WO2012014685A1 - 低品位ニッケル酸化鉱石からのフェロニッケル製錬原料の製造方法 - Google Patents
低品位ニッケル酸化鉱石からのフェロニッケル製錬原料の製造方法 Download PDFInfo
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- WO2012014685A1 WO2012014685A1 PCT/JP2011/066016 JP2011066016W WO2012014685A1 WO 2012014685 A1 WO2012014685 A1 WO 2012014685A1 JP 2011066016 W JP2011066016 W JP 2011066016W WO 2012014685 A1 WO2012014685 A1 WO 2012014685A1
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- sulfide
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- nickel oxide
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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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
- C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
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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
- C22B23/021—Obtaining nickel or cobalt by dry processes by reduction in solid state, e.g. by segregation 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
- C22B23/023—Obtaining nickel or cobalt by dry processes with formation of ferro-nickel or ferro-cobalt
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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
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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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
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
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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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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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 can be used in the field where nickel sulfide obtained from low-grade nickel oxide ore is used as a raw material for ferronickel smelting.
- Ferro-nickel an alloy of nickel and iron, used as a raw material for stainless steel, etc. is a nickel oxide ore such as laterite or garnierite ore that is put into a rotary kiln and dried, and then an electric furnace together with a reducing agent such as coke. In many cases, it is produced by a dry smelting method in which it is put into a melting furnace such as the above and reduced and melted at a temperature of about 650 ° C. At this time, a portion of the oxide ore is dried in the kiln and is directly converted into a briquetted nickel / iron mixed oxide without undergoing reductive melting.
- nickel oxide ores such as high-grade garnierite ore, which has been used for raw materials in general, have a nickel grade of approximately 2% or more, and there is a tendency to deplete such as laterite ore with a nickel grade of about 1-2% or less.
- the need to process low grade nickel oxide ore has increased.
- the nickel quality in the ore is low, it is necessary to process a larger amount of ore in order to produce the same amount of ferronickel, and the equipment scale increases accordingly.
- unfavorable effects such as an increase in investment related to production and an increase in labor related to production occur.
- nickel oxide ore often contains a large amount of water, and there is a problem that the fuel required for drying using a rotary kiln increases and the cost increases. For this reason, it has been studied to reduce the cost by concentrating the nickel of the low-grade nickel oxide ore to a high-nickel-grade raw material and using this concentrated raw material.
- Patent Document 1 there is a method called HPAL method as shown in Patent Document 1.
- the method of Patent Document 1 is a hydrometallurgical method based on high-temperature pressure leaching that recovers nickel from nickel oxide ore, simplification of the leaching step and the solid-liquid separation step, consumption of neutralizing agent and starch in the neutralization step.
- the present invention provides a smelting method that is simple and highly efficient as a whole process by reducing the amount of substances and using water repeatedly and efficiently.
- the method includes a neutralization step for forming a mother liquor, and a sulfurization step for blowing a hydrogen sulfide gas into the mother liquor to form a sulfide and a poor solution containing nickel and cobalt.
- nickel oxide ore is mixed with a sulfuric acid solution to form a slurry, and this slurry is heated in a high-pressure vessel such as an autoclave, and nickel and cobalt contained in the ore are leached into the sulfuric acid solution.
- the slurry is separated into a leachate and a leach residue using a thickener or a filter press.
- impurities are separated from the obtained leachate by adjusting the pH, and a sulfide is added to obtain a mixed sulfide of nickel and cobalt.
- the resulting mixed sulfide is transported to an existing wet smelter and leached using chlorine gas, sulfuric acid, etc., and cobalt and nickel are separated through a process such as solvent extraction, and purified by a method such as electrowinning. Collected as nickel metal or cobalt metal.
- the method of Patent Document 1 does not include a dry process such as a reduction process or a drying process, and has a small amount of energy. This is advantageous in terms of cost.
- many kinds of impurities such as cobalt, iron, aluminum, manganese, zinc, chromium, magnesium, and silicon other than nickel contained in nickel oxide ore are efficiently leached together with nickel from ore by sulfuric acid.
- a leach residue containing nickel and cobalt is formed by fixing and fixing a leach residue using iron contained in the ore as natrojarosite.
- extracting a nickel-containing extraction residue and a cobalt-containing back extract, and the nickel-containing extraction residue and the cobalt-containing back extract are neutralized with an alkali to obtain hydroxides.
- a method comprising the steps of obtaining The obtained nickel hydroxide is washed with an alkaline solution in the subsequent step to remove the contained sulfur and chlorine, and then ferronickel is produced by a process including existing firing and reduction melting steps. .
- the obtained nickel hydroxide often contains some sulfur due to the inclusion of sulfuric acid contained in the leachate.
- nickel oxide is produced by firing and reduction melting treatment without removing this sulfur, there is a problem that sulfur oxides are generated as in the case of Patent Document 1 described above.
- Patent Document 2 discloses that nickel hydroxide has a temperature of about 230 ° C. or more. A method is shown in which nickel hydroxide and water of crystallization are converted to sulfur and anhydrous nickel oxide.
- nickel hydroxide is roasted into nickel oxide in addition to a dry kiln that dries the adhering moisture before an electric furnace that reduces to ferronickel.
- a complicated process such as a process of changing and a process of removing sulfur before roasting is necessary, and production costs are high.
- Patent Document 3 has a report that improves the solid-liquid separation between the solid and liquid produced by the neutralization step. Specifically, this method uses sulfuric acid to leach nickel or cobalt from oxide ore to obtain a sulfuric acid leaching solution containing nickel or cobalt and a leaching residue, and a sulfuric acid leaching solution containing the leaching residue.
- PH is adjusted by reacting magnesium with magnesium to obtain a reaction solution containing nickel or cobalt and a reaction residue containing iron, and the solution obtained in the previous step is neutralized using a neutralizing agent And a neutralization step for obtaining a second neutralization solution containing nickel or cobalt and a second neutralization residue containing iron, and using the ore oxide between the leaching step and the neutralization step It further includes a pre-neutralization step for increasing the pH of the liquid obtained in (1).
