IMPROVEMENTS IN THE RECOVERY OF MANGANESE USED IN MAKING BLEACHING POWDER
Year: 1844

page_text: TO ALL TO WHOM THESE PRESENTS SHALL COME, we, FRANCOIS
STANILAS DE SUSSEX, of Bethnal Green, in the County of Middlesex, Chemist,
and ALEXANDER ROBERTSON ARROTT, of Torrington Square, in the same County,
Chemist, send greeting.
WHEREAS Her present most Excellent Majesty Queen Victoria, by Her
Letters Patent under the Great Seal of Great Britain, bearing date at West-
minster, the Twenty-ninth day of August, in the eighth year of Her reign,
did, for Herself, Her heirs and successors, give and grant unto us, the said
Francois Stanilas de Sussex and Alexander Robertson Arrott, Her especial
licence, full power, sole privilege and authority, that we, the said Francois
Stanilas de Sussex and Alexander Robertson Arrott, our exors, adñiors, and
assigns, or such others as we, the said Francois Stanilas de Sussex and
Alexander Robertson Arrott, our exors, adññors, or assigns, should at any time
agree with, and no others, from time to time and at all times during the term
of years therein expressed, should and lawfully might make, use, exercise, and
vend, within England, Wales, and the Town of Berwick-upon-Tweed, our
Invention of "IMPROVEMENTS IN THE RECOVERY OF MANGANESE USED IN MAKING
BLEACHING POWDER;" in which said Letters, Patent is contained a proviso that
we, the said Francois Stanilas de Sussex and Alexander Robertson Arrott, or,
one of us, shall cause a particular description of the nature of our said

page_text: Invention, and in what manner the same is to be performed, to be inrolled
in Her said Majesty's High Court of Chancery within six calendar months
next and immediately after the date of the said in part recited Letters Patent,
as in and by the same, reference being thereunto had, will more fully and
at large appear.
NOW KNOW YE, that in compliance with the said proviso, we, the said
Francois Stanilas de Sussex and Alexander Robertson Arrott, do hereby
declare that the nature of our said Invention, and the manner in which the
same is to be performed, are fully described and ascertained in and
following statement thereof (that is to say):-
the
The nature of our Invention is to regenerate or reproduce peroxide of man-
ganese, more or less pure, from salts and other combinations of that metal
which contain it in a lower state of oxidation. By this our Invention we can
and do reconvert the residuum that is left after the disengagement of chlorine
or of oxygen gas from manganese, and which residuum is a product of little
or no value, into a superoxide of manganese, which is peculiarly fitted by the
large quantity of oxygen which it contains to serve the purpose of affording
either ehlorine or oxygen again, according to the process it is subsequently
subjected to. The said residuary matters, after the extraction of the chlorine
in the manufacture of chloride of lime, commonly called bleaching powder,
and chloride or hyper-oxymuriate of potash, consist principally of chloride and
sulphate of manganese; but as these residuums may and have been occasionally
converted more or less into sulphuret of manganese when they are used to free
coal gas from its sulphur or sulphuretted hydrogen, we include not only the
above sulphate and chloride, but also the sulphuret of manganese among the
waste or refuse products which we convert into a valuable peroxide of that
metal. We apply, moreover, this our Invention to the conversion of all oxides
and the carbonate and other combinations of manganese whatsoever, whether
native or factitious, which contain the metal in an inferior state of oxidation
into a superoxide of manganese adapted to produce chlorine or oxygen gas.
And further, in conformity with the said proviso, we now describe the
manner in which our said Invention is to be carried into execution. The
said conversion of manganese, whether combined or uncombined from a lower
state of oxidation into the higher state of superoxide, is effected in two distinct
and successive operations.
First, it is well known that when peroxide of manganese, known in com-
merce as being used in making bleaching powder, and called in its purest
native state pyrolusite, or grey manganese ore, is digested with hydrochloric
acid, called in commerce muriatic acid, the excess of oxygen of the super-

