WO2016136087A1 - ニッケル酸化鉱石の湿式製錬方法 - Google Patents
ニッケル酸化鉱石の湿式製錬方法 Download PDFInfo
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- WO2016136087A1 WO2016136087A1 PCT/JP2015/084417 JP2015084417W WO2016136087A1 WO 2016136087 A1 WO2016136087 A1 WO 2016136087A1 JP 2015084417 W JP2015084417 W JP 2015084417W WO 2016136087 A1 WO2016136087 A1 WO 2016136087A1
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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
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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
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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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
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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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 hydrometallizing nickel oxide ore, and more specifically, valuable metals are recovered from hydrous smelting of saprolite-based ore containing a large amount of alkali metals such as magnesium and silica among nickel oxide ores by high efficiency. About how it can be.
- Patent Document 1 As a method for recovering valuable metals such as nickel and cobalt from low-grade nickel oxide ore with low nickel grade by wet smelting, for example, as shown in Patent Document 1, sulfuric acid is added to ore slurry and leached under high temperature and high pressure. A high-pressure acid leaching method (HPAL method: High Pressure Acid Leach method) is performed.
- HPAL method High Pressure Acid Leach method
- Limonite ore with high iron grade and low alkali component grades such as magnesium and silica there are two types of low-grade nickel oxide ores: Limonite ore with high iron grade and low alkali component grades such as magnesium and silica, and Saprolite ore containing a lot of alkali components. Limonite ore is mainly used as the raw material of the method.
- the sulfuric acid added in the leaching process reacts with the alkali component contained in the ore to form an alkali sulfate such as magnesium sulfate. Consumption tends to increase, which is economically disadvantageous. For this reason, when subjecting a saprolite-type ore to pressure leaching based on the HPAL method, the amount of valuable metals recovered and the amount of sulfuric acid consumed are limited to a certain amount, but in many cases Only a small part of the amount of saprolite ore produced.
- an atmospheric pressure leaching method has been studied as an effective utilization method of saprolite-based ore.
- it is a method of using saprolite-based ore as a neutralizing agent for free acid contained in a leachate obtained by the HPAL method, and is disclosed in, for example, Patent Document 2 and Patent Document 3.
- these methods are mainly used as a neutralizer for free acid or as a source of magnesium.
- these methods are valuable such as nickel and cobalt contained in saprolite ores.
- the metal recovery rate is low, and it is difficult to say that it is effectively used as a raw material.
- Patent Document 4 a method of leaching nickel or cobalt by atmospheric pressure leaching using saprolite-based ore as a raw material is disclosed, and it is said that a high recovery rate can be achieved.
- the time required for atmospheric pressure leaching is as long as 9.5 hours or more, and the production efficiency remains low.
- Patent Document 5 proposes a method in which a leaching residue obtained by atmospheric leaching is supplied to a pressure leaching process of the HPAL method, thereby recovering valuable metals. Specifically, the method disclosed in Patent Document 5 treats the entire amount of low-grade nickel oxide ore by atmospheric leaching and pressure leaching. However, at a reaction temperature of 95 ° C., which is a condition for atmospheric leaching, a residence time of 2 to 3 hours is still required in the reaction tank, which requires an increase in equipment scale, supply of a large amount of warming heat, and heat insulation. It is not efficient as actual operation.
- the atmospheric leaching according to Patent Document 5 is mainly intended to neutralize the free acid of the leaching solution obtained by the pressure leaching, so the magnesium leaching rate in atmospheric leaching is only about 42% to 50%. The amount of sulfuric acid consumed by magnesium during pressure leaching is still high.
- the process waste liquid containing sodium is used for multistage cleaning liquid of pressure leaching residue, diluting liquid of flocculant added at the time of solid-liquid separation such as thickener, slurrying of low grade nickel oxide ore, etc.
- solid-liquid separation such as thickener, slurrying of low grade nickel oxide ore, etc.
- iron which is an impurity component
- aluminum is removed as soda-olivine, thereby reducing the amount of sulfuric acid consumed by these impurity components.
- sulfate double salts such as natrojarosite and soda alunite may become scales in the autoclave.
- the process waste water containing sodium is a magnesium sulfate solution after recovering valuable metals, and magnesium sulfate is concentrated by circulation in the process system. Therefore, there is a possibility that crystal precipitation may occur in the process exceeding the saturation concentration, and there is a concern that filtration failure, piping blockage, and the like occur.
- JP-A-2005-350766 JP-A-60-75536 JP 2007-77459 A Special table 2008-530356 gazette JP-A-6-116660
- the present invention has been proposed in view of the above-described circumstances, and in the method of hydrometallurgy of nickel oxide ore for recovering nickel, cobalt, etc. from nickel oxide ore, acid consumption such as sulfuric acid used in leaching treatment
- An object of the present invention is to provide a method capable of reducing the amount and recovering valuable metals such as nickel and cobalt with high efficiency.
- the present inventors have made extensive studies to solve the above-described problems.
- As a result among the nickel oxide ores used as raw materials, only target saprolite ores containing a large amount of alkali components such as magnesium and silica are subjected to atmospheric pressure leaching under prescribed standardized leaching conditions, thereby achieving the target magnesium.
