ABSTRACT
The deleterious infl9ence of starch o n the refinability of raw sugar may
be demonstrated in the'laboratory by measuring the effect of starch on the
filtration behaviour of raw sugar processed by carbonatation. The high
negative correlation between starch content and filterability is indicative of
an exceptional relationship between starch and calcium carbonate crystallisa-
tion. A detailed analysis of the mechanism of the starch-carbonatation
interaction has revealed that starch does not perform as a single entitv but
rather in the form of its two major components.
Amylopectin is found dispersed predominantly within the body of the
carbonate lattice. This behavjqur is interpreted in terms of the special chargc
characteristics of the molecule, Moreover, in this fixed position the influence
of the adsorbed molecule onitye crystal surface properties during the reaction
is strictly limited : the result ib"that amylopectin is not instrumental in causing
excessive filtration difficulties.
Amylose is most certajnly capable of causing poor filterability. Its
activity stems from weakly bonded adsorption onto the crystal surface during
the course of the reaction. Some of this amylose is incorporated into the
growing crystal but mainly it~$ccumulates on the surface, often in such
quantities as to alter completely the crystal surface characteristics. This
protective colloid action prevents the formation of agglomerates, the presence
of which are essential for satisfactory filterability. In addition, the inter-
particle repulsion charge appears to decrease significantly: this creates a
drop in filtration rate. It is concluded that amylose has an influence which far
outweighs that of amylopectin on the carbonatation filterability of raw sugar.
INTRODUCTION
of starch present in the raw sugar. When compared with carbonatation refinery
filtration data, the results yielded by this test show low concurrent reliability.
The main reason for thisis the inability of the test (or any of its type) to account
for the "chemical" effect of starch during the carbonatation reaction.
Previous work in this laboratory14 has demonstrated the relative importance
of starch and suspended matter on the filterability of raw sugar which has
been processed on a laboratory carbonatation unit. Suspended matter certainly
does influence the filterability but only if present in excessive amounts before
the effect is of much importance. O n the other hand, even small amounts of
starch (50 ppm) have a definite measurable influence on the filterability of the
carbonatated liquor. Indeed starch when present in considerable quantities
(> 500 ppm) can produce such profound modifications to the carbonatation
slurry as to make successful filtration inordinately difficult.
In this paper an attempt has been made to clarify the mechanism of starch
interference with the carbonatation process. The study has been made with
reference to a representative selection of South African-produced very high
pol sugar ("S > 99,30) of export quality1 where the starch content is less than
150 ppm. The large majority of this type of sugar is refined overseas by the
carbonatation process. In addition, samples of other very high pol (vhp) sugar
which does not meet export specifications and which is refined locally by a
carbonatation process are included. The laboratory carbonatation filtering
behaviour of these sugars has been studied and attention has been drawn to
the relationship between the amount of starch present in the raw sugar and the
filtration rates resulting. The starch associated with the precipitates of these
reactions, together with some refinery precipitates, has been subjected to a
detailed analysis.
The mechanism of starch interaction with the carbonatation process which
leads to a decrease in filtering quality is discussed in terms of the distinct
physical and chemical properties of the two major molecular components of
raw sugar starch, viz amylose (straight-chain) and amylopectin (branch-chain)
normally present in the ratio of 3 :7, by weight.17 These two molecular entities
appear to interact with growing calcium carbonate crystals in very different
ways. The mode of adsorption of amylose is discussed as an important factor
contributing to loss in filterability.
EXPERIMENTAL
(i) Liquor Carbonatation
The laboratory carbonatation process usedLjnthis study differs materially
from the general industrial refining process in that the whole test is carried out
at constant conditions of pH, temperature and brix. This procedure offers
distinct advantages over the use of a scaled-dd$n version of the more complex
multi-stage liming process used in the refinery. Not only is control simplified
but product reproducibility is excellent. With the correct reaction conditions
it is possible to produce a carbonatation slurry which does not differ radically
from the corresponding refinery slurry in structure (as evidenced from trans-
mission electron photomicrographs of the crystals) or in behaviour (as evi-
denced from filtration data).
MANUFACTURING - PROCESSING
do ,
where "m" is the slope of the graph--versus V.
dV
do
I t is possible to calculate the value of f, for any sample by plotting the-
dV
against V graph, measuring its slope, m, and substituting the value in equn. (1).
The f, values shown in the Tables of results are percentage filterabilities relative
to the 100% filterability of a double-washed refined sugar (first boiling).
