Demineralization

G Gernigon, P Schuck, and R Jeantet, UMR 1253 INRA-Agrocampus Ouest, Rennes, France
H Burling, Arla Foods amba, Lund, Sweden
ª 2011 Elsevier Ltd. All rights reserved.

This article is a revision of the previous edition article by

H. Burling, Volume 4, pp 2745–2751, ª 2002, Elsevier Ltd.

Introduction electrodes. The two electrodes at each end of the cell

stack have separate rinse channels, through which a sepa-
In order to make nonhygroscopic whey powder as well as rate acidified stream is circulated to protect the electrodes
to make whey powder a suitable ingredient for certain from chemical attack. For whey treatment, the whey feed
foods, a reduction of the mineral content is needed. and acidified brine pass through alternate cells in the
Typically, whey contains 8–10% minerals on a dry weight stack.
basis. This can be problematic when processing whey,
especially when concentrating, crystallizing lactose, and
spray-drying whey. It is also a problem when using whey Operating Principle
and whey powders as food, especially for infant formulas,
where a 90–95% reduction in minerals is needed. This is Alternate cells in the electrodialysis stack act as concen-
necessary in order to mimic the mineral composition of tration and dilution cells, respectively. Whey is circulated
human milk. Critical ions for the preparation of infant through the dilution cells and a 5% brine carrier solution
formulas are Naþ, Kþ, Cl, and PO3 4 . For example, for through the concentration cells.
ice cream applications, in order to reduce the salty taste of When DC is applied across the cells, cations attempt to
ordinary whey powder, a 50–70% overall reduction in migrate to the cathode and anions to the anode, as shown
minerals is often enough. Addition of less demineralized in Figure 1. However, completely free migration between
whey powder is always a possibility. It should be remem- the cells is not possible because the membranes act as
bered that instead of using a specific demineralization barriers to ions of like charge. Anions can pass through an
process, like ion exchange or electrodialysis, ultrafiltration anion membrane but are stopped by a cation membrane.
in combination with pure lactose is an alternative for the Conversely, cations can pass through a cation membrane
manufacture of infant formulas. The necessary composi- but not an anion membrane. The net effect is depletion of
tion of macrocomponents can thus be reached in many ions in the whey (depletion) cells. The whey is thus
different ways. This article will focus on three main tech- demineralized, to an extent determined by the ash con-
nologies for whey demineralization, that is, electrodialysis, tent of the whey, residence time in the stack, current
ion exchange, and nanofiltration (NF). Combination of density, and flow viscosity.
these processes will also be mentioned. The electrodialysis plant can be run either continu-
ously or in batches. A batch system, which is often used
for demineralization levels above 70%, can consist of one
membrane stack over which the process liquid, for exam-
Electrodialysis ple, whey, is circulated until a certain ash level is reached.
This is indicated by the conductivity of the process liquid.
Electrodialysis is defined as the transport of ions through The holding time in a batch system can be as long as 5–6 h
semipermeable membranes under the driving force of an for 90% demineralization at 30–40  C. Preconcentration
electric field caused by an applied direct current (DC) of the whey to 20–30% dry matter (DM) is desirable for
source. The membranes used have both anion and cation maximum utilization of installed membrane area and low
exchange functions, making electrodialysis capable of electric power consumption. The whey concentrate
reducing the mineral content of a process liquid, for should be clarified before it enters the electrodialysis unit.
example seawater or whey. Figure 1 is a schematic repre- The high process temperature means that there is a
sentation of an electrodialysis unit. It consists of a number risk of bacterial growth in the product. A bacteriostatic
of compartments separated by alternate cation and anion compound such as hydrogen peroxide is therefore often
exchange membranes, which are spaced about 1 mm added to the whey, when allowed. The process liquid
apart. The end compartments contain electrodes. There heats up during the process, so cooling is needed if
can be as many as 200 cell pairs between each pair of it is necessary to maintain process temperature. In a

