IMPROVEMENTS IN WORKING OF CERTAIN SULPHURETS TO TRANSFORM THEM INTO METAL OR OXIDES, AND TO COLLECT THE LATTER; ALSO TO COLLECT THE OXIDES FROM OXIDIZED ORES EQUIVALENT TO THESE SULPHURETS
Year: 1846

page_text: TO ALL TO WHOM THESE PRESENTS SHALL COME, I, JEAN
JOSEPH ERNEST BARRUEL, of 172, Rue Saint Jacques, in the City of Paris,
in the Kingdom of France, Chemist, send greeting.
WHEREAS Her present most Excellent Majesty Queen Victoria, by Her
Royal Letters Patent under the Great Seal of Great Britain, bearing date
at Westminster, the Eleventh day of March, in the ninth year of Her reign,
did, for Herself, Her heirs and successors, give and grant unto me, the said
Jean Joseph Ernest Barruel, my exors, admors, and assigns, Her especial
licence, full power, sole privilege and authority, that I, the said Jean Joseph
Ernest Barruel, my exors, adiňors, and assigns, or such others as I, the said
Jean Joseph Ernest Barruel, my exors, admors, 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,
and in the Islands of Guernsey, Jersey, Alderney, Sark, and Man, and in Her
Majesty's Colonies and Plantations abroad, my Invention of "IMPROVEMENTS
IN WORKING OF CERTAIN SULPHURETS TO TRANSFORM THEM INTO METAL OR
OXIDES, AND TO COLLECT THE LATTER; ALSO TO COLLECT THE OXIDES FROM OXIDIZED
ORES EQUIVALENT TO THESE SULPHURETS;" in which said Letters Patent is
contained a proviso that I, the said Jean Joseph Ernest Barruel, shall cause
a particular description of the nature of my said Invention, and in what

page_text: 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, I, the said
Jean Joseph Ernest Barruel, do hereby declare that the nature of my said
Invention, and the manner in which the same is to be performed, are fully
described and ascertained in and by the following statement thereof, that is
to say:-
My Invention consists of certain improved processes for converting the
sulphuret of zinc and the sulphate of zinc into the metal, or the oxide of zinc
and the sulphuret of antimony into oxide of antimony, and for collecting the
oxide of antimony obtained from the sulphuret or other substances equivalent
thereto.
The first part of these improved processes consists in mixing the sulphuret
or the sulphate of zinc, or the sulphuret of antimony, with carbon and peroxide
of manganese; or,
Secondly, with carbon and the sesquioxide of iron; or,
Thirdly, with carbon and some calcareous substance (in manner and propor-
tions which will be afterwards described), and subjecting the mixture to the
requisite degree of heat.
I proceed to explain the application of these three processes to the
reduction of blende or sulphuret of zinc.
FIRST PROCESS.-REDUCTION OF BLENDE BY THE PEROXIDE OF MANGANESE
AND CARBON.
I would observe, as a general rule, that the quality of the sulphuret should
be first ascertained, for the proportions of the peroxide of manganese, oxide of
iron, calcareous material, and carbon, require to be varied to suit the quality
of the blend; taking, therefore, as an example, a blende composed as
follows:-

page_text: parts of carbon of coke in powder. If the peroxide of manganese was free
from other subtances eighty-four parts would suffice, and as coke contains
16% of ashes it requires forty parts instead of thirty-two or thirty-three
parts, which, if it were pure, would suffice. These materials are to be tho-
roughly mixed with a shovel and rake, and the mixture is then to be put into
any of the apparatus now commonly employed in the manufacture of zinc,
and the temperature raised to a white heat. At the commencement of the
operation a small portion of sulphurous acid is formed, then sulphuret of
manganese and oxide of zinc, and this latter is reduced by the carbon as the
temperature is raised to a white heat.
The carbon must be in excess.
This
is an indispensable condition of success, and for obtaining the fullest return.
D
-
I take of this blende one hundred parts, peroxide of iron (anhydrous) eighty-
parts, coke thirty-eight parts-if the oxide be a hydrate one hundred parts will
be requisite, and I repeat that it is necessary to know the quality of the mineral
operated upon, and that of the substances employed in its reduction. If the
ore of zinc contain a large portion of silex it will be beneficial to add a small
quantity either of chalk or of a calcareous ore of iron, in order to destroy the
silicate of zinc, which is with difficulty reducible by carbon.
Treating blende with carbon and calcareous substances, as marble, chalk,
lime, &c.. I will suppose the blende to be composed as follows:-
I mix together of this blende one hundred parts; carbonate of lime, chalk, or
marble, seventy parts; coke in powder, thirty-three parts. These materials
are separately reduced to coarse powder and then well mixed together with a
shovel and rake, and the mixture is put into the cylinders, retorts, or other
vessels used for the reduction of the ore. The mixture might be moistened,

page_text: but this mode of operating destroys the vessels rapidly, and is therefore preju-
dicial. If compact limestone or lias be employed the quantity of this
material must be augmented on account of the silex or argile which it
contains. Thus for one hundred parts of blende it will require seventy-five
parts of compact limestone, or of lias eighty-eight in lieu of the proportions
given above. In some localities the production of sulphate of zinc (white vitriol)
is a residuum resulting from previous operations for reducing the ores, and the
amount is considerable. In these cases the same process may be employed for
its reduction as that which I have described above for the reduction of blende.
The sulphate of zinc is first dried and pulverized, and then mixed with the
following materials in the proportions stated:-Sulphate of zinc (dry) one
hundred parts; carbonate of lime, in powder, sixty-three parts; coke or
charcoal, in powder, forty-five parts. These materials are mixed together, and
treated in vessels used for the extraction of zinc.
I claim in respect to this part of my Invention, the mixing of blende or
sulphuret of zinc, as likewise the sulphate of zinc with carbon and calcareous
matter, or carbon and peroxide of manganese, or carbon and the oxide of
native iron (sesquioxide), and submitting the mixture in any suitable apparatus
to a white heat, for the purpose of depriving the blende or the sulphate of
zinc of the sulphur contained therein, which mixing of the sulphuret or the
sulphate of zinc with the matters above specified may be combined with the
employment of any description of apparatus at present used for collecting the
oxide of zinc. But I do not limit myself to the precise proportions of the
materials herein-before given, as they will depend in some degree upon
circumstances, as explained above; neither do I claim any particular form of
apparatus for the reduction of the ore.
I now proceed to describe the application of my improvements to the con-
version of the sulphuret of antimony into the oxide of that metal, and to the
collection of the oxide. The natural sulphuret of antimony is first coarsely
pounded, but not separated from its gangue, and is then mixed with carbon
and a calcareous substance; but care must be taken that the latter material
be not in excess, in order not to produce a double sulphuret of calcium and
antimony, which, being difficult to decompose, would cause a loss in the pro-
duct.
If the sulphuret of antimony be pure, I consider the following to be
the most suitable proportion of the materials:-Sulphuret of antimony, one
hundred parts; calcareous matter, eighty-seven parts; carbon, twenty parts.
The materials are pounded separately, and then well mixed together. The
materials thus mixed may then be converted into oxide, and the oxide collected
by means of any of the apparatus or methods at present employed for those

page_text: purposes; but I prefer the following arrangement for collecting the oxide of
antimony-I use for this purpose a distilling vessel, having at one end a
neck which opens into the chamber wherein the oxide is collected, and at the
other end an aperture for the admission of air to the distilling vessel for the
purpose of converting the metal into oxide. This latter aperture is kept
closed during the reduction of the sulphuret, which is effected by introducing
the mixture of materials before named (or any material equivalent to the sul-
phuret of antimony) into the distilling vessel, and subjecting it to a red heat.
When the antimony is set free, the aperture for the admission of air is opened,
in order to produce a current of air, which burns the metal, and carries over
the volatilized oxide into the collecting chamber. A portion of sand or free-
stone coarsly pounded may be added to the materials to counteract the
tendency of the mixture to agglutinate, and for the same reason it is better
In this
to employ the sulphuret of antimony undivested of its "gangue."
operation, in lieu of the calcareous matter, peroxide of manganese may be
employed, or the hydrated peroxide of iron, as the brown or yellow .ores of
oxidated iron, hæmatite, or hydroxide, in about the following proportions :-
Sulphuret of antimony, one hundred parts to seventy-five parts of peroxide of
iron, or eighty-six parts of peroxide of manganese. In this case, likewise, the
sulphuret of antimony should be employed in its rough state on account of the
gangue it contains, which opposes the fusible tendency of the sulphuret. In
preparing oxide of antimony by my improved process, which is calculated to
afford it free from red or brown sulphuret, care should be taken, in order to
obtain it perfectly pure and of fine white color, that the air which is admitted
into the retort or vessel employed for the reduction of the ore should be free
from impurities. For this purpose, I connect the aperture of the vessel by
which the air is admitted with a chamber or vessel furnished with partitions
of cloth, wire gauze, or other suitable fabric permeable to the air but not to
the extraneous particles suspended in it, and through these partitions the air
is constrained to pass before it arrives at the distilling vessel, whereby it is
freed from such extraneous particles and rendered pure. In order to produce
the requisite draught of air; the chamber in which the oxide is collected is
connected with a draft flue, or any suitable ventilating apparatus, screens
formed of wire gauze, or other suitable fabric, to allow the passage of the air,
but to prevent the passage of the oxide, being placed before the exhausting
aperture so as to prevent the oxide being carried over by the draught. The
screens should be shaken at intervals, or continuously, to prevent their
becoming stopped up by the oxide depositing itself upon them, and this may
be effected by various simple mechanical arrangements.

page_text: I claim, under this head of my Invention, first, the decomposition of the
sulphuret of antimony, for the purpose of obtaining the oxide of that metal by
mixing the sulphuret with carbon and calcareous substances, or with carbon
and peroxide of manganese, or with carbon and peroxide of iron, as before
explained, and submitting the mixture in a suitable vessel or apparatus to the
requisite degree of heat.
Secondly, I claim for the purpose of collecting the oxide of antimony the
employment of a vessel having at one end an aperture for the escape of the
oxide, and at the other end an aperture for the admission of air to burn the
metal in the interior of the vessel, which, latter aperture is to be kept closed
until the metal is set free.
Thirdly, I claim the causing of the air which is to combine with the metal
in order to form the oxide of antimony, to pass through screens or sieves in a
continuous current by means of a blast flue, or any suitable ventilating appa-
ratus, to divest it of extraneous matter before entering the distilling vessel,
which is charged with the metal or with materials from which the metal may
be obtained.
In witness whereof, I, the said Jean Joseph Ernest Barruel, have
hereunto set my hand and seal, this Third day of September, One
thousand eight hundred and forty-six.
JEAN JOSEPH ERNEST (L.S.) BARRUEL.
Taken and acknowledged by Jean
Joseph Ernest Barruel
Barruel
(party
hereto), at Paris, in the Kingdom
of France, this Third day of Septem-
hon 201
A.
This is the Specification referred to in the Affidavit of James Murdoch,
sworn before me this 9th day of September, 1846,
W. HORNE.
James Murdoch, of Staple Inn, in the County of Middlesex, Patent Agent,
maketh oath and saith, that he is acquainted with the manner and character
of the handwriting of Jean Joseph Ernest Barruel, of Rue Saint Jacques, in
the City of Paris, in the Kingdom of France, Chemist; and this Deponent
further saith, that the signature "Jean Joseph Ernest Barruel," set, subscribed,

page_text: and written at the foot of the Specification hereunto annexed, and marked
with the letter A, and dated the Third day of September now instant, and
purporting to be executed by the said Jean Joseph Ernest Barruel, and
acknowledged by him before Thomas Pickford, Esquire, Her Britannic
Majesty's Consul at Paris aforesaid, is of the proper handwriting of the said
Jean Joseph Ernest Barruel. And this Deponent further saith, that he is
also acquainted with the manner and character of the handwriting of the said
Thomas Pickford, and that the signature "Thomas Pickford," set, subscribed,
or written in the margin of the said Specification, whereby it is stated that the
said Specification was acknowledged by him, the said Jean Joseph Ernest
Barruel, before the said Thomas Pickford, as Her said Britannic Majesty's
Consul at Paris, on the said Third day of September instant, is of the proper
handwriting of the said Thomas Pickford.