IMPROVEMENTS IN THE PREPARATION AND APPLICATION OF CERTAIN FATTY BODIES
Year: 1866

page_text: LETTERS PATENT to Clinton Edgcumbe Brooman, of the Firm of
Robertson, Brooman, and Company, of 166, Fleet Street, in the City
of London, Patent Agents, for the Invention of "IMPROVEMENTS IN THE
PREPARATION AND APPLICATION OF CERTAIN FATTY BODIES."-A commu-
nication from abroad by Mathias Paraf-Javal and Eugene Paraf-Javal,
both of Paris, France.
Sealed the 11th June 1867, and dated the 15th December 1866.
PROVISIONAL SPECIFICATION left by the said Clinton Edgcumbe Brooman
at the Office of the Commissioners of Patents, with his Petition, on
the 15th December 1866.
1, CLINTON EDGCUMBE BROOMAN, of the Firm of Robertson, Brooman,
and Company, of 166, Fleet Street, in the City of London, Patent Agents,
do hereby declare the nature of the said Invention for "IMPROVEMENTS IN
THE PREPARATION AND APPLICATION OF CERTAIN FATTY BODIES," to be as
follows:-
The object of this Invention is the improvement and application of a
reaction scientifically known in order to obtain products which have hitherto
been differently obtained, that is to say, a chemical reaction was known
theoretically, and the result of this reaction was also known theoretically, and
with this result I make products which have never been made thus, and
further certain improvements in connection with this reaction render it
practicable.

page_text: The scientific reaction is the action of alkalies on fatty matters, such as
oleic acid, olein or analogous bodies, the fusibility of which diminishes by
alkaline treatment; the result of this reaction is, among others, a substance
or a mixture of fatty substances less fusible which I will call hardened, fatty,
or adipose acids: The products which I make with these less fusible sub-
stances are candles and hard soaps which have never before been made thus.
The following are the improvements in the chemical reaction:-
1st. Instead of the alkalino-fatty mixture being heated only until the
appearance of hydrogen, as in the theoretical treatment, the heating is con-
tinued until the mixture becomes swollen or porous in consequence of the
disengagement of hydrogen, then sinks of itself, and becomes more compact.
2nd. Replacing potash by soda or other alkaline substance or by alkaline
mixtures.
3rd. When soda or potash has been employed and the soap of hardened
fatty acid formed has been separated at the ordinary temperature, as much as
possible from the excess solution of alkali and from the salts formed, there is
a time when, according to the scientific treatment, the refining or purifying of
the said soap of hardened acid cannot be continued, except by dissolving it by
several returns to hot water, and afterwards salting these solutions to separate
the soap at the ordinary temperature. But it is now found that these
additions of common salt render the recovered alkalies much more unfit for a
new operation, and necessitate costly treatments for the separation of the
chlorine. It is found that by cooling the watery solutions of these soaps
below the ordinary temperature I can separate them with a much smaller
addition of salts; and, further, instead of common salt, I add caustic, potash,
or soda or carbonates, which render the generation of the alkalies employed
much easier.
4th. As large quantities of acetic acid are formed in the reaction, I
extract it from the alkaline wash waters of the soap of hardened acid, and I
employ it for the ordinary uses of acetic acid, or I use it previously to
separate the hardened fatty acid from the soap, or I substitute for it in its
alkaline combinations some of the fatty acid to be treated. Or I introduce
into the sufficiently concentrated solution of alkali and acetate (with or
without pressure) by preference, under the influence of energetic cooling, a
current of carbonic acid which separates the greater part of the potash and
soda in the form of bicarbonate, little soluble, and leaves the acetates in the
mother water. Or I decarbonate by lime, and afterwards submit the filtered
liquid which contains little else than acetate and caustic alkali to the action
of great cooling, taking care that there is always sufficient soda for all the

