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Abstract
The use of antiscale products is very common in
the evaporation station of sugar factories. These
products are generally water-soluble polymers
like polyacrylates. Their role seems to be the
prevention of formation of calcium oxalate
scale. However the stability of calcium-acrylate
complexes and their behaviour after evaporation
are not well known.
Effects of antiscale on calcium oxalate solubility on white sugar turbidity and on sucrose
crystal growth rate were studied. It was demonstrated that antiscale protects evaporator from
abundant calcium oxalate scale formation. Yet,
they delay the problem of oxalate precipitation
and cannot prevent turbidity of final sugar. The
phenomenon is especially emphasized by decrease of temperature which affects both calcium oxalate solubility and antiscale sequestering
efficacy.
Effect of antiscales on growth rate and on
morphology of sucrose crystals was determined
by end-to-end laboratory crystallization and microboiler pilot methods. It was shown that antiscales inhibit sucrose crystal growth especially
Introduction
A distinctive property of white sugar is its extremely high purity. At an industrial scale, sugar
purity generally exceeds 99.8% and rarely falls
below 99.7%.
For a long time, the industrial users considered sugar as a raw material without problems.
Its quality was judged simply by visual comparison and few quality criteria such as ash content
and color of dissolved sugar. However, due to
the progress realized in food industry and analytical chemistry it was revealed that, small fraction of less than 0.2% of non-sucrose substances
are at the origin of numerous problems not only
for sugar industry but also for food industry customers.
As a consequence, rigorous criteria were adopted for the determination of sugar quality.
148
Turbidity measurements
Turbidity was determined according to ICUMSA method. Syrup solution with a concentration
of 50% D.S. was prepared and filtered through
a 0.45m-membrane filter. Absorbance was
measured at a wavelength of 420 nm before and
after filtration using a UV-2101 shimadzu spectrometer.
Concentration was controlled using refractometer from Euromex (Euromex microscopes,
Netherlands).
Effect of selected impurities on sucrose crystal growth rate and granulated sugar quality 149
% (1)
% (2)
1
1
3
3
15
99
99
97
97
85
To control growth rates and study sucrose morphology changes due to the presence of antiscale, the End-To-End method was used
(Figure1). The growing crystals were selected
under camera microscope and heated at work
temperature (30 0.1C) prior to introduction
in tubes. Growing crystals were selected from a
highly pure sugar obtained by three successive
crystallizations of an industrial sugar (quality
N1). Selection was based on crystal dimensions along the b and c crystallographic axis
(Lb / Lc = 1.65 0.06). Growth rates were determined at supersaturations between 1 and 1.1
Supersaturated solutions were preheated at 65C
to erase traces of nuclei and inhibit further spontaneous nucleation and then mixed with 100L/
L of antiscale. 10 crystals were introduced in
each tube filled with supersaturated solutions.
Tubes were fixed on a disc rotating at 6rpm
placed in a thermostated box (30 0.1 C). Di-
150
(2)
Effect of selected impurities on sucrose crystal growth rate and granulated sugar quality 151
152
Fig, 3: SEM micrographs of retained fraction on 0.45m-membrane filter from a turbid sugar
(100 I.U.)
Fig. 4: FTIR spectra of calcium oxalate monohydrate obtained from equimolar reaction between
calcium chloride and sodium oxalate at 85 C and of the retained fraction on 0.45 m
membrane filter from an aqueous solution of turbid sugar (50% D.S.)
Effect of selected impurities on sucrose crystal growth rate and granulated sugar quality 153
Fig. 5: FTIR spectra of calcium oxalate dihydrate crystals obtained at initial concentration of
130L/L from sugar solutions of: (A) 10%, (B) 25% and (C) 40% and composites Calcium
oxalate dihydrate-SiO2 obtained from sugar solutions at an intial calcium oxalate concentration of (D) 44 L/L and (E) 130 L/L (Yu et al., 2004)
Fig. 6: Thermal curves of retained fraction on 0.45 m-membrane filter from an aqueous turbid sugar
solution (50% D.S.) and of pure sugar from Merck
154
Effect of selected impurities on sucrose crystal growth rate and granulated sugar quality 155
Calcium oxalate formation is not only harmful for the quality of final sugar but also for the
heating capacity of evaporation station. Calcium
oxalates (COD and COM) represent about the
half (51% of the weight) of scale encountered
in multi-effect evaporator (Doherty, 2000). Because of its low thermal conductivity (20 times
lower than that of stainless steel and 60 times
156
Fig. 13: XRD spectra of scale samples scratched at evaporation station wall surfaces
in a French sugar beet factory not practicing decalcification
Effect of selected impurities on sucrose crystal growth rate and granulated sugar quality 157
Fig. 14: Scanning electron micrographs of scale samples scratched at evaporation station wall surfaces in a French sugar beet factory not practicing decalcification
158
Fig. 15: Soluble oxalate concentration versus dry matter in a thin juice free from antiscales during
evapo-concentration under vacuum at 85 C
Fig. 16: Soluble oxalate concentration versus dry matter in a thin juice mixed or not with 10 L/L
of antiscale during evapo-concentration under vacuum at 85 C
Effect of selected impurities on sucrose crystal growth rate and granulated sugar quality 159
160
Fig. 17: Soluble oxalate concentration versus time in a syrup (65% D.S.) obtained in laboratory
by concentrating under vacuum a thin juice (15% D.S.; 6 mgL1 soluble oxalate contents)
mixed with 10 L/L of antiscale at 85 C
Fig. 18: Sucrose crystal growth rate in pure solution and in presence of antiscales impurities
Effect of selected impurities on sucrose crystal growth rate and granulated sugar quality 161
storage aliquots of 5 mL were sampled at different time intervals and analyzed using HPLC to
determine soluble oxalate concentration.
