JP2006144102A - Method for recovering nickel and/or cobalt sulfide - Google Patents

Method for recovering nickel and/or cobalt sulfide Download PDF

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JP2006144102A
JP2006144102A JP2004338960A JP2004338960A JP2006144102A JP 2006144102 A JP2006144102 A JP 2006144102A JP 2004338960 A JP2004338960 A JP 2004338960A JP 2004338960 A JP2004338960 A JP 2004338960A JP 2006144102 A JP2006144102 A JP 2006144102A
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sulfide
cobalt
nickel
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alkali
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JP4457864B2 (en
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Chu Kobayashi
宙 小林
Hiroshi Shoji
浩史 庄司
Masaki Imamura
正樹 今村
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Sumitomo Metal Mining Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for recovering sulfide precipitates in which a mole ratio of S/(Ni+Co) is controlled to a value of ≤1.05 equivalent to that of a sulfide formed by using hydrogen sulfide, preferably a value in the vicinity of 1 which is a stoichiometric composition of NiS and CoS, as a method for recovering nickel and/or cobalt sulfide by adding an alkali sulfide to an acidic aqueous solution containing nickel and/or cobalt and precipitating the nickel and/or cobalt sulfide. <P>SOLUTION: In the method for recovering the nickel and/or cobalt sulfide, the inside of a reactor vessel is turned to be under nonoxidizing gas atmosphere and then the alkali sulfide is added to the aqueous solution and the sulfide is formed by precipitation, while maintaining an oxidation-reduction potential (Ag/AgCl electrode standard) at -300 to 100 mV. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、ニッケル及び／又はコバルト硫化物の回収方法に関し、さらに詳しくは、ニッケル及び／又はコバルトを含む酸性水溶液に硫化アルカリを添加して、ニッケル及び／又はコバルト硫化物を沈殿させ回収する方法において、Ｓ／（Ｎｉ＋Ｃｏ）モル比が、硫化水素を用いて生成された硫化物なみの１．０５以下、望ましくはＮｉＳ、ＣｏＳの化学量論組成である１近傍の値に制御された硫化物沈殿の回収方法に関する。   The present invention relates to a method for recovering nickel and / or cobalt sulfide, and more particularly, a method for adding nickel sulfide to an acidic aqueous solution containing nickel and / or cobalt to precipitate and recover nickel and / or cobalt sulfide. In which the S / (Ni + Co) molar ratio is controlled to a value close to 1.05, which is the stoichiometric composition of NiS and CoS, which is 1.05 or less that of a sulfide produced using hydrogen sulfide. The present invention relates to a method for collecting precipitates.

従来、不純物を含む酸性水溶液中に含有される重金属を選択的に沈殿させ回収する方法として、硫化剤を添加して、硫化反応によって該重金属を硫化物として沈殿させる方法が広く用いられている。例えば、硫化剤として硫化水素ガスを用いて、気相中の硫化水素濃度を調整して、重金属の硫化を制御する方法（例えば、特許文献１参照。）、又はニッケル、コバルトを含む酸性水溶液に、硫化剤として硫化アルカリを添加し、温度、ｐＨを調整して、ろ過分離性の良好な硫化物沈殿を得る方法（例えば、特許文献２参照。）等が提案されている。しかしながら、いずれの提案においても、以下に示すように、実用上解決すべき課題を有していた。   Conventionally, as a method for selectively precipitating and recovering heavy metals contained in an acidic aqueous solution containing impurities, a method of adding a sulfurizing agent and precipitating the heavy metals as sulfides by a sulfurization reaction has been widely used. For example, by using hydrogen sulfide gas as a sulfiding agent, adjusting the concentration of hydrogen sulfide in the gas phase to control sulfidation of heavy metals (for example, see Patent Document 1), or an acidic aqueous solution containing nickel and cobalt In addition, a method has been proposed in which alkali sulfide is added as a sulfiding agent and the temperature and pH are adjusted to obtain a sulfide precipitate having good filtration separation (see, for example, Patent Document 2). However, each proposal has a problem to be solved practically as described below.

すなわち、硫化剤として硫化水素を用いる方法では、毒性ガスである硫化水素ガスを直接扱うことから実用面では安全に配慮した細かな反応制御が必要となるとともに、設備面でも制限を受けるという問題がある。また、硫化水素を用いる硫化反応は、下記の式（１）に示すように、反応により酸を発生し、反応液のｐＨを低下させる。   That is, in the method using hydrogen sulfide as a sulfiding agent, since hydrogen sulfide gas, which is a toxic gas, is directly handled, fine reaction control in consideration of safety is necessary in practical use, and there is a problem that it is also limited in terms of equipment. is there. Further, in the sulfurization reaction using hydrogen sulfide, as shown in the following formula (1), an acid is generated by the reaction and the pH of the reaction solution is lowered.

ＭＳＯ４ ＋ Ｈ２Ｓ ＝ ＭＳ ＋Ｈ２ＳＯ４ ………（１）
（式中のＭは、重金属元素、例えばＮｉ、Ｃｏを表す。） MSO 4 + H 2 S = MS + H 2 SO 4 (1)
(M in the formula represents a heavy metal element such as Ni or Co.)

このため、硫化される元素に応じて、特定のｐＨ以下になると硫化物の再溶解が起こり、硫化反応は進まなくなる。したがって、効率良く硫化反応を進めるためには、反応液の元素濃度を特定の濃度以下に調整することによってｐＨの低下を制御するか、または、発生する酸をアルカリの添加によって中和しながら硫化反応を行うことが行なわれる。   For this reason, depending on the element to be sulfided, when the pH is lower than a specific value, re-dissolution of the sulfide occurs and the sulfurization reaction does not proceed. Therefore, in order to advance the sulfidation reaction efficiently, the decrease in pH is controlled by adjusting the element concentration of the reaction solution to a specific concentration or lower, or the generated acid is sulfidized while neutralizing by adding an alkali. The reaction is performed.

一方、硫化剤として硫化アルカリを用いる方法では、硫化アルカリは硫化水素ガスをアルカリ水溶液に吸収固定したものであり化学的に安定であることから、大規模な除害設備を持たずに簡便に使用することができる。また、反応においては、硫化アルカリ自体がアルカリ性であるので、硫化水素を用いた場合と異なり反応液のｐＨの低下が起らず、これに伴なう硫化物の再溶解は起らないという利点を持つ。このように、硫化アルカリによる硫化反応は、取り扱い面で有利なため、簡便な重金属の硫化固定法としては広く用いられている。   On the other hand, in the method using alkali sulfide as a sulfiding agent, alkali sulfide is obtained by absorbing and fixing hydrogen sulfide gas in an alkaline aqueous solution and is chemically stable, so it can be used easily without a large scale detoxification facility. can do. In addition, in the reaction, since the alkali sulfide itself is alkaline, unlike the case of using hydrogen sulfide, the pH of the reaction solution does not decrease, and the sulfide does not re-dissolve accompanying this. have. As described above, the sulfidation reaction with alkali sulfide is advantageous in terms of handling, and is therefore widely used as a simple heavy metal sulfidation fixing method.

