Improvements in the Manufacture or Production of Chlorine Compounds for Bleaching.
Year: 1891

page_text: Date of Application, 2nd June, 1891
Complete Specification Left, 2nd Mar., 1892-Accepted, 2nd Apr., 1892
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture or Production of Chlorine
Compounds for Bleaching.
I, Comte THOMAS DE DIENHEIM-BROCHOCKI of Rue de Cerisoles, Paris in
the Republic of France, do hereby declare the nature of this invention to be as
follows:-
The superiority of chlorozone over ordinary alkaline hypochlorites arises
from the fact that the former is the result of the combination of the alkaline base
with chlorine mixed with a certain proportion of hypochlorous acid while the latter
consist of the combination of the same base with chlorine alone.
The presence of hypochlorous or chlorous acid in the chlorine evidently changes
the molecular state of the gaseous mixture and consequently gives to the product
which it forms with the alkaline base different physical and chemical properties
from those which generally characterise the common hypochlorite.
Chlorozone notably possesses more active chlorine than real chlorine and only
contains a very slight excess of alkaline base. The common hypochlorite, on the
contrary, possesses more real chlorine than active chlorine and has a considerable
excess of alkaline base.
Owing to its composition, chlorozone furnishes to the bleaching industry a
decolourizing power much greater than does the common hypochlorite and when
used for bleaching it is not injurious to vegetable textile materials.
According to the process described in the Specification of Letters Patent No. 2349
of 1878 granted to Alexander Melville Clark as a communication from me
chlorozone is the product of the saturation of a caustic alkaline solution by
chlorinated gas, derived from chloride of lime by means of a suitable acid.
Now, chloride of lime serving thus as a raw material is itself a manufactured
product destined like chlorozone for the bleaching industry. Its price is relatively
high and this naturally influences the cost price of chlorozone.
According to my present invention and by a process hereinafter described
chlorozone is manufactured directly by gaseous chlorine taken from any source of
production without the necessity of employing chloride of lime and thus the cost
price of chlorozone can be very much reduced. In order to arrive at this result it.
is evidently necessary to modify this chlorine which, as produced by the ordinary
industrial processes, is neither pure nor cold enough and is not oxidised like that
produced by the decomposition of chloride of lime.
The new process is as follows:-
From a main pipe or passage the crude, but suitably cooled gaseous chlorine is
conveyed into a closed vessel containing water, or preferably a solution of a neutral
salt such as the chloride of calcium or of sodium or the like.
A current of air
also enters the said vessel both the chlorine and air being led to beneath the liquid
therein. If the chlorine be obtained from the Deacon process or be already mixed
with a large quantity of air the special provision for the admission of air is not.
needed.
The gaseous mixture bubbles through the liquid in the said vessel and is thus
freed from any acid vapours which it may contain and passes into a second closed
vessel containing fragments of coke or other material presenting a large surface
and moistened with concentrated sulphuric acid. In this vessel the mixture is
efficiently dried and passes into a closed vessel provided with electrodes in connection
with a generator of electricity so that a continuous discharge of eléctric sparks is
produced in the said vessel during the passage of the gaseous mixture and these
discharges effect the association of the ozone with the chlorine that is the oxidation

page_text: of the chlorine and the formation of hypochlorous or chlorous acid. It is not
necessary that the whole of the chlorine be transformed into hypochlorous acid the
smallest quantity sufficing to completely modify the whole of the gaseous mixture
in its molecular composition.
The chlorine thus modified, then passes into a fourth closed vessel containing
the concentrated solution of a caustic alkali into which the modified chlorine may
be caused to pass not only by its own pressure but also by means of suction which
draws at the same time the air through the preceding vessels. In proportion to the
combination of the chlorinated gas with the alkaline base the chlorozone is formed
in the said fourth vessel. In order to render it possible to work on a large scale
on very concentrated alkaline solutions and to attain the maximum saturation of the
base and also in order to give sufficient stability to the final product, the contents
of the said fourth vessel should be continuously cooled and the reaction taking
place should be successively presented to different parts of the same liquid.
The following arrangement has given excellent results:-
The liquid from the said fourth vessel passes through a worm or extended
passage in a cooling tank and discharges itself therefrom into a tank or tanks which
are preferably duplicate tanks so that either can be used as desired. From this
tank or these tanks the cooled liquid is taken by the pump to be again introduced
into the said fourth vessel.
In this manner a regular cycle is established between the said fourth vessel and
the said tank or tanks the liquid continuously circulating until it is completely
saturated.
If duplicate tanks be used when it is found that the product in one tank has
attained the desired chlorometric degree, the cock thereof is shut and the cock of
the other tank is opened so as to isolate the finished product of the first tank and
to continue the work with the contents of the second tank.
In this manner large quantities of chlorozone are produced at a minimum cost
and within a very small space.
Dated the 2nd day of June 1891.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, Agents.
COMPLETE SPECIFICATION.
Improvements in the Manufacture or Production of Chlorine
Compounds for Bleaching.
I, Comte THOMAS DE DIENHEIM BROCHOCKI of 6 Rue de Cerisoles, Paris in
the Republic of France, do hereby declare the nature of my invention and in what
manner the same is to be performed to be particularly described and ascertained
in and by the following statement :——
The superiority of "chlorozone over ordinary alkaline hypochlorites arises
from the fact that the former is the result of the combination of the alkaline base
with chlorine mixed with a certain proportion of hypochlorous acid while the latter
consist of the combination of the same base with chlorine alone.
The presence of hypochlorous or chlorous acid in the chlorine evidently changes
the molecular state of the gaseous mixture and consequently gives to the product
which it forms with the alkaline base physical and chemical properties different
from those which generally characterise the common hypochlorite.
Chlorozone notably possesses more active chlorine than real chlorine and only
contains a very slight excess of alkaline base. The common hypochlorite, on the
contrary possesses more real chlorine than active chlorine and has a considerable
excess of alkaline base.
Owing to its composition chlorozone furnishes to the bleaching industry a
decolourizing power much greater than does the common hypochlorite and when
used for bleaching, it is not injurious to vegetable textile materials.

page_text: According to the process described in the Specification of Letters Patent No. 2349
of 1878 granted to Alexander Melville Clark as a communication from me,
chlorozone is the product of the saturation of a caustic alkaline solution by
chlorinated gas, derived from chloride of lime by means of a suitable acid.
Now, chloride of lime serving thus as a raw material is itself a manufactured
product destined like chlorozone for the bleaching industry. Its price is relatively
high and this naturally influences the cost price of chlorozone.
According to my present invention and by a process hereinafter described
chlorozone is manufactured directly by gaseous chlorine taken from any source of
production without the necessity of employing chloride of lime and thus the cost
price of chlorozone can be very much reduced. In order to arrive at this result it
is evidently necessary to modify this chlorine which, as produced by the ordinary
industrial processes, is neither pure nor cold enough and is not oxidised like that
produced by the decomposition of chloride of lime.
The new process is as follows:-Crude or suitably cooled gaseous chlorine (with
air added if necessary that is if it be not already present with the chlorine) is
introduced into water or into a solution of a neutral salt and passes therethrough
so as to become freed from any acid vapours which it may contain and then is
treated with an agent for removing moisture. It is then subjected to the action of
electricity to effect the association of chlorine and ozone and the formation of
hypochlorous or chlorous acid. The gas is then passed through a concentrated
solution of caustic alkali cooling being effected all as hereinafter more particularly
described.
I will now more particularly describe my invention reference being made to the
accompanying diagram premising however that I do not limit myself to the
construction of apparatus which I have shewn.
A B C and D represent closed tanks or vessels and EF and F open tanks or
vessels.
From a main pipe or passage the crude but suitably cooled gaseous chlorine is
conveyed by the tube a into the closed vessel A containing water, or preferably
a solution of a neutral salt such as the chloride of calcium or of sodium or the like.
A current of air enters the said vessel A by the pipe both the chlorine and air
being led to beneath the liquid therein. If the chlorine be obtained from the
Deacon process or be already mixed with a large quantity of air the special
provision for the admission of air is not needed.
The gaseous mixture bubbles through the liquid in the said vessel A and is thus
freed from any acid vapours which it may contain and passes by the pipe c into the
second closed vessel B containing fragments of coke or other material presenting
a large surface and moistened with concentrated sulphuric acid. In this vessel the
mixture is efficiently dried and passes therefrom by the pipe d into the closed
vessel C provided with electrodes e in connection with a generator of electricity
so that a continuous discharge of electric sparks is produced in the said vessel
during the passage of the gaseous mixture and these discharges effect the association
of the ozone with the chlorine, that is the oxidation of the chlorine and the formation
of hypochlorous or chlorous acid. It is not necessary that the whole of the chlorine
be transformed into hypochlorous acid the smallest quantity sufficing to completely
modify the whole of the gaseous mixture in its molecular composition.
The chlorine thus modified, then passes by the pipe e into the closed vessel D
containing a concentrated solution of a caustic alkali into which the modified
chlorine may be caused to pass not only by its own pressure but also by means of
suction which may be created through a tube p in connection with an aspirator
which draws at the same time the air through the preceding vessels. In proportion
to the combination of the chlorinated gas with the alkaline base the chlorozone is
formed in the said vessel D. In order to render it possible to work on a large
scale on very concentrated alkaline solutions, and to attain the maximum saturation
of the base, and also in order to give sufficient stability to the final product, the
contents of the said vessel D should be continuously cooled and the reaction taking

page_text: place should be successively presented to different parts of the same liquid: The
following arrangement has given excellent results.
The liquid passes from the said vessel D, by the pipe through a"worin or
extended passage in a cooling tank E and is discharged therefrom into a tank or
tanks FF (preferably duplicate tanks so that either can be used as desired).
From this tank or these tanks the cooled liquid is taken by the pump / and tubes /2
to be again introduced into the said vessel D.
In this manner a regular cycle is established between the said vessel D and the
said tank or tanks (FF) the liquid continuously circulating until it is completely
saturated.
If duplicate tanks be used when it is found that the product in one tank has
attained the desired chlorometric degree, the cocks leading thereto and therefrom
are shut and the cocks of the other tank are opened so as to isolate the finished
product of the first tank and to continue the work with the contents of the second
tank.
In this manner large quantities of chlorozone are produced at a minimum cost
and within a very small space.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed declare that what I
claim is
1. The manufacture of chlorine compounds for bleaching substantially as herein-
before described.
2. In the manufacture of chlorine compounds for bleaching the use of purified
and dried chlorine gas and air and an alkali and a cooling appliance substantially
as hereinbefore described.
3. As a new production or manufacture "chlorozone" produced as hereinbefore
described.
Dated this 2nd day of March 1892
J. H. JOHNSON & CO.,
47, Lincoln's Inn Fields, London, W.C., Agents.