IMPROVEMENTS IN THE TREATMENT OF SUBSTANCES AND LIQUORS CONTAINING AMMONIA AND CYANOGEN, AND IN OBTAINING PRODUCTS THEREFROM.
Year: 1873

page_text: LETTERS PATENT to Arthur William Ellis, of Madeira Villas, Wood-
ford, in the County of Essex, Manufacturing Chemist, for the
Invention of "IMPROVEMENTS IN THE TREATMENT OF SUBSTANCES AND
LIQUORS CONTAINING AMMONIA AND CYANOGEN, AND IN OBTAINING PRODUCTS
THEREFROM.
"
Sealed the 20th June 1873, and dated the 7th April 1873.
PROVISIONAL SPECIFICATION left by the said Arthur William Ellis
at the Office of the Commissioners of Patents, with his Petition, on
the 7th April 1873.
I, ARTHUR WILLIAM ELLIS, of Madeira Villas, Woodford, in the
County of Essex, Manufacturing Chemist, do hereby declare the
nature of the said Invention for "IMPROVEMENTS IN THE TREATMENT OF
SUBSTANCES AND LIQUORS CONTAINING AMMONIA AND CYANOGEN, AND IN OBTAINING
PRODUCTS THEREFROM," to be as follows, that is to say :-
By the destructive distillation of amongst other substances pit coal
and shale ammoniacal liquor is produced. This liquor contains amongst
other matter ammonia, and frequently cyanogen, and on account of its

page_text: ammonia (which it yields in large quantities) has hitherto been com-
mercially used for the production of various salts of ammonia, such as
sulphate, muriate, and carbonate, and also for the manufacture of crude
caustic ammonia.
The course usually adopted, for instance in the manufacture of
sulphate of ammonia, is to apply heat to the ammoniacal liquor, and
thus expel the ammonia from the apparatus or still in which the liquor
is operated upon, and conduct the ammonia thus rendered volatile, and
with it the other vapors and gases at the same time produced, to a
vessel, cistern, or tank charged with a solution of sulphuric acid. The
vapors and gases being passed through this solution the ammonia is
attracted and retained in it, but cyanogen more or less free or in
combination escapes and is lost.
It is a known fact that cyanogen when brought into contact with a
mixture of the oxides or soluble salts of iron with the alkalis, such as
potash or soda, or their carbonates, is attracted and retained, and ferro-
cyanide of potassium or sodium depending upon the alkali used is
produced.
Ferrocyanide of potassium or sodium (generally potassium) has long
been used for the manufacture of the color or dye known as Prussian
blue.
It has been proposed in order to utilize the cyanogen which escaped
in the manufacture of ammonia to convey the vapors and gases which
were expelled from the vessel charged with sulphuric acid (in which
little or no condensation took place) into a solution of caustic alkali and
sulphate of iron contained in a second vessel, tank, back, or receiver, it
being assumed that this ferro-alkaline solution or mixture would attract
and retain the oyanogen passing through it. However in practice it
was found that although it did attract and retain some portion of the
cyanogen, the aqueous vapors which passed into this vessel with
the cyanogen condensed so rapidly that the ferro-alkaline solution or
mixture was weakened to such an extent that it lost in a great degree
its power of attracting and retaining the cyanogen; and moreover, that
the great bulk of steam which accompanied the cyanogen into this
vessel caused the vapors and gases to be passed through the solution or
mixture so rapidly that sufficient time was not allowed for the attraction
and retention of the cyanogen, so that partly by the dilution of the
solution or mixture and partly owing to the rapidity with which the

