Improvements in the Preparation or Manufacture of Formates and Nitrites.
Year: 1895

page_text: PROVISIONAL SPECIFICATION.
Improvements in the Preparation or Manufacture of Formates and
Nitrites.
I, Dr. MARTIN GOLDSCHMIDT. of No. 1 Carmestrasse, Charlottenburg, near
Berlin, in the German Empire, Manufacturer, do hereby declare the nature of
this invention to be as follows :-
This invention relates to the preparation or manufacture of formates and
nitrites.
Merz and Tibirica (Ber. d. d. Chem. Ges. XIII p. 23) have shown that those
processes for the production of formates are successful, in which carbonic oxide
gas is conducted over a layer of soda (preferably in the form of soda-lime) at a
comparatively high temperature, say 230° Centigrade..
Experiments which have been made with a view to ascertaining whether this
reaction is capable of being turned to account in the commercial production of
formates, on a large scale, from the bases mentioned above (especially potash and
soda), by treating them with carbonic oxide, have shown that the action of the
carbonic oxide upon the bases in question may be considerably promoted,
accelerated and made more productive, as regards the final result or "yield
(owing to the comparatively low temperature at which this method enables the
reaction to be performed), by causing the oxide of carbon to act upon the base
under pressure.
In order to carry out this process, the base should preferably be
so spread out or distributed as to present as large a surface as possible; for which
purpose indifferent bodies may, if desired, be made use of. Thus, where it is
desired to obtain alkaline formates, the alkali employed may be in the form of
alkali lime; or the base may be mixed with another body, such as, powdered
charcoal or carbon. In that case it is only necessary to submit the base, which
should preferably be reduced to powder and which may be placed in any suitable
receiver or chamber in which it is compressed and heated, to the action of carbonic
oxide (CO).
This process for the preparation of formates for industrial purposes, is all the
more valuable, in practice, because, while furnishing means for producing these
forinates, it at the same time affords the possibility of utilizing them in the
production of nitrites.
Hitherto it has been usual to produce nitrites by fusing together lead and a
nitrate (saltpetre for example). This method, however, has proved to be attended
by a serious drawback, inasmuch as it required the temperature to be raised to a
very high degree, while in addition to that, during the reaction, it necessitated the
obtaining of a mixture of molten lead and nitrate (a very difficult task, as the
nitrate is of considerably less specific gravity than the lead). Besides, the oxide
of lead obtained as a bye-product had to be used to some advantage, or the whole
process would be economically impracticable.
The object of this invention is to remedy these defects, and such object is
attained when the nitrite is produced by heating and fusing together nitrates and
formates. No violent rush of gas or explosion takes place in this operation,
notwithstanding the fact that the formates are organic bodies; but the nitrate
becomes easily converted into nitrite, even at a comparatively low temperature (the

page_text: liquid becoming effervescent); and this is more particularly the case in the
presence of a free base or a free alkali. In the case of sodium uitrite, this
reaction may be exemplified by the following equation:-
The following examples, in which the metal described as "Me" is assumed to
be sodium, may serve to illustrate the performance of this modified method:-
To begin with, a thorough mixture of equal quantities (by weight) of powdered
hydrate of soda and powdered saltpetre is prepared. This is best effected,
perhaps, by fusing together equal quantities (by weight) of hydrate of soda and
saltpetre and, after allowing the product of such fusion to cool, reducing it to the
condition of powder.
When this mixture is (very moderately) heated in an atmosphere of carbonic
oxide gas, in no case allowing it to reach the point of fusion, however, it will very
rapidly absorb considerable amounts of the oxide of carbon; a proportion of such
oxide of carbon, sufficient to convert half of the hydrate of soda available into
formate of soda, being easily attained.
Now if, after such absorption has ceased, the mixture saturated with carbonic
oxide, be removed from the carbonic oxide atmosphere, and a little further heated,
say just to the point of incipient fusion, the nitrate present will, under the action
of the formate which has just formed in accordance with the above equation, be
quantitively converted into nitrite.
Or the process may be carried out by adding to the above mentioned mixture
of nitrate and base, a substance (such as caustic lime, for example) which will
exercise no further action of its own, but which is capable of preventing the
continued fusion of the mass when the temperature is further raised. In this case
the mass will simply be sintered or baked together, as it were. The carbonic
oxide atmosphere may then be heated to a somewhat higher temperature, say, just
to the point of incipient "baking," when the carbonic oxide will be still more
readily absorbed, and the nitrite required will be obtained in one process, direct ;
so that it will appear as if carbonic oxide, base and nitrate had all reacted upon
each other in a heated atmosphere, with a direct formation of nitrite and carbonate
as a result. The action of carbonic oxide may be assisted by the employment of
pressure. The product of the fusion will only contain nitrite and soda, or caustic
lime (as the case may be) which may be removed by lixiviation with water.
separation of the product of the reaction itself is effected in the manner already
stated above.
The
This process is not only advantageous by reason of its simplicity and cheapness,
and of the ease and convenience with which it may be performed, what makes it
particularly valuable for the purpose of the trade, is that the bye-products,

page_text: obtained therefrom, may be utilized over and over again in repetitions of the same
process.
Dated this 12th day of September 1895.
D. YOUNG & Co.,
11 & 12 Southampton Buildings, London, W.C.,
Agents for the Applicant.
Improvements in the Preparation or Manufacture of Formates and
Nitrites.
I, Dr. MARTIN GOLDSCHMIDT, of No. 1, Carmerstrasse, Charlottenburg, near
Berlin, in the German Empire, Manufacturer, 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:-
This invention relates to the preparation or manufacture of formates and
nitrites.
Merz and Tibirica (Ber. d. d. Chem. Ges. XIII p. 23) have shown that
formates are produced when carbonic oxide (carbon monoxide) gas is conducted
over soda (preferably in the form of soda-lime) at a comparatively high tempera-
ture, say 230° Centigrade.
"
Experiments which have been made with a view to ascertaining whether this
reaction is capable of being turned to account in the commercial production of
formates, on a large scale, from the bases mentioned above (especially potash and
soda), by treating them with carbonic oxide, have shown that the action of the
carbonic oxide upon the bases in question may be considerably promoted,
accelerated and made more productive as regards the final result or yield,"
(owing to the comparatively low temperature at which this method enables the
reaction to be performed), by causing the carbonic oxide to act upon the base
under pressure.
In order to carry out this process, the base should preferably be
so spread out or distributed as to present as large a surface as possible; for
which purpose indifferent bodies may, if desired, be made use of. Thus, where it
is desired to obtain alkaline formates, the alkali employed may be in the form of
alkali lime; or the base may be mixed with another body, such as, powdered
charcoal or carbon. In that case it is only necessary to submit the base, which
should preferably be reduced to powder and which may be placed in any suitable
receiver or chamber in which it is compressed and heated, to the action of carbonic
oxide (CO).
This process for the preparation of formates for industrial purposes is all the
more valuable, in practice, because, while furnishing means for producing these
formates, it at the same time affords the possibility of utilizing them in the
production of nitrites.
Hitherto it has been usual to produce nitrites by fusing together lead and a
nitrate (saltpetre for example). This method, however, has proved to be
attended by a serious drawback, inasmuch as it required the temperature to be
raised to a very high degree, while in addition to that, during the reaction, it
necessitated the obtaining of a mixture of molten lead and nitrate (a very difficult
task, as the nitrate is of considerably less specific gravity than the lead). Besides,
the oxide of lead obtained as a bye-product had to be used to some advantage,
or the whole process would be economically impracticable.
The object of this invention is to remedy these defects, and such object is
attained when the nitrite is produced by heating and fusing together nitrates and
formates. No violent rush of gas, or explosion, takes place in this operation,

page_text: and of the ease and convenience with which it may be performed, what makes it
particularly valuable for the purposes of the trade, is that the bye-products
obtained therefrom, may be utilized over and over again, in repetitions of the
same process.
Having now particularly described and ascertained the nature of my said inven-
tion, and in what manner the same is to be performed, I declare that what I
claim is:-
1. A process for the manufacture of formates, consisting essentially in causing
carbonic oxide to act upon the base under pressure.
2. A process for the manufacture of nitrites by the aid of formates, consisting
in heating a nitrate or nitrates together with such formate, substantially as herein-
before described.
3. A process for the manufacture of nitrites in which the required base and
carbonic oxide-instead of the ready-made formate,--are caused to react with the
nitrate in a heated atmosphere, substantially as hereinbefore described.
Dated this 10th day of June 1896.
D. YOUNG & Co.,
11 & 12 Southampton Buildings, London, W.C.,
Agents for the Applicant.