Improvements in Obtaining Ammonia, Hydrochloric Acid, and Chlorine from Ammonium Chloride, also in Obtaining Chlorine from Hydrochloric Acid, and in the Apparatus used.
Year: 1892

page_text: Date of Application, 26th Aug.; 1892
Complete Specification Left, 26th May, 1893—Accepted, 29th July, 1893
PROVISIONAL SPECIFICATION.
Improvements in Obtaining Ammonia, Hydrochloric Acid, and
Chlorine from Ammonium Chloride, also in Obtaining Chlorine
from Hydrochloric Acid, and in the Apparatus used.
I, FREDERICK BALE of Coventry Hospital Droitwich, Worcestershire, Chemist,
do hereby declare the nature of this invention to be as follows:-
This invention has for its object the improvement in the methods of obtaining
ammonia, hydrochloric acid and chlorine from ammonium chloride, and in obtaining
chlorine from hydrochloric acid.
In my previous Patents on this subject viz. 14,000, and 14,001 of 1887 and 15,649
of the year 1889 I have described various processes for this purpose. In these
processes I have proposed the use of oxides in powder or their mixtures with
ammonium chloride in powder, the principle being, to fully decompose the
ammonium chloride and obtain its ammonia at a low temperature-below that
required for the volatilization of the ammonium chloride-whereby the ammonia
evolved is saved, and not partly destroyed as it would be, if high temperature
were used for its evolution.
The chlorides thus formed from the oxides used, are next heated with steam for
the production of hydrochloric acid, or with hot and dry air for the production
of chlorine; and thus the original oxides are regenerated, the whole mass is stirred
at intervals, and atmospheric air is used at the low temperature employed in
working for the expulsion of residual and free ammonia, hydrochloric acid, chlorine
and moisture from the retorts, and hot and cold air for otherwise regulating the
temperature. In Patent 15,649 of 1889 I have also proposed the use of a fused
salt as a medium for carrying on these reactions.
I will now describe what I have found, after some years of experimental work
and trials, on a fairly large scale, to be the best method for the evolution of the
ammonia from the ammonium chloride, whereby the ammonia is obtained without
loss beyond ordinary and unavoidable working losses, and also, how the hydro-
chloric acid, may be freely and fully obtained, and used for the production of
undiluted chlorine.
I find that nearly all the peroxides thus used, finally become sesquioxides, when
their chlorides are decomposed by a current of air or steam and in my previous
Patents I have shown that these sesquioxides cannot be used for the evolution of
the ammonia from the ammonium chloride, until they are reduced to a lower oxide
or oxidized to a higher. I also find that some of the best results for the ammonia,
are obtained by the use of magnesia, mixed with a monoxide of the heavy metals,
or with some chemically inactive substance under the required conditions; and that.
the chloride of magnesia formed is readily and easily decomposed on the passage of
steam, producing hydrochloric acid, for the production of chlorine as described
below.
Instead therefore of a mixture of magnesia and higher oxides, which would
periodically need reducing, 1 find it preferable to mix the magnesia in powder with
an equal weight of such substances as sand, common salt or chloride of potassium &c.
or a mixture of these. This mixture will prevent the fusion of the chloride,
sticking to the retort, and the flying of the oxide, when steam or air is passed
through.
When the powdered ammonium chloride is stirred into such a mixture, and
gradually heated, the ammonia is obtained nearly as possible without loss, and the
hydrochloric acid, on the passage of steam over the chloride formed, nearly as
possible pure. The ammonia is completely evolved at a temperature of 325° C.

page_text: to 350° C. The hydrochloric acid, is completely evolved below 500° C. Mos
of the ammonia is evolved below 100° C. and most. of the hydrochloric aci
below 250° C. At this or the higher temperature the hydrochloric acid is com
pletely decomposed, when used for the production of chlorine, as mentioned below
without the direct application of heat to the oxides or apparatus used.
I have also found that one of the chief sources of the loss of ammonia, has
arisen from liberating the chlorine, in the same retort or chamber as that used for
the liberation of the ammonia. When all precautions have been taken to clear the
retort from residual ammonia, some small portion is still retained in the retort or
mixture which is most difficult to remove, and is destroyed on the liberation of the
chlorine. When however hydrochloric acid is liberated in the same retort as the
ammonia, the reformation of the ammonium chloride takes place and the small
amount of residual ammonia is thus saved, and the elimination of moisture from the
chloride which has always been a difficulty is not here necessary.
In the next place I have found considerable difficulty in obtaining chlorine of
sufficient strength and low temperature for the ready manufacture of good bleach
from its being very considerably diluted with oxygen and nitrogen from the
method adopted; and although dilute chlorine of this kind can be utilized in a
Deacon bleach chamber, yet a much stronger chlorine is much to be desired.
This difficulty is overcome as follows, and one third, of the available chlorine
obtained strong and pure for this. or other purposes :-
The hot gaseous hydrochloric acid evolved as above described, or that obtained
from any other source, is dried and passed over or through peroxides, by which I
mean any oxide containing more oxygen than the monoxide (MO) as MO,,
MOMO &c. where M is any metal, and which oxide liberates oxygen on the
MO,
addition of an acid.
