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MANUFACTURING OF CASEIN, CO

PRECIPITATE AND CASEINATES

CASEIN
Casein is the major protein in cow’s milk and constitutes about 80% of the
total protein content of which the rest, some 20%, are the whey or serum proteins.
Casein characteristically occurs in form of casein micelles and these are spheroidal
particles. There are four main groups of casein molecules, designated. αS, β, γ, κ.
Very roughly there is 45% of αS casein, 37% of β, 15% of K and 3% of γ casein.
Genetic variants are known for all the casein and all have molecular with in the
range 20,000 – 30,000. Casein contains 0.7-0.9% phosphorus, covalently bound to
the protein by a serine ester linkage. Casein is consequently known as a phospho-
protein. All the amino acids that are essential to man are present in casein in high
proportions, with the possible exception of cysteine. Thus, casein may be considered
as a highly nutritious protein. Commercial casein is made from skimmilk by one of
two general methods – precipitation by acid or coagulation by rennet. As much of the
fat, whey proteins, lactose and minerals as possible must be removed by multistage
washing in water, as they reduce the quality of the casein as well as its keeping
quality. Dried, properly produced casein has a relatively good keeping quality and is
used mainly in the food and chemical industries.
According to PFA edible casein means like the product obtained by separating,
washing and drying the coagulum of skimmed milk. Edible acid casein means like
the product obtained by separating, washing and drying the acid precipitated
coagulum of skimmed milk. Edible non-animal rennet casein means like the product
obtained after washing and drying the coagulum remaining after separating the
whey from skimmed milk which has been coagulated by non-animal or by other
coagulating enzymes.
The product shall be white to pale cream or have greenish tinge, free from
lumps and any unpleasant foreign flavor.
Chemical parameter standards
Requirements Non-animal Acid casein Caseinates
rennet casein
Moisture Not more than 12% Not more than 12% Not more than 8%
m/m m/m m/m
Milk fat Not more than 2% Not more than 2% Not more than 2%
m/m m/m m/m
Milk Not less than 84% Not less than 90% Not less than 88%
protein(Nx6.38) on m/m m/m m/m
dry weight basis
Casein in protein Not less than 95% Not less than 95% Not less than 95%
m/m m/m m/m
Ash including P2O5 Not less than 7.5% Not less than 2.5% -
m/m m/m
Lactose Not less than 1.0% Not more than Not more than
m/m 1.0% m/m 1.0% m/m
Free acid ml 0.1 N - Not more than -
NaOH/gm 0.27%
pH value in 10 % - - Not more than 8%
Food additives- Stablizers
Calcium citrate, GMP
sodium citrate,
potassium citrate
Potassium salt of GMP
orthophosphoric
acid
Potassium salt of GMP
polyphosphoric
acid
Sodium salt of GMP
orthophosphoric
acid
Sodium salt of GMP
polyphosphoric
acid
Acidity regulators
Calcium carbonate, GMP
magnicium
cabonate
Sodium hydroxide, 2000mg/kg max.
Calcium hydroxide
Sodium phosphates GMP
Microbial standards for edible casein products
Total plate count Not more than 50,000/g
Coliform count, per g, Absent in 0.1 gm
Max
E.coli Absent in 1 gm
Salmonella Absent in 25 gm
Shigella Absent in 25 gm
Staphylococcus aureus Absent in 1 gm
Yeast and mould Absent in 1 gm
count
Anaerobic spore count Absent in 1 g
Listeria Absent in 1 g Receiving skim milk
monocytogenes ⇓
An important utilization of skim milk is in the Precipitating
production of industrial casein which is a non food item. ⇓
Because of its widespread demand, industrial casein is Draining and washing
prepared throughout the world. The casein precipitated ⇓
by various acids is called acid casein; free casein or Pressing
simply casein, while that precipitated by rennet is called ⇓
rennet casein. The two types of casein have different Milling and spreading
uses. Its primary industrial uses are as a binder in ⇓
paper, paint and adhesive products. Casein is being
slowly replaced in these industries by other proteins, Drying
modified starch and polyvinyl alcohol. At the same time ⇓
casein is being used in newer food products such as
filled milk, imitation milk coffee whiteness, instant Grinding

