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Elsevier Science Publishers B.V., Amsterdam, 1988 - Printed in The Netherlands 6
Elsevier Science Publishers B.V., Amsterdam, 1988 - Printed in The Netherlands 6
Godshall
Elsevier Science Publishers B.V., Amsterdam, 1988 — Printed in the Netherlands
^6
Chapter 5
ION EXCHANGE PROCESSES IN BEET SUGAR MANUFACTURE
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
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.
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
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
Exhaustion Regeneration
Na"*" form
JJ
Nl/
Softened second carb. juice
to evaporators Effluent
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.
Exhaustion Regeneration
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
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
Exhaustion Regeneration
II II
NI/
Soft second carb. juice Juice and calcium
to evaporators saccharate to carbonatation
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^
— i —
100
Juice solids treated (g/cn»3 r e si n )
Anion
Concentration
.. Original
Concentration
/
/
/ / X
/
/
TABLE 2
Overall changes in juice anion concentrations.
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.
Cantlev
Bury.
Exhaustion Regeneration
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
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
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
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
II
Nik
Treated syrup to flash evaporator
and crystallizer Effluent
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
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
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-
Evaporation/Crystallisation
Mother liquor Solids
Organic Nitrogen Compounde NH4,Na,K/S04
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
Regeneration
Animal Feed (R.N.S.)
1 *
\ !
Strong Weak Weak
Acid Base Base
Cation Anion Anion
\' —
· ______ _ f _
fertiliser
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.
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