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Soap-Making
Manual
By

E. G. Thomssen
A practical handbook on the raw materials,
their manipulation, analysis and control in
the modern soap plant.

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Contents
Soap-Making Manual ............................................................... 1
Contents .................................................................................... 2
PREFATORY NOTE. .................................................................... 4
CHAPTER I .................................................................................. 6
Raw Materials Used in Soap Making........................................ 6
OILS AND FATS. .......................................................................7
NATURE OF A FAT OR OIL USED IN SOAP
MANUFACTURE. ......................................................................7
SAPONIFICATION DEFINED. ................................................ 8
FATS AND OILS USED IN SOAP MANUFACTURE. .............. 9
FULLER'S EARTH PROCESS FOR BLEACHING TALLOW..10
METHOD FOR FURTHER IMPROVEMENT OF COLOR. .... 12
VEGETABLE OILS................................................................... 13
CHROME BLEACHING OF PALM OIL. ................................. 16
AIR BLEACHING OF PALM OIL. ........................................... 19
RANCIDITY OF OILS AND FATS. ......................................... 23
PREVENTION OF RANCIDITY. ............................................ 25
CHEMICAL CONSTANTS OF OILS AND FATS. ................... 26
OIL HARDENING OR HYDROGENATING. ......................... 26

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 GREASE. ................................................................................. 28
ROSIN (COLOPHONY, YELLOW ROSIN, RESINA). ........... 29
ROSIN SAPONIFICATION..................................................... 30
NAPHTHENIC ACIDS. ............................................................ 31
ALKALIS. ................................................................................ 32
CAUSTIC POTASH. ................................................................ 34
SODIUM CARBONATE (SODA ASH). ................................... 35
POTASSIUM CARBONATE. ................................................... 36
ADDITIONAL MATERIAL USED IN SOAP MAKING. ......... 36
FOOTNOTES: ......................................................................... 38
CHAPTER II............................................................................... 39
Construction and Equipment of a Soap Plant. ....................... 39
CHAPTER III ............................................................................. 44
Classification of Soap-Making Methods. ................................ 44
COLD PROCESS. .................................................................... 52
CARBONATE SAPONIFICATION.......................................... 54

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 PREFATORY NOTE.
The material contained in this work appeared several years ago
in serial form in the American Perfumer and Essential Oil Review.
Owing to the numerous requests received, it has been decided to
now place before those interested, these articles in book form.
While it is true that the works pertaining to the soapmaking
industry are reasonably plentiful, books are quite rare, however,
which, in a brief volume, will clearly outline the processes
employed together with the necessary methods of analyses from a
purely practical standpoint. In the work presented the author has
attempted to briefly, clearly, and fully explain the manufacture of
soap in such language that it might be understood by all those
interested in this industry. In many cases the smaller plants find it
necessary to dispense with the services of a chemist, so that it is
necessary for the soapmaker to make his own tests. The tests
outlined, therefore, are given as simple as possible to meet this
condition. The formulae submitted are authentic, and in many
cases are now being used in soapmaking.
In taking up the industry for survey it has been thought
desirable to first mention and describe the raw materials used;
second, to outline the processes of manufacture; third, to classify
the methods and illustrate by formulae the composition of various
soaps together with their mode of manufacture; fourth, to
enumerate the various methods of glycerine recovery, including
the processes of saponification, and, fifth, to give the most
important analytical methods which are of value to control[Pg iv]
the process of manufacture and to determine the purity and
fitness of the raw material entering into it.

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 It is not the intention of the author to go into great detail in this
work, nor to outline to any great extent the theoretical side of the
subject, but rather to make the work as brief as possible, keeping
the practical side of the subject before him and not going into
concise descriptions of machinery as is very usual in works on this
subject. Illustrations are merely added to show typical kinds of
machinery used.
The author wishes to take this opportunity of thanking Messrs.
L. S. Levy and E. W. Drew for the reading of proof, and Mr. C. W.
Aiken of the Houchin-Aiken Co., for his aid in making the
illustrations a success, as well as others who have contributed in
the compiling of the formulae for various soaps. He trusts that
this work may prove of value to those engaged in soap
manufacture.
E. G. T.

January, 1922

5
 CHAPTER I

Raw Materials Used in Soap Making.

Soap is ordinarily thought of as the common cleansing agent
well known to everyone. In a general and strictly chemical sense
this term is applied to the salts of the non-volatile fatty acids.
These salts are not only those formed by the alkali metals, sodium
and potassium, but also those formed by the heavy metals and
alkaline earths. Thus we have the insoluble soaps of lime and
magnesia formed when we attempt to wash in "hard water"; again
aluminum soaps are used extensively in polishing materials and
to thicken lubricating oils; ammonia or "benzine" soaps are
employed among the dry cleaners. Commonly, however, when we
speak of soap we limit it to the sodium or potassium salt of a
higher fatty acid.
It is very generally known that soap is made by combining a fat
or oil with a water solution of sodium hydroxide (caustic soda
lye), or potassium hydroxide (caustic potash). Sodium soaps are
always harder than potassium soaps, provided the same fat or oil
is used in both cases.
The detergent properties of soap are due to the fact that it acts
as an alkali regulator, that is, when water comes into contact with
soap, it undergoes what is called hydrolytic dissociation. This
means that it is broken down by water into other substances. Just
what these substances are is subject to controversy, though it is
presumed caustic alkali and the acid alkali salt of the fatty acids
are formed.

6
OILS AND FATS.
There is no sharp distinction between fat and oil. By "oil" the
layman has the impression of a liquid which at[Pg 2] warm
temperature will flow as a slippery, lubricating, viscous fluid; by
"fat" he understands a greasy, solid substance unctuous to the
touch. It thus becomes necessary to differentiate the oils and fats
used in the manufacture of soap.
Inasmuch as a soap is the alkali salt of a fatty acid, the oil or fat
from which soap is made must have as a constituent part, these
fatty acids. Hydrocarbon oils or paraffines, included in the term
"oil," are thus useless in the process of soap-making, as far as
entering into chemical combination with the caustic alkalis is
concerned. The oils and fats which form soap are those which are
a combination of fatty acids and glycerine, the glycerine being
obtained as a by-product to the soap-making industry.

NATURE OF A FAT OR OIL USED IN SOAP

MANUFACTURE.
Glycerine, being a trihydric alcohol, has three atoms of hydrogen
which are replaceable by three univalent radicals of the higher
members of the fatty acids, e. g.,

OH OR
C3 H5 OH + 3 ROH = C3 H5 OR + 3 H2O
OH OR

7
 Glycerine plus 3 Fatty Alcohols equals Fat or Oil plus 3 Water.
Thus three fatty acid radicals combine with one glycerine to
form a true neutral oil or fat which are called triglycerides. The
fatty acids which most commonly enter into combination of fats
and oils are lauric, myristic, palmitic, stearic and oleic acids and
form the neutral oils or triglycerides derived from these, e. g.,
stearin, palmatin, olein. Mono and diglycerides are also present in
fats.

SAPONIFICATION DEFINED.
When a fat or oil enters into chemical combination with one of
the caustic hydrates in the presence of water, the[Pg 3] process is
called "saponification" and the new compounds formed are soap
and glycerine, thus:

OR OH
C3H5 OR + 3 NaOH = C3H5 OH + 3 NaOR
OR OH
Fat or Oil plus 3 Sodium Hydrate equals Glycerine plus 3 Soap.
It is by this reaction almost all of the soap used today is made.
There are also other means of saponification, as, the hydrolysis
of an oil or fat by the action of hydrochloric or sulfuric acid, by
autoclave and by ferments or enzymes. By these latter processes
the fatty acids and glycerine are obtained directly, no soap being
formed.

8
FATS AND OILS USED IN SOAP
MANUFACTURE.
The various and most important oils and fats used in the
manufacture of soap are, tallow, cocoanut oil, palm oil, olive oil,
poppy oil, sesame oil, soya bean oil, cotton-seed oil, corn oil and
the various greases. Besides these the fatty acids, stearic, red oil
(oleic acid) are more or less extensively used. These oils, fats and
fatty acids, while they vary from time to time and to some extent
as to their color, odor and consistency, can readily be
distinguished by various physical and chemical constants.
Much can be learned by one, who through continued
acquaintance with these oils has thoroughly familiarized himself
with the indications of a good or bad oil, by taste, smell, feel and
appearance. It is, however, not well for the manufacturer in
purchasing to depend entirely upon these simpler tests. Since he
is interested in the yield of glycerine, the largest possible yield of
soap per pound of soap stock and the general body and
appearance of the finished product, the chemical tests upon which
these depend[Pg 4] should be made. Those especially important are
the acid value, percentage unsaponifiable matter and titer test.
A short description of the various oils and fats mentioned is
sufficient for their use in the soap industry.
Tallow is the name given to the fat extracted from the solid fat
or "suet" of cattle, sheep or horses. The quality varies greatly,
depending upon the seasons of the year, the food and age of the
animal and the method of rendering. It comes to the market

9
under the distinction of edible and inedible, a further distinction
being made in commerce as beef tallow, mutton tallow or horse
tallow. The better quality is white and bleaches whiter upon
exposure to air and light, though it usually has a yellowish tint, a
well defined grain and a clean odor. It consists chiefly of stearin,
palmitin and olein. Tallow is by far the most extensively used and
important fat in the making of soap.
In the manufacture of soaps for toilet purposes, it is usually
necessary to produce as white a product as possible. In order to do
this it often is necessary to bleach the tallow before saponification.
The method usually employed is the Fuller's Earth process.

