A Process for the Production of the Light Metals (Potassium, Sodium) and Anhydrous Oxides and Peroxides and Cyanides of these Metals.
Year: 1898

page_text: Date of Application, 30th Aug., 1898
Complete Specification Left, 30th May, 1899-.Accepted, 15th July, 1899
A Process for the Production of the Light Metals (Potassium, Sodium)
and Anhydrous Oxides and Peroxides and Cyanides of these
Metals.
I, GUIDO WOLFRAM, Ph.D., Chemist, of 1, Sossenheimerstrasse, Rödelheim, in
the German Empire, do hereby declare the nature of this invention to be as
follows:
I have discovered that on introducing a carbide into a molten hydrate of an
alkali there is produced a peculiar decomposition the products of which are car-
bonic oxide, hydrogen gas, and the vapour of the metal of the alkali.
Thus in carrying out this reaction there are present at the same time in the
reaction vessel the molten hydrate of the alkali and the corresponding light
metal in the form of vapour; and starting from this stage several commercially
important results can be obtained. First the vapour of the potassium or sodium
can be carried off and the metal obtained; or the vapour can be condensed and
the metal allowed to drip back into the vessel to produce the anhydrous
oxides; and by passing air or pure oxygen through the said anhydrous oxides
the peroxides can be produced. Cyanides may be produced by introducing nitro-
gen or nitrogen compounds into the vessel, this latter reaction taking place (for
instance) on the introduction of pure nitrogen, dry ammonia gas, or air the
oxygen of which has been converted into carbonic oxide. The conversion of the
oxygen into carbonic oxide is necessary, first, in order to prevent the injurious
effect which the free oxygen would exert upon the reaction and, secondly, because
a complete conversion to carbonic acid would also deleteriously affect the reaction.
In order to obtain completely anhydrous oxides it is necessary to heat the
reaction-mixture to a temperature between its melting point and red heat. The
reaction also takes place more readily with alkaline carbides than with calcium
carbide. If the carbide contain impurities, the reaction will be hindered.
The readiness with which metallic sodium can be obtained by means of the
above described process, permits of the latter being advantageously employed
in connection with many of the chemical reactions requiring the presence of
pure metallic sodium. Thus, for example, in the production of potassium cyanide
from yellow prussiate of potash, in which process pure metallic sodium inde-
pendently produced has hitherto been used, the necessary sodium may be obtained
in the form of vapour and as required, by adding calcium carbide to molten
sodic hydrate as already described; if now into the sodium vapour (which is
prevented, by suitable means, from escaping) anhydrous yellow prussiate of
potash be introduced, potassium cyanide of high percentage strength will be
obtained, along with cyanide of sodium. The potassium cyanide can be separated
by well known means from the precipitated iron and from the calcium oxide
resulting from the reaction.

page_text: A Process for the Production of the Light Metals (Potassium, Sodium)
and Anhydrous Oxides and Peroxides and Cyanides of these
Metals.
I, GUIDO WOLFRAM, Ph.D., Chemist, of 1, Sossenheimerstrasse, Rodelheim, in
the German Empire, 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;
-
I have discovered that on introducing a carbide into a molten hydrate of an
alkali there is produced a peculiar decomposition, the products of which are car-
bonic oxide, hydrogen gas, and the vapour of the metal of the alkali. There
are therefore present at the same time in the reaction vessel the molten hydrate
of the alkali and the corresponding light metal in the form of vapour; and
from this departure several commercially important results may be ob-
tained, viz;-
-
The vapour of the potassium or sodium may be carried off and the metal
obtained;
The vapour may be condensed and the metal allowed to drip back into the
vessel to produce the anhydrous oxides;
By passing air or pure oxygen through the said anhydrous oxides the peroxides
can be produced;
Cyanides may be produced by introducing nitrogen or nitrogen compounds
into the vessel, this latter reaction taking place (for instance) on the introduction
of pure nitrogen, dry ammonia gas, or air the oxygen of which has been con-
verted into carbonic oxide, this conversion to carbonic oxide being necessary,
first, in order to prevent the injurious effect which free oxygen would exert upon
the reaction and, secondly, because complete conversion to carbonic acid would
also deleteriously affect the reaction.
In order to obtain completely anhydrous oxides it is necessary to heat the
reaction-mixture to a temperature between its melting point and red heat. The
reaction takes place more readily with alkaline carbides than with calcium
carbide and if the carbide contains impurities, the reaction will be hindered.
The readiness with which metallic sodium can be obtained by means of the
above described process, permits of the latter being advantageously employed
in connection with many of the chemical reactions requiring the presence of
pure metallic sodium. Thus, for example, in the production of potassium cyanide
from yellow prussiate of potash, in which process pure metallic sodium inde-
pendently produced has hitherto been used, the necessary sodium may be obtained
in the form of vapour and as required, by adding calcium carbide to molten
sodic hydrate as already described; if now into the sodium vapour (which is
prevented, by suitable means, from escaping) anhydrous yellow prussiate of
potash be introduced, potassium cyanide of high percentage strength will be
obtained, along with cyanide of sodium. The potassium cyanide can be separated
by well known means from the precipitated iron and from the calcium oxide
resulting from the reaction.
The following examples illustrate the carrying out of my invention.
For the production of alkali metals from the alkali hydrates, two methods
may generally be employed:
1. The alkali hydrate is fused in a suitable apparatus until it becomes free
from water and then a carbide is gradually added to it; or
2. The alkali hydrate (free from water) is mixed in a suitable apparatus with

