JP2009173983A - Method for producing sulfide containing nickel and cobalt - Google Patents
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本発明は、ニッケル及びコバルトを含む硫化物の製造方法に関し、さらに詳しくは、加圧された反応容器内に、ニッケル及びコバルトを含む硫酸水溶液を導入し、かつ気相中に硫化水素を含む硫化用ガスを供給することにより、ニッケル及びコバルトを含む硫化物を製造する方法において、反応容器内に供給する硫化ガス中の硫化水素ガス濃度が、定常状態に用いられる９５〜１００容量％からそれ未満の濃度に低下したとき、例えば、硫化水素ガス合成設備の立ち上げ時などの非定常状態に際しても、硫化反応が効率的に行われ、ニッケル及びコバルトの高収率を維持することができる硫化物の製造方法に関する。 The present invention relates to a method for producing a sulfide containing nickel and cobalt. More specifically, the present invention relates to a sulfide containing hydrogen sulfide in a gas phase by introducing a sulfuric acid aqueous solution containing nickel and cobalt into a pressurized reaction vessel. In the method for producing a sulfide containing nickel and cobalt by supplying a working gas, the hydrogen sulfide gas concentration in the sulfide gas supplied into the reaction vessel is 95 to 100% by volume or less used in a steady state Sulfide that can efficiently perform a sulfidation reaction and maintain a high yield of nickel and cobalt even in an unsteady state such as when a hydrogen sulfide gas synthesis facility is started up. It relates to the manufacturing method.
従来、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。ところが、通常、硫化水素を用いた硫化反応においては、その制御が難しいとされ、回収対象となる重金属に応じて適切に硫化反応を制御するためには、酸化還元電位（ＯＲＰ）、ｐＨ等を調整する必要があった。しかしながら、硫化反応が、微細な硫化物殿物を生成させる反応であるため、生成した硫化物が電極等の制御機器の表面を被覆し、ＯＲＰやｐＨの正確な測定が困難となり、さらに、硫化水素ガスを溶液中に吹き込む場合には、生成した硫化物が硫化水素ガスの吹込み配管を閉塞させてしまい、硫化水素ガスの流量制御を安定して行うことも困難であった。 Conventionally, as a method for selectively precipitating and recovering heavy metals contained in an acidic aqueous solution, a method of adding a sulfurizing agent and precipitating the heavy metals as sulfides by a sulfurization reaction has been widely used. However, in the sulfidation reaction using hydrogen sulfide, it is usually difficult to control. In order to appropriately control the sulfidation reaction according to the heavy metal to be recovered, the oxidation-reduction potential (ORP), pH, and the like are set. There was a need to adjust. However, since the sulfurization reaction is a reaction that produces fine sulfide deposits, the generated sulfide coats the surface of control devices such as electrodes, making it difficult to accurately measure ORP and pH. When hydrogen gas is blown into the solution, the generated sulfide clogs the piping for blowing hydrogen sulfide gas, and it is difficult to stably control the flow rate of hydrogen sulfide gas.
この解決策として、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、液中のＯＲＰやｐＨを正確に制御することにより重金属の硫化反応を制御する方法（例えば、特許文献１参照。）、硫化反応の促進と同時に反応容器内面への生成硫化物の付着を抑制するため、硫化物種晶を添加する方法（例えば、特許文献２参照。）等が行われている。 As a solution to this, for example, a method of controlling the sulfurization reaction of heavy metals by adjusting the hydrogen sulfide concentration in the gas phase by using hydrogen sulfide gas as a sulfiding agent and accurately controlling the ORP and pH in the liquid (For example, refer to Patent Document 1), a method of adding a sulfide seed crystal (for example, refer to Patent Document 2) or the like is performed in order to prevent the sulfide from adhering to the inner surface of the reaction vessel at the same time as promoting the sulfurization reaction. It has been broken.
ところで、ニッケル製錬においては、従来、硫化ニッケル鉱を乾式製錬して、ニッケル品位が７０〜８０質量％程度のマットを得て、これを塩素浸出法に供し、次いで電解採取法で電気ニッケルを製造する方法が行われていた。
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こととともに、ニッケル品位が５０質量％程度まで上昇したニッケルとコバルトを含む硫化物（以下、ニッケルコバルト混合硫化物と呼称する場合がある。）を得ることができるという利点を有している。
By the way, in nickel smelting, conventionally, nickel sulfide ore is dry smelted to obtain a mat having a nickel quality of about 70 to 80% by mass, and this is subjected to a chlorine leaching method. The method of manufacturing was performed.
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. And a sulfide containing nickel and cobalt whose nickel quality has been raised to about 50% by mass (hereinafter sometimes referred to as nickel-cobalt mixed sulfide). ing.
前記高温加圧酸浸出法では、例えば、ニッケル酸化鉱石のスラリーに硫酸を添加し、高温高圧下で浸出し、ニッケル及びコバルトを含む浸出液を得る浸出工程、浸出スラリーの固体と液体を分離する工程、ニッケル、コバルトとともに、不純物元素を含む浸出液のｐＨを調整し、鉄等の不純物元素を含む中和澱物スラリーと浄液されたニッケル回収用母液を形成する中和工程、及び該ニッケル回収用母液に硫化水素ガスを供給し、ニッケルコバルト混合硫化物と貧液を形成する硫化工程を含む（例えば、特許文献２参照。）。 In the high-temperature pressurized acid leaching method, for example, sulfuric acid is added to a slurry of nickel oxide ore, and leaching is performed at a high temperature and high pressure to obtain a leachate containing nickel and cobalt, and a step of separating the solid and liquid of the leach slurry The neutralization step of adjusting the pH of the leachate containing impurity elements together with nickel and cobalt, forming a neutralized starch slurry containing impurity elements such as iron and the purified nickel recovery mother liquor, and for recovering the nickel It includes a sulfiding step of supplying hydrogen sulfide gas to the mother liquor and forming a poor solution with the nickel cobalt mixed sulfide (see, for example, Patent Document 2).
前記硫化工程では、前記ニッケル回収用母液を、耐圧性を有する加圧容器からなる反応容器に導入し、さらに反応容器の気相中に、上記プラントに設けられた硫化水素ガスの合成設備から供給される硫化用ガスを吹き込み、液相での硫化水素による硫化反応を制御することにより、生成されるニッケルコバルト混合硫化物を高収率で回収し、かつニッケル及びコバルトが十分に分離除去された貧液を得ることが、工程を経済的に管理する上で重要な技術課題である。なお、前記硫化水素ガスの合成設備から供給される硫化用ガスは、その定常的な運転状態では、その硫化水素濃度が９５〜１００容量％である。 In the sulfiding step, the nickel recovery mother liquor is introduced into a reaction vessel comprising a pressure vessel having pressure resistance, and further supplied from a hydrogen sulfide gas synthesis facility provided in the plant into the gas phase of the reaction vessel. The resulting nickel-cobalt mixed sulfide was recovered in a high yield by controlling the sulfurization reaction by hydrogen sulfide in the liquid phase, and nickel and cobalt were sufficiently separated and removed. Obtaining a poor solution is an important technical issue in managing the process economically. The sulfurizing gas supplied from the hydrogen sulfide gas synthesis facility has a hydrogen sulfide concentration of 95 to 100% by volume in a steady operation state.