FULLER'S EARTH PROCESS FOR BLEACHING

TALLOW.
From one to two tons of tallow are melted out into the bleaching
tank. This tank is jacketed, made of iron and provided with a good
agitator designed to stir up sediment or a coil provided with
tangential downward opening perforations and a draw-off cock at
the bottom. The coil is the far simpler arrangement, more cleanly
and less likely to cause trouble. By this arrangement compressed
air which is really essential in the utilization of the press (see
later) is utilized for agitation. A dry steam coil in an ordinary tank
may be employed in place of a jacketed tank, which lessens the
cost of installation.[Pg 5]
The tallow in the bleaching tank is heated to 180° F. (82° C.) and
ten pounds of dry salt per ton of fat used added and thoroughly
mixed by agitation. This addition coagulates any albumen and

10
dehydrates the fat. The whole mass is allowed to settle over night
where possible, or for at least five hours. Any brine which has
separated is drawn off from the bottom and the temperature of
the fat is then raised to 160° F. (71° C).
Five per cent. of the weight of the tallow operated upon, of dry
Fuller's earth is now added and the whole mass agitated from
twenty to thirty minutes.
The new bleached fat, containing the Fuller's earth is pumped
directly to a previously heated filter press and the issuing clear oil
run directly to the soap kettle.
One of the difficulties experienced in the process is the heating
of the press to a temperature sufficient to prevent solidification of
the fat without raising the press to too great a temperature. To
overcome this the first plate is heated by wet steam. Air delivered
from a blower and heated by passage through a series of coils
raised to a high temperature by external application of heat
(super-heated steam) is then substituted for the steam. The
moisture produced by the condensation of the steam is vaporized
by the hot air and carried on gradually to each succeeding plate
where it again condenses and vaporizes. In this way the small
quantity of water is carried through the entire press, raising its
temperature to 80°-100° C. This temperature is subsequently
maintained by the passage of hot air. By this method of heating
the poor conductivity of hot air is overcome through the
intermediary action of a liquid vapor and the latent heat of steam
is utilized to obtain the initial rise in temperature. To heat a small
press economically where conditions are such that a large output
is not required the entire press[Pg 6] may be encased in a small
wooden house which can be heated by steam coils. The cake in the

11
press is heated for some time after the filtration is complete to
assist drainage. After such treatment the cake should contain
approximately 15 per cent. fat and 25 per cent. water. The cake is
now removed from the press and transferred to a small tank
where it is treated with sufficient caustic soda to convert the fat
content into soap.
Saturated brine is then added to salt out the soap, the Fuller's
earth is allowed to settle to the bottom of the tank and the soap
which solidifies after a short time is skimmed off to be used in a
cheap soap where color is not important. The liquor underneath
may also be run off without disturbing the sediment to be used in
graining a similar cheap soap. The waste Fuller's earth contains
about 0.1 to 0.3 per cent. of fat.

METHOD FOR FURTHER IMPROVEMENT OF

COLOR.
A further improvement of the color of the tallow may be
obtained by freeing it from a portion of its free fatty acids, either
with or without previous Fuller's earth bleaching.
To carry out this process the melted fat is allowed to settle and
as much water as possible taken off. The temperature is then
raised to 160° F. with dry steam and enough saturated solution of
soda ash added to remove 0.5 per cent. of the free fatty acids,
while agitating the mass thoroughly mechanically or by air. The
agitation is continued ten minutes, the whole allowed to settle for
two hours and the foots drawn off. The soap thus formed
entangles a large proportion of the impurities of the fat.

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VEGETABLE OILS.
Cocoanut Oil, as the name implies, is obtained from the fruit of
the cocoanut palm. This oil is a solid, white fat at ordinary
temperature, having a bland taste and a characteristic[Pg 7] odor. It
is rarely adulterated and is very readily saponified. In recent years
the price of this oil has increased materially because cocoanut oil
is now being used extensively for edible purposes, especially in the
making of oleomargarine. Present indications are that shortly very
little high grade oil will be employed for soap manufacture since
the demand for oleomargarine is constantly increasing and since
new methods of refining the oil for this purpose are constantly
being devised.
The oil is found in the market under three different grades: (1)
Cochin cocoanut oil, the choicest oil comes from Cochin
(Malabar). This product, being more carefully cultivated and
refined than the other grades, is whiter, cleaner and contains a
smaller percentage of free acid. (2) Ceylon cocoanut oil, coming
chiefly from Ceylon, is usually of a yellowish tint and more acrid
in odor than Cochin oil. (3) Continental cocoanut oil (Copra,
Freudenberg) is obtained from the dried kernels, the copra, which
are shipped to Europe in large quantities, where the oil is
extracted. These dried kernels yield 60 to 70 per cent oil. This
product is generally superior to the Ceylon oil and may be used as
a very satisfactory substitute for Cochin oil, in soap manufacture,
provided it is low in free acid and of good color. The writer has
employed it satisfactorily in the whitest and finest of toilet soaps
without being able to distinguish any disadvantage to the Cochin

13
oil. Since continental oil is usually cheaper than Cochin oil, it is
advisable to use it, as occasion permits.
Cocoanut oil is used extensively in toilet soap making, usually in
connection with tallow. When used alone the soap made from this
oil forms a lather, which comes up rapidly but which is fluffy and
dries quickly. A pure tallow soap lathers very much slower but
produces a more lasting lather. Thus the advantage of using
cocoanut oil[Pg 8] in soap is seen. It is further used in making a
cocoanut oil soap by the cold process also for "fake" or filled
soaps. The fatty acid content readily starts the saponification
which takes place easily with a strong lye (25°-35° B.). Where
large quantities of the oil are saponified care must be exercised as
the soap formed suddenly rises or puffs up and may boil over.
Cocoanut oil soap takes up large quantities of water, cases having
been cited where a 500 per cent. yield has been obtained. This
water of course dries out again upon exposure to the air. The soap
is harsh to the skin, develops rancidity and darkens readily.
Palm Kernel Oil, which is obtained from the kernels of the palm
tree of West Africa, is used in soap making to replace cocoanut oil
where the lower price warrants its use. It resembles cocoanut oil
in respect to saponification and in forming a very similar soap.
Kernel oil is white in color, has a pleasant nutty odor when fresh,
but rapidly develops free acid, which runs to a high percentage.
Palm Oil is produced from the fruit of the several species of the
palm tree on the western coast of Africa generally, but also in the
Philippines. The fresh oil has a deep orange yellow tint not
destroyed by saponification, a sweetish taste and an odor of orris
root or violet which is also imparted to soap made from it. The
methods by which the natives obtain the oil are crude and depend

14
upon a fermentation, or putrefaction. Large quantities are said to
be wasted because of this fact. The oil contains impurities in the
form of fermentable fibre and albuminous matter, and
consequently develops free fatty acid rapidly. Samples tested for
free acid have been found to have hydrolized completely and one
seldom obtains an oil with low acid content. Because of this high
percentage of free fatty acid, the glycerine yield is small, though
the neutral oil should produce approximately 12 per cent.
glycerine. Some[Pg 9] writers claim that glycerine exists in the free
state in palm oil. The writer has washed large quantities of the oil
and analyzed the wash water for glycerine. The results showed
that the amount present did not merit its recovery. Most soap
makers do not attempt to recover the glycerine from this oil, when
used alone for soap manufacture.
There are several grades of palm oil in commerce, but in toilet
soap making it is advisable to utilize only Lagos palm oil, which is
the best grade. Where it is desired to maintain the color of the
soap this oil produces, a small quantity of the lower or "brass"
grade of palm oil may be used, as the soap made from the better
grades of oil gradually bleaches and loses its orange yellow color.
Palm oil produces a crumbly soap which cannot readily be
milled and is termed "short." When used with tallow and cocoanut
oil, or 20 to 25 per cent. cocoanut oil, it produces a very
satisfactory toilet soap. In the saponification of palm oil it is not
advisable to combine it with tallow in the kettle, as the two do not
readily mix.
Since the finished soap has conveyed to it the orange color of the
oil, the oil is bleached before saponification. Oxidation readily
destroys the coloring matter, while heat and light assist

15
materially. The methods generally employed are by the use of
oxygen developed by bichromates and hydrochloric acid and the
direct bleaching through the agency of the oxygen of the air.

CHROME BLEACHING OF PALM OIL.

