JP2004035968A - Method for separating platinum group element - Google Patents

Method for separating platinum group element Download PDF

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JP2004035968A
JP2004035968A JP2002196802A JP2002196802A JP2004035968A JP 2004035968 A JP2004035968 A JP 2004035968A JP 2002196802 A JP2002196802 A JP 2002196802A JP 2002196802 A JP2002196802 A JP 2002196802A JP 2004035968 A JP2004035968 A JP 2004035968A
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selenium
platinum
liquid
tellurium
separation
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JP4269586B2 (en
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Satoshi Okada
岡田 智
Takahiro Uno
宇野 貴博
Kazusuke Sato
佐藤 一祐
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Mitsubishi Materials Corp
三菱マテリアル株式会社
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a treatment method for effectively separating a platinum group element from selenium and tellurium, and collecting it. <P>SOLUTION: This method comprises alkali-leaching a substance containing selenium or the like and a platinum group element at a high temperature, migrating selenium or the like into a liquid, separating a solid from the liquid, separating the platinum group element contained in the solid from selenium or the like contained in the liquid, and adding an oxidizing agent to the separated solid in a hydrochloric acid solution to dissolve the platinum group element. The present treatment method collects the platinum group element at a high yield, because of dissolving selenium and tellurium under atmospheric pressure without using the oxidizing agent and separating them from the platinum group element, by alkali-leaching the substance containing selenium or the like and the platinum group element without heating it too much. <P>COPYRIGHT: (C)2004,JPO

Description

【0001】
【発明の属する技術分野】
本発明は、白金族元素と共にセレンを含む滓などから、白金族元素を効率良くセレンと分離して回収することができる処理方法に関する。
【0002】
【従来技術とその課題】
白金族元素は、銀製錬工程からでる銀アノードスライムや、このスライムに硝酸を加えて金以外の成分を浸出した後に還元して得たスライムなどを原料として回収されている。従来、これらのスライムを溶解するには、王水による溶解、または塩酸と過酸化水素による溶解、または塩酸と塩素ガス吹込みによる溶解が利用されている。
【0003】
ところが、白金族元素と共に大量のセレンが共存している場合、これを還元して沈殿化すると白金族のセレン化物が形成される場合が多い。この白金族セレン化物は王水や塩酸および過酸化水素では溶解し難く、特に過酸化水素を使用した場合にはセレン化物の表面で過酸化水素が分解するために酸化剤としての効果が殆ど無い。このため従来の溶解法では白金族セレン化物を溶解して、白金族元素をセレンと分離するのが難しい。また、焙焼によってセレンを酸化セレンの形で気化させて原料から除去する方法では、二酸化セレンの毒性によって環境が汚染される問題がある。
【0004】
また、銅電解澱物の金抽出後液に含まれる白金族元素とセレン・テルルとを分離する方法として、液中の塩素イオン濃度を1.5モル/L以下とし、60℃〜90℃の温度下で、8〜12%濃度の亜硫酸ガスを液中に吹き込み、白金族元素を還元して沈澱化し、液中のセレンと分離した後に、さらに亜硫酸ガスを吹き込んでセレンを還元して沈澱化する方法(特開2001−316735号)や、銅電解スライムの塩酸浸出液から溶媒抽出によって金および白金族を回収した抽出残液に二酸化硫黄を導入し、セレンおよびテルルを還元して沈澱化する方法(特許第3087758号:特開2001−207223)などが知られている。
【0005】
しかし、二酸化硫黄による二段階の還元処理は工程の管理が非常に難しく、しかも何れの沈澱においてもセレンまたは白金族元素の混入が避けられず、二酸化硫黄による還元だけでは分離が不十分である。また、白金族を溶媒抽出してセレンやテルルと分離する方法はコスト高であり、抽出後の回収処理も面倒である。さらに、これらの方法は何れもすでに溶液中に共存する白金族元素とセレンを分離するものであり、白金族元素とセレン等を含む処理滓の溶解に関するものではない。