The peroxides may be used in powder and stirred at times; or they may be
suspended in powder in fused chloride of zinc or other fused element or compound
as described in my previous Patents, and then the hot and dry HCl may be blown
through the fused salt containing the peroxide or passed over it when used in
powder: Or the well-known Deacon process may be used, only making these
peroxides or their mixtures into pills, marbles, bricks or balls by methods that are
well known and passing the hot gaseous hydrochloric acid through these piled in a
suitable furnace. In either case one third of the chlorine in the HCI is given off
pure and undiluted or nearly so.
Most of the peroxides when converted into chlorides by hydrochloric acid and
then have these chlorides reduced by oxygen or air, becomes as above mentioned
sesquioxides (M,O,) and from these of this composition the chlorine will be evolved
in this process. Thus
M₂O+ 6 HCI
3
=
2 MCI, + 3. OH, + Cl₂.
I have found that the chlorine can be obtained free from hydrochloric acid, if
the latter be carefully and slowly passed, or if the gases from the first chamber be
passed into a second containing the peroxides. Pure and undiluted chlorine, to
the extent of one-third that contained in the hydrochloric acid is thus obtained,
which may be passed at once into a Deacon bleach chamber or otherwise. used.
The remaining two-thirds, of the chlorine from the chlorides of the metals thus
formed is obtained as described in my previous Patents by instalments (as it were)
of from 9 to 12% mixed with (0 + N) by passing over or through the chlorides
this formed, dry and hot air or oxygen.
A Cowper, or other well known stove, used for heating the steam or air may be 5
employed for heating the hydrochloric acid if necessary.
produced may be used towards the end of the process for bleach-making, the
The strong chlorine thus
weaker chlorine at the beginning as is well understood by chemists, or the two may
be mixed as evolved by using a series of such furnaces, and passed together into
the bleach chamber or otherwise used: Or the two processes inay be carried on at 5
once by passing the hydrochloric acid, and air together over the peroxides, but

page_text: here the difficulty is increased in removing fully the hydrochloric acid from the
chlorine evolved.
Of the peroxides, the one I prefer is manganese, monoxides and salts of these
peroxides may be used but with less advantage. When monoxides (MO, M,O)
The above
are employed the dilute chlorine is the only kind possible to produce.
processes give the best results for the ammonia, hydrochloric acid, and chlorine.
The apparatus thus required, would be a combination of that already described
in my previous Patents, with the well known Deacon furnace for the Deacon
process, using the peroxides in powder and stirring, or in pills, marbles, balls, or
bricks, as described. Dry and hot air may be used where steam is used for the
production of chlorine, when necessary.
August 1905
FREDERICK BALE.
COMPLETE SPECIFICATION.
Improvements in Obtaining Ammonia, Hydrochloric Acid and
Chlorine from Ammonium Chloride, also in obtaining Chlorine
from Hydrochloric Acid, and in the Apparatus used.
I, FREDERICK BALE, of Coventry Hospital, Droitwich, Worcestershire, Chemist,
do hereby declare the nature of this invention and in what manner the same is to
be performed, to be particularly described and ascertained in and by the following
statement:
This invention has for its object, the improvement in the methods of obtaining
ammonia hydrochloric acid, and chlorine, from ammonium chloride, and in obtaining
chlorine from hydrochloric acid.
In my previous Patents on this subject, viz., 14,000, and 14,001, of the year 1887;
and 15,649, of 1889 I have described various processes for this purpose. In these
processes, I have proposed the use of oxides in powder, or their mixtures with
ammonium chloride, in powder, the principle being to fully decompose the
ammonium chloride, and obtain its ammonia at a low temperature-below that
required for the volatilization of the ammonium chloride-whereby the ammonia
evolved is saved, and not partly destroyed, as it would be, if a high temperature
were used for its evolution."
The chlorides thus formed from the oxides used, are next heated with steam for
the production of hydrochloric acid, or with hot and dry air for the production of
chlorine and thus the original oxides are regenerated. The whole mass is stirred
at intervals, and atmospheric air is used at the low temperature employed in
working, for the expulsion of residual, and free ammonia, hydrochloric acid, and
chlorine, and moisture from the retorts, and hot and cold air for otherwise
regulating the temperature. In Patent 15649 of 1889 I have also. proposed the use
of a fused salt as a medium for carrying on these reactions.
I will now describe what I have found after some years of experimental work,
and trials on a fairly large scale, to be the best method for the evolution of the
ammonia, from the ammonium chloride, whereby the ammonia is obtained without
loss, beyond unavoidable working losses, and also how the hydrochloric acid may be
I find
fully and freely obtained, and used for the production of undiluted chlorine.
that nearly all peroxides thus used finally become sesquioxides, when their
chlorides are decomposed by a current of air or steam, thus producing by air,
two-thirds of the total chlorine, dilute. or mixed with oxygen and nitrogen, or
yielding it as pure hydrochloric acid by steam, and after decomposing the
hydrochloric acid so got by passing it again over or through the peroxides for
chlorine.