このため、硫化工程の操業の定常状態では、硫化水素濃度９５〜１００容量％の硫化用ガスを気相中に吹き込んで反応容器内の圧力を所定値に制御しながら、反応容器中に導入するニッケル回収用母液のニッケル濃度、導入流量、温度、ｐＨ等の操業条件を所定値に管理するとともに、必要により硫化物種晶を添加して運転することにより、９５％以上のニッケル収率が確保されていた。 For this reason, in the steady state of the operation of the sulfiding step, a sulfurizing gas having a hydrogen sulfide concentration of 95 to 100% by volume is blown into the gas phase and introduced into the reaction vessel while controlling the pressure in the reaction vessel to a predetermined value. By controlling the operating conditions such as nickel concentration, introduction flow rate, temperature, pH, etc. of the mother liquor for nickel recovery to predetermined values and operating by adding sulfide seed crystals as necessary, a nickel yield of 95% or more is secured. It was.
しかしながら、例えば、硫化水素ガスの合成設備の定期的な設備保全のための休止から硫化水素ガスの製造を再開するためなど、該合成設備を立ち上げるときのように、硫化用ガスの供給が非定常な状態に際しては、立ち上げ当初は硫化用ガス中の硫化水素濃度は低く、徐々に増加して所望の９５〜１００容量％の範囲に回復する。この硫化水素濃度が低い硫化用ガスを反応容器に供給すると、硫化工程でのニッケル収率が大幅に低下し、それと同時に貧液中のニッケル含有量が増加してしまうという問題があった。例えば、反応容器内に供給する硫化ガス中の硫化水素ガス濃度が、操業の定常状態に用いられる９５〜１００容量％から８５％容量から９５容量％未満の範囲に低下すると、ニッケル収率は、硫化用ガス中の硫化水素ガス濃度の低下割合よりも大幅に低い、７０％程度にまで低下してしまう。
このため、硫化ガス中の硫化水素ガス濃度が、所望の９５〜１００容量％の範囲に回復するまでの間、硫化用ガスとして用いることを停止することが行われるが、このためには、この間に発生した硫化水素ガスを別途に無害化処理することが必要である。この無害化処理の実施においては、苛性ソーダ等の薬品コストが発生するとともに、硫化水素のコストの上昇を来たしていた。
However, for example, when the synthesis equipment is started up, such as when the production of hydrogen sulfide gas is resumed from the suspension for periodic equipment maintenance of the synthesis equipment for hydrogen sulfide gas, the supply of the sulfide gas is not In a steady state, the hydrogen sulfide concentration in the sulfiding gas is low at the beginning of startup, and gradually increases and recovers to a desired range of 95 to 100% by volume. When the sulfurizing gas having a low hydrogen sulfide concentration is supplied to the reaction vessel, the nickel yield in the sulfiding step is greatly reduced, and at the same time, the nickel content in the poor solution is increased. For example, when the concentration of hydrogen sulfide gas in the sulfide gas supplied into the reaction vessel is reduced from 95 to 100% by volume used in the steady state of operation to 85% to less than 95% by volume, the nickel yield is The hydrogen sulfide gas concentration in the sulfurizing gas is reduced to about 70%, which is significantly lower than the rate of decrease in the hydrogen sulfide gas concentration.
For this reason, the hydrogen sulfide gas concentration in the sulfurized gas is stopped from being used as a sulfurizing gas until it is restored to the desired range of 95 to 100% by volume. It is necessary to separately detoxify the hydrogen sulfide gas generated in the process. In carrying out this detoxification treatment, chemical costs such as caustic soda are generated, and the cost of hydrogen sulfide is increased.
以上の状況から、ニッケル及びコバルトを含む硫酸水溶液から、ニッケル及びコバルトを含む硫化物を製造する方法において、反応容器内に供給する硫化ガス中の硫化水素ガス濃度が、操業の定常状態に用いられる９５〜１００容量％から低下したときに、ニッケル及びコバルトの高収率を維持することができる硫化物の製造方法が望まれている。 From the above situation, in the method for producing a sulfide containing nickel and cobalt from a sulfuric acid aqueous solution containing nickel and cobalt, the hydrogen sulfide gas concentration in the sulfide gas supplied into the reaction vessel is used in the steady state of operation. There is a need for a method for producing sulfides that can maintain high yields of nickel and cobalt when reduced from 95-100 volume percent.
本発明の目的は、上記の従来技術の問題点に鑑み、加圧された反応容器内に、ニッケル及びコバルトを含む硫酸水溶液を導入し、かつ気相中に硫化水素を含む硫化用ガスを供給することにより、ニッケル及びコバルトを含む硫化物を製造する方法において、反応容器内に供給する硫化ガス中の硫化水素ガス濃度が、操業の定常状態に用いられる９５〜１００容量％からそれ未満の濃度に低下したとき、例えば、硫化水素ガス合成設備の立ち上げ時などの非定常状態に際しても、硫化反応が効率的に行われ、ニッケル及びコバルトの高収率を維持することができる硫化物の製造方法を提供することにある。 An object of the present invention is to introduce a sulfuric acid aqueous solution containing nickel and cobalt into a pressurized reaction vessel and supply a sulfurizing gas containing hydrogen sulfide in a gas phase in view of the above-mentioned problems of the prior art. Thus, in the method for producing a sulfide containing nickel and cobalt, the hydrogen sulfide gas concentration in the sulfide gas supplied into the reaction vessel is 95 to 100% by volume used in the steady state of operation and less than that. Production of sulfides capable of efficiently performing a sulfidation reaction and maintaining a high yield of nickel and cobalt even in an unsteady state such as when a hydrogen sulfide gas synthesis facility is started up, for example. It is to provide a method.
本発明者らは、上記目的を達成するために、加圧された反応容器内に、ニッケル及びコバルトを含む硫酸水溶液を導入し、かつ気相中に硫化水素を含む硫化用ガスを供給することにより、ニッケル及びコバルトを含む硫化物を製造する方法について、鋭意研究を重ねた結果、該硫化用ガス中の硫化水素ガス濃度が、操業の定常状態に用いられる９５〜１００容量％からそれ未満の濃度に低下した際に、該硫化水素ガス濃度に応じて、反応容器内に、硫酸水溶液にともない導入するニッケル及びコバルト投入量を、定常状態のときの投入量から特定の割合に減少させる操作を採用したところ、該硫化用ガス中の硫化水素ガス濃度の低下にかかわらず、硫化反応が効率的に行われ、ニッケル及びコバルトの高収率を維持することができることを見出し、本発明を完成した。 In order to achieve the above object, the present inventors introduce an aqueous sulfuric acid solution containing nickel and cobalt into a pressurized reaction vessel and supply a sulfurizing gas containing hydrogen sulfide in the gas phase. As a result of intensive research on a method for producing a sulfide containing nickel and cobalt, the hydrogen sulfide gas concentration in the sulfiding gas is less than 95 to 100% by volume used in the steady state of operation. When the concentration is lowered, an operation of reducing the amount of nickel and cobalt introduced into the reaction vessel in accordance with the hydrogen sulfide gas concentration with the sulfuric acid aqueous solution from the amount of the steady state to a specific ratio according to the hydrogen sulfide gas concentration. As a result, it was found that the sulfidation reaction was carried out efficiently and the high yield of nickel and cobalt could be maintained regardless of the decrease in the hydrogen sulfide gas concentration in the sulfiding gas. And, to complete the present invention.