【0006】
この他にセレンやテルルの回収に関して次の方法が従来から知られている。例えば、酸化剤を用いて金属セレンを酸化し、これをアルカリ金属の炭酸塩または水酸化物で中和してアルカリ金属セレン酸塩を製造する方法(特開昭60−176908号)、セレン含有物をアルカリ金属炭酸塩と反応させて水溶性スラリーにし、これを酸化雰囲気下で焙焼してペレットにした後に水浸出する方法(特開昭56−5306号)、含テルル銅スライムを酸化剤の存在下で鉱酸に溶解し、これにアルカリを加えて銅を沈澱分離した後に、中和してテルルを沈澱化する方法(特開昭56−84428号)などが知られている。しかし、これらは何れもセレンやテルルを酸化して溶解する方法であり、この方法では白金族元素とセレンとを溶解段階で分離することができない。
【0007】
また、白金族元素であるロジウムの回収については、ロジウムは酸化されやすく、難溶性の酸化ロジウムを生じるために溶液化が難しい。このロジウムを貴金属含有滓から分離する方法として、貴金属含有滓を炭素質還元剤と共に加熱し、得られた還元物を高温下で硫酸塩化剤と反応させてロジウムの硫酸塩を形成させる方法(特開平5−125461号)が知られているが、処理温度が高いうえに回収率が低いと云う問題がある。
【0008】
本発明は、セレンを含む白金族含有物の溶解処理方法について、従来の上記問題を解決したものであり、セレンを選択的に溶解して効率よく白金族元素と分離し、固形分に残る白金族元素を溶解して回収する処理方法を提供する。
【0009】
【課題を解決する手段】
すなわち、本発明によれば以下の処理方法が提供される。
(1) セレン白金族含有物を高温下でアルカリ浸出してセレン等を液中に移行させ、これを固液分離して固形分に含まれる白金族元素と液分に含まれるセレン等とを分離することを特徴とする白金族元素の分離方法。
(2) セレン白金族含有物を高温下でアルカリ浸出してセレン等を液中に移行させ、これを固液分離して固形分に含まれる白金族元素と液分に含まれるセレン等とを分離し、分離した固形分に塩酸酸性下で酸化剤を加えて白金族元素を溶解することを特徴とする白金族元素の分離方法。
(3) セレン白金族含有物を高温下でアルカリ浸出することによってセレンと共にテルルを液中に移行させて白金族元素と分離する上記(1)または(2)の分離方法。
(4) セレン白金族含有物を、60℃以上の温度下および1モル/L以上のアルカリ濃度下で浸出する上記(1)〜(3)の何れかに記載する分離方法。
(5) アルカリ浸出後に固液分離した固形分に、塩酸と共に過酸化水素または塩素ガスを添加して白金族元素を溶解する上記(1)〜(4)の何れかに記載する分離方法。
(6) 白金族元素がロジウム、ルテニウム、パラジウム、白金の一種または二種以上である上記(1)〜(5)の何れかに記載する分離方法。
(7) セレン白金族含有物が脱銅製錬スライムの塩酸浸出液から溶媒抽出によって金を分離した抽出残液の処理滓である上記(1)〜(6)の何れかに記載する分離方法。
(8) 脱銅製錬スライムを塩酸および過酸化水素によってスラリーにし、これを濾過して主に銀を含む浸出滓と、金、白金族元素およびセレン、テルルを含む浸出液とに分離し、次に、この浸出液の液性を調整した後に溶媒抽出によって浸出液から金を分離する一方、抽出残液に二酸化イオウを添加してセレンないしテルルを沈澱させ、これを固液分離して得た濾滓を高温下でアルカリ浸出する上記(1)〜(7)の何れかに記載する分離方法。
【0010】
【発明の実施の形態】
以下、本発明を実施例と共に具体的に説明する。
本発明の処理方法の概略を図1に示す。図示するように本発明の処理方法は、セレン白金族含有物を、高温下でアルカリ浸出してセレン等を液中に移行させ、これを固液分離して固形分に含まれる白金族元素と液分に含まれるセレン等とを分離することを特徴とする白金族元素の分離方法である。
【0011】
さらに本発明の分離方法は、上記アルカリ浸出して分離した固形分に塩酸酸性下で酸化剤を加えて白金族元素を溶解することを特徴とする白金族元素の溶解分離方法を含む。また、高温下のアルカリ浸出によってセレンと共にテルルを液中に移行させて白金族元素と分離する方法、白金族元素がロジウム、ルテニウム、パラジウム、白金の一種または二種以上である方法を含む。なお、本発明においてセレン白金族含有物とはロジウム等の白金族元素と共にセレン等を含有するものを云う。またセレン等とはセレンおよび/またはテルルを云う。
【0012】
セレン白金族含有物として、例えば、脱銅製錬スライムの塩酸浸出液から溶媒抽出によって金を分離した抽出残液の処理滓を用いることができる。この脱銅製錬スライムには金、銀、白金族元素、セレン、テルルなどの有価金属が多量に含まれている。この処理方法の一例を図2に示す。図示するように、上記脱銅スライムを塩酸および過酸化水素によってスラリーにし、これを濾過して主に銀を含む浸出滓と、金、白金族元素およびセレン、テルルを含む浸出液とに分離する。次に、この浸出液の液性を調整した後に溶媒抽出によって浸出液から金を分離する。一方、抽出残液には白金族元素、セレン、テルルが残留している。そこで、この抽出残液に二酸化イオウを添加してこれらの白金族元素、セレンおよびテルルを沈澱化し、処理滓として回収することができる。
【0013】
なお、上記抽出残液に二酸化イオウを添加してセレンとテルルを還元し、沈澱化させる際、テルルはセレンより還元電位が低く、セレンが沈澱した後にテルルが沈澱するので、セレン沈澱を濾別した後に、この濾液にさらに二酸化イオウを添加してテルルを沈澱化することによって両者を分離回収することができる。これらの還元の際に白金族元素はセレンないしテルルと共に沈澱する。本発明はセレン白金族含有物としてこれらのセレン沈澱滓あるいはテルル沈澱滓を用いることができる。
【0014】
セレン白金族含有物のアルカリ浸出は、1モル/L以上のアルカリ濃度下で行うのが適当であり、例えば5モル/L〜8モル/Lの範囲が好ましい。アルカリ濃度を1モル/L以上にすることにより、pH>14の強アルカリ性下でセレンやテルルの酸化還元電位が下がり、常圧下において酸化剤を用いずに、セレンおよびテルルをアルカリ溶液中に溶出させることができる。なお、常温ではこのセレンやテルルの溶出反応の進行が遅いので、60℃以上の温度下、好ましくは80℃程度の温度下で浸出を行うのが適当である。
