IMPROVEMENTS IN THE MANUFACTURE OR PRODUCTION OF AMMONIA OR AMMONIACAL PRODUCTS AND IN APPARATUS ΤΟ BE EMPLOYED THEREIN AND IN THE PREPARATION AND TREATMENT OF MATERIALS USED IN THE SAID MANUFACTURE PROAL
Year: 1883

page_text: LETTERS PATENT to Leon Quentin Brin and Arthur Brin, both of Paris in
the Republic of France but temporarily residing at the Grosvenor Hotel,
London. for an Invention of "IMPROVEMENTS IN THE MANUFACTURE OR
PRODUCTION OF AMMONIA OR AMMONIACAL PRODUCTS AND IN
APPARATUS
ΤΟ BE EMPLOYED THEREIN AND IN THE PREPARATION AND TREATMENT OF
MATERIALS USED IN THE SAID MANUFACTURE
PROVISIONAL SPECIFICATION left by the said Leon Quentin Brin and
Arthur Brin at the Office of the Commissioners of Patents on the
18th December 1883.
LEON QUENTIN BRIN and ARTHUR BRIN both of Paris in the Republic of
France but temporarily residing at the Grosvenor Hotel London IMPROVEMENTS
IN THE MANUFACTURE OR PRODUCTION OF AMMONIA OR AMMONIACAL PRODUCTS
AND IN APPARATUS TO BE EMPLOYED THEREIN AND IN THE PREPARATION AND
TREATMENT OF MATERIALS USED IN THE SAID MANUFACTURE
"
This Invention relates principally to the manufacture of ammonia or ammoniacal
products from Nitrogen especially nitrogen liberated in the process of making
oxygen as described in the Specification of Letters Patent No 1416 granted to
Peter Jensen and dated 7th April 1880 The process of manufacture according
to the present Invention is however not confined to the exclusive employment of
the pure nitrogen resulting from the manufacture of Oxygen according to the said
prior Invention but nitrogen manufactured from any other source may also be
employed.
The nitrogen is according to the present Invention moistened by watery vapour
or by steam or in any suitable way for example by passing it through any suitable
pump is caused to carry a certain quantity of water in suspension which may be
effected where pumps are used by the pistons of the pumps working in a hydraulic
chamber but in order to charge the said nitrogen fully with a greater quantity of
water or watery vapour on leaving the gas holder it is compelled to pass through
a damping apparatus in order that it may carry with it the quantity of water or

page_text: •
hydrogen necessary to enable it to be subsequently converted into ammonia
according to the process constituting the present Invention.
On leaving the damping apparatus the nitrogen propelled by a pump or by
compressing chambers in which it may be stored is conducted directly to retorts
which may resemble the retorts used in the manufacture of oxygen and nitrogen
as described in the Specification of the said former Invention.
The nitrogen passes through these retorts which are filled with a product which
may be termed "barytic coke" or carbon which is composed of coal or wood,
charcoal, tar and baryta these different products being preferably mixed or
combined and thoroughly calcined. If preferred lime or other earthy alkalies
(such for example as strontia) may be substituted for the baryta.
In traversing the pores of this barytic coke or carbon part of the previously
moistened nitrogen gas is converted into ammonia.
The ammonia thus formed is collected in a series of Woolf's bottles or other
suitable receptacles and containing acids such as hydrochloric acid or nitric or
sulphuric acid according to the nature of the salts that are to be formed, then in
order that the unconverted nitrogen leaving the acid or acids may not be wasted
it is caused to pass through another series of similar vessels containing an alkaline
substance such as lime, potash, soda or other products capable of neutralising the
acid vapours carried over.
In this manner the unconverted nitrogen thus separated passes into a gas holder
from whence it may be drawn and be again used until completely converted by
repassing through the series of apparatus as in the operation above described.
In order to restore the barytic coke or carbon to its original condition for rense
when it is found that the converting apparatus ceases to yield a sufficiently
concentrated ammonia a vacuum or partial vacuum may be employed.
