Improved Processes for the Treatment of Silicated Nickel Ores and Pyritic Ores of Nickel and Copper, or Nickel, Copper and Cobalt.
Year: 1891

page_text: Date of Application, 1st May, 1891
Complete Specification Left, 23rd Oct., 1891-Accepted, 28th Nov., 1591
PROVISIONAL SPECIFICATION.
Improved Processes for the Treatment of Silicated Nickel Ores
and Pyritic Ores of Nickel and Copper, or Nickel, Copper
and Cobalt.
I HENRI LOUIS HERRENSCHMIDT, of Petit Quévilly near Rouen, France
Metallurgist do hereby declare the nature of this invention to be as follows:-
My invention relates to improved processes for the treatment of silicated nickel
ores and pyritic ores of nickel and copper with or without cobalt.
Copper and Nickel Pyrites. Pyritic ores containing copper and nickel such as
those of Sudbury in Canada, or other like ores, after undergoing a preliminary
roasting are treated for the production of a matt containing about 30 per cent. of
copper, and 10 to 20 per cent. of nickel, the remainder consisting of iron and
sulphur. This matt is obtained by fusion in a cupola, or blast furnace with the
necessary fluxes for producing a fluid slag. When the pyritic ores of nickel and
copper are sufficiently rich in sulphur, it is only necessary to crush and wash them
so as to sulphate the nickel and copper, thereby avoiding the cost and loss incidental
to the fusion of the ore for obtaining the matt.
Silicated Nickel Ores. The silicated nickel ores of New Caledonia and other
similar ores, are treated for the purpose of obtaining a matt containing generally
about 30 per cent. of copper and 15 to 20 per cent. of nickel with some iron and
sulphur. For this purpose they are melted in a cupola or blast furnace along with .
a suitable proportion of copper pyrites or other cupreous matters and the necessary
fluxes, according to the composition of the hearth. The matts of copper and nickel
obtained from one or other of those classes of ore, silicated or pyritic, or any other
similar matts or the nickel and copper pyrites themselves if sufficiently rich in
sulphur to be directly treated, are crushed and then undergo the following treat-
ment in order to extract the useful metals contained.
Roasting the Matts. The crushed matts are first carefully roasted for the
purpose of converting as completely as possible the nickel and copper into sulphates
and the iron into oxide.
Lixiviation of the Sulphates. The matts or roasted ores are subjected to a
methodical lixiviation so as to obtain a sulphate liquor of a density of about 12°
Beaumé containing nickel copper and a little iron in the form of sulphates.
Chloridizing the Sulphates. The sulphates in the liquor are converted into
chlorides by the addition of a chloride preferably chloride of calcium (which may
be regenerated for use over again) sulphate of lime being precipitated.
Precipitation of the Iron. To the liquor, without decanting it, is added
precipitated hydrated oxide of copper or carbonate of copper, or there may be added
carbonate of lime which precipitates per-chloride of iron and a portion of the copper.
The liquor is then boiled when the whole of the iron remaining in solution in the
form of proto-chloride precipitates while the copper precipitated becomes redissolved.
There remains a pure nickel and copper liquor which is separated from the
precipitate containing sulphate of lime and iron either by decanting and washing or
by filtering and washing.
Separation of the Nickel and Copper. In order to separate in the chloridized
nickel and copper l'quor thus obtained, the nickel from the copper, oxide of nickel
or carbonate of nickel is employed. Nickel precipitated in the form of oxide or
carbonate in any nickel liquor will serve for the purpose. In practice it is
preferred to take a certain quantity of chlorides of nickel and copper liquor and
precip tate by means of milk of lime or an alkaline carbonate, the two metals in the
form of oxides or of carbonates, after which the liquor is decanted. The calcium
chloride decanted off may be employed to chloridize, at the beginning of the
ليم

page_text: treatment, a fresh batch of sulphate liquor. To the precipitated oxides of nickel
and copper or of carbonates obtained is added a fresh quantity of the chloride of
nickel and copper liquor, which gives rise to the following fundamental reaction ;-
The oxide or carbonate of nickel in the precipitate redissolves and is replaced by a
corresponding proportion of the copper in the liquor, which precipitates. After
letting settle and decanting there is added, to the same precipitate, fresh portions of
the initial chloride of nickel and copper liquor in succession, until there is no longer
any displacement of the metals, which indicates that there no longer remains any
uickel in the precipitate which is thenceforth exclusively cupreous. The operation
succeeds well in the cold. The nickel and copper of the last liquor are precipitated
by means of lime or an alkaline carbonate and serve for effecting the separation of
the metals in fresh chloridized liquors.
