ICEF9-2004

International Conference Engineering and Food

PURIFICATION OF FOOD STREAMS BY COMBINING ION EXCHANGE AND MEMBRANES

TECHNOLOGIES: APPLICATION OF DECALCIFICATION IN THE WHEY INDUSTRY

Marc-Andr THEOLEYRE, Francis GULA

APPLEXION, francis.gula@applexion.com ; marc-andre.theoleyre@applexion.com

Abstract

The presence of divalent ionic species in many food streams are a drawback for further processing steps
such as membrane filtration, crystallisation and chromatographic ion exclusion. Cationic ion exchange
resins operating in Na or K form have been widely used for eliminating the divalent ions for which they
present a high affinity. However the presence of complexing agent reduces the decalcification yield. Our
study has demonstrated that a combination of a strong base resin and a strong acid cation resin
regenerated in series with a monovalent salt solution can improve the decalcification process in whey
products. Used prior to the nanofiltration step, the new decalcification process permits to produce a highly
demineralised whey, up to 70% whereas without such a pre-treatment only 30% or 45% with diafiltration
are obtained. Furthermore additional benefits are anticipated either in the production of lactose after
crystallisation or by downsizing the demineralisation unit.

1. Introduction

The dairy industry produces large amount of whey, the bulk of it coming from the cheese or casein
making industries, according to the process different types of whey are produced. In order to be used in
the food industry (lactose production, WPC, demineralised powders,) they have to be further
processed. The main available techniques are ultrafiltration, reverse osmosis, nanofiltration, electrodyalis,
ion exchange or a combination of several of them. Nowadays nanofiltration is a common practice as a pre
concentration step before any further processing. Nevertheless the presence of calcium in the feed stock
remains detrimental to the process performances, therefore we have studied the possibility to implement
a decalcification system.

2. Description of the current status

The whey streams obtained from the cheese or casein production have a complex composition, the main
components being proteins, lactose and ashes, the later being mostly calcium, potassium, chlorides,
phosphates and lactic acid and a dry solid contents of 5 to 6% (table 1 & 2).

Table 1: Typical whey composition Table 2: Typical mineral composition (mg/l)

Sweet whey Acid whey Sweet whey Acid whey
pH >6 4.6 Calcium 550 1020
Dry solid (g/l) 65 65 Magnesium 60 90
NPN (g/l) 2.4 2.0 Sodium 470 470
Lactose (g/l) 47 48.6 Potassium 1440 1440
Lactic acid 1 5 Chlorides 1100 4200
Vitamins (mg/l) 7.5 7 Phosphates 470 640
Proteins (g/l) 6 6
Ashes (g/l) 5 7

Nanofiltration is widely used for the pre concentration of whey whatever are the next processing steps
such as lactose or demineralised whey production. Nanofiltration also provides a partial
demineralisation of the feed whey, the demineralisation rate without any special pre-treatment is about
30%, using diafiltration we can achieve up to 50% but the presence of divalent cations prevents the
nanofiltration process to reach higher values. The table 3 illustrates the high retention rate of divalent
species, which are retained by the NF membranes whereas monovalent ions are passing through
easily.
When lactose is manufactured, high calcium contents in the retentate cause precipitation problems
during the concentration and the crystallisation of the whey. Calcium presence is also detrimental to
the lactose quality.

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Table 3: Retention rate for various salts Table 4:Typical IX sequences

Muchetti & al(2000) Step Quantity Type
NF 50 ; 25C ; 15 bar TMP Production Feed
Sweetening off 1 to 2 BV Sweet water
Salts Retention Backwashing 1 to 2 BV Water
NaCl (0.1 mol.l-1) 0.25 Regeneration 1 to 2 BV Acid, salt or caustic
CaCl2 (0.1 mol.l-1) 0.60 Displacement 1 to 2 BV water
MgSO4 (0.1 mol.l-1) 0.95 Fast rinse 2 to 5 BV water
Na2SO4 (0.1 mol.l-1) 0.99 Sweetening on 1 to 2 BV Sweet water

The standard process used for the production of highly demineralised whey typically consists in a
nanofiltration unit followed by a demineralisation unit. An ion exchange resin cycle includes several
steps (table 4) each of them consuming important quantities of water or regenerant therefore it is
essential to optimise all these flows in order to improve the economical aspect of the demineralisation
process.

