JP5408412B2 - Platinum recovery process - Google Patents

Platinum recovery process Download PDF

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JP5408412B2
JP5408412B2 JP2009069205A JP2009069205A JP5408412B2 JP 5408412 B2 JP5408412 B2 JP 5408412B2 JP 2009069205 A JP2009069205 A JP 2009069205A JP 2009069205 A JP2009069205 A JP 2009069205A JP 5408412 B2 JP5408412 B2 JP 5408412B2
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platinum
precipitate
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哲 柴田
智 岡田
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Mitsubishi Materials Corp
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Description

本発明は、白金族金属を含有する溶液から白金族金属を効率よく回収する処理方法に関する。本発明の処理方法は、銅製錬などの白金回収工程の処理方法として好適である。   The present invention relates to a treatment method for efficiently recovering a platinum group metal from a solution containing the platinum group metal. The treatment method of the present invention is suitable as a treatment method for a platinum recovery step such as copper smelting.

白金は宝飾材料として貴重であり、また半導体材料や電子材料などに広く用いられているが、資源量は少なく希少金属である。このため製錬工程において処理液中からできるだけ白金を回収することが求められている。   Platinum is valuable as a jewelery material and is widely used in semiconductor materials and electronic materials, but it is a rare metal with a small amount of resources. For this reason, it is required to recover as much platinum as possible from the treatment liquid in the smelting process.

従来、白金の回収方法として、有機溶媒を用いる溶媒抽出法、白金族金属を選択的に沈殿させる沈澱化剤を用いる方法、蒸留を用いた方法、これらを組み合わせた方法などが知られている。   Conventionally, as a platinum recovery method, a solvent extraction method using an organic solvent, a method using a precipitating agent that selectively precipitates a platinum group metal, a method using distillation, a method combining these, and the like are known.

具体的には、例えば以下の回収方法が知られている。
（イ）白金の塩酸酸性水溶液からリン酸トリブチルを含有する有機溶媒を用いて白金を逆抽出した溶液から白金を沈澱させて回収する方法（特許文献１）。
（ロ）塩化白金酸液に中和剤を加え、弱酸性下でＳｎ、Ｂｉなどを沈澱させて分離し、さらにｐＨをアルカリ性に調整し、Ｆｅ、Ｃｕ、Ｎｉなどを沈澱させて分離した後に、塩酸を加え、さらに塩化アンモニウムを加えて塩化白金酸アンモニウム沈澱を生成させこれを回収し強熱して白金メタルを得る方法（特許文献２）。
（ハ）アミノ化合物およびヘテロポリ酸からなり白金族金属を選択的に沈澱させる沈澱化剤を用い、白金を含有する酸性溶液に該沈澱化剤を添加し、白金沈澱を分離回収する方法（特許文献３）。
（ニ）白金族含有溶液からＲｕを蒸留分離し、さらに有機溶媒を用いてＣｕ、Ｐｂ、Ｆｅなど抽出分離した後に、パラジウム、白金などを溶媒抽出によって順次回収する方法（特許文献４）。 Specifically, for example, the following recovery methods are known.
(A) A method in which platinum is precipitated and recovered from a solution obtained by back-extracting platinum from an acidic aqueous solution of platinum using an organic solvent containing tributyl phosphate (Patent Document 1).
(B) After adding a neutralizing agent to the chloroplatinic acid solution, precipitating and separating Sn, Bi, etc. under weak acidity, adjusting the pH to alkaline, and precipitating and separating Fe, Cu, Ni, etc. Then, hydrochloric acid is added, and further ammonium chloride is added to form an ammonium chloroplatinate precipitate, which is recovered and ignited to obtain platinum metal (Patent Document 2).
(C) A method of separating and recovering platinum precipitates by adding a precipitating agent comprising an amino compound and a heteropoly acid to selectively precipitate a platinum group metal, adding the precipitating agent to an acidic solution containing platinum (Patent Literature) 3).
(D) A method in which Ru is distilled and separated from a platinum group-containing solution, and further, Cu, Pb, Fe, and the like are extracted and separated using an organic solvent, and then palladium, platinum, and the like are sequentially recovered by solvent extraction (Patent Document 4).

