JPH06192761A - Separation and recovering method for molybdenum - Google Patents
Separation and recovering method for molybdenumInfo
- Publication number
- JPH06192761A JPH06192761A JP4357529A JP35752992A JPH06192761A JP H06192761 A JPH06192761 A JP H06192761A JP 4357529 A JP4357529 A JP 4357529A JP 35752992 A JP35752992 A JP 35752992A JP H06192761 A JPH06192761 A JP H06192761A
- Authority
- JP
- Japan
- Prior art keywords
- molybdenum
- aqueous solution
- extracted
- extractant
- acid
- 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.)
- Pending
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)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、溶媒抽出法によるモリ
ブテンの分離回収法に関し、更に詳しくは、モリブデン
以外にバナジウム、鉄、アルミニウムなどの金属が共存
する水溶液からモリブデンを選択的に分離回収する方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for separating and recovering molybdenum by a solvent extraction method, and more specifically, it selectively separates and recovers molybdenum from an aqueous solution in which metals such as vanadium, iron and aluminum coexist in addition to molybdenum. Regarding the method.
【０００２】[0002]
【従来技術】モリブデンは特殊鋼の製造のための添加
剤、耐熱材料や触媒等の原料金属としてわが国の産業に
欠かすことのできない重要な金属である。モリブデンを
含む鉱石としては輝水鉛鉱、黄鉛鉱、水鉛鉱等が挙げら
れるが、これらは北米、南米等の一部の地域に偏在して
おり、我が国においては原油の脱硫の使用済み触媒から
モリブデンの回収が行われている。このような１次資
源、２次資源を問わず、モリブデンの原料物質中には多
かれ少なかれ、かなりの鉄やアルミニウム分が含まれて
おり、さらに使用済みの脱硫触媒中にはこれらの他にバ
ナジウム、ニッケル、コバルトと言った重金属が含まれ
ている。従って、高純度のモリブデンを回収するために
は、これら共存する金属成分からモリブデンの効率的な
選択的分離が必要となる。ジアルキルリン酸などの酸性
抽出剤を用いて廃脱硫触媒の硫酸滲出液中から溶媒抽出
法を用いてモリブデンの回収を行う場合、モリブデンは
これらの共存金属に対してかなり選択的に抽出される
が、それでも鉄、アルミニウム、バナジウムはかなりの
量共抽出される。このため抽出後の溶媒中からこれらの
共抽出された金属分を取り除くことが重要な問題となっ
ている。さらに、モリブデンはジアルキルリン酸などの
酸性抽出剤に非常に低いｐＨ域からでも強力に抽出され
るため、硫酸や塩酸などの鉱酸による剥離は困難であ
る。一方、モリブデンは塩基性水溶液中では酸性抽出剤
には抽出されない陰イオン種として存在するため、アン
モニア水等の塩基性水溶液による剥離が提案されてい
る。しかしながら、酸性抽出剤とアンモニア水を振り混
ぜると、しばしば液の乳化等の問題が生ずるため、円滑
な操業ができないなどの問題があった。2. Description of the Related Art Molybdenum is an important metal indispensable to Japanese industry as a raw material metal for additives, heat-resistant materials and catalysts for the production of special steel. Examples of ores containing molybdenum include molybdenite, chalcopyrite, and galena, which are unevenly distributed in some areas such as North America and South America. Molybdenum is being recovered. Regardless of such primary resources and secondary resources, the raw material of molybdenum contains more or less a considerable amount of iron and aluminum, and the used desulfurization catalyst also contains vanadium in addition to these. It contains heavy metals such as nickel and cobalt. Therefore, in order to recover high-purity molybdenum, it is necessary to efficiently and selectively separate molybdenum from these coexisting metal components. When molybdenum is recovered from the sulfuric acid leachate of a waste desulfurization catalyst by using a solvent extraction method using an acidic extractant such as dialkyl phosphoric acid, molybdenum is extracted considerably selectively with respect to these coexisting metals. However, iron, aluminum and vanadium are still co-extracted in significant amounts. Therefore, it is an important problem to remove these co-extracted metal components from the solvent after extraction. Furthermore, since molybdenum is strongly extracted by an acidic extractant such as dialkylphosphoric acid even in a very low pH range, it is difficult to remove it with a mineral acid such as sulfuric acid or hydrochloric acid. On the other hand, molybdenum exists as an anion species that is not extracted by an acidic extractant in a basic aqueous solution, and therefore stripping with a basic aqueous solution such as ammonia water has been proposed. However, if the acidic extractant and ammonia water are shaken and mixed, problems such as emulsification of the liquid often occur, and there is a problem that smooth operation cannot be performed.
