Vous êtes sur la page 1sur 13

Lindeman, P.F. and OShea, M.G.

Proc. Aust. Soc. Sugar Cane Technol., Vol. 26, 2004


________________________________________________________________________________________________

COLORANT REMOVAL DURING CLARIFICATION


AND DECOLORISATION PROCESSES
By
PATRICIA F. LINDEMAN and MICHAEL G. OSHEA
BSES Limited, David North Plant Research Centre, Brisbane
moshea@bses.org.au
KEYWORDS: Colorant, HMW Colorant, Clarification, Decolorisation, Carbonatation,
Phosphatation, Activated Carbon, Ion-Exchange Resin.
Abstract
FOR PRODUCERS of raw sugar, current global conditions of oversupply and poor
economic returns are placing increasing emphasis on quality in order to maintain access
to premium markets. The key parameter in the eyes of most refiners of raw sugar is
colour. Consequently, much past research has concentrated on attempts to better
quantify the chemical nature of raw sugar colorants, assess their behaviour during
various processing stages, and understand their deleterious effects upon sugar quality.
High molecular weight (HMW) colorants have long been implicated in raw sugar
refinability issues. This paper describes detailed studies of colour removal in three
refineries that were conducted to formulate a more complete understanding of HMW
colorants, as well as allow the comparison of colorants across a range of sugars and
refining processes. Colour, phenolics, very high molecular weight (VHMW) and HMW
colorants were monitored through three refineries that use different combinations of
clarification and decolorising techniques, allowing the efficiency of removal of each
particular colorant to be evaluated at different stages through the different refineries.
Sampling of refinery streams was performed at varying times to attempt to capture
differences in the incoming raw sugars, as well as the service life of particular
decolorising systems, in order to gain a representative picture. The prior identification
of some specific HMW colorants as being difficult to remove in refineries has now
sharpened the focus on developing techniques to better understand and quantify HMW
colorants. Factory control measures aimed at minimising their production should
therefore produce better refining raw sugars, while processes that are known to produce
particular colorants implicated in poor refinability could be more carefully monitored
and maintained. The ultimate goal would be to apply such knowledge from refinery
studies in order to produce higher quality, better refining raw sugars.
Introduction
For producers of raw sugar, current global conditions of oversupply and poor economic
returns are placing increasing emphasis on quality in order to maintain access to premium markets.
Due in part to these circumstances, customers are now demanding higher standards in the raw sugar
they buy in the marketplace, and on the whole, raw sugar exporters are answering these demands by
striving to improve quality, with many now producing better quality raw sugars than have been

Lindeman, P.F. and OShea, M.G.


Proc. Aust. Soc. Sugar Cane Technol., Vol. 26, 2004
________________________________________________________________________________________________

previously supplied. It is therefore important that the Australian industry, which is highly geared
towards export markets, keeps pace with these changes and remains in a position to respond to these
challenges, both in research and technical terms.
Low colour is rated by many refiners as their most important quality criterion. The increased
availability of high pol, low colour raw sugars in the marketplace has placed increased pressure on
raw sugar producers to reduce colour levels. Despite the obvious importance of raw sugar colour, it
defies description by a simple analytical measurement. A wide variety of plant pigments and natural
colorants is liberated during the crushing of sugarcane, and a proportion of these find their way into
raw sugar crystals. The cane plant itself supplies primarily low molecular weight (LMW) plant
pigments (flavonoids, chlorophylls, carotenes, xanthophylls and phenolic compounds) which
contribute approximately 30% of all raw-sugar colour, but are among the easiest components to
remove during refining (Paton, 1992). Further work has shown that some 5060% of raw sugar
colorants by weight are high molecular weight (HMW) colorants, and that the contribution of these
colorants to total colour (as measured by standard techniques at 420 nm) was approximately twice
that of the corresponding LMW colorants (Lindeman and OShea, 2001). Additional complexity is
introduced by the fact that some LMW plant pigments may undergo polymerisation (enzymatic or
thermal) and/or oxidation to produce more highly coloured materials, and that other colour
precursors present (particularly amino acids and reducing sugars) also can produce colour upon
chemical transformation during processing.
By their very nature, standard colorimetric measurements inadequately describe this
colorant complexity, and cannot contribute useful information on the relativity of individual
components responsible for overall colour. Consequently, much past research has concentrated on
attempts to better quantify the chemical nature of raw sugar colorants, assess their behaviour during
various processing stages, and understand their deleterious effects upon sugar quality. With respect
to refining ability of raw sugars, HMW colorants have been extensively studied due to their
persistence during processing and higher tendency than LMW colorants to become incorporated in
growing sucrose crystals (Tu et al., 1974; Mantovani et al., 1986). We have previously described
implications of HMW colorants on refining quality issues by examining the effects of simulated
refinery decolorisation processes on a range of synthetically produced HMW colorants, and
discussed difficulties associated with their measurement and quantification (Lindeman and OShea
2001). Here we report data on HMW colorants within refinery processes obtained by analysing
appropriate factory samples.
During the 1970s, Norman Smith (California and Hawaiian Sugar Co.) tried to determine
whether different colorants were harder to remove during refining than others, and whether the
colorant composition varied between sugars from different sources (Smith, 1972, 1976). He
examined the efficiency of colour removal using size exclusion chromatography, attempted to use
reverse phase chromatography, followed colorant profiles through the refinery and concluded that
HMW material affected the overall colorant removal efficiency through the factory. However, there
were a number of problems with this work: the size exclusion columns were inadequate for
fractionation of HMW colorants, and the extraction and concentration methods (methanol extraction
and adsorbtion onto a hydrophobic resin) would have altered the colorant composition during the
investigation.
Since this early foray into refinability issues of raw sugars, HMW colorants and
polysaccharides have been described in various reports as having deleterious effects on refining