Packaging

Storage
breakfast, cereals, sausages, topping, ice-cream mixes and other foods where it is
used to supplement the protein already present.
Type of casein:
1. On the basis of coagulating agent used-
a. Acid casein
b. Rennet casein
2. On the basis of particular acid used-
a. Hydrochloric acid casein
b. Sulfuric acid casein
c. Lactic acid casein
i. Direct precipitation
ii. Self soured
3. On the basis of texture of the cured-
a. Grain curd casein
b. Cooked curd casein
c. Pressed curd casein
4. On the basis of use
a. Edible casein
b. Industrial/nonedible casein
General method of manufacture of acid casein:-
Receiving of milk – Fresh, clean, sweet skim milk, which is as fat free as possible
should be used.
Precipitating – Casein exists in milk as a calcium caseinate – calcium phosphate
complex, when 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
and H2PO4- ions at about pH 5.3 casein begins to precipitate out of solution. At the
isoelectric point of casein about pH 4.7 maximum precipitate occurs. The casein
coagulates as a watery, gel like curd. The gel is broken to allow water to be expelled
from it. The expulsion of water by contraction of the curd or syneresis is aided by
further development of acidity and by heating or a combination of both factors. The
precipitation of casein involves three considerations: acidity and pH, Temperature and
the speed at which it is stirred.
Effect of temperature – Temperature should be carefully controlled during
precipitation, since the casein curd is sensitive to heat. The kind of curd formed is
quite sensitive to heat, and if the acid is being developed through fermentation, the
rate of acid development is also sensitive to temperature. A jacketed vat is
recommended for this purpose, curd precipitated at temperature below 350 C is soft
and fine. Free between 350C and 380 C, the curd is coarse, provided stirring is not too
fast. The curd can be made firm in either of two ways by heating between 380 C and
480 C, the temperature depending on the acidity or pH lowered to 4.1 without raising
the temperature. Latter method also produces a curd that is easy to wash and drain.
Curd precipitated at about 430 C has a texture resembling chewing gum, being stringy,
lumpy and coarse containing no fine particles and separating cleanly from the whey.
When such and cools to below 430 C, it stiffens and can be broken easily by agitation
into coarse grain. Therefore to control the process of acid precipitation in making acid
casein the two variables of most concern are-
i. The pH of precipitation
ii. The temperature of precipitation
Draining and washing – The longer the casein curd stands in the whey, the more
difficult it becomes to remove the impurities i.e. whey protein, lactose, salts and acid.
Hence, the whey is removed promptly. The first step in this regard is to allow the curd
to little and then push it back from the outlet end of the vat, Next, the outlet strains is
fixed in position and another cloth lined strainer hung at the discharge end of the
outlet to recover small curd particles. Then the whey is drained off promptly.
As soon as the whey ceases to run freely, cold wash water is added in
quantities approximately equal to the amount of whey removed. The wash water is
made very slightly acidic (pH 4.1) especially for the first washing the curd is well
stirred in the wash water, but care is taken not to break it into fine particles, it is then
allowed to settle and wash water drained as above. It should be washed at least twice.
Pressing – The amount of water in washed curd and its ease of removal depend upon
the type of curd made. Normally it is not possible to reduce the moisture level in the
pressed and to less than 55%.
In batch pressing the washed and drained curd is shoveled into press cloths
supported in a form when all the curd is in the press cloths and on the press, the press
is tightened only moderately at first, but with increasing pressure as more of the free
water is pressed from the casein curd. The pressing operation is usually an overnight,
being started in the late afternoon and completed the following morning.
Curd can also be press continuously in mechanical driver roller presses where
one press is sufficient to obtain the expulsion of water necessary for subsequent
