Association AVH – 6e Symposium – Reims, mars 1999

Standpoint of cooling
crystallization as a method of
beet or cane sugar purification
G. MANTOVANI and G. VACCARI, University of Ferrara, Ferrara, Italy

ABSTRACT sico-chemical characteristics of the solution and

the crystallization conditions. If the crystals
The possible application of cooling crystallization
obtained do not have the desired purity they
as a method of beet or cane sugar purification is
may be dissolved and recrystallized. If necessary,
discussed. At the AvH Symposium in 1996 (Proc.
this operation can be repeated until crystals of
3rd Symposium - Sugar Crystallization - pp. 51-
the expected purity are obtained.
62 ), cooling crystallization and traditional eva-
porative crystallization were compared and the
When we speak about “crystallization condi-
advantages of cooling crystallization as far as the
tions”, we mean the different ways which make
crystal quality was concerned was pointed out.
it possible to reach and maintain supersatura-
In this paper, the authors reconsider the ideas
tion: evaporation, cooling, adiabatic evaporation
relating to the interfacial breakdown theory in
(Figure 1).
view of recent experiments carried out by
Lionnet (Trans IChemE, vol. 76, Part A, October
Although cooling crystallization is not a new
1998, pp803-807). Moreover, the cooling crys-
technology either in crystallographic research or
tallization experiments made both under labora-
in industry, it has traditionally been considered
tory conditions and on a pilot plant are revie-
of little importance in the sugar industry, where
wed. Such a technique can be profitably applied
it is only applied to massecuites obtained via
under various conditions i.e. to traditional thick
evaporative crystallization, before their centrifu-
juice, to concentrated raw juice both as such and
gation. Such a situation may be considered quite
after microfiltration steps, in cane sugar refine-
ries and to those sugar fractions originating from
chromatographic separations of both molasses
and raw juice. The authors conclude by presen-
ting a picture of the situation as regards adopting
of cooling crystallization technique by taking
into account the possibility of utilizing plants
which do not automatically require high invest-
ment costs.

INTRODUCTION
It is well-known that a very effective way of rea-
lizing an “Impurity Removal” from a solution is
the crystallization process. In fact, by crystalli-
zing a solute from an impure solution, most of
the impurities remain in the mother liquor,
whilst the crystals obtained have a high purity
the degree of which depends upon both the phy- Figure 1: Different crystallization conditions.

36
AVH Association – 6th Symposium – Reims, March 1999

INCLUSIONS AND IMPURITY

TRANSFER
We believe that it is by now continually stated
that the main reason, although not the only one,
for the presence of impurities inside sucrose
crystals is related to the phenomenon of inclu-
sions. Inclusions are formed by variable sized
pockets (Figure 3) containing mother liquor. The
composition of these inclusions, in terms of
concentrations of impurities, may however be
quite different from that of the growth solution.

Mullin (2) emphasizes clearly the main reasons

Figure 2: Yield of sucrose crystallization by cooling. for the presence of inclusions:
• rapid growth kinetics
surprising bearing in mind the great variation in
• large sizes of crystals
sucrose solubility as a function of temperature,
• type of seed
as well as the advantages presented by cooling
• phenomena of dissolution and regrowth
crystallization compared with the traditional
• phenomena of instability of the crystal sur-
crystallization via water evaporation.
face.
As far as sucrose solubility variation as a func-
In the paper which we presented here three
tion of temperature is concerned, Figure 2 clear-
years ago, we tried to research this question by
ly shows out that, if a saturated solution at 90°C
trying to correlate the phenomenon of the pre-
is crystallized by simply cooling to a room tem-
sence of inclusions in the crystals with the inter-
perature of 20°C, the amount of solute which
facial breakdown process at the crystal/solution
crystallizes is more than 50%.
interface.
Concerning the advantages of crystallization by
Such a problem has recently been reconsidered
simply cooling, in comparison with evaporative
by Lionnet, who has experimentally evaluated,
crystallization, of particular importance is the
in two interesting papers, the rates of impurity
quality of the crystals. We do not wish to make
transfer for different types of impurities. In the
here a comparison between evaporative and
first paper (3), Lionnet points out in particular
cooling crystallization, an item already discussed
that the impurity transfer rate Ri:
here during the 1996 Symposium (1). We would
prefer to delve into this subject by reporting Mass of impurity in crystal
Ri 5 }}}}
some recent experimental data, which can be Time 3 Surface area of Crystals
useful either from the theoretical point of view
or for their possible future applications in the is related to the growth rate G (kg/m2 s) and the
sugar world. concentration F (m/m) of an impurity in the
growth solution by the relationship:
Ri 5 constant Ga Fb
where a and b are constants, depending upon
the type of impurity.

He also postulates that Ri depends on the size of

the crystals according to a relationship such as:
Ri 5 constant Fc Dd
where D is the crystal characteristic dimension
(m) and c and d are constants which depend
upon the type of impurity.

