The adsorption law indicates that however much colouring matter is removed from the volume concentration (continuous phase) there must always be some left. After all that the decolorization processes can do, there still remains much colour that can only be removed by a chemical action of the ordinary sense. The amount of colouring matter of this kind is not large, but it is a deep red-brown, and when the gelatine sol has been evaporated and dried out the final product, if untreated, possesses this typical colour, and is known as glue. If, before gelation, a chemical bleaching action is applied to destroy this pigment, the product may be then dried out in a nearly colourless condition and is known as gelatine. Gelatine, therefore, is simply bleached glue. Many other definitions have been given, and many elaborate distinctions drawn, but the fact of bleaching is the essential difference. In these days when gelatine is so valuable, the higher-grade products are nearly always bleached, and the term "glue" is consequently more often applied to a lower-grade product, and is sometimes used in a sense implying this fact.
If it be desired to manufacture gelatine, it is fairly obvious that the task is lightened by observing the axiom that prevention is better than cure. If steps are taken to prevent the presence or development of such colouring matter, a great advantage is attained, for not only is the problem of bleaching easier, but also quicker and less expensive in chemicals. The nature of the colouring matters is but imperfectly investigated, but in the case of skin gelatine the pigment of the hair roots and epidermis is doubtless one factor. A long liming is said toassist in its destruction, possibly because this completes the loosening of epithelial structures and possibly because the alkali causes some hydrolysis of the pigment. In both skin and bone gelatine sols, however, there is a considerable tendency to develop the brown colouring matter typical of glue. This tendency is enhanced by an increase in temperature and also by the presence of acid or alkali. These facts seem to indicate that its development is associated with a partial hydrolysis of the gelatine in some direction. Rideal says this colouring matter is allied to caramel. In harmony with this is the experience that its development is greatest in products which have been "burnt,"i.e.subjected to unusually high temperature. The practical maxims which arise from these considerations are fairly obvious and widely known, viz. to conduct the extraction and evaporation at as low a temperature as possible and in as neutral a condition as practicable. The temperature is particularly important during evaporation (see Section VI., p.249).
Fortunately for manufacturers of gelatine, the colouring matter to be attacked is very susceptible both to reduction and to oxidation, and both types of bleach are widely used in practice. It is somewhat curious that the same colouring matter should be destructible both by reduction and by oxidation, but there is no doubt that each type gives a perfectly satisfactory bleaching action and can result in a practically colourless gelatine. On the other hand, the reduction is the more unstable reaction, for the glue colour slowly develops again in the gelatine on keeping it, even in a dried condition. Gelatine bleached by oxidation, however, retains its colour quite well, and even tends to improve with keeping. It is quite possible that quite different reactions are involved in the two processes, but in the light of the above facts it is somewhat surprising to observe Rideal's statement that reduction followed by oxidation has been successful in practice.
Although there is a wide choice of reducing and of oxidizing agents, those which are suitable for application to gelatine cover a verylimited field. This limitation arises not so much from the ineffectiveness of the bleach, as from the other effects of these substances upon the purity of the product and upon the elasticity of the gel which it can yield. Especially important is the lyotrope influence of the bleaching agent. Many reactive substances are ruled out simply because they either insolubilize the gelatine or weaken the gel it makes. Others are inadmissible on account of their poisonous nature. It must never be forgotten that whatever is used in bleaching is, like the gelatine itself, much concentrated during evaporation and drying. Its possible percentage in the finished product should be considered, and also the possibility that in these finishing operations what is present may not remain in solution, owing to supersaturation.
Bleaching by Reduction.—Of all the reducing agents suggested, sulphurous acid has proved to be much the most suitable and successful. It has been used with equal success both for bone and for skin gelatine, but on the whole has proved more suitable for the former.
Sulphurous acid can fulfil in this instance a double function, viz. that of acid solvent for the bone phosphate, and that of bleaching agent also. As it penetrates the bone material, dissolving the phosphate, it also exercises its bleaching influence on the gelatinous part of the material. Changes of liquor tend to complete both actions, so that a counter-current system is found most convenient. The "acid process" for the manufacture of bone gelatine has been previously described (Section II., pp.224-227), and the use of sulphurous acid in this connection is typified in the Bergmann process (p.227). In this process bleaching is in effect merely a continued treatment.
In the case of skin gelatine, also, sulphurous acid may fulfil a double function, viz. that of deliming agent as well as of bleaching agent. In such instance it is necessary to use excess of bleaching acid, some acting as deliming material and the remainder as bleaching agent. As it is desirable to get rid of the lime and soda salts, several changes ofliquor are given to the goods, possibly with intermediate washing. Here again approximation to a counter-current system is of advantage, as the employment of used bleach liquors for deliming purposes effects considerable economy of sulphurous acid. Indeed, there need be no waste acid at all.
Whether the material be for bone or skin gelatine, however, it will be seen that the extraction is conducted in an acid condition and the resulting sol is also acid. Most usually the decolorization and filtration processes are also conducted with such an acid sol. From what has been said (Section IV., p.235) of the value of dibasic inorganic acids as clarifying agents, it will be understood that the presence of sulphurous acid at this stage is of great advantage in the production of a clear and bright gelatine. Indeed, it is well known in trade circles that sulphurous acid gelatines are usually of exceptional clarity and brightness.
The disadvantage of sulphurous acid processes is also found in the same fact that both sol, gel and cake are in an acid condition. To complete the bleach it is sometimes necessary to add sulphurous acid to the sol after extraction, or even after evaporation, but this is to be avoided if possible. Usually the ideal attempted is that the bleaching action should be as much as possible before extraction; the excess of sulphurous acid is then washed off just before the extraction, as far as practicable, and the rest is boiled off during extraction. The ideal is practically never attained, for the acid is strongly adsorbed, and the result is that the finished article is always an acid gelatine, and sometimes indeed very decidedly such. The acid condition is objectionable in the case of some forms of filter press on account of the solvent action on the metals, and is objectionable in evaporation for similar reasons. Acid gelatines are also objectionable for many purposes for which gelatine is usually sold, and this limits the commercial possibilities of the product thus obtained.
Sulphurous acid is itself, of course, a gas, and whilst the gas itself has been used for treating the material (e.g.bones), it has beenfound not only more convenient but also more effective to use an aqueous solution. This is mainly because it is possible to attain a greater adsorption in a liquor. Unfortunately, however, sulphurous acid is not a very soluble gas, and although 8-10 per cent. solutions may be, with great care, obtained, they are really supersaturated and readily yield the gas, even with slight mechanical agitation. Solutions even of 2 to 3 per cent. strength are also liable to this, and the general experience is that 1 to 2 per cent. solutions are most economical and convenient for practical purposes. As the freight on weak solutions is prohibitive, the manufacturer using sulphurous acid is faced with the necessity either of purchasing cylinders of sulphur dioxide liquefied by pressure or making the gas and solution himself. The former is the most convenient course when only small amounts are required, but the latter preferable for a gelatine factory of any size. Sulphurous acid is easily manufactured by burning sulphur and leading the fumes by induced draught up a scrubber down which water slowly trickles. Forced draught may also be used, as in the Sachsenburg plant.
