Chemistry and Processing of Sugarbeet and Sugarcane, edited by M.A. Clarke and M. A.

Godshall
Elsevier Science Publishers B.V., Amsterdam, 1988 — Printed in the Netherlands
^6

Chapter 5
ION EXCHANGE PROCESSES IN BEET SUGAR MANUFACTURE

M. SHORE, N. W. BROUGHTON, D. SARGENT, G.C. JONES AND B. W. BROWN

SUMMARY

Many processes using ion exchange resins have been proposed for use in
the beet sugar industry. After a brief introduction outlining the nature of
ion exchange resins and the trends affecting their use in the industry, this
paper concentrates on processes that have been adopted successfully and that
have stood the test of time. The processes are split into those where the
resins are used as processing aids, e.g. décalcification and decolorization,
and those where the process recovers sugar, e.g. the Quentin process and
déminéralisation. The processes are set in the context of the chemistry of
ion exchange. The ion exchange reactions that take place during the passage
of sugar juice through a resin bed, and their effect on later stages of the
process are discussed with reference to data from British Sugar's factories
and Research Laboratories. Finally the future for ion exchange processes in
the beet sugar industry is assessed.

INTRODUCTION

Some of the earliest studies of ion exchange treatment of sugarbeet

juice were by Rumpler in 1901 (ref. 1). This is comparatively recent when
compared to the application of ion exchange and absorption to water
treatment, whose history goes back to the Ancient Greek Aristotle (ref. 2),
and perhaps even the biblical prophet Moses—who could not only part the
waters but also desalinate them (ref. 3)1
However, ion exchange in sugarbeet processing is really as old as the
beet themselves, since the beet are partially composed of pectic material
which exhibits ion exchange properties (ref. 4). Beet pulp has been
advocated as an ion exchange material for treating radioactive water (ref.
5). More pertinently to the sugar industry, its ion exchange properties are
of significance in the mechanism by which chemical additives are used to
assist in dewatering the residual pulp after the sugar has been extracted
(ref. 4 ) .
Many processes using ion exchange resins have been proposed for use in
the beet sugar industry, and there are already several excellent reviews on
the subject (refs. 6-8).
 47

Few of the ion exchange processes proposed on the basis of laboratory

studies or pilot-scale trials have been operated successfully on a factory
scale. To be successful, a process must be both technically feasible and
economically viable. This in turn is influenced by factors which can be
historical, geographical, economic, or political. This paper will
concentrate on processes which have been applied in sugar factories for some
years, and thus can be said to have stood the test of time.

ION EXCHANGE RESINS

Properties
Ion exchange resins consist of beads of a porous insoluble polymer to
which are attached chemical functional groups that can take part in ion
exchange reactions. Resins can be classified in a number of ways:
a) Functional groups. These fall into four basic types: sulphonic
acid, Rxx-SOs-.11"'' (strongly acidic cation exchange resins); carboxylic acid,
Rn-C02H (weakly acidic cation exchange resins); quaternary ammonium, Rn-
NR3"*".OH- (strongly basic anion exchange resins) and amino, R»-NR2 (weakly
basic anion exchange resins).
b) Resin form. This is the exchanging ion associated with the resin's
functional groups, e.g. strongly acidic cation exchange resins are commonly
used in the hydrogen, sodium or calcium form.
c) The polymer matrix to which the functional groups are attached.
This is generally either polystyrene (styrenic resins) or polyacrylate
(acrylic resins). Acrylic resins have greater resistance to organic fouling
(ref. 9) and hence are used extensively for gross decolorization of sugar
juices (refs. 10, 11).
d) The degree of crosslinkage in the matrix. This is usually expressed
as the percentage of erosslinking agent (divinylbenzene) added to the
polymer during manufacture. The amount of crosslinking determines both the
physical strength and the porosity of the resin beads—the higher the
crosslinkage the greater the resin's physical strength and the lower its
porosity, and vice versa.
e) The physical structure of the resin. Resins are either gels, with a
fairly uniform porous structure throughout the bead, or macroporous, with
additional large holes or "macropores" to give a sponge-like structure (ref.
12). Figure 1 shows electron micrographs of typical macroporous (IRA 900C)
i*8

and gel (IRA 401S) resins at 80,000 times magnification. This sponge-like
structure of the macroporous resins can be clearly seen contrasted with the
featureless surface of the gel resin. Macroporous resins can have a high
degree of erosslinking, and hence greater physical strength than gel resins,
while retaining a high porosity due to these macropores.
In the sugar industry macroporous resins are often used to treat syrups
and juices of high total solids concentration. Resin beads shrink
considerably in highly concentrated solutions and swell back to normal size
in dilute solutions, owing to the transfer of water between the resin bead
and the solution by osmosis. Hence, a great physical strain (known as
osmotic shock) is placed on the polymer matrix when, as part of the process,
the concentration of the solution passing through the resin bed changes
rapidly. This occurs, for example, when the concentrated juice is first
applied to the resin after regeneraton (sweetening-on), and also when the
juice is washed off the column at the end of the cycle (sweetening-off).
Gel resin beads tend to shatter under this kind of stress and hence are
generally only used for treating low concentration juices (for high purity
syrups, with low color and ash and long cycles. Ed.).
Swelling and shrinkage of the resin can also occur when the ionic form
of the resin is changed.

Ion exchange reactions

Ion exchange reactions are reversible and the equilibrium reactions
between a solution of a salt and a cationic (Resin-.H*) or anionic
(Re s in"*". OH - ) exchange resin can be expressed by chemical equations, of which
the following are typical for monovalent ions (refs. 6, 12):
Cation exchange resin:
Resin-.H- + M* X- - Resin-.M- + H* X" (1)
Anion exchange resin:
Resin*.OH- + M* X - = Resin*.X- + M* 0H~ (2)
For a strongly acidic cation exchange resin the equilibrium in equation
1 is displaced to the right, whereas with a weakly acidic resin the left to
right reaction is suppressed by the free acid H*X". Weakly acidic resins
have a high affinity for hydrogen ions and hydrogen form resin will only ion
exchange readily under alkaline conditions (equation 3).
 49

Weakly acidic cation exchange resin:

Rxx-C02H + M- X- + OH" - RA-C02-.M- + H20 + X" (3)

Gel resin: IRA 401S ( x 60,000)

'fili *#g|P^: -lÀfe^

Macroporous resin: IRA 900C ( x 60,000)

Fig. 1. Structure of gel and macroporous resins.

50

Similarly, anionic resins are classed as strongly or weakly basic

depending on whether the equilibrium for equation (2) is displaced to the
right or left respectively. Hence weakly basic anion exchange resins in
hydroxide form will only exchange ions readily under acid conditions
(equation 4).
Weakly basic anion exchange resin;
Rrx-NR2 + M + X- + H+ lU-NIUH-.X- + M- (4)
The equilibrium of these ion exchange reactions is also affected by the
relative concentrations of the ions competing for the exchange sites on the
resin and by the affinity of the resin for each ion. If, for example, the
resin in equation (1) has similar affinities for H- and M- then the position
of the equilibrium is decided by the relative concentrations of the two
cations. The cation present in greatest concentration will be favoured to
occupy the resin's exchange sites.
The affinity of an ion exchange resin for a particular ion depends on
the size and charge of the ion. In dilute solutions, the resin has a much
greater affinity for small highly charged ions than for large monovalent
ions. The relative affinities of a number of cations with a strongly acidic
cation exchange resin are shown below (ref. 13):
Fe 3 - > Al 3 - > Ca 2 - > Mg*- > ΝΗ*+ = K- > Na- > H-
In solutions of high ionic concentration the difference between the
affinities is reduced and in extreme cases reversed, with the absorption of
monovalent ions being favoured over multivalent ions (ref. 13). The
strongly basic anion exchange resin/anion affinities have been less studied
but for some of the more common ones known they are (ref. 14):
SO**" > citrate > N0 3 ~ > PO*3- > I~ > Cl"
The situation for weakly acidic or basic resins is rather different in
that their chemical natures give them very strong affinities for hydrogen
ions (weakly acidic cation exchange resins) or hydroxide ions (weakly basic
anion exchange resins), as discussed earlier. The difference in affinities
for divalent and monovalent cations is more marked for the weakly acidic
resins than strongly acidic resins (ref. 12), so hydrogen form weakly acidic
resin will exchange with divalent cations in solution but not readily with
monovalent cations.
 51

Kinetics
Another major factor in the performance of ion exchange resins is the
kinetics of ion exchange reactions. Three diffusion processes generally
control the rate of ion exchange (ref. 12). These are diffusion through the
bulk of the liquid, or to and from the ion exchange sites through a static
film of liquid around each resin bead, or through the pores of the resin.
The static film of water around each resin bead is held there by friction.
Ions diffuse through this layer to the resin at a rate that is directly
proportional to the ionic concentration in the bulk solution, and quite
independent of the resin's nature. Diffusion through the liquid film is
normally the rate determining step in water treatment (ref. 12), but this is
not necessarily the case in the sugar industry (when treating high
concentration juices or removing high molecular weight species such as
colour bodies, for example).
The working capacity of an ion exchange resin is affected by the flow
rate of liquid through the resin bed. If the flow rate is too fast to allow
the ions in solution to diffuse to and from the resin's exchange sites then
the working capacity of the resin will be reduced (ref. 12).
Significant pressure drops across resin beds are encountered at high
flow rates, and also with concentrated feed liquids. This problem is
countered by using large diameter resin beads, together with frequent
backwashing to classify the resin beds into layers of uniform particle size
distribution and to remove any resin fines. Large beads, however, have a
relatively low surface to volume ratio, and hence a decreased rate of
diffusion and ion exchange.
In the mid-1960's British Sugar started to install ion exchange
décalcification plants which operated at what were then considered quite
high flow rates (ref. 15). Therefore the ion exchange kinetics were of
particular importance in obtaining satisfactory plant performance. The
performance of resins in service was regularly monitored using tests
developed by British Sugar Research Laboratories for measuring a resin's
total ion exchange capacity and, independently, the rate of exchange (ref.
16). Subsequently these methods were adopted by the International
Commission for Uniform Methods of Sugar Analysis (ICUMSA) (ref. 17).
52

Other features
The high juice temperatures (up to 90°C) encountered in sugar factories
and refineries mean that the thermal stability of ion exchange resins is
generally of more importance for the sugar industry than in other industries
utilizing ion exchange processes. Both strongly and weakly acidic cation
exchange resins have high thermal stabilities, their maximum recommended
working temperatures being greater than 100°C (ref. 13). The quaternary
ammonium and amino groups of anion exchange resins are more susceptible to
thermal degradation than the sulphonic or carboxylic acid moieties of cation
exchange resins. The hydroxide form of a strongly basic anion exchange
resin is thermodynamically unstable even at ambient temperature, but
decomposes only very slowly at this temperature (ref. 18).
The rate of degradation increases steadily with increasing temperature,
so that the normal recommended maximum working temperatures of these
hydroxide form resins are from 40-60°C (ref. 13). Chloride form strongly
basic anion exchangers, and weakly basic anion resins in general, have
greater thermal stability, their recommended maximum working temperatures
being 75 - 80°C (ref. 13).
Another property of ion exchange resins is also of particular relevance
in the sugar industry. Their densities are low enough for them to float in
high concentration syrups.
In the U.S.A., resins used in a food industry must conform to the
appropriate Food & Drug Administration Regulations (ref. 19), and similar
regulations have been drafted for the E.E.C, (ref. 20).