738
 Whey Processing | Demineralization 739

factor shortening the lifetime of the anion membrane. The

theoretical background to this problem is as follows. At the
normal pH of whey, the main whey proteins are negatively
charged (anionic character) and move as such under the
influence of the electric field in the stack. These molecules,
which are too big to pass through the anion exchange
membranes, are deposited as a thin protein layer on the
face of the anion exchange membranes in the whey com-
partments. Techniques such as polarity reversal can be
used to dislodge these deposits.
Although frequent cleaning at high pH removes most
of the deposits, at least in older plants, disassembly of the
stack for manual cleaning is recommended at intervals of
2–4 weeks. The processing cost of electrodialysis depends
Figure 1 Schematic layout of an electrodialysis stack. very much on the degree of demineralization. Increasing
the demineralization level in steps from 50 to 75 to 90%
doubles the processing cost per step, as a rule of thumb.
continuous plant, consisting of, for example, five mem- Water treatment, electric power, chemicals, and steam
brane stacks in series, the holding time can be reduced to account for the operating costs of a demineralization plant.
10–40 min. The maximum demineralization level of such Wastewater treatment is a particularly expensive item.
a plant is 60–70%. In relation to capacity, the installed During production, lactose leaks through the membranes
membrane area is much larger in a continuous plant than to an extent of as much as 5–8% at 90% demineralization.
in a batch plant. The phosphate removed from the whey accumulates in
An electrodialysis plant can easily be automated and the waste stream. The cost of electric power amounts to
furnished with a programmed clean-in-place (CIP) system. 10–15% of the processing cost, while the chemicals used
The cleaning sequence normally includes water rinse, in the process, mainly hydrochloric acid, account for 5%.
cleaning with an alkaline solution (maximum pH 9), water The cost of steam used for preheating the product and cost
rinse, cleaning with hydrochloric acid (pH 1), and a final of cooling for controlling the process temperature are
water rinse. A typical cleaning program takes about 10–15%, depending on the demineralization level.
100 min.

Power Supply and Automation Ion Exchange

DC is used in the electrodialysis plant, which should have Industrial application of ion exchange often means pumping
facilities for regulating current in the range of 0–185 A the process liquid to be treated through a fixed-bed column
and voltage in the range of 0–400 V. Flow rates, tempera- filled with polymeric beads loaded with ions that are
tures, conductivity, pH of process water and product, exchangeable with the ions in the process liquid. The capa-
product inlet pressure, pressure difference between the city of the process is limited by the amount of ions on the
stacks, and current and voltage over each membrane stack resin in the fixed bed. After the ion exchange capacity has
are monitored and controlled during production. been used up, the adsorbed ions must be removed by
regeneration of the column by an appropriate regeneration
solution. After that, the flow of process liquid through the
Limiting Factors in Electrodialysis and
column can be resumed.
Processing Costs
Modern ion exchange resins are macromolecular porous
A major limiting factor for using electrodialysis in dairy plastic materials formed into beads with a diameter in the
processing is the cost of replacing membranes, spacers, range of 0.3–1.2 mm for technical applications. Chemically,
and electrodes, which constitute about 35–40% of the they act as insoluble acids or bases, which when converted
total running costs of the plant. Replacement is necessary to salts remain insoluble. The main characteristic of ion
due to fouling of the membranes, which in turn is caused exchange resins is their capacity to exchange the mobile
by (1) precipitation of calcium phosphate on the cation ions (counterions) that they contain for ions of the same
exchange membrane surfaces and (2) deposition of pro- charge sign contained in the solution to be treated. The
tein on the anion exchange membrane surfaces. exchange reactions are equilibrium reactions governed by a
The first problem can be handled by proper flow design constant. The concentration of ionic species is an important
over the membrane surface and regular acid cleaning. The factor for the driving force in the exchange reaction.
second problem, with adsorption of protein, is the main The functional groups of ion exchange resins for
740 Whey Processing | Demineralization

