JP7633141B2 - Method for recovering valuable elements, method for producing hydroxides of valuable elements, and method for producing oxides of valuable elements - Google Patents
Method for recovering valuable elements, method for producing hydroxides of valuable elements, and method for producing oxides of valuable elements Download PDFInfo
- Publication number
- JP7633141B2 JP7633141B2 JP2021196325A JP2021196325A JP7633141B2 JP 7633141 B2 JP7633141 B2 JP 7633141B2 JP 2021196325 A JP2021196325 A JP 2021196325A JP 2021196325 A JP2021196325 A JP 2021196325A JP 7633141 B2 JP7633141 B2 JP 7633141B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen peroxide
- cobalt
- substance
- catalyst
- valuable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Description
本発明は、少なくともモリブデンおよびコバルトを含有する物質（例えば、石油精製に用いられた使用済み脱硫触媒などの廃触媒）から有価元素を回収する方法、ならびに、有価元素の水酸化物の製造方法および有価元素の酸化物の製造方法に関する。 The present invention relates to a method for recovering valuable elements from a material containing at least molybdenum and cobalt (e.g., a waste catalyst such as a used desulfurization catalyst used in oil refining), as well as a method for producing a hydroxide of a valuable element and a method for producing an oxide of a valuable element.
従来、石油精製において、脱硫触媒を用いた脱硫が行なわれる。より詳細には、石油と高圧水素とを脱硫触媒上で反応させ、石油に含まれる硫黄分を硫化水素として除去する水素化脱硫が行なわれる。
このような脱硫触媒は、使用されるに従い、石油に含まれる重金属やタール分などで次第に被毒されて触媒活性が低下するため、定期的に交換される。この際、使用済み脱硫触媒（廃触媒）が発生する。
従来、資源循環の点から、廃触媒に含まれる種々の元素を回収する方法が提案されている（特許文献１）。
Conventionally, desulfurization using a desulfurization catalyst is performed in oil refining. More specifically, hydrodesulfurization is performed in which oil and high-pressure hydrogen are reacted on the desulfurization catalyst to remove sulfur content contained in the oil as hydrogen sulfide.
As such desulfurization catalysts become poisoned by heavy metals and tar contained in petroleum as they are used, their catalytic activity decreases, and so they must be replaced periodically, generating used desulfurization catalysts (spent catalysts).
Conventionally, from the viewpoint of resource circulation, methods for recovering various elements contained in spent catalysts have been proposed (Patent Document 1).
脱硫触媒は、例えば、アルミナなどの担体上に、モリブデン（Ｍｏ）、コバルト（Ｃｏ）等の金属元素を担持する。
モリブデンは、鋼に添加すると機械的強度や剛性が高まるため、特殊鋼やステンレス鋼に使用され、更に、高温で展性や延性に富むため、グリス等にも使用される。
近年、使用済み脱硫触媒などの廃触媒から、これらの元素（有価元素）を回収することが強く望まれている。
The desulfurization catalyst has a metal element such as molybdenum (Mo) or cobalt (Co) supported on a carrier such as alumina.
Molybdenum is used in special steels and stainless steels because adding it to steel increases its mechanical strength and rigidity. Furthermore, it is used in greases and the like because it is malleable and ductile at high temperatures.
In recent years, there has been a strong demand for recovering these elements (valuable elements) from waste catalysts such as used desulfurization catalysts.
そこで、本発明は、廃触媒などの物質からコバルト等の有価元素を回収できる新規な方法を提供することを目的とする。 The present invention aims to provide a new method for recovering valuable elements such as cobalt from materials such as waste catalysts.
本発明者らは、鋭意検討した結果、下記構成を採用することにより、上記目的が達成されることを見出し、本発明を完成させた。 As a result of intensive research, the inventors discovered that the above object can be achieved by adopting the following configuration, and thus completed the present invention.
すなわち、本発明は、以下の［１］～［１０］を提供する。
［１］少なくともモリブデンおよびコバルトを含有する物質を過酸化水素水に接触させて、上記物質から少なくともコバルトが浸出した浸出液を得て、上記浸出液をろ過して上記物質を分離することにより、ろ液を得て、上記ろ液にアルカリ処理を施し、生成したコバルト沈殿物をろ過によって分離する、有価元素の回収方法。
［２］上記過酸化水素水は、過酸化水素を含有し、上記物質の量に対する上記過酸化水素の量が、４０質量％以下である、上記［１］に記載の有価元素の回収方法。
［３］上記物質の量に対する上記過酸化水素の量が、５質量％以上である、上記［２］に記載の有価元素の回収方法。
［４］上記物質を、上記過酸化水素水に接触させるに先立って、粉砕する、上記［１］～［３］のいずれかに記載の有価元素の回収方法。
［５］上記過酸化水素水と上記物質との質量比（過酸化水素水／物質）が、２／１以上である、上記［１］～［４］のいずれかに記載の有価元素の回収方法。
［６］上記ろ液に上記アルカリ処理を施すことにより、上記ろ液のｐＨを７以上にする、上記［１］～［５］のいずれかに記載の有価元素の回収方法。
［７］上記物質が、廃触媒である、上記［１］～［６］のいずれかに記載の有価元素の回収方法。
［８］上記廃触媒が、使用済み脱硫触媒である、上記［７］に記載の有価元素の回収方法。
［９］上記［１］～［８］のいずれかに記載の有価元素の回収方法を用いて、有価元素の水酸化物を得る、有価元素の水酸化物の製造方法。
［１０］上記［１］～［８］のいずれかに記載の有価元素の回収方法を用いて、有価元素の酸化物を得る、有価元素の酸化物の製造方法。
That is, the present invention provides the following [1] to [10].