- JP-A-2005-350766 JP 2006-241529 (first page, second page, FIG. 1) JP 2007-77459 A
- the object of the present invention is to produce ferronickel from nickel sulfide ore obtained by wet refining of nickel oxide ore or from scraps and work-in-process products, and mixed sulfides containing nickel and cobalt.
- a first invention of the present invention for solving the above-mentioned problems is a method for producing a ferronickel raw material for forming a ferronickel raw material from nickel sulfide or a mixed sulfide containing nickel sulfide and cobalt sulfide. It is characterized by processing through the following steps.
- Nickel sulfide or a mixed sulfide of nickel sulfide and cobalt sulfide is made into a slurry, and when the nickel sulfide is dissolved by adding an oxidizing agent to the slurry, a concentrated solution containing nickel Or a re-dissolution step of obtaining a concentrate containing nickel and cobalt when the mixed sulfide is dissolved.
- a roasting step in which nickel hydroxide obtained in the hydroxylation step is heated and roasted to a temperature range of 230 ° C. or higher and 870 ° C. or lower to form nickel oxide.
- the nickel oxide obtained in the roasting step is washed with water using water having a water temperature of 50 ° C. or higher, and then fired at a temperature of 50 ° C. or higher to form nickel oxide after cleaning. Cleaning and holiday baking process.
- the particle size of the nickel sulfide or mixed sulfide before mixing with the oxidizing agent is in the range of 15 to 100 ⁇ m in terms of volume average diameter (MV). It is the manufacturing method of the characteristic ferronickel.
- the third invention of the present invention is a method for producing ferronickel, characterized in that, in the remelting step in the first invention, the remelting is performed at a temperature in the range of 60 ° C. or higher and 160 ° C. or lower.
- the fourth invention of the present invention is characterized in that, in the remelting step in the first invention, the oxidizing agent to be added is one or more of air, oxygen, hydrogen peroxide solution, and ozone gas. This is a method for producing ferronickel.
- the ferronickel is characterized in that, in the roasting step according to the first aspect, the roasting is performed in an inert atmosphere or an oxygen partial pressure in the reaction vessel of 10 ⁇ 8 atm or less. It is a manufacturing method.
- the sixth invention of the present invention is a method for producing ferronickel characterized in that in the solvent extraction step in the first invention, a sulfurizing agent is added to the obtained back extract to obtain cobalt sulfide.
- the seventh invention of the present invention is a method for producing ferronickel characterized in that, in the solvent extraction step in the first invention, soda ash is added to the obtained back extract to obtain cobalt carbonate.
- the eighth invention of the present invention is a method for producing ferronickel characterized in that, in the solvent extraction step in the first invention, an alkali is added to the obtained back extract to obtain cobalt hydroxide.
- a reducing agent and a binder are added to the nickel oxide after washing obtained in the first invention in an amount of 0.1 to 8% by weight of the nickel oxide after washing. It is a method for producing ferronickel, which is tempered and then calcined at a temperature of 50 ° C. or higher to obtain nickel oxide pellets.
- a tenth aspect of the present invention is the method for producing ferronickel according to the ninth aspect, wherein the reducing agent is at least one of pulverized coal, pulverized coal and pulverized coke.
- the eleventh invention of the present invention is the method for producing ferronickel according to the ninth invention, wherein the binder is one or more of bentonite and low grade nickel oxide ore.
- the nickel sulfide or the mixed sulfide containing nickel sulfide and cobalt sulfide in the first invention is subjected to solid-liquid separation after leaching nickel oxide ore using sulfuric acid at high temperature and pressure.
- the leachate obtained is neutralized and separated into a starch containing impurities and a filtrate, and a sulfurizing agent is added to the filtrate to separate zinc sulfide starch, and a sulfurizing agent is blown into the filtrate after the separation.
- This is a method for producing ferronickel, characterized in that it is a nickel sulfide obtained as described above, or a mixed sulfide containing nickel sulfide and cobalt sulfide.
- the nickel sulfide used in the first invention or the mixed sulfide containing nickel sulfide and cobalt sulfide is generated as scrap or work in process nickel hydroxide, nickel oxide, hydroxide It is a nickel sulfide formed by leaching at least one of cobalt and cobalt oxide with sulfuric acid and blowing a sulfiding agent into the leachate, or a mixed sulfide containing nickel sulfide and cobalt sulfide. Is a method for producing ferronickel.
- a low-grade nickel oxide ore can be used as a raw material for producing ferronickel.
- the ferronickel raw material can be directly charged into the electric furnace, and the processing in the rotary kiln can be omitted.
- a briquette with high strength can be obtained.
- the cost and energy required for ferronickel smelting can be reduced.
- Existing ferronickel smelting equipment can be used as it is.
- a mixed sulfide containing cobalt can be used as a raw material for ferronickel.
- Sulfides obtained from nickel oxide ore can be used separately as nickel or cobalt intermediate materials for different applications.
- Cobalt loss can be prevented.
- Ferronickel can be produced from nickel hydroxide with a high sulfur content.
- FIG. 1 It is a figure which shows the change of the removal rate (S removal rate) of the sulfur accompanying the baking temperature change at the time of washing the obtained thing with water, after roasting nickel hydroxide by changing temperature.
- a black circle is a value when the raw material is a mixed sulfide.
- 2 is a photograph showing reduced metal and slag generated from nickel oxide formed in Example 1.
- FIG. It is a figure which shows the cobalt concentration in the phase-separation state of the concentrate containing nickel and cobalt by the organic extractant used in the Example.