The chrome process of bleaching palm oil is more rapid and the
oxygen thus derived being more active will bleach oils which air
alone cannot. It depends upon the reaction:
Na2Cr2O7 + 8HCl = Cr2Cl6 + 2NaCl + 7O.
in which the oxygen is the active principle. In practice it is found
necessary to use an excess of acid over that theoretically
indicated.[Pg 10]
For the best results an oil should be chosen containing under 2
per cent. impurities and a low percentage of free fatty acids. Lagos
oil is best adapted to these requirements. The oil is melted by
open steam from a jet introduced through the bung, the melted oil
and condensed water running to the store tank through two sieves
(about 1/8 inch mesh) to remove the fibrous material and gross
impurities. The oil thus obtained contains fine earthy and fibrous
material and vegetable albuminous matter which should be
removed, as far as possible, since chemicals are wasted in their
oxidation and they retard the bleaching. This is best done by
boiling the oil for one hour with wet steam and 10 per cent.
solution of common salt (2 per cent. dry salt on weight of oil used)
in a lead-lined or wooden tank. After settling over night the brine
and impurities are removed by running from a cock at the bottom
of the vat and the oil is run out into the bleaching tank through an
oil cock, situated about seven inches from the bottom.

16
 The bleaching tank is a lead-lined iron tank of the approximate
dimensions of 4 feet deep, 4 feet long and 3-1/2 feet wide, holding
about 1-1/2 tons. The charge is one ton. A leaden outlet pipe is
fixed at the bottom, to which is attached a rubber tube closed by a
screw clip. A plug also is fitted into the lead outlet pipe from
above. Seven inches above the lower outlet is affixed another tap
through which the oil is drawn off.
The tank is further equipped with a wet steam coil and a coil
arranged to allow thorough air agitation, both coils being of lead.
A good arrangement is to use one coil to deliver either air or
steam. These coils should extend as nearly as possible over the
entire bottom of the tank and have a number of small downward
perforations, so as to spread the agitation throughout the mass.
The temperature of the oil is reduced by passing in air[Pg 11] to
110° F. and 40 pounds of fine common salt per ton added through
a sieve. About one-half of the acid (40 pounds of concentrated
commercial hydrochloric acid) is now poured in and this is
followed by the sodium bichromate in concentrated solution,
previously prepared in a small lead vat or earthen vessel by
dissolving 17 pounds of bichromate in 45 pounds commercial
hydrochloric acid. This solution should be added slowly and
should occupy three hours, the whole mass being thoroughly
agitated with air during the addition and for one hour after the
last of the bleaching mixture has been introduced. The whole
mixture is now allowed to settle for one hour and the exhausted
chrome liquors are then run off from the lower pipe to a waste
tank. About 40 gallons of water are now run into the bleached oil
and the temperature raised by open steam to 150° to 160° F. The
mass is then allowed to settle over night.

17
 One such wash is sufficient to remove the spent chrome liquor
completely, provided ample time is allowed for settling. A number
of washings given successively with short periods of settling do
not remove the chrome liquors effectually. The success of the
operation depends entirely upon the completeness of settling.
The wash water is drawn off as before and the clear oil run to
storage tanks or to the soap kettle through the upper oil cock.
The waste liquors are boiled with wet steam and the oil
skimmed from the surface, after which the liquors are run out
through an oil trap.
By following the above instructions carefully it is possible to
bleach one ton of palm oil with 17 pounds of bichromate of soda
and 85 pounds hydrochloric acid.
The spent liquors should be a bright green color. Should they be
of a yellow or brownish shade insufficient acid has[Pg 12] been
allowed and more must be added to render the whole of the
oxygen available.
If low grade oils are being treated more chrome will be
necessary, the amount being best judged by conducting the
operation as usual and after the addition of the bichromate,
removing a sample of the oil, washing the sample and noting the
color of a rapidly cooled sample.
A little practice will enable the operator to judge the
correspondence between the color to be removed and the amount
of bleaching mixture to be added.

18
 To obtain success with this process the method of working given
must be adhered to even in the smallest detail. This applies to the
temperature at which each operation is carried out particularly.

AIR BLEACHING OF PALM OIL.

The method of conducting this process is identical with the
chrome process to the point where the hydrochloric acid is to be
added to the oil. In this method no acid or chrome is necessary, as
the active bleaching agent is the oxygen of the air.
The equipment is similar to that of the former process, except
that a wooden tank in which no iron is exposed will suffice to
bleach the oil in. The process depends in rapidity upon the
amount of air blown through the oil and its even distribution. Iron
should not be present or exposed to the oil during bleaching, as it
retards the process considerably.
After the impurities have been removed, as outlined under the
chrome process, the temperature of the oil is raised by open steam
to boiling. The steam is then shut off and air allowed to blow
through the oil until it is completely bleached, the temperature
being maintained above 150° F. by occasionally passing in steam.
Usually a ton of oil is readily and completely bleached after the air
has[Pg 13] been passed through it for 18 to 20 hours, provided the
oil is thoroughly agitated by a sufficient flow of air.
If the oil has been allowed to settle over night, it is advisable to
run off the condensed water and impurities by the lower cock
before agitating again the second day.
When the oil has been bleached to the desired color, which can
be determined by removing a sample and cooling, the mass is

19
allowed to settle, the water run off to a waste tank from which any
oil carried along may be skimmed off and the supernatant clear oil
run to the storage or soap kettle.
In bleaching by this process, while the process consumes more
time and is not as efficient in bleaching the lower grade oils, the
cost of bleaching is less and with a good oil success is more
probable, as there is no possibility of any of the chrome liquors
being present in the oil. These give the bleached oil a green tint
when the chrome method is improperly conducted and they are
not removed.
Instead of blowing the air through it, the heater oil may be
brought into contact with the air, either by a paddle wheel
arrangement, which, in constantly turning, brings the oil into
contact with the air, or by pumping the heated oil into an elevated
vessel, pierced with numerous fine holes from which the oil
continuously flows back into the vessel from which the oil is
pumped. While in these methods air, light and heat act
simultaneously in the bleaching of the oil, the equipment required
is too cumbersome to be practical.
Recent investigations in bleaching palm oil by oxygen have
[1]

shown that not only the coloring matter but the oil itself was
affected. In bleaching palm oil for 30 hours with air the free fatty
acid content rose and titer decreased considerably.[Pg 14]
Olive Oil, which comes from the fruit of the olive trees, varies
greatly in quality, according to the method by which it is obtained
and according to the tree bearing the fruit. Three hundred
varieties are known in Italy alone. Since the larger portion of olive
oil is used for edible purposes, a lower grade, denatured oil,
denatured because of the tariff, is used for soap manufacture in

20
this country. The oil varies in color from pale green to golden
yellow. The percentage of free acid in this oil varies greatly,
though the oil does not turn rancid easily. It is used mainly in the
manufacture of white castile soap.
Olive oil foots, which is the oil extracted by solvents after the
better oil is expressed, finds its use in soap making mostly in
textile soaps for washing and dyeing silks and in the production of
green castile soaps.
Other oils, as poppy seed oil, sesame oil, cottonseed oil, rape oil,
peanut (arachis) oil, are used as adulterants for olive oil, also as
substitutes in the manufacture of castile soap, since they are
cheaper than olive oil.
Cottonseed Oil is largely used in the manufacture of floating and
laundry soaps. It may be used for toilet soaps where a white color
is not desired, as yellow spots appear on a finished soap in which
it has been used after having been in stock a short time.
Corn Oil and Soya Bean Oil are also used to a slight extent in
the manufacture of toilet soaps, although the oils form a soap of
very little body. Their soaps also spot yellow on aging.
Corn oil finds its greatest use in the manufacture of soap for
washing automobiles. It is further employed for the manufacture
of cheap liquid soaps.
Fatty Acids are also used extensively in soap manufacture.
While the soap manufacturer prefers to use a neutral oil or fat,
since from these the by-product glycerine is[Pg 15] obtained,
circumstances arise where it is an advantage to use the free fatty
acids. Red oil (oleic acid, elaine) and stearic acid are the two fatty
acids most generally bought for soap making. In plants using the

21
Twitchell process, which consists in splitting the neutral fats and
oils into fatty acids and glycerine by dilute sulphuric acid and
producing their final separation by the use of so-called aromatic
sulphonic acids, these fatty acids consisting of a mixture of oleic,
stearic, palmitic acids, etc., are used directly after having been
purified by distillation, the glycerine being obtained from
evaporating the wash water.
Oleic acid (red oil) and stearic acid are obtained usually by the
saponification of oils, fats and greases by acid, lime or water
under pressure or Twitchelling. The fatty acids thus are freed
from their combination with glycerine and solidify upon cooling,
after which they are separated from the water and pressed at a
higher or lower temperature. The oleic acid, being liquid at
ordinary temperature, together with some stearic and palmitic
acid, is thus pressed out. These latter acids are usually separated
by distillation, combined with the press cake further purified and
sold as stearic acid.
The red oil, sometimes called saponified red oil, is often semi-
solid, resembling a soft tallow, due to the presence of stearic acid.
The distilled oils are usually clear, varying in color from light to a
deep brown. Stearic acid, which reaches the trade in slab form,
varies in quality from a soft brown, greasy, crumbly solid of
unpleasant odor to a snow white, wax-like, hard, odorless mass.
The quality of stearic acid is best judged by the melting point,
since the presence of any oleic acid lowers this. The melting point
of the varieties used in soap manufacture usually ranges from
128° to 132° F. Red oil is used in the manufacture of textile soaps,
replacing olive oil foots soap for[Pg 16] this purpose, chlorophyll
being used to color the soap green. Stearic acid, being the hard
firm fatty acid, may be used in small quantities to give a better

22
grade of soap body and finish. In adding this substance it should
always be done in the crutcher, as it will not mix in the kettle. It
finds its largest use for soap, however, in the manufacture of
shaving soaps and shaving creams, since it produces the non-
drying creamy lather so greatly desired for this purpose. Both red
oil and stearic acid being fatty acids, readily unite with the alkali
carbonates, carbon dioxide being formed in the reaction and this
method is extensively used in the formation of soap from them.