特開平９−２４１７６８号公報JP-A-9-241768 特開平９−３１６５６０号公報JP 9-316560 A 特開２００５−１９４５４６号公報JP 2005-194546 A 特許第４１１６４９０号公報Japanese Patent No. 4116490

有機溶媒を用いる従来の回収方法は有機溶媒のコストが嵩み、特定の有機溶媒を用いるので実施が限られる。また、特殊な選択的沈澱剤を用いる方法も同様である。さらに蒸留処理と溶媒抽出処理を組合わせた方法は処理操作が煩雑である。また、塩化白金酸アンモニウム沈澱を生成させる方法は、沈澱時に共沈ないし巻き込んだ不純物は水や塩化アンモニウム水溶液による洗浄では除去しきれいと云う問題がある。   The conventional recovery method using an organic solvent is expensive because the cost of the organic solvent is high and a specific organic solvent is used. The method using a special selective precipitant is also the same. Furthermore, the combined operation of the distillation process and the solvent extraction process requires complicated processing operations. Further, the method of producing ammonium chloroplatinate precipitate has a problem that impurities co-precipitated or entrained during precipitation are removed and cleaned by washing with water or an aqueous ammonium chloride solution.

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、特殊な薬剤を用いることなく、簡単な処理操作によって、不純物の少ない白金メタルを回収する方法を提供する。   The present invention solves the above-mentioned problems in the conventional recovery method, and provides a method for recovering platinum metal with less impurities by a simple processing operation without using a special agent.

本発明の回収処理方法は、以下の構成によって上記問題を解決した白金の回収処理方法である。
〔１〕白金含有溶液に塩化アンモニウムを添加して塩化白金酸アンモニウムを沈殿させ、この沈澱を回収して塩酸酸性温水に溶解する工程を繰り返すことによって塩化白金酸アンモニウムを精製することを特徴とする白金の回収処理方法。
〔２〕白金含有溶液に塩化アンモニウムを添加して塩化白金酸アンモニウムを沈殿させ、この沈澱を回収して塩酸酸性温水に溶解する工程を繰り返すことによって塩化白金酸アンモニウムを精製した後に、チオ尿素を添加して白金チオ尿素錯体を沈澱させる上記[１]に記載する白金の回収処理方法。
〔３〕 塩化アンモニウムを添加して、ｐＨ０.５〜３および温度６０℃〜８０℃で、塩化白金酸アンモニウムを沈殿させる上記[１]または上記[２]に記載する白金の回収処理方法。
〔４〕チオ尿素を添加して数時間攪拌した後に、硫酸を添加して白金チオ尿素錯体を沈澱させる上記[２]に記載する白金の回収処理方法。
〔５〕白金含有溶液として白金と共にルテニウムを含有する溶液を用い、該溶液に塩化アンモニウムを添加して塩化白金酸アンモニウムを沈殿させ、液中に残る塩化ルテニウム酸アンモニウムを濾過して分離し、塩化白金酸アンモニウム沈澱を回収して塩酸酸性温水に溶解する工程を繰り返して白金とルテニウムを分離する塩化白金酸アンモニウム精製工程の後に、塩化白金酸アンモニウムの塩酸酸性溶液にチオ尿素を添加して白金チオ尿素錯体を沈澱させる上記[１]〜上記[４]の何れかに記載する白金の回収処理方法。
〔６〕白金チオ尿素錯体沈澱を回収して焼成することによって白金粉を回収する上記[１]〜上記[５]の何れかに記載する白金の回収処理方法。
〔７〕上記[６]の処理方法で得た白金粉を王水に溶解し、該溶解液を濾過して精製し、該精製した白金王水溶解液から白金を回収する白金の回収処理方法。


The recovery processing method of the present invention is a platinum recovery processing method that solves the above problems by the following configuration.
[1] Ammonium chloroplatinate is purified by repeating steps of adding ammonium chloride to a platinum-containing solution to precipitate ammonium chloroplatinate, collecting the precipitate and dissolving it in hydrochloric acid warm water. Platinum recovery process.
[2] Ammonium chloride is added to the platinum-containing solution to precipitate ammonium chloroplatinate, and the precipitate is recovered and purified by repeating steps of dissolving in hydrochloric acid warm water, and then thiourea is added. The method for recovering platinum as described in [1] above, wherein the platinum thiourea complex is precipitated by addition.
[3] The platinum recovery method described in [1] or [2] above, wherein ammonium chloride is added to precipitate ammonium chloroplatinate at a pH of 0.5 to 3 and a temperature of 60 ° C. to 80 ° C.
[4] The platinum recovery method as described in [2] above, wherein thiourea is added and stirred for several hours, and then sulfuric acid is added to precipitate a platinum thiourea complex.
[5] Using a solution containing ruthenium together with platinum as a platinum-containing solution, ammonium chloride is added to the solution to precipitate ammonium chloroplatinate, and the remaining ammonium ruthenate is filtered and separated. After the step of purifying ammonium platinate to separate the platinum and ruthenium by repeating the step of recovering the ammonium platinate precipitate and dissolving it in hydrochloric acid warm water, thiourea was added to the hydrochloric acid solution of ammonium chloroplatinate to remove The method for recovering platinum according to any one of [1] to [4] above, wherein the urea complex is precipitated.
[6] The platinum recovery method according to any one of [1] to [5] above, wherein platinum powder is recovered by recovering and baking the platinum thiourea complex precipitate.
[7] Platinum recovery method for dissolving platinum powder obtained by the processing method of [6] above in aqua regia, purifying the solution by filtration, and recovering platinum from the purified platinum aqua regia solution .


