WO2020225904A1 - ニッケル含有原料の処理方法 - Google Patents
ニッケル含有原料の処理方法 Download PDFInfo
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- WO2020225904A1 WO2020225904A1 PCT/JP2019/018554 JP2019018554W WO2020225904A1 WO 2020225904 A1 WO2020225904 A1 WO 2020225904A1 JP 2019018554 W JP2019018554 W JP 2019018554W WO 2020225904 A1 WO2020225904 A1 WO 2020225904A1
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- nickel
- raw material
- roasting
- containing raw
- sulfated
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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
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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
Definitions
- the present invention relates to a method for treating a nickel-containing raw material.
- 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.
- demand for secondary batteries using nickel compounds or metallic nickel as a positive electrode material is expected to increase as a power source for transportation equipment such as electric vehicles and electronic equipment.
- a stable supply of high-purity nickel sulfate compound is desired.
- Impurities that may be contained in low-purity nickel compounds include other metal compounds such as iron, copper, cobalt, manganese, and magnesium.
- a method for obtaining a high-purity nickel compound a method of dissolving metallic nickel whose nickel purity has been increased by an electrowinning method with a sulfuric acid solution and a solvent extraction method can be mentioned.
- the solvent extraction method a step of selectively extracting and removing other metal compounds or selectively extracting and extracting nickel compounds is carried out. In either case, in order to selectively extract a specific metal ion, a special drug is required, which is expensive.
- Patent Document 1 describes a method for obtaining water-soluble nickel sulfate by heat-treating nickel oxide powder having a specific gravity of more than 6.30 in sulfuric acid and then leaching it with hot water. ..
- Patent Document 1 lists 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 sulfuric acid used in the heat treatment. When concentrated sulfuric acid having a concentration of 95% is used in Patent Document 1 (Examples 7 to 9), a high temperature of 275 ° C. or higher is required.
- An object of the present invention is to provide a method for treating a nickel-containing raw material that can be efficiently treated even if the nickel-containing raw material contains a high concentration of magnesium.
- the first aspect of the present invention is a method for treating a nickel-containing raw material, which comprises an oxidative roasting step of oxidizing and roasting a nickel-containing raw material containing magnesium to magnesium oxide. is there.
- a second aspect of the present invention is characterized in that the nickel-containing raw material contains nickel ore and has a magnesium removing step of removing the magnesium component from the nickel-containing raw material after the oxidation roasting step.
- This is a method for treating a nickel-containing raw material according to the embodiment.
- a third aspect of the present invention is the nickel-containing raw material of the first or second aspect, which comprises a step of pulverizing the nickel-containing raw material containing the magnesium content before the oxidative roasting step. It is a processing method of.
- a fourth aspect of the present invention is the method for treating a nickel-containing raw material according to a second aspect, which comprises removing at least a part of silica contained in the nickel ore in the magnesium removing step.
- a fifth aspect of the present invention is a sulfated roasting step of obtaining a roasting product containing nickel sulfate by sulfated roasting the nickel-containing raw material from which the magnesium content has been removed after the magnesium removing step.
- the method for treating a nickel-containing raw material according to a second or fourth aspect which comprises the above.
- the nickel-containing raw material contains iron, and in the sulfated roasting step, nickel sulfate is thermodynamically more stable than nickel oxide in the Ni—SO system, and
- a nickel-containing raw material according to a fifth aspect which comprises heating and roasting under the conditions of oxygen partial pressure and sulfur dioxide partial pressure in which iron oxide is thermodynamically more stable than iron sulfate in the Fe—SO system. It is a processing method of.
- the nickel-containing raw material in the subsequent step utilizes the difference in properties between nickel oxide converted from the nickel content and magnesium oxide converted from the magnesium content. Can be facilitated. As a result, even a nickel-containing raw material containing a high concentration of magnesium can be efficiently treated.
- the second aspect by removing the magnesium content contained in the nickel-containing raw material, it is possible to facilitate the treatment of the nickel-containing raw material in the subsequent process.
- the particle size of the nickel-containing raw material can be adjusted to promote oxidative roasting of magnesium contained in the nickel-containing raw material.
- the fourth aspect it is possible to facilitate the treatment of the nickel-containing raw material in the subsequent process by removing the excess silica content and the like contained in the nickel-containing raw material.
- the nickel-containing raw material is treated by a pyrometallurgical method, it is not necessary to use liquid sulfuric acid, and the treatment becomes easy.
- the nickel content is converted to the nickel sulfate compound and the conversion from iron to iron sulfate is suppressed, the consumption of sulfur by iron is suppressed and the production efficiency of the nickel sulfate compound is suppressed. Can be improved.
- the treatment method of the present embodiment includes an oxidative roasting step of oxidizing and roasting a nickel-containing raw material containing magnesium to magnesium oxide.
- the nickel-containing raw material may be a nickel compound or metallic nickel as long as it contains a nickel element.
