[Footnote: Read before the Society of Arts, London, May, 1884.]
By Dr. WILLIAM RAMSAY, Professor of Chemistry at University College,
Bristol.
In this present age of scientific and technical activity, there is
one branch which has, I think, been the subject of an article in the
_Quarterly Journal of Science_. It is one which deserves attention. It
was there termed "The Investigation of Residual Phenomena," and I can
conceive no better title to express the idea. The investigator who
first explores an unknown region is content if he can in some measure
delineate its grand features--its rivers, its mountain chains, its
plains; if he be a geologist, he attempts no more than broadly to
observe its most important rock formations; if a botanist, its more
striking forms of vegetation. So with the scientific investigator. The
chemist or physicist who discovers a new law seldom succeeds in doing
more than testing its general accuracy by experiments; it is reserved
for his successors to note the divergence between his broad and sweeping
generalization and particular instances which do not quite accord with
it. So it was with Boyle's law that the volume of a gas varies in
inverse ratio to the pressure to which it is exposed; so it is with the
Darwinian theory, inasmuch as deterioration and degeneration play a part
which was, perhaps, at first overlooked; and similar instances may be
found in almost all pure sciences.
I conceive that the parallel from the technical point of view is a
double one. For just as every technical process cannot be considered
to be beyond improvement, there is always scope for technical
investigation; but the true residual phenomena of which I would speak
to-night are waste products. There is, I imagine, no manufacture in
which every substance produced meets with a market. Some products are
always allowed to run to waste, yet it is evident that every effort
consistent with economy should be made to prevent such waste; and it has
been frequently found that an attempt in this direction, though at first
unsuccessful, has finally been worked into such a form as to remunerate
the manufacturer.
It is my purpose to-night to bring under your notice methods by which
saving can be effected in the cloth industry. I am aware that these
methods have not much claim to novelty; but I also know that there are,
unfortunately, few works where they are practiced.
The first of these relates to the saving and utilization of the soap
used in wool scouring and milling. It is, perhaps, hardly necessary to
explain that woolen goods are scoured by being run between rollers,
after passing through a bath of soap, and this is continued for several
hours, the cloth being repeatedly moistened with the lye, and repeatedly
wrung out by the rollers. The process is analogous to ordinary washing;
the soap dissolves the greasy film adhering to the fibers, and the
"dirt" mechanically retained is thus loosened, and washed away. Now, in
order to dissolve this greasy matter, a considerable amount of soap must
be employed; and in the course of purification of the fabric, not merely
what may be characterized as "dirt" is removed, but also short fibers,
and various dye-stuffs with which the fabric has been dyed, many of
which are partially soluble in alkaline water; moreover, it invariably
happens that some dye does not combine with the fiber and mordant, thus
becoming fixed, but merely incrusts the fiber; hence this portion is
washed off when the retaining film of grease is removed from the fiber.
The suds, therefore, after fulfilling this purpose, are no longer a pure
solution of soap, but contain many foreign matters; and the problem is
so to treat these suds as to recover the fat in some condition available
for re-conversion into soap.
For this purpose wooden runnels are placed beneath the rollers, through
which the cloth passes in the scouring machine, so as to collect the
suds after they have been spent. These runnels lead to a wooden pipe or
runnel, which receives the spent suds from all the scouring machines,
and the whole of the waste, instead of being let off into the stream,
polluting it, delivers into a tank or trough, which may also be
constructed of wood, but, as it has to withstand the action of acid, is
better lined with lead. This tank is necessarily proportioned in size
to the number of scouring machines and the quantity of spent suds to
be treated. When a sufficient quantity has collected, oil of vitriol,
diluted with twice its bulk of water, is added, one workman pouring it
in gradually while another stirs the contents of the tank vigorously. At
short intervals, the liquid is tested by means of litmus paper, and
when it shows a faint acid reaction, by turning the blue paper red, the
addition of acid is stopped. The acid has then combined with the alkali
of the soap, while the fatty acids formerly in combination with the
alkali are liberated, and float to the surface of the liquid, carrying
with them the impurities in the shape of short fibers and dye stuffs;
the sand and heavier impurity, should any be present, sinks to the
bottom.
After standing for some hours, the separation is complete. In order to
separate the two layers, the tank is provided with an exit in the side,
near the bottom, closed by a sluice or valve. This valve is opened, and
the watery portion is allowed to escape into a sand filter bed.
The filter serves to retain any solid impurities which may still remain
suspended in the water; but it will be found that the escaping water is
nearly pure.