RANCIDITY OF OILS AND FATS.

Rancidity in neutral oils and fats is one of the problems the soap
manufacturer has to contend with. The mere saying that an oil is
rancid is no indication of its being high in free acid. The two terms
rancidity and acidity are usually allied. Formerly, the acidity of a
fat was looked upon as the direct measure of its rancidity. This
idea is still prevalent in practice and cannot be too often stated as
incorrect. Fats and oils may be acid, or rancid, or acid and
rancid. In an acid fat there has been a hydrolysis of the fat and it
has developed a rather high percentage of free acid. A rancid fat is
one in which have been developed compounds of an odoriferous
nature. An acid and rancid fat is one in which both free acid and
organic compounds of the well known disagreeable odors have
been produced.
It cannot be definitely stated just how this rancidity takes place,
any more than just what are the chemical products causing
rancidity. The only conclusion that one may draw is that the fats
are first hydrolyzed or split up into glycerine and free fatty acids.
This is followed by an oxidation of the products thus formed.[Pg 17]

23
 Moisture, air, light, enzymes (organized ferments) and bacteria
are all given as causes of rancidity.
It seems very probable that the initial splitting of the fats is
caused by enzymes, which are present in the seeds and fruits of
the vegetable oils and tissue of animal fats, in the presence of
moisture. Lewkowitsch strongly emphasizes this point and he is
substantiated in his idea by other authorities. Others hold that
bacteria or micro-organisms are the cause of this hydrolysis,
citing the fact that they have isolated various micro-organisms
from various fats and oils. The acceptance of the bacterial action
would explain the various methods of preservation of oils and fats
by the use of antiseptic preparations. It cannot, however, be
accepted as a certainty that bacteria cause the rancidity of fats.
The action of enzymes is a more probable explanation.
The hydrolysis of fats and oils is accelerated when they are
allowed to remain for some time in the presence of organic non-
fats. Thus, palm oil, lower grades of olive oil, and tallow, which
has been in contact with the animal tissue for a long time, all
contain other nitrogenous matter and exhibit a larger percentage
of free fatty acid than the oils and fats not containing such
impurities.
Granting this initial splitting of the fat into free fatty acids and
glycerine, this is not a sufficient explanation. The products thus
formed must be acted upon by air and light. It is by the action of
these agents that there is a further action upon the products, and
from this oxidation we ascertain by taste and smell (chemical
means are still unable to define rancidity) whether or not a fat is
rancid. While some authorities have presumed to isolate some of
these products causing rancidity, we can only assume the

24
presence of the various possible compounds produced by the
action[Pg 18] of air and light which include oxy fatty acids, lactones,
alcohols, esters, aldehydes and other products.
The soap manufacturer is interested in rancidity to the extent of
the effect upon the finished soap. Rancid fats form darker soaps
than fats in the neutral state, and very often carry with them the
disagreeable odor of a rancid oil. Further, a rancid fat or oil is
usually high in free acid. It is by no means true, however, that
rancidity is a measure for acidity, for as has already been pointed
out, an oil may be rancid and not high in free acid.
The percentage of free fatty acid is of even greater importance in
the soap industry. The amount of glycerine yield is dependent
upon the percentage of free fatty acid and is one of the criterions
of a good fat or oil for soap stock.

PREVENTION OF RANCIDITY.
Since moisture, air, light and enzymes, produced by the
presence of organic impurities, are necessary for the rancidity of a
fat or oil, the methods of preventing rancidity are given. Complete
dryness, complete purification of fats and oils and storage without
access of air or light are desirable. Simple as these means may
seem, they can only be approximated in practice. The most
difficult problem is the removal of the last trace of moisture.
Impurities may be lessened very often by the use of greater care.
In storing it is well to store in closed barrels or closed iron tanks
away from light, as it has been observed that oils and fats in
closed receptacles become rancid less rapidly than those in open
ones, even though this method of storing is only partially attained.

25
Preservatives are also used, but only in edible products, where
their effectiveness is an open question.

CHEMICAL CONSTANTS OF OILS AND

FATS.
Besides the various physical properties of oils and fats,[Pg 19] such
as color, specific gravity, melting point, solubility, etc., they may
be distinguished chemically by a number of chemical constants.
These are the iodine number, the acetyl value, saponification
number, Reichert-Meissl number for volatile acids, Hehner
number for insoluble acids. These constants, while they vary
somewhat with any particular oil or fat, are more applicable to the
edible products and are criterions where any adulteration of fat or
oil is suspected. The methods of carrying out the analyses of oils
and fats to obtain these constants are given in the various texts [2]

on oils and fats, and inasmuch as they are not of great importance
to the soap industry they are merely mentioned here.

OIL HARDENING OR HYDROGENATING.

It is very well known that oils and fats vary in consistency and
hardness, depending upon the glycerides forming same. Olein, a
combination of oleic acid and glycerine, as well as oleic acid itself
largely forms the liquid portion of oils and fats. Oleic acid
(C18H34O2) is an unsaturated acid and differs from stearic acid
(C18H36O2), the acid forming the hard firm portion of oils and fats,
by containing two atoms of hydrogen less in the molecule.
Theoretically it should be a simple matter to introduce two atoms

26
of hydrogen into oleic acid or olein, and by this mere addition
convert liquid oleic acid and olein into solid stearic acid and
stearine.
For years this was attempted and all attempts to apply the well
known methods of reduction (addition of hydrogen) in organic
chemistry, such as treatment with tin and acid, sodium amalgam,
etc., were unsuccessful. In recent years, however, it has been
discovered that in the presence of a catalyzer, nickel in finely
divided form[Pg 20] or the oxides of nickel are usually employed, the
process of hydrogenating an oil is readily attained upon a practical
basis.
The introduction of hardened oils has opened a new source of
raw material for the soap manufacturer in that it is now possible
to use oils in soap making which were formerly discarded because
of their undesirable odors. Thus fish or train oils which had up to
the time of oil hydrogenating resisted all attempts of being
permanently deodorized, can now be employed very satisfactorily
for soap manufacture. A Japanese chemist, Tsujimoto has shown
[3]

that fish oils contain an unsaturated acid of the composition

C18H28O2, for which he proposed the name clupanodonic acid. By
the catalytic hardening of train oils this acid passes to stearic acid
and the problem of deodorizing these oils is solved. [4]

At first the introduction of hardened oils for soap manufacture

met with numerous objections, due to the continual failures of
obtaining a satisfactory product by the use of same. Various
attempts have now shown that these oils, particularly hardened
train oils, produce extraordinarily useful materials for soap
making. These replace expensive tallow and other high melting
oils. It is of course impossible to employ hardened oils alone, as a

27
soap so hard would thus be obtained that it would be difficultly
soluble in water and possess very little lathering quality. By the
addition of 20-25% of tallow oil or some other oil forming a soft
soap a very suitable soap for household use may be obtained.
Ribot discusses this matter fully. Hardened oils readily saponify,
[5]

may be[Pg 21] perfumed without any objections and do not impart
any fishy odor to an article washed with same. Meyerheim states
[6]

that through the use of hydrogenated oils the hardness of soap is

extraordinarily raised, so that soap made from hardened
cottonseed oil is twelve times as hard as the soap made from
ordinary cottonseed oil. This soap is also said to no longer spot
yellow upon aging, and as a consequence of its hardness, is able to
contain a considerably higher content of rosin through which
lathering power and odor may be improved. Hardened oils can
easily be used for toilet soap bases, provided they are not added in
too great a percentage.
The use of hardened oils is not yet general, but there is little
doubt that the introduction of this process goes a long way toward
solving the problem of cheaper soap material for the soap making
industry.

GREASE.
Grease varies so greatly in composition and consistency that it
can hardly be classed as a distinctive oil or fat. It is obtained from
refuse, bones, hides, etc., and while it contains the same
constituents as tallow, the olein content is considerably greater,
which causes it to be more liquid in composition. Grease differs in
color from an off-white to a dark brown. The better qualities are
employed in the manufacture of laundry and chip soap, while the

28
poorer qualities are only fit for the cheapest of soaps used in
scrubbing floors and such purposes. There is usually found in
grease a considerable amount of gluey matter, lime and water.
The percentage of free fatty acid is generally high.
The darker grades of grease are bleached before being used. This
is done by adding a small quantity of sodium nitrate to the melted
grease and agitating, then[Pg 22] removing the excess saltpeter by
decomposing with sulphuric acid. A better method of refining,
however, is by distillation. The chrome bleach is also applicable.