page_text: cyanogen was forced through the solution or mixture, a great portion
of the cyanogen still escaped.
According to my Invention I pass the aqueous vapors together with
the gases evolved from the vessel charged with sulphuric acid either
directly or through an intermediate vessel or intermediate vessels, into
an ordinary condenser or refrigerator, before passing the cyanogen and
other gases into a solution or mixture formed of any of the well-known
agents capable of retaining and forming salts with cyanogen, such as
the oxides of iron, soluble salts of iron, either alone or mixed with
caustic alkalis or their carbonates, herein-after called the " combining
agent."
By adopting this process of treatment, I prevent not only the
mischievous dilution of the combining agent, but also cause the
cyanogen to pass more slowly through the combining agent, and thereby
increased facilities are afforded for attracting and retaining the
cyanogen.
Although by the use of the improvement above mentioned the
retention of the cyanogen is more completely and abundantly effected
than by any other method with which I am acquainted, I find that a
portion of the cyanogen still escapes, and to retain this I pass it into a
second, and if necessary other vessels, as many in number as the nature
of the gases in contact with the cyanogen and other varying circum-
stances render necessary. These vessels are so constructed as to cause
the gases to pass through the combining agent with which they are
charged.
I sometimes heat or warm and agitate the combining agent to facilitate
the attraction and retention of the cyanogen.
In cases in which sufficient pressure is not derived in the operation of
the expulsion of the ammonia to force the gases through the necessary
number of vessels containing the combining agent I drive or draw the
vapors and gases through it by any suitable contrivance.
In some cases where the residual liquor collected from the condensing
apparatus is found to be sufficienty rich in cyanogen, I proceed to treat
it in the manner above described, and so recover as much of the cyanogen
as it may be possible to recover; or I run the residual liquor into the
ammoniacal liquor store tank.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said Arthur William Ellis in the Great Seal Patent
Office on the 4th October 1873.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, ARTHUR
WILLIAM ELLIS, of Madeira Villas, Woodford, in the County of Essex,
Manufacturing Chemist, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Seventh day of April, in the year of
our Lord One thousand eight hundred and seventy-three, in the thirty-
sixth year of Her reign, did, for Herself, Her heirs and successors, give
and grant unto me, the said Arthur William Ellis, Her special licenco
that I, the said Arthur William Ellis, my executors, administrators,
and assigns, or such others as I, the said Arthur William Ellis, my
executors, administrators, and assigns, should at any time agree with,
and no others, from time to time and at all times thereafter during the
term therein expressed, should and lawfully might make, use, exercise
and vend, within the United Kingdom of Great Britain and Ireland,
the Channel Islands, and Isle of Man, an Invention for "IMPROVEMENTS
IN THE TREATMENT OF SUBSTANCES AND LIQUORS CONTAINING AMMONIA AND
CYANOGEN, AND IN OBTAINING PRODUCTS THEREFROM," upon the condition
(amongst others) that I, the said Arthur William Ellis, my executors
or administrators, by an instrument in writing under my, or their,
or one of their hands and seals, should particularly describe and
ascertain the nature of the said Invention, and in what manner the
same was to be performed, and cause the same to be filed in the Great
Scal Patent Office within six calendar months next and immediately
after the date of the said Letters Patent.
"
NOW KNOW YE, that I, the said Arthur William Ellis, do hereby
declare the nature of the said Invention, and in what manner the same
is to be performed, to be particularly described and ascertained in and
by the following statement thereof, that is to say :—
By the destructive distillation of amongst other substances pit coal
and shale ammoniacal liquor is produced. This liquor contains amongst
other matter ammonia and frequently cyanogen, and on account of its
ammonia (which it yields in large quantities) has hitherto been com-
mercially used for the production of various salts of ammonia, such as

page_text: sulphate, muriate, and carbonate, and also for the manufacture of crude
caustic ammonia.
The course usually adopted when ammoniacal liquor is used, for
instance in the manufacture of sulphate of ammonia, is to apply heat to
the ammoniacal liquor, and thus expel the ammonia from the apparatus
or still in which the liquor is operated upon, and conduct the ammonia
thus rendered volatile, and with it the other vapors and gases at the
same time evolved, to a vessel, cistern, or tank charged with sulphuric
acid. The vapors and gases being passed through this solution the
ammonia is attracted and retained in it, but the cyanogen, more or less
free or in combination, escaped and was lost.
It is a known fact that cyanogen when brought into contact with a
mixture of an oxide or a soluble salt of iron with an alkalis, such as
potash or soda or their carbonates, is attracted and retained, and ferro-
cyanide of potassium or sodium (depending upon the alkali used) is thus
produced.
Ferrocyanide of potassium or sodium (generally potassium) has long
been used for the manufacture of the color or dye known as Prussian
blue.
It has been proposed, in order to utilize the cyanogen which escaped
in the manufacture of sulphate of ammonia, that the vapors and gases
which were expelled from the vessel charged with sulphuric acid (in
which little or no condensation took place) should be conveyed into a
solution of caustic alkali and sulphate of iron contained in a second
vessel, tank, back, or receiver, it being assumed that this ferro-alkaline
solution or mixture would attract and retain the cyanogen passing
through it. However in practice it was found that although it did
attract and retain some portion of the cyanogen, the aqueous vapors
which passed into this vessel with the cyanogen condensed so rapidly
that the ferro-alkaline solution or mixture was weakened to such an
extent that it lost in a great degree its power of attracting and retaining
the cyanogen, and, moreover, that the great bulk of steam which accom-
panied the cyanogen into this vessel caused the vapors and gases to be
passed through the solution or mixture so rapidly that sufficient time
was not allowed for the attraction and retention of the cyanogen, so
that partly by the dilution of the solution or mixture, and partly owing
to the rapidity with which the cyanogen was forced through the solution
or mixture, a great portion of the cyanogen still escaped in contact or