demineralization purposes vary. First of all, a distinction (6) flow velocity restrictions, and (7) water rinse require-
between anion exchangers and cation exchange resins can ment after regeneration.
be made and within these groups there are both weak or
strong base and acid varieties, respectively. The group to
which the specific ion exchange resin belongs depends on Conventional Ion Exchange for Demineralization
the functional group. Strong cation exchange materials
often have sulfonic groups bound to the matrix. This A simple demineralization plant based on ion exchange is
group is ionized throughout the pH range 0–14, and there- shown in Figure 2. The whey enters the strong cation
fore active for exchange reactions to take place. The most exchanger, loaded in the hydrogen ion form, and con-
common weak acid exchange material has a carboxylic acid tinues to the weak base anion exchanger in its free base
functionality. This group is ionized at pH values above the form. The ion exchange columns are rinsed and regener-
isoelectric point, typically above pH 5–6. Strong base func- ated separately with dilute hydrochloric acid and sodium
tionality is based on quaternary amine groups. These hydroxide (or ammonia). Once a day, the columns are
disinfected by rinsing with water containing active chlo-
groups are dissociated throughout the pH range. Weak
rine. The following net reactions take place during
base ion exchange functionality is often based on tertiary
demineralization (NaCl is used to illustrate the salts of
amine groups, which are active in the pH range 0–7.
whey and R represents the insoluble resin exchange site):
From the point of view of ease of regeneration, it is
beneficial to use weak resins whenever possible. They can cation exchange:R-H þ Naþ þ Cl –
be regenerated with acid or alkali in excess in comparison Ð R-Na þ Hþ þ Cl –
with the theoretical need of just 10–50%. Strong resins
need 200–400% excess of regenerant to be fully con- anion exchange: R-OH þ Hþ þ Cl – Ð R-Cl þ H2 O
verted to the active form. The above reactions illustrate that by the ion exchange
For demineralization according to the classical proce- process the whey salts are exchanged for water.
dure, a strong cation exchanger in the hydrogen ion form The flow program in the ion exchange process
is often combined with a weak base anion exchanger includes the following steps:
working in the free base (hydroxyl) form. The whey
passes through the cation exchange column before the 1. exhaustion: 10–15 bed volumes of whey can be treated
anion exchange column. It is not possible to use a weak per regeneration cycle. The bed volume refers to the
acid cation exchange resin instead of a strong one, because volume of the cation exchanger;
of pH and the carboxyl functionality of the weak cation 2. regeneration;
exchange resin. The equilibrium constant for the 3. displacement of whey from the columns by water;
exchange reaction to occur is unfavorable. 4. backflushing;
Other important characteristics of ion exchangers that 5. contact with regeneration solution; and
are not further discussed are (1) ion exchange capacity, 6. water rinse.
(2) swelling properties, (3) mechanical strength, (4) flui- A typical cycle time is about 6 h: 2 h for exhaustion and
dization during backwashing of the bed, (5) pressure drop, 4 h for regeneration. The ion exchange vessels are often

Figure 2 Schematic diagram of an automatic whey demineralization plant.

 Whey Processing | Demineralization 741

made of rubber-lined mild steel to avoid corrosion pro-

blems. A conical shape is used specially for the anion
exchanger to allow for swelling of the bed during trans-
formation from the free base to the salt form. It is common
practice to regenerate the cation column in upflow (coun-
tercurrent to exhaustion). This system reduces the
consumption of regeneration chemicals by as much as
30–40%. The plant can easily be automated. Two or
three parallel ion exchange systems are needed for a
continuous flow of whey.