(iii) Starch analyis
For the routine analysis of starch in raw sugar the method described by
Matic13 was used. This method utilises as a standard a potato starch (BDH)
which contains 30% amylose. The absorption of the starch iodine complex of
the raw sugar is readl& 600 nm and compared with the standard potato starch
curve. As the amylose content of certain raw sugars deviates considerably
from the 30% norm, this method cannot be used where a precise assessment
of the total starch content is required.
I n the investigation of the starch in the calcium carbonate precipitates
and reaction filtrates, the % amylose may also vary considerably making the
standard method of analysis unsuitable. Recourse was taken to the method of
Bruijn and Vanis6 which is based on the acid hydrolysis of starch to glucose.
The glucose may then be estimated by the Hagedorn and Jensen1° method.
Concurrent with this procedure it is possible to calculate the % amylose present
by determining the "blue value"22 of the starch solution before hydrolysis.
RESULTS
The general relationship between the starch content of raw sugar and the
laboratory carbonatation filterability, f,, was determined for a representative
J. P. MURRAY, F. M. RUNGGAS AND M. VANIS
cross-section of vhp sugar of the 1972 season. Samples of export quality raw 1
sugar from 8 mills were studied together with 6 samples of lesser quality which
were assigned to local refining. Figur?<1 illustrates the relationship. I
01 I
50 100 150 200 250 300 350
Starch content of raw sugar, S, (ppm)
FIGURE 1. Relationship between laboratory carbonatation filterability, fc, and starch
content, S, of a number of South African raw sugars.
TABLE 11. Partitioning of pure amylose and pure amylopectin during carbonatation reaction
Amylose
Amylopectin ) in CaCO, precipitate
Raw sugar sample Crystal surface Crystal interior f, values
Designation
Amylose Amylopectin Amylose Amylopectin
PPm f 5 ppm f 5 ppm f 5 ppm rt 5
Control * - - - - 80
Control +100 ppm amylopectin - 5 - 35 65
Control +100 ppm amylose 30 - 15 - 28
* Export Quality Raw Sugar containing negligible quantity ( > 25 ppm) of natural starch,
prepared by Jaagbaan Sugar Mill.
The results in this table show that if amylose is present during the reaction
a significant part of it will be found on the crystal surface at the end of the
reaction. Conversely, amylopectin is mainly to be located firmly held within
J. P. MURRAY, F. M. RUNGGAS AND M. VANIS 1301
the crystal body with only a very small amount recoverable from the crystal
surface. The relative influence of each component on the value of fc is also
interesting. At the same concentrations, amylose,tis much more effective than
amylopectin in causing a deteri~ra$jon~~~in,'filterability. I n fact, the relative
influences of amylose, amylope6tin and potato starch can be demonstrated by
experimentally determining the concentration of each required to be added to
the starch-free raw sugar (of Table 11) to yield the same decrease in filtering
quality. From a drop in the original fc value of 80,O to 60,0, the added quantities
of amylose, amylopectin and potato starch required are respectively 30 ppm,
180 pprn and 70 ppm. Thus from the preceding results it is obvious that the
interaction of amylose with the calcium carbonate precipitation is of principal
importance in determining the carbonatation filterability.
The most important aspect of amylose influence is its apparent ability to
prevent effective agglomerate formation during the course of the reaction.
This is seen very clearly on examining electron photomicrographs of precipitates
in which the amylose content varies widely. Figure 2 shows at low magnification
a precipitate resulting from the laboratory processing of a high starch raw
sugar (325 pprn starch of which 100 pprn is amylose). There is a poor degree
of agglomeration: most particles consist of only 2 or 3 crystals which have
grown together. I n contrast, the precipitate (Fig. 3) derived from a low starch
export quality raw sugar (80 pprn starch - 25 pprn amylose) consists of large
well-formed agglomerates which yield a satisfactory carbonatation filterability,
fc, of 65,O. Figure 4 is a close-up of one of these particles and reveals that the
particle is composed of a large number of crystals which have fused together
and grown to form a mass almost 2 pm in diameter.
Figures 5, 6 and 7 indicate how agglomerates may appear in close contact
to one another during filtration. Figure 5 shows a precipitate from a raw sugar
containing 180 pprn starch. The individual particles are lcrge (approx 1 pm in
diameter) and irregularly shaped and the spaces between them - constituting
the leakage diameter - are relatively large. The particles appearing in Fig. 6
(from a sugar with 325 pprn starch) are smaller and more regular in shape
which results in a closer packing arrangement. The fc value of this precipitate
is 27,O comparehwith 40,O of Fig. 5. The cluster of particles in Fig. 7 is from
a very low starch raw sugar to which has been added pure amylose (approx
150 ppm) before carbonatation. The degree of agglomeration is very sparse
and indeed there are many single crystals. The individual particles are small
(approx 0,5 pm) and regular in shape: very close ~ a c k i n gresults. This sample
gives an fc value of less than 20,O.