【０００３】[0003]
【発明が解決しようとする課題】本発明が解決しようと
する課題は以下の２点に集約される。 （１）モリブデンと共に溶媒中に共抽出された鉄、バナ
ジウム、アルミニウムなどの金属成分の効果的なスクラ
ップ方法、ならびにそれを可能にする特定の酸性抽出剤
のスクリーニング。 廃脱硫触媒などを硫酸水溶液で処理して得られる金属成
分を含有する硫酸水溶液からモリブデンを効果的に抽出
することが可能な抽出剤としてはジ−（２−エチルヘキ
シル）リン酸（Ｄ２ＥＨＰＡ）や２−エチルヘキシルホ
スホン酸モノ−２−エチルヘキシルエステル〔（株）大
八化学工業製：商品名ＰＣ−８８Ａ〕等の酸性リン化合
物が挙げられる。しかしながら、これらの抽出剤では、
共抽出された金属のうち、特に鉄がかなり強力に抽出さ
れるため、酸水溶液でスクラップしても取り除くことは
困難である。従って高純度のモリブデンを回収するため
には、モリブデン以外の鉄、バナジウムなどの共抽出さ
れた金属を効果的にスクラップすることが可能な特定の
抽出剤と特定のスクラップ液とを見い出すことが必要と
なる。 （２）モリブデンの剥離液のスクリーニング。 前述のように酸性抽出剤に抽出されたモリブデンの剥離
はアンモニア水等の塩基性水溶液を用いることにより達
成されるが、液の乳化等の問題が発生するため、２相の
分離が容易で、しかもほぼ１００％の剥離が可能な特定
の抽出剤と特定の剥離液および最適な操作条件を見出す
ことが必要となる。The problems to be solved by the present invention are summarized in the following two points. (1) Effective scrap method of metal components such as iron, vanadium, aluminum co-extracted in a solvent together with molybdenum, and screening of a specific acidic extractant that enables it. Di- (2-ethylhexyl) phosphoric acid (D2EHPA) or 2 is used as an extractant capable of effectively extracting molybdenum from an aqueous sulfuric acid solution containing a metal component obtained by treating a waste desulfurization catalyst with an aqueous sulfuric acid solution. An acidic phosphorus compound such as ethyl-2-hexylphosphonic acid mono-2-ethylhexyl ester [manufactured by Daihachi Chemical Industry Co., Ltd .: trade name PC-88A] is exemplified. However, with these extractants,
Of the co-extracted metals, iron is particularly strongly extracted, so it is difficult to remove it even by scraping with an aqueous acid solution. Therefore, in order to recover high-purity molybdenum, it is necessary to find a specific extractant and a specific scrap liquid that can effectively scrap co-extracted metals other than molybdenum, such as iron and vanadium. Becomes (2) Screening of molybdenum stripping solution. As described above, exfoliation of molybdenum extracted in the acidic extractant can be achieved by using a basic aqueous solution such as ammonia water, but since problems such as emulsification of the liquid occur, separation of the two phases is easy, Moreover, it is necessary to find a specific extractant capable of almost 100% peeling, a specific stripping solution, and optimum operating conditions.