本発明の処理方法は、白金含有溶液から白金含有物を沈澱させ、これを回収して再び溶解して白金含有物を沈澱させる処理工程を繰り返すので、白金含有沈澱に含まれている不純物が段階的に除去され、不純物の少ない粉末状の白金メタルを回収することができる。   The treatment method of the present invention repeats the treatment step of precipitating the platinum-containing material from the platinum-containing solution, recovering it, dissolving it again, and precipitating the platinum-containing material. Thus, it is possible to recover the powdered platinum metal with less impurities.

銅製錬などでは、白金と共にルテニウムが含有されている場合が多いが、ルテニウムは白金と同族であるので、従来の処理方法ではこれの分離に手間がかかる。本発明の処理方法は、ｐＨの調整によって容易に白金とルテニウムを分離することができるので、実操業に適し、ルテニウム含有量の少ない白金メタルを回収することができる。   In copper smelting and the like, ruthenium is often contained together with platinum. However, since ruthenium is in the same family as platinum, the conventional treatment method takes time to separate it. Since the treatment method of the present invention can easily separate platinum and ruthenium by adjusting pH, it is suitable for actual operation and can recover platinum metal having a low ruthenium content.

回収した白金メタル粉末は、これを王水に溶解して溶解残渣（ルテニウム含有残渣）を濾別することによって白金王水溶解液を精製し、この白金王水溶解液からさらに不純物の少ない白金メタルを回収することができる。   The recovered platinum metal powder is dissolved in aqua regia and the dissolved residue (ruthenium-containing residue) is filtered to purify the platinum aqua regia solution. Can be recovered.

本発明の処理方法は、有機溶媒や特殊な成分の沈澱化剤などを使用せず、処理操作も簡単なので実施し易い   The treatment method of the present invention does not use an organic solvent or a special component precipitating agent, and is easy to carry out because the treatment operation is simple.

本発明に係る処理方法の概略を示す工程図。Process drawing which shows the outline of the processing method which concerns on this invention.

以下、本発明の処理方法を実施形態に基づいて具体的に説明する。本発明の処理方法の概略を図１に示す。   Hereinafter, the processing method of the present invention will be specifically described based on embodiments. An outline of the treatment method of the present invention is shown in FIG.

本発明の処理方法は、白金の回収処理方法において、白金含有溶液に塩化アンモニウムを添加して塩化白金酸アンモニウムを沈殿させ、この沈澱を回収して塩酸酸性温水に溶解する工程を繰り返すことによって塩化白金酸アンモニウムを精製することを特徴とする白金の回収処理方法である。   The treatment method of the present invention is a platinum recovery treatment method in which ammonium chloride is added to a platinum-containing solution to precipitate ammonium chloroplatinate and the precipitate is recovered and dissolved in hydrochloric acid warm water to repeat chlorination. A platinum recovery method characterized by purifying ammonium platinate.

さらに、本発明の処理方法は、図示するように、白金の回収処理方法において、白金含有溶液に塩化アンモニウムを添加して塩化白金酸アンモニウムを沈殿させ、この沈澱を回収して塩酸酸性温水に溶解する工程を繰り返すことによって塩化白金酸アンモニウムを精製した後に、チオ尿素を添加して白金チオ尿素錯体を沈澱させる白金の回収処理方法である。   Furthermore, as shown in the figure, the treatment method of the present invention is a platinum recovery treatment method, in which ammonium chloride is added to a platinum-containing solution to precipitate ammonium chloroplatinate, and this precipitate is recovered and dissolved in hydrochloric acid hot water. This is a platinum recovery treatment method in which after purifying ammonium chloroplatinate by repeating the process, a thiourea is added to precipitate a platinum thiourea complex.

〔白金含有溶液〕
本発明の処理方法は、白金含有溶液として、例えば、銅製錬における各種の酸浸出液について適用することができる。この酸浸出液は白金(Pt)と共にルテニウム(Ru)を含有するものでもよい。例えば、銅製錬の白金浸出液（白金の王水溶解液）には、一般に、白金２０〜５０g/L、ルテニウム５〜１０g/Lが含まれている。本発明の処理方法はこのような酸浸出液について適用することができる。 [Platinum-containing solution]
The treatment method of the present invention can be applied as a platinum-containing solution, for example, to various acid leaching solutions in copper smelting. This acid leaching solution may contain ruthenium (Ru) together with platinum (Pt). For example, platinum leaching solution (platinum aqua regia solution) of copper smelting generally contains 20 to 50 g / L of platinum and 5 to 10 g / L of ruthenium. The treatment method of the present invention can be applied to such an acid leaching solution.