ところで、近年、ニッケル酸化鉱石の湿式製錬法として、硫酸を用いた高温加圧酸浸出法（Ｈｉｇｈ Ｐｒｅｓｓｕｒｅ Ａｃｉｄ Ｌｅａｃｈ）が注目されている。この方法は、従来の一般的なニッケル酸化鉱の製錬方法である乾式製錬法と異なり、還元及び乾燥工程等の乾式工程を含まず、一貫した湿式工程からなるので、エネルギー的及びコスト的に有利であるという利点を有している。このような湿式製錬法では、浸出生成液として、ニッケル、コバルトとともに、鉄、マンガン、マグネシウム、クロム、アルミニウム等の不純物元素を含む硫酸水溶液が得られ、必要に応じて、鉄等の不純物元素を浄液工程で除去した後、ニッケル、コバルトを硫化物として分離回収する方法が用いられる。   By the way, in recent years, attention has been paid to a high pressure acid leaching method using sulfuric acid as a wet smelting method of nickel oxide ore. Unlike the conventional dry smelting method, which is a conventional nickel oxide ore smelting method, this method does not include dry processes such as reduction and drying processes, and is a consistent wet process. It has the advantage of being advantageous. In such a hydrometallurgical process, a sulfuric acid aqueous solution containing impurity elements such as iron, manganese, magnesium, chromium, and aluminum together with nickel and cobalt is obtained as a leaching solution, and if necessary, an impurity element such as iron Is removed in the liquid purification step, and then nickel and cobalt are separated and recovered as sulfides.

しかしながら、一般的に、ニッケル及び／又はコバルトを含む硫酸水溶液から硫化アルカリを用いて生成された硫化物沈殿には、そのＳ／（Ｎｉ＋Ｃｏ）モル比が、例えば、１．１〜１．２程度であり、硫化水素を用いて生成された硫化物と比べて高い数値であるとともに、酸化されやすいという問題がある。すなわち、このような硫化物を中間生成物として用いてニッケル及び／又はコバルトを分離回収する工程においては、酸化に伴なう溶液中の硫酸イオンの増加とともに、イオウ含有量の過多によるイオウ処理負荷の増加が大きな問題となる。例えば、前記硫化物沈殿が塩素等の酸化剤を用いて浸出される工程では、浸出生成液へのイオウの溶解の防止が最も重要な浸出要件である。   However, in general, a sulfide precipitate produced from an aqueous sulfuric acid solution containing nickel and / or cobalt using an alkali sulfide has an S / (Ni + Co) molar ratio of, for example, about 1.1 to 1.2. There is a problem that it is a high numerical value compared to a sulfide generated using hydrogen sulfide and is easily oxidized. That is, in the process of separating and recovering nickel and / or cobalt using such a sulfide as an intermediate product, the sulfur treatment load due to excessive sulfur content as well as an increase in sulfate ion in the solution accompanying oxidation. The increase is a big problem. For example, in the process where the sulfide precipitate is leached using an oxidizing agent such as chlorine, prevention of sulfur dissolution in the leaching product is the most important leaching requirement.

以上の状況から、硫化アルカリを用いて生成された硫化物沈殿の性状、特に、そのＳ／（Ｎｉ＋Ｃｏ）モル比を、硫化水素を用いて生成された硫化物なみの１．０５以下、望ましくは１近傍に改善することが望まれている。
特開２００３−３１３６１７号公報（第１頁、第２頁） 特開平６−８１０５０号公報（第１頁、第２頁） From the above situation, the properties of the sulfide precipitate produced using alkali sulfide, in particular, the S / (Ni + Co) molar ratio is 1.05 or less, preferably the same as that of sulfide produced using hydrogen sulfide. Improvement to the vicinity of 1 is desired.
JP 2003-316617 A (first page, second page) Japanese Patent Laid-Open No. 6-81050 (first page, second page)

本発明の目的は、上記の従来技術の問題点に鑑み、ニッケル及び／又はコバルトを含む酸性水溶液に硫化アルカリを添加して、ニッケル及び／又はコバルト硫化物を沈殿させ回収する方法において、Ｓ／（Ｎｉ＋Ｃｏ）モル比が、硫化水素を用いて生成された硫化物なみの１．０５以下、望ましくはＮｉＳ、ＣｏＳの化学量論組成である１近傍の値に制御された硫化物沈殿の回収方法を提供することにある。   In view of the above-mentioned problems of the prior art, an object of the present invention is to add an alkali sulfide to an acidic aqueous solution containing nickel and / or cobalt to precipitate and recover nickel and / or cobalt sulfide. (Ni + Co) Molar ratio is 1.05 or less of that of sulfide produced using hydrogen sulfide, preferably a method for recovering sulfide precipitates controlled to a value close to 1 which is the stoichiometric composition of NiS and CoS. Is to provide.

本発明者らは、上記目的を達成するために、ニッケル及び／又はコバルトを含む酸性水溶液に硫化アルカリを添加して、ニッケル及び／又はコバルト硫化物を沈殿させ回収する方法について、鋭意研究を重ねた結果、硫化アルカリの添加に先だって、反応容器内を特定のガス雰囲気下とするとともに、硫化アルカリを添加して、水溶液の酸化還元電位を特定範囲に保持しながら硫化反応を行なわせたところ、Ｓ／（Ｎｉ＋Ｃｏ）モル比が、硫化水素を用いて生成された硫化物なみの１．０５以下、さらにＮｉＳ、ＣｏＳの化学量論組成である１近傍の値に制御された硫化物沈殿が得られることを見出し、本発明を完成した。   In order to achieve the above object, the present inventors have conducted extensive research on a method for precipitating and recovering nickel and / or cobalt sulfide by adding an alkali sulfide to an acidic aqueous solution containing nickel and / or cobalt. As a result, prior to the addition of the alkali sulfide, the reaction vessel was placed in a specific gas atmosphere, and an alkali sulfide was added to perform a sulfurization reaction while maintaining the oxidation-reduction potential of the aqueous solution in a specific range. S / (Ni + Co) molar ratio is 1.05 or less of that of sulfide produced using hydrogen sulfide, and further, sulfide precipitation is controlled to a value close to 1 which is the stoichiometric composition of NiS and CoS. The present invention has been completed.

すなわち、本発明の第１の発明によれば、ニッケル及び／又はコバルトを含む酸性水溶液に硫化アルカリを添加して、ニッケル及び／又はコバルト硫化物を沈殿させ回収する方法において、
反応容器内を非酸化性ガス雰囲気下とした後、前記水溶液に硫化アルカリを添加し、酸化還元電位（Ａｇ／ＡｇＣｌ電極規準）を−３００〜１００ｍＶに保持しながら硫化物を沈殿生成させることを特徴とするニッケル及び／又はコバルト硫化物の回収方法が提供される。 That is, according to the first invention of the present invention, in the method of adding alkali sulfide to an acidic aqueous solution containing nickel and / or cobalt to precipitate and recover nickel and / or cobalt sulfide,
After making the inside of the reaction vessel under a non-oxidizing gas atmosphere, alkali sulfide is added to the aqueous solution, and the sulfide is precipitated while maintaining the oxidation-reduction potential (Ag / AgCl electrode standard) at −300 to 100 mV. A nickel and / or cobalt sulfide recovery method is provided.