[1] A method for recovering valuable elements, comprising the steps of: contacting a substance containing at least molybdenum and cobalt with a hydrogen peroxide solution to obtain a leachate in which at least cobalt has been leached from the substance; filtering the leachate to separate the substance to obtain a filtrate; subjecting the filtrate to an alkali treatment; and separating the resulting cobalt precipitate by filtration.
[2] The method for recovering a valuable element described in [1] above, wherein the hydrogen peroxide solution contains hydrogen peroxide, and the amount of the hydrogen peroxide relative to the amount of the substance is 40 mass% or less.
[3] The method for recovering a valuable element according to [2] above, wherein the amount of the hydrogen peroxide relative to the amount of the substance is 5 mass% or more.
[4] The method for recovering a valuable element according to any one of [1] to [3] above, wherein the substance is pulverized prior to contacting with the hydrogen peroxide solution.
[5] The method for recovering a valuable element according to any one of [1] to [4] above, wherein the mass ratio of the hydrogen peroxide solution to the substance (hydrogen peroxide solution/substance) is 2/1 or more.
[6] The method for recovering a valuable element according to any one of [1] to [5] above, wherein the filtrate is subjected to the alkali treatment to adjust the pH of the filtrate to 7 or higher.
[7] The method for recovering valuable elements according to any one of [1] to [6] above, wherein the substance is a waste catalyst.
[8] The method for recovering valuable elements according to the above [7], wherein the waste catalyst is a used desulfurization catalyst.
[9] A method for producing a hydroxide of a valuable element, comprising obtaining a hydroxide of the valuable element by using the method for recovering a valuable element according to any one of [1] to [8] above.
[10] A method for producing an oxide of a valuable element, comprising obtaining an oxide of a valuable element by using the method for recovering a valuable element according to any one of [1] to [8] above.
本発明によれば、廃触媒などの物質からコバルト等の有価元素を回収できる。 According to the present invention, valuable elements such as cobalt can be recovered from materials such as waste catalysts.
本発明の有価元素の回収方法は、少なくともモリブデンおよびコバルトを含有する物質を過酸化水素水に接触させて、上記物質から少なくともコバルトが浸出した浸出液を得て、上記浸出液をろ過して上記物質を分離することにより、ろ液を得て、上記ろ液にアルカリ処理を施し、生成したコバルト沈殿物をろ過によって分離する。
本発明によれば、少なくともモリブデンおよびコバルトを含有する物質から、簡便に、コバルトをコバルト沈殿物として回収できる。
The method for recovering valuable elements of the present invention includes contacting a substance containing at least molybdenum and cobalt with hydrogen peroxide to obtain a leachate in which at least cobalt has been leached from the substance, filtering the leachate to separate the substance to obtain a filtrate, subjecting the filtrate to an alkali treatment, and separating the resulting cobalt precipitate by filtration.
According to the present invention, cobalt can be easily recovered as a cobalt precipitate from a substance containing at least molybdenum and cobalt.
以下、本発明の好適な実施形態を、図１に基づいて説明する。
図１は、有価元素の回収方法の流れを示すフローチャートである。
A preferred embodiment of the present invention will now be described with reference to FIG.
FIG. 1 is a flow chart showing the flow of a method for recovering valuable elements.
少なくともモリブデンおよびコバルトを含有する物質としては、特に限定されないが、以下では、廃触媒を例に説明する。 There are no particular limitations on the substance that contains at least molybdenum and cobalt, but the following will use a spent catalyst as an example.
〈廃触媒の準備〉
廃触媒は、少なくともモリブデンおよびコバルトを含有する、例えば、使用済み脱硫触媒である。脱硫触媒は、例えば、アルミナ（Ａｌ２Ｏ３）などの担体上に、モリブデン（Ｍｏ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）などの金属元素を担持する。
<Preparation of spent catalyst>
The spent catalyst is, for example, a used desulfurization catalyst that contains at least molybdenum and cobalt. The desulfurization catalyst supports metal elements such as molybdenum (Mo), cobalt (Co), and nickel (Ni) on a support such as alumina (Al 2 O 3 ).