- the nickel compound is not particularly limited, and examples thereof 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 (elemental substance or alloy) is used as a nickel-containing raw material, it may be a shot or the like in which molten metal is fragmented. Nickel ore can also be used as the nickel-containing raw material. Examples of the nickel ore include one or more kinds of nickel oxide ore, nickel sulfide ore and the like. A nickel mat containing nickel sulfide as a main component can also be used as a nickel-containing raw material.
- nickel oxide ore examples include laterite ore containing nickel such as limonite and saprolite.
- the limonite may be limonite having a low iron content or limonite having a high iron content, and saprolite has a high nickel content (for example, a Ni content of 1.8 wt% or more) and a saprolite having a low nickel content (for example, a Ni content is low). (Less than 1.8 wt%) Saprolite may be used.
- the nickel sulfide ore include nickel sulfide ore (Pentland ore), millerite, chalcopyrite containing nickel, and pyrrhotite containing nickel.
- the nickel-containing raw material may or may not contain iron.
- the nickel-containing raw material contains iron, the iron content is separated from the nickel sulfate compound in a subsequent step, but from the viewpoint of energy consumption, it is desirable that the iron content in the raw material is small. Treatment is possible even if the iron content is higher than that of nickel, but it is preferable that the iron content is lower than that of nickel.
- the nickel-containing raw material is not limited to one type, and two or more types may be used. When two or more kinds of nickel-containing raw materials are used, these raw materials may be supplied in a mixed state or may be supplied separately.
- a sulfur-free nickel-containing raw material may be used, and / or a sulfur-containing nickel-containing raw material such as nickel sulfide ore, nickel sulfide, nickel matte, etc. may be used as at least a part of the raw material. You may.
- At least one nickel-containing raw material contains magnesium.
- nickel sulfide ores such as heazlewoodite and pentlandite may be contained in host rocks such as magnesium-containing serpentine.
- the proportion of nickel sulfide ore is about 0.2 to 5 wt%, and the particle size is about 2 ⁇ m to 1 mm.
- magnesium may be mixed in the nickel-containing raw material.
- the ratio of the nickel content to the magnesium content is not particularly limited, but for example, Mg / Ni may be about 5 to 15 or 8 to 12.5, or more.
- the nickel-containing raw material contains magnesium and iron
- the ratios thereof are not particularly limited, and examples thereof include Mg / Fe of about 0.6 to 2.
- the nickel-containing raw material may contain a high concentration of magnesium.
- the proportion of Mg is about 26% by weight.
- the proportion of magnesium in the nickel-containing raw material is, for example, 10% by weight or more, and includes 15% by weight, 20% by weight, 25% by weight, 30% by weight, or a ratio before, after, or in between.
- FIG. 1 shows a schematic configuration of a system for performing a sulfated roasting method using the treatment method according to the present embodiment.
- the processing system of this embodiment includes an oxidative roasting furnace 12 for carrying out the oxidative roasting step 10, a water addition device 22 and a classification device 24 for carrying out the magnesium removal step 20, and a sulfated roasting step 30. It includes a sulfate roasting furnace 32 for carrying out, a cooling unit 41 for carrying out the extraction step 40, and a melting tank 43.
- the particle size of the nickel-containing raw material 11 Prior to the oxidative roasting step 10, it is preferable to reduce the particle size of the nickel-containing raw material 11 by operations such as shredding, crushing, and polishing. Since the oxidative roasting reaction starts from the surface of the nickel-containing raw material 11, the smaller the particle size of the nickel-containing raw material 11, the shorter the reaction time, which is preferable.
- the means for pulverizing the nickel-containing raw material 11 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 of the nickel-containing raw material 11 after pulverization is not particularly limited. When the nickel-containing raw material is available in the form of fine particles, such as limonite ore, it may be supplied to the oxidative roasting step 10 as it is.
- Examples of the oxidation roasting furnace 12 include a stirring type roasting furnace, a rotary furnace type roasting furnace, and a fluidized roasting furnace having a fluidized bed.
- roasting of ore conventionally, after coarsely crushing the mined ore, roasting is performed using a stirring type roasting furnace or a rotary furnace type roasting furnace. In this case, the burden of pretreating the roasted object is small and the rotation speed is slow, but the reaction speed is slow and the apparatus becomes large. For this reason, a fluidized roasting furnace of a method in which an object to be roasted is roasted while being floated in combustion air has become widespread. By adopting a fluidized roasting furnace, the equipment can be miniaturized.
- the oxidation roasting furnace 12 can select the optimum method depending on the characteristics of the ore to be treated. For example, when the ore is mainly composed of fine limonite or the like, the scattering of fine powder can be suppressed by using a rotary furnace type roasting furnace.
- the roasting temperature (oxidative roasting temperature) in the oxidative roasting step of the present embodiment is preferably 600 ° C. or higher, for example.
- the upper limit of the oxidative roasting temperature is not particularly limited, but an oxidative roasting temperature of about 600 to 800 ° C. can be mentioned from the viewpoint of the cost of the refractory material of the oxidative roasting furnace 12.
- the oxidative roasting temperature include 600 ° C., 650 ° C., 700 ° C., 750 ° C., 800 ° C., or a temperature range before, after, or between these.
- the nickel-containing raw material 11 such as raw ore is crushed before the oxidative roasting step 10
- the structure of the oxidative roasting furnace 12 is not particularly limited, but the inlet of the nickel-containing raw material 11 and the outlet of the oxidative roasting product 13 may be provided on the side surface of the furnace body, for example, in an oblique direction.
- the outlet of the exhaust gas 14 may be provided in the upper part of the furnace body.
- the cost can be reduced by supplying the raw ore to the oxidation roasting step 10 using only a simple pretreatment method such as crushing without treating it by flotation.
- ores such as serpentine are crushed and then treated by flotation, they become fine particles and move to the floating side in the same way as metallic nickel, separating nickel from the components of the host rock and concentrating it. It becomes difficult to do.
- O 2 gas, air or the like may be supplied as an oxidant.
- the magnesium content is converted to magnesium oxide.
- the nickel content may be converted to nickel oxide.
- the iron content, sulfur content, etc. contained in the nickel-containing raw material 11 may be oxidized.
- Ores such as serpentine can be decomposed into MgO + SiO 2 by decomposing to form magnesium silicate such as MgSiO 2 and further oxidizing.
- the magnesium removing step 20 water 21 is added to the oxidative roasting product 13 by the water addition device 22.
- magnesium oxide reacts with water to form magnesium hydroxide.
- the magnesium content 26 is separated from the nickel-containing residue 25 by the classification device 24.
- the method for removing the magnesium content 26 from the oxidative roasting product 13 may be a method of separating by a difference in particle size as in the classification device 24, or a method of specific gravity difference, solubility, or any other method may be adopted.
- MgO changes to Mg (OH) 2 and is pulverized by the effect of volume expansion, which is preferable.
- the residue 25 having a small particle size can be obtained.
- the nickel-containing raw material 11 contains a silica content (SiO 2 ) such as nickel ore, at least a part of the silica content may be separated and removed from the residue 25 together with the magnesium content 26.
- the removal of the magnesium content 26 means that at least a part of the magnesium content 26 may be removed from the oxidative roasting product 13, but when the residue 25 is used as the sulfated roasting target 31. It is preferable to remove as much magnesium content 26 as possible.
- the sulfated roasting step 30 is carried out with the magnesium content 26 remaining in the sulfated roasted object 31, in addition to the excessive consumption of sulfur content, magnesium sulfate is mixed in the sulfated roasted product 33 to produce sulfuric acid. There may be a problem of separation of nickel and magnesium sulfate.
- the residue 25 of the classification device 24 obtained by removing the magnesium content 26 from the oxidation roasting product 13 is supplied to the sulfate roasting furnace 32 as the sulfated roasting object 31.
- the sulfated roasting furnace 32 include a stirring type roasting furnace, a rotary furnace type roasting furnace, and a fluidized roasting furnace having a fluidized bed. As described above, when the fluidized roasting furnace is adopted, the apparatus can be miniaturized.
- the sulfate roasting furnace 32 may be a roasting furnace different from the oxidation roasting furnace 12, but the oxidation roasting step 10 and the sulfate roasting step 30 may be carried out in the same roasting furnace.
- the structure of the sulfated roasting furnace 32 is not particularly limited, but the inlet of the sulfated roasting object 31 and the outlet of the sulfated roasting product 33 may be provided on the side surface of the furnace body, for example, in an oblique direction.
- the outlet of the exhaust gas 34 may be provided in the upper part of the furnace body.
- the sulfated roasting furnace 32 treats the sulfated roasting object 31 by sulfated roasting to convert the nickel content contained in the nickel-containing raw material 11 into nickel sulfate.
- the sulfuric acid roasting furnace 32 may be supplied with the sulfur content deficient in the sulfated roasting object 31, oxygen for oxidizing the sulfur content, and the like. In FIG. 1, for the sake of simplicity, the supply routes of various materials supplied to the sulfate roasting furnace 32 are not distinguished.
- an auxiliary substance or material may be supplied to the sulfated roasting furnace 32 for the purpose of improving the conversion efficiency of the sulfated roasting.
- a material harder than the nickel content contained in the sulfated roasting object 31 may be supplied to the sulfated roasting furnace 32 as a medium.
- the silica may also function as a medium.
- the material of the media is preferably softer than the inner wall material of the sulfate roasting furnace 32. As a result, deterioration, damage, etc. of the inner wall material can be reduced.
- Specific examples of the media include aluminum oxide such as synthetic alumina, zirconia, silica, silicon nitride, silicon carbide, tungsten carbide, and glass.
