IMPROVEMENTS IN THE PRODUCTION OF CYANURETS OR CYANIDES OF THE METALS OF THE ALKALIES AND ALKALINE EARTHS
Year: 1881

page_text: LETTERS PATENT to John Henry Johnson of 47, Lincoln's Inn Fields in the
County of Middlesex Gentleman for an Invention of "IMPROVEMENTS IN
THE PRODUCTION OF CYANURETS OR CYANIDES OF THE METALS OF THE
ALKALIES AND ALKALINE EARTHS" A communication from abroad by
Victor Alder of Vienna in the Empire of Austria Manufacturing Chemist
PROVISIONAL SPECIFICATION left by the said John Henry Johnson at
the Office of the Commissioners of Patents on the 22nd December 1881.
JOHN HENRY JOHNSON of 47 Lincoln's Inn Fields in the County of Middlesex
Gentleman "IMPROVEMENTS IN THE PRODUCTION OF CYANURETS OR CYANIDES
OF THE METALS OF THE ALKALIES AND ALKALINE EARTHS" A communication
from abroad by Victor Alder of Vienna in the Empire of Austria Manufacturing
Chemist
This Invention relates to improvements upon a former Invention in respect of
which Letters Patent were granted to me dated the Sth March 1880 No 1004.
I have ascertained that the convertion of the compounds of the alkalies and
alkaline earths into cyanurets or cyanides by the action of the nitrogen of the
air can only successfully be effected in the presence of carbonising gases (like
carburetted hydrogen, carbonic oxide or a mixture of the two) whereby metals
capable of fixing and transmitting the carbon (like iron, chrom, manganese, nickel
or cobalt) greatly promote the conversion.
According to the nature of the compounds to be coverted into cyanurets or
cyanides four distinct cases are possible which I shall hereinafter describe. For
the sake of brevity I shall term a mixture of nitrogen-gas with carbonising gases
(like carburetted bydrogen, carbonic oxide or a mixture of the two) "carbonizing
nitrogen and I shall designate the above mentioned metals (iron or the like)
which readily fix and transmit the "carbonising metals."
"
The operations are in all cases conducted in close vessels.

page_text: I. According to one modification the carbonates oxides or hydrates of the metals
of the alkalies or alkaline earths are exposed to calcination with charcoal in
carbonizing nitrogen gas whereby they are converted into cyanurets or cyanides.
This process however will be greatly promoted by the employment of carbonising
metals in conjunction with the said substances.
II. According to another modification the sulphates or sulphides of the metals
of the alkalies are mixed with carbonate of lime and charcoal and heated in
carbonising nitrogen-gas as hereinbefore described whereby the required cyanurets
or cyanides are also obtained. In this case also the addition of carbonising metals
promotes the process.
Caustic line may be substituted for carbonate of lime or the two may be used in
conjunction.
III. According to a further modification the sulphates or sulphides of the metals
of the alkalies are heated with charcoal and a inetal which energetically enters
into combination with sulphur (such for example as iron zine manganese copper,
nickel or cobalt) in carbonising nitrogen gas whereby they are converted into
cyanides or cyanurets.
IV. According to a further modification the sulphates or sulphides of the metals
of the alkaline earths (like strontianite or barytus) are heated with carburetted
hydrogen_or_with-products-of-the-dry-distillation-of-wood, coal-of-all-sorts,
bituminous slate, rosin, fats, oils, petroleum and the like, whereby carbonates or
oxides of the metals under treatment or a mixture of the two are obtained which
will be converted into cyanides or cyanurets in the manner herein before described
under the first modification.
As an example of the manner in which the Invention may be practically carried
into effect I proceed in the following manner.
a. I take the carbonate, oxide or hydrate of a metal of the alkalies or alkaline
earths which is soluble in water and impregnate with this solution charcoal, coke,
sawdust, or similar substances (which after heating yield a porous coal) and I
evaporate the water used for effecting the solution.
b. I use charcoal in powder and dry over it the above named solution and form
by the addition of sawdust, tar or rosin a mixture which after calcination becomes
porous.
In default of saw-dust I obtain a very porous body by heating wood to a
temperature of about 250° to 300° centigrade and pulverise it.
