AU2019426767A1 - Method for treating nickel-containing raw material - Google Patents

Method for treating nickel-containing raw material Download PDF

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Publication number
AU2019426767A1
AU2019426767A1 AU2019426767A AU2019426767A AU2019426767A1 AU 2019426767 A1 AU2019426767 A1 AU 2019426767A1 AU 2019426767 A AU2019426767 A AU 2019426767A AU 2019426767 A AU2019426767 A AU 2019426767A AU 2019426767 A1 AU2019426767 A1 AU 2019426767A1
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Australia
Prior art keywords
nickel
raw material
containing raw
medium
roasting
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AU2019426767A
Inventor
Kenzo Sauda
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JGC Corp
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JGC Corp
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Publication date
Application filed by JGC Corp filed Critical JGC Corp
Priority to PCT/JP2019/003332 priority Critical patent/WO2020157898A1/en
Publication of AU2019426767A1 publication Critical patent/AU2019426767A1/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/10Sulfates
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/02Obtaining nickel or cobalt by dry processes

Abstract

A medium to be bombarded with a nickel-containing raw material is introduced into a roasting furnace for roasting the nickel-containing raw material, and then the nickel-containing raw material is roasted while grinding the nickel-containing raw material with the medium.

Description

DESCRIPTION METHOD FOR TREATING NICKEL-CONTAINING RAW MATERIAL
Technical Field
[0001] The present invention relates to a method for treating a nickel-containing raw
material.
Background Art
[0002] A nickel sulfate compound, which is a raw material of various nickel
compounds or metallic nickel, has been used for electrolytic nickel plating, electroless
nickel plating, a catalyst material, or the like. Recently, a demand for a secondary
battery in which a nickel compound or metallic nickel is used as a positive electrode
material, as a power source of transportation equipment, for example, an electric vehicle
or the like, electronic equipment, or the like, is expected to increase in the future. Stable
feeding of a high-purity nickel sulfate compound has been desired to obtain a high
performance secondary battery.
[0003] Examples of impurities that may be contained in a low-purity nickel compound
can include other metal compounds such as iron, copper, cobalt, manganese, and
magnesium. A method for dissolving, in a sulfuric acid solution, metallic nickel having
a high purity of nickel by an electrowinning method, or a solvent extraction method has
been used as a method for obtaining a high-purity nickel compound. In the solvent
extraction method, a step of selectively extracting and removing other metal compounds
or selectively extracting and removing a nickel compound is performed. In either case,
in order to selectively extract specific metal ions, a special chemical is required, resulting in a high cost.
[0004] Known methods for manufacturing nickel sulfate also include a method in
which the anion of a nickel compound is exchanged with a sulfate ion through ion
exchange, and a method in which a nickel metal powder is dissolved in a sulfuric acid
solution with hydrogen gas generated. In addition, Patent Literature 1 discloses a
method for obtaining water-soluble nickel sulfate by heat-treating green nickel oxide
powder having a specific gravity of more than 6.30 in sulfuric acid and then leaching the
green heated nickel oxide powder with hot water. In Patent Literature 1, examples of
sulfuric acid used in the heat treatment include a 30% to 60% sulfuric acid solution
(Claims 1to 5) and 95% concentrated sulfuric acid (Claims 6 to 7). In Patent Literature
1, when the concentrated sulfuric acid having a concentration of 95% is used (Examples
7 to 9), a high temperature of 275°C or higher is required.
Citation List
Patent Literature
[0005] Patent Literature 1: US 3,002,814
Summary of Invention
Technical Problem
[0006] An object of the present invention is to provide a method for treating a nickel
containing raw material capable of treating the nickel-containing raw material by a dry
refining method.
Solution to Problem
[0007] A first aspect of the present invention is a method for treating a nickel
containing raw material, the method including: introducing a medium into a roasting
furnace for roasting a nickel-containing raw material to allow the medium to collide with
the nickel-containing raw material; and roasting the nickel-containing raw material while
grinding the nickel-containing raw material with the medium.
[0008] A second aspect of the present invention is the method for treating a nickel
containing raw material according to the first aspect, in which the roasting furnace has a
fluidized bed.
[0009] A third aspect of the present invention is the method for treating a nickel
containing raw material according to the first or second aspect, in which the medium is
rolled in the roasting furnace.
[0010] A fourth aspect of the present invention is the method for treating a nickel
containing raw material according to any one of the first to third aspects, in which the
medium fills 5 to 20 vol% of a space formed between a bottom of an object to be roasted
and an outlet port for a roasted product in the roasting furnace.
[0011] A fifth aspect of the present invention is the method for treating a nickel
containing raw material according to any one of the first to fourth aspects, in which in a
case where a component harder than the nickel-containing raw material is mixed and fed
with the nickel-containing raw material in addition to the medium, an addition amount of
the medium is reduced as compared to a case where the hard component is not mixed.
[0012] A sixth aspect of the present invention is the method for treating a nickel
containing raw material according to the second aspect, in which the medium has a
particle size or density which allows a flow velocity of the medium to be equal to or less
than a fluidization initiation velocity Umf.
[0013] A seventh aspect of the present invention is the method for treating a nickel
containing raw material according to any one of the first to sixth aspects, in which the
medium is formed of a material that is softer than an inner wall material of the roasting
furnace and harder than the nickel-containing raw material.
[0014] An eighth aspect of the present invention is the method for treating a nickel
containing raw material according to any one of the first to seventh aspects, in which the
nickel-containing raw material is roasted under conditions of an oxygen partial pressure
and a sulfur dioxide partial pressure at which nickel sulfate is more thermodynamically
stable than nickel oxide in a Ni-S-O system and iron oxide is more thermodynamically
stable than iron sulfate in an Fe-S-O system.
