IMPROVEMENTS IN TREATING CERTAIN MANGANESE COMPOUNDS FOR OBTAINING OXIDES OF MANGANESE AND OTHER PRODUCTS THEREPROM
Year: 1860

page_text: LETTERS PATENT to Christopher Binks, of Parliament Street, West-
minster, and John Macqueen, of Old Jewry, in the City of London, for
the Invention of "IMPROVEMENTS IN TREATING CERTAIN MANGANESE
COMPOUNDS FOR OBTAINING OXIDES OF MANGANESE AND OTHER PRODUCTS
THEREPROM."
Sealed the 16th November 1860, and dated the 19th May 1860.
PROVISIONAL SPECIFICATION left by the said Christopher Binks and
John Macqueen at the Office of the Commissioners of Patents, with
their Petition, on the 19th May 1860.
We, CHRISTOPHER BINKS, of Parliament Street, Westminster, and JOHN
MACQUEEN, of Old Jewry, in the City of London, do hereby declare the
nature of the said Invention for "IMPROVEMENTS IN TREATING CERTAIN
MANGANESE COMPOUNDS FOR OBTAINING OXIDES OF MANGANESE AND OTHER PRO-
DUCTS THEREPROM," to be as follows:-
The final object of our Invention is to produce peroxide of manganese, or
manganese in any other state of oxidation fit to be applied in chlorine making,
and in some cases to produce chlorine itself by operating chiefly upon inferior
oxides of manganese, or upon salts of manganese, or other manganese
compounds, and especially upon that compound consisting principally of

page_text: hydrochlorate of manganese, that is obtained as a residual product of the
action of hydrochloric acid upon oxide of manganeso in the manufacture of
chlorine; and intermediately our object is to produce certain other manganese
and chlorine compounds applicable in the operations required for producing
the said manganese oxides or chlorine finally.
And our Invention consists, first, in so applying atmospheric air or oxygen
gas from any other source (used cold or heated, or at ordinary or higher tem-
peratures, and passed into and through such mixtures by any ordinary means,)
to any salt of manganese in solution in water, and agent employed to
decomposo such salt, in order to liberate its oxide,) that the air or oxygen
shall be in contact with the oxide simultaneously with its liberation, or tho
decomposition of its salt for the purpose of inducing a nascent, or kind of
nascent, or simultaneous reaction between the oxygen, or that of the air and
the protoxide of manganese, and thereby obtaining the oxide in a higher or
full state of oxidation, and not, as heretofore, by applying the air subsequently
to the liberation or production of the oxide. And we so apply the gas or air
in order also in some cases by its agitating or heating action to facilitate in
other respects the reactions or decompositions to be brought about or effected
in such mixtures.
Secondly, our Invention consists in so applying atmospheric air or oxygen
gas from any other source, in order to raise the state of oxidation of inferior
-oxides of manganese, that it shall be forced or passed into and through water
in which such oxides are mixed or suspended, this operation being carried on
under ordinary temperatures, but preferably under a higher temperature
obtained either by heating the materials, or the gas or air previously to its
application; and in some cases we employ, in place of water only, in which to
suspend the oxides, some saline solution that is capable of attaining on
application of heat a higher temperature than 212° of Fahrenheit.
Thirdly, it consists in applying to any mixture of a solution in water of a
salt of manganese and an earthy carbonate, such, for example, as native
-carbonate of lime, intended to be used for forming carbonate of manganese,
highly heated atmospheric air, in order by passing it into and through the
water in which is dissolved or suspended these materials to aid or facilitato
their mutual reactions.
Fourthly, it consists in effecting the decomposition (that is, the expelling
therefrom of its carbonic acid, and giving to the residual protoxide a higher
.proportion of oxygen,) of carbonate of manganese by opposing it to the action
of highly heated atmospheric air or oxygen from some other source, when it,