The liquors previously decanted contain only nickel in the form of chloride.
These liquors are treated in two ways;—
1. By evaporation and calcination, producing pure oxide of nickel and hydro-
chloric acid;
2. By precipitation with lime, producing oxide of nickel and calcium chloride.
The separation of the nickel and copper is thus completely effected.
If, instead of preparing oxide of nickel and oxide of copper, it is desired to
directly produce sulphate of nickel and precipitated oxide of copper, the operation
is conducted in a slightly different manner.
Taking as before the initial sulphate of nickel and copper liquor, the iron is
removed with the aid of heat, by virtue of the above described reaction by means
of a washed precipitate of oxide of copper or of carbonate of copper. A certain
portion only of this sulphated liquor is chloridized and the nickel and
copper in this chloridized portion are precipitated by lime or an alkaline carbonate.
The precipitate thus obtained, after being washed serves to effect the displace-
ment of the metals in the sulphate liquor, the precipitated nickel redissolving in the
form of sulphate of nickel at the expense of an equivalent quantity of copper
which precipitates.
Modifications. The nickel and copper sulphate liquor may be treated directly
from the commencement of the operation, by employing soda or potash, or the
carbonate of either, as precipitating agents instead of lime. The separation of the
metals is effected in this case in the same manner as before but less advan-
tageously.
Presence of Cobalt. If the ores or matts under treatment contain cobalt in
addition to nickel and copper, will go along with the nickel and after separation
of the copper precipitate as before described, nickel and cobalt liquors will be
obtained instead of nickel liquors only. From a certain proportion A of these
nickel and cobalt liquors, the two metals are precipitated by means of lime. The
mixed precipitate of oxide of nickel and oxide of cobalt is transferred into a suitable
vessel with a sufficient quantity of water and is theu subjected to the combined
action of a current of chlorine gas and air blown in under pressure whereby
the highest degree of oxidation is attained, the oxides becoming converted
into peroxides of cobalt and nickel. To the mixed peroxides of cobalt
and nickel is added a fresh quantity B of the original cobalt and nickel
liquors from which the portion A was previously taken, and steam is blown
in to thoroughly agitate, the result being a singular displacement of the metals
as in the case of the separation of the nickel and copper. The nickel of the
precipitate redissolves and is replaced by an equivalent quantity of cobalt from the
liquor which peroxidizes and precipitates. As the fraction B of cobalt and nickel
liquor first added is so proportioned as not to displace the whole of the nickel in
the precipitate, it follows that only nickel will remain in solution after the reaction
is terminated. The solution which has thus become purely nickeliferous is decanted
and a fresh addition C of the original liquor is made which furnishes a second
nickel solution, provided it is still insufficient to take up the whole of the nickel
remaining in the precipitate peroxides treatel. When, after a last addition of

page_text: liquor, there remains in the precipitate only pure peroxide of cobalt, the operation
is completed. The several solutions containing nickel only are added together and
the metal is precipitated in the form of oxide of nickel by means of lime.
manner the separation of the nickel and cobalt is effected.
1001
In this
H. L.
HERRENSCHMIDT.
By A. M. & Wm. Clark,
53, Chancery Lane, London, Patent Agents.
H. L. HERRENSCHMIDT.
By A. M. & Wm. Clark,
53, Chancery Lane, London, Patent Agents.
COMPLETE SPECIFICATION.
Improved Processes for the Treatment of Silicated Nickel Ores
and Pyritic Ores of Nickel and Copper, or Nickel, Copper
and Cobalt.
