NZ292643A - Adjustment of ratio of whey protein to casein in skim milk - Google Patents
Adjustment of ratio of whey protein to casein in skim milkInfo
- Publication number
- NZ292643A NZ292643A NZ292643A NZ29264395A NZ292643A NZ 292643 A NZ292643 A NZ 292643A NZ 292643 A NZ292643 A NZ 292643A NZ 29264395 A NZ29264395 A NZ 29264395A NZ 292643 A NZ292643 A NZ 292643A
- Authority
- NZ
- New Zealand
- Prior art keywords
- milk
- retentate
- skim milk
- whey protein
- microfiltration
- Prior art date
Links
Landscapes
- Dairy Products (AREA)
- Peptides Or Proteins (AREA)
Description
New Zealand No. 292643 International No. PCT/NZ95/00086
TO BE ENTERED AFTER ACCEPTANCE AND PUBLICATION
Priority dates: 16.09.1994;
Complete Specification Filed: 15.09.1995
Classification:^) A23C9/14.142; A23C21/06; A23J1/20
Publication date: 26 August 1998 Journal No.: 1431
NEW ZEALAND PATENTS ACT 1953
COMPLETE SPECIFICATION
Title of Invention:
Physical separation of casein and whey proteins
Name, address and nationality of applicant(s) as in international application form:
NEW ZEALAND DAIRY BOARD, Pastoral House, 25 The Terrace, Wellington, New Zealand
292643
WO 96/08155 v *- v I PCT/NZ95/00086
1
PHYSICAL SEPARATION OF CASEIN AND WHEY PROTEINS TECHNICAL FIELD
This invention relates to the adjustment of the relative percentage of casein and whey proteins in a stream of skim milk to produce dairy products with predetermined compositions and properties.
BACKGROUND ART
The physical separation of casein and whey protein using microfiltration and ultrafiltration membranes is discussed in Chapter 2 "Milk Protein Fractionation", J L Maubois and J Ollivier, in the International Dairy Federation Special Issue 9201 entitled "New Applications of Membrane Processes", (1992).
This paper reviews membrane separation technologies developed over the previous decade and discusses some applications of them. It also discusses several possibilities for which such membranes might be used.
A paper entitled "New Applications of Membrane Technology in the Dairy Industry", J L Maubois, the Australian Journal of Dairy Technology, 1991 is a further discussion of those possibilities published at approximately the same time.
Both papers, while describing some specific uses of such technology, leave open several 25 possibilities. It is an object of this invention to go someway towards achieving those possibilities or at least to offer the public a useful choice.
European Patent Specification 542,583 describes microfiltration using diafiltration of milk followed by heat treatment and ultrafiltration to produce a concentrated product with good 30 microbiological quality and improved coagulation. This product is intended to be used in cheese making.
WO 96/08155 PCI7NZ95/00086
2
In New Zealand Patent 250,399 there is described a process for concentrating skim milk by a factor of 3 to 6 times by volume using ultrafiltration or microfiltration. The process is characterised in that a quantity of lactose equivalent to the dry matter in the retentate is dissolved. It is intended to be used as a base for products such as concentrates, deserts and 5 culinary or dietetic products.
US Patent 5,161,666 describes the ultrafiltration or microfiltration of milk and recovering the permeate from the process as a simulated human milk protein composition.
0 DISCLOSURE OF THE INVENTION
In one aspect the invention may broadly be said to consist in a method of adjusting the ratio of whey protein to casein in a supply of skim milk which comprises subjecting a first stream of said skim milk to microfiltration on a microfiltration membrane (as herein defined), recovering 5 the MF retentate therefrom, and:
either:
a. processing said MF retentate into a first dairy product, or b. combining some or all said MF retentate with a second stream of said skim milk and optionally processing said combined stream into a second dairy product, or
0 c. subjecting said MF retentate to ultrafiltration using an ultrafiltration membrane
(as herein defined) and recovering the UF retentate therefrom and processing said UF retentate into a third dairy product, and discarding or recovering the MF permeate from said microfiltration.
!5 In another aspect the invention may be said broadly to consist in a method of adjusting the ratio of whey protein to casein in a supply of skim milk which comprises subjecting a first stream of said skim milk to a microfiltration on a microfiltration membrane (as herein defined), and subjecting the MF permeate therefrom to ultrafiltration using an ultrafiltration membrane (as herein defined), and i0 either:
a. recovering the UF retentate therefrom and further processing said UF retentate into a fourth dairy product, or
I WO 96/08155 PCT/NZ95/00086
3
b. recovering the UF permeate therefrom and further processing said UF permeate into a fifth dairy product, or c. combining some or all said UF retentate and said UF permeate with a skim milk stream or a stream derived from skim milk and processing said combined
stream to form a sixth dairy product, or d. combining some or all said UF retentate with a second stream of said skim milk • and optionally processing said combined stream into a seventh dairy product,
and discarding or recovering the MF retentate from said microfiltration.
In yet another aspect the invention may be said broadly to consist in a dairy product produced from either of the above process embodiments of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is general flow diagram of embodiments of the process of the invention for the production of milk protein concentrate, whey protein concentrate enhanced in bovine serum albumin and immunoglobulin and globular protein concentrate or isolate.
Figure 2 is a flow diagram of a process for producing a cheese milk.
Figure 3 is a flow diagram of a process for producing a whey protein depleted milk protein concentrate.
Figure 4 is a flow diagram of two embodiments of a process for producing globular protein concentrate.
Figure 5 is a flow diagram of a process embodiment of the invention for producing a cheese ingredients powder.
Figure 6 is a flow diagram of a process embodiment of the invention for producing a low fat/ high calcium milk and globular protein concentrate and isolate.
WO 96/08155 PCT/NZ95/00086
4
Figure 7 is a flow diagram of process embodiments of the invention for producing whey protein depleted or enhanced skim or whole milk powder and recombined skim or whole milk powder with enhanced functional properties.
Figure 8 is a plot of compressive rigidity versus strain in feta cheeses.
Figure 9 is a plot of the storage modulus (G1) of globular protein concentrate and citric acid diafiltered globular protein concentrate using a Bohlin Rheometer (Sweden).
DEFINITIONS
In this specification the terms set out below have the following definitions:
Skim Milk - means skim milk separated from potable whole milk of mammals which, 15 optionally, has been pasteurised and which includes diluted, ultrafiltered, concentrated or partly or wholly demineralised skim milk or skim milk in which the carbohydrate level has been adjusted provided always that the original percentages of casein to whey protein have remained substantially unaltered.