すなわち、本発明の第１の発明によれば、加圧された反応容器内に、ニッケル及びコバルトを含む硫酸水溶液を導入し、かつ気相中に硫化水素を含む硫化用ガスを供給することにより、ニッケル及びコバルトを含む硫化物を製造する方法において、
前記硫化用ガス中の硫化水素ガス濃度が、操業の定常状態に用いられる９５〜１００容量％からそれ未満の濃度に低下した際に、該硫化水素ガス濃度に応じて、下記（１）又は（２）の操作を採用することを特徴とするニッケル及びコバルトを含む硫化物の製造方法が提供される。
（１）前記硫化用ガス中の硫化水素ガス濃度が８５〜９０容量％の場合において、前記反応容器内に、前記硫酸水溶液にともない導入するニッケル及びコバルト投入量を、定常状態のときの投入量に対し質量割合で３０〜３５％に減少させる。
（２）前記硫化用ガス中の硫化水素ガス濃度が９０容量％を超える場合において、前記反応容器内に、前記硫酸水溶液にともない導入するニッケル及びコバルト投入量を、定常状態のときの投入量に対し質量割合で５５〜６０％の割合に減少させる。
That is, according to the first invention of the present invention, by introducing a sulfuric acid aqueous solution containing nickel and cobalt into a pressurized reaction vessel and supplying a sulfurizing gas containing hydrogen sulfide in the gas phase. In a method for producing a sulfide containing nickel and cobalt,
When the hydrogen sulfide gas concentration in the sulfiding gas is reduced from 95 to 100% by volume used in the steady state of operation to a concentration lower than that, the following (1) or ( There is provided a method for producing a sulfide containing nickel and cobalt, which employs the operation of 2).
(1) When the hydrogen sulfide gas concentration in the sulfiding gas is 85 to 90% by volume, the amount of nickel and cobalt introduced into the reaction vessel with the sulfuric acid aqueous solution is the amount introduced in a steady state. The mass ratio is reduced to 30 to 35%.
(2) When the hydrogen sulfide gas concentration in the sulfiding gas exceeds 90% by volume, the amount of nickel and cobalt introduced into the reaction vessel with the sulfuric acid aqueous solution is changed to the amount introduced in a steady state. On the other hand, the mass ratio is reduced to 55 to 60%.
また、本発明の第２の発明によれば、第１の発明において、前記反応容器内に、製造されたニッケル及びコバルトを含む硫化物からなる種晶を、反応容器内に投入するニッケル及びコバルト量に対し１５０〜２００質量％に相当する割合で投入することを特徴とするニッケル及びコバルトを含む硫化物の製造方法が提供される。 According to the second invention of the present invention, in the first invention, nickel and cobalt are charged into the reaction vessel with a seed crystal made of sulfide containing nickel and cobalt produced in the reaction vessel. A method for producing a sulfide containing nickel and cobalt, characterized in that it is charged at a rate corresponding to 150 to 200% by mass with respect to the amount.
また、本発明の第３の発明によれば、第１又は２の発明において、前記反応容器内の圧力は、１００〜３００ｋＰａであることを特徴とするニッケル及びコバルトを含む硫化物の製造方法が提供される。 According to a third aspect of the present invention, there is provided the method for producing a sulfide containing nickel and cobalt according to the first or second aspect, wherein the pressure in the reaction vessel is 100 to 300 kPa. Provided.
また、本発明の第４の発明によれば、第１〜３いずれかの発明において、前記硫酸水溶液は、ニッケル酸化鉱石を高温高圧浸出法により湿式製錬する方法において、浸出及び固液分離工程で、ニッケル酸化鉱石のスラリーに硫酸を添加し、高温高圧下で浸出し、浸出スラリーを多段洗浄しながら、ニッケル及びコバルトとともに不純物元素を含む浸出液を得て、次いで、中和工程で、この浸出液のｐＨを調整し、不純物元素を含む中和澱物スラリーを分離して得られたニッケル回収用母液であり、かつニッケルとコバルトの合計濃度が２〜６ｇ／Ｌであることを特徴とするニッケル及びコバルトを含む硫化物の製造方法が提供される。 According to a fourth invention of the present invention, in any one of the first to third inventions, the aqueous sulfuric acid solution is a leaching and solid-liquid separation step in a method of hydrometallizing nickel oxide ore by a high temperature high pressure leaching method. Then, sulfuric acid is added to the slurry of nickel oxide ore and leached under high temperature and high pressure to obtain a leachate containing impurity elements together with nickel and cobalt while performing multistage cleaning of the leach slurry, and this leachate is then neutralized. The mother liquor for nickel recovery obtained by adjusting the pH of the solution and separating the neutralized starch slurry containing the impurity element, and the total concentration of nickel and cobalt is 2 to 6 g / L And a method for producing a sulfide comprising cobalt.
また、本発明の第５の発明によれば、第１〜４いずれかの発明において、前記硫酸水溶液の温度は、６５〜９０℃であることを特徴とするニッケル及びコバルトを含む硫化物の製造方法が提供される。 According to a fifth invention of the present invention, in any one of the first to fourth inventions, the temperature of the aqueous sulfuric acid solution is 65 to 90 ° C. A method is provided.
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、前記硫酸水溶液のｐＨは、３．０〜３．８であることを特徴とするニッケル及びコバルトを含む硫化物の製造方法が提供される。 According to a sixth aspect of the present invention, in any one of the first to fifth aspects, the sulfuric acid aqueous solution has a pH of 3.0 to 3.8, and is a sulfur containing nickel and cobalt A method of manufacturing an article is provided.
本発明のニッケル及びコバルトを含む硫化物の製造方法は、加圧された反応容器内に、ニッケル及びコバルトを含む硫酸水溶液を導入し、かつ気相中に硫化水素を含む硫化用ガスを供給することにより、ニッケル及びコバルトを含む硫化物を製造する方法において、反応容器内に供給する硫化ガス中の硫化水素ガス濃度が、操業の定常状態に用いられる９５〜１００容量％からそれ未満の濃度に低下したとき、例えば、硫化水素ガス合成設備の立ち上げ時などの非定常状態に際しても、硫化反応が効率的に行われ、ニッケル及びコバルトの高収率を維持することができるので、その工業的価値は極めて大きい。 In the method for producing a sulfide containing nickel and cobalt of the present invention, an aqueous sulfuric acid solution containing nickel and cobalt is introduced into a pressurized reaction vessel, and a sulfurizing gas containing hydrogen sulfide is supplied into the gas phase. Thus, in the method for producing a sulfide containing nickel and cobalt, the concentration of hydrogen sulfide gas in the sulfide gas supplied into the reaction vessel is reduced from 95 to 100% by volume used in the steady state of operation. When it is lowered, for example, in an unsteady state such as when the hydrogen sulfide gas synthesis facility is started up, the sulfidation reaction is efficiently performed, and the high yield of nickel and cobalt can be maintained. The value is extremely great.
以下、本発明のニッケル及びコバルトを含む硫化物の製造方法について、詳細に説明する。
本発明のニッケル及びコバルトを含む硫化物の製造方法は、加圧された反応容器内に、ニッケル及びコバルトを含む硫酸水溶液を導入し、かつ気相中に硫化水素を含む硫化用ガスを供給することにより、ニッケル及びコバルトを含む硫化物を製造する方法において、前記硫化用ガス中の硫化水素ガス濃度が、操業の定常状態に用いられる９５〜１００容量％からそれ未満の濃度に低下した際に、該硫化水素ガス濃度に応じて、下記（１）又は（２）の操作を採用することを特徴とする。
（１）前記硫化用ガス中の硫化水素ガス濃度が８５〜９０容量％の場合において、前記反応容器内に、前記硫酸水溶液にともない導入するニッケル及びコバルト投入量を、定常状態のときの投入量に対し質量割合で３０〜３５％に減少させる。
（２）前記硫化用ガス中の硫化水素ガス濃度が９０容量％を超える場合において、前記反応容器内に、前記硫酸水溶液にともない導入するニッケル及びコバルト投入量を、定常状態のときの投入量に対し質量割合で５５〜６０％の割合に減少させる。
Hereinafter, the manufacturing method of the sulfide containing nickel and cobalt of the present invention will be described in detail.
In the method for producing a sulfide containing nickel and cobalt of the present invention, an aqueous sulfuric acid solution containing nickel and cobalt is introduced into a pressurized reaction vessel, and a sulfurizing gas containing hydrogen sulfide is supplied into the gas phase. Thus, in the method for producing a sulfide containing nickel and cobalt, when the hydrogen sulfide gas concentration in the sulfiding gas is reduced from 95 to 100% by volume used in a steady state of operation to a concentration lower than that. Depending on the hydrogen sulfide gas concentration, the following operation (1) or (2) is employed.
(1) When the hydrogen sulfide gas concentration in the sulfiding gas is 85 to 90% by volume, the amount of nickel and cobalt introduced into the reaction vessel with the sulfuric acid aqueous solution is the amount introduced in a steady state. The mass ratio is reduced to 30 to 35%.
(2) When the hydrogen sulfide gas concentration in the sulfiding gas exceeds 90% by volume, the amount of nickel and cobalt introduced into the reaction vessel with the sulfuric acid aqueous solution is changed to the amount introduced in a steady state. On the other hand, the mass ratio is reduced to 55 to 60%.
本発明において、硫化用ガス中の硫化水素ガス濃度が、操業の定常状態に用いられる濃度から９５容量％未満に低下した際に、硫化用ガス中の硫化水素ガス濃度に応じて、反応容器内に導入するニッケル及びコバルト投入量（以下、投入量と呼称する場合がある。）を、定常状態のときの投入量からその所定の割合に大幅に減少させる操作を行うことが重要である。これによって、反応容器内に供給する硫化ガス中の硫化水素ガス濃度が、操業の定常状態に用いられる９５〜１００容量％からそれ未満の濃度に低下したときにも、硫化反応が効率的に行われ、ニッケル及びコバルトの高収率を維持することができる In the present invention, when the hydrogen sulfide gas concentration in the sulfurizing gas is reduced to less than 95% by volume from the concentration used in the steady state of operation, the reaction vessel contains It is important to carry out an operation for greatly reducing the amount of nickel and cobalt introduced into the reactor (hereinafter sometimes referred to as the amount of introduction) from the amount introduced in the steady state to a predetermined ratio. As a result, even when the concentration of hydrogen sulfide gas in the sulfide gas supplied into the reaction vessel is reduced from 95 to 100% by volume used in the steady state of operation to a concentration lower than that, the sulfurization reaction is efficiently performed. Can maintain high yields of nickel and cobalt
なお、硫化工程の操業の定常状態では、硫化水素濃度９５〜１００容量％の硫化用ガスを気相中に吹き込んで反応容器内の圧力を所定値に制御しながら、反応容器中に導入する硫酸水溶液のニッケル及びコバルト濃度及び導入流量により決められる投入量の他、温度、ｐＨ等の操業条件を所定値に管理するとともに、必要により硫化物種晶を添加して運転することにより、９５％以上のニッケル収率が確保されていた。 In the steady state of the operation of the sulfiding step, sulfuric acid introduced into the reaction vessel while blowing a sulfurizing gas having a hydrogen sulfide concentration of 95 to 100% by volume into the gas phase and controlling the pressure in the reaction vessel to a predetermined value. In addition to the input amount determined by the nickel and cobalt concentrations of the aqueous solution and the introduction flow rate, the operating conditions such as temperature and pH are controlled to predetermined values, and if necessary, the operation is performed by adding sulfide seed crystals. Nickel yield was ensured.
ここで、加圧下で行われる硫化水素を用いた硫化反応において、硫化用ガス中の硫化水素ガス濃度とニッケル収率の関係について説明する。すなわち、加圧された反応容器内に、ニッケル及びコバルトを含む硫酸水溶液を導入し、かつ気相中に硫化水素を含む硫化用ガスを供給することにより、ニッケル及びコバルトを含む硫化物を製造する方法において、反応溶液中に溶存する硫化水素濃度は、気相の硫化水素濃度と平衡し、また反応溶液中酸化還元電位は、溶存する硫化水素濃度と線形の関係があるので、硫化反応は、気相の硫化水素濃度に依存する所定の酸化還元電位のもとで、下記の式（１）にしたがって行われる。 Here, the relationship between the hydrogen sulfide gas concentration in the sulfurizing gas and the nickel yield in the sulfurization reaction using hydrogen sulfide performed under pressure will be described. That is, a sulfide containing nickel and cobalt is produced by introducing a sulfuric acid aqueous solution containing nickel and cobalt into a pressurized reaction vessel and supplying a sulfurizing gas containing hydrogen sulfide in the gas phase. In the method, the concentration of hydrogen sulfide dissolved in the reaction solution is balanced with the concentration of hydrogen sulfide in the gas phase, and the oxidation-reduction potential in the reaction solution is linearly related to the concentration of dissolved hydrogen sulfide. This is performed according to the following equation (1) under a predetermined oxidation-reduction potential that depends on the hydrogen sulfide concentration in the gas phase.
ＭＳＯ４ ＋ Ｈ２Ｓ ＝ ＭＳ ＋Ｈ２ＳＯ４ ………（１）
（式中のＭは、Ｎｉ、Ｃｏを表す。）
MSO 4 + H 2 S = MS + H 2 SO 4 (1)
(M in the formula represents Ni or Co.)
したがって、硫化反応は、ニッケル及びコバルトの硫化反応が十分に進行する酸化還元電位のもとでは、硫化水素の濃度により定量的に行われる。しかしながら、気相の硫化水素濃度が操業の定常状態に用いられる９５〜１００容量％の濃度よりも低いときには、硫酸溶液中に溶存する硫化水素量が少なくなり、しかもそれに依存する酸化還元電位が高めに維持されるため、ニッケル及びコバルトの硫化反応の進行が不十分となる領域となると考えられる。 Therefore, the sulfurization reaction is quantitatively performed based on the concentration of hydrogen sulfide under the oxidation-reduction potential at which the sulfurization reaction of nickel and cobalt sufficiently proceeds. However, when the hydrogen sulfide concentration in the gas phase is lower than the concentration of 95 to 100% by volume used in the steady state of operation, the amount of hydrogen sulfide dissolved in the sulfuric acid solution decreases, and the oxidation-reduction potential depending on it increases. Therefore, it is considered that the progress of the sulfidation reaction of nickel and cobalt is insufficient.
そのための対策として、前記操業条件を、供給する硫化水素ガス濃度の低下に見合うように変更することは容易でない。すなわち、前述のように硫化水素ガスを用いた硫化反応では、反応途上の液中の酸化還元電位及びｐＨを正確に測定することが困難であるからである。この中で、液中の硫化水素の溶存量と酸化還元電位の変化に、迅速かつ定量的に対応するためには、硫化用ガス中の硫化水素ガス濃度に応じて、反応容器内に投入するニッケル及びコバルト量を、定常状態のときの投入量からその所定の割合に減少させることが最も簡便で効果的であった。 As a countermeasure for this, it is not easy to change the operating conditions so as to meet the decrease in the concentration of hydrogen sulfide gas to be supplied. That is, as described above, in the sulfurization reaction using hydrogen sulfide gas, it is difficult to accurately measure the oxidation-reduction potential and pH in the liquid during the reaction. Among these, in order to respond quickly and quantitatively to changes in the dissolved amount of hydrogen sulfide and redox potential in the liquid, it is introduced into the reaction vessel according to the concentration of hydrogen sulfide gas in the sulfiding gas. It was the simplest and most effective to reduce the amount of nickel and cobalt from the amount charged in the steady state to the predetermined ratio.
すなわち、投入量の変更が、硫化用ガス中の硫化水素ガス濃度の低下割合と同じ程度の低下割合では、その効果が不十分であり、ニッケル及びコバルトの高収率が得られない。しかも、硫化用ガス中の硫化水素ガス濃度により液中の硫化反応の進行度合が変わるので、硫化用ガス中の硫化水素ガス濃度に応じて適切な投入量が選ばれる。 That is, when the change in the input amount is the same as the reduction rate of the hydrogen sulfide gas concentration in the sulfurizing gas, the effect is insufficient and a high yield of nickel and cobalt cannot be obtained. In addition, since the progress of the sulfidation reaction in the liquid varies depending on the hydrogen sulfide gas concentration in the sulfidizing gas, an appropriate input amount is selected according to the hydrogen sulfide gas concentration in the sulfiding gas.
例えば、硫化用ガス中の硫化水素ガス濃度が８５〜９０容量％の場合においては、反応容器内に導入するニッケル及びコバルト投入量としては、定常状態のときの投入量に対し質量割合で３０〜３５％に減少させる操作を採用する。すなわち、投入量の割合が定常状態のときの投入量に対し質量割合で３５％を超えると、ニッケル及びコバルト収率が９５％未満となる。一方、投入量の割合が定常状態のときの投入量に対し質量割合で３０％未満では、ニッケル及びコバルト収率は向上するが、生産効率が低下する。 For example, when the hydrogen sulfide gas concentration in the sulfurizing gas is 85 to 90% by volume, the amount of nickel and cobalt introduced into the reaction vessel is 30 to 30% by mass with respect to the amount charged in the steady state. Adopt the operation to reduce to 35%. That is, when the ratio of the input amount exceeds 35% by mass ratio with respect to the input amount in the steady state, the yields of nickel and cobalt are less than 95%. On the other hand, if the proportion of the input amount is less than 30% by mass with respect to the input amount in the steady state, the yield of nickel and cobalt is improved, but the production efficiency is lowered.
また、硫化用ガス中の硫化水素ガス濃度が９５容量％未満で９０容量％を超える値の場合においては、反応容器内に導入するニッケル及びコバルト投入量としては、定常状態のときの投入量に対し質量割合で５５〜６０％に減少させる操作を採用する。すなわち、投入量の割合が定常状態のときの投入量に対し質量割合で６０％を超えると、ニッケル及びコバルト収率が９５％未満となる。一方、投入量の割合が定常状態のときの投入量に対し質量割合で５５％未満では、ニッケル及びコバルト収率は向上するが、生産効率が低下する。 In addition, when the hydrogen sulfide gas concentration in the sulfurizing gas is less than 95% by volume and more than 90% by volume, the amount of nickel and cobalt introduced into the reaction vessel is set to a steady state input amount. On the other hand, an operation of reducing the mass ratio to 55 to 60% is adopted. That is, when the proportion of the input amount exceeds 60% by mass ratio with respect to the input amount in the steady state, the yield of nickel and cobalt becomes less than 95%. On the other hand, if the proportion of the input amount is less than 55% by mass relative to the input amount in the steady state, the yield of nickel and cobalt is improved, but the production efficiency is lowered.
したがって、例えば、硫化水素ガスの合成設備の定期的な設備保全のための休止から硫化水素ガスの製造を再開するためなど、該合成設備を立ち上げるときには、生成される硫化用ガス中の硫化水素濃度が上昇し、８５容量％以上の濃度に達したときに、硫化反応工程に供給を開始することが好ましい。その後、生成される硫化用ガス中の硫化水素濃度が９５〜１００容量％の範囲に回復するまでの間は、上記（１）又は（２）の操作を採用して、反応容器内に投入するニッケル及びコバルト量を調整して操業することにより、９５％以上のニッケル及びコバルトの高収率を得ることができる。なお、硫化用ガス中の硫化水素濃度が８５容量％に達するまでは、生成される硫化用ガスは無害化処理に供される。 Therefore, when the synthesis equipment is started up, for example, in order to restart the production of hydrogen sulfide gas from the suspension for periodic equipment maintenance of the hydrogen sulfide gas synthesis equipment, hydrogen sulfide in the generated sulfurizing gas is used. When the concentration increases and reaches a concentration of 85% by volume or more, it is preferable to start supplying to the sulfurization reaction step. Thereafter, until the hydrogen sulfide concentration in the generated sulfurizing gas is restored to the range of 95 to 100% by volume, the operation of (1) or (2) above is adopted and put into the reaction vessel. By operating by adjusting the amounts of nickel and cobalt, a high yield of nickel and cobalt of 95% or more can be obtained. In addition, until the hydrogen sulfide concentration in the sulfiding gas reaches 85% by volume, the generated sulfiding gas is subjected to a detoxification process.
上記製造方法に用いるニッケル及びコバルトを含む硫酸水溶液としては、特に限定されるものではなく、種々のものが用いられるが、この中で、ニッケル酸化鉱石を高温高圧浸出法により湿式製錬する方法で得られたニッケル回収用母液が好ましく用いられる。すなわち、本発明の方法は、前記高温加圧酸浸出法によりニッケル酸化鉱石を湿式製錬する方法において、その硫化工程でのニッケル及びコバルトを含む硫化物の製造方法として、好ましく適用される。 The sulfuric acid aqueous solution containing nickel and cobalt used in the above production method is not particularly limited, and various types are used. Among them, a nickel oxide ore is hydrometallized by a high-temperature high-pressure leaching method. The obtained nickel recovery mother liquor is preferably used. That is, the method of the present invention is preferably applied as a method for producing a sulfide containing nickel and cobalt in the sulfiding step in the method of hydrometallizing nickel oxide ore by the high-temperature pressure acid leaching method.
前記高温加圧酸浸出法によりニッケル酸化鉱石を湿式製錬する方法としては、特に限定されるものではないが、例えば、図１に表す工程フローにより行われる。図１は、高温加圧酸浸出法によるニッケル酸化鉱石の湿式製錬方法の実施態様の一例を表す工程図である。
図１において、ニッケル酸化鉱石５は、最初に、浸出工程１で、硫酸を用いた高温加圧浸出に付され、浸出スラリー６が形成される。次いで、浸出スラリー６は、固液分離工程２に付され、多段洗浄された後ニッケル及びコバルトを含む浸出液７と浸出残渣８に分離される。浸出液７は、中和工程３に付され、３価の鉄水酸化物を含む中和澱物スラリー９とニッケル回収用母液１０が形成される。最後に、ニッケル回収用母液１０は、硫化工程４に付され、ニッケル及びコバルトを含む硫化物１１とニッケル等が除去された貧液１２に分離される。
Although it does not specifically limit as a method of hydrometallizing nickel oxide ore by the said high temperature pressurization acid leaching method, For example, it is performed by the process flow shown in FIG. FIG. 1 is a process diagram showing an example of an embodiment of a method for hydrometallizing nickel oxide ore by a high-temperature pressure acid leaching method.
In FIG. 1,
前記ニッケル回収用母液としては、例えば、前記ニッケル酸化鉱石を高温高圧浸出法により湿式製錬する方法において、浸出及び固液分離工程で、ニッケル酸化鉱石のスラリーに硫酸を添加し、高温高圧下で浸出し、浸出スラリーを多段洗浄しながら、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浸出液を得て、次いで、中和工程で、この浸出液のｐＨを調整し、鉄等の不純物元素を含む中和澱物スラリーを分離して得られるものである。なお、上記ニッケル回収用母液中に、ニッケル及びコバルトを含む硫化物からニッケル及びコバルトを回収する工程において技術的問題を誘発する量の亜鉛を含有する場合には、ニッケル及びコバルトを含む硫化物を分離する前に、亜鉛硫化物を分離する硫化工程を別途設けることができる。
また、前記ニッケル回収用母液のニッケルとコバルトの合計濃度としては、特に限定されるものではないが、通常２〜６ｇ／Ｌである。ここで、ニッケル濃度としては、２〜５ｇ／Ｌ、コバルト濃度としては、０．１〜０．６ｇ／Ｌである。
As the mother liquor for nickel recovery, for example, in a method of hydrometallizing the nickel oxide ore by a high temperature high pressure leaching method, sulfuric acid is added to the nickel oxide ore slurry in the leaching and solid-liquid separation step, While leaching and leaching slurry are washed in multiple stages, a leachate containing impurity elements such as iron, manganese, magnesium, chromium and aluminum is obtained together with nickel and cobalt, and then the pH of the leachate is adjusted in the neutralization step. And a neutralized starch slurry containing an impurity element such as iron. In the case where the nickel recovery mother liquor contains zinc in an amount that induces technical problems in the step of recovering nickel and cobalt from the sulfide containing nickel and cobalt, the sulfide containing nickel and cobalt is added. Prior to the separation, a sulfurization step for separating the zinc sulfide can be separately provided.
The total concentration of nickel and cobalt in the mother liquor for nickel recovery is not particularly limited, but is usually 2 to 6 g / L. Here, the nickel concentration is 2 to 5 g / L, and the cobalt concentration is 0.1 to 0.6 g / L.
上記製造方法に用いる硫化用ガスとしては、高温加圧酸浸出法の実用プラントにおいて、該プラントに設けられた硫化水素ガスの合成設備から供給される硫化用ガスであり、該硫化用ガス中の硫化水素ガス濃度は、操業の定常状態においては９５〜１００容量％である。しかしながら、硫化用ガス中の硫化水素ガス濃度は、前記合成設備を立ち上げるときのように、硫化用ガスの供給が非定常な状態では、立ち上げ当初は硫化用ガス中の硫化水素濃度は低く、徐々に増加して所望の９５〜１００容量％の範囲に到達するものである。 The sulfurizing gas used in the above production method is a sulfurizing gas supplied from a hydrogen sulfide gas synthesis facility provided in the plant in a high-temperature pressurized acid leaching practical plant. The hydrogen sulfide gas concentration is 95 to 100% by volume in the steady state of operation. However, the hydrogen sulfide gas concentration in the sulfiding gas is low when the supply of the sulfiding gas is unsteady as in the case of starting up the synthesis facility. , Gradually increasing to reach the desired 95-100 volume% range.
上記製造方法において、反応容器内に投入するニッケル及びコバルト量の調整方法としては、硫化用ガス中の硫化水素ガス濃度に応じて、上記ニッケル及び／又はコバル硫酸水溶液の導入流量を絞ることにより行うことが最も簡便である。 In the above production method, the amount of nickel and cobalt introduced into the reaction vessel is adjusted by reducing the flow rate of the nickel and / or koval sulfuric acid aqueous solution according to the hydrogen sulfide gas concentration in the sulfurizing gas. Is the simplest.
上記製造方法において、必要に応じて、製造されたニッケル及びコバルトを含む硫化物からなる種晶を、反応容器内へ投入することができる。ここで、種晶の割合としては、特に限定されるものではないが、反応容器内に投入するニッケル及びコバルト量に対し１５０〜２００質量％に相当する量が好ましい。これによって、より低温度で硫化反応を促進させ、同時に反応容器内面への生成硫化物の付着を抑制することができる。すなわち、硫化物の核生成を種晶表面で起こさせ析出が起こりやすい状態とすることと、それにより硫化物の微細核が容器内部で発生するのを抑制することができることに起因している。また、種晶の粒径を調整することにより得られる粒子径を制御することができる。 In the above production method, if necessary, seed crystals made of sulfide containing nickel and cobalt can be introduced into the reaction vessel. Here, the ratio of the seed crystal is not particularly limited, but an amount corresponding to 150 to 200% by mass with respect to the amount of nickel and cobalt charged into the reaction vessel is preferable. As a result, the sulfidation reaction can be promoted at a lower temperature, and at the same time, the produced sulfide can be prevented from adhering to the inner surface of the reaction vessel. That is, it is caused by the fact that sulfide nucleation is caused to occur on the surface of the seed crystal and precipitation is likely to occur, and that it is possible to suppress the generation of sulfide fine nuclei inside the container. Moreover, the particle diameter obtained by adjusting the particle diameter of the seed crystal can be controlled.
上記製造方法に用いる反応容器内の圧力としては、特に限定されるものではないが、ニッケル及びコバルトの硫化反応を進行させるため、１００〜３００ｋＰａであることが好ましい。なお、硫化反応容器としては、多段に連結して用いることが効率的であり、その場合には、第１段を２５０〜３００ｋＰａとし、徐々に圧力を降下させ、最終段では１００〜１５０ｋＰａとすることが好ましい。これによって、硫化水素ガスが効率的に硫化反応に用いられる。 Although it does not specifically limit as a pressure in the reaction container used for the said manufacturing method, In order to advance the sulfurization reaction of nickel and cobalt, it is preferable that it is 100-300 kPa. In addition, as a sulfurization reaction vessel, it is efficient to use it connected in multiple stages. In that case, the first stage is 250 to 300 kPa, the pressure is gradually reduced, and the final stage is 100 to 150 kPa. It is preferable. Thereby, hydrogen sulfide gas is efficiently used for the sulfurization reaction.