economical. Moisture content depends largely on its initial condition. Precipitation of
the curd at a pH of 4.1 – 4.3 and the curd well washed in waters also of the proper pH
and at temperature of 40.50 C will give a firm, friable curd which will drain well and
press well.
Milling and spreading – After being pressed, the curd is milled to produce particles
of a uniform size and surface for drying. If it is not milled it dues unevenly, pressed
curd should be promptly milted and dried, in order to prevent spoilage by mould and
bacterial action.
Milting should be of the shredding variety the milted curd should be evenly
spread over standard perforated trays with a fixed amount of curd to ensure adequate
drying. The lowest tray should be of a finer mesh than the others and may be covered
with a cloth to catch fine particles falling from above.
Drying – It is essential to control the temperature and humidity of the intake air
correctly if the curd is to be efficiently drained. Once started drying should not be
interrupted till the moisture content has been reduced to less than 8%. The intake air
temperature may range from 71 to 770 C (1600 – 1700 F) while the outlet air
temperature should be between 52 and 570 C (125 – 1350 F) in order to avoid the risk
of discoloring the casein and impairing its solubility.
Tempering – It means the holding of the casein for a period (24 hrs) to allow efficient
cooling, hardening of the casein and evenness of moisture through out the batch,
casein shows variation in moisture content during a day’s run as it comes from drier.
Agitation is necessary for efficient tempering.
Grinding – The cool, tempered casein is ground to the desired particle size. The
casein must be cool before grinding because warm casein is plastic and causes “burn
on” of the rollers. The grinding is done by roller mills. The fineness of grinding
depends on the requirement of the user.
Sieving – After grinding, the casein is sifted into its various mesh sizes. Common
mesh sizes are 30-40 mesh casein 60 and 90 mesh casein. An object of the grinding
and sieving operations is to produce the highest proportion of the product in the size
range desired by the buyer.
Package – The dried casein, whether ground or ungrounded, is normally packaged
either in gunny bags lined inside with closely mover cloth or in heavy 3 ply paper bags
with polyethylene liners. Product is bagged according to mesh size.
Storage – The filled package of casein should be closed air-tight and transferred to a
clean, dry storage room maintained at a uniform temperature wide variation in
storage temperature will cause the casein to sweat and mould. It stored in a damp
atmosphere, it will absorb water and deteriorate. For long storage, it is best to stored
in a basement, away from sun.
Types of casein:
Casein may be typed according to the process used to precipitate it as
follows-
i) Hydrochloric acid casein
ii) Sulfuric acid casein
iii) Lactic acid casein
iv) Co-precipitated casein
v) Rennet casein
vi) Low viscosity casein
1. Hydrochloric acid casein :
It is also known as grain soluble casein, low in ash and readily soluble is
made by the grain curd process provided the pH and temperature are closely
controlled. A jacketed vat is essential for accurately controlling the
temperature. The best product is obtained by using Hcl.
2. Sulfuric acid casein :
It can be manufactured by employing a process identical with that for
Hcl casein. Also an high quality product can be produced by the use of H2SO4.
A reason is that it costs much less than Hcl.
3. Lactic acid casein :
The production of casein by the souring of skim milk by means of
cultures of lactic streptococci is preferred for economic reason.
The skim milk is held in vertical storage tanks for approximately 16-18
hours to coagulate. The skim milk is inoculated with 0.5 % starter at 27 0 C. As
the milk reaches the pH of precipitation and the Ca +2 salts are solubilizing and
dissociate from the casein. After the curd has formed the acid and heat cause
shrinkage of the curd with moisture expulsion.
All the above acid casein are formed by two methods-
i) Grain curd process casein –
a) Direct precipitation
b) Self soured
ii) Continuous process casein – There are two process-
a) Sheffield process
b) Universal process