【０００４】[0004]
【課題を解決するため手段】本発明者等は研究の結果、
Ｄ２ＥＨＰＡやＰＣ−８８Ａに比較して酸性の低い特定
のホスフィン酸化合物を抽出剤として用いればモリブデ
ンの選択的、効率的な抽出が達成され、しかも比較的低
濃度の硫酸などの鉱酸を用いることにより共抽出された
モリブデン以外の金属がスクラップされることを見出し
本発明を完成した。すなわち、本発明は、モリブデンの
分離回収方法において、下記一般式〔Ｉ〕で示されるホ
スフィン酸化合物を抽出剤として含有する抽出溶媒でモ
リブデンを抽出した後、該抽出溶媒に鉱酸水溶液を加え
てスクラップ（洗浄）し、しかる後、アンモニア水溶液
でモリブテンを剥離（逆抽出）することを特徴するモリ
ブテンの分離回収方法に関する。[Means for Solving the Problems] As a result of the research conducted by the present inventors,
Selective and efficient extraction of molybdenum is achieved by using a specific phosphinic acid compound having a lower acidity as compared with D2EHPA or PC-88A, and a relatively low concentration of mineral acid such as sulfuric acid is used. The present invention has been completed by finding that metals other than molybdenum coextracted with are scraped. That is, in the present invention, in the method for separating and recovering molybdenum, after extracting molybdenum with an extraction solvent containing a phosphinic acid compound represented by the following general formula [I] as an extractant, an aqueous mineral acid solution is added to the extraction solvent. The present invention relates to a method for separating and recovering molybdenum, which comprises scraping (cleaning) and then removing (back-extracting) molybdenum with an aqueous ammonia solution.
【化２】 （但し、Ｒ1およびＲ2は、炭素数３〜２５の直鎖または
側鎖を有するアルキル基、アルケニル基、シクロアルキ
ル基、アリール基、アラルキル基よりなる群からそれぞ
れ独立して選らばれた基である。）[Chemical 2] (However, R 1 and R 2 are groups independently selected from the group consisting of a linear or side chain alkyl group having 3 to 25 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group. It is.)
【０００５】一般式〔Ｉ〕で、Ｒ1およびＲ2が３未満の
炭素数の場合は、該抽出剤は水に解けやすく、抽出時に
水溶液に溶出してしまうので好ましくない。また、Ｒ1
およびＲ2の炭素数が２５より大きい場合は一般に使用
される希釈剤に溶けなくなるので好ましくない。本発明
で抽出剤として使用されるホスフィン酸化合物として
は、ジ−（２，４，４−トリメチルペンチル）−ホスフ
ィン酸、ジ−（２−エチルヘキシル）−ホスフィン酸、
ジ−（ｎ−オクチル）−ホスフィン酸、ジ−（２−メチ
ル−５−ヘキセニル）−ホスフィン酸、ジ−（ｐ−メチ
ルシクロヘキシル）−ホスフィン酸、ジ−（シクロヘキ
シル）−ホスフィン酸、ジフェニルホスフィン酸、ジ−
（ｐ−エチルフェニル）−ホスフィン酸、ジ−（ｐ−メ
チルフェニル）−ホスフィン酸などが例示される。特に
市販されているジ−（２，４，４−トリメチルペンチ
ル）−ホスフィン酸を成分とするＣｙａｎｅｘ ２７２
（アメリカン サイアナミッド社製）はコストの面など
からも好適である。前記の抽出剤は、希釈剤等と混合せ
ずに単独でまたは適当な希釈剤に溶解させて抽出溶媒と
して用いてもよい。希釈剤としては、ケロシン等の脂肪
族系希釈剤、ベンゼン、トルエン等の芳香族系希釈剤な
ど通常使用される水に不溶な有機溶媒が使用可能であ
る。前記抽出剤と希釈剤との混合比は、１：９９〜９
９：１の範囲が好ましく、特に好ましくは５：９５〜５
０：５０の範囲である。本発明で、廃脱硫触媒を硫酸水
溶液で溶解して得られるモリブデンなどの金属イオンを
含有する水溶液などからモリブデンを回収するには、ま
ず、金属イオンを含有する水溶液をｐＨ０．２以下、好
ましくは０〜０．２の間に調整した後、前述の抽出溶媒
と液−液接触させてモリブデンを抽出する。該抽出溶媒
を用いればこのｐＨ域においてもモリブデンを他の金属
に対して選択的に抽出できる。液−液接触の方法は、溶
媒抽出法において用いられる周知の方法のいずれもが使
用できる。抽出の際の抽出溶媒と水溶液との容積比は特
に限定されるものではないが、通常、１：１０〜１０：
１の範囲である。この容積比は、抽出溶媒中の抽出剤の
濃度、水溶液中の金属イオンの濃度、液−液接触の方法
等を考慮して決定される。In the general formula [I], when R 1 and R 2 have a carbon number of less than 3, the extractant is easily dissolved in water and is eluted in an aqueous solution during extraction, which is not preferable. Also, R 1
If the carbon number of R 2 and R 2 is larger than 25, it will not be dissolved in a diluent generally used, which is not preferable. Examples of the phosphinic acid compound used as an extractant in the present invention include di- (2,4,4-trimethylpentyl) -phosphinic acid, di- (2-ethylhexyl) -phosphinic acid,
Di- (n-octyl) -phosphinic acid, di- (2-methyl-5-hexenyl) -phosphinic acid, di- (p-methylcyclohexyl) -phosphinic acid, di- (cyclohexyl) -phosphinic acid, diphenylphosphinic acid , The-
Examples are (p-ethylphenyl) -phosphinic acid and di- (p-methylphenyl) -phosphinic acid. In particular, Cyanex 272 containing di- (2,4,4-trimethylpentyl) -phosphinic acid, which is commercially available, as a component