page_text: the carbonate, is mixed with or suspended in water, instead of effecting this
decomposition by exposing to heat and the conjoint action of atmospheric air
the carbonate in a dry state, as done heretofore, and further, in combining in
some cases the use of gaseous chlorine mixed with or applied conjointly with
the heated air in this operation.
Fifthly, it consists in applying carbonic acid gas used alone or conjointly
with atmospheric air, or with oxygen gas from any other source, to inferior
oxides of manganese, by passing the gas, or its mixture with oxygen or air into
and through water in which such oxides are mixed or suspended, in order, by
forming a carbonate of the protoxide out of one portion of such oxides, to
effect the peroxidation of the other portion; and, further, it consists in
effecting this peroxidation of the inferior oxides by application under the same
or similar conditions as just described of a mixture of gaseous chlorine and
atmospheric air, or these, or one or other of them, mixed with the carbonic
acid gas. It consists, further, in throwing into the resulting mixture of the
carbonate of manganese and the oxide, heated atmospheric air, in order again
to effect the decomposition of the carbonate that has been produced, with con-
sequent formation from it of an oxide, to be again treated with a fresh
application of carbonic acid, or that mixed with oxygen or air, or these or one
or other of them and chlorine for the purpose of peroxidation. In other
words, it consists in the alternate application of carbonic acid gas to form the
carbonate, and of heated air again to decompose this carbonate, with or
without the addition of chlorine in aid of the resulting peroxidation of the
oxide to be effected.
Sixthly, it consists in the application to hydrated protoxide, or other oxide
of manganese higher (as to the proportion of oxygen to the base) than the
protoxide, but inferior to the peroxide, of heated atmospheric air, when such
oxides are mixed with or suspended in solution in water of hydrochlorate of.
manganese, or of hydrochlorate of iron (the proto or the per-chloride), or of
hydrochlorate of magnesia, or of some other hydrochlorate, that is readily
decomposable under the action of oxygen or of heat, by passing the air into
or through such solution or mixture. Or it consists in a like aëration of such
oxides when suspended in or mixed with a solution of caustic alkali, in order
to effect a higher oxidation, or the peroxidation of such oxides.
Seventhly, it consists (for the purpose of producing peroxide of manganese)
in heating a mixture of sesquioxide of manganese, (or of any other oxide of
manganese that is intermediate in respect of its degree of oxidation between
the protoxide and the peroxide,) and hydrochlorate of magnesia, or of alumina,

page_text: or other hydrochlorate, and employing these (preferably) in quantities relatively
in excess of their equivalents to the oxide present, from which its acid can be
readily expelled on application of heat, till through the reactions between the
acids and the oxide) there occurs an incipient decomposition, or so much
chlorine is developed as serves on the subsequent addition to water to such a
mixture to peroxidize the remaining portion of the oxide of manganese
present.
Eighthly, it consists (for the purpose of producing peroxide of manganese
and chlorine) in the use of a combination of processes, or of a series of opera-
tions of the kind, and used in the order as follows, namely:-Into a mixture
of a solution in water of hydrochlorate of manganese and oxide of magnesium
(magnesia) in excess, or other similar base, is passed atmospheric air or
oxygen, until a superoxide (generally the sesquioxide) of the manganese and
hydrochlorate of a portion of the magnesia (or other base) are produced. The
application of the air (used heated preferably) is then continued till the
mixture becomes dry, or it is dried by heat otherwise applied, during which
process the oxide, or the greater proportion of it present, is peroxidized, and
can at this stage, if desired, be separated from the other compounds. But for
producing chlorine direct from this mixture, the dried mass is heated still
further, or longer, or to fuller decomposition, upon which gaseous chlorine is
evolved, and chloride of manganese and oxide of magnesium (magnesia)
remain. The addition then of water to this residual mass, and of atmospheric
air, or of oxygen, again yields a higher or the sesquioxide of manganese,
hydrochlorate of magnesia, and magnesia. To this is then added frce hydro-
chloric acid, to saturate or neutralize the free magnesia, and the whole being
again dried (preferably by aëration, by means of heated air,) and heated to
decomposition, produces again gaseous chlorine, and a residual mixture of
chloride of manganese and magnesia as before.
Ninthly, our Invention further consists in subjecting to mechanical pressure
(so as to solidify, or condense, or harden them,) artificially prepared oxides of
manganese; or it consists in cementing their particles together by applying to
such oxides a concentrated solution of some saline matter, as chloride of
manganese, or that salt fused, in order by such treatment of the oxides to
check the too rapid reactions between the hydrochloric acid and these oxides
in the ordinary process of their application in chlorine making.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said Christopher Binks and John Macqueen in the Great Seal
Patent Office on the 19th November 1860.
TO ALL TO WHOM THESE PRESENTS SHALL COME, we, CHRIS-
TOPHER BINKS, of Parliament Street, Westminster, and JOHN MACQUEEN, of
Old Jewry, in the City of London, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Nineteenth day of May, in the year of our Lord
One thousand eight hundred and sixty, in the twenty-third year of Her reign,
did, for Herself, Her heirs and successors, give and grant unto us, the said
Christopher Binks and John Macqueen, Her special licence that we, the said
Christopher Binks and John Macqueen, our executors, administrators, and
assigns, or such others as we, the said Christopher Binks and John Macqueen,
our 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 TREATING CERTAIN MANGANESE
COMPOUNDS FOR OBTAINING OXIDES OF MANGANESE AND OTHER PRODUCTS THEREFROM,"
upon the condition (amongst others) that we, the said Christopher Binks and
John Macqueen, our executors or administrators, by an instrument in writing
under our, or their, or one of their hands and seals, should particularly
describe and ascertain 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 calendar months next and immediately after
the date of the said Letters Patent.
NOW KNOW YE, that I, the said Christopher Binks, on behalf of myself
and the said John Macqueen, do hereby declare the nature of the said Inven
tion, and in what manner the same is to be performed, to be particularly
described and ascertained. in and by the following statement :-
In treating the residual liquor of chlorine makers, consisting chiefly of an
aqueous solution of hydro-cholorate of manganese, for the purpose of regaining
from it the manganese in form of an oxide, available for re-application in
producing chlorine, or for other purposes, it is the practice in some cases,
first, to precipitate the manganese as a protoxide, and then subsequently to
raise this oxide to some higher degree of oxidation by exposing it to atmo-
spheric air. This exposure and consequent oxidation have hitherto been