The yield of acid casein is roughly equal to the percentage of casein in
the skim milk and may vary from 2.8 to 3.2% depending on whether it is cow
or buffalo skim milk.
Acid casein is normally yellowish white in color for cow and chalky white
for buffalo milk, has a faint pleasant odour, a slightly acid taste, a total acidity
is--------, not more than 10% moisture, not more than 1% fat
(on moisture free basis), not more than 4.0% ash ( on moisture free basis), not
less than 14.25% nitrogen (on a moisture, fat and ash free basis).
4. Rennet casein:
This is normally light yellowish in color for cow and whitish for buffalo
milk has a faint agreeable odour is tasteless, has a pH of about 7.0, moisture
not more than 10% and approximately 4.5% ash.
High quality fresh sweet skim milk is essential. This is heated in a
jacketed vat up to 36 – 380 C. Sufficient rennet and Cacl2 are added to the
skim milk to give setting time of 20 – 30 minutes. The rennet should
previously have been diluted with water about 15 – 20 times, Cacl2 is also
used 1% solution. The coagulum is agitated for 2–5 minutes. The curd is
cooked at 540 – 660 C for 30 minutes. After cooking same process is followed
as in acid casein.
5. Low viscosity casein:
The major industrial use for acid casein is in the paper industry where it
is used as an adhesive to bind pigments to paper. Action of proteolytic
enzymes produced casein which had a much lower viscosity and procedure is
based on continuous process.
About 40% of skim milk is subjected to direct enzyme treatment. The
pH of this reaction is adjusted to 3.5 – 4.0 and its temperature is adjusted to
410 – 420C. Pepsin equivalent to 0.05% of casein is added. Three tanks in
series provide a holding stage of 45-60 minutes. After holding stage the
pepsin treated milk is blended with the remaining milk by being pumped into
it in the form of a spray as it is conveyed by pipeline to a riffle chute. The pipe
is of such size that the blended milk is held up about 15 seconds. The initial
pH of the blend should be about 5.0. After the holding treatment acid is
injected into the pipeline to lower the pH to 4.6. Steam is injected to raise the
temperature to 490C. Sufficient holding is made with the riffle chute for curd
formation to occur. To obtain a product low in Ca+2 and ash, the wash water
is adjusted to pH 4.2 – 4.3. Low viscosity reduces costs of drying caseinates
and in food products.
Defects in casein, their causes and prevention:
Name of defect Causes Prevention
Browning Overheating of casein when Maintaining the optimum
drying. casein drying temperature.
Presence of excess of fat in Using low fat skim milk for
casein during drying casein manufacture.
Presence of sulphuric Proper washing of curd
acid/sulfate in casein during
drying
Poor solubility Excessively high temperature Optimum temperature of
of cooking curd cooking curd
Overheating of casein during Maintaining optimum casein
drying drying temperature
Moulding of curd before Proper drying of the wet
drying curd
Low adhesive High ash content in casein Adequate washing of curd
strength
Moulding of curd before Prompt drying of wet curd.
drying
Uses of casein:
The two types of casein, i.e. acid and rennet, have separate uses and one type
cannot be used as a substitute for other.
A. The various uses of industrial casein are:
i) Rennet casein – Plastic (such as buckles, brush back, buttons, costume,
jewelry, umbrella handless etc.
ii) Acid casein –
1. Adhesive 2. Paper coating
3. Paint 4. Fibre
5. Bristles 6. Films
7. Leather-finish 8. Textile finish
9. Spreader for insecticide 10. Medicines (silver and mercury caseinate)
B. The food uses of casein are edible casein :
It may be defined as casein which has been isolated from skim milk by taking
special precautions to ensure its suitability for use in patented food and
pharmaceutical preparations. These precautions are concerned with-
 Strict control of the quantity of raw material (skim milk)
 Use of standard equipment and technique for production.
 Maintenance of strict hygienic condition of production.
 Packaging and storage under approved condition
In its original form or as sodium caseinate, edible casein is used in various
products such as-ice cream, coffee whiteness, imitation milk, whipping powder
instant breakfast, water, binders in sausage and protein hydrolysates.