【0015】
上記アルカリ浸出によって、セレンおよびテルルはアルカリ溶液中に溶出してコロイド状に分散する。一方、ロジウムやパラジウムなどの白金族元素は溶出せずに残留する。これを濾別して、セレンないしテルルの分散液と、白金族元素を含む固形分とに分離する。
【0016】
上記固液分離後、濾別した固形分に過酸化水素などの酸化剤を塩酸と共に添加し、白金、パラジウム、ロジウム、ルテニウムなどの白金族元素を溶出させる。白金族元素は過酸化水素によって酸化されると共に塩素イオンによって塩化物錯体となり、安定化されて液中に溶出する。過酸化水素は白金族元素を安定な酸化数のイオンにするために必要な当量、すなわち白金を4価、バラジウムを2価、ロジウムおよびルテニウムを3価に酸化するのに必要な当量を用いる。塩酸はそれぞれPtCl ,PdCl ,RhCl 3−,RuCl 3−に相当する量、および遊離塩酸として2モル/L以上を用いる。反応温度は反応を促進するため60℃以上が良く、また過酸化水素の分解を抑制するため80℃以下が適当であり、70℃程度の温度下で行うのが好ましい。この溶解処理によって、白金、パラジウム、ロジウム、ルテニウムなどが溶解した塩酸性溶液を得ることができる。
【0017】
【発明の効果】
本発明の処理方法によれば、セレン白金族含有物を60℃〜80℃程度の処理温度においてアルカリ浸出することによって、常圧下で酸化剤を用いずに、セレンやテルルを溶解して白金族元素から分離することができる。従って、白金族元素と共にセレンやテルルを含有する処理滓から容易にセレンおよびテルルを分離して白金族元素を概ね95%以上の収率で選択的に回収することができる。しかも、このアルカリ浸出の際に白金族元素は酸化されないため、難溶性の酸化ロジウムや酸化ルテニウムを生じることがなく、溶液化が容易である。この浸出残渣中の白金族元素を塩酸酸性下で酸化して塩化物錯体を形成させることによって白金族元素含有液を得ることができる。一方、溶出したセレンやテルルはコロイド状に分散しており、浸出液を中和するとメタルになって沈澱するので、これらも容易に回収することができる。因みに、従来の酸化剤を用いてアルカリ浸出する方法は加圧下で浸出を行い、セレン酸ソーダないし亜セレン酸ソーダなどが生じるので、その後のセレン回収工程が面倒である。一方、本発明の処理方法は、常圧下で酸化剤を用いずにセレンおよびテルルを溶解して白金族元素と分離するので、工程の管理および回収処理が容易である。
【0018】
【実施例】
以下、本発明の実施例および比較例を示す。なお、%は特に示さない限りwt%である。
〔実施例1〕
セレン白金族含有物(Se:65%,Te:30%,Pd:5%,Pt:0.5%,Rh:0.2%,Ru:0.4%)1kgを、5モル/Lの苛性ソーダ溶液10Lと混合して80℃に加熱して1時間保持したところ、大部分は溶解して液は濃い紫色になつた。これを冷却後に濾過し、残渣65gを回収した。この残渣を分析したところ、Pd、Pt、Rh、Ruの白金族元素が主成分として確認され、その品位はPd:80%、Pt:8%、Rh:3%、Ru:6%であった。なお、濾液にはSe:65g/LおよびTe:30g/Lが溶解していたが、白金族元素は検出されなかった。
【0019】
〔実施例2〕
セレン白金族含有物(Se:65%,Te:30%,Pd:5%,Pt:0.5%,Rh:0.2%,Ru:0.4%)1kgを、5モル/Lの苛性ソーダ溶液10Lと混合して80℃に加熱して1時間保持したところ、大部分は溶解して液は濃い紫色になつた。これを冷却後に濾過し、残渣65gを回収した。なお、濾液にはSe:65g/LおよびTe:30g/Lが溶解していたが、白金族元素は検出されなかった。この残渣を分析したところ、Pd、Pt、Rh、Ruの白金族元素が主成分として確認され、その品位はPd:80%、Pt:8%、Rh:3%、Ru:6%であった。この残渣を塩酸400mlと水100mlでリパルプし、液温を70℃に保ちながら過酸化水素120mlを徐々に添加した。過酸化水素の添加終了後、冷却して濾過した濾液を分析したところ、Pd:74g/L、Pt:7g/L、Rh:2.8g/L、Ru:5.5g/Lであった。
【0020】
〔実施例3〕
苛性ソーダ溶液の濃度を1モル/Lとし、加熱保持時間を5時間とした以外は実施例1と同様にしてアルカリ浸出を行った。この結果、75gの残渣を回収した。残渣の主成分はPd、Pt、Rh、Ruであり、その品位はPd:67%、Pt:7%、Rh:3%、Ru:5%であった。一方、濾液にはSe:63g/LおよびTe:28g/Lが溶解していたが、白金族元素は検出されなかった。
【0021】
〔実施例4〕
苛性ソーダ溶液の濃度を8モル/Lとし、加熱温度を60℃とした以外は実施例1と同様にしてアルカリ浸出を行った。この結果、65gの残渣を回収した。残渣の主成分はPd、Pt、Rh、Ruであり、その品位はPd:77%、Pt:8%、Rh:3%、Ru:6%であった。一方、濾液にはSe:64g/LおよびTe:29g/Lが溶解していたが、白金族元素は検出されなかった。
【0022】
〔比較例1、2〕
苛性ソーダ溶液の濃度を0.5モル/Lとした以外は実施例1と同様にしてアルカリ浸出を行ったところ、セレンおよびテルルは溶出せず、白金族元素をセレンおよびテルルから分離することができなかった(比較例1)。
また、反応温度を室温とした以外は実施例1と同様にしてアルカリ浸出を行ったところ、セレンおよびテルルは溶出せず、白金族元素をセレンおよびテルルから分離することができなかった(比較例2)。
【図面の簡単な説明】
【図1】本発明の処理方法の概略を示す工程図。
【図2】脱銅スライムの処理から本発明の処理方法に至る概略を示す工程図。
[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a treatment method capable of efficiently separating and recovering a platinum group element from selenium from a selenium containing selenium together with a platinum group element.
[0002]
[Prior art and its problems]