The dark brown fatty acid is mixed with a large amount of impurity, such
as short wool fibers, burrs, sand, and dye stuffs washed from the wool.
To remove water more completely, the semi-fluid mass is pumped from the
tank, and delivered into hair-cloth filters; the liquid which drains
from these bags finds its ways to the sand filters joining the drainage
which formerly passed out from the tank through the sluice. After being
turned over in the filter several times, the residue is transferred to
canvas sacks. These sacks are placed in a filter press, where they are
exposed to pressure while heated to a temperature sufficient to melt
the fat. The solid impurities remain in the bags, while the fatty acids
escape, and are received in a barrel or tank for the purpose. The fatty
acids, when cold, are of a deep brown color, and of the consistency
of butter. The residue is kept, and the method of treating it for the
recovery of indigo will afterward be described.
The fatty acids are now ready for conversion into soap. It may here be
remarked that, on distillation, they yield a nearly white fatty mass,
which, when treated with soda-lye, is capable of yielding a perfectly
white soap. But, for the clothworker's purpose, this purification is
unnecessary.
The conversion into soap is a very simple matter. As the fats are
acids--a mixture of palmitic, oleic, and stearic acids--and not the
glycerine salts of these acids, like ordinary fats, soap is made by
causing them directly to unite with caustic soda. The fats are melted
in a copper, by means of a steam-jacket, or coil of steam-pipe in the
copper, and the soda-lye is run in until complete union has taken place.
The exact point of neutralization can easily be found by taking out
a small sample after stirring, and dissolving it in some methylated
spirits. A few drops of alcoholic tincture of phenol-phthalein are then
added, and as soon as a faint red color appears, addition of soda is
stopped. This shows that the fatty acids have been over-saturated.
Addition of a little more fat renders them perfectly neutral, and the
soap is then ladled out into wooden moulds, lined with loose sheets of
zinc.
The resulting soap is of a brown color, but is perfectly adapted for the
purpose of wool-scouring. It should here be mentioned that, in practice,
the soap is always made somewhat alkaline; in point of fact, it contains
about 2 per cent. of free alkali. This is found to assist in scouring; I
presume that the free alkali forms a soap with the oil added to the wool
during spinning, and if no free alkali be present, this oil would not be
so thoroughly removed.
It will be noticed that in this simple method of soap-making, there is
no salting out to separate the true soap from the watery solution of
glycerine, for no glycerine is present. The apparatus may be of the
simplest nature, and on any required scale, proportionate to the size of
the mill. It is a process which requires no specially skilled labor; in
any works some hand may be told off to conduct the process as occasion
requires; and as a very large proportion of the fatty matter is
recovered, the soap-bill is reduced to a very small fraction of the
amount which would be paid were recovery not practiced. And lastly, the
streams are not polluted; the only waste is a little sulphate of soda,
which can hardly be regarded as a nuisance, inasmuch as it is a not
unfrequent constituent of many natural waters.
Let us now return to the solid matter from which the fatty acids have
been removed by pressure. This brown, earthly-looking cake consists of
vegetable impurity washed off from the cloth, of short fibers, and of
various dye stuffs. It is divided into two lots: That which contains
indigo, and that which contains none, or which contains too small a
quantity for profitable extraction. And it may here be remarked, that it
is advisable to collect the suds from cloth dyed with indigo separate
from that to dye which no indigo has been employed. The residue from
indigo-dyed cloth has always a more or less blue shade, and if much
indigo is present, the well-known copper-color is evident. Of course,
the amount of indigo must greatly vary, but it may rise to 8 or 10 per
cent. of the total weight of the refuse.
To recover the indigo from this refuse, the somewhat hard cakes are
broken up, placed in a tank, and allowed to steep in water. When quite
disintegrated, they are transferred to another tank--a barrel may be
used for small quantities--and thus this refuse is exposed to the
reducing action of copperas and lime. The indigo is converted into
indigo-white, and is rendered soluble, and it oxidizes on the surface,
forming a layer of blue froth on the top of the liquid, while the
remainder of the impurities sinks. This process of reduction may last
for twenty-four hours, and is helped by frequent stirring.
The indigo scum is preserved, and placed in filter cloths, where it is
thoroughly washed with water two or three times. The residue which has
sunk to the bottom is removed, dried, and forms a valuable manure,
owing to the amount of the nitrogen which it contains. Its value may be
increased by addition of weak vitriol, which exercises a decomposing
action on the nitrogenous matter, forming with it sulphate of ammonia.
