IMPROVE. MENTS IN THE MANUFACTURE OF AMMONIA
Year: 1860

page_text: LETTERS PATENT to William Clark, of 53, Chancery Lane, in the County
of Middlesex, Engineer & Patent Agent, for the Invention of "IMPROVE.
MENTS IN THE MANUFACTURE OF AMMONIA."—A communication from abroad
by Messrs. Louis Joseph Frédéric Marqueritte, Chemist, and Alfred
Lalouël de Sourdeval, both of Paris, in the Empire of France.
PROVISIONAL SPECIFICATION left by the said William Clark at tho
Office of the Commissioners of Patents, with his Petition, on the
24th April 1860
1, WILLIAM CLARK, of 53, Chancery Lane, in the County of Middlesex,
Engineer & Patent Agent,do hereby declare the nature of the said Invention
for "IMPROVEMENTS IN THE MANUFACTURE OF AMMONIA," to be as follows:-
It is unnecessary to enumerate the action which ammoniacal salts exert on
vegetation in general, as their influence and benificial effects are well known.
However, the natural and artificial sources of aminonia or azoted matters are
far froncommensurate withthe wantsof agriculture; as in almost every locality
manure is expensive. In fact, the manure of farms, night soil, guano, and
ammoniacal salts resulting from the treatment of stagnant waters,or from the
distillation of coal are far from being abundant or cheap.
The object & principal result of the present Invention is the manufacture
of ammonia by means of the azote of the air, and hence the preparation of
manure in quantities corresponding to the local wants.
By the process herein-after described it will be understood that where there
are combustible materials the preparation of ammonia will be unlimited, as
the source of azote (the air) is inexhaustible.

page_text: 1st,carbonate of baryta being taken,natural or artificial, (precipitated with
sulphuret by means of carbonic acid, or by an alkaline carbonate, it is calcined
in an earthen vessel with from 20 to 30 per cent. of resinous substance and
coal tar, with a certain quantity of pine or other sawdust. By this means
caustic baryta is obtained. When this operation is terminated the crucible is
withdrawn from the fire and left to cool down to a deep red colour, and then
plunged into water previously heated to 100°. By degrees the water
penetrates the pores of the crucible, the steam enters into contact with the
interior mass, and decomposes it under the simultaneous influence of the
baryta and small charcoal. There is, however, a production of gas, which
escapes & burns, but the temperature lessens gradually until it arrives at a
certain degree, where the production of ammonia commences, which is
indicated by the smell. At this moment the cover of the crucible is raised
the air thus enters and circulates freely,it penetrates the mass, which remains
in an incandescent state, by reason of the double action of the air, which oxi-
dizes the coal and the steam of the water, which hydrates the baryta,and thus
maintains thetemperature. Under thesecircumstancesconsiderable quantities
of ammoniaare produced, the crucible being placed in a cha'n ber or circum-
scribed space in which the ammoniacal matters are evolved. From this
chamber, by means of a pump or other extractor, these matters are withdrawn
and forced into water mixed with any kind of acid, or over substances which
will absorb the volatile alkalies, such as sulfate of iron, chlorides of manganese
of calcium, & others.) The operation can be also conducted in the following
manner: The mixture herein-before described is calcined in a retort of
earthenware or cast iron to obtain the caustic baryta, it is then allowed to
reduce in temperature, as done in the preparation of animal charcoal. A
current of air is then introduced into the retort saturated with steam in its
passage over water at 100°, if the temperature is too high it only disengages
hydrogen and inflaminable gas, and but little ammonia; if, on the contrary, it
is convenient to raise it to a little below 300°, the alkali is immediately
produced, and gives indication of the moment at which the operation should
commence & continue. When the disengagement of the ammonia has
ceased, the registers of the furnace are opened, an 1 it is raised into a bright
red-hot state without taking the mixture out of the oven; it is thus revivified,
so to speak, and will produce,under the influence of the current of damp air a
further considerable quantity of ammonia. The same mixture can serve a
certain number of times; however, as at cach operation the reduction of