In my previous Patents I have shown that these sesquioxides cannot be used for
the evolution of the ammonia from the ammonium chloride, until they are reduced to
a lower oxide, or oxidized to a higher. I also find that some of the best results for

page_text: the ammonia, are obtained by the use of magnesia, mixed with a monoxide of the
metals, or with some chemically inactive substance, under the required conditions,
and that the chloride of magnesium thus formed, is readily and easily decomposed,
on the passage of steam producing hydrochloric acid for the production of chlorine,
as described below.
Instead, therefore, of a mixture of magnesia and heavy oxides, which would
periodically need reducing, I find it preferable to mix magnesia in powder, with an
equal weight of such substances as common salt, chloride of potassium, powdered
glass, &c., or a mixture of these.
This mixture will prevent the fusion of the chloride, sticking to retort, and the
flying of the oxide, when steam or air is passed through.
When the powdered ammonium chloride is stirred into such a mixture, and
gradually heated, the ammonia is obtained nearly as possible without loss, and the
hydrochloric acid on the passage of steam over the chloride formed, nearly as
possible, pure. The ammonia is completely evolved at a temperature of 325° C.,
to 350° C. The hydrochloric acid is completely evolved below 550° C. Most of
the ammonia is evolved below 100° C., and most of the hydrochloric acid below
250° C. At the higher temperature, the hydrochloric acid is completely decom-
posed, when used for the production of chlorine, as mentioned below, without the
direct application of heat to the oxides, or apparatus used.
Equal weights of magnesic oxide, and ammonium chloride give good results, and
a continuous current of hydrochloric acid on heating after the ammonia is evolved,
the moisture present giving about 30% of the total hydrochloric acid.
After this, on passing superheated steam, the remaining hydrochloric acid is
evolved in a strong continuous current. This mixture remains throughout,
powdery and incoherent, and allows the ammonium chloride to be easily stirred
into it.
When the process is followed for the continuous production of chlorine from a
mixture of gaseous hydrochloric acid and air; instead of steam or air alone, I then
send a mixture in proper proportions of each of these through the retorts, first
heating the mixture of steam and air to the required temperature, and then passing
the issuing gases through the peroxide marbles in the cylinders as described
below.
I have also found that one of the chief sources of the loss of ammonia has arisen
from the liberation of the chlorine in the same retort or chamber as that used for
the liberation of the ammonia.
$
When all precautions have been taken to clear the retort from residual ammonia,
some small portion is still retained in the retort or mixture, which is most difficult
to remove, and is destroyed on the liberation of the chlorine. When, however,
hydrochloric acid is liberated in the same retort as the ammonia, the reformation of
ammonium chloride takes place and the small amount of residual ammonia is thus
saved, and the climination of moisture from the chloride, which has always been a
difficulty, is not here necessary.
The above mixtures of oxides in powder, and ammonic chloride in powder, do
well, and give good results for the ammonia.
The resulting mixture of chlorides and oxides, however, is not in the best
condition for the passage through it afterwards of steam, or air, inasmuch as the
powdered condition opposes the passage of the gases, unless the mixture is constantly
stirred, and retorts used in an oblique, or horizontal position.
This drawback is overcome as follows: and while retaining the advantageous
principle of mixtures, and a low temperature, for the evolution of the ammonia, I
also obtain the advantage of a large and extended active surface for the evolution
by steam, of hydrochloric acid, and of the passage of the gases through the
apparatus, in a downward direction.
A layer of oxide is placed on the bed of the retort, preferably several inches
thick, when the apparatus described in Figure 2, is used which is another form of
the apparatus described in Fig. 1. After the evolution of the ammonia, the

page_text: powdered mass continues to be stirred, and then a solution of ammonic chloride, or
a spray of hot water is admitted into the retort, in quantity to make the mixture
into a stiff paste. The oxides and chlorides present take up the moisture, and the
stirring converts them into coherent fragments, grains, or lumps of irregular
shape.
When this is sufficiently accomplished, to make the mass permeable to the gases,
the stirring is stopped, and heating continued for some time, till the ammonia is
evolved.
Steam, mixed with hydrochloric acid is next distilled off, and may be passed
through, and heated up in the Cowper stove, and afterwards passed into a retort,
When this
which is ready for the production of hydrochloric acid by steam.
ceases, steam superheated is passed through the fragments, and hydrochloric acid.
is evolved, and when the evolution is completed, there remains an incoherent mass
of oxides, which readily crumble to powder again when stirred. In this state, the
ammonic chloride is stirred into them, and the round of operations for the ammonia
and hydrochloric acid begun afresh.
For these purposes the retorts may be vertical. Figures 1, and 2, are vertical
sections of different forms of the apparatus, which is used for the evolution of the
ammonia, and hydrochloric acid (or chlorine, when necessary). The following will
describe its use, and mode of working.
The cylinder A, Figures 1, and 2, is of iron, lined with earthenware tiles, or
brick, or of earthenware, and placed in a chamber of brick, which is heated by the
furnace, F, by flues, through which the gases from F, circulate round the
cylinder.