Skim milk/
buttermilk

HCl and/ or Heating 900 C for
Cacl2 → 30 min

Cooling

Serum ← Separate
Co-precipitate: ⇓
Co-precipitate contains practically all the Precipitate
protein fractions of milk. Following the ⇓
addition of small quantities of calcium Water Washing
chloride or acid to the skim milk, the (+CaCl2)→ ⇓
Pressing

Drying

Coprecipitate
Manufacture of co-precipitate
mixture is heated to 85 – 950C and held at that temperature for a period of 1 – 20
minutes to allow interaction between the caseins and the whey proteins.
Precipitation of the proteins from the heated milk is then effected by controlled
addition of either calcium chloride solution (to produce high-calcium co-precipitate)
or diluted acid (to produce medium calcium or low-calcium co-precipitate, depending
upon the amount of acid added and the pH of the resulting whey). The curd is
subsequently washed and either dried to produce granular, insoluble co-precipitates
or dissolved in alkali as described for the methods for the manufacture of caseinates
to produce soluble or “dispersible” co-precipitates.
The curd formed by coprecipitate of casein and whey protein has physical
characteristic different from those of casein curd.
If casein is precipitated at 430 – 490C at a pH above 4.6, the curd will be fibrous and
sticky. A coprecipitated curd at even higher temp. & wide range of pH is seldom
fibrous or sticky. The difference in behavior of the curd of a coprecipitate from a
regular casein curd is due to the interaction of the casein with B-lactglobulin on
heating. A recovery of about 96% of the milk proteins was achieved under optimum
processing condition. The level of calcium in coprecipitation was determined by the
pH of precipitation. The amount of calcium chloride added, & the washing condition.
A low calcium product is considered to contain about 0.5-0.8% calcium and is
obtained by adding cacl2 equivalent to 0.03% of the wt. of skim milk before
preheating at 68°C followed by heating to 90°C and holding at this temp. for 15-20
min. Precipitation follows by acid addition to pH 4.6.
A medium calcium product (about 1.5% calcium) can be made by adding cacl 2
equivalent to 0.06% of the act of the skim milk before preheating, followed by 2
stages heating to 90°C. After a holding period of 10-12 min, proteins are precipitated
at a pH of about 5.3.
A very high calcium product (about 2.5-3.0% calcium) is obtained by holding
the milk heated to 90°C for 1-2 min; then adding cacl2 equivalent to about 0.2% the
wt. of skim milk. This is followed by a 20-25 sec holding time interval in a holding
tube. The addition of this amount of cacl2 suffices to precipitate the proteins without
the use of any acid to lower the pH.
To obtain maximum yields it was found necessary to avoid undue agitation
during separation of curd from the whey, Wash water temp. of 29°-35°C were found
satisfactory. The composition was affected particularly by amount of washing the
curd. The high fat content of the coprecipitate is attributed to retention in the curd of
fat protein complexes formed during manufacturing process which is undesirable.
Coprecipitate solubility properties are similar to that of casein. i.e. adjustment
of pH sufficed to put it into solution. For medium & high calcium coprecipitate, a
calcium-sequestering agent is necessary for minimum solubility at pH 1.0 Medium
calcium coprecipitates are solubilized by inclusion of 2.4% sodium tri polyphosphate
at pH 7.0. For a high calcium coprecipitate inclusion of 6% sodium tri polyphosphate
resulted in 85% solubility at pH 7.0. The solubility increased to 92-95% at pH 8.0.
Some insoluble aggregated whey
Average composition for
proteins are found in solutions of calcium
coprecipitate
coprecipitate at pH 7.0. To produce
Protein ( N X 6.38) 83 %
sediment free solutions of the calcium
Lactose 1.0%
coprecipitates, Homogenizing was found
Fat 1.5%
to be necessary. How the calcium
Moisture 4.0%
coprecipitate is dried also affects their
Ash (including Ca) 10.5
solubility. Coprecipitates dried in casein
%
Calcium 2.5%
drier are more difficult to put into solution than spray dried form. Coprecipitates
dried in casein drier are referred as a granular form.
Caseinate:
Caseinate may be defined as a 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 several diluted solutions of alkali as outlined in flow chart.
According to PFA edible caseinate means the dry product obtained by reaction of
edible casein or fresh casein curd with food grade neutilizing agents and which has
been subjected to an appropriate heat treatment. It shall be qualified by name of the
cation and drying process used (spray or roller dried).
Sodium caseinate
Caseinate for food use may be made either Wet acid casein curd
from wet, freshly precipitate casein curd or from or dry acid casein
edible grades of dry casein. The manufacturing ↓
procedure consists of preparing or aquous colloidal Water
suspension from acid casein at pH 6.7 by addition of

