AN IMPROVED PROCESS AND APPARATUS FOR THE EXTRACTION OF GLYCERINE OR THE LIKE FROM COMPOUNDS OR SUBSTANCES CONTAINING THE SAME, WHICH INVENTION COMPRISES THE MANUFACTURE OF VARIOUS GLYCERINE COMPOUNDS
Year: 1881

page_text: LETTERS PATENT to William Robert Lake, of the Firm of Haseltine, Lake,
& Co., Patent Agents, Southampton Buildings, London, for an Invention of
"AN IMPROVED PROCESS AND APPARATUS FOR THE EXTRACTION OF GLYCERINE
OR THE LIKE FROM COMPOUNDS OR SUBSTANCES CONTAINING THE SAME,
WHICH INVENTION COMPRISES THE MANUFACTURE OF VARIOUS GLYCERINE
COMPOUNDS." A communication from abroad by Paul Jean Baptisto Depoully
and Léon Droux, both of Paris, France.
PROVISIONAL SPECIFICATION left by the said William Robert Lake at
the Office of the Commissioners of Patents on the 18th May 1881.
WILLIAM ROBERT LAKE, of the Firm of Haseltine, Lake, & Co., Patent Agents,
Southampton Buildings, London. "AN IMPROVED PROCESS AND APPARATUS FOR
THE EXTRACTION OF GLYCERINE OR THE LIKE FROM COMPOUNDS OR SUBSTANCES
CONTAINING THE SAME, WHICH INVENTION COMPRISES THE MANUFACTURE OF
VARIOUS GLYCERINE COMPOUNDS." [A communication from abroad by Paul Jean
Baptiste Depoully and Léon Droux, both of Paris, France.]
This Invention relates chiefly to the extraction of glycerine from any mixture in
which it is to be found, principally from manufacturers' refuse, containing more or
less considerable proportions of salts, free alkali, free acid, and organic impurities.
The said Invention comprises apparatus for carrying the said Invention into
practice.
According to the present Invention the glycerine is combined with acid or acids
or other substances, which by combination therewith are capable of forming
glycerides insoluble in water. This combination may be effected by the action of heat
and in presence of the whole or a portion of the impurities contained in the mixture.
The salt and other foreign matters are easily eliminated simply by washing with
either cold or warm water. It is only necessary in order to obtain glycerine of a
good commercial quality to saponify by any of the usual means the glyceride or
Posion 471

page_text: glycerides so separated. These products may however be sold and used without
being saponified.
Any substances which may form insoluble compounds when combined with
glycerine may be employed instead of acid; for instance, instead of proper fatty
acids, I may employ neutral natural fatty compounds.
The lyes produced in soap works contain glycerine, alkaline salts, an excess of
alkali and organic impurities. According to this Invention the said lyes are saturated
with any fatty or other acid, and when so treated are partly evaporated. The
more or less fluid compound so obtained is heated together with acid, for instance,
with oleic acid. The combination takes place gradually.
This operation may be effected in any convenient apparatus, and the heat may
be produced either by superheated steam or by any other means.
When the operation is completed the product is liberated from any salts or other
impurities by washing it in water, and the said product is then saponified for the
extraction of glycerine.
The glycerides so obtained may be industrially employed without being saponified.
In the above instance monoleine, bioleine, trioleine, or mixtures of the same are
obtained, according to the proportions of the substances used in the operation.
Most of these glycerides are not yet commercially known and may be usefully
applied, for instance, for lubricating machinery, oiling fibres and fabrics, and for
lighting or other purposes.
The operation may be effected in any convenient apparatus; a good result is
however obtained by the following arrangement, that is to say :-
The matters to be treated are placed in a retort (of copper, wrought or cast iron,
or lead, as the case may be) and may be mechanically stirred. This retort is
completely enclosed in a jacket in which a suitable degree of temperature is
maintained, either by lateral furnaces, and by injection of steam, or by superheated
steam pipes.
When oleic acid is used, and generally when the temperature is high, it is
desirable to fill the retort with carbonic acid, in order to prevent any injurious
action of the air.
Any inert gas may be used instead of carbonic acid. When the preparation is
completed the apparatus is emptied by means of hot water after a partial cooling.
The glycerides are deprived of all the salts and the like by washing them in water,
and they are then saponified by the ordinary means.
Commercial glycerine is on one hand produced, whilst regenerated oleic acid is
on the other hand obtained; the latter may be employed in a similar operation.
Oleic acid may be replaced by any other fatty acid, such as palmitic or stearic
acids, or by a mixture of the same or any other acids capable of forming insoluble
glycerides.
Neutral, natural, vegetable, or animal fatty substances, various oils, palm oil, suet,
tallow, and the like, which are generally triacid glycerides, may be used instead of
acids, and will be transformed into diacid and monoacid glycerides. By the
saponification I obtain all the glycerine, that is to say, the proportion of glycerine
contained in the fatty substance and the glycerine of the solution treated by the
process.
Ethers of other alcohols than glycerine may also be used with regeneration of
the said alcohols.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed
by the said William Robert Lake in the Great Seal Patent Office on the
18th November 1881.
WILLIAM ROBERT LAKE, of the Firm of Haseltine, Lake, & Co., Patent Agents,
Southampton Buildings, London. "AN IMPROVED PROCESS AND APPARATUS FOR
THE EXTRACTION OF GLYCERINE OR THE LIKE FROM COMPOUNDS OR SUBSTANCES
CONTAINING THE SAME, WHICH INVENTION COMPRISES THE MANUFACTURE OF
VARIOUS GLYCERINE COMPOUNDS." A communication from abroad by Paul Jean
Baptiste Depoully and Léon Droux, both of Paris, France.
This Invention relates chiefly to the extraction of glycerine from any mixture in
which it exists, but principally from manufacturers' refuse or residues, containing
in considerable proportions salts, free alkalies, free acids, organic impurities, and the
like.
The said Invention is based the well known standard work of Berthelot,
relating to glycerides.
According to the present Invention the glycerine is combined with fatty acid,
in order to form glycerides insoluble in water. This combination is obtained by the
aid of heat, and in the presence of the impurities contained in the mixture. All
the salts and other foreign matters are eliminated by simple washing with cold or
hot water.
To obtain glycerine of good commercial quality it is simply necessary to saponify
by any of the well known means the glyceride or glycerides thus separated.
Tho
I will now proceed to describe as an example the commercial extraction of
glycerine from soap manufacturers' lyes. These lyes contain glycerine, salts, an
excess of caustic or carbonated alkali, organic impurities, and other matters.
These lyes are neutralized by any suitable acid in order to eliminate or decompose
the detrimental substances; they may be rendered acid, heated, and filtered or
decanted. The neutral lyes are evaporated and the crystals separated. If desired
they are washed in neutralised lye in order that no glycerine may be lost.
original volume being thus reduced as desired, the glycerine accumulates in the
mother waters, and the liquor is evaporated to a more or less pasty consistency.
This more or less fluid compound or product is heated and maintained at a tem-
perature of 170° to 175° centigrade with a fatty acid, such as oleic acid, for
example. The water will first be eliminated, and then the combination takes place
gradually, the water produced by the reaction being then eliminated in its turn.
When the proportions employed correspond to a trebly acidulated glyceride the
operation may be stopped, as soon as no more water runs out, with advantage.
When a smaller quantity of acid is used in proportion to the quantity of
glycerine, the completion of the operation will be ascertained by successive testings,
according to the proportion of glycerine and oleic acid used. There will be formed
mixtures of monolein, diolein, or triolcin, and the like, that is to say, bodies
containing one, two, or three inolecules of oleic acid to one molecule of glycerine.
It has been found preferable to employ more oleic acid than is required to produce
the monolein.
My improved process may be carried on in any convenient apparatus; a good
result is however obtained by the following arrangement, that is to say :-
The matters to be treated are placed in a retort (of copper, iron, lead, or other
suitable material), with or without a mechanical stirrer or agitator. This retort is
placed and completely enclosed in a jacket, and is maintained at the desired degree
of temperature by lateral furnaces, and by a jet of steam which enters the said
jacket, or by pipes through which superheated steam passes. The partially solid

page_text: and partially liquid mixture is thus prevented from being burned, and as all the
parts of the retort are heated to the same degree, the condensation of the water is
rendered impossible; it escapes by an outlet tube as the process proceeds, and does
not fall upon the products or compounds, so that saponification is prevented.
Moreover the formation of glycerides continues gradually until stopped.
As the fatty bodies (especially the oleic acid) are susceptible to change when
heated to a high temperature in the presence of air, I prefer to fill the retort with
carbonic acid or other inert gas; a gascous current will assist the reaction by
carrying away with it the aqueous vapour.
When the operation is completed the apparatus is emptied and cleared by means
of hot water after a partial cooling. Pure water is employed to remove the salts
and other soluble matters.
The glycerides thus artificially produced are treated by the same processes as
those employed in the manufacture of stearine candles from tallow, so as to obtain,
firstly, fatty acids, which can be used for another operation, and, secondly, the
water containing glycerine which simply requires to be evaporated to obtain com-
mercial glycerine. These processes consist in the saponification by lime with or
without pressure, followed by the separation of the waters containing glycerine
and the decomposition of the lime-soap by an acid. The said bodies may also be
saponified by means of superheated steam or by sulphuric acid.
The oleic acid may be replaced by other fatty acids, such, for instance, as
palmatic acid, stearic acid, or the like, or by mixtures of these various acids.
Moreover, neutral, natural, vegetal, or animal fatty substances, various oils in a
liquid or solid form, tallow, lard, and the like, which are generally triacid glycerides,
may be used instead of fatty acid, and when combined with a fresh quantity of
glycerine will form diacid and mononcid glycerides. By saponification I obtain the
whole of the glycerine, that is to say, the glycerine contained in the fatty substance,
and also that contained in the lye.
4
When I employ natural fatty substances, and all the water intermixed with
crystals and water of crystallisation is evaporated, I am enabled without incon-
venience to hermetically close the apparatus, as in this case the neutral fatty
body absorbs the water produced at the moment the glycerine enters into the
combination.
Moreover with the fatty acids I can work under pressure when once the free
water is evaporated.
In the above description I have mentioned as an example a temperature of
170° centrigrade. This temperature is that at which the complete de-hydration of
the glycerine takes place; it is therefore favourable to the formation of the ethers
of the glycerine in a limited time, but this temperature is not absolutely necessary,
as I may make use of any higher temperature, say 200° centigrade, the result
being the decomposition of a portion of the fatty substances used.
I am also enabled to operate with a temperature of from 100° to 170° centigrade,
but then the duration of the heating must be augmented; with too low a tem-
perature the operations require too long a time, and the result is not complete. It
is then necessary to recover the first washings and to extract the glycerine from
them.
Having thus fully described the said Invention, as communicated to me by my
foreign correspondents, and the manner of performing the same, I wish it understood
that I claim,
First. The extraction of glycerine from manufacturers' refuse and other mixtures
(especially the lyes obtained from soap-works or from low wines, or the refuse of
alcoholic fermentation) by the combination of the glycerine with fatty acids,
properly so called, and with natural neutral fatty bodies, which combination permits
the elimination by simple washing with water of the salts and other impurities
from the ordinary glycerine of commerce, and which combination can be obtained
either by heating in the open air, or in a retort without pressure, or in a suitable
vessel under pressure, substantially as set forth.

page_text: Second. The process for obtaining this result by the synthesis of a neutral fatty
body brought into contact with saline and other impurities, the water being driven
off by heat with or without the aid of a gaseous current in an open apparatus, so
that the completion of the reaction is permitted.
Third. The employment of the above described apparatus for carrying the said
process into effect, substantially as set forth.
Fourth. The total or nearly total synthesis of a neutral fatty body, without the
presence of an excess of fatty acid or glycerine.
Fifth. In the said process the production of monoacid and diacid glycerides,
monolein, diolein, monostearin, distearin, monopalmitin, dipalmitiu, and the like or
mixtures of the same.
In witness whereof, I, the said William Robert Lake, have hereunto set my
hand and seal, this Eighteenth day of November, in the year of our Lord
One thousand eight hundred and eighty one.