CHAPTER 22
Whey and Whey Products
22.1 INTRODUCTION
The liquid remaining after removal of the fat
and casein from milk by isoelectric or rennet co-
agulation of the casein is called whey. The term
milk serum is used for the supernatant liquid ob-
tained by ultracentrifuging skimmed (fat-free)
milk; 95% of the casein micelles are sedimented
by ultracentrifugation at 100,000 g for 1 hr. Milk
serum represents the aqueous phase of milk, un-
changed by the process of separation, although it
does contain small casein micelles.
The wheys prepared by isoelectric precipita-
tion or rennet coagulation are called acid whey
and sweet (rennet) whey, respectively. They dif-
fer in composition from each other (Table 22-1)
and from milk serum because of changes that
occur during their preparation. For example,
acid whey contains a much higher concentration
of calcium, magnesium, phosphate, and citrate
than sweet whey or milk serum owing to the so-
lution of the colloidal milk salts upon acidifica-
tion. If properly prepared, acid whey should be
free of casein. Commercially, acid whey is usu-
ally prepared from efficiently skimmed milk in
the manufacture of acid-coagulated cheeses (see
Chapter 16) or acid casein and is therefore es-
sentially free of fat, although it does contain
some phospholipids. Sweet whey is a byproduct
of the manufacture of rennet-coagulated cheese
or rennet casein and its composition varies de-
pending on its source (e.g., pH 6.2-6.6), depend-
ing on the extent of acidification that had oc-
curred prior to whey separation (hence the con-
centration of some salts varies somewhat). Most
cheeses are made from full-fat or partially
skimmed milk, and typically about 10% of the
fat in such milk is lost in the whey as a result of
the formation of free (nonglobular) fat during
pasteurization and pumping of the milk and the
loss of fat globules from the curd pieces during
cutting and cooking. Rennet casein is produced
from skimmed milk, and therefore the resulting
whey is essentially fat-free. As discussed in
Chapter 6, rennet coagulation involves cleavage
of K-casein, and the resulting macropeptides
formed are present in rennet whey. Other casein-
derived peptides may be present in whey if an
excessively proteolytic rennet substitute is used.
If the rennet coagulation process is incomplete
when the gel is cut, the whey may contain some
uncoagulated casein as well as small particles of
curd. The compositional data for acid and rennet
wheys shown in Table 22-1 are typical values,
although the values vary considerably.
It is apparent from Table 22-1 that whey con-
tains about 50% of the total solids of milk, in-
cluding essentially all of the lactose and whey
proteins (provided that the whey proteins were
not denatured by heat treatment prior to coagula-
tion), 50-100% of the milk salts (depending on
whether it was produced by acid or rennet co-
agulation), and some fat (depending on whether
skimmed or whole milk was used). Thus, whey
is a valuable source of food constituents from
which numerous food products are now pro-
Table 22-1 Typical Composition and pH of Whole Milk, Sweet (Rennet Casein and Cheddar Cheese)
Wheys, and Acid (Lactic and Mineral Acid) Wheys

Sweet Wheys Acid Wheys

Rennet Cheddar3 Lactic Acid Mineral Acid

Component Casein (g/L) Cheese Casein (g/L) Casein (g/L) Whole Milk (g/L)

Total solids 66.0 67.0 64.0 63.0 122.5

Total protein (N x 6.38) 6.6 6.5 6.2 6.1 33.0
Nonprotein nitrogen (NPN) 0.37 0.27 0.40 0.30
Lactose 52.0 52.0 44.0 47.0 47.0
Milk fat 0.20 3.0 0.30 0.30 35.0
Minerals (ash) 5.0 5.2 7.5 7.9 7.5
Calcium 0.50 0.40 1.6 1.4 1.2
Phosphate 1.0 0.50 2.0 2.0 2.0
Sodium 0.53 0.50 0.51 0.50 0.5
Lactate - 2.0 6.4
pH 6.4 5.9 4.6 4.7 6.7
a
Unseparated whey.