Advantageous Effects of Invention
[0015] According to the first aspect, since the nickel-containing raw material is treated
by a dry refining method, it is not necessary to use liquid sulfuric acid, and the treatment
is easily performed. Further, since the nickel-containing raw material is roasted while
grinding the nickel-containing raw material with the medium, a conversion reaction from
a nickel component of the nickel-containing raw material into a nickel compound can be
accelerated to improve reactivity.
[0016] According to the second aspect, a device is miniaturized as compared to a case
where a stirring type roasting furnace, a rotary furnace type roasting furnace, or the like
is used.
[0017] According to the third aspect, since the medium is rolled in the roasting furnace,
reactivity is further improved.
[0018] According to the fourth aspect, since movement of the medium is hardly inhibited, and a ratio of the medium to the object to be roasted is preferred, reactivity is further improved.
[0019] According to the fifth aspect, since the addition amount of the medium can be
reduced, a cost is reduced.
[0020] According to the sixth aspect, in the case where the roasting furnace has the
fluidized bed, the flow of the medium is suppressed, such that the medium can be
prevented from coming into contact with an inner wall of the roasting furnace, thereby
reducing deterioration, damage, or the like inside the roasting furnace.
[0021] According to the seventh aspect, it is easy to improve reactivity by the grinding
of the nickel-containing raw material and to reduce deterioration, damage, or the like of
the inner wall material at the same time.
[0022] According to the eighth aspect, even in a case where the nickel-containing raw
material contains an iron component, the nickel component is converted into nickel
sulfate and conversion from the iron component into iron sulfate is suppressed. Thus, it
is possible to suppress consumption of a sulfur component by the iron component and to
improve production efficiency of nickel sulfate.
Brief Description of Drawings
[0023] FIG. 1 is a cross-sectional view of the inside of a roasting furnace for
schematically illustrating a treatment method according to an embodiment.
FIG. 2 is a cross-sectional view for describing an action of a medium on a
nickel-containing raw material.
FIG. 3 is a cross-sectional view for describing a state in which particle
fragments of the nickel-containing raw material are aggregated.
FIG. 4 is a view illustrating a conceptual phase diagram of each of a Ni-S-O
system and an Fe-S-O system.
Description of Embodiments
[0024] In a treatment method of the present embodiment, an object to be roasted is
roasted in a roasting furnace. An example of the object to be roasted can include a
nickel-containing raw material.
[0025] The nickel-containing raw material may be a nickel compound or metallic
nickel as long as it contains a nickel element. A nickel compound is not particularly
limited, and examples thereof can include nickel salts such as nickel oxide, nickel
hydroxide, nickel sulfide, and nickel chloride. The nickel compound may be a hydrate.
The metallic nickel may be a nickel alloy such as ferronickel. When metallic nickel (a
simple substance or an alloy) is used as the nickel-containing raw material, metallic nickel
may be a shot formed of small pieces of a molten metal. Nickel ore can be used as the
nickel-containing raw material. Examples of the nickel ore can include one or more of
nickel oxide ore and nickel sulfide ore. Nickel matte containing nickel sulfide as a main
component or the like can be used as the nickel-containing raw material.
[0026] The nickel matte may have, for example, a composition (weight ratio) of 45 to
%ofNi,about20%ofFe,20to25%ofS,andaboutloorlessofCo. Further,nickel
matte in which a concentration of nickel is increased in a rotary furnace may have, for
example, a composition (weight ratio) of about 78% of Ni, about 1% of Co, about 1% of
Fe,andabout20%ofS. The nickel matte is in a state in which Ni 3 S 2 and metallic nickel
(Ni) are mixed with each other based on the amount of sulfur component. The
ferronickel may have, for example, a composition (weight ratio) of 18 to 23% ofNi, about
1% of Co, and 76 to 81% of Fe.
[0027] Examples of the nickel oxide ore can include laterite ores containing a nickel
component, such as limonite and saprolite. The limonite may be limonite containing a
small amount of an iron component or limonite containing a large amount of an iron
component. The saprolite may be saprolite in which a content of nickel is high (for
example, a content of Ni is 1.8 wt% or higher) or may be saprolite in which a content of
nickel is low (for example, a content of Ni is lower than 1.8 wt%). Examples of the
nickel sulfide ore can include pentlandite, millerite, chalcopyrite containing a nickel
component, and pyrrhotite containing a nickel component.
[0028] In the roasting step, the nickel-containing raw material preferably contains one
or more selected from the group consisting of nickel sulfide ore, nickel oxide ore, nickel
sulfide, nickel matte, nickel oxide, and ferronickel. The nickel-containing raw material
may or may not contain an iron component. An iron component is separated from a
nickel sulfate compound in a subsequent step, but it is desirable that the amount of the
iron component in the raw material is small, from the viewpoint of energy consumption.
The nickel-containing raw material may be used alone or in combination of two or more.
In a case where two or more kinds of the nickel-containing raw materials are used, these
raw materials may be fed in a mixed state or may be fed separately. In a case where
sulfating roasting is performed in the roasting step, a sulfur component may be fed from
the outside, and/or a nickel-containing raw material containing a sulfur component as at
least a part of the raw material, for example, nickel sulfide ore, nickel sulfide, and nickel
matte may be used.
[0029] Examples of the roasting furnace can include a stirring type roasting furnace, a
rotary furnace type roasting furnace, and a fluidized roasting furnace having a fluidized bed. In the related art, for roasting of ore or the like, sulfating roasting is performed using a stirring type roasting furnace or a rotary furnace type roasting furnace after coarsely crushing mined ore. In this case, a burden of pretreating an object to be roasted is reduced and a rotation speed is slow, but a reaction speed is slow and a device becomes large. Therefore, a fluidized roasting furnace of a type for roasting an object to be roasted while allowing the object to be roasted to flow in combustion air in a floating state has become widespread. The device can be miniaturized by adopting the fluidized roasting furnace.