Apart from its main influence during the carbonatation reaction, the
surface amylose contributes a secondary detrimental effect which becomes
evident only during the filtration process. This effect is related to the change
in close-packing of the filter cake particles caused by an amylose-induced de-
crease in surface ~ h a r g eWith
. ~ very high surface amylose concentration it may
lead to loss of cake incompressibility. The effect may be demonstrated by
measuring the fc of a high starch slurry: another sample is taken and before
filtration the particles are treated with a n amylase ("Termamyl", Novo
Industri AS) which removes by hydrolysis the great majority of the surface
amylose. The filtration rate of this sample is improved by up to 20% in
comparison with the untreated sample.16
1302 MANUFACTURING - PROCESSING
DISCUSSION
carbonate surfaces is also highly feasible.9 I t has been possible for us to show
by microelectrophoresis measurements (Rank Bros. Cambridge, Model Mk I1
-flat cell) that, in fact, this type of interaction does occur: the surface charge
on the precipitate drops significantly when tge crystal surface is covered by
an amylose layer.16
Amylose can be detected on the crystal surface very early on in the car-
bonatation reaction and it is adsorbed from solution throughout the whole
period. The large quantity of amylose which may be finally recovered from the
surface of the precipitate would suggest that it does not come exclusively from
adsorption in the final stages of the reaction but that there is a continuous
surface build-up. Some amylose is, of course, trapped by the growing crystal
surface and finds its way into the crystal interior where it may be detected only
by dissolving the carbonate crystal. However, it is the ever-present surface
layer which prevents the formation of agglomerates during the course of the
reaction. The adsorbed straight-chain molecules ( M Wt 105-106)17do not
appear to be capable of forming interparticle bridging which would aid
f l o ~ c u l a t i o n .Instead,
~ ~ ~ ~ ~ the amylose may be visualised as wrapping itself
around the growing crystallites, suppressing the surface charge (as demon-
strated) in its action as a protective colloid. The result of this interaction is
the production of a precipitate with poor agglomerate formation, low average
particle size distribution and mediocre filtration characteristics.
CONCLUSION
ACKNOWLEDGEMENTS
The authors wish to express their thanks to Dr Matic for helpful dis-
cussion; to the laboratory staff of Hulsar for carbonatation samples; to
Noodsberg Sugar Co Ltd, for the specially-prepared Jaagbaan raw sugar and
to other members of the SMRI staff, especially Mrs Day-Lewis, Mrs Dunsmore
and Mrs Coleman for analytical results, John Fitzgerald for statistical work
and Ray Carreyett for photography.
MANUFACTURING - PROCESSING
I I I I I I
0 1 2 0 1 2
P"-' P "'
FIGURE 6. Cluster of sparsely agglo- FIGURE 7. Cluster of very sparsely
merated particles from high starch sugar agglomerated particles from raw sugar with
(325 P P ~ ) . added amylose (150 ppm).
Poor filtration characteristics. Very poor filtration characteristics.
fc = 27,O. fc <20,0.
Original mag = 5 400 on 35 mm film. , Original mag = 5 400 on 35 mm film.
REFERENCES
1. Alexander, J. B. (1971). The evolution of a new look South African raw sugar. Proc
ISSCT 14:1619-1625.
2. Baumann, E. R. (1970). Polyelectrolyte coatings for filter me&a. Proc Filt Soc, 682-690.
3. Bennett, M. C. (1967, 1968). Liquor carbonatation (Parts I, 11, 111) Int Sugar J,
69:lOl-104; ibid 69:198-202; ibid 70:135-137, 173-175.
4. Bennett, M. C. (1972). Physical chemistry of phosphatation and carbonatation. Proc
Tech Session on Cane Sugar Refining Research.
5. Bruijn, J. and Vanis, M. (1970). Amylose-amylopectin ratio in the starch of sugarcane
juice and raw sugar. SMRI Comm no. 84.
6. Cowie, J. M. G. (1960). Amylose: molecular size and configuration. Makromol Chem,
42 :230-239.
