CHAPTER X.

_WATER AS USED IN THE TANNERY._

Of all the materials employed in tanning, none is of more indispensable importance than water, and its quality has undoubtedly great influence on tanning, though it is constantly blamed for faults and troubles which are really due to the mistakes of the tanner.

Water is chiefly used in tanneries for soaking and washing hides and skins, for making the limes, the bates, and the tanning liquors, for steam boilers, and in dyeing. For all these purposes it should be as free as possible from impurities, but since water is the most universal solvent in Nature, it is never found pure, but always contains mineral matter derived from the rocks and soil through which it has flowed, as well as organic impurities from decaying animal and vegetable matter. Associated with the latter are usually living organisms of putrefaction (_bacteria_) which may affect the quality of the water for tanning even more seriously than the mineral impurities. The purest natural waters are those which have flowed only over hard sandstones and volcanic rocks. Water sufficiently pure for laboratory use can only be obtained by distillation. The steam-water from heating pipes usually contains large quantities of dissolved iron, and often also volatile organic matters from the oil, etc., which finds its way into the boiler. It may sometimes be made fit for use by boiling (which precipitates the ferrous carbonate present), and subsequent settling or filtration. The use of steam-water containing iron is a frequent source of stains and discolorations in the tannery which more than counterbalances the advantage of its softness.

The “hardness” of natural waters is mostly due to the salts of lime and magnesia which they contain, which precipitate soap in the form of insoluble stearates and oleates, which are useless for washing. It is commonly estimated by determining the amount of a standard alcoholic soap solution which must be added in order to produce a permanent froth on shaking. Theoretically about 12 parts of soap (sodium stearate or oleate) are destroyed by 1 part of calcium carbonate or an equivalent quantity of other lime salts, with formation of insoluble lime soaps (calcium stearate or oleate). Really, the reaction is much more complicated, owing to the dissociation of the soap into free alkali and acid-salts on solution in water. Teed[61] estimates that ¹⁄₃ to ¹⁄₂ more is required than the theoretical quantity, and more in hot water than cold. This uncertainty is partially overcome by testing the soap solution against a known solution of calcium chloride. The presence of magnesia also complicates the test and leads to discrepant results.

[61] Journ. Soc. Chem. Ind., 1889, p. 256. Cp. also Allen, ibid. 1888, p. 795.

The methods of determining hardness originated by Hehner (see L.I.L.B., p. 19) are simpler and more accurate than the soap-test, and are to be preferred, except for direct determination of the suitability of a water for scouring with soap. “Degrees” of hardness in England are calculated as parts of CaCO₃ per 100,000, or sometimes grains per gallon (70,000 grains).

Hardness is of two kinds, “temporary” and “permanent”; the former being removed by boiling, while the latter is not so removed.

Temporary hardness consists of the carbonates of alkaline earths held in solution by an excess of carbonic acid. Lime combines with 1 molecule of carbon dioxide to form the ordinary normal carbonate (chalk), which is practically insoluble in water. When, however, excess of carbonic acid is present, hydric calcic carbonate (bicarbonate) which is fairly soluble is produced. This is easily demonstrated by passing carbon dioxide into somewhat diluted lime-water, which at first becomes turbid from precipitated chalk, but soon clears by formation of soluble hydric carbonate. If the solution be now boiled, the hydric carbonate is decomposed, and the excess of carbonic acid is driven off as CO₂, and the chalk again precipitated. The reactions are represented by the following equations:--

Ca(OH)₂ + CO₂ = CaCO₃ + OH₂. (1)

{ CaCO₃ CaCO₃ + CO₂ + OH₂ = { (2) { H₂CO₃

Magnesia forms soluble double carbonates in a similar manner, but on continued boiling gradually loses the whole of its carbonic acid, and is precipitated as magnesium hydrate, Mg(OH)₂.