[0030] In the case of the present embodiment, the roasting furnace has a fluidized bed.
FIG. 1 is a cross-sectional view of the inside of the roasting furnace for schematically
illustrating the treatment method according to the present embodiment. In order to allow
an object to be roasted 23 to form a fluidized bed 20, a gas inlet 12 is provided below a
furnace body 11 of a roasting furnace 10, and a gas outlet 13 is provided above the furnace
body 11. A gas dispersion plate 14 crossing the furnace body 11 in a radial direction is
provided at a bottom of the fluidized bed 20. Each of a feed port 15 for the object to be
roasted 23 and an outlet port 16 for a roasted product 24 is provided on a side portion of
the furnace body 11. In the case of the present embodiment, the feed port 15 is provided
above the outlet port 16. Each of a height of the feed port 15 and the outlet port 16 may
be about the same as a height of the fluidized bed 20. A floating layer 22 in which fine
particles such as the object to be roasted 23, components to be mixed with the object to
be roasted 23, and the roasted product 24 float may be formed above of the fluidized bed
20. The fluidized bed 20 and the floating layer 22 illustrated in FIG. 1 schematically
represent the concept of the embodiment by appropriately changing a scale.
[0031] Flowing gas flowing in through the gas inlet 12 passes through the gas dispersion plate 14 having a large number of holes to cause an upward flow over the entire cross section of the furnace body 11 and thus to allow the object to be roasted 23 to float.
When a flow velocity of the object to be roasted 23 in the furnace body 11 is adjusted to
equal to or more than a fluidization initiation velocity Umf of the object to be roasted 23
according to a parameter such as a flow rate of the flowing gas, a particle size of the object
to be roasted 23, a diameter (inner diameter) of the furnace body 11, or a filling density
of the objects to be roasted 23, the object to be roasted 23 flows to form the fluidized bed
20. In order to prevent the object to be roasted 23 from scattering outside the furnace
body 11, it is preferable that the flow velocity of the object to be roasted 23 is slower than
a free fall velocity of particles of the object to be roasted 23.
[0032] A medium 21 is fed into the roasting furnace 10 together with the object to be
roasted 23 or separately from the object to be roasted 23. The medium 21 may be fed
through the feed port 15 for the object to be roasted 23. A feed port for the medium 21
may be provided separately from the feed port 15. Even in a case where the medium 21
is fed through the feed port 15 for the object to be roasted 23, the object to be roasted 23
and the medium 21 may be fed separately, or may be fed into the roasting furnace 10 in a
state in which both are mixed together in advance.
[0033] A flow velocity of the medium 21 may be enough as long as the medium 21 is
rolled in the roasting furnace 10. The flow velocity of the medium 21 in the furnace
body 11 can be adjusted to equal to or less than a fluidization initiation velocity Umf of
the medium 21 or less than the fluidization initiation velocity Umf of the medium 21
according to a parameter such as the flow rate of the flowing gas, a particle size of the
medium 21, the diameter (inner diameter) of the furnace body 11, or a filling density of
the media 21. By suppressing the flow of the medium 21, it is possible to prevent the medium 21 from coming into contact with an inner wall of the roasting furnace 10 and to reduce deterioration, damage, or the like inside the roasting furnace 10, which is preferable. The medium 21 may float substantially vertically with respect to the fluidized bed 20 of the object to be roasted 23. In a case where the medium 21 remains in the vicinity of the gas dispersion plate 14, the medium 21 may be rolled in a substantially horizontal direction. A ratio of the floating media 21 to the rolling media
21 is not particularly limited, but can be adjusted by a change in the flow rate of the
flowing gas, a particle size distribution of the media 21, or the like.
[0034] A ratio of a filling amount of the media 21 to a volume of a space is preferably
to 20 vol%, the space being formed between the gas dispersion plate 14 forming a
bottom of the object to be roasted 23 and the outlet port 16 for the roasted product 24 in
the roasting furnace 10. That is, the media 21 are preferably filled in 5 to 20 vol% with
respect to the objects to be roasted 23 in the fluidized bed 20. When a proportion of the
medium 21 is too small, a range in which the medium 21 acts on the object to be roasted
23 is reduced. When the proportion of the medium 21 is too large, movement of the
medium 21 is reduced. When the proportion of the medium 21 is preferred, the medium
21 is more likely to collide with the object to be roasted 23, and a relative speed of the
medium 21 to the object to be roasted 23 at collision is also increased. Therefore, an
effect of improving reactivity during roasting is increased.
[0035] In a case where a component harder than the nickel-containing raw material
which is the object to be roasted 23 is mixed in the nickel-containing raw material, an
addition amount of the medium 21 can be reduced as compared to a case where the hard
component is not mixed. Since the hard component collides with a nickel-containing
raw material in a particulate form to grind the nickel-containing raw material, the hard component performs the same function as the medium 21. Examples of the hard component can include a silica component and an alumina component contained in nickel ore and the like. As for a proportion in which the amount of medium 21 is reduced depending on the amount of hard component, for example, in a case where the hard component is a silica component, a reduced proportion is 0.01 to 100 vol%, and in a case where the hard component is an alumina component, a reduced proportion is 0.1 to 10 vol% or the like.
[0036] A material of the medium 21 is preferably a material that is softer than an inner
wall material of the roasting furnace 10 and harder than the nickel-containing raw material.