Obtained results are given in Figure 17,
which shows a rapid decrease of soluble oxalate
concentration during the first days of storage followed by stabilization. This agrees with Cosmeur
(1999) and means that oxalate is responsible for
syrup turbidity in the form of insoluble calcium
oxalate probably combined with macromolecules.
The calcium oxalate formation is promoted by the
decrease of temperature (from 85 C to 25 2 C).
Decrease of temperature was described to affect
both antiscale sequestering efficacy and calcium
oxalate solubility (Bensouissi et al., 2007).
Sucrose crystal growth rate is a subject that attracted the interest of researchers both for its
theoretical and practical importance. The effect
of impurities like raffinose, glucose, fructose, invert sugar and dextran on sucrose crystal growth
was extensively investigated. The interest given
for such impurities can be attributed to its abundance in syrups and to the molecular similarities
that they had with sucrose molecule. Oppositely,
the effect of minor and hydrophilic impurities is
not well studied despite the affinity they have for
water and for sucrose itself.
Hydrophilic impurities can exist naturally in
beet and cane plant or can be intentionally added
to juices in order to facilitate some processing
unit operations. Antiscales are a good example
of hydrophilic impurities added in sugar factory.
As mentioned above, its addition prevents calcium oxalate crystallization at the evaporation
step. Following the evaporation, they have no
special role and certainly are present at the level
of several mg/L in stored syrup. As far as we are
aware, the effect of such impurities on growth
was never studied before. The aim of this section is to discuss their effect on sucrose crystal
growth and morphology.
The effect of 3 antiscales on the overall sucrose crystal growth rate and on the a, p/p'
and r/c faces growth rates were studied in
the range of supersaturation (11.105). As may
be observed in Figure 18, crystal growth rate
is decreased by the presence of antiscales. For
example at a supersaturation of s = 1.084 the
growth rate decreases by about 12.5% in presence of antiscale C. This decrease can be considered as non-negligible with regard to the amount
of antiscale used (100 L/L). We can also show
that growth rate as a function of supersaturation
follows a 2nd order kinetics law expectable from
a BCF type of growth. From face by face growth
rates results (Figure 19a; 19b and 19c), it can be
shown that antiscales inhibit the sucrose crystal
growth elongation in the direction of the crystallographic b axis. In fact, comparison of surface growth rates in presence of antiscales with
those in absence of antiscale show that p/p'
had the most affected growth. For example, at
a supersaturation of s = 1.084 and in presence
of 100 L/L of antiscale C, the growth rate of
the face p/p' is decreased by about 10.29%
whereas those of the faces r/c and a are respectively decreased by 6.29% and 6.21%.
Inhibition of crystal elongation in the b direction is clearly evidenced by the comparison
of Lb/Lc ratios of a great number of crystals obtained in a pilot crystallizer from pure sucrose
solutions mixed or not with 100 L/L of antiscale (Figure 20).
162
Effect of selected impurities on sucrose crystal growth rate and granulated sugar quality 163
(3)
and
Gv = N
G = (4 p/3 VM) r3 + 4 p r2 g
(7)
(4)
Where VM is the molecular volume, we can deduce the following expression for clusters total
free energy:
(5)
(9)
N VM = (4 p r3/3) N
(6)
(10)
Fig. 20: Lb /Lc ratio as a function of crystals size classes (Mean Aperture) obtained in pilot microboiler from a pure sucrose solution mixed or not with 100 L/L of antiscale
164
Table 2: Surface tension of pure sucrose solutions (10% D.S.) mixed or not with 100 L/L of antiscale
Sample
Ultra pure water
Sucrose solution without antiscale
Sucrose solution mixed with 100 L/L of antiscale A
Sucrose solution mixed with 100 L/L of antiscale C
Sucrose solution mixed with 100 L/L of antiscale D
Standard deviation
72.78
73.53
72.63
72.68
70.67
0.11
0.13
0.15
0.13
0.46
vincing to explain the inhibition effect of antiscale on the elongation of sugar crystals along
b axis.
Conclusions
From the experimental work presented in this
paper, it can be concluded that:
Particles at the origin of beet white sugar turbidity are mainly constituted of thin crystals
of calcium oxalate dihydrate. These crystals
are located at the surface as well as inside
of sugar crystals. Inside the sugar crystals it
seems that macromolecules play the role of
carrier for the calcium oxalate inclusion.
The adding of antiscale agents during the
evaporation step protects the evaporator
tubes from abundant scale formation, but delays the problem as the turbidity is concentrated in the syrup and final sugar especially
in case of storage.
To reduce sugar turbidity, decalcification
of thin juices seems to be the most efficient
method compared to the syrup filtration and
to the crystals washing methods.
Antiscale can decrease the overall sucrose
crystal growth rate probably by inhibiting
clusters formation needed to crystal growth.
Antiscales inhibit sucrose crystal elongation
in the b crystallographic direction probably
by a mechanism of specific surface adsorption as was observed by Mantovani (1996).
Effect of selected impurities on sucrose crystal growth rate and granulated sugar quality 165
Acknowledgements
The authors wish to thank the French sugar
profession for funding this work and Mr. Jean
GENOTELLE for the fruitful discussion of the
crystal growth section. Mr. James O'DONNELL
(Horiba Jobin-Yvon) is also thanked for making
grain size distribution measurements with Camsizer device possible.
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