page_text: effected by so agitating the moistened protoxide as to present fresh portions of
it from time to time to the action of the external air in contact with and
acting upon it superficially. It has been customary, also, to carry on this
operation at ordinary atmospheric temperatures, or sometimes to promote the
resulting effects by aid of the application of a higher temperature, but never
exceeding that obtainable by the use of steam of moderate pressure, giving
practically a heat not higher than 212° Fahrenheit. But this method is
imperfect because of the length of time needed to effect the higher oxidation
of any mass or reasonable quantity of oxide, and from the practical difficulties
or impossibility of obtaining through it the degree of oxidation that is essential
or desirable.
Now, our first improvement consists in having the atmospheric air present
and in actual contact with the hydrochlorate of manganose in solution at the
moment of effecting its decomposition, or of the liberation of its oxide from
the associated acid. The effect of the simultaneous action of the oxygen of
the air, and of the agent used to decompose the manganese salt, is to produce
an oxide in a state of oxidation higher than that of the protoxide, or than that
obtainable by the old method just above referred to.
In the practical use of our Invention, we prefer to proceed as follows,
namely: Into water holding in solution, or in which is mixed or suspended
the decomposing agent we cause atmospheric air to be forced or otherwise
passed in profusion, and to be so directed or distributed as on its passage
through the water to come in contact simultaneously or successively with every
portion of the solution, or of the materials suspended in it; and then to this
nërating mass we add gradually the hydrochlorate of manganesc, in form,
preferably, of a solution in water. The resulting decompositions and oxidation
of the liberated oxide can be carried on under ordinary atmospheric tempera-
tures, but we prefer to aid them by artificially heating the water or the
solution, or the air itself, previously to its contact with the water.
The decomposing agent may consist of baryta, or of magnesia, or of soda, or
of lime, or of mixtures of two or more of these, &c.; but selecting, for
example, the latter as a convenient and economical agent, the operation, in
further detail, is as follows:-Into a decomposing and aërating vat (fitted with
contrivances for steam heating its contents, or for having the gas or air thrown
in and distributed throughout them) is added caustic lime or cream of lime in
a proportion somewhat in excess of its chemical equivalent to the quantity of
the manganese salt intended to be operated upon. The steam for heating and
the current of air are then applied to the mixture, and the manganesc salt, or

