JP2010138490A - Method of recovering zinc - Google Patents
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Abstract
【課題】塩素濃度が高い塩化亜鉛溶液から、塩素およびナトリウムを実質的に含まない沈澱を生成させ、亜鉛製錬原料に適する亜鉛化合物を容易に回収する方法を提供する。
【解決手段】高塩素濃度の塩化亜鉛溶液に、液中のアルミニウム濃度を制限し、炭酸ソーダを加えてｐＨ６以上の液性下で塩基性炭酸亜鉛を沈殿させて、亜鉛を回収することを特徴とする亜鉛の回収方法であり、好ましくは、塩素濃度が６０g/L以上の塩化亜鉛溶液について、液中のアルミニウム濃度を２００mg/L以下に制限して炭酸ソーダを加えてｐＨ７以上の液性下で塩基性炭酸亜鉛を沈殿させる亜鉛の回収方法。
【選択図】図１To provide a method for easily recovering a zinc compound suitable for a zinc smelting raw material by producing a precipitate substantially free of chlorine and sodium from a zinc chloride solution having a high chlorine concentration.
SOLUTION: The zinc concentration is recovered by limiting the aluminum concentration in the solution to a zinc chloride solution having a high chlorine concentration, adding sodium carbonate, and precipitating the basic zinc carbonate under liquidity of pH 6 or higher. Preferably, in a zinc chloride solution having a chlorine concentration of 60 g / L or more, the concentration of aluminum in the solution is limited to 200 mg / L or less, sodium carbonate is added, and the pH is 7 or more. To recover zinc by precipitating basic zinc carbonate.
[Selection] Figure 1
Description
本発明は、塩化亜鉛溶液に炭酸ソーダ（Na2CO3）を添加して亜鉛含有沈殿を生成させ、亜鉛を回収する方法において、塩素およびナトリウムの混入量が少ない亜鉛含有沈殿を回収することができる亜鉛の回収方法に関する。 In the method of recovering zinc by adding sodium carbonate (Na 2 CO 3 ) to a zinc chloride solution and recovering zinc, the present invention recovers the zinc-containing precipitate with a small amount of chlorine and sodium. The present invention relates to a method for recovering zinc.
製鉄ダストを還元炉や還元焙焼炉などで加熱処理することによって、亜鉛を主成分とした金属酸化物（粗酸化亜鉛）が得られる。この粗酸化亜鉛は塩素を多量に含んでいるため、このままでは金属亜鉛として利用することができない。 A metal oxide (crude zinc oxide) containing zinc as a main component can be obtained by heat-treating the iron-made dust in a reduction furnace or a reduction roasting furnace. Since this crude zinc oxide contains a large amount of chlorine, it cannot be used as metallic zinc as it is.
そこで、この粗亜鉛酸化物を加熱して鉛および亜鉛を含有する塩化物として揮発分離させ、これを温水で浸出した液に、炭酸ソーダおよび苛性ソーダを添加して亜鉛を含む塩基性炭酸塩を沈澱させ、この亜鉛含有沈殿を硝酸溶解し、溶媒抽出によって銅、亜鉛を分離回収した後に、液を濃縮して硝酸鉛の結晶を回収する方法が知られている（特許文献１）。 Therefore, the crude zinc oxide is heated to volatilize and separate as a chloride containing lead and zinc, and sodium carbonate and caustic soda are added to the solution leached with warm water to precipitate basic carbonate containing zinc. In addition, a method is known in which the zinc-containing precipitate is dissolved in nitric acid, and copper and zinc are separated and recovered by solvent extraction, and then the liquid is concentrated to recover lead nitrate crystals (Patent Document 1).
上記回収方法において、粗亜鉛酸化物を加熱して揮発させた塩化物は鉛を多く含むため、この状態ではその残渣を埋設処理することができない。そこで、この塩化物に希硫酸を加えて亜鉛を溶出させる一方、鉛を硫酸鉛にして沈澱分離し、この濾液に亜鉛粉末を加えて銅とカドミウムを還元析出させ、これ濾過分離した濾液に炭酸ソーダを加え、炭酸亜鉛を沈澱させて亜鉛を回収する方法が知られている（特許文献１）。 In the above recovery method, since the chloride obtained by heating and volatilizing the crude zinc oxide contains a large amount of lead, the residue cannot be buried in this state. Accordingly, dilute sulfuric acid is added to the chloride to elute zinc, while lead is converted to lead sulfate and separated by precipitation. Zinc powder is added to the filtrate to reduce copper and cadmium, and the filtrate is separated into carbonate. A method of recovering zinc by adding soda and precipitating zinc carbonate is known (Patent Document 1).
一般に、アルミニウムが共存する亜鉛含有塩酸溶液に炭酸ソーダを加えて沈澱を生成させると、混在するアルミニウムの影響によってナトリウムを含有する亜鉛化合物〔Na2Zn3(CO3)4・３H2O〕が沈澱する。また、苛性ソーダを加えて沈澱を生成させると、塩素を含む亜鉛化合物〔Zn5(OH)8Cl2・H2O〕が沈澱する。これらはナトリウムまたは塩素を含有するので製錬原料として適さない。 In general, when sodium carbonate is added to a zinc-containing hydrochloric acid solution in which aluminum coexists, precipitates are formed, and the zinc compound containing sodium [Na 2 Zn 3 (CO 3 ) 4 · 3H 2 O] is affected by the influence of mixed aluminum. Precipitate. Further, when caustic soda is added to form a precipitate, a zinc compound containing zinc [Zn 5 (OH) 8 Cl 2 .H 2 O] precipitates. Since these contain sodium or chlorine, they are not suitable as smelting raw materials.
そこで、従来の上記回収方法では溶媒抽出などによって亜鉛を抽出しているが、手間がかかり、コスト高になる問題がある。また、上記亜鉛回収方法は、塩基性炭酸塩の硝酸溶解から溶媒抽出による亜鉛回収、およびその逆抽出による硫酸亜鉛の回収に至る処理工程が煩雑である。 Therefore, in the conventional recovery method described above, zinc is extracted by solvent extraction or the like, but there is a problem that it takes time and costs are increased. Further, the above zinc recovery method involves complicated processing steps from dissolution of basic carbonate in nitric acid to recovery of zinc by solvent extraction and recovery of zinc sulfate by reverse extraction.
本発明は、従来の回収方法における上記問題を解決したものであり、塩素濃度が高い亜鉛含有液においても、塩素およびナトリウムを実質的に含まない沈澱を生成させ、亜鉛製錬原料に適する亜鉛化合物を容易に回収する方法を提供する。 The present invention solves the above-mentioned problem in the conventional recovery method, and generates a precipitate substantially free of chlorine and sodium even in a zinc-containing liquid having a high chlorine concentration, and is a zinc compound suitable for a zinc smelting raw material Provide a method for easily recovering.
〔１〕請求項１に記載する方法は、亜鉛含有塩酸溶液に含まれる液中のアルミニウム濃度を２００mg/L以下にして、炭酸ソーダを加えてｐＨ６以上の液性下で塩基性炭酸亜鉛を沈殿させることによって、塩素およびナトリウムの混入を制限した亜鉛含有沈澱を回収することを特徴とする亜鉛の回収方法である。 [1] In the method described in claim 1, basic zinc carbonate is precipitated under a liquid condition of pH 6 or higher by adding sodium carbonate with the aluminum concentration in the liquid contained in the zinc-containing hydrochloric acid solution being 200 mg / L or lower. To recover a zinc-containing precipitate in which contamination of chlorine and sodium is restricted.
