Manufacture of Artificial Tartaric Acids by Means of Cellulose, Saccharine, or Amylaceous Substances.
Year: 1890

page_text: Date of Application, 28th Feb., 1890
Complete Specification Left, 27th Nov., 1890-Accepted, 14th Feb., 1891
Manufacture of Artificial Tartaric Acids by Means of Cellulose,
Saccharine, or Amylaceous Substances.
We, ADOLPHE AUGUSTE BREHIER, Chemist, and BENOIT GABRIEL TALBOT,
Merchant, both of Bordeaux, Gironde, France, do hereby declare the nature of this
invention to be as follows:-
Heretofore commercial tartaric acid was derived from the decomposition of
bitartrate of potash commonly called "tartar" which is found in the vats in which
wine has fermented.
According to our invention we manufacture tartaric acid in a commercial way
from cellulose, or saccharine, or amylaceous substances, and principally from glucoses,
saccharose, levulose, sorbine, mannite &c., and for this purpose we employ the
following process.
The principle of the process is based on the observation made by us that
saccharine matters, when exposed to the action of allotropic oxygen, whether in the
nascent state, or ozonized, become oxidized and are transformed into certain inter-
mediate acids, such as hexepic or trijenic acids, saccharic or glucosic acids &c., and
are then converted into tartaric acids (tartaric acid right or left inactive, and para
tartaric or racenic acid).
The nature of the tartaric acids thus obtained as also those of the intermediate
acids varies according to the body employed for the source of the active oxygen.
By way of example we will describe one of the processes which we have tried
with success, and which is based upon the use of oxygen obtained by the
decomposition of an alkaline permanganate in the presence of a current of chlorine.
We prefer the use of chlorine on account of its decolorising properties, which allow
of the obtainment of perfectly limpid colorless products.
The operation is as follows.
The cold glucose solution, indicating from 10° to 15° Be., is passed into a
cylindrical receptacle, the height of which should be at least twice its diameters ;
it should be of material which is not attacked by chlorine and oxygen combined
under a certain pressure, and it must be perfectly closed and air tight. The vessel
is put in communication with a vessel in which chlorine is generated, by means of
a tube which passes down into the saccharine liquid to near the bottom, while a
second tube, the orifice of which is a few centimetres below the cover serves to
liberate the excess of the gas, which accumulates on the surface of the liquid.
The other end of this tube passes into a recipient containing a liquid of a sufficient
density to maintain a pressure in the cylinder in which the decomposition is
effected.
This pressure should not be less than a column of mercury of from 8 to 10 centi-
metres. Lastly there is an opening in the cover of the vessel for the introduction
of the permanganate, which should be introduced partly before and partly during
the introduction of the chlorine gas; the process of oxidation is then allowed to
proceed regularly during four or five days. At the end of that time the degree of
acidity of the glucosic solution is ascertained, on taking a small sample which is
submitted to the acetimetric test by means of a titrated solution of carbonate of
soda. If this marks from 70° to 80% of Mohr's burette, the chlorination may be
considered completed. The said solution is then exposed to the air in a chamber
where the temperature is not less than 20° Cent.; the intermolecular process
continues by itself during from 3 to 4 days, at the end of which time, the degree of
acidity is again ascertained by the above mentioned means, and when the liquor
marks from 250° to 300° on the burette, the operation may be considered completed;

page_text: at this time all traces of chlorine or of hypochlorous acid will have disappeared
which is also a proof that the transformation is complete. A solution of tartaric
acid is thus obtained which is exceedingly limpid, which can be concentrated, and
which only requires to be freed from its impurities by filtration.
Without attempting to state in a precise manner the theory of the reactions
produced in our above described process, it may be explained by the following
equation:
which give exactly the form of tartaric acid dedoubable or racenic, in right or
left acid.
The intermolecular process which is effected during this reaction causes the
glucosic matters to undergo two transformations; the first causes the saccharine
molecule to pass into the glucosic acid state C H O', which then passes into the
state of tartaric acid, this last transformation takes place in maintaining a tempera-
ture of from 20° to 25° Centigrade.
D
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COMPLETE SPECIFICATION.
Manufacture of Artificial Tartaric Acids by Means of Cellulose,
Saccharine, or Amylaceous Substances.
We, ADOLPHE AUGUSTE BREHIER, Chemist, and BENOIT GABRIEL TALBOT,
Merchant, both of Bordeaux, Gironde, France, do hereby declare the nature of
this invention and in what manner the same is to be performed to be particularly
described and ascertained in and by the following statement :-
Heretofore commercial tartaric acid was derived from the decomposition of
bitartrate of potash commonly called "tartar "which is found in the vats in which
wine has fermented.
According to our invention we manufacture tartaric acid in a commercial way
from cellulose, or saccharine or amylaceous substances, and principally from glucose,
saccharose, levulose, sorbine, mannite &c., and for this purpose we employ the
following process.
The principle of the process is based on the observation made by us that
saccharine matters, when exposed to the action of allotropic oxygen, whether in the
nascent state, or ozonized, become oxidized and are transformed into certain inter-
mediate acids, such as hexepic or trijienic acids, saccharic or glucosic acids &c. and
are then converted into tartaric acids (tartaric acid right or left inactive, and para
tartaric or racemic acid).
The nature of the tartaric acids thus obtained, as also those of the intermediate
acids, varies according to the body employed for the source of the active oxygen.
By way of example, we will describe one of the processes which we have tried
with success, and which is based upon the use of oxygen obtained by the decom-
position of an alkaline permanganate in the presence of a current of chlorine. We
prefer the use of chlorine on account of its decolorising properties; which allow of
the obtainment of perfectly limpid colorless products.
The operation is as follows:-
The cold glucose solution, indicating from 100 to 15° Bé., is passed into a
cylindrical receptacle, the height of which should be at least twice its diameter: it

page_text: should be of material which is not attacked by chlorine and oxygen combined under
a certain pressure, and it must be perfectly closed and air tight.
The vessel is put in communication with a vessel in which chlorine is generated,
by means of a tube which passes down into the saccharine liquid to near the bottom,
while a second tube, the orifice of which is a few centimetres below the cover,
serves to liberate the excess of the gas which accumulates on the surface of the
liquid.
The other end of this tube passes into a recipient containing a liquid of a
sufficient density to maintain a pressure in the cylinder in which the decomposition
is effected. This pressure should not be less than a column of mercury of from 8
to 10 centimetres.
Lastly, there is an opening in the cover of the vessel for the introduction of the
permanganate, which should be introduced partly before and partly during the
introduction of the chlorine gas; and which is added in the proportion of two per
cent. of the glucose; the process of oxidation is then allowed to proceed regularly
during four or five days. At the end of that time the degree of acidity of the
glucosic solution is ascertained on taking a small sample which is submitted to the
acidimetric test by means of a titrated solution of carbonate of soda.
The titrated solution is for this purpose introduced by a Moores burette until
the glucosic solution has thereby been deprived of its acidity, which is ascertained
by means of litmus paper, the quantity of the titrated solution used, as indicated
on the divisions of the burette will indicate the degree of acidity, as is well known.
If the burette marks from 70° to 80°, the chlorination may be considered
completed.
The acid solution is then exposed to the air in a chamber where the temperature
is not less than 20° Cent.; the inter-molecular process continues by itself during
from 3 to 4 days, at the end of which time, the degree of acidity is again ascertained
by the above mentioned means, and when the liquor marks from 250° to 300° on the
burette, the operation may be considered completed; at this time all traces of
chlorine or of hypochlorous acid will have disappeared which is also a proof that
the transformation is complete.
A solution of tartaric acid is thus obtained which is exceedingly limpid, which
can be concentrated, and which only requires to be freed from its impurities by
filtration.
'
Without attempting to state in a precise manner the theory of the reactions
produced in our above described process, may be explained by the following.
When a current of nascent chlorine is passed during 4 or 5 days in contact with
a superoxide which can give up the whole or part of its oxygen, the group H² O is
eliminated by substitution of the oxygen, and the molecule of asymmetric carbon is
brought back to the formula C H4 08, which is hexepic acid, and C3 H O' which
is trijienic acid. In exposing the acids thus obtained by our process to the action
of air under a temperature which is not less than 20° to 25° Cent. during 4 or 5
days, the whole of the hexepic and trijienic acids are transformed into tartaric acids,
one molecule of carbonic acid being liberated.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, we declare that what we
claim is
1. In the manufacture of tartaric acid, the method of first treating saccharine or
glucosic matters with ozone, ozonised oxygen, or nascent oxygen and then exposing
the intermediate acids resulting from this action to the air for transforming them
into tartaric acid.
2. In the manufacture of tartaric acid, the use of permanganate of potash or
analogous salts in the presence of chlorine, for producing oxygen in the body of a
cold solution of the saccharine matters, the chlorine serving as agent for the
dissociation of the saccharine matter and for the decolorisation of the products
obtained, substantially as described.

page_text: 3. As new products, the tartaric acids obtained by the means herein described,
such acids being decolorised and purified and ready for use without its being
necessary to refine them after crystallisation; as also the alkaline or other salts
produced by the said tartaric acids after or during the operation of the trans-
formation of the saccharine matters.
4. The herein described process of transformation of the cellulose, saccharine or
amylaceous substances, whether effected by the action of allotropic oxygen
chemically prepared by any known process, or by the action of oxygen of the air
ozonised by means of electrolyses or by other means.
Dated this 27th day of November 1890.
ABEL & IMRAY,
Agents for the Applicants.