Trends
Until now, the main developments in ion exchange resin manufacture have
been in response to applications in water treatment, the largest use of
these materials. However, the sugar industry has always been eager to apply
new developments in ion exchange technology: as early as 1901 (ref. 1),
Rumpler reported attempts to treat beet sugar juices with natural alumino-
silicate materials. Subsequently the development of the early organic
resins in the 1930s, based on sulphonated coal (ref. 21) or phenol
formaldehyde (ref. 22), and of polystyrene (ref. 23) resins in the 1940s,
led to many attempts to incorporate resin processes in beet sugar factories.
In turn macroporous resins (ref. 12), and more recently acrylic (ref. 24)
 53

resins, were developed, largely to avoid organic fouling in water treatment,

and have been applied enthusiastically to sugar treatment processes where
their particular properties of increased physical strength or resistance to
fouling are expected to be of benefit.
Doubtless this trend will continue and any further types of resins
developed in the future, for whatever original purpose, will be examined for
possible uses in sugar processing. Recent research into the use of
inorganic ion exchangers is an example of this process (refs. 25, 26).
Often, a major factor affecting the viability of an ion exchange
process is the geographic location of the sugar factory. Climate influences
the length of the factory processing season, and problems such as evaporator
scaling that are acceptable in a factory with a short season may not be so
at another that must operate for twice as long without stopping.
In Southern Europe, beet juice purities are generally lower than
further north. For example, a British beet sugar factory might operate at a
typical thick juice purity of say 92Z sucrose on total solids, while for an
Italian factory the typical purity might be 88Z (ref. 27) or for a Sardinian
one as low as 83Z (ref. 28). As a result, in Southern Europe there is a
need for methods of increasing juice purity, and a great interest in ion
exchange techniques such as partial demineralization which achieve this.
The relative prices of white sugar and molasses will have a marked
effect on the viability of any sugar recovery process, since an increase in
recovered sugar invariably results in decreased molasses production. To a
lesser extent, the same is true of any process which alters the non-sugars
composition of the factory juice, and hence affects its overall molasses-
forming (or "melassigenic") properties. In the E.E.C, there is a three-tier
sugar price system linked to production quotas. Each country has allocated
to it 'Α' and 'Β' annual production quotas, and any further sugar produced
is exported at the lower world price. Thus a company making only 'Α' quota
sugar could obtain a higher price for any additional sugar recovered by ion
exchange than one already producing its full 'Α' and 'Β' quotas, where the
extra sugar recovered would be sold at world price.
The cost of régénérant needed for a process may also vary
geographically. For example, much of the magnesium salts in Europe are
found in the Stassfurt deposits in central Germany (ref. 29). Distance from
these deposits, and hence transport costs, has a marked effect on the
5^

profitability of the Quentin process which uses magnesium form resin (ref.
30).
Effluents and their effect on the environment are a major consideration
these days, and can affect the feasibility of operating ion exchange
processes at certain sites, particularly those far inland. This has led to
an interest in modifications to basic processes such as décalcification and
demineralization to eliminate or reduce the amount of effluent produced or
in some cases to recover it as a saleable by-product.

Resin fouling
Fouling of ion exchange resins can be defined as the presence of
substances, on or inside the resin beds, that reduces the performance of the
resin. Fouling can affect either the total ion exchange capacity or the
rate of ion exchange, or both.
Resin fouling is a major factor in determining the lifetime of an ion
exchange resin in a beet factory process, and can occur in several ways.
Appreciable amounts of suspended solids and colloids may be present in
the juice. These can block the resin bed causing a high pressure drop and
channelling of liquid through the bed. Also, they can coat the resin beads,
hindering ion diffusion into and out of the beads and reducing the rate of
exchange. These problems can be minimized by efficient juice filtration and
regular backwashing of the resin columns (ref. 15).
Similar problems occur if bacteria or algae are permitted to grow in
the column, forming slimes that can block the beds and contaminate the
product liquid (ref. 31). This problem does not occur in processes that run
at high temperatures, and where this is not possible, frequent sterilization
of the resin and the column interior walls with biocides may be required.
Fouling by precipitation of insoluble inorganic compounds inside the
resin beads can occur occasionally in juice treatment, as it does in water
treatment (ref. 32). Typical examples include removal of iron from
solutions by cation exchange resin and subsequent resin fouling by
precipitated hydrated ferric oxide; calcium sulphate fouling when
regenerating a cation exchange resin bearing calcium ions with sulphuric
acid or magnesium sulphate; magnesium hydroxide fouling when passing
alkaline solutions through magnesium form resin. In most cases inorganic
fouling is readily removed by treatment with dilute acid.
 55

The most important form of fouling is irreversible absorption or

"poisoning." Some organic compounds are irreversibly absorbed onto the
exchange sites in ion exchange resins and are not removed by the normal
regeneration procedure (ref. 9). In water treatment the compounds
responsible are referred to as humic acids (ref. 33). In sugar juice
treatment, organic nitrogenous compounds such as proteins and colour bodies
are responsible for fouling of both anion (refs. 34, 35) and cation (ref.
16) exchange resins. In an investigation into poor exchange performance in
British Sugar factories in 1972, which was hypothesized to be due to fouling
of the cation exchange resins, resins with nitrogen contents up to the
equivalent of 15Z protein on resin dry matter were found (ref. 16).
Effective in situ chemical cleaning techniques were developed using sodium
hypochlorite solution (ref. 16). For example, a resin whose working
capacity had been reduced to 22Z of that of new resin could be restored to
an 82Z working capacity.
Non-removable colour bodies cause resins to go black in service within
a few years, but do not necessarily have a significant effect on the ion
exchange properties (ref. 36).
One interesting phenomenon we have occasionally observed (ref. 37), but
not found reported elsewhere, is that a strongly acidic cation exchanger may
start to behave as if it is only weakly acidic, in that contact with acid
solution markedly reduces its subsequent ability to ion exchange in neutral
solutions. It is possible that this is due to absorption onto the resin
functional groups of proteins or other organic compounds bearing free
carboxylic acid groups.
Where possible, ion exchange processes in the sugar industry are
carried out at elevated temperatures to avoid bacterial activity and reduce
syrup viscosities. However, resin functional groups, particularly for
strongly basic anion exchange resins, are chemically degraded by operation
at too high a temperature (ref. 18). This is sometimes detectable by a
fishy amine odour in the treated juice. Like fouling, thermal degradation
of resins reduces ion exchange capacity and in some cases may reduce resin
life.
56

RESINS AS PROCESSING AIDS

Décalcification
Conventional process. The removal of calcium from water, to prevent
scale formation and improve the efficacy of soaps, was the oldest commercial
application of ion exchange, and it is many years since a similar technique
was first applied to the treatment of sugar juices (ref. 38). The
prevention of scale formation in the evaporators is of great importance for
efficient factory operation. Décalcification (softening) of second
carbonatation juice by ion exchange is a common way of preventing scale
formation, which has been used in many beet sugar factories throughout the
world (refs. 39, 40), including until recently most of the factories within
British Sugar (ref. 15). Décalcification has been particularly important
for us because we have a long processing season or campaign (138 days for
one factory in 1986/87).
The first plant at a British Sugar factory was installed in 1965, and
plants were subsequently installed at a further twelve of our factories
(ref. 15).
The British Sugar plants were designed and built in-house, but they
generally resemble plants at other sugar companies. Our plants have two to
four columns (depending on factory size), each up to nine feet (2.8 m) in
diameter and holding up to 320 cubic feet (9 m Ä ) of ion exchange resin. The
plants operate continuously, with the columns being run in parallel. One
column is on regeneration, while others are treating juice. The resin used
is a strongly acidic cation exchanger in sodium form. Gel resins are
normally used--in our experience the additional cost of the alternative
macroporous resins is not justified for this process. Regeneration is with
sodium chloride solution, and there are additional stages in the operating
cycle for washing off juice régénérant. Even small amounts of precipitated
calcium salts from carbonatation escaping filtration are removed by the
resin bed which acts as a sand filter. Hence a backwashing stage is also
included in the cycle, to clean and loosen the resin bed. The régénérant
effluent has a high inorganic content but a lower B.O.D. and organic content
than some of the ion exchange effluents, e.g. in decolorization. Disposal
of this effluent can be a problem in some circumstances. The
décalcification plants removed 19kg of CaO per cubic metre of resin,
 57

reducing the concentration of calcium ions to 6 - 8 ppm (ref. 15). A simple

schematic of the décalcification process is shown in Figure 2.

Exhaustion Regeneration

Second Carb. Juice 10Z NaCl

90°C 15-20 BV/hr 2-3 BV/hr

II

Strong acid cation resin||

Na"*" form

JJ

Nl/
Softened second carb. juice
to evaporators Effluent

Fig. 2. Conventional décalcification.

In 1972 British Sugar installed a commercially available continuous

moving bed ion exchange plant for décalcification at Ely factory (ref. 15).
Serious difficulties with resin transport and the balance of liquid flows
were experienced with it, due partly to the presence of insoluble solids in
the juice, and it was eventually replaced by a conventional plant.
Chemistry of decalcifcation. Décalcification (softening) of second
carbonatation juice is accomplished using a strongly acidic cation exchange
resin in the sodium form. It is often considered simply as an exchange of
calcium ions in the juice for sodium ions on the resin, according to the
following equilibrium:
2 Resin- . Na- + Ca 2 - - (Resin-)2 . Ca*- + 2Na-
In practice the resin does not remove all the calcium ions from the
juice, for two reasons:
58

(i) Some of the calcium is present as complexes which, being

negatively charged, do not participate in exchange reactions with the resin.
Calcium complexes with certain carboxylic acid anions; in British Sugar's
experience only citrate is of any quantitative significance in this respect
in second carbonatation juice (ref. 41).
(ii) Other cation exchange reactions occur, besides that of calcium for
sodium, which compete for sites on the resin or, indeed, displace calcium
from the resin (ref. 42). Potassium, sodium and ammonium are the principal
cations in the second carbonatation juice and these can be exchanged for the
sodium ions originally on the resin:
Resin- . Na+ + M + - Resin- . M + + Na +
Moreover, the high concentrations of these three cations in juice
relative to calcium can drive the main exchange reaction, by which calcium
is removed from the juice, in the reverse direction, thus:
(Resin)* . Ca 2 - + 2M"*- » 2 Resin- . M- + Ca 2 +
even though the resin has a higher affinity for calcium than for the
monovalent ions.
The various exchange reactions occurring in décalcification could have
a significant effect on the overall non-sugars composition of juice, and
therefore on the formation of molasses at the expense of white sugar
production. Several workers have investigated the relative amounts of
sodium/calcium and other cation exchange reactions taking place during
décalcification (refs. 43-45).
In a British Sugar investigation, reported in 1980 (ref. 42), it was
found that when a décalcification plant was operating under representative
conditions, the net effect during the exhaustion part of the cycle was the
removal of both calcium and potassium ions from the juice and their
replacement by sodium ions. Small quantities of ammonium ions were also
removed (see Figure 3 and Table 1). Most of the removal of potassium
occurred during the first two hours or so of each exhaustion. In the
remaining 17 hours of the exhaustion sequence a small proportion of the
potassium which had been removed was exchanged back into the juice for
calcium ions.
The observed exchanges were explicable in terms of the relative
concentrations of the various cations in juice and the relative strengths
with which they bind to the negatively charged sites in the resin beads.
 59

Other décalcification processes. Several modifications and

alternatives to the conventional décalcification process described above
have been developed.
A) The Gryllus Process
The Gryllus process, developed by Mrs. Eva Gryllus in Hungary, is one
of the best known (ref. 46). It utilizes the relative affinities of cation
exchange resins for monovalent and divalent ions at different concentrations
(see above). With second carbonatation juice the décalcification resin
preferentially takes up calcium ions from juice rather than sodium or
potassium ions. This situation is reversed when softened thick juice is
passed through the resin bed, so that the calcium ions on the resin tend to
exchange back into the juice to be replaced by sodium and potassium ions.
Thus the calcium ions effectively by-pass the evaporators (Figure 4).