Of the other reducing agents which have been used, sodium hydrosulphite (Na2SO2) deserves mention. It is a very powerful reducing agent, and has been found most useful when employed as an assistant to sulphurous acid. This reagent is usually added to the sol, after evaporation and before gelation. It is sold as a white powder, usually under trade names. Sometimes a mixture of bisulphite and powdered zinc replaces it, but this is objectionable for pure food gelatines. Its use also involves an impurity in the finished article, and a greater amount of "inorganic ash."
Bleaching by Oxidation.—Many oxidizing agents have been suggested for bleaching gelatine, but most of them have some practical disadvantage. Most of them contradict the maxim (previously noted, pp.222-223) that it is desirable to avoid adding any soluble substance, as this involves a permanent impurity, possibly concentrated to supersaturation in the finishing processes, and possibly involving a disadvantageous lyotropeinfluence. There is another objection to oxidizing agents also; whilst their bleaching action on the pigments is undoubted, some of them have also a special action upon the gelatine itself which is in reality akin to tanning, and may indeed involve an insolubilization of the gelatine. Thus, chlorine gas (which Meunier patented for tanning) has been used for bleaching gelatine, but the conditions of success have not yet been thoroughly elucidated, and it is problematical indeed whether the process is consistent with best results. Hypochlorites and bleaching powder have also a similar action, which has been utilized with some success in practice. Rideal suggests that a suitable concentration for these reagents is 1:2000, and emphasizes the care necessary. An advantage of all these chlorinations is the formation of the strongly antiseptic chloramines, which preserve the gelatine from putrefaction. Ozone has also been tried as an oxidation bleach for gelatine, but not successfully, partly on account of difficulties in controlling the quantity used. Peroxide of soda has also been used, but it is not only alkaline, but liable to contain sodium hydrate and carbonate as impurities, and this involves neutralization either before use or in the gelatine sol, and the consequent presence of sodium salts in the finished article. Peroxide of calcium is open to the same objections, except that calcium is more easily removed from the sol than sodium. Rideal's suggestion for removing this lime, viz. precipitation by a current of carbonic acid, merits attention in this and in other directions also. Rideal also states that in the case of an acid bone gelatine, a good peroxide of lime is almost an ideal reagent for bleaching, inasmuch as "the lime carries down phosphate, several impurities and colouring matters." It thus acts as bleach, as neutralizing agent, and as precipitant, and the precipitate itself is a strong adsorbent. On account of its freedom from bases, and because its residue is simply water, peroxide of hydrogen has been found of great service in practice, and in most factories it has shown itself superior not only to the other peroxides, but also to all other oxidizingagents. Its application is simple, a concentrated solution being added to the gelatine sol before or after evaporation. It is the most "fool-proof" of all the oxidizing agents used in bleaching, and it yields the purest product. Its bleaching action is perfectly satisfactory, but only in a non-acid sol. Hydrogen peroxide is moderately stable in acid solution, and its bleaching action is best in slightly alkaline solution. An acid sol bleaches too slowly, or not at all; an alkaline sol induces evolution of oxygen and consequent waste. The great disadvantage of peroxide of hydrogen is its great expense, which is enhanced by an increasing demand for it in other industries. A minor disadvantage is its instability, which leads to loss in transit and storage. It is sold usually in strengths indicated by the volume of oxygen obtained from unit volume of the solution, when treated with permanganate in a nitrometer (e.g."15 vols. peroxide").
It is a fortunate feature of both the oxidizing and reducing agents usually employed in bleaching, that they have considerable antiseptic power. This assists materially in preserving the gelatine from putrefaction during the critical period between extraction and concentration.
REFERENCES."Glue and Glue Testing," S. Rideal, D.Sc., 2nd ed., pp. 61-66, 78-82."Gelatine, Glue, and Allied Products," T. Lambert, pp. 29, 30, 49, 51."Chemical Engineering,"J.R. San. Inst., No. 2, 1910. S. Rideal.On adsorption phenomena:1. "Chemistry of Colloids," Dr. W. W. Taylor.2. "Chemistry of Colloids," V. Pöschl.3. "Chemistry of Colloids," Zsigmondy and Spear.4. "Chemistry and Physics of Colloids," E. Halschek.5. "Surface Tension and Surface Energy," Willows and Hatschek.
The evaporation of the weak gelatine sols (3-9 per cent.) obtained by the processes described in previous sections into sols of such concentration (20-55 per cent.) that they readily set to a stiff gel on cooling, is now an essential feature of gelatine manufacture, and is one of the most important processes.
In the early days of this industry, manufacturers aimed at obtaining a concentrated sol, as this saved time in drying, and so reduced the possibilities of putrefaction. The advent of evaporation has reduced these possibilities to a minimum, and has also enormously reduced the space required and the capital outlay needed in the drying sheds. It has, in addition, given the practical advantages involved in dealing up to the last minute with a much less viscous liquor. As the liquors extracted are weaker, the extraction is more complete and the decolorization more easily effected.
The earliest attempts at evaporation were not very successful, partly on account of the prolonged "stewing" which ruined the setting power, and partly because of the poor economy of heat. Thus in the open evaporators the sol was maintained at a high temperature for a long period, and this process only proved suitable for low-grade products.
A great stride forward was made by Howard's invention of the Vacuum Pan. This made it possible to undertake concentration at much lower temperatures, a most important improvement in the case of gelatine and other organic matters easily damaged by heat. The process, however, was still slow, and the sol exposed to heat for a long time, as must be the case when evaporation takes place in bulk. These disadvantages werestill fatal to the production of the highest-grade gelatine. There were also the practical difficulties of entrainment ("blowing over"), in which parts of the sol were carried away by the escaping vapour, and also of "incrustation" which so rapidly reduces the heating efficiency and evaporative capacity of the machine. The vacuum pan, however, presented two decided advantages—evaporation at a low temperature, and, as a corollary, the possibility of utilizing exhaust steam to attain this temperature.
Whilst the vacuum pan was a satisfactory machine for many branches of chemical engineering, the problem of evaporation was still unsolved for gelatine liquor because of the "stewing" involved, until the advent of the "film evaporator," which dealt with the liquor not in bulk, but in a continuous stream. In this way the product was only exposed to heat for a comparatively short time. Many evaporators of this type came into being, and rapid improvement was made in the constructional details. The film evaporators retained usually the advantage of evaporationin vacuo, so that it was now possible to evaporate gelatine sols by exposure for a short time to a comparatively low temperature. Of this type of evaporator, the Lillie, Yaryan, Schwager, Claassen, Greiner, Blair Campbell, and the Kestner machines are well-known examples.
