an 226
application in different fields of dairy technology and classified according to use like- 227
1. Membranes in extending shelf life of milk. 228
2. Membranes in whey processing. 229
3. Membranes in cheese industry. 230
4. Membranes in milk protein processing 231
5. Fractionation of milk fat. 232
6. Membranes in desalting or demineralization. 233
7. Other applications. 234
235
Membranes in extending shelf life of milk 236
Extended shelf life (ESL) milk products are products that have been treated in 237
a manner to reduce the microbial count beyond normal pasteurization, packaged under 238
extreme hygienic conditions, and which have a defined prolonged shelf life under 239
refrigerated conditions (Rysstad and Kolstad 2006). Milk can be processed by various 240
methods, resulting in a product with different microbiological status and keeping 241
ability, pasteurization is one of them and more popular method. But this process leads 242
to the reduction in nutritive value and quality of the product as well increasing cost of 243
the milk. The membrane technology proved to be suitable alternative to it by cold 244
pasteurization. Microfiltration constitutes an alternative to heat treatment to reduce 245
the presence of bacteria and improve the microbiological safety of dairy products 246
whilst preserving the taste (Pafylias et al. 1996). It is a non thermal method of 247
removing bacteria and spores from milk, whey and cheese brine and extending shelf 248
life without damaging sensory attributes (Meersohn 1989; Hansen 1988). The 249
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significant reduction of mesophilic, Salmonell and Listeria count have been reported 250
upon using MF with 1.4 µm pore size (Madec et al. 1992). Cold MF could also 251
minimize microbial fouling of the membrane and prevent the germination of 252
thermophilic spores (Fristch and Moraru 2008). Fristch and Moraru (2008) have been 253
performed a study to analyse microbiological, chemical, and somatic cell count to 254
evaluate the effect of MF on the composition of skim milk and they found that 255
permeate flux increased drastically when velocity was increased from 5 to 7 m/s. 256
By the suitable modifications in the membranes structure, design and 257
composition, it is possible to make milk free from bacteria (Pedersen 1992; Malmberg 258
and Holms 1988; Olesen and Jensen 1989; Maubois 1990). ESL milk has been 259
prepared by removing bacteria from milk by MF without causing any compositional 260
change (Bindith et al. 1996) or negligible change with the total protein was only 261
slightly decreased (0.02–0.03%) (Hoffmann et al. 2006). 262
By adding a filtrate circulatory system in the concentrate circulatory system of 263
membrane filters (better known as UTMP concept Uniform Transmembrane Pressure 264
concept), up to 99.70% of the bacterial load in skim milk has been achieved by Alfa 265
Laval (Pedersen 1992; Malmberg and Holms 1988). Tetra Alcross Bactocath of Alfa 266
Laval removes the bacteria and spores from milk by separating milk into cream and 267
skim milk and then separates the skim milk from bacteria and spores by 268
microfiltration, while retaining all bacteria and spores in retentate which is about 269
0.5% of the original milk volume. The retentate is mixed with suitable amount of 270
cream and mixed in filtered milk after pasteurizing it. As the heat treatment given to a 271
very small amount of milk, the organoleptic and sensory attributes of milk are 272
retained. It extends the shelf life of milk (Saboya and Maubois 2000) by 12 to 45 days 273
at 4°C (Goff and Grifiths 2006) thus placing milk in ESL category. This markedly 274
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enhances the keeping quality and shelf life of dairy products without causing any 275
major damage to the major constituents of milk. The denaturation of proteins 276
especially whey proteins during membrane filtration depends upon the concentration 277
factor and time temperature selected for the heat treatment (Pedersen 1992). 278
Numerous other studies had also been reported the similar findings (Olesen and 279
Jensen 1989; Puhan 1992). The major hitch is that it does not remove all pathogenic 280
bacteria from milk, thus still necessitate the heat treatment (Rosenberg 1995). 281
The somatic cell counts (SCC) increase in the milk of lactating cows suffering 282
from mastitis and thus severely affecting the quality of milk (Sharma et al. 2011; 283
2012a). Mastitis is one of the most important diseases which severely affect the 284
compositional quality of milk and contamination of milk with numerous pathogenic 285
bacteria (Sharma and Maiti 2010; Sharma et al. 2012b). This somatic cell counts can 286
be reduced up to 100% by the application of combined processes of MF 287
(microfiltration) followed by HHT (high heat treatment) (Pedersen 1992). Damerow 288
(1989) reported the extension of shelf life of refrigerated milk from 12 days to 18 289