page_text: and then gradually heated to red heat. The vapours of sodium thus produced
are distilled off and may be condensed in the well known manner, From
100 parts of caustic soda there may generally be obtained from 45 to 48 parts of
sodium.
EXAMPLE II.
Production of potassium cyanide and yellow prussiate of potash from caustic
potash.
100 parts (by weight) of caustic potash (free from water) are mixed with
42 parts (by weight) of calcium carbide (90%) in a suitable iron crucible and
the whole mass fused together by applying heat. The heating is preferably so
regulated that the lower part of the reaction vessel only becomes red hot in
order that the escape of the produced vapours of potassium may be prevented.
Into the mass thus heated is then introduced a weak current of a mixture of
carbonic oxide and nitrogen (produced for instance by passing a stream of air
over glowing coal) the gaseous current being preferably led as near to the bottom
of the reaction vessel as possible. The potassium vapours reduce the carbonic
oxide present to carbon and combine therewith, and at same time with the free
nitrogen to form potassium cyanide. Care must be taken that the gaseous cur-
rent passes but slowly through the reaction vessel and that vapours of potassium
are always in excess, otherwise if the gaseous current becomes too rapid, and if
carbonic oxide be in excess, carbon will separate out and the yield of potassium
cyanide will be lowered. If the reaction be carried out properly, 35 parts of
potassium cyanide may be obtained from. 100 parts (by weight) of caustic potash.
If the reaction be completed, the whole mass may then be lixiviated and the
potassium cyanide contained in the solution be converted in the usual manner into
yellow prussiate of potash which may be separated from the solution by crystalli-
zation or otherwise.
Having now particularly described and ascertained the nature of the said in-
vention and in what manner the same is to be performed I declare that what I
claim is:-
1. The process for the production of alkali metals from their hydrates, which
consists in fusing those hydrates, adding a suitable carbide (preferably calcium
carbide or an alkali carbide) to the molten mass and distilling off and condensing
the vapours of the alkali metals thus produced substantially as herein described.
2. The process for the production of alkali metals from their hydrates, which
consists in heating together alkali hydrates and a suitable carbide (preferably
calcium carbide or an alkali carbide) preferably to a low red heat, distilling off
and condensing the vapours of the alkali metals thus produced substantially as
herein described.
3. The process for the production of anhydrous alkali oxides, which consists
in heating and fusing together alkali hydrates and a suitable carbide as specified
in Claims 1 and 2, condensing and allowing to drip back into the reaction vessel
the vapours of alkali metals thus produced substantially as herein described.
4. The process for the production of alkali peroxides, which consists in heating
and fusing together alkali hydrates and a suitable carbide according to Claims Ï

page_text: and 2, condensing the vapours of the alkali metals thus produced within the
reaction vessel itself, and passing a stream of oxygen or a suitable mixture of
gases containing oxygen through the mass substantially as herein described.
5. The process for the production of alkali cyanides, which consists in heat-
ing and fusing alkali hydrates with a suitable carbide according to Claims 1
and 2, condensing the alkali metal vapours thus produced within the. reaction
vessel and introducing a current of nitrogen or a suitable mixture of gases con-
taining nitrogen, preferably nitrogen and carbonic oxide or a suitable nitrogen
compound, into the molten mass, all substantially as herein described.
6. In the production of alkali cyanides, preferably potassium cyanide from
yellow prussiate of potash, the process which consists in introducing yellow
prussiate of potash into the molten mass evolving alkali metal vapours and
obtained by fusing alkali hydrates preferably sodium hydrate with a suitable
carbide as described and claimed in Claims 1 and 2, preventing the alkali metal
vapours from escaping, and separating the alkali cyanides (particularly potas-
sium cyanide) thus produced from the melt in the usual manner.
071
1000
A. M. & WM. CLARK,
Chartered Patent Agents, 53, Chancery Lane, London.
A. M. & WM. CLARK,
Chartered Patent Agents, 53, Chancery Lane, London.