Output concentration (meq/100S)

35 J

30 J

0 1 2 3 4 5 15 16 17 18 19 20 mean
input
Time (hours)
Fig. 3. Typical exhaustion cycle of a décalcification column. Output
cation concentration is meq/100g apparent sucrose.
60

TABLE 1
Cation absorption during exhaustion.

Amount absorbed /keq/ m 3 resin

Cation First 10Z of cycle Complete cycle

Potassium .69 .55

Ammonium .06 .09
Calcium .03 .69

Exhaustion Regeneration

Second carb. Juice Soft thick juice

JL or Green Syrup

— ii
Macroporous strong acid ||
cation resin jj
Na-^/K-*- form jj

II

II
Softened second carb. juice Hard thick juice or green syrup
to evaporators to pans

Fig. 4. Simple schematic of Gryllus décalcification process.

The process eliminates the cost of salt régénérant, and the need to
treat spent régénérant effluent, compared to conventional décalcification.
It is also claimed to produce less molasses and more white sugar than
conventional décalcification. However, some advocates (refs. 47, 48) of
this process have tended to compare it with a theoretical décalcification
process in which only calcium/sodium exchange occurs, ignoring other
exchange reactions, and they have thereby distorted the relative merits of
the two processes. When evaluating the process, it is necessary to take
into account all the ion exchange reactions taking place, described above
 61

before estimating the relative effects on juice non-sugar composition and

hence on molasses formation.
This process is in use in several countries including Hungary, Chile
and Lebanon (ref. 49).
There have been some suggestions that putting the calcium ions back
into the thick juice could cause scale formation on the vacuum pans and
hence in the white sugar produced (ref. 50). To avoid this, a later version
of the process regenerates the column with a factory syrup from a stage
after the crystallization of the white sugar (ref. 51). This variation of
the Gryllus process is used in France, Morocco and Spain.
It is necessary to use a macroporous resin for the Gryllus process
because the changes in juice concentration impose a severe physical strain
on the resin beads through osmotic shock, which gel resins are unable to
withstand.
B) N.R.S. Process
A more recent alternative to conventional décalcification is the N.R.S.
process ("New Regeneration System") (refs. 52, 53) developed by the Imacti
Ion Exchange Company, now a subsidiary of Rohm and Haas (Figure 5). This
has been installed in several factories in Western Europe in the last few
years, sometimes by conversion of conventional décalcification plants. Once
again the new process avoids the effluent loadings created by conventional
brine regeneration. For the N.R.S. process, instead of the removed calcium
being returned to juice after evaporation, it is recycled to carbonatation
for precipitation.
If a décalcification column were to be regenerated with a solution of
sodium hydroxide instead of sodium chloride, the calcium removed from the
resin would precipitate as calcium hydroxide. However, in the presence of
sucrose and under certain pH and temperature conditions this displaced
calcium remains in solution as calcium saccharate.
62

Exhaustion Regeneration

Second carb. juice Soft second carb. juice

|| + NaOH
II <50
s!/ °c

Strong acid cation

resin Na"*" form

II II
NI/
Soft second carb. juice Juice and calcium
to evaporators saccharate to carbonatation

Fig. 5. N.R.S. décalcification.

Therefore, in the N.R.S. process the resin is regenerated with

decalcified thin juice to which sodium hydroxide has been added. The
calcium displaced from the resin reacts with sucrose in the juice to give
soluble calcium saccharate. The temperature of the juice must not be
greater than 50°C, otherwise the calcium saccharate will not form. The
spent régénérant, containing sodium hydroxide and calcium saccharate, is
recycled to the carbonatation purification stage, where carbon dioxide
decomposes the calcium saccharate complex forming sucrose and calcium
carbonate precipitate. Hence, the sucrose lost in the régénérant is
recovered at carbonatation.
Sodium hydroxide is more expensive than sodium chloride, but it is
reported that less of the former is required (ref. 53). As with
conventional décalcification the sodium ions added into the juice give rise
to increased molasses formation at the expense of white sugar production.
The relative merits of these various ion exchange processes for
décalcification depend on several factors, including the cost of régénérant,
effluent treatment, any juice dilution occurring during the process, and the
effect on non-sugars composition and hence on molasses formation. What is
cost-effective in one country may not be the best option in another.
 63

C) Weakly Acidic Cation Resin Process

Recently a process using hydrogen form weakly acidic cation exchange
resin to soften thin juice has been proposed (refs. 54, 55). The hot juice
is passed through the weakly acidic cation exchange resin (at high flow
rates to minimize inversion) and immediately made alkaline by addition of
active magnesium oxide. Hence the calcium ions and also some sodium and
potassium ions, are replaced by the much less melassigenic magnesium ions.
The high affinity of weakly acidic resins for calcium ions and their high
operating capacities allow the size of the plant to be appreciably smaller
than that for conventional décalcification. However, problems have been
experienced in scaling up the process, largely caused by the high flow rates
necessary for this process (ref. 55).

Decolorization
Sugar colour. Juice decolorization is not required under the range of
conditions normally occurring in beet sugar factories. In this respect the
beet sugar industry differs from the cane sugar industry, where
decolorization by ion exchange resins or carbonaceous materials has been a
standard procedure. Indeed some cane sugar refiners will refine beet raw
sugars in order to allow a maintenance period for their decolorization
plant.
Beet juice colour bodies fall into three main categories (refs. 56,
57):
i) melanoidins produced by the Maillard reaction of sugars with amino
acids;
ii) caramels formed by the degradation of sugar;
iii) melanins formed by enzymic oxidation of phenolic compounds.
The types of colour bodies in juice and their molecular weights change
through the process from raw juice to the final crystalline white sugar
(refs. 58, 59).
Studies by British Sugar have indicated that, for the normal ranges of
crystal sizes, white sugar colour consists of two components which may be
differentiated on the basis of molecular weight. These are internal colour
containing material of predominantly high molecular weight incorporated
within the crystal, and external colour, of lower average molecular weight,
6^

on the surface of the crystal resulting from a residual layer of mother

liquor (refs. 58, 59).
Removal of colour bodies from juice will improve white sugar quality
(by a reduction in white sugar colour) or have energy saving benefits from a
reduction in the amount of washing in the centrifuges.
Many of the colour bodies in beet juices are weakly anionic or
amphoteric (ref. 57), and hence can be removed by strongly basic anion
exchange resins. It has also been suggested that some colour bodies can be
attracted to the aromatic ring of the resin matrix (ref. 60). Thus the
mechanism of decolorizing is quite complex and much of the available
information is empirical.
Anion exchange resins in the chloride form are generally used for
decolorization in the sugar industry. The resin is regenerated with sodium
chloride solution, often adjusted to a slightly alkaline pH. Both styrenic
and, more recently, acrylic resins have been used. It has been reported
that acrylic resins are the more suitable for treating highly coloured
liquors, because of their greater resistance to organic fouling, and hence
their longer working life (refs. 10, 11). Styrenic resins are better for
treating lower coloured liquors (ref. 61). However, there has been a recent
report (ref. 62) that the longer working life does not always make the more
expensive acrylic resins more cost-effective overall.
Macroporous resins are often used, rather than gel resins, particularly
when decolorizing juices and syrups of high total solids, because of their
physical strength and resistance to osmotic shock.

British Sugar Studies

Laboratory studies. British Sugar has studied resin decolorization of
beet juices both in the laboratory and on a factory scale. Recent
laboratory work concentrated on the relative merits of treating different
juices and the accompanying chemical changes in juice non-sugar composition.
A styrene macroporous resin was used in most of the experiments.
The decolorization performance of the resin was strongly affected by
the total solids concentration (°Brix) of the juices (Figure 6). When 40
bed volumes of 66° Brix thick juice were treated, the bulked product juice
had a colour 65Z that of the feed juice. When the same amount of solids was
treated as a 15° Brix second carbonatation juice or diluted thick juice
 65

under commensurate conditions, decolorization was considerably improved, the

product juice having a colour only 352 that of the feed juice. We
hypothesize that the much higher viscosity of thick juice probably hinders
the diffusion of the colour bodies into the resin pores, thus impairing the
performance of the resin.
As well as removing colour the resin takes part in ion exchange
reactions with juice anions. The concentrations of readily measurable juice
anions were monitored during experiments on thick juice decolorizing. The
overall changes in some of these anions for the total amount of juice
treated are shown in Table 2 and Figure 7.

Diluted Thick Juice"

(15· Bx)

— i —
100
Juice solids treated (g/cn»3 r e si n )

Figure 6. Decolorization effect of brix.

 66

Anion
Concentration

.. Original
Concentration

/
/
/ / X
/
/

Bed Volumes Treated

Fig. 7. Decolorization changes in anion concentrations.

TABLE 2
Overall changes in juice anion concentrations.

Anion Change vs Untreated Juice

Chloride +81Z
Sulphate 0
Malate 0
Sulphite -16Z
Nitrate -53Z
 67

Most of the ion exchange was completed during the first 10 bed volumes
of juice treated. During this period anions (including sulphate, nitrate,
malate and sulphite) were taken up by the resin on its ion exchange sites,
and chloride ions were displaced from the resin into the juice. In the
remainder of the juice run, some of the anions on the resin (e.g. sulphate,
malate) were displaced, presumably by other juice anions with a greater
affinity for the resin, so that there was no overall uptake of the sulphate
or malate ions on the resin when considering the cycle as a whole.
Nitrate is one of the smaller juice anions and it may therefore be able
to penetrate further into the resin beads. This could explain why it is
taken up by the resin for most of the cycle length, so that its overall
concentration is halved.
The sulphite concentration never recovers to its initial level, and
this can possibly be ascribed to chemical reactions such as oxidation or
combination with colour bodies during passage through the resin bed. This
loss of sulphite may require an increase in the amount of sulphur dioxide
used in the sulphitation stage of the process, in order to prevent colour
formation in the sugar end of the factory process.
The appreciable rise in chloride concentration increases the overall
melassigenicity of the juice non-sugars and may adversely affect the target
molasses purity. The increase in melassigenicity can be seen by use of the
Polish test (refs. 63, 64) in comparing samples of molasses from two British
Sugar factories before and after treatment with a decolorizing resin (see
Table 3). The impact of the replacement of less melassigenic anions by
chloride ions (thought to be one of the most powerful melassigens (ref. 65))
can be seen in the changes in the main parameters obtained from the Polish
Test. These are the molasses formation constant (a), the free water
parameter (b) and the target molasses purity (T.M.P.). The lower the T.M.P.
the greater the amount of sucrose that can be crystallized out in the
factory.
68

TABLE 3
Decolorization and Melassigenicity.

Target molasses purity

Molasses (a) (b) Factory NS/W =

Cantlev

Untreated .23 .87 54.7 37.2

Decolorized .40 .33 56.0 50.2

Bury.