In general I use all soluble substances in a liquid form when the solvent, like
water, becomes easily removable. This is also applicable to the 2nd and 3rd
modifications of the process herein before described, when instead of the carbonates,
oxides, or hydrates of the first modification the soluble sulphates or sulphides are
treated over charcoal.
c. From the soluble materials to be converted into cyanides or cyanurets I form
with water and charcoal, coke graphite (in a very fine powdered state) a semifluid
mixture into which I introduce larger pieces of wood, coke, charcoal (acting only
as carriers) in such a quantity, that this semifiuid mixture covers. slightly the
before named carriers and the water in it is afterwards evaporated.
If the convertable compound is insoluble in water then I mix with it a solution
of potash, soda or borax in a sufficient quantity or I use as a binding agent tar or
resinous substances for obtaining by the action of heat the before mentioned
semifluid mixture which forms the porous cover.
The advantage of this method is that the gases forming cyanogen are exposed
to a much larger surface, vist; to points of contact as in the former process in
addition to which the volatilisation of the alkalies is hereby avoided.
same
If with this process I wish to use one of the carbonising metals I admix the
or its oxide in a finely divided state with the substances herein before
enumerated under the divisions a b and c. If salts of the before named carbonising
metals which at a certain temperature or by the action of steam give up their
oxides (like sulphate or chloruret of iron) are at disposal I saturate the charcoal

page_text: with the corresponding solution, dry it again and calcine the same in a suitable
closed iron vessel to a dull red heat by passing steam over it at the same time
until the whole of the acid is converted into sulphurous or hydrochloric acid
which can be condensed in a suitable condensing vessel. The remaining charcoal
contains the quantity of metal as oxide which has been employed as a dissolved
metallic salt and this oxide is in the following process of the production of the
cyanurets or cyanides reduced to metal. I employ those carbonising metals which
are cheapest to be obtained in commerce.
The substances employed are by preference used in about the following pro-
portions.
The weight of charcoal used varies from 1 to 5 times of the weight of the
compounds to be converted into cyanides or cyanurets.
The weight of the carbonising metal used in accordance with the 1st and 2nd
modifications varies from 0 to 10 times of the weight of the compounds
employed.
The weight of the carbonate of lime used in accordance with the second
modification varies from 1 to 4 times of the weight of the compounds
employed.
The proportion of the carbonising metals used in accordance with the 3rd
modification varies from an equal weight to 15 times of the weight of the
sulphates or sulphides employed.
If caustic lime is used alone, the weight of the same is equal to from one
to 3 times of the weight of the compound to be converted into cyanide or
cyanuret and when mixed with carbonising metals from 1 to 2 times of this
weight.
For the production of carbonising nitrogen I use either carburetted hydrogens
occurring in nature or such as are obtained by the dry distillation of coal of any
description bituminous slate, rosin, fats, oils petroleum and the like and I mix
such carburetted hydrogens either (1st) with the nitrogen-gas obtained from
atmospheric air as hereinafter described or (2nd) with the fire-gas escaping from a
flue either directly or after being drawn over heated charcoal in such a proportion
that the mixture of gas leaving the apparatus in which the cyanogen is produced
contains still a quantity of undecomposed carburetted hydrogen.
The requisite large quantity of nitrogen-gas is obtained from the atmospheric
air by withdrawing the oxygen from the latter by the employment of suitable
sulphides in preference by sulphide of barium which I mix with sawdust chaff,
lumps of charcoal or the like-moisten it with water and cause the air to pass
through a series of iron tubes or chambers over this mixture either by exhaustion
or pressure by which process the air is deprived of its oxygen and the pure
nitrogen gas thus obtained is used for the purposes of this Invention, or I dissolve
sulphide of barium which solution I cause to flow over porous substances such for
example as charcoal, pumice stone or the like contained in the before mentioned
tubes, vessels, or chambers of iron or masonry whilst a stream of air has to pass in
the opposite direction by which means the air is deprived of its oxygen. The two
methods may be employed in combination.
Pure nitrogen gas may also be obtained when the gases resulting from the
process of production of cyanogen (consisting chiefly of hydrogen and oxide of
carbon) are mixed with air and burned together. The result of this combination
will be water, carbonic acid, and nitrogen gas.-This mixture of gases is forced
under a pressure of several atmospheres through water, whereby nearly pure
nitrogen gas is obtained or the above mentioned gases are caused to pass over a
mixture of sulphate of baryum and charcoal heated in an iron retort or in a
reverbaratory furnace whereby the sulphate is reduced to sulphide of barium which
is used for the production of pure nitrogen gas according to the process previously
described.
