Year: 1886

page_text: I, PHILIP MIDDLETON JUSTICE of 55 and 56 Chancery Lane in the County of
Middlesex, Fellow of the Institute of Patent Agents do hereby declare the nature
of this invention (a communication from abroad by Hamilton Y. Castner of the City,
County and State of New York, United States of America) to be as follows:-
Heretofore sodium and potassium have been manufactured by intimately mixing
the carbonates of the alkalies with a carbonaceous material and a certain proportion
of lime, or the sulphate or carbonate of lime, and submitting the mixture to an
intense heat in iron cylinders or retorts, the alkali metal being thereby reduced
and distilled, and then condensed in appropriate receivers. The addition of lime
is necessary in this process to prevent the alkaline carbonate from fusing and
thereby separating from the carbon.
By this mode of manufacture it has been found that to attain any practical
result, the carbon in the mixture must be largely in excess of the amount required
theoretically to perform the reduction, owing to the fact that the mixture must be
kept froin fusing, to prevent the separation of the carbon and alkali. The excess
of carbon is absolutely necessary to assure an extended contact between the
particles of carbon and alkali while being heated. The effect of this excess of
carbon is to produce in the gas resulting from the reduction a large proportion of
carbonate oxide, which combines with the alkaline metal forming a carbide or a
carboxide from which the metal cannot be separated by distillation. The lime
necessarily added forms with the soda or potassa compounds (known respectively
as soda lime and potash lime) from which carbon will not reduce the alkaline
metal.
The required heat to perform the reduction and distill the metal, by this process
is very high, consequently the iron retorts are soon rendered worthless.
The amount of sodium produced by the above described manufacturing operation
at the present time, owing to the causes enumerated, rarely exceeds one-third of
the amount contained in the charge; and with potassium much less is obtained.
A certain process is also mentioned in scientific works whereby the alkaline metals
are produced by decomposing the hydrates of the alkali with iron filings at a white
heat. This process has never received practical application, chiefly owing to the
intense heat necessary to perform the reaction, and also to the fact that oxide of
iron produced when the reaction has partially taken place, combines with the
alkali forming ferrate of soda or potassium.
The object of my invention is to decompose either the carbonate or the hydrate
of an alkali when in a state of fusion, without employing an excess of carbon, and
thereby obtain a large yield of metal with but little waste. To accomplish this
result I fuse a mixture of the alkali and the carbide of a metal, or its equivalent,
Price G671

page_text: in a fine state of division as is hereinafter described. By the equivalent of a
carbide I mean a mixture of carbon and a metal finely ground or in a fine state,
held together by mechanical means and from which the metal cannot be separated
excepting by the aid of acids, and which is of such weight that it will not separate
from the alkali in the process of the manufacture of the potassium or sodium.
Regarding the actual compounds known as carbides very few have been
prepared, the most common one, however is made by calcining anhydrous Ferro-
cyanide of potassium in the absence of air; the following reaction taking place
viz
K4 Fe C6 N 6 + Heat = 4K ON + Fe O2 + 2 N.
Potassium Ferrocyanide producing Potassium Cyanide, Carbide of Iron and
Nitrogen. The carbide is separated from the Cyanide by treating the mass with
water, the carbide being insoluble. In place of using an actual chemical com-
pound of this kind I prefer to prepare one of the following substitutes which fully
answers the purposes of a carbide. Any easily reducible metal or its oxide in a
fine state of division is well mixed with a hydrocarbon, such as tar, bituminous
coal &, preference being given to the hydrocarbon containing the least amount of
mineral matter, and the mixture is charred or coked without access of air. The
result after so heating will be a hard heavy mass of "metallic coke," containing
the metal in a minute form, intimately mixed with the carbon from the Hydro-
carbon.
"
I prefer to use either metallic iron, previously reduced, in a fine state, or the
sesquioxide of iron combined with the hydrocarbon, owing to their low value, but
do not confine myself to the use of iron alone combined with the carbon as other
metals will answer fully as well. In producing this so called "Carbide of Iron
I use such proportions of hydrocarbon and metallic iron, or iron sesquioxide, as will
give, after heating a coke, containing 30 per cent of carbon and 70 per cent of iron.
This corresponds in composition to the known compound of carbon and iron Fe C 2.
I do not confine myself to this relative proportion of carbon and iron. This metallic
or metallized coke prepared as described, is finely ground and is then ready_for
use with the carbonated or hydrated alkali as is hereinafter described.
66
The
Carbide" is mixed with alkali in proportions which may be readily calculated
from the reactions hereinafter described, and the mixture is submitted to a bright
red heat in iron crucibles, connected with the usual condenser for sodium or
potassium. When the mixture in the crucible reaches the proper temperature, fusion
takes place and the reduction immediately commences, sodium or potassium being
distilled from the crucible to the condenser. I prefer using the Hydrated alkali for
the production of the metal owing to its being more fusible than the carbonate, but
do not confine my claims to the use of the hydrates only. The reactions which
of which the
take place vary with the proportions of alkali and "carbide"
following is a description:
4 Na HO+ Fo C2 = Na 2 CO 3 + Fe + 4 H + CO + 2 Na.
This reaction takes place when using 10 lbs. of Dry Caustic Soda and 5 lbs of
"Carbide" equivalent to one and a half pounds of carbon. As a result two and
seven-eighths pounds of sodium are produced or one half of that contained in the
charge or mixture.
16
2 Na HO+ Fe C2 = Na CO + Fe + 2 H + Na + 00.
"
This reaction takes place when using 10 lbs, of dry caustic soda and 10 lbs of
Carbide," equivalent to 3 lbs of carbon. As a result 23 of sodium are produced
or one-half of that contained in the charge. The excess of carbon combines with
the soda and part of the sodium to form "Carboxide." By the term "Carboxide
in this reaction I mean a mixture of metallic sodium, carbon, carboxide of sodium,
sodium di-oxide and carbonate of soda which by analysis would show the carbon,
sodium and oxygen to be present in the mixture in the proportion to form
carboxide of sodium. The following reaction is deduced froin the two previous