Untreated .17 .93 50.3 30.5

Decolorized .26 .71 53.1 40.1

The increase in (a) after decolorization is a strong indication of

higher melassigenicity, as is the increase in T.M.P. When calculated under
the conditions prevailing at each of the factories the increase in T.M.P. is
small but significant. If the T.M.P. calculations are extrapolated to
infite non-sugar to water ratio where the T.M.P. becomes dependent on the
non-sugars (the influence of water being minimal), the data clearly show the
effect of the ion exchange reactions occurring during the decolorization
process on juice melassigenicity. The increase in melassigenicity means
that some sucrose is lost to molasses as a result of the decolorization
process.
A small increase in juice purity might be anticipated purely on the
basis of the chloride ions having a lower molecular weight than the ions
they replace in the juice. For greater precision, the change in juice
purity of the treated juice was measured indirectly by gravimetric analysis
of the spent régénérant. An increase of about 0.5 purity units was measured
over the first 5Z of the decolorization cycle for second carbonatation
juice. However, over the full cycle length the purity increase was less
than 0.1 units (within experimental error). Similar results were obtained
with thick juice. It seems likely that any increase in sugar recovery
because of this very small purity increase would be nullified by the
increase in non-sugar melassigenicity.
The laboratory results can be summarized as follows:
 69

1) juice concentration has a considerable effect on the efficiency of

resin decolorization. Dilute juices (e.g. second carbonatation juice) are
decolorized with much greater efficiency than concentrated juices (e.g.
thick juice).
2) the ion exchange reactions taking place during decolorization result
in a large increase in juice chloride concentration, together with a
significant decrease in sulphite concentration.
3) the decolorization process increases the juice melassigenicity.
4) there is no significant purity increase during decolorization.
This work will be describe4 in greater detail in a paper to be
published in 1988.
Factory studies. British Sugar has operated factory-scale decolorizing
plants for treatment of thick juice, the plants being conversions of
décalcification plants (described above). The first conversion (York
factory, 1976) was temporary--the plant being used to decolorize a stored
juice during an off-season refining run. The plant reverted to
décalcification mode for the next beet decolorization from décalcification
and vice versa was found to be very practical and was repeated in subsequent
years.
Conversion of a décalcification plant to decolorization involves a
change of resin, regulation of the temperatures of syrup, régénérant and
water to below 75°C (to avoid resin damage), and the handling of sweet
waters from the sweeten-on and sweeten-off stages. The sodium chloride
regeneration system is unchanged. A simple schematic of the decolorization
process is shown in Figure 8. A second conversion (Bury factory, 1985), has
been used to obtain factory development data on decolorization of beet
juices and it has confirmed the results of our laboratory studies.
The degree of decolorization in the factory was very similar to that
obtained in the laboratory. There was no detectable change in the purity of
the treated juice, and the concentration profiles of the juice anions showed
no significant differences from the laboratory results. There was a very
good correlation between relatively small changes in the juice Brix, and the
decolorizing performance of the resin. This can be seen in Figure 9 where
the decolorization curves obtained in the factory and the laboratory are
compared. The deviations observed in the factory curve correlate exactly
with small variations in the feed juice concentration, the performance of
70

the resin deteriorating as the concentration increased and improving as it

decreased.

Exhaustion Regeneration

Thick Juice 10Z NaCl

75°C || 3 B.V./hr. 75°C || 3 B.V./hr.

II
V
i

I
II
II
|| Macroporous strong
I base anion resin
|| Cl- form
II
« i
II
II
II
Mk Effluent
Decolorized thick juice
to pans

Fig. 8. Decolorization at British Sugar, Bury Factory.

Laboratory sugar boilings on factory treated juice showed that white sugar
colour decreased in proportion to the degree of decolorization of the thick
juice. Benefits from juice decolorization are likely to be in terms of an
improvement in white sugar quality rather than any clear cut cost savings.
British Sugar Research Laboratories are currently looking further at targeted and
specialized decolorization as one potential means of improving white sugar
quality.
 71

Bed Volumes Treated

Fig. 9. Comparison of factory and laboratory decolorization.

Other Plants. Very little decolorization of beet sugar thick juice has been
reported (refs. 66, 67). Almost all beet juice decolorization is performed on
dissolved raw or remelt sugars and so is similar to decolorization in cane sugar
refineries. Examples in beet sugar refining include the refineries at Arlov
(SSA, Sweden) (ref. 11), Eisdorf (Pfeifer and Langen, Germany) (ref. 68),
Tirlemont (Raffinerie Tirlemontoise, Belgium) (ref. 69) and Porkkala (Finn Sugar,
Finland) (ref. 70). Raw/remelt sugar decolorization is also carried out in Italy
(ref. 71), U.S.S.R. (ref. 72), Poland and Iran (ref. 73).
Beet juices are generally decolorized at 65 - 67° Brix and 75 - 80°C. While
this may be the most convenient way of treating raw and remelt sugars and high
concentration factory syrups, British Sugar Research Laboratories' findings
suggest that these are not the optimum conditions for decolorization. Much
better decolorization is achieved with lower concentration juices, e.g. 15° Brix
second carbonatation juice.
There is a particularly interesting process at Tirlemont (refs. 69, 74),
where a new decolorizing plant was installed in 1982 to facilitate production of
a special, high quality, white sugar (less than 4 E.E.C, points). The plant has
72

three anion exchange columns operating in parallel, with two on stream and one
regenerating at any given time. The columns are of the double deck type,
containing two 6 m 3 resin beds one above the other separated by a screen, to give
a two-stage decolorization process. The plant uses the floating bed technique
developed by Bayer with the syrup passed through in an upward flow (ref. 74).
The resin floats in this syrup, and forms packed beds at the tops of the columns.
Régénérant and water are passed through in a downward flow, and the resin sinks
to give packed beds on the baseplates. This countercurrent system gives good
efficient regeneration.
The plant uses a styrenic macroporous decolorizing resin. The resin in the
upper (polishing) bed in each column is expected to last longer in service than
resin in the lower bed, because the upper bed treats syrup that has already been
partially decolorized by the lower bed, and it is also the first bed that the
régénérant passes through. When the resin from the lower bed is eventually
discarded, it will be replaced by the resin from the upper bed, which in turn
will be replaced by new resin. In this way the second (polishing) stage in the
decolorizing treatment, in the upper bed, will always be done by resin in
relatively good condition.
Most other refineries use two columns in series for juice decolorization
(refs. 68, 70). The first column may contain acrylic resin for gross
decolorization followed by a styrenic resin for polishing. However, a recent
factory trial at the Arlov refinery in Sweden, where the performances of styrenic
and acrylic decolorizing resins were directly compared (ref. 62), indicated that
a purely styrenic two stage decolorization system may perform better than the
acrylic/styrene system. It was reported that although the styrene resin
decolorization capacity deteriorated more quickly than that of the acrylic resin,
the former removed approximately 30Z more colour from the juice over the greater
part of the normal working lives of these resins.

Powdered Resins
All the processes described so far use resin in columns, in the conventional
way. However, there is an alternative means of decolorizing. The resin can be
added into the liquor to be treated, then filtered off and discarded, in the same
way that a powdered carbon can be used. Because the resin is used only once, the
technique is not cost-effective using normal bead-form resins. However, if the
resin is in the form of a powder then the exchange process is very efficient
 73

compared to a bead resin, since all the ion exchange sites are close to the
surface and therefore readily accessible. In tests on liquid sugars equivalent
decolorization was found to require about one hundred times more bead form resin
(by weight) than powdered resins (ref. 75).
Ecosorb precoat formulations of powdered resins produced by the Graver Co.
in the U.S.A. have been used in several cane and beet refineries in North
America, for the polishing stage of liquid sugar decolorizing (ref. 76).
Recently a powdered cation resin in the sodium form has also been
introduced, intended for juice décalcification (ref. 76).
British Sugar Research Laboratories have evaluated the use of powdered anion
exchange resins for decolorization of liquid sugar, in order to produce a special
high quality liquid sugar. Following development work, factory trials showed
that addition of a particular powdered resin to a 15 tonne mix of liquid sugar
(typical colour 20 ICUMSA units) reduced its colour by about 4 units per kilogram
of resin added (ref. 75).
The use of powdered resin avoids the capital cost of an ion exchange plant
that would only be used occasionally.

Miscellaneous Processes
Inversion. In acidic solutions, the disaccharide sucrose is hydrolyzed to a
virtually equimolar mixture of glucose and fructose. This process is commonly
known as "inversion" and the glucose/fructose mixture as "invert syrup."
There is a significant market for invert syrups made from sucrose (ref. 77).
Production methods include inversion by acid addition (ref. 78), by resin (ref.
77), and by invertase enzymes (ref. 79). Reported advantages of using cation
exchange resins for inversion are the ease of separation of the resin catalyst
from the sucrose (ref. 80), low colour formation (ref. 77), and no impurities
introduced into the product (ref. 77). The disadvantages include relatively high
capital costs, and the difficulty of obtaining complete inversion with resins.
The ratio of invert sugars to sucrose in the product can be varied by changing
the flow rate, or the temperature of the resin columns. Generally a solution of
granulated white sugar (or liquid sugar) is the feedstock.
Strongly acidic cation exchange resins in the hydrogen form catalyze the
inversion of sucrose by means of the hydrogen ions associated with the resin.
This catalysis has been extensively studied by several workers and is thought to
be basically similar to normal acid inversion in being a pseudo first order
7^

reaction (refs. 80-83). However, other workers have observed deviations from
first order kinetics (refs. 83-85), indicating that this is too simple a
description of the catalysis. These deviations have been at least partially
ascribed to the concomitant degradation of the products fructose and glucose by
both heterogeneous and homogeneous catalysis (ref. 83). The rate of inversion
increases rapidly with temperature, the rate constant tripling between 40°C and
70°C (ref. 80). Other factors that increase the rate of inversion are long
contact times (i.e. low flow rates), low solution pH, and highly porous resins.
Invert/sucrose mixtures are produced on an industrial scale from a variety
of grades of granulated and liquid sugars. A typical example is at the Franken
Company's Ochsenfurt beet sugar factory in West Germany (ref. 77). When a low
grade sugar feedstock is used it is decolorized and demineralized before
inversion. Typically a 50-60° Brix low-grade sucrose solution is decolorized by
passing it through one or two beds of strongly basic anion exchange resin in the
chloride form at high temperature. For inversion, the juice temperatures is
adjusted to 30-50°C (depending on the degree of inversion required) and then
passed through a number of hydrogen-form strongly acidic cation exchange resin
beds in series. The inverted juice is then neutralized by passage through a bed
of anion exchange resin in the hydroxide form before evaporation to give the
final product syrup.
pH Control. Careful control of juice pH in beet factories is necessary to
ensure efficient operation and good sugar quality. In 1970 British Sugar
Research Laboratories investigated increases in thick juice pH occurring in the
evaporators at Brigg and Spalding factories (ref. 86). These pH increases were
due to an increase in the amount of acidic compounds in the beet juice that were
eliminated during the process. The cause was thought to be the local growing
conditions during the 1969/70 campaign.
A technique by which thick juice pH could be controlled was developed on a
laboratory scale (ref. 86). This involved the controlled addition to and removal
from second carbonatation juice of a hydrogen-form strongly acidic cation
exchange resin. The cation exchange reactions on the resin released hydrogen
ions into the juice, thus preventing pH increases later on in the process. The
process is unique in that the drop in juice pH was exactly equivalent to that
which would have been produced if the acid used in regeneration had been added to
the juice. In effect the efficiency in the use of acid régénérant was 100Z
 75

In partial demineralization, strongly basic anion exchange resins are

sometimes used to adjust juice pH to a desired value before evaporation (ref.
28). This stabilizes the juice in the evaporators.
Water treatment. All beet sugar factories require purified water for such
purposes as boiler feed water. Since the introduction of high pressure boilers,
purification techniques of increasing sophistication have been needed. The sugar
industry is no different from any other industry requiring purified water, ion-
exchange plants of standard design being used to provide the necessary
demineralized water (ref. 87). Apart from the normal contaminants in water
supplies (humic acids, minerals, etc) contamination with compounds such as
natural beet oils, fatty acids and sucrose can occur in sugar factories.