The contents of the before mentioned vessels or chambers consisting of porous

page_text: substances impregnated with sulphide of barium become in time inactive and
require to be regenerated by a simple reduction as described under the division b.
The water contained in the nitrogen gas. is before the employment of the latter
withdrawn by passing the same through heated vessels filled with pieces of bricks.
or pumice stone.
The process of the formation of the nitrogen gas is carried on in iron or earthen
tubes, retorts or like apparatus in which the oxidising action of the fire-gases is
eliminated in such a manner, that the materials before described contained in these
vessels are exposed to a suitable heat (calcination) and the mixture of the
carbonising nitrogen gas is caused to pass through, whereby a very large
proportion of the alkalies employed are converted into cyanides or cyanurets.
The carbonising nitrogen gas can also be produced in a generator by converting
the combustible material into a gaseous form under the action of compressed air.
The gases generated are burnt with a sufficient quantity of air and employed for
the preliminary heating and eventually for the reduction of the material employed.
After sufficient heating the current of air is shut off and only the gases of the
generator (consisting chiefly of carbonising nitrogen) or mixed with nitrogen gas
previously heated are conducted through the apparatus in which the materials
(to be converted) are contained.
For the nitrogen gas previously heated may be substituted a quantity of air-if
the gases coming from the generator are rich with carburetted hydrogen. It is
essential, that the gases leaving the generator, in which the formation of the
carbonizing nitrogen takes place should contain still undecomposed carburetted
hydrogen.
The cyanides or cyanurets thus obtained find numerous applications in industry,
metallurgy and in the arts. The advantages of the Invention consist in the
cheap and commercial production of nitrogen-gas, of the cyanides and cyanurets in
large quantities and in the conversion and reapplication of waste materials.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed
by the said John Henry Johnson in the Great Seal Patent Office on the
22nd June 1882.
JOHN HENRY JOHNSON of 47 Lincoln's Inn Fields in the County of Middlesex
Gentleman "IMPROVEMENTS IN THE PRODUCTION OF CYANURETS OR CYANIDES
OF THE METALS OF THE ALKALIES AND ALKALINE EARTHS" A communication
from abroad by Victor Alder of Vienna in the Empire of Austria.
This Invention relates to improvements upon, a former Invention in respect of
which Letters Patent were granted to me dated the 8th March 1880 No. 1004.
I have ascertained that the conversion of the compounds of the alkalies and
alkaline earths in cyanurets or cyanides by the action of the nitrogen of the air
can only successfully be effected in the presence of carbonizing gases (like
carburetted hydrogen, carbonic oxide or a mixture of the two) whereby metals
capable of fixing and transmitting the carbon (like iron, chrom, manganese, nickel or
cobalt) greatly promote the conversion.
According to the nature of the compounds to be converted into cyanurets or
cyanides four distinct cases are possible which I shall hereinafter describe.
For sake of brevity I shall term a mixture of nitrogen-gas with carbonizing
gases) like carburetted hydrogen carbonic oxide or a mixture of the two)
carbonising nitrogen" and I shall designate the above mentioned metals (iron or
the like) which readily fix and transmit the carbon "carbonising metals."
The operations are in all cases conducted in close vessels.
I. According to one modification the carbonates oxides or hydrates of the metals
of the alkalies or alkaline carths are exposed to calcination with charcoal in
carbonising nitrogen gas whereby they are converted into cyanurets or cyanides.
This process however will be greatly promoted by the employment of carbonising
metals in conjunction with the said substances.
II. According to another modification the sulphates or sulphides of the metals of
the alkalies are mixed with carbonate of lime and charcoal and heated in
carbonising nitrogen-gas as herein before described whereby the required cyanurets
or cyanides are also obtained. In this case also the addition of carbonising metals
promotes the process.
Caustic lime may be substituted for carbonate of lime or the two may be used in
conjunction.
III. According to a further modification the sulphates or sulphides of the metals
of the alkalies are heated with charcoal and a metal which energetically enters into
combination with sulphur (such for example as iron, zinc, manganese, copper
nickel or cobalt) in carbonising nitrogen gas, whereby they are converted into
cyanides or cyanurets.