Each cylinder has an apparatus, S, S, for stirring its contents, and a hopper, H,
through which the ammonic chloride descends into the cylinder, by the plug, P.
These stirrers in revolving, present the mixture to the jets J, J, giving a spray of
water, or solution of ammonic chloride; and also cut the pasty mass vertically, and
horizontally, into fragments or grains, or lumps.
Each cylinder has also a passage, M, for the admission of steam or hot water, or
a solution of ammonic chloride, thronga jets, J, J, and others for the exit of the
ammonia, and hydrochloric acid, through syphons s', s, from which the gases
pass to the conduit c, c. The syphon passages s', s, for the exit of the gases are
filled with loosely piled fragments, or lumps of flint, brick, &c., and may be cleared
from adhering powder, by a jet of steam, and at intervals the passages may thus be
kept clear, if necessary, without interrupting the process. A grating is placed at
both ends of these syphons.
For the agglomeration of the mixture of oxide and chloride of magnesium by
heat, and a solution of ammonic chloride, or spray of hot water, and its passage to
powder again, I have found that a mixture of 100 parts of magnesium oxide
to 50 of ammonic chloride aud 25 of china-clay, adamant, or pau-scale give good
results, and the change of the mixture, after the ammonia is evolved, from the
state of powder to lumps and fragments by moisture and stirring, and again,
the passage from this coherent, and granular condition, after the elimination of the
hydrochloric acid, to the powdery, and incoherent state, when the ammonic
chloride in powder is stirred into it, is well accomplished, by using the above
proportions, and with little or no volatilization of the ammonic chloride.
Adamant is known in the building trade. It is a durable acid resisting cement,
and will stand a high temperature. Pan-scale is the incrustation formed on the
bottom of salt pans, during the evaporation of brine and consists chiefly of a
mixture of the sulphates of calcium, and of magnesium and sodium.
About two-thirds of the ammonic chloride is added at first in powder, and after,
one-third in solution, for agglomerating the mixture. The water used being chiefly
evolved as hydrochloric acid afterwards.
Starting from the granular, and fragmentary condition after the hydrochloric
acid has been evolved, the process would be as follows, for using the ammonic
chloride in powder, and after a solution of ammonic chloride for agglomerating

page_text: the mixture. To reduce the temperature of the fragments from about 550° C., at
which the hydrochloric acid is completely evolved, to about 200° C. This is
done by passing cold air through the fragments, through the jets J, J. This air
heated up in its passage, is used in the continuous process below mentioned, mixed
with dry and heated hydrochloric acid gas for the production of chlorine, or for
heating up the fragments of oxide and chloride in other retorts, for the production
of hydrochloric acid after agglomerating them, as mentioned above.
The temperature being thus reduced to 200° C. the ammonic chloride in powder
is let into the retort, through the hopper H, and the stirrer set in motion. The
fragments and lumps are easily reduced to powder, and mixed with the powdered
ammonic chloride. The stirring is continued till nearly all the animonia is
evolved in order to bring the mixture in contact with the hot sides of the retort and
to facilitate the passage of the gas to the exit at the bottom of the retort. When
the ammonia is nearly evolved the temperature will have reached about 200° C.
A spray of hot water, or preferably, one of a solution of ammonic chloride is
now let into the retort, from the jets, J, J, and the stirring being continued, the
mixture passes from the pasty condition, into the state of grains fragments, or
lumps, and the ammonia is given off, and completely driven out by a current of
cold air, the temperature being below 160° C. at which magnesic chloride gives off
hydrochloric acid. When this is accomplished, and the mass is made permeable
to the steam, or air-which is seen by its appearance at the exit-the stirring is
stopped. The temperature will now be about 150° C. The heated air mentioned
above, is now passed through the fragments, and hydrochloric acid, steam, and
air are given off, which might be used for the production of chlorine as mentioned.
Superheated steam may be passed into the retort instead of the heated air, and
the hydrochloric acid evolved, utilized as desired, or a mixture of superheated
steam, and heated air may be used, and the gases evolved used for the continuous
production of chlorine, as hereafter described. When the hydrochloric acid is
fully evolved, the temperature will be about 550° C. and the round of operations
may be recommenced.
The first portions of the ammonia pass away by a pipe at the top of the
apparatus, when the solution of ammonium chloride is added, and the bottom exit
being closed by a valve, v.
When the mixture has assumed the form of fragments on stirring, this passage is
closed, and the remaining portion of the ammonia passes out in a downward course,
at the bottom exit.
The above jets, J, J, in Figure 1, may be replaced by dead plates, overlapping
each other, like a Venetian blind.
The agglomeration of the mixture, and the evolution of the hydrochloric acid,
may be carried out in a second retort, or cylinder.
For this purpose, cylinders may be furnished with a due arrangement of grids
and manholes, for charging, and discharging the material, as shown in cylinder, B.
Figure 1, K, being the discharging exit.
The stirrers, S, S, also may have other forms than those shown in Figures 1, and 2.