alkali, usually drying. The basic problem of the Grinding
process is the relatively high viscosities sodium

caseinate solution at moderate concentrations.
Dilute alkali
Factors involved in the control of viscosity are

concentration pH and temperature. At their optimum,
Dissolving
the concentration of sodium caseinate that can be
handled is 20-25% at a temperature of 900 – 930C and ↓
pH of 6.2 – 6.7. As a consequence the output of spray Casein solution
drier drying caseinate is about that of drying milk ↓
concentrate of 40 – 45% total solids. Drying ( spray or
Starting materials: roller process)
The best flavour in dried sodium caseinate is ↓
obtained in a product manufactured from fresh wet Caseinate powder
Basic steps involved in the manufacture of
curd, calcium in a cause of variation in viscosity and a spray or roller dried caseinates from acid
casein curd or dry acid casein. Alkali may
curd of uniformity low calcium content is desired. The be sodium hydroxide, potassium hydroxide,
lactose content should be low since, this sugar reacts calcium hydroxide, or ammonia.
with the casein during drying to cause discoloration of the product. Also through the
same reaction i.e. between lactose and the α-amino group of lysine, the nutritional
value of product is decreased.
The most commonly used alkali in the production of sodium caseinate is sodium
hydroxide (NaOH) solution, with strength of 2.5 M or 10%. The quantity of NaOH
required is generally 1.7 - 2.2% by weight of the 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 is both
greater than those of NaOH. They
are therefore generally used only
for specific purposes, such as in the
manufacture of citrated caseinates.
The very high viscosity of
sodium caseinate solutions of
moderate concentration limits their
solids content for spray drying to
about 20%.
Regarding the processing
procedures, it should be mentioned
that the dissolving time is directly
related to the particle size and that
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 alkali.
After the final casein wash, the
curd may be dewatered to about
45% solids and then remixed with
water (to 25 - 30% solids) before
entering the colloid mill. The
temperature of the emerging slurry
should be below 450C, since it has
been observed that milled curd can
re-agglomerate at higher
temperatures. Generally the slurry
is collected in a jacketed tank provided with an effective agitator and also integrated
in a circulation 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 raise the temperature as quickly as possible to 60 – 75 0C to reduce the viscosity.
The dissolving time for sodium caseinate prepared in batches is usually 30 – 60 min.
For efficient atomisation, the sodium caseinate solution must have a constant
viscosity when it is fed to the spray drier. It is common practice to minimise the
viscosity by preheating the solution to 90 – 950C just prior to spray drying.
Dissolving technique:
Well made wet curd contains 55-60% moisture. Consequently 45kg of a 20%
solution would entail the addition of 22.5 kg of water and alkali to 22.5kg of 50%
moisture and two factors are there which affect the dissolving property – mixing
process depends on the number of undispersed particles in the mix at that stage of
mixing. As a result if it is attempted to make a physical mixture of 20% casein and
then add alkali to the mixture, a very high viscosity is attained.
Second problem with wet and which may responsible for the above effect is
that the particles in the presence of alkali form a viscous coating on the surface
which resists further dissolving action.
These two problems are resolved by adding the wet curd and alkali into a vat
equipped with a powerful agitator. A large capacity centrifugal pump is attached to
the out let of vat and used to re-circulate the contents. The alkali is added to the vat
on suction side of this pump so that vigrous mixing action within the pump prevents
formation of heavy viscous surface on the curd particles. By this arrangement it is
reported that wet curd and alkali can be added without undue difficulty. Sodium
casenate solutions before spray drying must be standardized for viscosity rather
than concentration. The relationship between refractive index of sodium caseinate
and their concentration is liner between 15 – 265 and is represented by the
equation-
%.TS = 490.67 R – 651.67
Where R is refractive index at 400 C.
Temperature control:
There are two limiting factors in the use of high temperature in sodium casein
manufacture.
1. Tendency for curd particles to tougher in hot water and
become even hard to dissolve in alkali.
2. Effect of high temperature on the quality of the dried
caseinate.