page_text: ones and can be made to take place by combining these two reactions or using
20 pounds dry caustic soda and 15 lbs of "carbide" equivalent to 4 pounds of
carbon, when this is done and the mixture heated, both the previous reactions take
place, producing the same result, but by carrying on the reaction the carboxide of
sodium reacts with the carbonate of soda producing metallic sodium, and carbon
di-oxide as follows
as follows:
3 Na HO+ Fe C2 = 3 Na + Fe + 3 H + CO + CO2.
It will be seen from this that all the sodium of the caustic soda is liberated in an
atmosphere composed of hydrogen, carbonic oxide and carbon di-oxide which has
no effect upon sodium when in a vaporized state. The metallic iron of the
Carbide" also possibly exerts an influence upon the oxygen of the alkali, and
would thus account for the lower temperature at which the reaction takes place
between the carbon and the oxygen of the alkali. Previous to my use of a
"Metallic Carbide" these reactions could not be performed, as the caustic alkali
would fuse and separate from the carbon, and when the reaction was tried without
fusion as before described, lime had to be added which prevented a perfect reaction
and also prevented the alkali from coming in direct contact with the necessary
amount of carbon so that all the alkali could be reduced and liberated. By the
use however, of a metallic carbide or its equivalent as described to perform the
reduction, the alkali may be fused while the carbon is held in suspension throughout
the fused mass in a most minute and active form, thereby being in intimate contact
with all particles of the alkali and accomplishing a result hitherto deemed impossible.
The reactions when the carbonate of soda is used are somewhat similar to those
already described, and will be apparent to any one skilled in the art. In making
potassium the reactions are the same as in the use of caustic or carbonate of soda,
the only difference being in the relative weights of alkali and "Carbide."
"
A stream of carbon di-oxide (dry) may be passed through the crucible in which
the reduction takes place, but although it will assist in removing and protecting
the sodium vapours it is not indispensable to the success of the process.
After the mixture of alkali and Carbide" has been submitted to heat and the
metal reduced and distilled there remains in the crucible all the iron in a finely
divided metallic state, together with a small amount of carbon and carbonate of
soda, the amount depending upon the relative proportion of alkali and carbide used.
The least amount of soda remains when the proportions of caustic soda and carbide
are as 10 is to 7 and a half. The crucibles containing the residues after treatment
are placed in warm water, the carbonate of soda dissolving, leaving the iron ready
when collected and dried to mix with the hydrocarbon and produce the carbide.
The solution of carbonate of soda is treated in the usual manner for producing
caustic soda.
By this method the yield of alkali metal closely approaches the theoretical
amount contained in the charge, the heat necessary for the reduction is not so high
as heretofore required and the accomplishment of the result requires less skilful
management.
In referring to the combination of carbon and metal as the equivalent of a
carbide, no actual chemical combination is inferred, but merely a mechanical
combination.