Their arms may be made on the principle of the ploughshare, and thus not only
cut the solidifying mass, but also turn it over at the same time, when both the
operations for the ammonia, and hydrochloric acid are carried out in one, and
the same retort.
In the next place I have found considerable difficulty in obtaining chlorine from
ammonic chloride of sufficient strength for the ready manufacture of good bleach,
from its being very considerably diluted with oxygen and nitrogen, from the
method adopted and although dilute chlorine of this kind can be utilized in a
Deacon bleach chamber, yet a much stronger chlorine is much to be desired, for
the production of strong bleach in ordinary chambers. This difficulty is overcome
as follows, and about one-third of the available chlorine, obtained in the first
instance, strong and pure, for this or other purposes.
The hot, gaseous hydrochloric acid evolved as above described, or that obtained

page_text: from any other process or source, whether from ammonic chloride, or not, is first
dried by passing it through strong sulphuric acid and then through a Cowper, or
similar stove, heated up to the required temperature, and then passed over or
through metallic peroxides or their mixtures. The hydrochloric acid may be
passed directly over or through the peroxides, without this preliminary drying and
heating up, and the washing and drying performed the usual way, before the
chlorine is admitted to the bleach chamber.
By peroxides, I mean any oxide containing more oxygen than the monoxide,
as, M, MO, M₂O, MO, &c. where M is any metal, capable of uniting with
oxygen, or, which oxide liberates oxygen on the addition of an acid. "Such
peroxides are alone effectual in giving strong chlorine from gaseous hydrochloric
acid in this process.
The chief peroxides available for this purpose, are those of manganese, bismuth,
lead, cobalt, tin and iron &c. which would exist chiefly as sesquioxides in this
process, or as manganites.
The oxides formed from the passage of air or steam over the chlorides of these
metals, act as sesquioxides (M₂O) do, in liberating chlorine from hydrochloric
acid, and also in their action on ammonic chloride, as shewn in my previous
Patents.
Mixtures of peroxides may be used. A very good mixture being equivalent
quantities of peroxide of manganese, cobalt, and lead. I prefer the peroxide
(MnO3) of manganese above all others, when made into marbles as described
hereafter. This peroxide forms maganites also, with most of the other oxides,
and thus gives a larger yield of strong chlorine.
The peroxides may be used in powder and stirred at times, or they may be
suspended in powder, in fused chloride of zinc, or other fused element, or
compound, and then the hot and dry hydrochloric acid may be blown through the
fused salt containing the peroxide, or passed over the peroxide, when used in
powder.
The well known Deacon process is preferred, however and these peroxides or
their mixtures are made into balls or bricks, by methods that are well known, and
the hot, gaseous hydrochloric acid passed through these piled in a suitable
furnace. Furnaces on the Deacon type, or those similar in principle, and
construction, are preferred. The peroxides or their mixtures, are bound together,
and made into marbles balls, &c., by using about equal weights of the peroxides
and pan-scale in powder, adamant in powder, or china-clay in powder, and making
this into a thick paste, and then into marbles or balls, by any of the machines in
use for this purpose, and afterwards drying. All these binding materials give hard
and durable marbles.
In either case, about one-third of the chlorine in the hydrochloric acid used, is
given off at first from the peroxides, pure, and undiluted, or nearly so. Most of the
peroxides when mixed with other oxides and converted into chlorides by
hydrochloric acid, and then have their chlorides reduced by oxygen, or air and
steam, become, as above mentioned sesquioxides, (M,Os), or manganites, and from
these of this composition, the chlorine will be chiefly evolved in this process,
I have found on a small working scale that the chlorine can be obtained free
from hydrochloric acid, if the latter be carefully and slowly passed or if the gases
from the first chamber be passed into a second containing the peroxides. Pure
and undiluted chlorine to the extent of about one-third that contained in the
hydrochloric acid used, is thus obtained, which may be passed at once into a bleach
chamber, or otherwise used.
The small amount of hydrochloric acid, and steam in quantity, would be removed

page_text: from the chlorine, if necessary, on the manufacturing scale, by the usual means, or
by continuing the gases through other cylinders.
When the power of the marbles to absorb hydrochloric acid is nearly spent, the
gas is diverted into another series, or batches of similar cylinders.
The remaining two-thirds of the chlorine, from the chlorides of the metals thus
formed, is obtained by passing over or through them dry and hot air or oxygen.
I may, however, obtain the remaining two-thirds of the chlorine in the marbles
as gaseous hydrochloric acid, by passing steam superheated, instead of air, through
the cylinders, and from the hydrochloric acid evolved, obtain strong chlorine, by
passing the hydrochloric acid through the peroxide marbles, in a second, and similar
cylinder. The advantage of this would be to obtain all the chlorine strong, and
undiluted with air, and at the same time to work the cylinders for the two operations,
at about the same temperature, and with a considerable saving in fuel, and wear
and tear of plant.
1 thus pass first of all over the marbles in the cylinders, strong and dry
gaseous hydrochloric acid, and obtain strong chlorine, then steam superheated, and
obtain hydrochloric acid mixed with steam, from the chlorides formed, and from
this hydrochloric acid I again obtain strong chlorine as at first.
