Improvements in the Manufacture of Nickel.
Year: 1890

page_text: Date of Application, 12th Aug., 1890.
Complete Specification Left, 12th May, 1891-Accepted, 13th June, 1891
471
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Nickel.
I, LUDWIG MOND, of Winnington Hall, Northwich, Cheshire, do hereby declare
the nature of this invention to be as follows:-
4444
This invention has for its object improvements in obtaining pure metallic nickel
from its oxide or from a mixture of its oxide with other metallic oxides or impurities,
or from impure metallic nickel.
For this purpose the oxide of nickel (which may contain any number of
impurities) is reduced to the metallic state by treating it with carbonic oxide or
with hydrogen or a gaseous mixture contaiming these gases, at a temperature of
between 350° and 400° C., or by heating the oxalate of nickel, either by itself or in
a current of hydrogen, to the temperature required for its complete décomposition.
The finely divided metal so obtained is allowed to cool to ordinary temperature and
is then treated with carbonic oxide gas which may be mixed with other gases but
should be free from oxygen or halogens. The nickel combines with the carbonic
oxide and forms a readily volatile compound called nickel-carbon-oxide, which is
easily carried off by the excess of the gas employed.
The mixture of the vapour of this compound and other gases so obtained is passed
through tubes or vessels in which it is heated to about 180° C. when the nickel-
carbon-oxide is decomposed again into nickel and carbonic oxide. The nickel
separates out perfectly pure, in coherent metallic masses more or less attached
to the sides of the tubes or vessels in which the gas has been heated, and the
carbonic oxide can be used over again to treat fresh masses of the reduced
oxide.
After some time the action of the finely divided nickel upon carbonic oxide
becomes less energetic. It is then heated up to 350° to 400° C. in a current of
carbonic oxide or hydrogen and cooled down again to ordinary temperature, by
which means its energy is restored.
Impure metallic nickel obtained in any other way than the one indicated can also
be treated in the same way to obtain the pure metal, but the action is more rapid
the more finely the nickel is divided. All the impurities in the nickel or the oxide,
even cobalt, are not in the least acted upon by carbonic oxide, and remain behind
after the nickel has been volatilized.
Doted this 12th day of Anœust. 1890.
W. P. THOMPSON & BOULT,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Nickel.
I, LUDWIG MOND of Winnington Hall, Northwich in the County of Cheshire,
Manufacturing Chemist, 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:-
This invention has for its object improvements in obtaining pure metallic nickel
from its oxide or from a mixture of its oxide with other metallic oxides or impurities
or from impure metallic nickel, and enables me rapidly and economically to extract
pure metallic nickel from its ores.
It is based on the remarkable fact that nickel when exposed under certain
conditions to the action of carbonic oxide gas forms with it a gaseous product whose
formula is Ni (CO), from which the nickel can subsequently be separated. I have
found that this action goes on in the presence of all other bodies provided that came
1'

page_text: is taken that the nickel is in the metallic state and that it acts with sufficient rapidity
to give economical results provided that the nickel or the mixtures in which it is
present are sufficiently finely divided or present sufficient surface for the free action
of the gas.
It can therefore be applied directly to the extraction of nickel from its
orcs as well as to the separation of nickel from mixtures or substances containing it
in the form of oxide or in the metallic state.
The principal nickel ores used in the metallurgy of this metal contain the nickel
in combination with arsenic and sulphur besides other metals and gangue. These
ores have first to be submitted to the process of calcination, as is well understood,
in order to convert the nickel into the form of oxide and to drive off the arsenic;
sulphur and other volatile compounds formed as far as practicable; by the subse-
quent stages of my process hereafter described the oxide of nickel is reduced to
metallic nickel and this latter volatilized by treatment with carbonic oxide.
If the
arsenic and sulphur have not been completely driven off by the first calcination, as
is generally the case, the residuum after volatilizing part of the nickel is subjected
to a fresh calcination and if necessary this is repeated several times, till all the nickel
is volatilized.
In dealing with nickel ores which contain nickel oxide in chemical combination
with silicic acid, arsenic acid or other substances not removable by calcination, I
prefer to treat such ores so as to convert the nickel into nickel speiss or nickel matte,
as is well understood, and to subject the latter to calcination as aforesaid. The
mixture of oxides of nickel and foreign substances resulting from such calcination
must be finely comminuted.