The original residue from the filter-press, if it does not contain
indigo, may be at once put to similar use.
In large works, which dye their own goods, it is well known that the
"fermentation vat" is in general use for indigo-dyeing. But this vat
requires constant superintendence, and must be kept in continual action;
besides, it is successful only on a comparatively large scale. And,
moreover, it requires skilled labor. Small works, or works in which
dyeing is only occasionally practiced, find it more convenient to use
Schützenberger and Lalande's process. Although this process is well
known, a short description of it may not here be out of place.
The process depends on the reduction of indigo to indigo-white, or
soluble indigo, by means of hyposulphite, or, as it is generally termed
to avoid confusion with antichlore, rightly named thiosulphate of soda,
hydrosulphite of soda. The formula of this substance is NaHSO_{2}, as
distinguished from what is commonly known as hyposulphite of soda,
Na_{2}S_{2}O_{3}. It is produced by the action of zinc-dust on the acid
sulphite of soda. The zinc may be supposed to remove oxygen from the
acid sulphite, NaHSO_{3}, giving hyposulphite, NaHS0_{2}. The reduction
of the acid sulphite is best performed in a cask, which can be closed at
the top, so as to avoid entrance of air. The acid sulphite of soda, at a
strength of 50 or 60 Twaddell (specific gravity 1.26 to 1.3), is placed
in the cask, and zinc-dust is added, with frequent stirring. The liquid
is then mixed with milk of lime, and after again thoroughly stirring,
the liquid is allowed to settle, and the clear is decanted into the
dyeing-copper. The indigo, in the frothy state in which it is skimmed
from the purifying barrels or tanks, is then added, with sufficient lime
to dissolve it when it has been reduced. It is heated gently by a steam
coil, to about 90° Fahr., and the goods are dyed in it. The colors
obtained by means of this indigo are light in shade, and the goods must
be dipped several times if dark shades are required. But it is found
better in practice not to attempt to dye dark shades by this process;
the ordinary indigo-vat is better adapted for such work. The object of
not wasting indigo is sufficiently attained by employing it for the
purpose to which it is best adapted. Of course the recovered indigo may
be used in the ordinary manner. I merely mention the most convenient way
of disposing of it in works where only a small quantity is recovered,
and which do not practice dyeing on an extensive scale.
I have now to ask you to turn to a different subject, namely, the
scouring of wool, not by the usual agent, water, but by a liquid,
bisulphide of carbon, made by the action of sulphur vapor on red hot
coke or charcoal.
This, again, is not wholly a new process, for various attempts have
been made to dissolve out the yolk, or _suint_, or greasy matter from
unwashed wool, as it comes from the back of the sheep. Fusel oil
has been patented for this purpose. Carbon disulphide has also been
patented, but, as will afterward be shown, the old method of removing it
from the wool injured the color and quality of the fiber, so as to make
the application of this scouring agent a failure.
Wool in its unwashed state contains a considerable proportion of what is
termed _suint_. This consists of the fatty matter exuded as perspiration
from the sheep, along with, or in some form of combination with, potash
derived from the grass on which the sheep feed. _Suint_ was first
investigated by Vauquelin. He obtained it by evaporating, after
filtration, the water in which raw fleeces had been washed. The residue
is of a brown color, and has a saline, bitter taste. On addition of an
acid to its solution in water, it coagulates, and a fatty matter rises
to the surface. It is, in fact, a potash soap, to a great extent
containing carbonate and acetate of potash, along with chloride of
potassium and lime, probably in combination also with fatty acids. It is
usually mixed with sand and carbonate of lime.
In 1828, M. Chevreul, who is still alive in Paris, although nearly a
century old, published an analysis of merino wool. It consisted of:
Per cent.
Pure wool 31.23
Soluble _suint_ 32.74
Insoluble 8.57
Earthy matter 27.46
------
100.00
It is easily seen that _suint_ forms a very important constituent of raw
wool. Its proportion varies, of course, according to the nature of the
pasture on which the sheep are fed, the climate, etc. Wool from Buenos
Ayres, for example, contains much less than that analyzed by M.
Chevreul; its amount is only 12 per cent. of the weight of the raw wool.
This _suint_ contains always about 52 per cent. of residue when ignited.
The composition of this residue is:
Per cent.