page_text: acetic acid to be converted into acetate of soda, which is less soluble, and
in consequences crystallizes much easier than acetate of potash. The crystal-
lation thus finished, there remains nothing. more in the mother water than
caustic alkali and a little acetate which will be recovered by a fresh operation;
I thus avoid the bicarbonatation and the cost of reconverting the bicarbonates
into caustic alkalies. Or I precipitate the raw hardened soap by lime and
obtain a precipitate of hardened soap of lime, carbonate and oxalate of lime,
and there remains a solution of caustic alkali and of alkaline acetate which I
treat as before explained. The hardened soap of lime well washed is treated
as hereafter explained.
Indecomposing the bicarbonates by heat there remain carbonates which can
be rendered caustic by the usual processes, and the carbonic acid disengaged
by the heat serves to make new bicarbonates. The alkaline acetate which
remains after the bicarbonatation is treated in different manuers, or it is com-
pletely neutralized with acetic acid, and serves for the ordinary uses of alkaline
acetates. Or a new portion of oleic acid is heated with the solution of acetate
to saponification, and the acetic acid which. is disengaged is collected and
delivered for use in the form of acetic acid or of acetate more commercial than
those of potash and soda; or, again, this acetic acid serves to decompose the
hard acid soap which has been produced, and is thus again converted into
acetate of soda or potash, or into acetate of lime, or of baryta, and others, if the
hard soap is soap of lime, baryta, or others. These last acetates are deli-
vered into commerce, or the acetic acid is displaced by a cheaper acid, by
sulphuric acid, for example, and then there remains as the final residue artificial
sulphate of lime or of bartya, this last having a cominercial value, and in all
cases it is found that by these means the alkalies are regenerated, and advan-
tage derived from the acetic acid without being obliged to adopt what is known
as the Leblanc process; however, when the sulphate or other salt of potash or
of soda is required. I decompose the hardened soap by sulphuric acid or other
acid, the salt of which is required.
I have mentioned that either hardened soap of lime or baryta can be
obtained; the following are the circumstances:- When the hardened soap of
soda or of potash is sufficiently purified or refined according to the methods I
have described, I precipitate all the fatty acid from its solution by means of
lime or baryta, which produces on the one hand a solution of nearly pure
caustic soda or potash, and on the other an insoluble hardened soap of lime
or of baryta which I decompose either with sulphuric acid or with acetic acid
displaced by oleic acid; by this means I always employ the same portion of
alkali which serves only as an intermediary. I lose only the small quantities

page_text: contained in the wash water which are too weak to be concentrated; the
great economy effected is obvious.
5th. According to the scientific treatment the hardened acid is crystallized
at two operations when once separated from the soap in alcohol, and is thus
obtained white and pure; but it is found by this method there is great loss
of alcohol which renders this method of purification too costly to work com-
mercially. I overcome this difficulty by carrying on these crystallizations in
retorts which permit of collecting all the volatilized alcohol, or in a close
vessel. The crystallization being completed, the mother alcohol is separated
out of contact with the air from the crystallized and redistilled hardened acid,
andthe crystallized hardened acid is heated in the apparatus until all the alcohol
with which it was imperfectly impregnated is volatilized; by this means alcohol
is not lost, or at most only traces if the close apparatus or stills are defective,
and the same alcohol serves for an indefinite number of times. To economize
still more, cheaper solvents can be used, such as spirit of wood, sulphuret of
carbon, hydrocarburets, and others; the purification of the hardened fatty
acids may also be effected by distilling them. I extract from the alkaline
solutions the small quantities of oxalic acid formed by adding a suitable
quantity of lime, and the mixture of carbonate and oxalate of lime which
remains undissolved is washed and treated by the known processes for the
separation of oxalic acid from its calcareous combination.
I claim also the hardening under heat, with the aid of alkalies, of the fatty
matters which may have been previously modified by nitrous, hypontric, sul-
phurous or other acids, when this hardening is effected by the improved pro-
cesses, or when the hardened acids obtained serve for the manufacture of
candles or hard soaps. Where I have herein used the expressions "hardened
acids," "hardened soaps, "I have meant acids and soaps obtained harder by the
reaction under heat of alkalies on the fatty matters. By the aid of scientific
data and of the improvements herein-before described, the manufacture of
hardened acids and accessory products will be clearly understood.
With regard to the application which I make of these hardened acids for
the manufacture of candles and hard soaps, it is sufficient to point out these
applications in order to be understood by all candle and soap makers;
I may,
however, remark, that this Invention includes mixing with these hardened
acids other fatty bodies, such as the fatty or adipose acids as they have hitherto
been made, fatty bodies such as tallow, wax, and others, combustible or light
giving substances such as paraffin.
The proportion of alkalies can be greatly varied, and either one or several
of the foregoing improvements can be used for the hardening of the fatty