- the present invention relates to a production method for producing ferronickel from nickel sulfide or a mixed sulfide composed of nickel and cobalt (hereinafter referred to as nickel sulfide), and leaching nickel into a solution from nickel sulfide or the like Impurities are separated and further separated from cobalt by solvent extraction, and then again converted to nickel hydroxide with an alkali. Next, this nickel hydroxide is roasted to obtain nickel oxide, and the sulfur content is separated by washing and calcination, and reduced and melted as it is to obtain ferronickel.
- nickel sulfide or nickel-cobalt mixed sulfide used in the present invention is charged in a high-pressure vessel such as an autoclave together with sulfuric acid by using a manufacturing process shown in FIG.
- Nickel sulfides produced by sulfidation can be used through leaching of nickel in the ore, followed by solid-liquid separation, pH adjustment, dezincing, and the like.
- a nickel mat obtained by sulfiding and roasting nickel oxide using an electric furnace or the like can also be used.
- the nickel / cobalt mixed sulfide obtained by the fixing operation is a method of recovering nickel as a hydroxide through re-leaching with an oxidant and separation of nickel and cobalt by a solvent extraction operation. It is characterized by. Hereafter, each process is demonstrated using an accompanying drawing.
- Nickel sulfide or the like usually contains various impurity components such as valuable metals such as cobalt, aluminum, magnesium, manganese, iron, and chromium, in addition to nickel as a recovery purpose.
- the slurry concentration is preferably selected so that the concentrate obtained by re-dissolution does not become supersaturated. Specifically, considering the occurrence of scaling and clogging troubles due to the precipitation of nickel sulfate crystals in industrial leaching reaction vessels and liquid feed pipes, the slurry concentration is 10 to 40% by weight, preferably 15 to 25% by weight. It is desirable to keep it in the range of%.
- the particle size of the sulfide or mixed sulfide to be used is 15 to 100 ⁇ m, preferably 20 to 40 ⁇ m in terms of the volume average diameter (MV) measured with Microtrac.
- MV volume average diameter
- an oxidizing agent is added to the obtained slurry to re-dissolve nickel sulfide and the like and leached into the solution.
- the leaching reaction is performed according to the following chemical formula 1.
- Air or the like can be used as the oxidizing agent to be used.
- the liquid temperature in the reaction vessel is set to 60 ° C. or higher and high concentration oxygen, hydrogen peroxide solution or ozone is used as the oxidizing agent, the oxidation is promoted and the operation can be performed with a compact equipment scale. Further, it is effective to accelerate the reaction by applying pressure by using a closed container such as an autoclave. After redissolving, solid-liquid separation is performed into the leaching residue and the concentrated liquid using means such as a filter press. The separated leaching residue is returned to the slurry before re-dissolution and repeatedly undergoes the re-dissolution step again.
- the neutralized solution containing nickel and cobalt obtained in the iron removal step is subjected to solvent extraction to separate nickel and cobalt.
- the neutralized solution is used as an aqueous phase, and an organic phase composed of an organic solvent containing a phosphoric acid ester-based acidic extractant is mixed therewith, and further, alkali is added to adjust pH to cobalt in the organic phase.
- alkali is added to adjust pH to cobalt in the organic phase.
- the aqueous phase and the organic phase are separated, diluted acid is added to the obtained organic phase, the nickel extracted in the previous stage is back-extracted into the aqueous phase, and then the washing stage and the organic phase are separated.
- the extracted cobalt is back-extracted to the aqueous phase side by addition of dilute acid, and then the back-extraction stage separates both phases.
- most of the nickel remains in the extraction liquid.
- the phosphoric acid ester-based acidic extractant to be used is not particularly limited, and any phosphoric acid-based acidic extractant can be used as long as the separation of nickel and cobalt is good.
- the pH adjustment in the solvent extraction stage can be easily performed using an aqueous solution containing an alkali agent such as sodium hydroxide.
- the equilibrium pH of the aqueous phase is desirably maintained at about 5.
- 98% or more of cobalt contained in the concentrated liquid can be extracted by appropriately setting the volume ratio between the organic phase and the aqueous phase and the number of extraction stages.
- cobalt extracted into the organic phase is back extracted as a sulfate and can be used as it is as a raw material for cobalt sulfate, cobalt oxide, cobalt hydroxide and the like.
- alkali various types can be used as the alkali to be added.
- slaked lime is not preferable because gypsum may be formed and precipitated and mixed with the precipitate to lower the nickel quality, so it is suitable to use magnesium hydroxide or sodium hydroxide. .
- the reaction temperature is preferably 60 ° C. or higher, and is preferably the boiling point or lower in view of stability during the reaction.
- existing types such as a filter press, Nutsche, Denver filter, and centrifuge can be used.
- Nickel hydroxide obtained by the hydroxylation step is converted to ferronickel through a “roasting step” and a “washing and calcination step” as shown in FIG.
- Nickel hydroxide obtained in the hydroxylation step is formed into nickel oxide in the roasting step.
- the roasting conditions are 230 ° C. or higher and 870 ° C. or lower, preferably 600 ° C. or higher and 750 ° C. or lower in an inert or reducing atmosphere.
- This roasting process is accompanied by the crystal water that nickel hydroxide has, whereas sulfur contaminated with nickel hydroxide can be easily removed by washing with water when adhering to nickel hydroxide. It was thought that removal of sulfur by washing with water alone was difficult because the sulfur contained in the crystal structure of nickel hydroxide was present. Therefore, a method was used in which nickel hydroxide was roasted to decompose the crystal water and convert it to nickel oxide, so that sulfur was not taken into the crystal. It is effective to roast at a temperature higher than the temperature at which crystal water decomposes. In the case of nickel hydroxide, it is effective to set the temperature to about 230 ° C. or more.
- the roasting temperature is preferably in the range of 600 ° C. or higher and 750 ° C. or lower in consideration of handling properties in actual operation, actual oxidation reaction speed and thermal efficiency.
- roasting existing ones such as a kiln, a fluid roasting furnace, and a tubular furnace can be used.
- oxygen such as in the air
- the sulfate formed by the attached sulfur is decomposed and sulfur is volatilized as sulfur oxide (SO x ) gas.
