JP6539922B1 - Method for producing nickel sulfate compound - Google Patents

Abstract

The present invention provides a method for producing a nickel sulfate compound capable of producing a nickel sulfate compound even in a gas phase atmosphere. An oxygen partial pressure p (O2) and a sulfur dioxide partial pressure p (SO2) can be used to make nickel sulfate thermodynamically more stable than nickel oxide in the Ni-S-O system, and Fe--S--O. As a condition under which iron oxide is thermodynamically more stable than iron sulfate in the system, it has a roasting step of heating the nickel-containing raw material to form a nickel sulfate compound. [Selected figure] Figure 1

Description

  The present invention relates to a method of producing a nickel sulfate compound.

  Heretofore, nickel sulfate compounds have been used as raw materials for various nickel compounds or metallic nickel in applications such as electrolytic nickel plating, electroless nickel plating, and catalyst materials. In recent years, an increase in demand for a secondary battery using a nickel compound or metallic nickel as a positive electrode material as a power source for transportation devices such as electric vehicles and electronic devices is expected. In order to obtain a high performance secondary battery, stable supply of a high purity nickel sulfate compound is desired.

  Impurities which may be contained in the low purity nickel compound include other metal compounds such as iron, copper, cobalt, manganese, magnesium and the like. Conventionally, a solvent extraction method is mentioned as a method of obtaining a high purity nickel compound. In the solvent extraction method, steps of selectively extracting and removing other metal compounds or selectively extracting and removing nickel compounds are performed. In either case, special agents are required to selectively extract specific metal ions, which is expensive.

  As a method of producing nickel sulfate, a method of exchanging anions of a nickel compound to a sulfate radical by an ion exchange method, and a method of dissolving nickel metal powder in a sulfuric acid solution while generating hydrogen gas are also known. Further, Patent Document 1 describes a method for obtaining water-soluble nickel sulfate by heat-treating green nickel oxide powder having a specific gravity of 6.30 or more in sulfuric acid and then leaching with hot water. ing. In Patent Document 1, as the sulfuric acid used for the heat treatment, a sulfuric acid solution with a concentration of 30% to 60% (claims 1 to 5) and a concentrated sulfuric acid with a concentration of 95% (claims 6 to 7) are mentioned. When concentrated sulfuric acid with a concentration of 95% is used in Patent Document 1 (Examples 7 to 9), a high temperature of 275 ° C. or more is required.

U.S. Pat. No. 3,002,814

  In the method of obtaining nickel sulfate using liquid phase sulfuric acid, the amount of sulfuric acid consumption increases due to the dissolution of the iron component coexisting with nickel in the raw material in sulfuric acid, and there is a risk that hydrogen gas may be generated during the reaction Etc. are concerned.

  This invention is made in view of the said situation, and makes it a subject to provide the manufacturing method of the nickel sulfate compound which can manufacture a nickel sulfate compound also in a gaseous-phase atmosphere.

According to the first aspect of the present invention, the partial pressure of oxygen and the partial pressure of sulfur dioxide are such that nickel sulfate is thermodynamically more stable than nickel oxide in Ni-S-O system, and oxidized in Fe-S-O system. A method for producing a nickel sulfate compound, comprising a roasting step of heating a nickel-containing raw material containing an iron component to form a nickel sulfate compound as a condition under which iron is thermodynamically more stable than iron sulfate. is there.

  A second aspect of the present invention is the method for producing a nickel sulfate compound according to the first aspect, wherein the roasting temperature is in the range of 400 to 750 ° C. in the roasting step.

According to a third aspect of the present invention, in the roasting step, the common logarithm log p (O ₂ ) of oxygen partial pressure in the unit of atmospheric pressure (atm) is in the range of −4 to −6 and in the unit of atmospheric pressure (atm). A method for producing a nickel sulfate compound according to the first or second aspect, wherein the common logarithm log p (SO ₂ ) of the sulfur dioxide partial pressure is in the range of −1 to +1. The common logarithm is a logarithm with a base of 10 (log ₁₀ ).

  According to a fourth aspect of the present invention, there is provided a nickel sulfate compound according to any one of the first to third aspects, comprising a water dissolving step of dissolving the nickel sulfate compound in water after the roasting step. It is a manufacturing method.