上記製造方法に用いる硫酸水溶液のｐＨは、特に限定されるものではないが、硫化反応を進行させるため、３．０〜３．８であることが好ましい。すなわち、硫酸水溶液のｐＨが３．０未満では、前段の中和工程で鉄、アルミニウム等を十分に除去できない。一方、硫酸水溶液のｐＨが３．８を超えると、ニッケルやコバルトの水酸化物の生成が懸念される。 The pH of the aqueous sulfuric acid solution used in the above production method is not particularly limited, but is preferably 3.0 to 3.8 in order to promote the sulfurization reaction. That is, when the pH of the sulfuric acid aqueous solution is less than 3.0, iron, aluminum and the like cannot be sufficiently removed in the previous neutralization step. On the other hand, when the pH of the sulfuric acid aqueous solution exceeds 3.8, there is a concern about the formation of nickel or cobalt hydroxide.
上記製造方法に用いる硫酸水溶液の温度は、特に限定されるものではないが、６５〜９０℃であることが好ましい。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、９０℃を超えると、温度を上昇するためにコストがかかること、反応速度が速いため反応容器への硫化物の付着起こること等の問題点も多い。 Although the temperature of the sulfuric acid aqueous solution used for the said manufacturing method is not specifically limited, It is preferable that it is 65-90 degreeC. That is, the sulfurization reaction itself is generally promoted at a higher temperature. However, when the temperature exceeds 90 ° C., the temperature increases, and the reaction rate is high, so that the sulfide is attached to the reaction vessel. There are many problems.
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、また、硫化水素ガス濃度分析方法は、ＵＶタイプの測定器で行った。 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. The metal analysis method used in Examples and Comparative Examples was ICP emission analysis, and the hydrogen sulfide gas concentration analysis method was performed using a UV type measuring instrument.
（実施例１、２、３、比較例１〜５）
ニッケル酸化鉱の高温加圧酸浸出法プラントから産出された、ニッケル濃度４．０ｇ／Ｌ及びコバルト濃度０．３ｇ／Ｌの組成を有し、ｐＨが３．３で、液温度が６５℃のニッケル回収用母液を用いて、並流式の硫化反応槽（４段）のそれぞれが所定の圧力になるように硫化水素を含む硫化用ガスを気相部に挿入して、ニッケルコバルト混合硫化物を製造した。また、硫化反応槽の第４段から回収されたニッケルコバルト混合硫化物を、種晶として硫化反応槽の第１段へ繰り返した。ここで、種晶の量は、ニッケル回収用母液により反応容器内に投入するニッケル及びコバルト量に対し１８０質量％に相当する量であった。また、硫化反応槽の内圧としては、第１段が２７０ｋＰａ、第２段が２２０ｋＰａ、第３段が１８０ｋＰａ及び第４段が１５０ｋＰａであった。また、硫化反応槽の気−液界面の面積としては、４段合計で２０〜３０ｍ２であった。
(Examples 1, 2, 3, Comparative Examples 1-5)
Produced from a high-temperature pressure acid leaching process plant for nickel oxide ore and having a nickel concentration of 4.0 g / L and a cobalt concentration of 0.3 g / L, a pH of 3.3 and a liquid temperature of 65 ° C. Using nickel recovery mother liquor, a sulfiding gas containing hydrogen sulfide is inserted into the gas phase so that each of the cocurrent sulfiding reaction tanks (four stages) has a predetermined pressure, and nickel cobalt mixed sulfide Manufactured. Further, the nickel cobalt mixed sulfide recovered from the fourth stage of the sulfurization reactor was repeated as a seed crystal to the first stage of the sulfurization reactor. Here, the amount of the seed crystal was an amount corresponding to 180% by mass with respect to the amount of nickel and cobalt charged into the reaction vessel by the mother liquor for nickel recovery. The internal pressure of the sulfurization reactor was 270 kPa for the first stage, 220 kPa for the second stage, 180 kPa for the third stage, and 150 kPa for the fourth stage. In addition, the area of the gas-liquid interface of the sulfurization reactor was 20 to 30 m 2 in total for the four stages.
このときの操業の定常状態では、硫化用ガスの硫化水素ガス濃度としては、９５〜１００容量％、及びニッケル回収用母液の導入流量としては、３７５ｍ３／ｈであり、ニッケルの投入量としては１５００ｋｇ／ｈである操業条件で行われ、ニッケル収率は９７％が得られた。 In the steady state of the operation at this time, the hydrogen sulfide gas concentration of the sulfurizing gas is 95 to 100% by volume, the introduction flow rate of the nickel recovery mother liquor is 375 m 3 / h, and the input amount of nickel is A nickel yield of 97% was obtained under an operating condition of 1500 kg / h.
続いて、硫化用ガスの供給が非定常な状態を想定して、硫化水素ガス濃度が８５〜９０容量％の範囲の値の場合において、ニッケル回収用母液の導入流量を変えてニッケルの投入量を、上記操業の定常状態のニッケルの投入量（１５００ｋｇ／ｈ）に対し質量割合で３３％（実施例１）、４６％（比較例１）、６０％（比較例２）、又は７３％（比較例３）としたときのニッケル収率を求めた。結果を表１に示す。 Subsequently, assuming that the supply of the sulfurizing gas is in an unsteady state, when the hydrogen sulfide gas concentration is in the range of 85 to 90% by volume, the amount of nickel input is changed by changing the flow rate of the nickel recovery mother liquor. Is 33% (Example 1), 46% (Comparative Example 1), 60% (Comparative Example 2), or 73% (by weight) with respect to the amount of nickel input (1500 kg / h) in the steady state of the above operation. The nickel yield was determined as Comparative Example 3). The results are shown in Table 1.
また、硫化水素ガス濃度が９５容量％未満で９０容量％を超える値の場合において、ニッケル回収用母液の導入流量を変えてニッケルの投入量を、上記操業の定常状態のニッケルの投入量（１５００ｋｇ／ｈ）に対し質量割合で５５％（実施例２）、６０％（実施例３）、７３％（比較例４）、又は８６％（比較例５）としたときのニッケル収率を求めた。結果を表１に示す。
なお、ニッケル収率は、そのときのニッケルの投入量に対して硫化物として回収されたニッケルの割合で表す。
In addition, when the hydrogen sulfide gas concentration is less than 95% by volume and more than 90% by volume, the amount of nickel introduced is changed by changing the flow rate of the nickel recovery mother liquor, and the amount of nickel introduced in the steady state of operation (1500 kg). / H), the nickel yield was determined when the mass ratio was 55% (Example 2), 60% (Example 3), 73% (Comparative Example 4), or 86% (Comparative Example 5). . The results are shown in Table 1.
The nickel yield is expressed as the ratio of nickel recovered as sulfide to the amount of nickel input at that time.