- Magnesium is leached to grade, and then the leaching residue obtained by the atmospheric leaching and the limonite ore with less alkali components are subjected to pressure leaching, so that the amount of sulfuric acid consumed by the pressure leaching treatment is effective.
- the present invention was completed by discovering that valuable metals such as nickel and cobalt can be recovered with high efficiency. That is, the present invention provides the following.
- the present invention is a method of hydrometallizing nickel oxide ore for recovering valuable metals such as nickel and cobalt from nickel oxide ore, wherein the nickel oxide ore is low magnesium grade having a magnesium grade of 2% by weight or less.
- the step (B) for obtaining a normal pressure leaching residue, the limonite-based ore obtained in the step (A) and the normal pressure leaching residue obtained in the step (B) are mixed, and the acidity is obtained under high temperature and high pressure.
- This is a hydrometallurgical method of nickel oxide ore comprising a step (C) of leaching under pressure by reacting with sulfuric acid in an atmosphere to obtain a pressure leaching solution.
- the acid consumption such as sulfuric acid used in the pressure leaching treatment is effectively reduced, Valuable metals such as nickel and cobalt can be recovered with high efficiency.
- FIG. 6 is a graph showing the relationship of the free acid concentration to the reaction time in the atmospheric pressure leaching process of Examples 1 to 4.
- FIG. 4 is a graph showing the relationship of iron concentration to free acid concentration in atmospheric leaching treatments of Examples 1 to 4.
- FIG. 6 is a graph showing the relationship of iron concentration to solution pH in atmospheric pressure leaching treatment of Examples 1 to 4.
- FIG. 3 is a graph showing the relationship of magnesium grade in the leaching residue relative to [Fe 2 (SO 4 ) 3 + sulfuric acid] / ore Mg equivalent in the atmospheric leaching treatment of Examples 5 to 10.
- FIG. 6 is a graph showing the relationship of the free acid concentration in the final liquid after reaction with respect to [Fe 2 (SO 4 ) 3 + sulfuric acid] / ore Mg equivalent in the atmospheric pressure leaching treatment of Examples 5 to 10.
- FIG. 6 is a graph showing the relationship between the free acid concentration and the nickel leaching rate in the pressure leaching treatment of Examples 11 to 13 and Comparative Examples 1 to 3.
- the nickel oxide ore hydrometallurgy method is a method for recovering valuable metals such as nickel and cobalt by leaching a low-grade nickel oxide ore having a low nickel quality. Specifically, among the low-grade nickel oxide ores, the sulfuric acid consumed in pressure leaching is obtained by performing atmospheric pressure leaching on saprolite ore containing a large amount of magnesium, silica, etc., and then performing pressure leaching. In this method, valuable metals such as nickel and cobalt are recovered with high efficiency from low-grade nickel oxide ore.
- the method for hydrometallizing nickel oxide ore includes the following steps (A) to (C).
- nickel oxide ore used as a raw material is sorted into limonite ore and saprolite ore based on magnesium grade, and only the selected saprolite ore is usually used with a pressurized leachate.
- Perform pressure leaching treatment In the atmospheric pressure leaching treatment, the amount of acid contained in the pressure leaching solution and the molar ratio of the amount of magnesium contained in the saprolite ore that is the subject of the atmospheric pressure leaching treatment are normalized, and the atmospheric pressure leaching treatment is performed. Reduce the leaching residue magnesium grade to the target magnesium grade. Subsequently, the limonite ore obtained by sorting and the atmospheric leaching residue obtained by the atmospheric leaching treatment are mixed, and sulfuric acid is added under high temperature and high pressure to perform pressure leaching.
- the magnesium quality of the atmospheric leaching residue can be further reduced to the target magnesium quality in a shorter time. It can be reduced efficiently, and the equipment scale required for the atmospheric pressure leaching process can be reduced.
- a wet smelting method for recovering valuable metals from low-grade nickel oxide ore will be described.
- a wet smelting method for nickel oxide ore to which this method can be applied will be described.
- the following nickel oxide ore wet smelting method shows a specific example of recovering nickel and cobalt by a high-temperature pressure acid leaching method (HPAL method) using a sulfuric acid solution.
- HPAL method high-temperature pressure acid leaching method
- FIG. 1 is a process diagram showing the flow of a hydrometallurgical method using a nickel oxide ore HPAL method.
- the wet smelting method of nickel oxide ore includes a leaching process S1 in which a sulfuric acid solution is added to a slurry of nickel oxide ore and leaching (pressure leaching) at high temperature and high pressure, and leaching treatment
- the solid-liquid separation step S2 for obtaining a leachate containing impurity elements together with nickel and cobalt by separating the leach residue while washing the leach slurry obtained by the multistage cleaning, and adjusting the pH of the leachate to neutralize excess acid in the leachate
- the neutralization starch (neutralization residue) containing the impurity element is separated and removed to obtain a neutralization final solution containing nickel and cobalt, and a sulfidizing agent is added to the neutralization final solution to
- sulfidizing step S4 for producing a mixed sulfide containing nickel and cobalt, and leaching residue slurry separated from the solid-liquid separation step S2 and the impurity metal contained in the poor liquid discharged from the sulfidizing step S4 And a final neutralization step S5 for discharging and removed by.
