WO2020044849A1 - Method for producing nickel sulfate compound - Google Patents
Method for producing nickel sulfate compound Download PDFInfo
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- WO2020044849A1 WO2020044849A1 PCT/JP2019/028455 JP2019028455W WO2020044849A1 WO 2020044849 A1 WO2020044849 A1 WO 2020044849A1 JP 2019028455 W JP2019028455 W JP 2019028455W WO 2020044849 A1 WO2020044849 A1 WO 2020044849A1
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- nickel
- nickel sulfate
- sulfate compound
- iron
- roasting
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to a method for producing a nickel sulfate compound.
- Priority is claimed on Japanese Patent Application No. 2018-161837 filed on August 30, 2018, the content of which is incorporated herein by reference.
- nickel sulfate compounds have been used as raw materials for various nickel compounds or metallic nickel for applications such as electrolytic nickel plating, electroless nickel plating, and catalyst materials.
- demand for secondary batteries using a nickel compound or metallic nickel as a positive electrode material is expected to be increased as a power source for transportation equipment such as electric vehicles and electronic equipment.
- stable supply of a high-purity nickel sulfate compound is desired.
- Examples of impurities that may be contained in the low-purity nickel compound include other metal compounds such as iron, copper, cobalt, manganese, and magnesium.
- a solvent extraction method has been used as a method for obtaining a high-purity nickel compound.
- a step of selectively extracting and removing other metal compounds or selectively extracting and extracting nickel compounds is performed.
- a special agent is required, and the cost is high.
- Patent Document 1 describes a method for obtaining water-soluble nickel sulfate by subjecting green nickel oxide powder having a specific gravity of more than 6.30 to heat treatment in sulfuric acid and then leaching with hot water. ing.
- Patent Document 1 describes sulfuric acid solutions having a concentration of 30% to 60% (claims 1 to 5) and concentrated sulfuric acid having a concentration of 95% (claims 6 to 7) as the sulfuric acid used for the heat treatment. In the case of using concentrated sulfuric acid having a concentration of 95% in Patent Document 1 (Examples 7 to 9), a high temperature of 275 ° C. or higher is required.
- the iron content coexisting with nickel in the raw material is dissolved in sulfuric acid, so that the consumption of sulfuric acid increases, and hydrogen gas may be generated during the reaction. And so on.
- the present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method for producing a nickel sulfate compound capable of producing a nickel sulfate compound even in a gas phase atmosphere.
- the first aspect of the present invention is to reduce the oxygen partial pressure and the sulfur dioxide partial pressure by making nickel sulfate thermodynamically more stable than nickel oxide in the Ni—SO system and oxidizing in the Fe—SO system.
- a method for producing a nickel sulfate compound characterized by having a roasting step of heating a nickel-containing raw material containing iron and producing a nickel sulfate compound under conditions where 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 a range of 400 to 750 ° C. in the roasting step.
- a common logarithm log p (O 2 ) of oxygen partial pressure in units of atmospheric pressure (atm) is in a range of ⁇ 4 to ⁇ 6
- the common logarithm is a logarithm (log 10 ) with the base being 10.
- the nickel sulfate compound according to any one of the first to third aspects further 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 after the water dissolving step, there is provided a solid-liquid separation step of separating the liquid phase containing the nickel sulfate compound and the solid phase containing the iron component. Is a method for producing a nickel sulfate compound.
- the nickel-containing raw material includes at least one selected from the group consisting of nickel sulfide ore, nickel sulfide, nickel matte, nickel oxide, and ferronickel.
- a seventh aspect of the present invention is characterized in that, before the roasting step, an oxidizing roasting step of oxidizing and roasting the nickel-containing raw material under conditions different from the roasting step is provided.
- the nickel-containing raw material contains iron
- the nickel is converted to a nickel sulfate compound, and the conversion of iron to iron sulfate is suppressed. Can be suppressed, and the production efficiency of the nickel sulfate compound can be improved.
- the reduction of iron is suppressed, and iron can coexist with the nickel sulfate compound in the form of iron oxide, iron sulfide, and the like. Can be easily processed.
- the formation of the nickel sulfate compound can be promoted under the condition where the oxygen partial pressure is low and the sulfur dioxide partial pressure is high.
- iron can be easily removed by preferentially dissolving the nickel sulfate compound.