〈粉砕〉
廃触媒は、後述するように、過酸化水素水に接触させるが、これに先立って、粉砕することが好ましい。これにより、高効率な浸出が期待できる。廃触媒がアルミナ担体を有する（アルミナ骨格を有する）脱硫触媒である場合は、特に有用である。
廃触媒を粉砕する方法としては、特に限定されず、ボールミル、ジェットミル等を用いる公知の方法によって、簡便に粉砕できる。
粉砕後における廃触媒の粒度としては、１０００μｍ以下が好ましく、５００μｍ以下がより好ましい。
Crush
As described later, the spent catalyst is brought into contact with hydrogen peroxide water, but it is preferable to crush it prior to this. This is expected to result in highly efficient leaching. This is particularly useful when the spent catalyst is a desulfurization catalyst having an alumina support (having an alumina skeleton).
The method for pulverizing the spent catalyst is not particularly limited, and the spent catalyst can be easily pulverized by a known method using a ball mill, a jet mill, or the like.
The particle size of the pulverized waste catalyst is preferably 1000 μm or less, and more preferably 500 μm or less.
〈過酸化水素水との接触：浸出液の取得〉
廃触媒を、任意で粉砕した後、過酸化水素水（過酸化水素の水溶液）に接触させる。接触の方法は、特に限定されず、例えば、廃触媒を過酸化水素水に浸漬させることにより両者を接触させる方法が挙げられる。
これにより、廃触媒に含まれるモリブデンおよびコバルトのうち、少なくともコバルトを、過酸化水素水に浸出させる。
すなわち、得られる浸出液は、廃触媒、ならびに、この廃触媒から溶け出した成分であるコバルトを含有するスラリーである。このスラリーは、後述するように、例えば、強酸性である。
Contact with hydrogen peroxide: Acquisition of leachate
The waste catalyst is optionally pulverized and then contacted with hydrogen peroxide (aqueous solution of hydrogen peroxide). The contact method is not particularly limited, and for example, a method of contacting the two by immersing the waste catalyst in hydrogen peroxide can be mentioned.
As a result, at least the cobalt out of the molybdenum and cobalt contained in the spent catalyst is leached into the hydrogen peroxide solution.
That is, the obtained leachate is a slurry containing the spent catalyst and cobalt, which is a component dissolved from the spent catalyst. This slurry is, for example, strongly acidic, as described later.
ところで、浸出液にコバルトだけでなく、モリブデンも多量に浸出している場合、後述するアルカリ処理を実施すると、一定量のモリブデンも共沈するため、得られるコバルト沈殿物の品位が低下しやすい。
また、モリブデンは、一般には、アルカリ側のｐＨで沈殿する元素ではないため、廃液に多くのモリブデンが残留して廃棄されることとなり、モリブデンのロスが増加する。
Incidentally, when a large amount of molybdenum as well as cobalt is leached into the leachate, when the alkali treatment described below is carried out, a certain amount of molybdenum is also coprecipitated, and the quality of the obtained cobalt precipitate is likely to decrease.
Furthermore, since molybdenum is not generally an element that precipitates at alkaline pH levels, a large amount of molybdenum remains in the waste liquid before it is discarded, resulting in increased loss of molybdenum.
そこで、本発明者らが検討した結果、高濃度の過酸化水素水を廃触媒に接触させると、モリブデン、コバルト等の各種金属が多量に浸出すること、および、過酸化水素水の濃度を低下させると、主としてコバルトのみが選択的に浸出することを見出した。
これは、コバルトが他の金属元素より過酸化水素による酸化を受けやすいためと考えられる。このため、希薄な過酸化水素水を廃触媒に接触させることにより、他の金属元素（例えばモリブデン）と比較して、コバルトが多く浸出した浸出液が得られる。
As a result of the inventors' investigations, they found that when a high concentration of hydrogen peroxide solution is brought into contact with a waste catalyst, various metals such as molybdenum and cobalt are leached in large quantities, and that when the concentration of the hydrogen peroxide solution is reduced, mainly only cobalt is selectively leached.
This is believed to be because cobalt is more susceptible to oxidation by hydrogen peroxide than other metal elements, and therefore, by contacting the spent catalyst with dilute hydrogen peroxide, a leachate containing more cobalt than other metal elements (e.g., molybdenum) is obtained.
以上の点から、本実施形態においては、廃触媒に接触する過酸化水素水が含有する過酸化水素の量を、廃触媒の量（乾燥質量）に対して、一定値以下にすることが好ましい。
具体的には、廃触媒の量に対する過酸化水素の量（以下、便宜的に、「過酸化水素量ｐ」ともいう）は、４０質量％以下が好ましく、３０質量％以下がより好ましく、２０質量％以下が更に好ましい。これにより、廃触媒からコバルトのみを選択的に浸出させやすくなる。
From the above points, in this embodiment, it is preferable to set the amount of hydrogen peroxide contained in the hydrogen peroxide solution that comes into contact with the spent catalyst to a certain value or less relative to the amount (dry mass) of the spent catalyst.