ROSIN (COLOPHONY, YELLOW ROSIN,

RESINA).
Rosin is the residue which remains after the distillation of
turpentine from the various species of pines. The chief source of
supply is in the States of Georgia North and South Carolina. It is a
transparent, amber colored hard pulverizable resin. The better
grades are light in color and known as water white (w. w.) and
window glass (w. g.). These are obtained from a tree which has
been tapped for the first year. As the same trees are tapped from
year to year, the product becomes deeper and darker in color until
it becomes almost black.
The constituents of rosin are chiefly (80-90%) abietic acid or its
anhydride together with pinic and sylvic acids. Its specific gravity
is 1.07-1.08, melting point about 152.5 C., and it is soluble in
alcohol, ether, benzine, carbon disulfide, oils, alkalis and acetic
acid. The main use of rosin, outside of the production of
varnishes, is in the production of laundry soaps, although a slight

29
percentage acts as a binder and fixative for perfumes in toilet
soaps and adds to their detergent properties. Since it is mainly
composed of acids, it readily unites with alkaline carbonates,
though the saponification is not quite complete and the last
portion must be completed through the use of caustic hydrates,
unless an excess of 10% carbonate over the theoretical amount is
used. A lye of 20° B. is best adapted to the saponification of rosin
when caustic hydrates are employed for this purpose, since weak
lyes cause frothing. While it is sometimes considered that rosin is
an adulterant for soap, this is hardly justifiable, as it adds to the
cleansing properties of soap. Soaps containing[Pg 23] rosin are of
the well known yellowish color common to ordinary laundry
soaps. The price of rosin has so risen in the last few years that it
presents a problem of cost to the soap manufacturer considering
the price at which laundry soaps are sold.

ROSIN SAPONIFICATION.

As has been stated, rosin may be saponified by the use of

alkaline carbonates. On account of the possibility of the soap
frothing over, the kettle in which the operation takes place should
be set flush with the floor, which ought to be constructed of
cement. The kettle itself is an open one with round bottom,
equipped with an open steam coil and skimmer pipe, and the
open portion is protected by a semi-circular rail. A powerful grid,
having a 3-inch mesh, covers one-half of the kettle, the sharp
edges protruding upwards.
The staves from the rosin casks are removed at the edge of the
kettle, the rosin placed on the grid and beaten through with a
hammer to break it up into small pieces.

30
 To saponify a ton of rosin there are required 200 lbs. soda ash,
1,600 lbs. water and 100 lbs. salt. Half the water is run into the
kettle, boiled, and then the soda ash and half the salt added. The
rosin is now added through the grid and the mixture thoroughly
boiled. As carbon dioxide is evolved by the reaction the boiling is
continued for one hour to remove any excess of this gas. A portion
of the salt is gradually added to grain the soap well and to keep
the mass in such condition as to favor the evolution of gas. The
remainder of the water is added to close the soap and boiling
continued for one or two hours longer. At this point the kettle
must be carefully watched or it will boil over through the further[Pg
24] escape of carbon dioxide being hindered. The mass, being in a

frothy condition, will rapidly settle by controlling the flow of

steam. The remaining salt is then scattered in and the soap
allowed to settle for two hours or longer. The lyes are then drained
off the top. If the rosin soap is required for toilet soaps, it is
grained a second time. The soap is now boiled with the water
caused by the condensation of the steam, which changes it to a
half grained soap suitable for pumping. A soap thus made
contains free soda ash 0.15% or less, free rosin about 15%. The
mass is then pumped to the kettle containing the soap to which it
is to be added at the proper stage. The time consumed in thus
saponifying rosin is about five hours.

NAPHTHENIC ACIDS.
The naphtha or crude petroleum of the various provinces in
Europe, as Russia, Galacia, Alsace and Roumania yield a series of
bodies of acid character upon refining which are designated under
the general name of naphthenic acids. These acids are retained in

31
solution in the alkaline lyes during the distillation of the naphtha
in the form of alkaline naphthenates. Upon adding dilute
sulphuric acid to these lyes the naphthenates are decomposed and
the naphthenic acids float to the surface in an oily layer of
characteristic disagreeable odor and varying from yellow to brown
in color . In Russia particularly large quantities of these acids are
[7]

employed in the manufacture of soap.

The soaps formed from naphthenic acids have recently been
investigated and found to resemble the soaps made from
[8]

cocoanut oil and palm kernel oil, in that they are[Pg 25] difficult to
salt out and dissociate very slightly with water. The latter property
makes them valuable in textile industries when a mild soap is
required as a detergent, e. g., in the silk industry. These soaps also
possess a high solvent power for mineral oils and emulsify very
readily. The mean molecular weight of naphthenic acids
themselves is very near that of the fatty acids contained in
cocoanut oil, and like those of cocoanut oil a portion of the
separated acids are volatile with steam. The iodine number
indicates a small content of unsaturated acids.
That naphthenic acids are a valuable soap material is now
recognized, but except in Russia the soap is not manufactured to
any extent at the present time.

ALKALIS.

The common alkali metals which enter into the formation of

soap are sodium and potassium. The hydroxides of these metals
are usually used, except in the so called carbonate saponification
of free fatty acids in which case sodium and potassium carbonate
are used. A water solution of the caustic alkalis is known as lye,

32
and it is as lyes of various strengths that they are added to oils and
fats to form soap. The density or weight of a lye is considerably
greater than that of water, depending upon the amount of alkali
dissolved, and its weight is usually determined by a hydrometer.
This instrument is graduated by a standardized scale, and while
all hydrometers should read alike in a liquid of known specific
gravity, this is generally not the case, so that it is advisable to
check a new hydrometer for accurate work against one of known
accuracy. In this country the Baumé scale has been adopted, while
in England a different graduation known as the Twaddle scale is
used. The strength of a lye or any solution is determined by the
distance the instrument[Pg 26] sinks into the solution, and we speak
of the strength of a solution as so many degrees Baumé or
Twaddle which are read to the point where the meniscus of the lye
comes on the graduated scale. Hydrometers are graduated
differently for liquids of different weights. In the testing of lyes
one which is graduated from 0° to 50° B. is usually employed.
Caustic soda is received by the consumer in iron drums
weighing approximately 700 lbs. each. The various grades are
designated as 60, 70, 74, 76 and 77%. These percentages refer to
the percentage of sodium oxide (Na2O) in 100 parts of pure
caustic soda formed by the combination of 77-1/2 parts of sodium
oxide and 22-1/2 parts of water, 77-1/2% being chemically pure
caustic soda. There are generally impurities present in
commercial caustic soda. These consist of sodium carbonate,
sodium chloride or common salt and sometimes lime. It is
manufactured by treating sodium carbonate in an iron vessel with
calcium hydroxide or slaked lime, or by electrolysis of common
salt. The latter process has yet been unable to compete with the
former in price. Formerly all the caustic soda used in soap making

33
was imported, and it was only through the American
manufacturer using a similar container to that used by foreign
manufacturers that they were able to introduce their product. This
prejudice has now been entirely overcome and most of the caustic
soda used in this country is manufactured here.

CAUSTIC POTASH.
The output of the salts containing potassium is controlled
almost entirely by Germany. Formerly the chief source of supply
of potassium compounds was from the burned ashes of plants, but
about fifty years ago the inexhaustible salt mines of Stassfurt,
Germany, were discovered.[Pg 27] The salt there mined contains,
besides the chlorides and sulphates of sodium, magnesium,
calcium and other salts, considerable quantities of potassium
chloride, and the Stassfurt mines at present are practically the
entire source of all potassium compounds, in spite of the fact that
other localities have been sought to produce these compounds on
a commercial basis, especially by the United States government.
After separating the potassium chloride from the magnesium
chloride and other substances found in Stassfurt salts the
methods of manufacture of caustic potash are identical to those of
caustic soda. In this case, however, domestic electrolytic caustic
potash may be purchased cheaper than the imported product and
it gives results equal to those obtained by the use of the imported
article, opinions to the contrary among soap makers being many.
Most of the caustic potash in the United States is manufactured at
Niagara Falls by the Niagara Alkali Co., and the Hooker
Electrochemical Co., chlorine being obtained as a by-product. The
latter concern employs the Townsend Cell, for the manufacture of

34
electrolytic potash, and are said to have a capacity for making 64
tons of alkali daily.
Since the molecular weight of caustic potash (56) is greater than
that of caustic soda (40) more potash is required to saponify a
pound of fat. The resulting potash soap is correspondingly heavier
than a soda soap. When salt is added to a potassium soap double
decomposition occurs, the potassium soap being transformed to a
sodium soap and the potassium uniting with the chlorine to form
potassium chloride. This was one of the earliest methods of
making a hard soap, especially in Germany, where potash was
derived from leeching ashes of burned wood and plants.[Pg 28]

SODIUM CARBONATE (SODA ASH).

