NEW UTILIZATIONS OF THE ACID RESIDUES RESULTING FROM THE MANUFACTURE OF CHLORINE
Year: 1873

page_text: LETTERS PATENT to Frédéric Kuhlmann, of Paris, France, Professor
of Chemistry, for the Invention of "NEW UTILIZATIONS OF THE ACID
RESIDUES RESULTING FROM THE MANUFACTURE OF CHLORINE."
Scaled the 15th August 1878, and dated the 8th March 1873.
PROVISIONAL SPECIFICATION left by the said Fródório Kuhlmann at
the Office of the Commissioners of Patents, with his Petition, on
the 8th March 1878.
I, FRÉDÉRIO KUHLMANN, of Paris, France, Professor of Chemistry, do
hereby declare the nature of the said Invention for "NEW UTILIZATIONS
OF THE ACID RESIDUES RESULTING FROM THE MANUFACTURE OF CHLORINE," to bo
as follows:-
My Invention relates to the utilization of the residues of the manu-
facturo of chlorine, consisting for tho most part of chloride of manganeso
and chlorido of iron, which on being decomposed with a slight excess of
lime produce hydrated protoxido of manganese, together with more or
less oxide of iron.

page_text: 1st. The oxides are superoxidized according to the Weldon regenerativo
process by injecting a current of air into a large sheet-iron vessel
containing water in which the oxides are held in suspension. This method
gives however but very uncertain results, and it is rarely that the oxide
regenerated liters 70 degrees, that is to say, 70 per cent. of binoxide.
In order to render this treatment both more expeditious and more perfect
by increasing the oxidizing power of the air injected the latter may be
ozonized by bringing it in contact with essence of terpentine or with
sticks of phosphorus, or it may be with the aid of an electric current.
As however this mode of operating does not considerably increase the
oxidizing power of the air, and as the electric action can only be
obtained at a large expense, I by preference avail myself of the oxidizing
power of hyponitric acid which is utilized with such advantage in the
manufacture of sulphuric acid for producing continuously the combina-
tion of the oxygen of the air with the sulphurous acid.
By the contact of the hyponitric acid with the hydrated protoxide of
manganese and the subsequent action of heat which is suspended before
the binoxide of manganese becomes decomposed the most favorable
results are obtained.
The following is the method of operation:-Hydrated oxide of
manganese is obtained by the action of milk of lime on the residues of
the manufacture of chlorine, a large excess of lime being carefully
avoided. In order that the oxide regenerated may be as rich as possible
it is preferable to first treat the crude chloride of manganese with chalk
which separates the whole of the iron in the form of carbonate. This ?
oxide when well washed and consolidated is then treated with nitric acid,
whereby it is dissolved and gives nitrate of protoxide of manganese.
This salt is dried and heated in a closed vessel at a temperature which
(without driving off the oxygen from the binoxide formed) evolves all
the nitrous elements in the form of hyponitric acid and deutoxide of 8
azote; the latter by mixing with air also forming hyponitric acid.
I cause the hyponitric acid to be absorbed by the hydrated oxide of
manganese, and the manganesic salt thus regenerated without the aid of
any fresh nitric acid is calcined and gives off nitrous vapors as before,
which are absorbed in turn after having been mixed with a sufficient 8
quantity of air.
The action of the nitrous gas on the protoxide of manganese may be

page_text: readily produced by stirring the oxide with water in a cask or closed
vessel provided with stirrers for facilitating the contact of the hydrated
protoxido with the gaseous acids. Thus with the exception of the waste
in the manipulation the nitrous principle will act for an indefinite time,
and there is no real loss except where an excess of lime is found mixed
with the hydrated oxide. The binoxide thus regenerated by the acid
residues of chlorine contains 88 per cent. of binoxide, caro being taken
to suspend the calcination before the oxygen is driven off.
2ndly. The hydrated precipitates of oxide of manganese and oxide of
iron obtained by the action of lime on the residues of the manufacture of
chlorine may also be transformed into anhydrous oxides applicablo in
metallurgy, and more especially in the Bessemer process. For this
purposo it is desirable to obtain the oxides of manganese and iron in the
smallest bulk possible so as to facilitate their transport at a cheap rate,
and this object is effected by separating the oxide of iron by a
preliminary treatment with chalk. It is essential that carbonate of lime
be used free from phosphate in preparing the lime to be used for
precipitating the oxide.
The hydrated oxide precipitate is allowed to deposit on filters composed
of coarse matting placed on a layer of slag mixed with coal, ashes, or
other pervious body, resting on sloping brickwork to allow the solution
of chloride of calcium to run off, the concentrated portion of the latter
being utilizable for various purposes. Any other expeditious mode of
filtration may however be adopted.
The hydrated oxides become consolidated on the filters more or less,
according to the period they are allowed to remain thereon, and in
summer this consolidated mass may be dried in the open air for the
purpose of being calcined in reverberatory furnaces, while in winter or .
in damp seasons the mass may be at once placed in calcining furnaces.
The product obtained from these furnaces consists of anhydrous oxide
containing more or less oxygen, and may be used in metallurgy as a
substitute for the natural oxides of manganesic iron, its value depending
on the quantity of manganese and metallic iron it contains.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said Frédéric Kuhlmann in the Great Seal Patent Office
on the 25th August 1878.
1
TO ALL TO WHOM THESE PRESENTS SHALL COME; I, FRÉDÉRIO
KUHLMANN, of Paris, France, Professor of Chemistry, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent bearing date the Eighth day of March, in the year of our Lord
One thousand eight hundred and seventy-three, in the thirty-sixth year
of Her reign, did, for Herself, Her heirs and successors, give and grant
unto me, the said Frédéric Kuhlmann, Her special license that I, the
said Frédéric Kuhlmann, my executors, administrators, and assigns, or
such others as I, the said Frédéric Kuhlmann, my executors, admini-
strators, 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 "NEW UTILIZATIONS OF THE ACID RESIDUES
RESULTING FROM THE MANUFACTURE OF CHLORINE," upon the condition (amongst
others) that I, the said Frédéric Kuhlmann, my executors or admini-
strators, by an instrument in writing under my, or their, or one of
their hands and seals, should particularly describe and ascertain tho
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 calendar months next and immediately after the date
of the said Letters Patent.
1
NOW KNOW YE, that I, the said Frédéric Kuhlmann, 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 thereof, that is to say :-
My Invention relates to the utilization of the residues of the manu-
facture of chlorine, consisting for the most part of chlorido of manganese,
and chloride of iron, which on being decomposed by a slight excess of
lime produce hydrated protoxide of manganese together with more or
less oxide of iron.
1st. The oxides are peroxidized, according to the Weldon regenerating
_sely iniecting a current of air into a large sheet-iron vessel con-