A further advance in solving this problem was the application of the principle of multiple-effect evaporation. The vapour driven off during evaporation possesses of course many heat units, and is of very considerable volume. In multiple-effect evaporators this vapour is used to work a similar evaporator, and the evaporated liquor passes immediately into what is practically a second machine, and is further evaporated by the heat from the vapour just driven from it. Such an arrangement would be termed a double-effect evaporator. The vapour from the second effect may of course be similarly used to operate a third effect, and the vapour from this to work a fourth effect, and so on. Thus, we may have triple effect, quadruple effect, etc., even up tooctuple effect. The great advantage of multiple-effect evaporation is in the saving of costly steam. Reavell gives the following figures to illustrate the economy thus obtained:—
WATER EVAPORATED PER 100 UNITS STEAM.
There is naturally a limit beyond which the capital cost of the machine neutralizes the advantage of steam economy, and it is seldom that octuple effects are used. There are probably more triple effects in use than any other machine.
An essential and important part of the modern evaporator is the "condenser," in which the vapour from the last effect is conducted into water (jet condensers) or over cooled surfaces (surface condensers), with a view to producing and maintaining the vacuum.
A lasting vacuum cannot be maintained without an air-pump, as air is often introduced (1) with the steam, having entered the boiler dissolved in the feed water; (2) by leakage from the atmosphere into the condenser and the connected vacuous spaces; and (3) in jet condensers, in solution with the circulating condenser water. That from the first two sources may be reduced, but the third is beyond control: hence if high vacua are necessary, surface condensers are to be preferred. Dissolved air is usually 5-20 per cent. of the water volume, and is least for sea-water. It should be noted that water leaving a surface condenser is in a very air-free state, and therefore particularly suitable for boiler supply. Apart from the capital cost of a condenser the chief cost of maintaining a vacuum is in pumping the circulating water, of which up to 70 lbs. is usual per lb. of steam condensed.
If : W = weight of steam condensed (lbs. per hour);Q = weight of cooling water circulated (lbs. per hour);Ti= inlet temperature (°F.) of cooling water;To= outlet temperature (°F.) of cooling water;thenTo= Ti+ 1050 (W/Q)
It will be understood that for high vacua, low temperature of cooling water (Ti) is more important than copious supply (Q/W). It is advantageous, however, to choose a site yielding plenty of cold water, such as a river or canal side. Otherwise it is often necessary to use cooling towers or spray nozzles. The cooling is by evaporation (= 60 to 80 per cent. of W), cold water replacing that evaporated, and yielding water 75° to 80° F. If Ti= 80° F. and Q/W = 70°, a vacuum of 28.34" is possible, but the 0.34" should be allowed for the partial pressure of the air, determined exactly by the air entering and by the displacement of the air-pump.
Another feature of the modern evaporator is the "heater" or "calorifier," by which the liquor to be evaporated is led in a continuous rapid stream through heated tubes immediately prior to its entry into the first effect. It is the aim of the heater to raise the temperature of the liquor to the temperature of evaporation, and so to avoid this being necessary in the first effect. The heater thus further avoids stewing, ensures steady running, and effectively increases the capacity of a machine.
It is noteworthy that superheated steam is not desirable for working an evaporator. The principle of evaporation by steam is not merely that the temperature of the liquor is raised to boiling point; it is that in the condensation of the heating steam its latent heat is yielded to the liquor being evaporated. To evaporate quickly, therefore, the heating steam must condense rapidly. Hence, as superheated steam has a rate of condensation 20-30 times slower than saturated steam, the latter is much to be preferred. A slight superheating, however, may be justifiable where the steam has any distance to travel before use. It is the fact that it is the latent heat of steam which is mainly utilized which gives steam its great practical advantage over hot non-condensable gases. Steam in condensing yields an enormously greater number of heat units per lb. than hot waste gases. Steam has also the advantage of more constant temperature.
The capacity and efficiency of an evaporator depends upon a good many factors, some of which are worthy of discussion at this point.
The transference of heat and the amount of evaporation are directly proportional to the mean temperature difference between the heating steam and the liquor being evaporated. These temperatures, however, both vary somewhat, the steam losing part of its pressure and temperature as it passes along the heating surface; the liquid generally increases in temperature. The mean difference in temperature, moreover, is not the arithmetic mean between the smallest and largest temperature differences, but is given by the following expressions, which yield results not wide apart:—
If θa= temperature difference at commencement;θe= " " " end;and θm= mean temperature difference;then
equation for temperature and evaporation
This mean temperature difference is in practice usually spoken of as the "temperature head" or "heat drop." It will be clear that this temperature head is increased by using steam at higher pressure (temperature), and by evaporating under reduced pressure. Since most liquids have their boiling points reduced about 40° C. by operatingin vacuo, the advantage of the vacuum is apparent. It should be remembered that the temperature head has not the same value in any part of the scale: it has more value higher up the scale, because the steam is denser and more heat units come in contact with a given area in a given time. It must also be remembered that whilst the pressure gauge is a most useful indicator of steam temperature, it is not necessarily accurate. The pressure in the hot space is thesumof the pressures of air and steam, and since the temperature (the important condition) of the hot space depends upon the pressure of thesteam, and not on the sum of the pressures, the temperature in a steam space is always ratherlower than would be supposed from the pressure indicated by the gauge.
The transference of heat is influenced by the velocity of both the heating fluid and the fluid being heated over the heating surface. The more rapidly each fluid moves, the more rapid is the transference of heat, because a greater number of particles of both fluids are brought to the heating surface in any given time. This is popularly known as the effect of "circulation," and is illustrated by the advantage of stirring a liquid being heated in bulk. In the film evaporators the circulation is through tubes at high speed (up to 2 miles a minute), and the maximum effect in this sense is thus obtained. The increase in heat transference is not directly proportional to the increase in velocity, but in a lower ratio, sometimes approximately the square root of the velocity. In such a case, if either velocity be quadrupled, the heat transference is doubled. Other advantages of high velocity are that the heating steam more readily sweeps away condensed steam from the heating surface, and the high-speed film similarly "scours" away "incrustations" on the interior of the tubes.
The transference of heat is also proportional to the conductivity of the metal forming the heating surface. For gelatine liquors, copper tubes are almost invariably employed, the advantage being great even when price is taken into consideration. The following conductivity coefficients illustrate this point (calories per hour through 1 sq. metre of metal 1 metre thick, with a temperature difference of 1° C.):—
The coefficient of heat transmission decreases the more with increasing thickness of wall, the worse conductor is the metal. For copper tubes, however, this decrease is usually unimportant.