One of the most important reactions in connection with temporary hardness is that caused by the addition of calcium hydrate (slaked lime), which forms the basis of Clark’s softening process. When an equivalent amount of lime is added to a solution of hydric calcic carbonate, it displaces the water of the “half-bound” carbonic acid, forming a second molecule of calcium carbonate, which is precipitated together with that originally present, as is represented in the following equation:--

CaCO₃ } } + Ca(OH)₂ = 2CaCO₃ + 2OH₂. (3) H₂CO₃ }

Hydric magnesium carbonate is also precipitated by lime, but the reaction is somewhat different, the magnesia being removed as hydrate as follows:--

{ MgCO₃ { + 2Ca(OH)₂ = 2CaCO₃ + 2OH₂ + Mg(OH)₂. (4) { H₂CO₃

It will be noted that 2 equivalents of lime are required to precipitate 1 of magnesia. Two molecules of sodium hydrate (NaOH) or potassium hydrate (KOH) may be substituted for 1 of Ca(OH)₂ with similar results, and in some cases it is practically advantageous to use the former, as the sodium carbonate formed in precipitating the temporary hardness reacts again on the permanent, throwing down the lime and magnesia as carbonates. (See p. 101.)

The use of lime for softening temporary hard waters was originally proposed by Thomas Henry, F.R.S., of Manchester, but was first applied as a practical process by Clark, who, after adding the requisite quantity of lime to the water in a mixing vat, allowed it to stand in a large tank to clear by subsidence, the precipitated carbonate of lime taking from 6 to 12 hours to settle. The process in its original form is a perfectly satisfactory one, except for the capacious settling tanks which are required, which in some cases are inconvenient and expensive. Messrs. Archbutt and Deeley[62] have patented a modification of the Clark process, by which the time of subsidence is much shortened, and according to which the precipitated carbonate of lime of previous operations is allowed to remain in the tank, and the fresh charge of water and lime is mixed up with it by means of steam-injectors, which blow in a current of air through perforated pipes at the bottom of the tank, and at the same time very slightly warm the water. The action goes on much more rapidly at a slightly raised temperature than in the cold; and rather curiously, the stirred up precipitate, instead of increasing the time of clearing, settles rapidly and carries down with it that formed in the new operation. It is particularly suitable for treating waters containing magnesia, from which a compound of lime and magnesia is apt to be precipitated in a colloid form which chokes filter-cloths and will not readily settle. After softening, the water is usually “carbonated” by passing the gases produced by burning coke into the floating exit-pipe through which it falls, in order to retain any remaining traces of carbonates of lime and magnesia in a soluble form, and prevent their subsequent precipitation in the pipes. The apparatus is made by Messrs. Mather and Platt, of Manchester, and its arrangement is shown in Figs. 19 and 20.

[62] Journ. Soc. Chem. Ind., 1891, p. 511.

Several modifications of the Clark process have been introduced, in which the precipitation is carried on continuously instead of intermittently. The most important of these is the Porter-Clark, in which one portion of the water to be softened flows through an agitator containing excess of lime, with which it forms saturated lime-water, which is passed slowly up a cylinder where it deposits the excess of suspended lime. The clear lime-water so produced is mixed with a fresh portion of the water to be softened in a second cylinder also provided with an agitator, the proportion of the two liquids being regulated by cocks. The carbonate of lime is at once precipitated, and is removed by passage through a filter press. This process is in successful operation on a considerable scale at Messrs. Hodgsons’ tannery at Beverley.

Several other forms of filter have also been employed with success, and also methods in which the treated water traverses tanks with sloping partitions on which the carbonate of lime is deposited. The latter plan was originally patented in France by Gaillet-Huet, and has been introduced into England by Stanhope.

So far as is yet known, from the tanner’s point of view, it is hardly necessary to make any distinction between lime and magnesia, either or both of which may be considered simply as “hardness.” A hard water probably softens dried hides more slowly than a purer water, though it is possible that the observed difference in the time required may be due in many cases to the lower temperature of wells from which hard water is generally derived. In the actual “limes” the hardness of the water can have no appreciable influence, though if sodium sulphide be used alone for unhairing, a certain waste occurs from temporary hardness which may render it advisable to add a little lime. It is in washing the hides free from lime that the influence of hard water is first distinctly felt. If limy goods, after unhairing, are placed in a water with much temporary hardness, the same action occurs as in Clark’s water-softening process, and chalk is deposited in the surface of the hides, making them harsh and apt to “frize” or roughen the grain in “scudding.” The common, but not wholly satisfactory expedient is to add a little lime, or better, a few pailfuls of lime liquor to the water before putting in the hides. The best plan is to use a properly softened water. Permanent hardness is not injurious in this way.