3. The scope of our work

The purpose of this work is to evaluate the implementation of a whey softening process operating in a
chemical free mode, the salts from the whey itself being used as regenerant. Such a process will
considerably improve lactose crystallisation and will allow to achieve high demineralisation rate of
whey on improving nanofiltration performances through a combination of IX and NF techniques while
optimising regenerant consumption.

Decalcification with ion exchange resin: This is a well known process, the cationic resin exchange its
monovalent cations against the divalent species for which it has a higher affinity. The exchange can
be illustrated with the following equations:

Exchange cycle:
2(RSO3-Na) + Ca2+ (RSO3) 2-Ca + 2 Na+
Regeneration cycle:
(RSO3) 2-Ca + 2 Na+ 2 (RSO3-Na) + Ca2+

Ca =
[Ca]resin.[Na]2feed
The affinity coefficient K Na depends on the type of ion exchange resin, typical
[Ca]feed.[Na]2resin
values in an aqueous solution for a standard gel type cation resin are the following K H = 1.56
Na

; K H = 4.06 ; K H = 2.59 , K H = 1.72 . These affinity coefficients illustrate the higher selectivity for
Ca Mg K

divalent species compared to monovalent for a cationic resin.

However this process requires an excess of monovalent ions for reversing the reaction. In a standard
decalcification process the NaCl regeneration rate required is about 200 to 300 %.

Moreover the divalent ions may form complexes with phosphates, organic acids,.. Thus they cannot be
fully eliminated by the resin. This results in a very low operating capacity, such a drawback can be
partly solved by using weak acid or chelating resins which presents a higher affinity for divalent.
However weak acid resins can exchange ions only when the feed solution has a pH value higher than
the one of the resin (typical pK of WAC 5.0 to 6.0) which is not the case of some acid whey; chelating
resins might be envisaged however both types require concentrated acid for regeneration moreover
they may present some regulatory issues.

In order to achieve a higher divalent ions removal which are incompletely eliminated through the
previous options we have used a strong base resin operating in chloride form (figure 1) in front of the
cationic unit. The strong base resins have the property to exchange all anionic species including
those affecting the divalent ions removal. The strong base resins show the following selectivity pattern:

Citrate>tartrate>phosphate>bisulfate>nitrate>nitrite>chloride>hydroxide

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Therefore the troublesome organic acids will be preferentially fixed, including phosphates using the
following design

Monovalent salts

SBA SAC
(Cl) (Na
Feed or K)
whey

To NF

Figure 1: Improved softening process

4. Experimental results

The testing results have been summarized in table 5, we can notice that this resin combination
considerably improve divalent removal (92%) and cycle length while applying a standard, in series
NaCl regeneration procedure. With the same regeneration rate, the capacity was much higher than
with the conventional single step process.
We have now to consider an optimised regeneration process resulting in a minimum or almost no
chemical consumptions. In order to regenerate in series these units, we need a monovalent salt
solution with a certain concentration; this can be obtained from various sources depending on the
factory design such as
Mother liquor from the lactose crystallisation unit
Raffinate from the lactose recovery through ion exclusion chromatographic plant
Demineralisation plant effluent after neutralisation
NF permeate

As an example, mother liquor has been tested as regenerant stream. The efficiency was close to salt
solution, similar softening effect with a similar regeneration rate.

Table 5: Comparison in between the two decalcification processes for sweet whey
Design SAC SBA + SAC SBA + SAC
Regenerant Salt Salt Mother liquors
Cycle (BV) 26 35 25
% Ca + Mg removal 77 92 88
Operating capacity (eq/l) 0.50 0.80 0.58
Ionic load (eq/l) 0.65 0.88 0.65
Regeneration level (eq/l) 2.4 2.4 1.7
Regeneration rate (%) 480 300 290

Following main conclusions can be drawn from the table 5:

The standard softening processing gives poor results: low capacity, high regeneration rate.
The presence of phosphates and some organic acids (citric, lactic) decreases the removal of
divalent species by complexing them.
By using a SBA resin in front of the SAC unit, we have been able to considerably improve the
divalent ions removal, higher operating capacity has been achieved, lower leakage and lower
regeneration rate. The regeneration rate has been reduced to such a level that mother liquors
from the crystallisation unit contain a sufficient amount of monovalent salts for regenerating
the SAC. Thereby, no additional chemicals are required.