7. Davis, C. W. (1959). Filterability of raw sugar. Int Sugar J, 61 :300-302.
8. Douwes-Dekker, K. (1964). The filterability of raw sugars. Proc S I T 23rd Ann Meet,
159-170.
9. Foster, J. F. (1965). Starch: chemistry and technology. Academic Press, New York
354-375. .
10. Hagedorn, H. C. and Jensen, B. N. (1948). Ferricyanide micromethod fbr determination
of glucose. Polarimetry, Saccharimetry and the Sugars (ed Bates, J.) US Government
Printing Office, Washington, 178-179.
11. Hertzberg, A. M. and Mountfort, C. B. (1959). The measurement of filterability and
a method for design of a factory filter station. Trans Instn Chem Engrs 37:5-8.
12. Kitchener, J. A. (1969). Colloidal minerals: chemical aspects of their dispersions,
flocculation and filtration. Proc Filt Soc, 553-560.
13. Matic, M. (1971). Starch determination in raw sugar by colorimetric methods. Proc
ISSCT, 14:1434-1443.
14. Murray, J. P. (1972). Filtering quality of raw sugar: influence of starch and insoluble
suspended matter. S Afr Sug J, 585-598.
15. Murray, J. P. Unpublished results.
1306 MANUFACTURING - PROCESSING
16. Nicholson, R. I. and Horsley, M. (1956). The design and performance of a new test
filter. Proc ISSCT, 14:271-287.
17. Radley, J. A. (1968). Starch and its derivatives. 4th ed, Chapman and Hall, London
91-138.
18. Somasundaran, P. and Agar, G. E. (1967). ' T h e zero points of charge of calcite.
J. Colloid and Interface Scij 24:433-440.
19. Somasundaran, P. (1969). Adsorption of starch and oleate and interaction between
them on calcite in aqueous solutions. J. Colloid and Interface Sci, 31 :557-565.
20. Tu, C. C. (1968). Filterability of Hawaiian commercial sugars. Proc ISSCT, 13:435-442.
21. Walles, W. E. (1968). $:Role of flocculant molecular weight in the coagulation of
suspensions. J. Colloid and Interface Sci, 27:797-803.
22. Whistler, R. L. (1964). Methods in Carbohyd Chem, Academic Press, New York,
4:170-174.
23. Yamane, T., Suzuki, K., Kaga, T. and Takamizawa, Y. (1969). The detrimental
effects of impurities occluded in affined sugars on the sugar refining processes. Proc Res Soc
Japan Sugar Refin Tech, 21 :95-99.
RESUMEN
La influencia negativa del almiddn en la calidad d e refinacidn del azljcar
cruda puede ser demostrada en el laboratorio midiendo el efecto del almid6n
en el comportamiento d e la filtraci6n d e azljcar cruda elaborada por car-
bonataci6n. La alta correlaci6n negativa entre el contenido d e almid6n y la
filtrabilidad es indicativa d e una relaci6n excepcional entre almid6n y la
cristalizaci6n d e carbonato de calcio. U n detenido anilisis del mecanismo
de la interacci6n almid6n-carbonataci61-1 ha revelado que el almid6n n o se
comporta como una entidad singular sin0 m i s bien en la forma de sus dos
componentes principales.
La amilopectina se encuentra dispersa primordialmente dentro del cuerpo
d e la estructura del carbonato. Este comportamiento es interpretado en t6r-
minos de las caracteristicas d e la carga especial d e la mol6cula. M i s aljn en
esta posicidn fija la influencia d e la mol6cula absorbida en las propiedades
d e la superficie del cristal durante la reacci6n e s t i estrictamente limitada: el
resultado es que la amilopectina n o juega u n papel importante en las
dificultades de filtracibn.
La amilasa c o n toda probabilidad puede ocasionar mala filtrabilidad. S u
actividad se origina d e su dBbil adsorci6n en la superficie del cristal durante
el curso d e la reacci6n. Parte d e esta amilasa es incorporada al cristal en
crecimiento pero la mayor parte se acumula en la superficie, a veces en tal
proporcidn que altera totalmente las caracteristicas d e la superficie del cristal.
Esta acci6n coloidal protectora impide la formaci6n d e aglomerados, la
presencia d e 10s cuales es esencial para una filtrabilidad satisfactoria. Ademis,
la carga de repulsidn entre particulas parece reducirse en forma significativa:
Bsto causa una reducci6n en la velocidad de filtraci6n. Se concluye que
la amilasa tiene una influencia m u y superior a la d e la amilopectina en la
filtrabilidad de la carbonatacidn del azljcar cruda.