WO2017141693A1 - 中和処理方法、ニッケル酸化鉱石の湿式製錬方法 - Google Patents
中和処理方法、ニッケル酸化鉱石の湿式製錬方法 Download PDFInfo
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- WO2017141693A1 WO2017141693A1 PCT/JP2017/003397 JP2017003397W WO2017141693A1 WO 2017141693 A1 WO2017141693 A1 WO 2017141693A1 JP 2017003397 W JP2017003397 W JP 2017003397W WO 2017141693 A1 WO2017141693 A1 WO 2017141693A1
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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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- 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
- 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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- 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 neutralization treatment method, and more specifically, a neutralization treatment method capable of improving the sedimentation property of the obtained neutralized starch, and a nickel oxide ore to which the neutralization treatment method is applied.
- the present invention relates to a hydrometallurgical method.
- an alkali solution such as calcium carbonate (CaCO 3 ) or slaked lime (Ca (OH) 2
- an acidic solution containing valuable components for recovery and impurity components to be separated.
- the neutralization process which adjusts pH by adding as follows is given, and the process which isolate
- the neutralization process mentioned above is represented by the following reaction.
- Fe 3+ + 3OH ⁇ ⁇ Fe (OH) 3 (i) CaCO 3 + 2H + ⁇ Ca 2+ + H 2 O + CO 2 (ii) Fe 2 (SO 4 ) 3 + 3CaCO 3 + 9H 2 O ⁇ 2Fe (OH) 3 + 3CaSO 4 .2H 2 O + H 2 O (iii)
- the neutralized starch mainly composed of gypsum (CaSO 4 ⁇ 2H 2 O) produced by the neutralization reaction described above is known to have fine particles and high bulk, and poor sedimentation and filterability. .
- the neutralized starch produced by the neutralization reaction is industrially subjected to solid-liquid separation, for example, it is often carried out using a thickener or the like, and after roughly solid-liquid separation with a thickener or the like, In addition, a process of further precisely filtering the liquid using a filter press or the like is generally performed.
- the neutralized starch is bulky and has poor sedimentation and filterability. Therefore, rough treatment with thickener or the like results in insufficient solid-liquid separation, and neutralized starch as floating particles in the supernatant. It may cause an unfavorable situation where things flow in.
- a method for improving the sedimentation characteristics and filterability of such neutralized starch a method of adding a condensing agent or a coagulant, a method of adding seed crystals, a method of increasing the reaction temperature, etc. are known. Yes.
- Patent Document 1 in the neutralization step, by improving the sedimentation characteristics of the neutralized starch, the neutralization equipment is made compact and the filterability is improved and the SS content of the supernatant liquid is reduced.
- a predetermined amount of hematite is added to the liquid to be neutralized, and then neutralization is performed by adding calcium carbonate, calcium hydroxide, etc. to improve the sedimentation characteristics of the neutralized starch to be produced.
- This is a method of reducing the bulk of the Japanese starch.
- the amount of hematite added is 50% or more by weight with respect to the starch produced by neutralization.
- Patent Document 2 discloses a wastewater treatment method for separating and recovering high-density aluminum starch having a high density from acidic wastewater containing aluminum ions discharged in the hydrometallurgy of nickel oxide ore. .
- an acidic wastewater containing aluminum ions is added with a solid containing alkali and iron to form a slurry, and the slurry is left to stand for solid-liquid separation. It is a method of generating.
- the present invention has been proposed in view of such circumstances, and can improve the sedimentation property of the neutralized starch produced by the neutralization treatment and reduce suspended particles in the supernatant after solid-liquid separation. It is an object of the present invention to provide a method that can reduce the filtration load.
- the present inventors have made extensive studies to solve the above-described problems. As a result, a neutralized starch with good sedimentation properties can be obtained by adding a neutralizing agent to the sulfuric acid acidic solution to be treated and adding a specific amount of iron oxide to carry out the neutralization treatment. As a result, the present invention was completed.
- a neutralized slurry is produced by adding a neutralizing agent containing calcium to a sulfuric acid acidic solution to adjust the pH.
- a neutralizing agent containing calcium is added to the sulfuric acid acidic solution.
- the pH of the post-neutralized solution obtained by separating from the neutralized slurry in the first invention is adjusted to be in the range of 3.15 to 3.25.
- the neutralization method is a simple procedure for separating from the neutralized slurry in the first invention.
- the acidic solution is obtained by subjecting the nickel oxide ore to a leaching treatment with sulfuric acid in a wet smelting method of nickel oxide ore.