表１より、実施例１〜３では、硫化用ガスの硫化水素ガス濃度供給が９５％未満に低下した際に、ニッケルの投入量を、操業の定常状態のニッケルの投入量に対し所定の割合に減少させることにより本発明の方法に従って行われたので、高いニッケル収率が得られることが分かる。
これに対して、比較例１〜５では、ニッケルの投入量の割合がこれらの条件に合わないので、ニッケル収率が低いこと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 1, in Examples 1 to 3, when the hydrogen sulfide gas concentration supply of the sulfurizing gas was reduced to less than 95%, the amount of nickel input was a predetermined ratio with respect to the amount of nickel input in a steady state of operation. It can be seen that a high nickel yield can be obtained because the process was carried out according to the method of the present invention by reducing the amount.
On the other hand, in Comparative Examples 1-5, since the ratio of the input amount of nickel does not meet these conditions, it can be seen that satisfactory results cannot be obtained due to the low nickel yield.
以上より明らかなように、本発明のニッケル及びコバルトを含む硫化物の製造方法は、加圧された反応容器内に、ニッケル及びコバルトを含む硫酸水溶液を導入し、かつ気相中に硫化水素を含む硫化用ガスを供給することにより、ニッケル及びコバルトを含む硫化物を製造する方法において、前記硫化用ガス中の硫化水素ガス濃度が、操業の定常状態に用いられる９５〜１００容量％からそれ未満の濃度に低下した際に、ニッケル及びコバルトの高収率を維持する方法として好適である。特に、例えば、硫化水素ガス合成設備の立ち上げ時などの非定常状態に際して、有効に活用することができる。 As apparent from the above, the method for producing a sulfide containing nickel and cobalt according to the present invention introduces an aqueous sulfuric acid solution containing nickel and cobalt into a pressurized reaction vessel and introduces hydrogen sulfide into the gas phase. In a method for producing a sulfide containing nickel and cobalt by supplying a sulfide gas containing sulfur, the hydrogen sulfide gas concentration in the sulfide gas is less than 95 to 100% by volume used in a steady state of operation. It is suitable as a method for maintaining a high yield of nickel and cobalt when the concentration is reduced to a low concentration. In particular, it can be effectively used in an unsteady state such as when a hydrogen sulfide gas synthesis facility is started up.
１ 浸出工程
２ 固液分離工程
３ 中和工程
４ 硫化工程
５ ニッケル酸化鉱石
６ 浸出スラリー
７ 浸出液
８ 浸出残渣
９ 中和澱物スラリー
１０ ニッケル回収用母液
１１ 硫化物
１２ 貧液
DESCRIPTION OF SYMBOLS 1 Leaching process 2 Solid-liquid separation process 3 Neutralization process 4
Claims (6)
前記硫化用ガス中の硫化水素ガス濃度が、操業の定常状態に用いられる９５〜１００容量％からそれ未満の濃度に低下した際に、該硫化水素ガス濃度に応じて、下記（１）又は（２）の操作を採用することを特徴とするニッケル及びコバルトを含む硫化物の製造方法。
（１）前記硫化用ガス中の硫化水素ガス濃度が８５〜９０容量％の場合において、前記反応容器内に、前記硫酸水溶液にともない導入するニッケル及びコバルト投入量を、定常状態のときの投入量に対し質量割合で３０〜３５％に減少させる。
（２）前記硫化用ガス中の硫化水素ガス濃度が９０容量％を超える場合において、前記反応容器内に、前記硫酸水溶液にともない導入するニッケル及びコバルト投入量を、定常状態のときの投入量に対し質量割合で５５〜６０％の割合に減少させる。 In a method for producing a sulfide containing nickel and cobalt by introducing a sulfuric acid aqueous solution containing nickel and cobalt into a pressurized reaction vessel and supplying a sulfurizing gas containing hydrogen sulfide in the gas phase. ,
When the hydrogen sulfide gas concentration in the sulfiding gas is reduced from 95 to 100% by volume used in the steady state of operation to a concentration lower than that, the following (1) or ( A method for producing a sulfide containing nickel and cobalt, wherein the operation of 2) is employed.
(1) When the hydrogen sulfide gas concentration in the sulfiding gas is 85 to 90% by volume, the amount of nickel and cobalt introduced into the reaction vessel with the sulfuric acid aqueous solution is the amount introduced in a steady state. The mass ratio is reduced to 30 to 35%.
(2) When the hydrogen sulfide gas concentration in the sulfiding gas exceeds 90% by volume, the amount of nickel and cobalt introduced into the reaction vessel with the sulfuric acid aqueous solution is changed to the amount introduced in a steady state. On the other hand, the mass ratio is reduced to 55 to 60%.
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| WO2011145644A1 (en) * | 2010-05-18 | 2011-11-24 | 住友金属鉱山株式会社 | Method for controlling reaction in sulfuration reaction step |
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| WO2014021062A1 (en) | 2012-07-31 | 2014-02-06 | 住友金属鉱山株式会社 | Hydrogen sulfide gas production plant system and method for recovering and using hydrogen sulfide gas |
| JP2014141408A (en) * | 2014-02-27 | 2014-08-07 | Sumitomo Metal Mining Co Ltd | Hydrogen sulfide gas production plant system and method for recovering and using a hydrogen sulfide gas |
| JP2014141749A (en) * | 2014-04-02 | 2014-08-07 | Sumitomo Metal Mining Co Ltd | Method of reducing nickel recovery loss, wet metallurgy method for nickel oxide ore and sulfurization processing system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2011145644A1 (en) * | 2010-05-18 | 2011-11-24 | 住友金属鉱山株式会社 | Method for controlling reaction in sulfuration reaction step |
| JP2011241446A (en) * | 2010-05-18 | 2011-12-01 | Sumitomo Metal Mining Co Ltd | Method for controlling reaction in sulfuration reaction step |
| AU2011255953B2 (en) * | 2010-05-18 | 2015-06-18 | Sumitomo Metal Mining Co., Ltd. | Method for controlling reaction in sulfuration reaction step |
| WO2013027603A1 (en) * | 2011-08-22 | 2013-02-28 | 住友金属鉱山株式会社 | Nickel recovery loss reduction method, hydrometallurgical method for nickel oxidized ore, and sulfuration treatment system |
| US8916115B2 (en) | 2011-08-22 | 2014-12-23 | Sumitomo Metal Mining Co., Ltd. | Nickel recovery loss reduction method, hydrometallurgical method for nickel oxidized ore, and sulfuration treatment system |
| WO2014021062A1 (en) | 2012-07-31 | 2014-02-06 | 住友金属鉱山株式会社 | Hydrogen sulfide gas production plant system and method for recovering and using hydrogen sulfide gas |
| US9321646B2 (en) | 2012-07-31 | 2016-04-26 | Sumitomo Metal Mining Co., Ltd. | Hydrogen sulfide gas production plant system and method for recovering and using hydrogen sulfide gas |
| JP2014141408A (en) * | 2014-02-27 | 2014-08-07 | Sumitomo Metal Mining Co Ltd | Hydrogen sulfide gas production plant system and method for recovering and using a hydrogen sulfide gas |
| JP2014141749A (en) * | 2014-04-02 | 2014-08-07 | Sumitomo Metal Mining Co Ltd | Method of reducing nickel recovery loss, wet metallurgy method for nickel oxide ore and sulfurization processing system |
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