Thus in order to remove the mixed carbonic acid and oxide which may be
formed in the barytic coke or carbon and would prevent its proper action in the
process it is subjected to the following operation.
By means of pumps or exhausting or forcing apparatus which may be the same
pumps as were used for exhausting and forcing the gases as aforesaid and which
are provided with valves for this purpose a vacuum or partial vacuum is produced
in the retorts whilst they are heated to from about 480 to 570 degrees Fahrenheit
the carbonic acid and gases which interfere with the process are thereby extracted
and after a few minutes the barytic coke or carbon is again ready for re-use.
The following is a description of the operation of the manufacture of aminonia
or ammoniacal products according to the present Invention beginning at the
delivery of nitrogen from the gas holder as the manufacture of this gas as well as
that of oxygen has been completely described in the said former Specification
The nitrogen drawn by the pump is forced through the moisening apparatus
containing cotton wicks or other capillary substances which by dipping in water
have the effect of moistening the gas which flows in contact therewith. The
moistening apparatus is surmounted by a vessel containing water and acting as a
Mariotte's vase in order to supply water automatically and maintain the proper
level in the lower chamber containing the wicks. The moistened nitrogen issuing
from this apparatus is conducted by a pipe to the converter, this pipe communicates
with a hygrometric balance composed of a glass bell in which works a delicate
balance carrying in one of its seales a hygrometric substance which when its
weight increases causes the beam to deflect and indicate upon a dial the degree of
moisture in the gases as they pass on their way to the retorts which are heated
by means of a gas furnace producing carbonic oxide at a variable temperature
(from 480 to 570 degrees Fahrenheit it is believed will be found sufficient to give
good results)
The nitrogen slightly charged with water becomes converted into ammonia and
is condensed in vessels containing the acids indicated; the free nitrogen is
separated from the acid vapours in the next vessels containing the alkalies which
absorb the acid vapours carried over.

page_text: Thus freed, the nitrogen returns along a pipe to the gas holder to be employed
anew by the action of the pump and set of valves which send it back into the
general circulation of the various apparatus as hereinbefore described.
It is preferred to employ a furnace and retorts having a pyrometer for
regulating the temperature composed of a suitable bar jointed at its extremities
and acting upon a bent lever connected to a register for admitting air to the
combustion chamber so as to prevent the temperature of the retorts from rising
above the proper limit.
It is preferred to employ an arrangement for closing the retorts in which is
employed a plug in the form of a truncated cone and having a screw thread upon
which works a screwed sleeve which fixes the conduit which has a conical extremity
and supplies air to the materials contained in the retort.
In manufacturing the bereinbefore described barytic coke or carbon it is preferred
to proceed as follows:-
By preference caustic baryta is used and it is mixed with about its own weight
of bituminous or other coal or coke and making an intimate mixture by grinding
the substances together after which the mixture is moistened or made into a paste
by the addition of tar or other heavy hydrocarbons when it is again by preference
passed through rollers or other mechanical equivalents in order to bring the tar
into intimate contact with every part of the mixture of carbon and baryta the
paste thus produced is placed either in covered crucibles or in retorts similar to
those employed in the manufacture of illuminating gas and submitted to destructive
distillation. The heating operations of the crucible or retort should continue until
scarcely any more gases of any kind are evolved.
The barytic coke thus produced when taken out of the retorts or crucibles should
be immediately placed in vessels which will protect it effectually from moisture and
air until it has cooled and become ready for use.
The result of this operation is a barytic coke which consists mostly of an intimate
and porous agglomeration of carbon and metallic barium. This porous substance.
is capable of decomposing water very rapidly at a comparatively low heat.
In place of the operation being conducted as hereinbefore described the nitrogen
may be moistened and the operation he conducted as hereinafter described and by
the use of an apparatus arranged as follows. We will describe it as arranged for
conducting the process according both to the prior Invention as described in the
said former Specification of Patent No 1416 A.D. 1880 and to the present
Invention.
