Indira Gandhi

National Open University

BPVI-016
School of Agriculture Dairy Products – III

Block

4
BY – PRODUCTS
UNIT 12

Skim milk – Casein and Caseinates 5

UNIT 13

Whey – Whey Powder, Lactose and Whey Protein Concentrates 19

UNIT 14

Buttermilk and Ghee Residue 39

UNIT 15

New Technologies in By-Product Utilization (Membrane Processing,

Reverse Osmosis and Ultra Filtration) 54
Programme Design Committee
Prof. H.P. Dikshit Prof. Panjab Singh
Ex. Vice Chancellor Vice Chancellor
IGNOU, New Delhi Banaras Hindu University, Banaras (U.P.)

Prof. S.C. Garg, Shri A.N.P. Sinha

Acting Vice Chancellor Former Additional Secretary
IGNOU, New Delhi Ministry of Food Processing Industries
Delhi

Ministry of Food Processing Industries Milk Plant, Gwalior:

New Delhi :
• Mr. K.K. Maheshwary
• Mr. R.K. Bansal, Consultant
• Mr. V.K. Dahiya, Tech. Officer
(Milk Products)
NDRI, Karnal, Haryana:
• Dr. S. Singh, JD (Academics)
• Dr. S.P. Agrawala, Head (Dairy Engg.)
• Dr. Rajvir Singh, Head (Dairy Eco.)
• Dr. K.L. Bhatia, Ex-Principal Scientist
• Dr. S.K. Tomar, Principal Scientist
• Dr. B.D. Tiwari, Ex. Principal Scientist
• Dr. Dharam Pal, Principal Scientist
• Dr. A.A. Patel, Principal Scientist
Mother Dairy, Delhi:
Dr. P.N. Reddy
Former Quality Control Manager
Shri M.E. Khan, Manager - Plant Operation
Delhi Milk Scheme, Delhi:
Shri Ashok Bansal, DGM
CITA, New Delhi:
Shri Vijay Sardana
Mahaan Protein, Mathura (U.P.):
Dr. Ashwani Kumar Rathor, GM Technical
IGNOU, New Delhi (SOA Faculty Members):
• Dr. M.K. Salooja, Dy. Director
• Dr. M.C. Nair, Dy. Director
• Dr. Indrani Lahiri, Asstt. Director
• Dr. P.L. Yadav, Sr. Consultant
• Dr. D.S. Khurdiya, Sr. Consultant
• Sh. Jaya Raj, Sr. Consultant
• Sh. Rajesh Singh, Consultant

Programme Coordinators : Prof. Panjab Singh, Dr. M.K. Salooja and Dr. P.L. Yadav

Block Preparation Team

Writer Course Coordinator
Dr. A.K. Rathour Dr. M.K. Salooja
Dr. V.K. Gupta Dr. P.L. Yadav
Editors Dr. J.S. Sindhu
Dr. P.L. Yadav Dr. S. Singh
Dr. J.S. Sindhu
Dr. M.K. Salooja

Material Production
Mr. Rajiv Girdhar, SO (Publication) Secretarial Assistance
Mr. Vinay Sehgal

Word Processing
Mr. Bhim Singh

October, 2006
© Indira Gandhi National Open University, 2006
ISBN-81-266-2595-3
All rights reserved. No part of this work may be reproduced in any form, by mimeograph or any other
means, without permission in writing from the Indira Gandhi National Open University.
Further information on Indira Gandhi National Open University courses may be obtained from the
University's office at Maidan Garhi, New Delhi-110 068.
Printed and published on behalf of the Indira Gandhi National Open University, New Delhi by
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BLOCK INTRODUCTION
The term by-products may not sound as important as the main products manufactured
from milk. Nevertheless they consist a very important category of dairy products
including skimmed milk, casein and cuseinate, whey, whey powder, whey proteins
concentrate, buttermilk and ghee residue. Some of the by-products like skimmed
milk, butter milk and whey if not properly utilized may create acute problem of
environmental pollution. However, if utilized properly these by-products may
contribute significantly to the income of the plant and turn it into a profit making unit
if it is running in loss but if it is already a profit making unit than there will be further
increase in the its profit. These by-products if properly utilized and converted into
products having longer self life like skimmed milk powder, butter milk powder and
whey powder in the flush season can be utilized to agument the fluid milk supply in
the lean season.
Unit – 12 Method of manufacturing of acid and rennet casein including temperature
of precipitation, draining of whey, washing, pressing, milling, drying and grinding of
casein is given in this unit. Method of manufacturing of different caseinates like
sodium and calcium caseinate and their composition is also given.
Unit – 13 In this unit the composition of different type of whey and their utilization
is explained. Method of manufacturing of condensed whey, sweetened whey, whey
protein concentrate whey powder, crude lactose and whey beverages and drinks is
also given alongwith refining of lactose and its grades.
Unit – 14 Physico-chemical composition of sweet cream butter milk and its
processing for the utilization in the manufacturing of beverages, market milk, fermented
milk, Paneer and Cheese and utilization of sour cream butter milk is given in this unit.
The chemical composition, nutritioinal, antioxagenic and flavouing properties of ghee
residue and its utilization in the manufacturing of candy, chocolate, edible pastes,
burfi type sweets and bakery products is also discussed.
Unit – 15 The new technologies like membrane processing, reverse osmosis and
ultra filtration used in the utilization of by-products from milk along with application
of these technologies in dairy industry is discussed in this unit.
UNIT 12 SKIM MILK – CASEIN AND
CASEINATES
Structure
12.0 Objectives
12.1 Introduction
12.2 Legal Standards
12.3 Acid Casein
• Raw Material
• Precipitation
• Temperature of Precipitation
• Draining
• Washing
• Pressing
• Milling and Drying
• Grinding, Sieving, Bagging