SUGAR RECOVERY WITH RESINS

Quentin Process
Background. For several decades alkali metal cations were suspected of
being highly melassigenic (i.e. they hold sugar in the molasses and prevent it
being recovered as crystalline white sugar). During the mid-1950s Quentin (refs.
88, 89) and Moebes (refs. 90, 91) independently confirmed this and quantified the
melassigenic effect of the alkali and alkaline earth ions. They showed that the
effect of the ions decreased in the order K > Na > Ca > Mg, potassium and sodium
ions being very much more melassigenic than magnesium ions.
In these laboratory studies, they used ion exchange to make syrups where the
majority of cations had been replaced by the specific ion under examination. It
occurred to them that the same procedure might be applied on a factory scale, and
both workers devised ion exchange processes to substitute magnesium or calcium
ions for potassium and sodium ions in factory syrups or juices with the aim of
reducing molasses purity. In the Quentin process there was direct ion exchange
of potassium and sodium ions in low green syrup for magnesium. The initial
Moebes process (refs. 90, 92) involved exchange of the potassium and sodium ions
in second carbonatation juice for ammonium ions. The juice was subsequently
limed, gassed and filtered, thus introducing calcium ions and raising the pH to
about 10.5, before conversion to thin juice and evaporation in the usual way.
After the initial development work on both processes, the greater simplicity of
the Quentin process has caused it to be considerably more favoured (further
developments of the Moebes and other ammonia processes are mentioned below).
76

The Quentin process was successfully tested on a pilot plant in Germany in

the 1955/56 campaign (ref. 89), and then put into full-scale operation. It was
patented in Germany in 1960 (ref. 93). Development and refinement was swift and
within twenty years over 50 European and American factories were using the
process.
Chemistry of Process. The Quentin process consists essentially of passage
of low green syrup through a bed of strongly acidic cation exchange resin in the
magnesium form to exchange about 502 of the potassium and sodium ions for
magnesium ions.
The treated juice has a lower potassium : sodium ratio than the feed syrup
(refs. 30, 94) indicating that a greater proportion of the potassium ions in the
juice exchange for magnesium than is the case for sodium. These results are
explicable in terms of the resin's greater affinity for potassium compared to
sodium.
Macroporous resin is used, because the high solids concentration of the
syrup puts a severe physical strain on the resin through osmotic shock.
The low green syrup treated is the feed to the final crystallization stage
in the beet sugar factory, and the additional sugar recovered is obtained at this
crystallization. The process recovers additional sugar in at least two ways:
(i) Reduction in weight of non-sugars: since magnesium ions have an
equivalent weight of 12.15 compared with 39.1 and 23 for potassium and sodium
ions respectively, the weight of non-sugars is decreased by the exchange and
hance the weight of molasses produced should be correspondingly reduced. If the
molasses purity is unchanged by the process, the expected sugar recovery for 50Z
exchange of potassium and sodium for magnesium ions would be about 0.14Z on beet.
(ii) Reduction in cation melassigenesis: magnesium ions are less
melassigenic than potassium and sodium ions, and this is usually assumed to be
due to their greater hydration compared with potassium and sodium ions (refs. 91,
94). This effectively reduces the amount of water available for solution of
sucrose in magnesium molasses and hence favours increased crystallization of
sugar. Thus molasses produced with magnesium exchange would be expected to be
more completely exhausted than without exchange, and thus should be of lower
purity.
As a further reason for reduced sugar in magnesium molasses it has been
suggested (ref. 95) that crystallization of sugar occurs more quickly than with
 77

normal molasses and hence that a greater proportion of sugar than usual is
crystallized in the pans.
The total sugar recovered by these mechanisms is 0.3 to 0.5Z sugar on beet
for 40-502 exchange of sodium and potassium for magnesium (refs. 94, 96-100).
Very similar results have been obtained from British Sugar's Quentin plant at
Brigg factory (ref. 30).
British Sugar Quentin plant. The economic viability of the process depends
mainly upon the relative prices of white sugar, molasses and magnesium chloride
régénérant, as the operating and capital costs are low compared with those for
other methods of sugar recovery, such as the Steffen process. As the process in
effect recovers white sugar at the expense of loss of molasses then, in simple
terms, there has to be a sufficiently large differential between white sugar
revenue gained and molasses revenue lost to make a profit after paying capital
and régénérant costs. Owing to changes in world market conditions, this
differential greatly increased in 1974, and as a result British Sugar Research
Laboratories investigated the possibility of installing an experimental Quentin
plant in a British Sugar factory for operation in the 1975/76 compaign (ref. 30).
A Quentin plant (Figure 10) is broadly similar to a décalcification plant in
that both are for batch ion-exchange processes using a single resin, and
investigation showed that it would be feasible and relatively inexpensive to
adapt one of our décalcification plants as a Quentin plant. The resin
requirement for a Quentin plant is often stated as 6m3 per 1,000 tonnes of beet
sliced per day (refs. 94, 99, 101), and this was confirmed on the Brigg plant
(ref. 30). This is greater than is normally required for décalcification, but
our Brigg factory had a modern décalcification plant of sufficient size for
conversion. This was carried out in 1975 (ref. 30), and the plant has operated
successfully ever since. The original ion exchange columns were utilized, as
were many of the tanks and other ancillary items of plant. Additional plant was
required for handling sweet water arising from unavoidable dilution at the start
and end of each juice cycle.
78

Exhaustion Reeeneration

Low green syrup 70°Brix MgCl* or MgSO* (kieserite)

II II
90° C || 2 BV/hr. IX mg || 3 BV/hr.

II

Macroporous strong acid

cation resin Mg2"*" form

Nik
Treated syrup to flash evaporator
and crystallizer Effluent

Fig. 10. Quentin process at British Sugar, Brigg Factory.

Subsequent changes in the sugar price, and the current E.E.C, sugar
quotas, have decreased the viability of installing further Quentin plants at
present, but experience shows this process to be one of the best means of
increasing sugar recovery.
Alternative régénérants. Most of the world's magnesium chloride is
produced as a by-product of the potash industry and large amounts are
available from the Stassfurt potash deposits in Germany (ref. 29). It is
imported into the U.K. as a solution containing only 8.5Z w/w of magnesium
and thus most of the weight transported is water. Transport costs to the
U.K. are therefore a significant proportion of the cost of this régénérant.
In 1980, the régénérant cost comprised nearly 40Z of the total running costs
of our Brigg Quentin plant—a level where the profitability of the process
in the United Kingdom was principally determined by this one factor.
Furthermore, the cost of magnesium chloride had doubled from 1975 to 1978,
considerably reducing profitability.
 79

Alternative sources of magnesium chloride, and of other soluble

magnesium compounds were investigated by British Sugar Research Laboratories
(ref. 30). The only alternative and sufficiently cheap bulk source of
soluble magnesium available in the U.K. was found to be kieserite, an
agricultural grade magnesium sulphate monohydrate.
Kieserite is also found mainly in the same Stassfurt deposits in
massive, compact or granular beds up to 12 ft thick with layers alternating
with potassium and sodium chlorides. As sold, the higher grades of
kieserite are crystalline solids (crude MgSO« . H 2 0) containing about 13-
162 magnesium and 6-92 insoluble matter. The quantity of sodium and
potassium salts depends upon the source. It is extensively used as a
fertilizer in the U.K. and several fertilizer manufacturers import the
material.
Kieserite is slow to wet and dissolve even in warm water, and it
easiily solidifies to a concrete-like mass when wetted or partially
extracted with water. These factors precluded the use of a standard design
saturator (as used for dissolving salt in the original décalcification
plant) for preparation of kieserite solution. However, British Sugar
designed, perfected and patented (ref. 101) a technique to dissolve all the
extractable magnesium sulphate and produce a clear and colourless solution
with a residue having little tendency to solidify. Solutions containing up
to 52 Mg w/v could be produced by these means. Laboratory studies and
factory-scale experiments showed that equivalent Quentin regeneration to
magnesium chloride was obtained with kieserite containing up to 12 K and
12 Na on kieserite. As would be expected, at higher levels of sodium and
potassium the performance deteriorates because of the effect of these ions
on the regeneration equilibrium.
Since 1980 the Brigg Quentin plant has operated successfully with
kieserite régénérant, at a substantial cost saving.
The problem of high régénérant costs was not unique to the United
Kingdom, and other workers have explored other possible alternatives (ref.
103). Regeneration with calcium salts would give substantially reduced
regeneration costs but also would probably reduce the amount of sugar
recovered. Quentin molasses (high in magnesium content) has been suggested
as a possible régénérant, in a variation of the Quentin process analogous to
Gryllus décalcification (ref. 103).
80

Demineralization
Theory of demineralization. The terms demineralization or deionization
are used to describe ion exchange processes by which ionic mineral purities
are removed from water. Similar techniques can be used in the beet sugar
industry to remove juice non-sugars (refs. 6, 77). In partial
demineralization, a proportion of the non-sugars is removed to increase
juice purity and hence extract additional sugar in the factory process. In
total demineralization, all non-sugars are removed from juice to give a
saleable liquid sugar product directly. In both cases the basic process
involves passing juice through a cation exchange resin in hydrogen form and
an anion exchange resin in hydroxide form. The hydroxide ions released by
removal of juice anions onto the anion exchange resin neutralize the
hydrogen ions released by removal of juice cations onto the cation exchange
resin, so the juice non-sugars are effectively replaced with water.
Although juice contains many non-isolated or weakly ionized non-sugars,
as well as simple cations and anions, all can be removed from the juice by a
combination of cation and anion exchange resins. For total demineralization
it is essential to include a strongly acidic cation exchange resin, because
this is the only type of resin which will remove betaine, a nitrogeneous
non-sugar present in significant amounts in beet juices (10-15Z of juice
non-sugars) (ref. 104). However, this type of resin causes inversion of
sucrose. For minimum inversion the juice is normally treated at a solids
concentration of 15-30° Brix, and requires stringent precautions against
mesophilic bacterial activity in the plant.
Complete demineralization cannot be achieved by only one column each of
cation and anion exchange resin, because the ion exchange reactions are
reversible. Further pairs of cation and anion exchange columns are
required, the number needed to produce a high purity product depending on
the purity of the feed juice. A similar effect can be obtained by
intimately mixing cation and anion exchange resins in a single mixed bed.
Hydrogen ions released by ion exchange on one bead are immediately
neutralized by hydroxide ions released from a neighboring bead. This
displaces the equilibrium reactions towards complete demineralization and
gives the effect of an almost infinite number of alternate cation and anion
exchange columns.
 81