Therefore, it is easy to improve reactivity by the grinding of the nickel-containing raw
material and to reduce deterioration, damage, or the like of the inner wall material at the
same time. In a case where an acidic component such as sulfuric acid is used for a
reaction, an acid resistant lining material is preferred as the inner wall material. Specific
examples of the medium 21 can include aluminum oxides such as synthetic alumina,
zirconia, silica, silicon nitride, silicon carbide, tungsten carbide, and glass. A particle
shape of the medium 21 is not particularly limited, and examples thereof can include a
spherical shape, a columnar shape, and a polyhedral shape. An average particle size of
the media 21 may be, for example, 0.02 to 10 mm. In a case where the roasted product
24 is water-soluble, the medium 21 can be separated according to solubility in water.
Thus, the medium 21 is preferably insoluble or sparingly soluble in water.
[0037] As described above, in the present embodiment, the medium 21 is introduced
into the roasting furnace 10 to allow the medium 21 to collide with the object to be roasted
23, and the object to be roasted 23 is roasted while grinding the object to be roasted 23.
Therefore, reactivity of the object to be roasted 23 is improved. For example, in a case where the nickel-containing raw material which is the object to be roasted 23 is nickel matte containing a sulfur component such as Ni 3 S2 and a type of roasting is sulfating roasting, when the roasting is performed in an atmosphere containing sulfur dioxide (SO 2 ), nickel sulfate (NiSO4) can be obtained as the roasted product 24 by a dry refining method without a treatment by a wet refining method using liquid sulfuric acid. S02isgenerated as gas by combustion of the sulfur component in the object to be roasted 23 or a sulfur component fed from the outside, and S02 comes into contact with the nickel component in the object to be roasted 23, thereby producing nickel sulfate. A reaction formula between Ni3 S 2 (solid) in the raw material and an external sulfur component (S) and oxygen (02) is as follows.
[0038] S (solid) + 02 (gas) -- S02 (gas)
Ni3 S 2 (solid) + 502 (gas) + S02 (gas) -- 3NiSO4 (solid)
Ni (solid) + S02 (gas) + 02 (gas) -- NiS04 (solid)
[0039] As illustrated in FIG. 2, in a case where a particle 30 is in a state in which a
product layer 32 such as NiS04 precipitates on a surface of a nickel-containing raw
material 31 such as Ni 3 S2 during roasting, when the surface of the nickel-containing raw
material 31 is not exposed to the atmosphere, it is difficult for the reaction to continuously
proceed. The nickel-containing raw material 31 is roasted while grinding the particles
by medium particles 33 during roasting, such that reactivity of the nickel-containing
raw material 31 is improved. In a case where the particles 30 of the nickel-containing
raw materials 31 flow by a fluidized roasting furnace, the product layers 32 are crushed
due to collision between the particles 30 during roasting, such that the reaction can be
faster in comparison with using a rotary roasting furnace or the like. When the medium
particle 33 harder than the nickel-containing raw material 31 is present, the product layer
32 is crushed due to collision with the medium particles 33, and the surface of the nickel
containing raw material 31 is thus exposed. Further, a roasting reaction is accelerated
by grinding of the surface of the nickel-containing raw material due to collision with the
hard medium particles 33, for example, by a mechanochemical reaction such as a
structural change of the nickel-containing raw material due to compression, activation by
kinetic energy received from the medium particles 33, or an increased opportunity for a
direct reaction between the nickel-containing raw material and S particles or S02 gas.
[0040] In addition, in a case where the nickel-containing raw material 31 contains a
sulfur component such as Ni 3 S 2 , the sulfur component in the raw material is oxidized to
generate S02 gas during roasting. As a result, the particles may crack. As illustrated
in FIG. 3, in a fractured piece 35 of the particle having the product layer 32, the nickel
containing raw material 31 may be exposed to a fracture surface 36, and the fracture
surfaces 36 may adhere to each other due to their affinity, thereby forming coarse particles.
A proportion of a surface area of the coarse particle is reduced, which causes a reduction
in reactivity. When the medium particles 33 are mixed during roasting, these coarse
particles can be crushed to restore the reactivity.
[0041] Further, it is known that in a case where a phase of Ni3 S 2 is changed from a
Ni3 S 2 to J-Ni 3 S 2 at around 632°C and contains about 3 3 % of sulfur, Ni3 S 2 is in a molten
state at about around 645°C. Accordingly, when the temperature is raised to about
645°C or higher, a melt is generated, and the melt coagulates to form a mass. As a result,
fluidization deteriorates. In the present embodiment, the medium particles 33 are mixed
during roasting, such that it is possible to prevent fluidization of the particles 30 from
deteriorating during roasting.
[0042] It is preferable that the nickel-containing raw material is sulfated roasted under conditions of an oxygen partial pressure and a sulfur dioxide partial pressure at which nickel sulfate is more thermodynamically stable than nickel oxide in a Ni-S-O system and iron oxide is more thermodynamically stable than iron sulfate in an Fe-S-O system.
Therefore, even in a case where the nickel-containing raw material contains an iron
component, the nickel component is converted into nickel sulfate and conversion from
the iron component into iron sulfate is suppressed. Thus, it is possible to suppress
consumption of the sulfur component by the iron component and to improve production
efficiency of nickel sulfate.
[0043] It is preferable to reduce a particle size of the nickel-containing raw material by
operations such as shredding, crushing, and grinding, prior to the roasting step. Since a
reaction is initiated from a surface of the raw material in the roasting step, the smaller the
particle size of the raw material, the shorter the reaction time, which is preferable. A
crushing means is not particularly limited, but one or two or more of a ball mill, a rod
mill, a hammer mill, a fluid energy mill, and a vibration mill can be used. A particle
size after crushing is not particularly limited. In a case of a raw material available in a
form of fine particles, such as limonite ore, the raw material may be fed to the roasting
step as it is.