There is provided a decarbonizing apparatus filled with trays charged with lime
to absorb the carbonic acid from the atmospheric air in its passage through it.
And also an oven or retort bench with the first retort or retorts filled with caustic
baryta or other material used for the separation of the oxygen from the nitrogen of
the air. Means are provided for regulating the quantity of air admitted. In
connection with the said bench there is a pyrometer to act as a heat regulator.
The retort or retorts communicates or communicate with an air vessel (provided
with a vacuum gauge) which communicates with a double acting pump for
producing a vacuum or partial vacuum in the said air vessel and for forcing the
nitrogen into a receiver on the passage leading to which there is a valve or stop
cock. There is also a valve or stop cock on a pipe leading from this passage into
the atmosphere. The said receiver is furnished with a pressure guage to indicate
the pressure of the nitrogen in it. A pipe or passage leads from the said Receiver
and dips into a washer or scrubber containing water to moisten the Nitrogen in its
passage-A pipe or passage leads from this washer to a boiler kept at a high heat
to vaporize instantaneously the water entering thereinto from a tank through a
regulator cock provided with a quadrant and intended to further and perfectly
moisten the nitrogen on its passage through it-A connecting pipe is provided
between the boiler and the said tank to equalize pressure in both-From the boiler
a pipe or passage leads to perforated pipes through which the moistened Nitrogen
.

page_text: passes into the second retort containing the Barytic Coke or Carbon The said
retort has an outlet leading to the vessel or vessels in which the ammonia is fixed
or combined. A culvert or pipe connected with a generator of Carbonic Oxide is
used for heating purposes and outlets are provided for the oxide of Carbon to
the different fire places of the apparatus. The operation with this apparatus is as
follows:-
The decarbonizing apparatus having been filled with trays containing slightly
hydrated lime such as are used for extracting the Carbonic Acid in illuminating
gas works and Caustic Baryta having been put into the retort or retorts in the first
oven or retort bench and water having been put in the water tank and also in the
scrubber or washer and Barytic coke having been placed in the said retort therefor
and water or solutions of Sulphuric Acid placed into the vessel into which the
Ammonia when produced is to be conducted heat is applied to the first Retort
bench either by ordinary solid fuel or by using Carbonic Oxide and when the
Retort or Retorts is or are at about a blue or very dull red heat the pump is set
in motion and the stop cock or valve for air is opened just enough to admit a
quantity of air freed from Carbonic Acid into the first retort or retorts and in order
to regulate that quantity in proportion to the capacity of absorption of the volume
of the Baryta contained in the said Retort or retorts the Nitrogen passing from the
pump should be tested and if not free from Oxygen the admission of air should be
gradually diminished until all the Oxygen is absorbed by the Baryta in the first
Retort or retorts. The Nitrogen is forced by the pump into the receiver After a
lapse of time (which is easily found by practice) the Baryta in the first Retort is
peroxidized and Oxygen is again detected at the pipe which leads to the
atmosphere. The stop cock of this pipe is then opened and the stop cocks for air
and in the passage from the pump to the receiver are closed the fire in the oven or
bench is increased to bring the first retort or retorts therein to a red heat and
during this time the pump forms a vacuum or partial vacuum in the said Retort or
Retorts (the amount of which vacuum is shewn on the vacuum gauge). At this
point of the operation the reduction of the peroxide of Barium into Protoxide
commences and pure Oxygen can be collected if desired.
When no more Oxygen is given out by the Baryta in the first Retort or Retorts
that fact is ascertained by the gauge shewing almost a perfect Vacuum whereupon
the temperature is immediately lowered in the bench of the first Retort or Retorts
by means of dampers.
