The Philippine Agricultural Review Part 7

From the Dutch department of agriculture in Java the Bureau of Agriculture has imported seed of the best robusta coffee available for distribution, as well as a considerable quant.i.ty of seed of the ordinary robusta cultivated in that island. All readers who are interested in planting robusta coffee are cordially invited to communicate with the Bureau of Agriculture.

CANE-JUICE CLARIFICATION.

By Cleve. W. Hines, M. S., Station Superintendent.

The clarification of the juice forms one of the most important operations in sugar manufacture, since the higher the purity of the juice to be concentrated, the greater the percentage of sucrose that will crystallize, and the easier it will be to make a marketable sugar. If a high-grade sugar, or even yellow clarified sugar is to be made, this work should receive still greater attention.

Before considering the methods to pursue and the reagents to use, it is well to decide first upon the grade of sugar it is desirable to make. If ordinary centrifugal sugar testing 96 is desired, it will usually be practical to use only lime in the clarification, since in these Islands cane reaches full maturity, and consequently the purity of the normal juice will be quite high, sometimes as high as 90 or 92 (apparent purity). If, however, it is desired to make a white plantation sugar, or granulated sugar, it will be advisable to subject the juice to an acidifying or bleaching treatment, as well as to the lime treatment. Usually sulphurous acid is used for this purpose, but sometimes phosphoric acid, or a form of it, is employed. It is generally best to administer the acidifying agent before the application of the lime, since this raises the acidity and permits a larger amount of the lime to be used. However, this process is reversed by some manufacturers, and very good results are often reported.

In the acidifying of any cane juice, care must be exercised that too high an acidity is not reached, since acids have an inverting effect upon sucrose, thus causing a noticeable loss. This of course depends upon the degree of acidity carried, the temperature maintained, and the methods followed during the time the juice remains acid.

When it is desired to make a high-grade crystal for granulated sugar, the clarification must be more complete, and a water-white thick liquor should result, without subsequent treatment by bleaching agents and other chemicals, except the neutralizing of the slightly yellowish tint, which will be mentioned later.

Reagents Used in Clarification.

There is a great variety of reagents at the command of the sugar manufacturer, each of which has certain merits over others, and all are valuable in their place when properly used. It will therefore be the duty of the operator to select those which best meet his individual conditions.

It is the purpose of this article to give a brief survey of the more common reagents which, under certain conditions, may be used to advantage in these Islands.

Lime.--This is perhaps one of the most common and most widely used of all the reagents. Since the object in view is to increase the purity of the juice, it is obvious that the purest rock obtainable should be used in the preparation of the lime. Another reason why a good lime should be employed, is that one of the main impurities of the lime rock is magnesium, which, when mixed with cane juice, becomes very troublesome in the incrusting of the evaporator tubes, thus greatly lowering the coefficient of heat transmission.

Much of the lime on the market in the Philippines has been made without any attempt to select pure clean limestone or sh.e.l.ls. This is not suitable for putting into cane juice, and will result in a great deal of trouble whenever used in modern evaporating plants. There is, however, an abundant supply of limestone found in various parts of the Philippines, which a.n.a.lyses show to be almost free from impurities, and which will make a most excellent lime for clarifying purposes if burned properly. At present there is no modern plant for burning this rock on a large scale and consequently much of the work is done in a very crude and unsatisfactory manner. Most of the lime for clarification, in modern sugar factories, is imported, and const.i.tutes a very heavy expense. If a lime kiln were installed in conjunction with some of our sugar factories, fresh and well-burned lime might be made as needed. The carbon dioxide could be used in the juice clarification, as is done in Java, and thus a good grade of plantation sugar could easily be manufactured. Any excess of burned lime might very readily be sold to other factories, which now use only high-priced imported lime.

The lime used should be of the unslaked type, and should be protected from the air until a short time before using. The process of preparing this consists of heating lime rock to a very high temperature, in a kiln for that purpose, whereby the limestone is broken into two component parts, expressed by the following chemical equation: CaCO3 (limestone) heated to high temperature-->CaO (calcium oxide) + CO2 (carbon dioxide). This calcium oxide, commonly known as "quick lime,"

is the substance desired in clarification. It should be slaked by being placed in water just before it is desired for use. This milk of lime should not be used until after the high temperature caused by the violent chemical action has subsided. On account of the heat involved and the high alkalinity in local portions, it is never safe to apply crude lime to the juice without previously slaking it in water, nor is it advisable to use a quant.i.ty of juice to mix this lime, as is quite often practiced in these Islands, since in this case there may be a loss of sucrose, with a resulting dark-colored product, which will impair the color of the clarified juice. The following chemical equation will express the reaction when this lime is slaked: CaO (calcium oxide) + H2O (water)-->Ca(OH)2 (calcium hydroxide).