Volume Concentration Factor - means the ratio of the volume of the feed liquid to the retentate in an ultrafiltration or microfiltration process.
Microfiltration Membrane - means a microfiltration membrane that is permeable to water, minerals and lactose and partially permeable to whey protein and has a high retention of casein 25 protein and fat. A microfiltration membrane typically has a pore size of 0.05 to 0.5^m, more typically 0.07 to 0.2fim.
Ultrafiltration Membrane - means a membrane which is permeable to water, minerals and lactose and has a high retention of whey proteins, casein protein and fat. An ultrafiltration 30 membrane typically has a molecular weight cut off of less than 100,000 dalton, more typically less than 30,000 dalton.
WO 96/08155 PCT/NZ95/00086
Traditional Casein Process - means the precipitation of casein from pasteurised skim milk by traditional processes such as acidification with inorganic or organic acids or using an appropriate enzyme, such as rennin.
UHT Treatment - means sterilisation by holding at a high temperature for a short time. Typically, temperatures of 130-150°C and times of 1-120 seconds are used; more typically, temperatures of 137-145°C and times of 2-6 seconds are used.
All of the percentages in the following examples are expressed on a weight of component to 10 weight of total composition basis.
MODES OF CARRYING OUT THE INVENTION Example 1 - Microfiltration of Skim Milk
TABLE 1 - Typical New Zealand Skim Milk Composition
Component
Skim Milk
Ash (%)
0.76
Lactose (%)
.17
Fat (%)
0.06
Casein Protein (%)
2.88
Whey Protein (%)
0.58
Total Protein (%)
3.67
Referring to Figure 1, when a skim milk 10 is subjected to microfiltration on a microfiltration 25 membrane 12 at 50°C and a volume concentration factor of 2.5, resulting MF retentate 14 and MF permeate 20 will have the compositions set out in Table 2. The microfiltration membrane is sold by Societe des Ceramiques Techniques (French) as a "Type Z ultrafiltration membrane". The membrane material is mainly zirconia but other metallic oxides can be used. The pore size is0.1|im.
6
TABLE 2 - MF Retentate and Permeate Compositions
Component
MF Retentate
MF Permeate
Ash (%)
1.23
0.49
Lactose (%)
4.27
.27
Fat (%)
0.15
<0.05
Casein Protein (%)
7.84
<0.05
Whey Protein (%)
0.96
0.36
Total Protein (%)
8.90
0.64
When the MF permeate 20 is subjected to ultrafiltration on the ultrafiltration membrane 22 at 50°C and a volume concentration factor of 35, resulting UF retentate 26 and UF permeate 24 will have the following typical compositions.
TABLE 3 - UF Retentate and Permeate Compositions
Component
UF Retentate
UF Permeate
Ash (%)
0.76
0.43
Lactose (%)
4.30
4.60
Fat (%)
<0.5
0.00
Total Protein (%)
16.5
0.27
Although a processing temperature of 50°C was used in this and the following examples, ultrafiltration and microfiltration may typically be conducted at temperatures between about 25 5°C and 60°C, preferably 10°C to 50°C. The upper and lower limits are determined by factors such as undesired precipitation or denaturation well known to those skilled in the art.
Microfiltration in this and the following examples was conducted with trans-membrane pressures of less than 3 bar, preferably less than 1 bar and more preferably less than 0.3 bar.
WO 96/08155 PCT/NZS5/00086
7
Example 2 - Preparation of Whey Depleted Milk Protein Concentrate
.. V*
Referring to Figure 1, a stream of skim milk 10 is processed by microfiltration 12 using a polymeric or a ceramic (with commercially available metallic oxide coating) membrane with a 5 pore size of up to 0.2 jam. The preferred membrane is a zirconium oxide membrane of 0.1 (im pore size. During microfiltration volume concentration factors in the range of 1-5, more typically between 2-4, can be employed. Retentate 14 and permeate 20 result from the microfiltration process. The retentate stream contains the fat, essentially all of the casein protein and a reduced proportion of the whey protein, lactose and minerals.
The permeate stream 20 contains the remainder of whey proteins, lactose and the minerals. The retentate stream 14 can be processed by ultrafiltration 36, dewatered in evaporator 28 and dried in drier 29 to produce a milk protein concentrate 34 or retentate stream 14 can be dried in drier 29, with or without ultrafiltration 36 or with or without evaporation 28, to produce 15 milk protein concentrate 34.
When microfiltration is enhanced by diafiltration using water, more typically demineralised water 43, the resulting milk protein concentrate will have a further whey protein depletion of up to 75% (that is, 75% of whey protein is removed and 25% remains) when three diafiltration 20 stages are employed. The diafiltration medium can be the UF permeate 24 of ultrafiltration 22 or any other medium of similar composition as an alternative or in addition to demineralised water 43. Volume concentration factors in the diafiltration step are in the range of 1-20, more typically in the range of 5-15. The percentage removal of components from skim milk is set out in Table 4.
TABLE 4 - Percentage Depletion
Skim Milk Component
Percentage Depletion
Whev Protein up to 75%
Lactose up to 99.5%
Ash up to 60%
8
Microfiltration 12 and ultrafiltration 36 can be manipulated by varying the ratio of diafiltration liquid to retentate to obtain milk protein concentrates having a total protein range in excess of 40% and whey protein depletion of up to 75%. Compositions of three typical milk protein concentrates prepared in this way are profiled in Table 5.
TABLE 5 - Typical Compositions of Milk Protein Concentrates
MPC
A
B
C
Total Protein (%)
56
70
85
Casein Protein (%)
40-53
50-65
65-80
Whey Protein (%)
3-16
-20
-20
Ash (%)
8-9
8-9
7-8
Lactose (%)
28-30
14-16
<0.5
Fat (%)
0.9-1.1
1.5-1.6
>1.7
Example 3 - Production of Globular Protein Concentrate/Isolate
Referring to Figure 4, the permeate 20 from the microfiltration process 12 or the diafiltration process on the microfilter 12 or both together, are then processed by ultrafiltration 22. The 20 retentate 26 is dried in drier 33, with or without concentration in evaporator 32, to produce globular protein concentrate/isolate stream 42 (GPC/GPI) that is low in fat. When retentate 26 is subjected to diafiltration on the ultrafilter 22 using demineralized water 43, a GPC/GPI stream 42 is recovered. The GPC contains up to 90% protein, the GPI contains >90% protein. When retentate 26 is subjected to diafiltration with acidified water, a GPC/GPI stream 42 with improved 25 gel strength is recovered. Table 6 gives a typical compositional attributes of GPC, GPI and a whey protein isolate made using a traditional ion exchange process.