- the removal of impurities containing iron from the nickel sulfate compound is facilitated through the solid-liquid separation step.
- the sixth aspect it is possible to use a nickel-containing raw material that is relatively easy to procure, so that productivity can be improved.
- the iron content, the sulfur content, and the like contained in the nickel-containing raw material can be oxidized, so that the efficiency of impurity separation after the roasting step can be improved.
- FIG. 2 is a configuration diagram illustrating a device used in an embodiment.
- the nickel sulfate is thermodynamically more stable than the nickel oxide in the Ni—SO system, as shown in FIG.
- a roasting step of heating a nickel-containing raw material to generate a nickel sulfate compound is performed under a condition in which iron oxide is more thermodynamically stable than iron sulfate in the Fe—SO system.
- FIG. 1 is an example of a conceptual phase diagram of a Ni—SO system and an Fe—SO system.
- the boundary of each phase in the Ni-SO system is indicated by a dashed line (-----), and the boundary of each phase in the Fe-SO system is indicated by a dashed line (----).
- the chemical formula attached to the arrow indicates a thermodynamically stable phase on the side from 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 in the state diagram shown in FIG. 1 shows the logarithm of the SO 2 partial pressure, the upper as SO 2 partial pressure is high, the lower the lower SO 2 partial pressure.
- Examples of nickel sulfate contained in the Ni—SO system include NiSO 4 , and examples of nickel oxide include NiO.
- the boundary line LNi indicates a boundary line between a region where nickel sulfate is thermodynamically stable and a region where nickel oxide is thermodynamically stable.
- borderline L Ni than SO 2 partial pressure and the partial pressure of O 2 is high region nickel sulfate is the thermodynamically stable phase.
- nickel oxide becomes a thermodynamically stable phase.
- Examples of the iron sulfate contained in the Fe—SO system include FeSO 4 and Fe 2 (SO 4 ) 3 , and examples of the iron oxide include Fe 2 O 3 .
- a boundary line L Fe indicates a boundary line between a region where iron sulfate is thermodynamically stable and a region where iron oxide is thermodynamically stable.
- iron sulfate becomes a thermodynamically stable phase.
- the iron oxide becomes a thermodynamically stable phase.
- Ni Nickel sulfate is a thermodynamically stable phase in the -SO system and iron oxide in the Fe-SO system. Therefore, by roasting a system containing nickel (Ni), oxygen (O), and sulfur (S) under the conditions of the overlapping region A, the formation of iron sulfate can be performed even when iron is present in the system. It is possible to convert the nickel content to nickel sulfate while suppressing it.
- the roasting temperature is preferably in the range of 400 to 750 ° C, more preferably in the range of 550 to 750 ° C. With such a roasting temperature, reduction of iron is suppressed, and iron can coexist with a nickel sulfate compound in a state of iron oxide, iron sulfide, etc. Post-processing can be facilitated. Further, at these temperatures, the carbonate is decomposed, so that it is possible to prevent the carbonate from dissolving in water and remaining as an impurity even in the case where the carbonate is mixed, so that the post-process can be performed. Can be easily processed.
- the logarithmic log p (O 2 ) of the O 2 partial pressure in units of atmospheric pressure (atm) is preferably in the range of ⁇ 4 to ⁇ 6, and log p (O 2 ) is ⁇ 5.
- the range of from to -6 is more preferable.
- the partial pressure of SO 2 in the roasting step is preferably such that the logarithm log p (SO 2 ) of the partial pressure of SO 2 in the unit of atmospheric pressure (atm) is in the range of ⁇ 1 to +1 and the log p (SO 2 ) is in the range of ⁇ 1 to A range of 0 is more preferred.
- the total pressure of the roasting atmosphere is not excessively increased by setting the partial pressure of SO 2 to about the normal pressure or lower (the common logarithm of the partial pressure is substantially 0 or less), thereby facilitating the handling of the equipment. be able to.
- the nickel-containing raw material may be a nickel compound or metallic nickel as long as it contains a nickel element.
- the nickel-containing raw material in the roasting step preferably contains at least one selected from the group consisting of nickel sulfide ore, nickel sulfide, nickel matte, nickel oxide, and ferronickel.