In order to separate by my method the nickel from the impurities or foreign
matters mixed or combined with its oxide it is necessary first of all to reduce the
oxide so that the nickel may be present in the metallic state.
For this purpose !
treat it with reducing gases, preferably with carbonic oxide or with hydrogen or a
gaseous mixture containing these gases at a temperature varying according to the
gases used between 350° C. and 500° C:
•
If these gases consist of nearly pure hydrogen the temperature of 350° C. is
sufficient. If on the other hand, diluted carbonic oxide is used, a temperature of
upwards of 500° C. is required to effect a speedy and complete reduction.
The effect of this treatment is to produce very finely divided metallic nickel in
the mixture. This is allowed to cool to about 50° C, which 1 find to be the most
suitable temperature. If preferred, it may be cooled to ordinary atmospheric
temperature, as the compound will form at a temperature as low as 0° C. From this
up to 150° C. it is possible to work, but I prefer the temperature given above,
When the mixture has cooled sufficiently it is subjected to the action of a stream
of carbonic oxide gas, either pure or in mixture with other gases.
Neither oxygen
nor the halogens must be present. As pure carbonic oxide is expensive to make it
will be found more economical to work with mixtures of nitrogen, hydrogen and
carbonic oxide such as are cheaply manufactured by many processes now in common
use and known as water-gas or producer-gas. These are effective if care be taken
that neither oxygen nor the halogens are present.
.
The nickel combines with the carbonic oxide present and passes off with the
excess of the gas employed, and the mixture of the nickel compound thus formed
and the other gases present is passed through chambers, tubes or vessels in which
it is heated to a suitable temperature when the nickel separates out. The most
suitable temperature for this purpose varies according to the composition of the
gaseous mixture from about 180° C. to about 250° C.
If this range of temperature be exceeded, the nickel becomes contaminated with
carbon owing to its power of absorbing carbon from carbonic oxide and forming
carbonic acid, while at temperatures below 180° C. the deposition of the nickel will
be less rapidly and less completely effected. The nickel separates out perfectly
pure when the above conditions are observed, and is found in coherent metallic
masses more or less attached to the sides of the tubes or vessels in which the gas
has been heated. The carbonic oxide is also regenerated and the saine gases can'

page_text: be used over and over again to extract the metal. There are considerable advan-
tages in thus using the same gases over and over again because the danger arising
out of the poisonous qualities of the nickel carbon-oxide are thus almost wholly
overcome inasmuch as the gases never leave the closed apparatus in which the
treatment is carried out. If therefore the nickel compound should be incompletely
decomposed no danger arises, and the metal contained therein is not lost but will
be deposited in the subsequent operations.
Other methods than the one already described can be adopted for heating and
decomposing the nickel-carbon oxide, such as mixing a hot inert gas with the gases
containing it, or it may be passed through hot liquids of a sufficiently high boiling
point and subsequently separated therefrom by decantation or evaporation or other-
wise. If it is not desired to decompose the nickel-carbon-oxide at the moment of
manufacture the gases containing it can be passed through refrigerating apparatus
with or without the use of pressure to hasten the condensation. The nickel-carbon-
oxide is thus obtained as a liquid and can be bottled. Or the gases containing it
can be passed through a liquid capable of absorbing it (such as benzole, petroleum,
tar-oils, &c. &c.) so as to obtain a solution of it which can be kept and stored. The
nickel can at any time be separated from the liquid nickel-carbon-oxide or its
solution by heating to the required temperature.
The above process may also be applied to extract pure nickel from an impure
metallic mixture, the action being more rapid the more finely the metal is divided.
The impurities and foreign substances remain behind after the nickel is removed.
After some time the action of the nickel on the carbonic oxide is found to become
less energetic. It is then heated up to a temperature of about 350° C. while the
current of carbonic oxide gas used for volatilizing the nickel is continued, and
cooled down again below 150° C., by which means its energy is restored.
In carrying out this invention on a large scale 1 prefer to use an apparatus which
I have patented for this purpose under the title of :-
*
Improvements in apparatus for treating solids by gases; also applicable to other
purposes" (No. 10957 of the 10th August 1887).
This apparatus consists of two cylinders fixed one inside the other, which turn
round their axis together and are arranged so that the substances to be treated
pass through the annular space between the two cylinders in one direction, whilst
the gras passes in the opposite direction, and which are provided with longitudinal
For projections and a helix in the annular space so as to move the solid substance
forward slowly and to constantly expose fresh surfaces to the action of the gas.
arrange a number of such cylinders (or other similar apparatus properly constructed
for the transport and stirring of solid substances) in a series so connected by
conduits, transporting screws or elevators that the solid substance and the gases
passing through them can readily be taken from one to the other in succession.
In a certain number of cylinders constituting a series, the reduction of the oxide
and the revivifying are carried out by passing carbonic oxide or hydrogen or
water-gas through them, previously heated to the required temperature, while
through the others a current of carbonic oxide, preferably at a temperature of 50° C.
is passed in succession in a direction opposite to that taken by the solid substance:
The solid substance passes through the whole series of cylinders in succession.
Those cylinders which are used for the reduction and revivifying may be placed
in furnaces so as to heat them to the required temperature, but I prefer to raise the
gases used for these purposes in properly constructed superheaters, to such
temperature that external heating of the cylinders becomes unnecessary.
A series of cylinders may consist of such number and be of such total length as
is sufficient for the complete extraction of the nickel from the substance under
treatment by passing once through them, or this substance may be passed repeatedly
through the apparatus until all the nickel is extracted.
In using a substance of a compact nature it will be advisable to take it out of
the apparatus and regrind it from time to time.
The carbonic oxide circulating through the apparatus in the direction opposite

page_text: to the course of the substance under treatment, becomes more and more loaded
with nickel-carbon-oxide, and after leaving the apparatus it is passed through a
series of tubes or chambers heated to a temperature varying from about 180° C. to
about 250° C. according to the composition of the gases to be decomposed, in which
the nickel is deposited in a very pure state and the carbonic oxide set free again.
On leaving these tubes or chambers the gas is returned to the cylinders and can
be used over and over again, as its composition after the nickel has been separated
is practically the same as it originally was. I prefer to use for this purpose
carbonic oxide obtained by the incomplete combustion of dry coke or anthracite,
but, as the same gas is used over continuously, a purer carbonic oxide such as can
be obtained by passing carbonic acid through incandescent coke or anthracite, may
with advantage be made use of at comparatively small expense.
The nickel, which is deposited in the tubes or chambers above mentioned, is from
time to time removed from these, which must be so constructed as to be easily
accessible for taking out the nickel. I prefer to use two sets of such tubes or
chambers so as to be able to empty one while working the other, and I coat their
inner surface with graphite or loam so as to prevent the nickel from adhering
thereto, or I introduce into the tubes thin metallic sheets, bent so as to fit the
tubes, upon which sheets the nickel is deposited and from which it is easily
removable. The nickel is thus obtained in coherent, bright metallic masses of
great purity quite ready for the market.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed, I declare that what 1
claim is
1. The improvement in the manufacture of nickel, which consists in the extraction
of this metal from substances or mixtures containing it (without previous removal
of mineral or other foreign matters with which it is found) by calcination, reduction
and treatment with carbonic oxide whereby the nickel is volatilized in the form of
nickel-carbon-oxide gas at a low temperature, and subsequently obtaining the
nickel from this compound by the application of heat substantially as described.
2. The improvement in the manufacture of nickel, which consists in extracting
this metal from oxide of nickel contaminated or mixed with other substance or
substances by reducing the same at a suitable temperature by means of carbonic
oxide, hydrogen or other reducing gases, and treating the resulting mass with
carbonic oxide substantially as described.
3. The improvement in the manufacture of nickel which consists in extracting
this metal from substances or mixtures containing nickel in the metallic state, by
treatment with carbonic oxide substantially as described.
4. In the manufacture of nickel by the use of carbonic oxide as above described
the regenerating and using over and over again the same carbonic oxide gas for
volatilizing fresh quantities of nickel in the form of nickel-carbon-oxide gas
substantially as described.
5. In the manufacture of nickel, the use of impure carbonic oxide such as that
known as water-gas and producer gas to extract the nickel substantially as
described.
6. Obtaining pure metallic nickel by passing the gaseous mixture containing
nickel-carbon-oxide through refrigerating apparatus (whereby the compound is
obtained in the liquid state) or by passing such gaseous mixture through liquids
capable of absorbing the nickel-carbon-oxide and subsequently decomposing by
heat the liquid nickel-carbon-oxide or its solution so obtained substantially as
described.