Lindeman, P.F. and OShea, M.G.


Proc. Aust. Soc. Sugar Cane Technol., Vol. 26, 2004
________________________________________________________________________________________________

quality as outlined below. Both are difficult to remove during refining and are capable of producing
crystal shape defects during crystallisation. Past CSR Research (Smith, 1982) has shown that when
the removal of polymeric colorants during clarification is efficient, there is reduced consumption of
bone char during decolorisation processes. The SPRI group reported the fractionation of HMW
colorants in the order of 101000 kDa (Clarke et al., 1985), and have also used tests to attempt to
predict whether a sugar will decolourise well (Clarke et al., 1984). Subsequent work focussed on
fractionating HMW colorants, and examining differences between colorant profiles for raw sugars
known to be hard or easy to refine, which concluded that the quantity of very high molecular
weight (VHMW) colorant components appeared to correlate with the difficulty of refining
(Godshall et al., 1989). Other reports outlined an apparent association between HMW colorants and
polysaccharide material that travels through all processing steps, impacting on processing efficiency
and therefore ending up in the white sugar crystal (Godshall et al., 1987; Godshall and Clarke
1988).
Materials and methods
HPLC analysis of HMW colorants
All HPLC analyses were performed on a Shimadzu 10Avp instrument equipped with
Shimadzu SPD-M10A diode array and RID-10A refractive index detectors. Separations were
conducted on either a Toyopearl TSK-Gel G4000PWXL size exclusion column (300 by 7.8 mm) or
a Pharmacia Superose 12 cross-linked agarose gel permeation column (300 mm by 10 mm internal
diameter). For the former of these separations, samples were prepared by dialysis in Spectra/Por 7
1000 MW cut-off tubing for 2 days against MilliQ water followed by a final dialysis against the
HPLC mobile phase (MilliQ water containing 14 mM KH2PO4 and 34 mM K2HPO4).
Reproducibility was maintained by quantitative transfer and dilution of the contents of the dialysis
sac to known volume, and separation was achieved by elution with the above mobile phase at a flow
rate of 0.8 mL/min. In the case of Superose 12 separations, the conditions reported by Bento et al.
(1997) were duplicated: injection of 200 L of 40 brix raw sugar solution followed by elution at
0.3 mL/min with water containing 30% acetonitrile and 5mM ammonium acetate.
Colour analysis UV spectroscopy
The method used was adapted from that of Nguyen et al. (1996). Raw sugar (12.5 g), syrup
(18 g) or refined sugar (50 g) was dissolved in deionised water (100 mL). The sample was divided
into three portions and the aliquots buffered to pH 4, pH 7, and pH 9 respectively, with 1M HCl and
NaOH solutions, followed by filtration through a Millipore Millex HA 0.45 m filter. The
absorbance was read at 420 nm in a Perkin-Elmer Lambda 2 Spectrophotometer, using a 1 cm
plastic cuvette with water as the reference. Refractive indices were determined on a hand-held
Atago PR-101 digital refractometer in order to correct for concentration. The colour reading was
calculated as:
Colour =

Absorbance(420) x 1000
Cell length x Concentration ( g / mL )

Indicator values (IV) were calculated from these colour measurements as the ratio of colour
at pH 9 to that of pH 4. When used across different process streams, these figures allow a
qualitative assessment of the types of colorants that have been removed.