page_text: its solution, gradually added. In due time the decomposition of the man-
ganese salt and super-oxidation of the liberated protoxide are completed. The
solution of hydrochlorate of lime that is formed is then decanted off, and the
precipated oxide may, if desirable, be washed with a little free diluted bydro-
chloric or other acid, to remove the excess of lime, and it is then fit for
re-application in chlorine making in the usual manner, or for production of
oxygen gas, &c.; or if, when so obtained, the manganeso is not fully
peroxidized, it can, previously to such applications, be treated for further
oxidation by one or other of the methods herein-after described.
It is not essential to adhere strictly to the details of the operations as just
given, for these may, in some cases, be varied by using the manganese salt in
excess of the decomposing agent, or by using the two in their exact equivalent
proportions, by reversing the order of addition of the one to the other, that is,
by adding the decomposing agent gradually to the solution of the manganese
hydrochlorate, by conducting the operations cold, by omitting the uso for
heating of the steam, and warming by the use of the air itself previously
heated, or otherwise, or by emptying the air heated to a higher degree than.
that obtainable by application of boiling water or of ordinary steam, by mixing:
the air with high-pressure steam previously to its contact with the materials,.
or by carrying the concentration of the saline solution present so far that on
application of heat it attains a higher temperature than 212° of Fahrenheit;.
or the process may be varied by having the air compressed into the solution
of the salt, or into the water used in the operation.
The apparatus we prefer to use is a vat, furnished with a moveable or false
bottom, perforated with numerous small holes, below or through which the air
passed, and thence comes, as it ascends through the water, in intimate and
Successive or constant contact with the solution or the materials suspended in
it. For heating the air separately, we prefer to employ an apparatus similar
to or the same as that well-known kind that is used in heating the current of
air applied in the hot air blast furnaces in iron smelting, acting under a
pressure proportionate to the depth of the water through which it has to be
passed.
Secondly, our improvements consist in effecting the higher oxidation of
inferior oxides of manganese by exposing them, when mixed with or suspended
in water, to the action of atmospheric air, or of oxygen gas passed into or
through such water, using, by preference, though not of necessity, heat to
facilitate the operation, the heating of the mixture or of the gas or air being
effected by any of the methods referred to in reference to our first improve-

page_text: ments. In the practice of this part of our Invention, previously prepared
bydrated protoxide of manganese or sesquioxide, or hydrated sesquioxide, or
any mixture of these, or manganese in any state of oxidation intermediate
between the protoxide and the peroxide, or that is inferior to the peroxide, is
mixed with or suspended in water, and then the oxygen gas or atmospheric air
is forced or otherwise passed into and through it in profusion, till the full
degree of oxidation, capable of being attained under such conditions, is given
to the oxide. This operation can be carried on under ordinary temperatures,
or at 212° Fahrenheit. But we prefer, in order chiefly to keep up the
temperature in large masses of materials, to apply the air or oxygen heated to
from 400° to 600° Fahrenheit; or it may be used at a degree even higher
than that under which oxygen is expelled from dry peroxide of manganese;
for the presence of the water in this case exercises on the temperature of the
mixture the requisite modifying action for completing, but not again destroying,
the higher state of oxidation required.
The kind of apparatus we prefer to employ (but without restricting the
operation to such only) is the same or similar to that already described in
reference to our first improvement.
Thirdly, in preparing carbonate of manganese by the reaction between a
solution of hydrochlorate of manganese and some insoluble carbonate; it is
found difficult in some cases to effect the decomposition, and particularly so
when carbonate of lime is the decomposing agent, and it is selected from
certain of its native sources. The organism or hard crystaline structure of
these lime carbonates offers impediments to the action of the hydrochlorate
unless previously destroyed; and this is at present done by subjecting the
mixture to a high temperature obtained by steam under high pressure.
Now our improvement consists in subjecting the mixture of the solution of
hydrochlorate of manganese and the lime carbonate, or any native carbonate
of lime, or carbonate of magnesia, to the action of strongly heated atmospheric
air passed into and through it in the manner and by the same or similar con-
trivances employed in reference to the preceding parts of our Invention. The
high temperature required we either obtain by using the solution of the
hydrochlorate so concentrated, that on application of heat applied externally
to the vessel containing it, it shall reach to the degree required, and thence
impart its heat to the air when passed into it; or we obtain it by previously
heating the air itself, in which case we prefer to raise it to about 480°
Fahrenheit or thereabouts, but without restriction to that degree. The effect
of the application of the air so heated is to maintain the heat in large masses of