〔第一沈澱化工程〕
白金含有溶液（元液）に塩化アンモニウム〔NH4Cl〕を添加して攪拌し、塩化白金酸アンモニウム〔(NH4)2PtCl6〕を沈殿させる。塩化アンモニウムの添加量は元液に含まれる白金ないし白金およびルテニウムを十分に沈澱化させる量が好ましい。具体的には、例えば、元液の白金濃度約２g/Lに対して、塩化アンモニウム５０g/L〜１５０g/Lが適当である。元液に塩化アンモニウムを添加して一晩程度（６〜１８時間程度）攪拌すると良い。 [First precipitation step]
Ammonium chloride [NH 4 Cl] is added to the platinum-containing solution (original solution) and stirred to precipitate ammonium chloroplatinate [(NH 4 ) 2 PtCl 6 ]. The amount of ammonium chloride added is preferably such that platinum or platinum and ruthenium contained in the original solution are sufficiently precipitated. Specifically, for example, 50 g / L to 150 g / L of ammonium chloride is appropriate for a platinum concentration of about 2 g / L in the original solution. Ammonium chloride may be added to the original solution and stirred overnight (about 6 to 18 hours).

上記沈澱生成工程において、溶液はｐＨ３以下の酸性が適当であり、ｐＨ０.５〜３が好ましい。元液に白金と共にルテニウムが含まれている場合、ｐＨは１〜３がより好ましい。このｐＨ領域で、塩化白金酸アンモニウム〔(NH4)2PtCl6〕が沈澱し、ルテニウムは塩化ルテニウム酸アンモニウム〔(NH4)2RuCl6〕を形成し、その大部分は液中に残るので、これを固液分離することによって、白金とルテニウムを分離することができる。溶液がこれよりも強塩酸性になると、塩化物イオン濃度が高くなるために塩化ルテニウム酸アンモニウム〔(NH4)2RuCl6〕が沈殿しやすくなり、白金とルテニウムの分離性が低下するので好ましくない。 In the precipitation generation step, the solution is suitably acidic at pH 3 or less, preferably pH 0.5-3. When ruthenium is contained in the original solution together with platinum, the pH is more preferably 1 to 3. In this pH range, ammonium chloroplatinate [(NH 4 ) 2 PtCl 6 ] precipitates and ruthenium forms ammonium ruthenate [(NH 4 ) 2 RuCl 6 ], most of which remains in the solution. By separating this from solid and liquid, platinum and ruthenium can be separated. If the solution is stronger than hydrochloric acid, the chloride ion concentration becomes higher, so ammonium chloride ruthenate [(NH 4 ) 2 RuCl 6 ] tends to precipitate, and the separation between platinum and ruthenium is reduced, which is preferable. Absent.

一般に、銅製錬の白金酸溶解液は酸性溶液であるので、そのまま塩化アンモニウムを添加すればよい。ｐＨが高い白金含有溶液には塩酸を添加してｐＨを下げればよい。   In general, since the smelting platinum acid solution of copper smelting is an acidic solution, ammonium chloride may be added as it is. To the platinum-containing solution having a high pH, hydrochloric acid may be added to lower the pH.

上記沈澱生成後、濾過して沈殿物を回収する。この濾液には塩化アンモニウムによって沈澱を生じない不純物（Ｆｅ，Ｎｉ，Ｃｒ，Ｃｏ等のベースメタル）が溶存しているので、濾過処理して沈殿物と濾液を分離し、上記不純物を除去する。 After the precipitate is formed, the precipitate is recovered by filtration. Since impurities (base metals such as Fe, Ni, Cr, and Co) that do not cause precipitation due to ammonium chloride are dissolved in the filtrate, the precipitate is separated from the filtrate by filtration, and the impurities are removed.

元液に白金と共にルテニウムが含まれている場合には、塩化アンモニウムを添加することによって、ルテニウムは白金と同様に塩化ルテニウム酸アンモニウムを形成する。その大部分は濾液に含まれるが、一部は沈澱物に取り込まれるので、以下の処理工程に示すように、沈澱化処理と溶解処理を繰り返すことによって、沈澱物に含まれているルテニウムおよび不純物を段階的に分離することができる。   When ruthenium is contained together with platinum in the original solution, ruthenium forms ammonium ruthenate as with platinum by adding ammonium chloride. Most of it is contained in the filtrate, but a part of it is taken up in the precipitate. As shown in the following processing steps, ruthenium and impurities contained in the precipitate are obtained by repeating the precipitation treatment and dissolution treatment. Can be separated in stages.