- the leaching solution is a neutralization treatment method in which a leaching residue generated by the leaching treatment is added as the iron oxide.
- the fourth invention of the present invention is a nickel oxide ore hydrometallurgy method in which nickel oxide ore is leached using sulfuric acid to leach nickel, and nickel is recovered from the obtained leachate.
- a wet smelting method of nickel oxide ore wherein iron oxide in an amount corresponding to 200 wt% to 500 wt% of the amount of the neutralized starch produced is added to the leachate.
- the fifth invention of the present invention is the method for hydrometallizing nickel oxide ore according to the fourth invention, wherein the iron oxide is a leaching residue produced by the leaching treatment.
- generated by a neutralization process can be improved, the suspended particle in the supernatant liquid after solid-liquid separation can be reduced, and the load of the filtration process in a post process is also possible. Can be reduced.
- present embodiments specific embodiments of the present invention (hereinafter referred to as “present embodiments”) will be described in detail.
- the present invention is not limited to the following embodiments and does not change the gist of the present invention.
- Various changes can be made within the range.
- the expression “X to Y” (X and Y are arbitrary numerical values) means “X or more and Y or less” unless otherwise specified.
- Neutralization treatment method >> In the neutralization treatment method according to the present embodiment, a neutralization slurry is generated by adding a neutralizing agent containing calcium to a sulfuric acid acidic solution to adjust the pH, and a neutralized starch and a post-neutralized solution are obtained. It is the neutralization method to isolate
- a neutralizing agent is added to the sulfuric acid acidic solution to be treated, and a specific amount of iron oxide is added for neutralization treatment. Specifically, iron oxide in an amount corresponding to 200% to 500% by weight of the amount of neutralized starch produced is added.
- a sulfuric acid acidic solution containing as an impurity an elemental component that becomes a precipitate by a neutralizing agent containing calcium can be used.
- a leachate obtained by leaching treatment using sulfuric acid in a hydrometallurgical process of nickel oxide ore can be used. The details of the leachate will be described later including the flow of the hydrometallurgical process.
- Examples of the neutralizing agent include calcium, and examples thereof include calcium carbonate (CaCO 3 ) slurry and slaked lime (Ca (OH) 2 ) slurry.
- the pH of the resulting neutralized solution is in the range of 3.0 to 4.0 by adding the above-described neutralizing agent to the sulfuric acid acidic solution. It is preferable that the range be 3.15 to 3.25.
- the neutralizing agent is added to the sulfuric acid acidic solution to be processed, and iron oxide is added.
- the amount of iron oxide added is equivalent to 200% to 500% by weight of the amount of neutralized starch produced by the neutralization treatment.
- Iron oxide acts as a so-called seed crystal of the neutralized starch produced.
- the amount of iron oxide added in the range of 200% to 500% by weight with respect to the neutralized starch to be produced particles of the neutralized starch are grown based on the iron oxide as a seed crystal, Refinement of the neutralized starch can be suppressed. Thereby, the sedimentation property of the neutralized starch can be improved, and the clarity of the supernatant can be increased.
- the added amount of iron oxide is less than 200% by weight with respect to the neutralized starch to be produced, it is not sufficient as an amount for acting as a seed crystal, and the fine amount of gypsum Nuclei are generated, the sedimentation property is deteriorated, and the clarity of the supernatant liquid is deteriorated.
- the amount of iron oxide added exceeds 500% by weight with respect to the neutralized starch to be produced, the seed crystals are excessively present, so that the solid in the solid-liquid separation process The load increases, and on the contrary, the clarity of the supernatant liquid is deteriorated.
- the amount of iron oxide added is preferably an amount corresponding to 250% to 350% by weight of the amount of neutralized starch produced by the neutralization treatment.
- an addition amount preferably, by adding iron oxide in such an addition amount, refinement
- the solid load can be reduced during solid-liquid separation.
- iron oxide Although it does not specifically limit as iron oxide, It is preferable that it is a thing hardly soluble with respect to the sulfuric acid acidic solution which is a process target. Moreover, as this iron oxide, a leaching residue obtained in a leaching step of a nickel oxide ore wet smelting process, which will be described in detail later, can be used. This leaching residue is mainly composed of hematite (Fe 2 O 3 ).
- the neutralizing agent containing calcium is added to the sulfuric acid acidic solution, and it corresponds to 200% to 500% by weight of the amount of the neutralized starch produced. Add the amount of iron oxide to neutralize.