IV. According to a further modification the sulphates or sulphides of the metals
of the alkaline earths (like strontianite or barytus) are heated with carburetted
hydrogen or with products of the dry distillation of wood, coal of all sorts,
bituminous slate, rosin, fats, oils, petroleum and the, like whereby carbonates or
oxides of the metals under treatment or a mixture of the two are obtained which
will be converted into cyanides or cyanurets in the manner hereinbefore described
under the first modification.
As an example of the manner in which the Invention may be practically carried
into effect I proceed in the following manner.
a I take the carbonate oxide or hydrate of a metal of the alkalies or alkaline
earths which is soluble in water and impregnate with this solution charcoal coke,
sawdust or similar substances (which after heating yield a porous coal) and I
evaporate the water used for effecting the solution.

page_text: b. I use charcoal in powder and dry over it the above named solution and form
by the addition of saw dust tar or rosin a mixture which after calcination becomes
porous. In default of sawdust I obtain a very porous body by heating wood to a
temperature of about 250° to 300° Centigrade and pulverize it.
In general I use all soluble substances in a liquid form when the solvent like
water becomes easily removable. This is also applicable to the second and third
modifications of the process herein before described when instead of the carbonates
oxides or hydrates of the first modification the soluble sulphates or sulphides are
treated over charcoal.
c From the soluble materials to be converted into cyanides or cyanurets I form
with water and charcoal, coke graphite (in a very fine powdered state) a semi fluid
mixture into which I introduce larger pieces of wood, coke, charcoal (acting only
as carriers) in such a quantity that this semifluid mixture covers slightly the
before named carriers and the water in it is afterwards evaporated. If the
convertable compound is insoluble in water then I mix with it a solution of potash
soda or borax in a sufficient quantity or I use as a binding agent tar or resinous
substances for obtaining by the action of heat the before mentioned semifluid
mixture which forms the porous cover.
The advantage of this method is that the gases forming cyanogen are exposed to
-a-much-larger-surface-videlicit-to-points-of-contact-as-in-the-former-process.in
addition to which the volatilisation of the alkalies is hereby avoided.
same
If with this process I wish to use one of the carbonising metals I admix the
or its oxide in a finely divided state with the substances herein before
enumerated under the divisions a band c. If salts of the before named
carbonising metals which at a certain temperature or by the action of steam give
up their oxides (like sulphate or chloruret of iron) are at disposal I saturate the
charcoal with the corresponding solution dry it again and calcine the same in a
suitable closed iron vessel to a dull red heat by passing steam over it at the
same time until the whole of the acid is converted into sulphurous or hydro-
chloric acid which can be condensed in a suitable condensing vessel. The
remaining charcoal contains the quantity of metal as oxide which has been
employed as a dissolved metallic salt and this oxide is in the following process
of the production of the cyanurets or cyanides reduced to metal.
I employ those carbonising metals which are cheapest to be obtained in
commerce.
The substances employed are by preference used in about the following
proportions.
The weight of charcoal used varies from 1 to 5 times of the weight of the
compounds to be converted into cyanides or cyanurets
The weight of the carbonising metal used in accordance with the first and second
modifications varies from 0 to 10 times of the weight of the compounds employed.
The weight of the carbonate of lime used in accordance with the second
modification varies from / to 4 times of the weight of the compounds employed.
The proportion of the carbonising metals used in accordance with the third
modification varies from an equal weight to 15 times of the weight of the sulphates
or sulphides employed.
If caustic lime is used alone the weight of the same is equal to from one to
3 times of the weight of the compound to be converted into cyanide or cyanuret
and when nixed with carbonising metals from 1 to 2 times of this weight.
For the production of carbonising nitrogen, I use either carburetted hydrogens
occurring in nature or such as are obtained by the dry distillation of coal of any
description bituminous slate rosin fats oils petroleum and the like and I mix such
carburetted hydrogene either first with the nitrogen gas obtained from atmo-
spheric air as hereinafter described or second With the fire gas-escaping from a flue
either directly or after being drawn over heated charcoal in such a proportion that
the mixture of gas leaving the apparatus in which the cyanogen is produced
contains still a quantity of undecomposed carburetted hydrogen.