page_text: oxide combines with the hydrogen of the acid to form water, and leaves the
chlorine of a portion of the acid free, while the manganese, partially stripped
of its oxygen, combines with the rest of the muriatic acid to form chloride of
manganese. Likewise when sulphuric acid, common salt, or chloride of
sodium and peroxide of manganese, are so mixed and treated as to be made
to react upon one another, the hydrochloric acid which is disengaged by the
sulphuric acid is converted by the oxygen from the manganese into water and
chlorine, while both the soda produced from the common salt, and the par-
tially deoxidized peroxide of manganese, combine with the sulphuric acid into
sulphate of soda and sulphate of manganese. We convert either the chlorides
sulphate, sulphuret, or carbonate of manganese into sesquioxide or deutoxide
of manganese by one or other of the three following processes:-
First, we subject dried chloride of manganese to a strong heat, produced
either by the united action of burning fuel and a jet or jets of an oxyhydrogen
flame, or of a stream of atmospheric air thrown upon the burning fuel by a
fain or other suitable impulsive power, thus forming a kind of blowpipe or
blast furnace, by which the chemical decomposition and reaction are rendered.
quicker and more complete. The furnace is constructed like an ordinary
reverberatory furnace, with the addition of a box or chest of iron, open at top
and set in the fireplace close to the bridge, which box is filled with iron
turnings, borings, filings, or other small fragments of iron, upon which in
their strongly ignited state water is allowed to trickle or drop down slowly
from a pipe so as to be decomposed and to disengage a stream of hydrogen,
which stream is impelled over the bridge of the furnace by means of a fan or
other blowing machine acting at the entrance or door of the fireplace. The
manner in which the furnace is regulated is as follows:-The fuel, either
common coals, coke, anthracite, wood, &c., is first lighted upon the grate, and
being subjected to the blast of air soon creates such a degree of temperature
as to raise the box of iron turnings to a red white heat, in which state the
water being allowed to trickle down is decomposed with disengagement of
hydrogen gas. The chloride of manganese may be exposed on the hearth of
the reverberatory furnace in a more or less concentrated liquid state or in a
dry state to the action of the intensely powerful flame generated as above
described, and becomes thereby decomposed with disengagement of hydro-
chloric acid gas, and of separation of protoxide of manganese. The hydro-
chloric acid gas is condensed by means of a vault or large chimney containing
wet coke or nodules of flint, as often practised in the decomposition of common
salt in soda manufactories. Instead of the above-described compound
hydrogen flame, we employ sometimes a simple reverberatory, furnace, fired

page_text: with ordinary fuel, and with or without blast of air, on the hearth of which we
resolve chloride of manganese into bydrochloric acid and peroxide of manganese,
but we prefer the compound flame of hydrogen.
In our second process, instead of acting upon chloride of manganese by the
flame of combustible matter on the hearth of the furnace, we subject the
chloride of manganese put into a retort made of fire clay to an intense heat,
by which we expel the chlorine partly in the state of hydrochloric acid, and
partly in that of chlorine, while the oxide of manganese left in the retort is to
be afterwards peroxidized by a process presently to be described.
In our third process we mix together chloride of manganese and carbonate
of lime or quicklime in the proper equivalent proportions for their mutual
decomposition, and we subject that mixture to the strong heat of the above-
described compound bydrogen flame, whereby we obtain a mixture of chloride
of calcium and oxide of manganese, which is to be peroxidized by a process
about to be described. Magnesia or magnesian limestone may be substituted
for lime or its carbonate in this process. When the carbonate of lime is
used with too low a heat in the furnace a carbonate of manganese may be
formed. In all cases the resulting mixture of chloride of calcium or magne-
sium and oxide of manganese is to be treated with water, so as to dissolve out
the said chlorides and leave the oxide of manganese.
We now proceed to describe our Invention for decomposing sulphate of
manganese, however formed, so as to obtain from it an oxide of manganese, to
be peroxidized by a subsequent process. We mix the sulphate of manganese
with sawdust, ground coke, or charcoal, or any like combustible matter, but
only in such proportions as to be capable of decomposing the sulphuric acid
when the mixture is subjected to a strong calcining heat, in a retort of iron or
fire clay, whereby we obtain a sulphuret of manganese mixed with more or
less oxide of manganese. We finish this operation by introducing into the
said residuary mixture fragments of coke, charcoal, or coals, and continuing
the application of heat for some time while the mouth of the retort is left open;
whereby we desulphurate the manganese and convert it into an oxide. In
case any salt or other compound of soda should have been mixed with the
sulphate of manganese, the soda compound is to be separated from the man-
ganese by solution of water, after the above-described calcination in the
retorts. The sulphuret of manganese sometimes produced in coal gas works
as a residuum of the purification of the gas may be desulphurated in a retort
as above described, or prefably by exposing it mixed with pieces of coke, char-
coal, or wood, on the hearth of the above-described reverberatory furnace.
The coke or other combustible matter should not be used in powder but in