page_text: materials, and to break up the structural organism of these hard or native
carbonates, and bringing them into a fit condition for reaction with the
hydrochlorate and consequent formation of the carbonate of manganese.
The heat in this operation is not in its action (conjointly with that of the
oxygen of the air) upon the resulting carbonate to be kept up so long as again
to decompose the carbonate.
Fourthly, in using artificial carbonate of manganese for production from it
of an oxide of manganese to be applied in chlorine making, or to other uses, it is
now the practice to expose the dry carbonate to a temperature high enough
in the presence of atmospheric air to expel the carbonic acid, and leave an
oxide in some state of oxidation intermediate between the pro and the peroxide.
But there attends this operation the practical difficulty of so exactly adjusting
the degree of heat, that on the one hand the full proportion of oxygen
attainable under it shall be absorbed by the manganese, and on the other
hand, this oxygen shall not under any inadvertant exercise of that heat be
again expelled. Now, our improvement consists in mixing or suspending
the carbonate of manganese in water, and then in driving into and through this
mixture, heated atmospheric air, till under the degree of heat used, or the
continued conjoint action of the high temperature and of the oxygen of the
air, the carbonate is decomposed, with formation, finally, of an oxide of the
manganese fit for application in chlorine making and to other purposes.
The degree of heat to which we prefer (but not to limit ourselves to the
use of) to raise the air previously to its application ranges between 500° and
600° Fahrenheit; and the relative proportion of water to the carbonate
which it is expedient to have present, ranges from two to three times the
weight of the carbonate. This operation may be in some cases varied by
superadding gascous chlorine to the hot air sent in to decompose the carbonate.
Fifthly, our improvements consist in applying carbonic acid gas or that
mixed with free oxygen gas or with atmospheric air to the hydrated protoxide
of manganese and to other manganese oxides of a higher state of oxidation
than the protoxide, but inferior to that of the peroxide, when one or other
or mixtures of these are mixed with or suspended in water, or when such
oxidos are being nascently set free in form of the protoxide or are produced in
some higher form of oxidation under the conjoint action of decomposing agents
and of atmospheric air, as in some of our improved operations herein-before
described, under head of our first improvements; the object of such application
of carbonic acid gas, or of that mixed with oxygen or of atmospheric air, being
the formation of the peroxide through the conjoint action of the carbonic acid

page_text: and the oxygen when acting upon the protoxide and when acting upon the
higher oxides through the same transformation of a portion of the base into a
carbonate of the protoxide, and the consequent transposition of the excess of
oxygen present to the other portion of the base present, in other words to form
out of the inferior oxide so acted upon a peroxide and a carbonate of the
protoxide, or to substitute carbonic acid gas for the dilute aqueous acids hitherto
used for peroxidizing on this principle inferior oxides of manganese, and to aid
the operation by the presence in some cases of oxygen gas or of the oxygen
contained in atmospheric air. In the practical application of this part of
our Invention we prefer to proceed as follows:-When carbonic acid gas
is used we procure it from any of its ordinary sources, but we prefer to
employ the gaseous mixture obtained through the combustion of carbonaceous
matter in atmospheric air, that is, carbonic acid gas and nitrogen gas chiefly,
or these gaseous products mixed with a portion of fresh or unexhausted
air, or as such a mixture is procured on passing an excess of air through
ignited carbonaceous matter. The air is preferably forced through closed
retorts or chambers containing ignited charcoal, or coke, or anthracite,
and thence into the decomposing or aerating vats in is held the oxide of
manganese and water is the mixtures for yielding the oxides as already
described. Instead of employing these gaseous products mixed, we prefer
first to apply to the oxide carbonic acid, thereby forming the carbonate,
and then to apply the oxygen or the atmospheric air free from carbonic
acid in order to again decompose the carbonate.
These mixed gaseous
products are applied either direct and at the high temperatures at which
they issue from the ignited carbon, or are previously cooled to a greater or
less extent according to the condition of the oxide or the mixture yielding
them, the higher temperatures being employed when it is the sesquioxide
chiefly that is present, and the lower temperatures when it is the protoxide
that is in excess. After transformation of the oxide into the carbonate
and the cognate peroxide, then the current of gaseous carbonate acid or
mixed gases is suspended, and one or other of the methods for decomposing
the carbonate that has been formed and remains present, is resorted to as
thoso are described above under the fourth part of our improvements, or as they
are berein-after described under our head of further improvements.
Sixthly, it is well known that when bydrochloric acid is combined with
certain bases, as, for example, those of magnesia or alumina, the application
thereto of a moderately high temperature expels the acid, and leaves the base
in its original condition. It is also known that if there be present, mixed with