days at 8°C by the combined application of MF and HHT without compromising 290
sensory attributes by reducing the numbers of psychrotrops. A thermal treatment or 291
combination of heat treatment and membrane filtration are involved in the production 292
of ESL milk (Lorenzen et al. 2011). The MF process is more efficient in removing 293
bacteria and spores than the bactofugation (Stack and Sillen 1998) and thus extends 294
the shelf life more than the UHT milk. With the direct epifluorescent filter 295
technique (DEFT) technology, keeping quality of milk can be judged in short time by 296
concentrating the bacterial cells and their spores as well as somatic cells by 297
membranes followed by quantification of these by epifluorescent microscopy (Pettifer 298
1982). 299
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Recently narrow pore sizes in smooth inert silicon nitride surface microsieves 300
have been prepared by micro-machining technology. These membranes reduced the 301
fouling significantly by lower transmembrane process due to higher permeability to 302
pass the liquids (Kuiper 2000). The microsieves also reduce the microbial count 303
significantly in milk (Van Rijn and Kromkamp 2000). Brans et al. (2004) emphasized 304
the selectivity of these microsieves to retain bacteria and spores and passing the milk 305
components. 306
307
Membranes in whey processing 308
Whey is a dairy by-product which is obtained during the preparation of milk 309
products viz. cheese, paneer and casein. Paneer is an Indian dairy product similar to 310
soft cheese prepared by coagulating casein with citric acid, lactic acid or tartaric acid 311
(Kumar et al. 2011a; Kumar et al. 2008). Whey is simply drained in most of the cases 312
in developing countries. This causes huge loss of valuable nutrients as well as creating 313
environmental hazards. The separation or concentration of whey nutrients by 314
traditional method is cumbersome and time consuming. By application of different 315
membrane filtration technology, the nutrients in whey are concentrated, fractionalized 316
or purified into valuable products such as whey protein concentrate/ isolates, α-317
lactalbumin, β-lactoglobulin, lactose and salts (Fig. 4). Up to 60% more saving on 318
fuel has been reported in whey concentration by applying RO over the traditional 319
evaporation methods (Morales et al. 1990a and b; Wright 1982). By application of UF 320
and DF, the protein content of the whey protein concentrate can be increased by 35-321
85% of the total solids whereas by removing bacteria and fat by passing whey through 322
MF, the protein content of whey protein isolates can be increased to 90% of the total 323
solid content (Lipnizki 2010). 324
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The membrane separation of bacteria and spores also leads to production of 325
high quality whey protein concentrate (WPC) and whey protein isolates (WPI) with 326
inherent functional properties from whey (Lipnizki 2010) as it avoid the denaturation 327
of whey or serum proteins. These whey proteins are used in food industry for their 328
high biological value as well as their ability to improve the functional properties 329
(emulsifying, foaming and gelling) of the food products (Harper 1992). The removal 330
of as much lipids as possible from whey by efficient membrane function produces 331
whey protein concentrate with good keeping quality (Harper 1992). At present the 332
WPC are prepared on industrial scales by using UF, however fouling of membranes 333
still remains a concern. The protein content is increased in whey protein concentrates 334
as well as purification of proteins is done with the membranes. UF and RO have 335
application in production of concentrated whey and whey protein concentrates 336
(Sienkiewicz and Riedel 1990). 337
The development of off-flavour in these whey products due to the impurities 338
of lipids and protein remain the major concern (Morr and Ha 1993; Morr and Ha 339
1991). The presence of lipids in whey causes the problem of rancidity and shorten the 340
storage life. A number of studies have been suggested that the removal of residual fat 341
from whey by thermocalcic precipitation under which phospholipids are aggregated 342
by calcium under heat treatment for 8 min at 50°C followed by removal of the 343
precipitates by MF and UF (Maubois 1997; Fauquant et al. 1985; Pearce et al. 1992, 344
Harper 1992; Lee and Merson 1976; Merin et al. 1983; Gesan et al. 1995). The 345
advances in MF make it easier to direct removal of lipoproteins by separating the 346
transmembrane pressure from the inlet pressure limiting the fouling (Pearce et al. 347
1992) 348
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With the use of membrane technology, it is possible to concentrate and 349
separate whey proteins in their un-denatured form with high functional property in 350