This calcium hydroxide is a substance which is very caustic, and care must be exercised in handling it. Like all bases, it has a great affinity for acid, and consequently its first action is to neutralize part of the acids present. It then coagulates alb.u.mins and alb.u.minoids, which form a part of the impurities, and throws down insoluble salts of sulphates, carbonates and phosphates, and of the bases iron and aluminum. These act as mechanical precipitants, a.s.sisting in bringing down other impurities. The compounds of calcium are practically insoluble in cold cane juices, and may be readily filtered, or settled, and the supernatant liquor drawn off. In the addition of lime, as well as in the application of other reagents, much care must be observed that the proper amount is added. If too little is used, there will be poor clarification and settling of the precipitate, while if too much is used, so that alkalinity is reached, and the juice heated to a high temperature, there will be a darkening of the juice caused by the decomposition of the reducing sugars by the calcium, and the formation of dark-colored compounds, which are very hard to remove. If the juice is limed to three-tenths or four-tenths cubic centimeter acidity against N/10 NaOH, using phenolphthalein as an indicator, there will be little or no chance of trouble. With the above dangers in view, it is not safe to employ the haphazard methods of liming usually practiced here, but the milk of lime should always be made of stated density and a measured or weighed amount should be supplied to each clarifier of juice, corresponding to prevailing conditions.

Sulphur dioxide.--Where a better grade of sugar than 96 test is desired, it is often advisable to subject the juice to further treatment, one reason for which is to increase the acidity so that a larger amount of lime may be added to effect the clarification. In addition to this the sulphur acts to some extent directly as a clarifying agent, by precipitating some of the impurities. It also acts as a bleaching agent by extracting the oxygen from the impurities and lastly it acts as a disinfectant. It is formed by burning crude sulphur in a stove made for that purpose. S (sulphur) + O (oxygen heat)-->SO2 (sulphur dioxide).

Sometimes bombs filled with liquid sulphur dioxide are purchased for this purpose. These are inconvenient to use, and this method is ordinarily more expensive than the usual one of burning the sulphur and producing the gas directly at the factory.

Sulphur dioxide is a heavy gas which is very readily absorbed in water, and at a temperature of zero C. nearly 80 per cent by volume of the gas will be taken up.

At 40 C. only about 18 per cent by volume of the gas will be absorbed. It may readily be seen that the percentage of gas contained in the juice when saturated will be determined by the temperature.

The following equation expresses the absorption of sulphur dioxide in water at ordinary temperature:

SO2 (sulphur dioxide) + H2O (water at low temperature)-->H2SO3 (sulphurous acid).

Another thing of very great importance is the cooling of the gases to condense any water that may be present so that no hot gas will reach the juice to be treated or combine with water in the pipes. The equation represented when high temperatures are used is as follows:

SO2 (sulphur dioxide) + H2O (water) + O (high temperature)-->H2SO4 (sulphuric acid).

This last-named acid is very corrosive and a powerful investing agent. It therefore has the property of rapidly destroying sucrose, especially at a high temperature.

In the burning of sulphur it is well that as thorough a combination as possible be obtained, else there will be a loss of sulphur, which will deposit in the tubes and choke them, and more time will be required for the process. The fumes from a well-regulated sulphur furnace should contain from 15 to 16 per cent sulphurous acid. The theoretical percentage obtainable is about 21 per cent of the acid.

Carbon dioxide.--In recent years carbon dioxide gas has found a very useful application in the cane-sugar factories, where a good grade of plantation sugar is desired.

Java factories have been the foremost in elaborating a system, through their eminent technologists, so that today one may find the bulk of the sugars they turn out from certain factories of a very satisfactory grade and color. The method they use requires a great deal of skill and attention in order to yield results that are satisfactory. It is patterned after the process used in beet-sugar factories, with some distinct modifications, which make it applicable to a juice containing glucose, as is always the case with cane juices.