duced. In this chapter, the principal products
produced from whey are described briefly. The
reader should refer to Sienkiewiez and Riedel
(1990) for a detailed discussion on whey and
whey utilization. Certain aspects of whey pro-
teins are covered in Fox (1992) and certain as-
pects of lactose and its derivatives in Fox (1997)
and International Dairy Federation (1993).
Traditionally, whey was regarded as a waste
product and was disposed of by the cheapest
possible method—fed to animals (especially
pigs), spray irrigated onto land, dumped in wa-
terways, or treated as effluent. Some whey is
still disposed of by such methods, but dumping
of whey is unacceptable today for environmental
reasons, and improved technology makes it pos-
sible to recover whey constituents in a cost-ef-
fective manner. World production of whey is
about 160 million tonnes per annum, represent-
ing about 7 million tonnes of lactose and 1 mil-
lion tonnes of whey protein.
22.2 CLARIFICATION OF WHEY
The curd fines may be removed using a vi-
brating screen separator but are removed more
often using a centrifugal separator (clarifier).
The fines are recovered as a concentrate (e.g.,
50% dry matter), which is pressed and may be
used in processed cheese or similar products.
Removal of fines facilitates further processing
of whey (e.g., by ultrafiltration).
Fat, which is typically present at a level of
about 0.3% (w/w) in bulk cheese whey, is recov-
ered from the clarified whey using centrifugal
separators, typically to levels of 0.07%, w/w.
The resultant whey cream (~ 50% fat) is nor-
mally used for the manufacture of whey butter,
which is used as a food ingredient in, for ex-
ample, processed cheese products.
The phospholipids in whey exist as lipoprotein
particles, which block ultrafiltration membranes,
reducing the flux rate of the plant. A number of
methods have been developed to aggregate the
lipoprotein particles, such as by adding CaCl2 and
raising the pH to around 7.5. The flocculated cal-
cium phosphate-lipoprotein particles may be re-
moved by sedimentation, by centrifugation, or
preferably by microfiltration. The lipoproteins
have good emulsification properties and may be
used in a number of food applications. The clari-
fied whey is subjected to further processing.
22.3 CONCENTRATED AND DRIED
WHEY PRODUCTS
Whey powders have been produced for many
years and have several applications in the food
industry, including as ingredients for bakery and
meat products and ice cream. The value of whey
powders can be increased and their range of ap-
plications extended by one of several process
modifications.
22.3.1 Nonhygroscopic Whey Powder
Lactose, which represents about 70% of the
total solids in whey, is difficult to crystallize, and
if the lactose is not properly crystallized, the whey
powder is hygroscopic, making it unstable during
storage. Nonhygroscopic whey powder is pro-
duced by concentrating the whey to 50-60% total
solids, seeding the concentrate with lactose crys-
tals to induce crystallization, and, when crystalli-
zation is complete, drying the concentrate.
22.3.2 Demineralized Whey Powder
One of the important applications of whey
solids is in the manufacture of infant formulae.
Human milk contains more lactose (~ 7%) and
less casein (~ 1% total protein and a whey
protein:casein ratio of 60:40, compared with
20:80 for bovine milk) than cow milk. Many
modern baby formulae based on cow milk are
humanized; that is, their lactose content and
casein:whey protein ratio are adjusted to ap-
proximate those in human milk. This adjustment
is usually made by blending bovine whey and
skimmed milk. However, the concentration of
salts in bovine milk is 3-4 times higher than that
in human milk and places an undesirably high
renal load on the baby. The problem may be re-
solved by reducing the concentration of ions in
whey by electrodialysis and/or ion exchangers.
22.3.3 Delactosed and Delactosed-
Demineralized Whey Powder
For many food applications, it is desirable to
use a whey product with a higher than normal
protein content. This may be achieved by the
processes described below for the production of
whey protein products or alternatively by crys-
tallizing out some of the lactose. The latter
method involves concentrating the whey, seed-
ing it with lactose to induce crystallization, and
removing the lactose crystals by centrifugation
or filtration. The mother liquor may or may not
be demineralized (see Section 22.3.2) and spray-
dried to yield a protein-rich whey powder.
22.4 LACTOSE
Lactose is a sugar unique to milk (see Chapter
3). Among commercially available sugars, lac-
tose has many unusual properties:
• low solubility
• difficult to crystalize
• a tendency to form supersaturated solutions
• low sweetness
• low hygroscopicity when properly crystal-
ized
• a tendency to adsorb flavors and pigments
These characteristics create problems for the
dairy industry, but methods have been devel-
oped for managing and controlling the problems.
In fact, some of these characteristics are ex-