  A fifth aspect of the present invention is characterized in that the nickel-containing raw material comprises one or more selected from the group consisting of nickel sulfide ore, nickel sulfide, nickel mat, nickel oxide, and ferronickel. It is a manufacturing method of the nickel sulfate compound of any one of-aspect.

  According to the first aspect, even when the nickel-containing raw material contains iron, the nickel is converted to the nickel sulfate compound and the conversion from iron to iron sulfate is suppressed. Can be suppressed to improve the generation efficiency of the nickel sulfate compound.

  According to the second aspect, reduction of iron content is suppressed, and iron content can co-exist with the nickel sulfate compound in the state of iron oxide, iron sulfide and the like. Processing can be facilitated.

  According to the third aspect, the formation of the nickel sulfate compound can be promoted under the conditions of low oxygen partial pressure and high sulfur dioxide partial pressure.

  According to the fourth aspect, removal of iron can be facilitated by preferentially dissolving the nickel sulfate compound.

  According to the fifth aspect, since the nickel-containing raw material which is relatively easy to procure can be used, productivity can be improved.

It is a notional phase diagram of Ni-SO system and Fe-SO system. It is a flowchart which shows the outline of the manufacturing method of the nickel sulfate compound of embodiment. It is a block diagram which illustrates the apparatus used in the Example.

  Hereinafter, the present invention will be described based on preferred embodiments.

  In the method for producing a nickel sulfate compound according to this embodiment, as shown in FIG. 1, the oxygen partial pressure and the sulfur dioxide partial pressure are thermodynamically more stable than nickel oxide in nickel-s-O-based nickel sulfate, And it has a roasting process which heats a nickel containing raw material and produces a nickel sulfate compound as conditions which iron oxide becomes thermodynamically stable rather than iron sulfate in Fe-S-O type | system | group.

FIG. 1 is an example of a conceptual state diagram of Ni—S—O system and Fe—S—O system. The boundary line of each phase in the Ni-S-O system is indicated by a broken line (----), and the boundary line of each phase in the Fe-S-O system is indicated by an alternate long and short dash line (---) . The chemical formulas attached to the arrows indicate thermodynamically stable phases on the side of each boundary line toward the arrow. The horizontal axis in the state diagram shown in FIG. 1 shows the logarithm of the partial pressure of O _2, the right side as the O ₂ partial pressure is high, the left as O ₂ partial pressure is low. The vertical axis of the phase diagram shown in FIG. 1 indicates the logarithm of the SO ₂ partial pressure, and the SO ₂ partial pressure is higher toward the upper side, and the SO ₂ partial pressure is lower toward the lower side. The unit of partial pressure is, for example, the pressure (atm = 101325 Pa).

Examples of nickel sulfate contained in the Ni-S-O system include NiSO ₄ , and examples of nickel oxide include NiO. In the phase diagram shown in FIG. 1, the boundary line L _Ni indicates the boundary line between the region in which nickel sulfate is thermodynamically stable and the region in which nickel oxide is thermodynamically stable. Nickel sulfate is a thermodynamically stable phase in the region where the SO ₂ partial pressure and the O ₂ partial pressure are higher than the boundary line L _Ni . In addition, in a region where the SO ₂ partial pressure and the O ₂ partial pressure are lower than the boundary line L _Ni , nickel oxide is a thermodynamically stable phase.

Examples of iron sulfate contained in the Fe-S-O system include FeSO ₄ and Fe ₂ (SO ₄ ) ₃ , and examples of iron oxide include Fe ₂ O ₃ . In the phase diagram shown in FIG. 1, the boundary line L _Fe indicates the boundary line between the region in which iron sulfate is thermodynamically stable and the region in which iron oxide is thermodynamically stable. Iron sulfate is a thermodynamically stable phase in the region where the SO ₂ partial pressure and the O ₂ partial pressure are higher than the boundary L _Fe . In the region where the SO ₂ partial pressure and the O ₂ partial pressure are lower than the boundary line L _Fe , iron oxide is a thermodynamically stable phase.

According to the state diagram shown in FIG. 1, SO ₂ partial pressure and the partial pressure of _{O 2} is lower than the boundary line _{L Fe,} and, SO ₂ partial pressure and the partial pressure of _{O 2} is in the higher region A than the boundary line _{L Ni,} Ni In the -S-O system, nickel sulfate is a thermodynamically stable phase, and in the Fe-S-O system, iron oxide is a thermodynamically stable phase. Therefore, by roasting a system containing nickel (Ni), oxygen (O) and sulfur (S) under the conditions of this overlapping region A, iron sulfate can be produced even if iron is present in the system. The nickel content can be converted to nickel sulfate while being suppressed.