While carbonate of soda is widely distributed in nature the
source of supply is entirely dependent upon the manufactured
product. Its uses are many, but it is especially important to the
soap industry in the so called carbonate saponification of free
fatty acids, as a constituent of soap powders, in the neutralization
of glycerine lyes and as a filler for laundry soaps.
The old French Le Blanc soda process, which consists in treating
common salt with sulphuric acid and reducing the sodium
sulphate (salt cake) thus formed with carbon in the form of
charcoal or coke to sodium sulphide, which when treated with
calcium carbonate yields a mixture of calcium sulphide and
sodium carbonate (black ash) from which the carbonate is
dissolved by water, has been replaced by the more recent Solvay
ammonia soda process. Even though there is a considerable loss
of salt and the by-product calcium chloride produced by this
process is only partially used up as a drying agent, and for

35
refrigerating purposes, the Le Blanc process cannot compete with
the Solvay process, so that the time is not far distant when the
former will be considered a chemical curiosity. In the Solvay
method of manufacture sodium chloride (common salt) and
ammonium bicarbonate are mixed in solution. Double
decomposition occurs with the formation of ammonium chloride
and sodium bicarbonate. The latter salt is comparatively
difficultly soluble in water and crystallizes out, the ammonium
chloride remaining in solution. When the sodium bicarbonate is
heated it yields sodium carbonate, carbon dioxide and water; the
carbon dioxide is passed into ammonia which is set free from the
ammonium chloride obtained as above by treatment with lime
(calcium oxide) calcium chloride being the by-product.[Pg 29]
Sal soda or washing soda is obtained by recrystallizing a solution
of soda ash in water. Large crystals of sal soda containing but 37%
sodium carbonate are formed.

POTASSIUM CARBONATE.
Potassium carbonate is not extensively used in the manufacture
of soap. It may be used in the forming of soft soaps by uniting it
with free fatty acids. The methods of manufacture are the same as
for sodium carbonate, although a much larger quantity of
potassium carbonate than carbonate of soda is obtained from
burned plant ashes. Purified potassium carbonate is known as
pearl ash.

ADDITIONAL MATERIAL USED IN SOAP

MAKING.

36
 Water is indispensable to the soap manufacturer. In the soap
factory hard water is often the cause of much trouble. Water,
which is the best solvent known, in passing through the crevices of
rocks dissolves some of the constituents of these, and the water is
known as hard. This hardness is of two kinds, temporary and
permanent. Temporarily hard water is formed by water, which
contains carbonic acid, dissolving a portion of calcium carbonate
or carbonate of lime. Upon boiling, the carbonic acid is driven
from the water and the carbonate, being insoluble in carbon
dioxide free water, is deposited. This is the cause of boiler scale,
and to check this a small amount of sal ammoniac may be added
to the water, which converts the carbonate into soluble calcium
chloride and volatile ammonium carbonate. Permanent hardness
is caused by calcium sulphate which is soluble in 400 parts of
water and cannot be removed by boiling.
The presence of these salts in water form insoluble lime soaps
which act as inert bodies as far as their value for the common use
of soap is concerned. Where the percentage of lime in water is
large this should be removed.[Pg 30] A method generally used is to
add about 5% of 20° B. sodium silicate to the hard water. This
precipitates the lime and the water is then sufficiently pure to use.
Salt, known as sodium chloride, is used to a large extent in soap
making for "salting out" the soap during saponification, as well as
graining soaps. Soap ordinarily soluble in water is insoluble in a
salt solution, use of which is made by adding salt to the soap
which goes into solution and throws any soap dissolved in the lyes
out of solution. Salt may contain magnesium and calcium
chlorides, which of course are undesirable in large amounts. The
products on the market, however, are satisfactory, thus no detail
is necessary.

37
 Filling materials used are sodium silicate, or water glass, talc,
silex, pumice, starch, borax, tripoli, etc.
Besides these other materials are used in the refining of the oils
and fats, and glycerine recovery, such as Fuller's earth,
bichromates of soda or potash, sulphate of alumina, sulphuric and
hydrochloric acids and alcohol.
A lengthy description of these substances is not given, as their
modes of use are detailed elsewhere.

FOOTNOTES:
[1] Seifensieder Zeit, 1913, 40, p. 687, 724, 740.

[2] Official Methods, see Bull. 107, A. O. A. C., U. S. Dept. Agricult.

[3] Journ. Coll. of Engin. Tokyo Imper. Univ. (1906), p. 1. Abs. Chem. Revue f. d. Fett-u. Harz,
Ind. 16, p. 84; 20, p. 8.

[4] Meyerheim—Fort. der Chem., Physik. und Physik. Chem. (1913), 8. 6, p. 293-307.

[5] Seifs. Ztg. (1913), 40, p. 142.

[6] Loc. cit.

[7] Les Matieres Graisses (1914), 7, 69, p. 3367.

[8] Zeit. f. Angew. Chem. (1914), 27, 1, p. 2-4.

[Pg 31]

38
 CHAPTER II

Construction and Equipment of a Soap

Plant.
No fixed plan for the construction and equipment of a soap
plant can be given. The specifications for a soap factory to be
erected or remodeled must suit the particular cases. Very often a
building which was constructed for a purpose other than soap
manufacture must be adapted for the production of soap. In either
case it is a question of engineering and architecture, together with
the knowledge obtained in practice and the final decision as to the
arrangement is best solved by a conference with those skilled in
each of these branches.
An ideal soap plant is one in which the process of soap making,
from the melting out of the stock to the packing and shipping of
the finished product, moves downward from floor to floor, since
by this method it is possible to utilize gravitation rather than
pumping liquid fats and fluid soaps. Convenience and economy
are obtained by such an arrangement.
The various machinery and other equipment for soap
manufacture are well known to those connected with this
industry. It varies, of course, depending upon the kind of soap to
be manufactured, and full descriptions of the necessary
machinery are best given in the catalogs issued by the
manufacturers of such equipment, who in this country are most
reliable.

39
 To know just what equipment is necessary can very easily be
described by a brief outline of the process various soaps undergo
to produce the finished article. After the saponification has taken
place in the soap kettle the molten soap is run directly into the
soap frames,[Pg 32] which consist of an oblong compartment,
holding anywhere from 400 to 1,200 pounds, with removable
steel sides and mounted upon trucks, in which it solidifies. In
most cases it is advisable to first run the soap into a crutcher or
mixer which produces a more homogeneous mass than if this
operation is omitted. Color and perfume may also be added at this
point, although when a better grade of perfume is added it must
be remembered that there is considerable loss due to volatilization
of same. When a drying machine is employed the molten soap is
run directly upon the rollers of this machine, later adding about
1.0% zinc oxide to the soap from which it passes continuously
through the drying chamber and is emitted in chip form ready for
milling. After the soap has been framed, it is allowed to cool and
solidify, which takes several days, and then the sides of the frame
are stripped off. The large solid cake is cut with wires by hand or
by a slabber into slabs of any desired size. These slabs are further
divided into smaller divisions by the cutting table. In non-milled
soaps (laundry soaps, floating soaps, etc.), these are pressed at
this stage, usually by automatic presses, after a thin hard film has
been formed over the cake by allowing it to dry slightly. In making
these soaps they are not touched by hand at any time during the
operation, the pressing, wrapping and packing all being done by
machinery. For a milled soap the large slabs are cut into narrow
oblong shapes by means of the cutting table to readily pass into
the feeder of the chipper, the chips being spread upon trays and
dried in a dry house until the moisture content is approximately
15%.

40
 The process of milling is accomplished by passing the dried soap
chips through a soap mill, which is a machine consisting of
usually three or four contiguous, smooth,[Pg 33] granite rollers
operated by a system of gears and set far enough apart to allow
the soap to pass from a hopper to the first roller, from which it is
constantly conveyed to each succeeding roller as a thin film, and
finally scraped from the last roller to fall into the milling box in
thin ribbon form. These mills are often operated in tandem, which
necessitates less handling of soap by the operator. The object of
milling is to give the soap a glossy, smooth finish and to blend it
into a homogeneous mass. The perfume, color, medication or any
other material desired are added to the dried soap chips prior to
milling. Some manufacturers use an amalgamator to distribute
these uniformly through the soap, which eliminates at least one
milling. When a white soap is being put through the mill, it is
advisable to add from 0.5% to 1% of a good, fine quality of zinc
oxide to the soap, if this substance has not been previously added.
This serves to remove the yellowish cast and any translucency
occasioned by plodding. Too great a quantity of this compound
added, later exhibits itself by imparting to the soap a dead white
appearance. Inasmuch as the milling process is one upon which
the appearance of a finished cake of toilet soap largely depends, it
should be carefully done. The number of times a soap should be
milled depends upon the character of a soap being worked. It
should of course be the object to mill with as high a percentage of
moisture as possible. Should the soap become too dry it is
advisable to add water directly, rather than wet soap, since water
can more easily be distributed through the mass. As a general
statement it may be said it is better policy to overmill a soap,
rather than not mill it often enough.