- the volatilized sulfur oxide requires an exhaust gas treatment facility for recovering and detoxifying it, which increases costs. Therefore, roasting is preferably performed in a non-oxidizing atmosphere such as inert or reducing to prevent the generation of sulfur oxides.
- the concentration of oxygen remaining in the atmosphere is not generally defined because it has a relationship with the partial pressure of sulfur oxide (SO x ), but in general, the concentration is lower than 10 ⁇ 8 atm by correcting the partial pressure. It is preferable.
- This method of burning nickel oxide changes not optimally because the optimal form and shape changes depending on the roasting equipment and exhaust gas line, etc. It is only necessary to keep it sufficient for moisture volatilization or residual hydroxide decomposition. Further, the heat source is not limited to the exhaust gas at the time of roasting, and any heat source can be used.
- the temperature of the washing water is preferably in the range of 50 ° C. or more and 100 ° C. or less.
- the surface of the nickel oxide after washing obtained after removing sulfur by washing with water after roasting has an amount of adhering water remaining on the surface of nickel oxide of several to more than 20%.
- the remaining adhering water can be removed at a certain ratio by blowing air with an air blow or filtering with denver, for example.
- the fine nickel oxide powder has a problem that it is easily scattered in the furnace or during handling, or is liable to adhere to the furnace wall and cause a problem in operation. Therefore, in the present invention, a method of pelletizing nickel oxide and putting it in a reduction furnace was used. Pelletization is performed by charging nickel oxide powder into a kneading machine or a disk-shaped pelletizer and kneading while adding a constant concentration of water to obtain granular pellets.
- the moisture content can be adjusted by dehydration using an airblow or Denver, or by baking at a lower temperature.
- a reducing agent is mixed at the time of pelletization and a binder such as bentonite is further mixed, better adhesive strength can be obtained, and at the same time, nickel oxide particles and the reducing agent are located in the vicinity. Reduction from nickel oxide to ferronickel in the furnace proceeds efficiently and stably.
- the reducing agent pulverized coal, powdered coke, or the like can be used.
- the particle sizes of the reducing agent and nickel oxide powder are preferably equal.
- the pellet contains a clay component, but nickel oxide and the reducing agent to be added contain almost no clay component, and therefore it is obtained. There is a limit to the strength that can be achieved. Therefore, it is preferable to use a compression kneader that easily develops a strong binding force for pelletization.
- the addition amount of the binder is not generally defined by the kind of the binder, and can be determined by appropriately comparing the addition amount and the strength to be obtained. For example, when bentonite is used, the amount of nickel oxide is 0. If an amount of about 1 to 8% by weight is added, sufficient strength can be obtained.
- the heat-resistant container containing the slurry was placed in an electrically heated autoclave having an internal volume of 3.5 liters, covered and heated to 245 ° C. while stirring with a stirrer, and maintained for 1 hour. Thereafter, heating was stopped while stirring was continued, and the mixture was naturally cooled to room temperature. After cooling to room temperature, the autoclave was opened and the leach slurry was removed.
- the above leached slurry was solid-liquid separated using Nutsche and 5C filter paper, Ni: 6.0 g / L, Co: 0.4 g / L, Fe: 3.5 g / L, Al: 4.1 g / L, Mn : Separated into a leachate having a composition of 4.5 g / L and a leach residue.
- a calcium carbonate slurry having a concentration of 20% by mass was added to the leaching slurry to adjust the pH to 2.5 to neutralize the remaining sulfuric acid, and solid-liquid separation and residue washing were performed. And after adding calcium carbonate and adjusting pH to 3.2 and neutralizing, it isolate
- the mixed sulfide slurry was charged into an autoclave apparatus and heated to 120 ° C. While maintaining this temperature, pure oxygen was blown in from a cylinder at a flow rate of 30 ml for 5 hours while stirring at 400 rpm, and leaching reaction was carried out to redissolve. After completion of the predetermined reaction, the leaching slurry was taken out from the autoclave, filtered with a Nutsche, and separated into a leaching residue and a nickel / cobalt concentrate.
- the composition of the obtained nickel and cobalt concentrate was Ni 46 g / L, Co 3.1 g / L, and Mn 0.01 g / L.
- the weight of the residue was 65 g.
- the composition was Ni42g / L, Co ⁇ 0.01g / L, Mn ⁇ 0.1g / L.
- the composition of the back extract was Ni ⁇ 0.1 g / L, Co 15.0 g / L, and Mn ⁇ 0.01 g / L. This shows that nickel and cobalt were sufficiently separated.
- the nickel hydroxide was 15 g per sample, and a total of 5 samples were taken and each was put in an alumina crucible.
- the crucible was placed in an electric furnace having an internal volume of 5 liters, and nitrogen gas was flowed from the cylinder at a flow rate of 0.5 liters per minute into the furnace to completely replace the inert atmosphere.
- Each sample was individually heated to 4 temperatures of 250 ° C., 450 ° C., 650 ° C., and 750 ° C. and held for 1 hour to roast nickel hydroxide into a form of nickel oxide.
- FIG. 4 shows the state of the sample before baking and after baking at 250 ° C. and 650 ° C.
- FIG. 5 shows the sulfur removal rate when the roasted product obtained by roasting at each temperature is washed with hot water of 50 ° C. The roasted product having a higher roasting temperature tends to have a higher sulfur removal rate by washing. is there.
- “ ⁇ : white circle” indicates the result for nickel sulfide
- “ ⁇ : black circle” indicates the result for mixed sulfide.
- the sulfur removal rate When roasted at 650 ° C., the sulfur removal rate can be estimated to be about 70%. When roasted at 750 ° C., about 90% of sulfur can be removed by washing with water. In addition, even when roasting at a temperature exceeding 850 ° C., the sulfur removal rate seems to be almost the same as that at 850 ° C. or lower, and it is not necessary to roast at temperatures exceeding 850-870 ° C. at which sulfur can be completely oxidized. .
- the nickel in the filtrate was analyzed by ICP, and the ratio of elution from nickel oxide was examined, but it was hardly eluted as 0.01% or less.
- the temperature was raised to 1500 ° C. under an inert atmosphere in which nitrogen gas was flowed at a flow rate of 1 liter per minute, and the temperature was raised and maintained for 1 hour. After a lapse of time, it was cooled to room temperature while maintaining an inert atmosphere, and slag and reduced metal in the crucible were recovered. This is shown in FIG.
- the obtained slag and metal were dissolved with nitric acid and analyzed using ICP.
- the sulfur grade in the metal was 0.4%
- the distribution ratio of sulfur to the slag was about 65%
- the Ni grade in the slag was 0.1%.
- ferronickel can be smelted using nickel hydroxide obtained from a low-grade nickel oxide ore as a raw material instead of the above-described conventional high-grade garnierite ore. It could be confirmed.
- nickel oxide ore was leached with sulfuric acid and sulfided to form a nickel-cobalt mixed sulfide.
- a nickel / cobalt concentrate obtained by dissolving the obtained mixed sulfide slurry in an autoclave was used as a starting liquid.
- the composition of this starting solution was a nickel concentration of 46 to 118 g / L and a cobalt concentration of 4.1 to 8.4 g / L.
- the nickel / cobalt concentrate is mixed with a phosphonic acid ester-based acidic extractant (manufactured by Daihachi Chemical Co., Ltd., trade name: PC88A) at a ratio of oil to water ratio of 1 to 2, and further 320 g / L.
- a sodium hydroxide aqueous solution was added to adjust the pH to 4.5, and the mixture was allowed to stand for 5 minutes, followed by phase separation.
- the cobalt concentration in each phase (aqueous solution and organic solvent) in that case is shown in FIG. 7 together with the case of “Cyanex272”.
- Table 1 shows the nickel and cobalt concentrations of each solution during the first stage extraction.
- the nickel concentration of the aqueous solution (extracted residue) after extraction is 44 to 110 g / L
- the cobalt concentration is 0.6 to 0.9 g / L
- the nickel concentration in the organic solvent after extraction is 2.
- the cobalt concentration was 0 to 3.4 g / L and the cobalt concentration was 6.3 to 7.8 g / L, indicating excellent nickel and cobalt separability.
- Example 1 The same method as in Example 1 was used except that the atmosphere in the roasting step was changed to an oxidizing atmosphere by flowing air through an electric furnace.
- the roasting temperature was 650 ° C., and the temperature was maintained for 1 hour.
- sulfur oxide gas was generated.
- Sulfur quality in the product after roasting also decreased due to the volatilization of sulfur. Therefore, it was found that the raw material of ferronickel cannot be obtained by oxidation roasting with air.
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Abstract
Description
特許文献1の方法は、ニッケル酸化鉱石からニッケルを回収する高温加圧浸出に基づく湿式製錬方法において、浸出工程と固液分離工程の簡素化、中和工程での中和剤消費量及び澱物量の削減、さらに効率的な水の繰り返し使用法等によってプロセス全体として簡素で、かつ高効率な製錬方法を提供するものである。
その得られた混合硫化物は、既存の湿式精錬所に運び、塩素ガスや硫酸等を用いて浸出され、溶媒抽出等の工程を通してコバルトとニッケルを分離し、電解採取などの方法により高純度なニッケルメタルやコバルトメタルとして回収される。
また、ニッケル酸化鉱石に含有されるニッケル以外のコバルトや鉄、アルミニウム、マンガン、亜鉛、クロム、マグネシウム、ケイ素等の多種類の不純物の多くは、硫酸によって鉱石からニッケルと共に浸出されるために効率的な手段により分離回収することが製錬プロセス上の重要課題であったが、中和工程や硫化工程によって、ニッケルと効果的に分離でき、不純物の少ないニッケル硫化物及びコバルト硫化物を得ることができる。例えばニッケル品位が1~2質量%程度の低品位ニッケル酸化鉱石の製錬方法として有力な技術であると見られている。
このように、ニッケル硫化物からフェロニッケルを製錬することは容易でなかった。
得た水酸化ニッケルは、後工程でアルカリ液を用いて洗浄することで、含まれる硫黄と塩素を除去し、その後既存の焼成及び還元熔解工程を含んだプロセスによりフェロニッケルを製造するものである。
また、上述のように湿式反応により水酸化物を得る場合、一般に微細な粒子を形成する場合が多く、後段の還元熔融工程において、微細な粒子を炉内に直接装入すると、水酸化物粒子が飛散したり、炉壁に溶着したりして、操業のトラブルを生じたり、反応効率が向上しない懸念がある。さらに微細な水酸化ニッケルの粒子には、付着水や結晶水、さらには上述の中和前の硫酸酸性溶液の一部の巻き込みに由来する硫黄が含まれやすい。これらの含水した粒子が直接高温の電気炉内に投入されると、結晶水や付着水が原因となって水蒸気爆発を生じたり、硫黄分が腐食性のガスを生成し設備の劣化を促進するなどの恐れもある。
この方法は、具体的には硫酸を使用して、酸化鉱石から、ニッケルまたはコバルトを浸出し、ニッケルまたはコバルトを含む硫酸浸出溶液と浸出残渣とを得る浸出工程と、浸出残渣を含む硫酸浸出溶液とマグネシウムとを反応させてpH調整し、ニッケルまたはコバルトを含む反応液と、鉄を含む反応残渣とを得る反応工程と、前工程において得られた液を、中和剤を使用して中和し、ニッケルまたはコバルトを含む第二中和液と、鉄を含む第二中和残渣とを得る中和工程とを含み、浸出工程と中和工程との間に、酸化鉱石を用いて前工程で得られた液のpHを上昇させる予備中和工程をさらに含むものである。
(1)低品位なニッケル酸化鉱をフェロニッケル製造の原料に利用できる。
(2)フェロニッケル原料は電気炉に直接投入することができ、ロータリーキルンでの処理を省略できる。
(3)強度の高いブリケットを得ることができる。
(4)フェロニッケル製錬に要するコストとエネルギーを低減できる。
(5)既存のフェロニッケル製錬の設備がそのまま利用できる。
(6)コバルトを含有する混合硫化物をフェロニッケルの原料に利用できる。
(7)ニッケル酸化鉱石から得た硫化物を、異なる用途向けのニッケルあるいはコバルト中間原料として使い分けて供給できる。
(8)コバルトのロスを防止できる。
(9)硫黄分が多い水酸化ニッケルからフェロニッケルを生産できる。
なお、その他にもニッケル酸化物を、電気炉などを用いて硫化焙焼して得たニッケルマットなどを用いることもできる。
以下、添付図面を用いて各工程を説明する。
ニッケル硫化物等には、回収目的であるニッケルのほかにも、有価物であるコバルトやアルミ、マグネシウム、マンガン、鉄、クロムなど様々な不純物成分が含まれているのが普通である。
そのスラリー濃度は、再溶解で得られる濃縮液が過飽和とならないように選定することが望ましい。具体的には、工業的な浸出反応容器内や送液配管内での硫酸ニッケルの結晶析出によるスケーリングや閉塞トラブルの発生を考慮すると、スラリー濃度を10~40重量%、好ましくは15~25重量%の範囲に抑えることが望ましい。
また、反応槽の液温は60℃以上とし、酸化剤に高濃度酸素、過酸化水素水やオゾンを用いると酸化が促進され、それだけコンパクトな設備規模で操業できる。さらにオートクレーブなど密閉容器を用い加圧して反応させることも反応促進には効果的である。
再溶解後は、フィルタープレス等の手段を用いて、浸出残渣と濃縮液とに固液分離する。この分離された浸出残渣は、再溶解前のスラリーに戻され、繰り返し再度再溶解工程を経る。
再溶解工程で得られたニッケルやコバルトを含有する濃縮液にアルカリを加えて濃縮液を中和、固液分離して、中和澱物と中和後液を生成した。濃縮液中の鉄分は中和澱物に分配されている。
脱鉄工程で得られたニッケルやコバルトを含有する中和後液を溶媒抽出してニッケルとコバルトを分離する。
具体的には、その中和後液を水相とし、これに燐酸エステル系酸性抽出剤を含む有機溶媒からなる有機相を混合し、さらにアルカリを添加してpHを調整して有機相にコバルトを抽出する。その後水相と有機相を分離し、得られた有機相には希酸を加え、前段で抽出されているニッケルを水相中に逆抽出し、その後両相を分離する洗浄段、有機相に抽出されたコバルトを希酸添加により水相側へ逆抽出し、その後両相を分離する逆抽出段から構成される。ここで、ニッケルの大部分は、抽残液中に留まる。
ここで、水相の平衡pHは、約5に保持されることが望ましい。なお、有機相と水相との体積比率及び抽出段数を適切に設定することにより、濃厚液に含有されたコバルトの98%以上を抽出することができる。また、逆抽出段において、有機相中に抽出されたコバルトは、硫酸塩として逆抽出され、硫酸コバルトや酸化コバルト、水酸化コバルトなどの原料としてそのまま利用できる。
溶媒抽出工程で得られた抽残液に、アルカリを添加してpHを調整し、水酸化ニッケルの沈澱を得る。抽残液中のニッケルは水酸化ニッケルを生成するので濾過して固液分離して回収する。得られる水酸化ニッケル中のニッケル品位は35~45重量%のものが得られる。
この水酸化工程では、抽残液のpHを6.5~8.0の範囲に調整することが好ましく、pHが6.5未満であると、ニッケル水酸化物の一部が再溶解してロスになるなど効率が低下する。一方、8.0を越えても得られる水酸化ニッケルの収率は向上せずアルカリの消費が増加するだけで効率が低下する。
しかし、例えば、消石灰を用いると、石膏が生成析出して沈殿物に混じりニッケル品位を低下させてしまうことがあるので好ましいとはいえず、水酸化マグネシウムや水酸化ナトリウムを用いることが適している。
濾過にはフィルタープレス、ヌッチェ、デンバー濾過機、遠心分離機など既存の種類のものを利用することができる。
[焙焼工程]
水酸化工程で得られた水酸化ニッケルは、焙焼工程で酸化ニッケルに形成される。
その焙焼条件は、230℃以上870℃以下、好ましくは600℃以上750℃以下の温度範囲において、不活性あるいは還元雰囲気下で行われる。
焙焼する温度は、結晶水が分解する温度よりも高い温度で焙焼することが効果的で、水酸化ニッケルの場合は具体的には230℃程度以上の温度とすることが有効である。
そのため、硫酸ニッケルの分解温度を超えた温度で焙焼し、複雑な塩を水溶性の単純な塩の形態に変えてから硫黄分を除くことが有効である。
したがって、実操業におけるハンドリング性や実際の酸化反応の速度や熱効率を考えると焙焼温度は600℃以上750℃以下の範囲とすることが好ましい。
焙焼の際に空気中などの酸素存在下で行うと、付着した硫黄が形成する硫酸塩は分解し、硫黄は硫黄酸化物(SOx)ガスとして揮発する。この揮発した硫黄酸化物は、回収し無害化処理するための排ガス処理設備が必要となるためにコストが増大する。したがって、焙焼は不活性や還元性など非酸化性の雰囲気の下で行い、硫黄酸化物の生成を防ぐと良い。
雰囲気に残存する酸素濃度は、硫黄酸化物(SOx)の分圧との関係もあるので一概に規定されるものではないが、一般には分圧に直して10-8atmより低い濃度とすることが好ましい。
焙焼工程で得られた酸化ニッケルを水洗浄し、次いで假焼して表面に残存する硫黄を分離する。また、この際に還元剤を加えると、酸化ニッケル表面に残存する水分を利用してペレットを形成できるので、還元時の反応性がさらに向上する。
具体的には酸化ニッケルを、まず50℃以上の温水で洗浄する。次に酸化ニッケルを假焼して水分を分離する。これら一連の工程を経る。
その場合の洗浄水の温度は、50℃以上100℃以下の範囲とすることが好ましい。
そこで本発明では、酸化ニッケルをペレット化して還元炉に入れる方法を用いた。ペレット化は、酸化ニッケルの粉末を混錬機や円盤状のペレタイザーに装入し、一定濃度の水分を付加しながら混錬することで行われ、粒状のペレットを得ることができる。
逆に水分が多すぎる際は、粉がスラリー化しペレットが成形できない。このような場合には、エアーブロウやデンバーを用いて脱水したり、さらには低い温度で假焼したりして水分率を調整できる。
還元剤と酸化ニッケル粉の粒度は同等であることが好ましい。また、強度のあるペレットを得るには、ペレット中に粘土質成分を含有していることが好ましいが、酸化ニッケルや加える還元剤には、粘土質成分はほとんど含有されておらず、そのために得られる強度に限界がある。そこで、ペレット化には強い結合力を発現させやすい圧縮混錬機を使用することが好ましい。
このバインダーの添加量は、バインダー種類により一概に規定されるものではなく、適宜添加量と得られる強度とを比較して決定できるが、例えばベントナイトを用いる場合には、酸化ニッケルの物量の0.1~8重量%程度となる量を添加すれば十分な強度が得られる。
先ず、ニッケル酸化鉱から硫化物を製造する図1の製造工程に従って、Ni:1.1質量%、Co:0.1質量%、Fe:42.0質量%、Mn:0.8質量%、Al:2.7質量%の成分組成を有するラテライト鉱を、乾燥重量換算で500g採取して容積3リットルの耐熱容器に入れ、これに濃度64質量%の硫酸溶液150gと水を加えて、スラリー濃度が30質量%になるように調整した。
時間経過後、固液分離し硫化澱物、すなわちニッケル・コバルト混合硫化物と硫化後液とに分離した。
次に、得られたニッケル・コバルト混合硫化物200dry-g(組成:Ni57.0wt%、Co4.5wt%、Mn0.01wt%)を分取し、純水2リットルを添加して固形濃度(スラリー濃度)が9.1wt%になるように調整して混合硫化物スラリーを作製した。
所定の反応が終了後、オートクレーブから浸出スラリーを取り出し、ヌッチェで濾過し、浸出残渣とニッケル・コバルト濃縮液とに分離した。
得られたニッケル、コバルト濃縮液の組成は、Ni46g/L、Co3.1g/L、Mn0.01g/Lであった。また残渣の重量は65gであった。
得られた中和後液を水相とし、これに燐酸エステル系酸性抽出剤(Cyanex社製 Cyanex272:Cyanexは登録商標)を油水比が1となる割合で混合し、水酸化ナトリウムを添加してpHを4.7に調整後、ミキサーセトラーに入れて混合して静置した。
その後、両相を分離する3段の抽出段、得られた有機相と硫酸溶液を混合して有機相にコバルトを抽出させたままで有機相に抽出されたニッケルのみを水相側へ逆抽出させる1段の洗浄段、有機/水相比が5となる割合で混合して有機相に抽出されたコバルトを逆抽出する2段の逆抽出段、から構成される設備を用いて、溶媒抽出処理してニッケルを含有する抽出残液とコバルトを含有する逆抽出液を作製した。
この得られた抽出残液に、水酸化マグネシウムのスラリーを添加し、pHを7.3に調整、中和してニッケルを水酸化物の形態として固液分離した。得られた水酸化ニッケルの組成は、Ni:36.9wt%、Co:0.26wt%、Fe:<0.01wt%、Mn:<0.01wt%であった。
その水酸化ニッケルを、1サンプルにつき15gとし、計5サンプルを採取して、それぞれをアルミナ製のルツボに入れた。ルツボは内容積5リットルの電気炉に入れ、窒素ガスをボンベから毎分0.5リットルの流量で炉内に流して完全に不活性雰囲気に置換した。それぞれのサンプルを250℃、450℃、650℃、750℃、の4温度に個々に昇温し、1時間保持して水酸化ニッケルを酸化ニッケルの形態に焙焼した。
図4に焙焼前、250℃および650℃焙焼後のサンプルの様子を示す。
図5に各温度で焙焼して得た焙焼物を50℃の温水で水洗浄した際の硫黄除去率を示すが、焙焼温度が高い焙焼物ほど、洗浄による硫黄除去率が高い傾向がある。なお、図5において、「○:白抜き丸印」はニッケル硫化物、「●:黒丸印」は混合硫化物における結果を示すものである。
次に、上記で得た焙焼後の酸化ニッケルを回収して純水を添加し、50℃に維持して1時間攪拌した後、5Cの濾紙を用いて濾過して濾液と洗浄後焙焼物(洗浄後酸化ニッケル)とを分離した。得られた酸化ニッケルの粒径は1mm以下であった。
その作製したペレットを、アルミナ製のトレイ内に入れ、200℃に昇温して維持し、12時間保持した。その後、そのペレット28gと実際のフェロニッケル製錬工程における還元キルンから生成した焼鉱300g、ならびに1mm以下の粒度に篩い分けたコークス10gとを混合して、アルミナるつぼ内に入れ、内容積5リットルの電気炉内に装入して窒素ガスを毎分1リットルの流量で流した不活性雰囲気の下で1500℃に昇温し、昇温後1時間保持した。時間経過後、不活性雰囲気に保ったまま室温にまで冷却し、ルツボ中のスラグと還元メタルとを回収した。その様子を図6に示す。
この始液の組成は、ニッケル濃度46~118g/L、コバルト濃度4.1~8.4g/Lであった。
表1に1段抽出時の各溶液のニッケルおよびコバルト濃度を示す。1段の抽出で、抽出後の水溶液(抽残液)のニッケル濃度は44~110g/L、コバルト濃度は0.6~0.9g/L、抽出後の有機溶媒中のニッケル濃度は2.0~3.4g/L、コバルト濃度は6.3~7.8g/Lとなり優れたニッケル、コバルト分離性を示した。
焙焼工程における雰囲気を、電気炉に空気を流して酸化雰囲気とした以外は実施例1と同様の方法を用いた。
焙焼温度は650℃とし、昇温後1時間保持した。焙焼中は硫黄酸化物ガスが発生した。焙焼後物中の硫黄品位も硫黄が揮発し減少していた。したがって空気を吹き込んだ酸化焙焼ではフェロニッケルの原料を得ることができないことがわかった。
Claims (13)
- ニッケル硫化物、あるいはニッケル硫化物とコバルト硫化物を含む混合硫化物からフェロニッケル原料を形成するフェロニッケル原料の製造方法であって、下記工程を経て処理することを特徴とする。
(1)ニッケル硫化物、あるいはニッケル硫化物とコバルト硫化物の混合硫化物を、スラリーとし、前記スラリーに酸化剤を添加して、前記ニッケル硫化物を溶解した場合にはニッケルを含有する濃縮液、あるいは前記混合硫化物を溶解した場合にはニッケルおよびコバルトを含有する濃縮液を得る再溶解工程。
(2)再溶解工程で得られた濃縮液にアルカリを添加し、中和澱物と中和後液とを得る脱鉄工程。
(3)脱鉄工程で得られた中和後液と有機抽出剤を混合して抽出有機と抽残液とに分離し、次いで抽出有機から逆抽出液と逆抽出後有機とを得る溶媒抽出工程。
(4)溶媒抽出工程で得られた抽残液にアルカリを添加、混合して水酸化ニッケルを形成する水酸化工程。
(5)水酸化工程で得られた水酸化ニッケルを230℃以上、870℃以下の温度範囲に加熱、焙焼して酸化ニッケルを形成する焙焼工程。
(6)焙焼工程で得られた酸化ニッケルを、水温50℃以上の水を用いて水洗浄し、次いで50℃以上の温度で假焼することによって、洗浄後酸化ニッケルを形成することを特徴とする洗浄・假焼工程。 - 前記再溶解工程における酸化剤と混合する前のニッケル硫化物あるいは混合硫化物の粒度が、体積平均径(MV)で表した値で15~100μmの範囲であることを特徴とする請求項1記載のフェロニッケルの製造方法。
- 前記再溶解工程における再溶解が、60℃以上、160℃以下の温度範囲で行われることを特徴とする請求項1記載のフェロニッケルの製造方法。
- 前記再溶解工程における前記酸化剤が、空気、酸素、過酸化水素溶液およびオゾンガスの内、いずれか1種類以上のものであることを特徴とする請求項1記載のフェロニッケルの製造方法。
- 前記焙焼工程における焙焼が、不活性雰囲気もしくは反応容器内の酸素分圧を10-8atm以下の状態で行われることを特徴とする請求項1記載のフェロニッケルの製造方法。
- 前記溶媒抽出工程によって得られた前記逆抽出液に、硫化剤を添加してコバルト硫化物を得ることを特徴とする請求項1記載のフェロニッケルの製造方法。
- 前記溶媒抽出工程によって得られた前記逆抽出液に、ソーダ灰を加えて、炭酸コバルトを得ることを特徴とする請求項1記載のフェロニッケルの製造方法。
- 前記溶媒抽出工程によって得られた逆抽出液に、アルカリを加えて、水酸化コバルトを得ることを特徴とする請求項1記載のフェロニッケルの製造方法。
- 前記洗浄・假焼工程により得られた前記洗浄後酸化ニッケルに、還元剤およびバインダーを前記洗浄後酸化ニッケルの0.1~8.0重量%となる量を加えて、混練し、次いで50℃以上の温度で假焼して酸化ニッケルペレットを得ることを特徴とする請求項1記載のフェロニッケルの製造方法。
- 前記還元剤が、粉炭、微粉炭、粉コークスの少なくとも1種類以上のものであることを特徴とする請求項9記載のフェロニッケルの製造方法。
- 前記バインダーが、ベントナイト、低品位ニッケル酸化鉱のいずれか1種類以上のものであることを特徴とする請求項9記載のフェロニッケルの製造方法。
- 前記ニッケル硫化物、あるいはニッケル硫化物とコバルト硫化物を含む混合硫化物が、
ニッケル酸化鉱石を硫酸によって高温加圧浸出した後、固液分離して得られた浸出液を中和して、不純物を含む澱物と濾液に分離し、さらに前記濾液に硫化剤を添加して亜鉛硫化澱物を分離し、前記亜鉛硫化物を分離した残濾液に硫化剤を吹き込むことで得られるニッケル硫化物、あるいはニッケル硫化物とコバルト硫化物を含む混合硫化物であることを特徴とする請求項1記載のフェロニッケルの製造方法。 - 前記ニッケル硫化物、あるいはニッケル硫化物とコバルト硫化物を含む混合硫化物が、スクラップや工程仕掛品として発生した水酸化ニッケル、酸化ニッケル、水酸化コバルト、酸化コバルトの少なくとも1種類以上を硫酸によって浸出した浸出液を生成し、前記浸出液に硫化剤を吹き込むことによって形成されたニッケル硫化物、あるいはニッケル硫化物とコバルト硫化物の混合硫化物であることを特徴とする請求項1記載のフェロニッケルの製造方法。
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AU2011283904B2 (en) | 2014-01-16 |
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CN102918171B (zh) | 2014-03-12 |
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US20130074653A1 (en) | 2013-03-28 |
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