Platinum group elements are recovered as silver anode slime from a silver smelting process or slime obtained by leaching components other than gold by adding nitric acid to the slime and reducing the slime. Conventionally, to dissolve these slimes, dissolution with aqua regia, dissolution with hydrochloric acid and hydrogen peroxide, or dissolution by blowing hydrochloric acid and chlorine gas has been used.
[0003]
However, when a large amount of selenium coexists with a platinum group element, when this is reduced and precipitated, platinum group selenide is often formed. This platinum group selenide hardly dissolves in aqua regia, hydrochloric acid, and hydrogen peroxide.Especially, when hydrogen peroxide is used, hydrogen peroxide decomposes on the surface of the selenide, so it has almost no effect as an oxidizing agent. . Therefore, it is difficult to dissolve the platinum group selenide and separate the platinum group element from selenium by the conventional dissolving method. Further, in the method of removing selenium from raw materials by vaporizing selenium in the form of selenium oxide by roasting, there is a problem that the toxicity of selenium dioxide pollutes the environment.
[0004]
In addition, as a method of separating the platinum group element and selenium / tellurium contained in the solution after the gold extraction of the copper electrolytic deposit, the chloride ion concentration in the solution is set to 1.5 mol / L or less, At a temperature, sulfuric acid gas having a concentration of 8 to 12% is blown into the liquid to precipitate and reduce the platinum group element. After separating from the selenium in the liquid, selenium is further blown into the liquid to precipitate the selenium. (Japanese Patent Application Laid-Open No. 2001-316735) or a method in which sulfur dioxide is introduced into an extraction residue obtained by recovering gold and platinum groups from a hydrochloric acid leachate of copper electrolytic slime by solvent extraction, and selenium and tellurium are reduced to precipitate. (Japanese Patent No. 3087758: JP-A-2001-207223) and the like are known.
[0005]
However, the two-stage reduction treatment with sulfur dioxide is very difficult to control the process, and selenium or a platinum group element is inevitably mixed in any of the precipitations, so that separation by sulfur dioxide alone is insufficient. Further, the method of extracting the platinum group with a solvent to separate it from selenium or tellurium is expensive, and the recovery process after the extraction is troublesome. Furthermore, all of these methods separate the platinum group element and selenium which are already present in the solution, and do not relate to the dissolution of the processing residue containing the platinum group element and selenium.
[0006]
In addition to the above, the following methods are conventionally known for recovering selenium and tellurium. For example, a method of producing alkali metal selenate by oxidizing metal selenium using an oxidizing agent and neutralizing the metal selenium with an alkali metal carbonate or hydroxide (Japanese Patent Application Laid-Open No. 60-176908). By reacting the product with an alkali metal carbonate to form a water-soluble slurry, roasting it in an oxidizing atmosphere to form pellets, and leaching with water (JP-A-56-5306). A method of dissolving in a mineral acid in the presence of, adding an alkali thereto to precipitate and separate copper, and then neutralizing to precipitate tellurium (JP-A-56-84428) is known. However, each of these methods is a method of oxidizing and dissolving selenium or tellurium, and this method cannot separate the platinum group element and selenium in the dissolving stage.
[0007]
Further, in recovering rhodium, which is a platinum group element, rhodium is easily oxidized and hardly turns into a solution because it produces insoluble rhodium oxide. As a method for separating the rhodium from the noble metal-containing slag, a method in which the noble metal-containing slag is heated together with a carbonaceous reducing agent, and the obtained reduced product is reacted with a sulfate agent at a high temperature to form a sulfate of rhodium (particularly, Japanese Unexamined Patent Publication (Kokai) No. 5-125461) has a problem that the processing temperature is high and the recovery rate is low.
[0008]
The present invention solves the above-mentioned conventional problems with respect to a method for dissolving a platinum-group-containing material containing selenium, and selectively dissolves selenium to efficiently separate it from a platinum-group element, and forms platinum remaining in a solid content. Disclosed is a method for dissolving and recovering a group III element.
[0009]
[Means to solve the problem]
That is, according to the present invention, the following processing method is provided.
(1) Alkaline leaching of selenium platinum group-containing substances at high temperature to transfer selenium and the like into a liquid, and solid-liquid separation of the selenium and the like to form a platinum group element contained in a solid and a selenium contained in a liquid. A method for separating a platinum group element, which comprises separating.
(2) Alkaline leaching of the selenium platinum group-containing substance at a high temperature to transfer selenium and the like into a liquid, and solid-liquid separation of the selenium and the like to separate the platinum group element contained in the solid and the selenium contained in the liquid. A method for separating a platinum group element, comprising adding an oxidizing agent to a separated solid content under acidic conditions of hydrochloric acid to dissolve the platinum group element.
(3) The separation method according to (1) or (2) above, wherein tellurium is transferred together with selenium into the liquid together with selenium by alkali leaching the selenium platinum group-containing substance at a high temperature to separate from platinum group elements.
(4) The separation method according to any one of the above (1) to (3), wherein the selenium platinum group-containing substance is leached at a temperature of 60 ° C. or more and an alkali concentration of 1 mol / L or more.
(5) The separation method according to any one of the above (1) to (4), wherein hydrogen peroxide or chlorine gas is added together with hydrochloric acid to the solid content subjected to solid-liquid separation after alkali leaching to dissolve the platinum group element.
(6) The separation method according to any one of (1) to (5) above, wherein the platinum group element is one or more of rhodium, ruthenium, palladium, and platinum.
(7) The separation method according to any one of the above (1) to (6), wherein the selenium platinum group-containing substance is a slag of an extraction residue obtained by separating gold from a hydrochloric acid leachate of a copper-free smelting slime by solvent extraction.
(8) The copper-free smelting slime is slurried with hydrochloric acid and hydrogen peroxide, and the slurry is separated by filtration into a leachate mainly containing silver and a leachate containing gold, platinum group elements and selenium and tellurium, After adjusting the liquid property of the leachate, gold was separated from the leachate by solvent extraction, while sulfur dioxide was added to the extraction residue to precipitate selenium or tellurium, and the filter cake obtained by solid-liquid separation of the sediment was removed. The separation method according to any one of the above (1) to (7), wherein alkali leaching is performed at a high temperature.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be specifically described with examples.
FIG. 1 shows an outline of the processing method of the present invention. As shown in the figure, in the treatment method of the present invention, a selenium platinum group-containing substance is leached with alkali at a high temperature to transfer selenium and the like into a liquid, and this is separated into a solid-liquid to form a platinum group element contained in a solid content. A method for separating a platinum group element, comprising separating selenium and the like contained in a liquid component.
[0011]
Further, the separation method of the present invention includes a method of dissolving and separating a platinum group element, wherein an oxidizing agent is added to the solid content separated by alkali leaching under hydrochloric acid to dissolve the platinum group element. In addition, the method includes a method in which tellurium is transferred into a liquid together with selenium by alkali leaching at a high temperature to separate it from the platinum group element, and a method in which the platinum group element is one or more of rhodium, ruthenium, palladium, and platinum. In the present invention, the selenium-platinum-group-containing substance refers to a substance containing selenium or the like together with a platinum-group element such as rhodium. Selenium and the like refer to selenium and / or tellurium.
[0012]
As the selenium platinum group-containing material, for example, a treated slag of an extraction residue obtained by separating gold from a hydrochloric acid leachate of a copper-free smelting slime by solvent extraction can be used. This decopper smelting slime contains a large amount of valuable metals such as gold, silver, platinum group elements, selenium and tellurium. FIG. 2 shows an example of this processing method. As shown in the figure, the decopperized slime is slurried with hydrochloric acid and hydrogen peroxide, and filtered to separate into a leaching slag containing mainly silver and a leaching solution containing gold, a platinum group element and selenium and tellurium. Next, after adjusting the liquid properties of the leachate, gold is separated from the leachate by solvent extraction. On the other hand, a platinum group element, selenium, and tellurium remain in the extraction residue. Then, sulfur dioxide is added to the residual extract to precipitate these platinum group elements, selenium and tellurium, and can be recovered as treated slag.
[0013]
In addition, when sulfur dioxide is added to the above extraction residue to reduce selenium and tellurium and precipitate, tellurium has a lower reduction potential than selenium, and tellurium precipitates after selenium precipitates. After the addition, sulfur dioxide is further added to the filtrate to precipitate tellurium, whereby both can be separated and recovered. During these reductions, the platinum group elements precipitate with selenium or tellurium. In the present invention, these selenium precipitates or tellurium precipitates can be used as the selenium platinum group-containing material.
[0014]
The alkali leaching of the selenium platinum group-containing substance is suitably performed at an alkali concentration of 1 mol / L or more, for example, preferably in the range of 5 mol / L to 8 mol / L. By increasing the alkali concentration to 1 mol / L or more, the oxidation-reduction potential of selenium and tellurium is reduced under strong alkalinity of pH> 14, and selenium and tellurium are eluted in an alkaline solution without using an oxidizing agent under normal pressure. Can be done. Since the elution reaction of selenium and tellurium proceeds slowly at normal temperature, it is appropriate to perform leaching at a temperature of 60 ° C. or more, preferably at a temperature of about 80 ° C.
[0015]
Due to the alkaline leaching, selenium and tellurium are eluted and dispersed in a colloidal form in the alkaline solution. On the other hand, platinum group elements such as rhodium and palladium remain without being eluted. This is separated by filtration to separate into a dispersion of selenium or tellurium and a solid containing a platinum group element.
[0016]
After the solid-liquid separation, an oxidizing agent such as hydrogen peroxide is added to the filtered solid content together with hydrochloric acid to elute platinum group elements such as platinum, palladium, rhodium and ruthenium. The platinum group element is oxidized by hydrogen peroxide and becomes a chloride complex by chlorine ions, stabilized, and eluted in the liquid. Hydrogen peroxide is used in an equivalent amount necessary to convert the platinum group element into an ion having a stable oxidation number, that is, an equivalent amount necessary to oxidize platinum to tetravalent, baradium to divalent, and rhodium and ruthenium to trivalent. Each hydrochloride PtCl 6 -, PdCl 4 -, RhCl 6 3-, amount equivalent to RuCl 6 3-, and using the above 2 mol / L as the free hydrochloric acid. The reaction temperature is preferably 60 ° C. or higher to promote the reaction, and is preferably 80 ° C. or lower to suppress the decomposition of hydrogen peroxide, and is preferably performed at a temperature of about 70 ° C. By this dissolution treatment, a hydrochloric acid solution in which platinum, palladium, rhodium, ruthenium and the like are dissolved can be obtained.
[0017]
【The invention's effect】
According to the treatment method of the present invention, the selenium or tellurium is dissolved under normal pressure without using an oxidizing agent by subjecting the selenium platinum group-containing material to alkali leaching at a treatment temperature of about 60 ° C. to 80 ° C. Can be separated from elements. Therefore, selenium and tellurium can be easily separated from the treated slag containing selenium and tellurium together with the platinum group element, and the platinum group element can be selectively recovered with a yield of about 95% or more. Moreover, since the platinum group element is not oxidized during the alkali leaching, hardly soluble rhodium oxide or ruthenium oxide is not generated, and the solution can be easily formed. A platinum group element-containing liquid can be obtained by oxidizing the platinum group element in the leaching residue under hydrochloric acid to form a chloride complex. On the other hand, the eluted selenium and tellurium are dispersed in a colloidal state, and when the leachate is neutralized, it precipitates as a metal and can be easily recovered. Incidentally, in the conventional method of leaching with an alkali using an oxidizing agent, leaching is performed under pressure, and sodium selenate or sodium selenite is generated, so that the subsequent selenium recovery step is troublesome. On the other hand, the treatment method of the present invention dissolves selenium and tellurium at normal pressure without using an oxidizing agent and separates the selenium and tellurium from the platinum group element.
[0018]
【Example】
Hereinafter, Examples and Comparative Examples of the present invention will be described. In addition,% is wt% unless otherwise indicated.
[Example 1]
1 kg of a selenium platinum group-containing material (Se: 65%, Te: 30%, Pd: 5%, Pt: 0.5%, Rh: 0.2%, Ru: 0.4%) was added at a concentration of 5 mol / L. When mixed with 10 L of caustic soda solution, heated to 80 ° C. and held for 1 hour, most of the solution was dissolved and the solution turned deep purple. This was filtered after cooling, and 65 g of a residue was recovered. When this residue was analyzed, platinum group elements of Pd, Pt, Rh, and Ru were confirmed as main components, and the grades were Pd: 80%, Pt: 8%, Rh: 3%, and Ru: 6%. . Note that Se: 65 g / L and Te: 30 g / L were dissolved in the filtrate, but no platinum group element was detected.
[0019]
[Example 2]
1 kg of a selenium platinum group-containing material (Se: 65%, Te: 30%, Pd: 5%, Pt: 0.5%, Rh: 0.2%, Ru: 0.4%) was added at a concentration of 5 mol / L. When mixed with 10 L of caustic soda solution, heated to 80 ° C. and held for 1 hour, most of the solution was dissolved and the solution turned deep purple. This was filtered after cooling, and 65 g of a residue was recovered. Note that Se: 65 g / L and Te: 30 g / L were dissolved in the filtrate, but no platinum group element was detected. When this residue was analyzed, platinum group elements of Pd, Pt, Rh, and Ru were confirmed as main components, and the grades were Pd: 80%, Pt: 8%, Rh: 3%, and Ru: 6%. . The residue was repulped with 400 ml of hydrochloric acid and 100 ml of water, and 120 ml of hydrogen peroxide was gradually added while maintaining the liquid temperature at 70 ° C. After the completion of the addition of hydrogen peroxide, the filtrate filtered after cooling was analyzed, and it was found that Pd: 74 g / L, Pt: 7 g / L, Rh: 2.8 g / L, and Ru: 5.5 g / L.
[0020]
[Example 3]
Alkaline leaching was performed in the same manner as in Example 1 except that the concentration of the caustic soda solution was 1 mol / L and the heating and holding time was 5 hours. As a result, 75 g of a residue was recovered. The main components of the residue were Pd, Pt, Rh, and Ru, and the grades were Pd: 67%, Pt: 7%, Rh: 3%, and Ru: 5%. On the other hand, 63 g / L of Se and 28 g / L of Te were dissolved in the filtrate, but no platinum group element was detected.
[0021]
[Example 4]
Alkaline leaching was performed in the same manner as in Example 1 except that the concentration of the caustic soda solution was 8 mol / L and the heating temperature was 60 ° C. As a result, 65 g of a residue was recovered. The main components of the residue were Pd, Pt, Rh, and Ru, and the grades were Pd: 77%, Pt: 8%, Rh: 3%, and Ru: 6%. On the other hand, 64 g / L of Se and 29 g / L of Te were dissolved in the filtrate, but no platinum group element was detected.
[0022]
[Comparative Examples 1 and 2]
When alkali leaching was performed in the same manner as in Example 1 except that the concentration of the caustic soda solution was changed to 0.5 mol / L, selenium and tellurium were not eluted, and the platinum group element could be separated from selenium and tellurium. No (Comparative Example 1).
When alkali leaching was performed in the same manner as in Example 1 except that the reaction temperature was changed to room temperature, selenium and tellurium were not eluted, and the platinum group element could not be separated from selenium and tellurium (Comparative Example) 2).
[Brief description of the drawings]
FIG. 1 is a process chart showing an outline of a processing method of the present invention.
FIG. 2 is a process chart showing an outline from the treatment of copper removal slime to the treatment method of the present invention.

Claims (8)

  1. セレン等と白金族元素の含有物(セレン白金族含有物と云う)を高温下でアルカリ浸出してセレン等を液中に移行させ、これを固液分離して固形分に含まれる白金族元素と液分に含まれるセレン等とを分離することを特徴とする白金族元素の分離方法。A substance containing selenium and the like and a platinum group element (referred to as a selenium platinum group containing substance) is leached with an alkali at a high temperature to transfer selenium and the like into a liquid. And separating selenium and the like contained in a liquid component.
  2. セレン白金族含有物を高温下でアルカリ浸出してセレン等を液中に移行させ、これを固液分離して固形分に含まれる白金族元素と液分に含まれるセレン等とを分離し、分離した固形分に塩酸酸性下で酸化剤を加えて白金族元素を溶解することを特徴とする白金族元素の分離方法。The selenium platinum group-containing substance is alkali-leached at a high temperature to transfer selenium and the like into a liquid, and the solid-liquid separation is performed to separate a platinum group element contained in a solid content and a selenium etc. contained in a liquid component, A method for separating a platinum group element, comprising adding an oxidizing agent to a separated solid content under hydrochloric acid to dissolve the platinum group element.
  3. セレン白金族含有物を高温下でアルカリ浸出することによってセレンと共にテルルを液中に移行させて白金族元素と分離する請求項1または2の分離方法。3. The separation method according to claim 1, wherein tellurium is transferred together with selenium into the liquid together with selenium by alkali leaching of the selenium platinum group-containing material at a high temperature to separate the selenium from the platinum group element.
  4. セレン白金族含有物を、60℃以上の温度下および1モル/L以上のアルカリ濃度下で浸出する請求項1〜3の何れかに記載する分離方法。The separation method according to any one of claims 1 to 3, wherein the selenium platinum group-containing substance is leached at a temperature of 60C or more and an alkali concentration of 1 mol / L or more.
  5. アルカリ浸出後に固液分離した固形分に、塩酸と共に過酸化水素または塩素ガスを添加して白金族元素を溶解する請求項1〜4の何れかに記載する分離方法。The separation method according to any one of claims 1 to 4, wherein the platinum group element is dissolved by adding hydrogen peroxide or chlorine gas together with hydrochloric acid to the solid content subjected to solid-liquid separation after alkali leaching.
  6. 白金族元素がロジウム、ルテニウム、パラジウム、白金の一種または二種以上である請求項1〜5の何れかに記載する分離方法。The separation method according to any one of claims 1 to 5, wherein the platinum group element is one or more of rhodium, ruthenium, palladium, and platinum.
  7. セレン白金族含有物が脱銅製錬スライムの塩酸浸出液から溶媒抽出によって金を分離した抽出残液の処理滓である請求項1〜6の何れかに記載する分離方法。The separation method according to any one of claims 1 to 6, wherein the selenium platinum group-containing substance is a slag of an extraction residue obtained by separating gold from a hydrochloric acid leaching solution of a copper-free smelting slime by solvent extraction.
  8. 脱銅製錬スライムを塩酸および過酸化水素によってスラリーにし、これを濾過して主に銀を含む浸出滓と、金、白金族元素およびセレン、テルルを含む浸出液とに分離し、次に、この浸出液の液性を調整した後に溶媒抽出によって浸出液から金を分離する一方、抽出残液に二酸化イオウを添加してセレンないしテルルを沈澱させ、これを固液分離して得た濾滓を高温下でアルカリ浸出する請求項1〜7の何れかに記載する分離方法。The copper-free smelting slime is slurried with hydrochloric acid and hydrogen peroxide, which is separated by filtration into a leach slag containing mainly silver and a leachate containing gold, a platinum group element and selenium and tellurium. After adjusting the liquid properties of the extract, the gold is separated from the leachate by solvent extraction, while sulfur dioxide is added to the extraction residue to precipitate selenium or tellurium. The separation method according to any one of claims 1 to 7, wherein alkali leaching is performed.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011068528A (en) * 2009-09-28 2011-04-07 Jx Nippon Mining & Metals Corp Method for recovering tellurium from copper electrolysis precipitation
JP2011214092A (en) * 2010-03-31 2011-10-27 Jx Nippon Mining & Metals Corp Method for treating reducing slag containing selenium and tellurium
JP2012211028A (en) * 2011-03-30 2012-11-01 Pan Pacific Copper Co Ltd Method for recovering tellurium from alkali leaching residue containing tellurium
JP2012211027A (en) * 2011-03-30 2012-11-01 Pan Pacific Copper Co Ltd Method for recovering tellurium
CN103588181A (en) * 2013-10-30 2014-02-19 四川鑫龙碲业科技开发有限责任公司 Wet method for preparing low-sulfur refined selenium

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011068528A (en) * 2009-09-28 2011-04-07 Jx Nippon Mining & Metals Corp Method for recovering tellurium from copper electrolysis precipitation
JP2011214092A (en) * 2010-03-31 2011-10-27 Jx Nippon Mining & Metals Corp Method for treating reducing slag containing selenium and tellurium
JP2012211028A (en) * 2011-03-30 2012-11-01 Pan Pacific Copper Co Ltd Method for recovering tellurium from alkali leaching residue containing tellurium
JP2012211027A (en) * 2011-03-30 2012-11-01 Pan Pacific Copper Co Ltd Method for recovering tellurium
CN103588181A (en) * 2013-10-30 2014-02-19 四川鑫龙碲业科技开发有限责任公司 Wet method for preparing low-sulfur refined selenium

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