Lindeman, P.F. and OShea, M.G.


Proc. Aust. Soc. Sugar Cane Technol., Vol. 26, 2004
________________________________________________________________________________________________

Phenolic analysis
The method used was an adaptation of the standard method for phenolics analysis (Method
29: Phenolic acidsDetermination in raw sugar, syrups and cane juice) in the BSES [1991]
Standard Laboratory Manual for Australian Sugar Mills, Volume 2, Analytical Methods and
Tables.) The following alterations were made to the standard method:
1 cm quartz cells used instead of 2 cm quartz cells.
For ease of running sample batches, samples were filtered through Sartorius 0.8 m syringe
filters instead of Whatman Number 1 filter papers.
For syrup samples, appropriate dry equivalent weights were calculated for each sample to
ensure that phenolic levels would be approximately within the standard calibration range.
Refinery sampling
Three refineries were sampled, each operating under a different combination of
clarification/decolorisation processes. Sampling was intended to examine average measures of
performance of the respective unit processes and to reflect overall differences between them. As
such, samples were taken at various times across the process without allowances being made for
appropriate time delays, as the sampling was not intended to follow the production of refined white
sugar from a particular batch of raw sugar. Volumes of approximately 500 mL were taken for all
samples and they were transferred to an appropriate freezer storage facility until required for
analysis. Prior to analysis, samples were thawed to room temperature in a water bath. All samples
were subjected to colour, HMW colorant, phenolic and total amino nitrogen analyses, although the
latter set of these is not discussed in this paper.
Samples taken included:

Melter liquor (ML) after affination and before clarification.

Filtered raw liquor (FRL) after clarification and filtration but before decolorisation.

Intermediate liquor (INT) sample point half way through decolorisation.

Final liquor (FL) after final carbon/resin column.

Clarification efficiency was defined as the colour change in going from ML to FRL, with
decolorisation efficiency similarly defined as the change from FRL to FL. The following samples
were taken:
Refinery 1: carbonatation/activated carbon, 8 week sampling period.

14 sample sets across clarification (ML, FRL).

39 sample sets across decolorisation (FRL, INT, FL).

Lindeman, P.F. and OShea, M.G.


Proc. Aust. Soc. Sugar Cane Technol., Vol. 26, 2004
________________________________________________________________________________________________

Refinery 2: phosphatation/activated carbon, 4 week sampling period.

10 sample sets across clarification (ML, FRL).

39 sample sets across decolorisation (FRL, INT, FL).

Refinery 3: phosphatation/ion exchange resin, three separate sampling periods covering 12


decolorisation cycles of regeneration.

25 sample sets across clarification (ML, FRL).

62 sample sets across decolorisation (FRL, INT, FL).

For the three refineries sampled, Table 1 shows the average colour results for the process
streams analysed and the appropriate indicator values (defined earlier).
Table 1 Average colour values and indicator values for refinery process streams.
Process stream

pH 4

Colour
pH 7

pH 9

Indicator
value

Refinery 1
Carbonatation/activated
carbon
Raw sugar
Melter liquor (ML)
Filtered raw liquor (FRL)
Intermediate liquor (INT)
Fine liquor (FL)

989
914
402
166
84

1676
1913
708
247
128

3319
2681
1220
308
153

3.35
2.93
3.04
1.86
1.82

Refinery 2
Phosphatation/activated
carbon
Raw sugar
Melter liquor (ML)
Filtered raw liquor (FRL)
Intermediate liquor (INT)
Fine liquor (FL)

775
608
484
306
129

1619
1070
906
506
193

3311
1891
1817
891
262

4.27
3.11
3.76
2.91
2.03

Refinery 3
Phosphatation/ion exchange
Raw sugar
Melter liquor (ML)
Filtered raw liquor (FRL)
Intermediate liquor (INT)
Fine liquor (FL)

569
341
205
106
47

1199
604
390
183
75

2840
1387
1009
552
241

4.99
4.07
4.93
5.21
5.16

Discussion
Detailed studies of colorant removal across refinery processes assist in developing a more
complete understanding of the behaviour of individual colorants and potential refinability issues.
Combinations of available unit refining processes are capable of removing colorants to differing

Lindeman, P.F. and OShea, M.G.