Carbonate of potash 86.78
Chloride of potassium 6.18
Sulphate of potash 2.83
Silica, alumina, etc. 4.21
------
100.00
In 1859, MM. Maumene and Rogelet patented the use of the water in
which wool has been washed as a source of potash, and at present the
extraction of potash from _suint_ is practiced in France on a large
scale. The wool is washed in a systematic manner, in casks, with cold
water, which runs out of the last cask with specific gravity 1.1. These
washings are evaporated to dryness, and the residue is calcined in iron
retorts, the gas evolved being used for illuminating purposes. The
remaining cinder, consisting of a mixture of charcoal and carbonate of
potash, is treated with water, whereby the latter is dissolved out.
The residue left on evaporation of this water consists largely--almost
entirely--of white carbonate of potash. At present there are works at
Rheims, Elboeuf, Fourmier, and Vervier, which yield about 1,000 tons of
carbonate of potash annually. Now, only 15,000 tons are made per annum
by Leblanc's process. In 1868, 62,000 tons of wool were imported into
Britain from Australia alone, and from this 7,000 to 8,000 tons of
carbonate of potash might have been recovered, the value of which is
£260,000. Yet it was all wasted! And this estimate does not include the
fats of the _suint_, which are worth an even greater sum.
Now, it is evident that there is here a profitable source of economy. So
far as I am aware, no work in this country saves its washings. The water
all goes to pollute the nearest river.
The use of carbon disulphide has again been introduced, and it is to be
hoped with better success, for methods have been devised whereby the
wool is not injured by it, but is even rendered better than when scoured
by the old process of washing with carbonate of soda and water, or by
soap. The process is due to Mr. Thomas J. Mullings. Briefly described,
it consists in exposing the wool, placed in a hydro-extractor, to the
action of bisulphide of carbon; the machine is then made to revolve, and
the excess of solvent is expelled, carrying with it the fatty matters;
the solvent finds its way into a tank, from which it flows into a still,
heated with steam; the carbon disulphide, which boils at a very low
temperature, distills over, and is again ready for use, while the
residue in the still consists of _suint_ washed from the wool. To
remove the last trace of carbon disulphide from the wool in the
hydro-extractor, cold water is admitted, and when the wool is soaked,
the machine again revolves. On expulsion of the water, the wool is ready
for washing in the ordinary machines, but with cold water only instead
of hot soapsuds.
The distinguishing features of Mr. Mullings' process are, method by
which loss of carbon disulphide is avoided, and the extraction of
that solvent by means of cold water. The apparatus consists of a
hydro-extractor or centrifugal machine of special construction, fitted
with a bell-shaped cover, which can be lifted into and out of position
by means of a weighted lever. The rim of this cover fits into an annular
cup filled with water, which surrounds the top of the machine, forming
an effective seal or joint. Upon the spindle of this machine is
suspended, as in ordinary forms of the hydro-extractor, a perforated
basket, and in this basket is placed the wool to be treated. The cover
being closed, the carbon disulphide is admitted, and passing through the
wool, the greasy matter is dissolved, and along with the solvent enters
a reservoir. The machine is now set in motion, and the bulk of the
solvent is drawn off. Cold water is then admitted, and the machine being
again caused to rotate, the whole of the bisulphide is expelled. It is
a curious fact that, although wool soaks remarkably easily with carbon
disulphide, and at once becomes wet, cold water expels and replaces
almost all that liquid. This operation takes about twenty minutes, and
at one operation about 1½ cwt. of raw wool may be treated. The wool is
then washed in suitable washing machines of the ordinary type, but with
cold water, no soap or alkali being employed. The bisulphide of carbon,
mixed with water, flows into a reservoir, provided with diaphragms to
prevent splashing, and consequent loss by evaporation. From its gravity
it sinks, forming a layer below the water; it is then separated and
recovered by distillation, and may be used in subsequent operations.
The point in which this process differs from the old and unsuccessful
ones formerly tried, is in the expulsion of the carbon disulphide. It
was imagined that it was necessary to expel it by means of heat or
steam. Now, when wool moist with bisulphide is heated, it invariably
turns yellow. No heat must, therefore, be employed. As already remarked,
the solvent is expelled with cold water.
The residue, after distillation of the carbon disulphide, is a grayish
colored, very viscous oily matter, still retaining a little bisulphide,
as may be perceived from the smell. It has not the composition of
ordinary _suint_, inasmuch as it contains no carbonate of potash, and
indeed little mineral matter of any kind. A sample which I analyzed
lost in drying 36.2 per cent., the loss consisting of water and carbon
disulphide. It gave a residue on ignition amounting only to 1.6 per
cent. of the original fatty matter, or 2.5 per cent. of the dried fat.