- Leaching step S1 a sulfuric acid solution is added to a slurry of low-grade nickel oxide ore (ore slurry) using a pressure reaction vessel such as a high-temperature pressure vessel (autoclave), and 220 ° C. to 280 ° C.
- the ore slurry is stirred while being pressurized under a high temperature condition of 0 ° C. to generate a leaching slurry composed of a leaching solution and a leaching residue.
- Nickel oxide ores are mainly so-called laterite ores, such as limonite ore with high Fe grade and low alkaline component grade, and saprolite ore containing many alkali components such as magnesium and silica. Is mentioned.
- the nickel content in the laterite ore is usually 0.8% to 2.5% by weight, and is contained as a hydroxide or a siliceous clay (magnesium silicate) mineral.
- the iron content in laterite ore is 10 to 50% by weight and is mainly in the form of trivalent hydroxide (goethite). Contained.
- an oxide ore containing valuable metals such as nickel, cobalt, manganese, and copper, for example, manganese nodules existing in the deep sea bottom may be treated. it can.
- a leaching reaction represented by the following formulas (i) to (iii) and a high-temperature thermal hydrolysis reaction represented by the following formulas (iv) and (v) occur, and nickel or cobalt And the like, and leaching of the leached iron sulfate as hematite is performed.
- Solid-liquid separation process (leaching residue washing process)
- the leaching slurry formed by the pressure leaching process in the leaching step S1 is subjected to multistage cleaning, and solid-liquid separation is performed into a leaching solution containing nickel and cobalt and a leaching residue.
- an anionic flocculant can be added to perform solid-liquid separation processing in order to promote sedimentation separation of the leach residue.
- the solid-liquid separation process is performed by solid-liquid separation equipment such as a thickener. Specifically, the leaching slurry is first diluted with a cleaning liquid, and then the leaching residue in the slurry is concentrated as a thickener sediment. Thereby, the nickel content adhering to the leaching residue can be reduced according to the degree of dilution.
- the solid-liquid separation step S2 is also referred to as a leaching residue cleaning step.
- the solid-liquid separation step S2 it is preferable to perform solid-liquid separation while washing the leach slurry in multiple stages.
- the multi-stage cleaning method for example, a continuous AC multi-stage cleaning method in which a cleaning liquid is brought into contact with the leaching slurry in an alternating current can be used. Thereby, the cleaning liquid newly introduced into the system can be reduced, and the recovery rate of nickel and cobalt can be improved to 95% or more.
- the cleaning liquid (cleaning water) is not particularly limited, but it is preferable to use a liquid that does not include nickel and does not affect the process.
- the cleaning liquid preferably, the poor liquid obtained in the subsequent sulfurization step S4 can be used repeatedly.
- the pH of the resulting neutralized final solution is 4 or less, preferably 3.0 to 3.5, more preferably 3.1 to 3, while suppressing the oxidation of the separated leachate.
- the neutralized starch produced as described above is settled and separated to produce a neutralized final solution that becomes a mother liquor for nickel recovery.
- the slurry obtained by the neutralization treatment (neutralization slurry) is subjected to a solid-liquid separation treatment using a solid-liquid separation device such as a thickener to separate and remove the neutralized starch. .
- a sulfidizing agent such as hydrogen sulfide gas is blown into the neutralized final solution which is the mother liquor for nickel recovery to cause a sulfidation reaction.
- a mixed sulfide (nickel / cobalt mixed sulfide) and a poor liquid (post-sulfurized liquid) in which the nickel concentration is stabilized at a low level are obtained.
- step S4 when zinc is contained in the mother liquor (neutralization final solution) for nickel and cobalt recovery, zinc is selectively used as sulfide prior to separation of nickel and cobalt as sulfide. Can be processed.
- the nickel / cobalt mixed sulfide slurry is settled and separated using a solid-liquid separator such as thickener to separate and recover the nickel / cobalt sulfide from the bottom of the thickener, and the aqueous solution component overflows. Recovered as a solution after sulfidation.
- Final neutralization step S5 the discharge standard is satisfied for the leaching residue slurry discharged from the solid-liquid separation step S2 and the poor liquid (post-sulfurization liquid) discharged from the sulfidation step S4.
- a neutralization treatment (detoxification treatment) for adjusting to a predetermined pH range is performed.
- the method of detoxification treatment in the final neutralization step S5, that is, the pH adjustment method is not particularly limited, but for example, by adding a neutralizing agent such as calcium carbonate (limestone) slurry or calcium hydroxide (slaked lime) slurry. It can be adjusted to a predetermined range.
- a neutralizing agent such as calcium carbonate (limestone) slurry or calcium hydroxide (slaked lime) slurry.
- the wet smelting method of nickel oxide ore according to the present embodiment is a method in which an atmospheric pressure leaching process is incorporated into the above-described wet smelting method. Specifically, the nickel oxide ore used as a raw material is sorted into limonite ore and saprolite ore based on the magnesium grade, and only the high-grade magnesium saprolite ore is subjected to atmospheric pressure leaching treatment using pressurized leachate. I do.