また、本発明の第２の発明によれば、第１の発明において、前記酸化還元電位（Ａｇ／ＡｇＣｌ電極規準）は、−３００〜５０ｍＶであることを特徴とするニッケル及び／又はコバルト硫化物の回収方法が提供される。   According to a second invention of the present invention, in the first invention, the oxidation-reduction potential (Ag / AgCl electrode standard) is −300 to 50 mV, and nickel and / or cobalt sulfide A recovery method is provided.

また、本発明の第３の発明によれば、第１の発明において、前記非酸化性ガスは、中性ガスであることを特徴とするニッケル及び／又はコバルト硫化物の回収方法が提供される。   According to a third aspect of the present invention, there is provided the nickel and / or cobalt sulfide recovery method according to the first aspect, wherein the non-oxidizing gas is a neutral gas. .

また、本発明の第４の発明によれば、第１の発明において、前記硫化アルカリは、硫化ナトリウム又は水硫化ナトリウムであることを特徴とするニッケル及び／又はコバルト硫化物の回収方法が提供される。   According to a fourth aspect of the present invention, there is provided the nickel and / or cobalt sulfide recovery method according to the first aspect, wherein the alkali sulfide is sodium sulfide or sodium hydrosulfide. The

また、本発明の第５の発明によれば、第１の発明において、硫化反応の温度は、７０〜９５℃であることを特徴とするニッケル及び／又はコバルト硫化物の回収方法が提供される。   According to a fifth aspect of the present invention, there is provided the nickel and / or cobalt sulfide recovery method according to the first aspect, wherein the temperature of the sulfurization reaction is 70 to 95 ° C. .

また、本発明の第６の発明によれば、第１〜５いずれかの発明において、硫化アルカリの添加による硫化物の沈殿生成に先だって、前記水溶液中に硫化水素、又は硫化アルカリを添加して、酸化還元電位（Ａｇ／ＡｇＣｌ電極規準）を１００ｍＶ以下に調整することを特徴とするニッケル及び／又はコバルト硫化物の回収方法が提供される。   According to the sixth invention of the present invention, in any one of the first to fifth inventions, hydrogen sulfide or alkali sulfide is added to the aqueous solution prior to the precipitation of sulfide by addition of alkali sulfide. There is provided a method for recovering nickel and / or cobalt sulfide, wherein the oxidation-reduction potential (Ag / AgCl electrode standard) is adjusted to 100 mV or less.

本発明のニッケル及び／又はコバルト硫化物の回収方法は、ニッケル及び／又はコバルトを含む酸性水溶液に硫化アルカリを添加して、ニッケル及び／又はコバルト硫化物を沈殿させ回収する方法において、得られる硫化物沈殿のＳ／（Ｎｉ＋Ｃｏ）モル比を、硫化水素を用いて生成された硫化物なみの１．０５以下、望ましくは１近傍の値に制御することができ、これによって、得られた硫化物沈殿からニッケル及び／又はコバルトを回収する工程において、イオウ含有量の過多によるイオウ処理負荷の増加を防止することができるので、その工業的価値は極めて大きい。   The method for recovering nickel and / or cobalt sulfide according to the present invention is a sulfide obtained by adding an alkali sulfide to an acidic aqueous solution containing nickel and / or cobalt to precipitate and recover nickel and / or cobalt sulfide. The S / (Ni + Co) molar ratio of the product precipitate can be controlled to a value of 1.05 or less, preferably close to 1, that of a sulfide produced using hydrogen sulfide, whereby the obtained sulfide In the process of recovering nickel and / or cobalt from the precipitate, an increase in sulfur treatment load due to an excessive sulfur content can be prevented, so that its industrial value is extremely high.

以下、本発明のニッケル及び／又はコバルト硫化物の回収方法を詳細に説明する。
本発明のニッケル及び／又はコバルト硫化物の回収方法は、ニッケル及び／又はコバルトを含む酸性水溶液に硫化アルカリを添加して、ニッケル及び／又はコバルト硫化物を沈殿させ回収する方法において、反応容器内を非酸化性ガス雰囲気下とした後、水溶液に硫化アルカリを添加し、酸化還元電位（Ａｇ／ＡｇＣｌ電極規準）を−３００〜１００ｍＶに保持しながら硫化物を沈殿させることを特徴とする。 Hereinafter, the nickel and / or cobalt sulfide recovery method of the present invention will be described in detail.
The method for recovering nickel and / or cobalt sulfide according to the present invention comprises adding an alkali sulfide to an acidic aqueous solution containing nickel and / or cobalt to precipitate and recover nickel and / or cobalt sulfide. After placing in a non-oxidizing gas atmosphere, alkali sulfide is added to the aqueous solution, and the sulfide is precipitated while maintaining the oxidation-reduction potential (Ag / AgCl electrode standard) at −300 to 100 mV.

本発明において、硫化アルカリの添加に先立ち、反応容器内を非酸化性ガス雰囲気下とすることと、硫化アルカリの添加後にニッケル及び／又はコバルトを含む酸性水溶液の酸化還元電位（Ａｇ／ＡｇＣｌ電極規準）を−３００〜１００ｍＶに保持することとが重要である。これによって、生成する硫化物沈殿の酸化反応を防止して、Ｓ／（Ｎｉ＋Ｃｏ）モル比が低い、すなわち、硫化水素を用いて生成された硫化物なみの１．０５以下、望ましくはＮｉＳ、ＣｏＳの化学量論組成である１近傍の値に制御された沈殿を得ることができる。   In the present invention, prior to the addition of the alkali sulfide, the inside of the reaction vessel is placed in a non-oxidizing gas atmosphere, and the oxidation-reduction potential of the acidic aqueous solution containing nickel and / or cobalt after the addition of the alkali sulfide (Ag / AgCl electrode standard). ) At −300 to 100 mV is important. This prevents an oxidation reaction of the generated sulfide precipitate, and the S / (Ni + Co) molar ratio is low, that is, 1.05 or less, preferably NiS, CoS, similar to that of sulfide generated using hydrogen sulfide. It is possible to obtain a precipitate controlled to a value in the vicinity of 1 which is the stoichiometric composition.

ここで、反応容器内を非酸化性ガス雰囲気下とすることの作用を明らかにするため、ニッケル及び／又はコバルト硫化物の生成反応と酸化反応によるＳ／（Ｎｉ＋Ｃｏ）モル比の上昇について説明する。なお、Ｓ／（Ｎｉ＋Ｃｏ）モル比とは、例えば、ニッケル、コバルト混合硫化物中の、（Ｎｉ、Ｃｏ）Ｓの形態でのイオウと単体イオウの合計量と、（Ｎｉ＋Ｃｏ）量との比率をモル比で表したものであり、このモル比が高いほどイオウは不安定な形態であるということができる。すなわち、Ｓ／（Ｎｉ＋Ｃｏ）モル比は、硫化物の安定性を測る指標の一つとして用いることができ、この値が大きいほど硫化物として不安定であり酸化され易いということができる。   Here, in order to clarify the effect of making the inside of the reaction vessel in a non-oxidizing gas atmosphere, the increase in the S / (Ni + Co) molar ratio due to the formation reaction of nickel and / or cobalt sulfide and the oxidation reaction will be described. . The S / (Ni + Co) molar ratio is, for example, the ratio between the total amount of sulfur and elemental sulfur in the form of (Ni, Co) S in the nickel and cobalt mixed sulfide and the amount of (Ni + Co). It can be said that the higher the molar ratio, the more unstable the sulfur. That is, the S / (Ni + Co) molar ratio can be used as one of the indices for measuring the stability of sulfides, and it can be said that the larger the value, the more unstable the sulfides and the easier they are oxidized.

