JP2004218001A - How to treat selentellur - Google Patents
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- JP2004218001A JP2004218001A JP2003006391A JP2003006391A JP2004218001A JP 2004218001 A JP2004218001 A JP 2004218001A JP 2003006391 A JP2003006391 A JP 2003006391A JP 2003006391 A JP2003006391 A JP 2003006391A JP 2004218001 A JP2004218001 A JP 2004218001A
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Abstract
【課題】セレンとテルルの混合物から効率よくセレンとテルルを分離する処理方法を提供する。
【手段】セレンテルル混合物を銅熔錬工程に導入してセレンおよびテルルと銅を合金化し、これを銅電解して電気銅を回収する一方、セレンおよびテルルを銅電解スライムに蓄積させ、この銅電解スライムを硫酸酸化浸出してテルルを溶出することによって浸出残渣に残るセレンから分離し、好ましくは、この浸出液に金属銅を加えてテルル化銅を回収し、また、浸出残渣（脱銅スライム）を貴金属回収工程に導入してスライムに含まれるセレンを回収する処理方法。
【選択図】 図１A method for efficiently separating selenium and tellurium from a mixture of selenium and tellurium is provided.
A selenium and tellurium mixture is introduced into a copper smelting process to alloy selenium and tellurium with copper, which is electrolyzed with copper to recover electrolytic copper. The slime is separated from selenium remaining in the leaching residue by leaching the tellurium by sulfuric acid oxidizing leaching. Preferably, metallic copper is added to the leaching solution to recover copper telluride, and the leaching residue (decopper slime) is also removed. A treatment method for recovering selenium contained in slime by introducing it into a precious metal recovery process.
[Selection diagram] Fig. 1
Description
【０００１】
【発明の属する技術分野】
本発明は、セレンとテルルの混合物から効率よくセレンとテルルを分離する処理方法に関する。本発明の処理方法は、銅電解スライムから貴金属を回収するプロセスにおいて、金抽出後液を還元処理して得た還元滓からセレンテルルと白金族とを分離回収する処理工程において、セレンとテルルの分離方法として好適である。なお、本発明において、セレンテルル混合物とはセレンとテルルの混合物を意味し、例えば脱銅スライムからの金抽出後液から白金族含有残渣を濾別して得られる濾液を中和して生じる沈殿などである。また、セレンテルル白金族含有物とは少なくともセレンとテルルの何れかと白金族元素を含有するものを云い、セレンテルルとはセレンおよび／またはテルルを云う。
【０００２】
【従来の技術】
銅製錬の銅電解工程では、電解液に不溶な不純物が残渣として副生する。この副生物中にはＰｔ、Ｒｈ、Ｉｒなどの白金族元素、セレン、テルル、金、銀、銅がかなりの量含まれており、これらの金属を分離回収する方法がこれまで多数提案されている。例えば、白金族元素は、銀精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金属成分を浸出した後に還元して得たスライムなどから回収されている。従来、これらのスライムを溶解するには、王水による溶解、塩酸と過酸化水素による溶解または塩酸と塩素ガス吹き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セレンやテルルが共存しているセレンテルル白金族含有物の場合、これを還元して沈殿させると白金族元素がセレンテルルと化合物を形成してしまい、王水や塩酸および過酸化水素では溶解し難くなって分離回収ができなくなる欠点がある。とくに過酸化水素はセレン化物等の化合物表面で分解するため酸化剤としての効果を殆ど発揮することができない。また、このような化合物を焙焼して酸化セレンや酸化テルルの形で気化分離する方法があるが、その毒性による環境汚染の問題がある。