- the neutralization starch which suppressed refinement
- a solution (slurry) containing such a neutralized starch is subjected to solid-liquid separation using a solid-liquid separation device such as thickener, thereby obtaining a supernatant liquid with high clarity (post-neutralized liquid). it can.
- the neutralized starch with good sedimentation is a high-density starch having a low bulk, it is easy to handle the neutralized starch.
- this neutralization treatment method can be applied to the treatment in the neutralization step in the hydrometallurgical process of nickel oxide ore, for example.
- a sulfuric acid acidic solution a leachate obtained by subjecting a raw material nickel oxide ore slurry to a leaching treatment using sulfuric acid under high temperature and high pressure can be used.
- This leachate contains impurity components such as aluminum in addition to valuable metals such as nickel and cobalt.
- HPAL method high temperature pressurization acid leaching method
- FIG. 1 is a process diagram showing an example of the flow of a hydrometallurgical process for nickel oxide ore.
- leaching process S1 is performed in which sulfuric acid is added to a raw material nickel oxide ore slurry and leaching is performed under high temperature and high pressure, and leaching residue is separated from the leaching slurry.
- Leaching step S1 sulfuric acid is added to a nickel oxide ore slurry (ore slurry) using a high-temperature pressure reaction tank such as an autoclave, and the temperature is about 230 ° C. to 270 ° C., and the pressure is about 3 to 5 MPa.
- the leaching slurry consisting of the leaching solution and the leaching residue is generated.
- Nickel oxide ores include so-called laterite ores such as limonite ore and saprolite ore.
- Laterite ore usually has a nickel content of 0.8% to 2.5% by weight and is contained as a hydroxide or siliceous clay (magnesium silicate) mineral.
- the iron content is 10% to 50% by weight and is mainly in the form of trivalent hydroxide (goethite), but partly divalent iron is contained in the siliceous clay.
- oxide ores containing valuable metals such as nickel, cobalt, manganese, and copper, such as manganese nodules existing in the deep sea floor, can be used.
- the leaching process in the leaching step S1 for example, a leaching reaction represented by the following formulas (i) to (v) and a high-temperature thermal hydrolysis reaction occur, leaching as sulfates such as nickel and cobalt, and leached iron sulfate. Is fixed as hematite (Fe 2 O 3 ). However, since the immobilization of iron ions does not proceed completely, the leaching slurry obtained usually contains divalent and trivalent iron ions in addition to nickel, cobalt and the like.
- the pH of the obtained leachate is 0.1 to 1.0 from the viewpoint of the filterability of the leaching residue containing hematite produced in the subsequent solid-liquid separation step S2. It is preferable to adjust.
- the amount of sulfuric acid added to the autoclave charged with the ore slurry is not particularly limited, but an excessive amount such that iron in the ore is leached is used.
- an excessive amount such that iron in the ore is leached is used.
- it is about 300 kg to 400 kg per ton of ore.
- a solid-liquid separation process is performed using a solid-liquid separation apparatus such as a thickener.
- the leaching slurry is first diluted with a cleaning liquid, and then the leaching residue in the leaching slurry is concentrated as a thickener sediment.
- nickel and cobalt adhering to a leaching residue can be reduced according to the dilution degree.
- the recovery rate of nickel and cobalt can be improved by connecting the thickeners having such functions in multiple stages.
- Neutralization process In the neutralization process S3, neutralization containing an impurity component is performed by adding a neutralizing agent such as calcium carbonate (limestone) slurry or calcium hydroxide (slaked lime) slurry to the obtained leachate. A starch and a post-neutralization solution that is a mother liquor for nickel recovery are obtained.
- a neutralizing agent such as calcium carbonate (limestone) slurry or calcium hydroxide (slaked lime) slurry
- a neutralizing agent is added to the leachate so that the pH of the resulting neutralized solution is within a predetermined range, and the neutralized solution serving as a base for the nickel recovery mother liquor, impurities Forms neutralized starch containing aluminum and iron as elements.
- the neutralization step S3 by performing the neutralization treatment (cleaning treatment) on the leachate in this way, the excess acid used in the leaching treatment by the HPAL method is neutralized to produce a neutralized final solution, and a solution Impurities such as aluminum ions and trivalent iron ions remaining therein are removed as neutralized starch.
- the neutralization method mentioned above can be applied to the neutralization process in this neutralization process S3, and refinement
- miniaturization can be suppressed and the neutralized starch which improved the sedimentation property can be produced
- sulfidation step S4 a sulfurized acid solution containing nickel and cobalt is used as a sulfidation reaction start solution, and hydrogen sulfide gas is blown into the sulfidation reaction start solution to cause a sulfidation reaction.