Proc. Aust. Soc. Sugar Cane Technol., Vol. 26, 2004
________________________________________________________________________________________________

degrees. The best quality refined sugar able to be produced by a given refinery is therefore a
function of the types of colorants present in the raw sugar, and the processes employed to remove
them. Optimum process combinations have been previously assessed by Davis (2001), and this
work sought to apply this concept within an Australian refining perspective.
During this study, colorants were monitored through refineries that employ different
clarification and decolorising techniques, thereby allowing the relative efficiency of removal of
particular colorants to be evaluated. Where possible, sampling of refinery streams was performed in
order to maximise variability by reflecting the age and colour load of incoming raw sugars, as well
as the service life of particular decolorising systems employed.
HMW colorant separations
Much effort has been expended on enhancing the analytical separation capacity and
resolution for HMW colorants. However, this task is extremely difficult due to the nature of the
colorants in question.
HMW colorants consist of a diverse range of polymers, and exhibit heterogeneity both in
terms of molecular weight distribution and in chemical functionality. This inherent diversity
prevents any relatively simple separation method from characterising the mixture in detail.
A number of approaches towards the separation of HMW colorants by size exclusion liquid
chromatography have been described in the literature, and a summary of these was presented in a
previous paper on HMW colorants (Lindeman and OShea, 2001).
That paper described methods for the low and high resolution separation of HMW colorants
on the basis of size. Low resolution separations were employed after dialysis to remove LMW
colorants, and enabled the reproducible separation of VHMW colorants from HMW colorants
(Figure 1). The VHMW colorant peak contains considerable carbohydrate character and is of much
higher molecular size.

Absorbance (420 nm)

2.5

HMW

2.0
1.5

VHMW

1.0
0.5
0.0
4

12

16

20

24

Retention time (min)

Fig. 1Size-exclusion HPLC separation of HMW colorants isolated by dialysing


raw sugar. Detection is at 420 nm.

Lindeman, P.F. and OShea, M.G.


Proc. Aust. Soc. Sugar Cane Technol., Vol. 26, 2004
________________________________________________________________________________________________

Despite being unable to further resolve HMW colorants, this analysis proved capable of
reproducibly measuring relative amounts of VHMW and HMW colorants classes. Attempts were
made to include internal standards (e.g. polyethylene glycol), but problems were experienced in
terms of resolution and some intermittent cases of peak overlap between the internal standard and
the HMW colorant peak.
In the end, sufficient reproducibility was obtained by careful treatment of the retentate from
dialysis, ensuring that quantitative transfer of material from the dialysis sac was attained and
constant volumes were used for analysis.
Results generated from these separations were used to evaluate the effectiveness of refinery
processes for HMW colorant removal despite the fact that higher resolving separation methods can
be performed.
Lindeman and OShea (2001) also reported improved HMW colorant separations using
Superose 12 columns first reported by Bento et al. (1997), which resolved HMW colorants into a
number of distinct peaks on the basis of size.
A typical chromatogram of raw sugar colorants run under these conditions is shown in
Figure 2, although here a refractive index detector has been used as an alternative to the evaporative
light scattering detector employed in the original report.
Similar separations have been reported by Mersad et al. (2003a, 2003b), who used Superose
12 chromatography to examine the molecular size of synthetically derived colorants, as well as to
compare the size of raw sugar colorants. The resolution shown in Figure 2 for raw sugar colorants
is, however, markedly better than that reported by Mersad.
Quantitation and reproducibility of the results from this separation proved problematic
without a suitable internal standard. As can be seen from the chromatogram in Figure 2, finding an
internal standard for use is not a simple matter, since considerable portions of the retention time
sweep contain substrate peaks.
In the end, a polyethylene glycol standard was found with an appropriate retention time and
was used as an internal standard for comparative purposes (not shown in Figure 2). However, the
results obtained still suffered from resolution difficulties and ultimately provided only qualitative
rather than quantitative assessments.
Similar investigations with various sodium polystyrene sulfonates (SPS) as internal
molecular weight standards proved equally problematic in our hands (results not described here).
For the subsequent analysis of HMW colorants in refinery process streams, the lower resolution
method was used due to increased confidence in the ability to provide quantitative results.