TABLE 6 -
9
Typical compositions of GPC, GPI and a whey protein isolate
GPC
GPC
GPI
WPI
Total Protein f%)
53.5
84.0
>90
>90
Ash (%)
9.0
2.46
2.4
1.8
Lactose (%)
32.5
8.30
4.5
6.5
Fat (%)
1.0
0.23
0.2
0.8
Moisture (%)
4.0
4.78
<2.9
<0.9
Na (mM/kg)
_
74
220
K (mM/kg)
117
Ca (mM/kg)
75.3
73
50
P04 (mM/kg)
-
16.8
<0.5
Typical amino acid profile of the GPI stream 42 is given in Table 7.
TABLE 7 - Typical Amino Acid Profile of GPI
Amino acid
(%)
Amino acid
(%)
Cys
3,0
Tyr
4.3
His
2.1
Val
.2
He
.3
Ala
7.0
Leu
13.1
Arg
2.6
Lys
.4
Asx
11.5
Met
2.3
Glx
18.4
Phe
4.2
Gly
2.0
Thr
.6
Pro
.1
Trp
2.0
Ser
4.8
£ WO 96/08155
Example 4
- Production of BSA + IG enhanced protein concentrate
Referring to Figure 1, a skim milk stream 10 is subjected to microfiltration 12 as described in Example 1. The permeate stream 20 is subjected to ultrafiltration 22 possibly including 5 diafiltration, to produce a GPC/GPI stream 42 as in Example 3.
A retentate stream 16 which is rich in casein is processed on its own or in a blend with a second skim milk stream 11 by a traditional casein process 40 to make casein 41 and a casein whey stream 39.
The traditional casein process 40 used is as follows:
The acid casein is produced by mixing pasteurized skim milk with dilute mineral acid at 20°C to a pH of 4.6. The mixture is heated to 50-55°C to aid the agglomeration of the casein particles. 15 Following a short period of residence in "cooking" line and "acidulation" vat, the resultant curd is separated from the whey, washed and dried (Southward, CR & Walker N L (1980) The Manufacture and Industrial Use of Casein. New Zealand Journal of Dairy Science and Technology, 15, 201-217).
The casein whey 39 will be rich in bovine serum albumin (BSA) and more importantly in immunoglobulins (IgG). The casein whey 39 can be processed by ultrafiltration 44 with or without diafiltration to produce retentate 46 which is dried in drier 49, with or without evaporator 48, resulting in a whey protein concentrate 50 enhanced in BSA and IG. HPLC analysis of this WPC showed that the IG component of the protein was enhanced by 80% compared with a 25 standard mineral acid WPC.
Typical compositions of a standard mineral acid and BSA+IG enhanced wheys are shown in Table 8 below.
TABLE 8
11
- Typical Compositions of Standard and BSA+IG enhanced wheys
Component
Traditional mineral acid whey
—— 1
BSA+IG enhanced whey
Ash (%)
0.77
0.68
Lactose (%)
4.44
4.54
Total Protein (%)
0.69
0.50
Total Solids (%)
.90
.67
Water
94.10
94.33
BSA (% of total protein)
6
IgG (% of total protein)
18
Example 5 - Preparation of Whey Protein Depleted MPCs
Referring to Figure 3, a stream of skim milk 10 is processed by microfiltration 12 as in example 15 1 using a polymeric or ceramic membrane with a porosity of up to 0.2 Jim, producing a retentate stream 14 with reduced whey proteins. Volume concentrations of up to 5 can be employed. The retentate stream 14 is combined with either UF permeate 24 or demineralized water 43 and diafiltered (microfiltration membranes) 12 using a concentration factor of up to 5. Further diafiltration can be carried out to achieve a further reduction of the whey protein in the retentate. 20 The retentate is then dried 29 with or without prior evaporation 28. The MF permeate 20 is subjected to ultrafiltration 22 as in example 1. The permeate 24 is either used for diafiltration (as above) or discarded.
The composition ranges of the final milk protein concentrate are as in Table 5.
Example 6 - Use of Whey Protein Depleted MPC's
The milk protein concentrates prepared in example 5 have reduced whey protein content. The major uses of milk protein concentrates (MPCs) are recombined cheeses (soft and semi-soft), for 30 processed cheese and cheese milk extension for natural cheese manufacture (soft, semi-soft and hard). They can provide superior functional and sensory attributes in food products like Feta cheese, Mexican Panela cheese etc.
12
For recombined cheeses, standard MPCs have the advantage that a high total solids (up to 40%) cheesemilk can be used. This results in very little cheese whey being produced during manufacture, and also the incorporation of the whey proteins in the cheese curd i.e. higher yields are achieved. However, the incorporation of the whey proteins has a significant effect on the 5 functional properties of the final product. By manipulating the level of whey proteins in the MPCs one can control the functional properties of a cheese to meet the requirements of particular markets. This is a major benefit. For example in recombined soft cheeses a firmer texture cheese is produced as the level of whey protein is reduced.
In cheese milk extension, standard MPCs are used to increase cheese yields, but the whey proteins go with the cheese whey. A major benefit of a whey protein depleted MPC (of the same total protein as a standard MPC) is a further increase in yield and a decrease of whey proteins in the cheese whey.
Example 7 - The Manufacture of Recombined Feta Cheese using Whey Protein Depleted Milk Protein Concentrate
Anhydrous milk fat (AMF), milk protein concentrate (MPC) and water are mixed together to make a recombined cheesemilk with a total solids of about 40%. The cheesemilk is then
homogenised and pasteurised. Cheese starter, rennet and calcium chloride are added to the cheesemilk. The product is then filled into containers and incubated at 30°C for 24 hours after which time a brine solution is added to the cheese. The cheese is stored at 5°C and is ready for consumption in about 10 days.