native whey as compared to traditional sweet cheese whey (Maubois 2002). Native 351
whey protein concentrates (NWPC) and native whey protein isolates (NWPI) are 352
produced by UF concentrating the native whey (Maubois et al. 2001), showing 353
excellent gelling, foaming and reconstituability on drying (Ostergaard 2003). At 354
present, these native whey proteins are utilized extensively in human nutrition (Boirie 355
et al. 1997) as an integral component of weight balancing products (Burton-Freeman 356
2008) and in baby foods due to lower risk of hyperthreoninemia due to lack of 357
glycomacropeptides which in turn is rich in threonine (Rigo et al. 2001; Boehm et al. 358
1998). The individual whey protein can be concentrated or fractionated by application 359
of membrane technology. This facilitates the production of WPC with the enrichment 360
of specific proteins or with single proteins. The composition of whey proteins differ 361
very little from that of membrane permeates obtained during concentration of the 362
casein, this difference is due to presence of peptides from caseins such as 363
glycomacropeptides during the preparation of cheese (Brans et al. 2004). Doyen et al. 364
(1996) reported that the main concern during the preparation of whey protein 365
concentrate is fouling as membranes with different permeability have the comparable 366
flux due to the pressure independent flux regime. A typical whey micro-filtration 367
process may run in long cycles of about 24 h, which offer great potential for the 368
formation of bacterial biofilms leading to reduced membrane performances. 369
Membrane fouling is already considered a major disadvantage to their application 370
because of deposition of proteins and minerals that are difficult to clean 371
(Muthukumaran et al. 2005; Popovic et al. 2010; Anand et al. 2012). 372
373
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Membranes in Cheese industry 374
The concentrating the milk before cheese making opens a new arena in cheese 375
industry reducing the cost as well as hasten the whole procedure of cheese making 376
(Henning et al. 2006). The membrane technology separates lactose from the milk fat 377
and protein (Siebert et al. 2001). 378
Membrane technology is used to separate κ-casein- glycomacropeptid (GMP), 379
which have pharmaceutical uses in controlling the adhesion of E. coli cells to the 380
intestine walls, protects against influenza and prevents adhesion of tartar to teeth 381
(Maubois and Ollivier 1997). Membrane filtration technology has number of 382
applications in cheese industry such as improving the nutritive quality, better 383
compositional control and yield of cheese by increasing the total solid content, 384
utilization of whey during preparation of cheese, comparatively reducing the 385
requirement of rennet and starter culture. According to Rosenberg (1995) the UF 386
technology in cheese processing is highly remunerative by concentrating milk by a 387
factor of 1.2- 2.0 times leading to fewer requirements of processing equipments, 388
better compositional and quality control as well as improving the yield of cheese due 389
to higher protein content. By removing the water during concentration of milk by the 390
application of membrane filtration technology, it is possible to make cheese without 391
whey, thus do not require the use of cheese vat and avoid cumbersome processing 392
steps of removal and draining of whey. However, some workers have been reported 393
the negative impact on the ripening of semi-hard and hard cheese by increase the 394
whey content due to concentration of milk (Qvist et al.1986; Qvist 1987). Lipnizki 395
(2010) called UF as complementary process of cheese making. 396
The quality of cheese brine is maintained easily by membrane filters by 397
removing bacteria and spores as well as other extraneous matters and maintaining the 398
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chemical balance of brine. The cheese brine should be pre-filtered by a filter with 399
pore size of 100 µm (Ottosen and Konigsfeldt 1999). The above mentioned effects 400
lead to production of high quality cheese with superior flavour and shelf life. 401
Lipnizki (2010) found the superior quality of cheese made by membrane filtered brine 402
than the cheese prepared from traditional process. 403
404
Use of UF in cheese making 405
UF are commonly used for the standardization of milk to be used for cheese 406
making thus alleviating the problem of compositional variations and increase the milk 407
casein:protein ratio (Johnson and Lucey 2006). The higher recovery of milk 408
components are possible by UF followed by high treatment of cheese milk (Guinee et 409
al. 1995; Guinee et al. 2006). With the application of UF, good quality fresh and brine 410
cheese is obtained in higher amount (Puhan 1992; Mistry and Maubois 1993; Ottosen 411