The transference of heat is also much influenced by the viscosity ofthe liquor being evaporated; the greater the viscosity, the lower the coefficient of heat transmission. Unfortunately for this process of evaporation, gelatine sols are exceedingly viscous, and thus the difficulty in obtaining a concentrated sol is thus greatly enhanced.
The transference of heat is often greatly hindered by incrustations of the tubes, which incrustations generally conduct heat very badly. Thus the relative heat conductivities of copper and chalk are as 1000:5.
The amount of heat transferred is of course determined also by the area of the heating surface. The amount of evaporation needed thus determines the number of tubes (of standard size) in the evaporator, and thus the capacity of the machine. An evaporator should have its heating surface area chosen with a view to the duty required of it.
In practice the working of an evaporator is often not a very difficult matter, and large numbers of machines are operated by unskilled labour. Troubles generally arise from inconstant steam pressure, incrustation, leakages of air, which reduce the vacuum, the temperature head, and hinder heat transmission. For the evaporation of gelatine liquors the Yaryan, the Kestner, and the Blair-Campbell film evaporators are the most widely used. The velocity of the liquor through some of these machines is so great that occasionally no vacuum is used. The temperature obtained is high (200° F.), but the time is very short, if rapid cooling of the evaporated liquor is arranged.
REFERENCES."Evaporating, Condensing and Cooling Apparatus," by E. Hausbrand. Scott, Greenwood & Son (1916 Ed.)."Evaporation," by E. Kappeschaar. Norman Rodger (1914)."Evaporation in the Chemical Industry," by J.A. Reavell, M.I.Mech.E.,J.S.C.I., 1918, April 11th."Glue and Glue Testing," S. Rideal, D.Sc., pp. 56-59."Gelatine, Glue, and their Allied Products," T. Lambert, pp. 26-29."Notes on Condensing Plant," J.M. Newton, B.Sc.,J. Junior Inst.Engineers, Aug., 1912.
The conversion of a gelatine sol into cakes of gelatine has been much simplified by the advent of the evaporator. Before this machine was used much trouble was experienced with putrefaction, and in hot and thundery weather, especially on the Continent, it was often necessary to suspend operations. Evaporation has, however, materially contributed to the possibility of rapid and satisfactory cooling and drying.
From the time the weak sol is decolorized and bleached, the finishing processes consist essentially in the removal of water. This is now usually done partly by evaporation of the sol, and partly by the desiccation of the gel. There is an obvious elasticity in method, and factory practice does actually vary considerably in the relative proportions of these two alternatives. Some factories evaporate to a 20 per cent. sol, approximately, and rely upon drying sheds and lofts to complete the desiccation: other factories evaporate up to a 55 per cent. gelatine sol, and so can manage with less shed room. Something depends upon local conditions, but the main issue is between the cost of steam in evaporation and the cost of land and buildings required for sheds. On the whole the modern tendency is to evaporate more, for this course has the additional advantage of speed, involving both a quicker turnover and less liability of putrefaction. Lower-grade products need relatively greater evaporation to form a gel of equal rigidity.
After evaporation and bleaching, the concentrated sol is first cooled rapidly until it has set to a stiff gel, then cut up into cakes according to the size required, these being dried out on network framesarranged in tiers, through which a draught of air is usually forced or induced. This general description is of course applicable to many factories with innumerable variations in detail, most of which variations originate in local convenience and are unessential parts of the manufacture.
An essential principle is that the cooling or gelation should be done rapidly, not only to avoid putrefaction but also to avoid the action of heat on the elasticity of the gel. A hot sol or gel is liable to hydrolysis and loss of setting power, and should have its temperature quickly reduced, but a warm sol or gel (say 100° F.) is most liable to putrefaction, so that the cooling should be continued quickly. On the other hand, the gel should not be frozen. For cooling purposes a copious supply of cold water is most usually employed, but some factories have installed refrigerators. These plants operate by the rapid evaporation of liquefied gases such as carbon dioxide, sulphur dioxide, or ammonia, so arranged as to cool a solution of common salt, which forms the circulating liquor and is returned after use to the refrigerator. Where such plants are used, it is natural that their use should be extended to the drying sheds to cool the air entering in the height of summer. In some factories the cooling is attained neither by cold water nor cooled brine, but merely by cold air.
The kind of vessel in which gelation is induced varies widely in different factories. For lower-grade products metal boxes are used, heavily galvanized iron being the most common material. If the liquor be muddy, deep boxes are preferred, but if clear, rapid cooling is best attained by having them long and shallow, and so exposing a relatively greater area to the cooling action. In either case the boxes may contain up to ½ cwt. of jelly. Lambert mentions boxes 24" × 6", which are 5" deep; Cavalier suggests rectangular moulds holding 30 litres. In place of galvanized sheet iron, boxes of sheet zinc or of wood lined with zinc are sometimes used. In any case the most scrupulous cleanliness should be observed in all cooling-house work, and in some factories the mostelaborate precautions are taken for cleansing vessels, tools, floors, etc., and even for their disinfection and sterilization. Iron, tinned iron, and copper cooling vessels are ruled out on account of their tendency to rust and tarnish, and the last is unjustifiably expensive. Many of these vessels are unsuitable for pure food gelatines in which traces of copper, zinc and arsenic are held to be very objectionable. For the best gelatines, therefore, a very shallow vessel (¼" to ½" deep) with a sheet glass bottom is preferred, and the concentrated sol is run on to this for gelation.
Glue (or gelatine) which has set in this way is sometimes called "cast glue." That which sets in metal boxes in blocks is termed "cut glue," because the blocks of jelly need subsequently to be cut into slabs of the desired size and shape. Jelly blocks may be cut by hand with the "wire knife" which yields a characteristic wavy appearance to the finished product. This may also be done by machinery, the block of gel being placed on a series of correctly spaced wires and forced through the network by hydraulic pressure. A cutting machine (Schneible) has also been used to cut up blocks of jelly into slices of the required thickness, but these machines have not made great headway in this country. It will be clear that cast glue is cooled more rapidly than glue in blocks; it is therefore not surprising to note Lambert's statement that the former comprises the larger proportion on the market.
The cut or cast cakes are next placed upon network frames, and a series of such frames are placed on a bogey. The bogey is run along tram lines into the drying tunnel, through which air is forced or induced by a fan. Many such bogeys are, of course, passed into each tunnel, and as many tunnels as required may be constructed. Care is necessary to expose the cakes evenly to the action of the air. It is mostly necessary to warm the air at the inlet by means of steam pipes and so increase its drying power. This is especially necessary in winter or wet weather. In summer, however, it is often arranged that the air is cooled before enteringthe sheds. This is accomplished by passing the air through pipes from a refrigerator. When heated air is used, it is stated by Lambert that the maximum temperature should be 25.5° C. (78° F.); Rideal considers 21° C. (70° F.) should be the maximum. In all cases the drying power of the air is easily ascertained from a wet-and-dry bulb thermometer, and the amount of air passing along the shed from a wind gauge. Lambert states that drying normally occupies four to five days. The final product is still a gel, of course, and contains from 10 to 18 per cent. of water. It appears, however, very hard and solid. The dried cakes are removed from the frames and transferred to the warehouse, where they are sorted according to quality and packed in bags or tin-lined boxes. Some material is ground to powder.