Specifically, the amount of hydrogen peroxide relative to the amount of the spent catalyst (hereinafter, for convenience, also referred to as "hydrogen peroxide amount p") is preferably 40 mass% or less, more preferably 30 mass% or less, and further preferably 20 mass% or less. This makes it easier to selectively leach only cobalt from the spent catalyst.
一方、過酸化水素量ｐが低すぎると、コバルトが十分な浸出されないおそれがある。
このため、過酸化水素量ｐは、５質量％以上が好ましく、７質量％以上がより好ましく、１０質量％以上が更に好ましい。
On the other hand, if the amount of hydrogen peroxide p is too low, there is a risk that cobalt will not be leached sufficiently.
For this reason, the amount p of hydrogen peroxide is preferably 5% by mass or more, more preferably 7% by mass or more, and even more preferably 10% by mass or more.
なお、例えば、後述する質量比（過酸化水素水／廃触媒）が１０／１である場合、過酸化水素水の濃度（過酸化水素水における過酸化水素の含有量）が４質量％であれば、過酸化水素量ｐは４０質量％になる。 For example, if the mass ratio (hydrogen peroxide solution/waste catalyst) described below is 10/1, and the concentration of hydrogen peroxide solution (the hydrogen peroxide content in hydrogen peroxide solution) is 4 mass%, the amount of hydrogen peroxide p will be 40 mass%.
過酸化水素水と廃触媒との質量比（過酸化水素水／廃触媒）は、効率良く浸出できるという理由から、２／１以上が好ましく、３／１以上がより好ましい。
一方、使用する過酸化水素水が適量となり、反応容器の増大およびコスト増を抑制できるという理由から、質量比（過酸化水素水／廃触媒）は、５０／１以下が好ましく、３０／１以下がより好ましい。
The mass ratio of the hydrogen peroxide solution to the waste catalyst (hydrogen peroxide solution/waste catalyst) is preferably 2/1 or more, and more preferably 3/1 or more, for the reason that efficient leaching can be achieved.
On the other hand, the mass ratio (hydrogen peroxide solution/waste catalyst) is preferably 50/1 or less, and more preferably 30/1 or less, because the amount of hydrogen peroxide solution used is appropriate and an increase in the reaction vessel and costs can be suppressed.
廃触媒を過酸化水素水に接触させる時間（接触時間）は、廃触媒内部の有価元素を十分に浸出できるという理由から、１０分以上が好ましく、１５分以上がより好ましい。
一方で、接触時間を過剰に長くしても、浸出は定常状態に達し、浸出率の向上は望めない。このため、接触時間は、１８０分以下が好ましく、１２０分以下がより好ましい。
通常、事前に廃触媒を粉砕した場合は、１時間あれば廃触媒内部の有価元素を十分に浸出できる。
The time for which the spent catalyst is brought into contact with the hydrogen peroxide solution (contact time) is preferably 10 minutes or more, and more preferably 15 minutes or more, for the reason that the valuable elements inside the spent catalyst can be sufficiently leached out.
On the other hand, if the contact time is excessively long, the leaching reaches a steady state and no improvement in the leaching rate can be expected. Therefore, the contact time is preferably 180 minutes or less, and more preferably 120 minutes or less.
Usually, if the spent catalyst is crushed in advance, it takes about one hour to sufficiently leach out the valuable elements inside the spent catalyst.
過酸化水素水を酸性にすることにより、廃触媒から有価元素を効率的に浸出できる。
もっとも、廃触媒が使用済み脱硫触媒である場合、酸を過酸化水素水に添加しなくてもよい。廃触媒中の硫化物が、過酸化水素によって硫酸体となり、硫酸イオンとなって過酸化水素水中に溶解することで、硫酸添加と同様の効果を発現するからである。実際に、過酸化水素水中に廃触媒（使用済み脱硫触媒）を入れると、ｐＨは速やかに低下する。
By making the hydrogen peroxide solution acidic, valuable elements can be efficiently leached out from the spent catalyst.
However, if the waste catalyst is a used desulfurization catalyst, it is not necessary to add an acid to the hydrogen peroxide solution. This is because the sulfides in the waste catalyst are converted into sulfates by hydrogen peroxide, and the sulfate ions dissolve in the hydrogen peroxide solution, providing the same effect as adding sulfuric acid. In fact, when the waste catalyst (used desulfurization catalyst) is placed in the hydrogen peroxide solution, the pH drops rapidly.
〈ろ過による廃触媒の分離：ろ液の取得〉
次に、浸出液をろ過する。これにより、固形分である廃触媒を浸出液から分離して、ろ液を得る。ろ液は、廃触媒から溶け出した成分であるコバルトを、少なくとも含有する。
ろ過の方法は、対象とする固形分を分離して所望のろ液を取得できれば、特に限定されず、従来公知の方法を適宜採用できる。これは、後述するろ過においても、同様である。
Separation of spent catalyst by filtration: Obtaining filtrate
Next, the leachate is filtered, whereby the solid content of the spent catalyst is separated from the leachate to obtain a filtrate, which contains at least cobalt, which is a component dissolved from the spent catalyst.
The filtration method is not particularly limited as long as it can separate the target solid content and obtain the desired filtrate, and any conventionally known method can be appropriately adopted. This also applies to the filtration described below.
ろ過の残渣である廃触媒については、モリブデンは浸出せずに残留している一方で、コバルトは浸出しており除去されている。すなわち、乾式などの従来の方法では、廃触媒からコバルトを除去することは困難であったが、本実施形態によれば、これが実現できる。
このため、ろ過の残渣である廃触媒を、フェロモリブデン等の生産に供することができ、簡便に、モリブデンをリサイクルできる。
In the waste catalyst, which is the residue of the filtration, molybdenum remains without being leached, while cobalt is leached and removed. In other words, it was difficult to remove cobalt from the waste catalyst by conventional methods such as the dry method, but this can be achieved by the present embodiment.
Therefore, the waste catalyst, which is the residue after filtration, can be used to produce ferromolybdenum, etc., and molybdenum can be recycled easily.
〈アルカリ処理：コバルト沈殿物の生成〉
次に、ろ液にアルカリ処理を施して、コバルト沈殿物を生成させる。すなわち、ろ液に、水酸化ナトリウム、水酸化カリウムなどのアルカリを添加することにより、ろ液中のコバルトが水酸化コバルトとして沈殿する。
ろ液にアルカリ処理を施すことにより、ろ液のｐＨを調整するが、このｐＨは、十分なコバルト回収率を得る目的から、７以上が好ましく、８以上がより好ましく、９以上が更に好ましい。
一方、中和のための酸が少量となり経済的であるという理由から、このｐＨは、１３．５以下が好ましい。
<Alkaline treatment: formation of cobalt precipitate>
Next, the filtrate is treated with an alkali to produce a cobalt precipitate. That is, by adding an alkali such as sodium hydroxide or potassium hydroxide to the filtrate, the cobalt in the filtrate is precipitated as cobalt hydroxide.
The filtrate is subjected to an alkali treatment to adjust the pH of the filtrate. In order to obtain a sufficient cobalt recovery rate, the pH is preferably 7 or more, more preferably 8 or more, and even more preferably 9 or more.
On the other hand, the pH is preferably 13.5 or less because the amount of acid required for neutralization is small and therefore economical.
〈ろ過によるコバルト沈殿物の回収〉
次に、コバルト沈殿物が生成したろ液をろ過する。これにより、固形分であるコバルト沈殿物を、ろ液から分離する。こうして、廃触媒からコバルトをコバルト沈殿物として回収できる。
回収されるコバルト沈殿物は、例えば、コバルトの水酸化物である。更に、このコバルトの水酸化物を乾燥すれば、コバルトを酸化物の形態（つまり、コバルトの酸化物）にできる。乾燥の方法は、特に限定されず、公知の方法を採用できる。
コバルト沈殿物が分離されたろ液（残液）は、廃液として廃棄される。
Recovery of cobalt precipitate by filtration
Next, the filtrate containing the cobalt precipitate is filtered. This separates the solid cobalt precipitate from the filtrate. In this way, cobalt can be recovered from the spent catalyst as the cobalt precipitate.
The recovered cobalt precipitate is, for example, a hydroxide of cobalt. If the hydroxide of cobalt is dried, the cobalt can be converted into an oxide (i.e., an oxide of cobalt). The drying method is not particularly limited, and a known method can be used.
The filtrate (residual liquid) from which the cobalt precipitate has been separated is discarded as waste liquid.
以上説明したように、本実施形態によれば、廃触媒からコバルトを選択的に浸出させてコバルト沈殿物として回収でき、一方で、モリブデンは廃触媒に残留させて回収できる。
このため、本実施形態によれば、例えば、廃触媒からモリブデンおよびコバルトを共に浸出させ、個別に回収する方法と比べて、工程を簡略化できる。
一般的には、多段階の工程が必要な場合、設備が複雑になり、建設費などのコストが増大する（実用的には、ある程度の大きさの設備規模で実施し、スケールメリットを享受することが求められる）。このため、本実施形態においては、コスト面でも優位性がある。
また、本実施形態においては、熱効率等の面から設備を大型化せざるを得ない焙焼等の熱処理を実施しないため、この点からも、設備を簡素化できる。
As described above, according to this embodiment, cobalt can be selectively leached from the spent catalyst and recovered as a cobalt precipitate, while molybdenum can be recovered by leaving it in the spent catalyst.
Therefore, according to this embodiment, the process can be simplified compared to, for example, a method in which molybdenum and cobalt are both leached from a spent catalyst and then separately recovered.
Generally, when a multi-stage process is required, the equipment becomes complicated, and costs such as construction costs increase (for practical purposes, it is required to implement the process on a certain scale of equipment to enjoy economies of scale). For this reason, the present embodiment is also advantageous in terms of cost.