[0044] FIG. 4 is a view illustrating an example of a conceptual phase diagram of each
of aNi-S-O system and anFe-S-O system. Boundary lines between phases in the Ni-S
o system are indicated by broken lines (-----), and boundary lines between phases in the
Fe-S-O system are indicated by alternate long and short dash lines(----). Chemical
formulas along with the arrows show thermodynamically stable phases on the sides from
the boundary lines toward the arrows. In the state view illustrated in FIG. 4, a horizontal
axis represents a logarithm of the 02 partial pressure. The 02 partial pressure is higher on the more right side of the horizontal axis, and the 02 partial pressure is lower on the more left side of the horizontal axis. In the phase diagram illustrated in FIG. 4, a vertical axis represents a logarithm of the S02 partial pressure. The S02 partial pressure is higher on the upper side of the vertical axis, and the S02 partial pressure is lower on the lower side of the vertical axis. A unit of the partial pressure is, for example, atmospheric pressure (atm = 101,325 Pa).
[0045] An example of the nickel sulfate contained in the Ni-S-0 system can include
NiSO4 , and an example of the nickel oxide contained in the Ni-S-0 system can include
NiO. In the phase diagram illustrated in FIG. 4, a boundary line LNi indicates a boundary
line between a region in which nickel sulfate is thermodynamically stable and a region in
which nickel oxide is thermodynamically stable. In a region in which the S02 partial
pressure and the 02 partial pressure are higher than the boundary line LNi, the nickel
sulfate becomes a thermodynamically stable phase. In addition, in a region in which the
S02 partial pressure and the 02 partial pressure are lower than the boundary line LNi, the
nickel oxide becomes a thermodynamically stable phase.
[0046] Examples of the iron sulfate contained in the Fe-S-0 system can include FeSO 4
and Fe2(SO 4 )3, and an example of the iron oxide contained in the Fe-S-0 system can
include Fe203. In the phase diagram illustrated in FIG. 4, a boundary line LFe indicates
a boundary line between a region in which iron sulfate is thermodynamically stable and
a region in which iron oxide is thermodynamically stable. In a region in which the S02
partial pressure and the 02 partial pressure are higher than the boundary line LFe, the iron
sulfate becomes a thermodynamically stable phase. In addition, in a region in which the
S02 partial pressure and the 02 partial pressure are lower than the boundary line LFe, the
iron oxide becomes a thermodynamically stable phase.
[0047] According to the phase diagram illustrated in FIG. 4, in a region A in which the
S02 partial pressure and the 02 partial pressure are lower than the boundary line LFe and
the S02 partial pressure and the 02 partial pressure are higher than the boundary line LNi,
the nickel sulfate in the Ni-S-0 system becomes a thermodynamically stable phase, and
the iron oxide in the Fe-S-0 system becomes a thermodynamically stable phase. Then,
a system containing nickel (Ni), oxygen (0), and sulfur (S) is roasted under a condition
of the overlapping region A, such that the nickel component can be converted into nickel
sulfate while suppressing production of iron sulfate, even when the iron component
coexists in the system.
[0048] In a case where the roasting step according to the present embodiment is
sulfating roasting, a roasting temperature (sulfating roasting temperature) in the sulfating
roasting step is preferably 400 to 750°C, and more preferably 550 to 750°C. As a
specific example, the sulfating roasting temperature may be 400°C, 450°C, 500°C, 550°C,
600°C, 650°C, 700°C, 750°C, or a temperature in a range of lower or higher than these
temperatures or in the middle of these temperatures. At such a roasting temperature, the
reduction of the iron component is suppressed, and thus, the iron component can coexist
with a nickel sulfate compound in a form of iron oxide, iron sulfide, or the like.
Therefore, aggregation of particles in a roasted product can be suppressed, and a treatment
in a subsequent step can be easily performed. In addition, at the above temperature, a
carbonate is decomposed. Therefore, even in a case where the carbonate is mixed, it is
possible to prevent the carbonate from being dissolved in water and thus remaining as an
impurity, and it is possible to easily perform a treatment in a subsequent step.
The sulfating roasting temperature is still more preferably 600 to 700°C. At
the above temperature, even in a case where the object to be roasted contains manganese
(Mn) as an impurity derived from the nickel-containing raw material, the manganese
forms a spinel structure with iron, and thus, the manganese can be easily removed as an
insoluble matter.
[0049] As for the 02 partial pressure in the sulfating roasting step, a common logarithm
log p(O2) of the 02 partial pressure in terms of the atmospheric pressure (atm) unit is
preferably in a range of -4 to -6, and log p(O2) is more preferably in a range of -4 to -5 or
-5 to -6 depending on a condition and the like. When the 02 partial pressure is reduced,
the S02 partial pressure tends to increase even in the overlapping region A of FIG. 4.
Therefore, production of nickel sulfate can be accelerated while suppressing production
of iron sulfate. The optimum region deviates slightly depending on the sulfating
roasting temperature, and as the temperature becomes higher, the optimum region moves
to a side where log p(O2) in the overlapping region A becomes large (a side where log
p(O2) is closer to zero (0)).
[0050] As for the S02 partial pressure in the sulfating roasting step, a common
logarithm log p(S02) of the S02 partial pressure in terms of the atmospheric pressure
(atm) unit is preferably in a range of -1 to +1, and logp(S02) is more preferably in a range
of -I to 0. Even in the overlapping region A of FIG. 4, production of a sulfate can be
accelerated by further increasing the S02 partial pressure. Further, when the S02 partial
pressure is set to about a normal pressure or a pressure equal to or lower than the normal
pressure (a common logarithm of the partial pressure is about 0 or less), the total pressure
of a roasting atmosphere in the sulfating roasting step does not become excessive, and
thus, the facility can be easily handled.