Recombined feta cheese was made by the above process using a standard MPC and a whey protein depleted MPC. The texture of these cheeses was measured and compressive rigidity and strain values were calculated. Figure 8 shows a plot of these values for each of the cheese samples. The cheeses made from the reduced whey protein MPCs (35 and 37) exhibited higher rigidity and lower strain values compared with the control cheeses (38 and 45). This indicates that more brittle
and firmer cheese can be produced with MPCs with reduced whey protein.
^ WO 96/08155 Example 8
13
Functional globular protein concentrates
Referring to Figure 4, a stream of skim milk 10 is processed by microfiltration 12 as in example 1 using a polymeric or ceramic membrane with a porosity of up to 0.2 urn to produce MF 5 permeate stream 20. Volume concentrations up to 5 can be used. The pH of MF permeate stream 20 is adjusted to be £ 5 using organic or mineral acid 79, typically citric, hydrochloric, sulphuric or phosphoric or lactic acid (could be from lactic starters) or combinations thereof. The pH adjusted MF permeate stream 82 is then processed with or without diafiltration by ultrafiltration 22 as in example 1 to produce UF retentate stream 84, which is dried 33, with or without prior 10 evaporation, to generate firm gelling >80% (protein) globular protein concentrate 86, which has a superior flavour, low fat (<0.5%) and a high gel strength. Typical compositions of GPC and citric acid diafiltered GPC are given in Table 9.
TABLE 9 - Typical Compositions of GPC and of Citric Acid Diafiltered GPC
Component
GPC
Citric Acid Diafiltered GPC
Ash (%)
2.46
3.61
Lactose (%)
8.30
8.30
Fat (%)
0.23
0.22
Total Protein (%)
84.0
83.5
Calcium (mM/kg)
75.3
49.8
Phosphate (mM/kg)
16.8
16.4
Magnesium (mM/kg)
17.2
11.0
Sodium (mM/kg)
92.0
417.0
Potassium (mM/kg)
158.0
99.0
Citrate (mM/kg)
0.22
1.86
The gel strength of GPC at 11% protein and 75°C was measured to be 350 g/cm2 whereas the gel strength of citric acid diafiltered GPC under the same conditions was measured to be 900 g/cm2.
WO 96/08155 PCT7NZ95/00086
14
The storage modulus (G1) of GPC and citric acid diafiltered GPC determined using a Bohlin Rheometer is shown in Figure 9. In Figure 9, o is globular protein concentrate, • is citric acid diafiltered globular protein concentrate and A is the temperature in degrees celsius. The results indicate that under the same temperature programming, at 120 min, the G' of citric acid diafiltered 5 GPC is about 7 times higher than the G1 of the standard GPC.
In a modification of the above process alternative MF permeate stream 21 can be concentrated by ultrafiltration (as in example 1) to a volume concentration factor range of 20 to 100. The preferred volume concentration factor is between 30-50. The UF retentate stream 26 is then 10 diafiltered with acidified water 52 and dried 33 'with or without evaporation to produce the >80% GPC stream 86.
Example 9 - Preparation of whey protein depleted cheese milk
It is well documented that the ratio of casein protein to whey protein varies with the stage of lactation, plane of nutrition and other factors in seasonally based pastoral fanning. This affects the quality of cheese made by the process, because casein is the milk component which forms the initial gel, controlling retention of cheese yielding materials and the rate of moisture loss during processing (IDF bulletin 9301). Standardizing the cheese milk casein and whey protein levels will 20 improve the plant efficiency and product quality. A typical process for this is as follows.
Referring to Figure 2, a stream of skim milk 10 is processed by microfiltration 12 as in example 1 using a polymeric or ceramic membrane with a porosity of up to 0.2 Jim. Volume concentration factors up to 5 can be employed. The MF permeate 20 stream is processed by ultrafiltration 22 25 producing UF retentate 26 and UF penneate 24 streams. The whole or part of the streams of MF retentate 14, UF retentate 26, UF Permeate 24 and cream 70 are combined together resulting in a cheese milk 72 with a predetermined casein to whey protein ratio.
This ability to standardise the cheese milk content allows higher equipment utilization and optimized yield throughout the daiiy season. It also gives improved process control on moisture, pH and salt-in-moisture.
£ WO 96/08155
The resulting cheese has consistently acceptable functional and sensory properties because of the ability to standardise the ingredient.
Example 10 - Preparation of whey protein depleted cheese ingredients powder
Processed cheese foods are food gels. The gelling properties of casein and whey proteins are different. Whey proteins gels are irreversible type whereas the casein gels are shear-thin type. Because of this it can be difficult to control the texture of mixed whey protein and casein gels. Examples are processed cheese, recombined processed cheese and stretch cheese. Standardizing 10 the casein to whey protein ratio in the cheese ingredients would therefore help to produce products with consistent functional performance. A typical process for cheese ingredients production would be as follows.
Referring to Figure 5, a stream of skim milk 10 is processed by microfiltration 12 as in example 15 1 using a polymeric or ceramic membrane with a porosity of up to 0.2 pm. Volume concentrations up to 5 can be employed. The permeate 20 is processed by ultrafiltration 22 as in example 1 producing UF retentate 26 and UF permeate 24 streams. The MF retentate 14, UF retentate 26, UF Permeate 24 and cream 70 are combined together resulting in stream 74 which is dried in drier 29, with or without evaporation, resulting in a cheese ingredients powder 76 with 20 a predetermined casein to whey protein ratio.
The cheese ingredients powder may be used for processed cheese, recombined cheeses and cheese milk extension.
Example 11 - Low Fat/High Calcium UHT Milks
Referring to Figure 6, a stream of skim milk 10 is processed by microfiltration 12 as in example 1, using a polymeric or ceramic membrane with a porosity of up to 0.2 |im. The volume concentration factor should be carefully selected such that the calcium level in the final product 30 is greater than 0.2% but the fat level is below 0.1%. For the typical skim milk composition (as set out in Table 1) containing 0.12% calcium, typical volume concentration factor is 1.5. The retentate 14 can then be processed in a UHT plant 90 to produce a low fat/high calcium milk 94.
£ WO 96/08155 PCT/NZ95/00086
16
Optionally, retentate 14 can be obtained by processing the skim milk to a typical volume concentration factor of 2, blended with skim milk 10 at appropriate ratio to produce blended milk 88 having a calcium content that is greater than 0.2%, a fat content that is less than 0.1%. The blended milk is then processed in a UHT plant 90 to produce low fat/high calcium milk 94. In 5 another option, retentate 14, MF permeate 20 and UF permeate 24 can be carefully blended in appropriate ratio, such that blended milk will have a calcium level that is greater than 0.2% but a fat level that is less than 0.1%. The blended milk 89 is then processed in a UHT plant 90 to produce a low fat/high calcium milk 94.