I HENRI LOUIS HERRENSCHMIDT, of Petit Quevilly near Rouen, France,
Metallurgist do hereby declare the nature of this invention and in what manner the
same is to be performed, to be particnlarly described and ascertained in and by the
following statement :-
My invention relates to improved processes for the treatment of silicated nickel
ores and pyritic ores of nickel and copper with or without cobalt.
Copper and Nickel Pyrites. Pyritic ores containing copper and nickel such as
those of Sudbury in Canada, or other like ores, after undergoing a preliminary
roasting are treated for the production of a matt containing about 30 per cent. of
copper, and 10 to 20 per cent. of nickel, the remainder consisting of iron and sulphur.
This matt is obtained by fusion in a cupola, or blast furnace with the necessary fluxes
for producing a fluid slag. When the pyritic ores of nickel and copper are
sufficiently rich in sulphur, it is only necessary to crush and wash them so as to
sulphate the nickel and copper, thereby avoiding the cost and loss incidental to the
fusion of the ore for obtaining the matt.
Silicated Nickel Ores. The silicated nickel ores of New Caledonia and other
similar ores, are treated for the purpose of obtaining a matt containing generally
about 30 per cent. of copper and 15 to 20 per cent. of nickel with some iron and
sulphur. For this purpose they are melted in a cupola or blast furnace along with
a suitable proportion of copper pyrites or other cupreous matters and the necessary
fluxes, according to the composition of the hearth. The matts of copper and nickel
obtained from one or other of these classes of ore, silicated or pyritic, or any other
similar matts or the nickel and copper pyrites themselves if sufficiently rich in
sulphur to be directly treated, are crushed and then undergo the following treat-
ment in order to extract the useful metals contained.
Roasting the Matts. The crushed matts are first carefully roasted for the
purpose of converting as completely as possible the nickel and copper into sulphates
and the iron into oxide.
Lixiviation of the Sulphates. The matts or roasted ores are subjected to
a methodical lixiviation so as to obtain a sulphate liquor of a density of about
12° Beaumé containing nickel copper and a little iron in the form of sulphates.
Chloridizing the Sulphates. The sulphates in the liquor are converted into
chlorides by the addition of a chloride preferably chloride of calcium (may be
regenerated for use over again) sulphate of lime being precipitated.
Precipitation of the Iron. To the liquor, without decanting it, is added
precipitated hydrated oxide of copper or carbonate of copper, or there may be
added carbonate of lime which precipitates per-chloride of iron and a portion of
the copper. The liquor is then boiled when the whole of the iron remaining in
solution in the form of proto-chloride precipitates while the copper precipitated
becomes redissolved. There remains a pure nickel and copper liquor which is
separated from the precipitate containing sulphate of lime and iron either by
decanting and washing or by filtering and washing.

page_text: Separation of the Nickel and Copper. In order to separate in the chloridized
nickel and copper liquor thus obtained, the nickel from the copper, oxide of nickel
or carbonate of nickel is employed. Nickel precipitated in the form of oxide or
carbonate in any nickel liquor will serve for the purpose. In practice it is preferred
to take a certain quantity of chlorides of nickel and copper liquor and precipitate
by means of milk of lime or an alkaline carbonate, the two metals in the form of
oxides or of carbonates, after which the liquor is decanted. The calcium chloride
decanted off may be employed to chloridize, at the beginning of the treatment, a
fresh batch of sulphate liquor. To the precipitated oxides of nickel and copper or
of carbonates obtained is added a fresh quantity of the chloride of nickel and copper
liquor, which gives rise to the following fundamental reaction;-The oxide or
carbonate of nickel in the precipitate redissolves and is replaced by a corresponding
proportion of the copper in the liquor, which precipitates. After letting settle and
decanting there is added, to the same precipitate, fresh portions of the initial
chloride of nickel and copper liquor in succession, until there is no longer any
displacement of the metals, which indicates that there no longer remains any nickel
in the precipitate which is thenceforth exclusively cupreous. The operation succeeds
well in the cold. The nickel and copper of the last liquor are precipitated by
means of lime or an alkaline carbonate and serve for effecting the separation of the
metals in fresh chloridized liquors.