41
 After the soap has been thoroughly milled it is ready for
plodding. A plodder is so constructed as to take the[Pg 34] soap
ribbons fed into the hopper by means of a worm screw and
continuously force it under great pressure through a jacketed
cylinder through which cold water circulates in the rear to
compensate the heat produced by friction and hot water at the
front, to soften and polish the soap which passes out in solid form
in bars of any shape and size depending upon the form of the
shaping plate through which it is emitted. The bars run upon a
roller board, are cut into the required length by a special cake
cutting table, allowed to dry slightly and pressed either
automatically or by a foot power press in any suitable soap die.
The finished cake is then ready for wrapping and after due time in
stock reaches the consumer.
Besides the various apparatus mentioned above there are many
other parts for the full equipment of a modern soap plant, such as
remelters, pumps, mixers, special tanks, power equipment, etc. As
has been stated, however, practical experience will aid in judging
the practicability as to installation of these. The various methods
of powdering soap are, however, not generally known. Where a
coarse powder is to be produced, such as is used for common
washing powders, no great difficulty is experienced with the well
known Blanchard mill. In grinding soap to an impalpable powder
the difficulties increase. The methods adapted in pulverizing
soaps are by means of disintegrators, pebble mills and chaser
mills. The disintegrator grinds by the principle of attrition, that is,
the material is reduced by the particles being caused to beat
against each other at great velocity; a pebble mill crushes the
substance by rubbing it between hard pebbles in a slowly
revolving cylinder; the chaser mill first grinds the material and

42
then floats it as a very fine powder above a curb of fixed height.
The last method is particularly adapted for the finest of powder
(140 mesh and over).

[Pg 35]

43
 CHAPTER III

Classification of Soap-Making Methods.

In the saponification of fats and oils to form soap through the
agency of caustic alkalis, as has been stated, the sodium or
potassium salts of the mixed fatty acids are formed. Sodium soaps
are usually termed hard soaps, and potassium soaps soft. There
are, however, a great many varieties of soaps the appearance and
properties of which depend upon their method of manufacture
and the oils or fats used therein.
The various methods adopted in soap making may be thus
classified:
1. Boiling the fats and oils in open kettles by open steam with
indefinite quantities of caustic alkali solutions until the finished
soap is obtained; ordinarily named full boiled soaps. These may
be sub-divided into (a) hard soaps with sodium hydrate as a base,
in which the glycerine is recovered from the spent lyes; (b) hard
soaps with soda as a base, in which the glycerine remains in the
soap, e. g., marine cocoanut oil soaps; (c) soft potash soaps, in
which the glycerine is retained by the soap.
2. Combining the required amount of lye for complete
saponification of a fat therewith, heating slightly with dry heat
and then allowing the saponification to complete itself. This is
known as the cold process.
3. Utilizing the fatty acid, instead of the neutral fat, and
combining it directly with caustic alkali or carbonate, which is

44
incorrectly termed carbonate saponification, since it is merely
neutralizing the free fatty acid and thus is not a saponification in
the true sense of the word. No glycerine is directly obtained by
this method, as it is[Pg 36] usually previously removed in the
clearage of the fat by either the Twitchell or autoclave
saponification method.
In the methods thus outlined the one most generally employed
is the full boiled process to form a sodium soap. This method of
making soap requires close attention and a knowledge which can
only be obtained by constant practice. The stock, strength of lyes,
heat, amount of salt or brine added, time of settling, etc., are all
influencing factors.
The principles involved in this process are briefly these:
The fat is partly saponified with weak lyes (usually those
obtained from a previous boiling in the strengthening change are
used), and salt is added to grain the soap. The mass is then
allowed to settle into two layers. The upper layer is partly
saponified fat; the lower layer, or spent lye, is a solution of salt,
glycerine, and contains any albuminous matter or any other
impurity contained in the fat. This is known as the killing or
glycerine change. Strong lyes are now added and the fat entirely
saponified, which is termed the strengthening change. The mass
is then allowed to settle and the fluid soap run off above the
"nigre." This operation is called the finish or finishing change.
The method may be more fully illustrated by a concrete example
of the method of manufacture of a tallow base:

Charge—
Tallow 88 per cent.

45
 Cocoanut oil 10 per cent.
Rosin w. w. 2 per cent.
Amount charge 10 tons

About five tons of tallow and one ton of cocoanut oil are pumped
or run into the soap kettle and brought to a boil with wet steam
until it briskly comes through the hot fat. The caustic soda
(strengthening lyes from former[Pg 37] boilings may be used here) is
gradually added by the distributing pipe, any tendency to thicken
being checked by the introduction of small quantities of brine
("salt pickle"). If the lye is added too rapidly the soap assumes a
granular appearance, indicating that the addition of same must be
discontinued. Water should then be added and the mass boiled
through until it again closes. When the addition of the proper
amount of caustic soda is nearing its completion the soap
gradually thins. The steam is now cut down to about one turn of
the valve, and brine is rapidly added or salt shoveled in. In ten to
fifteen minutes the steam again breaks through and, from the
appearance of the soap, it can be seen whether sufficient brine has
been added. A sample taken out by means of a long wooden
paddle should show the soap in fine grains with the lyes running
from it clear. The steam is then shut off and the soap allowed to
settle from one and one-half to two hours. In all settlings the
longer time this operation is permitted to continue, the better will
the subsequent operations proceed.
The mixture now consists of a partly saponified layer of fat
above the spent lyes. The lyes are drawn off until soap makes its
appearance at the exit pipe. The valve is then closed and the soap
blown back into the kettle by steam. The lyes thus obtained are
known as spent lyes, from which the glycerine is recovered. They

46
should show an alkalinity of approximately 0.5 per cent. if the
operation is carefully carried out.
The remaining tallow is now added and the above operations
repeated.
After the spent lyes have been drawn off, the soap is closed with
water and the proper percentage of rosin soap previously formed,
or rosin itself is added to the mass in the kettle. More lye is then
allowed to flow in until the[Pg 38] mixture is up to "strength." This is
usually tested by the "bite" on the tongue of a small cooled
sample. After boiling until the steam comes through, the mass is
grained with salt as before and allowed to settle one and one-half
to three hours. These lyes, known as strengthening lyes are run to
storage to be used subsequently with fresh fat to take up the
caustic soda contained therein.
The soap is now ready for finishing and is first boiled through
and tried for strength. A drop of phenolphthalein (1 per cent.
phenolphthalein in 98 per cent. alcohol) is allowed to drop on the
molten soap taken up on a trowel. The red color should be
instantly produced and develop to a full deep crimson in a few
seconds, or more lye must be added until this condition is
realized. Should it flash a deep crimson immediately it is on the
strong side. This cannot be conveniently remedied; it can only
serve as a guide for the next boil, but in any case it is not of any
serious consequence, unless it is too strong.
With the steam on, the soap is now examined with a trowel
which must be thoroughly heated by working it about under the
surface of the hot soap. The appearance of the soap as it runs from
the face of the trowel indicates its condition. It is not possible to
absolutely describe the effect, which can only be properly judged

47
by practice, yet the following points may serve as a guide. The
indications to be noticed are the shape and size of the flakes of
soap as the sample on the trowel breaks up and runs from the hot
iron surface, when the latter is turned in a vertical position, as
well as the condition of the iron surface from which the soap
flakes have fallen. A closed soap will run slowly into a
homogeneous sheet, leaving the trowel's surface covered with a
thin layer of transparent soap; a grained mass will run rapidly
down in tiny grains, about one-half an inch in diameter or less,
leaving the hot trowel[Pg 39] absolutely dry. The object of the finish
is to separate the soaps of the lower fatty acids from those of the
higher, and both from excess of liquid. A point midway between
"open" and "closed" is required to arrive at this point.
Having arrived at the above condition, the soap is allowed to
settle anywhere from one to three days and then run off through
the skimmer pipes to the nigre and framed or pumped to the tank
feeding the drying machine.
The stock thus obtained should be fairly white, depending upon
the grade of tallow used and slightly alkaline to an alcoholic
phenolphthalein solution. If removed at exactly the neutral point
or with a content of free fat the soap will sooner or later develop
rancidity. The soap thus obtained is an ordinary tallow base, and
the one by far greatest used in the manufacture of toilet soaps.
The percentage of cocoanut oil indicated is not fixed and may
readily be varied, while in fine toilet soap the rosin is usually
eliminated.
In the manufacture of full boiled soda soaps in which no
glycerine is obtained as a by-product, it being retained in the soap
itself, the soap formed is known as a "run" soap. The process is