Unfortunately it is not the grain alone which is injured by the use of hard water for washing the hides, but on coming into the liquors the precipitated bases combine with the acids and tannins, forming compounds which oxidise and darken when exposed to the air, and which are the commonest causes of stains and markings on all descriptions of leather. Even when goods are drenched or bated before tanning the injury is not prevented, since the weak organic acids which are capable of removing the lime (as such) from the hide have little effect on the precipitated carbonate, which can only be dissolved by the use of stronger acids. It must be noted that the same injurious effect on limed goods is produced by free carbonic acid, which may be present even in soft waters.

When temporarily hard waters are employed for leaching tanning materials, the carbonic acid is displaced by the tannins, which form compounds similar to those just mentioned, which are incapable of tanning, and darken and discolour when exposed to the air. Though the amount of lime present in a liter of even the hardest water is very small, yet in the aggregate of thousands of gallons used weekly in a good-sized yard it amounts to something very considerable, and as the molecular weight of tannins is very high, the quantity destroyed is many times that of the lime present. This loss can be prevented (_a_) by the addition of sufficient mineral acid to convert the temporary into permanent hardness, (_b_) by the use of oxalic acid, which precipitates the whole of the lime as oxalate, or, (_c_) best of all, by softening the water by suitable treatment before use. Each part of temporary hardness reckoned as CaCO₃ (L.I.L.B., p. 19), requires 1·26 parts of crystallised oxalic acid or 0·98 parts of H₂SO₄, or say one part of ordinary oil of vitriol of sp. gr. 1·840 per 100,000 parts of water.

As the lime and magnesia of temporarily-hard water is thrown down by boiling, it is deposited in steam boilers as a soft precipitate, much of which can be blown out by suitable sludging; but if oils or fats obtain access to the boiler, a soft, bulky, adherent deposit is formed, keeping the water from the plates, which may become red hot, and lead to collapse or explosion. This effect is not produced by mineral oils, which, on the contrary, tend to prevent adherence of scale to the plates, and as suitable mineral oils are not only cheaper, but much less injurious to the working parts of steam engines than animal or vegetable oils or tallow, they should always be used in preference for cylinder purposes.

Water which is temporarily hard owing to calcium and magnesium carbonates, is unsuitable for _dyeing_, as the carbonates react with basic dyes, precipitating the colour-base, and so rendering a part of the dye useless. Further, as this precipitate is deposited on the skins it causes uneven dyeing and gives rise to spots and streaks. In dyeing with basic dyes, therefore, it is advisable to add sufficient acetic acid to the water before use to exactly neutralise the carbonates present. Of course this treatment is quite unnecessary when acid dyes are employed, as acid is usually added with the dye, and with dyewoods the presence of a little calcium salt is advantageous.

As each “degree” of total hardness represents a soap-destroying power of at least 2 oz. of soap per 100 gallons of water, allowance must be made in making up “fat-liquors” with soap and oil for the loss of soap due to its precipitation by the mineral matter in the water. The sticky lime-soaps are apt to adhere to the leather and interfere with glazing; so that it is much better to employ a soft water.

_Permanent hardness_ of water is generally caused by sulphates of lime and magnesia, and more rarely by chlorides and nitrates. As none of these can be precipitated by lime, permanent hardness cannot be removed by Clark’s process, nor can it produce the injurious effect on limed hides which have been attributed to temporary hardness. Neither can the lime and magnesia present combine with the tannins if used for leaching, since they are already fixed by stronger acids, and at most can only act injuriously by slightly lessening the solubility of the tannins. Even this effect cannot be regarded as proved, though it deserves further investigation.[63] Permanent hardness is therefore of little moment as regards the ordinary uses of the tannery, though it has considerable influence in some of the processes of dyeing, and acts very injuriously where soap is used for scouring, as in the washing of sheep-skins for wool mats, since each part of lime reckoned as carbonate destroys at least twelve parts of pure soap (sodium stearate or oleate), producing a sticky and insoluble lime-soap which adheres to the fibre. In sole-leather tanning, permanent hardness is sometimes advantageous, especially if it be due to calcium and magnesium sulphates, and Vignon recommended that sulphuric acid should be added to the water before use in quantity sufficient to exactly neutralise the carbonates which cause temporary hardness, as magnesium and calcium sulphates are not injurious, but tend to plump the hides. It must be remembered, however, that the carbonic acid liberated may still have prejudicial effects on limed hides.