At that stage, we have looked at the impact of the permutation of divalent/monovalent species on the
demineralisation rate of the downstream nanofiltration unit, the results are illustrated in the table 6.

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Table 6: Impact of the pre-treatment on the NF performances for two types of raw material
Concentration VCF : 3, Diafiltration : 3 l water/l retentate
Acid whey Sweet whey
D.S. Inlet salts Demineralisat D.S. Inlet salts Demineralisat
% (eq/Kg DS) rate (%) % (eq/Kg DS) rate (%)
Feed 6.7 1.78 4.2 1.66
NF Concentration 18.0 1.40 21.4 11.6 1.09 34.4
Diafiltration 17.0 1.16 34.7 11.0 0.73 56.2
SAC+NF Concentration 16.0 0.84 52.9 - - -
Diafiltration 14.0 0.40 77.4 - - -
SBA+SAC+NF Concentration 15.0 0.68 61.5 11.4 0.91 45.2
Diafiltration 14.0 0.15 91.8 10.8 0.48 71.0

In that experiment, the feed whey solution has been concentrated 3 times on the NF system and a
diafiltration sequence has been added using 3 litre of water per litre of retentate; the test was run in a
batch mode. Surprisingly no significant effect on the membranes flux has been noticed in any
experiment, however a drastic difference has been observed regarding the demineralisation rate. The
main monovalent and divalent ionic species have been measured by capillary electrophoresis, the salt
concentration is an average. The results are detailed in table 6 from which hereafter comments can be
made:
The demineralisation rate noticed with acid whey is on the low side compared to other
published data for NF alone, the one with sweet whey is more in line with what is
commonly observed.
For both types of whey, the new decalcification system provides a tremendous
improvement of the overall demineralisation rate (up to 70% or 90% with diafiltration).

5. Complete process integration

The integration of the decalcification can be implemented without increasing the reagent consumption
on coupling these unit operations either in the production of highly demineralised whey (figure 3) or
lactose (figure 4).

Whey

Regenerant Decalcificat waste

REVERSE DECALCIFICATION
OSMOSIS

NANOFILTRATION

Water
HCl
NaOH

DEMINERALISATION DEMINERALISATION
ANIONIC CATIONIC

Demineralised
whey

Figure 3: Integrated effluent free process design for the production of fully demineralised whey

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International Conference Engineering and Food

Whey

Regenerant
Decalcificat waste

DECALCIFICATION

CONCENTRATION

Mother
liquor CRYSTALLISATION

Lactose

Figure 4: Integrated effluent free process design for lactose production

6. Conclusions

The combination of an improved decalcification process consisting in coupling a strong base resin
with a strong acid cation resin regenerated in series with a monovalent salt solution, allows to
achieve a high softening rate event with sweet whey. This new process prevents the scaling in
downstream concentration steps such as reverse osmosis or evaporation. Prior to the
nanofiltration unit it permits to produce a highly demineralised whey up to 70% whereas without
such a pre-treatment only 30% or 45% with diafiltration are obtained.
The demineralisation rate can further improve (90%) through a demineralisation plant which is
now of a much smaller size therefore consuming far less regenerant.
It is possible to use a new decalcification system in the dairy industry with the following benefits
No additional reagent consumption on coupling the unit operations
A smaller deionisation system resulting in a lower reagent consumption
An improvement of the nanofiltration performances
An improvement of the lactose crystallisation unit performances
The possibility to achieve higher lactose recovery through a ion exclusion process

ABBREVIATIONS

IX Ion exchange resins NF Nanofiltration

SAC Strong Acid Cation DS Dry Solid
SBA Strong Base Anion VCF Volumetric Concentration Factor
WAC Weak Acid Cation
BV Bed Volumes

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