Moreover, Lionnet points out that the effect of

temperature is very important, because a 10°C
Figure 3: Inclusions of mother inside sucrose crystal decrease of temperature decreases the value of

37
Association AVH – 6e Symposium – Reims, mars 1999

Ri of an amount of 20-40%, depending upon the
type of impurity.
In his second paper (4), Lionnet discusses the
problem from more theoretical standpoint by
reconsidering the question of the “constitutional
supersaturation” which we mentioned in our
lecture in 1996 (1) and comparing the situation
with what actually occurs in the crystallization
from melts (5, 6, 7) .
The equation to be applied is as follows:
ln [(1 2 ke)/ke] 5 ln [(1 2 ka)/ka] 2 (d/D)f
where ka is the ratio between the concentrations
of impurity in the solid and liquid phases, res-
pectively, under equilibrium conditions and ke is
the same ratio under non-equilibrium condi-
tions (non-zero growth speeds). d is the interfa-
cial film thickness, D the diffusion coefficient of
the impurity in the solution and f is a linear crys-
tal growth velocity.
In his conclusions the author emphasizes that
there is a critical minimum crystallization veloci-
ty below which the interfacial instability does
not occur, but that such a velocity is practically
impossible to maintain in the traditional evapo-
rative crystallization systems. As a consequence,
the crystals obtained include more or less great
amounts of impurities. The author does not
mention the effect exerted by vapour bubbles on
the crystal surface, an effect which certainly
influences the process of interfacial breakdown
and thus intensifies the problem of inclusion of
mother liquor during the evaporative crystalliza-
tion.
• the temperature factor cannot be utilized in
order to decrease the inclusion of mother
liquor;
• it is impossible to go down below the criti-
cal minimum crystallization velocity, below
which liquor capture is not favoured.
EXPERIMENTS ON COOLING
CRYSTALLIZATION
Cooling crystallization, as such, is simpler than
evaporative crystallization. Effectively, after
having reached the desired concentration at the
desired temperature, we have only to add the
seed and cool the magma while following a
cooling profile scheduled in a system which,
from the mass point of view, is closed.
Our first experiences with the utilization of
cooling crystallization were carried out about
ten years ago. The aim was to obtain commercial
white sugar even when starting from deep-
coloured juices such as those which can be
found under Italian weather and soil conditions
and, in general, for beet growth in the
Mediterranean area. In effect, colour may be
considered as representing the “Achilles’ heel” of
the sugar end: when the juice colour is dark,
increasingly complex crystallization schemes
must be used together with recrystallizations
(refinery processes). These complicate the pro-

Bearing in mind what is mentioned above, it is

obvious that, as far as the crystal quality is
concerned, evaporative crystallization is certain-
ly unfavourable compared with cooling crystalli-
zation. The latter, of course, does not promote
the formation of vapour bubbles and makes it
possible to suitably decrease the crystallization
rate, consequently minimizing the effects pro-
moted by the formation of inclusions. In fact, in
evaporative crystallization:
• we cannot slow down beyond a certain
limit the evaporation of water, either for
energetic reasons or due to the instability of
the solution (colour formation, etc.);
• the concentration of impurities necessarily Figure 4: Basic scheme of a cooling-crystallization in three
increases during the evaporation of water; stages.

38
AVH Association – 6th Symposium – Reims, March 1999

the high potential of cooling crystallization for

“impurity removal”, we have tried to use this
technology to replace the traditional calco-car-
bonic purification, which is creating increasing
problems. The ecological, environmental and
energy problems are well known (Figure 6), and
in particular, the limestone and fuel consump-
tion, the production of sludges, the water
consumption, the complexity of the plants, as
well as the limited advantages obtained for a
number of years now for the purification yield,
as a result of peculiar agronomical and climatic
conditions.

Bearing in mind the less drastic conditions under

which cooling crystallization take place when
compared with evaporational crystallization, we
have tried to crystallize factory raw juices direct-
ly as such without any purification treatment
Figure 5 : Continuous Cooling Crystallization of thick juice.
(Figure 7).
cess from the technological-plant point of view,
Obviously, the sugar obtained, originating from
so increasing energy consumption and produc-
a cloudy solution such as raw juice, is a raw
tion costs.
sugar which needs refining. The good results
obtained allowed us to obtain another patent
The experiments carried out in the laboratory (12) which at the moment is not yet industrially
and then on a pilot plant (8, 9) allowed us to applied because the experiments are still in the
conclude (Figures 4 and 5) that, even starting
from particularly dark-coloured thick juice
(6,000 - 7,000 I.U.), it is possible to directly
obtain commercial white sugar following a
three-strikes scheme, without any recrystalliza-
tion.
,,,
,,,,,,,,,,,
The good results obtained made it possible for a
,

,,,,,
patent (10) to be granted but the relevant pro-
cesses have not yet been industrially realized for
,

various reasons. In fact, further experiments

must be carried out by testing vertical cooling
crystallizers of the industrial type, and significant
,

funding needs to be allocated for the construc-

tion of new plants. Moreover, it is difficult for
the sugar world to automatically accept a new
,

technology which is quite different from that

which has been followed for the past 200 years;
and there is no demonstrative industrial plant,
which requires a large investment of money at
,
,,,
,

the investor’s risk. These difficulties persist even

,

though it has been authoritatively shown that

cooling crystallization could realize an energy
saving in comparison with crystallization of the
traditional type (11).

Trusting to the possibility that the problems

mentioned above can be solved, bearing in mind Figure 6: Flow diagram of a beet sugar factory.

39
Association AVH – 6e Symposium – Reims, mars 1999
Raw juice
Low temp. concentration
1st raw sugar
1st cooling crystallization
run-off
Low temp. concentration
2nd cooling crystallization
2nd raw sugar
Affination
Melting
Filtration
Crystallization
Refined sugar
Figure 7: Counter-current concentration at low temperatu-
re and cooling crystallization of beet raw juice.
development stage. Similar experiments have
been recently made in Ukraina (13) and the
results were incouraging. The ecological-envi-
ronmental types of advantages obtainable from
this new technology have promoted a funding
from the European Union in order to finance
further research (Suclean – “Copernicus” pro-
ject). Such a project will study this subject inten-
sively through the cooperation of various resear-
ch groups working within both the academic
and industrial world (University of Ferrara,
University of Warsaw, University of Prague,
Umist, Tecnimont, Chepos) (14).
In view of the good results obtained for a num-
ber of years now by microfiltration processes, (a
technology which started in the sugar area in the
seventies), we decided to verify the possibility of
obtaining commercial white sugar without any
refining via the direct crystallization of raw juice
after a microfiltration step. The relevant results
have shown (14, 15) that if the microfiltered raw
juice has magnesium removed before concentra-
tion (possibly carried out at low temperature)
and cooling crystallization (Figures 8 and 9),
through a three- strikes scheme, it is possible to
obtain commercial white sugar directly from the
first strike together with very well exhausted
molasses. The overall crystallization yields are
comparable with those obtained from the tradi-
tional calco-carbonic process. Our experiments
are in progress in order to evaluate the advan-
tages of such a new technological scheme, either
from the energy or water consumption points of
view.
We have even tried to involve the cane sugar
refining sector in cooling crystallization by pro-
Molasses posing the simplified working scheme (17)
shown in Figure 10.
Cooling crystallization has even awakened the
interest of the American Crystal Sugar Company
(USA) for whom we examined the possibility of
applying cooling crystallization to the sugar-rich
fraction (“extract”) originating from a SMB
(Simulated Moving Bed) chromatographic sepa-
ration process using molasses as the raw mate-
rial (18, 19, 20). Good results were obtained
(21) by adopting a three-strikes cycle and obtai-
ning commercial white sugar after the first stri-
ke and a particularly well exhausted molasses,
which allowed us to obtain a particularly high
overall crystallization yield (Figure 11).
Moreover, the Amalgamated Research Inc.
(USA), which would like to replace the traditio-
nal calco-carbonic purification process with a
Raw juice
Microfiltration
Softening
Concentration
1st cooling crystallization White sugar
run-off
Concentration
2nd Prod. sugar
2nd cooling crystallization
run-off
Concentration
3rd Prod. sugar
3rd cooling crystallization Molasses
Figure 8: Cooling crystallization cycle of microfiltered and
softened raw juice.
40
AVH Association – 6th Symposium – Reims, March 1999

Microfiltered
raw juice Color = 4680 I.U.
Standard Concentration
Purity = 87.58
Bx = 86.13 Purity = 90.11
Color = 5500 I.U.
White sugar
S/NS = 7.05 1st cooling crystallization
80°C 30°C Col. in sol. = 23.2 I.U.
Ash = 0.0053%
run-off Yield = 61.59%
Concentration Cryst./run-off = 0.92

Total yield Bx = 84.52 Purity = 77.78

2nd Crist. sugar 2nd cooling crystallization
Yield = 45.44% 80°C 30°C
84.78% Cryst./run-off = 0.43 run-off

Concentration
Bx = 89.01 Purity = 65.63
3rd Crist. sugar 3rd cooling crystallization Molasses
Yield = 43.67% 80°C 30°C Purity = 51.82
Cryst./run-off = 0.34 Brix = 85.27
S/NS = 1.08

Figure 9: Flow diagram for exhaustive cooling crystallization of extract.

chromatographic treatment of the microfiltered crystallization. Thus, we are commencing a

raw juice using the same SMB technology
favourably applied to molasses treatment (22,
23, 24, 25), has supplied us with a certain
amount of “extract” coming from raw juice. We
are working on this extract with the aim of set-
ting up a cooling crystallization scheme in seve-
ral strikes. The results are very promising and
will be completed in the near future.
Further to the possibilities in regard to cane
sugar processing, the cane sugar production
world is also becoming interested in cooling
Raw sugar
Affination
study of a cooperative project with a South
American Company for the utilization of cooling
crystallization of cane juice concentrated via dia-
lysis at low temperature.
REVIEW
From the brief glimpses outlined above we can
understand that cooling crystallization is capable
of favourably replacing all the various fields of
application where evaporative crystallization is
normally utilized: from beet to sugar cane, from
sugar refining to advanced technological pro-
Raw sugar
cesses where the traditional calco-carbonic puri-
fication technique is eliminated.
Affination

Now we have to try to explain why cooling crys-

tallization remains only an odd, although inter-
Phosphatation Carbonatation
esting, technology without any real industrial
application.
Filtration Filtration

Decolorization Decolorization Undoubtedly the non-availability of a demons-

Filtration
Traditional Crystallization Cooling Crystallization
(A)
Figure 10: Basic Scheme of the traditional system of raw
sugar refining (A) and utilizing cooling crystallization (B).
trative industrial plant, which is difficult to set
Filtration
up for the reasons mentioned above, damps the
enthusiasm of people asking to visit an industrial
plant in operation. However, we believe that
there is another reason which hinders the accep-
tance of the new technology and it is is the pro-
(B)
posal to use as cooling crystallizers, continuous
vertical plants cooled by water and operating by
the “plug flow” principle (Figure 12).

41
Association AVH – 6e Symposium – Reims, mars 1999

Extract Color = 5185 I.U.

Standard Concentration
Bx = 70.34
Purity = 91.74 Bx = 87.97 Purity = 93.58
Color = 6215 I.U. White sugar
1st cooling crystallization
80°C 30°C Color = 32.11 I.U.
Ash = 0.006%
Bx = 73.44 Purity = 83.04 Yield = 66.41%
Concentration

Total yield Bx = 88.87 Purity = 83.04

2nd Crist. sugar 2nd cooling crystallization
Color = 112 I.U. 80°C 30°C
93.42% Ash = 0.014% Bx = 79.52 Purity = 64.76
Yield = 62.46%
Concentration
Bx = 90.15 Purity = 64.76
3rd Crist. sugar 3rd cooling crystallization Molasses
Color = 115 I.U. 80°C 30°C Brix = 84.78
Ash = 0.015% Purity = 42.10
Yield = 60.44%

Figure 11: Flow diagram for exhaustive cooling crystallization of extract.

Such plants are not at the moment in operation

in the sugar factories, so that the adoption of the
cooling crystallization technology would require
the elimination of old plants and new capital
investment for the new crystallizers. Such a pro-
posal is obviously difficult to be accepted by the
Sugar Companies which, on the other hand,
have at their disposal inside their factories, boi-
ling pans and traditional mixers which were in
operation in factories which are now closed.
Therefore, it would be possible to solve the pro-
blem by adopting the cooling crystallization
technique by using traditional boiling pans and
mixers according to the scheme shown in
Figure 13. Figure 13: Cooling crystallization using the traditional “pan
+ crystallizer” plants.

cold water Seed In other words, “batch” crystallizations could be

set up following the same criteria we have been
con. sol. using for a number of years now in our labora-
water
tories. A boiling pan (mainly working as a
concentrator) should be connected with a cer-
tain number of cooling crystallizing mixers, the
number of which should be proportional to the
ratio between the total crystallization time and
the concentration time in the pan. After having
concentrated the juice inside the pan, at a cer-
tain temperature and up to a pre-determined
Brix value, the juice is discharged into the
water-cooled mixer. After addition of seed, the
Cold water scheduled cooling profile of the magma is care-
fully followed utilizating a computerized system.
Magma
At the end of cooling, the magma should be
Figure 12: Continuous Cooling Crystallizer. transferred directly to the centrifugation step.

42
AVH Association – 6th Symposium – Reims, March 1999
Figure 14: Pilot plant scheme.
We are planning to carry out a first scaling-up of
the process using a pilot plant made available by
the ERIDANIA Company. Such a plant is shown
in Figure 14 and can handle about 100 kg of
juice. Preliminary experiments have already
given encouraging results.
CONCLUSIONS
Based on the points discussed above, we wish to
emphasize that the “impurity removal”, which
can be realized via the crystallization process,
can be improved if “cooling crystallization” is
adopted. Moreover, the latter not only allows us
to obtain commercial white sugar even with
very dark-coloured juices, but it can also allow
us to eliminate problems involved in the tradi-
tional calco-carbonic purification process.
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