25. Sulphitation Defecation is a universal and indispensable process. With sulphitation it is different; most of the world’s sugar factories do without it. But it is the most widespread process auxiliary to defecation. Action of sulphurous acid on juice The action of sulphur dioxide, SO, on juice is as follows: (J) It eliminates colouring matters (a property common to all acids) (2) It reduces to colourless compounds the ferric salts which have been formed by contact with mills, tanks and pipes. Sulphur Sulphur dioxide is prepared from sulphur, wl delivered in the form of small sticks or cylinders. Sicilian or American sulphur is superior to that from India and Java, Sicilian sulphur in fact is in the form of octahedral or a-type sulphur, the melting point of which (114°C) is well below that of @ or prismatic sulphur and of the precipitated or -form 200°C). Combustion of sulphur Sulphur dioxide is a gas resulting from the combustion of sulphur: S + 0: + S02 32g + 32g = 64g Hence, | kg of sulphur requires 1 kg of oxygen; the reaction releases 2,217 kcal per kg of sulphur (3,990 B.T.U./Ib.). Combustion takes place at a temperature of 363°C (685°F). If the combustion were to take place with the theoretical quantity of air, the weight of air required would be: 100 eed, Wel Jag = 43 times the weight of sulphur (air contains 23.15% of oxygen by weight). Similarly, the maximum volume of sulphur dioxide in the combustion gases is 21% (air contains 20.84% of oxygen, by volume). However, it would not be possible to obtain complete combustion with this amount of ox-408 SULPHITATION Ch, 25 ygen, and it is necessary to allow an excess of air above theoretical, If it proved necessary to use 100% excess air, a weight of air equal to cight or nine times the weight of sulphur would have to be introduced, and one would obtain only 10% of SO; in the gas. Generally, 12-16% is obtained, or an average of 14%. Precaution. In the presence of water, sulphur burns to give sulphuric anhydride, SO,, in- stead of sulphurous anhydride, SO:. On reacting water, SO; immediately forms sulphuric acid. It is therefore necessary to exercise the greatest possible care to avoid the in- troduction of water into the sulphur furnace. Accordingly, the air for combustion of the sulphur should always be dried. For this pur- pose, the air is passed over quicklime, which has a great affinity for water and absorbs the moisture from the ai It is advisable to renew the quicklime before it has become completely saturated, This may be done for example at each change of shift, that is, every 8 h. This is a detail which does not always receive sufficient attention in certain sulphitation factories, and it proves very ex- pensive in loss of sugar, and in corrosion of plates and of pipes. Sulphur furnaces In Fig. 25.1 is shown a sulphur furnace of the type most commonly used, being that furnished with the Quarez sulphitation apparatus. Itis composed of trays in the form of drawers sliding in suitable guides. On the lower tray, by which the combustion air enters, is placed the quicklime. The air then passes to the upper plate, on which is spread the sulphur. Baffles deflect the air and force it to pass in contact with the quicklime and the sulphur. In the absence of these baffles the output of the furnace would fall by half. At the outlet of the sulphur compartment the gas, which now contains 12-16% of SO2, rises to the aspirator of the sulphitation apparatus, by way of a sublimation chamber and a jacketed water-cooled flue. ‘The water which has served to cool this flue then passes over the furnace, which it cools in turn, These precautions have the object of: (J) Protecting the metal of the furnaces, which would corrode very quickly if it were taken to red heat (2) Condensing the portion of the sulphur which has sublimed. In the furnace, the greater part of the sulphur burns to form SOz, but there is always some which sublimes and rises in the form of vapour, especially if insufficient air is admitted. (3) Cooling the sulphurous gas before allowing it to come into contact with the juice. ‘Temperature. At 1,200°C (2,200°F), sulphur dioxide decomposes: SO; — S + O2 and the nascent oxygen immediately reacts with the ambient SO: to produce sulphur trioxide, or sulphuric anhydride:SULPHITATION APPARATUS 409 SO: + 0 — SO; This reaction begins to be noticeable above 900°C (1,650°F). This is a further important reason against allowing any part of the furnace to reach red heat, or forcing the combustion to a local high rate (this is possible with certain furnaces using compressed air supplied through nozzles), To remove any sulphuric acid which may have formed, the gas is generally washed by bub- bling through water. The Quarez furnaces, in which combustion is well controlled, do not provide washers, and the gas which they produce is practically free from sulphuric acid, if the furnace is well operated. The furnace temperature is 320 ~350°C (610~660°F), with 260— 290°C (500 550°F) at the outlet. A temperature of 300°C (570°F) should not be exceeded at this point, as this would cause sublimation, After the cooler, the gas temperature should drop to between 100 and 205°C (212—400°F). Capacity. For optimum performance, the tray area for a sulphur furnace should provide for a capacity of 20-25 kg sulphur/m?