Lindeman, P.F. and OShea, M.G.


Proc. Aust. Soc. Sugar Cane Technol., Vol. 26, 2004
________________________________________________________________________________________________

Relative detector response

1.2
1.0
0.8

B3

B4

refractive index
B2

420 nm

B1

0.6

0.4
0.2

B3

B4

0.0
5

10

15

20

25

30

35

40

45

50

55

60

Retention time (min)


Fig. 2High resolution size-exclusion HPLC separation of colorants in a raw sugar
solution run under conditions reported by Bento (1997). Detection was performed
with refractive index and UV (420 nm) detectors.

Colorant removal across clarification processes


The reviews by Bennett (1972) and Saranin (1972), and significant papers by Kennedy and
Smith (1976), Clarke et al. (1985), Bardwell et al. (1985) and Davis (2001) give a detailed
understanding of the chemistry of colour removal in the carbonatation and phosphatation processes.
Briefly, it has been shown that, in the case of carbonatation, impurities are trapped within the
growing calcium carbonate crystals, rather than being adsorbed onto the surface after precipitation.
Therefore, any colorant that has some acidic or anionic character and is capable of forming a weak
linkage with calcium will be incorporated into the precipitate and thus removed from the process
stream. Thus, carbonatation has a high affinity for polymeric colorants that are anionic at the
carbonatation pH, and for amino nitrogen, which is polar. It is less effective at removing plant
colorants that are not as highly charged. Phosphatation removes colorants by the ability of
tricalcium phosphate precipitates to occlude and absorb colorants, particularly fine colloidal solids
and soluble colorants. In a similar fashion as carbonatation, this process is designed to primarily
remove anionic colorants. The choice of clarification process must take into consideration the
efficiency of colour removal, since this is the primary aim of sugar refining, but cost is also an
important issue. In this regard, phosphatation processes require a lower capital cost to install, but
does run at somewhat higher operating costs (Davis, 2001).
Figure 3 shows the average percentage removal of colour (pH 7), phenolics, VHMW and
HMW colorants across the clarification processes of all three refineries. In this figure, the
calculations are based on the percentage removal of the particular species in clarification as a
proportion of the total removed across the process from raw sugar to fine liquor. It is clear that the
carbonatation process has achieved higher levels of decolorisation across the board than both
phosphatation processes. This was anticipated according to the previously mentioned literature
reviews and reports, particularly so for the polymeric VHMW and HMW colorants for which
carbonatation has a particular affinity (Kennedy and Smith, 1976). Clarke et al. (1985) surveyed
five refineries and reported that generally carbonatation removed more phenolics and amine

Lindeman, P.F. and OShea, M.G.


Proc. Aust. Soc. Sugar Cane Technol., Vol. 26, 2004
________________________________________________________________________________________________

colorants than did phosphatation, although it was also stated that phenolics can be formed during
carbonatation. The two phosphatation refineries produced similar results for most parameters with
the exception of VHMW colorants. The observed differences between the two phosphatation
processes were probably influenced by the degree of colour removal in the previous affination
stages (data not presented here) which has not been taken into consideration for these calculations.

COLOUR

100

PHENOLIC
VHMW

% REMOVED

80

HMW
60
40
20
0
-20

CARBONATATION
(REFINERY 1)

PHOSPHATATION
(REFINERY 2)

PHOSPHATATION
(REFINERY 3)

Fig. 3Removal of colour (pH 7) and colorants across the clarification processes
for each refinery. Calculations are all based on the percentage removal of colour or
colorant based on the feed material into the process.

