Process for the Manufacture of Chlorine, which may be Employed in Combination either with the Ammonia-soda Process or with the Leblanc-soda Process.
Year: 1889

page_text: Date of Application, 27th May, 1889
Complete Specification Left, 20th Feb., 1890-Accepted, 19th Apr., 1890
Process for the Manufacture of Chlorine, which may be Employed
in Combination either with the Ammonia-soda Process or with
the Leblanc-soda Process.
I, JOSEPH JEAN ALSBERGE, of 14 Rue du Gouvernement, Ghent, in the Kingdom
of Belgium, Chemical Engineer, do hereby declare the nature of this invention to be
as follows:-
My process for the manufacture of chlorine, when combined with the ammonia-
soda process, has for its point of departure either the chlorides of calcium or of
magnesium which are obtained in the regeneration of the ammonia, or the chloride of
ammonium itself. In the latter case the mother liquors of the soda manufacture are
evaporated. As the evaporation of the chloride of ammonium will cause a liberation
of vapour of ammoniacal water there may be used, with advantage, apparatus with
triple effect, for example. A solid residue is thus obtained, containing chloride of
sodium and chloride of ammonium.
These two salts are introduced into suitable apparatus which are heated to about
300° C.
The sublimation of the chloride of ammonium alone is effected and the vapours
hereof are directed into powdered artificial binoxide of manganese, which is kept in
motion at a temperature of about 300° C.
The chlorine of the chloride of ammonium combines with the manganese, producing
chloride of manganese; the oxygen and the ammonia are disengaged, the latter being
returned to the manufacture of soda, together with the chloride of sodium which was
mixed with the chloride of ammonium before the sublimation. The chloride of
manganese thus produced is mixed with an excess of artificial binoxide of manganese
and with nitric acid. On gently heating this mixture the chlorine is disengaged and
there is obtained as residue, nitrate of manganese combined with binoxide of
manganese and nitric acid in excess. If the operations are properly conducted,
90 per cent., and more, of the chlorine gas contained in the chloride of manganese can
be regained. For preventing any loss of traces of nitric acid which might be carried
mechanically with the chlorine, it is advisable to cause the gas to pass into a washing
apparatus of suitable construction for retaining the nitric acid vapours. Apparatus
containing sulphuric acid, such as is used in the Dunlop process is suitable for the
purpose.
The regeneration of the nitric acid and the binoxide of manganese which constitutes
the last stage of the process is very readily produced.
At 150° C. already the nitrate of manganese is entirely decomposed into artificial
binoxide of manganese and nitrous vapours (hyponitrous acid) which, in contact with
water and air become converted into nitric acid.
Instead of regenerating the nitric acid by calcining the metallic nitrates obtained,
the nitrous vapours mixed with aqueous vapour and air may be passed over a slightly
heated mixture of binoxide of manganese and chlorides. There are formed in this
case gaseous compounds of chlorine from which the latter may be easily disengaged.
The operation is continuous, as the chlorides are converted into nitrates which only
have to be heated to be again decomposed.
It is evident that my process also extends to all the other metallic chlorides, such as
chlorides of calcium and magnesium already mentioned, of which the corresponding
nitrates can serve for the regeneration of the nitric acid, and which can, in the
presence of the latter and of binoxide of manganese, give up the chlorine as in the
case of the chloride of manganese above described.

page_text: The separation of the metallic nitrates thus obtained is easily effected either by
heating, owing to the different temperatures at which they decompose, or by means of
any suitable known reactions. They may also be simultaneously calcined and the
oxides thus produced be then introduced into ammonia-regenerating apparatus.
In this case the binoxide of manganese remains unattacked and the energetic bases
alone decompose the chloride of ammonium.
It is more particularly by the use of the chloride of manganese that my process is
rendered applicable to the Leblanc-soda process. The chloride of manganese which
is obtained is evaporated to dryness and is then treated exactly as described. It is to
be observed that the artificial binoxide, being in the molecular condition, neutralizes
almost completely hydrochloric acid, which under these circumstances is the point of
departure of the cycle of operations.
It remains to be stated that in taking chloride of ammonium as the point of
departure in my process, and with the view of producing oxygen, there is obtained
one volume of this gas for every four volumes of chlorine.
Dated thich dose of 1000
ABEL & IMRAY,
Agents for the Applicant.
Process for the Manufacture of Chlorine, which may be Employed
in Combination either with the Ammonia-soda Process or with
the Leblanc-soda Process.
I, JOSEPH JEAN ALSBERGE, of 14 Rue du Gouvernement, Ghent, in the Kingdom
of Belgium, Chemical Engineer, 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 :-
My process for the manufacture of chlorine, when combined with the ammonia
soda process, has for its point of departure either the chlorides of calcium or of
magnesium which are obtained in the regeneration of the aminonia, or the chloride
of ammonium itself. In the latter case the mother liquors of the soda manufacture
are evaporated. As the evaporation of the chloride of ammonium will cause a
liberation of vapour of ammoniacal water there may be used, with advantage,
apparatus with triple effect, for example. A solid residue is thus obtained, con-
taining chloride of sodium and chloride of ammonium.
These two salts are introduced into suitable apparatus which are heated to about
300° Cent. The sublimation of the chloride of ammonium alone is effected and
the vapors hereof are directed into powdered artificial sesquioxyde of manganese,
which is kept in motion at a temperature of about 300° C.
The chlorine of the chloride of ammonium combines with the manganese producing
chloride of manganese: the oxygen and the ainmonia are disengaged, the latter
being returned to the manufacture of soda together with the chloride of sodium
which was mixed with the chloride of ammonium before the sublimation. The
chloride of manganese thus produced is mixed with an excess of artificial binoxide of
manganese and with nitric acid. On gently heating this mixture the chlorine is
disengaged and there is obtained as residue, nitrate of manganese combined with
binoxide of manganese and nitric acid in excess. If the operations are properly
conducted, 90 per cent., and more, of the chlorine gas contained in the chloride of
manganese can be regained. For preventing any loss of traces of nitric acid which
might be carried mechanically with the chlorine, it is advisable to cause the gas to
pass into a washing apparatus of suitable construction for retaining the nitric acid
vapours. Apparatus containing sulphuric acid, such as is used in the Dunlop process
is suitable for the purpose.
The regeneration of the nitric acid and the binoxide of manganese which constitutes
the last stage of the process, is very readily produced. At 160° C. already the nitrate

page_text: of manganese is entirely decomposed into artificial binoxide of manganese and nitrous
vapours (hyponitrous acid) which, in contact with water and air becomes converted
into nitric acid.
This regeneration may be very well effected in a series of tanks or in a tower.
The water or weak acid descends in this case upon materials which are not acted upon,
while the nitrous vapours mixed with air travel upwards. The last traces of nitrous
vapour can afterwards be absorbed in a Gay Lussac tower.
It is evident that my process also extends to all the other metallic chlorides, such
as chlorides of calcium and magnesium already mentioned, of which the corresponding
nitrates can serve for the regeneration of the nitric acid, and which can, in the presence
of the latter and of binoxide of manganese, give up the chlorine as in the case of the
chloride of manganese above described.
The separation of the metallic nitrates thus obtained is easily effected either by
heating owing to the different temperatures at which they decompose, or by means of
any suitable known reactions. They may also be simultaneously calcined and the
oxides thus produced be then introduced into ammonia regenerating apparatus. In
this case the binoxide of manganese remains unattacked, and the energetic bases alone
decompose the chloride of ammonium.
It is by the use of the chloride of manganese that my process is rendered applicable
to the Leblanc soda process. The chloride of manganese which is obtained in this
process is then treated exactly as described.
It is to be observed that, for the Leblanc process, recourse may be had directly to
hydrochloric acid, not dissolved, but in gaseous forin, as it comes from the sulphate
furnaces. This gaseous hydrochloric acid is simply introduced into nitric acid con-
taining artificial binoxide of manganese in suspension.
The chlorine is perfectly disengaged, as in the operations already described. The
entire installation consists of a few stills into which the gaseous acid is made to
bubble, and which contains nitric acid having binoxide of manganese in suspension.
Having now particularly described and ascertained the nature of my said Inven-
tion and in what manner the same is to be performed I declare that what I
claim is
1. Process for the manufacture of chlorine combined with the manufacture of soda
by the Leblanc process or by the ammonia soda process, such process consisting either
in the use of chloride of ammonium producing chloride of manganese, or in the use of
any chloride which, with artificial binoxide of manganese and nitric acid in excess,
will yield chlorine with formation of the corresponding nitrates, and with regeneration
of the nitric acid and the binoxide of manganese employed substantially as herein
described.
2. The method of replacing the chloride of manganese in the Leblanc process by
gaseous hydrochloric acid as it comes from the sulphate furnace, substantially as
herein described.