About one-third of the total chlorine in the chlorides formed, is thus removed
each time, as strong chlorine, from the hydrochloric acid got by passing steam, and
after repeating this operation three times, the residual chlorine in the marbles may
be removed by air, or neglected, as about four-fifths of the total chlorine in the
hydrochloric acid used, will have been obtained strong, and two volumes of steam
at the lower temperature, will have done as much as about ten volumes of air, in
liberating chlorine at the higher temperature.
Drying in strong sulphuric acid, and heating up again in a Cowper stove before
each operation may be followed, and the Cowper, or other well known stove used
for heating the steam, or air, may be employed for heating, when necessary, the
hydrochloric acid.
I prefer, however, to have three stoves, one each for heating the air, steam, and
hydrochloric acid, which could then be kept at their proper and uniform temperature,
for these operations.
The strong chlorine thus produced, may be used towards the end of the process,
for bleach making, and when air is used for its evolution from the chlorides, the
weaker chlorine at the beginning, as is well understood by chemists, or the two kinds
may be mixed as evolved, by using a series of such retorts, having a common
chlorine conduit, and then passed together into the bleach chamber, or otherwise used.
The two processes may however be carried on at once, or simultaneously, by
passing hydrochloric acid gas and air together, over the peroxides; but here the
difficulty is increased in removing hydrochloric acid from the chlorine evolved,
unless special precautions are taken.
The complete decomposition of the hydrochloric acid gas, and the freedom of the
chlorine formed from this gas depends:
(1st) On the temperature used in its decomposition. If the gas be heated
strongly in a Cowper, or other stove, to a temperature of about (550° C.),
and the marbles be raised to this temperature, I have found that the chlorine
is practically free from hydrochloric acid, the latter being completely
decomposed, when the following precautions are observed also.
(2nd) The rate at which the hot hydrochloric acid gas is passed through the
marbles, and the quantity of gas should be in proportion to the size of
retort, or mass of peroxides.
(3rd) The absolute dryness of the marbles, and the dryness of the hydrochloric
acid, and air, by passing them through strong sulphuric acid, and then heating
them up to 500° C. or 550° C., in a Cowper stove.
This being observed, a continuous current of strong chlorine is obtained free, or
nearly so, from hydrochloric acid.
Before the admission of the hydrochloric acid gas, the marbles in the cylinders

page_text: are dried, by passing through them hot and dry air of a temperature of about
550° C.
There are thus several methods by which I may obtain strong chlorine from the
gaseous hydrochloric acid, and metallic peroxides, and fit to be used at once for
bleach making.
(1st.) I may obtain it by the alternative process, of first passing dry hydrochloric
acid gas through the peroxide marbles, and when their power to absorb and evolve
chlorine is nearly spent, diverting the gaseous hydrochloric acid current into
another cylinder, or batches of cylinders, and then passing dry and heated air
through the marbles.
About one-third of the total chlorine is thus at first, obtained, strong, but mixed
with much steam, and some hydrochloric acid.
If the temperature be maintained at about 550° C., and the dried hydrochloric
acid gas be carefully passed, the chlorine on leaving the bottom of the cylinders,
is practically free from hydrochloric acid, and, after drying in sulphuric acid, may
be passed at once into a bleach chamber, or mixed with dilute chlorine afterwards
obtained.
The
I now pass through the cylinders again, dry hydrochloric acid gas.
hydrochloric acid brings away with it, steam and moisture from the marbles, and I
again dry it in strong sulphuric acid, and send it into a cylinder ready for the
production of chlorine from hydrochloric acid. Dry and hot air is now admitted
into the cylinders, and diluted chlorine is given off, containing from 15, to 20 per cent.
of chlorine, mixed with air, and if the drying of the marbles and the air have been
carefully done, it will be free from hydrochloric acid, and may be passed into the
common chlorine conduit, and mixed with the strong chlorine obtained at first; and
the, round of operations recommenced.
(2.) As a continuous process for the production of chlorine, I may carry on the
above two reactions simultaneously, by passing a mixture of air and hydrochloric
acid, in proper proportions;, through the marbles in the cylinders.
The gaseous mixture should be first dried in strong sulphuric acid, and then
passed through a Cowper stove, and then heated to a temperature of about
500° C.-550° C.; and if the drying, has been carefully done, the gases on leaving
the bottoms of the cylinders, are for practical purposes, free from hydrochloric acid,
and after cooling and drying, may be passed into a bleach chamber, or otherwise
used.
(3.) In place of heated air as an alternative process, I may use superheated steam,
as above mentioned, and obtain all the available chlorine strong.
(4.) As a continuous process also, which may be used with more or less advantage,
for producing chlorine from hydrochloric acid gas, the latter mixed with superheated
steam, may be passed together through the marbles in the cylinders, in about
equivalent quantities.
The issuing gases may be separated by the usual means, or otherwise, treated in
other cylinders.
(5.) I may also use with more or less advantage mixtures of hydrochloric acid
gas, steam superheated, and heated air, or, oxygen in proper proportions
(a) simultaneously and continuously, or
(b) alternately.