The first factor can be overcome by the use of powerful re-circulating pump, a
powerful agitator in the mixing vat followed finally by putting the solution through a
colloid mill.
The second factor is related to the amount above 70 0C, caseinate solutions on
prolonged exposure to such temperature show discoloration unless the solution is
virtually free of lactose.
pH Control:
The pH viscosity curve for sodium caseinate is at a minimum in the pH range
6.6-7.0. Addition of acid causes localized precipitation which is undesirable. Good pH
meter is necessary in the processing room. It should be equipped with a temperature
compensator, a glass electrode and a flushing type calomel electrode. The viscous,
sticky sodium caseinate solution readily causes blacking of the normal sintered
glass, calomel electrode surface.
It was state that curd used as a starting material should have low calcium
content.
Viscosity index:
It is necessary to have viscometer in the lab. It is essential that a particular
spray drier may work best at viscosity equipment to a lower value than 20% cone.
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 destabilised by heating, especially at pH values below 6. It
has been found that during the dissolving process, the reaction between acid casein
curd and calcium hydroxide 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 on rollers. Most of the ammonia evaporates during this process.
Other caseinates
Magnesium caseinate has been briefly mentioned in the literature. Compounds of
casein with aluminium have been prepared for medical use or for use as an
emulsifier in meat products. Heavy metal derivates 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 dietic products.
Extruded sodium caseinate
It is possible to produce sodium caseinate from casein in the presence of a limited
amount of water by using extrusion techniques. Most of the published information
gives dry casein as the starting material. Water and alkali are added to form a
mixture for extrusion. The casein/ water mixture may have a moisture content of 10
– 30%. The extrusion technique used in production of caseinates is likely to become
highly competitive with the traditional batch technique.
Uses of caseinates:
Sodium caseinate
A casein application of growing importance is its use as a raw material for the
manufacture of sodium caseinate. The casein is easily dissolved in a diluted alkali,
and the liquid is then spray-dried to a powder. This powder is much more soluble
than casein and is being increasingly used by the food industry. It is often used as an
emulsifier in cured meats and is found in a number of new products, such as milk
and cream substitutes. As sodium caseinate is highly viscous when dissolved, the
maximum obtainable concentration is 20% at 55 – 60 C.
Calcium caseinate
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. The viscosity of calcium caseinate is somewhat lower than that of
sodium caseinate at the same concentration.
Calcium co-precipitate
This product can also be dissolved in alkali and spray dried, and has much the same
field of application as caseinate, but with the difference that in the production of
calcium co-precipitate, it is possible to adapt the process for the purpose of
regulating colour, solubility, and ash content in closer conformity to the users’
requirements. One of the most important advantages of casein and caseinate from a
nutritional point of view is the relatively high content of the essential amino acid
lysine. Moreover, tests have shown that the lysine keeps much longer, thanks to the
absence of lactose in the environment. This suggests that milk proteins can be more
conveniently stored in the form of casein and caseinate than, for example, as dried
milk powder. Casein produced for industrial use must satisfy long-established
demands for chemical purity. The new trend shows that casein and precipitate are
intermediate products which find their way into a host of food products and must
therefore satisfy strict demands in respect of bacteriological as well as chemical
purity. Process lines must be so designed and constructed that they ensure hygienic
manufacturing conditions. As casein is a seasonal product to a much greater extent
than many other dairy products, the possibility must be provided to run the
production line in multiple shifts without an undue demand for manual labour; water
consumption must also be kept within reasonable limits. In these circumstances,
therefore, it is of interest to be able to plan continuous production lines,
incorporating for example centrifugal machines for dewatering the casein and
recovery of casein losses from the whey and wash water.

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