Process Limitations and Costs

Whey is a liquid with a high ash content, which means
short runs between regenerations with high consumption
of regeneration chemicals. These facts lead to a high salt Figure 3 The SMR process for demineralization. A, whey; B,
load in the wastewater from both the whey and from the demineralized whey powder; C, condensate with NH3 and CO2;
surplus of regeneration chemicals. Consumption of rinse D, new regeneration solution; E, spent regeneration solution; F,
whey salts; G, NH3 and CO2; H, precipitate of MgNH4PO4.
water is also high, especially from washing out excess
sodium hydroxide from the weak anion exchange resin.
Losses of whey proteins occur due to adsorption cation exchange: R-NH4 þ Naþ þ HCO3 –
phenomena, primarily on the anion exchange resin.
Consumption of regeneration chemicals accounts for Ð R-Naþ þ NH4þ þ HCO3 –
60–70% of the operating costs. The process is primarily
designed for 90–95% demineralization but any level can NH4HCO3 is a thermolytic salt (sometimes used as bak-
be chosen if a bypass system is used. ing powder), which decomposes to NH3, CO2, and H2O
when heated. This happens during the subsequent eva-
poration of the whey, offering the possibility of
An Alternative Ion Exchange Process recovering the NH3 and CO2 vaporized from the whey
to make new regeneration solution (NH4HCO3). Part of
In order to reduce the consumption of regeneration the used regeneration solution after passing the columns,
chemicals and thus also create a better waste situa- containing surplus of regeneration salt (about 100% of
tion for a demineralization plant, the R&D theoretical need is used during regeneration), is collected
Department of the Swedish Dairies’ Association, for vaporization in a distillation tower. Figure 4 shows the
SMR, developed an alternative ion exchange process. industrial layout of the SMR process. The description of
In this process, several different unit operations are the flow arrangement is given below. The whey first
linked together, namely, ion exchange, evaporation, enters the anion exchange column regenerated in bicar-
distillation, and absorption in order to recover the bonate form and then the cation exchange column in
regenerant, NH4HCO3, as illustrated in Figure 3. In ammonium form. This is in reverse order compared
this process, the whey is first treated with the anion with the classical ion exchange demineralization
exchange resin regenerated in the bicarbonate form. procedure.
During anion exchange, the anions of whey are In practical design, the ion exchange systems are
exchanged for HCO 3 . After this, the whey enters paired, one working on whey while the other is being
the cation exchange column regenerated in the regenerated. With two pairs of columns, an uninterrupted
ammonium form. During the passage of the whey flow of whey is obtained. The cycle time is 4 h (2 h for ion
through this column, the cations in the whey are exchange and 2 h for regeneration). After passing through
exchanged for NHþ 4 . Thus after the process, the the ion exchange unit (1) the cool whey is used for heat
whey salts are exchanged for ammonium bicarbonate, recovery in the absorption tower and as cooling medium
NH4HCO3. The reactions can be summarized as
in the condenser (9). Then, the whey enters the evapora-
follows:
tor (3) and finally the demineralized whey concentrate is
spray-dried (10). The condensate from evaporator stage 2,
anion exchange: R-HCO3 þ Naþ þ Cl – which is especially rich in ammonia, is separated from the
Ð R-Cl þ Naþ þ HCO3 – other condensate streams and continues to the absorption
742 Whey Processing | Demineralization

Figure 4 Flow sheet of a full-scale production plant based on the SMR process. A, whey; B, whey powder; C, condensate; D, CO2 and NH3;
E, water; F, disinfectant; G, wastewater; H, phosphate salt; J, CO2 and NH3; 1, ion exchanger; 2, ion exchanger; 3, heat recovery; 4, condenser;
5, evaporator; 6, spray tower; 7, adsorption column; 8, fresh regeneration solution; 9, spent regeneration solution; 10, stripping solution.