一般に、酸性水溶液中のニッケル（コバルトも同様である。）イオンは、下記の式（２）、又は（３）にしたがって、硫化アルカリ（ＮａＨＳ、Ｎａ２Ｓ）との反応によって、粒径の細かな硫化物粒子を生成する。 In general, nickel (cobalt) ions in an acidic aqueous solution are finely divided by reaction with alkali sulfide (NaHS, Na 2 S) according to the following formula (2) or (3). Produce sulphide particles.

Ｎｉ２＋＋ＮａＨＳ ＝ ＮｉＳ＋Ｈ＋＋Ｎａ＋ ………（２） Ni 2+ + NaHS = NiS + H + + Na + (2)

Ｎｉ２＋＋Ｎａ２Ｓ ＝ ＮｉＳ＋２Ｎａ＋ ………（３） Ni 2+ + Na 2 S = NiS + 2Na + (3)

この際、前記酸性水溶液中に酸素が存在すると、下記の式（４）にしたがって、酸化反応による硫化物粒子の再溶解が起こる。   At this time, if oxygen is present in the acidic aqueous solution, re-dissolution of sulfide particles by an oxidation reaction occurs according to the following formula (4).

ＮｉＳ＋２Ｈ＋＋１／２Ｏ２ ＝ Ｎｉ２＋＋Ｓ０＋Ｈ２Ｏ ………（４） NiS + 2H + + 1 / 2O 2 = Ni 2+ + S 0 + H 2 O (4)

ここで、硫化ニッケル（コバルトも同様である。）中のイオウは、単体イオウまで酸化された形で沈殿中に残留するので、ニッケル、コバルト混合硫化物中のＳ／（Ｎｉ＋Ｃｏ）モル比は上昇する。   Here, since sulfur in nickel sulfide (the same applies to cobalt) remains in the precipitate in an oxidized form to elemental sulfur, the S / (Ni + Co) molar ratio in the mixed sulfide of nickel and cobalt increases. To do.

このＳ／（Ｎｉ＋Ｃｏ）モル比の上昇を具体例で説明する。
本発明の方法にしたがって生成したニッケル、コバルト混合硫化物を用いて、酸化反応による硫化物のＳ／（Ｎｉ＋Ｃｏ）モル比を求めた。
まず、硫化反応始液として表１に示すコバルトを含む硫酸ニッケル水溶液を装入した反応容器内の気相部を非酸化性ガスとしてアルゴンガスを用いてガス置換後、常圧で昇温を開始し反応温度の８０℃まで加熱した。なお、反応容器としては、ガス吹込みノズルを装備したものを用いた。 This increase in the S / (Ni + Co) molar ratio will be described with a specific example.
The nickel / cobalt mixed sulfide produced according to the method of the present invention was used to determine the S / (Ni + Co) molar ratio of the sulfide by the oxidation reaction.
First, the gas phase in the reaction vessel charged with the nickel sulfate aqueous solution containing cobalt shown in Table 1 as the sulfurization reaction starting solution was replaced with argon gas as a non-oxidizing gas, and then the temperature was raised at normal pressure. The reaction temperature was heated to 80 ° C. The reaction vessel used was equipped with a gas blowing nozzle.

Figure 2006144102
Figure 2006144102

次いで、水溶液中のニッケルとコバルトの全量をＮｉＳ、ＣｏＳとして硫化する反応当量に等しい水硫化ソーダを添加後、３０分攪拌し、硫化物のスラリーを作成した。得られた硫化物沈殿のＳ／（Ｎｉ＋Ｃｏ）モル比は、１．００であった。   Next, after adding sodium hydrosulfide equivalent to the reaction equivalent of sulfiding the entire amount of nickel and cobalt in the aqueous solution as NiS and CoS, the mixture was stirred for 30 minutes to prepare a sulfide slurry. The S / (Ni + Co) molar ratio of the obtained sulfide precipitate was 1.00.

その後、反応容器のガス吹込みノズルを大気開放にして攪拌だけを行い、反応液の酸化還元電位（ＯＲＰ、常温）と硫化物のＳ／（Ｎｉ＋Ｃｏ）モル比の経時変化を測定した。
結果を図１に示す。図１は、反応液のＯＲＰと硫化物のＳ／（Ｎｉ＋Ｃｏ）モル比の経時変化を示す。なお、図中の横軸、時間３０分に対応するプロットは、水硫化ソーダを添加後、３０分攪拌して得られた酸化反応前の硫化物を示す。
図１より、液のＯＲＰ上昇、すなわち、酸化反応の進展とともに、硫化物のＳ／（Ｎｉ＋Ｃｏ）モル比が１．０から１．２程度まで上昇することが分かる。 Thereafter, the gas blowing nozzle of the reaction vessel was opened to the atmosphere and only stirring was performed, and the change over time in the oxidation-reduction potential (ORP, room temperature) of the reaction solution and the S / (Ni + Co) molar ratio of the sulfide was measured.
The results are shown in FIG. FIG. 1 shows the change over time in the ORP of the reaction solution and the S / (Ni + Co) molar ratio of the sulfide. In addition, the horizontal axis | shaft in a figure and the plot corresponding to time 30 minutes show the sulfide before the oxidation reaction obtained by adding sodium hydrosulfide and stirring for 30 minutes.
FIG. 1 shows that the S / (Ni + Co) molar ratio of sulfide increases from about 1.0 to about 1.2 as the liquid ORP increases, that is, the oxidation reaction progresses.

したがって、Ｓ／（Ｎｉ＋Ｃｏ）モル比の低い硫化物を得るためには、硫化物の酸化の原因となる水溶液中に溶存する酸素を除去することが肝要である。この手段として、反応容器内の気相部を非酸化性ガスで十分に置換することによって水溶液中に溶存する酸素を低減することが有効である。
この際、生成された硫化物の酸化反応が起らないので、添加されたイオウの反応効率も上昇する。すなわち、反応当量以上の余分の硫化アルカリの添加を節減することができるので効率的である。 Therefore, in order to obtain a sulfide having a low S / (Ni + Co) molar ratio, it is important to remove oxygen dissolved in the aqueous solution that causes oxidation of the sulfide. As this means, it is effective to reduce oxygen dissolved in the aqueous solution by sufficiently replacing the gas phase portion in the reaction vessel with a non-oxidizing gas.
At this time, since the oxidation reaction of the generated sulfide does not occur, the reaction efficiency of the added sulfur is also increased. That is, the addition of excess alkali sulfide exceeding the reaction equivalent can be saved, which is efficient.