page_text: a hydrochlorate of this kind, one of the higher oxides of manganese, the result
of the application to such a mixture of a decomposing heat is to resolve the
hydrochloric acid into water and chlorine.
Now, a further part of our improvements consist in a succession or series of
operations in which this property is applied, under certain conditions, to peroxi-
dize oxide of manganese to be afterwards applied in chlorine making by any
of the usual methods, or under certain other conditions, to yield chlorine
simultaneously with the operations of treating the hydrochlorate of manganese
for recovery of its oxide; and our improvements under this part are as follows
namely: A solution of hydrochlorate of manganese is decomposed by addi-
tion to it (preferably) of magnesia, atmospheric air being caused to be in
contact with these materials at the time the decomposition is effected, as
berein-before described, generally under the head of our first improvements,
and the immediate or intermediate result is the formation of sesqui-oxide of
manganese and bydrochlorate of magnesia; but the process of aëration being
further continued, then follow reactions (accompanied by a kind of nascent
decomposition of the hydrochloric acid), terminating in the peroxidation of
the manganese; and at this stage the operation can be suspended, and (the
hydrochlorate of magnesia being washed out) the peroxide of manganeso
obtained in a condition to bo reapplied in chlorine making or to any other
purpose. Or, instead of suspending the operations at this point, the mixturo
thus obtained can be treated as follows, namely:-The aëration is suspended
and the mixture, removed to a convenient heating apparatus, is exposed to a
heat which dries it, and effects a decomposition of as much of its hydrochloric
acid, through reaction between it and the oxide of manganese, as is sufficient
on re-addition of water to the mass to peroxidize the remainder of the oxide
present, and which peroxide is regained as before by washing from it tho still
undecomposed portion of the magnesian hydrochlorate. Or a further and
different treatment of the mixture, as obtained at the end of the first process,
is as follows, namely:-Another equivalent of bydrochlorate of magnesia,
obtained from any other source, is added to it, and the aëration and the result-
ing mixture dried and heated to decomposition in any convenient apparatus,
upon which gaseous chlorine is evolved, and there is left a residue, consisting of
one equivalent of chloride of manganese and two equivalents of caustic mag-
nesia. The re-addition to this residue of water under the conjoint action, as
before, of atmospheric air, resolves its elements again into peroxide of manga-
nese, one equivalent of magnesia, and one of bydrochlorate of magnesia, and
the adding to this of an equivalent of free bydrochloric acid gives again a

page_text: mixture, wnica on being dried and neated yields gaseous chlorine and the re-
applicable residue as before.
Seventhly, in place of using water only with which to mix, or in which to
suspend inferior oxides of manganese, in order to operate upon them for their
super or peroxidation, a further part of our Invention consists in employing
solutions of hydrochlorate of manganese itself, or some other hydrochlorate
that is readily decomposable under the conjoint action of oxygen and of a
moderately high temperature, as that of magnesia or of iron, (and in this last
case, either the protochloride or the perchloride can be resorted to,) as the
vehicle. Into and through such a solution, when holding in it protoxide or
sesquioxide, anhydrous or hydrated, we cause strongly heated atmospheric air
or oxygen gas to be passed in profusion. We conduct this operation either at
ordinary temperatures of the atmosphere, or employ a heat equal to or pre-
ferably greater than that of 212° Fahrenheit; and obtain this heat either by
warming the solution itself by heat applied externally to the vessel containing
it or by steam passed directly into it along with the air or gas, or we prefer
previously to heat the atmospheric air itself that is used to from 400° to 600°
Fahrenheit; and we apply this, as stated, till the consequent actions upon the
salt or solution and upon the oxide present result in peroxidizing the manganese.
We vary this operation in some cases by substituting for the solutions just
described, a solution of caustic alkali, in which we suspend the manganese oxide,
and this mixture we aërate in the manner stated. And we further vary these
operations by causing the air or oxygen so passed into and through the alkaline
solutions to be mixed with a portion of gaseous chlorine, in order in some
cases to facilitate the ultimate peroxidation of the manganese.
We vary the above operations in these cases where the salts of iron or the
action of the oxides of iron contained in them are concerned as intermediate
agents in the superoxidation of the manganese, by adding peroxide of iron to
a solution of hydrochlorate of manganese, and heating and aërating this
mixture, as above described; or, we use, and heat, and aërate, as before,
a mixture of solutions of the protochlorides of iron and manganese along with
some re-agent, capable of, and in quantity requisite for, abstracting one-half
the acid present, and of liberating its associated protoxide.
Eighthly, in applying to artificially prepared oxides of manganese the hydro-
chloric acid for the manufacture of chlorine, there may be a tendency to too
rapid an action between these, and the gas consequently be evolved somewhat
suddenly. To check this, we cause the oxide to be previously compressed by
means of any convenient mechanical contrivance; and this is best eflected