- the nickel-containing raw material may contain iron or may not contain iron. The iron content is separated from the nickel sulfate compound in a later step, but from the viewpoint of energy consumption, the lower the iron content in the raw material, the more desirable.
- the nickel-containing raw material is not limited to one kind, and two or more kinds may be used. When two or more nickel-containing raw materials are used, these raw materials may be supplied in a mixed state, or may be supplied separately.
- the nickel matte includes, for example, a composition (weight ratio) of 45 to 55% Ni, about 20% Fe, 20 to 25% S, and about 1% or less Co. Further, as a nickel mat whose nickel concentration is increased in a converter, for example, a composition (weight ratio) of about 78% of Ni, about 1% of Co, about 1% of Fe, and about 20% of S can be cited. Ferronickel includes, for example, a composition (weight ratio) of 18 to 23% of Ni, about 1% of Co, and 76 to 81% of Fe.
- the particle diameter of the nickel-containing raw material Prior to the roasting step, it is preferable to reduce the particle diameter of the nickel-containing raw material by operations such as shredding, pulverization, and attrition. Since the reaction starts from the surface of the raw material in the roasting step, the smaller the particle diameter of the raw material, the shorter the reaction time, which is preferable.
- the crushing means is not particularly limited, but one or more of a ball mill, a rod mill, a hammer mill, a fluid energy mill, a vibration mill and the like can be used.
- the particle size after the pulverization is not particularly limited, but is, for example, about 1 to 1000 ⁇ m, or about 10 to 100 ⁇ m. In the case of a raw material that 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 device for performing the roasting step is not particularly limited, and examples thereof include a rotary kiln, a fluidized bed heating furnace, and an electric furnace.
- an inert gas such as nitrogen (N 2 ) or argon (Ar) may be supplied to the roasting device. These inert gases can also be used as carriers when supplying volatile components such as gas and vapor to the roasting apparatus. If the nickel-containing raw material has a low sulfur content, the sulfur content may be supplied to the roasting step.
- the source of the sulfur content is not particularly limited, but includes elemental sulfur, sulfur oxide, sulfuric acid, sulfate, sulfide and the like.
- preliminary oxidation roasting is performed under conditions different from the roasting process for the purpose of oxidizing iron, sulfur, and the like contained in the raw materials.
- a step may be provided.
- O 2 gas or the like may be supplied as an oxidizing agent.
- FIG. 2 schematically illustrates a method for producing a nickel sulfate compound according to the present embodiment.
- a roasted product 11 containing a nickel sulfate compound is obtained.
- a solution 21 containing a nickel sulfate compound is obtained in a water dissolving step S2 in which water 20 is supplied to the roasted product 11 and the nickel sulfate compound is dissolved in water.
- the iron component contained in the roasted product 11 is in a state of being hardly soluble in water such as iron oxide and iron sulfide, it is separated into a solid phase and a liquid phase in the solid-liquid separation step S3.
- a 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, for example, a purifying 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 impurities 42 such as cobalt.
- a nickel compound 41 can be obtained.
- the water added to the roasted product in the water dissolving step is preferably pure water treated so as not to contain impurities.
- the water treatment method is not particularly limited, but includes one or more of filtration, membrane separation, ion exchange, distillation, disinfection, chemical treatment, adsorption and the like.
- tap water obtained from a water source, industrial water, or the like may be used, or water obtained by treating wastewater 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., where 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 dissolving operation at a temperature lower than the boiling point of water. Further, the solution obtained in the water dissolving step preferably has a concentration at which NiSO 4 does not precipitate even at room temperature, and it is preferable to maintain a heated state with a solution having a higher concentration than that.
- the method of solid-liquid separation is not particularly limited, and examples thereof include a filtration method, a centrifugal separation method, and a sedimentation separation method.
- the apparatus has a high performance of separating fine particles contained in the solid phase.
- the type of filtration is not particularly limited, and examples thereof include gravity filtration, reduced pressure filtration, pressure filtration, centrifugal filtration, filtration with a filter aid, and compression squeezing. Pressure filtration is preferred because it allows easy adjustment of the differential pressure and enables rapid separation.
- Examples of impurities that can coexist with the nickel sulfate compound include iron (Fe), cobalt (Co), and aluminum (Al).
