IMPROVE- MENTS IN THE UTILIZATION OF CHLORIDE OF MANGANESE (RESIDUE OF THE MANUFACTURE OF CHLORINE) IN THE MANUFACTURE OF PEROXIDE OF MANGANESE, CHLORINE, AND HYDROCHLORIC ACID, AND IN APPARATUS FOR THE SAME
Year: 1866

page_text: LETTERS PATENT to William Clark, of 53, Chancery Lane, in the County
of Middlesex, Engineer and Patent Agent, for the Invention of "IMPROVE-
MENTS IN THE UTILIZATION OF CHLORIDE OF MANGANESE (RESIDUE OF THE
MANUFACTURE OF CHLORINE) IN THE MANUFACTURE OF PEROXIDE OF MANGANESE,
CHLORINE, AND HYDROCHLORIC ACID, AND IN APPARATUS FOR THE SAME." -A
communication from abroad by Eugène Alphonse Cotelle, Distiller,
of 29, Boulevart St. Martin, Paris.
.
Sealed the 29th January 1867, and dated the 11th August 1866.
11th
PROVISIONAL SPECIFICATION left by the said, William Clark, at the
Office of the Commissioners of Patents, with his Petition, on the
: August 1866.
I, WILLIAM CLARK, of 53, Chancery. Lane, in the County of Middlesex,
Engineer and Patent Agent, do hereby declare the nature of the said Invention
for "IMPROVEMENTS IN THE UTILIZATION OF CHLORIDE OF MANGANESE (RESIDUE OF
THE MANUFACTURE OF CHLORINE) IN THE MANUFACTURE OF PEROXIDE OF MANGANESE,
CHLORINE, AND HYDROCHLORIC ACID, AND IN APPARATUS FOR THE SAME," to be as
follows:
The object of this Invention is the production of peroxide of manganese,
chlorine, and hydrochloric acid, from the chloride of manganese forming the
residue of the manufacture of chlorine.

page_text: The Invention is based on a known principle in chemistry, viz., that
metallic chlorides may be decomposed at a high temperature in the presence
of oxygen and form chlorine, which becomes disengaged, and also metallic oxide.
The dry chloride of manganese I have found by experiment to be readily
decomposable in the presence of air at a red heat. For this purpose I
employ an apparatus whereby I am enabled to utilize the chloride of
manganese, the residue of the manufacture of chlorine, and to obtain from it,
1st, hydrochloric acid in excess; 2ndly, peroxide of manganese; and 3rdly,
chlorine which may be transformed into bypochlorite of lime, soda, or potash.
The apparatus of this Invention consists, 1st, of a furnace similar to those
used in the manufacture of sulphate of soda, and in which I operate at a red
heat, and in the presence of air, the desiccation and decomposition of the
chloride of manganese ; 2ndly, of a series of chambers for condensing the water
and the hydrochloric acid; and, 3rdly, of an ordinary chamber containing
chloride of lime (hypochlorite) in which the chlorine liberated is absorbed.
A, large retort made of refractory bricks, similar to those used for sulphate of
soda; the sole of this retort is flat and slightly inclined from front to back,
each end being closed by a door of refractory bricks; a funnel mouthed tube
passes through the door at the front end for conveying the liquid chloride of
manganese into the retort, which is kept at a red heat heat continually; an
orifice is also left in this door for the introduction of air of about half the size
of the escape pipes. B, furnace for heating the retort. The products of com-
bustion after circulating round the retort pass away to the chimney through a
channel not shown in the Drawing. C, escape pipe of the gases in the retort,
communicating with a series of chambers, thirty in number, in which the
water and hydrochloric acid are condensed. D, chamber containing chloride
of lime in which the chlorine is absorbed. E, pipe for producing a draught
in communication with a chimney. F, channel under the furnace, in which is
placed the oxide of manganese after it is withdrawn from the retort. An
artificial current of air transforms the manganese into peroxide of manganese
by reason of the high temperature retained.
Action of the Apparatus.-When the retort A is at a red heat the chloride
of manganese is run in, when the water and hydrochloric acid become
volatilized and pass out into the chambers before mentioned, where they become
condensed; the heat and the flow should be regulated so as to always keep
the retort heated to redness. The chloride in proportion as it advances towards
the end of the furnace becomes first of a pasty consistency and then solid, being
decomposed by the current of air passing through the retort; the chloride