page_text: matters. A single example will be sufficient to complete the details already
given. Thus if oleic acid is to be operated upon and with potash the oleic
acid or oleate of potash is heated with two or three times as much hydrate of
potash to a temperature about equalling the fusion point of potash, hydrogen
is disengaged, and the heating is continued until the mixture which was
swollen and porous in consequence of the disengagement of the hydrogen,
sinks and becomes a compact mass. The potash which was at the bottom of
the vessel isolated from the soap becomes incorporated by degrees with the
mass, and finishes by disappearing entirely at the end of the operation. If
the heating is continued longer without raising the temperature no incon-
veniences need be feared, but if the temperature is raised too high a destruc-
tion of the fatty matter is produced; if it is not sufficiently heated the
hardening of the acid will not take place, or will be incompletely or very
slowly effected. Should the temperature rise too high it suffices to add a
small quantity of water, or to introduce a current of steam on the mixture.
When the reaction is finished the whole is treated by water, and the hardened
fatty acids, the alkalies, the acetic acid, and the oxalic acid are separated, as
before explained.
I claim also the action of the alkaline hydrates in excess at high pressure
upon the fatty matters to convert them into hardened fatty acids.
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said Clinton Edgcumbe Brooman in the Great Seal Patent Office
on the 14th June 1867.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, CLINTON
EDGCUMBE BROOMAN, of the Firm of Robertson, Brooman, and Company, of
166, Fleet Street, in the City of London, Patent Agents, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Fifteenth day of December, in the year of our Lord
One thousand eight hundred and sixty-six, in the thirtieth year of Her reign,
did, for Herself, Her heirs and successors, give and grant unto me, the said
Clinton Edgcumbe Brooman, Her special licence that I, the said Clinton
Edgcumbe Brooman, my executors, administrators, and assigns, or such others
as I, the said Clinton Edgcumbe Brooman, my executors, administrators, and
assigns, should at any time agree with, and no others, from time to time and
at all times thereafter during the term therein expressed, should and lawfully
might make, use, exercise, and vend, within the United Kingdom of Great