The oil appears, from some experiments which I made, to be a mixture of
a glycerine salt and a cholesterine salt of fatty acids. It distills
without much decomposition, giving a brown-yellow oil, which fluoresces
strongly, and has a somewhat pungent smell. The molecular weight was
determined by saponification with alcoholic potash, and subsequent
titration of the excess of potash employed. This was found to equal
546.3. This would correspond to a mixture of 18.7 parts of stearate,
palmitate, and oleate of glycerine, with 81.3 parts of the same acids
combined with cholesteryl. But this is largely conjecture. The
boiling point of the oil is high, much above the range of a mercurial
thermometer, so that it is difficult to gain an insight into its
composition.
An objection which has been raised to this process is that the use of
such an easily inflammable substance as bisulphide of carbon is attended
by great risk of fire. Were the bisulphide to be exposed to free air,
there might be force in this objection; but there is no reason why it
should ever be removed from under a layer of water. The apparatus, to
make all safe, should not be under the same roof as the mill; and no
open fire need be used in the building set apart for it. It is easy to
rotate the centrifugal machine by a belt from the mill, but better by a
small engine attached, the power for which can be conducted by a small
steam-pipe, and the distillation of the bisulphide can also be conducted
without danger by the use of steam, as its boiling point is a very low
one. The question may be naturally asked, "How do the wool and fabric
made from the wool scoured by this process, compare with that scoured in
the usual way?" To answer this question I may refer to a test made by
Messrs. Isaac Holden & Co., at their works at Roubaix. A sample of wool
was divided into two portions, one of which was scoured by the usual
method, and the other by the turbine or Mullings' process. Skilled
workers then span each sample to as fine a thread as possible. Now
the thinness to which a wool can be spun is evidence of its power of
cohesion--in other words, its strength. The weight of 1,000 meters of
the wool cleaned by the new process bore to that scoured by the old
process the proportion of 1,015 to 1,085, showing that a considerably
finer thread had been produced. And in total quantity, 67.53 kilos.
of the former corresponded to 71.77 kilos. of the latter, showing
a proportionately less waste. Such fine yarn had never before been
obtained from similar wool. The yarn of the soap-washed wool could not
be spun, for it could not withstand the strain; whereas, that scoured by
the new process gave an admirable thread.
Another test to which it was subjected may be cited. It is the custom in
France, before the wool is scoured, to put it through a sorting process,
by which all the short lengths are weeded out. On a quantity exceeding
11,000 kilogrammes, half of which was scoured by the turbine process,
and half by the ordinary process, the former in scouring lost in weight
2 per cent. less than the latter, although the short length extracted
from the moiety thus treated weighed only 10 kilogrammes, while that
taken from the other weighed over 150 kilogrammes. This saving, even
with the unequal treatment, amounted in value to from 30 to 40 centimes
per kilogramme.
In order that the importance of this application may be realized, I
shall conclude with some figures:
The raw wool imported into England, in the year 1882, amounted to
1,487,169 bales, its total value being about £22,000,000. The cost of
washing this wool by the old process, with carbonate of soda, amounts to
about ½d. per lb. of the raw material. The cost for the total quantity
of wool imported is at least £1,214,000. But it is customary to wash
wool with soap, especially for the combing trade, and the cost is then
about 1d. per lb. The cost of scouring by the new process is about £1
5s. per ton, or 0.13d. per lb. Taking the least favorable comparison,
were all the imported wool (home-grown wool is here left out of the
calculation, for want of sufficient returns) cleansed by the turbine
process, the actual saving would be £1,214,500 _minus_ £315,700, or
nearly £900,000 per annum.
It is thus seen that there is room for a very important economy in
the treatment of wool. I have endeavored to show how economy may be
practiced in scouring by the old process with soap, and how one dye
stuff may be profitably recovered. It is to be hoped that means of
extracting other dyes from the residue may soon follow. Unless the
process were too costly to repay the trouble of extraction, it would
be well worth practicing; for it would not merely be a solution of the
problem of how to avoid waste, but would at the same time prevent the
pollution of our streams, now, unfortunately, only too rarely pellucid;
and were the last process to have as successful a future as I hope it
may have, a very important saving of expense would result, and a large
quantity of valuable fatty matter would no longer be thrown away.
* * * * *
[Illustration: SUGGESTIONS IN DECORATIVE ART.--DESIGNS FOR IRON GATES.]
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