page_text: carbonate and hydrate of baryta, and the oxygen of the air which passes
burns a certain proportion of the charcoal; it ends in its being insufficient, it
then becomes necessary to add inore of the original mixture. I would remark,
that it is always the same baryta which is used, and on this head there is no
repeated expense.
After having first employed air, I have been naturally induced to operate
with airdeprived of oxygen with pure azote,and have found by these means the
quantity of ammonia obtained from the same weight of baryta was more con-
siderable. 1 prepare pure azote by passing air subjected to a red heat on
filings of iron or copper, and on sulfuret of calcium, which can be constantly
regenerated by calcining the sulphate of lime produced with charcoal. I also
employ air which has been calcined on an excess of charcoal, and which
contains neither oxygen nor carbonic acid, and even calcin l air with a de-
ficiency of cal purified of its carbonic acid by passing it on the liine; azote
appears to be preferable to air, as the presence of oxygen diminishes the
resulting aminonia, which, forming carbonic acid, weakens the action of
the baryta by carbonating it, or by combining the azote with the hydrogen
produced by the decomposition of the vapour of the water.
It must be further understood that baryta, and all other alkalies, such as
potash, soda,strontian, lime, and others can be substituted for the baryta, and
employed in the same way to produce the saine results.
I als claim the preparation of cyanides and ferro-cyanides with ammonia,
prepared by the process above described.
SPECIFICATION in pursuance of the conditions of the Letters l'atent, filed
by the said William Clark in the Great Seal Patent Office on the
24th October 1860.
TO ALL 10 WHOM THESE PRESENTS SHALL COME, I, WILLIAM
CLARK, of 53, Chancery Lane, in the Conaty of Middlesex, Engineer and
Patent Agent, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Twenty-fourth day of April, in the year of our Lord
One thousand eight hundred and sixty, in the twenty-third year of Her
reign, did, for Herself, Her heirs and successors, give and grant unto me, the
said William Clark, Her special licence that I, the said William Clark,
my executors, administrators, and assigns, or such others as I, the said
William Clark, my executors, administrators, and assigns, should at any

page_text: time agree with, and no others, from time to time and at all times there.
after 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 "IMPROVE-
MENTS IN THE MANUFACTURE OF AMMONIA," a cominunication from abroad by
Messrs. Louis Joseph Frédéric Marqueritte & Alfred Lalouël de Sourdeval,
both of Paris, in the Empire of France, upon the condition (amongst others)
that I, the said William Clark, my executors or administrators, by an instru-
ment 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 Seal Patent Office within six calendar months next and
immediately after the date of the said Letters Patent.
NOW KNOW YE, that I, the said William Clark, do hereby declare the
nature of the said Invention, and in what manner the same is to be per-
formed, to be particularly described and ascertained in and by the following
statement (that is to say):-
It is unnecessary to refer to the action which ammoniacal salts exert on
vegetation in general, as their influence and benificial effects are well known.
While it may be observed that the natural and artificial sources of ammonia
or azoted matters are far from commensurate with the wants of agriculture; in
almost every locality manure is expensive. In fact, the manure of farms,
night soil, guano, and ammoniacal salts resulting from the treatment of
stagnant waters, or from the distillation of coal, are neither abundant nor
cheap.
The object and principal result of the present Invention is the manufacture
of ammonia by means of the azote of the air, and hence the preparation of
manure in quantities to correspond to the local wants.
By the process herein-after described it will be understood that where there
are combustible materials the preparation of ammonia will be unlimited, as
the source of azote (the air) is inexhaustible.
DESCRIPTION OF PROCESS.
1st, carbonate of baryta being taken (natural or artificial, precipitated with
sulphur by means of carbonic acid, or by alkaline carbonate.) it is to be
calcined in an earthen vessel, with from twenty to thirty per cent. of resinous
substance and coal tar, with a certain quantity of pine or other sawdust. By
this means caustic baryta is obtained. When this operation is terminated, the
crucible is withdiawi. from the fire and left to cool down to a deep red color,

