JP2015190000A - Recovery method of platinum group - Google Patents
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- JP2015190000A JP2015190000A JP2014067450A JP2014067450A JP2015190000A JP 2015190000 A JP2015190000 A JP 2015190000A JP 2014067450 A JP2014067450 A JP 2014067450A JP 2014067450 A JP2014067450 A JP 2014067450A JP 2015190000 A JP2015190000 A JP 2015190000A
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Abstract
Description
本発明は、白金族金属を含む原料から、高純度の白金族金属を効率よく回収する方法に関する。 The present invention relates to a method for efficiently recovering a high-purity platinum group metal from a raw material containing the platinum group metal.
白金族金属（以下、白金族）は工業的には非鉄金属製錬の副産物や使用済み触媒などから回収されている。例えば、銅やニッケルの精練工程で生じる陽極スライムあるいはニッケルの精練工程で生じる抽出残渣には、金、銀、白金、パラジウムなどが含まれており、従来、これらの製錬残渣から白金や金などの貴金属が回収されている。例えば、脱銅スライムを塩化浸出し、浸出滓から銀や鉛を回収し、浸出液からは溶媒抽出によって金を回収し、また金抽出後液には白金族やセレン等が含まれているので、金抽出後液から白金族を回収している。 Platinum group metals (hereinafter referred to as platinum groups) are industrially recovered from by-products of non-ferrous metal smelting and spent catalysts. For example, anodic slime produced in the copper and nickel scouring process or extraction residue produced in the nickel scouring process contains gold, silver, platinum, palladium, etc. Of precious metals have been recovered. For example, leaching of copper removal slime, silver and lead are recovered from the leachate, gold is recovered from the leachate by solvent extraction, and the gold extracted solution contains platinum group, selenium, etc. The platinum group is recovered from the solution after gold extraction.
従来の溶媒抽出による白金族の回収方法は、アルカリ土類や重金属が十分に分離されないため、回収される白金族の純度が低いと云う問題があり、この対策として、アルカリ土類および重金属を最初に溶媒抽出によって取り除いた後に、Ｐｄ、Ｐｔ、Ｉｒを順に溶媒抽出によって回収し、その後、溶液を中和してＲｈ沈澱物を回収する方法が知られている（特許文献１：特開２００４−３３２０４１号公報）。 The conventional platinum group recovery method by solvent extraction has a problem that the purity of the recovered platinum group is low because the alkaline earths and heavy metals are not sufficiently separated. In this method, Pd, Pt, and Ir are sequentially recovered by solvent extraction after being removed by solvent extraction, and then the Rh precipitate is recovered by neutralizing the solution (Patent Document 1: Japanese Patent Application Laid-Open No. 2004-2005). 332041).
さらに、不純物元素を含む原料から高純度の白金族を回収する方法として、白金族含有物を浸出する第一工程、浸出生成液から不純物元素を溶媒抽出する第二工程、抽出残液からパラジウムを溶媒抽出する第三工程、抽出残液から陽イオン型不純物元素を溶媒抽出する第四工程、抽出残液を加水分解して白金を分離する第五工程、沈澱からルテニウムを浸出分離する第六工程、イリジウムを溶媒抽出し、イリジウムを含む逆抽出生成液とロジウムを含む抽出残液を得る第七工程の各工程を有する白金族の相互分離方法が知られている（特許文献２：特開２００５−９７６９５号公報）。 Furthermore, as a method for recovering the high purity platinum group from the raw material containing the impurity element, the first step of leaching the platinum group-containing material, the second step of solvent extraction of the impurity element from the leaching product solution, and palladium from the extraction residual liquid. The third step of solvent extraction, the fourth step of solvent extraction of cationic impurity elements from the extraction residue, the fifth step of hydrolyzing the extraction residue to separate platinum, the sixth step of leaching and separating ruthenium from the precipitate Further, there is known a platinum group mutual separation method having each step of a seventh step of solvent extraction of iridium to obtain a back extraction product solution containing iridium and an extraction residual solution containing rhodium (Patent Document 2: Japanese Patent Laid-Open No. 2005-2005). -97695).
しかし、特許文献１の方法は、Ｐｄ濃度が高い原料では、Ｒｕ蒸留のときにＰｄの沈殿が生じ、蒸留残液の回収が困難になるため適用し難いと云う問題がある。また、特許文献２の方法は、白金が複数の工程に分散するため、白金の一次実収率が低く、白金回収工程の繰返しが多くなるという問題がある。 However, the method of Patent Document 1 has a problem that it is difficult to apply a raw material having a high Pd concentration because precipitation of Pd occurs during Ru distillation and it becomes difficult to recover the distillation residue. Moreover, since the method of patent document 2 disperse | distributes platinum to a some process, there exists a problem that the primary yield of platinum is low and the repetition of a platinum recovery process increases.
上記問題を解消した回収方法として特許文献３に記載する回収方法が提案されている。この方法は、白金族含有溶液からパラジウムを溶媒抽出し、抽出残液にヒドラジンを添加して還元滓を生成させ、該還元滓に含まれる白金族金属を塩化溶出し、この溶解液に酸化剤を加えてルテニウムを蒸留させて回収し、この蒸留残液から他の白金族を回収する方法であり、白金族の回収率が高い効果を有している。一方、この方法はＲｕ蒸留後にＰｔを溶媒抽出するので、Ｒｕ蒸留がＰｔ回収のボトルネックになる場合が懸念される。 As a recovery method that solves the above problems, a recovery method described in Patent Document 3 has been proposed. In this method, palladium is solvent-extracted from a platinum group-containing solution, hydrazine is added to the extraction residue to produce reduced soot, and platinum group metals contained in the reduced soot are eluted with chloride. Is added, and ruthenium is recovered by distillation, and another platinum group is recovered from this distillation residue, which has a high recovery rate of the platinum group. On the other hand, since this method solvent-extracts Pt after Ru distillation, there is a concern that Ru distillation may become a bottleneck for Pt recovery.