[0051] In order to maintain the condition in which the 02 partial pressure is low in the
roasting furnace, an inert gas such as nitrogen (N2 ) or argon (Ar) may be fed to the roasting furnace. The inert gas can be used as a carrier when feeding a volatile component such as gas or steam to the roasting furnace. In a case where the amount of the sulfur component contained in the nickel-containing raw material is small, a sulfur component may be fed in the sulfating roasting step. A feedstock of a sulfur component
(sulfur source) is not particularly limited, and examples thereof can include solid sulfur
(elementary sulfur (S)), a sulfur oxide (SO 2 or the like), sulfuric acid (H 2 SO 4 ), a sulfate,
a sulfide, and sulfide ore such as iron pyrite (FeS2). In a case where the sulfur source is
elemental sulfur, it is preferable to generate SO2 gas in an oxygen-enriched state.
[0052] Before the sulfating roasting step is performed under the condition of the
overlapping region A, an oxidizing roasting step may be added to oxidize the iron
component, the sulfur component, and the like contained in the raw material. In the
oxidizing roasting step, as an oxidant, 02 gas or the like may be fed. The oxidizing
roasting step may be performed in the same roasting furnace as in the sulfating roasting
step, or an oxidizing roasting furnace different from the furnace used in sulfating roasting
may be provided.
[0053] A roasted product containing a nickel sulfate compound is obtained through the
sulfating roasting step. A solution containing the nickel sulfate compound is obtained
through a water dissolution step of dissolving the nickel sulfate compound in water by
feeding water to the roasted product. As described above, since the iron component
contained in the roasted product in the sulfating roasting step becomes a form which is
sparingly soluble in water, such as iron oxide or iron sulfide, the solution containing the
nickel sulfate compound is separated into a solid phase and a liquid phase by solid-liquid
separation, such that a nickel sulfate compound is obtained as a liquid phase, and
impurities containing iron and the like are separated as a solid phase. Further, if necessary, for example, a purification step is performed to separate nickel sulfate, cobalt sulfate, and the like, thereby obtaining a nickel sulfate compound from which impurities such as cobalt are removed.
[0054] In the water dissolution step, water added to the roasted product is preferably
pure water that is treated so as not to contain impurities. The water treatment method is
not limited but may be, for example, one or more selected from filtration, membrane
separation, ion exchange, distillation, sterilization, chemical treatment, and adsorption.
As water for dissolution, tap water, industrial water, or the like obtained from a water
source may be used, or water obtained by treating drainage water generated in other
processes may be used. Two or more types of water may also be used. The dissolution
can be performed with an acidic solution of sulfuric acid having a pH of about 4 as well
as with pure water. For example, in a region to be an oxidation region in measurement
of an oxidation-reduction potential at the pH of the solution of about 4 to 5, for example,
3.8 to 5.5, it is advantageous to selectively extract the nickel sulfate compound into an
aqueous phase while suppressing dissolution of other impurities such as a sulfate, which
is preferable.
[0055] Solubility of nickel sulfate in water is highest at 150°C, at which 55 gof NiSO 4
is dissolved in 100 g of the solution, but 22 gofNiSO 4 is dissolved in 100 g of the solution
even at 0°C. Therefore, it is desirable to perform the dissolution operation at a
temperature equal to or lower than a boiling point of water. In addition, it is preferable
that the solution obtained in the water dissolution step has a concentration at which NiSO 4
does not precipitate even at a normal temperature, and it is preferable that the solution is
maintained in a heated state at a concentration of NiSO 4 higher than the concentration.
[0056] A solid-liquid separation method after the water dissolution step is not particularly limited, and examples thereof can include a filtration method, a centrifugal separation method, and a precipitation separation method. It is preferable to use a device having a high performance for separation of the media and fine particles contained in the solid phase. For example, in filtration, a filtration method is not particularly limited, and examples thereof can include gravity filtration, reduced pressure filtration, pressurized filtration, centrifugal filtration, filtration with addition of a filter aid, and compression squeeze filtration. Pressurized filtration is preferred in terms of easy adjustment of a differential pressure and quick separation.
[0057] Examples of the impurities that can coexist with the nickel sulfate compound
can include iron (Fe), cobalt (Co), and aluminum (Al). In a case where these metal salts
become sulfates in the roasting step, when the nickel sulfate compound is dissolved in
water, iron sulfate, cobalt sulfate, and the like are also dissolved. Further, in water, for
example, iron precipitates as oxides such as FeOOH, Fe203, and Fe304, and thus, the
impurities are easily removed from the nickel sulfate compound. In the sulfating
roasting step of the present embodiment, conditions are set so that the iron component
does not easily become iron sulfate. Therefore, the nickel sulfate compound is subjected
to water dissolution and solid-liquid separation to obtain a nickel sulfate compound
having a small amount of an iron component. A residue containing iron oxide and the
like after the nickel sulfate compound is dissolved can be reused as an iron component
for cement. In addition, the residue containing a large amount of an iron component
such as iron oxide can also be used in production of pig iron or the like as a raw material
for iron production using a melt-reduction furnace, an electric furnace, or the like, or used
for a pigment, ferrite, a magnetic material, a sintered material, or the like. In particular,
in a case where an area where a nickel-containing raw material is produced is a remote area away from industrial areas, cities, and the like, it is advantageous to commercialize an iron component locally, similarly to the nickel component, from the viewpoint of transportation costs and the like. For example, when pig iron is produced using an electric fumace installed in a refining step of ferronickel and a volume reduction is performed, it is easy to carry out the pig iron as an unprocessed iron metal.
[0058] Among the impurities, a metal having a lower ionization tendency than
hydrogen (H), such as copper (Cu), gold (Au), silver (Ag), or a platinum group metal
(PGM), remains as a solid in the water dissolution step, and can thus be removed in a
solid-liquid separation step. In addition to the impurities, a compound such as As, Pb,
or Zn can be included in the solid removed in the solid-liquid separation step. The solid
including these impurities can be recycled as valuable resources.