- a small amount of nickel and cobalt sulfide and a poor liquid (post-sulfurized liquid) in which the concentration of nickel and cobalt is stabilized at a low level are generated.
- zinc when zinc is contained in the solution after neutralization, zinc can be selectively separated as sulfide prior to separation of nickel and cobalt as sulfide.
- the sulfidation treatment in the sulfidation step S4 can be performed using a sulfidation reaction tank or the like, and hydrogen sulfide gas is blown into the gas phase portion in the reaction tank with respect to the sulfidation reaction starting liquid introduced into the sulfidation reaction tank.
- a sulfurization reaction is caused by dissolving hydrogen sulfide gas therein.
- the obtained slurry containing nickel and cobalt sulfides is charged into a settling separator such as a thickener and subjected to settling separation, and only the sulfide is separated from the bottom of the thickener. to recover.
- the aqueous solution component overflows from the upper part of the thickener and is recovered as a poor solution.
- recovered poor liquid can also be repeatedly used for solid-liquid separation process S2.
- Final neutralization step S5 the poor pH containing impurity elements such as iron, magnesium and manganese discharged in the sulfurization step S4 described above is within a predetermined pH range that satisfies the discharge standard. Apply neutralization treatment (detoxification treatment) to be adjusted.
- a neutralizing agent such as calcium carbonate (limestone) slurry or calcium hydroxide (slaked lime) slurry is added to a predetermined range. can do.
- the final neutralization residue is generated by the neutralization treatment using such a neutralizing agent and stored in the tailing dam.
- the neutralized solution satisfies the discharge standard and is discharged out of the system.
- Neutralization treatment is performed by adding iron oxide in an amount corresponding to 200% to 500% by weight of the amount of the Japanese starch, thereby generating a neutralized starch in which the impurity components are immobilized and a post-neutralized solution.
- the leaching step S1 was obtained in this way.
- a specific amount of iron oxide together with a neutralizing agent to the leachate and applying a neutralization treatment, it is possible to suppress the refinement of the neutralized starch produced and improve the sedimentation of the neutralized starch. Can be made.
- suspended particles in the supernatant liquid that becomes the post-neutralization liquid can be reduced, and a post-neutralization liquid with high clarity can be obtained.
- the leaching residue generated in the leaching step S1 and separated from the leachate is used as the iron oxide. Therefore, efficient and stable operation can be performed as a whole of the hydrometallurgical process.
- the leaching residue obtained by the leaching process in the leaching step S1 is mainly composed of hematite (Fe 2 O 3 ), and the leaching residue is thickener or the like by the solid-liquid separation process in the solid-liquid separation step S2. It is collected from the bottom part.
- the leachate after separating and removing the leach residue is transferred to a neutralization tank or the like for neutralization, but a neutralizing agent is added to the leachate transferred to the neutralization tank.
- a neutralized starch with good sedimentation can be generated by a simple operation.
- a part of the neutralized starch obtained in the neutralization step S3 can be used repeatedly in the solid-liquid separation step S2.
- the above-described neutralization treatment is also performed. It is also possible to apply a method. Specifically, the neutralizing agent is added to the post-sulfurized liquid that has been transferred to the neutralization tank, and the leaching residue recovered in the solid-liquid separation step S2 is used as a specific ratio as iron oxide. In the same manner, a neutralized starch having good sedimentation properties can be produced by a simple operation.
- Example 1 In the hydrometallurgical process of nickel oxide ore, sulfuric acid was added to the slurry of nickel oxide ore and leaching was performed under high temperature and high pressure. Thereafter, the slurry after the leaching treatment was subjected to a solid-liquid separation treatment to separate the leaching solution and the leaching residue, thereby obtaining a leaching solution containing valuable metals such as nickel.
- the leachate had a liquid temperature of room temperature and a pH of 3.04.
- neutralization was performed using the obtained leachate as an initial solution.
- a calcium carbonate (CaCO 3 ) slurry having a solid amount of 20 wt% to 30 wt% was used.
- iron oxide was added.
- the neutralizing agent was added so that the pH of the post-neutralization solution after the neutralization treatment was 3.21.
- hematite Fe 2 O 3
- the amount of hematite added as iron oxide was an amount corresponding to 274% by weight with respect to the produced neutralized starch.