Then the valve for air is gradually opened to admit again the atmospheric air
into the first Retort or Retorts and when the Nitrogen free from Oxygen passes
out at the outlet from the pump the stop Cock on the passage communicating
between the pump and the Receiver is first opened and afterwards the Stop Cock
on the pipe therefrom leading to the atmosphere is closed the Nitrogen being pumped
into the receiver and these operations may be alternately carried out. Having
now made a sufficient quantity of Nitrogen and collected it in the receiver
preferably under a pressure of about three or four atmospheres and the gas fire
having been lighted or heat otherwise applied under the boiler and under the
second Retort the Barytic coke or Carbon contained in the latter having reached
the temperature of about 300° Fahrenheit an equivalent quantity of water to that
of the volume of nitrogen to charge the said second Retort should be let into the
boiler by opening the graduated stop cock on the pipe leading from the water tank
simultaneously with the introduction of the Nitrogen
The valve or stop cock giving outlet from the second retort is then closed and
the stop cock on the passage from the Receiver is fully opened thus filling with
Nitrogen and vapours of water the whole of that part of the apparatus extending
therefrom to the said outlet from the second Retort As soon as the pressures
shewn on the pressure gauges of the Receiver and the second retort are equal the
stop cocks on the passages from the water tank and from the receiver are closed and
the stop cock on the outlet from the second retort containing the Barytic Coke is

page_text: gradually opened to let the ammoniacal gas formed in the Retort flow out and
come into contact with the acid or water contained in the vessel provided for the
purpose.
As soon as it is observed that there is no more internal pressure in the second
Retort the said stop cock is closed and the stop cocks on the passages from the
water tank and from the receiver are opened and the same operations are repeated
as hereinbefore described alternately But should it be found desirable to make
the process continuous and not alternate then the stop cock on the passage from
the receiver may be left open the stop cock admitting the water into the boiler
being also opened and regulated to admit a given quantity of water in a given
time proportionate to the amount of Nitrogen passing through the second retort
(or a series of them) containing the Barytic Carbon which quantity of Nitrogen
can be regulated by means of the stop cock on the outlet.
After the operation of producing Ammonia has been carried on for a certain
time the Barytic Coke in the second Retort or Retorts will have become less
active in the production of Ammonia and it will be found advantageous to take
out a sample of the Barytic Coke and examine it whether it is deficient in Carbon
and if not it may be made active again by breaking it into smaller pieces thus
exposing new surfaces when it may again be used in the Retorts to produce
Ammonia-Or the Retort containing the Barytic Coke might be made to rotate
while the Ammonia is being produced thus exposing continuously new surfaces.
Should the sample be found to be deficient in Carbon then the Barytic Coke
must be taken out of the Retort or Retorts, ground over again mixed with Coal
or Coke and tar and calcined in the same manner as hereinbefore described for
making the new Barytic Coke

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent and
of an Order of the Lord Chancellor filed by the said Leon Quentin Brin and
Arthur Brin in the Patent Office on the 2nd July 1884.
LEON QUENTIN BRIN and ARTHUR BRIN, both of Paris in the Republic of
France but temporarily residing at the Grosvenor Hotel, London "IMPROVEMENTS
IN THE MANUFACTURE OR PRODUCTION OF AMMONIA OR AMMONIACAL PRODUCTS
AND IN APPARATUS TO BE EMPLOYED THEREIN AND IN THE PREPARATION AND
TREATMENT OF MATERIALS USED IN THE SAID MANUFACTURE
"
This Invention relates principally to the manufacture of ammonia or ammoniacal
products from Nitrogen especially Nitrogen liberated in the process of making
oxygen as described in the Specification of Letters Patent granted to Peter Jensen
for an Invention communicated to him by us and dated seventh April One
thousand eight hundred and eighty N° 1416 The process of manufacture
according to the present Invention is however not confined to the exclusive
employment of the pure nitrogen resulting from the manufacture of Oxygen
according to the said prior Invention but nitrogen manufactured from any other
source may also be employed.