1988; Pedersen and Ottosen 1992). Maubois et al. (1969) first patented the procedure 412
of production of cheese on industrial basis from UF retentate by using MMV method 413
by concentrating the milk by 5-7 times and getting the high quality curd. MMV is 414
suitable for making soft, fresh and feta cheese. The increase in the viscosity and 415
buffering capacity of such cheese milk needs certain procedural modifications in the 416
process of cheese making (Pouliot 2008). UF of milk is done to save cost during 417
preparation of semi-hard and hard cheese by increasing the salt and whey protein 418
concentration but it causes compromised sensory and functional properties (Mistry 419
and Maubois 1993) with slower ripening rate due to decreased proteolysis (de Koning 420
et al. 1981). This reduced proteolysis is due to reduced substrate for chymosin action 421
and lower rennin as well as presence of more whey proteins (Neocleous et al. 2002). 422
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Some reports mentioned that UF have not given good results in making of 423
fresh cheese from acidified curd as it is difficult to process high acidic milk by these 424
traditional membranes. Upon increasing the pH before fermentation results in poor 425
sensory attributes with enhanced proteolysis and mineral contents. With the 426
introduction of advanced ceramic and polysulfone membranes, it is possible to apply 427
UF to acidic milk with pH 4.4-4.6 in the production of better quality of fresh cheese 428
(Jelen and Renz-Schauen 1989). A 13-14% saving of skim milk has been reported 429
during preparation of quarg cheese with the application of UF process as compared 430
with traditional process (Pedersen and Ottosen 1992). Based on the concentration 431
factors and increase in the protein content, there are three different types of retentate 432
obtained in the UF viz. low concentrated retentate (LCR), medium or intermediate 433
concentrated retentate (MCR) and liquid pre-cheese (LPC) (Rosenberg 1995; Henning 434
et al. 2006) (Table 2). 435
436
Use of MF in cheese making 437
The MF milk is very suitable for cheese making due to its superior microbial 438
quality achieved after removing bacteria and spores from milk, as well as 439
optimization of the different major milk components. With this it is possible to make 440
all types of cheese from different types of milk. By application of MF, the casein 441
concentrated milk can be obtained. The MF pre-treatment of cheese milk improves 442
the firmness of curd, accelerate ripening (Caron et al. 1997; Pierre et al. 1992; 443
Maubois 2002), reduce the amount of additives e.g. CaCl2
(Schafroth et al. 2005) and 444
facilitates heating at higher temperature (Samuelsson et al. 1997). Further the UHT 445
milk need higher amount of rennet for coagulation. By application of UF, UHT milk 446
is coagulated with lesser amount of rennet by compensating the hindrance to 447
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coagulation arises from the formation of complexes between k-casein and β-448
lactoglobulin by reduction of the zeta potential of the casein micelle (Mistry and 449
Maubois 1993). 450
The MF has future possibilities in standardization of protein in cheese milk 451
and fortification with casein micelle powder (Mistry and Maubois 1993). 452
Bacofugation is a method of removal of 99.99% bacteria and spores from milk by two 453
stage centrifugation in bactofuge. This process is not an alternate to pasteurization, 454
but a complementary process. This milk is needed to pass through heat treatment at 455
130°C for 3-4 seconds. The MF followed to HTT is more efficient than single stage 456
bactofugation in terms of microbial quality. But this treatment of MF followed by 457
HTT modifies rennet coagulation and increases the water holding capacity, thus 458
necessitates the adjustments in the parameters during cheese preparation (Pedersen 459
and Ottosen 1992). 460
461
Membrane in milk protein processing 462
Milk proteins especially caseins play important role in white turbid appearance 463
and viscosity of milk. By application of ultra filtration, the level of protein content in 464
milk is adjusted without adding any extraneous protein source such as casein, whey 465
protein concentrate etc. by changing in water content of the whole milk. This causes 466
minimum change in the physico-chemical properties and sensory attributes of the 467
milk while standardizing the nutritional value of milk by maintaining the constant 468
composition of milk irrespective to the variation caused by the genetic as well as 469
environmental factors (Maubois 1989; Puhan 1992). The level of milk proteins, 470
lactose, fat and mineral depends upon the extent of UF. Adding of 1% ultra filtered 471
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protein enriched milk in skim milk has improved the viscosity and sensory attributes 472
to similar to full cream milk (Quinones et al. 1997). 473
474