本発明に用いる非酸化性ガスとしては、特に限定されるものではなく、液中の酸化還元電位を低下することができる窒素、不活性ガス等の中性ガス、及び水素、亜硫酸ガス、硫化水素等の還元性ガスが用いられるが、この中で、特に、取扱上容易な中性ガスが好ましい。   The non-oxidizing gas used in the present invention is not particularly limited. Neutral gases such as nitrogen and inert gas that can lower the oxidation-reduction potential in the liquid, and hydrogen, sulfurous acid gas, and hydrogen sulfide. Of these, a reducing gas such as a neutral gas is particularly preferable.

本発明に用いる非酸化性ガスの装入量は、特に限定されるものではなく、反応容器内の気相部を置換することができる量が用いられるが、硫化反応始液の履歴による液性、使用される反応容器の容量、形状等、非酸化性ガス種等により異なるので、事前の予備試験により、硫化反応において酸化還元電位を所定値に保持することができる適切な量が求められる。ここで、非酸化性ガスの装入量を節減するためには、ガス吹込みノズルを装備し容器内の気相部の雰囲気調整が行なえる密閉様式の反応容器、例えば、加圧雰囲気を形成することができる密閉容器を用いることができる。   The amount of the non-oxidizing gas used in the present invention is not particularly limited, and an amount capable of replacing the gas phase in the reaction vessel is used. Since the volume and shape of the reaction vessel used vary depending on the non-oxidizing gas species and the like, an appropriate amount capable of maintaining the oxidation-reduction potential at a predetermined value in the sulfidation reaction is required by a preliminary test. Here, in order to reduce the amount of non-oxidizing gas charged, a sealed reaction vessel equipped with a gas blowing nozzle and capable of adjusting the atmosphere of the gas phase inside the vessel, for example, a pressurized atmosphere is formed. An airtight container that can be used can be used.

さらに、本発明において、水溶液に硫化アルカリを添加し、酸化還元電位を所定値に保持しながら硫化物を沈殿させることに重要な意義を有する。すなわち、水溶液の酸化還元電位（Ａｇ／ＡｇＣｌ電極規準）は、−３００〜１００ｍＶ、好ましくは−３００〜５０ｍＶに保持する。すなわち、酸化還元電位（Ａｇ／ＡｇＣｌ電極規準）を１００ｍＶ以下に保持することによって、得られる硫化物のＳ／（Ｎｉ＋Ｃｏ）モル比を１．０５以下にすることができる。また、５０ｍＶ以下に保持することで、得られる硫化物のＳ／（Ｎｉ＋Ｃｏ）モル比を１．００近傍にすることができる。一方、酸化還元電位（Ａｇ／ＡｇＣｌ電極規準）を−３００ｍＶ未満で保持しても、硫化物のＳ／（Ｎｉ＋Ｃｏ）モル比に対してこれ以上の効果は見られない。   Furthermore, in the present invention, it is important to add an alkali sulfide to an aqueous solution to precipitate the sulfide while maintaining the oxidation-reduction potential at a predetermined value. That is, the oxidation-reduction potential (Ag / AgCl electrode standard) of the aqueous solution is kept at −300 to 100 mV, preferably −300 to 50 mV. That is, by maintaining the oxidation-reduction potential (Ag / AgCl electrode standard) at 100 mV or less, the S / (Ni + Co) molar ratio of the obtained sulfide can be made 1.05 or less. In addition, by maintaining it at 50 mV or less, the S / (Ni + Co) molar ratio of the obtained sulfide can be made close to 1.00. On the other hand, even if the oxidation-reduction potential (Ag / AgCl electrode standard) is maintained at less than −300 mV, no further effect on the S / (Ni + Co) molar ratio of sulfide is observed.

ここで、硫化アルカリ添加後の水溶液の酸化還元電位と共存する硫化物沈殿のＳ／（Ｎｉ＋Ｃｏ）モル比の関係について、具体例を用いて詳細に説明する。
まず、硫化反応始液として表１に示すコバルトを含む硫酸ニッケル水溶液を装入した反応容器（内容積２Ｌ）内の気相部をアルゴンガス又は硫化水素ガスで置換し、気相中の酸素濃度を種々に調整後（結果的に、水溶液中のＯＲＰも調整される。）、常圧で昇温を開始し反応温度の８０℃まで加熱した。なお、反応容器としては、ガス吹込みノズルを装備したものを用いた。次いで、所定の添加当量（反応当量に対する割合）の硫化アルカリを添加して硫化反応を行なった。反応時間は硫化アルカリ添加後３０分とした。ここで、硫化水素ガスを用いた場合は、水溶液を昇温後、予め０．０１ＭＰａ程度の硫化水素ガスを吹込み、ＯＲＰ調整をした後、硫化アルカリを加えた。 Here, the relationship between the redox potential of the aqueous solution after addition of the alkali sulfide and the S / (Ni + Co) molar ratio of the sulfide precipitate coexisting will be described in detail using a specific example.
First, the gas phase portion in the reaction vessel (internal volume 2 L) charged with the nickel sulfate aqueous solution containing cobalt shown in Table 1 as the sulfurization reaction starting solution was replaced with argon gas or hydrogen sulfide gas, and the oxygen concentration in the gas phase After various adjustments (as a result, ORP in the aqueous solution is also adjusted), the temperature was raised at normal pressure and heated to a reaction temperature of 80 ° C. The reaction vessel used was equipped with a gas blowing nozzle. Next, a predetermined addition equivalent (ratio to the reaction equivalent) of alkali sulfide was added to carry out a sulfurization reaction. The reaction time was 30 minutes after the addition of alkali sulfide. Here, when hydrogen sulfide gas was used, after raising the temperature of the aqueous solution, hydrogen sulfide gas of about 0.01 MPa was blown in advance to adjust the ORP, and then alkali sulfide was added.

その後、硫化反応終了後のスラリーを常温まで冷却しｐＨとＯＲＰを測定した後、ろ過した。得られた沈殿を真空乾燥してニッケル、コバルト及びイオウを分析してＳ／（Ｎｉ＋Ｃｏ）モル比を求めた。結果を図２に示す。図２は、ＯＲＰ（Ａｇ／ＡｇＣｌ電極規準）と硫化物沈殿のＳ／（Ｎｉ＋Ｃｏ）モル比の関係を示す。また、図２には、硫化剤として硫化水素ガスを用いた場合も参考として示した。この際、硫化水素ガスとの反応終了後、反応容器の圧力がゲージで０．１ＭＰａとなるようにガス圧を調整し、硫化水素が過剰になるようにした。   Thereafter, the slurry after completion of the sulfurization reaction was cooled to room temperature, measured for pH and ORP, and then filtered. The resulting precipitate was vacuum dried and analyzed for nickel, cobalt and sulfur to determine the S / (Ni + Co) molar ratio. The results are shown in FIG. FIG. 2 shows the relationship between ORP (Ag / AgCl electrode standard) and S / (Ni + Co) molar ratio of sulfide precipitation. FIG. 2 also shows a case where hydrogen sulfide gas is used as a sulfiding agent for reference. At this time, after completion of the reaction with the hydrogen sulfide gas, the gas pressure was adjusted so that the pressure in the reaction vessel became 0.1 MPa with a gauge so that hydrogen sulfide was excessive.