  The roasting temperature is preferably in the range of 400 to 750 ° C, and more preferably in the range of 550 to 750 ° C. With such roasting temperature, the reduction of iron is suppressed, and iron can coexist with the nickel sulfate compound in the state of iron oxide, iron sulfide, etc., so that the aggregation of particles in the roasted product is suppressed, Post-processing can be facilitated. Further, at these temperatures, since the carbonate is decomposed, it is possible to prevent the carbonate from being dissolved in water and remaining as an impurity even when the carbonate is mixed, and the post-process Processing can be facilitated.

As the O ₂ partial pressure in the sinter process, the normal logarithm log p (O ₂ ) of the O ₂ partial pressure by the pressure (atm) unit is preferably in the range of −4 to −6, and the log p (O ₂ ) is −5 The range of -6 is more preferable. By lowering the O ₂ partial pressure, the SO ₂ partial pressure tends to be high also in the overlapping region A of FIG. 1, so it is possible to promote the formation of nickel sulfate while suppressing the formation of iron sulfate.

The SO ₂ partial pressure in the roasting step, pressure (atm) preferably common logarithm log p (SO ₂₎ in the range of -1 to +1 of the SO ₂ partial pressure in units, log p (SO ₂₎ is -1 A range of 0 is more preferable. In the overlapping region A of FIG. 1, the generation of sulfate can be promoted by further increasing the SO ₂ partial pressure. Furthermore, by setting the SO ₂ partial pressure in the range of about normal pressure or less (the common logarithm of partial pressure is about 0 or less), the total pressure of the roasting atmosphere does not become too large, and the handling of the facility becomes easy be able to.

  As a nickel containing raw material, as long as it contains a nickel element, it may be a nickel compound or metallic nickel. The nickel-containing raw material in the roasting step preferably contains one or more selected from the group consisting of nickel sulfide ore, nickel sulfide, nickel mat, nickel oxide, and ferronickel. The nickel-containing raw material may contain iron or may not contain iron. Iron content is separated from the nickel sulfate compound in a later step, but from the viewpoint of energy consumption, it is preferable that the iron content in the raw material be as low as possible. The nickel-containing raw material is not limited to one type, and two or more types may be used. When using 2 or more types of nickel containing raw materials, these raw materials may be supplied in the mixed state, and may be supplied separately.

  Examples of the nickel mat include a composition (weight ratio) of 45 to 55% of Ni, about 20% of Fe, 20 to 25% of S, and about 1% or less of Co. Furthermore, as a nickel mat in which the nickel concentration is raised in the converter, for example, a composition (weight ratio) of about 78% Ni, about 1% Co, about 1% Fe, and about 20% S can be mentioned. Examples of ferronickel include a composition (weight ratio) of 18 to 23% of Ni, about 1% of Co, and 76 to 81% of Fe.

  Prior to the roasting step, it is preferable to reduce the particle size of the nickel-containing raw material by operations such as shredding, grinding, and attrition. In the roasting step, the reaction starts from the surface of the raw material, so the smaller the particle diameter of the raw material, the shorter the reaction time, which is preferable. The grinding means is not particularly limited, but one or more of ball mill, rod mill, hammer mill, fluid energy mill, vibration mill and the like can be used. The particle diameter of the pulverized powder is not particularly limited, and may be, for example, about 1 to 1000 μm or about 10 to 100 μm. In the case of a raw material which can be obtained in the form of fine particles, such as limonite ore, it may be supplied to the roasting step as it is.

The roasting apparatus for carrying out the roasting step is not particularly limited, and examples thereof include a rotary kiln, a fluidized bed type heating furnace, an electric furnace and the like. In order to maintain the low O ₂ partial pressure condition in the roasting apparatus, an inert gas such as nitrogen (N ₂ ) or argon (Ar) may be supplied to the roasting apparatus. These inert gases can also be used as a carrier for supplying volatile components such as gas and steam to the roasting apparatus. When the nickel-containing raw material has a low sulfur content, the sulfur content may be supplied to the roasting step. The source of sulfur content is not particularly limited, and examples include elemental sulfur, sulfur oxides, sulfuric acid, sulfates, and sulfides.