page_text: mixed with large volumes of aqueous vapor and gases. The portion
which so escaped with the aqueous vapors and gases were either at once
passed into a furnace to be decomposed, or the cyanogen and other gases
with it were first deprived by condensation of the aqueous vapors in
contact with them, which aqueous vapors when condensed retained some
cyanogen in solution, but a valuable proportion of cyanogen still escaped
and was lost.
In order to retain this, and to render the manufacture of a ferro-
cyanide of sodium or potassium of commercial value, I pass the aqueous
vapors together with the gases evolved from the vessel charged with
sulphuric acid into an ordinary condenser or refrigerator, thus at once
doing away with the large volume of vapor, and enormously reducing
the bulk to be operated upon, and then pass the cyanogen and other
gases into a solution or mixture formed of any of the well-known agents
capable of retaining and forming salts with cyanogen, such as the oxides
of iron, soluble salts of iron, used either alone or mixed with caustic
alkalis or their carbonates, and which solution or mixture of oxide or a
soluble salt of iron and alkali is herein called "the combining agent."
If, however, the cyanogen be passed into a mixture or solution of oxide
or soluble salt of iron I subsequently add a solution of caustic alkali to
dissolve the cyanogen substances.
By adopting these processes of treatment I prevent not only the mis-
chievous dilution of the combining agent, but also cause the cyanogen
to pass more slowly through the combining agent, and thereby increased
facilities are afforded for attracting and retaining the cyanogen.
Although by the use of the improvement above described the retention
of the cyanogen is more completely and abundantly effected than by
any other method with which I am acquainted, I find that a portion of
the cyanogen still escapes, and to retain this I pass it into a second,
and, if necessary, other similar vessels containing the same reagent, as
in number as the nature of the gases in contact with the cyanogen
and other varying circumstances render necessary; and these vessels
are so constructed as to cause the gases to pass through the combining
agent with which they are charged. I sometimes heat or warm and
agitate the combining agent to facilitate the attraction and retention of
the cyanogen.
many
In cases in which sufficient pressure is not derived in the operation of
the expulsion of the ammonia to force the gases through the necessary

page_text: number of vessels containing the combining agent, I drive or draw the
vapors and gases through it by any suitable contrivance.
In cases in which the residual liquor collected from the condensing
apparatus is found to be sufficiently rich in cyanogen I run it into the
ammoniacal liquor store tank.
The vessel or vessels in which the "combining agent" is placed,
should be made of iron, and may be of any convenient form, but it is
necessary that it should be so constructed, that as large a surface as
practicable of the combining agent can be brought into contact with
the gases passing through it; to effect this purpose I use a vessel of a
cylindrical form as the one in which an agitator can be the more easily
adapted, and made to traverse and expose to the action of the gases
the entire mass of the "combining agent." To this vessel is fitted an
agitator and an inlet pipe, to which a series of coils of a smaller diameter
placed at or near the bottom of the vessel, and perforated with minute
holes, the collective areas of which are equal to the area of the larger or
inlet pipe, are connected, and through which the gases from the con-
denser are passed into and thus through the combining agent. To the top
of this vessel is also fitted an outlet pipe for the gases, and at the bottom
an outlet for drawing off the contents of the vessel. For the convenience
of testing the "combining agent" from time to time, two or three trial
cocks are placed below the level of the contents, and in order to ascertain
the height of the liquor a glass guage should be fitted to the vessel.
The apparatus above described is only suitable for such "combining
agents" as can be held in solution or suspension, and for all others an
ordinary purifier such as is used in the purification of gas answers well.
As an example, when cyanogen is sought to be retained in the form
of ferrocyanide of sodium, I proceed as follows:-Into the vessel above
described I place the "combining agent," in this case formed of a
mixture of hydrated oxide of iron and caustic soda in the proportions
indicated by the composition of ferrocyanide of sodium, I have found
that a mixture composed of the hydrated oxide resulting from the pre-
cipitation of the iron in one hundred and thirty-nine parts of ordinary
commercial sulphate of iron and a solution of one hundred and four
parts of commercial caustic soda answers well, but it is necessary to
bear in mind, that as the sulphate of iron and caustic soda of commerce
contain varying proportions of iron and sodium, it is necessary to test
these salts, and then calculate the quantities that will furnish the neces-

page_text: sary equivalents (that is 1 Eq. Fe and 2 Eq. Na). The agitator being
set in motion, the gases from the condenser are then turned on and are
driven through the "combining agent" until it ceases to take up more
cyanogen, which can be ascertained by taking a sample from time to
time from the trial cocks herein-before described. So soon as the
samples so taken show that the alkali of the combining agent has
become neutral, the contents of the vessel are run out, and allowed to
settle. The clear liquor is crude ferrocyanide of sodium, and can be
sold in that state, or Prussian blue can be developed from it in the usual
well-known manner adopted when ferrocyanide of potassium is used for
that purpose. The same operation as herein-before described is to be
performed when caustic potash is used with hydrate of iron.
Having thus described my Invention and the means which I adopt
in carrying the same into effect, I would have it understood that what I
claim is, the utilization of the gaseous cyanogen in manner herein-before
described after the process of condensation herein-before described has
taken place, and I would also have it understood that I do not claim to
operate on the volatile portion of the cyanogen until after it has been
passed through an ordinary condenser.
In witness whereof, I, the said Arthur William Ellis, have hereunto
set my hand and seal, this Fourth day of October, in the year of
our Lord One thousand eight hundred and seventy-three.
ARTHUR W. ELLIS. (L.S.)
Signed, sealed, and delivered by the
above-named Arthur William Ellis
in the presence of
JOHN GREENFIELD,
Clerk to Messrs. Bell and Crowder,
Victoria Buildings,
Queen Victoria St.,
London, E.C.