〔第一溶解工程〕
回収した沈澱物を塩酸酸性温水に溶解する。水温は６０℃以上が適当であり、６０℃〜８０℃が好ましい。水温が６０℃より低いと上記沈澱が溶解し難く、８０℃より高くても溶解速度はあまり変わらない。温水の量は白金３ｇに対して水０.５Ｌ〜１.５Ｌが適当であり、約１Ｌが好ましい。温水の量がこれより少ないと上記沈澱が溶解し難く、一方、温水量がこれより多いと後の濾過処理の負担が増すので好ましくない。 [First dissolution step]
The collected precipitate is dissolved in hydrochloric acid warm water. The water temperature is suitably 60 ° C. or higher, preferably 60 ° C. to 80 ° C. If the water temperature is lower than 60 ° C, the precipitate is difficult to dissolve, and even if it is higher than 80 ° C, the dissolution rate does not change much. The amount of hot water is suitably 0.5 L to 1.5 L of water with respect to 3 g of platinum, and preferably about 1 L. If the amount of hot water is less than this, the precipitate is difficult to dissolve, whereas if the amount of hot water is more than this, the burden of subsequent filtration treatment is increased, which is not preferable.

温水の塩酸濃度はｐＨ０.５〜３になる濃度が適当であり、ｐＨ１程度が好ましい。温水のｐＨが３より高いと、次工程で塩化アンモニウムを添加したときに、イオン形態が変化することによって塩化白金酸アンモニウムとして沈殿し難くなる。一方、温水のｐＨが０.５より低すぎると、塩化白金酸アンモニウムと共に塩化ルテニウム酸アンモニウムが沈澱し易くなり、白金とルテニウムの分離性が低下する。   The concentration of hydrochloric acid in warm water is suitably such that the pH is 0.5-3, and is preferably about pH 1. When the pH of the warm water is higher than 3, when ammonium chloride is added in the next step, it is difficult to precipitate as ammonium chloroplatinate by changing the ionic form. On the other hand, if the pH of the warm water is lower than 0.5, ammonium chloride ruthenate is likely to precipitate together with ammonium chloroplatinate, and the separability of platinum and ruthenium decreases.

〔第二沈澱化工程〕
上記塩酸酸性溶解液に塩化アンモニウムを添加して再び塩化白金酸アンモニウム沈澱を生成させる。このとき上記溶解液のｐＨがｐＨ０.５〜３であるので、このｐＨ範囲で塩化白金酸アンモニウムが沈澱するが、塩化ルテニウム酸は溶解度が高いので沈澱せず液中にそのまま溶存する。従って、これを濾過することによって塩化白金酸アンモニウムと塩化ルテニウム酸アンモニウムを分離することができる。塩化白金酸アンモニウム沈澱は濾過して回収する。 [Second precipitation step]
Ammonium chloride is added to the hydrochloric acid acidic solution to form an ammonium chloroplatinate precipitate again. At this time, since the pH of the solution is 0.5 to 3, ammonium chloroplatinate precipitates within this pH range, but ruthenium chloride is dissolved in the solution as it is without precipitation because of its high solubility. Therefore, by filtering this, ammonium chloroplatinate and ammonium chloride ruthenate can be separated. The ammonium chloroplatinate precipitate is recovered by filtration.

塩化アンモニウムの添加量は、液中の白金を十分に沈澱化させる量が好ましい。具体的には、例えば、第一沈殿化工程と同様に、液中の塩化アンモニウム濃度が５０g/L〜１５０g/Lになる量が適当である。   The amount of ammonium chloride added is preferably an amount that sufficiently precipitates platinum in the solution. Specifically, for example, in the same manner as in the first precipitation step, an amount such that the ammonium chloride concentration in the liquid is 50 g / L to 150 g / L is appropriate.

〔第二溶解工程〕
回収した沈殿物を再び塩酸酸性温水に全て溶解させて塩化白金酸アンモニウム溶解液にする。なお、上記第二沈澱化工程によって沈澱物に含まれるルテニウムは少ないので、第二溶解工程ではルテニウム濃度が低い溶解液を得ることができる。塩酸酸性温水は第一溶解工程と同様にｐＨ０.５〜３、好ましくはｐＨ１程度になる塩酸濃度が適当である。 [Second dissolution step]
The collected precipitate is again dissolved in hydrochloric acid warm water to make an ammonium chloroplatinate solution. In addition, since there is little ruthenium contained in a precipitate by the said 2nd precipitation process, the solution with a low ruthenium density | concentration can be obtained in a 2nd melt | dissolution process. Hydrochloric acid warm water is suitable to have a hydrochloric acid concentration of pH 0.5-3, preferably about pH 1, as in the first dissolution step.

上記第一沈澱化工程から第二溶解工程までの処理工程を必要に応じて繰り返すと良い。これらの処理工程を繰り返すことによって、塩化白金酸アンモニウム沈澱に含まれる不純物を段階的に低下させることができ、また、白金とルテニウムの分離効果を高めることができ、精製された塩化白金酸アンモニウム溶解液を得ることができる。 The treatment steps from the first precipitation step to the second dissolution step may be repeated as necessary. By repeating these treatment steps, impurities contained in the ammonium chloroplatinate precipitate can be lowered stepwise, and the separation effect of platinum and ruthenium can be enhanced, and the purified ammonium chloroplatinate solution can be dissolved. A liquid can be obtained.

〔第三沈澱化工程〕
塩化白金酸アンモニウムの第二溶解液（ｐＨ０.５〜３、好ましくはｐＨ１程度）にチオ尿素を加えて白金チオ尿素錯体沈澱〔Pt(thiourea)4(HSO4)2〕を生成させる。チオ尿素の添加量は第二溶解液中での濃度が２.５〜７.５mol/L、好ましくは５mol/L程度になる量が適当である。半日程度攪拌すると良い。 [Third precipitation step]
Thiourea is added to a second solution of ammonium chloroplatinate (pH 0.5-3, preferably about pH 1) to form a platinum thiourea complex precipitate [Pt (thiourea) 4 (HSO 4 ) 2 ]. The amount of thiourea added is appropriate such that the concentration in the second solution is 2.5 to 7.5 mol / L, preferably about 5 mol / L. Stir for about half a day.

チオ尿素を添加して半日程度攪拌した後に、硫酸を加えてさらに攪拌すると良い。硫酸の添加量は白金の１〜８倍当量が好ましい。   After adding thiourea and stirring for about half a day, sulfuric acid may be added and further stirred. The addition amount of sulfuric acid is preferably 1 to 8 times equivalent to platinum.

生成した白金チオ尿素錯体沈澱を濾過し、回収した沈澱物を焼成して水分、尿素および硫酸根を揮発させることによって、白金メタルを得ることができる。焼成温度は５００℃以上が適当であり、焼成時間は４時間以上が好ましい。この白金メタルは粉末状であり、ルテニウムおよびＦｅ，Ｎｉ，Ｃｒ，Ｃｏなどのベースメタルの不純物が少ない高品質の白金である。   Platinum metal can be obtained by filtering the produced platinum thiourea complex precipitate and calcining the collected precipitate to volatilize moisture, urea and sulfate radicals. The firing temperature is suitably 500 ° C. or more, and the firing time is preferably 4 hours or more. This platinum metal is in the form of powder, and is high-quality platinum with few impurities in the base metal such as ruthenium and Fe, Ni, Cr, Co.

上記白金粉を王水に溶解する。白金は王水に溶解するが、ルテニウムは沈殿を形成するので、これを固液分離することによって、白金王水液を精製し、白金粉に僅かに含まれるルテニウムを除去することがことでる。精製した白金王水溶解液からは既知の方法で白金を回収することができる。   The platinum powder is dissolved in aqua regia. Platinum dissolves in aqua regia, but ruthenium forms a precipitate. By separating this from solid and liquid, the platinum aqua regia solution is purified to remove ruthenium slightly contained in the platinum powder. Platinum can be recovered from the purified platinum aqua solution by a known method.

本発明の実施例を以下に示す。
〔実施例１〕
白金含有酸浸出液（Pt:１.４g/L、pHゼロ以下）１Ｌに、室温下、塩化アンモニウムを液中濃度が１００g/Lになる量を添加し、一晩攪拌し、生成した沈澱物を濾過して塩化白金酸アンモニウム沈澱を回収した。この沈澱を塩酸酸性温水（白金３ｇに対して水１Ｌになる量、60℃〜80℃、pH１の塩酸濃度）に完全に溶解させた。この溶解液に塩化アンモニウムを液中濃度が１００g/Lになる量を添加し、一晩攪拌し、生成した沈澱物を濾過して塩化白金酸アンモニウム沈澱を回収した。塩化白金酸アンモニウムの再溶解、再沈澱化の操作をもう一度繰り返した後、塩化白金酸アンモニウム沈澱３.８ｇ(wet)を回収した。回収した沈澱の全量を塩酸酸性温水（白金３ｇに対して水１Ｌになる量、60℃〜80℃、pH１の塩酸濃度）に完全に溶解させた。この溶解液にチオ尿素を液中濃度が５mol/Lになる量を添加し、半日攪拌した後に、白金の４倍当量の硫酸を加えて攪拌し、白金チオ尿素錯体の沈澱を形成させ、これを濾過して回収した。回収した沈澱を５５０℃で４時間焼成し、白金メタル粉末１.３５ｇを回収した（回収率９６.４％）。この白金メタル粉末はＧＤ−ＭＳ分析を行ったところ９９.９％Ｐｔであった。 Examples of the present invention are shown below.
[Example 1]
To 1 L of platinum-containing acid leachate (Pt: 1.4 g / L, pH below zero), add ammonium chloride in an amount of 100 g / L of ammonium chloride at room temperature and stir overnight. Filtration recovered the ammonium chloroplatinate precipitate. The precipitate was completely dissolved in hydrochloric acid warm water (amount of 1 L of water with respect to 3 g of platinum, hydrochloric acid concentration of 60 ° C. to 80 ° C., pH 1). To this solution, ammonium chloride was added in an amount such that the concentration in the solution was 100 g / L, stirred overnight, and the resulting precipitate was filtered to recover the ammonium chloroplatinate precipitate. After re-dissolution and reprecipitation of ammonium chloroplatinate, another 3.8 g (wet) of ammonium chloroplatinate was recovered. The total amount of the collected precipitate was completely dissolved in hydrochloric acid acidic warm water (amount of 1 L of water with respect to 3 g of platinum, hydrochloric acid concentration of 60 ° C. to 80 ° C., pH 1). Add an amount of thiourea in the solution to a concentration of 5 mol / L in the solution, and stir for half a day. Then add sulfuric acid equivalent to 4 times the platinum and stir to form a platinum thiourea complex precipitate. Was recovered by filtration. The collected precipitate was baked at 550 ° C. for 4 hours, and 1.35 g of platinum metal powder was collected (recovery rate 96.4%). This platinum metal powder was 99.9% Pt by GD-MS analysis.

〔実施例２〕
白金含有酸浸出液（Pt:2.4g/L、Ru:1.2g/L、pHゼロ以下）１Ｌに、室温下、塩化アンモニウムを液中濃度が１００g/Lになる量を添加し、一晩攪拌し、生成した沈澱物を濾過して塩化白金酸アンモニウム沈澱を回収した。この沈澱を塩酸酸性温水（白金３ｇに対して水１Ｌになる量、60℃〜80℃、pH１の塩酸濃度）に完全に溶解させた。この溶解液に塩化アンモニウムを液中濃度が１００g/Lになる量を添加し、一晩攪拌し、生成した沈澱物を濾過して塩化白金酸アンモニウム沈澱を回収した。塩化白金酸アンモニウムの再溶解、再沈澱化の操作をもう一度繰り返した後、塩化白金酸アンモニウム沈澱６.６ｇ(wet)を回収した。回収した沈澱の全量を塩酸酸性温水（白金３ｇに対して水１Ｌになる量、60℃〜80℃、pH１の塩酸濃度）に完全に溶解させた。この溶解液にチオ尿素を液中濃度が５mol/Lになる量を添加し、半日攪拌した後に、白金の４倍当量の硫酸を加えて攪拌し、白金チオ尿素錯体の沈澱を形成させ、これを濾過して回収した。回収した沈澱を９００℃で４時間焼成し、白金メタル粉末２.３５ｇを回収した（回収率９７.９％）。この白金メタル粉末を王水に溶解し、濾過して白金の精製王水溶解液を得た。この白金の精製王水溶解液から既知の方法で白金粉を回収した。この白金メタル粉末はＧＤ−ＭＳ分析を行ったところ白金粉末のルテニウム濃度は５０ppm以下であり、９９.９％Ｐｔであった。 [Example 2]
To 1 L of platinum-containing acid leachate (Pt: 2.4 g / L, Ru: 1.2 g / L, pH zero or less), add an amount of ammonium chloride in the solution to a concentration of 100 g / L at room temperature and stir overnight. The produced precipitate was filtered to recover an ammonium chloroplatinate precipitate. The precipitate was completely dissolved in hydrochloric acid warm water (amount of 1 L of water with respect to 3 g of platinum, hydrochloric acid concentration of 60 ° C. to 80 ° C., pH 1). To this solution, ammonium chloride was added in an amount such that the concentration in the solution was 100 g / L, stirred overnight, and the resulting precipitate was filtered to recover the ammonium chloroplatinate precipitate. After re-dissolution and reprecipitation of ammonium chloroplatinate, another 6.6 g (wet) of ammonium chloroplatinate was recovered. The total amount of the collected precipitate was completely dissolved in hydrochloric acid acidic warm water (amount of 1 L of water with respect to 3 g of platinum, hydrochloric acid concentration of 60 ° C. to 80 ° C., pH 1). Add an amount of thiourea in the solution to a concentration of 5 mol / L in the solution, and stir for half a day. Then add sulfuric acid equivalent to 4 times the platinum and stir to form a platinum thiourea complex precipitate. Was recovered by filtration. The collected precipitate was calcined at 900 ° C. for 4 hours to recover 2.35 g of platinum metal powder (recovery rate 97.9%). This platinum metal powder was dissolved in aqua regia and filtered to obtain a purified aqua regia solution of platinum. Platinum powder was recovered from this platinum purified aqua regia solution by a known method. This platinum metal powder was subjected to GD-MS analysis. As a result, the ruthenium concentration of the platinum powder was 50 ppm or less, which was 99.9% Pt.

Claims (7)

白金含有溶液に塩化アンモニウムを添加して塩化白金酸アンモニウムを沈殿させ、この沈澱を回収して塩酸酸性温水に溶解する工程を繰り返すことによって塩化白金酸アンモニウムを精製することを特徴とする白金の回収処理方法。
Recovering platinum characterized by purifying ammonium chloroplatinate by repeating the process of adding ammonium chloride to a platinum-containing solution to precipitate ammonium chloroplatinate, collecting the precipitate and dissolving it in hydrochloric acid warm water Processing method.
白金含有溶液に塩化アンモニウムを添加して塩化白金酸アンモニウムを沈殿させ、この沈澱を回収して塩酸酸性温水に溶解する工程を繰り返すことによって塩化白金酸アンモニウムを精製した後に、チオ尿素を添加して白金チオ尿素錯体を沈澱させる請求項１に記載する白金の回収処理方法。
Ammonium chloride is added to the platinum-containing solution to precipitate ammonium chloroplatinate, and after purifying ammonium chloroplatinate by repeating the steps of collecting and dissolving the precipitate in hydrochloric acid warm water, thiourea is added. The method for recovering platinum according to claim 1, wherein the platinum thiourea complex is precipitated.
塩化アンモニウムを添加して、ｐＨ０.５〜３および温度６０℃〜８０℃で、塩化白金酸アンモニウムを沈殿させる請求項１または請求項２に記載する白金の回収処理方法。
The method for recovering platinum according to claim 1 or 2, wherein ammonium chloride is added to precipitate ammonium chloroplatinate at a pH of 0.5 to 3 and a temperature of 60C to 80C.
チオ尿素を添加して数時間攪拌した後に、硫酸を添加して白金チオ尿素錯体を沈澱させる請求項２に記載する白金の回収処理方法。
The method for recovering platinum according to claim 2 , wherein the platinum thiourea complex is precipitated by adding sulfuric acid after adding thiourea and stirring for several hours.
白金含有溶液として白金と共にルテニウムを含有する溶液を用い、該溶液に塩化アンモニウムを添加して塩化白金酸アンモニウムを沈殿させ、液中に残る塩化ルテニウム酸アンモニウムを濾過して分離し、塩化白金酸アンモニウム沈澱を回収して塩酸酸性温水に溶解する工程を繰り返して白金とルテニウムを分離する塩化白金酸アンモニウム精製工程の後に、塩化白金酸アンモニウムの塩酸酸性溶液にチオ尿素を添加して白金チオ尿素錯体を沈澱させる請求項１〜請求項４の何れかに記載する白金の回収処理方法。
 Using a solution containing ruthenium together with platinum as a platinum-containing solution, ammonium chloride is added to the solution to precipitate ammonium chloroplatinate, and the ammonium ruthenate chloride remaining in the solution is filtered and separated. After the step of recovering the precipitate and dissolving it in hydrochloric acid hot water to separate platinum and ruthenium , after the purification step of ammonium chloroplatinate, thiourea was added to the acidic solution of ammonium chloroplatinate to form a platinum thiourea complex The method for recovering platinum according to any one of claims 1 to 4, wherein the platinum is precipitated.
白金チオ尿素錯体沈澱を回収して焼成することによって白金粉を回収する請求項１〜請求項５の何れかに記載する白金の回収処理方法。
The method for recovering platinum according to any one of claims 1 to 5, wherein platinum powder is recovered by recovering and baking the platinum thiourea complex precipitate.
請求項６の処理方法で得た白金粉を王水に溶解し、該溶解液を濾過して精製し、該精製した白金王水溶解液から白金を回収する白金の回収処理方法。 A platinum recovery treatment method, wherein the platinum powder obtained by the treatment method of claim 6 is dissolved in aqua regia, the solution is purified by filtration, and platinum is recovered from the purified platinum aqua regia solution.
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