The network of the drying frames has been made from many materials. Cotton or string netting is very common, but is liable to sag and to get dirty. It also has a short life. Ordinary galvanized iron soon loses its galvanizing cover, and the iron then is liable to rust. Attempts have been made to use sheet zinc and other alloys, which are cut or punched into nets with square or diamond-shaped holes. These were found to warp and break. Rideal's conclusion, which is confirmed by the general experience, is that the best material is a heavily galvanized iron wire netting. He suggests that it should have 15 to 25 per cent. of its weight of zinc, and that it should be strengthened by stiffer ribs arranged both longitudinally and transversely.
Many attempts have been made, and many patents taken out, with the object of making the cooling, cutting, and drying processes as continuous and as quick as possible, and with a view to saving labour, which is rather costly at this stage. These attempts, however, have only met with indifferent success. A common idea is that a continuous supply should fall upon a revolving appliance, and be instantly congealed in a thin state, which last lends itself to more rapid desiccation. Vacuum drying has also been attempted.
REFERENCES."Glue and Glue Testing," S. Rideal, D.Sc., pp. 68-74."Glue, Gelatine, and Allied Products," T. Lambert, pp. 30-35.Chem. Zeit., 1911, 85, 17 (Cavalier).PATENTS.Eng. Patent (1894) 11,426 (Hewitt).Eng. Patent (1898) 2,400 (Brauer).Fr. Patent (1909) 398,598 (Lehmann),J.S.C.I., 1909, 897.U.S. Patent (1912) 1,047,165 (American Glue Co.).
Gelatine and glue have both been put to an immense variety of uses, and the list is constantly extending. Indeed, no one who considers the following account of their applications can doubt that gelatine and glue have become a necessary part of our civilization.
Gelatine for edible purposes certainly forms a very considerable part of the total used, and great pains are now taken to obtain a pure product. Thus, a gelatine with more than 1.4 parts per million of arsenic, or more than 30 parts per million of copper, is not considered good enough for "pure food." The food value of gelatine, compared with other proteids, is exceedingly low; its use in this connection has no connection with the "calories" of heat energy it will yield. It is used almost entirely because of its property of forming a gel. Table jellies form, of course, one popular use of gelatin, but the manufacture of sweets makes also a great demand upon the gelatine trade. Culinary operations often require a little gelatine, especially is it used in pies and soups. An extension of the same idea is found in its employment for many manufactured foods,e.g.tinned meats, meat extracts, and the concentrated foods. The use of gelatine in connection with the first of these received a big impetus during the war period. In gelatine for any of these purposes, the presence of excess of sulphurous acid is objectionable, as its taste is easily noticed.
Gelatine for medicinal purposes finds an ever-growing number of applications. Gelatine capsules for holding greasy liquids and solutions of nauseous drugs are increasingly popular, for the dose may be swallowed without unpleasantness. In making these capsules some sugaris also used, and the finished article is often protected from atmospheric moisture by treatment with a weak solution of alum. In a similar way pills are often coated with a 33 per cent. gelatine sol. Such pills are not only pleasanter to swallow, but are less liable, after being dried, to stick together in the box. Alcohol solutions of drugs (or essences, perfumes, etc.) may be suitably stored in gelatine instead of metal tubes. Medicated wines are detannated by gelatine before the addition of drugs which would have been precipitated by the tannin. The British Pharmacopœia specifies four kinds of "Lamellæ," which are small discs of gelatin and glycerin, each containing a minute but definite dose of some powerful alkaloid. Glycerin jelly is a mixture of gelatin glycerin with some water. It is used for chapped and rough hands; the mixture is also used for glycerin suppositories, and for mounting microscopic sections. The mixture also forms the basis of gelato-glycerin, used in nasal bougies, and of glyco-gelatin for medicated lozenges. Gelatine insolubilised by formalin (formo-gelatin) has been used for making tabloids, wound dressings, and artificial silk.
Gelatine is in constant demand for bacteriological work, for which purpose a high-grade product is desired. Nutrient media for the culture of bacteria are solidified by 10-15 per cent. of gelatin, and the growth of colonies of bacteria often show typical formations. By inoculating into a melted and sterile quantity and setting quickly in a flat dish after mixing, the number of bacteria in the volume introduced can be judged from the number of colonies which develop. Bacteria are also distinguished often as "liquefying" or "non-liquefying" according to their type of culture on nutrient gelatine media. Gelatine for such work should be neutral and of high clarity.
The gelatine required for photographic purposes is also a high-class product. It should be neutral, colourless, and free from chlorides and other mineral salts. Grease also is objectionable. Gelatine is used in the numerous carbon processes, in which the principle is that gelatineis made insoluble in water by the action of potassium dichromate under the action of light. It is used also in Poiteoin process for copying engineering drawings, which is based upon the power of a ferric salt to render gelatine insoluble so long as it is not exposed to the actinic rays.
Gelatine is used in the manufacture of the "crystalline glass" used for decorative purposes. Advantage is taken of the immense contractile force it exerts on drying. When ground glass is coated with gelatine, and the latter dried, it tears away the surface of the glass itself, and leaves peculiar fern-like patterns. Inorganic salts dissolved in the sol influence the nature of the pattern obtained.
Gelatine is used also very largely in the textile trades, for finishing coloured yarns and threads, for sizing woollen and worsted warps, and for thickening the dyestuffs used in printing fabrics. It is also used for finishing white straw hats; as a size in the manufacture of high-class papers, and as a wax substitute for covering corks and bottle necks.
Glue is used instead of gelatine in all cases where colour is not a matter of much moment. The fact that it has not been bleached makes no difference to its suitability in such a case, and the cost is substantially reduced. Thus, for dark-coloured straw hats, textiles, sweets, papers, and in all suitable woolwork, glue is used in place of the more expensive article.
A very large quantity of glue is used in the manufacture of matches, where it functions as the material binding the "head" to the stem. A 15-50 per cent. sol is used, containing nitrate or chlorate of potash as oxidizing agent. The mixture is kept at 38° C. and the phosphorus cautiously added, and when this is emulsified, the friction ingredients (sand, glass, etc.) are also added. The glue acts also in preventing premature oxidation. Glue is also used in making the match-boxes, and similarly in making sand, emery, and glass papers and cloths.