- the atmospheric pressure leaching treatment it is carried out in an amount normalized by the molar ratio of the amount of acid contained in the pressurized leachate and the amount of magnesium contained in the saprolite ore that is the subject of the atmospheric pressure leaching treatment, Reduce the leaching residue magnesium grade to the target magnesium grade. Thereafter, the limonite ore obtained by sorting and the atmospheric leaching residue obtained by atmospheric leaching are mixed, and sulfuric acid is added under high temperature and high pressure to perform pressure leaching.
- the amount of nickel oxide ore used for atmospheric leaching can be reduced, and magnesium leaching of saprolite ore can be promoted by atmospheric leaching.
- pressure leaching is achieved.
- the amount of sulfuric acid used in can be effectively reduced. This makes it possible to leach valuable metals such as nickel and cobalt contained in nickel oxide ore at a high leaching rate even at low acid concentrations, and recover valuable metals from nickel oxide ore as a raw material with high efficiency. can do.
- FIG. 2 is a process diagram showing the flow of the nickel oxide ore hydrometallurgical method according to the present embodiment.
- the nickel oxide ore hydrometallurgy method according to the present embodiment uses nickel oxide ore as a raw material as a low magnesium grade limonite ore and a high magnesium grade saprolite ore. It was calculated that the free acid concentration and the presence form contained in the pressure leachate obtained by the pressure leaching step S13 with respect to the ore sorting step S11 and the saprolite-type ore sorted in the ore sorting step S11 were trivalent.
- An atmospheric pressure leaching process in which an atmospheric pressure leaching is performed by adding a pressure leachate whose sulfuric acid concentration is adjusted so that the value obtained by dividing the total value of the iron ion concentration by the magnesium grade contained in the saprolite ore is equal to or less than a predetermined equivalent. Pressurization for pressure leaching by mixing S12, the limonite ore selected in the ore sorting step S11 and the atmospheric leaching residue obtained in the atmospheric leaching step S12 And an output step S13.
- nickel oxide ore used as a raw material is sorted into limonite ore and saprolite ore based on magnesium grade.
- nickel oxide ores used as raw materials limonite ores have high iron quality, while magnesium, which is an alkaline component, has low quality.
- saprolite ores are high magnesium grade ores containing a large amount of alkali components such as magnesium and silica.
- “limonite ore ⁇ magnesium grade: 1.3 wt% ⁇ saprolite ore” is known.
- a high-magnesium grade saprolite ore containing a large amount of alkali components, that is, magnesium grade exceeding 2% by weight is selected.
- the nickel oxide ore used as a raw material is sorted based on the magnesium grade, which is an alkaline component, so that only the selected saprolite ore having a high magnesium grade is leached at the atmospheric pressure leaching step S12 described later. Make it available for processing. This makes it possible to carry out smelting using saprolite ore effectively, and to reduce the amount of ore used for atmospheric leaching and perform atmospheric leaching treatment in a short time.
- Normal pressure leaching process (Regarding the normal pressure leaching process)
- a normal pressure leaching process is performed on the saprolite ore selected in the ore selection step S11.
- the atmospheric leaching in the atmospheric leaching step S12 is performed by adding a pressure leaching solution obtained in the pressure leaching step S13 described later.
- the total value of the free acid concentration contained in the pressurized leachate and the iron ion concentration calculated assuming that the existence form is trivalent is contained in the saprolite ore.
- Normal pressure leaching by adding a pressure leaching solution with the sulfuric acid concentration adjusted so that the value divided by the magnesium grade ([Fe 2 (SO 4 ) 3 + sulfuric acid] / ore Mg equivalent) is 1.5 mol / mol equivalent or less It is characterized by doing.
- the blending ratio of the pressurized leachate used for the leaching process and the saprolite-based ore is normalized by the molar ratio of the acid amount contained in the pressurized leachate and the magnesium amount contained in the ore.
- the leachate obtained in the pressure leaching step S13 described later contains iron ions derived from iron contained in the ore (for example, in the form of iron sulfate (Fe 2 (SO 4 ) 3 )).
- the iron ions become hydroxide as the pH of the solution increases, and it acts as an acid, consuming Mg (OH) 2 contained in the slurry of saprolite ore.
- this atmospheric pressure leaching step S12 by adding sulfuric acid as necessary, the leaching of magnesium from the saprolite ore can be further promoted, and the solid-liquid ratio in the atmospheric pressure leaching is increased. be able to.
- a solid-liquid separation process After performing the normal pressure leaching process on the saprolite ore in the normal pressure leaching step S12, a solid-liquid separation process is performed in which the obtained normal pressure leaching slurry is solid-liquid separated into a normal pressure leaching solution and a normal pressure leaching residue (solid liquid Separation step S14).
- solid-liquid separation processing method in solid-liquid separation process S14, For example, it can carry out using solid-liquid separation apparatuses, such as a thickener.
- Pressure leaching process> (About pressure leaching process)
- the slurry of limonite ore having a low magnesium quality selected in the ore sorting step S11 and the slurry of the atmospheric pressure leaching residue obtained by the atmospheric pressure leaching treatment in the atmospheric pressure leaching step S12 are mixed. Sulfuric acid is added to it and subjected to pressure leaching under high temperature and pressure.