page_text: and then plunged into water previously beated to one hundred degrees
centigrade. By degrees the water penetrates the pores of the crucible, the
steam enters into contact with the interior mass and decomposes it under the
simultaneous influence of the baryta and small charcoal. There is at the
onset a production of gas, which escapes and burns, but the temperature
lessens gradually until it arrives at a certain degree, where the production of
ammonia commences, which is indicated by the smell. At this moment the
cover of the crucible is raised, the air then enters & circulates freely, it
penetrates the mass which remains in an incandescent state, by reason of the
double action of the air which oxidizes the charcoal, and the steam of the
water which hydrates the baryta, & thus maintains the temperature. In these
circumstances considerable quantities of ammonia are produced, the crucible
being placed in a chamber or circumscribed space in which the ammoniacal
matters are evolved. From this chamber, by means of a pump or other
extractor, these matters are withdrawn and forced into water mixed with any
kind of acid, there to traverse the substances, which will absorb the volatile
alkalies (such as sulphate of iron, chloride of manganese, of calcium, and
others). The operation can be also conducted in the following manner :-
The mixture herein described is to be calcined in a retort of earthenware
or cast iron to obtain the caustic baryta, it is then allowed to reduce in
temperature, as in the preparation of animal charcoal, a current of air is then
introduced into the retort, which air is previously saturated with steam by
passingit over water at the boiling point; if the temperature is too high it
only disengages hydrogen and inflamable gas, and but little ammonia; if,
on the contrary, it is convenient to raise it to a little below three hundred
degrees centigrade, the alkali is immediately produced, also an indication of
the moment at which the operation cominences, and how long it should be con-
tinued. When the disengagement of the ammonia has ceased, the registers or
dampers of the furnace are opened, and it is raised to a bright red-hot state
without taking the mixture out of the oven; it is then revivified, so to speak,
aud will produce under the influence of the current of damp air a further
considerable quantity of ammonia. The same mixture will serve a certain
number of times, but as at each operation the reduction of carbonate and
hydrate of baryta, and the oxygen of the air which passes burns a certain pro-
portion of the charcoal, ultimately it becomes insufficient for the purpose,
it is then necessary to add more of the original mixture. I would remark,
that it is always the same baryta which is used, and on this head there is no
repeated expense.
After having first employed air, I have been naturally induced to operate

page_text: with air deprived of oxygen&with pureazoto, the quantityof ammonia obtained
from the same weight of baryta was then more considerable. I prepare pure
azote by passing air subjected to a red heat on fillings of iron or copper, and
on sulphuret ofcalcium, which can be constantly regenerated by calciuing the
sulphate of lime produced with charcoal. I also employ air which has been
calcined on an excess of charcoal, and which contains neither oxygen nor
carbonic acid, and even calcined air (where there is a deficiency of carbon)
purified of its carbonic acid by passing it over lime. Azote appears to be
preferable to air, as the presence of oxygen diminishes the resulting ammonia,
and, forming carbonic acid, weakens the action of the baryta by carbonating
it, or by the oxygen combining with the azote, and the hydrogen produced by
the decomposition of the vapour of the water.
It must bo further understood that baryta and all other alkalies, such as
potash, soda, strontian, lime, and others can be substituted for the baryta,and
employed in the same way to produce the same results.
Having described the naturo of this Invention, and the manner of per-
forming the same, I declare that what I claim as the Invention to be protected
by the herein-before in part recited Letters Patent is, the manufacture of
ammonia by means,
First, of a mixture of caustic baryta and comminuted or small charcoal,
prepared as above described, or otherwise.
Secondly, by passing a current of air or azote charged with steam over the
mixture herein-before described, and under the conditions above specified.
I also claim the preparation of cyanides and ferro-cyanides with ammonia,
prepared by the process abovo described.
In witness whereof, I, the said William Clark, have hereunto set my
hand and seal, this Twenty-fourth day of October, in the year of our
Lord One thousand eight hundred and sixty,
Witness,
W. G. E. SWINNOCK,
53, Chancery Lane.
W. CLARK. (L.S.)