There is a large consumption of glue by joiners, carpenters, cabinet-makers, and all kinds of woodwork and fancy work. It is used inthe manufacture of furniture of all kinds, of pianos, organs, billiard tables, panels, picture frames, and of toys and brushes. Mixed with white lead, chalk, and sawdust, it forms a composition used for mirror frames, rosettes, etc. Glue is used for veneering, for mosaics, plaques, trays, fingerplates, leather wall coverings, and for staining floors.
There is also a considerable sale for glue in bookbinding, for which a sweet, light-coloured, and strong product is required. It has been found particularly suitable for leather bindings where the grain has been artificially printed or embossed (see pp.97and117), and in finishing and gilding.
The compositions used for printing rollers all contain gelatine or glue together with sugar or glycerin and possibly oil and soap. They are often hardened with formalin. Similar mixtures are used for the beds of hectographs.
Glue (together with waste leather) is used in the manufacture of imitation leather and leather substitutes. Cotton and wool fibres are often incorporated, and sometimes textile fabrics.
Much glue is converted into "size," which is a weak gel used as a filling rather than as an adhesive agent. A low-grade glue is often therefore preferred for such purposes, as having "body" rather than "strength." Size is often sold in cake, but sometimes in the form of the gel itself, in which case it may never have been evaporated. Indeed, size is often overboiled glue, made by crude and out-of-date methods. It is largely used in the paper trade, and for wallpapers, millboards, papier-mache, paper and cardboard boxes, etc. Mixed with logwood and iron, and possibly alum, it formed the "blue size" once largely used by bootmakers as a foundation for blacking, and is similarly used in currying (p.82). Size is also used in making oil paints and varnishes. Distemper is a size with which is incorporated whiting or gypsum and coloured pigments. In all applications of size, it is common to use antiseptics. Salicylic acid has been widely used in this sense. Low-grade glue is used for the manufacture of cheap brushes and for fly-papers.
Innumerable patents have been taken out and mixtures invented for the production of plastic materials, which frequently involve gelatine or glue. Thus, gelatine and glue are used in making plaster casts, and for imitation ivory, wood, stone, and rubber. Many of these inventions have been investigated by Rideal, who points out the features common to most of them. Usually a viscous sol is thickened by the addition of inert fibres and powders, and with the object of making the preparation more waterproof it is customary to incorporate oils, fats, waxes, tars, and resins before the gel is set. The surface is hardened by "tanning" with formalin or tannin solution, finally painted or varnished.
Equally innumerable are the inventions, recipes, and patents for making glues that shall remain liquid. The convenience of this ideal is obvious, but many of the suggestions are useless. It is quite easy to incorporate into a gel substances which keep it liquid—any soluble substances with a lyotrope influence of the iodide type will do this—but these also prevent the glue setting when used. Even in small quantity they will influence the tenacity of the joint. Other methods depend upon a partial hydrolysis of the protein. Amongst the most successful of these attempts are to dissolve 3 parts of glue either in 12-15 parts saccharate of lime, or in 9 parts of 33 per cent. acetic acid.
Many special glues and cements are made from commercial glue, according to the purpose required. "Marine glue" contains no glue; it is made from shellac and rubber mixed with benzene or naphtha. Its advantage is waterproofness.
REFERENCES."Glue and Glue Testing," S. Rideal, D.Sc., 2nd ed."Uses of Glue," chap. iii. p. 83."Uses of Gelatine," chap. iv. p. 100."Special Glues," p. 108."Liquid Glues," p. 119."Gelatine, Glue, and their Allied Products," T. Lambert."Uses of Glue and Gelatine," chap. ix. p. 80."Liquid Glues and Cements," chap. viii. p. 69.
The manufacture of gelatine and allied products has received a great stimulus in this country from the circumstances arising from the European War. The large restriction of continental—especially French and Belgian—supplies of gelatine, led to greater demands for the British-made product, and resulted not merely in a period of greater prosperity, but in a period in which much greater efforts were made to supply a high-grade article in larger quantities. Most manufacturers strove to make high-class gelatine rather than low-grade glue, great extensions were made, and many new businesses were established. The development of the leather trades, more particularly in respect of greater production, caused a bigger supply of raw material for skin gelatine, and the slaughter of home animals for food caused a more plentiful supply of bones. At the same time it was realized that greater production not only reduced working costs, but also that a bigger turnover in any one factory involved a proportionately less capital outlay. These facts tend to counterbalance the heavy freight on the raw materials. Production is thus not only on a larger scale but more intensive.
One of the greatest difficulties of this industry is to produce a regular or standard article, for the raw material is so exceedingly variable in quality; that for skin gelatine tends also to become less valuable. In such a case, as Rideal has truly remarked, to ensure that supplies to customers shall be always "up to sample," which is often a matter of contract—"exact and regular working, strict cleanliness,observance of temperatures and other physical data, and scientific supervision", are clearly necessary. "Rule of thumb" is never quite certain to produce the same article twice. In past years British methods of manufacture have been far too empirical. As in other industries, "rule of thumb" must inevitably be replaced by scientific principle. The advances in colloid chemistry of this last decade or so have, in the author's opinion, supplied the clue to this line of development. In the preceding pages emphasis has been laid upon the importance of the adsorption law, the lyotrope series, and the valency rule. The manufacturer or supervisor who understands and can apply these generalizations will find his task vastly easier and his factory more efficient. Much remains to be learnt, however, and the industry would certainly benefit by research work, for which there is a fertile field.
There is also considerable room for improvement in the methods of chemical engineering usually employed. Whilst the heat engineers have certainly done much to solve the question of evaporation and drying, there is still great scope in the more economical application of heat in extraction, and the last word can hardly have been said on the problem of clarification and decolorization. There is indeed almost as much scope for research by the chemical engineer as by the colloid chemist.
The industry also exhibits, in common with the leather and many other trades, the same tendency to save labour, both by careful arrangement of the factory and by the installing of mechanical labour-saving devices. Thus, lifts, runaways, hoists, trucks are increasingly used to move the solids, and pipes and pumps to move the liquors. As ever, there is scope for the mechanical engineer.
If some of these problems are vigorously tackled during the present reconstruction period, there is little doubt that the gelatine and glue industry will be in a much better position to cope with all possible competition in the future.
From what has been said in Section VIII. as to the wide uses ofgelatine and glue, it will be seen that general prosperity in trade is conducive to better trade conditions in the gelatine and glue industry. It is similarly true that a general trade slump affects the glue trade adversely. The severe trade depression which commenced in 1920 has had this effect, and has made economic production much more difficult as well as more essential. As often is the case, the larger factories and firms can better face the difficulties, and there can be little doubt that if the depression be long continued there will be a tendency for the smaller factories to be closed down and for the larger firms to unite. As in the leather trade, both the War boom and the Peace slump have caused the gelatine and glue trade to develop along the lines of the great trusts. It may be reasonably expected, moreover, that these will be intimately connected with the leather trusts. This fact, together with the heavy freight charges on the raw material, tends also to make the skin glue factories gravitate towards the leather centres.