page_text: Britain and Ireland, the Channel Islands, and Isle of Man, an Invention for
"IMPROVEMENTS IN THE PREPARATION AND APPLICATION OF CERTAIN FATTY
BODIES," (communicated to me from abroad by Mathias Paraf-Javal and
Eugène Paraf-Javal, both of Paris, France), upon the condition (amongst
others) that I. the said Clinton Edgcumbe Brooman, my executors or admi-
nistrators, by an instrument in writing under my, or their, or one of their hands
And seals, should particularly describe and ascertain the nature of the said
Invention, and in what manner the same was to be performed, and cause the
same to be filed in the Great Seal Patent Office within six calendar months
next and immediately after the date of the said Letters Patent.
- NOW KNOW YE, that I, the said Clinton Edgcumbe Brooman, do hereby
declare the nature of the said Invention, and in what manner the same is to be
performed, to be particularly described and ascertained in and by the following
statement thereof, that is to say :-
The object of this Invention is the improvement and application of a
feaction scientifically known in order to obtain products which have hitherto
been differently obtained, that is to say, a chemical reaction was know
theoretically, and the result of this action was also known theoretically, and
with this result I make products which have never been made thus, and
further certain improvements in connection with this reaction render it more
practicable.
The scientific reaction is the action of alkalies or fatty matters such as oleic
acids, olein, or analogous bodies, the fusibility of which diminishes by alkaline
treatment, the effect of which is to oxidize them; the result of this reaction is,
among others, a substance or a mixture of fatty substances less fusible, which
I will call hardened fatty or adipose acids, and which have been produced by
the oxidation of oleic acid or other fatty body submitted to oxidation. The
products which I make with these less fusible substances are candles and
hard soaps which have never before been made thus.
The following are the improvements in the chemical reaction:-
1st, instead of the alkalino-fatty mixture, being heated only until the
appearance of hydrogen, as in the theoretical treatment, the heating is con-
tinued until the mixture becomes swollen and porous in consequence of the
disengagement of hydrogen and until a higher temperature would decompose
the fatty acids.
2ndly, replacing potash by mixtures of potash with other alkalies.
3rdly, when potash pure or mixed with another alkali has been employed
and the soap of hardened fatty acid formed has been separated at the ordinary
tomperature (after previous treatment with a quantity of water to ebullition

page_text: insufficient for its solution) as much as possible from the salts formed, there
is a time when, according to the scientific treatment, the refining or purifying
of the said soa of hardened acid cannot be continued except by dissolvingit by
several returns to hot water, and afterwards salting these solutions to separate
the soap at the ordinary temperature. But it is now found that these ad-
ditions of common salt reader the recovered alkalies much more unfit for a new
operation, and necessitate costly treatments for the separation of the chlorine.
It is found that by cooling the watery solutions of these soaps below the ordi-
nary temperaturë I can separate them with a much smaller addition of
salts, and further, instead of common salt I add caustic potash or soda, or
carbonates or sulphates, which render the generation of the alkalies employed
much easier.
4thly, as large quantities of acetic acid are forined in the reaction I extract
it from the alkaline wash waters of the soap of hardened acid, and I employ
it for the ordinary uses of acetic acid, or I use it previously to separate the
hardened fatty acid from the soap, or I substitute for it in its alkaline combi-
nations some of the fatty acid to be treated. Or I introduce into the sufficiently
concentrated solution of alkali and acetate (with or without pressure). by
preference under the influence of energetic cooling, a current of carbonic acid
which separates the greater part of the potash and soda in the form of bicar
bonate, little soluble, and leaves the acetates in the mother water. Or I
decarbonate by lime,and afterwards submit the filtered liquid which contains
little else than acetate and caustic alkali to the action of great cooling, taking
care that there is always sufficient soda for all the acetic acid to be converted
into acetate of soda, which is less soluble,and in consequence crystallizes much
easier than acetate of potash; the crystallization thus finished there remains
nothing more in the mother water than caustic alkali and a little acetate
which will be recovered by a fresh operation. I thus avoid the bicarbonation
and the cost of reconverting the bicarbonates into caustic alkalies.. Or I
precipitate the raw hardened soap (previously deprived of a great part of the
excess of alkali by means of a treatment with a quantity of water too small to
dissolve the soap) by lime, baryta, or a body having analogous properties, and
I obtain a precipitate of hardened soap of lime or baryta, carbonate and oxalate
of line or baryta, and there remains a solution of caustic alkali and of
alkaline acetate, which I treat as before explained. The hardened soap of
lime or baryta well washed is treated as hereafter explained.
In decomposing the bicarbonates by heat there remain carbonates which
can be rendered caustic by the usual processes, and the carbonic acid dis-
engaged by the heat serves to make new bicarbonates. The alkaline acetate