- iron sulfate, cobalt sulfate, and the like also dissolve when the nickel sulfate compound is dissolved in water. Further, in water, for example, iron precipitates as an oxide such as FeOOH, Fe 2 O 3 , Fe 3 O 4, etc., and it becomes easy to remove impurities from the nickel sulfate compound.
- conditions are set such that iron does not easily turn into iron sulfate. Therefore, by passing through the solid-liquid separation step, a crude nickel sulfate compound containing less iron can be obtained.
- metals having a lower ionization tendency than hydrogen (H), such as copper (Cu), gold (Au), silver (Ag), and platinum group metals (PGM), remain as solids in the water dissolving step. It can be removed by a liquid separation step.
- the solid removed by the solid-liquid separation step may include compounds such as arsenic (As), lead (Pb), and zinc (Zn), in addition to the impurities described above. Solids containing these impurities can be recycled as valuables.
- the solution obtained in the water dissolving step and the solid-liquid separation step contains a nickel sulfate compound as a main component, it can be transported and used as a solution of the nickel sulfate compound or as a solid of the nickel sulfate compound by drying or the like. it can.
- techniques such as solvent extraction, electrodialysis (Electrowinning), electrorefining (Electrorefining), ion exchange, and crystallization are used. Can be used.
- an extractant that can extract cobalt into a solvent preferentially or selectively over nickel. This allows the nickel sulfate compound to remain in the aqueous solution to allow for efficient purification.
- the extractant include organic compounds having a functional group capable of binding to a metal ion, such as a phosphinic acid group and a thiophosphinic acid group.
- an organic solvent capable of separating the extractant from water may be used as a diluent.
- the diluent is preferably an organic solvent that is hardly miscible with water.
- the target nickel sulfate compound may be crystallized from the solution by at least one factor such as a change in temperature, a decrease in the solvent, and the addition of another substance.
- purification is enabled by leaving at least a part of the impurities in the liquid phase.
- Specific examples include an evaporation crystallization method and a poor solvent crystallization method.
- a solution is concentrated by boiling or evaporating under reduced pressure to crystallize a nickel sulfate compound.
- the poor solvent crystallization method is a crystallization method used in the production of pharmaceuticals and the like.
- an organic solvent is added to a solution containing a nickel sulfate compound to precipitate a nickel sulfate compound.
- an organic solvent miscible with water is preferable, 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.
- concentration range in which the organic solvent is miscible with water it is preferable to mix the organic solvent at a concentration to which the organic solvent is added to such an extent that the nickel sulfate compound is precipitated.
- the organic solvent can be mixed with water at an arbitrary ratio as long as the concentration allows precipitation of the nickel sulfate compound.
- 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 such an extent that crystallization is not hindered.
- 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.
- the nickel sulfate compound precipitated by crystallization can be separated from the solution by solid-liquid separation.
- the method of solid-liquid separation is not particularly limited, and examples thereof include a filtration method, a centrifugation method, and a sedimentation method.
- the metal dissolved in the solution is preferably neutralized and removed from the solution by a method such as precipitation.
- the purified solution is mainly composed of a mixture of water and an organic solvent, the water and the organic solvent can be separated by a method such as distillation.
- the following effects can be obtained. (1) Since a nickel sulfate compound with high added value can be produced from various nickel-containing raw materials, production can be performed even near a place of demand, and transportation costs can be reduced. (2) A highly pure nickel sulfate compound can be produced. (3) The production of iron sulfate can be suppressed in the roasting step. Further, generation of hydrogen (H 2 ) gas can also be suppressed. (4) The roasted product is a chemical species in which iron is hardly dissolved in water, and nickel is easily dissolved in water as a nickel sulfate compound, so that iron is easily removed. (5) It is possible to easily remove impurities including iron. (6) Equipment cost can be reduced as compared with the conventional method, and existing equipment can be used as a roasting furnace. (7) Before the roasting step, iron contained in the nickel-containing raw material can be oxidized, and the efficiency of iron removal can be improved.
- Example-1 Roasting test
- a test of sulfuric acid roasting was performed using the test apparatus 100 shown in FIG. After weighing 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 was provided with a thermometer 104 such as a thermocouple capable of measuring an ambient temperature, an injection pipe 105 capable of injecting various gases, and an outlet 106 for exhaust gas generated inside.