Fractionalization of milk protein 475
Chemically milk is emulsion of fat globules in aqueous phase made of 476
suspended and dissolved milk proteins (casein and whey), lactose and salts. By 477
separating these wide ranges of milk components of different sizes by using 478
membranes (Fig. 3) will transform dairy industry into very efficient and profitable 479
enterprises. Jimenez-Lopez et al. (2008) described membrane pore size homogeneity, 480
concentration polarization phenomena and membranes fouling as main factors 481
determine the fractionalization of milk components. The milk protein concentrates 482
(with 50-85% protein in the products) and milk concentrates (with more than 85% 483
protein in the products) are increasing prepared by using MF (Novak 1992). The 484
composition, heat stability, rheological and textural properties of these protein rich 485
products depends on the type of membrane used and processing conditions such as, 486
temperature, pH, time of processing. The judicious use of these factors should be 487
selected based on the ultimate use of the MPC and MP (Novak 1992; Hallstrom and 488
Dejmek 1988). The functional properties of protein concentrates can be maintained by 489
keeping the time temperature minimum, thus causing the minimum denaturation of 490
whey proteins. Novak (1992) suggested UF processing at 50-60°C with high flow rate 491
to minimize the whey protein denaturation for desired rheological properties. 492
A lot of work has performed to recover valuable protenecious components 493
from dairy waste streams (Chakravorty and Singh 1990). Dairy proteins are valuable 494
products and, used as high-value food additives, nutraceuticals and therapeutics. 495
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Recently a number of papers have published to recover the protein using MF, UF and 496
NF processes (Akred et al. 1979; Grossman and Bergman 1992). 497
Govindasamy-Lucey et al. (2007) and Lawrence et al. (2008) separated the 498
whey protein from skimmed milk by polymeric microfiltration in permeate flux. Mass 499
flux form of permeated whey protein with permeates flux, mainly determine the whey 500
protein concentration and fractionalization (Piry et al. 2008). MF of milk separates 501
the casein micelles and whey proteins (Maubois et al. 1987). Whey proteins are 502
separated and reduced in filtrate by MF (Kulozik and Kersten 2002). The various milk 503
proteins such a casein and serum or whey proteins are separated in a simple and 504
economic method by applying membrane filters of 0.2 µm pore size at constant TMP, 505
without the need of application of heat and chemicals. 506
With the advancement of newer technology in membrane process, it is 507
possible to recover growth factor from whey (Gauthier et al. 2006). Attempts have 508
been made capture the growing market of health foods by separating 509
immunoglobulins and growth factors from colostrum by application of MF and UF 510
with suitable modifications (Piot et al. 2004; Regester et al. 2003). 511
512
Casein 513
Casein is the major milk protein. Membrane technology has revolutionized the 514
casein industry. Application of different membranes types with desired pore size 515
either alone or in combination with enzymatic action, chromatography lead to the 516
concentration, fractionalization and purification of milk proteins. The physico-517
chemical properties of casein in relation to membranes largely depend upon the ionic 518
strength as well as temperature (Mulvihill 1992). Thus by applying suitable 519
temperature, ionic strength with proper membrane, it is possible to concentrate and 520
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fractionate casein as β-casein at 5°C (Terre et al. 1986), skim milk at 4°C and pH 4.2-521
4.6 (Famelart et al. 1989) using MF and UF separating β-casein in permeates and α 522
and κ-casein in retentate (Murphy and Fox 1990). During microfiltration, casein 523
micelles always shown minute whey protein concentration (Brans et al. 2004) and the 524
permeate containing major milk whey protein known as native or ideal whey similar 525
in composition to sweet cheese whey (Fauquant et al. 1988) but devoid of 526
caseinomacropeptides, cheese starters or chymosin. 527
The native casein can be concentrated in retentate by passing the skim milk 528
into MF with 0.2µm pore size (Maubois and Ollivier 1992; Fauquant et al. 1988). 529
Upto 90% casein concentration is possible by DF and it can be used for industrial, 530
pharmaceutical as well as edible purposes (Maubois and Ollivier 1992). The 531
concentrated casein and native casein micelles can be prepared through ceramic, 532
ceraflow, membralox membrane with different flux (Brans et al. 2004; Pouliot et al. 533
1996; Punidadas and Rizvi 1998; Vadi and Rizvi 2001; van Rijn and Kromkamp 534
2001). The significant improvement was recorded in flux with 65kPa transmembrane 535