(American Cyanamid Co., Ltd.) is also suitable in terms of cost. The above-mentioned extractant may be used as an extraction solvent without being mixed with a diluent or the like, either alone or dissolved in an appropriate diluent. As the diluent, a water-insoluble organic solvent that is usually used, such as an aliphatic diluent such as kerosene and an aromatic diluent such as benzene and toluene, can be used. The mixing ratio of the extractant and the diluent is 1: 99-9.
The range of 9: 1 is preferable, and 5:95 to 5 is particularly preferable.
The range is 0:50. In the present invention, in order to recover molybdenum from an aqueous solution containing a metal ion such as molybdenum obtained by dissolving a waste desulfurization catalyst in an aqueous sulfuric acid solution, first, an aqueous solution containing a metal ion is adjusted to pH 0.2 or less, preferably After adjusting to 0 to 0.2, molybdenum is extracted by bringing the above-mentioned extraction solvent into liquid-liquid contact. If the extraction solvent is used, molybdenum can be selectively extracted with respect to other metals even in this pH range. As the liquid-liquid contact method, any of the well-known methods used in the solvent extraction method can be used. The volume ratio of the extraction solvent and the aqueous solution at the time of extraction is not particularly limited, but is usually 1:10 to 10 :.
The range is 1. This volume ratio is determined in consideration of the concentration of the extractant in the extraction solvent, the concentration of metal ions in the aqueous solution, the liquid-liquid contact method, and the like.
【０００６】ついで、抽出されたモリブデンを含有する
抽出溶媒に、鉱酸水溶液を加えてスクラップ（洗浄）す
ることにより、モリブデンと共に共抽出された比較的微
量の金属成分を抽出溶媒中から除去する。スクラップの
際の液−液接触の方法も、溶媒抽出法において用いられ
る周知の方法のいずれもが使用されうる。この場合の金
属を含有する抽出溶媒と水溶液との容積比は特に限定さ
れるものではないが、通常、１：１以下である。この容
積比は、抽出溶媒中の金属の濃度、スクラップ水溶液中
の鉱酸の濃度、液−液接触の方法等を考慮して決定され
る。鉱酸としては、硫酸、硝酸、塩酸などが例示される
が、特に硫酸は好適である。本発明での、モリブデンと
共に共抽出された鉄、バナジウムなどの比較的微量の金
属成分をスクラップする鉱酸水溶液のｐＨは、０．２以
下、好ましくは０〜０．２の範囲にあることが望まし
い。ｐＨ、０以下の強酸性の鉱酸水溶液も使用可能であ
る。鉱酸水溶液のｐＨが０．２よりも高い場合は、モリ
ブデン以外の金属成分をスクラップする効果が小さいの
で好ましくない。Then, a relatively small amount of metal component co-extracted with molybdenum is removed from the extraction solvent by adding an aqueous solution of mineral acid to the extracted solvent containing the extracted molybdenum and scraping (washing). Both the liquid-liquid contact method for scraping and the well-known methods used in solvent extraction methods can be used. In this case, the volume ratio of the metal-containing extraction solvent and the aqueous solution is not particularly limited, but is usually 1: 1 or less. This volume ratio is determined in consideration of the metal concentration in the extraction solvent, the mineral acid concentration in the scrap aqueous solution, the liquid-liquid contact method, and the like. Examples of the mineral acid include sulfuric acid, nitric acid, hydrochloric acid and the like, and sulfuric acid is particularly preferable. In the present invention, the pH of the mineral acid aqueous solution for scraping a relatively small amount of metal components such as iron and vanadium co-extracted with molybdenum is 0.2 or less, preferably in the range of 0 to 0.2. desirable. A strongly acidic mineral acid aqueous solution having a pH of 0 or less can also be used. When the pH of the aqueous solution of mineral acid is higher than 0.2, the effect of scraping metal components other than molybdenum is small, which is not preferable.