page_text: Improvements in the Manufacture of Sodium and Potassium.
I, PHILIP MIDDLETON JUSTICE of 55 and 56 Chancery Lane in the County of
Middlesex Fellow of the Institute of Patent Agents do hereby declare the nature
of this invention (a communication to me from abroad by Hamilton Y. Castner
of the City County and State of New York, United States of America) and in
what manner the same is to be performed, to be particularly described and ascer-
tained in and by the following statement :-
Heretofore sodium and potassium have been manufactured by intimately mixing
the carbonates of the alkalies with a carbonaceous material and a certain proportion
of lime or the sulphate or carbonate of lime, and submitting the mixture to an
intense heat in iron cylinders or retorts, the alkali metal being thereby reduced
and distilled, and then condensed in appropriate receivers. The addition of lime
is necessary in this process to prevent the alkaline carbonate from fusing, and
thereby separating from the carbon. By this mode of manufacture it has been
found that to attain any practical result the carbon in the mixture must be largely
in excess of the amount required theoretically to perform the reduction, owing to
the fact that the mixture must be kept from fusing, to prevent the separation of
the carbon and alkali. The excess of carbon is absolutely necessary to assure an
extended contact between the particles of carbon and alkali while being heated.
The effect of this excess of carbon is to produce in the gas resulting from the
reduction a large proportion of carbonic oxide, which combines with the alkaline
metal, forming a carbide or carboxide, from which the metal cannot be separated
by distillation. The lime necessarily added forms, with the soda or potassa,
compounds (known respectively as "soda-lime" and "potash-lime") from which
carbon will not reduce the alkaline metal. The required heat to perform the
reduction and distill the metal by this process is very high, consequently the iron
retorts are soon rendered worthless.
The amount of sodium produced by the above-described manufacturing operation
at the present time, owing to the causes enumerated, rarely exceeds one third of
the amount contained in the charge, and with potassium much less is obtained.
A certain process is also metioned in scientific works whereby the alkaline metals
are produced by decomposing the hydrates of the alkali with iron filings at a
white heat. This process has never received practical application, chiefly owing to
the intense heat necessary to perform the reaction, and also to the fact that oxide
of iron produced when the reaction has partially taken place combines with the
alkali, forming ferrate of soda or potassium.
The object of my invention is to decompose either the carbonate or the hydrate
of an alkali when in a state of fusion, without employing an excess of carbon, and
thereby obtain a large yield of metal with but little waste. To accomplish this
result, I fuse a mixture of the alkali and the carbide of a metal or its equivalent in
a fine state of division, as is hereinafter described. By the equivalent of a carbide

page_text: I mean a mixture of carbon and a metal finely ground or in a fine state, held
together by mechanical means, and from which the metal cannot be separated,
excepting by the aid of acids, and which is of such weight that it will not separate
from the alkali in the process of the manufacture of the potassium or sodium.
Regarding the actual compounds known as "carbides" very few have been
prepared, the most common one, however, is made by calcining anhydrous ferro-
cyanide of potassium in the absence of air, the following reaction taking place, vizı
K、 Fe C¿ Ñ¿ + Heat = 4 K C N + Fe Ơ + N,
potassium ferro-cyanide producing potassium cyanide, carbide of iron, and nitrogen.
The carbide is separated from the cyanide by treating the mass with water, the
carbide being insoluble.
In place of using an actual chemical compound of this kind, I prefer to prepare
one of the following substitutes, which fully answers the purposes of a carbide.
Any easily reducible metal or its oxide in a fine state of division is well mixed
with a bydrocarbon such as tar, bituminous coal, &c.-preference being given to
the hydrocarbon containing the least amount of mineral matter, and the mixture
is charred or coked without access of air. The result, after so heating, will be a
hard heavy mass of "metallic coke" containing the motal in a minute form
intimately mixed with the carbon from the hydrocarbon. I prefer to use either
metallic iron, previously reduced in a fine state, or the sesquioxide of iron combined
with the hydrocarbon, owing to their low value, but do not confine myself to the
use of iron alone combined with the carbon, as other metals will answer fully
as well.
In producing this so called "carbide" of iron" I use such proportions of hydro-
carbon and metallic iron or iron sesquioxide as will give, after heating, a coke
containing thirty per cent, of carbon and seventy per cent of iron. This corresponds
in composition to the known compound of carbon and iron-Fe C₂. I do not
confine my claims to this relative proportion of carbon and iron. This metallic or
metallized coke, prepared as described, is finely ground, and is then ready for use
with the carbonated or hydrated alkali, as is hereinafter described. The
"carbide" is mixed with alkali in proportions which may be readily calculated
from the reactions hereinafter described, and the mixture is submitted to a bright
red heat in iron crucibles connected with the usual condenser for sodium or
potassium. When the mixture in the crucible reaches the proper temperature,
fusion takes place and the reduction immediately commences, sodium or potassium
being distilled from the crucible to the condenser. I prefer using the hydrated
alkali for the production of the metal, owing to its being more fusible than the
carbonate, but do not confine my claims to the use of the hydrates only. The
reactions which take place vary with the proportions of alkali and carbide, of
which the following is a description:
4 Na HO + Fe C₂ = Na, CO₂ + Fo + H¿ + CO + Na.
This reaction takes place when using ten pounds of dry caustic soda and five
pounds of carbide, equivalent to one and a half pound of carbon. As a result, two
and seven-eighths pounds of sodium are produced, or one half of that contained in
the charge or mixture.
2 Na HO+Fe C₂ = Na CO + Fc + H₂ + Na + CO.
This reaction takes place when using ten pounds of dry caustic soda and ten
pounds of carbide, equivalent to three pounds of carbon. As a result, two and
seven eighths of sodium are produced, or one half of that contained in the charge.
The excess of carbon combines with the soda and part of the sodium to form
carboxide. By the term "carboxide" in this reaction I mean a mixture of metallic
sodium, carbon carboxide of sodium, sodium dioxide, and carbonate of soda, which,
by analysis, would show the carbon, sodium, and oxygen to be present in the
mixture in the proportion to form carboxide of sodium. The following reaction is