/h (4—5 Ib./sq.ft./h). It is sometimes possible to work at 35 kg/m?/h (7 1b./sq.ft./h) (Honig'), Where compressed air is used, air requirements may be estimated at 6 m? (assumed at 0°C and 760 mm pressure) per kg of sulphur (100 cu.ft./Ib.). This quantity corresponds to a gas of about 12% SO. Lime consumption. In practice, this may be estimated at 0.3 kg/m? (0.02 Ib./cu.t.) of air introduced into the furnace. This corresponds 10 about 1.75 kg CaO/kg sulphur. The consumption of quicklime therefore should be about twice that of sulphur. Sulphur consumption. The quantity of sulphur consumed depends on the clarification pro- cedure adopted, on the final acidity sought, and on the quantity of lime added in the defeca- tion, For a given final pH of juice, it may be reckoned that each kg of sulphur used corresponds to an additional consumption of 2.2 Ib of lime? In general, when sulphitation of juices is practised, sulphur consumption is 0.25-0.50 parts per 1,000 of cane, or 0.30.45 kg per tonne cane (0.6 ~ 1.0 Ib./ton). If both juice and syrup are sulphited, about 0.9 kg (2 Ib.) of sulphur is used per tonne of cane, Sulphitation apparatus Formerly, the sulphitation apparatus almost universally adopted in French sugar factories was the Quarez, so called after the name of its inventor (Fig. 25.1), It consists of a rectangular tank divided into 2 unequal and connected compartments. The juice to be sulphited is fed into the smaller compartment. It is picked up by a pump which takes it to the SO; aspirator. This is designed in the form of a nozzle, on the usual principle of an ejector. Thus it produces an aspiration of the sulphurous gas, and the sulphitation takes410 SULPHITATION Ch. 25 Suiphur furnace Circulation pump Fig. 25.1. Quarez and sulphur furnace place by contact and mixing in the vertical descending column returning the juice to the tank. The nitrogen and oxygen accompanying the SO: in the furnace gases are released as bub- bles at the bottom of this column and are rejected to the atmosphere by a small vent pipe. The pump is designated by the name “Quarez circulation pump”. Its output regulates the degree of sulphitation obtained. The SO: content of the juice will therefore be varied by regulating the speed of this pump. In general, it should be capable of an output at least equal to 1.5 times the volume of juice to be treated The Quarez is now being replaced by a sulphitation column, which eliminates the circula- tion pump, and the standard sulphur furnace with trays is being replaced by a rotary furnace, which is more efficient (Fig. 25.2). Sulphitation procedures The standard sulphitation process was the following: (a) Cold sulphitation, Starting with the mixed juice: Sulphite to pH of 3.8 (control by methyl orange or bromphenol blue) Lime to pH of 7.0 (control by bromeresol purple or phenol red) Heat to boiling and pump to the clarifier.. SULPHITATION PROCEDURES 4ul Fig. 25.2, Rotary sulphur furnace and sulphitation column (Fives Cail - Babcock). The sulphitation may be stopped at a pH of 4.0 or 4.5 according to the results obtained. The final pH sought is 6.9-7.0. In other words, the juice passing to the heaters should be neutral, or slightly acid Before the advent of pH control, this point was obtained by checking that the juice did not turn phenolphthalein paper pink, nor turn litmus paper blue. (b) Hot sulphitation. Sulphitation involves the production of calcium sulphite. This salt is more soluble cold than hot, the minimum solubility occurring in the neighbourhood of 75°C (165°F); it is thus deposited in the tubes of the heaters, in cold sulphitation. To avoid this drawback, the standard sulphitation process is modified as follows. Starting from the mixed juice, it undergoes: Heating to 70—80°C (160 —175°F) Sulphitation Liming Heating to boiling Pumping to clarifier. In 1945, the sulphitation procedure in use in Java was the following?: Heating to 50°C (122°F) Liming412 SULPHITATION Ch. 25 Sulphitation to pH of 7.2 Reheating to boiling Settling. From the point of view of colour and colloid elimination, the Java procedure, investigated in the laboratory in India, was judged to be the best sulphitation process. Hot sulphitation reduces appreciably the quantities of lime and SO, required. (©) Fractional liming and sulphitation, Hot sulphitation is sometimes used with success in the clarification of refractory juices. When it proves insufficient, better results are sometimes obtained by modifications similar to the following procedure, for example, which was developed in India‘: Pre-liming to pH of 8.0 Heating to 50 or 70°C (122 or 158°F) Sulphitation to pH of 5.1-5.3 Second liming to pH of 7.0-7.2 Reheating to boiling. In Mauritius, where the juices are easier to treat, the following has been devised: Heating to 55 or 60°C (130° or 140°F) Pre-liming to 0.4 g CaO per litre Sulphitation to 0.4 g SO: per litre Final liming