【０００７】さらに、本発明では、スクラップした後、
モリブデンを含有する該抽出溶液からモリブデンをアン
モニア水溶液を用いて水溶液中に剥離（逆抽出）する。
モリブデンは高濃度の酸性水溶液中からでも抽出される
ため、酸性抽出剤による抽出において一般的に用いられ
ているような高濃度の酸では剥離はできない。一方、モ
リブデンはアンモニア水等の塩基性水溶液中では、酸性
抽出剤では抽出されない陰イオン種として存在するた
め、このような水溶液による剥離が考えられる。しかし
ながら、酸性リン化合物を塩基性水溶液に接触させる
と、時として液の乳化、粘稠化等の不都合な現象が起こ
り操業を困難にするため、アンモニア水溶液で剥離が可
能な特定の抽出剤を選定することが重要となる。本発明
者らは研究の結果、ジアルキルホスフィン酸などの前述
の一般式〔Ｉ〕で示される特定の抽出剤を用いれば、ア
ンモニア水溶液でモリブデンを効率的に剥離できること
を見い出した。特に本発明で使用される抽出剤において
は、５〜７体積％のアンモニア水溶液を用いれば１回の
接触で約９０％程度の剥離が可能で、しかも良好な相分
離が得られる。従ってこのような剥離液と数回振り混ぜ
ることによりほぼ１００％の剥離が可能となる。剥離の
際の液−液接触の方法も、溶媒抽出法において用いられ
る周知の方法のいずれもが使用されうる。この場合の金
属を含有する抽出溶媒と水溶液との容積比は特に限定さ
れるものではないが、通常１：１以下である。この容積
比は、抽出溶媒中の金属の濃度、剥離水溶液中のアンモ
ニアの濃度、液−液接触の方法等を考慮して決定され
る。Further, in the present invention, after scrapping,
From the extraction solution containing molybdenum, molybdenum is stripped (back-extracted) into an aqueous solution using an aqueous ammonia solution.
Since molybdenum is extracted even from a high-concentration acidic aqueous solution, exfoliation cannot be performed with a high-concentration acid generally used in extraction with an acidic extractant. On the other hand, molybdenum exists in a basic aqueous solution such as aqueous ammonia as an anionic species that is not extracted by an acidic extractant, and therefore peeling by such an aqueous solution is considered. However, when an acidic phosphorus compound is brought into contact with a basic aqueous solution, inconvenient phenomena such as emulsification and thickening of the solution sometimes occur, making operation difficult, so a specific extractant that can be stripped with an aqueous ammonia solution is selected. It becomes important to do. As a result of research, the present inventors have found that molybdenum can be efficiently stripped with an aqueous ammonia solution by using a specific extractant represented by the above general formula [I] such as dialkylphosphinic acid. Particularly in the extractant used in the present invention, if an aqueous solution of 5 to 7% by volume is used, about 90% of the exfoliation can be achieved with one contact, and good phase separation can be obtained. Therefore, almost 100% peeling is possible by shaking and mixing with such a peeling liquid several times. Either a liquid-liquid contact method at the time of peeling or a well-known method used in the solvent extraction method can be used. In this case, the volume ratio of the metal-containing extraction solvent and the aqueous solution is not particularly limited, but is usually 1: 1 or less. This volume ratio is determined in consideration of the metal concentration in the extraction solvent, the ammonia concentration in the stripping aqueous solution, the liquid-liquid contact method, and the like.