図２より、液中のＯＲＰ（Ａｇ／ＡｇＣｌ電極規準）が１００ｍＶ以下において、硫化物沈殿のＳ／（Ｎｉ＋Ｃｏ）モル比は１．０５以下に、また、液中のＯＲＰ（Ａｇ／ＡｇＣｌ電極規準）が５０ｍＶ以下において、硫化物沈殿のＳ／（Ｎｉ＋Ｃｏ）モル比が硫化水素ガスによる場合と同様に１．００近傍になることが分かる。   From FIG. 2, when the ORP (Ag / AgCl electrode standard) in the liquid is 100 mV or less, the S / (Ni + Co) molar ratio of the sulfide precipitate is 1.05 or less, and the ORP (Ag / AgCl electrode standard in the liquid). ) Is 50 mV or less, it can be seen that the S / (Ni + Co) molar ratio of the sulfide precipitate is close to 1.00 as in the case of hydrogen sulfide gas.

本発明に用いるニッケル及び／又はコバルトを含む酸性水溶液としては、特に限定されるものではなく、種々の工程から産出されるニッケル及び／又はコバルトを含む硫酸、塩酸、硝酸等の酸性水溶液が挙げられるが、この中で、ニッケル酸化鉱石の湿式製錬法、例えば、硫酸を用いた高温加圧酸浸出法の浸出生成液として産出される、ニッケル、コバルトとともに、鉄、マンガン、マグネシウム、クロム、アルミニウム等の不純物元素を含む硫酸水溶液が好ましく用いられる。   The acidic aqueous solution containing nickel and / or cobalt used in the present invention is not particularly limited, and examples thereof include acidic aqueous solutions such as sulfuric acid, hydrochloric acid and nitric acid containing nickel and / or cobalt produced from various processes. However, among these, nickel, cobalt, and iron, manganese, magnesium, chromium, and aluminum are produced as a leaching product of a nickel oxide ore hydrometallurgical process, for example, a high-temperature pressure acid leaching process using sulfuric acid. An aqueous sulfuric acid solution containing an impurity element such as is preferably used.

本発明に用いる酸性水溶液のｐＨとしては、ニッケルとコバルト沈殿率の上昇のためには、ｐＨが１以上が好ましく、２以上がより好ましい。上記高温加圧酸浸出法から得られる硫酸水溶液のｐＨは１〜４であり、特に浄液（不純物元素を除去）処理後の硫化反応始液のｐＨは３〜４であるので、硫化アルカリを用いる硫化反応が支障なく行なえる。   The pH of the acidic aqueous solution used in the present invention is preferably 1 or more and more preferably 2 or more for increasing the nickel and cobalt precipitation rate. Since the pH of the sulfuric acid aqueous solution obtained from the above high-temperature pressure acid leaching method is 1 to 4, and particularly the pH of the sulfurization reaction starting solution after the purification treatment (removal of impurity elements) is 3 to 4, The sulfurization reaction used can be performed without any problem.

本発明に用いる硫化アルカリとしては、特に限定されるものではないが、市販品として容易に入手される硫化ナトリウム又は水硫化ナトリウムが好ましい。   Although it does not specifically limit as an alkali sulfide used for this invention, Sodium sulfide or sodium hydrosulfide easily obtained as a commercial item is preferable.

本発明に用いる硫化反応の温度は、特に限定されるものではなく、７０〜９５℃が好ましく、８０℃程度の比較的低温度がより好ましい。すなわち、硫化反応自体は一般的に高温ほど促進されるが、７０℃未満では、硫化反応の速度が遅いので反応時間が長くなる。一方、９５℃を超えると、温度を上昇するためにコストがかかること等の経済性の問題点も多い。   The temperature of the sulfurization reaction used in the present invention is not particularly limited, and is preferably 70 to 95 ° C, and more preferably a relatively low temperature of about 80 ° C. That is, the sulfidation reaction itself is generally promoted at higher temperatures, but if it is less than 70 ° C., the reaction time becomes longer because the speed of the sulfidation reaction is slow. On the other hand, when the temperature exceeds 95 ° C., there are many economical problems such as high costs for increasing the temperature.

以下に、本発明の方法の工業的な実施方法の一例を説明する。下記の酸化還元電位の制御は、反応系への空気の進入を遮断する段階、溶液中の酸素も除去する段階、及び硫化反応で沈殿を生成する段階からなる。
（１）まず、反応容器として、加圧雰囲気を形成することができる密閉容器を使用し、ニッケル及び／又はコバルトを含む硫化反応始液を装入後、容器内を非酸化性ガスを用いてガス置換する段階。これによって、溶存酸素の供給を防止し、硫化時の溶存酸素による硫化物の酸化を抑制する。
（２）次に、所定の温度に昇温した後、硫化反応始液に少量の硫化水素、又は硫化アルカリを添加して、酸化還元電位（Ａｇ／ＡｇＣｌ電極規準）を１００ｍＶ以下、望ましくは５０ｍＶ以下まで下げる段階。これによって、非酸化性ガスの置換による酸化還元電位の調整が不十分な場合には、酸化還元電位を所望値に調整することができる。
（３）その後、硫化アルカリを添加し、酸化還元電位（Ａｇ／ＡｇＣｌ電極規準）を１００ｍＶ以下、望ましくは５０ｍＶ以下に保持しながら硫化沈殿反応を行う段階。
以上のように、硫化アルカリの添加による硫化物の沈殿生成に先だって、硫化反応始液に硫化水素、または硫化アルカリを添加して、酸化還元電位を所望値に予備的に調整する段階を含むことができる。 Below, an example of the industrial implementation method of the method of this invention is demonstrated. The control of the oxidation-reduction potential described below consists of a step of blocking air from entering the reaction system, a step of removing oxygen in the solution, and a step of generating a precipitate by a sulfurization reaction.
(1) First, as a reaction vessel, a sealed vessel capable of forming a pressurized atmosphere is used. After charging a sulfurization reaction starting solution containing nickel and / or cobalt, the inside of the vessel is used with a non-oxidizing gas. Gas replacement step. This prevents the supply of dissolved oxygen and suppresses the oxidation of sulfide by dissolved oxygen during sulfidation.
(2) Next, after raising the temperature to a predetermined temperature, a small amount of hydrogen sulfide or alkali sulfide is added to the sulfurization reaction starting solution, and the oxidation-reduction potential (Ag / AgCl electrode standard) is 100 mV or less, preferably 50 mV. Step down to below. As a result, when the redox potential is not sufficiently adjusted by replacing the non-oxidizing gas, the redox potential can be adjusted to a desired value.
(3) Thereafter, an alkali sulfide is added, and a sulfidation precipitation reaction is performed while maintaining the oxidation-reduction potential (Ag / AgCl electrode standard) at 100 mV or less, preferably 50 mV or less.
As described above, prior to the formation of a sulfide precipitate by addition of an alkali sulfide, a step of preliminarily adjusting the oxidation-reduction potential to a desired value by adding hydrogen sulfide or alkali sulfide to the sulfurization reaction starting solution is included. Can do.

また、本発明の硫化アルカリを用いる硫化物沈殿の回収方法は、硫化水素を用いる硫化物沈殿の生成と組合せて用いることができる。例えば、まず、ニッケル及び／又はコバルトを含む酸性水溶液の反応当量の１００％未満の硫化アルカリを用いて硫化反応を行ない、これに引き続いて、硫化水素による硫化物の沈殿生成を行なうこともできる。   Moreover, the method for recovering a sulfide precipitate using the alkali sulfide of the present invention can be used in combination with the generation of a sulfide precipitate using hydrogen sulfide. For example, first, a sulfurization reaction can be performed using an alkali sulfide having a reaction equivalent of less than 100% of an acidic aqueous solution containing nickel and / or cobalt, followed by the formation of a sulfide precipitate by hydrogen sulfide.

以下に、本発明の実施例及び比較例によって本発明をさらに詳細に説明するが、本発明は、これらの実施例によってなんら限定されるものではない。なお、実施例及び比較例で用いた金属の分析方法は、ＩＣＰ発光分析法で行った。   Hereinafter, the present invention will be described in more detail by way of examples and comparative examples of the present invention, but the present invention is not limited to these examples. In addition, the analysis method of the metal used by the Example and the comparative example was performed by the ICP emission analysis method.

（実施例１）
硫化反応始液として表１に示すコバルトを含む硫酸ニッケル水溶液を用いた。また、反応容器としては、ガス吹込みノズルを装備したものを用いた。まず、反応容器（内容積２Ｌ）内に上記硫酸ニッケル水溶液１Ｌを装入した後、反応容器の気相部を予備試験から求められた十分量のアルゴンガスで置換した後、常圧で昇温を開始し反応温度の８０℃まで加熱した。次いで、硫化アルカリとして、反応当量の３３．３％の硫化ナトリウムを添加して硫化反応を行なった。反応時間は硫化アルカリ添加後３０分とした。このときのｐＨとＯＲＰは、硫化アルカリ反応後のスラリーを常温まで冷却し測定した。その後、スラリーを０．４５μｍのメンブレンフィルターで固液分離して得られた沈殿を真空乾燥してニッケル、コバルト及びイオウを分析し、Ｓ／（Ｎｉ＋Ｃｏ）モル比を求めた。結果を表２に示す。 Example 1
A nickel sulfate aqueous solution containing cobalt shown in Table 1 was used as a sulfurization reaction starting solution. As the reaction vessel, a reactor equipped with a gas blowing nozzle was used. First, 1 L of the nickel sulfate aqueous solution was charged into the reaction vessel (internal volume 2 L), the gas phase portion of the reaction vessel was replaced with a sufficient amount of argon gas obtained from a preliminary test, and then the temperature was raised at normal pressure. And was heated to a reaction temperature of 80 ° C. Then, 33.3% sodium sulfide as a reaction equivalent was added as an alkali sulfide to carry out a sulfurization reaction. The reaction time was 30 minutes after the addition of alkali sulfide. The pH and ORP at this time were measured by cooling the slurry after the alkali sulfide reaction to room temperature. Thereafter, the precipitate obtained by solid-liquid separation of the slurry with a 0.45 μm membrane filter was vacuum-dried to analyze nickel, cobalt and sulfur, and the S / (Ni + Co) molar ratio was determined. The results are shown in Table 2.

（実施例２）
硫化アルカリとして、反応当量の６６．７％の硫化ナトリウムを用いた以外は実施例１と同様に行ない、このときのｐＨとＯＲＰを求め、その後、Ｓ／（Ｎｉ＋Ｃｏ）モル比を求めた。結果を表２に示す。 (Example 2)
The same procedure as in Example 1 was carried out except that 66.7% sodium sulfide as the reaction equivalent was used as the alkali sulfide, and the pH and ORP at this time were determined, and then the S / (Ni + Co) molar ratio was determined. The results are shown in Table 2.

（実施例３）
硫化アルカリとして、反応当量の３３．３％の水硫化ナトリウムを用いた以外は実施例１と同様に行ない、このときのｐＨとＯＲＰを求め、その後、Ｓ／（Ｎｉ＋Ｃｏ）モル比を求めた。結果を表２に示す。 (Example 3)
The same procedure as in Example 1 was carried out except that 33.3% sodium hydrosulfide in reaction equivalent was used as the alkali sulfide, and the pH and ORP at this time were determined, and then the S / (Ni + Co) molar ratio was determined. The results are shown in Table 2.

（実施例４）
硫化アルカリとして、反応当量の６６．７％の水硫化ナトリウムを用いた以外は実施例１と同様に行ない、このときのｐＨとＯＲＰを求め、その後、Ｓ／（Ｎｉ＋Ｃｏ）モル比を求めた。結果を表２に示す。 Example 4
The same procedure as in Example 1 was carried out except that 66.7% of sodium hydrosulfide as the reaction equivalent was used as the alkali sulfide. The pH and ORP at this time were determined, and then the S / (Ni + Co) molar ratio was determined. The results are shown in Table 2.

（実施例５）
硫化アルカリとして、反応当量の９０．４％の水硫化ナトリウムを用いた以外は実施例１と同様に行ない、このときのｐＨとＯＲＰを求め、その後、Ｓ／（Ｎｉ＋Ｃｏ）モル比を求めた。結果を表２に示す。 (Example 5)
The same procedure as in Example 1 was performed except that sodium hydrosulfide having a reaction equivalent of 90.4% was used as the alkali sulfide, and the pH and ORP at this time were determined, and then the S / (Ni + Co) molar ratio was determined. The results are shown in Table 2.

（実施例６）
硫化アルカリとして、反応当量の１００％の水硫化ナトリウムを用いた以外は実施例１と同様に行ない、このときのｐＨとＯＲＰを求め、その後、Ｓ／（Ｎｉ＋Ｃｏ）モル比を求めた。結果を表２に示す。 (Example 6)
The same procedure as in Example 1 was carried out except that 100% of the reaction equivalent of sodium hydrosulfide was used as the alkali sulfide. The pH and ORP at this time were determined, and then the S / (Ni + Co) molar ratio was determined. The results are shown in Table 2.

（実施例７）
硫化反応始液として表１に示すコバルトを含む硫酸ニッケル水溶液を用いた。また、反応容器としては、ガス吹込みノズルを装備したものを用いた。まず、反応容器（内容積２Ｌ）内に上記硫酸ニッケル水溶液１Ｌを装入した後、反応容器の気相部を予備試験から得られた十分量のアルゴンガスで置換した後、常圧で昇温を開始し反応温度の８０℃まで加熱した。次に、液中に０．０１ＭＰａ程度の硫化水素ガスを吹込み、ＯＲＰ（Ａｇ／ＡｇＣｌ電極規準）を−２００ｍＶに調整した。次いで硫化アルカリとして、反応当量の３３．３％の水硫化ナトリウムを添加して硫化反応を行なった。反応時間は硫化アルカリ添加後３０分とした。このときのｐＨとＯＲＰは、硫化アルカリ反応後のスラリーを常温まで冷却し測定した。その後、スラリーを０．４５μｍのメンブレンフィルターで固液分離して得られた沈殿を真空乾燥してニッケル、コバルト及びイオウを分析し、Ｓ／（Ｎｉ＋Ｃｏ）モル比を求めた。結果を表２に示す。 (Example 7)
A nickel sulfate aqueous solution containing cobalt shown in Table 1 was used as a sulfurization reaction starting solution. As the reaction vessel, a reactor equipped with a gas blowing nozzle was used. First, 1 L of the nickel sulfate aqueous solution was charged into the reaction vessel (internal volume 2 L), the gas phase portion of the reaction vessel was replaced with a sufficient amount of argon gas obtained from the preliminary test, and then the temperature was raised at normal pressure. And was heated to a reaction temperature of 80 ° C. Next, about 0.01 MPa of hydrogen sulfide gas was blown into the liquid, and the ORP (Ag / AgCl electrode standard) was adjusted to -200 mV. Subsequently, 33.3% of sodium hydrosulfide as a reaction equivalent was added as an alkali sulfide to carry out a sulfurization reaction. The reaction time was 30 minutes after the addition of alkali sulfide. The pH and ORP at this time were measured by cooling the slurry after the alkali sulfide reaction to room temperature. Thereafter, the precipitate obtained by solid-liquid separation of the slurry with a 0.45 μm membrane filter was vacuum-dried to analyze nickel, cobalt and sulfur, and the S / (Ni + Co) molar ratio was determined. The results are shown in Table 2.