12.4 Rennet Casein

12.5 Yield
12.6 Caseinate
• Sodium Caseinate
• Calcium Caseinate
• Other Caseinates

12.7 Uses of Caseins and Caseinates

12.8 Lets Sum Up
12.9 Key Words
12.10 Some Useful Books
12.11 Answers to Check Your Progress

12.0 OBJECTIVES
After reading this we should be able to:
• Learn about the different types of caseins and caseinates available
• manufacture casein and caseinates
• Know the standards and specifications for caseins and caseinates
• Know about the industrial and food uses of casein and caseinates
• Learn the processing factors affecting the quality and yield of casein and
caseinates

12.1 INTRODUCTION
Skim milk is the byproduct of the cream, butter and ghee industry. It is rich in solids-
not-fat content and has high nutritional value. In dairy plants it is mostly utilized either
5
in standardization for the manufacture of the main dairy products or preserved by
By – Products removing moisture in spray dried form to obtain skim milk powder. The skim milk
when utilized in either of these two forms or consumed, as a liquid is not considered
as a byproduct. It is regarded as a byproduct only when it is either not economically
utilized or utilized for derived byproducts like casein and related products,
coprecipitates, protein hydrolysates, etc.
Casein is the major protein in milk and constitutes about 80% of the total protein
content and about 20%, is the whey or serum proteins. Commercial-casein is made
from skim milk by one of the two general methods – precipitation by acid to make
acid casein or coagulation with rennet to make rennet casein. In addition to these
two main types there are other commercially available casein products of importance,
viz.: (1) Coprecipitate, made by heating skim milk to a high temperature and then
precipitating the casein/whey protein complex, usually with calcium chloride. The
coprecipitate also contains whey proteins and calcium and (2) Caseinates, commonly
sodium caseinate which is obtained from acid casein dissolved in sodium hydroxide

12.2 LEGAL STANDARDS

According to PFA, skimmed milk means the product prepared from milk from which
almost all the milk fat has been removed mechanically. It shall contain not more than
0.5% milk fat and not less than 8.5 % milk solids-not-fat. There is no PFA definition
for casein and caseinates.
Requirement for edible casein International standards BIS
(IDF 45:1969) Standards
Extra Standard
grade grade IS: 1167-
1965
Moisture, % by wt., max. 12 12 10
Total ash, % by wt. (on dry - - 2.5
basis), max.
Copper, max. 5 ppm 5 ppm -
Lead, max. 5 ppm 5 ppm -
Iron, max. 20 ppm 20 ppm -
Acid insoluble ash, % by wt. (on - - 0.1
dry basis), max.
Fat % by wt. (on dry basis), max. 1.7 2.25 1.5
Nitrogen, % by wt. (on dry - - 14.5
basis), min.
Protein, % by wt. (on dry basis), 95 90 -
min.
Total acidity in terms of ml 0.1N - - 6-14
NaOH/g, max.
Free acidity in terms of ml 0.01 0.20/g 0.27/g 5.6/10 g
N NaOH, max.
Lactose, % by wt., max. 0.2 0.1 -
Bacterial counts, per g, max. 30,000 100,000 50,000
Coliform count, max. Negative Negative in 10 per g
in 0.1 g 0.1 g
Mould count, per g., max - - 50
Yeast and Mould count, per g., 50 100 -
max.
Thermophilic organisms, per g., 5,000 5,000 -
max.
Optional requirements
Staphylococci (beta haemolytic Negative Negative -
coagulates positive), per g
6 Salmonella, per 100 g Negative Negative -
 Skim milk – Casein and
12.3 ACID CASEIN Caseinates

There are two types of caseins available in the market: edible casein and industrial
casein. The above two types of caseins can be either acid casein or rennet casein.
Edible casein is a long established dairy byproduct finding its use as an ingredient in
many dairy and food products. The general development in technologies and the
new uses in foods have increased the production and demand of this byproduct. Its
manufacture differs from industrial casein (i.e. non edible) in that it is produced
under sanitary conditions. Further, during its manufacture, food grade chemicals are
to be used and it is sufficiently heat treated to make its safe for human consumption.
Appropriate national and international standards for this byproduct calls for rigorous
control during its manufacture. The intensive investigation in manufacturing
technologies over the years and the introduction of efficient plant designs have
immensely improved the technology of edible casein.
i. Manufacturing Process
i) Raw material & its influence: In order to produce high quality casein, the
raw material, skimmed milk, must be of good quality. A skim milk with a
developed acidity of not greater than 0.15% lactic acid must be used. The fat
content should not exceed 0.02-0.03%. If bacteria had time to act on the
protein in the milk as a result of a change in acidity, this will affect the colour
and consistency of the casein, which will acquire a grayish colour and smoother
consistency. Excessive heating of the milk before precipitation will not only
cause assorted interactions among the lactose, casein and whey protein
constituents but also give the casein a yellow or at worst a brownish colour.
Some authorities hold that heat treatment of milk for casein manufacture causes
slight insolubility.
In order to produce casein of a good bacteriological quality, without high heat
treatment of the skim milk, the pasteurization plant may also contain a
Microfiltration (MF) plant. To satisfy the high demands on the quality of casein
intended for use in the food industry, not only must the production line be
carefully planned right from the reception of milk, but the treatment and handling
of the raw material prior to this stage must also be carefully controlled.
ii) Precipitation: Casein exists in milk as calcium caseinate-calcium phosphate
complex. When an acid is added to milk, this complex is dissociated. As the
pH of milk is lowered, the calcium is displaced from the casein molecules by
hydronium ions, H3O+ and the calcium phosphate associated with the complex
is converted into soluble Ca+2 ions and H3PO4 ions. At about 5.3 pH, the casein
begins to precipitate out of solution and at the isoelectric point of casein (about
pH 4.6), maximum precipitation occurs. At this pH all the calcium is solubilized.
Not only is the calcium from the caseinate molecule removed but also the calcium
phosphate is liberated in soluble form. This makes it possible to wash these
soluble salts from the curd and achieve a low ash content in the final product.
It might be expected that all the casein in a sample of milk would be precipitated
simply by adding sufficient acid to bring the pH value to approximately 4.6.
However, the reaction of acid with caseinate complex is not instantaneous and
the pH will tend to rise slowly with time. Therefore, ample time should be
allowed for achieving equilibrium conditions. When casein is precipitated from
skim milk by the direct addition of acid, the temperature and pH of precipitation
and mechanical handling of the curd during its formation is very important in
determining the subsequent properties of the curd. 7
By – Products Any of the acid precipitation processes (hydrochloric acid casein, sulphuric
acid casein or lactic casein process) can be used to produce edible quality
casein. The choice of the method for reducing the pH of skim milk to precipitate
casein is largely governed by economics. In terms of cost of acid, a lactic
fermentation process is attractive especially when, with large scale processing
by modern methods, the tendency for higher capital and operational costs are
minimized.
For lactic acid casein, the pasteurized skimmed milk is cooled to 22-26oC. A
mesophilic, non-gas producing starter is then added at the rate of 0.5 to 1.0%.
The skimmed milk is then incubated at this temperature for 14-16 hours during
which the pH reduces to 4.6 giving a coagulum. If the acidulation process is
too rapid, it can result in problems such as uneven quality and reduced casein
yield. The slow coagulating cultures exhibit less proteolysis and increased protein
yield. Large tanks are usually used. This means that it can take such a long time
to empty the tank that the degree of acidity may vary.
The precise rate of acid production by the starter is not important as coagulation
usually takes place several hours before processing begins and at about 4.5
pH, the culture is in stationary phase of growth. The coagulum is cooked to
50-55oC to create a curd firm enough for subsequent processing. The acid and
heat help in syneresis of whey.
The use of mineral acids, on the other hand, has the advantage of a completely
continuous operation with no holding time for coagulation. Hydrochloric acid
has been found with experience, to be a superior coagulating agent. When
sulphuric acid or hydrochloric acid is used to precipitate curd, it should be
diluted before being added to the skim milk; otherwise local action of the acid
may injure the curd, even though the agitation is rapid. Within reasonable limits,
the more dilute the acid; the better will be the quality of casein produced. In
practice, hydrochloric acid is used in dilutions ranging from 1 part in 3 to 1 part
in 9 parts water and sulphuric acid is diluted 1 part in 20 parts water.
iii) Temperature of Precipitation: Curd precipitated at temperature below 35oC
is very soft and fine, and consequently, is slow to settle and difficult to wash
without losses. Precipitated at temperatures between 35oC and 38oC, the curd
is coarse provided stirring is not too fast. Stirring is necessary to distribute the
acid uniformly, but rapid stirring at temperatures below 38oC produces a curd
so fine that it settles very slowly during drainage and washing and may be lost
to some extent in the whey and washings. Much more rapid equilibrium, more
complete precipitation and, therefore, better yields are obtained by rapid and
complete mixing before precipitation.
The curd can be made firm in either of two ways, by heating to a temperature
above 38oC, or lowering further the pH to 4.1. Curd precipitated at above
43oC has a texture resembling chewing gum, being stringy, lumpy and coarse,
containing practically no fine particles, and separating cleanly from the whey.
However, this type of curd is difficult to wash.
iv) Draining of Whey: After precipitation has been completed and the curd has
settled, the whey should be removed from contact with curd as soon as possible.
The longer the curd stands in contact with whey, the more difficult it is to wash
out acids, slats, whey protein and lactose, as the freshly broken curd tends to
anneal itself, thereby enclosing these constituents within the protein film.
v) Washing: As soon as the whey is removed from the curd, wash water should
be added equal in quantity to whey that has been drained off. The curd should
8
 be well stirred in the wash water, either by rakes or by mechanical agitators, Skim milk – Casein and
Caseinates
but care should be taken not to break the curd into fine particles. Firm and
friable curd particles are required to avoid creation of excessive fines. Rubbery
and plastic curds cannot be washed efficiently. Three separate washings of
casein curd are required with contact times of 15 to 20 min. each.
Washing is required to improve the quality of casein. Large amounts of lactose,
minerals and acids are trapped within the curd. It is necessary to allow sufficient
holding time during each washing stage to permit diffusion of these whey
components from the curd into the wash water. The diffusion rate depends on
the size and permeability of curd particles, and the purity, amount and rate of
movement of wash water. Smaller size and better permeability of curd particles
are important for efficient washing.
pH of wash water: The pH of wash water should be about 4.6 for first two
washings to avoid the formation of a gelatinous layer over the curd particles in
excessively acid water and softening and redispersion of the curd in alkaline
water. Formation of gelatinous layer over the curd particles inhibits drainage of
salts and lactose from the particles. For pH adjustment, sulphuric acid is
preferred, as casein is much less soluble in this acid, than in hydrochloric acid.
The third wash should be given with neutral water.
Temperature of wash water: The temperature of the first wash should be the
same as the precipitation temperature to give good curd shrinkage. With lactic
acid casein, higher temperature (70oC or more) is necessary at some stage to
reduce the bacteria, which multiply during incubation of milk with starter. The
temperature of the last wash water is to be adjusted to 32 to 40oC for better
expulsion of water during subsequent pressing.
vi) Pressing: Pressing is required for dewatering of washed casein curd. The
curd after pressing should have moisture content of 55-60 percent. The pressing
of curd should not be for less than 12 to 15 hrs with 3-4 kg/sq. cm pressures.
vii) Milling and Drying: The pressed curd is milled to produce particles of uniform
size and surface for drying. Otherwise, uneven drying occurs. Large particles
or lumps my dry on the outside forming a hard, impervious outer surface that
prevents the diffusion of the remaining moisture from the interior of the particle.
The ground curd is evenly spread on trays. Not more than 0.9 to 1.1 kg curd
should be placed on each standard tray of 74 x 75 cm.
Proper control of humidity of air coming in contact with the curd is essential for
efficient drying. A temperature of 52 to 57oC for the air entering a tunnel dryer
is suitable for any type of curd. During the early stages of drying it is desirable
to circulate a portion of air so that the surface of the particles will not become
fully dried while the interior is still moist. Drying once started should not be
interrupted, but should continue until the percentage of moisture is about 8%.
viii) Grinding, Sifting and Bagging: Casein is generally ground by the use of
roller mills. Prior to grinding the curd must be cooled and hardened. Cooling is
achieved by storage in an agitated holding bin and/or by pneumatic conveyance
or fluidized cooling. Attempts to mill curd, which is either too hot or too moist,
will cause clogging of the rollers.
Following milling, the casein is passed through a sifter to yield the desired particle
size, e.g. 30 mesh casein.
9
By – Products The casein is then packed in sacks or bags of 100 to 200 lb capacity. Burlap sacks
lined with closely woven cloth or with heavy papers of by three-ply paper bags may
also be used.