tower (4), where it forms the liquid base for the new 5. low operating temperature (4–6  C), enhancing the
regeneration solution. The condensates from evaporator microbiological status of the end product;
stages 1, 3, and 4 are used to rinse off the ion exchangers, 6. high yield of whey solids compared to classical ion
giving further recovery of ammonia in these condensates. exchange and electrodialysis; and
The recovery of ammonia is 75–80% in the process. Most of 7. optimum heat recovery.
the CO2 stripped off during evaporation is recovered in
gaseous form from the mechanical vacuum pump of the Process Limitations and Costs
evaporator. This gas flows directly into the bottom of the
absorption tower, where it is almost completely absorbed in In most cases, depending on the cost of chemicals, the
the synthesis of NH4HCO3. Overall recovery of CO2 is more operating cost of the SMR process is 30–70% lower than
than 90%. To compensate for losses of NH3 and CO2 in the that of the classical ion exchange process. The equipment
process, fresh quantities of NH4HCO3 are injected into the for plant design of an SMR plant includes more compo-
circulation flow of the absorption tower (4). The part of the nents than the classical ion exchange process. Therefore,
regeneration solution which is rich in NH4HCO3 is collected the capital costs are somewhat higher. For optimum prof-
in a tank (8), where the phosphate from whey is precipitated itability, a plant greater than 100 m3 is needed.
by addition of MgCl2. When the precipitate of magnesium
ammonium phosphate (MgNH4PO4) has settled, the super- Nanofiltration
natant liquid is pumped to the top of the distillation tower (9)
and at the same time preheated in a plate heat exchanger (not An interesting alternative to electrodialysis and ion
shown in the figure) using the bottom liquid in the distilla- exchange is NF. NF is a membrane pressure-driven pro-
tion tower as the heating medium. About 10% of the liquid is cess in between reverse osmosis and ultrafiltration. It is
stripped off as vapor, which in turn is condensed by using the named after the mean pore diameter, which is approxi-
whey after ion exchange as cooling medium (2). mately 1 nm. Thus, the separation area for molecules,
In summary, the SMR process has the following especially charged monovalent ions like Naþ, Kþ, and
characteristics: Cl, lies in the molecular range of 100–1000 Da. The
normal operating pressure is typically 2–3 MPa.
1. low running costs due to recovery of the regeneration Apart from steric exclusion and considering the low
chemicals; value of pore diameter, the membrane separation char-
2. low losses of whey solids and only half of the salt acteristic is to a large extent determined by electrostatic
discharge compared to the classical ion exchange forces in the membrane matrix because of the electric
process; charges of its carboxyl groups; this causes ions to avoid
3. small variations in pH of the whey (6.5–8.2), resulting regions of low dielectric constant. Moreover, the role of
in minimum losses of denatured whey proteins due to the retention of multivalent co-ions (salts and/or pro-
adsorption on the columns; teins) in the facilitated transmission of monovalent ions
4. high demineralization efficiency (more than 90%); has been demonstrated.
 Whey Processing | Demineralization 743