- the temperature was raised to a specified temperature in the electric furnace 103, and the sample was steamed.
- dry air or SO 2 gas containing nitrogen gas can be supplied periodically while always injecting argon gas.
- the exhaust gas discharged from the outlet 106 passes through the gas analyzer 107 and can be treated by the exhaust gas treatment device 108. Data on various gas volumes and analytical values were collected on a computer.
- the composition of the nickel compound used in the test was a nickel sulfide alloy in which the content of iron was reduced by converter treatment of a 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 rose to the specified temperature, and after reaching the specified 680 ° C., air was supplied for 20 minutes to burn iron and oxidized to oxidize iron. At the same time as air was injected, the weight of the sample was reduced and the evolution 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, a certain amount of 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 NiSO 4 .
- XRD X-ray diffraction
- Example-2 Water dissolution test
- the roasted product produced from 5 g of the nickel compound in Example-1 was put into 100 g of pure water and stirred at 90 ° C. to dissolve. 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 spectrometer. Further, from this concentration, the amount contained in the solution, that is, the total amount dissolved in pure water was determined for each metal, and the amount contained in the 5 g sample used for sulfuric acid roasting was set to 100% and dissolved in pure water. 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. Table 1 shows the results of the determination of the dissolution rate.
- Example 1 From the results, it was confirmed that the iron content in the roasted product was hardly dissolved, and Ni and Co were easily dissolved. This indicates that the sulfuric acid roasting of Example 1 can produce a high-purity nickel sulfate compound having a low iron content.
- the present invention can be used for the production of various types of nickel compounds or high-purity nickel sulfate compounds useful as raw materials for metallic nickel used in electric parts such as secondary batteries, chemical products, and the like.
- S1 roasting step
- S2 water dissolving step
- S3 solid-liquid separation step
- S4 refining step
- 10 nickel-containing raw material
- 11 roasted product
- 20 water
- 21 solution
- 31 crude nickel sulfate Compound
- 32 impurities separated in the solid-liquid separation step
- 40 purification agent
- 41 purified nickel sulfate compound
- 42 impurities separated in the purification step.
Abstract
Description
本願は、2018年8月30日に、日本に出願された特願2018-161837号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a method for producing a nickel sulfate compound.
Priority is claimed on Japanese Patent Application No. 2018-161837 filed on August 30, 2018, the content of which is incorporated herein by reference.
差圧の調整が容易で、迅速な分離が可能となる加圧濾過が好ましい。 In the solid-liquid separation step, the method of solid-liquid separation is not particularly limited, and examples thereof include a filtration method, a centrifugal separation method, and a sedimentation separation method. Desirably, it is preferable that the apparatus has a high performance of separating fine particles contained in the solid phase. For example, in the filtration method, the type of filtration is not particularly limited, and examples thereof include gravity filtration, reduced pressure filtration, pressure filtration, centrifugal filtration, filtration with a filter aid, and compression squeezing.
Pressure filtration is preferred because it allows easy adjustment of the differential pressure and enables rapid separation.
(1)種々のニッケル含有原料から、付加価値の高い硫酸ニッケル化合物を製造することができるので、需要地の近くでも生産が可能となり、輸送費を削減することができる。
(2)高純度の硫酸ニッケル化合物を生成することができる。
(3)焙焼工程において硫酸鉄の生成を抑制することができる。また、水素(H2)ガスの発生も抑制することができる。
(4)焙焼生成物は、鉄分が水に溶解しにくい化学種になり、ニッケル分が硫酸ニッケル化合物として水に溶解しやすくなるので、鉄分の除去が容易になる。
(5)鉄分を含む不純物の除去を容易に行うことができる。
(6)従来法に比べて設備コストを低減することができ、焙焼炉として既存の設備を使用することも可能である。
(7)焙焼工程の前に、ニッケル含有原料に含まれる鉄分を酸化させることができ、鉄分除去の効率を向上させることができる。 According to the method for producing a nickel sulfate compound of the present embodiment, the following effects can be obtained.
(1) Since a nickel sulfate compound with high added value can be produced from various nickel-containing raw materials, production can be performed even near a place of demand, and transportation costs can be reduced.
(2) A highly pure nickel sulfate compound can be produced.
(3) The production of iron sulfate can be suppressed in the roasting step. Further, generation of hydrogen (H 2 ) gas can also be suppressed.