The nitrogen is according to the present Invention moistened by watery vapour
or by steam or in any suitable way (for example by passing it through any
suitable pump) is caused to carry a certain quantity of water in suspension which
may be effected where pumps are used by the pistons of the pumps working in
a hydraulic chamber but in order to charge the said nitrogen fully with a greater
quantity of water or watery vapour on leaving the gas holder it is compelled to
pass through a damping apparatus in order that it may carry with it the quantity
of water or hydrogen necessary to enable it to be subsequently converted into
ammenia according to the process constituting the present Invention.
On leaving the damping apparatus the nitrogen propelled by a pump or by
compressing chambers in which it may be stored is conducted directly to retorts
which may resemble the retorts used in the manufacture of oxygen and nitrogen
as described in the Specification of the said former Invention.
The nitrogen passes through these retorts which are filled with a product
composed of coal or wood charcoal tar and baryta these different products being
preferably mixed or combined and thoroughly calcined-If preferred lime or other
earthy alkalies (such for example as strontia) may be substituted for the baryta―
I will call this product "barytic coke" or carbon.
In traversing the pores of this barytic coke or carbon part of the previously
moistened nitrogen gas is converted into ammonia.
The aminonia thus formed is collected in a series of Woolf's bottles or other
suitable receptacles containing acids such as hydrochloric acid or nitric or sulphuric
acid according to the nature of the salts that are to be formed then in order that
the unconverted nitrogen leaving the acid or acids may not be wasted it is caused
to pass through another series of similar vessels containing an alkaline substance
such as lime potash, soda or other products capable of neutralising the acid vapours
carried over.
In this manner the unconverted nitrogen thus separated passes into a gas holder
from whence it may be drawn and be again used until completely converted by
repassing through the series of apparatus as in the operation above described.
In order to restore the barytic coke or carbon to its original condition for
reuse when it is found that the converting apparatus ceases to yield a sufficiently
concentrated ammonia a vacuum or partial vacuum may be employed

page_text: Thus in order to remove the mixed carbonic acid and oxide which may be
formed in the barytic coke or carbon and would prevent its proper action in the
process it is subjected to the following operation.
By means of pumps or exhausting or forcing apparatus which may be the same
pumps as were used for exhausting and forcing the gases as aforesaid and which
are provided with valves for this purpose a vacuum or partial vacuum is produced
in the retorts whilst they are heated to from about 480 to 570 degrees Fahrenheit
the carbonic acid and gases which interfere with the process are thereby extracted
and after a few minutes the barytic coke or carbon is again ready for use-
Figure 1 of the accompanying drawings is a general view of an apparatus for
carrying this Invention into effect-Figure 2 shows the apparatus which it is
preferred to employ for extracting oxygen from atmospheric air Figure 3 shews
a furnace and figure 4 illustrates means for closing the retorts as hereinafter
described.
The following is a description of the operation of the manufacture of ammonia
or ammoniacal products according to the present Invention beginning at the
delivery of nitrogen from the gas holder a Figure 1 as the manufacture of this
gas as well as that of oxygen has been completely described in the said former
Specification.
The nitrogen drawn by the pump 6 Figure 1 is forced through the moistening
apparatus c (containing cotton wicks or other capillary substances which by
dipping in water have the effect of moistening the gas which flows in contact
therewith-The said moistening apparatus c is surmounted by a vessel & containing
water and acting as a Mariotte's vase in order to supply water automatically and
maintain the proper level in the lower chamber c containing the wicks-The
moistened nitrogen issuing from this apparatus is conducted by a pipe to the
converter f. The said pipe communicates with a hygrometric balance e composed
of a glass bell in which works a delicate balance carrying in one of its scales a
hygrometric substance which when its weight increases causes the beam to deflect
and indicate upon a dial the degree of moisture in the gases as they pass on
their way to the retorts g which are heated by means of a gas furnace to a
temperature of froin 480 to 570 degrees Fahrenheit which will be found sufficient
to give good results)
The nitrogen slightly charged with water becomes converted into ammonia and
is condensed in vessels 1. 1 and 2 containing the acids herein before indicated, the
free nitrogen is separated from the acid vapours in the next vessels 3. 4. 5 and 6
containing the alkalies which absorb the acid vapours carried over
Thus freed, the nitrogen returns along a pipe h to the gas holder a to be
employed anew by the action of the pump b which sends it back into the general
circulation of the various apparatus as hereinbefore described.