page_text: whilst the oxide is in a moist state, and it is left finally in hard cakes or lumps ;,
or, we effect conveniently the same object by moistening a mass of the oxide
with some hot concentrated saline solution, preferably with a solution of hydro-
chlorate of manganese, which, on cooling and crystalizing, serves to bind
together the particles, and solidify the mass in a manner easily broken into
convenient sizes for after application.
What we claim as our Invention is,--
Firstly, the causing atmospheric air or oxygen gas, or oxygen from any other
source, to be in contact with a salt of manganese in solution simultaneously
with any decomposition of the salt that shall set free its oxide, for the purpose
of super-oxidizing the oxide, or, in some cases, of aiding the decomposition.
Secondly, the passing of atmospheric air, or of oxygen gas, or oxygen from
any other source, either cold, or previously or simultaneously heated to the
extent herein-before described, into and through water, in which is mixed or
suspended, or being liberated, protoxide of manganese or any other inferior
oxide of manganese, for the purpose of raising such oxide to a higher or full
state of oxidation.
Thirdly, the application of strongly heated atmospheric air, or of oxygen
gas, or of oxygen from any other source, to mixtures of hydrochlorate of man-
ganese in solution, and native or other carbonate of lime, or carbonates of lime,
and magnesia, in order to facilitate the re-actions between or decompositions
of these substances.
Fourthly, the application of strongly heated atmospheric air, or of oxygen
gas, or of oxygen from any other source, or of these or any one or more of
them mixed with chlorine, to carbonate of manganese mixed with or suspended
in water, in order to effect the decomposition of the carbonate and super-
oxidation of its protoxide.
Fifthly, the application of carbonic acid gas, or of that mixed with oxygen
gas or with atmospheric air to the lower oxides of manganese when in contact
with or suspended in water, and the process of alternately so applying car-
bonic acid gas and oxygen, or atmospheric air alone or when mixed with
chlorine, in order to effect the peroxidation or super-oxidation of such oxides
or of a portion of them.
Sixthly, the peroxidizing of sesqui or of any other oxide of manganese inter-
mediate (in respect of its proportion of oxygen) between the sesqui and the
peroxide, by beating it along with some hydrochlorate, such as the hydro-
chlorate of magnesia, in the manner as herein above described.
Seventhly, the application of atmospheric air or of oxygen gas with or with-

page_text: out the addition thereto of chlorine to inferior oxides of manganese when such
oxides are mixed with or suspended in any caustic alkaline solution, or in a
solution of certain hydrochlorates, as those of manganese or iron, or of mag-
nesia, for the purpose of effecting the super or peroxidation of such oxides, as
herein-before described.
Eighthly, the production of peroxide of manganese and of chlorine by means
of the series or combination of processes as herein-before described under the
head of our sixth improvement.
Ninthly, the methods of condensing or hardening artificial oxides of man-
ganese for their application in chlorine making, as herein above described.
In witness whereof, I, the said Christopher Binks, on behalf of myself
and the said John Macqueen, have hereunto set my hand and seal,
this Nineteenth day of November, in the year of our Lord One
thousand eight hundred and sixty.
Witness,
WH. BOWERS,
71, Fleet Street, London.
CHRISTOPHER BINKS. (L.S.)