page_text: deduced from the two previous ones, and can be made to take place by combining
these two reactions or using twenty pounds dry caustic soda and fifteen pounds of
carbide, equivalent to four and a half pounds of carbon. When this is done and
the mixture heated, both the previous reactions take place, producing the same
result, but by carrying on the reaction the carboxide of sodium reacts with the
carbonate of soda, producing metallic sodium and carbon dioxide as follows:
Na, CO, + Na CO
Naz + CO₂.
Thus the reaction actually taking place when ten pounds of dry caustic soda are
fused with seven and a half pounds of carbide equivalent to two and one fourth
pounds of carbon, is as follows:
3 Na HO + Fe C, = 3 Na Fe + 3 H + CO + CO..
It will be seen from this that all the sodium of the caustic soda is liberated in an
atmosphere composed of hydrogen, carbonic oxide, and carbon dioxide, which has
no effect upon sodium when in a vaporized state. The metallic iron of the carbide
also possibly exerts an influence upon the oxygen of the alkali, and would thus
account for the lower temperature at which the reaction takes place between the
carbon and the oxygen of the alkali. Previous to my use of a metallic carbide
these reactions could not be performed, as the caustic alkali would fuse and
separate from the carbon, and when the reaction was tried without fusion, as before
described, lime had to be added, which prevented a perfect reaction, and also
prevented the alkali from coming in direct contact with the necessary amount of
carbon, so that all the alkali could be reduced and liberated. By the use, however,
of a metallic carbide, or its equivalent, as described, to perform the reduction, the
alkali may be fused while the carbon is held in suspension throughout the fused
mass in a most minute and active form, thereby being in intimate contact with all
particles of the alkali, and accomplishing a result hitherto deemed impossible. The
reactions when the carbonate of soda is used are somewhat similar to those already
described, and will be apparent to any one skilled in the art. In making potassium
the reactions are the same as in the use of caustic or carbonate of soda, the only
difference being in the relative weights of alkali and carbide. I have sometimes
used a stream of carbon dioxide (dry) passed through the crucible in which the
reduction takes place, and although it assists in removing and protecting the
sodium vapours it is not indispensable to the success of the process. After
the mixture of alkali and carbide has been submitted to heat and the metal
reduced and distilled there remains in the crucible all the iron in a finely divided
metallic state, together with a small amount of carbon and carbonate of soda,
which depends upon the relative proportion of alkali and carbide used. The least
amount of soda remains when the proportions of caustic soda and carbide are as
ten is to seven and a half. The crucibles containing the residues after the treat-
ment are placed in warm water, the carbonate of soda dissolving, leaving the iron
ready, when collected and dried, to mix with the hydrocarbon and produce the
carbide. The solution of carbonate of soda is treated in the usual manner for
producing caustic soda. By this method the yield of alkali metal closely approaches
the theoretical amount contained in the charge, the heat necessary for the reduction
is not so high as heretofore required, and the accomplishment of the result requires
less skilful management.
In referring to the combination of carbon and metal as the equivalent of a
carbide, no actual chemical combination is inferred, but a mechanical combination.
Having now particularly described and ascertained the nature of the said
invention, and in what manner the same is to be performed, as communicated to
me by my foreign correspondent, I declare that what I claim is-
1. In a process for manufacturing sodium or potassium, performing the reduction
by diffusing carbon in a body of alkali in a state of fusion at moderate temperatures,
substantially as described.

page_text: 2. In a process of manufacturing sodium or potassium, performing the reduction
by means of the carbide of a metal or its equivalent, substantially as set forth.
3. In the process of manufacturing sodium or potassium, mechanically combining
a metal and carbon to increase the weight of the reducing material, and then
mixing this product with the alkali and fusing the latter, whereby the reducing
material is held in suspension throughout the mass of fused alkali, substantially as
described.
4. In the process of reduction, performing the dioxidization by the carbide of a
metal or its equivalent, substantially as described.