- This pressure leaching step S13 corresponds to the leaching step (pressure leaching step) S1 of the hydrometallurgical process whose process diagram is shown in FIG. 1, and the atmospheric pressure leaching residue obtained by the limonite ore and the atmospheric pressure leaching process. Is subjected to a pressure leaching treatment using sulfuric acid. In addition, since the specific description of the leaching process is the same as that of the leaching step S1, it is omitted here.
- the pressure leachate separated by the solid-liquid separation process is transferred to the atmospheric pressure leaching process S12 for performing the atmospheric pressure leaching process on the saprolite ore having a high magnesium grade as described above, and is used for the atmospheric pressure leaching process.
- the solid-liquid separation step S15 by directly solid-liquid separating the pressure leaching slurry obtained through the pressure leaching step S13, a leachate with a high free acid concentration can be obtained, and the atmospheric pressure leaching step
- the solid-liquid ratio of atmospheric leaching in S12 can be increased.
- the normal pressure leachate obtained by the normal pressure leaching (normal pressure leaching process using the pressure leachate) for the saprolite ore in the normal pressure leaching step S12 is transferred to the neutralization step S16.
- the leaching residue obtained by the pressure leaching in the pressure leaching step S13 is subjected to, for example, AC multi-stage washing (residue washing step S17) and the recovered cleaning liquid is also treated. Can do.
- This neutralization step S16 corresponds to the neutralization step S3 of the hydrometallurgical method shown in the process diagram of FIG. A neutralized starch containing an impurity element (neutralization residue) and a neutralized final solution that becomes a mother liquor for nickel recovery are generated.
- neutralization residue an impurity element
- neutralized final solution that becomes a mother liquor for nickel recovery
- the final neutralization liquid (mother liquid) obtained by the neutralization process in the neutralization process S16 is transferred to the sulfurization process S18 and subjected to the sulfurization process.
- This sulfidation step S18 corresponds to the sulfidation step S4 of the hydrometallurgical method shown in the flow chart of FIG. 1, and a sulfidizing agent such as hydrogen sulfide gas is blown into the neutralized final solution which is a mother liquor for nickel recovery.
- a sulfurization reaction is caused to obtain a mixed sulfide containing nickel and cobalt with a small amount of impurity components (nickel / cobalt mixed sulfide) and a poor liquid (post-sulfurized liquid) in which the nickel concentration is stabilized at a low level.
- the specific description of the sulfiding treatment is omitted here because it is the same as that of the sulfiding step S4.
- This final neutralization step S19 corresponds to the final neutralization step S5 of the hydrometallurgical process whose process diagram is shown in FIG. Neutralizes heavy metal ions contained in liquid and pressure leaching residue.
- the final neutralized starch slurry from which heavy metals have been removed from the aqueous solution is transferred to a tailing dam (tailing dam).
- Examples 1 to 4 Place the sulfuric acid solution of sulfuric acid concentration shown in Table 1 below or the HPAL leachate of iron concentration and sulfuric acid concentration shown in Table 1 below (pressurized leachate generated by pressure leaching) in a separable flask with a baffle plate with a capacity of 1000 mL The mixture was heated to 90 ° C. using an oil bath.
- a low-grade nickel oxide ore having a predetermined magnesium grade is added so as to have a predetermined [Fe 2 (SO 4 ) 3 + sulfuric acid] / ore Mg equivalent (mol / mol) shown in Table 1 below.
- Table 1 shows a predetermined [Fe 2 (SO 4 ) 3 + sulfuric acid] / ore Mg equivalent (mol / mol) shown in Table 1 below.
- atmospheric pressure leaching treatment was performed for 6 hours.
- 15 mL each was sampled and subjected to filtration treatment.
- the chemical analysis was conducted. Table 2 below summarizes the measurement results of the free acid concentration at each reaction time, and FIGS. 3 to 5 show graphs of the free acid concentration and various chemical analysis results.
- Example 1 and Example 2 are examples in which the sulfuric acid / ore Mg equivalent ratio (mol / mol) (not considering Fe) is set to the same level.
- Table 2 and FIG. 3 after the elapse of 6 hours (360 minutes) from the start of the reaction, in Example 1, the free acid concentration in the final solution of atmospheric leaching treatment was reduced to 2.1 g / L.
- Example 2 using the pressure leaching solution the free acid concentration of the atmospheric leaching treatment final solution decreased only to 8.4 g / L.
- FIG. 3 is a graph showing the relationship of the free acid concentration to the reaction time.
- Example 3 and Example 4 are examples in which iron is calculated as an acid and (iron + acid) / ore Mg equivalent ratio (mol / mol) is set to the same level.
- Table 2 and FIG. 3 after each reaction time, the free acid concentration of Example 1 and Example 2 was higher in Example 4 although the free acid concentration in the final solution of atmospheric leaching treatment was slightly higher. Compared with the difference in concentration, the difference in free acid concentration between Example 3 and Example 4 is as small as about 1 g / L, which can be said to be within the same range.
- FIG. 4 is a graph showing the relationship of iron concentration to free acid concentration.
- FIG. 4 shows that in Example 2, the iron concentration also decreased from the vicinity where the free acid concentration became 12 g / L or less.
- FIG. 5 is a graph showing the relationship of the iron concentration to the pH of the solution subjected to the leaching treatment. From the results shown in the graph of FIG. 5, for example, the decrease in iron concentration in Example 2 is considered to be due to hydroxylation precipitation of trivalent iron ions (Fe 3+ ).
- Example 5 to 10 An HPAL leachate (pressure leachate) having an iron concentration and a free sulfuric acid concentration shown in Table 3 below was placed in a 500 mL baffled separable flask, and heated to 90 ° C. using an oil bath.
- a low-grade nickel oxide ore having a predetermined magnesium grade is added so as to have a predetermined [Fe 2 (SO 4 ) 3 + sulfuric acid] / ore Mg equivalent (mol / mol) shown in Table 3 below.
- a normal pressure leaching process was performed with stirring at 700 rpm for 3 hours. After 1, 2, and 3 hours had elapsed from the start of the reaction, 15 mL each was sampled and filtered, and then the free acid concentration of the filtrate was measured. Further, chemical analysis was performed on the atmospheric leaching residue obtained by sampling, and the magnesium quality was confirmed. 6 and 7 show the measurement results.
- FIG. 6 is a graph showing the relationship of the magnesium quality in the leaching residue produced by atmospheric leaching with respect to [Fe 2 (SO 4 ) 3 + sulfuric acid] / ore Mg equivalent. From FIG. 6, it is possible to confirm the amount of acid and the reaction time necessary to obtain a target magnesium-grade leaching residue of normal grade by high-pressure leaching from high magnesium grade ore.
- FIG. 7 is a graph showing the relationship of the free acid concentration in the post-reaction final solution with respect to [Fe 2 (SO 4 ) 3 + sulfuric acid] / ore Mg equivalent. From FIG. 7, when the reaction time of the atmospheric leaching treatment is 3 hours or less, [Fe 2 (SO 4 ) 3 + sulfuric acid] / Ore Mg is used to keep the free acid concentration of the atmospheric leaching final solution low. It turns out that it is desirable to adjust an equivalent to 1.5 (mol / mol) or less.
- Leaching slurry (35% by weight) comprising a normal-grade leaching residue having the metal grade shown in Table 4 below and a normal-pressure leaching solution (normal pressure leaching final solution) having the concentrations shown in Table 5 below, and a low-grade metal grade shown in Table 4
- Magnesium grade nickel oxide ore (40 wt% slurry: dilution is tap water) is mixed in the quantity (g) and liquid quantity (L) shown in Table 4 and Table 5, and the amount shown in Table 6 below is mixed therewith. Sulfuric acid and water were added to adjust each to a slurry having a concentration of 28% by weight.
- the prepared slurry was put into an autoclave having a capacity of 3 liters, and pressure leached by batch processing at a reaction temperature of 245 ° C. and a holding time of 1 hour.
- the leaching residue slurry obtained by the pressure leaching treatment was filtered and solid-liquid separated, and the free acid concentration of the obtained leaching solution was measured. Further, the concentration of each component in the leachate and the component quality in the obtained leach residue were measured by chemical analysis, and the leach rate of each component was calculated.
- the concentration of each component of the obtained leachate (pressurized leachate) is shown in Table 6 below, and the leach rate of each component is shown in Table 7 below.
- Tables 6 and 7 show that valuable metals can be leached at a high leaching rate even when the free acid concentration is low, that is, without using an excessive amount of sulfuric acid. This can be understood more clearly when compared with the results of Comparative Examples 1 to 3 described later.
- the leaching residue slurry obtained by the pressure leaching treatment was filtered and solid-liquid separated, and the free acid concentration of the obtained leaching solution was measured. Further, the concentration of each component in the leachate and the component quality in the obtained leach residue were measured by chemical analysis, and the leach rate of each component was calculated.
- the concentration of each component of the obtained leachate (pressurized leachate) is shown in Table 9 below, and the leaching rate of each component is shown in Table 10 below.
- FIG. 8 is a graph showing the relationship between the free acid concentration and the nickel leaching rate in Examples 11 to 13 and Comparative Examples 1 to 3. As shown in FIG. 8, it can be seen that according to the methods implemented in Examples 11 to 13, valuable metals can be recovered efficiently and at a high recovery rate.
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Abstract
Description
本実施の形態に係るニッケル酸化鉱石の湿式製錬方法は、ニッケル品位の低い低品位ニッケル酸化鉱石に対して浸出処理を施してニッケルやコバルト等の有価金属を回収する方法である。具体的には、低品位ニッケル酸化鉱のうち、マグネシウムやシリカ等を多く含むサプロライト系鉱石に対して常圧浸出を行い、その後、加圧浸出を行うことによって、その加圧浸出において消費する硫酸の使用量を効果的に低減させ、低品位ニッケル酸化鉱石からニッケル及びコバルト等の有価金属を高効率で回収する方法である。
工程(A):原料とするニッケル酸化鉱石を、マグネシウム品位が2重量%以下である低マグネシウム品位のリモナイト系鉱石と、マグネシウム品位が2重量%を越える高マグネシウム品位のサプロライト系鉱石とに選別する鉱石選別工程。
工程(B):工程(A)で得られたサプロライト系鉱石に対して、下記の工程(C)における加圧浸出により得られる加圧浸出液に含まれる遊離酸濃度と存在形態が3価であるとして算出した鉄イオン濃度との合計値をそのサプロライト系鉱石に含まれるマグネシウム品位で除した値が1.5mol/mol当量以下となるように硫酸濃度を調整した加圧浸出液を添加して常圧浸出し、常圧浸出液と常圧浸出残渣とを得る常圧浸出工程。
工程(C):工程(A)で得られたリモナイト系鉱石と、工程(B)で得られた常圧浸出残渣とを混合し、高温高圧下の酸性雰囲気で硫酸と反応させることにより加圧浸出し、加圧浸出液を得る加圧浸出工程。
図1は、ニッケル酸化鉱石のHPAL法を用いた湿式製錬方法の流れを示す工程図である。図1の工程図に示すように、ニッケル酸化鉱石の湿式製錬方法は、ニッケル酸化鉱石のスラリーに硫酸溶液を添加して高温高圧下で浸出(加圧浸出)する浸出工程S1と、浸出処理により得られた浸出スラリーを多段洗浄しながら浸出残渣を分離してニッケル及びコバルトと共に不純物元素を含む浸出液を得る固液分離工程S2と、浸出液のpHを調整して浸出液中の余剰酸を中和するとともに不純物元素を含む中和澱物(中和残渣)を分離除去してニッケル及びコバルトを含む中和終液を得る中和工程S3と、中和終液に硫化剤を添加して硫化処理を施しニッケル及びコバルトを含む混合硫化物を生成させる硫化工程S4と、固液分離工程S2から分離した浸出残渣スラリーと硫化工程S4から排出された貧液に含まれる不純物金属を中和除去して排出する最終中和工程S5とを有する。
浸出工程S1では、高温加圧容器(オートクレーブ)等の加圧反応槽を用いて、低品位ニッケル酸化鉱石のスラリー(鉱石スラリー)に硫酸溶液を添加して、220℃~280℃の高い温度条件下で加圧しながら鉱石スラリーを攪拌することによって加圧浸出し、浸出液と浸出残渣とからなる浸出スラリーを生成させる。
MO+H2SO4⇒MSO4+H2O ・・(i)
(なお、式中Mは、Ni、Co、Fe、Zn、Cu、Mg、Cr、Mn等を表す)
2Fe(OH)3+3H2SO4⇒Fe2(SO4)3+6H2O ・・(ii)
FeO+H2SO4⇒FeSO4+H2O ・・(iii)
・高温熱加水分解反応
2FeSO4+H2SO4+1/2O2⇒Fe2(SO4)3+H2O ・・(iv)
Fe2(SO4)3+3H2O⇒Fe2O3+3H2SO4 ・・(v)
固液分離工程S2では、浸出工程S1における加圧浸出処理で形成された浸出スラリーを多段洗浄して、ニッケル及びコバルトを含む浸出液と浸出残渣とに固液分離する。この固液分離工程S2では、浸出残渣の沈降分離の促進のために、例えばアニオン系の凝集剤等を添加して固液分離処理を行うことができる。
中和工程S3では、固液分離工程S2にて分離された浸出液のpHを調整し、不純物元素を含む中和澱物を分離して、ニッケルやコバルトを含む中和終液を得る。
硫化工程S4では、ニッケル回収用の母液である中和終液に対して、硫化水素ガス等の硫化剤を吹き込んで硫化反応を生じさせ、不純物成分の少ないニッケル及びコバルトを含む混合硫化物(ニッケル・コバルト混合硫化物)と、ニッケル濃度を低い水準で安定させた貧液(硫化後液)とを得る。
最終中和工程S5では、固液分離工程S2から排出された浸出残渣スラリーと、硫化工程S4から排出された貧液(硫化後液)に対して、排出基準を満たす所定のpH範囲に調整する中和処理(無害化処理)を施す。
ここで、上述した従来のニッケル酸化鉱石の湿式製錬方法(図1)において、原料とするニッケル酸化鉱石として例えばサプロライト鉱石等のマグネシウム品位の高い高マグネシウム鉱石を使用した場合には、浸出工程S1における加圧浸出処理で使用する硫酸とアルカリ成分であるマグネシウムとが反応してアルカリ硫酸塩を形成するようになり、そのマグネシウムによる干渉作用によって添加した硫酸の効力が下がり、硫酸を過剰に消費する方向に進む(例えば下記反応式を参照)。
MgO+H2SO4 ⇒ MgSO4+H2O
MgSO4+H2SO4 ⇒ Mg(HSO4)2
鉱石選別工程S11では、原料とするニッケル酸化鉱石を、マグネシウム品位に基づいて、リモナイト系鉱石と、サプロライト系鉱石とに選別する。原料とするニッケル酸化鉱石のうち、リモナイト系鉱石は、鉄品位が高く、一方でアルカリ成分であるマグネシウムの品位が低い。これに対して、サプロライト系鉱石は、マグネシウムやシリカ等のアルカリ成分を多く含む高マグネシウム品位の鉱石である。なお、区分として、「リモナイト系鉱石<マグネシウム品位:1.3重量%<サプロライト系鉱石」が知られている。