[0059] The solution obtained through the water dissolution and solid-liquid separation
contains the nickel sulfate compound as a main component. Therefore, the solution of
the nickel sulfate compound can be transported and used as it is, or as a solid of the nickel
sulfate compound by drying or the like. In a case where it is desirable to reduce the
impurities in the solution, for example, cobalt sulfate or the like, depending on use,
techniques such as solvent extraction, electrodialysis, electrowinning, electro refining,
ion exchange, and crystallization can be used.
[0060] In the case of the solvent extraction, it is preferable to use an extractant capable
of preferentially or selectively extracting cobalt rather than nickel into a solvent.
Therefore, purification can be efficiently performed by leaving the nickel sulfate
compound in an aqueous solution. Examples of the extractant can include organic
compounds having a functional group that can bind to a metal ion, such as a phosphinic
acid group and a thiophosphinic acid group. In the solvent extraction, as a diluent, an organic solvent capable of separating the extractant from water may be used. By dissolving the extractant bonded to a metal ion such as cobalt in the diluent, the cobalt is easily separated from the aqueous solution containing nickel sulfate compound without using a large amount of the extractant. The diluent is preferably an organic solvent which is immiscible with water.
[0061] In the case of the crystallization, the nickel sulfate compound to be targeted
may be crystallized from the solution by at least one factor such as a change in
temperature, a reduction in solvent, or addition of other substances. In this case,
purification may be performed by leaving at least a part of the impurities in a liquid phase.
Specific examples thereof can include an evaporation crystallization method and a poor
solvent crystallization method. In the evaporation crystallization method, a solution is
concentrated by boiling or evaporation under reduced pressure to crystallize the nickel
sulfate compound. The poor solvent crystallization method is a crystallization method
used in pharmaceutical production or the like, and in the poor solvent crystallization
method, for example, an organic solvent is added to a solution containing a nickel sulfate
compound to precipitate the nickel sulfate compound. The organic solvent used in the
crystallization is preferably an organic solution which is miscible with water, and
examples of the organic solvent can include one or more selected from the group
consisting of methanol, ethanol, propanol, isopropanol, butyl alcohol, ethylene glycol,
and acetone. Two or more of the organic solvents may be used. As for a concentration
range in which the organic solvent is mixed with water, it is preferable that the organic
solvent is mixed with water at a concentration at which the organic solvent is added to
the extent that the nickel sulfate compound precipitates, and it is more preferable that the
organic solvent is freely mixed with water in any ratio. The organic solvent added in the crystallization step is not limited to an anhydrous organic solvent, and may be a water containing organic solvent to the extent that it does not interfere with the crystallization.
A ratio of water to the organic solvent is not particularly limited, but may be set to, for
example, 1:20 to 20:1, and is preferably about 1:1, for example, 1:2 to 2:1.
[0062] In a case where the solid nickel sulfate compound is obtained through the
crystallization or the like, the nickel sulfate compound may be in a state of anhydride,
monohydrate, dihydrate, pentahydrate, hexahydrate, or heptahydrate of nickel sulfate.
The nickel sulfate compound precipitated by the crystallization can be separated from the
solution by solid-liquid separation. A solid-liquid separation method is not particularly
limited, and examples thereof can include a filtration method, a centrifugal separation
method, and a sedimentation separation method. The metal dissolved in the solution is
preferably neutralized and removed from the solution by a method such as precipitation.
In a case where the purified solution mainly contains a mixture of water and the organic
solvent, it is possible to separate the water and the organic solvent from each other by a
method such as distillation.
[0063] According to the sulfating roasting of the present embodiment, the following
effects can be obtained.
(1) The conversion reaction from the nickel component of the nickel-containing
raw material into the nickel compound such as nickel sulfate can be accelerated to
improve reactivity. In a case where the nickel-containing raw material containing a
nickel component and a sulfur component is sulfated roasted, or in a case where the
nickel-containing raw material is reacted with solid sulfur (elementary sulfur) at a normal
temperature in the sulfating roasting furnace, the conversion reaction from the nickel
component and the sulfur component into nickel sulfate can be accelerated to improve reactivity.
(2) A high-purity nickel sulfate compound can be produced from the nickel
containing raw material by the sulfating roasting.
(3) Production of iron sulfate can be suppressed in the sulfating roasting step.
In addition, generation of hydrogen (H 2 ) gas can also be suppressed.
(4) Since the roasted product is a chemical species in which an iron component
is difficult to dissolve in water and contains a nickel component which is easily dissolved
in water as a nickel sulfate compound, the iron component is easily removed.
(5) The facility cost can be reduced as compared to a method according to the
related art.
(6) Since the conversion reaction of the nickel-containing raw material can be
accelerated, for example, in a case where iron is fed in a form of iron oxide, the conversion
reaction proceeds without formation of iron sulfate by iron oxide or formation of a ferrite
alloy of iron and nickel. Therefore, it is possible to obtain a roasted product containing
high-purity nickel sulfate.
[0064] Hereinabove, the present invention has been described based on preferred
embodiments, but the present invention is not limited to the above-described
embodiments, and various modifications can be made without departing from the gist of
the present invention.
[0065] The object to be roasted is not limited to a nickel-containing raw material, and
a material containing metals (Cu, Zn, Co, Fe, and the like) other than nickel can also be
considered. The roasting of the nickel-containing raw material according to the above
described embodiments can be applied to roasting for obtaining a metal compound from
the raw material containing another metal. A type of roasting when the object to be roasted is roasted is not limited to sulfating roasting, and examples thereof can include oxidizing roasting, chloride roasting, and reduction roasting. In the roasting step, in a case where the object to be roasted reacts with a gas component, the reaction gas component is not particularly limited, and examples thereof can include S02, S, 02, C1 2
, HCl, and CO. The gas component may be any one of a gas phase, a liquid phase, or a
solid phase at a normal temperature. In addition, a substance that is a liquid or a solid
at a normal temperature may be fed to the roasting furnace to generate a gas component
in the roasting furnace by a decomposition reaction, an oxidation reaction, a reduction
reaction, or the like. The roasted product is not limited to a sulfate, and examples thereof
can include a sulfide, an oxide, a chloride, and an alloy.