12.4 RENNET CASEIN

Skim milk, normally pasteurized at 72oC for 15-20 seconds is used for the production
of rennet casein. The milk is then cooled to 30oC. Sufficient rennet and calcium
chloride is added to the skim milk to give a setting time of 20-30 min. The rennet
should be previously diluted to 15-20 times its weight with water. Then the rennet is
added. A gel forms after 15-20 minutes. It is then cut and the coagulum is stirred
while being heated to about 60oC. The high temperature is necessary to deactivate
the enzyme. Cooking time is approximately 30 min washing and remaining steps are
the same as that of acid casein. Here the wash water is neutral.

12.5 YIELDS
i) Actual yield : Actual yields of casein are usually considered as kg of casein
bagged per 100 kg of skim milk. This is used as a measure of the processing
efficiency. The accuracy of yields depends on:
• the frequency of measuring – weekly, monthly, etc.
• comparison with yields at the same time in previous seasons
• relationship to the theoretical yield
The percentage of casein in the skim milk varies with the fat content of the
whole milk, type and time of the season depending on feed available, and
between different areas.
ii) Quantity of skim milk: This can be measured by the formula given below:
W = [(C-M) / (C-S)] x 100
Where, W = weight of skim milk per 100 kg of whole milk
C = fat content of cream
M = fat content of milk
S = fat content of skim milk
iii) Theoretical yield: Assume a casein composition of: 85% casein; 10-12%
moisture; 2-4% other milk solids and a skim milk casein content of – 2.8%
Then theoretical yield per 100 kg skim milk
= 100/85 x 2.8 = 3.3%
The table below indicates the theoretical yield for different fat contents in
whole milk.Table-12.2.
% Fat in milk % Casein in milk% Casein in skim milk % Yield from skim milk
% Fat in % Casein in % Casein in skim % Yield from skim
milk milk milk milk
3.2 2.2 2.27 2.67
3.6 2.35 2.44 2.87
4.0 2.52 2.63 3.09
4.4 2.64 2.76 3.24
4.8 2.73 2.87 3.38
5.2 2.87 3.03 3.56
10
iv) Processing factors affecting yield: A high production of fines will result in a Skim milk – Casein and
Caseinates
reduced yield. Fines production is increased by:
– over acidification or uneven precipitation of curd
– inefficiency in acid-skim milk mixing
– low cooking temperatures
– excessive pumping or agitation of curd
– over acid or alkaline wash waters.
These factors may account for fines losses of up to 10% of expected casein yield.
Some degree of fines recovery is possible by the use of hydro clones or settling
techniques. However, there is no substitute for correct processing procedures.
Over drying of casein can cause substantial reduction in the expected yield. Casein
should not be dried to levels excessively below those specified by the market.
Check Your Progress I
1. What will be the influence of skim milk on the quality of casein?
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2. How edible casein differs from industrial casein?
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3. Give the basis of classification of casein.
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4. What will be the influence of temperature of precipitation on quality of curd
obtained?
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12.6 CASEINATE
Caseinate may be defined as the chemical compound of casein and light metals, for
instance monovalent sodium (Na+) or divalent calcium (Ca++). Caseinates can be
produced from freshly precipitated (wet) acid casein curd or from dry acid casein
by reaction with any of the several diluted solutions of alkali i.e. sodium hydroxide,
potassium hydroxide, calcium hydroxide or ammonia. The casein, which is intended
11
for manufacture into sodium caseinate, must have a low calcium content (<0.15%
By – Products on dry matter basis) in order to produce a caseinate solution with a low viscosity,
and a low lactose content (< 0.2% on dry matter basis) to produce sodium caseinate
with the best colour, flavour and nutritional value.
i. Sodium Caseinate
For the manufacture of caseinates, fresh acid casein curd is preferred over dried
casein as a raw material, since the former yields caseinates with blander flavour than
does the latter. Caseinates prepared from dry casein will also incur the additional
manufacturing costs associated with drying, dry processing, bagging and storage of
casein prior to its conversion to sodium caseinate. However, in countries, which
import casein, buyers may still prefer to purchase casein and produce their own
sodium caseinate rather than purchase sodium caseinate.
Irrespective of the starting material used, the main difficulties experienced in the
conversion of acid casein to the manufacture of sodium caseinate consists of formation
of a casein suspension, solubilization of casein using sodium hydroxide, and drying
of the sodium caseinate produced.
Problems in drying sodium caseinate are:
a. a very high viscosity of sodium caseinate solutions of moderate concentration,