The object of applying any clarifying material is to effect a rise in purity, and it is especially desirable to remove, in all cases, the substance added, since this itself would tend to act as an impurity and thus give a lower coefficient, if not properly removed. The lime, which has been added previously, may be partly removed, as the original precipitate formed, and any free lime or compound which may be easily decomposed will combine with carbon dioxide, forming calcium carbonate or limestone, which is quite insoluble and may be very easily filtered off.

Ca(OH)2 (calcium hydroxide) + CO2-->CaCO3 (calcium carbonate) + H2O (water).

Whether single or double carbonation is used, the same general methods are employed, and results are expressed by the same chemical equation.

As stated before, the carbon dioxide may be recovered from the kilns during the burning of lime, as is commonly done in the beet-sugar industry, or it may be purchased in the form of liquid CO2 contained in heavy iron containers. It is also feasible to use flue gases for this purpose, where a good combustion is obtained, and after they have been properly treated.

Phosphoric acid.--It is sometimes advisable to apply a form of phosphoric acid as a clarifying and precipitating agent after the lime. This may be used in various forms depending upon the individual desires of the operator.

The compound usually found on the market may consist of one of the following (or a combination of them):

H3PO4 (ortho phosphoric acid).

CaH4(PO4)2 (mono-calcium phosphate).

Ca2H2(PO4)2 (dicalcium phosphate).

Na2HPO4 (sodium phosphate).

The sodium phosphate contains very little acidity, and the main purpose of its use is based on the principle that the sodium is readily given up for any soluble calcium that may be present. This forms the insoluble calcium phosphate, which is easily removed as a precipitate or filtered off. The "Reserve Factory" in Louisiana has been using this reagent in their clarification for a long time, where a very good grade of granulated sugar is made.

Besides these forms of phosphorous, various compounds may be found on the market, under trade names, which have as their base the above acid. "Clariphos" is one of these compounds, which has found extensive use in many of the Louisiana sugar factories.

Another is known as "phospho-gelose," which is a combination of dicalcium phosphate Ca2H2(PO4)2 and infusorial silica. It is a patented preparation and is made by the absorption of phosphoric acid by a powdery compound known as "Kieselguhr." After the absorption, the compound is heated to expel the water, and then resaturated. This work is repeated several times until the finished product, which is very hydroscopic, contains about 25 per cent of phosphoric acid.

Kieselguhr.--This is a fine light powder containing a high percentage of silica. It is used purely for its mechanical effect in forming particles upon which the impurities may collect, and thus be more readily carried to the bottom. This material often prolongs the workings of the filter presses by collecting the gummy material, which would otherwise gather on the filter cloths. Kieselguhr was used in the beet-sugar industry of Europe many years ago, and is extensively used now for the same purpose in the United States.

Hydrosulphites.--These are preparations of great bleaching power, found on the market under various trade names. One of these, widely used in the United States, in both the beet and cane-sugar industries, is known as "Blankit." This is dehydrated sodium hydrosulphite with the chemical formula, Na2S2O4. It has a much greater bleaching and reducing action than sulphurous acid, and oxydizes very readily in combination with moisture, forming sulphate. On this account it is well to purchase the reagent in small parcels for this climate, and to carefully guard the stored material from moisture. This substance, which is a white powder, dissolves very easily in water, forming an alkaline liquid, although this point is sometimes hard to distinguish on account of hydrogen atoms liberated.

There is a bleaching preparation made in France known as "Redo,"

which is simply calcium hydrosulphite (CaS2O4). This is used in the sugar industry to some extent, but it is claimed by many that the results obtained are not as good as those obtained from the sodium compound and that it deteriorates more easily.

Hydrosulphites, unlike sulphurous acid, will bleach equally as well in alkaline or neutral medium, as in an acid medium. There is therefore less danger from loss of sugar by inversion when they are used, while the permanency of their effect is about the same. In any case where juices have been bleached by sulphites, the result may be considered as but temporary, since upon exposure to air and light the product a.s.sumes a darker color. Hydrosulphites should therefore be introduced as late in the process as possible. Where the material in the vacuum pan is to be bleached, it is well to introduce this reagent just before striking grain, thus furnishing a bright clear material which will act as film over the nucleous of sucrose in the grain.

The chemical equation representing the change which takes place with this reagent is as follows:

Na2S2O4 (sodium hydrosulphite) + O (oxygen) + H2O (water)-->2(Na H S O3).