Examples
[0066] An electric furnace (furnace core tube: SUS316L, outer diameter of 50 mm,
length of 400 mm, maximum temperature of 1,100°C) manufactured by Takasago
Industry Co., Ltd. was installed so that the furnace core tube was vertically installed and
a gas dispersion plate was installed at the bottom of the furnace core tube, thereby
configuring a fluidized roasting furnace. 1,000 g of nickel matte (composition: Ni 3 S 2 ,
average particle size: 0.3 mm, density: 3.5 g/cm 3, Mohs hardness: 4 to 5) was fed to the
fluidized roasting furnace. In Examples in which a medium was used, since a volume
of the nickel matte was 285 mL, 28 mL of the media (material: synthetic a-alumina,
density: 4 g/cm3 , Mohs hardness: 9, average particle size: 1 mm) was filled.
[0067] A gas adsorption tube and a vacuum pump were installed on an upper portion
of the fluidized roasting furnace. In the case of a sulfur combustion method, a
combustion burner was inserted through a side surface of the furnace core tube, and a direction of the combustion burner was adjusted so that the combustion gas became a spiral flow. Sulfating roasting of the nickel matte was performed while feeding flowing air through a lower portion of the fluidized roasting furnace, maintaining a fluidized bed of the nickel matte, and combusting sulfur with the combustion burner. A part of a roasted product was taken out during roasting, and a recovery rate (wt%) of nickel sulfate was measured based on a ratio of the nickel matte to the nickel sulfate.
[0068] In Examples in which the media were mixed with the nickel matte, the recovery
rate of nickel sulfate reached 90% after 10 minutes, 95% after 20 minutes, and 98% after
minutes, from the start of roasting.
In Comparative Examples in which the media were not mixed with the nickel
matte, the recovery rate of nickel sulfate reached 70% after 10 minutes, 90% after 20
minutes, and 95% after 30 minutes, from the start of roasting.
Industrial Applicability
[0069] The present invention can be used for producing a high-purity nickel sulfate
compound which is useful as a raw material of various nickel compounds or metallic
nickel, used for an electrical part such as a secondary battery, a chemical product, or the
like.
Reference Signs List
[0070] 10 Roasting furnace
11 Furnace body
12 Gas inlet
13 Gas outlet
14 Gas dispersion plate
Feed port
16 Outlet port
Fluidized bed
21 Medium
22 Floating layer
23 Object to be roasted
24 Roasted product
Particle during roasting
31 Nickel-containing raw material
32 Productlayer
33 Medium particle
Fractured piece
36 Fracture surface

Claims (8)

1. A method for treating a nickel-containing raw material, the method
comprising:
introducing a medium into a roasting furnace for roasting a nickel-containing
raw material to allow the medium to collide with the nickel-containing raw material; and
roasting the nickel-containing raw material while grinding the nickel
containing raw material with the medium.
2. The method for treating a nickel-containing raw material according to claim
1, wherein
the roasting furnace has a fluidized bed.
3. The method for treating a nickel-containing raw material according to claim
1 or 2, wherein
the medium is rolled in the roasting furnace.
4. The method for treating a nickel-containing raw material according to any
one of claims I to 3, wherein
the medium fills 5 to 20 vol% of a space formed between a bottom of an object
to be roasted and an outlet port for a roasted product in the roasting furnace.
5. The method for treating a nickel-containing raw material according to any
one of claims 1 to 4, wherein
in a case where a component harder than the nickel-containing raw material is mixed and fed with the nickel-containing raw material in addition to the medium, an addition amount of the medium is reduced as compared to a case where the hard component is not mixed.
6. The method for treating a nickel-containing raw material according to claim
2, wherein
the medium has a particle size or density which allows a flow velocity of the
medium to be equal to or less than a fluidization initiation velocity Umf.
7. The method for treating a nickel-containing raw material according to any
one of claims 1 to 6, wherein
the medium is formed of a material that is softer than an inner wall material of
the roasting furnace and harder than the nickel-containing raw material.
8. The method for treating a nickel-containing raw material according to any
one of claims 1 to 7, wherein
the nickel-containing raw material is roasted under conditions of an oxygen
partial pressure and a sulfur dioxide partial pressure at which nickel sulfate is more
thermodynamically stable than nickel oxide in a Ni-S-O system and iron oxide is more
thermodynamically stable than iron sulfate in an Fe-S-O system.
AU2019426767A 2019-01-31 2019-01-31 Method for treating nickel-containing raw material Pending AU2019426767A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114956393A (en) * 2022-08-02 2022-08-30 山东凤鸣桓宇环保有限公司 Nickel-containing electroplating wastewater treatment process
CN114956393B (en) * 2022-08-02 2022-10-25 山东凤鸣桓宇环保有限公司 Nickel-containing electroplating wastewater treatment process

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6228088B2 (en) * 1980-03-10 1987-06-18 Sumitomo Metal Mining Co
JP6708038B2 (en) * 2016-07-21 2020-06-10 住友金属鉱山株式会社 Method for producing nickel oxide
JP6870231B2 (en) * 2016-07-27 2021-05-12 住友金属鉱山株式会社 Nickel oxide manufacturing method, fluidized roasting furnace

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114956393A (en) * 2022-08-02 2022-08-30 山东凤鸣桓宇环保有限公司 Nickel-containing electroplating wastewater treatment process
CN114956393B (en) * 2022-08-02 2022-10-25 山东凤鸣桓宇环保有限公司 Nickel-containing electroplating wastewater treatment process

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