- the particle shape of the medium is not particularly limited, and examples thereof include a spherical shape, a columnar shape, and a polyhedral shape. Examples of the average particle size of the media include 0.02 to 10 mm.
- the media is preferably insoluble or sparingly soluble in water because the media can be separated according to the solubility of water.
- the sulfated roasting step 30 a sulfated roasted product 33 containing a nickel sulfate compound is obtained.
- the nickel sulfate solution 44 is obtained by the water dissolution step of supplying water to the sulfated roasted product 33 in the dissolution tank 43 and dissolving the nickel sulfate compound in water.
- the sulfated roasted product 33 is cooled by the cooling unit 41 before adding water to the sulfated roasted product 33. Further, the sulfated roasted product 33 may be crushed before adding water to the sulfated roasted product 33.
- the solid phase residue 45 is precipitated in the dissolution tank 43. Therefore, a nickel sulfate solution 44 is obtained as a liquid phase from the dissolution tank 43, and a residue 45 containing iron oxide is separated as a solid phase. Further, if necessary, for example, in order to separate nickel sulfate and cobalt sulfate or the like, a nickel sulfate compound from which impurities such as cobalt have been removed can be obtained by performing a purification step of the nickel sulfate solution 44.
- the separation of iron contained in the sulfated roasted product 33 is not limited to the method based on the difference in solubility, but the method based on the difference in magnetism, specific gravity, particle size, etc., or two or more of these methods are adopted. May be good.
- the oxygen partial pressure and the sulfur dioxide partial pressure are thermodynamically more stable than nickel oxide in the Ni—SO system, and the Fe—SO system. It is preferable that the condition is such that iron oxide is more thermodynamically stable than iron sulfate.
- the nickel-containing raw material contains iron
- the nickel content is converted to nickel sulfate and the conversion of iron to iron sulfate is suppressed, so that the consumption of sulfur by iron is suppressed.
- the production efficiency of nickel sulfate can be improved.
- FIG. 2 is an example of a conceptual phase diagram of the Ni—SO system and the Fe—SO system.
- the boundary line of each phase in the Ni-SO system is indicated by a broken line (---), and the boundary line of each phase in the Fe-SO system is indicated by a alternate long and short dash line (-...-). ..
- the chemical formulas attached to the arrows show thermodynamically stable phases on the side from each boundary toward the arrow.
- the horizontal axis of the state diagram shown in FIG. 2 shows the logarithm of the O 2 partial pressure, the right side has a higher O 2 partial pressure, and the left side has a lower O 2 partial pressure.
- the vertical axis of the phase diagram shown in FIG. 2 shows the logarithm of the SO 2 partial pressure, the upper side has a higher SO 2 partial pressure, and the lower side has a 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 L Ni indicates the boundary line between the region where nickel sulfate is thermodynamically stable and the region where nickel oxide is thermodynamically stable.
- nickel sulfate becomes a thermodynamically stable phase.
- nickel oxide becomes a thermodynamically stable phase.
- the boundary line L Fe indicates the boundary line between the region where iron sulfate is thermodynamically stable and the region where iron oxide is thermodynamically stable.
- iron sulfate becomes a thermodynamically stable phase.
- iron oxide becomes a thermodynamically stable phase.
- 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 Nickel sulfate in the —SO system and iron oxide in the Fe—SO system are thermodynamically stable phases. Therefore, by roasting a system containing nickel (Ni), oxygen (O), and sulfur (S) under the condition of the overlapping region A, iron sulfate is produced even if iron coexists in the system. Nickel content can be converted to nickel sulfate while suppressing it.
- the roasting temperature (sulfated roasting temperature) in the sulfated roasting step of the present embodiment is preferably in the range of 400 to 750 ° C., more preferably in the range of 550 to 750 ° C.
- Specific examples of the sulfated roasting temperature include 400 ° C., 450 ° C., 500 ° C., 550 ° C., 600 ° C., 650 ° C., 700 ° C., 750 ° C., or a temperature range before, after, or in between.
- the reduction of iron content is suppressed, and iron content can coexist with the nickel sulfate compound in the state of iron oxide, iron sulfide, etc., so that the coagulation of particles in the roasting product is suppressed.
- the processing of the post-process can be facilitated.
- the carbonate is decomposed, so that even if the carbonate is mixed, it is possible to prevent the carbonate from being dissolved in water and remaining as an impurity in the subsequent step. Can be facilitated.
- the sulfuric acid roasting temperature is preferably 600 to 700 ° C.
- manganese manganese
- the object to be roasted contains manganese (Mn) as an impurity derived from the nickel-containing raw material, manganese forms a spinel structure with iron to remove manganese as an insoluble matter. It will be easier to do.
- the O 2 partial pressure in sulfation roasting step, pressure (atm) common logarithm log p of O 2 partial pressure (O 2) is preferably in the range of -4 to -6 in units, depending on the conditions, log p (O 2) is -4 to -5, or log p (O 2) is more preferably in the range of -5 to -6.