The liquors previously decanted contain only nickel in the form of chloride.
These liquors are treated in two ways;-
1. By evaporation and calcination, producing pure oxide of nickel and hydro-
chloric acid.
2. By precipitation with lime, producing oxide of nickel and calcium chloride.
The separation of the nickel and copper is thus completely effected.
If, instead of preparing oxide of nickel and oxide of copper, it is desired to
directly produce sulphate of nickel and precipitated oxide of copper, the operation
is conducted in a slightly different manner.
Taking as before the initial sulphate of nickel and copper liquor, the iron is
removed with the aid of heat, by virtue of the above described reaction by
means of a washed precipitate of oxide of copper or of carbonate of copper. A
certain portion only of this sulphated liquor is chloridized and the nickel and
copper in this chloridized portion are precipitated by lime or an alkaline carbonate.
The precipitate thus obtained, after being washed serves to effect the displacement
of the metals in the sulphate liquor, the precipitated nickel redissolving in the forin
of sulphate of nickel at the expense of an equivalent quantity of copper which
precipitates.
Modifications. The nickel and copper sulphate liquor may be treated directly
from the commencement of the operation, by employing soda or potash, or the
carbonate of either, as precipitating agents instead of lime. The separation of
the metals is effected in this case in the same manner as before but less advan-
tageously.
Presence of Cobalt. If the ores or matts under treatment contain cobalt in
addition to nickel and copper, it will go along with the nickel and after separation
of the copper precipitate as before described, nickel and cobalt liquors will be
obtained instead of nickel liquors only. From a certain proportion A. of these
nickel and cobalt liquors, the two metals are precipitated by means of lime. The
mixed precipitate of oxide of nickel and oxide of cobalt is transferred into a
suitable vessel with a sufficient quantity of water and is then subjected to the
combined action of a current of chlorine gas and air blown in under pressure
whereby the highest degree of oxidation is attained, the oxides becoming converted
into peroxides of cobalt and nickel. To the mixed peroxides of cobalt and nickel
is added a fresh quantity B of the original cobalt and nickel liquors from which the
portion A was previously taken, and steam is blown in to thoroughly agitate, the
result being a singular displacement of the metals, as in the case of the separation
of the nickel and copper. The nickel of the precipitate redissolves and is replaced

page_text: by an equivalent quantity of cobalt from the liquor which peroxidizes and
precipitates. As the fraction B of cobalt and nickel liquor first added is so propor-
tioned as not to displace the whole of the nickel in the precipitate, it follows that only
nickel will remain in solution after the reaction is terminated. The solution which
has thus become purely nickeliferous is decanted and a fresh addition C of the
original liquor is made which furnishes a second nickel solution, provided it is still
insufficient to take up the whole of the nickel remaining in the precipitated
peroxides treated. When, after a last addition of liquor, there remains in the
precipitate only pure peroxide of cobalt, the operation is completed. The several
solutions containing nickel only are added together and the metal is precipitated in
the form of oxide of nickel by means of lime. In this manner the separation of the
nickel and cobalt is effected.
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 I
claim is-
1st. The herein described method of separating the iron which fouls the sulphates
of nickel and copper liquors by means of copper precipitated in the form of oxile or
carbonate, as specified.
2nd. The herein described method of separating the nickel from the copper in
sulphate or chloride liquors of these two metals, by means of precipitated oxide or
carbonate of nickel, as specified.
3rd. The herein described method of separating the nickel from the cobalt, by
means of peroxide of nickel, as specified.
4th. The series of operations constituting the herein described process of treating
silicated nickel ores and nickel pyrites, whether or not they contain copper or
cobalt.
Dated this 23rd day of October 1801
H. L. HERRENSCHMIDT.
By A. M. & Wm. Clark,
53, Chancery Lane, London, Chartered Patent Agents.
H. L. HERRENSCHMIDT.
By A. M. & Wm. Clark,
, Chancery Lane, London, Chartered Patent Agents.