【０００８】アンモニア水溶液中に剥離されたモリブデ
ンは周知の方法により、例えば、該水溶液に硝酸を加え
てモリブデン酸（Ｈ2Ｍ0Ｏ4）として沈殿させて回収す
る。また抽出溶媒は繰り返しモリブデンの抽出に使用さ
れる。The molybdenum exfoliated in the aqueous ammonia solution is recovered by a known method, for example, by adding nitric acid to the aqueous solution to precipitate molybdic acid (H 2 M 0 O 4 ) and recovering it. Also, the extraction solvent is repeatedly used to extract molybdenum.
【０００９】[0009]
【実施例】以下に本発明の実施例を述べるが、本発明は
これらの実施例に限定されるものではない。 実施例１（モリブデンの抽出１） ジ−（２，４，４−トリメチルペンチル）ホスフィン酸
を成分とするＣｙａｎｅｘ ２７２（アメンカン サイ
アナミッド社製）を工業用の希釈剤であるＥＸＸＳＯＬ
Ｄ８０（エクソン化学社製）に体積比で２０％の割合
で希釈した溶媒を用いて不純物としての５０ｍＭの濃度
の硫酸ナトリウムとそれぞれ０．３ｇ／１の濃度のモリ
ブデン（ＶＩ）、バナジウム（ＩＶ）、鉄（ＩＩＩ）、
アルミニウム、ニッケル及びコバルトの内、いずれか１
種類の金属イオンを含む水溶液に、適量の硫酸を添加す
ることによりｐＨを調整した水溶液と４０℃の温度で体
積比１：１の割合で１１７時間振り混ぜたところ、図１
に示すような各金属の抽出百分率とｐＨとの関係の結果
を得た。図１の結果より該抽出溶媒を用いれば、ｐＨが
約０ではモリブデンが９５％抽出されるのに対して、そ
れ以外の金属の抽出はほとんど認められないことがわか
る。EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. Example 1 (Extraction of molybdenum 1) Cyanex 272 (manufactured by Amenkan Cyanamid) containing di- (2,4,4-trimethylpentyl) phosphinic acid as a component is an industrial diluent EXXSOL.
Sodium sulfate having a concentration of 50 mM and molybdenum (VI) and vanadium (IV) having a concentration of 50 g each were used as impurities using a solvent diluted with D80 (manufactured by Exxon Chemical Co., Ltd.) at a volume ratio of 20%. , Iron (III),
Any one of aluminum, nickel and cobalt
As shown in FIG. 1, the mixture was shaken for 117 hours at a volume ratio of 1: 1 at a temperature of 40 ° C. with an aqueous solution whose pH was adjusted by adding an appropriate amount of sulfuric acid to the aqueous solution containing various kinds of metal ions.
The result of the relationship between the extraction percentage of each metal and pH was obtained as shown in FIG. From the results of FIG. 1, it can be seen that, when the extraction solvent is used, 95% of molybdenum is extracted at a pH of about 0, whereas other metals are hardly extracted.
【００１０】実施例２（モリブデンの抽出２） モリブデン、バナジウム、鉄、アルミニウム、コバルト
及びニッケルを表１および表２に示す割合で、同時に含
有し、様々なｐＨに調整した水溶液と、Ｃｙａｎｅｘ
２７２（アメリカン サイアナミッド社製）を工業用の
希釈剤であるＥＸＸＳＯＬ Ｄ８０（エクソン化学社
製）に体積比で４０％の割合で希釈した溶媒とを４０℃
の温度で、水相と有機相の体積比が１：１で、２４時間
振り混ぜたところ表１および表２に示す結果が得られ
た。表１および表２の結果よりｐＨが０付近ではモリブ
デンが他の金属に対して非常に選択的に抽出されている
ことが明らかである。Example 2 (Extraction of Molybdenum 2) An aqueous solution containing molybdenum, vanadium, iron, aluminum, cobalt and nickel in the proportions shown in Tables 1 and 2 simultaneously and adjusted to various pH values, and Cyanex.
A solvent obtained by diluting 272 (manufactured by American Cyanamid) with EXXSOL D80 (manufactured by Exxon Chemical Co., Ltd.) which is an industrial diluent at a volume ratio of 40% is used at 40 ° C.
When the volume ratio of the aqueous phase to the organic phase was 1: 1 and the mixture was shaken for 24 hours, the results shown in Tables 1 and 2 were obtained. From the results of Table 1 and Table 2, it is clear that molybdenum is extracted very selectively with respect to other metals when the pH is around 0.
【表１】 [Table 1]
【表２】 [Table 2]
【００１１】実施例３（モリブデンを含有する溶媒のス
クラップ） モリブデン、バナジウム、鉄、アルミニウムを表３〜表
５に示す濃度で、一緒に含有する抽出溶媒〔Ｃｙａｎｅ
ｘ ２７２（アメリカン サイアナミッド社製）を工業
用の希釈剤であるＥＸＸＳＯＬ Ｄ８０（エクソン化学
社製）に体積比で４０％の割合で希釈した溶媒〕と、
０．８５Ｎの硫酸水溶液（ｐＨ０．２）とを４０℃の温
度で、水相と有機相の体積比が１：１で、２４時間振り
混ぜたところ表３〜表５に示す結果が得られた。表３〜
表５の結果よりバナジウム、鉄、アルミニウムは特にこ
れらの含有量が小さい領域において効率的にスクラップ
されることがわかる。Example 3 (Scrap of Solvent Containing Molybdenum) Extraction solvent [Cyane] containing molybdenum, vanadium, iron and aluminum in the concentrations shown in Tables 3 to 5 together.
x 272 (manufactured by American Cyanamid Co., Ltd.) in a diluent for industrial use, EXXSOL D80 (manufactured by Exxon Chemical Co., Ltd.) at a volume ratio of 40%],
When a 0.85N sulfuric acid aqueous solution (pH 0.2) was shaken at a temperature of 40 ° C. at a volume ratio of the aqueous phase to the organic phase of 1: 1 for 24 hours, the results shown in Tables 3 to 5 were obtained. It was Table 3-
From the results in Table 5, it can be seen that vanadium, iron and aluminum are efficiently scrapped, especially in the region where the content of these is small.
【表３】 [Table 3]
【表４】 [Table 4]
【表５】 [Table 5]
【００１２】実施例４（モリブデンの剥離） 表６に示す濃度のモリブデン、バナジウム、鉄、アルミ
ニウムを含有する抽出溶媒〔Ｃｙａｎｅｘ ２７２（ア
メリカン サイアナミッド社製）を工業用の希釈剤であ
るＥＸＸＳＯＬ Ｄ８０（エクソン化学社製）に体積比
で４０％の割合で希釈した溶媒〕と、６及び７体積％の
濃度のアンモニア水溶液とを４０℃の温度で、水相と有
機相の体積比が１：１で、２４時間振り混ぜたところ表
６に示す結果が得られた。Example 4 (Exfoliation of molybdenum) An extraction solvent containing molybdenum, vanadium, iron and aluminum in concentrations shown in Table 6 [Cyanex 272 (manufactured by American Cyanamid) was used as an industrial diluent EXXSOL D80 (exon). (Produced by Kagaku) at a volume ratio of 40%] and an aqueous ammonia solution having a concentration of 6 and 7% by volume at a temperature of 40 ° C. and a volume ratio of an aqueous phase and an organic phase of 1: 1. After shaking for 24 hours, the results shown in Table 6 were obtained.
【表６】 表６の結果より、モリブデンと共に共抽出されたバナジ
ウム、鉄、アルミニウムの内、バナジウムはかなりの程
度モリブデンと同時に剥離されるが、鉄とアルミニウム
は全く剥離されない。[Table 6] From the results shown in Table 6, among vanadium, iron and aluminum co-extracted with molybdenum, vanadium is exfoliated at the same time as molybdenum, but iron and aluminum are not exfoliated at all.
【００１３】[0013]
【効果】本発明によれば、純度の高いモリブデンを高収
率で回収することができ、しかも長期間の安定な操業が
できる。[Effect] According to the present invention, molybdenum with high purity can be recovered in high yield, and stable operation can be performed for a long period of time.
【図１】実施例１における各金属の抽出百分率とｐＨと
の関係を示すグラフである。FIG. 1 is a graph showing the relationship between the extraction percentage of each metal and pH in Example 1.