(常圧浸出工程について)
常圧浸出工程S12では、鉱石選別工程S11で選別したサプロライト系鉱石に対して常圧浸出処理を施す。常圧浸出工程S12における常圧浸出では、後述する加圧浸出工程S13により得られる加圧浸出液を添加して行う。
MgO+H2O ⇒ Mg(OH)2
H2SO4+Mg(OH)2 ⇒ MgSO4+2H2O
Fe2(SO4)3+3MgO+3H2O ⇒ 3MgSO4+2Fe(OH)3
常圧浸出工程S12においてサプロライト鉱石に対する常圧浸出処理を行った後、得られた常圧浸出スラリーを、常圧浸出液と常圧浸出残渣とに固液分離する固液分離処理を行う(固液分離工程S14)。固液分離工程S14における固液分離処理方法としては、特に限定されないが、例えばシックナー等の固液分離装置を用いて行うことができる。
(加圧浸出工程について)
加圧浸出工程S13では、鉱石選別工程S11で選別したマグネシウム品位の低いリモナイト系鉱石のスラリーと、常圧浸出工程S12における常圧浸出処理で得られた常圧浸出残渣のスラリーとを混合し、それに硫酸を添加して高温高圧下で加圧浸出を施す。
加圧浸出工程S13においてリモナイト鉱石と常圧浸出残渣との混合物に対する加圧浸出処理を行った後、得られた浸出スラリー(加圧浸出スラリー)を、浸出液(加圧浸出液)と浸出残渣(加圧浸出残渣)とに固液分離する固液分離処理を行う(固液分離工程S15)。固液分離工程S15における固液分離処理方法としては、特に限定されないが、例えばシックナー等の固液分離装置を用いて行うことができる。
(中和工程について)
図2の工程図に示すように、常圧浸出工程S12におけるサプロライト鉱石に対する常圧浸出(加圧浸出液を用いた常圧浸出処理)により得られた常圧浸出液は、中和工程S16に移送されて中和処理が施される。なお、中和工程S16における中和処理では、加圧浸出工程S13における加圧浸出により得られた浸出残渣を例えば交流多段洗浄して(残渣洗浄工程S17)回収された洗浄液も併せて処理することができる。
中和工程S16における中和処理により得られた中和終液(母液)は、硫化工程S18に移送されて硫化処理が施される。
硫化工程S18における硫化処理により得られた貧液と、残渣洗浄工程S17にて多段洗浄された浸出残渣(加圧浸出残渣)は、最終中和工程S19に移送されて排出基準を満たす所定のpH範囲に調整する中和処理(無害化処理が)が施される。
容量1000mLの邪魔板付きセパラブルフラスコに、下記表1に示す硫酸濃度の硫酸水、又は、下記表1に示す鉄濃度及び硫酸濃度のHPAL浸出液(加圧浸出により生成した加圧浸出液)を入れ、オイルバスを用いて90℃に加温した。
500mLの邪魔板付きセパラブルフラスコに、下記表3に示す鉄濃度及び遊離硫酸濃度のHPAL浸出液(加圧浸出液)を入れ、オイルバスを用いて90℃に加温した。
下記表4に示す金属品位の常圧浸出残渣と下記表5に示す濃度の常圧浸出液(常圧浸出終液)とからなる浸出スラリー(35重量%)と、表4に示す金属品位の低マグネシウム品位ニッケル酸化鉱石(40重量%スラリー:希釈は水道水)とを、表4及び表5に示す物量(g)、液量(L)で混合させ、そこに、下記表6に示す量の硫酸と水を添加して、濃度が28重量%のスラリーにそれぞれを調整した。
下記表8に示す金属品位を有する、高マグネシウム品位のニッケル酸化鉱石(サプロライト系鉱石)を、下記表9に示す硫酸添加量で、上述した実施例11~13と同様の方法により加圧浸出した。
Claims (1)
- ニッケル酸化鉱石からニッケルやコバルト等の有価金属を回収するニッケル酸化鉱石の湿式製錬方法であって、
前記ニッケル酸化鉱石を、マグネシウム品位が2重量%以下である低マグネシウム品位のリモナイト系鉱石と、マグネシウム品位が2重量%を越える高マグネシウム品位のサプロライト系鉱石とに選別する工程(A)と、
前記工程(A)で得られたサプロライト系鉱石に対して、下記工程(C)における加圧浸出により得られる加圧浸出液に含まれる遊離酸濃度と存在形態が3価であるとして算出した鉄イオン濃度との合計値を該サプロライト系鉱石に含まれるマグネシウム品位で除した値が1.5mol/mol当量以下となるように硫酸濃度を調整した該加圧浸出液を添加して常圧浸出し、常圧浸出液と常圧浸出残渣とを得る工程(B)と、
前記工程(A)で得られたリモナイト系鉱石と、前記工程(B)で得られた常圧浸出残渣とを混合し、高温高圧下の酸性雰囲気で硫酸と反応させることにより加圧浸出し、加圧浸出液を得る工程(C)と
を含むニッケル酸化鉱石の湿式製錬方法。
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EP15883377.2A EP3252177B1 (en) | 2015-02-24 | 2015-12-08 | Wet smelting method for nickel oxide ore |
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