The compositions of low fat/high calcium UHT milks with reduced whey protein levels are set out in Table 10. These products displayed better long-term storage characteristics (6-8 months), particularly increased resistance to gelation compared with low fat/high calcium UHT milks produced by ultrafiltration (4-7 months). If the UHT operation is not used, the low fat/high calcium milk can be sold for local markets with or without further heat treatment.
TABLE 10 - Low Fat/High Calcium Milk Composition
Example 12 - Manufacture of Milk Powders through Partial Separation of Casein
Protein and Whey Protein Fractions
Component
Compositions
Total Solids
-13%
Water
87-90%
Total protein
-6.5%
Minerals
0.9-1.2%
Lactose
4-5.5%
Calcium
*0.2%
Fat
*0.1%
Milk powders for recombining and reconstitution rarely exhibit ideal performance in the applications for which they were intended. Many of these shortcomings seem to be linked to milk
17
composition and in some cases it seems that relatively minor changes in composition can lead to remarkable improvements in performance. In particular, it has been found that the ratio of casein protein to whey protein has an important influence on the performance of milk powders in several applications. Moreover, it has been found that the efficiency of milk powder manufacture is determined to a large extent by the relationship between milk viscosity and total solids, which is in turn strongly dependent on the casein protein to whey protein ratio of the milk being dried. The following describes how microfiltration can be used in a milk powder production plant to manipulate the composition of milk in order to improve both the processing of the milk and the performance of the subsequent milk powder.
Referring to Figure 7, a typical skim milk 10 is processed by microfiltration 12 as in example 1 using polymeric or ceramic membranes with a pore size of up to 0.2 gm. Appropriate volume concentration factors for the microfiltration process are selected depending upon the protein concentration of the milk stream being microfiltered. For New Zealand skim milk (which typically contains about 3.5% protein), volume concentration factors of 1.5 to 4 are best employed. The MF retentate 14 contains most of the casein and some (typically 50-80%) of the whey protein found in the original skim milk 10. The MF permeate 20 contains almost no casein but part of the lactose, free minerals and whey proteins (typically 20-50%) found in the original skim milk 10. Thus the MF process separates skim milk into a whey-protein-contained stream (the MF permeate 20) and a whey-protein-depleted stream (the MF retentate 14). These streams can be further processed in various ways to produce milk powders that have adjusted casein protein to whey protein ratios (see schemes 1 and 3 below). Alternatively, the two streams (14 and 20) can be subjected to different processing regimes (e.g., different heat treatments) before being recombined and evaporated and dried to produce a milk powder that is identical to a standard milk powder in compositional terms but that has an improved balance between functional and/or flavour properties (see scheme 2 below).
Scheme I: Whev-Protein-Enhanced Milk Powders
The MF permeate 20 is processed by ultrafiltration 22 to produce a UF retentate 26 and a UF permeate 24. The UF retentate 26 contains typically 20-50% of the whey protein found in the original skim milk 10 and can be combined with a second stream 11 of the original skim milk to produce a whey-protein-enhanced skim milk 55. The UF retentate 26 and the skim milk 10 can
) WO 96/08155 PCT/NZ95/00086
18
each be further processed in any manner before being mixed to form whey-protein-enhanced skim milk 55 if this is desired. Cream 70 may or may not be added to 55 and the resulting whey-protein-enhanced whole milk or whey-protein-enhanced skim milk can then, optionally, be evaporated on an evaporator (which is not shown) and subsequently dried on drier 47 to produce 5 a whey-protein-enhanced whole or skim milk powder 60.
Whey-protein-enhanced powders have been found to perform better than standard powders in recombined cultured products. For example, use of whey-protein-enhanced powders in the manufacture of recombined yoghurts leads to reduced syneresis and increased gel strength 10 compared with yoghurts made from standard powders. Similarly, cultured beverages made from whey-protein-enhanced powders show reduced sedimentation and shorter fermentation times than cultured beverages made from standard powders
Scheme 2: Milk Powders with Standard Composition 15 The MF permeate 20 is recombined with the MF retentate 14 after one or both streams have been subjected to further processing. This may involve simply subjecting the MF retentate 14 and the MF permeate 20 to different heat treatments before recombining the two streams and evaporating and drying or it may involve further separations. For example, the MF permeate 20 may be processed by ultrafiltration 22 to produce a UF permeate 24 and a UF retentate 26. The UF 20 retentate 26 contains typically 20-50% of the whey protein separated from the original skim milk 10 and the UF permeate 24 contains most of the lactose and most of the free minerals separated from the original skim milk 10. Each of streams can then be subjected to different heat treatments and/or any other desired processes before all streams are recombined to produce a skim milk 56 that has identical composition to a standard skim milk. Cream 70 may or may not be added to the 25 skim milk 56 to produce a whole milk or a skim milk 56 which can then, optionally, be evaporated on an evaporator (which is not shown) and subsequently dried on drier 47 to produce a whole milk powder or a skim milk powder 59. Careful selection of the heat treatments for each stream allows production of skim or whole milk powders with desired combinations of functional and flavour properties.
Evaporation of whey protein depleted streams like the MF retentate 14 can typically be continued to higher total solids than standard skim milk. As a result, the overall evaporation and drying of
WO 96/08155 PCT/NZ95/00086
19
skim milk can be conducted more efBciently if different streams (e.g., the MF retentate and the MF permeate) are evaporated separately than if the complete skim milk is evaporated. Thus, milk powders made using the split-stream processing ideas described here can be evaporated and dried more efBciently than standard skim and whole milk powders.
Scheme 3: Whev-Protein-Depleted Milk Powders
The MF permeate 20 is processed by ultrafiltration 22 to produce a UF retentate 26 and a UF permeate 24. The UF permeate 24 contains most of the lactose found in the original skim milk 10 and can be combined with the MF retentate 14 to produce a skim milk 53 that is depleted 10 (typically 20-50%) in whey protein. This whey-protein-depleted skim milk 53 can then be combined with a third skim milk stream 13 in any proportions to produce a skim milk 57 that is typically up to 50% whey-protein-depleted. Cream 70 may or may not be added to skim milk 57 and the resulting whey-protein-depleted whole milk or whey-protein-depleted skim milk can then, optionally, be evaporated on an evaporator (which is not shown) and subsequently dried on drier 15 47 to produce a whey-protein-depleted whole or skim milk powder 58.