In the laboratory, thick juice can be completely demineralized to give

a pure colourless sucrose solution (plus some invert sugars) by passing it
down a single mixed bed of strongly acidic cation exchange resin and weakly
basic anion exchange resin (ref. 105). At a relatively slow flow rate of
about 0.3 bed volume/hour, 1.4 bed volumes of a water-white 99.95Z purity
(expressed as X sucrose plus invert on total solids) juice was produced from
undiluted 60° Brix thick juice, before colour and betaine started to leak
through the resin bed.
However, the advantage of mixed bed demineralization is offset by the
practical difficulties of operating such a system. The resins must be
completely separated from each other prior to regeneration. This is
normally achieved by careful backwashing (anion exchange resins are
generally less dense than cation exchange resins), and regeneration is
carried out with balanced flows of régénérant and water to prevent each
régénérant contacting the wrong resin. Juice demineralization plants use
alternate cation and anion exchange columns, with a final mixed bed column
for polishing where a high quality product is required.
It is common to follow strongly acidic cation exchange resin columns by
columns of weakly basic anion exchange resin. The high affinity of weakly
basic resins for hydroxide ions (much higher than that of strongly basic
anion exchange resins) means that less régénérant is required to restore the
resin to the hydroxide form. They can also be regenerated by ammonia
solution rather than the much more expensive sodium hydroxide solution
necessary for strongly basic resins. This appreciably reduces regeneration
costs.
Weak/strong resin combinations (either weakly acidic/strongly basic or
strongly acidic/weakly basic) require the juice to be passed through the
strongly acidic or strongly basic resin first. Weakly ionized resins need
the pH change caused by the ion exchange reactions on the strongly ionized
resins, producing an acidified or an alkaline juice, in order to function
effectively. The weakly acidic/strongly basic resin combination is more
expensive to regenerate than the strongly acidic/weakly basic combination
and the former could not be used for total demineralization as it would not
remove betaine.
Weak/weak resin combinations only work in mixed beds, where the
intimate contact of anion and cation exchange resins displaces the ion
82

exchange equilibrium towards complete demineralization, and are rarely used.

They would also not remove betaine.
An alternative approach to demineralization was developed by Moebes
(refs. 106, 107) and by Vajna (refs. 108, 109). Instead of using cation and
anion exchange resins in the hydrogen and hydroxide forms respectively,
their processes used ammonium form cation exchange resins and either
hydroxide or carbonate/bicarbonate form anion exchange resins. Thus the
process replaced juice cations and anions with ammonium hydroxide or
carbonate. These were driven off in the evaporators and recovered by
condensation, so that the treated juice was effectively demineralized. This
process has the advantage of eliminating the problem of inversion that
occurs with hydrogen form cation resins. It has been installed in a few
factories, notably at Enns in Austria (refs. 110, 111), but in general has
not been particularly successful. A recent variation of this process, which
may show more promise, has been proposed by Schoenrock (refs. 54, 55).
Factory processes. Many schemes for the demineralization of a
wide variety of beet juice syrups and dissolved sugars have been prepared
(refs. 112-114), but only comparatively few have been put into factory
operation (refs. 115-118). Demineralization is an expensive process, its
economic viability depending on a number of factors, including the relative
prices of the final product, the feedstock and the molasses no longer
produced; the possible utilization of eliminated non-sugars and spent
régénérants as
saleable by-products ; the efficiency of the plant and the number of days per
year it is operational.
The French beet sugar factory at Vauciennes has a total
demineralization plant built by the Applexion Co. (ref. 118) (see Figure
11). The feedstock is a stored thick juice so the plant can be run
throughout the year. The stored thick juice is diluted to 35° Brix with
sweet water from the ion exchange columns, and cooled to 10°C to minimize
inversion. The first stage of the process consists of three parallel
streams of two columns each, containing a strongly acidic cation exchange
resin (in hydrogen form) followed by a weakly basic anion exchange resin (in
hydroxide form). The second stage consists of two parallel streams of three
columns each. These contain a non-ionic absorbent (for colour, odour and
taste removal), a hydrogen form strongly acidic cation exchange resin and a
 83

hydroxide form strongly basic anion exchange resin. The third stage is a
mixed bed of cation and anion exchange resins. The final product from this
stage, a pure sugar solution containing about 1% invert, is evaporated and
either sold as a liquid sugar or crystallized to give very high quality
white sugar.
The cation exchange resins are regenerated with sulphuric acid, the
weakly basic anion exchange resins with ammonium hydroxide and the strongly
basic anion exchange resins with sodium hydroxide. All the spent
régénérants are mixed together, concentrated and crystallized to give two
by-products. The crystalline material, consisting mainly of ammonium,
sodium and potassium sulphates, is sold as a fertilizer and the mother
liquor which is rich in nitrogen compounds and other organic non-sugars, is
sold as an animal feed supplement.

Exhaustion

Strong Weak
Acid Base Strong Strong
Absorbent Acid Base SAC/
Cation Anion
Cation Anion

Regeneration
H-SO. NaOH H2S04/foaOH
4
i _ 4-

Strong Weak Strong Strong

Acid Base Acid Base
Cation Anion Absorbent! Cation Anion

Evaporation/Crystallisation
Mother liquor Solids
Organic Nitrogen Compounde NH4,Na,K/S04

Fig. 11. Applexion demineralization at Vauciennes.

m

The French factory at Nassandres has a partial demineralization plant,

also built by Applexion. This resembles the first stage of the Vauciennes
plant, with a strongly acidic cation exchanger (sulfuric acid régénérant)
then weakly basic anion exchanger (ammonia régénérant). These are followed
by treatment on a strongly basic anion exchanger (sodium hydroxide
régénérant) to adjust the product pH in order to stabilize the juice. The
plant treats a sugar-end syrup, part of which is stored so that the ion
exchange process can be run throughout the year. Essentially, the purpose
of the demineralization plant is to remove some of the juice non-sugars and
hence recover additional sugar. The spent régénérants are reprocessed in a
similar way to those from the Vauciennes plant, to give saleable by­
products.
Partial demineralization is widely used in Southern Europe, where poor
beet quality gives low thin juice purities (e.g. as low as 87-89Z in Italy
(ref. 27) and 82-842 in Sardinia (ref. 28)). The thin juice is usually
treated with a three column system similar to the Nassandres plant. A
strongly acidic cation exchange resin and weakly basic anion exchange resin
remove non-sugars, to give say a 922 purity product juice, and thereby
considerably increase sugar extraction. Finally, a strongly basic anion
resin raises the pH of the treated juice and thus stabilizes it before
evaporation.
In the U.S.A., Bichsel has worked for many years on juice
demineralization. He developed a partial demineralization system at the
Holly Sugar Corporation's Hamilton City plant (ref. 116). This involved
passing a mixture of a sugar end green syrup diluted with thin juice through
a strongly acidic cation exchange resin followed by two columns of weakly
basic anion exchange resins (see Figure 12). The output was sent back to
the feed to the white pans.
The plant was later modified on the pilot scale into a total
demineralization system designed to treat stored thick juice and produce
liquid sugar (ref. 119). This latter process was intended to operate all
year round. A two-stage demineralization process was used, with diluted and
cooled thick juice (30° Brix, 8°C) being passed through the bed of cation
exchange resin and two beds of weakly basic anion exchange resin, as before.
This was followed by two demineralization columns both containing beds of
strongly basic anion exchange resin and strongly acidic cation exchange
 85

resin, in the hydroxide and hydrogen forms respectively. The beds of anion
and cation resin were separated by a screen and regenerated separately.
The weakly basic anion exchange resins were regenerated with ammonia.
The spent régénérant from these columns was passed down the cation exchange
resin column (before their regeneration with sulphuric acid), stripping off
colour bodies, betaine and other nitrogenous organic compounds. This
reconstituted non-sugars solution was then used as an animal feed supplement
by spraying it onto beet pulp. The strongly basic anion resins were
regenerated with sodium hydroxide. The spent régénérant from these columns
could be mixed with the spent sulphuric acid régénérant from the cation
exchange columns to give a by-product rich in ammonium sulphate, which could
be used as a fertilizer (refs. 120, 121).
This regeneration scheme was devised primarily to deal with the
effluent disposal problem, which threatened the viability of the process,
and also to reduce costs. Thus, a potential liability was transformed into
a positive asset. In later work, Bischel introduced a very similar partial
demineralization plant into the American Crystal Moorhead factory (ref.
122).
A novel partial demineralization process has been developed recently by
the French sugar company Generale Sucriere and the resin company Rohm and
Haas (ref. 123). One of the several unusual features is that both resins
used are types that are only weakly ionized. Weakly acidic cation exchange
resin (in hydrogen form) and weakly basic anion exchange resin (in hydroxide
form) are intimately mixed with a batch of thick juice by air agitation.
Individually, these weakly ionized resins would be unable to ion exchange to
any great extent because the chemical equilibrium favors the reverse
reaction. However, removal of the released hydrogen or hydroxide ions by
the other resin alters the equilibrium (as described above) and permits a
substantial demineralization to take place. During the next step,
sweetening off with sweet water from the previous cycle, the cation and
anion exchange resins are separated due to their relative densities compared
to that of the sweet water. The resins are regenerated by the normal
techniques for mixed beds, using sulphuric acid and ammonia, and the spent
régénérants are combined and processed into saleable by-products.
86

Exhaustion

Strong Weak Weak

Acid Base Base
Cation Anion Anion

Regeneration
Animal Feed (R.N.S.)
1 *
\ !
Strong Weak Weak
Acid Base Base
Cation Anion Anion

\' —
· ______ _ f _
fertiliser

Fig. 12. Bichsel partial demineralization; Hamilton City. (- 1st

stage regeneration; 2nd stage regeneration).

Chromatography
The idea of using ion exchange resins to separate sucrose from non-
sugars by chromatography, rather than ion exchange was suggested by Dow
Chemical Company in 1953 (ref. 124). The Chromatographie separation of
sucrose from ionic and other non-sugars on an industrial scale takes place
by two main mechanisms:
Separation by molecular size - the molecular sieve effect. If a
solution containing a mixture of large and small molecules is applied to a
column of an ion exchange resin, those molecules small enough to enter the
bead pores will be separated from the larger molecules. The large molecules
are excluded by their size from the pores and travel down the column through
the voids between the beads. Hence they have a much shorter pathway through
 87

the resin bed than the molecules capable of penetrating the bead pores, and
are therefore eluted from the column first. The resin porosity is chosen to
achieve the separation required.
Ion exclusion - the Donnan membrane effect. Donnan membrane theory
states that ions in solution tend to be repelled from an ion exchange resin
by like ions occupying the resin's ion exchange sites. Hence ionic
compounds will tend to pass through the void volume of a column of resin
rather than through the resin itself, and will therefore have a shorter
pathway through the resin bed than non-ionic compounds which travel through
the pores of the resin beads. If an impure sucrose solution (dilute
molasses for example) is applied to a column of strongly acidic cation resin
in the sodium form and eluted with water, the sodium and potassium ions on
the juice will tend to be excluded from the resin pores. With a resin of
the appropriate porosity the sucrose will penetrate the resin beads and will
therefore be eluted after the ionic compounds. It should be noted that the
Donnan membrane effect does not totally exclude ions from the resin and thus
prevent ion exchange reactions taking place, but merely induces a tendency
for the ionic compounds to pass around the resin beads, rather than through
them.
These two separation mechanisms are the basis of processes for the
Chromatographie desugarization of molasses developed in several countries,
including Finland (ref. 125) (see Chapter 7), Germany (refs. 126, 127) and
Japan (ref. 128).
Ion exclusion processes require feedstocks that are very low in
multivalent ions (e.g. Ca, Mg). These ions are absorbed onto the resin's
ion exchange sites and their presence breaks down the Donnan membrane
effect, thus causing the sucrose/ionic non-sugars separation to deteriorate.
Thus the process is not suitable for molasses from factories operating the
Quentin process.
There is another separation mechanism that is employed in separating
fructose from glucose (ref. 77). An invert syrup is applied to a strongly
acidic cation exchange resin in the calcium form. The fructose forms a
complex with the calcium ions on the resin and hence is delayed with respect
to glucose, so that the glucose is eluted first.
88