In addition, in this embodiment, a heat treatment such as roasting, which would require a large-scale facility from the standpoint of thermal efficiency, is not performed, and therefore the facility can be simplified in this respect as well.
以下に、実施例を挙げて本発明を具体的に説明する。ただし、本発明は、以下に説明する実施例に限定されない。 The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the examples described below.
〈実施例１〉
図１に基づいて説明した流れに沿って、少なくともモリブデンおよびコバルトを含有する物質である廃触媒から有価元素を回収した。
Example 1
Following the flow explained based on FIG. 1, valuable elements were recovered from a spent catalyst, which is a substance containing at least molybdenum and cobalt.
《廃触媒の準備》
廃触媒として、石油精製プラントより供試された、使用済み間接脱硫触媒を用いた。
この廃触媒は、直径２～３ｍｍおよび長さ３～５ｍｍ前後の円筒形であり、アルミナ担体に種々の元素が担持されていた。
廃触媒の組成をＩＣＰ（誘導結合プラズマ）発光分光分析法によって求めた。廃触媒の組成を下記表１に示す。
<Preparation of spent catalyst>
The waste catalyst used was a used indirect desulfurization catalyst provided by an oil refinery plant.
This spent catalyst was cylindrical with a diameter of 2 to 3 mm and a length of about 3 to 5 mm, and various elements were supported on an alumina carrier.
The composition of the spent catalyst was determined by ICP (inductively coupled plasma) emission spectrometry and is shown in Table 1 below.
《粉砕》
準備した廃触媒１０ｋｇを、１００Ｌの純水と混合し、湿式ボールミルを用いて、１２０分間粉砕した。粉砕後の廃触媒のメジアン径は、１２μｍであった。粉砕後の廃触媒の粒度分布を図２に示す。
Shatter
10 kg of the prepared spent catalyst was mixed with 100 L of pure water and pulverized for 120 minutes using a wet ball mill. The median diameter of the pulverized spent catalyst was 12 μm. The particle size distribution of the pulverized spent catalyst is shown in FIG. 2.
《過酸化水素水との接触およびろ過》
次に、粉砕後の廃触媒と純水との混合物に、過酸化水素水（濃度：３５質量％）を、上述した過酸化水素量ｐが１５質量％となる量で添加し、その後、１５分撹拌して、浸出液を得た。
得られた浸出液をろ過することにより、廃触媒を分離して、ろ液を得た。ろ過（吸引ろ過）には、５Ｃろ紙（保持粒子径：１μｍ）を用いた（以下同様）。
Contact with hydrogen peroxide and filtration
Next, hydrogen peroxide solution (concentration: 35% by mass) was added to the mixture of the crushed waste catalyst and pure water in an amount such that the above-mentioned hydrogen peroxide amount p became 15% by mass, and then the mixture was stirred for 15 minutes to obtain a leachate.
The resulting leachate was filtered to separate the waste catalyst and obtain a filtrate. For the filtration (suction filtration), 5C filter paper (retention particle size: 1 μm) was used (hereinafter the same).
《アルカリ処理およびろ過》
ろ液にアルカリ処理を施した。すなわち、ろ液に水酸化ナトリウム水溶液を添加することにより、ろ液のｐＨを１２に調整し、１時間経過させた。これにより、ろ液中にコバルト沈殿物を生成させた。
コバルト沈殿物が生成したろ液をろ過することにより、コバルト沈殿物を分離して、回収し、乾燥した。乾燥したコバルト沈殿物の組成をＩＣＰ発光分光分析法によって求めた。コバルト沈殿物の組成を下記表２に示す。
Alkaline treatment and filtration
The filtrate was subjected to an alkali treatment, that is, an aqueous solution of sodium hydroxide was added to the filtrate to adjust the pH of the filtrate to 12, and the filtrate was left for one hour, whereby a cobalt precipitate was formed in the filtrate.
The filtrate containing the cobalt precipitate was filtered to separate, recover and dry the cobalt precipitate. The composition of the dried cobalt precipitate was determined by ICP emission spectrometry. The composition of the cobalt precipitate is shown in Table 2 below.
なお、金属元素は水酸化物の形態で沈殿しており、例えば、コバルト沈殿物は、Ｃｏ（ＯＨ）３・Ｈ２Ｏの式で表されると仮定する。 It is assumed that the metal element is precipitated in the form of a hydroxide, for example, a cobalt precipitate is represented by the formula Co(OH) 3.H2O .
《評価》
下記式に基づいて、コバルト歩留り（単位：質量％）を求めた。結果を下記表２に示す。コバルト歩留りの値が大きいほど、廃触媒から多くのコバルトをコバルト沈殿物として回収できたと評価できる。
コバルト歩留り＝１００×（コバルト沈殿物中のコバルト量／準備した時点での廃触媒中のコバルト量）
"evaluation"
The cobalt yield (unit: mass%) was calculated based on the following formula. The results are shown in Table 2. It can be evaluated that the larger the cobalt yield value, the more cobalt was recovered from the spent catalyst as cobalt precipitate.