ploited in the production of improved dairy
products, such as instant milk powders and Io w-
hydroscopicity icing sugar mixtures (see Fox,
1997). Consequently, a substantial market has
developed for lactose, although very small in
comparison with that for sucrose (~ 250,000
tonnes per annum of pure lactose in comparison
with 95 million tonnes per annum of sucrose).
As noted above, lactose is produced by con-
centrating whey to 50-60% total solids, seeding
it with lactose crystals, and recovering of the
crystals by centrifugation or filtration. If extra
high purity lactose is required, the first crop of
crystals may be dissolved and recrystallized.
The market for lactose appears to be relatively
limited, but lactose can be converted, enzymati-
cally, chemically, or physically, to a range of
useful derivatives:
• Lactulose (Figure 22-1). Lactulose is
formed when the glucose moiety of lactose
 is isomerized to fructose by a mild alkaline
treatment. Lactulose is not hydrolyzed by
(3-galactosidase in the human intestine and
passes to the lower intestine, where it may
act as a laxative or promote the growth of
bifidobacteria, which can have beneficial
effects on the microbial ecology of the
lower intestine (Figure 22-2).
• Lactitol (Figure 22-3). The carbonyl group
of lactose may be reduced to an alcohol,
lactitol, by chemical or electrolytic meth-
ods. Lactitol is not hydrolyzed in the human
intestine and hence may be used as a
nonnutritive sweetener. It is claimed to
have anticholesterolemic and anticario-
genic properties. Lactitol may be esterified
with one or more fatty acids to produce a
range of food-grade emulsiflers.
• Lactobionic acid. Lactose may be oxidized
to lactobionic acid, which may be dehy-
drated to lactobionic acid lactone (Figure
22—4). Both derivatives have a number of
food and industrial applications, but the
volumes used are small.
• Glucose-galactose syrups. Lactose may be
hydrolyzed by (3-galactosidase (lactase) or
by free acid or cation exchangers to pro-
duce glucose-galactose syrups, which are
sweeter and more soluble than lactose.
Such syrups have several applications in
food products but in most cases are not cost
competitive with glucose, glucose-fructose,
or sucrose.
• Galacto-oligosaccharides. p-galactosidase
normally functions as a hydrolase, but un-
der certain conditions it may function as a
transferase, with the production of galacto-
oligosaccharides (Figure 22-5) involving
various bond types not digested in the hu-
man intestine. These oligosaccharides pass
into the large intestine, where they serve to
promote the growth of Bifidobacterium spp.
22.5 WHEY PROTEINS
Bovine whey contains two main proteins, (3-
lactoglobulin and a-lactalbumin, with lesser
amounts of blood serum albumin and immuno-
globulins (mainly IgGi) and trace amounts of
several proteins, especially lactotransferrin, and
several enzymes (see Chapter 3). Many of these
proteins have desirable nutritional, functional,
and, in some cases, pharmaceutical properties.
Numerous methods are available for the recov-
ery of whey proteins in toto and, more recently,
for the isolation of individual proteins.
The first and simplest of these is heat denatur-
ation and recovery of the aggregated protein,
known as lactalbumin. The product is insoluble,
has very poor functional properties and is used
mainly in nutritional fortification of foods.
Whey protein concentrates (WPC, 30-80%
protein), prepared by ultrafiltration, are widely
used as functional ingredients, such as for the
preparation of gels, foams, and emulsions (see
Fox, 1992).
Products with a higher protein content (up to
95%; known as whey protein isolates) have bet-
ter functionalities and are produced by ion ex-
change chromatography. Alternatively, sepa-
rated whey is ultrafiltrated to 15% dry matter
and microfiltered to remove fat. The defatted
permeate is further concentrated by ultrafiltra-
tion and diafiltration to about 20% dry matter
and spray dried. The product typically contains
92% protein, less than 0.5% fat, and 96% dry
matter. Since production costs are high, whey
protein isolates are produced on a small scale.
The properties of some whey proteins make
them more suitable for certain applications than
others. For example, the gelation properties of (3-
lactoglobulin are superior to those of a-lactalbu-
min, but (3-lactoglobulin is less suitable for the
fortification of infant formulae, since it does not
occur in human milk and many human infants
are allergic to it. Several methods have been de-
veloped for the fractionation of whey proteins,
but most are not amenable to industrial-scale
production and none is used on a truly commer-
cial scale. Presumably, the efficacy of these
methods will be improved, costs will probably
decrease, and demand will increase, and conse-
quently the fractionation of whey proteins on a
commercial scale may become a reality.
Some of the minor whey proteins are poten-
tially very valuable as nutraceuticals. Much in-
 Pyranose form Furanose form