(4) The roasted product is a chemical species in which iron is hardly dissolved in water, and nickel is easily dissolved in water as a nickel sulfate compound, so that iron is easily removed.
(5) It is possible to easily remove impurities including iron.
(6) Equipment cost can be reduced as compared with the conventional method, and existing equipment can be used as a roasting furnace.
(7) Before the roasting step, iron contained in the nickel-containing raw material can be oxidized, and the efficiency of iron removal can be improved.
図3に示す試験装置100を用いて硫酸焙焼の試験を実施した。受皿101の上にサンプルとして5gのニッケル化合物を計量した後、この受皿101を、電気炉103の中に設置したガラス容器102の内側にセットした。ガラス容器102には雰囲気温度を計測できる熱電対等の温度計104と、各種のガスを注入できる注入管105と、内部で発生した排ガスの出口106を設けた。電気炉103で規定温度に昇温してサンプルを蒸し焼きとした。注入管105においては、常時アルゴンガスを注入しながら、定期的に乾燥空気もしくは窒素ガスを含むSO2ガスが供給できるようにした。出口106から排出される排ガスは、ガス分析装置107を経て排ガス処理装置108で処理できるようにした。各種のガス量と分析値のデータはコンピュータに収集した。 (Example-1: Roasting test)
A test of sulfuric acid roasting was performed using the
Ni:78%、Co:1%、Fe:1%、S:20% The composition of the nickel compound used in the test was a nickel sulfide alloy in which the content of iron was reduced by converter treatment of a nickel mat, and the composition was as follows.
Ni: 78%, Co: 1%, Fe: 1%, S: 20%
実施例-1で5gのニッケル化合物から生成した焙焼生成物を、純水100gの中に入れて90℃で攪拌し溶解した。溶解液の一部をサンプリングし、原子吸光分光分析計を用いて金属ごと(Ni,Fe,Co)に溶解液中の濃度を求めた。さらに、この濃度から溶解液に含まれる量、すなわち純水に溶解した全量を金属ごとに定量し、硫酸焙焼に用いた5gのサンプル中に含まれる量を100%として、純水に溶解した割合(溶解率)を求めた。例えばNiの溶解率は、焙焼生成物に含まれるNiのうち、純水に溶解したNiの割合を意味する。溶解率を求めた結果を表1に示す。 (Example-2: Water dissolution test)
The roasted product produced from 5 g of the nickel compound in Example-1 was put into 100 g of pure water and stirred at 90 ° C. to dissolve. 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 spectrometer. Further, from this concentration, the amount contained in the solution, that is, the total amount dissolved in pure water was determined for each metal, and the amount contained in the 5 g sample used for sulfuric acid roasting was set to 100% and dissolved in pure water. 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. Table 1 shows the results of the determination of the dissolution rate.
Claims (7)
- 酸素分圧および二酸化硫黄分圧を、Ni-S-O系において硫酸ニッケルが酸化ニッケルよりも熱力学的に安定となり、かつ、Fe-S-O系において酸化鉄が硫酸鉄よりも熱力学的に安定となる条件下として、鉄分を含むニッケル含有原料を加熱し、硫酸ニッケル化合物を生成させる焙焼工程を有することを特徴とする硫酸ニッケル化合物の製造方法。 The oxygen partial pressure and the sulfur dioxide partial pressure were determined to be such that nickel sulfate is thermodynamically more stable than nickel oxide in the Ni—SO system, and iron oxide is more thermodynamic than iron sulfate in the Fe—SO 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 generate a nickel sulfate compound as a condition to be stable.
- 前記焙焼工程において、焙焼温度が400~750℃の範囲であることを特徴とする請求項1に記載の硫酸ニッケル化合物の製造方法。 方法 The method for producing a nickel sulfate compound according to claim 1, wherein in the roasting step, the roasting temperature is in a range of 400 to 750 ° C.
- 前記焙焼工程において、気圧(atm)単位による酸素分圧の常用対数log p(O2)が-4~-6の範囲であり、気圧(atm)単位による二酸化硫黄分圧の常用対数log p(SO2)が-1~+1の範囲であることを特徴とする請求項1または2に記載の硫酸ニッケル化合物の製造方法。 In the roasting step, the common logarithm log p (O 2 ) of the oxygen partial pressure in the unit of atmospheric pressure (atm) is in a range of −4 to −6, and the common logarithm log p of the sulfur dioxide partial pressure in the unit of the atmospheric pressure (atm). 3. The method for producing a nickel sulfate compound according to claim 1, wherein (SO 2 ) is in the range of −1 to +1.