In the case of sweet whey (membrane negatively Combination of Processes

charged), the retention of polyvalent anions leads to the
presence of higher amounts of negative charges in the For large demineralization installations, that is, those
retentate, which results in an increased transmission of processing more than 400 m3 day1 of whey, invest-
Cl and an increased retention of Naþ and Kþ and Ca2þ ment in combined technologies may be of interest.
in order to maintain the electroneutrality. The deminer- The combinations used are electrodialysis or NF in
alization efficiency is thus almost restricted to removal of combination with the classical ion exchange process.
monovalent ions. The benefits are reduced costs of chemicals but the
For a volume reduction ratio of 4–5 during filtration of capital costs are higher and more complicated pro-
whey, an ash removal from whey of 40–60% is obtainable. cesses are more difficult to run.
It corresponds to 70–80% for monovalent co-ions (which Many modern demineralization plants are combina-
are Naþ, Kþ, and Hþ for acid whey and Cl and OH for tions of classical ion exchange with NF. By doing this, the
sweet whey) and 40–70% for monovalent counterions ionic load on the ion exchangers is reduced by about 30%
(which are Naþ, Kþ, and Hþ for sweet whey and Cl in combination with lower volumes to treat. The size of
and OH for acid whey). Divalent ions are reduced in the the columns can be reduced by the same figure, in
range of 3–20%. principle.
Partial demineralization is often needed in various When electrodialysis and classical ion exchange are
situations when manufacturing dairy ingredients, for combined, the whey first passes the electrodialysis step to
example, various whey protein concentrate products, in about 50% demineralization level. After that, the whey
order to adjust the mineral composition. passes on to the ion exchange plant.
Another effect of NF is the concomitant concentration
of the whey up to a DM of 20–22%, which helps to
economize the evaporation costs. See also: Dehydrated Dairy Products: Dairy Ingredients
By combining with water dilution of the NF retentate in Non-Dairy Foods; Infant Formulae. Milk Protein
and renewed filtration (diafiltration), the ash reduction Products: Whey Protein Products. Milk Salts:
can be driven from 35–50 up to 60–70% but at the Distribution and Analysis; Interaction with Caseins.
expense of increased cost, water utilization, and by-pro- Whey Processing: Utilization and Products.
duct (nanofiltrate) production. In contrast, in newer types
of NF membranes, the loss of organic molecules has been
improved, especially lactose.
Indeed the loss of lactose and the loss of nonprotein N Further Reading
and protein in NF are today lower than those found in
Delaney RAM (1976) Demineralization of cheese whey. Australian
electrodialysis or ion exchange, making retentate more Journal of Dairy Technology 31: 12–17.
valuable and leading to a permeate with lower biological Hoppe GK and Higgins JJ (1992) Demineralization. In: Zadow JG (ed.)
oxygen demand (BOD). Whey and Lactose Processing, pp. 91–131. London: Elsevier
Applied Science.
Urea does leak quite extensively. Also, organic acids Houldsworth DW (1980) Demineralization of whey by means of ion
like lactic and acetic acid can pass through the membrane exchange and electrodialysis. Journal of the Society of Dairy
to a large extent, presenting the possibilities of deacidifi- Technology 33: 45–51.
Jeantet R (1995) Nanofiltration de liquides laitiers. Thèse de l’ENSAR
cation of acid whey. Corresponding salts of these acids are 95-18-B-65, Agrocampus Quest.
strongly retained by the membrane. Jeantet R, Schuck P, Famelart MH, and Maubois JL (1996)
The benefits of NF are low investment costs and Nanofiltration benefit for production of spray-dried demineralized
whey powder. Le Lait 76: 283–301.
simple installations, which are easy to run. Moreover, Jönsson H and Arph SO (1987) Ion exchange for demineralization of
the amount of effluents is greatly reduced in comparison cheese whey. International Dairy Federation Bulletin 212: 91–98.
with the other demineralization processes, and the gener- Kelly PM, Horton BS, and Burling H (1991) Partial demineralization of
whey by nanofiltration. International Dairy Federation Special Issue
ated effluents have a lower BOD. Demineralization by 9201: 130–140.
electrodialysis and ion exchange is usually known to Rousset F and Reboux P (1997) Nanofiltration and ion exchange for the
generate high amounts of effluents. Moreover, it has demineralization of whey. In: Whey, Proceedings of the 2nd
International Whey Conference, pp. 93–99. Chicago, IL, October.
been demonstrated that the running costs of these demi- Brussels, Belgium: International Dairy Federation.
neralization techniques are 25–55% higher than NF, due Sienkiewicz T and Riedel C-L (1990) Whey and Whey Utilization, 2nd
to their combination with evaporation concentration. edn. Gelsenkirchen, Germany: Verlag Th. Mann.
Vasiljevic T and Jelen P (2000) Comparison of nanofiltration and
NF is a fast-growing technology in the dairy world ultrafiltration of cottage cheese whey and whey permeate.
today for different application purposes. Milchwissenschaft 55: 145–149.