to pH of 7.4 Reheating to boiling. Should sulphitation be done before or after liming? Sulphitation may equally well be done before liming, or liming before sulphitation, The im- portant point is that the same final pH should be reached in the juice going to the subsiders. However, it is not entirely unimportant which method is followed. The rapidity of settling and the volume of muds depend on the reaction of the medium in which the precipitate is formed: (@ If it is formed in an alkaline medium, it will be hydrated, hence an increase in the volume of muds (b) If formed in an acid medium, the speed of settling will be greater and the muds more compact. In practice, the following differences are acknowledged: (A) Liming before sulphitation. Settling is slower; volume of muds is greater, requiring a greater capacity in filter presses. Hot pre-liming decreases these disadvantages. (2) Sulphitation before liming. It follows that, in general, the second process is preferable. It is particularly indicated in the case of treating immature cane, as is the general practice in Louisiana. A good coagulation of impurities requires that before the addition of lime, the sulphitation should be made:ADVANTAGES AND DISADVANTAGES OF SULPHITATION 413 (@) At high acidity (pH 3.8 ~4.0) and low temperature (30 ~ 40°C; 86~ 104°F) (6) At low acidity (pH 5.1 ~ 5.3) and high temperature (70- 75°C; 160- 165°F). From the point of view of impurity elimination, which is measured by rise in purity bet- ween raw and clarified juice, reports are conflicting. For example, we have noted two con- tradictory points of view coming from the same country (India), It is probable, then, that results alter according to circumstances, and it is best to try both methods. Indian technologists moreover insist that the two operations, liming and sulphitation, should be carried out simultaneously, as nearly as possible. They are carried out in the one vessel, and this ensures that the results are superior to those obtained either with sulphitation first or with liming first. I is important to ensure above all that the juice is not held at high alkalinity and high temperature at the same time, as this would destroy reducing sugars and would increase for- mation of colour. Advantages and disadvantages of sulphitation On comparing the practical results of sulphitation with those of ordinary defecation, the following advantages and disadvantages may be noted: Advantages: (J) The juice settles more rapidly (hence improved capacity of subsiders) (2) The massecuites are less viscous and boil faster (3) Better crystallisation in consequence (4) Marked improvement in colour of the sugar (5) Savings in time in clarification and boiling (6 Slight gain in capacity of centrifugals (7) Better elimination of phosphates and waxes (Douwes Dekker’), leading to better refin- ing quality and filterability of the sugar produced Disadvantages: (1) Much heavier deposits in heaters; these may be avoided by sulphiting hot, but this in- volves an increase in the heating surface required (2) Higher ash content of the sugar obtained® (3) Greater expense (Quarez, circulation pump, sulphur, corrosion of vessels and pipes, etc.). Sulphitation of syrup ‘One of the best methods of obtaining white sugar is to proceed to a second sulphitation, after evaporation. Lime is added, and sulphur dioxide. The operation is generally carried out on the syrup, after the multiple effects, but in Hawaii sulphitation of juice from the 3rd effect has been practised, removing this juice from the 3rd effect and returning it continuously. Lime and SO; were added simultaneously, maintaining the pH in the neighbourhood of 7.0. The quantity of lime varied from 1.6 to 2.0 kg/tonne cane (3.5~4.5 Ib./ton), and that of sulphur from I.4 to 1.8 ke/tonne (3 ~ 4 Ib./ton)®, The juice treated was filtered on a Vallez414 SULPHITATION Ch. 25 filter, and the cakes obtained sent to the Oliver filter used in clarification, On entering the 4th effect, the pH was 7.1. ‘The processes vary somewhat, but generally consist of heating, sulphiting, and filtering. Deerr!? recommends adding milk of lime to the extent of 22.5% on weight of syrup, or 0.3-0.4% of quicklime, Sulphitation to neutrality follows immediately; the dense precipitate formed is filtered, and the juice is re-sulphited to a slight acidity. In India‘! the syrup is maintained between 6.0 and 5.5 pH, and consumes only 0.1 ~0.2 kg of sulphur/tonne cane (0.25 -0.4 Ib./ton), REFERENCES Hontc, Principles of Sugar Technology, Vol. I. Elsevier, Amsterdam, 1953, p. 682. S. MALLEA et al., Int. Sugar J., 60 (1953) 158. N. Venma ano K. S. G. Dass, Sugar, 40 (10) (1945) 44 R. PARASHAR AND K, SHANKAR, Jnr. Sugar J., 44 (1942) 184. V. RAMANYYA AND A. S. SastR¥, Sugar, 36 (I) (1941) 29. R, Parasia, Int, Sugar J., 43 (1941) 373, Douwss DekkeR, Sugar Azucar, 59 (4) (1968) 50. P. Meave, Cune Sugar Handbook, 91h edn., Wiley, New York, 1963, p- 109. ‘Sugar, 38 (10) (1943) 34 N, Detar, Cane Sugar, Norman Rodger, London, 1921, p. 291 S..N, GuNDU Rao AND K. SHANKAR, Pacts about Sugar, 35 (6) (1940) 30. OnpYoson