Cobalt yield = 100 x (amount of cobalt in the cobalt precipitate / amount of cobalt in the spent catalyst at the time of preparation)
更に、下記式に基づいて、モリブデンロス（単位：質量％）を求めた。結果を下記表２に示す。モリブデンロスの値が小さいほど、多くのモリブデンを廃触媒から浸出させないで、廃触媒に残留させたまま回収できたと評価できる。
モリブデンロス＝１００×｛１－（浸出液から分離した時点での廃触媒中のモリブデン量／準備した時点での廃触媒中のモリブデン量）｝
Furthermore, molybdenum loss (unit: mass%) was calculated based on the following formula. The results are shown in Table 2. The smaller the molybdenum loss value, the more molybdenum was evaluated to have been recovered without being leached out of the spent catalyst and remaining in the spent catalyst.
Molybdenum loss = 100 x {1 - (amount of molybdenum in the spent catalyst when it was separated from the leachate / amount of molybdenum in the spent catalyst when it was prepared)}
〈実施例２〉
過酸化水素量ｐを４０質量％に変更した以外は、実施例１と同様にして、コバルト沈殿物を回収し、コバルト沈殿物の組成、コバルトの歩留りおよびモリブデンロスを求めた。結果を下記表２に示す。
Example 2
Except for changing the amount of hydrogen peroxide p to 40 mass%, the cobalt precipitate was recovered, and the composition of the cobalt precipitate, the cobalt yield, and the molybdenum loss were determined in the same manner as in Example 1. The results are shown in Table 2 below.
〈実施例３〉
過酸化水素量ｐを５０質量％に変更した以外は、実施例１と同様にして、コバルト沈殿物を回収し、コバルト沈殿物の組成、コバルトの歩留りおよびモリブデンロスを求めた。結果を下記表２に示す。
Example 3
Except for changing the amount of hydrogen peroxide p to 50 mass %, the cobalt precipitate was recovered, and the composition of the cobalt precipitate, the cobalt yield, and the molybdenum loss were determined in the same manner as in Example 1. The results are shown in Table 2 below.
〈評価結果まとめ〉
上記表２に示すように、実施例１（過酸化水素量ｐ：１５質量％）では、コバルト歩留りは７１質量％であり、得られたコバルト沈殿物は、良質なコバルト原料として精錬メーカー等においてリサイクル可能な品質であった。
実施例２（過酸化水素量ｐ：４０質量％）では、実施例１と比較して、コバルト歩留りが大きく増加した。
実施例３（過酸化水素量ｐ：５０質量％）では、実施例１～２と比較して、モリブデンロスが増加していた。
<Summary of evaluation results>
As shown in Table 2 above, in Example 1 (amount of hydrogen peroxide p: 15% by mass), the cobalt yield was 71% by mass, and the obtained cobalt precipitate was of such a quality that it could be recycled by a refining manufacturer or the like as a high-quality cobalt raw material.
In Example 2 (amount of hydrogen peroxide p: 40 mass %), the cobalt yield was significantly increased compared to Example 1.
In Example 3 (amount of hydrogen peroxide p: 50 mass %), the molybdenum loss was increased as compared with Examples 1 and 2.
Claims (7)
前記浸出液をろ過して前記物質を分離することにより、ろ液を得て、
前記ろ液にアルカリ処理を施し、生成したコバルト沈殿物をろ過によって分離し、
前記過酸化水素水は、過酸化水素を含有し、
前記物質の量に対する前記過酸化水素の量が、２０質量％以下であり、
前記物質が、廃触媒であり、
前記廃触媒が、使用済み脱硫触媒である、有価元素の回収方法。 contacting a substance containing at least molybdenum and cobalt with hydrogen peroxide to obtain a leachate in which at least cobalt has been leached from the substance;
filtering the leachate to separate the material, thereby obtaining a filtrate;
The filtrate is subjected to an alkali treatment, and the resulting cobalt precipitate is separated by filtration;
The hydrogen peroxide solution contains hydrogen peroxide,
The amount of hydrogen peroxide relative to the amount of the substance is 20% by weight or less;
The substance is a spent catalyst,
The method for recovering valuable elements, wherein the waste catalyst is a used desulfurization catalyst .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021196325A JP7633141B2 (en) | 2021-12-02 | 2021-12-02 | Method for recovering valuable elements, method for producing hydroxides of valuable elements, and method for producing oxides of valuable elements |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021196325A JP7633141B2 (en) | 2021-12-02 | 2021-12-02 | Method for recovering valuable elements, method for producing hydroxides of valuable elements, and method for producing oxides of valuable elements |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2023082501A JP2023082501A (en) | 2023-06-14 |
| JP7633141B2 true JP7633141B2 (en) | 2025-02-19 |
Family
ID=86728567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021196325A Active JP7633141B2 (en) | 2021-12-02 | 2021-12-02 | Method for recovering valuable elements, method for producing hydroxides of valuable elements, and method for producing oxides of valuable elements |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7633141B2 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010540767A (en) | 2007-09-21 | 2010-12-24 | リサーチ インスティチュート オブ インダストリアル サイエンス アンド テクノロジー | Method for producing iron nickel-containing raw material and cobalt-containing raw material from petrochemical desulfurization catalyst recycling residue, method for producing stainless steel raw material using iron nickel-containing raw material, and method for producing ferronickel |
| JP2011016707A (en) | 2009-06-12 | 2011-01-27 | Dowa Holdings Co Ltd | Chalcogen compound powder, chalcogen compound paste, and methods for manufacturing them |