page_text: taining water in which the oxides are held in suspension. This method,
however, gives but very uncertain results, and it is rarely that tho
oxido regenerated reaches 70 degrees, that is to say, 70 per cent. of bin-
oxide, in addition to which great expense is incurred in the construction of
the apparatus. In order to render this treatment both more expeditious
and more perfect I increase the oxidizing power of the air injected with
which object the air may be oxonized either by bringing it in contact
with essence of turpentine, or with sticks of phosphorus, or it may be
with tho aid of an electric current. As however this modo of operating
does not considerably increase the oxidizing power of the air, and as the
electric action can only be obtained at a large expenso, I by preference
avail myself of the oxidizing power of hyponitric acid which is utilized
with such advantage in the manufacture of sulphuric acid for producing
continuously the combination of the oxygen of the air with the sul-

page_text: The action of the nitrous gas on the protoxide of manganese may be
readily produced by stirring this oxide with water in a cask or closed
vessel provided with stirrers for facilitating the contact of the hydrated
protoxide with the gaseous acids. Thus, with the exception of the wasto
in the manipulation, the nitrous principle will act for an indefinite time,
and there is no real loss except in cases where an excess of lime is found
mixed with the hydrated oxide. The binoxido thus regenerated by the
acid residues of chlorine will contain as much as 88 per cent. of bin-
oxide by taking care to suspend the calcination before such a temperature
is attained as would causo the oxygen to be driven off.
2ndly. The hydrated precipitates of oxide of manganese and oxide of
iron obtained by the action of lime on the residues of the manufacturo
of chlorine may also be transformed into anhydrous oxides applicable in
metallurgy, and more especially in the Bessemer process. For this
purpose it is desirable to obtain the oxides of manganese and iron in the 1
most compact form, so as to facilitate their transport at a cheap rate, and
this object may be effected by separating the oxide of. iron by means of
chalk (although this is unnecessary, as the oxide of iron is itself utilized
in metallurgy), but if this separation be effected it is essential that chalk
free from phosphate of lime be employed. The same precaution as to
the absence of phosphate should be taken with the lime used for pre-
cipitating the oxide of manganese.
The precipitated hydrated oxide is allowed to deposit on filters com-
posed of coarse matting or fabric placed on a layer of slag mixed with
coal ashes or other pervious body resting on sloping brickwork, to allow 2
the solution of chloride of calcium to run off, the concentrated portion of
the latter being utilized for various purposes. Any other expeditions
mode of filtration may however be adopted.
The hydrated oxides become consolidated on the filters, more or less,
according to the period they are allowed to remain thereon, and in s
summer this consolidated mass may be dried in the open air, and after-
wards calcined in reverberatory furnaces, while in winter or in damp
seasons the mass may be at once introduced in calcining furnaces. The
product obtained from these furnaces consists of anhydrous oxide con-
taining more or less oxygen, and suitable for use in metallurgy as a 3
substitute for the natural oxides of manganesic iron,

page_text: I also utilize the residues of manganeso during certain stages of the
manufacture of sulphuric acid, and I combine the regeneration of tho
poroxide of manganese with the condensation of the nitrous gases
cscaping from the lead chambers as a substitute for the Gay Lussac
5 column.
This object may be affected with the aid of a fan or air pump, by
which the gasos from the chambers are conveyed into cylinders in which
hydrated protoxide of manganeso is set in motion by mechanical means
in contact with the quantity of air necessary for the oxidation of the
O binoxide of azoto. The reaction being terminated, the nitrate of man-
ganese produced is dried and calcined, the vapors of which calcination
may be utilized for supplying the lead chambers, or for converting fresh
'supplies of protoxide of manganese into nitrato.
To prevent the sulphuric acid passing off from becoming mixed with
, deutoxide of azote or other nitrous gases, said gases before boing absorbed
by the protoxide of manganese undergo a preliminary washing in water
which is afterwards conducted into the chambers.
Having described the nature of my Invention and the manner in
which the same is to be performed, I declare that what I claim as my
Invention to be protected by the hercin-before in part recited Letters
Patent is,-
1st. The application of the residues of the manufacture of chlorine in
the preparation of binoxide of manganese, by peroxidizing the protoxido
of manganese by means of ozonized air, or preferably by means of nitric
acid or nitrous gases, all as horein-beforo described.
2nd. The application of the precipitate of oxide of manganeso in
metallurgical operations.
In witness whereof, I, the said Frédéric Kuhlmann, have hereunto
set my hand and seal, this Twonticth day of August, in the year