In addition, prior to performing the roasting step under the conditions of the overlapping region A, preliminary oxidation roasting under conditions different from the above-described roasting step is performed for the purpose of oxidizing iron, sulfur and the like contained in the raw material. A process may be provided. In the preliminary oxidation roasting step, O ₂ gas or the like may be supplied as an oxidant.

  The outline of the manufacturing method of the nickel sulfate compound of this embodiment is illustrated in FIG. By the above-described roasting step S1 of the nickel-containing raw material 10, a roasted product 11 containing a nickel sulfate compound is obtained. Water 20 is supplied to the roasted product 11, and the nickel sulfate compound is dissolved in water. In the water dissolving step S2, a solution 21 containing the nickel sulfate compound is obtained. As described above, since iron contained in the roasted product 11 is in a state of low solubility in water, such as iron oxide and iron sulfide, by separating into solid phase and liquid phase in the solid-liquid separation step S3. Crude nickel sulfate compound 31 is obtained as a liquid phase, and impurities 32 containing iron and the like are separated as a solid phase. Further, if necessary, the purification agent 40 is added to the crude nickel sulfate compound 31 to remove coexisting substances such as cobalt, and the purification step S4 is performed to remove the impurities 42 such as cobalt, etc., purified sulfuric acid Nickel compound 41 can be obtained.

  The water to be added to the roasted product in the water dissolving step is preferably pure water that has been treated so as not to contain impurities. The water treatment method is not particularly limited, and examples thereof include one or more of filtration, membrane separation, ion exchange, distillation, disinfection, chemical treatment, adsorption and the like. As the water for dissolution, clean water obtained from a water source, industrial water or the like may be used, or water treated with waste water generated in another process may be used. Two or more types of water may be used.

The solubility of nickel sulfate in water is highest at 150 ° C., and 100 g of solution contains 55 g of NiSO _4, but even at 0 ° C., 100 g of solution contains 22 g of NiSO ₄ . For this reason, it is desirable to carry out the dissolution operation below the boiling point of water. Further, the solution obtained in the water dissolution step preferably has a concentration at which NiSO ₄ does not precipitate even at normal temperature, and a solution with a higher concentration than that is preferably maintained in a heated state.

  In the solid-liquid separation step, the method of solid-liquid separation is not particularly limited, and filtration, centrifugation, sedimentation, etc. may be mentioned. Desirably, it is preferable to use an apparatus with high separation performance of microparticles contained in the solid phase. For example, in the filtration method, the type of filtration is not particularly limited, and gravity filtration, vacuum filtration, pressure filtration, centrifugal filtration, filter aid addition type filtration, squeezing filtration, etc. may be mentioned. Pressure filtration is preferred, which allows for easy adjustment of differential pressure and rapid separation.

Examples of impurities that can coexist with the nickel sulfate compound include iron (Fe), cobalt (Co), aluminum (Al) and the like. When 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. Furthermore, in water, for example, iron precipitates as an oxide of FeOOH, Fe ₂ O ₃ , Fe ₃ O ₄ or the like, and the removal of impurities from the nickel sulfate compound becomes easy. In the roasting step of the present embodiment, conditions are set such that the iron content is unlikely to become iron sulfate, and therefore, a crude nickel sulfate compound with little iron content can be obtained through the solid-liquid separation step.

  Among the impurities, for example, copper (Cu), gold (Au), silver (Ag), platinum group metals (PGM), and metals having a lower ionization tendency than hydrogen (H) remain as solids in the water dissolution step. It can be removed by the liquid separation step. The solid removed by the solid-liquid separation step may contain, in addition to the above-described impurities, compounds such as As, Pb, Zn and the like. Solids containing these impurities can also be recycled as valuables.

  The solution obtained by the water dissolution step and the solid-liquid separation step is transported and used as a solution of the nickel sulfate compound as it is a solution of the nickel sulfate compound or as a solid of the nickel sulfate compound by drying etc. it can. Depending on the application, when it is desired to reduce, for example, cobalt sulfate as an impurity in the solution, techniques such as solvent extraction, electrodialysis, electrorefining, ion exchange, crystallization etc. It can be used.

  In the case of solvent extraction, it is preferable to use an extractant capable of extracting cobalt preferentially or selectively into the solvent over nickel. This allows efficient purification, leaving the nickel sulfate compound in aqueous solution. As an extractant, the organic compound which has a functional group which can couple | bond with metal ions, such as a phosphinic acid group and a thio phosphinic acid group, is mentioned. In solvent extraction, an organic solvent capable of separating the extractant from water may be used as a diluent. Dissolving an extractant bound to a metal ion such as cobalt in a diluent facilitates separation from an aqueous solution containing a nickel sulfate compound without using a large amount of the extractant. The diluent is preferably an organic solvent which is not miscible with water.

  In the case of crystallization, the target nickel sulfate compound may be crystallized from the solution by at least one factor such as temperature change, decrease of solvent, addition of other substances, and the like. At this time, purification is possible by leaving at least a part of the impurities in the liquid phase. Specific examples include evaporative crystallization and poor solvent crystallization. In the evaporative crystallization method, the 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 and the like, and for example, an organic solvent is added to a solution containing a nickel sulfate compound to precipitate a nickel sulfate compound. The organic solvent used for the crystallization is preferably an organic solvent miscible with water, and examples thereof include one or more selected from the group consisting of methanol, ethanol, propanol, isopropanol, butyl alcohol, ethylene glycol and acetone. Two or more organic solvents may be used. With respect to the concentration range in which the organic solvent is mixed with water, it is preferable to mix at a concentration to which the organic solvent is added to the extent that the nickel sulfate compound precipitates, and it is more preferable to freely mix it at any ratio. The organic solvent added in the crystallization step is not limited to an anhydrous organic solvent, but may be a water-containing organic solvent to the extent that there is no hindrance to crystallization. The ratio of water to the organic solvent is not particularly limited, but may be set, for example, in the range of 1:20 to 20: 1, but is preferably about 1: 1, for example, 1: 2 to 2: 1.

  When solid nickel sulfate compound is obtained through crystallization etc., it is in the state of anhydride of nickel sulfate, monohydrate, dihydrate, pentahydrate, hexahydrate, heptahydrate etc. May be The nickel sulfate compound precipitated by crystallization can be separated from the solution by solid-liquid separation. Although the method of solid-liquid separation is not particularly limited, filtration, centrifugation, sedimentation, etc. may be mentioned. The metal dissolved on the solution side is preferably neutralized and removed from the solution by a method such as precipitation. When the purified solution is mainly composed of a mixture of water and an organic solvent, water and the organic solvent can be separated by a method such as distillation.

According to the method for producing a nickel sulfate compound of the present embodiment, the following effects can be obtained.
(1) Since nickel sulfate compounds having high added value can be produced from various nickel-containing raw materials, production is possible even near the demand area, and transportation costs can be reduced.
(2) A highly pure nickel sulfate compound can be produced.
(3) The formation of iron sulfate can be suppressed in the roasting step. In addition, the generation of hydrogen (H ₂ ) gas can also be suppressed.
(4) The roasted product is a chemical species in which the iron content is difficult to dissolve in water, and the nickel content is easily dissolved in water as a nickel sulfate compound, so the iron content can be easily removed.
(5) The equipment cost can be reduced compared to the conventional method, and it is also possible to use the existing equipment as a smoldering furnace.

  Although the present invention has been described above based on the preferred embodiments, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the scope of the present invention.

  Hereinafter, the present invention will be specifically described by way of examples.

(Example 1: roasting test)
The sulfuric acid roasting test was carried out using the test apparatus 100 shown in FIG. After measuring 5 g of a nickel compound as a sample on the pan 101, the pan 101 was set inside a glass container 102 installed in an electric furnace 103. The glass container 102 is provided with a thermometer 104 such as a thermocouple capable of measuring the ambient temperature, an injection pipe 105 into which various gases can be injected, and an outlet 106 for exhaust gas generated inside. The temperature was raised to a specified temperature by the electric furnace 103, and the sample was steamed and baked. In the injection pipe 105, dry air or SO ₂ gas containing nitrogen gas can be periodically supplied while constantly injecting argon gas. The exhaust gas discharged from the outlet 106 was processed by the exhaust gas processing device 108 through the gas analyzer 107. Data of various gas amounts and analysis values were collected by computer.