本発明は従来の回収方法における上記問題を解決した白金族の回収方法を提供する。本発明の回収方法は、Ｐｔ回収工程をＲｕ蒸留工程より先に行うので、Ｐｔ回収がＲｕ蒸留によって影響されず、白金族の分離性が良く、高純度の白金族金属を効率よく回収することができる。 The present invention provides a platinum group recovery method that solves the above-mentioned problems in conventional recovery methods. Since the recovery method of the present invention performs the Pt recovery step before the Ru distillation step, the Pt recovery is not affected by the Ru distillation, the platinum group separability is good, and the high purity platinum group metal is efficiently recovered. Can do.
本発明は以下の構成を有する白金族の回収方法に関する。
〔１〕白金族含有溶液からパラジウムを溶媒抽出した残液を還元する第一還元工程、回収した第一還元滓を塩酸と酸化剤で溶解する第一塩化溶出工程、この溶解液を水で希釈する工程、希釈した溶解液から白金を沈澱させて回収する白金沈殿工程、この回収後液を還元する第二還元工程、この第二還元滓を塩酸と酸化剤で溶解する第二塩化溶出工程、この溶解液を酸化蒸留してルテニウムを回収する工程、この蒸留残液からロジウムを沈澱させて回収する工程を有することを特徴とする白金族の回収方法。
〔２〕希釈工程において、第一塩化溶出で得た溶解液（第一クロリネーション液）を水で希釈して塩素濃度を０.１〜０.４mol/Lに調整する上記[１]に記載する白金族の回収方法。
〔３〕白金沈殿工程において、希釈した第一クロリネーション液にアンモニウム塩を添加して白金を沈澱させる上記[１]または上記[２]に記載する白金族の回収方法。
〔４〕第二還元工程において、白金回収後液にアルカリを添加してｐＨ２〜１４に調整した後に水和ヒドラジンを添加し、生成した第二還元滓を回収する上記[１]〜上記[３]に記載する白金族の回収方法。
〔５〕第二塩化溶出工程において、白金回収後液から回収した第二還元滓に塩酸と過酸化水素を添加して該還元滓を溶解し、ルテニウムおよびロジウム含有液を得る上記[１]〜上記[４]の何れかに記載する白金族の回収方法。
〔６〕第二塩化溶出工程において得たルテニウムおよびロジウム含有液に臭素酸塩を添加して蒸留し、酸化ルテニウムを蒸留させる上記[１]〜上記[５]の何れかに記載する白金族の回収方法。
〔７〕ルテニウム蒸留残液に塩酸を加えた後にアルカリを添加してｐＨ調整し、さらに亜硝酸ナトリウムを加えて加熱し、冷却後、塩化アンモニウムを加えてロジウムを沈澱させる上記[１]〜上記[６]の何れかに記載する白金族の回収方法。
The present invention relates to a platinum group recovery method having the following configuration.
[1] A first reduction step of reducing a residual solution obtained by solvent extraction of palladium from a platinum group-containing solution, a first chloride elution step of dissolving the recovered first reduced soot with hydrochloric acid and an oxidizing agent, and diluting the solution with water A platinum precipitation step of precipitating and recovering platinum from the diluted solution, a second reduction step of reducing the recovered solution, a second chloride elution step of dissolving the second reduced soot with hydrochloric acid and an oxidizing agent, A platinum group recovery method comprising a step of recovering ruthenium by oxidative distillation of the solution and a step of recovering rhodium by precipitation from the distillation residue.
[2] In the dilution step, the solution (first chlorination solution) obtained by the first chloride elution is diluted with water to adjust the chlorine concentration to 0.1 to 0.4 mol / L. To recover platinum group.
[3] The platinum group recovery method according to [1] or [2] above, wherein in the platinum precipitation step, platinum is precipitated by adding an ammonium salt to the diluted first chlorination solution.
[4] In the second reduction step, alkali is added to the solution after platinum recovery to adjust the pH to 2 to 14, and then hydrated hydrazine is added to recover the generated second reduced soot [1] to [3] ] The platinum group recovery method described in the above.
[5] In the second chloride elution step, hydrochloric acid and hydrogen peroxide are added to the second reduced soot collected from the solution after platinum recovery to dissolve the reduced soot, thereby obtaining a ruthenium- and rhodium-containing solution [1] to The platinum group recovery method according to any one of the above [4].
[6] The platinum group of any one of [1] to [5] above, in which bromate is added to the ruthenium and rhodium-containing liquid obtained in the second chloride elution step and distilled to distill ruthenium oxide. Collection method.
[7] After adding hydrochloric acid to the ruthenium distillation residue, adjusting the pH by adding alkali, further adding sodium nitrite and heating, after cooling, adding ammonium chloride to precipitate rhodium [6] The platinum group recovery method according to any one of [6].
〔具体的な説明〕
本発明の回収方法は、白金族含有溶液からパラジウムを溶媒抽出した残液を還元する第一還元工程、回収した第一還元滓を塩酸と酸化剤で溶解する第一塩化溶出工程、この溶解液を水で希釈する工程、希釈した溶解液から白金を沈澱させて回収する白金沈殿工程、この白金回収後液を還元する第二還元工程、この第二還元滓を塩酸と酸化剤で溶解する第二塩化溶出工程、この溶解液を酸化蒸留してルテニウムを回収する工程、この蒸留残液からロジウムを沈澱させて回収する工程を有することを特徴とする白金族の回収方法である。
[Specific description]
The recovery method of the present invention includes a first reduction step of reducing a residual solution obtained by solvent extraction of palladium from a platinum group-containing solution, a first chloride elution step of dissolving the recovered first reduced soot with hydrochloric acid and an oxidizing agent, and this solution A step of diluting the solution with water, a platinum precipitation step of precipitating and recovering platinum from the diluted solution, a second reduction step of reducing the solution after recovering the platinum, and a step of dissolving the second reduced soot with hydrochloric acid and an oxidizing agent. A platinum group recovery method comprising a dichloride elution step, a step of recovering ruthenium by oxidative distillation of the solution, and a step of precipitating and recovering rhodium from the distillation residue.
〔白金族含有溶液〕
本発明に係る白金族の回収方法は、製錬残渣などの白金族を含有する原料から白金族を浸出させた溶液を原料として用いることができる。製錬残渣などを塩酸と酸化剤（過酸化水素など）を用いて塩化溶解すれば白金族を含有する溶液が得られる。例えば、脱銅スライムや製錬スクラップなどの製錬残渣を塩化溶解した液には、パラジウム(Pd)が約60000mg/l前後、金(Au)が約15000mg/l前後、白金(Pt)が約10000mg/l前後、ルテニウム(Ru)が約3000mg/l前後、ロジウム(Rh)が約500mg/l前後含まれている。
[Platinum group-containing solution]
The platinum group recovery method according to the present invention can use, as a raw material, a solution obtained by leaching a platinum group from a raw material containing a platinum group such as a smelting residue. A solution containing a platinum group can be obtained by smelting smelting residue and the like using hydrochloric acid and an oxidizing agent (such as hydrogen peroxide). For example, in a solution in which smelting residue such as decopperized slime and smelting scrap is dissolved in chloride, palladium (Pd) is about 60000 mg / l, gold (Au) is about 15000 mg / l, platinum (Pt) is about It contains around 10000 mg / l, ruthenium (Ru) around 3000 mg / l, and rhodium (Rh) around 500 mg / l.
〔Ａｕ抽出工程〕
製錬残渣などの塩酸浸出液を原料の白金族含有溶液として用いる場合には、好ましくは、最初に金(Au)および鉄(Fe)を除去する。溶媒抽出によってＡｕおよびＦｅを除去することができる。最初にＡｕを分離回収することによって、その後のパラジウム(Pd)等の回収を容易に進めることができる。Ａｕの抽出溶媒としてはＤＢＣ（ジブチルカルビトール）を用いることができる。白金族含有溶液に塩酸を添加して塩酸濃度が４mol/L以上になるように調整した後にＤＢＣを混合すると良い。ＤＢＣにはＡｕと共にＦｅが抽出される。ＤＢＣに抽出したＡｕは通常の方法で逆抽出して回収すれば良い。
[Au extraction process]
When a hydrochloric acid leaching solution such as a smelting residue is used as a raw material platinum group-containing solution, preferably, gold (Au) and iron (Fe) are first removed. Au and Fe can be removed by solvent extraction. By separating and recovering Au first, subsequent recovery of palladium (Pd) and the like can be facilitated. DBC (dibutyl carbitol) can be used as an extraction solvent for Au. After adding hydrochloric acid to the platinum group-containing solution to adjust the hydrochloric acid concentration to 4 mol / L or more, DBC may be mixed. Fe is extracted together with Au into DBC. Au extracted into DBC may be recovered by back-extraction by a normal method.
〔Ｐｄ抽出工程〕
Ａｕ抽出残液に含まれるＰｄを溶媒抽出する。Ｐｄの抽出溶媒としてはＤＨＳ（ジヘキシルスルフィド）を用いることできる。Ａｕ抽出残液に苛性ソーダを添加して塩酸濃度が３mol/L以下になるまで中和した後にＤＨＳを混合するのが好ましい。Ａｕ抽出後液の塩酸濃度を３mol/L以下に調整することによって、Ｐｄ逆抽出における溶媒の変性や沈殿の発生を抑制することができる。
[Pd extraction process]
Pd contained in the Au extraction residual liquid is subjected to solvent extraction. DHS (dihexyl sulfide) can be used as an extraction solvent for Pd. It is preferable to add DHS after adding caustic soda to the Au extraction residue to neutralize the hydrochloric acid concentration to 3 mol / L or less. By adjusting the concentration of hydrochloric acid in the solution after Au extraction to 3 mol / L or less, it is possible to suppress the denaturation of the solvent and the occurrence of precipitation in the Pd back extraction.
ＤＨＳ溶媒に抽出したＰｄは通常の方法で逆抽出して回収すれば良い。例えば、抽出したＰｄを含むＤＨＳ溶媒を塩酸洗浄した後に、アンモニアと塩化アンモニウムの水溶液を混合してＰｄを逆抽出し、この逆抽出液に塩酸を加えてＰｄイエローを沈澱させる。回収したＰｄイエローをアンモニア水溶液で溶解し、この溶液にヒドラジンを加えてＰｄを還元析出させることによって、高純度のＰｄメタルを回収することができる。例えば、このＰｄイエローから収率９９％で純度９９.９５％のＰｄメタルを回収することができる。 Pd extracted in the DHS solvent may be recovered by back extraction using a conventional method. For example, after washing the extracted DHS solvent containing Pd with hydrochloric acid, ammonia and an aqueous solution of ammonium chloride are mixed to back-extract Pd, and hydrochloric acid is added to the back extract to precipitate Pd yellow. High purity Pd metal can be recovered by dissolving the recovered Pd yellow with an aqueous ammonia solution, and adding hydrazine to this solution to reduce and precipitate Pd. For example, Pd metal having a yield of 99% and a purity of 99.95% can be recovered from this Pd yellow.
〔第一還元工程〕
Ｐｄ抽出残液を還元して還元滓を回収する。例えば、好ましくは、Ｐｄ抽出残液に苛性ソーダを添加してｐＨ１０〜１３に調整した後に、水和ヒドラジン（H2NNH2？H2O）を添加して還元滓を生成させる。抽出残液のｐＨが10を下回ると還元反応が不十分になる。一方、ｐＨが１３を上回ると還元滓が分散し、その濾過性が低下する。
[First reduction process]
The reduced residue is recovered by reducing the Pd extraction residue. For example, preferably, caustic soda is added to the Pd extraction residue to adjust the pH to 10 to 13, and then hydrated hydrazine (H 2 NNH 2 ? H 2 O) is added to generate reduced soot. When the pH of the extraction residual liquid is less than 10, the reduction reaction becomes insufficient. On the other hand, when the pH exceeds 13, the reduced soot is dispersed and its filterability is lowered.
Ｐｄ抽出後液に含まれる白金族はほぼ全量が還元されて還元滓に含まれる。Ｐｄ抽出後液に含まれる白金族を還元して回収することによって、Ｐｄ抽出後液に含まれるＤＨＳ溶媒の有機物を取り除き、次工程に有機物が混入するのを防止する。さらに白金族（Ｒｕ、Ｐｔ、Ｒｈ）が還元滓に濃縮されるので、これらの回収率を高めることができる。 The platinum group contained in the solution after Pd extraction is almost entirely reduced and is contained in the reduced soot. By reducing and recovering the platinum group contained in the liquid after Pd extraction, the organic substance of the DHS solvent contained in the liquid after Pd extraction is removed, and the organic substance is prevented from being mixed into the next step. Furthermore, since the platinum group (Ru, Pt, Rh) is concentrated in the reducing soot, the recovery rate thereof can be increased.
〔第一塩化溶出工程〕
Ｐｄ抽出後液から回収した還元滓に塩酸と酸化剤（過酸化水素など）を加えて加熱し、還元滓を溶解して該還元滓に含まれる白金族を塩化溶出（クロリネーション）させる。この塩化溶出によって還元滓に含まれている白金族のほぼ全量が溶出する。例えば、Ｐｔ、Ｒｈ、Ｒｕの何れも９９％以上が溶出する。溶解液（第一クロリネーション液）の塩酸濃度は１〜６mol/Lが好ましい。この塩酸濃度で溶解することによって、白金回収後の第二還元工程での中和処理に使用するアルカリ量を低減することができる。
[First chloride elution step]
Hydrochloric acid and an oxidizing agent (hydrogen peroxide, etc.) are added to the reduced soot collected from the solution after Pd extraction and heated to dissolve the reduced soot and elute the platinum group contained in the reduced soot (chlorination). This chloride elution elutes almost all of the platinum group contained in the reduced soot. For example, 99% or more of Pt, Rh, and Ru is eluted. The concentration of hydrochloric acid in the solution (first chlorination solution) is preferably 1 to 6 mol / L. By dissolving at this hydrochloric acid concentration, the amount of alkali used for the neutralization treatment in the second reduction step after platinum recovery can be reduced.
〔希釈工程〕
溶解液（第一クロリネーション液）を水で希釈し、塩素濃度を０.１〜０.４mol/Lに調整する。塩素濃度が０.４mol/Lより高いと、アンモニウム塩を添加したときに白金と共にルテニウムおよびロジウムが沈澱するため、白金を選択的に沈殿させることができない。また、塩素濃度が０.１mol/L未満ではＰｔイエローの生成が進まず、次工程の白金回収でのロスが５％以上になる。概ね溶解液の９倍容量以上の水を加えて１０倍希釈以上にすると良い。
[Dilution process]
The dissolved solution (first chlorination solution) is diluted with water, and the chlorine concentration is adjusted to 0.1 to 0.4 mol / L. When the chlorine concentration is higher than 0.4 mol / L, ruthenium and rhodium are precipitated together with platinum when an ammonium salt is added, so that platinum cannot be selectively precipitated. Further, when the chlorine concentration is less than 0.1 mol / L, the production of Pt yellow does not proceed, and the loss in platinum recovery in the next step becomes 5% or more. In general, it is preferable to dilute 10 times or more by adding 9 times or more volume of water of the solution.
〔白金沈殿工程〕
希釈した溶解液にアンモニウム塩を添加して白金を沈澱させる。例えば、該溶解液に塩化アンモニウムを添加すると白金は塩化白金酸アンモニウム[(NH4)2PtCl6] （Ｐｔイエロー）の沈殿を生じる。溶解液に含まれているルテニウムおよびロジウムは塩化物イオン（RuCl3+、RhCl4 -）のまま液中に残り沈殿しないので、白金をルテニウムおよびロジウムから分離することができる。沈殿した塩化白金酸アンモニウム（Ｐｔイエロー）を固液分離して回収する。
[Platinum precipitation process]
Ammonium salt is added to the diluted solution to precipitate platinum. For example, when ammonium chloride is added to the solution, the platinum precipitates ammonium chloroplatinate [(NH 4 ) 2 PtCl 6 ] (Pt yellow). Since ruthenium and rhodium contained in the solution remain as chloride ions (RuCl 3+ , RhCl 4 − ) and do not precipitate in the solution, platinum can be separated from ruthenium and rhodium. The precipitated ammonium chloroplatinate (Pt yellow) is recovered by solid-liquid separation.
〔第二還元工程〕
白金含有沈殿を分離した後液（白金回収後液）を還元して還元滓を生成させる。例えば、白金回収後液に苛性ソーダなどのアルカリを添加してｐＨを調整し、次いで水和ヒドラジンを添加して還元滓を生成させる。ｐＨは２〜１４が好ましい。ｐＨ２未満では、ＲｕがＲｕ(ＯＨ)2Ｃｌ+やＲｕ4(ＯＨ)12 4+等の形態で安定であるため、ヒドラジンを添加してもＲｕを含む還元滓が生成し難く、Ｒｕを回収できない。ｐＨ１４を超えると還元滓が著しく微小化して還元滓の濾過性が極度に低下する。なお、Ｒｕを含む還元滓の生成および該還元滓の濾過性の両方が良好なｐＨ領域はｐＨ２〜６である。このｐＨ領域では白金回収後液中のルテニウムおよびロジウム（RuCl3+、RhCl4 -）はほぼ全量が還元されて還元滓に含まれる。
[Second reduction step]
After the platinum-containing precipitate is separated, the liquid (post-platinum recovery liquid) is reduced to produce reduced soot. For example, an alkali such as caustic soda is added to the solution after platinum recovery to adjust the pH, and then hydrated hydrazine is added to produce reduced soot. The pH is preferably 2-14. Below pH 2, Ru is stable in a form such as Ru (OH) 2 Cl + or Ru 4 (OH) 12 4+ , so that reduced soot containing Ru is hardly generated even when hydrazine is added, and Ru is recovered. Can not. When the pH exceeds 14, the reduced soot is remarkably miniaturized and the filterability of the reduced soot is extremely reduced. In addition, the pH range where both the production | generation of the reduced soot containing Ru and the filterability of this reduced soot are favorable is pH 2-6. In this pH range, ruthenium and rhodium (RuCl 3+ , RhCl 4 − ) in the solution after platinum recovery are almost entirely reduced and are contained in the reduced soot.
〔第二塩化溶出工程〕
白金回収後液から回収した還元滓を塩酸と酸化剤で溶解する。例えば、該還元滓に塩酸と酸化剤（過酸化水素など）を加えて加熱し、還元滓を溶解する。この塩化溶出によって還元滓に含まれているルテニウムおよびロジウムのほぼ全量が溶出し、ルテニウムおよびロジウム含有液（第二クロリネーション液）を得ることができる。
[Second Chloride Elution Process]
The reduced soot recovered from the solution after platinum recovery is dissolved with hydrochloric acid and an oxidizing agent. For example, hydrochloric acid and an oxidizing agent (such as hydrogen peroxide) are added to the reduced soot and heated to dissolve the reduced soot. By this leaching of chloride, almost all of ruthenium and rhodium contained in the reduced soot are eluted, and a ruthenium and rhodium-containing liquid (second chlorination liquid) can be obtained.
〔Ｒｕ回収工程〕
第二クロリネーション液を酸化蒸留してルテニウムを回収する。例えば、第二クロリネーション液に酸化剤を添加して蒸留し、酸化ルテニウムを蒸留させて回収する。酸化剤は臭素酸塩、例えば臭素酸ナトリウム（ＮａＢｒＯ3）などを用いると良い。
酸化剤を添加する第二クロリネーション液のｐＨは１〜５が好ましい。ｐＨが１より低いと酸化反応が急激に進行塩素ガス等が大量に発生する危険がある。一方、ｐＨが５より高いと液中のルテニウムがルテニウム酸イオン（HRuO5-）を形成し、ルテニウムを効率よく蒸留することができない。なお、第二塩化溶出工程で得た第二クロリネーション液のｐＨは約０であるから、苛性ソーダを添加しｐＨを１〜５に調整した後に酸化剤を添加するのが好ましい。
[Ru recovery process]
Ruthenium is recovered by oxidative distillation of the second chlorination solution. For example, an oxidizing agent is added to the second chlorination liquid and distilled, and ruthenium oxide is distilled and recovered. As the oxidizing agent, a bromate such as sodium bromate (NaBrO 3 ) may be used.
The pH of the second chlorination liquid to which the oxidizing agent is added is preferably 1 to 5. If the pH is lower than 1, there is a risk that the oxidation reaction proceeds rapidly and a large amount of chlorine gas or the like is generated. On the other hand, if the pH is higher than 5, ruthenium in the liquid forms ruthenate ions (HRuO 5- ), and ruthenium cannot be distilled efficiently. In addition, since the pH of the 2nd chlorination liquid obtained at the 2nd chloride elution process is about 0, it is preferable to add an oxidizing agent after adding caustic soda and adjusting pH to 1-5.
液中のルテニウム（RuCl3+）は酸化されると揮発性の酸化ルテニウム（RuO4）になるので容易に蒸留することができる。蒸留温度は約７５℃〜約１００℃、好ましくは約８０℃であれば良い。蒸留した酸化ルテニウムガスを塩酸に吸収させ、塩化ルテニウム酸として回収することができる。 When ruthenium (RuCl 3+ ) in the liquid is oxidized, it becomes volatile ruthenium oxide (RuO 4 ) and can be easily distilled. The distillation temperature may be about 75 ° C to about 100 ° C, preferably about 80 ° C. Distilled ruthenium oxide gas can be absorbed in hydrochloric acid and recovered as ruthenium chloride.
〔Ｒｈ回収工程〕
Ｒｕ蒸留残液からロジウムを沈澱させて回収する。好ましくは、Ｒｕ蒸留残液に還元剤を加え、残留している酸化剤を分解する。例えば、該蒸留残液に塩酸ヒドロキシアミンを加えて、残留している臭素酸ナトリウムを分解する。この分解処理により、次のＲｈ回収で臭素酸ナトリウムと亜硝酸ナトリウムの反応を防止する。
[Rh recovery process]
The rhodium is precipitated and recovered from the Ru distillation residue. Preferably, a reducing agent is added to the Ru distillation residue to decompose the remaining oxidizing agent. For example, the residual sodium bromate is decomposed by adding hydroxyamine hydrochloride to the distillation residue. This decomposition treatment prevents the reaction between sodium bromate and sodium nitrite in the next Rh recovery.
Ｒｕ蒸留残液に塩酸を加えた後にアルカリを添加してｐＨ２〜４に調整する。ｐＨ２〜４に調整することによって、鉄などの不純物が沈殿として析出することを抑制し、ロジウムの純度を高めることができる。ｐＨ２未満になると、亜硝酸ナトリウムが分解しＮＯ2を発生するため望ましくない。 Hydrochloric acid is added to the Ru distillation residue and then alkali is added to adjust the pH to 2-4. By adjusting to pH 2-4, it can suppress that impurities, such as iron, precipitate as precipitation, and can improve the purity of rhodium. If the pH is less than 2, sodium nitrite decomposes and generates NO 2, which is not desirable.
ｐＨ調整したＲｕ蒸留残液に亜硝酸ナトリウムを加えて約８０℃に加熱し、該残液に含まれるロジウムを亜硝酸化する。これを室温まで冷却した後に塩化アンモニウムを加えると、ロジウムは硝酸ロジウム塩[Na(NH4)2Rh(NO２)6]の沈澱を生じるので、これを固液分離して回収する。この方法によって、高純度のロジウムを９０％以上の高収率で回収することができる。 Sodium nitrite is added to the pH-adjusted Ru distillation residue and heated to about 80 ° C. to nitrite the rhodium contained in the residue. When ammonium chloride is added after cooling to room temperature, rhodium causes precipitation of rhodium nitrate salt [Na (NH 4 ) 2 Rh (NO 2 ) 6 ], which is recovered by solid-liquid separation. By this method, high-purity rhodium can be recovered with a high yield of 90% or more.
本発明の回収方法は、白金を回収した後にルテニウムおよびロジウムを回収するので、白金の回収工程がルテニウムおよびロジウムの回収工程の影響を受けず、効率よく白金を回収することができる。
また、本発明の回収方法では、白金を沈澱させて固液分離する化学分離処理によって回収するので、溶媒抽出とは異なり、溶液の処理が容易であり、次の第二還元工程のための液性の調整も容易である。
さらに、白金の回収は第一クロリネーション液を水で希釈して塩素濃度を下げた後に白金を沈澱させる方法であり、白金と液中のルテニウムおよびロジウムとの分離性が良い。
Since the recovery method of the present invention recovers ruthenium and rhodium after recovering platinum, the platinum recovery process is not affected by the recovery process of ruthenium and rhodium, and platinum can be recovered efficiently.
Further, in the recovery method of the present invention, platinum is recovered by a chemical separation process in which solid-liquid separation is performed, so that unlike solvent extraction, the solution can be easily processed and the liquid for the next second reduction step can be obtained. It is easy to adjust the sex.
Furthermore, platinum recovery is a method in which platinum is precipitated after diluting the first chlorination liquid with water to lower the chlorine concentration, and the separability between platinum and ruthenium and rhodium in the liquid is good.
また、本発明の回収方法によれば、回収した白金族の純度が高く、回収率も高い。具体的には、純度９９.９％以上の白金族を回収することができ、白金およびパラジウムの回収率は９９％以上であり、ルテニウムおよびロジウムの回収率は９０％以上である。 Moreover, according to the recovery method of the present invention, the purity of the recovered platinum group is high and the recovery rate is also high. Specifically, a platinum group having a purity of 99.9% or higher can be recovered, the recovery rate of platinum and palladium is 99% or higher, and the recovery rate of ruthenium and rhodium is 90% or higher.
本発明の実施例を以下に示す。溶液の濃度はＩＣＰを用いて測定した。固形分の濃度は王水により固形分を全量溶解した後に溶解液をＩＣＰで測定することで求めた。 Examples of the present invention are shown below. The concentration of the solution was measured using ICP. The concentration of the solid content was determined by measuring the dissolved solution with ICP after dissolving the entire solid content with aqua regia.
〔実施例１〕
白金族含有液の調製：製錬残渣を塩酸と過酸化水素で溶解して白金族含有液７６Ｌを調製した。該溶液の白金族濃度を表１に示す。
Ａｕ溶媒抽出：この白金族含有液をジブチルカルビトール（ＤＢＣ）２４Ｌと３０分混合し、ＡｕおよびＦｅを抽出した。このＡｕ抽出残液の白金族濃度を表１に示した。
Ｐｄ溶媒抽出：このＡｕ抽出残液（塩酸濃度５mol/L）に苛性ソーダを加えて中和し、次いでジヘキシルスルフィド（ＤＨＳ）１１９Ｌを３時間混合してＰｄを抽出した。回収したＰｄメタルの残留濃度およびＰｄ抽出残液の白金族濃度を表２に示した。
第一還元：このＰｄ抽出残液に苛性ソーダを添加してｐＨ１２に調整した。次いで水和ヒドラジンを添加し３０分混合して還元処理し、固液分離して還元滓３.３kgを回収した。この還元滓および残液の白金族濃度を表３に示す。この結果に示すように、白金族のほぼ全量が還元されて還元滓に含まれている。
第一塩化溶出：第一還元滓を塩酸および過酸化水素で溶解し、溶解液（第一クロリネーション液）１１Ｌを得た。第一クロリネーション液の白金族濃度を表４に示す。表示するように、白金族は何れも浸出率９９％以上であった。
希釈：第一クロリネーション液に約９容量倍の水１０１Ｌを加えて３０分混合し、塩素濃度０.４mol/Lに調整した。
白金回収：希釈した第一クロリネーション液に塩化アンモニウム４.８kgを添加し、生成した沈殿を固液分離し、Ｐｔイエローを回収した。該Ｐｔイエローを焙焼し粗白金メタルを得た。これを王水で溶解した後、既存の化学分離法で精製し、純度９９.９５％の精白金メタルを回収した。その収率は８８％であった。ＰｔメタルおよびＰｔ回収残液の白金族濃度を表５に示す。
第二還元：Ｐｔ回収後液に苛性ソーダを添加してｐＨ５に調整し、次いで水和ヒドラジンを添加し３０分混合して還元処理し、固液分離して還元滓１.９kgを回収した。この還元滓と残液の白金族濃度を表６に示す。この結果に示すように、ＲｕおよびＲｈのほぼ全量が還元されて還元滓に含まれている。
第二塩化溶出：第二還元滓を塩酸および過酸化水素で溶解し、溶解液（第二クロリネーション液）５.８Ｌを得た。第二クロリネーション液のＲｕおよびＲｈ濃度を表７に示す。表示するように、ＲｕおよびＲｈは何れも浸出率９９％以上であった。
Ｒｕ回収：第二クロリネーション液を蒸留装置に入れ、臭素酸ナトリウムを混合し、８０℃でＲｕを酸化蒸留した。回収した酸化ルテニウムガスを塩酸に吸収させ、塩化ルテニウム酸４３３ｇを得た。また、この蒸留残液に塩酸を加え、臭素酸を分解した。Ｒｕ蒸留残液の白金族濃度を表８に示す。
Ｒｈ回収：Ｒｕ蒸留残液に苛性ソーダを加えてｐＨ４に中和し、次いで、ＮａＮＯ2とＮＨ4Ｃｌを加えて加熱し、亜硝酸アンモニウム塩〔Na(NH4)2Rh(NO2)6〕６４ｇを回収した。
[Example 1]
Preparation of platinum group-containing liquid : The smelting residue was dissolved in hydrochloric acid and hydrogen peroxide to prepare a platinum group-containing liquid 76L. The platinum group concentration of the solution is shown in Table 1.
Au solvent extraction : This platinum group-containing liquid was mixed with 24 L of dibutyl carbitol (DBC) for 30 minutes to extract Au and Fe. The platinum group concentration of this Au extraction residual liquid is shown in Table 1.
Pd solvent extraction : This Au extraction residue (hydrochloric acid concentration 5 mol / L) was neutralized by adding caustic soda, and then 119 L of dihexyl sulfide (DHS) was mixed for 3 hours to extract Pd. Table 2 shows the residual concentration of the recovered Pd metal and the platinum group concentration of the Pd extraction residual liquid.
First reduction : Caustic soda was added to the Pd extraction residue to adjust the pH to 12. Next, hydrazine hydrate was added and mixed for 30 minutes for reduction treatment, and solid-liquid separation was performed to recover 3.3 kg of reduced soot. Table 3 shows the platinum group concentration of the reducing soot and the residual liquid. As shown in this result, almost all of the platinum group is reduced and contained in the reduced soot.
First chloride elution : The first reduced soot was dissolved with hydrochloric acid and hydrogen peroxide to obtain 11 L of a solution (first chlorination solution). Table 4 shows the platinum group concentration of the first chlorination liquid. As shown, all platinum groups had a leaching rate of 99% or higher.
Dilution : About 9 volumes of water 101L was added to the first chlorination solution and mixed for 30 minutes to adjust the chlorine concentration to 0.4 mol / L.
Platinum recovery : 4.8 kg of ammonium chloride was added to the diluted first chlorination liquid, and the resulting precipitate was subjected to solid-liquid separation to recover Pt yellow. The Pt yellow was roasted to obtain crude platinum metal. This was dissolved in aqua regia and purified by an existing chemical separation method to recover 99.95% pure platinum metal. The yield was 88%. Table 5 shows platinum group concentrations of Pt metal and Pt recovery residual liquid.
Second reduction : After the Pt recovery, caustic soda was added to adjust the pH to 5, then hydrated hydrazine was added and mixed for 30 minutes for reduction treatment, followed by solid-liquid separation to recover 1.9 kg of reduced soot. Table 6 shows the platinum group concentration of the reducing soot and the remaining liquid. As shown in this result, almost all of Ru and Rh are reduced and are contained in the reduced soot.
Second chloride elution : The second reduced soot was dissolved with hydrochloric acid and hydrogen peroxide to obtain 5.8 L of a solution (second chlorination solution). Table 7 shows the Ru and Rh concentrations of the second chlorination liquid. As indicated, both Ru and Rh had a leaching rate of 99% or higher.
Ru recovery : The second chlorination liquid was put into a distillation apparatus, sodium bromate was mixed, and Ru was oxidatively distilled at 80 ° C. The recovered ruthenium oxide gas was absorbed into hydrochloric acid to obtain 433 g of ruthenium chloride acid. Further, hydrochloric acid was added to the distillation residue to decompose bromic acid. Table 8 shows the platinum group concentration of the Ru distillation residue.
Rh recovery : Caustic soda is added to Ru distillation residue to neutralize to pH 4, then NaNO 2 and NH 4 Cl are added and heated to obtain 64 g of ammonium nitrite [Na (NH 4 ) 2 Rh (NO 2 ) 6 ]. It was collected.
〔実施例２〕
実施例１の第一クロリネーション液におのおの水２００L（約２０容量倍）、水４４Ｌ（約４容量倍）、を加えて３０分混合した後に、塩化アンモニウムを添加し、生成した沈殿を固液分離し、Ｐｔイエローを回収した。該ＰｔイエローおよびＰｔ回収残液の白金族濃度を表９に示す。水２００Ｌで希釈した試料Ａ１はＰｔメタル中のＲｕ量およびＲｈ量が少なく、Ｐｔがよく分離されている。一方、水４４Ｌで希釈した試料Ａ２はＰｔメタル中のＲｕ量およびＲｈ量が多く、塩素濃度が高いとＰｔの分離性が低下するので、第一クロリネーション液の水希釈は塩素濃度が０.１〜０.４mol/Lになる範囲が好ましい。
[Example 2]
After adding 200 L of water (about 20 vol. Times) and 44 L of water (about 4 vol. Times) to the first chlorination liquid of Example 1 for 30 minutes, ammonium chloride was added and the resulting precipitate was solid-liquid. Separated and recovered Pt yellow. Table 9 shows platinum group concentrations of the Pt yellow and Pt recovery residual liquid. Sample A1 diluted with 200 L of water has a small amount of Ru and Rh in the Pt metal, and Pt is well separated. On the other hand, the sample A2 diluted with 44 L of water has a large amount of Ru and Rh in the Pt metal, and if the chlorine concentration is high, the separation of Pt decreases, so that the water dilution of the first chlorination liquid has a chlorine concentration of 0. A range of 1 to 0.4 mol / L is preferable.
〔実施例３〕
実施例１の第二還元工程において、Ｐｔ回収後液のｐＨ調整（ｐＨ５）をｐＨ２（試料Ｂ１）、ｐＨ１４（試料Ｂ２）に変え、各々に水和ヒドラジンを添加し、生成した還元滓を固液分離して回収した。試料Ｂ２の濾過時間は実施例１の約１０倍であった。回収した各々の還元滓に含まれる白金族の含有量を表１０に示す。
Example 3
In the second reduction step of Example 1, the pH adjustment (pH 5) of the solution after Pt recovery was changed to pH 2 (sample B1) and pH 14 (sample B2), hydrated hydrazine was added to each, and the resulting reduced soot was solidified. The liquid was separated and recovered. The filtration time for Sample B2 was about 10 times that of Example 1. Table 10 shows the content of platinum group contained in each of the recovered reducing soots.
〔比較例１〕
実施例１の第一クロリネーション液を水で希釈せずに塩化アンモニウムを添加し、生成した沈殿を固液分離し、Ｐｔイエローを回収した。該ＰｔイエローからＰｔメタルを得た。ＰｔメタルおよびＰｔ回収残液の白金族濃度を表１１に示す。この結果に示すように、水で希釈せずに白金を沈澱させると、ＰｔメタルのＲｕ量およびＲｈ量が多く、ＲｕおよびＲｈとＰｔの分離性が低い。
[Comparative Example 1]
Ammonium chloride was added without diluting the first chlorination liquid of Example 1 with water, and the resulting precipitate was subjected to solid-liquid separation to recover Pt yellow. Pt metal was obtained from the Pt yellow. Table 11 shows platinum group concentrations of Pt metal and Pt recovery residual liquid. As shown in this result, when platinum is precipitated without diluting with water, the amount of Ru and Rh of Pt metal is large, and the separation between Ru, Rh and Pt is low.
本発明の回収方法は、製錬残渣の浸出後液や白金族金属のスクラップ溶解液を原料として高い回収率で白金族金属を回収することができ、これらの産業分野において好適に利用することができる。 The recovery method of the present invention can recover a platinum group metal at a high recovery rate from a smelted residue leaching solution or a platinum group metal scrap solution as a raw material, and can be suitably used in these industrial fields. it can.
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