亜鉛含有塩酸溶液に、液中のアルミニウム濃度を２００mg/L以下に制限し、炭酸ソーダを加えて、ｐＨを６以上に調整することによって、塩素およびナトリウムを実質的に含まない塩基性炭酸亜鉛〔Zn5(CO3)2(OH)6：hydrozinsite〕の沈殿を生成させることができる。この炭酸亜鉛は塩素およびナトリウムを実質的に含まないので亜鉛製錬原料として用いることができる。 Basic zinc carbonate substantially free of chlorine and sodium is obtained by limiting the aluminum concentration in the zinc-containing hydrochloric acid solution to 200 mg / L or less and adding sodium carbonate to adjust the pH to 6 or more. Zn 5 (CO 3 ) 2 (OH) 6 : hydrozinsite] can be produced. Since this zinc carbonate does not substantially contain chlorine and sodium, it can be used as a zinc smelting raw material.
〔２〕請求項２に記載する方法は、塩素濃度６０g/L以上の亜鉛含有塩酸溶液について、液中のアルミニウム濃度を２００mg/L以下に制限し、液温５０℃以上で塩基性炭酸亜鉛を沈殿させる請求項１に記載する亜鉛の回収方法である。 [2] In the method described in claim 2, in a zinc-containing hydrochloric acid solution having a chlorine concentration of 60 g / L or more, the aluminum concentration in the solution is limited to 200 mg / L or less, and basic zinc carbonate is added at a liquid temperature of 50 ° C. or more. The method for recovering zinc according to claim 1, wherein the zinc is precipitated.
塩素濃度が６０g/L以上の塩素濃度の高い亜鉛含有塩酸溶液でも、液中のアルミニウム濃度を２００mg/L以下に制限し、液温５０℃以上にすることによって、塩素およびナトリウムを実質的に含まない上記塩基性炭酸亜鉛の沈殿を生成させることができる。 Even in a zinc-containing hydrochloric acid solution with a chlorine concentration of 60 g / L or more and high chlorine concentration, the aluminum concentration in the solution is limited to 200 mg / L or less, and the solution temperature is 50 ° C. or more. No precipitate of the basic zinc carbonate can be produced.
〔３〕請求項３に記載する方法は、亜鉛含有塩酸溶液に、炭酸ソーダを加えてｐＨを４以上〜６未満に調整して液中のアルミニウムを水酸化アルミニウム沈殿にし、該沈澱を固液分離して液中のアルミニウム濃度を２００mg/L以下にする脱アルミ工程と、上記水酸化アルミニウム沈殿を分離した濾液に炭酸ソーダを加えて、ｐＨ６以上の液性下で、塩基性炭酸亜鉛を沈殿させて、該沈殿を回収する亜鉛沈澱回収工程とを有する請求項１または請求項２に記載する亜鉛の回収方法である。 [3] In the method described in claim 3, sodium carbonate is added to a zinc-containing hydrochloric acid solution to adjust the pH to 4 or more and less than 6 to make aluminum in the solution into aluminum hydroxide precipitate. Separating the aluminum concentration in the liquid to 200 mg / L or less, adding sodium carbonate to the filtrate from which the aluminum hydroxide precipitate has been separated, and precipitating basic zinc carbonate under liquidity of pH 6 or higher The zinc recovery method according to claim 1, further comprising a zinc precipitation recovery step of recovering the precipitate.
亜鉛と共にアルミニウムを含有する高塩素濃度の塩酸溶液について、液中のアルミニウム濃度を２００mg/L以下にする脱アルミ工程を設け、液中のアルミニウム濃度を上記濃度以下に低減した後に亜鉛含有沈澱を生成させることによって、塩素およびナトリウムを実質的に含まない塩基性炭酸亜鉛を沈殿させることができる。この脱アルミ工程は、次工程の亜鉛回収工程と同様に炭酸ソーダを用いることができるので、液性の調整が容易であり、実施しやすい。 For a high chlorine concentration hydrochloric acid solution containing aluminum together with zinc, a dealumination process is performed to reduce the aluminum concentration in the solution to 200 mg / L or less, and after the aluminum concentration in the solution is reduced to the above concentration or less, a zinc-containing precipitate is formed. By doing so, basic zinc carbonate substantially free of chlorine and sodium can be precipitated. Since this dealumination process can use sodium carbonate similarly to the zinc recovery process of the next process, liquidity adjustment is easy and easy to implement.
〔４〕請求項４の方法は、亜鉛含有塩酸溶液が、製錬廃棄物や有価金属の塩酸浸出液に亜鉛を投入して含有金属を析出させ固液分離した液分である請求項１〜請求項３の何れかに記載する亜鉛の回収方法である。
インジウム、スズ、カドミウムなどが含まれている塩化物溶液から、これらの金属を回収する方法として、処理液に亜鉛を投入してインジウムを還元析出させ、回収する方法が知られている。本発明の方法は、インジウム等を回収した後の液分から亜鉛を効率よく回収することができる。
[4] In the method of claim 4, the zinc-containing hydrochloric acid solution is a liquid component obtained by depositing zinc into a hydrochloric acid leaching solution of smelting waste or valuable metals to precipitate the contained metal, and solid-liquid separation. Item 4. The method for recovering zinc according to any one of Item 3.
As a method for recovering these metals from a chloride solution containing indium, tin, cadmium and the like, a method of recovering and depositing indium by introducing zinc into a treatment solution is known. The method of the present invention can efficiently recover zinc from the liquid after recovering indium and the like.
〔５〕請求項５の方法は、高塩素濃度の塩化亜鉛溶液が、製錬廃棄物や有価金属の塩酸浸出液に亜鉛を投入して含有金属を析出させ固液分離した液分である請求項１〜請求項４の何れかに記載する金属亜鉛の製造方法である。
回収した亜鉛含有沈澱はナトリウムおよび塩素の含有量が概ね０.１wt％以下であって、実質的にナトリムおよび塩素を含まない塩基性炭酸亜鉛であるので、これを亜鉛電解液に直接に溶解して亜鉛を電解採取し、電気亜鉛を製造することができる。
[5] In the method of claim 5, the zinc chloride solution having a high chlorine concentration is a liquid obtained by depositing zinc into a hydrochloric acid leachate of smelting waste or valuable metals to precipitate the contained metal, and solid-liquid separation. It is a manufacturing method of metallic zinc in any one of Claims 1-4.
The recovered zinc-containing precipitate has a sodium and chlorine content of about 0.1 wt% or less and is a basic zinc carbonate substantially free of sodium and chlorine. Therefore, it is dissolved directly in the zinc electrolyte. Zinc can be electrolyzed to produce electrozinc.
本発明の方法は、高塩素濃度の塩化亜鉛溶液について、炭酸ソーダを用いながら、溶液のｐＨ調整によって、塩素およびナトリウムを実質的に含まない塩基性炭酸亜鉛を沈殿させことができる。この沈殿は製錬原料に適するので、埋立処理せずに亜鉛の回収と再利用を促進することができる。 In the method of the present invention, basic zinc carbonate substantially free of chlorine and sodium can be precipitated by adjusting the pH of the solution while using sodium carbonate for a high chlorine concentration zinc chloride solution. Since this precipitation is suitable for smelting raw materials, recovery and reuse of zinc can be promoted without landfill treatment.
本発明の方法において用いる炭酸ソーダは一般的な薬液あり、また苛性ソーダを併用する必要がなく、処理工程も簡単であるので、容易に実施することができる。 Sodium carbonate used in the method of the present invention is a general chemical solution, and it is not necessary to use caustic soda in combination, and the treatment process is simple, so that it can be easily carried out.
以下、本発明を実施形態に基づいて具体的に説明する。
本発明の方法は、亜鉛含有塩酸溶液に含まれる液中のアルミニウム濃度を２００mg/L以下にして、炭酸ソーダを加えてｐＨ６以上の液性下で塩基性炭酸亜鉛を沈殿させることによって、塩素およびナトリウムの混入を制限した亜鉛含有沈澱を回収することを特徴とする亜鉛の回収方法である。本発明の亜鉛回収方法について、処理工程の一例を図１に示す。
Hereinafter, the present invention will be specifically described based on embodiments.
In the method of the present invention, the concentration of aluminum in the solution contained in the zinc-containing hydrochloric acid solution is adjusted to 200 mg / L or less, sodium carbonate is added, and basic zinc carbonate is precipitated under a solution having a pH of 6 or more. A zinc recovery method characterized by recovering a zinc-containing precipitate in which sodium contamination is limited. An example of the processing steps for the zinc recovery method of the present invention is shown in FIG.
〔塩化亜鉛溶液〕
本発明の回収方法において用いる亜鉛含有塩酸溶液は、例えば、有価金属の塩酸浸出液に亜鉛を投入して液中の金属を析出させ、これを固液分離した液分などを用いることができる。
[Zinc chloride solution]
As the zinc-containing hydrochloric acid solution used in the recovery method of the present invention, for example, a liquid obtained by depositing zinc into a hydrochloric acid leaching solution of a valuable metal to precipitate the metal in the liquid and solid-liquid separate it can be used.
インジウム、スズ、カドミウムなどを含む原料を塩酸に溶解し、この塩酸溶解液に金属インジウムを添加してスズを析出させて固液分離し、次いで上記溶解液に硫化源を添加して硫化カドミウムを沈澱させて固液分離した後に、該溶解液に亜鉛を添加して液中に含まれるインジウムを析出させ、固液分離して回収する方法が知られている。この固液分離した液分には多量の亜鉛が含まれている。本発明の方法は、このような処理液から亜鉛を回収する方法として好適に利用することができる。 A raw material containing indium, tin, cadmium, etc. is dissolved in hydrochloric acid. Metal indium is added to this hydrochloric acid solution to precipitate tin, and solid-liquid separation is performed. Then, a sulfidation source is added to the above solution to add cadmium sulfide. A method is known in which after precipitation and solid-liquid separation, zinc is added to the dissolved solution to precipitate indium contained in the solution, followed by solid-liquid separation and recovery. A large amount of zinc is contained in the liquid component separated into solid and liquid. The method of the present invention can be suitably used as a method for recovering zinc from such a treatment liquid.
亜鉛含有塩酸溶液中のアルミニウム濃度を２００mg/L以下、好ましくは１００mg/L以下、さらに好ましくは５０mg/L以下に制限する。液中のアルミニウム濃度がこれより高いと、炭酸ソーダを加えて沈澱を生成させたときに、ナトリウム含有沈澱物〔Na2Zn3(CO3)4・３H2O等〕になりやすく、これは製錬原料に適さないので好ましくない。アルミニウム濃度が高い溶液については、液中のアルミニウムを除去する工程（脱アルミ工程）を設けるとよい。アルミニウム濃度が２００mg/L以下の溶液は脱アルミ工程を設けなくてもよい。 The aluminum concentration in the zinc-containing hydrochloric acid solution is limited to 200 mg / L or less, preferably 100 mg / L or less, and more preferably 50 mg / L or less. If the aluminum concentration in the liquid is higher than this, when sodium carbonate is added to form a precipitate, it tends to be a sodium-containing precipitate (Na 2 Zn 3 (CO 3 ) 4 · 3H 2 O, etc.). Since it is not suitable for a smelting raw material, it is not preferable. For a solution having a high aluminum concentration, a step of removing aluminum in the solution (aluminum removal step) may be provided. A solution having an aluminum concentration of 200 mg / L or less may not be provided with a dealumination process.
本発明の回収方法は、塩素濃度が６０g/L以上の高い塩素濃度の塩酸溶液についても、実質的に塩素を含有しない亜鉛含有物を沈澱させることができる。塩素濃度が６０g/L以上の塩酸濃度が高い溶液で沈澱を生成させると沈澱に塩素が混入しやすいが、本発明の回収方法では液中のアルミニウム濃度を上記範囲に制限することによって塩素濃度６０g/L以上の溶液でも実質的に塩素を含まない沈澱を生成させることができる。 The recovery method of the present invention can precipitate a zinc-containing material that does not substantially contain chlorine even in a hydrochloric acid solution having a high chlorine concentration with a chlorine concentration of 60 g / L or more. When precipitation is generated in a solution having a high hydrochloric acid concentration with a chlorine concentration of 60 g / L or more, chlorine is likely to be mixed into the precipitate. However, in the recovery method of the present invention, the chlorine concentration is 60 g by limiting the aluminum concentration in the liquid to the above range. A precipitate containing substantially no chlorine can be produced even with a solution of / L or more.
〔脱アルミ工程〕
アルミニウム濃度が高い亜鉛含有塩酸溶液に炭酸ソーダを添加してｐＨを４以上〜６未満、好ましくはｐＨ４.５〜５.５に調整すると、液中のアルミニウムが水酸化物になって沈澱し、アルミニウム濃度が低くなる。なお、亜鉛の一部も水酸化亜鉛になって沈澱するが僅かな量である。これらを濾別してアルミニウムを液中から除去する。
[Dealloying process]
When sodium carbonate is added to a zinc-containing hydrochloric acid solution having a high aluminum concentration to adjust the pH to 4 or more and less than 6, preferably 4.5 to 5.5, the aluminum in the solution becomes a hydroxide and precipitates. The aluminum concentration is lowered. A part of zinc also becomes zinc hydroxide and precipitates, but only a small amount. These are filtered off to remove aluminum from the liquid.
亜鉛含有塩酸溶液のｐＨが４より低いと、水酸化アルミニウムを十分に除去し難く、また上記ｐＨが６より高いと、亜鉛が水酸化物沈澱になる量が増えるのでｐＨ４.５〜５.５の範囲が好ましい。炭酸ソーダの添加量は液のｐＨが４以上〜６未満、好ましくはｐＨ４.５〜５.５程度になり、液中のアルミニウム濃度が２００mg/L以下になるまで添加するとよい。 When the pH of the zinc-containing hydrochloric acid solution is lower than 4, it is difficult to sufficiently remove aluminum hydroxide. When the pH is higher than 6, the amount of zinc that becomes a hydroxide precipitate increases, so that the pH is 4.5 to 5.5. The range of is preferable. The addition amount of sodium carbonate is preferably added until the pH of the solution is 4 or more to less than 6, preferably about 4.5 to 5.5, and the aluminum concentration in the solution is 200 mg / L or less.
脱アルミ工程において、溶液の塩素濃度が９０g/L以上であるときは、水を加えて溶液を希釈し、塩素濃度を９０g/Lに調整して炭酸ソーダを添加するとよい。塩素濃度が９０g/Lより高過ぎるとアルミニウムが沈澱し難くなる。 In the dealumination process, when the chlorine concentration of the solution is 90 g / L or more, it is preferable to dilute the solution by adding water, adjust the chlorine concentration to 90 g / L, and add sodium carbonate. If the chlorine concentration is higher than 90 g / L, aluminum is difficult to precipitate.
〔亜鉛沈澱回収工程〕
アルミニウム濃度を２００mg/L以下に低減した亜鉛含有塩酸溶液に、炭酸ソーダを加えて攪拌し、ｐＨ６以上、好ましくはｐＨ８以上に調整する。液中に含まれる亜鉛化合物は加水分解して塩基性炭酸亜鉛〔Zn5(CO3)2(OH)6〕の沈殿が生成する。液中のアルミニウム、および炭酸ソーダからのナトリウムは、大部分が液中に残り、上記沈澱に混入する量は僅かであり、概ね０.１wt％以下である。
[Zinc precipitation recovery process]
Sodium carbonate is added to a zinc-containing hydrochloric acid solution whose aluminum concentration has been reduced to 200 mg / L or less and stirred to adjust the pH to 6 or more, preferably 8 or more. The zinc compound contained in the liquid is hydrolyzed to form a precipitate of basic zinc carbonate [Zn 5 (CO 3 ) 2 (OH) 6 ]. Most of the aluminum in the liquid and sodium from sodium carbonate remain in the liquid, and the amount mixed into the precipitate is small, and is generally 0.1 wt% or less.
溶液のｐＨが５より低いと塩基性炭酸亜鉛の沈澱が生成し難い。炭酸ソーダは、溶液のｐＨが６以上になり、沈澱が生成しなくなるまで添加するとよい。概ね１時間程度静置して熟成させた後に洗浄し、固液分離して上記炭酸亜鉛沈澱を回収する。 When the pH of the solution is lower than 5, precipitation of basic zinc carbonate hardly occurs. Sodium carbonate is preferably added until the pH of the solution becomes 6 or more and no precipitation occurs. After standing for about 1 hour and aging, the product is washed and separated into solid and liquid to recover the zinc carbonate precipitate.
亜鉛沈澱回収工程において、沈殿生成時の液温は５０℃以上が好ましい。液温を５０℃以上にすればナトリウムを実質的に含まない沈澱を生成させることができる。洗浄はリパルプ洗浄を行うとよい。デカンテーション洗浄では洗浄水量および処理回数が多くなる。 In the zinc precipitation recovery step, the liquid temperature during precipitation is preferably 50 ° C. or higher. When the liquid temperature is set to 50 ° C. or higher, a precipitate containing substantially no sodium can be produced. Washing may be performed by repulp washing. In decantation cleaning, the amount of cleaning water and the number of treatments increase.
固液分離して回収した上記炭酸亜鉛沈澱は実質的に塩素およびナトリウムを含有していないので、亜鉛製錬原料として再利用することができる。具体的には、例えば、回収した炭酸亜鉛沈澱を必要に応じて乾燥した後に、亜鉛電解液に直接に溶解して亜鉛を電解採取し、電気亜鉛を製造することができる。本発明の方法は回収した炭酸亜鉛沈澱を製錬原料として金属亜鉛を製造する方法を含む。 Since the zinc carbonate precipitate recovered by solid-liquid separation does not substantially contain chlorine and sodium, it can be reused as a zinc smelting raw material. Specifically, for example, after the collected zinc carbonate precipitate is dried as necessary, it can be directly dissolved in a zinc electrolytic solution to electrolyze zinc to produce electrozinc. The method of the present invention includes a method of producing metallic zinc using the recovered zinc carbonate precipitate as a smelting raw material.
以下、本発明の実施例を比較例と共に示す。
〔実施例１〕
塩化亜鉛溶液に炭酸ソーダを添加して液のｐＨ、および液温を表１に示すように調整して沈澱を生成させ、塩化亜鉛溶液と同じ液量の洗浄水で沈殿を２回洗浄した。塩化亜鉛溶液の塩素濃度、および亜鉛濃度、アルミニウム濃度、加水分解時のｐＨ、沈澱物の析出相、亜鉛、アルミニウム、塩素の含有量を表１に示した。
Examples of the present invention are shown below together with comparative examples.
[Example 1]
Sodium carbonate was added to the zinc chloride solution to adjust the pH and temperature of the solution as shown in Table 1 to form a precipitate, and the precipitate was washed twice with the same amount of washing water as the zinc chloride solution. Table 1 shows the chlorine concentration of the zinc chloride solution, the zinc concentration, the aluminum concentration, the pH during hydrolysis, the precipitated phase of the precipitate, and the contents of zinc, aluminum, and chlorine.
表１に示すように、塩化亜鉛溶液のアルミニウム濃度が低いので試料１〜２の沈殿物はナトリウム、塩素、およびアルミニウムの含有量が何れも０.１wt％未満であり、実質的にこれらを含まない沈殿物になる。一方、試料３〜４は塩化亜鉛溶液のアルミニウム濃度が高いので、ナトリウムを含む沈澱物になる。また、試料５〜６は加水分解時の液温が低過ぎるのでナトリウムを含む沈澱物になる。試料７は塩素濃度が低いが、アルミニウム濃度が高いので、ナトリウムを含む沈澱物になる。試料８はアルミニウム濃度および塩素濃度が高いので、ナトリウムと共に僅かに塩素を含む沈殿物になる。 As shown in Table 1, since the aluminum concentration of the zinc chloride solution is low, the precipitates of Samples 1 and 2 each contain less than 0.1 wt% of sodium, chlorine, and aluminum, and substantially contain these. There will be no precipitate. On the other hand, samples 3 to 4 are precipitates containing sodium because the aluminum concentration of the zinc chloride solution is high. Moreover, since the liquid temperature at the time of a hydrolysis is too low, the samples 5-6 become a precipitate containing sodium. Sample 7 has a low chlorine concentration, but has a high aluminum concentration, so it becomes a precipitate containing sodium. Since the sample 8 has high aluminum concentration and chlorine concentration, it becomes a precipitate containing slightly chlorine together with sodium.
〔実施例２〕
塩化亜鉛溶液〔Cl:190g/L、Zn:90g/L、Al:1.6g/L、pH2〜3〕１Ｌに、水を加えて塩素濃度を６０〜９０g/Lに希釈し、炭酸ソーダを液のｐＨが４.５〜５.５になるまで添加して水酸化アルミニウム沈澱を生成させ、これを濾別して液中のアルミニウム濃度を２５mg/Lに低減した。この濾液に炭酸ソーダを加えてｐＨ８.０に調整し、液温６０℃で１時間攪拌し、沈澱を生成させた。沈殿物に含まれる亜鉛、ナトリウム、塩素の含有量を測定したところ、亜鉛は５９wt％、アルミニウム、ナトリウム、および塩素は何れも０.１wt％以下であった。この結果を表２に示した。
[Example 2]
Zinc chloride solution [Cl: 190g / L, Zn: 90g / L, Al: 1.6g / L, pH2-3] To 1L, add water to dilute the chlorine concentration to 60-90g / L. Was added until a pH of 4.5 to 5.5 was reached to form an aluminum hydroxide precipitate, which was filtered off to reduce the aluminum concentration in the liquid to 25 mg / L. Sodium carbonate was added to the filtrate to adjust the pH to 8.0, and the mixture was stirred at a liquid temperature of 60 ° C. for 1 hour to form a precipitate. When the contents of zinc, sodium and chlorine contained in the precipitate were measured, zinc was 59 wt%, and aluminum, sodium and chlorine were all 0.1 wt% or less. The results are shown in Table 2.
Claims (5)
The concentration of aluminum in the zinc-containing hydrochloric acid solution was reduced to 200 mg / L or less, and sodium carbonate was added to precipitate basic zinc carbonate under a pH of 6 or more, thereby limiting the mixing of chlorine and sodium. A method for recovering zinc, comprising recovering a zinc-containing precipitate.
The zinc recovery method according to claim 1, wherein the zinc concentration hydrochloric acid solution having a chlorine concentration of 60 g / L or more is used to limit the aluminum concentration in the solution to 200 mg / L or less and to precipitate basic zinc carbonate at a liquid temperature of 50 ° C or more. .
Sodium carbonate is added to the zinc-containing hydrochloric acid solution to adjust the pH to 4 or more and less than 6 to convert the aluminum in the liquid to aluminum hydroxide precipitation, and the precipitate is solid-liquid separated to reduce the aluminum concentration in the liquid to 200 mg / L. A dealumination step to be described below, and a zinc precipitation recovery step for adding sodium carbonate to the filtrate from which the aluminum hydroxide precipitate has been separated to precipitate basic zinc carbonate under a pH of 6 or higher and recovering the precipitate The method for recovering zinc according to claim 1 or claim 2 comprising:
The zinc-containing hydrochloric acid solution is a liquid obtained by depositing zinc into a hydrochloric acid leaching solution of smelting waste or valuable metals to precipitate the contained metal, and solid-liquid separation. Collection method.
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