which limits the solids content for spray drying to 20%
b. the formation of a relatively impervious, jelly like viscous coating on the surface
of casein particles which impedes their dissolution on addition of alkali.
To overcome the former difficulty, it is essential that the pH and temperature are
controlled during conversion as these influence viscosity, while the latter can be
overcome by reducing the particle size by passing a curd-water mixture through a
colloid mill prior to addition of alkali.
The most commonly used alkali in the production of sodium caseinate is sodium
hydroxide, with strength of 2.5 M or 10%. The quantity of NaOH required is generally
1.7-2.2% by weight of casein solids in order to reach a final pH, generally about
6.7.
Other alkalis, such as sodium bicarbonate, or sodium phosphates, may be used, but
the amounts required and their cost both are greater than those of NaOH. They are
therefore, generally used only for specific purposes, such as that in the manufacture
of citrated caseinates.
The dissolving time of the alkali is directly related to the particle size of curd and the
particle size reduction prior to addition of sodium hydroxide rather than afterwards
produces a more rapid reaction. Consequently, the curd is passed through a colloid
mill prior to addition of the alkali.
After the final casein wash, the curd may be dewatered to about 45% solids and
then remixed with water (to 25 to 30% total solids) before entering the colloid mill.
The temperature of the emerging slurry should be below 45oC, since it has been
observed that milled curd can reagglomerate at higher temperatures. Generally the
slurry is collected in a jacketed tank provided with an effective agitator and also
integrated in a circular system with a high capacity pump.
The addition of diluted alkali must be carefully controlled with the aim of reaching a
final pH of about 6.7. Preferably, the alkali is dosed into the recirculation line just
upstream of the pump. Once the alkali has been added to the slurry, it is important to
12 raise the temperature as quickly as possible to 60–75oC to reduce the viscosity.
However, care should be taken to avoid holding the hot (> 70oC) concentrated Skim milk – Casein and
Caseinates
sodium caseinate solution for extended periods prior to drying, since it is possible
for brown colour to develop in the solution due to reaction between the protein and
residual lactose. During the dissolving operation, the incorporation of air should be
kept to a minimum since caseinate solutions form very stable foams.
The homogenous sodium caseinate solution is usually spray dried in a stream of hot
air. For efficient atomization, the sodium caseinate solution must have a constant
viscosity when it is fed to the spray dryer. It is a common practice to minimize the
viscosity by preheating the solution to 90-95oC just prior to spray drying.
The moisture content of spray dried sodium caseinate should be less than 5% for
satisfactory storage. The low solids content of the feed solution produces spray
dried powder with a low bulk density. It may vary from 0.25 g/ml to 0.4 g/ml.
Generally pressure nozzle dryers, operating at 100–250 bars produce a caseinate
with higher bulk density than from the disc atomizing dryers.
ii. Calcium Caseinate
The preparation of calcium caseinate follows the same general lines as for sodium
caseinate with a couple of important exceptions. Calcium caseinate solutions are
liable to be destabilized by heating, especially at pH values below 6.
The sensitivity decreases with an increase in pH or a decrease in the concentration
and is manifested as a reversible heat gelation. During the dissolving process, it has
been found that the reaction between acid casein curd and calcium hydroxide (the
alkali which is most commonly used in the production of calcium caseinate) proceeds
at a much slower rate than between curd and sodium hydroxide. To increase the
rate of reaction between casein and calcium hydroxide, the casein may first be
dissolved completely in ammonia. Calcium hydroxide in sucrose solution is then
added and the calcium caseinate solution is dried. Most of the ammonia evaporates
during the process. The calcium caseinate obtained by this process has moisture
content of 4.5%, protein 84%, sucrose 5.8% and calcium 1.0% with nutritional
properties similar to those of the original casein.
iii. Other Caseinates
Magnesium caseinate is prepared from casein and a magnesium base or basic salt
such as magnesium oxide, magnesium hydroxide, carbonate or phosphate.
Compounds of casein with aluminum may be prepared for medicinal use or for use
as an emulsifier in meat products. Heavy metal derivatives of casein, which have
been used principally for therapeutic purposes, include those containing silver,
mercury, iron and bismuth. Iron and copper caseinates have also been prepared by
ion exchange for use in infant and dietetic products.

12.7 USES OF CASEINS AND CASEINATES

i. Rennet Casein
Rennet casein is a product different from acid casein. In industry it is used principally
in the production of artificial substances in the plastic category. Casein polymerized
with formalin is known as galalith, and synthetic fibers of casein are known as lanital.
In spite of the large supply of various plastics, which compete directly with galalith,
there is still some demand for galalith production. Small quantities of edible rennet
casein are also used as a raw material for processed cheese. Rennet casein is insoluble
in water.
13
By – Products ii. Acid Casein
Acid casein dominates the world markets it is used in the chemical industry as an
additive in paper manufacture for the glazing of paper of fine quality. For paper
industry applications, it is particularly important that the casein is free from fat and
contains no particles of foreign or burnt matter that might make spots on the paper.
To obtain extremely low fat content in skim milk it should be passed through a micro
filtration plant (MF) in combination with pasteurization. Each industry has its own
strict quality specifications. The paint and cosmetic industries are also large users of
casein. It also has industrial uses in the manufacture of glue.
Edible casein is used as water absorbing nutrient protein for enriching some baby
foods and diets for diabetics with milk protein, in certain pasta products and types
of bread, as addition to some sausage as well as in the production of condiments for
soups.
iii. Caseinates
Sodium caseinate is the most commonly used water-soluble form of casein and
used in the food industry. The two main reasons for using sodium caseinate as an
ingredient in foods are its functional properties and nutritive value. Sodium caseinate
is valued for its ability to emulsify fat in the production of modified dairy products
such as coffee whiteners, whipped cream and ice cream. It also possesses very
good water binding and whipping properties. Industries of meat processing, baking
and modified dairy products are the largest consumer of sodium caseinate. The
various food products in which sodium caseinate is used consist of various kinds of
sausages, meat based and milk based instant breakfasts, non dairy creams, desserts,
sauces, soups, bread, crackers, dietetic products and various protein enriched
products.
For certain applications, calcium caseinate may be chosen instead of sodium caseinate.
One reason being the wish to reduce the sodium content of the product to a minimum.
iv. Composition of Caseinates
The quality standards for sodium caseinate vary from country to country. The typical
composition of sodium and calcium caseinate, produced from well-washed acid
casein, is shown in Table 12.3.
Table-12.3: Typical composition of caseinates:
Sodium caseinate Calcium caseinate
Moisture (%) 3.8 3.8
Protein (N x 6.38) (%) 91.4 91.2
Ash (%) 3.6 3.8
Lactose (%) 0.1 0.1
Fat (%) 1.1 1.1
Sodium (%) 1.2-1.4 <0.1
Calcium (%) 0.1 1.3-1.6
Iron (mg/kg) 3-20 10-40
Copper (mg/kg) 1-2 1-2
Lead (mg/kg) <1 <1
PH 6.5-6.9 6.8-7.0

Check your progress I

1. What difficulties are encountered during manufacture of caseinates?
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 ................................................................................................................... Skim milk – Casein and
Caseinates
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2. How calcium caseinate differs from sodium caseinate?
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3. What are the uses of sodium caseinate?
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4. Define ‘caseinate’?
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5. Give the average composition of sodium caseinate.
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12.8 LET US SUM UP

Casein is made by acid precipitation from unheated or short time heat-treated
separated milk, which has a fat content of not more than 0.05%. Higher temperatures
would reduce the solubility since whey proteins become precipitated. Whey and
lactose are removed from the curd thus obtaining by heating and by washing with
warm water. The resulting product is crude casein. The crude casein is dried to
moisture content of about 8% and the final product contains 80-90% protein, no
more than 2% fat and 2-4% ash.
There are two types of caseins available in the market: edible casein and industrial
casein. The above two types of caseins can be either acid casein or rennet casein.
Edible casein is a long established dairy byproduct finding its use as an ingredient in
many dairy and food products. The general development in technologies and the
new uses in foods have increased the production and demand of this byproduct. Its
manufacture differs from industrial casein (i.e. non edible) in that it is produced
under sanitary conditions. Further, during its manufacture, food grade chemicals are
to be used and it is sufficiently heat treated to make its safe for human consumption.
Appropriate national and international standards for this byproduct calls for rigorous
control during its manufacture. The intensive investigation in manufacturing
technologies over the years and the introduction of efficient plant designs has
immensely improved the technology of edible casein.
Caseinates are made from edible grade dry granular casein or from freshly precipitated
wet curd. Sodium caseinate is the most commonly used water-soluble form of casein 15
By – Products and is used in the food industry. The two main reasons for using sodium caseinate as
an ingredient in foods are its functional properties and nutritive value.
The manufacture of sodium caseinate consists of formation of a casein suspension,
solubilization of casein using sodium hydroxide, and drying of the sodium caseinate
produced.

12.9 KEY WORDS

Atomization : In the spray dryer the product to be dried is
atomized to reduce the particles so small in
size that due to their large surface area they
surrender their moisture practically
instantaneously. The particles are preferably
uniform in size, generally ranging from 50-150
microns in diameter.
Byproduct : A product obtained during the course of
manufacture or as a consequence of the
manufacture of the main product.
Bulk density of powder : This is regarded as weight per unit volume
and generally expressed as g/ml.
Coprecipitates : A coprecipitate of milk proteins is the product,
which separates as the solid phase after the
heat treatment and precipitation of dairy fluid,
which contains both casein and heat,
coagulated whey proteins.
Industrial casein : Casein which is not fit for edible purposes.
Casein which is not manufactured under
sanitary conditions.
Isoelectric point of casein : Isoelectric points of casein components
depend on the ions of other kinds present in
the solutions. A practical value for precipitation
of casein from milk is pH 4.7.
Microfiltration : A membrane separation technique basically
used for reduction of bacteria in skim milk,
whey and brine. Also used for defatting whey.
It has a membrane pore size of 0.1 to 10
micron and the operating pressures are in the
range of 1 to 25 psi g.
Milling : This refers to the mechanical operation of
cutting the casein curd into small pieces with
the help of a cheese mill.
Protein hydrolysates : Casein hydrolysates can be manufactured by
acid, alkaline or enzymatic hydrolysis of
casein. The technological advantages are
improved solubility, gelation, emulsification,
heat stability, etc.
Spray dryer : Spray drying consists of atomizing the milk to
form spray of very minute droplets, which are
16 directed, into a large drying chamber where
 they are mixed with a current of hot air. Due Skim milk – Casein and
Caseinates
to the large surface area, the milk particles
are instantly dried to a fine powder, which is
removed continuously.
Syneresis of whey : This refers to the expulsion of whey and
contraction of the curd. The factors controlling
loss of whey and contraction of curd are:
cutting, temperature, acidity, agitation and
time.

12.10 SOME USEFUL BOOKS

Ahmad Tufail.1999. (4th ed). Dairy Plant Engineering and Management. Kitab Mahal,
Allahabad.
Fox, P.F. (Ed.). 1989. Developments in Dairy Chemistry – 4. Elsevier Science
Publishing Co., Inc., New York.
Kessler, H.G. (1st ed). 1981. Food Engineering and Dairy Technology. Publishing
House Verlog A. Kessler, Germany.
Robinson, R.K. (2nd ed). 1994. Modern Dairy Technology Vol. I. Chapman Hall.
UK.
Webb, H.H. and Johnson, A.H. 1970. Fundamentals of Dairy Chemistry. The AVI
Publ. Co. Inc., Westport, Connecticut, USA.
Webb, B.H. and Whittier, E.O. 1970. By-products from milks. The AVI Publ. Co.
Inc., Westport, Connecticut, USA.

12.11 ANSWERS TO CHECK YOUR PROGRESS

Your answer should include the following points:
Check Your Progress 1
1. Skim milk - developed acidity - not greater than 0.15% lactic acid. Fat content
– not more than 0.02-0.03%. If developed acidity – casein of grayish colour,
smoother consistency. Excessive heating of the milk – yellow, brownish colour
casein - slight insolubility.
2. i. it is produced under sanitary conditions
ii. only food grade chemicals are to be used
iii. sufficiently heat treated to make its safe for human consumption.
3. i. On the basis of: - coagulating agent used: acid casein, rennet casein
ii. Particular acid used: hydrochloric acid casein, sulfuric acid casein, lactic
acid casein
iii. Method of manufacture: edible casein, industrial casein
4. i. Curd precipitated at below 35oC: very soft and fine-slow to settle and
difficult to wash without losses
ii. Temperature between 35oC and 38oC: coarse curd, easy to wash
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By – Products iii. Temperatures greater than 38oC: rubbery curd resembling chewing gum,
being stringy, lumpy.
Check Your Progress - 2
1. i. a very high viscosity of sodium caseinate solutions of moderate
concentration, which limits the solids content for spray drying to 20%
ii. the formation of a relatively impervious, jelly like viscous coating on the
surface of casein particles which impedes their dissolution on addition of
alkali.
2.
Sodium caseinate Calcium caseinate
Sodium (%) 1.2-1.4 <0.1
Calcium (%) 0.1 1.3-1.6
Dissolved in Sodium hydroxide Calcium hydroxide

3. Functional properties and nutritive value–water binding and whipping properties;

ability to emulsify fat - coffee whiteners, whipped ream and ice cream -Used in
various kinds of sausages, meat based and milk based instant breakfasts, non
dairy creams, desserts, sauces, soups, bread, crackers, dietetic products and
various protein enriched products.
4. The chemical compound of casein and light metals, for instance monovalent
sodium (Na+) or divalent calcium (Ca++) can be produced from freshly
precipitated (wet) acid casein curd or from dry acid casein by reaction with
any of the several diluted solutions of alkali i.e. sodium hydroxide, potassium
hydroxide, calcium hydroxide or ammonia.
5.
Moisture (%) 3.8
Protein (N x 6.38) (%) 91.4
Ash (%) 3.6
Lactose (%) 0.1
Fat (%) 1.1
Sodium (%) 1.2-1.4
PH 6.5-6.9

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