Carbonatation performs effectively regarding colour removal, with 63% of the input colour
being removed. This compares favourably with the two phosphatation refineries which returned
colour removal figures of 15% and 35% respectively. With respect to phenolics, carbonatation
removes very little material, and that removed is probably polymeric in nature rather than LMW or
monomeric phenolics. Levels of VHMW colorant drop over carbonatation (ML to FRL) (not
shown) to a greater extent than do the corresponding HMW colorant levels. This result is expected
based on prior observations of carbonatation being an efficient remover of very high molecular
weight and uncharged or colloidal materials, and is of course a reflection of the fact that
clarification is designed to remove these species. Further evidence for this can be found in the
indicator values which increase slightly across carbonatation, indicating that carbonatation is
selectively removing polymeric colorants (low IV colorants) over LMW colorants (high IV
colorants), thereby reducing pH 4 colour to a greater extent than pH 9 colour.
The two phosphatation processes performed less well than carbonatation with respect to
overall colour removal. As outlined above, some of the variation observed between the
phosphatation results can be attributed to the efficiency of the previous affination stage. The
variation observed was particularly large for the VHMW colorants. Phosphatation removes a small
amount of phenolic material, with the negative result observed at one refinery most likely being due
to recycle streams. The indicator value has significantly increased across clarification, indicating
that phosphatation must be removing substantial quantities of polymeric material with respect to
LMW colorants. This is of course a good outcome, as these materials are not easily removed during
subsequent decolorisation.

Lindeman, P.F. and OShea, M.G.


Proc. Aust. Soc. Sugar Cane Technol., Vol. 26, 2004
________________________________________________________________________________________________

Colorant removal across decolorisation processes


Virtually all refineries utilise either activated carbon or ion-exchange processes to achieve
decolorisation of liquor streams. Activated carbon colour removal relies on surface forces to create
a stronger attraction between the carbon surface and the colorant than exists between the colorant
and the sugar liquor stream (Dominguez and Hyndshaw, 1977). The colorant molecules are tightly
held against the surface of the carbon particles and the large surface areas involved mean that very
large quantities of colorant can be adsorbed and removed from solution before the carbon reaches
the point where it is exhausted and requires regeneration. Due to the physical adsorption processes,
carbon is not specific for the removal of particular types of colorants, but does a very good job at
removing flavonoid and phenolic colorants (Bardwell et al., 1985), while struggling somewhat to
remove amino-nitrogen colorants and their derivatives (Riffer, 1988).
Ion-exchange resins on the other hand decolorise by having anionic groups on colour bodies
displacing chloride ions in the resin matrix, although some physical adsorption probably also takes
place. The selectivity of resins for colorants is a function of the ionic charge and aromatic character
of both resin and colorant and, as a result, resin does not remove as broad a range of colorants as
activated carbons.

100

COLOUR
VHMW

PHENOLIC
HMW

% REMOVED

80
60
40
20
0
CARBON
(REFINERY 1)

CARBON
(REFINERY 2)

RESIN
(REFINERY 3)

Fig. 4Removal of colour (pH 7) and colorants across the decolorisation


processes for each refinery. Calculations are based on the percentage removal of
colour or colorant from the feed material into that process.

As shown in Figure 4, the decolorisation procedures employed were particularly efficient


and achieved similar overall levels despite some differences in removal of particular colorant
species. Comparisons must be carefully interpreted here since no account is taken of the quality of
raw sugar used in each refinery, nor the efficiency of affination and clarification stages at the
refinery front end, both of which will affect subsequent process performance as the decolorisation
systems are not being observed under similar colorant loadings.
For comparative purposes, the colour removal (measured at pH 7) across activated carbon
for both refineries studied (708 to 128 and 906 to 193 ICUMSA colour unitsTable 1) compares

Lindeman, P.F. and OShea, M.G.


Proc. Aust. Soc. Sugar Cane Technol., Vol. 26, 2004
________________________________________________________________________________________________