Evaporation of the whey-protein-depleted stream 57 can typically be continued to higher total solids than is the case if standard skim or whole milk is evaporated. As a result, evaporation and drying of whey-protein-depleted skim or whole milk can be carried more efficiently than 20 evaporation and drying of standard skim or whole milk. Recombined milks made from whey-protein-depleted milk powders show a reduced tendency to foul heated surfaces and a reduced tendency to gel when heated.
292643
PCT/NZ v 5 / 0 0 0 8 6 RECEIVED 0 3 JUL TO
Claims (93)
1. A process of adjusting the ratio of whey protein to casein in a supply of skim milk which comprises subjecting a first stream of said skim milk to microfiltration on a microfiltration membrane (as herein defined), recovering the MF retentate therefrom, and; either; (a) drying said MF retentate and recovering it as a milk protein concentrate depleted in whey proteins; or (b) subjecting said MF retentate to ultrafiltration using an ultrafiltration membrane (as herein defined) and recovering the UF retentate therefrom and further processing said UF retentate and, discarding or recovering the MF permeate from said microfiltration.
2. A process as claimed in claim 1 wherein said step (a) is used.
3. A process as claimed in claim 1 wherein said step (b) is used and said UF retentate is recovered as a milk protein concentrate depleted in whey proteins.
4. A milk protein concentrate having the following composition: Component Amount Total Protein (%W/W) 40-95 Casein Protein (%W/W) 35-90 Whey Protein (%W/W) 3-20 Ash (%W/W) 6-10 Lactose (%WAV) <0.5-50 Fat (%W/W) 0.5-2.0 aA 0 a . -r fcr/Nzb 5/000 «L9Z 643 RECEIVED 0 3 JUL 21
5. A milk protein concentrate having the following composition: Component Amount Total Protein (%) 56 Casein Protein (%) 40-53 Whey Protein (%) 3-16 Ash (%) 8-9 Lactose (%) 28-30 Fat (%) 0.9-1.1
6. A milk protein concentrate whenever prepared by a process according to any one of claims 1, 2 and 3.
7. A process of adjusting the ratio of whey protein to casein in a supply of skim milk which comprises subjecting a first stream of said skim milk to microfiltration on a microfiltration membrane (as herein defined), recovering the MF retentate therefrom, subjecting the MF permeate therefrom to ultrafiltration on an ultrafiltration membrane (as herein defined) and using the UF permeate therefrom as a diafiltration liquid to diafilter said MF retentate on said MF membrane, and recovering said diafiltered MF retentate as a milk protein concentrate.
8. A milk protein concentrate whenever prepared from a process according to claim 7.
9. A process of adjusting the ratio of whey protein to casein in a supply of skim milk which comprises subjecting a first stream of said skim milk to microfiltration on a microfiltration membrane (as herein defined), and subjecting the MF permeate therefrom to ultrafiltration using an ultrafiltration (as herein defined), recovering the UF retentate therefrom and further processing said UF retentate, and discarding or recovering said MF retentate from said microfiltration. amended sheet ipea/au new zealand 1 3 NOV 1996 pate: nt office 22
10. A process as claimed in claim 9 wherein the pH of said MF permeate is adjusted to ^5 prior to subjecting it to said ultrafiltration.
11. A process as claimed in claim 9 or 10 wherein said UF retentate is recovered as globular protein concentrate.
12. A process as claimed in claim 9 or 10 wherein said further processing of said UF retentate comprises diafiltration of said retentate and recovering a globular protein isolate.
13. A process as claimed in any one of claims 9 to 12 which includes the step of drying the product therefrom.
14. Globular protein concentrate whenever prepared by a process according to claim 11.
15. Globular protein isolate whenever prepared by a process according to claim 12.
16. Globular protein concentrate powder whenever prepared by a process as claimed in claim 13.
17. Globular protein isolate powder whenever prepared by a process as claimed in claim 13.
18. A process of adjusting the ratio of whey protein to casein in a supply of skim milk which comprises subjecting a first stream of said skim milk to microfiltration on a microfiltration membrane (as herein defined), recovering the MF retentate therefrom, and subjecting said MF retentate to a traditional casein making process (as herein defined) and subjecting casein whey recovered from said traditional casein making process to ultrafiltration using an ultrafiltration membrane (as herein defined) and recovering the UF 2 Q 2 6 <4 3 PCT/NZ y5/ooos J RECEIVEO 0 3 JUL « 23 retentate therefrom as whey protein concentrate enhanced in bovine senim albumin and immunoglobulin.
19. Whey protein concentrate with enhanced bovine serum albumin and immunoglobulin whenever prepared by a process according to claim 18.
20. A process of adjusting the ratio of whey protein to casein in a supply of skim milk which comprises subjecting a first stream of said skim milk to a microfiltration on a microfiltration membrane (as herein defined), and subjecting the MF permeate therefrom to ultrafiltration using an ultrafiltration membrane (as herein defined), and combining some or all of said UF retentate and said UF permeate with said MF retentate to form a skim cheese milk, and discarding or recovering the MF retentate from said microfiltration.
21. A process according to claim 20 wherein a stream of cream is combined with said skim cheese milk to form whole cheese milk.
22. A process as claimed in either of claims 20 or 21 which comprises the additional step of drying said cheese milk into a cheese ingredients powder.
23. A process as claimed in any one of claims 20 to 22 in which said cheese milk or cheese milk powder is processed into cheese.
24. Cheese milk whenever prepared by a process according to claims 20 or 21.
25. Cheese ingredients powder whenever prepared by a process according to claim 22.
26. Cheese prepared from cheese milk according to claim 24 or from cheese ingredients according to claim 25. im£w zealand 1 3 NOV 1996 patent office AMENDED SHEET IPEA/AU V 0 9 £ / 7 PCiyNZ y 5 / U 0 U 8 5 £ £ 0 ^ J RECEIVED 2 3 AUC '986 24
27. Cheese according to claim 26 which is feta cheese.
28. A process of adjusting the ratio of whey protein to casein in a supply of skim milk which comprises subjecting a first stream of said skim milk to a microfiltration on a first microfiltration membrane (as herein defined), and subjecting the MF permeate therefrom to ultrafiltration using an ultrafiltration membrane (as herein defined), and recovering the UF penneate therefrom and combining it with the MF retentate from said first microfiltration membrane and, optionally, a stream of skim milk and subjecting the combination to microfiltration on a second microfiltration membrane (as herein defined) and recovering the milk protein concentrate with reduced whey protein thereby derived.
29. Milk protein concentrate whenever prepared by a process according to claim 28.
30. A process of adjusting the ratio of whey protein to casein in a supply of skim milk which comprises subjecting a first stream of said skim milk to a microfiltration on a microfiltration membrane (as herein defined) to a volume concentration factor of at least 1.5, recovering the MF retentate therefrom, and (a) subjecting said MF retentate to UHT treatment (as herein defined) and recovering a low fat/high calcium UHT milk, or (b) combining some or all of said MF retentate with a second stream of said skim milk and subjecting said combined stream to UHT treatment (as herein defined), and recovering a low fat/high calcium milk.
31. A process as claimed in claim 30 wherein said step (a) is used and a low fat/high calcium UHT milk product is recovered.
32. A process as claimed in claim 30 wherein said step product recovered is low fat/high calcium UHT milk. AMENDED SHEtfl IPEA/AU (b) is used and wherein the new zealand 1 3 NOV 1996 patent office Z 9 26 4. 3 PCT/xz ^ cs \J *f y) RECEIVED 2 3 AUG 19 25
33. A process of adjusting the ratio of whey protein to casein in a supply of skim milk which comprises subjecting a first stream of said skim milk to a microfiltration on a microfiltration membrane (as herein defined), and subjecting a first stream of the MF permeate therefrom to ultrafiltration using an ultrafiltration membrane (as herein defined), recovering the UF permeate therefrom and combining it with a second stream of the MF retentate from said microfiltration and subjecting the combined stream to UHT treatment (as herein defined) to form a low fat/high calcium milk.
34. A process according to claim 33 wherein an additional stream of skim milk is combined with said UF permeate, said MF retentate and said other stream of MF permeate prior to said UHT treatment.
35. Low fat/high calcium UHT milk whenever prepared by a process according to any one of claims 30 to 34.
36. A process of adjusting the ratio of whey protein to casein in a supply of skim milk which comprises subjecting a first stream of said skim milk to microfiltration on a microfiltration membrane (as herein defined), recovering the MF retentate and the MF permeate therefrom, and processing by a process other than sterilization said MF permeate separately from said MF retentate, said processed MF retentate and MF permeate being recombined into a skim milk of altered functional properties.
37. A process as claimed in claim 36 wherein said processing of said MF retentate comprises heating said MF retentate.
38. A process according to either claim 36 or 37 wherein said processing of said MF permeate comprises heating said MF permeate. new zealand 1 3 NOV 1996 patent office AMENDED SHEET IPEA/AU 292643 i*' C X; N w r\ f n. ^ -w/ •J V RECEIVED 2 3 AUG 26
39. Recombined skim milk whenever prepared by a process according to any one of claims 36 to 38.
40. A process according to any one of claims 36 to 38 wherein cream is added to the recombined skim milk recovered therefrom to form a recombined whole milk.
41. Recombined whole milk whenever prepared by a process according to claim 40.
42. A process as claimed in any one of claims 36 to 38 which includes the additional step of drying said recombined skim milk.
43. Recombined skim milk powder whenever prepared by a process according to claim 42.
44. A process as claimed in claim 4<J which includes the additional step of drying said recombined whole milk.
45. Recombined whole milk powder whenever prepared by a process according to claim 44.
46. A process of adjusting the ratio of whey protein to casein in a supply of skim milk which comprises subjecting a first stream of said skim milk to microfiltration on a microfiltration membrane (as herein defined), recovering the MF retentate and the MF permeate therefrom combining some or all of said MF retentate with a second stream of said skim milk, subjecting said MF permeate to ultrafiltration using an ultrafiltration membrane (as herein defined) combining said UF permeate with said MF retentate and with said second stream of skim milk and recovering said combined stream as a whey protein depleted skim milk. j""" new ZEALAND 1 13 i patent ;^nce , AMENDED SHEET IPEA/AU 29 2^43 ?RE'ciEIVED' 21 AUG 27
47. A process as claimed in claim 46 wherein cream is added to said whey protein depleted skim milk to form a whey protein depleted whole milk.
48. Whey protein depleted skim milk whenever prepared by a process according to claim 46.
49. Whey protein depleted whole milk whenever prepared by a process according to claim 47.
50. A process according to either of claims 46 or 47 which includes the additional step of drying said whey protein depleted skim or whole milk.
51. Whey protein depleted skim milk powder whenever prepared by a process according to claim 50.
52. Whey protein depleted whole milk powder whenever prepared by a process according to claim 50.
53. A process of adjusting the ratio of whey protein to casein in a supply of skim milk which comprises subjecting a first stream of said skim milk to a microfiltration on a microfiltration membrane (as herein defined), and subjecting the MF permeate therefrom to ultrafiltration using an ultrafiltration membrane (as herein defined), and combining some or all of said UF retentate with a second stream of said skim milk to form a whey protein enhanced skim milk.
54. Whey protein enhanced skim milk whenever prepared by a process according to claim 53, new zealand 1 3 NOV 1996 patent office AMENDED SHEET IPEA/AU 292643 PCT/Nzy 5 / U U U u u RECEIVED 2 3 AUG 1996 28
55. A process according to claim 53 wherein a stream of cream is mixed with said whey protein enhanced skim milk to form a whey protein enhanced whole milk.
56. A whey protein enhanced whole milk whenever prepared by a process according to claim 55.
57. A process according to either of claims 53 or 56 wherein said whey protein enhanced skim milk or whey protein enhanced whole milk is dried to a powder.
58. Whey protein enhanced skim milk powder whenever prepared by a process according to claim 57.
59. Whey protein enhanced whole milk powder whenever prepared by a process according to claim 57.
60. A process according to any one of claims 1-3, 7, 9-13, 18, 20-23, 28, 30-34, 36-38, 40, 42, 44, 46, 47, 50, 53, 55 and 57 wherein said microfiltration or said ultrafiltration is conducted at a temperature within the range of between about 5°C and 60°C.
61. A process according to claim 60 wherein said temperature range is between about 10°C and 50°C.
62. A process according to any one of claims 1-3, 7, 9-13, 18, 20-23, 28, 30-34, 36-38, 40, 42, 44, 46, 47, 50, 53, 55 and 57 wherein the transmembrane pressure during said ultrafiltrafion or said microfiltration is no more than about 3 bars.
63. A process according to claim 62 wherein said pressure is no more than about 1 bar. new zealand AMENDED SHEET IPEA/AU 1 3 NOV 1996 patent office 292643 29
64. A process according to claim 63 wherein said pressure is about 0.3 bar.
65. A dairy product produced by any one of claims 1-3, 7, 9-13, 18, 20-23, 28, 30-34, 36-38, 40, 42, 44, 46, 47, 50, 53, 55, 57 and 60 to 64.
66. The use of a dairy product produced by a process according to any one of claims 1-3, 7, 9-13, 18, 20-22, 28, 30-34, 36-38, 40, 42, 44, 46, 47, 49, 53, 55, 57 and 60-64 in the production of a subsequent dairy product.
67. The use of a milk protein concentrate prepared by a process according to any one of claims 1-3,7 and 28 in a process for the production of a recombined cheese.
68. A process as claimed in any one of claims 1 to 3 substantially as herein described with reference to example 2 and figure 1.
69. A milk protein concentrate substantially as herein described with reference to example 2.
70. A process as claimed in claim 7 substantially as herein described with reference to example 5 and figure 3.
71. A milk protein concentrate substantially as herein described with reference to example 5.
72. A process as claimed in any one of claims 9 to 13 substantially as herein described with reference to examples 3 and 8 and figure 4.
73. Globular protein concentrate substantially as herein described with reference to- N..~. PA7c :\!T OFFIC examples 3 and 8. i 19 MAR 1997 292643
74. Globular protein isolate substantially as herein described with reference to example 3.
75. A process as claimed in claim 18 substantially as herein described with reference to example 4 and figure 1. \
76. Whey protein concentrate as claimed in claim 19 substantially as herein described with reference to example 4.
77. A process as claimed in any one of claims 20 to 23 substantially as herein described with reference to examples 9 or 10 and figures 2 or 5.
78. Cheese milk substantially as herein described with reference to example 9.
79. Cheese ingredients powder substantially as herein described with reference to example 10.
80. Recombined feta cheese substantially as herein described with reference to example 7.
81. A process as claimed in claim 28 substantially as herein described with reference to example 5 and figure 3.
82. A process as claimed in any one of claims 30 to 33 substantially as herein described with reference to example 11 and figure 6.
83. A low fatliigh calcium UHT milk substantially as herein described with reference to example 11. '"n.z. patent office IS MAR 1397 31 v tjh* X
84. A process as claimed in any one of claims 36 to 38 substantially as herein described with reference to example 12 and figure 7.
85. Recombined skim milk or skim milk powder substantially as herein described with reference to example 12.
86. A process as claimed in claim 40 substantially as herein described with reference to example 12.
87. Recombined whole milk or whole milk powder substantially as herein described with reference to example 12 and figure 7.
88. A process as claimed in claim 46 or claim 47 substantially as herein described with reference to example 12 and figure 7.
89. Whey protein depleted skim milk or skim milk powder substantially as herein described with reference to example 12.
90. Whey protein depleted whole milk or whole milk powder substantially as herein described with reference to example 12.
91. A process as claimed in claim 53 substantially as herein described with reference to example 12 and figure 7.
92. Whey protein enhanced skim milk and skim milk powder substantially as herein described with reference to example 12.
93. Whey protein enhanced whole milk and whole milk powder substantially as herein described with reference to example 12. END OF CLAIMS INTELLEC'f UAL PROPERTY OFFICE OF N.Z. 2 2 JUN 1998 RECEIVED
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NZ292643A NZ292643A (en) | 1994-09-16 | 1995-09-15 | Adjustment of ratio of whey protein to casein in skim milk |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NZ26447494 | 1994-09-16 | ||
NZ292643A NZ292643A (en) | 1994-09-16 | 1995-09-15 | Adjustment of ratio of whey protein to casein in skim milk |
PCT/NZ1995/000086 WO1996008155A1 (en) | 1994-09-16 | 1995-09-15 | Physical separation of casein and whey proteins |
Publications (1)
Publication Number | Publication Date |
---|---|
NZ292643A true NZ292643A (en) | 1998-08-26 |
Family
ID=26651385
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NZ292643A NZ292643A (en) | 1994-09-16 | 1995-09-15 | Adjustment of ratio of whey protein to casein in skim milk |
Country Status (1)
Country | Link |
---|---|
NZ (1) | NZ292643A (en) |
-
1995
- 1995-09-15 NZ NZ292643A patent/NZ292643A/en not_active IP Right Cessation
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU700748B2 (en) | Physical separation of casein and whey proteins | |
Carter et al. | Invited review: Microfiltration-derived casein and whey proteins from milk | |
Rosenberg | Current and future applications for membrane processes in the dairy industry | |
AU2008318411B2 (en) | Methods for casein production | |
Jovanović et al. | Whey proteins-properties and possibility of application | |
CA2428943C (en) | Dairy products with reduced average particle size | |
DK2649884T4 (en) | PROCEDURE FOR CREATING CREAM CHEESE | |
Hammam et al. | Progress in micellar casein concentrate: Production and applications | |
IE48398B1 (en) | A process for treating a protein source and a food product having a treated protein source prepared by the process | |
CN102802426A (en) | Product and process for its preparation | |
JP2023091041A (en) | Methods for making high-protein greek yogurt using membrane systems before and after fermentation | |
FI129057B (en) | A method for producing a spoonable acidified milk product | |
AU2004263066A1 (en) | Production of protein composition from a dairy stream and its use as an ingredient in the manufacture of a cheese | |
KR20160021760A (en) | Spreadable high protein cream cheese products and methods of making the same | |
US20030078392A1 (en) | Milk and cheese modification process, including methods of extracting beta-lactoglobulin and caseins from milk and milk products, and novel products thereby produced | |
NZ292643A (en) | Adjustment of ratio of whey protein to casein in skim milk | |
JPS61170341A (en) | Production of beverage obtained by fermentation of whey | |
Jovanović et al. | Serum proteini-osobine i mogućnost primjene |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
RENW | Renewal (renewal fees accepted) | ||
RENW | Renewal (renewal fees accepted) | ||
RENW | Renewal (renewal fees accepted) | ||
EXPY | Patent expired |