48
used most extensively in the manufacture of marine soaps by
which the method may be best illustrated. This soap is known as
marine soap because of its property of readily forming a lather
with salt water and is mostly consumed aboard vessels.
Marine soaps are manufactured by first placing in the kettle a
calculated amount of lye of 25 deg. to 35 deg. B., depending upon
the amount of moisture desired in the finished soaps, plus a slight
excess required to saponify a known weight of cocoanut oil. With
open steam on, the cocoanut oil is then gradually added, care
being taken that the soap does not froth over. Saponification takes
place readily and when the oil is entirely saponified the finished[Pg
40] soap is put through the process known as running. This

consists in constantly pumping the mass from the skimmer pipe

back into the top of the kettle, the object being to prevent any
settling of the nigre or lye from the soap, as well as producing a
homogeneous mass. It is customary to begin the saponification in
the morning, which should be completed by noon. The soap is
then run for about three hours and framed the next morning.
After having remained in the frame the time required to solidify
and cool, the soap is slabbed and cut into cakes. This process is
difficult to carry out properly, and one not greatly employed,
although large quantities of marine soap are purchased by the
government for use in the navy and must fulfill certain
specifications required by the purchasing department.
In making potash soaps it is practically impossible to obtain any
glycerine directly because of the pasty consistency of the soap, and
no graining is possible because the addition of salt to a soft soap,
as already explained, would form a soda soap. Large quantities of
soft soaps are required for the textile industries who desire mostly
a strong potash soap, and the large number of automobiles in use

49
at the present time has opened a field for the use of a soft soap for
washing these. A soap for this purpose must be neutral so as not
to affect the varnish or paint of automobiles.
A suitable soap for textile purposes may be made as follows:

Red oil 80 parts

House grease 20 parts
Caustic soda lye, 36 degs. B. 3 parts
Carbonate of potash 5-1/2 parts
Caustic potash 23-1/4 parts

Olive oil, corn oil, soya bean oil, olive oil foots or cottonseed[Pg 41]
oil may replace any of the above oils. A large quantity of
cottonseed oil will cause the soap to fig.
To carry out the process, the caustic potash and carbonate of
potash are dissolved and placed in the kettle together with the
soda lye, and the oils added. This is most satisfactorily
accomplished by being finished the day before the boiling is
begun. The next day the boiling is begun and water added to bring
the soap up to the desired percentage of fatty acid, due allowance
being made for the water formed by the condensation of the open
steam in boiling. Care must be taken that the soap in the kettle
does not swell and run over during the saponification. A good
procedure is to use open steam for a period of about two hours,
then close the valve and allow the saponification to continue
without boiling, and repeat this until it is entirely saponified. After
the saponification has been completed the soap is briskly boiled
all day and the proper corrections made; that is, if too alkaline,
more oil is added, and if free fat is present, more potash. About 2

50
per cent. carbonate of potash is the proper amount for a soap
containing 50 per cent. fatty acid. The soap is sampled by allowing
it to drop on a clean, cold glass surface. In so doing, the soap
should not slide or slip over the glass surface when pressed
thereon, but should adhere to the glass, or it is too alkaline. A
sample worked between the fingers showing too much stringiness
should have more strong potash and oil added. A sample taken
out in a pail and allowed to cool over night will serve as a guide as
to the body of the soap in the kettle. When the soap has thus been
properly finished it is run into barrels.
For an automobile soap the following is a good working formula:

Corn oil 1,000 parts

Potash lye, 31-1/2 degs. B. 697 parts
[Pg 42]

Proceed as in the directions just given for textile soap in placing

charge in the kettle. When the kettle is boiling up well, shut off the
steam and the saponification will complete itself. The soap may be
run into the barrels the next day.
A heavy soap with a smaller percentage of fat may be made as
follows:

Corn oil 1,000 parts

Potash lye, 24-1/2 degs. B. 900 parts

Boil until the soap bunches, and shovel the finished soap into
barrels. Upon standing it will clear up. By the addition of more
water the yield of soap per pound of oil may be run up to 300 per
cent.

51
 After soft soaps have been allowed to stand for some time the
phenomenon known as "figging" often occurs. This term is
applied to a crystalline-like formation, causing spots of a star-like
shape throughout the soap. This is undoubtedly due to the
stearine content of the soap crystallizing out as it cools, and
forming these peculiarly-shaped spots. It more generally occurs in
the winter and may be produced artificially by adding a small
quantity of soda to the potash lye before saponification.
The oils usually employed in the manufacture of potash soaps
are cottonseed oil, corn oil, soya bean oil, olive oil foots, red oil,
cocoanut oil, grease and the various train oils. The usual
percentage yield is from 225 per cent. to 300 per cent., based
upon the weight of oil used. In calculating the weight of a soft
soap it is to be remembered that since potassium has a higher
molecular weight (56) than sodium (40), the corresponding soap
formed is that much greater in weight when compared with a
sodium soap. Rosin may be added to soft soaps as a cheapening
agent.[Pg 43]

COLD PROCESS.

The cold process for manufacturing soap is the simplest method

of soap making, and the equipment required is small when
compared to the other methods. All the more expensive
equipment that is necessary is a crutcher, a tank to hold the lye,
frames, a slabber or cutting table, and a press. Yet, in spite of the
simplicity of thus making soap, the disadvantages are numerous
for the production of a good piece of soap. The greatest difficulty
is to obtain a thorough combination of oil or fat and lye so that
there will not be an excess of one or the other in the finished soap.

52
At its best there is either a considerable excess of free fat which
later exhibits itself in producing rancidity or uncombined caustic,
which produces an unpleasant effect on the skin when the soap is
consumed for washing. The latter objection, of course, can only be
applied to toilet soaps.
Cocoanut oil is used very largely in the manufacture of cold-
made soaps as it is well adapted for this purpose, although it is by
no means true that other oils may not be employed. Since by this
process of manufacture no impurity contained in the fat or oil is
removed in the making of the soap, it is necessary that in order to
obtain a fine finished product, any impurity contained in these
may be removed if present, or that the fats be as pure as can be
obtained. If inedible tallow is used for cold-made soap, it is
advisable to bleach it by the Fuller's Earth Process.
The carrying out of this method is best illustrated by an example
of a cold-made cocoanut oil soap.

Charge:
Cochin cocoanut oil 846 parts
Lye (soda), 35 degs. B. 470 parts
Water 24 parts
[Pg 44]

The oil is run into the crutcher and the temperature of the oil
raised to 100 degs. F. by dry steam. The lye and water are at room
temperature. After all the oil is in the crutcher, the lye and water
are slowly added to prevent any graining of the soap. Toward the
end the lye may be added more rapidly. When all the lye is in, the
mass is crutched for about three hours, or until upon stopping the

53
crutcher a finger drawn over the surface of the soap leaves an
impression. If this condition is not realized, the soap must be
mixed until such is the case. Having arrived at this point, the
mixture is dropped into a frame which should remain uncovered.
The heat produced by the further spontaneous saponification will
cause the soap to rise in the middle of the frame. After having set
for some days it is ready to be slabbed and cut into cakes.
A potash soap may be made by the cold process just as readily as
a soda soap. Soaps of this type may be made by either of these
formulae in a crutcher:

Olive oil foots 600

Potash lye, 18 degs. B. hot, 20 degs. B. cold 660
or
Corn oil 800
Rosin 200
Potash lye, 27 degs. B. 790
Water 340

Heat the oils to 190 degs. F., add the lye and crutch until the
soap begins to bunch, when it is ready to be run into barrels where
the saponification will be completed.
Semi-boiled soaps differ from those made by the cold process in
temperature. In making semi-boiled soaps the fats are usually
heated to 140° F. The addition of the[Pg 45] lye raises the
temperature to 180°—200° F. when saponification takes place.

CARBONATE SAPONIFICATION.

54
 The method of the formation of soap by the utilization of the
fatty acid directly, from which the glycerine has already been
removed by some method of saponification other than with
caustic soda, and neutralizing this with alkali, is becoming
increasingly popular. The glycerine is more easily recovered from
a previous cleavage of the fats or oils, but a soap made from the
mixed fatty acids thus obtained is seldom white in color and
retains an unpleasant odor. Since soda ash or sodium carbonate is
cheaper than caustic soda and readily unites with a fatty acid, it is
used as the alkali in the carbonate saponification. The process is
similar to that already given under Rosin Saponification. About 19
per cent. by weight of the fatty acids employed of 58 per cent. soda
ash is dissolved in water until it has a density of 30 degs. B., and
the solution is run into the kettle, which is usually equipped with a
removable agitator. The fatty acids, previously melted, are then
slowly added while the mixture is boiled with open steam and
agitated with the stirring device. The fatty acids instantly unite
with the carbonate and rise in the kettle, due to the generation of
carbon dioxide, and care must be exercised to prevent boiling
over. After all the fatty acid has been added, and the mass is
boiled through the saponification must be completed with caustic
soda, as there is as yet no practical method known which will split
a fat entirely into fatty acid and glycerine. Thus about 10 per cent.
of the fatty acids are true neutral fats and require caustic soda for
their saponification. This is then added and the soap completed,
as in full-boiled soaps.
In carrying out this method upon a large scale, large[Pg 46]
sue\Neanderthal\doroteer\Neanderthal\Josephine\ quantities of
carbon dioxide are formed during the boiling of the soap, which
replaces a quantity of the air contained therein. The kettle room

55
should therefore be well ventilated, allowing for a large inflow of
fresh air from out of doors.

[Pg 47]

56
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