In figure 2 a represents a moistening apparatus with wicks dipping in a water
tank, b represents a furnace with retorts c for fixing the oxygen, d a drier for the
gases coming from the moistening apparatus, e a pyrometer for regulating the
admission to the retorte, f is a pump drawing and forcing the gases in the retorts,
and g a gas holder serving as a magazine for the gases produced.
It is preferred to employ a furnace and retorts like that shewn at figure 3
having a pyrometer for regulating the temperature composed of a suitable bar
jointed at its ends p and q and acting upon a bent lever d connected to a register
or damper e for admitting air to the combustion chamber f so as to prevent the
temperature of the retorts from rising above the proper limit
It is preferred to employ an arrangement for closing the retorts like that shewn
in tigure 4 in which is employed a plug a in the form of a truncated cone and
having a screw thread at 6 upon which works a screwed sleeve c which fixes the
conduite which has a conical extremity f and supplies air to the materials contained
in the retort h.

page_text: In manufacturing the hereinbefore described barytic coke or carbon it is preferred
to proceed as follows.-
By preference caustic baryta is used and it is mixed with about its own weight
of bituminous or other coal or coke and making an intimate mixture by grinding
the substances together after which the mixture is moistened or made into a paste
by the addition of tar or other heavy hydrocarbons when it is again by preference
passed through rollers or other mechanical equivalents in order to bring the tar
into intimate contact with every part of the mixture of carbon and baryta the
paste thus produced is placed either in covered crucibles or in retorts similar to
those employed in the manufacture of illuminating gas and submitted to destructive
distillation-The heating operations of the crucible or retort should continue until
scarcely any more gases of any kind are evolved.
The barytic coke or carbon thus produced when taken out of the retorts or
crucibles should be immediately placed in vessels which will protect it effectually
from moisture and air until it has cooled and become ready for use.
The result of this operation is a barytic coke or carbon which consists mostly
of an intimate and porous agglomeration of carbon and metallic barium-This
porous substance is capable of decomposing water very rapidly at a comparatively
low heat.
Having now described and particularly ascertained the nature of our said
Invention and the manner in which the same is or may be used or carried into
effect we would observe in conclusion that what we consider to be novel and original
and therefore claim as the Invention secured to us by the hereinbefore in part
recited Letters Patent is.
First The process of and apparatus for the manufacture or production of
ammonia or ammoniacal products herein before described with reference to the
combined apparatus illustrated by figures 1 and 2 of the accompanying drawings.
Second The process of and apparatus for the manufacture or production of
ammonia or ammoniacal products hereinbefore described with reference to the
apparatus illustrated by figure 1 of the accompanying drawings.
Third-The manufacture of what we have herein before termed barytic coke or
carbon substantially as hereinbefore described.
Fourth The revivication of what we have hereinbefore termed barytic coke or
carbon in the manner substantially as herein before described.
Fifth The arrangement of pyrometer for automatically regulating the
temperature of the furnace for heating the retorts substantially as and for the
purpose herein before described and illustrated by figure 3 of the accompanying
drawings.
Sixth The employment of a hygrometric balance and dial for indicating the
degree of moisture of the gases on their way to the retorts substantially as
herein before described with reference to figure 1 of the accompanying drawings.
•
In witness whereof we the said Leon Quentin Brin and Arthur Brin have to
this our Specification set our hands and seals this first day of July One thousand
eight hundred and eighty four.