pressure having flow velocity of 12.5 metre/ second (Krstic et al. 2002). 536
By use of membrane process accompanied with other advance technology as 537
liquid chromatography, leads to purification of casein derived bioactive peptides as β-538
casein derived peptides shows morphine-mimicking, cardiovascular and 539
immunostimulating activities (Maubois and Leonil 1989; Maubois and Ollivier 1992; 540
Mulvihill 1992). 541
Papadatos et al. (2003) found that although there was higher profit in the 542
production of cheddar and mozzarella cheese by MF milk in North America but the 543
profit changed little with the increase in concentration of casein from 2 to 3 times. 544
The fouling is major concern than selectivity during the concentration of casein in 545
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milk as some whey proteins are their in casein and vice versa and thus affecting the 546
yield of cheese as well as whey concentrates (Brans et al. 2004). The performance of 547
MF should be improved to make the casein production competitive. 548
549
Fractionalization of whey protein 550
Whey proteins are obtained by concentrating and purification from whey, a 551
dairy by-product obtained in cheese and casein industry. The β-lactoglobulin is 552
separated by the membrane process followed by heat treatment (Amundson et al. 553
1982; Maubois et al. 1987; Pearce 1987). The β lactoglobulin can be fractionized 554
from defatted whey proteins by using MF and centrifugation followed by purification 555
by UF with electrodialysis (ED) or DF (Maubois 1997). The α-lactalbumin is 556
separated and purified by applying UF on solubilised MF retentate at neutral pH 557
(Rosenberg 1995). With the introduction of inorganic membranes with 558
polyvinylimidazole derivates, the pure α-lactalbumin can be obtained in filtrate but 559
the fouling proves major constraint (Chaufer et al. 1991; Bottomley 1993; Chen and 560
Wang 1991). The whey proteins can be separated from WPI by applying UF/DF with 561
more than 99% purity (Mailliart and Ribadeau-Dumas 1988). The use of hydrophilic 562
cellulose membrane made it possible to separate low molecular weight compounds 563
from high molecular weight compounds (Mehara and Donnely 1993). Lactoferrin and 564
lactoperoxidase are recovered from defatted WPC on industrial scale by using ion-565
exchange chromatography (Perraudin 1991). Both these proteins help to maintaining 566
the quality and shelf life of milk and dairy products. 567
β-lactoglobulin is purified by diafiltration of supernatant (Maubois et al. 568
1987), while immunoglobulins are separated from whey protein concentrates by using 569
membrane technology (Scott and Lucas 1989). 570
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571
Membranes in milk fat processing 572
Traditionally, cream is separated from whole milk by centrifugation. The 573
defatted or skim milk is used for various dairy products with low fat and other 574
properties. The lighter fat globules moves towards the centre and heavier skim milk 575
move towards periphery under the centrifugal force. These processes are energy 576
intensive and damage the fat globular membrane due to the combined action of heat 577
and shear force. The cream separation is also possible by applying membranes. This 578
process saves energy and produces skim milk with good storage quality as well as 579
improved sensory attributes cream without causing any damage to fat globular 580
membranes. 581
The fat globules are surrounded by a thin unit membrane made up of 582
phosphoprotein and lipids. Goudedranche et al. (2000) reported the fractionation of 583
fat globules by application of membranes of 2µm size. The size of fat globules have 584
profound impact on textural and sensory attributes as the cream with smaller fat 585
globules have fine texture and improved flavour than cream with large fat globules. 586
587
Membranes in desalting or demineralization 588
Demineralization or desalting is mostly done for whey in dairy. The removal 589
of minerals from whey increases its value (Kelly et al. 1991; Horton 1987). The 590
cheese whey is rich in salt and acids and the reduction or demineralization of whey is 591
essential before its use. Moreover, the drainage of this whey may further aggravate 592
the environmental pollution. The demineralization is done by electrodialysis and ion 593
exchange process (Greiter et al. 2002) in the dairy industry to get up to 60% reduction 594
of minerals (Kelly et al. 1991). In electrodialysis, the presence of electric potential 595
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and the two types of membrane i.e. one is permeable to cations and one for anions 596
facilitates the removal of ions in the absence of transmembrane pressure. The 597
efficiency of electrodialysis can be increased by pre-concentrating up to 20% dry 598
matter, it by either RO or evaporation. By ion exchange, desalting of whey is done by 599
passing it over ion exchange column. The rate of removal of ions depends upon the 600
resin used in the column as well as the type of ions. The need of lots of water and 601
chemicals for regeneration of resins is the major limitations of this technology. 602
The NF membranes with 200-1000 cut off are best suited for demineralization 603
of whey as these are permeable to salt and monovalent ions but impermeable to 604
organic compounds (Horton 1987) as due to low pH, organic acids the carboxyl group 605
is bound it. This technology simultaneously demineralises whey at the time of 606
concentrating it. This helps in saving in term of cost, time and water disposal (Kelly et 607
al. 1991). The mostly negative charge of proteins impedes the removal of opposite 608
positive charge ions and at the same time facilitates the same negative charged ions as 609
chloride ions. The NF is more economical than electrodialysis and method of choice 610
for partial desalting of whey. NF membranes are highly permeable to water and 611
monovalent ions. The mineral contents of the whey is reduced by 35% and ash 612
content by 3-4 times in addition to increase concentration of whey by applying 613
nanofiltration (NF), making it suitable for the people having cardiovascular diseases. 614
The mineral content of whey is further reduced by 45% by applying DF (Kelly et al. 615
1992; Lipnizki 2010). The reduction of mineral content in whey, liquor and brines on 616
industrial scale can done mainly by NF (Horton 1997b; Horton 1997c; Horton 1998; 617
Kelly et al. 1991; van der Horst et al. 1995). Daifiltration also causes the removal of 618
ions to a greater extent. 619
620
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Other uses 621
With the help of membrane technology, several novel products are introduced 622
in market as lactose free milk for lactose intolerant people, low calcium milk, non fat 623
yoghurt, high protein low lactose ice cream, protein fortified low fat milk, whey based 624
beverages etc. The milk protein concentrate (MPC) containing 50-58% proteins of 625
good functionality are prepared by application of MF, UF and diafiltration (DF) 626
technologies either alone or in combinations. Standardized milk is prepared by adding 627
UF permeates ((Puhan 1991). Condensed milk is prepared by removing moisture from 628
the milk. Traditionally, water is evaporated by heating the milk in an energy intensive 629
method of preparing condensed milk. By applying RO (reverse osmosis), milk is 630
condensed by removing about 70% of its water and retaining all other components of 631
milk without undergoing any thermal processing. During preparation of fermented 632
dairy milk such as cheese, yoghurt and curd, the protein and total solids standardized 633
UF milk show better textural and nutritional properties than those of prepared by 634
either adding milk powdered or evaporated milk (Puhan 1992; Becker and Puhan 635
1989). The use of different membranes accompanied with suitable heat treatments 636
leads to the development of several dairy products with unique characteristics as 637
better compositional control, binding, texture, juiciness etc. Rosenberg (1995) also 638
observed the improvement in the sensory scores as well as quality of such products in 639
comparisons to the traditional products. It is easier to control the textural and 640
compositional properties of milk by membrane filtration technology, but it 641
necessitates better attention to the selection of starter and incubation/ ripening 642
conditions such as temperature, time and pH (Lipnizki 2010; Rosenberg 1995; Horton 643
1997a). Rosenberg (1995) noted that such changes is due to the increasing content of 644
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lactose and minerals, higher osmotic pressure, change in the pH, change in ionic 645
strength as well accumulation of some inhibitory compounds in the UF treated milk. 646
The transport cost of milk is reduced by membrane technology by pre- 647
concentrating it, removing the water and lactose or dewatering it at farm level and 648
thus decreases the volume of transported milk without damaging its sensory attributes 649
(Halladay 1998; Zall 1987a; Zall 1987b; Rattray and Jelen 1996; Renner and Abd El 650
Salam 1991). RO to milk produce permeate of protein and minerals while UF 651
produces permeate consisting of water and lactose (Cheryan 1998). 652
653
FUTURE TRENDS 654
Still the development of filtration techniques and their application at mass 655
level is not complete. Hence there is need of progressing development of innovative 656
applications based on the technique and need of dairy industry. In current, the 657
membrane processes for milk and milk products have a rather low capacity owing to 658
strong flux decline by fouling or processes are energy demanding because of the high 659
cross-flow velocity that is required to control fouling. Moreover, methods to control 660