page_text: The requisite large quantity of nitrogen gas is obtained from the atmospheric
air by withdrawing the oxygen from the latter by the employment of suitable
sulphides in preference by-sulphide of barium which I mix with saw dust chaff
lumps of charcoal or the like moisten it with water and cause the air to pass
through a series of iron tubes or chambers over this mixture either by exhaustion
or pressure by which process the air is deprived of its oxygen and the pure
nitrogen gas thus obtained is used for the purposes of this Invention or I dissolve
sulphide of barium which solution I cause to flow over porous substances such for
example as charcoal pumice stone or the like contained in the before mentioned
tubes, vessels, or chambers of iron or masonry whilst a stream of air has to pass in
opposite direction by which means the air is deprived of its oxygen-The two
methods may be employed in combination.
Pure nitrogen gas may also be obtained when the gases resulting from the
process of production of cyanogen (consisting chiefly of hydrogen and oxide of
carbon) are mixed with air and burned together. The result of this combustion
will be water, carbonic, acid and nitrogen gas. This mixture of gases is forced
under a pressure of several atmospheres through water whereby nearly pure
nitrogen gas is obtained or the above mentioned gases are caused to pass over a
mixture of sulphate of barium and charcoal heated in an iron retort or in a
reverberatory furnace whereby the sulphate is reduced to sulphide of barium which
is used for the production of pure nitrogen gas according to the process previously
described.
The contents of the before mentioned vessels or chambers consisting of porous
substances impregnated with sulphide of barium become in time inactive and
require to be regenerated by a simple reduction as described under the division b.
The water contained in the nitrogen gas is before the employment of the latter
withdrawn by passing the saine through heated vessels filled with pieces of bricks
or pumice stone.
The process of the formation of the nitrogen gas is carried on in iron or earthen
tubes retorts or like apparatus in which the oxidising action of the fire gases is
eliminated in such a manner that the materials before described contained in these
vessels are exposed to a suitable heat (calcination) and the mixture of the carbonising
nitrogen gas is caused to pass through whereby a very large proportion of the
alkalies employed are converted into cyanides or cyanurets.
The carbonising nitrogen gas can also be produced in a generator by converting
the combustible material into a gaseous form under the action of compressed air.
The gases generated are burnt with a sufficient quantity of air and employed for
the preliminary heating and eventually for the reduction of the materials employed.
After sufficient heating the current of air is shut off and only the gases of the
generator (consisting chiefly of carbonising nitrogen) or mixed with nitrogen gas
previously heated are conducted through the apparatus in which the materials (to
be converted) are contained.
For the nitrogen gas previously heated may be substituted a quantity of air if
the gases coming from the generator are rich with carburetted hydrogen.
It is essential that the gases leaving the generator in which the formation of the
carbonising nitrogen takes place should contain still undecomposed carburetted
hydrogen. The cyanides or cyanurets thus obtained find numerous applications in
industry metallurgy and in the arts. The advantages of the Invention consist in
the cheap and commercial production of nitrogen gas of the cyanides and cyanurets
in large quantities and in the conversion and reapplication of waste materials.
Having now described and particularly ascertained the nature of the said
Invention and the manner in which the same is or may be used or carried into
effect I would observe in conclusion that what I consider to be novel and original
and therefore claim as the Invention secured to me by the herein before in part
recited Letters Patent is;-
First, The conversion of the carbonates, oxides, hydrates, sulphates or sulphides
of the metals of the alkalies and alkaline earths into cyanides or cyanurets by the

page_text: employment of nitrogen gas of the air in combination with carbonising gases (oxide
of carbon carburetted hydrogen and the like) in closed apparatus with or without
the use of suitable carbonising metals or of caustic or of carbonate of lime or of a
mixture of same.
Second The process herein before described under division C consisting in the
employment and mixture of materials forming a large covering surface over picces
of wood charcoal coke and the like (which act as bearers) and in the exposing of
such materials to the action of the gases producing cyanogen.
Third :—The method of producing pure nitrogen gas from the air by with-
drawing from the latter the oxygen through suitable sulphides as herein before
described.
In witness whereof I the said John Henry Johnson have to this my
Specification set my hand and seal this Twenty second day of June One
thousand eight hundred and eighty two.
J. HENRY JOHNSON. (L.S.)