page_text: disengaged becomes cooled in the condensers and then absorbed in the chloride
of lime chamber, the oxide of manganese remaining on the sole of the retort;
when a sufficiently large quantity has been collected the door is opened at the
end of the retort, and by means of an iron rake the whole is caused to fall into
small carriages which are allowed to remain in the channel F the necessary
time for peroxidation.
According to a modification in the action of the apparatus instead of
introducing the chloride of manganese in a liquid form I use it in a solid or
partly dried state. In this manner the apparatus is made capable of a larger
production, the mass is more easily handled, there is less water to be condensed,
and it requires a much less number of condensing chambers. The desiccation
of the chloride of manganese is effected as follows:-The liquid chloride is
placed in a receptacle formed of bricks laid in mastic silicate of soda and
amianthus, under the crown of this receptacle passes the waste heat of a
decomposing furnace, the flame of which is thus brought in contact with the
liquid and so readily evaporates it, especially if stirred from time to time, any
noxious vapours disengaging may be conveyed into a receptacle filled with
chalk, by which they become absorbed. If the chloride be in the mass it is
preferable to place it in the decomposing furnace. In order to absorb the
carbonic acid and the moisture of the air entering into the apparatus, which
would impede the production of chloride, I place a small tube in front of the
air induction orifice filled with quicklime, which may be renewed when it has
lost its efficacy.
The claim is for the treatment of chloride of manganese for industrial
purposes in the manner described in order to obtain therefrom peroxide of
manganese, hydrochloric acid, and chlorine, as also for the arrangement of
apparatus described and represented, or any mere modification thereof.
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said William Clark in the Great Seal Patent Office on the
9th February 1867.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, WILLIAM
CLARK, of 58, Chancery Lane, in the County of Middlesex, Engineer and
Patent Agent, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Eleventh day of August, in the year of our Lord

page_text: One thousand eight hundred and sixty-six, in the thirtieth year of Her reign,
did, for Ierself, Her heirs and successors, give and grant unto me, the
said William Clark, Her special licence that I, the said William Clark, my
executors, administrators, and assigns, or such others as I, the said William
Clark, my executors, administrators, and assigns, should at any time agree
with, and no others, from time to time and at all times thereafter during
the term therein expressed, should and lawfully might make, use, exercise,
and vend, within the United Kingdom of Great Britain and Ireland, the
Channel Islands, and Isle of Man, an Invention for "IMPROVEMENTS IN THE
UTILIZATION OF CHLORIDE OF MANGANESE (RESIDUE OF THE MANUFACTURE OF
CHLORINE) IN THE MANUFACTURE OF PEROXIDE OF MANGANESE, CHLORINE, AND
HYDROCHLORIC ACID, AND IN APPARATUS FOR THE SAME," a communication to me
from abroad by Eugène Alphonse Cotelle, Distiller, of 29, Boulevart St. Martin,
Paris, upon the condition (amongst others) that I, the said William Clark,
my executors or administrators, by an instrument in writing under my, or
their, or one of their hands and seals, should particularly describe and ascer-
tain the nature of the said Invention, and in what manner the same was
to be performed; and cause the same to be filed in the Great Seal Patent
Office within six cal_dar months next and immediately after the date of the
said Letters Patent.
NOW KNOW YE, that I, the said William Clark, do hereby declare the
nature of the said Invention, and in what manner the same is to be performed,
to be particularly described and ascertained in and by the following statement,
reference being had to the Sheet of Drawings hereunto annexed, and to the
letters and figures marked thereon (that is to say):
:-
The object of this Invention is the production of peroxide of manganese,
chlorine, and hydrochloric acid, from the chloride of manganese forming the
residue of the manufacture of chlorine.
The Invention is based on a known principle in chemistry, viz., that metallic
chlorides may be decomposed at a high temperature in the presence of oxygen
forming chlorine, which becomes disengaged, and metallic oxide. The dry
chloride of manganese I have found by experiment to be readily decomposable
at a red heat in the presence of air. For this purpose I employ an apparatus
whereby I am enabled to utilize the chloride of manganese, forming the residue
of the manufacture of chlorine, and obtain from it, 1st, bydrochloric acid in
excess; 2ndly, peroxide of manganese; and, 3rdly, chlorine, which may be
tiansformed into hypochlorite of lime, soda, or potash.
.