- 前記焙焼工程の後に、前記硫酸ニッケル化合物を水に溶解させる水溶解工程を有することを特徴とする請求項1~3のいずれか1項に記載の硫酸ニッケル化合物の製造方法。 (4) The method for producing a nickel sulfate compound according to any one of (1) to (3), further comprising a water dissolving step of dissolving the nickel sulfate compound in water after the roasting step.
- 前記水溶解工程の後に、前記硫酸ニッケル化合物を含む液相と、鉄分を含む固相とを分離する固液分離工程を有することを特徴とする請求項4に記載の硫酸ニッケル化合物の製造方法。 5. The method for producing a nickel sulfate compound according to claim 4, further comprising a solid-liquid separation step of separating the liquid phase containing the nickel sulfate compound and the solid phase containing iron after the water dissolving step.
- 前記ニッケル含有原料が、ニッケル硫化鉱、ニッケル硫化物、ニッケルマット、酸化ニッケル、フェロニッケルからなる群から選択される1種以上を含むことを特徴とする請求項1~5のいずれか1項に記載の硫酸ニッケル化合物の製造方法。 The method according to any one of claims 1 to 5, wherein the nickel-containing raw material includes at least one selected from the group consisting of nickel sulfide ore, nickel sulfide, nickel matte, nickel oxide, and ferronickel. A method for producing the nickel sulfate compound according to the above.
- 前記焙焼工程の前に、前記焙焼工程とは異なる条件により、ニッケル含有原料の酸化焙焼を行う酸化焙焼工程を有することを特徴とする請求項1~6のいずれか1項に記載の硫酸ニッケル化合物の製造方法。 The method according to any one of claims 1 to 6, further comprising, before the roasting step, an oxidizing roasting step of oxidizing and roasting the nickel-containing raw material under conditions different from the roasting step. The method for producing a nickel sulfate compound of the present invention.
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CN113403486A (en) * | 2021-06-18 | 2021-09-17 | 国家电投集团黄河上游水电开发有限责任公司 | Process for removing iron from nickel sulfide concentrate leachate by goethite method |
CN113416855A (en) * | 2021-06-18 | 2021-09-21 | 国家电投集团黄河上游水电开发有限责任公司 | Method for preparing nickel sulfate from nickel sulfide concentrate leaching solution |
CN115159594A (en) * | 2022-08-01 | 2022-10-11 | 中伟新材料股份有限公司 | Method for preparing metal sulfate |
CN115159594B (en) * | 2022-08-01 | 2024-05-14 | 中伟新材料股份有限公司 | Method for preparing metal sulfate |
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CN113800578B (en) * | 2021-08-03 | 2022-11-15 | 广东邦普循环科技有限公司 | Method for preparing nickel sulfate by using low-nickel ferronickel |
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Cited By (6)
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CN113403486A (en) * | 2021-06-18 | 2021-09-17 | 国家电投集团黄河上游水电开发有限责任公司 | Process for removing iron from nickel sulfide concentrate leachate by goethite method |
CN113416855A (en) * | 2021-06-18 | 2021-09-21 | 国家电投集团黄河上游水电开发有限责任公司 | Method for preparing nickel sulfate from nickel sulfide concentrate leaching solution |
CN113416855B (en) * | 2021-06-18 | 2022-10-18 | 国家电投集团黄河上游水电开发有限责任公司 | Method for preparing nickel sulfate from nickel sulfide concentrate leaching solution |
CN113403486B (en) * | 2021-06-18 | 2023-05-26 | 国家电投集团黄河上游水电开发有限责任公司 | Iron removal process of nickel sulfide concentrate leaching solution by goethite method |
CN115159594A (en) * | 2022-08-01 | 2022-10-11 | 中伟新材料股份有限公司 | Method for preparing metal sulfate |
CN115159594B (en) * | 2022-08-01 | 2024-05-14 | 中伟新材料股份有限公司 | Method for preparing metal sulfate |
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