（比較例１）
反応容器のガス吹込みノズルを大気開放した状態で行ない、非酸化性ガスでの置換を行なわなかったこと、及び硫化アルカリとして、水硫化ナトリウムを用いたこと以外は実施例１と同様に行ない、このときのｐＨとＯＲＰを求め、その後、Ｓ／（Ｎｉ＋Ｃｏ）モル比を求めた。結果を表２に示す。 (Comparative Example 1)
Performed in the same manner as in Example 1 except that the gas blowing nozzle of the reaction vessel was opened to the atmosphere, the replacement with non-oxidizing gas was not performed, and sodium hydrosulfide was used as the alkali sulfide. The pH and ORP at this time were determined, and then the S / (Ni + Co) molar ratio was determined. The results are shown in Table 2.

Figure 2006144102
Figure 2006144102

表２より、実施例１〜７では、反応容器内のガス置換及び硫化反応の酸化還元電位で、本発明の方法に従って行われたので、１．０５以下の低いＳ／（Ｎｉ＋Ｃｏ）モル比が得られることが分かる。これに対して、比較例１では、反応容器のガス置換及び酸化還元電位がこれらの条件に合わないので、Ｓ／（Ｎｉ＋Ｃｏ）モル比によって満足すべき結果が得られないことが分かる。   From Table 2, in Examples 1-7, since the gas substitution in the reaction vessel and the oxidation-reduction potential of the sulfurization reaction were performed according to the method of the present invention, a low S / (Ni + Co) molar ratio of 1.05 or less was obtained. You can see that On the other hand, in Comparative Example 1, since the gas replacement and oxidation-reduction potential of the reaction vessel do not meet these conditions, it can be seen that satisfactory results cannot be obtained by the S / (Ni + Co) molar ratio.

以上より明らかなように、本発明のニッケル及び／又はコバルト硫化物の回収方法は、ニッケル及び／又はコバルトを含む酸性水溶液、特に、ニッケル酸化鉱の湿式製錬法から得られる硫酸水溶液から、イオウ含有量が低いニッケル、コバルト混合硫化物を効率的に回収する方法として好適である。この硫化物は、ニッケルとコバルトの分離回収用の湿式精錬法の原料として好ましく用いられる。   As is clear from the above, the method for recovering nickel and / or cobalt sulfide of the present invention is based on an acidic aqueous solution containing nickel and / or cobalt, in particular, a sulfuric acid aqueous solution obtained from a hydrometallurgical method of nickel oxide ore. It is suitable as a method for efficiently recovering nickel and cobalt mixed sulfides having a low content. This sulfide is preferably used as a raw material for a wet refining method for separating and recovering nickel and cobalt.

反応液のＯＲＰと硫化物のＳ／（Ｎｉ＋Ｃｏ）モル比の経時変化を表す図である。It is a figure showing the time-dependent change of ORP of a reaction liquid, and S / (Ni + Co) molar ratio of sulfide. ＯＲＰ（Ａｇ／ＡｇＣｌ電極規準）と硫化物沈殿のＳ／（Ｎｉ＋Ｃｏ）モル比の関係を表す図である。It is a figure showing the relationship between ORP (Ag / AgCl electrode standard) and S / (Ni + Co) molar ratio of sulfide precipitation.

Claims (6)

ニッケル及び／又はコバルトを含む酸性水溶液に硫化アルカリを添加して、ニッケル及び／又はコバルト硫化物を沈殿させ回収する方法において、
反応容器内を非酸化性ガス雰囲気下とした後、前記水溶液に硫化アルカリを添加し、酸化還元電位（Ａｇ／ＡｇＣｌ電極規準）を−３００〜１００ｍＶに保持しながら硫化物を沈殿生成させることを特徴とするニッケル及び／又はコバルト硫化物の回収方法。 In a method for adding nickel sulfide and / or cobalt sulfide to an acidic aqueous solution containing nickel and / or cobalt to precipitate and recover nickel and / or cobalt sulfide,
After making the inside of the reaction vessel under a non-oxidizing gas atmosphere, alkali sulfide is added to the aqueous solution, and the sulfide is precipitated while maintaining the oxidation-reduction potential (Ag / AgCl electrode standard) at −300 to 100 mV. A method for recovering nickel and / or cobalt sulfide. 前記酸化還元電位（Ａｇ／ＡｇＣｌ電極規準）は、−３００〜５０ｍＶであることを特徴とする請求項１に記載のニッケル及び／又はコバルト硫化物の回収方法。   2. The method for recovering nickel and / or cobalt sulfide according to claim 1, wherein the oxidation-reduction potential (Ag / AgCl electrode standard) is −300 to 50 mV. 前記非酸化性ガスは、中性ガスであることを特徴とする請求項１に記載のニッケル及び／又はコバルト硫化物の回収方法。   The method for recovering nickel and / or cobalt sulfide according to claim 1, wherein the non-oxidizing gas is a neutral gas. 前記硫化アルカリは、硫化ナトリウム又は水硫化ナトリウムであることを特徴とする請求項１に記載のニッケル及び／又はコバルト硫化物の回収方法。   The method for recovering nickel and / or cobalt sulfide according to claim 1, wherein the alkali sulfide is sodium sulfide or sodium hydrosulfide. 硫化反応の温度は、７０〜９５℃であることを特徴とする請求項１に記載のニッケル及び／又はコバルト硫化物の回収方法。   The method for recovering nickel and / or cobalt sulfide according to claim 1, wherein the temperature of the sulfurization reaction is 70 to 95 ° C. 硫化アルカリの添加による硫化物の沈殿生成に先だって、前記水溶液中に硫化水素、又は硫化アルカリを添加して、酸化還元電位（Ａｇ／ＡｇＣｌ電極規準）を１００ｍＶ以下に調整することを特徴とする請求項１〜５に記載のニッケル及び／又はコバルト硫化物の回収方法。   Prior to precipitation of sulfide by addition of alkali sulfide, hydrogen sulfide or alkali sulfide is added to the aqueous solution to adjust the redox potential (Ag / AgCl electrode standard) to 100 mV or less. Item 6. The method for recovering nickel and / or cobalt sulfide according to Item 1-5.
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