- generated by the leaching process was used as hematite
- the residence time in the reaction vessel was 0.7 hours to 1.0 hour, and the reaction temperature was maintained at about 55 ° C.
- the resulting neutralized slurry is solid-liquid separated using a thickener, and the turbidity of the supernatant (liquid after neutralization) obtained by separating with the thickener is measured. did. In addition, it measured using the scattered light turbidimeter.
- the turbidity of the supernatant liquid was 24 NTU, and the water area load with respect to the water area of the thickener of the supernatant liquid was 29.3 m 3 / D / m 2 .
- the neutralizing agent was added so that the pH of the post-neutralization solution after the neutralization treatment was 3.22. Other than that, it processed like Example 1.
- the turbidity of the supernatant liquid was 38 NTU, and the water area load with respect to the water area of the thickener of the supernatant liquid was 34.2 m 3 / D / m 2 .
- the turbidity of the supernatant was 83 NTU, and the water area load relative to the water area of the thickener of the supernatant was 32.9 m 3 / D / m 2 .
- the turbidity of the supernatant liquid was 62 NTU, and the water area load relative to the water area of the thickener of the supernatant liquid was 33.5 m 3 / D / m 2 .
- Table 1 summarizes the results of the neutralization treatment performed in the examples and comparative examples.
- Example 1 and Example 2 the neutralization treatment was performed by adding iron oxide corresponding to 200% to 500% by weight to the neutralized starch to be produced.
- a post-neutralization solution having a high degree of clarity of 40 NTU or less was obtained.
- a high density neutralized starch having a high sedimentation rate and a low bulk was obtained.
- Comparative Example 1 and Comparative Example 2 the turbidity of the supernatant obtained in comparison with the Example was high, and the neutralized starch having a slower sedimentation rate than that of the Example and having a high bulk was produced.
Abstract
Description
Fe3++3OH- → Fe(OH)3 ・・・(i)
CaCO3+2H+ → Ca2++H2O+CO2 ・・・(ii)
Fe2(SO4)3+3CaCO3+9H2O →
2Fe(OH)3+3CaSO4・2H2O+H2O ・・・(iii)
本実施の形態に係る中和処理方法は、硫酸酸性溶液にカルシウムを含む中和剤を添加してpHを調整することによって中和スラリーを生成させ、中和澱物と中和後液とに分離する中和処理方法である。
本実施の形態に係る中和処理方法では、上述したように、処理対象として、カルシウムを含む石灰石や消石灰等の中和剤の添加により沈殿物を形成する元素を含む硫酸酸性溶液を用いる。
図1は、ニッケル酸化鉱石の湿式製錬プロセスの流れの一例を示した工程図である。図1に示すように、ニッケル酸化鉱石の湿式製錬プロセスは、原料のニッケル酸化鉱石のスラリーに硫酸を添加して高温高圧下で浸出処理を施す浸出工程S1と、浸出スラリーから浸出残渣を分離してニッケル及びコバルト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不純物元素を中和澱物スラリーとして分離し中和後液を得る中和工程S3と、中和後液に硫化水素ガスを添加することでニッケル及びコバルトの硫化物を生成させる硫化工程(ニッケル回収工程)S4とを有する。さらに、この湿式製錬プロセスは、硫化工程S4にて排出された貧液を回収し、それらを無害化して最終中和残渣を生成する最終中和工程S5を有する。