The composition of the nickel compound used for the test was a nickel sulfide alloy in which the iron content was reduced by the converter treatment of the nickel mat, and the composition was as follows.
Ni: 78%, Co: 1%, Fe: 1%, S: 20%

Sulfuric acid roasting was performed at 680 ° C. on a 5 g sample. Argon gas was purged for 20 minutes until the sample was heated to the specified temperature, and after reaching the specified 680 ° C., air was supplied to burn for 20 minutes in order to oxidize iron. As the air was injected, the weight of the sample decreased and the generation of SO ₂ gas was observed. Thereafter, the gas to be injected was switched to SO ₂ , and sulfuric acid roasting was performed for 40 minutes while adjusting the O ₂ partial pressure and the SO ₂ partial pressure. During the sulfuric acid roasting, constant SO ₂ consumption was confirmed. As a result of analyzing the roasted product by X-ray diffraction (XRD), it was confirmed that the iron content was changed to Fe ₂ O ₃ and the Ni content was changed to the form of NiSO ₄ .

Example 2 Water Dissolution Test
The roasted product produced from 5 g of the nickel compound in Example 1 was placed in 100 g of pure water and dissolved by stirring at 90 ° C. A part of the solution was sampled, and the concentration in the solution was determined for each metal (Ni, Fe, Co) using an atomic absorption spectrophotometer. Furthermore, based on this concentration, the amount contained in the solution, that is, the total amount dissolved in pure water was quantified for each metal, and the amount contained in the 5 g sample used for sulfuric acid calcination was dissolved in pure water as 100%. The ratio (dissolution rate) was determined. For example, the dissolution rate of Ni means the ratio of Ni dissolved in pure water to Ni contained in the roasted product. The results of determination of the dissolution rate are shown in Table 1.

  From this result, it was confirmed that iron in the roasted product was hardly dissolved and Ni and Co were easily dissolved. From this, it can be seen that the sulfuric acid roasting of Example 1 can produce a high-purity nickel sulfate compound with less iron content.

  INDUSTRIAL APPLICABILITY The present invention can be used for the production of high purity nickel sulfate compounds useful as raw materials for various nickel compounds or metallic nickel used for electrical parts such as secondary batteries, chemical products and the like.

S1 roasting step S2 water dissolution step S3 solid-liquid separation step S4 purification step 10 nickel-containing raw material 11 roasted product 20 water 21 solution 31 crude nickel sulfate Compound 32: Impurity separated in the solid-liquid separation step 40: Purification agent 41: Purified nickel sulfate compound 42: Impurity separated in the purification step

Claims (7)

In the Ni-S-O system, nickel sulfate is more thermodynamically stable than nickel oxide, and in the Fe-S-O system, iron oxide is more thermodynamically stable than iron sulfate. A method for producing a nickel sulfate compound, comprising a roasting step of heating a nickel-containing raw material containing an iron component to form a nickel sulfate compound as the condition which becomes stable.   The method for producing a nickel sulfate compound according to claim 1, wherein the roasting temperature is in the range of 400 to 750 ° C in the roasting step. In the roasting step, the common logarithm log p (O ₂ ) of oxygen partial pressure in atmospheric pressure (atm) is in the range of −4 to −6, and the common logarithm log p of sulfur dioxide partial pressure in atmospheric pressure (atm) The method for producing a nickel sulfate compound according to claim 1, wherein (SO ₂ ) is in the range of −1 to +1.   The method for producing a nickel sulfate compound according to any one of claims 1 to 3, further comprising a water dissolving step of dissolving the nickel sulfate compound in water after the roasting step. The method for producing a nickel sulfate compound according to claim 4, comprising a solid-liquid separation step of separating a liquid phase containing the nickel sulfate compound and a solid phase containing an iron component after the water dissolution step. The said nickel containing raw material contains 1 or more types selected from the group which consists of a nickel sulfide ore, a nickel sulfide, a nickel mat, nickel oxide, and ferronickel, The any one of the Claims 1-5 characterized by the above-mentioned. The manufacturing method of the described nickel sulfate compound. Before the roasting step, the different conditions from that of the roasting process, according to any one of claims 1 to 6, characterized in that it has an oxidation roasting step for oxidizing roasting of nickel-containing material Of the production of nickel sulfate compounds.

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