page_text: distinct pieces, whereby it may be readily separated from the oxide of man-
ganese afterwards by means of a sieve, or other suitable means.
We shall now describe our manner of performing the second operation or
series of operations whereby we convert the sesquioxide or deutoxide of man-
ganese produced in the before-described processes, as also all the lower oxides
or carbonates of manganese, whether natural or factitious, into superoxide, fit
for affording chlorine by the action of hydrochloric acid and oxygen by heat,
and we accomplish the said peroxidizement in or other of the three following
ways:-
First, I convert the said oxides or carbonates from their lower to the much
bigher state of oxidation of an acid of manganese by subjecting a mixture of.
them and alkaline matter, such as potash or soda, either caustic or carbonated,
on the hearth of a reverberatory furnace, to the joint agency of heat and
atmospherical oxygen, which may be impelled and diffused by mechanical
means, and we find that about one part of the oxide or carbonate of manga-
nese mixed with about three parts of alkaline matter form a suitable propor-
tion for the production of an acid of manganese. The said mixture being
fused with the production of manganese, or permanganate of potash or soda,
according as one or other alkali has been used in the mixture, the fused mass
is run or ladled out of the furnace, and when cold is dissolved in hot water.
This solution of what is sometimes called chameleon mineral, on being
exposed freely to the air becomes decomposed by the absorption of carbonic
acid
gas into peroxide of manganese, which precipitates in a black powder and
carbonated alkali, which remains in solution. Where carbonic acid gas can
be conveniently procured at a very cheap rate, the above-described decompo-
sition of the chameleon mineral may be promoted by a due application of the
said acid gas, or otherwise the alkaline bicarbonates obtained from a preceding
decomposition of chameleon mineral may be employed for decomposing the
fresh-made solution of chameleon, whereby a precipitate of peroxide of man-
ganese is immediately obtained. The supernatant alkaline liquor is in all
cases decanted or run off for subsequent use. We also decompose chameleon
mineral with the production of peroxide of manganese by the action of various
organic products, such as starchy or gummy matter, but we greatly prefer to
effect the production of peroxide of manganese by carbonic acid gas, or an
alkaline bicarbonate.
Our second method of producing peroxide of manganese from its lower
oxide or carbonate consists in subjecting a mixture of about one equivalent
chemical proportion of either of these, and about one equivalent of lime to
the chlorine expelled by heat from chloride of manganese contained in a retort,

page_text: as heretofore described, or by treating an equivalent proportion of that lower
oxide of manganese called by chemists deutoxide or sesquioxide, with one half
of an equivalent of aqueous hydrochloric acid. We obtain simultaneously one
half of an equivalent proportion of protochloride of manganese in solution, and
one half of an equivalent of peroxide of manganese precipitated. A like
reaction with the production of protochloride of manganese and black peroxide
may be effected by treating the said sesquioxide with hydrochloric acid in one
vessel, and transmitting therefrom the chlorine disengaged into another vessel
containing a like sesquioxide in a moist state.
Our third method of converting into peroxide the lower oxide or carbonate
of manganese, consists in directing over the surface of either of these in a
moist state the deutoxide of azote, frequently called nitrous gas, which is
obtained as a waste product in certain chemical operations, as in the manufac-
ture of oxalic acid or nitrate of lead or copper, &c. In this case the nitrous
gas becomes reduced to a lower state of oxidation, and by imparting oxygen to
the lower oxide of manganese converts it into peroxide.
We claim the production of peroxide of manganese from the lower oxides
of that metal by the several methods herein-before described and fully set.
forth, believing them to be new, useful, and practical.
In witness whereof, I, the said Francois Stanilas de Sussex, have hereunto
my hand and seal, this Twenty-eighth day of February, in the
year of our Lord One thousand eight hundred and forty-five.