Figure 22-1 Chemical structure of lactulose.

 LACTULOSE
Oral intake
Non-absorption and migration
to large intestine
Utilization DV Bifidobacteriwn
Production of organic acids
and lowering of intestinal pH
Moderate faecal Suppression of
excretion NH3 production
Ensuring intestinal Lessening burdens
function to hepatic function
Figure 22-2 Significance of lactulose in health.
terest has focused on lactoferrin (lactotrans-
ferrin), which is present at a very much higher
concentration in human milk than in bovine
milk. Lactoferrin is a nonheme iron-binding
protein that has bacteriostatic and other physi-
ological properties and serves as a source of bio-
logically available iron. Because lactoferrin is
cationic at the pH of milk (at which most other
milk proteins are anionic), it can be easily iso-
lated from milk or whey and has been used to
supplement infant formulae and other special di-
etary products.
Lactoperoxidase is also cationic at the pH of
milk and may be readily isolated. In the presence
of H2O2 and the thiocyanate anion, lactoperoxi-
dase is a very effective bactericidal agent and
has been used as an additive in milk replacers for
calves and piglets.
Not cariogenic
Favourable change of
intestinal microflora
Suppression of intestinal
putrefactive bacteria
Suppression of production
of harmful substances
Vitamin synthesis
The (glyco)macropeptide (GMP) produced
from K-casein upon the renneting of milk con-
tains no aromatic amino acids and therefore is
suitable for patients suffering from phenylketon-
urea. It is also claimed to have several interest-
ing physiological effects. Methods have been
developed for the preparation of GMP on a pilot
scale.
22.6 WHEY CHEESE
The whey proteins are recovered as soft
cheese by heating a mixture of whey and skim or
whole milk, adjusted to pH 6.0, at 9O0C. Ricotta
and variants thereof, Anari and Manouri, are ex-
amples of this type of cheese; they are discussed
in Chapters 16 and 17.
 Lactitol, 4-O-p-D-galactopyranosyl-D-sorbitol

Lactitol monoester (Lactyl palmitate)

Figure 22-3 Structure of lactitol and its conversion to lactyl palmitate.
 LACTOSE
Gal ({51-*-4) GIu
I Hydrolysis