favourably with other reported values for activated carbon (Debwe, 2001), where typical removals
were from 800 to 350 ICUMSA colour units for the change FRL to FL. Further literature reports
claim a decolorisation efficiency of 83% for a French refinery using granular activated carbon, with
the two systems studied here achieving 82% and 79% respectively (Mabillot, 1996). Decolorisation
with activated carbon is particularly effective at removing ionisable colorants that have a high
impact on pH 9 colour, but does not act particularly well on polymeric colorants; hence a
considerable drop was observed in indicator values across both processes sampled. In agreement
with the observations of Bardwell et al. (1985), the carbon decolorisation columns outperformed the
resin column for the removal of phenolics.
For one of the activated carbon refineries (Refinery 1), results for the removal of VHMW
colorants were extremely variable with virtually none removed, and the reasons for this are not
clear. Considerably better data on VHMW colorant removal was obtained from the remaining two
refineries, with the expected trend of carbon removing VHMW colorants to a greater extent than
resin observed. Similarly for HMW colorants, carbon appeared to perform slightly better than resin,
although this result was probably not significant based on the number of samples taken and the
variation observed. The trend was expected as VHMW colorants are less charged, contain
significant polysaccharide character and would not be anticipated to bind to activated carbon. On
the other hand, the HMW components are more highly coloured and charged, and contain higher
proportion of phenolic/flavonoid type materials, thereby having a greater overall affinity for carbon.
These data also support past observations of Clarke et al. (1985) that VHMW impurities are
difficult to remove during refining processes.
In the case of decolorisation with ion exchange resin, overall colour removal was similar to
that of the activated carbon systems being around 80%. However, there was no significant change
in indicator value observed across the process. This is a reflection of the different affinity of resin
for removing pH sensitive and insensitive colorants as described above for activated carbon. For
phenolics, the efficiency of removal was satisfactory but somewhat below that of the activated
carbon as expected. As was observed for the carbon decolorisation systems, the removal of VHMW
colorants from FRL to FL was not as efficient as for HMW colorants, again due to VHMW
colorants having slightly less overall charge and therefore being less likely to be adsorbed by resin.
Conclusions
These detailed studies of colour removal in various refineries were intended to formulate a
more complete understanding of HMW colorants and potential refinability issues, as well as
allowing the comparison of colorants across a range of sugars and refining processes. Colour,
phenolics, VHMW and HMW colorants were monitored through three refineries that use different
combinations of clarification and decolorising techniques, allowing the efficiency of removal of
each particular colorant to be evaluated at different stages through the different refineries. Sampling
of refinery streams was performed at different times to reflect the age and colour load of incoming
raw sugars, as well as the service life of particular decolorising systems, in order to gain a
representative picture.
This paper has demonstrated methods by which HMW colorants can be separated from one
another, and that such separation methods can assist in tracking colorants across refinery processes.
The prior identification of some specific HMW colorants as being difficult to remove in refineries
(Lindeman and OShea, 2001) has now sharpened the focus on developing techniques to better

Lindeman, P.F. and OShea, M.G.


Proc. Aust. Soc. Sugar Cane Technol., Vol. 26, 2004
________________________________________________________________________________________________

understand and quantify HMW colorants. Factory control measures aimed at minimising their
production should therefore produce better refining raw sugars, while processes that are known to
produce particular colorants implicated in poor refinability could be more carefully monitored and
maintained. The ultimate goal would be to apply such knowledge from refinery studies in order to
produce higher quality, better refining raw sugars.
Other sugar industry research groups have also indicated concerns about their inability to
quantitate such species, and without a doubt, this remains a key endeavour in colorant research.
Future advances in chromatographic techniques and molecular detection methods may provide the
tools to better monitor and understand the behaviour of specific HMW colorants during process.
Acknowledgements
This study could not have proceeded without the tremendous support of the refineries where
sampling was conducted. The authors would also like to thank Dr Graham Leonard, Dr Don
Mackintosh and Niall Masel (BSES Limited) for their support and technical assistance. This study
was partly funded by a grant from the Sugar Research and Development Corporation (SRDC).
REFERENCES
Bardwell, D.J., Croker, J.R. and Paton, N.H. (1985). Recent applications of colour fractionation in
CSR refineries. Proc. Sugar Ind. Technol., 44: 5387.
Bennett, M.C. (1972). Physical chemistry of phosphatation and carbonatation. Proc. Tech. Sess. Cane
Sugar Ref. Res., 6275.
Bento, L.S.M., Pereira, M.E. and S, S. (1997). Improved analysis of sugar colorants: By gel
chromatography with UV and ELS. Int. Sugar J., 99: 555562.
BSES (1991). The Standard Laboratory Manual for Australian Sugar MillsVolume 2 Analytical
Methods and Tables. BSES, Indooroopilly.
Clarke, M.A., Blanco, R.S. and Godshall, M.A. (1984). Color tests and other indicators of raw sugar
refining characteristics. Proc. Sugar Proc. Research Conf., 284302.
Clarke, M.A., Blanco, R.S., Godshall, M.A. and To, T.B.T. (1985). Color components in sugar
refinery processes. Proc. Sugar Ind. Technol., 44: 5387.
Davis, S.B. (2001). The chemistry of colour removal: a processing perspective. Proc. S. Afr. Sugar
Technol Ass., 75: 328336.
Debwe, M. (2001). Operation and performance of the granular activated carbon plant at Nchalo. Proc.
S. Afr. Sugar Technol., 75: 337340.
Dominguez, A.R. and Hyndshaw, A.Y. (1977). Activated carbon for refining sugar. Proc. Int. Soc.
Sugar Cane Technol., 16: 26452656.
Godshall, M.A. and Clarke, M.A. (1988). High molecular weight (HMW) color in raw and refined
sugars. Proc. Sugar Ind. Technol., 47: 180193.