First, using hydrochloric acid alone, and then superheated steam, mixed with hot
and dry air, as before mentioned.
The hydrochloric acid and steam are removed from the chlorine by the usual
means, or by those above mentioned.
The gases however, produced in these last processes {4 and 5 (a) and (b)} are
best, sent through a series of cylinders containing the peroxides, and joined together
on the principle of the Hargreave cylinders, the chlorine in its passage through the
cylinders, may then be practically freed from hydrochloric acid, and used at once
after cooling and drying, for the production of bleach.
I will now describe the apparatus which experience has shewn to be best suited
B

page_text: JUL
His purpose, with reference to the "accompanying drawings. The figures are
not drawn to scale. They are of such proportion and simplicity, as best to shew
principles.
I do not confine myself to details illustrated, as it is evident these may be
varied.
The following are the chief features of the apparatus:-Figure 4 is referred to.
(1st.) A heated chamber of brick, divided into compartments A, and B, containing
cylinders of iron, enamelled, or lined with tiles, or any other acid resisting coating.
(2nd.) Each cylinder has openings with covers at the top, for supplying the
marbles, or removing the same.
(3rd.) Each cylinder has an outlet pipe, or false bottom, b, b, for the chlorine,
which is joined to a common conduit c, c, for the chlorine, and in which the weak
and strong chlorine become mixed.
(4th.) Each cylinder has one or two man-holes for removing material, and the
'heated chamber, several iron plates, as doors for entrance.
(5th.) The valves I prefer to be globular, working on globular valve seatings,
and actuated, and controlled by spindles, having screws, or levers.
(6th.) Each cylinder has also, three inlet pipes, one each for the hydrochloric
acid, air, and steam.
The operation is as follows:-
-
When the peroxides or their mixtures with other oxides & salts are made into
marbles as described, and piled in a Deacon, or similar furnace.
Reference is made to Figure 4 which is a vertical section of the entire apparatus,
Figure 3, a plan.
The peroxides in marbles are placed inside the cylinders A, B, which are heated
by gases, which circulate around them from the fire F, through flues, LL
These cylinders stand on a grating, or have a perforated bottom bb, through which
the gases pass to the conduit, c. Gaseous hydrochloric acid is admitted through C,
to the cylinders, and steam through S, while v, n, are conduits also, for the admission
of air when required.
In commencing work, hot and dry hydrochloric acid is admitted through C, and
the plug P is open, and p, is shut. A current of strong chlorine is evolved from A,
and passes through C, to be utilized as required.
When the power of the marbles in A to absorb chlorine is nearly spent, the
hydrochloric acid current is diverted into another cylinder, or batch of cylinders,
and plug, p, opened.
A current of superheated steam is now passed through S, into A, and the
hydrochloric acid dried and then passed through a Cowper stove to be heated up,
when it is passed into B, where about one-third of its chlorine is evolved strong and
pure.
While cylinder A is exposed to a current of hot, dry air to convert its monoxide
(MO), completely into peroxide (M₂O,), and superheated steam is sent through
cylinder B, through steam-pipe S', when the fixed hydrochloric acid is again evolved
dried, and heated up as before, to about 550° C., and passing into A, gives strong
chlorine as before.
The remaining chlorine now in A, as chloride may be got by air through the
plug V, or neglected, as about four-fifths of the original chlorine in the hydrochloric
acid, has thus been got, strong and pure, and the round of operations may be
recommenced by passing hot air through A, to completely convert the monoxide into
peroxide (M,Os), and then sending through the cylinder, hot and dry hydrochloric
acid as at first.
Instead of using superheated steam as above mentioned, hot and dry air may be
used, and passed through plugs e, i, into the marbles, and both cylinders, or series
of cylinders may be used at once for this purpose, when this alternative process is
followed.
:
2
Dilute chlorine containing from 15 to 20 per cent. mixed with (0+N) will
appear at r, e, which may be mixed with the strong chlorine, or otherwise treated.

page_text: When the continuous process of producing chlorine is followed, a mixture in
proper proportions of hot and dry air, and hydrochloric acid gas, is passed
through C, from the ammonia retorts, before mentioned, or elsewhere, into both
cylinders, or series of such, at once, the plugs 1', and, p, being opened, when a
continuous current, containing about 40 per cent. chlorine or more mixed with
(0+ N) will appear at the bottom of the cylinders, and if the necessary precautions
of drying the gases have been observed, it may be used after cooling at once, for
the production of strong bleach.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
1. The combined process for the improvement in the manufacture and production
of ammonia chlorine, and hydrochloric acid, from ammonium chloride, and of
chlorine from its hydrochloric acid, which consists in mixing with powdered
magnesia, or some other powdered monoxide, some substance in powder to prevent
fusion and cohesion, such as described, then mixing with these ammonium chloride
in powder and heating the mixture at a low temperature in a suitable retort, till all
the ammonia is evolved, then raising the temperature, and utilizing the moisture
present for the elimination of part of the hydrochloric acid from the chloride of
magnesium formed, using the steam and hydrochloric acid thus evolved as described;
then stirring or not, and passing superheated steam through the retort, to complete
the reduction of the chloride, and using the hydrochloric acid thus evolved by
passing it hot and dry into a heated chamber or retort, such as described, containing
peroxides or their mixtures, made into marbles, balls, &c., and piled in the chamber;
removing the excess of hydrochloric acid from the chlorine evolved, by passing the
gases through a second, and similar chamber, or series of chambers, or by the usual
means of washing; drying the strong chlorine thus obtained, and using it alone for
the production of bleach, or mixed with that obtained afterwards, by passing hot
and dry air over the chlorides formed, or with that got by the other processes
described, and then beginning the round of operations anew.