Gal + GIu
I Internal rearrangement
T
Gal (1—^-2) GIu
GaI(I-^-S)GIu
Lactose Gal (1-^-6) GIu
(Allolactose)

Transglycosylation

I
GaI(I-^-S)GaI
Gal (1-^-6) Gal

Gal (1—^6) Gal (1 —^4) GIu (6'galactosyl lactose)

Gal (1—^-3) Gal (1 —^4) GIu (3'galactosyl lactose)

Gal (l-*-6) Gal (1 -*-6) GIu

I
Gal (1-^-6) Gal (1 -*^6) Gal

Tetrasaccharides

Pentasaccharides

I
Hexasaccharides

Lactobionic acid-5-lactone

Figure 22-4 Structure of lactobionic acid and its 8- Figure 22-5 Possible reaction products from the ac-
lactone. tion of p-galactosidase on lactose.
 The whey proteins are also incorporated into
some forms of Queso bianco produced from
whole milk and acidified to pH 5.4 by heating at
9O0C. They may be incorporated into Quarg by
using ultrafiltration technology or the Centri-
Whey process (whey is heated at 9O0C to dena-
ture the whey proteins, which are then recovered
by centrifugation, added to milk for the next
batch of cheese, and become incorporated into
the Quarg).
Heating milk damages or destroys its rennet
coagulation properties (see Chapter 6), but these
properties can be restored by acidifying the
cheese milk or supplementing it with CaCl2.
This approach has been proposed as a means for
increasing the yield of rennet-coagulated cheese
but is used to a very limited extent.
The whey proteins can be incorporated into
rennet-coagulated cheese by preconcentrating
the milk to the total solids content of the particu-
lar variety by ultrafiltration and coagulating the
pre-cheese by rennet. This technology has been
quite successful for soft cheeses but not, to date,
for semi-hard or hard cheeses (see Chapter 17).
Finally, whey, usually mixed with whole
milk, may be concentrated by thermal evapora-
tion to about 87% solids to produce a unique
family of cheeses, examples of which are
Mysost and Gjetost (see Chapters 16 and 17).
These cheeses are quite different from all other
cheeses—they have a sweet taste (owing to the
high level of lactose), a brown color (due to the
REFERENCES
Fox, P.P. (1992). Advanced dairy chemistry: Vol. 1. Proteins
(2d ed.). London: Elsevier Applied Science.
Fox, P.F. (1997). Advanced dairy chemistry: Vol. 3. Lactose,
water, salts and vitamins (2d ed.). London: Chapman &
Hall.
Maillard reaction between lactose and proteins),
and a fudgelike consistency.
22.7 FERMENTATION PRODUCTS
Lactose in whey or, more usually, in ultrafil-
tration permeate may be used in various fermen-
tation processes. The most widespread of the
fermentation products is ethanol, which is being
produced on a commercial scale in several facto-
ries. Other fermentation products include acetic
acid (from ethanol), lactic acid, and propionic
acid (produced from lactic acid by Propionibac-
terium spp.). Lactose may also be used as a more
general fermentation substrate but is not cost-
competitive with sucrose in the form of molas-
ses. The production of yeast biomass from whey
fermentation has been considered but it is not
economical.
22.8 CONCLUSION
Whey, which contains about 50% of the total
solids of milk and was regarded as a waste
stream until recently, can serve as the raw mate-
rial for the production of a wide range of food
products and food ingredients. Some of these are
being produced profitably on a commercial
scale. It is likely that as new technologies are
developed, new and improved food ingredients
derived from or based on whey will be devel-
oped.
International Dairy Federation. (1993). Proceedings of the
IDF Workshop on Lactose Hydrolysis [Bulletin No. 289].
Brussels: Author.
Sienkiewicz, T., & Riedel, C.-L. (1990). Whey and whey uti-
lization (2d ed.). Gelsenkirchen-Buer, Germany: Verlag
Thomas Mann.