page_text: The apparatus of this Invention consists, 1st, of a furnace similiar to those
used in the manufacture of sulphate of soda, and in which I effect at a red
heat and in the presence of air the desiccation and decomposition of the chloride
of manganese; 2ndly, of a series of chambers for condensing the water and
the bydrochloric acid; and, 3rdly, of a chamber containing chloride of lime
(hypochlorite) in which the chlorine is absorbed as in ordinary.
A, large retort made of refractory bricks, similar to those used for sulphate of
soda; the sole of this retort is flat and slightly inclined from front to back, each
end having an opening closed by a door of refractory clay; a funnel-mouthed
tube passes through the door at the front end for conveying the liquid chloride
of manganese into the retort, which is kept at a red heat continually; an
orifice is also left in this door for the introduction of air, it is of about half the
size of the escape pipes. B, furnace for heating the retort. The products of
combustion after circulating round the retort pass away to the chimney through
a channel not shown in the Drawing. C, escape pipe of the gases from the
retort, communicating with a series of chambers, thirty in number, in which
the water and hydrochloric acid are condensed. D, chamber containing chloride
of lime in which the chlorine is absorbed. E, pipe for producing a draught in
communication with a chimney. F, space under the furnace, in which is placed
the oxide of manganese after it is withdrawn from the retort. An artificial
current of air transforms the manganese into peroxide of manganese by reason
of the high temperature maintained.
ACTION OF THE APPARATUS.
So soon as the retort A is at a red heat the chloride of manganese is run.
in, when the water and hydrochloric acid become volatilized and pass out into.
the chambers before mentioned, where they become condensed; the heat and
the supply should be regulated so as to always keep the retort heated to
redness. The chloride in proportion as it advances towards the end of the
furnace becomes first of a pasty consistency and then solid, being decomposed
by the current of air passing through the retort; the chlorine disengaged
becomes cooled in the condensers, and is then absorbed in the chloride of lime
chamber, while the oxide of manganese remains on the sole of the retort;
when a sufficiently large quantity has been collected the door is opened at.
the end of the retort and by means of an iron rake the whole is caused to fall
into small carriages, which are allowed to remain in the channel F the
necessary time for peroxidation.

page_text: According to a modification in the action of the apparatus instead of
introducing the chloride of manganese in a liquid form I use it in a solid or
partly dried state. In this manner the apparatus may be made capable
of a larger production, the mass is more easily handled, there is less water
to be condensed, and it requires a much less number of condensing
chambers. The desiccation of the chloride of. manganese is effected as
follows-The liquid chloride is placed in a receptacle formed of bricks
laid in mastic silicate of soda, and amianthus, under the crown of this
receptacle passes the waste heat of the decomposing furnace, the flame of
which is thus brought in contact with the liquid and so readily evaporates it,
especially if stirred from time to time, any noxious vapours disengaging may be
conveyed into a receptacle filled with chalk, by which they become absorbed.
If the chloride be in the mass it is preferable to place it in the decomposing
furnace. In order to absorb the carbonic acid and the moisture of the air
entering into the apparatus, which would impede the production of chloride of
lime, I cause the air to pass through a small space filled with quicklime before
entering the apparatus, which may be renewed when it has lost its efficacy.
1
From the foregoing description it will be seen that with the exception of
the waste unavoidable in the manufacture, the same manganese will serve for
an indefinite period, and that a double amount of chlorine will be obtained
with the same quantity of hydrochloric acid; the same result may also be
obtained in a still simpler manner by ceasing the production of chloride of
manganese. For this purpose it is simply necessary to place the peroxide of
manganese in the above described apparatus, and introduce therein a continuous
jet of hydrochloric acid, this will cause a production of chlorine and chloride
of manganese, but the latter being decomposed by the heat forms hydrochloric
acid and protoxide of manganese, which will be constantly peroxidized by the
current of air, so that by suitably regulating the temperature and flow of the
hydrochloric acid the latter will disengage the whole of its chlorine and the
peroxide of manganese will be indefinitely regenerated.
Having described the nature of this Invention, and the manner of performing
the same, I declare that what I claim as the Invention to be protected by the
herein-before in part recited Letter Patent is,-
The treatment of chloride of manganese on a scale suitable for industrial
purpose, whether in a liquid or solid state in the manner herein-before
described, in order to obtain therefrom peroxide of manganese, hydrochloric
acid, and chlorine, the same manganese being treated for an indefinite number
of times.

page_text: I also claim the production of chlorine repeatedly from the same manganese
without leaving any residue of chloride of manganese, all in the manner
herein-before described.
Lastly, I claim the arrangement of apparatus represented in the
accompanying Drawings employed for the purposes of this Invention, which
may however be modified without departing from the principle thereof.
In witness whereof, I, the said William Clark, have hereunto set my
hand and seal, this Ninth day of February, in the year of our Lord.
One thousand eight hundred and sixty-seven.
Witness,
JAMES DAISH,
53, Chancery Lane,
London.
W. CLARK. (L.S.)