2. The combined process for the improvement in the manufacture and production
of ammonia, hydrochloric acid, and chlorine, from ammonic chloride, which consists
in agglomerating, into lumps, or fragments, the mixture of oxide, and chloride, after
the ammonia has been evolved, by a spray of hot water, or by one of a solution of
ammonic chloride, and stirring; distilling off first, the residual ammonia, when a
solution of ammonic chloride is used; and after, from the moisture present, obtaining
a mixture of hydrochloric acid and steam, by heat, using this mixture as described,
and then passing through the fragments, superheated steam, and passing the
hydrochloric acid evolved, into the peroxide pills or marbles, in another cylinder,
for the production of strong chlorine, as described, and the change of the fragments
of oxide formed, to the state of powder again by stirring, and beginning the
round of operations anow.
3. The improvement in the process for obtaining hydrochloric acid from
ammonium chloride, which consists in utilizing the moisture present from the
5 decomposition of the ammonium chloride, together with that added for the
agglomeration of the mixture, for the elimination of a part of the hydrochloric
acid from the chloride, and using the mixture of steam and hydrochloric acid thus
evolved, as described.
4. In the manufacture of chlorine from ammonic chloride, the initial process for
the continuous production of chlorine, which consists in passing through the
ammonia retorts after the ammonia has been evolved, a mixture in proper pro-
portions, of superheated steam, and dry air, heated to the required temperature,
and passing the issuing gases through the peroxide marbles in the cylinders, and
further completing the round of operations as described.
5 5. In the manufacture of aminonia hydrochloric acid, and chlorine, from
ammonium chloride, the use of the apparatus herein described.

page_text: 6. The process for the manufacture and production of chlorine, from hydro-
chloric acid, by passing gaseous hydrochloric acid over or through peroxides or
their mixtures, or peroxides mixed with other oxides and salts, and made into
marbles, balls, &c., and piled in a suitable chamber, heated to a dull redness,
removing the excess of hydrochloric acid, and steam, by passing the mixed gases
through strong sulphuric acid, and then heating them up in a Cowper stove, and
passing them into a second chamber or removing the hydrochloric acid by the
usual means of washing; drying the strong chlorine thus obtained, and using it for
the production of bleaching powder, or mixing it with the weaker chlorine got by
passing hot and dry air over the residual chlorides formed, and reproducing the
original peroxides, or sesquioxides, or manganites.
7. The alternative process for the production of chlorine from ammonium
chloride, by passing over or through the chlorides formed from the peroxides, by
the decomposition of the hydrochloric acid gas, heated and dry air, and repro-
duction of the original peroxides, or sesquioxides, or, manganites, as described.
8. The continuous process for the production of strong chlorine, by passing over
or through the chlorides formed from the peroxides, by the decomposition of the
hydrochloric acid gas, superheated steam, using the hydrochloric acid thus evolved,
in another retort containing peroxides, for the production of strong chlorine,
removing the hydrochloric acid thus fixed again as chloride, by superheated steam,
and again passing the hydrochloric acid evolved, into a retort through the
peroxides, and continuing this process; thus obtaining nearly all the available
chlorine in the hydrochloric acid, strong, and oxidizing the lower oxide formed, to
peroxide, or sesquioxide again, and beginning the round of operations with a fresh
charge of hydrochloric acid gas.
9. The process for the continuous production of chlorine from ammonium
chloride by the simultaneous action of a mixture of dry and heated hydrochloric
acid gas, and heated and dry air on the peroxides, or their mixtures with other
oxides & salts dried and heated to a dull red heat, with reproduction of sesqui-
oxides, or manganites.
10. In the manufacture of chlorine from hydrochloric acid gas, the use of the
combined apparatus, and parts of the same as described and illustrated.
11. In the manufacture of chlorine from ammonium chloride, the use of
peroxides or their mixtures with other oxides and salts for the decomposition of
the hydrochloric acid gas evolved, as herein described.
12. The continuous and alternative processes for producing chlorine from hydro-
chloric acid gas, air, and superheated steam, by passing in about equivalent
quantities over the peroxide pills in the cylinders
(1.) A mixture of hydrochloric acid gas, superheated steam, and hot air, or
(2.) Hydrochloric acid gas alone; and afterwards over the chlorides formed,
a mixture of superheated steam, and hot and dry air.
Dated this 18th day of May 1893.
FRED. BALE: