Improvements relating to the Manufacture of Nickel and Cobalt.
Year: 1894

page_text: Date of Application (in United Kingdom), 6th Apr., 1894
Complete Specification Left, 31st Dec., 1894-Accepted, 6th Apr., 1895
Improvements relating to the Manufacture of Nickel and Cobalt.
I, PIERRE MANHES, Metallurgical Engineer, of 3 Rue Sala, Lyon, in the
Republic of France, do hereby declare the nature of this invention to be as
follows:-
My invention relates to the manufacture of nickel and cobalt.
For the purpose of producing nickel and cobalt the ores of these metals are
nearly always treated by fusion for matt. Sulphurous ores bear the sulphur necessary
for the formation of the matt, while non-sulphurous ores are supplied with sulphurated
materials or sulphur in the first fusion of these ores. The matt produced is then
either successively roasted and fused, or preferably treated in the converter by the
Manhes process.
Whatever method may be employed the iron may be easily
enough and completely enough eliminated, but it is not the same with the sulphur.
The product obtained is always a sulphide of nickel or a crude nickel containing a
comparatively large proportion of sulphur, the ulterior treatment of which has
beretofore necessitated long, difficult and costly operations producing only a metal
of very imperfect quality.
According to my said invention I treat this sulphide of nickel or crude nickel
for obtaining by a simple, rapid, and economic method ingots of nickel similar to
those of the other usual metals and adapted for the uses of the various industries
which require commercially pure nickel. It will therefore be understood that my
process has for its starting point the treatment of sulphide of nickel or of crude
nickel previously almost altogether freed from iron by one of the processes
hereinbefore mentioned or by any other process.
For the sake of simplicity I shall hereinafter mention only nickel, it being quite
understood that the whole process may likewise be applied to cobalt in order to
obtain the latter in a metallic state.
In the course of long and numerous experiments I have found that the sulphur
contained in crude nickel freed from iron can be completely eliminated by the
simple fusion of this metal in mixture and in contact with certain basic or alkaline
These reagents are
reagents or fluxes mixed with chlorides of the same nature.
lime, baryta, magnesia, soda, potash or other similar substances from the chemical
point of view, to which chlorides of calcium, lime, barium, magnesium, sodium,
potassium or the like are added. A portion of the sulphur is eliminated in the
state of sulphurous acid, while the other portion con bined with reagents added for
forming a scoria which is almost exclusively a basic or alkaline sulphide according
to the nature of the reagents employed.

page_text: Although use may be made of the various reagents before enumerated or of
other similar reagents, I usually employ in practice a mixture of lime and chloride
of calcium or better still chloride of lime, as these materials are preferable from an
economic point of view and give moreover excellent results.
Having thus explained the nature of my invention and the principles upon which
it is based, I will now summarily describe a metallurgical operation, taking as an
example the treatment of a crude nickel produced by the working of matt in the
converter by a first fusion, the matt containing very little iron, but enclosing still a
more or less large proportion of sulphur.
The fusion with the special reagents hereinbefore mentioned may be effected in
any suitable apparatus, in the metallurgical furnace, on the sole or in the crucible,
on condition that the apparatus or furnace in question can easily produce and
maintain the high temperature necessary for the fusion of the pure nickel. In
practice I preferably operate upon the sole and in a reverberatory furnace heated
by gas, such as the Siemens furnace or other similar furnace provided that it shall
be able to fulfil the desired conditions as regards the temperature.
I must here observe that, whatever apparatus or furnace may be used, it must
be provided in the interior with a neutral or basic lining, not in view of any
reaction to be obtained in the metallurgical operation, but because the nature of
the reagents employed renders the use of acid walls or linings impossible.
The furnace being suitably heated I commence by providing the surface of the
sole with a sufficiently thick layer of the mixture of lime and chloride of lime so as
to form a kind of false sole the object of which will hereinafter be explained. Then
I introduce into the furnace the crude nickel granulated or crushed to pieces after
having been mixed with a sufficient quantity of the same reagents. Next I close
the door of the furnace and heat slowly, the temperature being gradually raised
until the fusion of the materials introduced into the furnace is complete. During
this fusion the crude metal in contact with the reagents gives up to the latter the
greatest part of the sulphur which it contains, while another part is eliminated in
the state of sulphurous acid. By reason of its density the molten nickel gradually
separates from the scoria formed and reaches the bottom of the furnace; there it
encounters the false sole made of lime and chloride of lime, traverses it slowly and
while transforming it into scoria gives up to the same the little sulphur which it
may still have retained. When the fusion of the materials is complete there
remains upon the sole of the furnace commercially pure metallic nickel upon which
is a scoria formed almost exclusively of sulphide of calcium. When the operation
has reached this point the scoria is first caused to flow out and then the nickel
which on leaving the furnace is passed into moulds adapted for the various uses to
which the metal may be put.
If the operation has been well conducted and the temperature has been sufficient
all the materials at the moment of the casting must be in a state of perfect fluidity.
The scoria contains only insignificant traces of nickel, which however is not lost,
for this scoria is melted again with the ore in the furnace wherein the first fusion
or preliminary melting of the ore takes place. It constitutes in fact a doubly
valuable flux by reason of the lime and the sulphur which it contains.
employing this scoria an important saving is achieved by the lime in the fusion of
silicated or silicious ores, and by the sulphur in the fusion of non-sulphurous ores
to which a sulphurizing element which is almost always very costly must be
added.
When
It will be understood that I do not limit myself exactly to the foregoing
description, as my improved process may be variously modified without departing
from the scope of my invention.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C., Agents for the Applicant.

page_text: Improvements relating to the Manufacture of Nickel and Cobalt.
I, PIERRE MANHES, Metallurgical Engineer, of 3 Rue Sala, Lyon, in the
Republic of France, do hereby declare the nature of this invention and in what
manner the same is to be performed, to be particularly described and ascertained
in and by the following statement :-
My invention relates to the manufacture of nickel and cobalt.
For the purpose of producing nickel and cobalt the ores of these metals are
nearly always treated by fusion for matt. Sulphurous ores bear the sulphur
necessary for the formation of the matt, while non-sulphurous ores are supplied
The matt
with sulphurated materials or sulphur in the first fusion of these ores.
produced is then either successively roasted and fused, or preferably treated in the
converter by the Manhes process. Whatever method may be employed the iron
may be easily enough and completely enough eliminated, but it is not the same
with the sulphur. The product obtained is always a sulphide of nickel or a crude
nickel containing a comparatively large proportion of sulphur, the ulterior
treatment of which has heretofore necessitated long, difficult and costly operations
producing only a metal of very imperfect quality.
According to my said invention 1 treat this sulphide of nickel or crude nickel
for obtaining by a simple, rapid and economic method ingots of nickel similar to
those of the other usual metals and adapted for the uses of the various industries
which require commercially pure nickel. It will therefore be understood that my
process has for its starting point the treatment of sulphide of nickel or of crude
nickel previously almost altogether freed from iron by one of the processes herein-
before mentioned or by any other process.
For the sake of simplicity I shall hereinafter mention only nickel, it being quite
understood that the whole process may likewise be applied to cobalt in order to
obtain the latter in a metallic state.
In the course of long and numerous experiments I have found that the sulphur
contained in crude nickel freed from iron can be completely eliminated by the
simple fusion of this metal in mixture and in contact with certain basic or alkaline
These reagents are
reagents or fluxes mixed with chlorides of the same nature.
lime, baryta, magnesia, soda, potash or other similar substances from the chemical
point of view, to which chlorides of calcium, lime, barium, magnesium, sodium,
potassium or the like are added. A portion of the sulphur is eliminated in the
state of sulphurous acid, while the other portion combines with reagents added for
forming a scoria which is almost exclusively a basic or alkaline sulphide according
to the nature of the reagents employed.
Although use may be made of the various reagents before enumerated or of other
similar reagents, I usually employ in practice a mixture of lime and chloride of
calcium or better still chloride of lime, as these materials are preferable from an
economic point of view and give moreover excellent results.
Having thus explained the nature of my invention and the principles upon which
it is based, I will now summarily describe a metallurgical operation, taking as an
example the treatment of a crude nickel produced by the working of matt in the
converter by a first fusion, the matt containing very little iron, but enclosing still
a more or less large proportion of sulphur.
The fusion with the special reagents hereinbefore mentioned may be effected in
any suitable apparatus, in the metallurgical furnace, on the sole or in the crucible,

page_text: on condition that the apparatus or furnace in question can easily produce and
maintain the high temperature necessary for the fusion of the pure uickel. In
practice I preferably operate upon the sole and in a reverberatory furnace
heated by gas, such as the Siemens furnace or other similar furnace provided
that it shall be able to fulfil the desired conditions as regards the temperature.
I must here observe that whatever apparatus or furnace may be used, it must be
provided in the interior with a neutral or basic lining, not in view of any reaction
to be obtained in the metallurgical operation, but because the nature of the reagents
employed renders the use of acid walls or linings impossible.
The furnace being suitably heated I commence by providing the surface of the
sole with a sufficiently thick layer of the mixture of lime and chloride of lime so as
to form a kind of false sole the object of which will hereinafter be explained.
Then I introduce into the furnace the crude nickel granulated or crushed to pieces
after having been mixed with a sufficient quantity of the same reagents. Next I
close the door of the furnace and heat slowly, the temperature being gradually
raised until the fusion of the materials introduced into the furnace is complete.
During this fusion the crude metal in contact with the reagents gives up to the
latter the greatest part of the sulphur which it contains, while another part is
eliminated in the state of sulphurous acid. By reason of its density the molten
nickel gradually separates from the scoria formed and reaches the bottom of the
furnace; there it encounters the false sole made of lime and chloride of lime,
traverses it slowly and while transforming it into scoriæ gives up to the same the
little sulphur which it may still have retained. When the fusion of the materials
is complete there remains upon the sole of the furnace commercially pure metallic
nickel upon which is a scoria formed almost exclusively of sulphide of calcium.
When the operation has reached this point the scoria is first caused to flow out and
then the nickel which on leaving the furnace is passed into moulds adapted for the
various uses to which the metal may be put.
As to the proportions of the reagents to be employed for obtaining the complete
desulphuration of the materials treated it is impossible to indicate the same in a
precise manner, these proportions depending, even for an equal proportion of
sulphur, on various circumstances such as the temperature of the apparatus, the
greater or smaller division of the materials, the degree of purity of the reagents
employed and the like.
By way of example however I may indicate the following: I commence by
employing for 1 part of sulphur contained in the materials under treatment
5 parts of one of the basic or alkaline reagents indicated above, lime, soda, potash,
and the like and 1 part of one of the chlorides likewise above stated, I allow these
reagents to act, following the progress of the desulphuration by means of samples
taken in the metallurgical bath; if it appears necessary I augment by addition
the quantity of reagents employed, and proceed with the casting of the metal
when the examination of the samples shows me that the desulphuration is
complete.
It will be understood that the quantities of reagents which I have mentioned
above are indicated only by way of example, that I do not limit my invention to
these proportions, but I reserve on the contrary the right of employing such
quantities of these reagents as experience may show me to be useful or necessary.
If the operation has been well conducted and the temperature has been sufficient
all the materials at the moment of the casting must be in a state of perfect fluidity.
The scoria contains only insignificant traces of nickel, which however is not lost,
for this scoria is melted again with the ore in the furnace wherein the first fusion
or preliminary melting of the ore takes place. It constitutes in fact a doubly
valuable flux by reason of the lime and the sulphur which it contains.
employing this scoria an important saving is achieved by the lime in the fusion of
silicated or silicious ores and by the sulphur in the fusion of non-sulphurous ores
to which a sulphurizing eleinent which is almost always very costly must
be added.
When

page_text: Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
A process for the simple and economical production of pure commercial nickel
by refining sulphide of nickel or crude nickel previously freed from iron as much as
possible, the said process being based upon the elimination of the sulphur by
employing special alkaline or basic reagents mixed with chlorides of the same
nature, substantially as herein before set forth.
Dated this 29th day of December 1894.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C., Agents for the Applicant.