page_text: Or
which remains after the bicarbonatation is treated in different manners.
it is completely neutralized with acetic acid, and serves for the ordinary uses
of alkaline acetates. Or a new portion of oleic acid is heated with the
solution of acetate to saponification, and the acetic acid which is disengaged
is collected and delivered for use in the form of acetic acid, or of acetate more
commercial than those of potash and soda; or again this acetic acid serves to
decompose the hard acid soap which has been produced, and is thus again
converted into acetate of soda or potash; or into acetate of lime or of baryta,
or others if the hard soap is soap of lime, baryta, or others. These last
acetates are delivered into commerce, or the acetic acid is displaced by a cheaper
acid, by sulphuric acid for example, and then there remains as the final
residue artificial sulphate of lime or of bary ta, this last having a commercial
value, and in all cases it is found that by these means the alkalies are rege-
nerated, and advantage derived from the acetic acid without being obliged to
adopt what is known as the Leblanc process. However, when the sulphate
or other salt of potash or of soda is required I decompose the hardened soap
by sulphuric acid or other acid, the salt of which is required.
I have mentioned that either hardened soap of lime or baryta can be
obtained; the following are the circumstances:-When the hardened soap of
soda or of potash is sufficiently purified or refined according to the methods
I have described, I precipitate all the fatty acid from its solution by means of
lime or baryta, which produces on the one hand a solution of nearly pure
caustic soda or potash, and on the other an insoluble hardened soap of lime
or of baryta, which I decompose either with sulphuric acid or other cheap
acid, or with the acetic acid displaced by oleic acid. By this means I always
employ the same portion of alkali which serves only as an intermediary; I loce
only the small quantities contained in the wash water which are too weak to
be concentrated; the great economy effected is obvious.
5thly,according to the scientific treatment the hardened acid is crystallized
at two operations when once separated from the soap in alcohol, and is thus
obtained white and pure. But it is found that by this method there is great loss of
alcohol which renders this methodofpurificationtoocostlytowork commercially
I overcome this difficulty by carrying on these crystallizations in retorts or
other close vessels which permit of effecting the solution, filtration, crystal
lization, and if required, the pressing so as to collect all the volatilized alcohol
The crystallization being completed the mother alcohol is separated out of
contact with the air from the crystallized and redistilled hardened acids; and
the crystallized hardened acids are (after pressing if necessary) heated in
the apparatus until all the alcohol with which it was impregnated is volatilized

page_text: and re-collected. By this means alcohol is not lost, or at most only traces if
the close apparatus or stills are defective, and the same alcohol serves for an
indefinite number of times.
To economize still more cheaper solvents can be used, such as spirit of
wood, sulphuret of carbon, hydrocarburets, and others. The purification of
the hardened fatty acids may also be effected by distilling them. I extract
from the alkaline solutions the oxalic acid formed by adding a suitable
quantity of lime, baryta, or other analogous oxides, and the mixture of
carbonate and oxalate of lime which remains undissolved is washed and
treated by the known processes for the separation of oxalic acid from its
calcareous combination, and by successive additions of lime, baryta, etc. I
obtain the oxalate and the carbonate separate, which diminishes the cost of
extracting oxalic acid.
I claim also the hardening under heat with the aid of alkalies of the fatty
matters which may have been previously modified by nitrous, hyponitric,
sulphurous, or other acids, when this hardening is effected by the improved
processes, or when the hardened acids obtained serve for the manufacture of
candles or hard soaps.
Where I have herein used the expressions "hardened acids," "hardened
soaps," I have meant acids and soaps obtained with fatty matters hardened by
the treatment under heat with alkalies or by other means of oxidation.
By the aid of scientific data, and of the improvements herein-before
described, the manufacture of hardened acids and accessory products will be
clearly understood. With regard to the application which I make of these
hardened acids for the manufacture of candles and soaps, it is sufficient to
point out these applications in order to be understood by all candle and soap
makers.
I may, however, remark that this Invention includes mixing with these
hardened acids other fatty bodies, such as the fatty or adipose acids as they
have hitherto been made, fatty bodies, such as tallow, wax, and others,
cofnbustible or light-giving substances, such as paraffin.
The proportions of alkalies can be greatly varied, and either one or
several of the foregoing improvements can be used for the hardening of the
fatty matters. A single example will be sufficient to complete the details
already given. Thus, if oleic acid is to be operated upon and with potash the
oleic acid or oleate of potash is heated with two, three, or more equivalents
of hydrate of potash to a temperature about equalling the fusion point of
hydrate of potash. At the commencement water and afterwards hydrogen
is disengaged and the heating is continued until the mixture which was swollen

page_text: and porous in consequence of the disengagement of the hydrogen sinks and
becomes à compact mass. The potash which was at the bottom of the vessel
isolated from the soap becomes incorporated by degrees with the inass and
finishes by disappearing entirely at the end of the operation. If the heating
iscontinued longer without raising the temperature too much,noinconveniences
need be feared, but if the temperature is raised too high a destruction of the
fatty matters is produced. If it is not sufficiently heated the hardening of
the acid will not take place or will be incompletely or very slowly effected.
The portion of unhardened acid will then be found in the products of this
treatment, and it could be separated by the means usually employed, such
as pressing or by crystallization in alcohol or a liquid acting in the sam
manner as herein-before explained. Should the temperature rise too high
it suffices to add a small quantity of water or to introduce a current of steam
on the mixture. When the reaction is finished the whole is treated by water
and the hardened fatty acids, the alkali, the acetic acid, and the oxalic acid
are separated as before-explained. The moment when the heat produced
by the reaction itself suffices to accelerate this reaction ought to be well
noticed; this moment will be known when the swelling assumes unusual
proportions. It is then that it is necessary to be ready to moderate the heat
from one moment to another.
I claim also the action of the alkaline hydrates in excess at high pressure
upon the fatty matters to convert them into hardened fatty acids.
In order to make with oleic acid soaps harder than customary, the oleic
acid or alkaline oleate or oil rich in olein is heated with several equivalents
of a solution of hydrate of potash until the reaction takes place, then there is
added oleic or other fatty acid or a fat or oil in quantities equivalent to the
alkali unsaponified, then I proceed to saponification and in this mannerobtain
harder soaps. Or after the hardening a part of the alkali employed may be
separated by treatments under heat with a quantity of water insufficient to
dissolve the hard soap.
Finally I claim as improvements in the application of the fatty bodies the
manufacture of candles and soaps from hardened fatty acids by the treatment
under heat of liquid fatty bodies such as oleic acid with potash.
And I claim as improvements in the preparation of the fatty bodies or in
the process the economical employment of other alkalies than potash, the
employment of mixtures of alkalies; the employment of an equivalent alkali
in the state of carbonate for the saponification of the fatty acid, whereby
I produce economy of decarbonation of this equivalent alkali; the extraction
of the acetic acid and of the oxalic acid from the products of the reaction;

page_text: the extraction of the acetic acid by means of oleic acid; the substitution of
sulphate, carbonate, or alkaline hydrate for ordinary salt to separate the
soap of hardened acid from the excess of alkali and from the alkaline salts,
whereby I produce economy in the regeneration of the alkali employed for
the hardening the decomposition of the hardened soap by lime or baryta or
analogous body in order to separate the combined alkali easily and more
economically; the employment of cooling below the ordinary temperature in
order the better to separate the hardened soap from the mother waters with
a base of alkalies; the mode by which the loss of alcohol during the treatment
of the hardened acids is diminished by operating in close vessels out of contact
with the air; the substitution of cheaper liquids such as sulphuret of carbon,
spirit of wood, and hydrocarburets for alcohol; and the purification of the
hardened fatty acids by distilling them, all substantially as herein-before
described.
In witness whereof, I, the said Clinton Edgcumbe Brooman, have
hereunto set my hand and seal, this Fourteenth day of June, One
thousand eight hundred and sixty-seven.
C. E. BROOMAN. (u.s.)