THE FUTURE
It is always very risky to predict the future in any industry, and this
is particularly so in one such as ours which is subject to influence by such
unreliable factors as international politics and the weather I However it
may be possible to suggest a few trends.
First, we live in a time of great technological changes and
developments. Some of these areas of change, such as biotechnology, require
separation processes, and as a result could lead to developments in the
field of ion exchange. In turn these may also prove to have uses within, the
sugar industry—there are some strong similarities between factory juices
and the fermentation broths from biotechnology processes.
Developments in some areas of ion exchange resin technology would be
particularly welcome in the sugar industry. For example, strongly basic
anion exchange resins with greater thermal stability would be of benefit in
decolorization processes, as would a resin combining a styrenic resin's
decolorization capacity with an acrylic resin's increased resistance to
organic foulants. In demineralization a resin that will remove betaine
without inversion of sucrose would be of considerable interest. These are
just a couple of examples of where developments in ion exchange resin
technology would be of benefit to the sugar industry.
Second, new ways are still being developed for applying the traditional
types of resins in beet sugar factories of which the recent French partial
demineralization process just mentioned is an example. As our industry
changes and becomes even more efficient, as every industry must, further
opportunities and needs may arise for the use of ion exchange. The
treatment of effluents, to avoid pollution and improve our environment, is a
possible example.
So, ion exchange processes are still being developed in laboratories
for application in the beet sugar industry, and it is likely that they will
continue to be developed in the future. Which ones will prove to be
practicable on a factory-scale is often hard to say, but it is likely that
some will pass the test.
In short, ion exchange has been applied in the beet sugar industry for
many years, and we believe it will continue to be applied for many more.
 89

CONCLUSIONS
1) Ion exchange processes are an important part of the beet sugar
industry and may become of greater importance in the future.
2) The major ion exchange processes fall into two groups: process
aids (e.g. décalcification and decolorization) and sugar recovery techniques
(e.g. Quentin, demineralization and Chromatographie desugarization).
3) Décalcification is a very successful process, but recently it has,
in some cases, been under pressure from the general increasing concern over
the environment (spent régénérant disposal) and competition from
antiscalants. These concerns have, at least partially, been answered by the
Gryllus and N.R.S. modifications to the décalcification process.
4) Decolorization, essential in the cane industry, is much less widely
used in sugar beet factories because it is, in the main, unnecessary and, in
normal factory processes, its economic benefits are a little tenuous. In
certain circumstances, e.g. in beet refineries or for the production of very
high quality liquid sugar, decolorization is economically viable. Further
research by both the sugar industry and by resin manufacturers is required
to develop the optimum decolorization process, one that does not introduce
undesirable ions (e.g. chloride ions) into the juice and that is not limited
by the thermal stability of the resins.
5) The practicability of the Quentin process depends on economic (the
relative prices of white sugar and molasses; régénérant costs) and
environmental (effluent disposal) factors. Some of the current research
into the Quentin process is on alternative regeneration systems which may
increase its profitability. The Quentin process remains one of the simplest
and best methods of sugar recovery, but can only recover a part of the
molasses sugar.
6) Partial demineralization is an essential part of some beet factory
processes, particularly those in areas where the quality of the beet (and
hence the beet juice) is relatively poor.
7) Total demineralization is an expensive process, its practicability,
in common with other sugar recovery processes, depending on a number of
factors. Some workers have concentrated on obtaining saleable by-products
(ranging from animal feeds and fertilizers to specific chemicals such as
betaine and amino acids) from the spent régénérants. Total demineralization
processes are appreciably more profitable when they can be run all year
90

round, with stored juices (e.g. thick juice, molasses) used as the feedstock
in the off-season. Modern demineralization processes are designed to
operate in this manner, and this is certainly the future for these
processes.
8) Chromatographie desugarization of the sugar juices is an
alternative to the Quentin and demineralization sugar recovery processes.
Much research into different Chromatographie techniques for sugar recovery
is currently being performed, and new commercially viable processes may soon
be developed.

REFERENCES
1 A. Z. Rumpier, Verin Deutscher Zucker Int. 53 (1903) 798.
2 Aristotle (ca. 330 BC) Works, Vol. 7, p993b. Clarendon Press London
1927.
3 Exodus 15, 23-25.
4 M. Shore, J. A. Adams, N. W. Broughton, N. Bumstead and G. C. Jones,
Some aspects of the chemistry of pulp pressing aids. Zuckerindustrie.
109 (1984) 215.
5 W. Th. J. P. Langenhorst, M. Tels and J. C. Vlugter, H. I. Waterman,
J., Cation exchangers on a sugar-beet pulp base. Application for
decontaminating radioactive waste water. Biochemical and
Microbiological Technol. & Eng. 3 (1961) 7.
6 A. Carruthers and J.F.T. Oldfield, Z., Methods for the assessment of
beet quality. I. Purity determination using a clarified extract from
brei. II. Determination of particular non-sugars in beet. III.
Summation of non-sugars. Zuckerin. 11 (1961) 23 and 85.
7 S. Landi and G. Mantovani, Ion exchange in the beet sugar industry.
Sugar Technol. Rev. 3 (1975) 1.
8 K. J. Parker, Ion exchange in the sugar industry. Chem. Ind.
(1972), 782.
9 R. Kunin, Acrylic-based ion exchange resins and adsorbents. Amber-Hi-
Lites. 175 (1984).
10 D. S. Martin, W. Hunter and B.W. Drean, Decolorizing resins—plant
development at Westburn refinery. Sugar Ind. Technol, 41, (1982), 69.
11 G. A. Akesson and K. A. Lilja, The sugar refining process at SSA,
Arlov division, Sweden (rebuilt 1981). Sugar Int. Technol. 43 (1984)
213.
12 T. V. Arden, Water purification by ion exchange. Butterworths, London
(1968).
13 Ion Exchange Resins, 6th Edition. BDH (1981).
14 R. Kunin and R.J. Myers, J. Amer. Chem. Soc. 69 (1947) 2874.
15 T. Lubienski and B. Mackay, Thin juice décalcification in The British
Sugar Corporation. British Sugar Corp. 22nd Tech. Conf. (1974).
16 J.F.T. Oldfield, C.W. Harvey and M. Shore, Procedures to assess and
reduce the deterioration of décalcification resins in service. Int.
Sugar J. 75 (1973) 70.
17 ICUMSA Proceedings, 16th Session (1974) 375.
18 R. Kunin, Helpful hints in ion exchange technology. Amber-Hi-Lites.
137 (1973).
 91

19 U.S. F. & D.A. Regulations CFR 21 Part 173.25. Ion Exchange Resins.
20 Council of Europe Draft Resolution on Ion Exchange Resins Use in Food
Processing (1984).
21 0. Samuelson, Ion exchange separations in analytical chemistry. John
Wiley & Sons, London (1963).
22 B. A. Adams and E.L. Holmes, J. Soc. Chem. Ind. 54 (1935) IT.
23 G. D'Alelio. U.S. Patent, 2,366,007 (1942).
24 C. H. McBurney. U.S. Patent 2,591,573 (1949).
25 K. Shinbori, Y. Sugimato, T. Ando, S. Sakai, Toyo Soda Mgf. Co. Ltd.
and Japan Organo Co. Ltd. 4,264,373.
26 S. L. Cheng, Rpt. Taiwan Sugar Research Inst. 106 (1984) 31.
27 G. Assalini and G. Brandoli, Second carbonatation juice treatment
by means of ion exchangers applied to continuous equipments "Aconex"
and "Preconex." Suer. Belge 91 (1972) 107.
28 C. Barraque and R. Nicol, Deionization of ion-exchangers of second
carbonatated juice, and thorough treatment of waste water produced.
Ind. Alim. Agr. 100 (1983) 853.
29 J. Mellor, Comparative treatise on inorganic and theoretical chemistry.
Halstead Press IV.
30 J.F.T. Oldfield, M. Shore, C.W. Harvey, D. Gyte and G.C. Jones, Quentin
Process. British Sugar Corp. 24th Tech. Conf. (1978).
31 P. Pelosi and J. McCarthy. Chemical Engineering 89 (1982) 75.
32 R. Kunin, Helpful hints in ion exchange technology (cont.). Amber-Hi-
Lites. 131 (1972).
33 R. Kunin, Acrylic-based ion exchange resins and adsorbents. Part 3.
Amber-Hi-Lites. 175 (1984).
34 F. Maekawa, K. Kawasaki, Y. Horiki and T. Saito, Studies on desalting
of sugar solution with ion-exchange resin in a sugar refinery.
1. Contamination of the type 1 strongly basic anion-exchange resin by
desalting sugar solution in the reverse system. 2. Restorative
treatment on the type 1 strongly basic anion-exchange resin contami­
nated by desalting sugar solution in the reverse system. Proc.
Research Soc. Japan Refineries Tech. 28 (1978) 78.
35 F. Schneider, D. Schliephake and J. Paleos, Adsorption of colouring
matter on decolorizing resins. Int. Sugar J. 70 (1968) 67 and 77.
36 G.C. Jones. Unpublished British Sugar Internal Report. (1981).
37 A. S. McGrath and G.C. Jones. Unpublished British Sugar Internal
Report (1982).
38 E. Warner, Z. Zuckerind. 1 (1952) 413.
39 P. Smit, Deliming of sugar factory juices by ion exchangers. Sucr.
Beige. 82 (1962) 82.
40 Z.D. Zhuravleva and K.P. Goncharova, Operation of the installation
for softening juice at Otrada Sugar Factory. Sakhar. Prom. 46 (1972)
31.
41 A. Carruthers, J.F.T. Oldfield and M. Shore, A.E. Wool, Pectin and
polysaccharides in beet juice and molasses. British Sugar Corp. 9th
Tech. Conf. (1956).
42 J.F.T. Oldfield, M. Shore, N.W. Broughton and G.C. Jones, Juice décal­
cification and its effect on molasses production. British Sugar Corp.
25th Tech. Conf. (1980).
43 S. Zagrodski and H. Zaorska, The influence of de-liming of sugar
factory juices on losses of sugar in molasses. Suer. Belge. 81 (1961)
137.
92

44 F. Durdik and J. Burianek, Softening of thin juice by means of cation-

exchangers. I. Mechanism of ion-exchange in softening and
regeneration. Effect of softening on the quality of thin juice.
Listy Cukr. 76 (1960) 2.
45 L. Wieninger and N. Kubradinov. Jahresber. Zuckerforschungs - Institut
(Wien). (1969) 107.
46 E. Gryllus and H.F. Delavier, BMA-Zsigmond-Gryllus process: A new
process for thin juice deliming. 1. Principles of thin juice
deliming. Z. Zuckerind. 25 (1975) 493.
47 F. Durdik and H.J. Delavier, Z. Zuckerind. 28, (1977), 27..
48 E. H. Felber, New process for deliming thin juice water without
regenerating agents and waste water. J. Amer. Soc. Sugar Beet Technol.
16 (1971) 279.
49 Anon. BMA Information No. 16 (Dec.) (1977) 725.
50 J. Ponant, Gryllus Effect. Sucr. Fr. 120 (1979) 263.
51 Y. Le Henaff and D. Herve, Ind. Aliment, Agr. 94 (1977) 725.
52 P. L. Mottard, The Imacti process for juice décalcification. Int.
Sugar J. 85 (1983) 233.
53 X. Lancrenon and P. Printemps, Processes for deliming sugar juices.
Int. Sugar J. 86 (1984) 41.
54 K. W. Schoenrock, A. Gupta and D. Costesso, New approaches to the
application of ion exchange in the sugar industry. Proc. 1976 Tech.
Sess. Cane Sugar Refining Res. (1977) 118.
55 K. W. Schoenrock, Thin juice softening over the hydrogen form of a weak
catex. A.S.S.B.T. (1985).
56 D. J. McWeeny, M. E. Knowles, J. F. Hearne, Chemistry of non-enzymatic
browning in foods and its control by sulphites. J. Sci. Fd. Agric. 25,
(1974) 735.
57 H. E. Nursten, Food Chemistry. 6 (1980) 263.
58 M. Shore, N. W. Broughton, J. V. Dutton and A. Sissons, Factors
affecting white sugar colour. Sugar Technol. Rev. 12 (1984) 1.
59 N. W. Broughton, B. J. Houghton, A. Sissons, Factors affecting white
sugar colour. 2. The sources of white sugar colour. Zuckerind. Ill
(1986) 1039.
60 W. Fries, R. M. Walker, Proc. 1980 Tech. Session Cane Sugar Refining
Res. p.171.
61 W. Fries, Cane sugar decolorization by ion-exchange resins. Int. Sugar
J. 84 (1982) 325.
62 N.G.H. Hindefelt, K. A. Lilja, Acrylic resin and styrene resin for
decolorization. A full-scale comparison. Int. Sugar J. 88 (1986) 148.
63 K. Wagnerowski (translated by D. Mottard-Dabrowska). Rationalisation
du Processus d'Equisèment de la Melasse. Association pour la Promotion
Industrie Agriculture (1983).
64 J. P. Brandley. Unpublished British Sugar Internal Report (1985).
65 F. Heitz, Melassigenic power of ions. C.I.T.S. 17 (1983) 585.
66 H. Schiweck, Physical and chemical properties of an acidic colour-
substance isolated from the regeneration effluents of a decolorizing
column for remelt liquors. Zucker. 16 (1963) 555.
67 E. Steineck. Jahresber. Zuckerforschungs-Institut (Wien). (1967-8),
49.
68 H. Eichhorn. Int. Sugar J. 84 (1982) 135.
69 M. Braeckman, The new sugar house at Tirlemont refinery. 17th C.R.
Assem. C.I.T.S. (1983) 403.
 93

70 L. Ramm-Schmidt and G. Hyoky, New resin decolorization station at

Finnish Sugar Porkkala refinery. Sugar Ind. Technol. 43 (1984) 241.
71 S. Landi and G. Mantovani, Operating parameters of an ion-exchange
decolorization plant in a sugar factory. Ind. Sacc. Ital. 65 (1972)
132.
72 Ya. 0. Kravets, V.N. Eremenko, G.V. Buzetskaya, L.D. Naumova,
Decolorization of refinery syrups with porous anion exchanger AV-
17-2P. Sakh. Prom. 7 (1982) 31.
73 S. Gielzynski, Use of ion-exchange columns for decolorization of
remelt syrups. Gaz. Cukrow. 89 (1981) 100.
74 G. Siegers and F. Martinola (Bayer). Paper presented at the
International Conference on Ion Exchange, Cambridge (1984).
75 G. C. Jones, A. S. McGrath. Unpublished British Sugar Internal Report
(1983).
76 A. Tavares, R. Forman and R. Kunin, Refinery and laboratory studies
on the use of Ecosorb precoat formulations for the clarification and
decolorization of cane and beet sugar syrups. Sugar Ind. Technol. 42
(1983) 192.
77 N. Marignetti and G. Mantovani, Liquid sugar. Sugar Technol. Rev. 7
(1979) 3.
78 R. Carolan, Manufacture of table syrup in Ireland. Int. Sugar J. 54
(1952) 106.
79 Anon. Susswaren 13 (1969) 186.
80 G. Siegers and R. Martinola, Sucrose inversion with cation-exchange
resins. Int. Sugar J. 87 (1985) 23.
81 I. Bodamer and R. Kunin, Heterogeneous catalytic inversion of sucrose
with cation-exchange resins. Ind. Eng. Chem. 43 (1951) 1082.
82 K. Taufel and K.S. Grunert, On the behavior of saccharides towards
ion-exchange resins. 3. Rate of hydrolysis and activation energy
in the homogeneous, heterogeneous and combined catalysis of sucrose.
Archiv, der Pharmazie 66 (1961) 439.
83 E. Berghofer, H. Kalushofer and L. Wieninger, Sucrose inversion with
cation exchangers. 1. Literature review. 2. Work carried out by
the authors themselves. Zucker 30 (1977) 196.
84 M. Takeda and T. Imura, Catalytic inversion of sucrose with ion-
exchange resin. J. Schimonoseki Univ. Fisheries 13 (1964) 103.
85 E. Berghofer, H. Kloushofer and L. Wieninger, Sucrose inversion with
cation exchangers. 1. Literature review. 2. Work carried out by
the authors themselves. Zucker 30 (1977) 187.
86 J.F.T. Oldfield, M. Shore and M. Senior. Int. Sugar J. 72 (1970) 187.
87 Betz Handbook of Industrial Water Conditioning, 6th Edition. (1968),
p. 103.
88 G. Quentin, Influence of inorganic cations on the solubility of
sucrose in molasses. Zucker 7 (1954) 407.
89 G. Quentin, Effect of cations on the solubility of sucrose in molasses
and the possibilities of technological evaluation of the differential
influence on solubility. Zucker 10 (1957) 408.
90 E. Moebes, The chemical and physical behavior of non-sugars in
molasses formation and refining. Z. Zuckerind. 7 (1957) 382.
91 E. Moebes, Influence of cations on the solubility of sucrose and the
viscosity of impure beet sugar solutions. Zucker. 10 (1957) 78.
92 E. Moebes and L. Wieninger, Effect of exchange of alkali ions for
calcium on the processing and yield of sugar juices. Zucker 8 (1955)
129.
*

93 G. Quentin. German Patent 974,408.

94 H. Neumann. Zucker 8 (1955) 129.
95 Robert Reichling and Co., K. G., 'Quentin Process.'
96 R. Pieck, J. Houssiau, R. Vandewijer, Some data on the variation in
the solubility and other physical properties of sucrose in the
presence of non-sugars in the form of K, Ca or Mg. Sucr. Belge 87
(1968) 319 and 371.
97 G. Quentin, Discussion of experience with the magnesium chloride
process. Z. Zuckerind. 14 (1964) 683.
98 J. Huberlant, Some thoughts on the Quentin Process. Suer. Belge 86
(1967) 505.
99 K. Schoenrock, Application and utility of magnesium exchange in the
beet sugar process. J.A.S.S.B.T. 16 (1971) 299.
100 Colloque Applexion. (4/6/1975) p. 95.
101 British Sugar Corporation. British patent 1,576,100.
102 V. I. Smagina, V. S. Shterman, A. R. Sapronov and G. S. Tereschenko,
Use of epsomite for increasing the sugar yield from final massecuite.
Sakh. Prom. 8 (1984) 21.
103 G. Assalini, G. Brandoli. EP 16922, A6 Mar. 1980, No. 80110028.9,
p. 15, October 1980.
104 B. P. Baker, Composition, properties and uses of molasses and related
products. United Molasses Trading Company Ltd.
105 G. C. Jones, C. W. Harvey. Unpublished British Sugar Internal Report
(1974).
106 E. Moebes, The 'Carbonate Process,' a method for the purification
of thin juice. Zucker. 13 (1960) 254.
107 E. Moebes, Pilot scale experiments with the carbonate process in the
1960/61 campaign. Zucker. 14 (1961) 497.
108 S. Vajna, Juice purification by demineralization by ion-exchangers.
Zucker 12 (1959) 186.
109 S. Vajna, Demineralization process by ion-exchange in the ammonium
cycle. Z. Zuckerind. 9 (1959) 279.
110 Sugar Chemical Co. Etablissement Fr. PI,386,961 (1964).
111 Ennser Zuckerfabriks A.-G. Fr. P.1,505,433 (1967).
112 Y. Ito, Y. Owada, S. Shinada, "Reverse two bed" system
demineratlization of sugar liquor with ion-exchange resin. Proc. Res.
Soc. Japan Sugar. Refineries Technol. 20 (1968) 39.
113 F. Perschak, Experiments on production of liquid sugar by ion-
exchange demineralization of molasses solutions. Zucker 22 (1969) 666.
114 D. Herve and X. Lancrenon, New ion-exchange processes in sugar
factories. Ind. Aliment. Agr. 98 (1981) 613.
115 S. Oikawa and A. Miyahara, Beet juice demineralization. Sugar J. 33
(1971) 19.
116 S. E. Bichsel and D. A. Hoover, Operation of the Hamilton City experi­
mental ion exchange plant. J.A.S.S.B.T. 15 (1969) 324.
117 S. E. Bichsel, H. A. Davis and A. Sandre, Synopsis of the Moorhead
deionization plant operating and economic characteristics. Suer. Belge
98 (1979) 67.
118 J. Foucart and J. Paleos, The new liquid sugar process at the
Vauciennes Factory. British Sugar Corp. 28th Tech. Conf. (1986).
119 L. T. Zanto and S. E. Bichsel, Direct production of liquid sugar
from ion exchange treated thick juice. J.A.S.S.B.T. 16 (1970) 149.
 95

120 J. A. Levad, T. D. Carpenter and S. E. Bichsel, Utilization of

concentrated ion-exchange non-sugar waste on dried beet pulp.
J.A.S.S.B.T. 16 (1971) 348.
121 R. F. Olson, A. M. Sandre and S. E. Bichsel, Utilization of a
deionization plant waste régénérant stream to produce a valuable
granular fertilizer by-product. Suer. Belge 98 (1979) 11.
122 S. E. Bichsel, H. A. Davis and A. Sandre, Synopsis of the Moorhead
deionization plant operating and economic characteristics. Suer. Belge
98 (1979) 67.
123 G. Rousseau. In: Ion Exchange Technology, eg. D. Naden, M. Streat,
Published by Horwood, Chichester (1984) 381.
124 R. M. Wheaton and W. C. Bauman. Ind. Eng. Chem. 45 (1953) 228.
125 H. Hongisto and M. Loisa, Finnsugar separation process for
desugarization of molasses. Z. Zuckerind. 27 (1977) 279.
126 Anon. Zuckerind. 108 (1983) 636.
127 H. G. Schneider and J. Mikule, Recovery of sugar from beet molasses
by the P[fiefer] and L[angen] exclusion process. Int. Sugar J. 77
(1975) 259.
128 K. Sayama, Y. Senba, T. Kawamoto, S. G. Kenkyukaishl, Chromatographie
separation of molasses constituents. 1. Recovery of sucrose from
molasses. Proc. Res. Soc. Japan Sugar Refineries' Technol. 29 (1980)
1.