International Sugar Journal 2009 Vol. 111 No. 1324 pp.

234, 236-238

Quality changes during storage of raw and VLC sugar: Effects of pH and moisture*
M. Saska and V. Kochergin Audubon Sugar Institute Louisiana State University Agricultural Center St.Gabriel, Louisiana 70776, USA

Abstract A review of sugar quality data from eight Louisiana sugar mills revealed fairly significant increase of color and pol loss in storage. In order to gain more understanding of the mechanisms of the changes in storage and to explore what options may exist for reducing sucrose and quality loss, several aspects of sugar storage were investigated in laboratory thermal storage tests at various sugar moisture and pH levels. The results of the storage tests confirmed that sugar inversion in storage is accelerated by increasing sugar moisture, in agreement with the safety factor concept. However, when pH of the sugar before storage was raised with small doses of dilute milk-of-lime, the sugar inversion in storage was greatly reduced or eliminated even at moisture levels up to 2%. The color increase was also less the higher were the sugar pH and sugar moisture. Although confirmation will require additional longer-term full-scale testing, it appears based on the laboratory thermal tests that increasing the sugar pH with small dose of milk-of-lime directly in the centrifugals may be a cost effective way to reduce significantly sucrose loss and color increase during storage of raw and VLC sugar.

Introduction Increasing energy costs are among the factors behind the trend towards higher quality raw sugar. Production in the mill and transportation to a refinery of a very low color (VLC) and very high polarization (VHP) raw sugar shifts the purification load to the cane processing facility, the mill, where energy needs are met by combustion of bagasse. Any quality loss in storage and transport from the mill to the refinery will directly affect the overall cost of production of refined sugar.

_____________________________________________________________________________ * A more detailed account of the results and other aspects of raw and VLC sugar storage may be found in ref. (1), or by contacting the authors at msaska@agcenter.lsu.edu, or vkochergin@agcenter.lsu.edu 1

Table I: Raw sugar quality changes in storage. Eight Louisiana sugar mills, 2006 2007 shipping season data.

Data from several Louisiana factories (Table I) revealed fairly significant increases during storage of whole and affined sugar color and reduction of sugar pol when expressed on dry matter basis (sugar purity). Because of the three-month sugarcane processing season, raw sugar in Louisiana is stored in warehouses for up to ten months, and over that period, based on the 2006 2007 data, the whole color is expected to increase by 50-150 % and the affined color by 15-70 %. This has significant impact on the de-colorization load in the refinery. There is also a noticeable although quite variable loss of sucrose. Unlike the color, the sugar purity drop correlates fairly well (Figure 1) with the initial safety factor, defined as usual as SF = Moisture / [100 Polarization] which is also listed in Table I. This is related to the accelerating effect described later of the sugar moisture on the inversion rate of sucrose in the molasses film on the crystal surface at the acidic conditions prevalent in standard raw sugars. The safety factor was designed to indicate the safe range of moisture and polarization (SF < 0.25) for the sugar to keep well in storage. This reflects the traditional experience with storage of conventional raw sugar, and even then it is no guarantee that deterioration in storage will not occur. It is unknown how well this factor may reflect the storability of very low color sugar with range of parameters (polarization, color, invert, etc.) quite different that the traditional high-color low-pol raw sugars. The SF limit of 0.25 was exceeded on occasions by several of the mills (1), but in storage it trended lower, presumably as the sugar moisture equalized during storage. As the safety factor appears largely unrelated to the rate of color generation in storage (data not shown), the temperature of the sugar at the time when put in storage must be a major

factor. This has been noted many times before and was quite obvious from inspection of the one warehouse at one of the mills (1) that does not have the ability to cool the sugar before storage by slinging. Figure 1: Effect of the initial safety factor on sugar purity drop in storage. 2006 2007 Louisiana shipping season data.

In order to investigate the effects of various sugar quality parameters on its storability, it is desirable to have a rapid test that would indicate how a particular sugar might behave in long term storage, and whether any modifications in the process are possible so that the sugar loss and color increase in storage are reduced or eliminated. To that effect a series of tests were done by storing the sugars in sealed containers at elevated temperatures. Besides the quality of the parent sugar, two experimental variables were tested, viz. the moisture of the sugar and its pH after adjustment with small doses of calcium oxide.

Experimental Procedures Sugar samples were held in air-tight 300 mL heavy glass wide-mouth bottles at various temperatures for various periods of time. Eventually, a temperature of 70 C and a period of 5 days were settled on. At those conditions the changes in sugar quality (color and invert sugar content) were in most cases quite marked. Similar experimental conditions were used before (2) in an important work on sucrose and invert degradation during storage of final molasses. In the first few tests, the bottles were filled with the sample only partially, with air taking up the rest of the volume. It became quickly obvious by comparison with identical tests where the residual air was replaced with nitrogen, that the sugar degradation was accelerated in the presence of air. Therefore, in the following tests the bottles were packed full and tight with sugar, with the intention to approximate more closely the conditions in bulk storage. Because of the hightemperature bottle top liners, no moisture was lost during storage. When the tests were to be done at various sugar moisture levels, the sugar was first predried at 60 C under vacuum, and then its moisture raised to the desired level by accurately 3

weighing in the pre-determined amount of de-ionized water onto 350 g of pre-dried sugar, and homogenizing the moisture by shaking in a closed plastic container for a few minutes. When the pH level of the sugar was to be adjusted (tests 7, 8, 9, 10, and 11) pre-determined amount of a calcium oxide suspension in de-ionized water was weighed in instead or in addition to de-ionized water. In test 4, the pH of the sugar was adjusted by applying dilute milk-of-lime in lieu of the wash water directly in a pilot centrifugal as explained in more detail further in the text. Sugar color was determined according to the ICUMSA Method GS1/3-7(2002) at pH 7.0 and also using the same procedure but at pH 8.5 in order to allow direct comparison with the commercial data measured at that pH. Glucose and fructose were determined according to the ICUMSA Method GS1/2/3-4(1998) with lactose as the internal standard. Sugar moisture was determined by drying at about 60 C under vacuum, for about 2 to 3 hours, and must therefore be considered as the external rather than total moisture. The sugar pH was recorded before the pH adjustment required in the measurement of color, and is therefore at about 20 Brix for lower color sugars and 10 Brix for high color raw sugars. Results In test 4 (Figures 2 and 3) the parent sugar was a VLC sugar with color of about 600 IU. The thermal storage of this sugar was tested at 0, 1 and 2 % moisture. The color increased two to three-fold (Figure 2, upper left graph), and a 0.6 0.7% loss of sucrose was apparent from the invert sugar increase at 1 and 2% moisture (Figure 3, upper left graph). This is consistent with the expectations based on the safety factor concept. The parent sugars for the other three experiments in Test 4 were prepared by mingling the VLC sugar with a saturated liquor prepared from the same sugar. The magma was then spun in a 0.5 m ID basket centrifuge and washed in the centrifuge for two seconds with water (upper right graph), and with 18 and 36 g/L calcium oxide suspension in water. The two-second wash corresponded to about 0.5 % on the sugar basis. The sugars thus produced had a color (pH 7.0) 320, 330 and 360 IU respectively. Each of the three sugars was then subjected to the same thermal storage test at 0, 1 and 2 % moisture. It is evident that raising pH of the sugar with dilute milk-of-lime had a drastic effect on reducing the sucrose loss; the invert still increased in storage but about 10 times less than when the sugar pH was un-adjusted; from about 3,000 mg/kg in sugar stored at its natural slightly acidic pH, to less than 300 mg/kg when calcium oxide was used. The data in Figure 2 show that the higher pH does not promote color formation in storage; on the contrary, there is a small but reproducible reduction of the color generation in storage with increasing calcium oxide dose. Moisture, unlike in acidic environment, appears to have also a positive effect on reducing color development in storage and sucrose inversion. Clearly, this is contrary to the concept of the safety factor, and may indicate that this concept may not apply if the sugar pH is increased before storage as in these tests. In the remaining tests 7 11 (Figures 3 and 4), the effects of sugar pH and moisture were further evaluated with different sugars brought from the mills; a high quality VLC sugar in Test 7, standard raw sugars in Tests 8, 10 and 11 and a high color deteriorated raw sugar in Test 9. The difference in these tests was that accurately known amounts of milk-of-lime were applied to pre-dried sugar samples in the laboratory as explained in the Procedures section, rather than by washing the sugar in the centrifugal with dilute milk-of-lime as in Test 4. Nevertheless, the

results confirmed the trends observed in test 4: raising the pH of the sugar before storage significantly reduced sucrose inversion during storage and the color increase in storage was reduced as well. Clearly, without pH adjustment moisture in the sugar promoted sucrose inversion but the increase was reduced or even eliminated by raising sugar pH with as little as 100 mg calcium oxide per 1 kg sugar. At ash levels 0.1 to 0.3 % in raw sugar, the effect of the lime addition on ash in sugar is negligible. Conclusions An increase of the sugar color of up to 600 color units (at pH 8.5) per month, and a loss of sucrose of up to 0.16 % / month during industrial storage of raw sugar in Louisiana are relatively high. A five-day, 70 C laboratory thermal storage test was developed to study the effects of pH of the sugar and its moisture on sucrose loss in storage and color increase. It was found that by adjusting the sugar pH with small dose of dilute milk-of-lime (50 200 mg/kg sugar), either directly by replacing water with dilute milk-of lime in the centrifugal wash system, or by applying directly onto the sugar before storage, the sucrose inversion loss was greatly reduced or even eliminated, even at very high moisture levels. Increasing the pH of the sugar before storage also appeared to reduce the color generation during storage. Acknowledgments Funding from the American Sugar Cane League and cooperation of the Louisiana sugar mills are gratefully acknowledged.

References (1) Kochergin and Saska, Storage and production of VLC and VHP sugar. Paper #944, Proceedings 2008 Meeting of Sugar Industry Technologists, Leipzig, Germany, May 2008. (2) Mauch and Kraus, Behaviour of d-glucose and f-fructose in the sugar manufacturing process and their enzymatic-photometric determination. Proc. XVI Congress ISSCT, 1977, 2829 2845.

Figure 2: Sugar color (pH 7.0) after storage. Parent sugar was washed in centrifugal with water or milk-of-lime, and stored at 0, 1 and 2% moisture (Test 4). The dotted horizontal line indicates the sugar color before storage. Water
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Figure 3: Sugar color (pH 7.0) after storage: Effects of CaO dose (in mg/kg sugar) and moisture. The dotted horizontal line indicates the sugar color before storage. . Test 7 0 Test 8 1600
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Figure 4: Invert sugar content in mg/kg after storage, at 0, 1 and 2 % moisture. The parent sugar was prepared by washing VLC sugar in a centrifugal with water or dilute milk-of-lime (Test 4). The dotted horizontal line indicates invert sugar content before storage. Water Water 10000
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Figure 5: Invert sugar (mg/kg) after storage, at 0.5 to 2.0 % moisture. Effects of CaO dose in mg/kg sugar. The dotted horizontal line indicates the invert sugar content before storage. Test 7 Test 9
6000 5000 4000 3000 2000 1000 0 0.5 1.0 0 50 100 150 200 4000 3500 3000 2500 2000 1500 1000 500 0 0.5 1.0 0 50 100 150 200

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