In the leather trades by far the most important and valuable bye-products are obtained from the hides and skins themselves, and all these are obtained before the tannage proper is commenced. The leather trades use only the dermis (corium) or true skin for the manufacture of leather, and as we have noted (Part I., Section II., p.16) this prepared and purified dermis is called "pelt." The cuttings and trimmings from the pelt form the most valuable bye-product of the leather trades, and are the raw material of the gelatine and glue industries (Part V., Section II., p.221). Many portions of the pelt, indeed, such as ears, noses, and cows' udders, are quite useless for any other purposes. Other portions, such as cheeks, faces, and even bellies, may be made either into glue or leather according to the state of trade. Hardly less important to the same industry are the cuttings of adipose tissue removed in "fleshing" the hides and skins. These, though yielding less protein, yield also, however, the valuable animal greases (Part V., Section II., p.227). To obtain both these products in a purer condition the removal of "flesh" after "soaking," but before "liming" (Part I., Section II., p.18), has been favoured by some, especially in America.
Amongst the epithelial structures of the hides and skins, we have several protein bye-products which have some commercial value. Thehorns of cattle are now almost invariably removed before reaching the leather manufacturer, but have some little value. This part of the epidermis is not solid keratin. A "pith" is easily removed after boiling in water. The outer parts, too, are often coarse and somewhat damaged, but if removed by scraping reveal often a rather beautiful structure of varying colour. There is some opening for this product in the manufacture of small articles of horn, but much of it, together with hoofs, is roasted and crushed for making fertilizers. The hair of cattle, goat, etc., has also a commercial value. This is removed after liming, and needs subsequent purification (Part I., Section II., p.22). The hair is well washed with water, using either repeated changes or a continuous supply, the operation being carried out in paddles or similar machines which stir up the hair in the water. When clean, the hair is transferred to a centrifugal machine or "spinner," in which much adhering water is removed. This is a great assistance in drying out, which is the next and final operation. In drying, the hair is laid upon steam-heated boxes or pipes, and a current of warmed air passed over or through it by means of a fan. It is better to have the hair "turned" occasionally. This ensures quicker as well as more even drying. The product is made up into large bales and sold for the manufacture of felts, mattresses, etc. White hair is usually kept separate and commands a larger price. The power consumed in driving the washing machinery, the centrifuges and the drying fan, together with the fuel required for the drying steam, and the labour involved throughout, make it doubtful whether this bye-product is worth either the capital outlay or the working costs necessitated. Many manufacturers avoid this treatment altogether, therefore, and the wet limed hair is sold direct to the fertilizer factory. A less price is obtained, but much expense is saved. Especially when the animals have only their short summer coats, this course is preferred.
In the case of the wool from sheepskins the product is much more valuable. The wool, indeed, is often the primary consideration.Unfortunately this sometimes results in the neglect of the pelt. The removal of wool from sheepskins forms a special industry known as "fellmongering," which has been previously described (Part II., Section IV., p.110). Pains are taken to clean the wool even before removal from the pelt, by the liberal use of water and the "burring machine." There is much variation in quality, and care is taken to keep the various grades separate, even during the "pulling" operation. From the fellmonger the wool passes to the "wool stapler," and forms the basis of one of our most important mechanical industries, the manufacture of woollen cloths. Wool is also removed from sheep by the periodic shearing, and in this case does not reach the fellmonger at all.
Apart from the raw material itself, there are few bye-products of the leather trades which are of commercial importance. The sludge from the pits of the limeyard contains, in addition to much lime and chalk, a certain proportion of protein matter. This is derived partly from the blood and dung associated with the hide, partly from the solution of the corium hide substance, partly from the solution of the softer keratins, and partly also undissolved and loose hair. This bye-product is rather difficult to deal with, as it will not easily dry. It is indeed sometimes a problem to dispose of it, except in rural districts, where the farmers appreciate its manurial value and will usually cart it away for a nominal fee. Where possible, it is better to let it drain and settle on land, and pile it up in heaps to dry further. Soak-pit sludge has a distinctly greater value as manure, on account of the greater proportion of dung proteins. As some lime is often used in these pits, the product is a really useful fertilizer.
The only other bye-product of the leather trades is waste leather itself. For small pieces of leather there is always some little opening in producing small articles, such as washers for taps, etc., and there is also the possibility of shredding or pulping and making an artificial leather. The best leather substitutes, indeed, are made from wasteleather. Nevertheless, there is always a certain amount of waste leather which only finds an outlet in the fertilizer factory. Such material is usually steamed or roasted to make it brittle, and then crushed in a disintegrator. It is then mixed in with other materials, but is sometimes solubilized by the action of sulphuric acid. Leather seldom contains less than 30 per cent. protein.
REFERENCES."Chemical Fertilizers and Parasiticides," S.H. Collins, M.S., F.I.C. (Companion volume in this series on Industrial Chemistry.)"Wool Wastes," Part II., Section V., p. 75."Hoofs, Horns, Leather," Part III., Section II., p. 115."Gelatine, Glue, and Allied Products," T. Lambert.
From the skin gelatine and glue trades the most valuable bye-product is the grease, which is obtained from the "fleshings" of the adipose tissue. These fleshings are themselves a bye-product of the leather trades. The recovery and purification of this grease has been dealt with previously (Part V., Section II., p.227). In the skin glue trade the only other bye-product is the residue from the extraction process (Part V., Section III., p.230). This residue is known usually as glue "scutch," and is composed of the proteins of the skin which are insoluble in hot water. These insoluble portions are obtained from all layers of the skin. There is much hair often in scutch, the hyaline or glassy layer (grain), and the elastic fibres of the corium are also insoluble, and a proportion is derived from the fibres of the adipose tissue on the flesh side. All these portions are fairly rich in nitrogen, and the scutch has, therefore, considerable value to makers of fertilizers. It is liable to contain also a percentage of grease, which is usually removed by steaming under hydraulic pressure. This process recovers a valuable bye-product and increases the manurial value of the scutch. There is always left in scutch some of the gelatinous skin substance which, strictly speaking, should have been removed during extraction. There is, however, a practical limit beyond which it does not pay to do this. When this limit is reached the cost of steam in extracting, and also in evaporating and drying, together with the loss of time and labour involved by occupation of the plant, is greater than the value of the possible product.
From the bone-glue industry, the grease is similarly a valuablebye-product, but there is also another of equal importance, viz. the phosphate of lime, which comprises about half the raw material. As previously described in Part IV., Section II., p.225, this is usually extracted after the grease, by solution in weak hydrochloric acid. The solution is neutralized in lead-lined vats with milk of lime, a precipitate of di-and tri-calcium phosphates being obtained. Calcium chloride is left in solution, and the precipitate should be, therefore, well washed if it be desired to have dry phosphate. The bone-glue industry is, generally speaking, much more intimately connected with the fertilizer trades than the skin-glue trades, indeed the extraction of the bones for glue is not always advisable, in which case the protein matter as well as the phosphatic matter of the bones are employed for making "bone manures." For details of this industry the reader is referred to a companion volume in this series on "Chemical Fertilizers."