浸出工程S1では、オートクレーブ等の高温加圧反応槽を用い、ニッケル酸化鉱石のスラリー(鉱石スラリー)に硫酸を添加して、温度230℃~270℃程度、圧力3~5MPa程度の条件下で撹拌し、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で生成した浸出スラリーを洗浄して、ニッケルやコバルト等の有価金属を含む浸出液とヘマタイトを主成分とする浸出残渣とに分離する。
中和工程S3では、得られた浸出液に対して、炭酸カルシウム(石灰石)スラリーや水酸化カルシウム(消石灰)スラリー等の中和剤を添加して、不純物成分を含む中和澱物と、ニッケル回収用母液である中和後液とを得る。
硫化工程S4では、ニッケル及びコバルトを含む硫酸酸性溶液である中和後液を硫化反応始液として、その硫化反応始液に対して硫化水素ガスを吹き込むことによって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の硫化物と、ニッケルやコバルトの濃度を低い水準で安定させた貧液(硫化後液)とを生成させる。
最終中和工程S5では、上述した硫化工程S4にて排出された鉄、マグネシウム、マンガン等の不純物元素を含む貧液に対して、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、中和工程S3での処理、つまりニッケル酸化鉱石のスラリーに硫酸を添加して浸出して得られた、ニッケル等を含む硫酸酸性溶液である浸出液に対する中和処理においては、上述した中和処理方法を適用することができる。
ニッケル酸化鉱石の湿式製錬プロセスにおいて、ニッケル酸化鉱石のスラリーに硫酸を添加して高温高圧下で浸出処理を施した。その後、浸出処理後のスラリーに対して固液分離処理を施すことによって浸出液と浸出残渣とを分離して、ニッケル等の有価金属が含まれる浸出液を得た。なお、その浸出液は、液温が常温で、pH3.04であった。
実施例2では、酸化鉄としてのヘマタイトの添加量を、生成する中和澱物に対して重量比で490%に相当する量とした。なお、中和処理後の中和後液のpHが3.22となるように中和剤を添加した。その以外は、実施例1と同様にして処理した。
比較例1では、中和始液である浸出液として、pHが2.53のものを用いた。そして、その浸出液に中和剤を添加して、pHが3.25となるように調整して中和処理を施した。このとき、酸化鉄としてのヘマタイトを、生成する中和澱物に対して重量比で180%に相当する量を添加した。その以外は、実施例1と同様にして処理した。
比較例2では、酸化鉄としてのヘマタイトの添加量を、生成する中和澱物に対して重量比で1080%に相当する量とした。なお、中和処理後の中和後液のpHが3.23となるように中和剤を添加した。その以外は、実施例1と同様にして処理した。
Claims (5)
- 硫酸酸性溶液にカルシウムを含む中和剤を添加してpHを調整することによって中和スラリーを生成させ、中和澱物と中和後液とに分離する中和処理方法において、
前記硫酸酸性溶液に、生成する中和澱物の量の200重量%~500重量%に相当する量の酸化鉄を添加する
中和処理方法。 - 前記中和スラリーから分離して得られる中和後液のpHが3.15~3.25の範囲となるように調整する
請求項1に記載の中和処理方法。 - 前記硫酸酸性溶液が、ニッケル酸化鉱石の湿式製錬方法において該ニッケル酸化鉱石に対して硫酸により浸出処理を施して得られる浸出液であり、
前記酸化鉄として、前記浸出処理により生成される浸出残渣を添加する
請求項1又は2に記載の中和処理方法。 - ニッケル酸化鉱石に対して硫酸を用いて浸出処理を施してニッケルを浸出させ、得られた浸出液からニッケルを回収するニッケル酸化鉱石の湿式製錬方法において、
前記浸出液に、カルシウムを含む中和剤を添加してpHを調整することによって中和スラリーを生成させ、中和澱物と中和後液とに分離する中和工程を含み、
前記中和工程では、
前記浸出液に、生成する中和澱物の量の200重量%~500重量%に相当する量の酸化鉄を添加する
ニッケル酸化鉱石の湿式製錬方法。 - 前記酸化鉄は、前記浸出処理により生成される浸出残渣である
請求項4に記載のニッケル酸化鉱石の湿式製錬方法。
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JPH02102787A (ja) * | 1988-10-13 | 1990-04-16 | Sumitomo Metal Ind Ltd | 酸洗廃液の処理方法 |
JP2004089918A (ja) * | 2002-09-02 | 2004-03-25 | Sumitomo Metal Mining Co Ltd | 鉄酸化物を用いた溶液中のMg低減方法 |
JP2004225120A (ja) * | 2003-01-23 | 2004-08-12 | Sumitomo Metal Mining Co Ltd | 中和澱物の沈降性改善方法 |
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CA1303815C (en) * | 1987-06-30 | 1992-06-23 | Solex Research Corporation Of Japan | Method for neutralization treatment of sulfuric acid containing iron ions |
DE19812260A1 (de) * | 1998-03-20 | 1999-09-23 | Bayer Ag | Verfahren zur Herstellung von Eisenoxid-Pigmenten aus Dünnsäure aus der TiO¶2¶-Herstellung |
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JPH02102787A (ja) * | 1988-10-13 | 1990-04-16 | Sumitomo Metal Ind Ltd | 酸洗廃液の処理方法 |
JP2004089918A (ja) * | 2002-09-02 | 2004-03-25 | Sumitomo Metal Mining Co Ltd | 鉄酸化物を用いた溶液中のMg低減方法 |
JP2004225120A (ja) * | 2003-01-23 | 2004-08-12 | Sumitomo Metal Mining Co Ltd | 中和澱物の沈降性改善方法 |
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