[63] Recent investigations by Nihoul (‘Influence de la nature de l’eau sur l’extraction des matières tannantes,’ Bulletin de la Bourse aux Cuirs de Liège, Sept. 1901) on the tanning waters of Belgium seem to show that permanent hardness is more injurious in the extraction of tannin than has generally been supposed.

Permanent hardness is most objectionable in waters employed for boiler-feeding, and calcium sulphate is especially so, as it becomes nearly insoluble in water at 150° C. or 55 lb. steam-pressure, and is deposited on the plates as a hard crystalline scale which has to be chipped off with a hammer. Where many boilers have to be worked with a hard water, it is much the most satisfactory to soften the water with caustic soda, or with lime and soda together before it comes into the boiler, but in cases where the plant required would be too costly, boiler-compositions are sometimes used with good effect, though considerable caution is advisable, since some of them affect the plates injuriously. The active constituent of many boiler-compositions is soda-ash or sodium carbonate, which acts by double decomposition with the calcium sulphate, forming sodium sulphate, and precipitating calcium carbonate as a sediment which is easily washed out. Most tanning materials, and even spent tan liquors, will prevent or lessen incrustation if mixed with the feed water, but sometimes corrode the plates if used too freely. This danger is lessened if they are used in conjunction with soda. Heavy mineral oils, either introduced in small quantity with the feed water, or painted on the sides of the boiler when cleaned, are useful in preventing the formation of a coherent scale.

The removal of permanent hardness from water is easily effected in most of the forms of apparatus employed for the softening of water by lime, by using a calculated quantity of sodium carbonate in addition. The reaction is represented in the case of calcium sulphate by the following equation--

CaSO₄ + Na₂CO₃ = CaCO₃ + Na₂SO₄.

The conversion of magnesium sulphate into carbonate may be similarly effected, but as the latter is somewhat soluble, an additional equivalent of lime must be used to precipitate it as hydrate. Magnesium salts, from their solubility, do not cause scale on boilers (though the chloride is apt to produce corrosion), but they are equally destructive of soap with the calcium salts. Caustic soda will remove temporary hardness, and after becoming converted into carbonate will further react on any permanent hardness present; and its use is therefore sometimes convenient in small softening plants, but it is not more effective, and considerably more costly than a suitable mixture of lime and sodium carbonate. Even with these, Archbutt states that the cost of softening permanent hardness is about ten times as great as that of removing temporary hardness with lime only.[64]

[64] Proceedings of Inst. of Mech. Engineers, 1898, pp. 404-54, in which much valuable information on water-softening is given.

As regards the influence of other impurities, our knowledge is far from complete, but the following are the most important matters likely to be present.

_Mud_ under any circumstances is objectionable. It frequently contains organic slime and organisms which encourage the putrefaction of hides placed in it to wash or soften. It also almost invariably contains iron as one of its constituents, and hence stains leather and gives dark coloured liquors. It is not easily removed by filtration, as large filter-beds are expensive and difficult to keep in order, and much space is required to clear water by subsidence. Some mechanical filter which can be easily cleaned, and used under pressure, offers the best chance of success. The Pulsometer Company make one consisting of sponge tightly packed below a perforated piston. To cleanse the filter a stream of water is passed the reverse way, and the piston raised and worked up and down, either by hand or power, so as to loosen and knead the sponge. Filter-presses, in which cloths, or in some cases sand, are used as the filtering medium, are also well adapted for the purpose. If a water be softened by Clark’s or other process the precipitated chalk carries down the mud with it, together with most of the organisms.