REFERENCES."Chemical Fertilizers and Parasiticides," S.H. Collins, M.Sc."Bones," Part II., Section V., p. 72."Precipitated Bone Phosphate," Part III., Section III., p. 157."Bone Manures," Part III., Section V., p. 173."Gelatine, Glue, and Allied Products," T. Lambert.
Although there are those who consider that animal proteins are both undesirable and unnecessary as foods, it is nevertheless true that man is almost universally a carnivorous animal. The animal world provides mankind with one of its chief sources of food, and especially of protein foods. Protein foods are unquestionably essential, and animal protein foods differ chiefly from those of vegetable origin in the fact that they contain generally much more protein. Of the proteins noted in our Introduction, the keratins have no value as foods; the gelatins have some value as culinary material, but little actual food value; whilst the albumins comprise practically all the useful animal food proteins. Whilst the actual flesh of animals is the principal source of food proteins—both as to quantity and food value—other parts of animals,e.g.kidneys, liver, blood, brains, tongue, are used and relished. The most important sources of animal food proteins are from fish, fowl, sheep, cattle, and pigs, the meat from these being roughly in the same sequence as to digestibility. There are, however, many other animals of which the flesh is quite edible, but most of the above are specially farmed and propagated primarily for their food value.
As the animal food proteins are exceedingly putrescible, they are usually consumed within a short time of the animal being killed. It is perhaps natural, therefore, that many efforts have been made to discover means of preserving such foods. These efforts form the basis of some important industries, and though they can hardly be included as chemical industries, it will not be out of place in this volume to point out that these efforts present analogies with, as well as differences from themethods used for preserving hides and skins (Part I., Section I., p.12). The curing of hides and skins is a temporary preservation from putrefaction until the opportunity is convenient for the permanent preservation (i.e.tannage). The preservation of meats is analogous to curing inasmuch as more drastic treatment might indeed make them non-putrescible, but would also render them indigestible and unsuitable for food. Thus drying, salting, drying and salting, pickling and freezing, are just as suitable for preserving food proteins as for hide and skin proteins. Hence we have dried meats, salt bacon, pickled beef, frozen mutton, etc. To a limited extent smoking (fish, bacon, etc.) has been employed as a cure. When it has been applied to skins it is usually combined with a fat tannage. There is, however, one method of preservation of proteins, inapplicable to skins, which has been eminently successful and useful for food proteins, viz. sterilization by boiling. The food has been placed in tins, hermetically sealed, and thoroughly sterilized. Hence have appeared corned beef, tinned tongue, sardines, etc., which merely illustrate the immense possibilities involved. A noteworthy advantage of this method of preserving animal food proteins, is that the food is already cooked and prepared for immediate consumption.
Another line of effort is the preparation of concentrated foods. Just as animal foods are on the whole more concentrated in protein than vegetable foods, so these prepared animal foods are more concentrated than animal flesh, and generally also more soluble. Such preparations of animal protein are obviously useful when there is difficulty in swallowing and when journeys are necessary into regions of poor food supply. It is a little doubtful, one must say, whether the concentration is as great in some cases as is claimed.
Yet another industry based upon the animal proteins is the manufacture of meat extracts. These are not merely concentrated extracts of animal flesh, but contain especially the stimulative properties of animal food proteins. There is now little doubt of the value of these preparationsas stimulants, and it is claimed for them that they not only have food value, but also that they increase the food value of other foods used with them. Together with these products may be classed all the miscellaneous tonic foods, in which proteins are blended with carbohydrates and often also with drugs. These aim at the cure of specific disorders, such as nervous debility, sleeplessness, etc. Their claims are often extravagant. Amongst all the multitude of prepared foods, there deserve particular mention the partly predigested foods. In cases where the digestive functions are weak or disordered these products have been of real service.
One of the most useful and valuable of animal food proteins is obtained from hen eggs. The "white" of eggs is almost pure albumin, and there is much protein in the yolk also. Eggs are now produced and imported by the million, and form a most important item in the country's dietary, the protein being in a very easily digestible form.
It is also necessary to refer to the importance of cows' milk as a source of animal food protein. The amount of protein in milk (4-5 per cent.) is not large, but it is united with fats, carbohydrates, salts, and vitamines in such proportions, that milk is about the only article which may reasonably present a claim of being a complete food. Milk, moreover, forms the staple diet of infants and young children, so that its protein is certainly of great importance. As an infant food, cows' milk is not altogether ideal. Even when the proportions of fat, carbohydrate, and protein have been adjusted to resemble human milk, there remains the difficulty that some of the proteins of milk (especially the casein) are too indigestible for young infants. This difficulty has been only partly surmounted by those industries engaged in manufacturing infant foods. Some claim to remove the bulk of the casein; others to have rendered it digestible by treatment with enzymes; others, again, simply claim to supply concentrated cows' milk. Tinned milk, generally concentrated to some extent, now forms a useful additionto animal food products. The casein of milk also finds some outlet for industrial purposes. When treated with formaldehyde it yields an artificial horn much used for the preparation of imitation tortoiseshell. Skim milk is treated with caustic soda or carbonate of soda, the casein precipitated by acid, pressed, impregnated with formaldehyde, and dried. The product is termed "galalith." It can be distinguished from real tortoiseshell by the action of fuming nitric acid (seeJ.C.S.I., 1909, 101).
The utilization of the blood of animals, which is very rich in protein, as a foodstuff has long been known, but has met with a good deal of prejudice in this country. This prejudice has arisen not merely from the objection to blood as food, but also from the fact that such foods have been particularly liable to putrefaction and hence to cause poisoning. The shortage of all foodstuffs occasioned by the European War did much to overcome this prejudice, and there were considerable developments in the manufacture of black pudding and similar preparations of animal blood. The same circumstances made it necessary to consider more seriously the possibilities of other butchers' offal as human food, and resulted in new preparations of tinned animal proteins being placed on the food market.
The author would like to record his opinion that by no means the last word has been said on the question of drying as a method for preserving animal food proteins. There is much to be said for this method on every ground in theory, and it is evidently an increasing success in practice. Dried milk has been followed by dried eggs, and in view of the success of the method when applied to fruits and vegetables, there seems a prospect of better success in respect of dried meats. After all, animal food proteins are chiefly lyophile colloids, and though desiccation presents some practical difficulties, the subsequent imbibition (assisted perhaps by lyotrope influences) seems to be the ideal method for restoring preserved protein to its original condition.