| JP2017115179A (en) | 2015-12-22 | 2017-06-29 | 日本リサイクルセンター株式会社 | Collection method of valuable materials |
| WO2020175556A1 (en) | 2019-02-26 | 2020-09-03 | 住友金属鉱山株式会社 | Positive electrode active material for lithium ion secondary battery, method for manufacturing positive electrode active material for lithium ion secondary battery, and lithium ion secondary battery |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5934653B2 (en) * | 1981-08-26 | 1984-08-23 | 工業技術院長 | Method for extracting valuable metals from used desulfurization catalysts |
| US4927794A (en) * | 1985-06-26 | 1990-05-22 | Chevron Research Company | Leaching cobalt, molybdenum, nickel, and vanadium from spent hydroprocessing catalysts |
| JP3355362B2 (en) * | 1991-12-05 | 2002-12-09 | 太陽鉱工株式会社 | Method for leaching valuable metals from spent catalyst |
-
2021
- 2021-12-02 JP JP2021196325A patent/JP7633141B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010540767A (en) | 2007-09-21 | 2010-12-24 | リサーチ インスティチュート オブ インダストリアル サイエンス アンド テクノロジー | Method for producing iron nickel-containing raw material and cobalt-containing raw material from petrochemical desulfurization catalyst recycling residue, method for producing stainless steel raw material using iron nickel-containing raw material, and method for producing ferronickel |
| JP2011016707A (en) | 2009-06-12 | 2011-01-27 | Dowa Holdings Co Ltd | Chalcogen compound powder, chalcogen compound paste, and methods for manufacturing them |
| JP2017115179A (en) | 2015-12-22 | 2017-06-29 | 日本リサイクルセンター株式会社 | Collection method of valuable materials |
| WO2020175556A1 (en) | 2019-02-26 | 2020-09-03 | 住友金属鉱山株式会社 | Positive electrode active material for lithium ion secondary battery, method for manufacturing positive electrode active material for lithium ion secondary battery, and lithium ion secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2023082501A (en) | 2023-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3703813B2 (en) | Method for separating and recovering valuable metals | |
| US4554138A (en) | Leaching metals from spent hydroprocessing catalysts with ammonium sulfate | |
| JP5157943B2 (en) | Method for recovering nickel from sulfuric acid aqueous solution | |
| JP2751093B2 (en) | Method for recovering valuable metals from spent catalyst | |
| US4432953A (en) | Leaching cobalt from spent hydroprocessing catalysts with sulfur dioxide | |
| US7837960B2 (en) | Process for separating and recovering base metals from used hydroprocessing catalyst | |
| JP5925776B2 (en) | Method for separating and recovering metals | |
| US8287618B2 (en) | Method or process for recovering Mo, V, Ni, Co and Al from spent catalysts using ultrasonic assisted leaching with EDTA | |
| US20110129397A1 (en) | Method for recovering valuable metal from waste catalyst | |
| KR101487549B1 (en) | A Separation and Recovery Process of Metals from Petroleum Desulfurization Waste Catalyst | |
| JP2022142809A (en) | Method for recovering valuable elements | |
| JP2020001996A (en) | Method for producing nickel sulfate compound | |
| JP7633141B2 (en) | Method for recovering valuable elements, method for producing hydroxides of valuable elements, and method for producing oxides of valuable elements | |
| JP2022142889A (en) | Recovery method of valuable elements | |
| JP7621840B2 (en) | Method for recovering valuable elements | |
| JP3102331B2 (en) | Method for recovering valuable metals from waste Ni catalyst | |
| JP5673471B2 (en) | Method for removing copper ions in aqueous nickel chloride solution and method for producing electronickel | |
| JP7359181B2 (en) | Method of recovering valuable elements | |
| JP7621841B2 (en) | Method for recovering valuable elements | |
| JP7359180B2 (en) | Method of recovering valuable elements | |
| JP2006314986A (en) | Method for recovering molybdic acid | |
| AU2002242946A1 (en) | Process for the recovery of nickel from spent catalyst | |
| JP2022143159A (en) | Recovery method of valuable elements | |
| CA1154601A (en) | Cobalt leaching process | |
| CN114921655A (en) | Method for recovering tungsten-cobalt waste residue |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20240206 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20240206 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20240924 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20241029 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20241216 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20250128 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20250206 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7633141 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |