JP5804275B2 - Method for purifying tungsten-containing alkaline solution - Google Patents
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本発明は、タングステン含有アルカリ溶液に含まれているバナジウムを除去する精製方法に関し、好ましくは、タングステンの損失が格段に少なく、バナジウムを選択的に簡単に効率よく除去する精製方法に関する。 The present invention relates to a purification method for removing vanadium contained in a tungsten-containing alkaline solution, and preferably relates to a purification method for removing vanadium selectively and easily and efficiently, with much less loss of tungsten.
超硬合金はタングステンを主成分とし切削工具などに多く使用されている。この超硬合金にはタングステンの他にバナジウムなどの微量成分が含まれており、超硬合金スクラップからタングステンを回収する処理工程において、超硬合金スクラップを酸化焙焼した後、苛性ソーダによってＷＯ3を浸出するとバナジウムも溶出し、バナジウムを微量含有するタングステン酸ナトリウム溶液が得られる。 Cemented carbide is mainly used for cutting tools, etc., mainly composed of tungsten. This cemented carbide contains trace elements such as vanadium in addition to tungsten. In the process of recovering tungsten from cemented carbide scrap, after oxidizing and roasting the cemented carbide scrap, WO 3 is added by caustic soda. When leached, vanadium is also eluted, and a sodium tungstate solution containing a minute amount of vanadium is obtained.
タングステン酸ナトリウム溶液（Ｎａ2ＷＯ4−Ｎａ2ＣＯ3溶液）からバナジウムを除去する方法として、該溶液に塩化マグネシウム（ＭｇＣｌ2）のアンモニア溶液を添加してバナジン酸アンモニウム（ＮＨ4ＶＯ3）あるいはバナジン酸マグネシウム（ＭｇＯ・Ｖ2Ｏ5）などとして沈澱させ、これを固液分離する方法が知られている（非特許文献１）。 As a method for removing vanadium from a sodium tungstate solution (Na 2 WO 4 -Na 2 CO 3 solution), an ammonium solution of magnesium chloride (MgCl 2 ) is added to the solution and ammonium vanadate (NH 4 VO 3 ) or A method is known in which magnesium vanadate (MgO · V 2 O 5 ) is precipitated and separated into solid and liquid (Non-patent Document 1).
従来の上記処理方法は、タングステン酸ナトリウム溶液をイオン交換樹脂を用いて、タングステン酸アンモニウム溶液にするときに、通液前のタングステン酸ナトリウム溶液に塩素イオンが含まれていると、イオン交換樹脂の交換容量が低下して生産性に影響を及ばすと云う問題がある。 In the conventional treatment method described above, when the sodium tungstate solution is made into an ammonium tungstate solution using an ion exchange resin, if the sodium tungstate solution before passing contains chlorine ions, There is a problem that the exchange capacity is lowered and the productivity is affected.
また、タングステンとバナジウムを含む微酢酸溶液に鉛化合物を添加すると、バナジン酸鉛の沈澱を生じるが、タングステンも同時に沈澱し、タングステンの損失が大きい（非特許文献２）。 In addition, when a lead compound is added to a fine acetic acid solution containing tungsten and vanadium, precipitation of lead vanadate is caused, but tungsten is also precipitated at the same time, and the loss of tungsten is large (Non-patent Document 2).
本発明は、従来の処理方法の上記問題を解決したものであり、タングステン酸ナトリウム溶液に塩素が残留せず、タングステンの損失が格段に少なく、バナジウムを選択的に簡単に効率よく除去する精製方法を提供する。 The present invention solves the above-mentioned problems of the conventional processing method, and does not leave chlorine in the sodium tungstate solution, the loss of tungsten is remarkably small, and a purification method that selectively and efficiently removes vanadium selectively. I will provide a.
本発明によれば、以下に示す構成によって上記問題を解決したタングステン含有アルカリ溶液の精製方法が提供される。
〔１〕バナジウムを含むタングステン含有アルカリ溶液に、酸化鉛、酢酸鉛、硝酸鉛、硫酸鉛の少なくとも一種を添加し、該溶液のｐＨを９.５〜１２に調整してバナジウムを沈澱化し、生成した沈澱を濾別することによってバナジウムを除去することを特徴とするタングステン含有アルカリ溶液の精製方法。
〔２〕酸化鉛、酢酸鉛、硝酸鉛、硫酸鉛の少なくとも一種の添加量が、バナジウム濃度５００mg/Lに対して５g/L以上の割合である上記[１]に記載するタングステン含有アルカリ溶液の精製方法。
〔３〕生成する沈澱がバナジウムを含む水酸化物である上記[１]または上記[２]に記載するタングステン含有アルカリ溶液の精製方法。
〔４〕タングステン含有アルカリ溶液がタングステン酸ナトリウム溶液であり、タングステン酸ナトリウム溶液をイオン交換樹脂に通液してタングステン酸アンモニウム溶液にするパラタングステン酸アンモニウムの製造工程に適用される上記[１]〜上記[３]の何れかに記載する精製方法。
According to the present invention, there is provided a method for purifying a tungsten-containing alkaline solution that solves the above problems with the following configuration.
[1] Add at least one of lead oxide, lead acetate, lead nitrate and lead sulfate to a tungsten-containing alkaline solution containing vanadium and adjust the pH of the solution to 9.5 to 12 to precipitate vanadium. A method for purifying a tungsten-containing alkaline solution, characterized in that vanadium is removed by filtering out the deposited precipitate.
[2] The tungsten-containing alkaline solution according to the above [1], wherein the addition amount of at least one of lead oxide, lead acetate, lead nitrate and lead sulfate is 5 g / L or more with respect to the vanadium concentration of 500 mg / L. Purification method.
[3] The method for purifying a tungsten-containing alkaline solution according to the above [1] or [2], wherein the precipitate formed is a hydroxide containing vanadium.
[4] The tungsten-containing alkaline solution is a sodium tungstate solution, and is applied to a process for producing ammonium paratungstate by passing the sodium tungstate solution through an ion exchange resin to form an ammonium tungstate solution. The purification method according to any one of [3] above.
本発明の精製方法は、タングステン含有アルカリ溶液に含まれるバナジウムを選択的に効率よく除去することができ、溶液のｐＨを調整することによってタングステンの損失が少なく、バナジウムの除去率を格段に高めることができる。従って、超硬工具等のスクラップからタングステンを回収する処理工程において、浸出液のバナジウム濃度が高くても効率よくタングステンを回収することができる。 The purification method of the present invention can selectively and efficiently remove vanadium contained in a tungsten-containing alkaline solution, and by adjusting the pH of the solution, there is little loss of tungsten, and the vanadium removal rate is significantly increased. Can do. Therefore, in the process of recovering tungsten from scrap such as cemented carbide tool, tungsten can be recovered efficiently even if the vanadium concentration of the leachate is high.
本発明の精製方法は、タングステン含有アルカリ溶液をイオン交換樹脂に通液する際に、イオン交換樹脂の交換容量を低下させる塩素イオンが残留しないので、イオン交換樹脂によるタングステン酸イオンの交換容量を低下させずに処理することができる。 In the purification method of the present invention, when a tungsten-containing alkaline solution is passed through an ion exchange resin, there is no residual chlorine ion that lowers the exchange capacity of the ion exchange resin. Can be processed without.
以下、本発明を実施形態に基づいて具体的に説明する。
本発明の精製方法は、バナジウムを含むタングステン含有アルカリ溶液に、酸化鉛、酢酸鉛、硝酸鉛、硫酸鉛の少なくとも一種を添加し、該溶液のｐＨを９.５〜１２に調整してバナジウムを沈澱化し、生成した沈澱を濾別することによってバナジウムを除去することを特徴とするタングステン含有アルカリ溶液の精製方法である。
Hereinafter, the present invention will be specifically described based on embodiments.
In the purification method of the present invention, at least one of lead oxide, lead acetate, lead nitrate, and lead sulfate is added to a tungsten-containing alkaline solution containing vanadium , and the pH of the solution is adjusted to 9.5 to 12, thereby adding vanadium. A method for purifying a tungsten-containing alkaline solution, characterized in that vanadium is removed by precipitating and filtering out the formed precipitate.
〔タングステン含有アルカリ溶液〕
本発明の処理対象であるタングステン含有アルカリ溶液は、例えば、超硬合金スクラップを酸化焙焼した後に苛性ソーダによって浸出した溶液、あるいはタングステン鉱石の製錬処理工程から回収した溶液などであり、具体的には、タングステン酸ナトリウム溶液（Ｎａ2ＷＯ4−Ｎａ2ＣＯ3溶液、Ｎａ2ＷＯ4−ＮａＯＨ溶液）などであり、微量のバナジウムを含む溶液である。
[Tungsten-containing alkaline solution]
The tungsten-containing alkaline solution to be treated according to the present invention is, for example, a solution leached by caustic soda after oxidizing and roasting cemented carbide scrap, or a solution recovered from a smelting process of tungsten ore. Is a sodium tungstate solution (Na 2 WO 4 -Na 2 CO 3 solution, Na 2 WO 4 -NaOH solution) or the like, which is a solution containing a small amount of vanadium.
〔沈澱生成〕
バナジウムを含むタングステン含有アルカリ溶液に、鉛化合物を添加してバナジウムを含む沈澱を生成させる。タングステン含有アルカリ溶液に含まれるバナジウムはバナジン酸イオンを形成しており、鉛化合物が添加されると鉛と反応してバナジン酸鉛になり、水酸化鉛との複塩〔Ｐｂ5(ＶＯ4)3ＯＨ〕を生じる。
(Precipitation formation)
A lead compound is added to a tungsten-containing alkaline solution containing vanadium to form a precipitate containing vanadium. Vanadium contained in the tungsten-containing alkaline solution forms vanadate ions. When a lead compound is added, it reacts with lead to lead vanadate to form a double salt with lead hydroxide [Pb 5 (VO 4 ) 3 OH].
タングステン含有アルカリ溶液は強アルカリ性であり、例えばｐＨ１２以上の領域、あるいは遊離ＮａＯＨが４０g/L以上でも、液中に含まれるバナジウムは鉛と反応して沈澱するが、ｐＨが中性領域に近いほどバナジウムはよく沈澱する。一方、ｐＨ９未満になると液中のタングステンが沈澱し始めるので、タングステンの損失を抑えてバナジウムの沈澱を進めるには、硫酸等を添加してｐＨ９.５〜１２、好ましくはｐＨ１０〜１１に調整すると良い。従来、微酢酸溶液に鉛化合物を添加するとバナジン酸鉛の沈澱を生じることが知られているが、タングステンも同時に沈澱するのでタングステンの損失が大きいことから、本発明の方法はアルカリ液性下でバナジウムを沈澱させる。 The tungsten-containing alkaline solution is strongly alkaline. For example, even when the pH is 12 or higher, or even when the free NaOH is 40 g / L or higher, vanadium contained in the solution reacts with lead and precipitates. Vanadium precipitates well. On the other hand, since the tungsten in the liquid begins to precipitate when the pH is less than 9, in order to suppress the loss of tungsten and advance the vanadium precipitation, sulfuric acid or the like is added to adjust the pH to 9.5 to 12, preferably 10 to 11. good. Conventionally, it has been known that the addition of a lead compound to a fine acetic acid solution causes precipitation of lead vanadate. However, since tungsten is also precipitated at the same time, the loss of tungsten is large. Precipitate vanadium.
タングステン含有アルカリ溶液に添加する鉛化合物は酸化鉛、酢酸鉛、硝酸鉛、硫酸鉛の少なくとも一種を用いることができる。なお、酢酸鉛よりも酸化鉛のほうがバナジウムの沈澱効果が良い。また、液中に塩素イオンを残留させないためには酸化鉛などが良く、塩化鉛を併用する場合には塩化鉛の量は少ないほうが好ましい。
As the lead compound added to the tungsten-containing alkaline solution, at least one of lead oxide, lead acetate, lead nitrate, and lead sulfate can be used. In addition, the precipitation effect of vanadium is better with lead oxide than with lead acetate. Further, lead oxide or the like is good for preventing chlorine ions from remaining in the liquid, and when lead chloride is used in combination, the amount of lead chloride is preferably small.
酸化鉛、酢酸鉛、硝酸鉛、硫酸鉛の少なくとも一種の添加量は、バナジウム濃度５００mg/Lにおいて５g/L以上が好ましい。鉛化合物の添加量がこれより少ないとバナジウムが十分に沈澱せず、液中のバナジウム残量が多くなる。上記鉛化合物の添加量の上限は未反応の鉛化合物量が少なくなるように定めればよい。
The added amount of at least one of lead oxide, lead acetate, lead nitrate and lead sulfate is preferably 5 g / L or more at a vanadium concentration of 500 mg / L. If the amount of lead compound added is less than this, vanadium will not sufficiently precipitate, and the remaining amount of vanadium in the liquid will increase. What is necessary is just to set the upper limit of the addition amount of the said lead compound so that the amount of unreacted lead compound may decrease.
本発明の精製方法は、タングステン酸ナトリウム溶液をイオン交換樹脂に通液してタングステン酸アンモニウム溶液にするパラタングステン酸アンモニウムの製造工程に適用することができる。例えば、超硬合金スクラップを酸化焙焼した後に苛性ソーダによって浸出したタングステン酸ナトリウム溶液に、鉛化合物を加え、ｐＨ９.５〜１２、好ましくはｐＨ１０〜１１に調整し、生成した沈澱を濾別することによってバナジウムの濃度を大幅に低減したタングステン酸ナトリウム溶液を得ることができる。 The purification method of the present invention can be applied to a production process of ammonium paratungstate by passing a sodium tungstate solution through an ion exchange resin to make an ammonium tungstate solution. For example, a lead compound is added to a sodium tungstate solution leached by caustic soda after oxidative roasting of cemented carbide scrap, adjusted to pH 9.5 to 12, preferably pH 10 to 11, and the generated precipitate is filtered off. Thus, a sodium tungstate solution having a greatly reduced vanadium concentration can be obtained.
このように精製したタングステン酸ナトリウム溶液をイオン交換樹脂に通液してタングステン酸イオン（ＷＯ4 2-）を吸着させた後、アンモニアと塩化アンモニウムの混合液を溶離液として用い、この混合液をイオン交換樹脂に通液してタングステン酸イオンを溶離させ、タングステン酸アンモニウム溶液を得る。このタングステン酸アンモニウム溶液を加熱濃縮することによって、バナジウム含有量が数ppm以下のパラタングステン酸アンモニウムを得ることができる。 The purified sodium tungstate solution is passed through an ion exchange resin to adsorb tungstate ions (WO 4 2- ), and then a mixed solution of ammonia and ammonium chloride is used as an eluent. The solution is passed through an ion exchange resin to elute tungstate ions to obtain an ammonium tungstate solution. By heating and concentrating this ammonium tungstate solution, ammonium paratungstate having a vanadium content of several ppm or less can be obtained.
〔参考例１〕
バナジウム(Ｖ)を含むタングステン(Ｗ)含有アルカリ溶液１Ｌに塩化鉛粉末９.７ｇを添加し、１８℃で４時間撹拌して沈澱を生成させ、これを固液分離し、濾液のＷ濃度およびＶ濃度を測定した。処理前の溶液のＷ濃度およびＶ濃度、濾液のＷ濃度およびＶ濃度を表１に示す。
[ Reference Example 1]
9.7 g of lead chloride powder was added to 1 L of tungsten (W) -containing alkaline solution containing vanadium (V) and stirred at 18 ° C. for 4 hours to form a precipitate, which was separated into solid and liquid, and the W concentration of the filtrate and V concentration was measured. Table 1 shows the W and V concentrations of the solution before the treatment and the W and V concentrations of the filtrate.
〔実施例２、３〕
鉛化合物として酢酸鉛１４.７ｇ、酸化鉛８.７ｇを用い、それ以外は実施例１と同様にして沈澱を生成させ、固液分離した。処理前の溶液のＷ濃度およびＶ濃度、濾液のＷ濃度およびＶ濃度を表１に示す。
[Examples 2 and 3]
As the lead compound, 14.7 g of lead acetate and 8.7 g of lead oxide were used, and a precipitate was produced in the same manner as in Example 1 and separated into solid and liquid. Table 1 shows the W and V concentrations of the solution before the treatment and the W and V concentrations of the filtrate.
表１に示すように、実施例１〜３の何れにおいても、処理前の溶液のＷ濃度と濾液のＷ濃度はあまり変わらず、一方、濾液のＶ濃度は大幅に低下しており（約１/５に低下）、バナジウムが選択的に沈澱し、除去されている。なお、塩化鉛や酢酸鉛を用いたときよりも、酸化鉛を用いたほうが濾液中のバナジウム濃度が低く、少ない添加量でバナジウムがよく沈澱し、バナジウムの除去効果が高い。 As shown in Table 1, in any of Examples 1 to 3, the W concentration of the solution before the treatment and the W concentration of the filtrate were not significantly changed, while the V concentration of the filtrate was greatly reduced (about 1 Vanadium is selectively precipitated and removed. In addition, the vanadium concentration in the filtrate is lower when lead oxide is used than when lead chloride or lead acetate is used, and vanadium precipitates well with a small addition amount, and the effect of removing vanadium is high.
〔実施例４〜１２〕
表２に示すＷ濃度およびＶ濃度を有する溶液１Ｌに、酸化鉛を添加し、一部は硫酸を添加してｐＨを調整し、沈澱を生成させた後に固液分離し、濾液のＷ濃度およびＶ濃度を測定した。この結果を表２に示した。また、実施例５において、生成した沈澱を回収してＸ線回折によって化合物を調べたところ、バナジン酸鉛と水酸化鉛の複塩〔Ｐｂ5(ＶＯ4)3ＯＨ〕であることを確認した。
[Examples 4 to 12]
Lead oxide is added to 1 L of the solution having the W concentration and V concentration shown in Table 2, and a part of the solution is adjusted to pH by adding sulfuric acid to form a precipitate, followed by solid-liquid separation. V concentration was measured. The results are shown in Table 2. In Example 5, the produced precipitate was recovered and the compound was examined by X-ray diffraction. As a result, it was confirmed that it was a double salt of lead vanadate and lead hydroxide [Pb 5 (VO 4 ) 3 OH]. .
表２に示すように、酸化鉛の添加量が２〜４g/Lでは濾液のＶ濃度が高く、バナジウムが十分に沈澱していないので、酸化鉛の添加量は５g/L以上が好ましい。また、ｐＨ１０〜１２に調整するとバナジウムの沈澱が進み、濾液のＶ濃度が格段に低下する。一方、ｐＨ９になるとタングステンが沈澱し始め、濾液のＷ濃度が低下するので、タングステンの損失を防ぐにはｐＨ９以上が好ましい。処理時間は１時間ほどでよい。 As shown in Table 2, when the amount of lead oxide added is 2 to 4 g / L, the V concentration of the filtrate is high and vanadium is not sufficiently precipitated. Therefore, the amount of lead oxide added is preferably 5 g / L or more. Further, when the pH is adjusted to 10 to 12, precipitation of vanadium proceeds, and the V concentration of the filtrate is remarkably reduced. On the other hand, when pH 9 is reached, tungsten begins to precipitate, and the W concentration of the filtrate decreases. Therefore, pH 9 or higher is preferable in order to prevent loss of tungsten. The processing time may be about 1 hour.
Claims (4)
The tungsten-containing alkaline solution is a sodium tungstate solution, and is applied to a process for producing ammonium paratungstate by passing the sodium tungstate solution through an ion exchange resin to form an ammonium tungstate solution. The purification method described in any one.
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