_Iron_ is always an objectionable impurity in the tannery, though it is less injurious to the quality than the appearance of the leather produced, and indeed German sole-leather tanners frequently put old iron in the handlers to darken the colour of the leather, and apparently, if not really, to quicken the tannage. It must not be present in waters used for dyeing. Iron oxide is frequently present as a mud merely, and in this case can be removed by filtration. It is rarely in solution in any other form than that of acid carbonate, since sulphate or chloride could not exist in presence of bicarbonate of lime. In this form, iron is precipitated at once by boiling or on the addition of lime, like the temporary hardness due to other bases, in the form of ferric hydrate, and more slowly by oxidation on exposure to the air. The mud produced by softening waters which contain iron must be completely removed by filtration, or subsidence, before the water is used for leaching, or the iron will redissolve in the acids of the liquors. Iron is not perceptibly injurious in the limes, but in the bates and wash-pits sometimes causes stains, which are scarcely visible till blackened by the tanning liquors. In presence of sulphur (from sulphide of sodium or the decomposition of sulphates by the sulphur-bacteria nearly always present in bates and soaks), the stains become bluish or greenish black, and a black deposit is frequently produced on the sides of the pit, in which the threads of sulphur-bacteria (_Thiothrix_) can often be recognised by the microscope. As ferric salts not only combine with the tannins, but are themselves tanning agents (see p. 198), they are rapidly absorbed by leather, and iron is always present in leather ash. (For detection and estimation see L.I.L.B., p. 218.)

_Alumina_, except as clay, is rarely present in waters, and probably harmless in any water likely to be used in tanning.

_Soda_ is sometimes present in considerable amount, as sulphate, chloride, or carbonate. The sulphate is probably inoperative. The chloride, if present in material quantities, prevents plumping, and may be the cause of thin and soft leather, and in large amounts will greatly impede the proper exhaustion of many tanning materials. Sodium carbonate is sometimes present in considerable quantities, as in some of the waters of the Leeds district. It may coexist with temporary hardness, and produces similar injurious effects. Waters in which it is present cannot have any real permanent hardness. It may be neutralised by the very cautious addition of an acid; or by admixture of a permanent-hard water. It tends to increased plumping in the limes, but neutralises the free acids of the tan-liquors which are necessary in sole-leather tanning.

_Copper_, _lead_, and other metallic bases are not likely to be present in any waters used for tanning in quantities sufficient to be injurious.

_Sulphuric acid_ rarely occurs free in water, and then only in such traces as would be harmless for tanning, though possibly injurious to steam boilers. As sulphates it is most common. Alkaline sulphates are not known to have any deleterious action. The sulphates of lime and magnesia are the principal cause of permanent hardness, q.v. Iron sulphate is sometimes found in colliery waters.

_Nitrates and nitrites_ in water are usually the result of “previous” sewage contamination, and are only important as an indication of the possible presence of the putrefactive ferments, and are of little moment in waters only used for manufacturing purposes, while they seem to be even useful in promoting the “working” of bran drenches, by supplying the nitrogen required by the ferment.

_Chlorine_ is seldom or never present in water in the free state, but only in the form of chlorides, most frequently of sodium chloride (common salt), the effect of which has been referred to above, and also at p. 88. The action of other chlorides is probably similar as regards the swelling of hide. _Magnesium chloride_ is very objectionable as a constituent of boiler-waters, as it liberates hydrochloric acid at high temperatures, and corrodes the plates at the surface of the water. This injury can be prevented by addition of soda.

_Carbonic acid_ has been referred to under temporary hardness. Its presence in the free state is a matter of some importance to the tanner (see p. 99).

_Silicic acid_ in a soluble form is present in some waters in considerable quantity. Such waters are said to harden leather, but of this the writer has no personal experience.

Few accurate researches have been made on the effect of the impurities of water on tanning,[65] and though, from what has already been said, it will be seen that they are not without effect it is probable that in many cases the water is blamed for troubles which are simply the result of mismanagement, and credited with virtues which are really due to careful and skilful manufacture.

[65] See Nihoul, ‘Influence de l’eau sur l’extraction des matières tannantes,’ Bulletin de la Bourse aux Cuirs de Liège, Sept. 1901.

The hardness of water, and the dissolved carbonic acid which it contains, are, together with its temperature, the principal factors which determine whether a hide will plump or fall in it. Almost the only accurate investigation of this point has been made by W. Eitner.[66] He placed pieces of hide, unhaired by sweating, and quite flat and fallen, in water for four days at a temperature of 46° F. (8° C.), with the following results:--

1. In distilled water Scarcely at all plumped. 2. „ water saturated with CO₂ Well plumped. 3. „ „ with lime bicarbonate, 20° German} Tolerably plump. scale of hardness } 4. „ „ „ magnesia bicarbonate, 20° do. „ „ 5. „ „ „ lime sulphate 20° do. Well plumped. 6. „ „ „ magnesia sulphate, 20° do Best plumped. 7. „ „ „ magnesium chloride, 20° do. Not at all plumped. 8. „ „ „ common salt, 20° do. „ „

(1 German degree of hardness corresponds to 1 of CaO in 100,000.)

[66] Gerber, iii. (1877) p. 183.

The peculiarities which were shown by the hide pieces on removal from the water were maintained throughout the tanning, which was conducted in imitation of the German method, the hide being swollen and coloured through in weak birch-bark liquors, made with distilled water and acidified in each case with equal quantities of lactic acid, and finally laid away, till tanned, in a mixture of oak bark and valonia. No. 6, from magnesium sulphate, was the best; then No. 2; No. 3 was less good, but all the pieces from 1 to 6 were firm, close and of good substance and texture, No. 1 having swelled well in the sour liquor. On the other hand, 7 and 8 scarcely swelled in liquor, but remained flat throughout, and were looser, thinner and of finer fibre. From this experiment it is clear that while sulphates and carbonates exert a favourable influence on plumping, chlorides do the reverse, as they themselves not only do not plump, but they place the hides in an unfavourable condition for the plumping action of acids in the liquors. These experiments are quite borne out by the writer’s experience in practice. The water at the Lowlights Tannery, which in dry weather was mostly obtained from beds of what was originally sea-sand, and which consequently contained a very abnormal proportion of chlorides (up to 68 pts. NaCl per 100,000), required special and very careful management to make thick leather, notwithstanding the fact that it contained a considerable quantity of calcium and magnesium sulphates. These facts also indicate the importance of the thorough removal of salt from hides intended for sole-leather. Plumping is not a desirable thing in leather intended for dressing purposes, and it is possible that the use of a small percentage of salt in the liquors or wash waters might in some cases enable bating to be dispensed with. Like a bate, salt would dissolve a small proportion of hide substance (see p. 65). There is no practicable means of removing chlorides from water, but Eitner suggests the addition of a small quantity of sulphuric acid to water containing much temporary hardness (bicarbonates), in order to convert it into permanent hardness (sulphates), which, as stated above, plumps better. The amount required may be calculated from an acidimetric determination of temporary hardness (see L.I.L.B., p. 19). A simple but not very accurate guide, is to add enough acid to purple, but not to redden litmus paper even after moving the latter about in the water for some minutes. In practice the acid must of course be very thoroughly mixed with the water by stirring and plunging. It must be borne in mind that Eitner’s experiment was on sweated hides, and that with limed hide, which is kept plump by the dissolved lime retained in the hide, different results as regards carbonic acid and bicarbonates would be obtained. Both these would convert the lime in the hide into chalk, which is insoluble and inert, and the hide would fall, at any rate when the lime was completely carbonated, while hides would remain plumpest in waters most free from substances capable of neutralising lime. From this we may conclude, what may be _a priori_ expected, that the purer the water, the plumper limed hides remain in it. In soft but peaty waters, hides fall rapidly, from the neutralisation of the lime by the weak organic acids of the peat. Such waters are dangerous for domestic use from their solvent action on lead, but this danger can be entirely removed by storing the water in limestone reservoirs, or allowing it to flow slowly through a limestone culvert before use. In some towns in the north of England a small quantity of lime is added so as to neutralise the water as it leaves the reservoir and before it enters the mains.

Wherever the conditions of putrefaction or decaying organic matter are present, as in a bate, hides fall rapidly, and in extreme cases even the presence of the stronger acids will not maintain plumpness. Eitner mentions the case of a stream at Vissoko in Bosnia, which was in special repute among the tanners from its power of pulling down hides rapidly, and which took its rise in a common on which the pigs of the town were pastured. The causes of this action are no doubt due to the products of putrefaction, but are somewhat obscure. Bacteria present in water are a frequent source of injury in the soaks, and probably in other stages of the tanning process.

Rain water and the water of streams in mountain districts of hard igneous rock are generally nearly free from mineral constituents. This is the case with the Glasgow water from Loch Katrine, and the Thirlmere water which supplies Manchester. Such water, if cold enough, and free from mud and organic impurity, is the best for almost every purpose in the tannery. Most river-water contains material quantities of mineral matter, though it is usually softer than that of springs or wells.

For further details as to the chemical examination of water, and the methods of determining the amounts of its different constituents, see L.I.L.B., pp. 18 _et seq._