Lindeman, P.F. and OShea, M.G.


Proc. Aust. Soc. Sugar Cane Technol., Vol. 26, 2004
________________________________________________________________________________________________

Godshall, M.A., Clarke, M.A., Dooley, C.D. and Roberts, E.J. (1987). Large colorant and
polysaccharide molecules in raw cane sugars. Proc. Sugar Ind. Technol., 46: 193211.
Godshall, M.A., Clarke, M.A., Dooley, C.D. and Roberts, E.J. (1989). High molecular weight color
in refineries. Proc. 1988 Sugar Proc. Research Conf., 7595.
Kennedy, A.M. and Smith, P. (1976). Color in refineries. Proc. Sugar Ind. Technol., 35: 156160.
Lindeman, P.F. and OShea, M.G. (2001). High molecular weight (HMW) colorants and their impact
on the refinability of raw sugar. A study of Australian and overseas raw sugars. Proc. Aust. Soc.
Sugar Cane Technol., 23: 322329.
Mabilllot, M. (1996). Granular activated carbon decolourisation station at Eridania Becghin-Say Nantes
Refinery, France. Sugar Ind. Technol., 55: 922.
Mantovani, G., Vaccari, G., Sgualdino, G., Aquilano, D. and Rubbo, M. (1986). Coloring matter
inclusions in sucrose crystals. Proc. Int. Soc. Sugar Cane Technol., 19: 663669.
Mersad, A., Fargues, C., Lewandowski, R. and Decloux, M. (2003a). Sugar colorants: molar masses
and retention by cross-flow filtration assessed by size exclusion chromatography on Superose
12. Zuckerindustrie, 128: 434442.
Mersad, A., Lewandowski, R., Heyd, B. and Decloux, M. (2003b). Colorants in the sugar industry:
laboratory preparation and spectrometric analysis. Int. Sugar J., 105: 269281.
Nguyen, H.H., Rowe, G., McCunnie, K.A. and Player, M.R. (1996). Rapid analytical methods for
colour and ash in raw sugar. Proc. Aust. Soc. Sugar Cane Technol., 18: 341349.
Paton, N.H. (1992). The origin of colour in raw sugar. Proc. Aust. Soc. Sugar Cane Technol., 14: 817.
Riffer, R. (1988). The nature of colorants in sugarcane and cane sugar manufacture. In: Clarke, M.A.
and Godshall, M.A. ed. Chemistry and Processing of Sugarbeet and Sugarcane. 186207.
Elsevier Science Publishers, Amsterdam.
Smith, N.H. (1972). Gel filtration for determining efficiency of colour removal in processed raws. Proc.
Tech. Sess. Cane Sugar Ref. Res., 17.
Smith, N.H. (1976). Fractionation of sugar colorants by high pressure liquid chromatography. Proc.
Tech. Sess. Cane Sugar Ref. Res., 1934.
Smith, P. (1982). Analytical techniques for the separation of colour components and their application in
sugar processing in CSR factories. Proc. Sugar Proc. Research Conf., 256263.
Saranin A.P. (1972). Technology of phosflotation of sugar melt. Sugar Technol. Rev., 2: 172.
Tu, C.C., Kondo, A. and Sloane, G.E. (1974). The role of high and low molecular weight colorants in
sugar color. Proc. Int. Soc. Sugar Cane Technol., 15: 13931401.

Vous aimerez peut-être aussi