- pressure (atm) common logarithm log p of O 2 partial pressure (O 2) is preferably in the range of -4 to -6 in units, depending on the conditions, log p (O 2) is -4 to -5, or log p (O 2) is more preferably in the range of -5 to -6.
- log p (O 2 ) in the overlapping region A moves to the larger side (closer to zero (0)).
- log p (O 2 ) may be selected from, for example, -8 or more and 0 or less.
- the SO 2 partial pressure in the sulfation roasting step pressure (atm) preferably common logarithm log p (SO 2) range is -1 to + 1 SO 2 partial pressure in units, log p (SO 2) is - The range of 1 to 0 is more preferable. Even in the overlapping region A of FIG. 2, the production of sulfate can be promoted by 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 in the sulfated roasting step does not become excessive. The handling of equipment can be facilitated. Depending on the relationship with log p (O 2 ) and the sulfuric acid roasting temperature, log p (SO 2 ) may be selected from, for example, -4 or more and +1 or less.
- an inert gas such as nitrogen (N 2 ) or argon (Ar) may be supplied to the roasting furnace. These inert gases can also be used as carriers when supplying volatile components such as gas and steam to the roasting furnace.
- the SO 2 partial pressure can be adjusted, for example, by controlling the supply amount of the sulfur source. If the nickel-containing raw material has a low sulfur content, the sulfur content may be supplied to the sulfate roasting step.
- Sources of sulfur include solid sulfur (elementary sulfur, S), sulfur oxides (SO 2 etc.), sulfuric acid (H 2 SO 4 ), sulfates, sulfides, which are solid at room temperature.
- Examples thereof include sulfide ores such as luteinite (FeS 2 ).
- S sulfur
- SO 2 gas oxygen-enriched state
- Sulfur may be burned in an oxygen-containing atmosphere to produce sulfur oxides.
- the range of the preferable voltage division can be obtained from the positions of the boundary line L Ni and the boundary line L Fe by examining the above-mentioned phase diagram according to the sulfated roasting temperature.
- the sulfurization roasting temperature is 650 to 750 ° C.
- the preferred partition coefficient ranges are log p (O 2 ) of about -8 to -4 and log p (SO 2 ) of about -2 to +2.
- Log p (O 2 ) is about -3 to -2
- log p (SO 2 ) is about -3 to +1
- log p (O 2 ) is about -1 to
- log p (SO 2 ) is about -4 to -4.
- About 0 is mentioned.
- the water added to the sulfated roasted products 33 and 42 in the dissolution tank 43 as the water dissolution step is preferably pure water 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.
- clean 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 kinds of water may be used.
- a sulfuric acid acidic solution having a pH of about 4.
- the nickel sulfate compound is suppressed while suppressing the dissolution of other impurities such as sulfate. Is preferable because it is advantageous for selectively extracting the aqueous phase.
- NiSO 4 nickel sulfate in water
- solubility of nickel sulfate in water is highest at 150 ° C., and 55 g of NiSO 4 is dissolved in 100 g of solution, but 22 g of NiSO 4 is dissolved in 100 g of solution even at 0 ° C. Therefore, it is desirable to carry out the dissolution operation below the boiling point of water.
- water-soluble nickel sulfate solution 44 obtained in step preferably in a concentration of NiSO 4 does not precipitate even at room temperature, it is preferable to maintain the heated state of the nickel sulfate solution 44 in it than NiSO 4 high concentration .
- the temperature of the sulfated roasted products 33, 42 or the temperature of water before performing the dissolution operation is preferably set to an appropriate temperature.
- a cooling unit 41 is provided between the sulfate roasting furnace 32 and the melting tank 43.
- the cooling unit 41 may be a batch type or a continuous type.
- the sulfated roasted products 33 and 42 may be left to stand until the desired temperature is lowered without adding water.
- the cooling unit 41 may be provided in the pipe connecting between the sulfate roasting furnace 32 and the melting tank 43.
- a heat exchanger may be provided to recover excess residual heat from the sulfated roasted products 33 and 42, and the recovered residual heat may be used as various heat sources.
- a step of crushing the sulfated roasted products 33 and 42 may be added before adding water to the sulfated roasted products 33 and 42.
- the means for crushing the sulfated roasted products 33 and 42 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. Grinding of the sulfated roasted products 33, 42 may be started before cooling the sulfated roasted products 33, 42, or may be started after cooling the sulfated roasted products 33, 42. ..
- the solid-liquid separation method is not particularly limited, and examples thereof include a filtration method, a centrifugation method, and a sedimentation separation method.
- a solid-liquid separation tank When a solid-liquid separation tank is installed separately from the dissolution tank 43, it is preferable to use a solid-liquid separation tank having high separation performance of solid-phase fine particles to be the residue 45, for example, a filtration tank, a centrifugal separation tank, and the like.
- a settling tank and a settling tank can be mentioned.
- the filtration method is not particularly limited, and examples thereof include gravity filtration, reduced pressure filtration, pressurized filtration, centrifugal filtration, filtration aid-added filtration, and squeezed filtration. Pressurized filtration is preferable because the differential pressure can be easily adjusted and quick separation is possible.
- impurities that can coexist with the nickel sulfate compound include iron (Fe), cobalt (Co), and aluminum (Al).
- iron sulfate, cobalt sulfate and the like are also dissolved when the nickel sulfate compound is dissolved in water. Further, in water, for example, iron FeOOH, precipitated as Fe 2 O 3, Fe 3 O 4 oxide such like, to facilitate removal of impurities from the nickel sulfate compound.
- conditions are set so that the iron content does not easily become iron sulfate.
- a nickel sulfate solution 44 having a low iron content can be obtained by undergoing water dissolution and solid-liquid separation.
- the residue 45 containing iron oxide and the like after separating the nickel sulfate solution 44 can also be reused as iron in cement.
- the iron oxide separated from the residue 45 can be used for the production of pig iron or the like as a raw material for iron making using a melt-reduction furnace, an electric furnace or the like, or for pigments, ferrites, magnetic materials, sintered materials and the like.
- the area where nickel-containing raw materials are produced is a remote area away from industrial areas, cities, etc., it is advantageous to commercialize iron as well as nickel from the viewpoint of transportation costs. is there. For example, if pig iron is produced using an electric furnace provided in the smelting process of ferronickel and the volume is reduced, it will be easy to carry it out as iron ingots.
- metals having a lower ionization tendency than hydrogen (H), such as copper (Cu), gold (Au), silver (Ag), and platinum group metal (PGM), remain as solids in the water dissolution process and are therefore solid. It can be removed by a liquid separation step.
- the solid removed by the solid-liquid separation step may contain compounds such as As, Pb, and Zn. Solids containing these impurities can also be recycled as valuable resources.
- the nickel sulfate solution 44 obtained through water dissolution and solid-liquid separation contains a nickel sulfate compound as a main component, it is 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. be able to.
- impurities in the nickel sulfate solution 44 for example, cobalt sulfate, solvent extraction, electrodialysis, electrowinning, electrorefining, etc. Techniques such as ion exchange and crystallization can be used.
- an extractant capable of preferentially or selectively extracting cobalt into the solvent over nickel. This allows the nickel sulfate compound to remain in the aqueous solution 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 the diluent.
- the diluent is preferably an organic solvent that is immiscible 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 solvent, and addition of another substance. At this time, purification is possible 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.
- 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.
- an organic solvent is added to a solution containing a nickel sulfate compound to precipitate a nickel sulfate compound.
- the organic solvent used for 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 kinds of organic solvents may be used.
- concentration range in which the organic solvent is miscible 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 is precipitated, and it is more preferable to mix freely at an arbitrary 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 crystallization.
- the ratio of water to the organic solvent is not particularly limited, but may be set in the range of, for example, 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 solid-liquid separation method is not particularly limited, and examples thereof include a filtration method, a centrifugation method, and a sedimentation separation method.
- the metal dissolved on the solution side 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.
- the magnesium content contained in the nickel-containing raw material can be removed to improve the yield of the nickel sulfate compound.
- the conversion reaction from the nickel-containing raw material to nickel sulfate can be accelerated, and the reactivity is improved.
- High-purity nickel sulfate compound can be produced from nickel-containing raw materials by sulfated roasting.
- the production of iron sulfate can be suppressed in the sulfated roasting step. In addition, the generation of hydrogen (H 2 ) gas can be suppressed.
- the sulfated roasted product becomes a chemical species in which iron is difficult to dissolve in water, and nickel is easily dissolved in water as a nickel sulfate compound, so that iron can be easily removed.
- the equipment cost can be reduced as compared with the conventional method.
- the conversion reaction of the nickel-containing raw material can be promoted, for example, when iron is supplied in the state of iron oxide, the iron oxide has an opportunity to form iron sulfate and an iron-nickel ferrite alloy is formed. The conversion reaction proceeds without giving an opportunity to do so. Therefore, a sulfated roasted product containing high-purity nickel sulfate can be obtained.
- the object to be roasted is not limited to nickel-containing raw materials, but raw materials containing metals other than nickel (Cu, Zn, Co, Fe, etc.) can also be considered. It is also possible to apply the roasting of the nickel-containing raw material according to the above-described embodiment to the roasting for obtaining the compound of the metal from the raw material containing another metal.
- the above-mentioned method for treating nickel-containing raw materials can also be used for a process different from the sulfated roasting of the oxidized roasted product.
- Example 1 The raw ore having a high magnesium content was pulverized using a ceramic tabletop ball mill so that the average particle size was 150 ⁇ m.
- the main components are serpentine containing Mg and silica (82.89%), and chlorite containing Fe (Magnetite) (9). .06%, Brucite containing Mg content 4.65%, Heezlewood ore containing Ni content 2.92%, Pentland ore containing Ni content 0.19%, Calling stone containing Mg content (Coalingite) was 0.08%, chlorite containing Mg and the like was 0.07%, and olivine containing Mg or Fe was 0.04%.
- the total proportion of minerals listed here as the main components is 99.88%.
- the proportion of serpentine is the sum of 82.25% Mg-Serpentine and 0.64% Fe-Serpentine.
- the pyrolysis curve of serpentine was collected from the above crushed raw ore using a TG / DTA (thermogravimetric / differential thermal) analyzer. As a result, it was found that although there were variations in the samples, they were thermally decomposed at 600 ° C to 650 ° C. In addition, as a result of X-Ray analysis, the raw ore had a peak showing the chemical formula Mg 3 Si 2 (OH) 4 O 5 of serpentine, but this peak disappeared after oxidative roasting. A detection peak of X-Ray appeared in the portion showing the chemical formulas of Mg 2 SiO 4 and Mg SiO 3 . From this result, it was found that the oxidative roasting temperature is preferably 650 ° C. or higher.
- Example 2 A siliconit electric furnace (core tube: SUS316L, outer diameter 50 mm ⁇ 400 mm length, maximum temperature 1500 ° C.) was installed so that the tube was vertical, and a gas dispersion plate was installed at the bottom.
- core tube SUS316L, outer diameter 50 mm ⁇ 400 mm length, maximum temperature 1500 ° C.
- a gas dispersion plate was installed at the bottom.
- 1000 g of the same raw ore (including Mg and Ni) as in Example 1 is crushed to an average particle diameter of 2 mm and 1000 g is supplied, and flow air is supplied from the lower part to maintain the flow state.
- a gas absorption pipe and a vacuum pump were installed on the exhaust gas side. Oxygen was supplied from the gas dispersion plate so that the raw ore flowed.
- the oxidative roasting temperature of the raw ore was 650 ° C.
- Example 3 It was experimentally confirmed how many grams of various compounds were dissolved and saturated in 100 ml of pure water at 25 ° C. As a result, magnesium oxide (MgO) 0.0086 g of magnesium hydroxide [Mg (OH) 2] is 0.0012 g, magnesium sulfate (MgSO 4) is 25.5 g, manganese (MnSO 4) and sulfuric acid 39.3g , Nickel sulfate (NiSO 4 ) was 65 g.
- Example 4 To the residue of nickel from which Mg and silica were removed in Example 2, equimolar sulfur (S) was added, assuming that the nickel was nickel sulfide ore (Ni 3 S 2 ). Sulfation roasting was carried out at 650 ° C. for 30 minutes in an electric furnace using the same roasting test apparatus used for the oxidative roasting of Example 2. The sulfated roasted product was dissolved in pure water to obtain a nickel sulfate solution. As a result of comparing the total amount of Ni in the raw ore before oxidative roasting with the total amount of Ni that could be recovered as a nickel sulfate solution after sulfated roasting and water dissolution, 98% of Ni was recovered.
- the present invention can be used for producing various nickel compounds used for electric parts such as secondary batteries, chemical products, etc., or high-purity nickel sulfate compounds useful as raw materials for metallic nickel.
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Abstract
Description
さらに硫酸化焙焼温度は、600~700℃であることが好ましい。この温度であれば、焙焼対象物がニッケル含有原料に由来する不純物としてマンガン(Mn)を含む場合であっても、マンガンが鉄とのスピネル構造を形成することにより、マンガンを不溶物として除去しやすくなる。
(1)ニッケル含有原料に含まれるマグネシウム分を除去して、硫酸ニッケル化合物の収率を向上することができる。
(2)ニッケル含有原料から硫酸ニッケルへの転換反応を早めることができ、反応性が向上する。
(3)硫酸化焙焼により、ニッケル含有原料から高純度の硫酸ニッケル化合物を生産することができる。
(4)硫酸化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。
(5)硫酸化焙焼生成物は、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。
(6)従来法に比べて設備コストを低減することができる。
(7)ニッケル含有原料の転換反応を促進することができるため、例えば、鉄が酸化鉄の状態で供給される場合に、酸化鉄が硫酸鉄を形成する機会及び鉄-ニッケルのフェライト合金を形成する機会を与えず転換反応が進む。そのため、高純度の硫酸ニッケルを含有する硫酸化焙焼生成物を得ることができる。
マグネシウム分の含有割合が高い生鉱石をセラミック製の卓上ボールミルを使って、平均粒子径が150μmとなるように粉砕した。利用した生鉱石のミネラル組成(重量比)は、主な成分を挙げると、Mg分とシリカ分を含む蛇紋石(Serpentine)が82.89%を占め、Fe分を含む磁鉄鉱(Magnetite)が9.06%、Mg分を含むブルース石(Brucite)が4.65%、Ni分を含むヒーズルウッド鉱が2.92%、Ni分を含むペントランド鉱が0.19%、Mg分を含むコーリング石(Coalingite)が0.08%、Mg分等を含む緑泥石(Chlorite)が0.07%、Mg分又はFe分を含むカンラン石(Olivine)が0.04%であった。ここで主な成分として挙げた鉱物の割合を合計すると99.88%である。なお、蛇紋石(Serpentine)の割合は、82.25%のMg-Serpentineと0.64%のFe-Serpentineとの合計である。
シリコニット社製のら管電気炉(炉心管:SUS316L、外形50mm×400mm長さ、最高温度1500℃)を、ら管が縦型になるように設置し、下部にガス分散板を設置した。この焙焼試験装置に、実施例1と同じ(Mg分及びNi分を含む)生鉱石を平均粒子径2mmに粉砕して1000g供給し、また流動用空気を下部から供給し流動状態を保持すると共に、排ガス側にはガス吸収管とバキュームポンプを設置した。酸素はガス分散板から生鉱石が流動するように供給した。生鉱石の酸化焙焼温度は650℃とした。0.5時間酸化焙焼した後、酸化焙焼生成物が高温の間に水を噴霧した結果、MgO+H2O→Mg(OH)2の式で表される反応が起こり、酸化焙焼生成物が粒子径150μm~0.8mmまで粉砕された。X-Rayでの分析で酸化焙焼生成物にMg(OH)2を示すピークを確認した。この水噴霧により得られた粉砕物を振動篩と比重差分離によりニッケル分を濃縮したところ、Mg(OH)2とSiO2をほとんど分離することができた。
25℃の100mlの純水中に何グラムまで各種化合物が溶解して飽和するかを実験で確かめた。その結果は、酸化マグネシウム(MgO)が0.0086g、水酸化マグネシウム〔Mg(OH)2〕が0.0012g、硫酸マグネシウム(MgSO4)が25.5g、硫酸マンガン(MnSO4)が39.3g、硫酸ニッケル(NiSO4)が65gであった。この結果から、酸化マグネシウム及び水酸化マグネシウムを溶解度により硫酸ニッケルから分離除去することは容易であるが、硫酸マグネシウム及び硫酸マンガンを溶解度により硫酸ニッケルから分離することは容易でないと推測された。
実施例2でMg分及びシリカ分が除去されたニッケル分の残渣に対し、ニッケル分が硫化ニッケル鉱(Ni3S2)であると想定して、等モルの硫黄(S)を添加した。実施例2の酸化焙焼に用いたものと同じ焙焼試験装置を用いて、電気炉にて650℃で30分間、硫酸化焙焼を実施した。硫酸化焙焼生成物を純水に溶解し、硫酸ニッケル溶液を得た。酸化焙焼前の生鉱石中の全Ni量と、硫酸化焙焼及び水溶解後に硫酸ニッケル溶液として回収できた全Ni量で比較した結果、98%のNi分が回収できていた。
Claims (6)
- マグネシウム分を含有するニッケル含有原料を酸化焙焼して、前記マグネシウム分を酸化マグネシウムとする酸化焙焼工程を有することを特徴とするニッケル含有原料の処理方法。
- 前記ニッケル含有原料がニッケル鉱石を含み、前記酸化焙焼工程の後に前記ニッケル含有原料から前記マグネシウム分を除去するマグネシウム除去工程を有することを特徴とする請求項1に記載のニッケル含有原料の処理方法。
- 前記酸化焙焼工程の前に、前記マグネシウム分を含有する前記ニッケル含有原料を粉砕する工程を有することを特徴とする請求項1又は2に記載のニッケル含有原料の処理方法。
- 前記マグネシウム除去工程において、前記ニッケル鉱石に含まれるシリカ分の少なくとも一部を除去することを特徴とする請求項2に記載のニッケル含有原料の処理方法。
- 前記マグネシウム除去工程の後に、前記マグネシウム分が除去された前記ニッケル含有原料を硫酸化焙焼して硫酸ニッケルを含有する焙焼生成物を得る硫酸化焙焼工程を有することを特徴とする請求項2又は4に記載のニッケル含有原料の処理方法。
- 前記ニッケル含有原料は鉄分を含有し、前記硫酸化焙焼工程は、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酸素分圧及び二酸化硫黄分圧の条件下で加熱焙焼することを特徴とする請求項5に記載のニッケル含有原料の処理方法。
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JPH03505612A (ja) * | 1988-03-31 | 1991-12-05 | サイコネン,ペッカ,ユハニ | 非鉄金属有価物、特にニッケル、コバルト、銅及び亜鉛を、それら金属を含有する原料から溶融物及び溶融物被覆硫酸化を用いて回収する方法 |
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