Claims (1)
記一般式〔Ｉ〕で示されるホスフィン酸化合物を抽出剤
として含有する抽出溶媒でモリブデンを抽出した後、該
抽出溶媒に鉱酸水溶液を加えてスクラップし、しかる
後、アンモニア水溶液でモリブテンを剥離することを特
徴するモリブテンの分離回収方法。 【化１】 （但し、Ｒ1およびＲ2は、炭素数３〜２５の直鎖または
側鎖を有するアルキル基、アルケニル基、シクロアルキ
ル基、アリール基、アラルキル基よりなる群からそれぞ
れ独立して選らばれた基である。）1. A method for separating and recovering molybdenum, wherein molybdenum is extracted with an extracting solvent containing a phosphinic acid compound represented by the following general formula [I] as an extracting agent, and then an aqueous mineral acid solution is added to the extracting solvent to scrap. Then, after that, the molybdenum is separated and recovered with an aqueous ammonia solution. [Chemical 1] (However, R 1 and R 2 are groups independently selected from the group consisting of a linear or side chain alkyl group having 3 to 25 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group. It is.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4357529A JPH06192761A (en) | 1992-12-24 | 1992-12-24 | Separation and recovering method for molybdenum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4357529A JPH06192761A (en) | 1992-12-24 | 1992-12-24 | Separation and recovering method for molybdenum |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06192761A true JPH06192761A (en) | 1994-07-12 |
Family
ID=18454598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4357529A Pending JPH06192761A (en) | 1992-12-24 | 1992-12-24 | Separation and recovering method for molybdenum |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06192761A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100944039B1 (en) * | 2008-02-20 | 2010-02-24 | (주)광양합금철 | Method for recovering molybdenum and copper product using solvent extraction from waste water |
| WO2011005736A2 (en) | 2009-07-07 | 2011-01-13 | Cytec Technology Corp. | Processes for recovering metals from aqueous solutions |
| US20110140037A1 (en) * | 2009-12-15 | 2011-06-16 | Cytec Technology Corp. | Methods and compositions for the removal of impurities from an impurity-loaded organic salt |
| US8968698B2 (en) | 2009-07-07 | 2015-03-03 | Cytec Technology Corp. | Processes for recovering metals from aqueous solutions |
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-
1992
- 1992-12-24 JP JP4357529A patent/JPH06192761A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100944039B1 (en) * | 2008-02-20 | 2010-02-24 | (주)광양합금철 | Method for recovering molybdenum and copper product using solvent extraction from waste water |
| WO2011005736A2 (en) | 2009-07-07 | 2011-01-13 | Cytec Technology Corp. | Processes for recovering metals from aqueous solutions |
| CN102482731A (en) * | 2009-07-07 | 2012-05-30 | 塞特克技术公司 | Processes for recovering metals from aqueous solutions |
| US8328900B2 (en) | 2009-07-07 | 2012-12-11 | Cytec Technology Corp. | Processes for recovering metals from aqueous solutions |
| JP2012532989A (en) * | 2009-07-07 | 2012-12-20 | サイテク・テクノロジー・コーポレーシヨン | Method for recovering metals from aqueous solutions |
| US8968698B2 (en) | 2009-07-07 | 2015-03-03 | Cytec Technology Corp. | Processes for recovering metals from aqueous solutions |
| US9822425B2 (en) | 2009-07-07 | 2017-11-21 | Cytec Technology Corp. | Processes for recovering metals from aqueous solutions |
| US20110140037A1 (en) * | 2009-12-15 | 2011-06-16 | Cytec Technology Corp. | Methods and compositions for the removal of impurities from an impurity-loaded organic salt |
| CN102655921A (en) * | 2009-12-15 | 2012-09-05 | 塞特克技术公司 | Methods and compositions for the removal of impurities from an impurity-loaded organic salt |
| US8435411B2 (en) | 2009-12-15 | 2013-05-07 | Cytec Technology Corp. | Methods and compositions for the removal of impurities from an impurity-loaded organic salt |
| CN102655921B (en) * | 2009-12-15 | 2015-05-20 | 塞特克技术公司 | Methods and compositions for the removal of impurities from an impurity-loaded organic salt |
| CN113929139A (en) * | 2021-11-11 | 2022-01-14 | 中国科学院过程工程研究所 | Extracting agent and method for preparing vanadyl sulfate from acidic solution containing vanadium, molybdenum and nickel |
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