fouling have increased the complexity in equipment and operation. Besides fouling, 661
selectivity is an important issue for membrane fractionation of milk (Saxena et al. 662
2009). Therefore, we need innovative techniques in particular development of cheap, 663
easily available, superior and longer lasting membranes, and offer new perspectives. 664
By the suitable modifications in the membranes structure, design and composition, it 665
is possible to make milk free from bacteria. Also need to expand the application of 666
these membranes in the field of dairy sector. As consumers are looking for products 667
with increased freshness and higher quality, the retail requires products with extended 668
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shelf life. This is the current and future challenge for membrane technology in dairy 669
industry. 670
671
CONCLUSION 672
The introduction of membrane technology into dairy science witnesses 673
phenomena of mutual benefit for membranes as well as for dairy industry. The 674
marked improvement in the nutritive quality and sensory attributes of the existing 675
dairy products with higher yield in addition to development of several new dairy 676
products became possible by the application of membrane technology. With 677
continuing the efforts for the development of superior membranes will further expand 678
the role of membranes in dairy processing. 679
680
ACKNOWLEDGMENT 681
682
This study was supported by a grant from the Next-Generation BioGreen 21 Program 683
(No. PJ009032022012), Rural Development Administration, Republic of Korea, 684
Hence the authors are thankful to this organization. 685
686
687
688
689
690
691
692
693
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1
2
3
4
5
6
7
8
Fig. 1. Membrane processing mechanism. 9
10
11
12
Semi-permeable
membrane
Pressure applied
Retentate
Permeate
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1
2
3
Fig. 2. Milestones in the development of membrane technologies for protein 4
separation/purification (Adopted from Saxena et al., 2009). 5
6
7
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1
2
3
4
Fig. 3: Components in milk: size indication and membrane processes. MF: microfiltration, UF: 5
ultrafiltration, NF: nanofiltration, RO: reverse osmosis (Adopted from: Daufin et al. 2001). 6
7
8
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1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
Figure 4: Diagrammatic representation of use of membrane in whey processing. 34
35
36
37
38
WHEY
Electrodialysis and
ion exchange
UF
NF
Demineralized and
Concentrated
whey
MF
Removal of bacteria & Fat
WPI
Thermocalcic
precipitation of
phospholipids
MF
Defatted whey
UF
Defatted whey
concentrate
WPC DF
WPC
(35-85% protein)
Permeates
Demineralized
whey
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Table 1 Commonly used membrane techniques in dairy industry
Type Pore size Molecular
weight cut off
Pressure and Principle Compounds in
retentate
Use
Microfiltration 0.2-2µm >200kDa Low pressure (below 2 bar)
driven membrane process
Low retentate,
separation
of protein, bacteria
and other
particulates
- Skim milk and cheese
- Dextrose clarification
- Bacteria removal
Ultrafiltration 1-500 µm 1-200 kDa
Medium pressure (1-10
bar) pressure driven
process to overcome the
viscosity
Large retentate with
casein micelles, fat
globules, colloidal
minerals, bacteria
and somatic cells
- Standardization of milk,
reduction of calcium and
lactose.
- Protein, whey, milk
concentration
Nanofiltration 0.5 - 2
nm
300-1000 Da Medium to high pressure
(5-40 bar), mass transfer
phenomena by size
exclusion and electrostatic
interactions,
low productivity,
separate
monovalents salt and
water
Desalting of whey,
lactose free milk, volume
reduction
Reverse
osmosis or
Hyperfiltration
No pores 100 Da
High pressure, 10-100 bar, Based on the
principle of
solubility, low
productivity
volume reduction,
recovery of total solids
and water
Adopted data from- Rosenberg 1995; Pouliot 2008; Childress and Elemelech 2000.
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Table 2 Role of UF in concentrating cheese milk.
Retentate Concentration
Factor
Types of cheese Remark
Low concentrated
retentate (LCR)
1.2-2: 1 cheddar, brick, cottage cheese,
colby, mozarella, edam, saint
paulin, quag
4.5-5% more protein in cheese,
Increase yield, efficient utilization of
cheese vat, good compositional control
Medium/ concentrated
retentate (MCR)
2-6: 1 Cheddar, feta, havarti, gouda,
and blue cheese
6-8% more yield, need special cheese
making equipment
Liquid pre-cheese (LPC) Same as of cheese
curd
feta, mozzarella, quarg,
camembert, ricotta, cream
cheese, mascarpone and saint
mauri
Very economical, cheese vat not
required, minimum whey drainage
Adopted data from- (Rosenberg 1995; Henning et al. 2006; Mistry and Maubois 1992; van Leeuwen et al., 1987)
Page 52 of 52
International Journal of Dairy Technology
International Journal of Dairy Technology