【０００４】
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殿させる方法（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イオウを導入し、セレンテルルを還元して沈殿させる方法（特許第３０８７７５８号、特開２００１−２０７２２３号）などが知られている。
【０００５】
しかし、これらの方法では、塩酸濃度、温度、亜硫酸ガス濃度、亜硫酸ガス量などのセレン還元時に制御するパラメータが多いため制御が難しく、白金族元素とセレンテルルの回収率が低下するなどの問題がある。さらに、二酸化イオウによる二段階還元処理は工程の管理が非常に難しく、しかも何れの沈殿においてもセレンテルルまたは白金族元素の混入が避けられず、二酸化イオウによる還元だけでは分離が不十分である。また、溶媒抽出によって白金族とセレンテルルとを分離する方法はコスト高であり、抽出後の回収処理も煩雑で手間がかかる欠点がある。
【０００６】
さらに、銅電解スライムに対して塩酸および二酸化イオウ処理する代わりに硫酸酸性溶液で酸素富化ガス加圧条件下浸出処理する方法（特開平５−３１１２５８号）、銅電解スライムに硫酸酸性溶液で酸素富化ガス加圧条件下浸出処理した後、塩素イオン、チオ硫酸ナトリウム溶液処理して脱銀した後、銅を添加する方法（特開平５−３１１２６４号）も提案されている。しかし、このような酸素富化ガス加圧条件下に銅を使用する方法は工程管理が難しく、非常なコスト高になり、実用性は乏しいという欠点がある。
【０００７】
この他に、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ばい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に鉱酸に溶解し、これにアルカリを加えて銅を沈殿分離した後に中和してテルルを沈殿下する方法（特開昭５６−８４４２８号）、銅電解スライム等の原料に塩酸などの強酸処理し、化合物を含むものについては塩素などの酸化剤を併用し、テルルの抽出溶媒としてブチルカルビトールを使用する方法（特開２０００−２３９７５３号）などが知られている。しかし、これらの方法は工程数が多く、しかも、セレンテルルのの回収効率が低い。
【０００８】
さらに、テルルを回収する方法として、銅やニッケルの電解精製で得たアノードスライムを湿式処理して難溶性銀化合物を分離し、これをアンモニア等で浸出して銀を分離し、テルルを含有する残渣を炭酸ソーダで浸出する方法（特開２００１−１１５４７号）、金を溶媒抽出した際のテルル含有濾液を還元してセレンを析出させた後に硫酸加圧浸出に戻して脱銅浸出液に浸出させる方法（銅澱物湿式処理技術の確立、資源と素材、Ｖｏｌ．１１６， ｐ．４８４，２０００年）などがある。しかし、難溶性銀化合物からテルルを回収する方法はテルルの移行率が低いち云う問題がある。また、テルルを含む濾液を加圧浸出に戻す方法はテルルがメタル状であると浸出が不十分になり、プロセス内の滞留量が増えてしまうという問題がある。
【０００９】
【発明が解決しようとする課題】
本発明は、従来の上記処理方法の問題を解決したものであり、セレンとテレルの混合物について、セレンおよびテレルを銅と合金化し、さらにこれを銅電解して電気銅を回収する一方、セレンおよびテルルをスライム化し、この銅電解スライムの浸出処理によってテルルを溶出してセレンと分離し、効率よくセレンとテルルを処理できるようにした処理方法を提供するものである。
【００１０】
【課題を解決するための手段】
すなわち、本発明は以下の構成からなるセレンテルルの処理方法に関する。
（１）セレンテルル混合物を銅熔錬工程に導入してセレンおよびテルルと銅を合金化し、これを銅電解して電気銅を回収する一方、セレンおよびテルルを銅電解スライムに蓄積させ、この銅電解スライムを硫酸酸化浸出してテルルを溶出させることによって、テルルを浸出残渣に残るセレンと分離することを特徴とするセレンテルルの処理方法。
（２）セレンテルル白金族含有物を高温下でアルカリ浸出し、セレンテルルを含む浸出液と白金族を含む浸出残渣とに分離するアルカリ浸出工程の後に、この浸出液に硫酸または塩酸を加えて中和し、セレンテルル混合物を沈殿させ、この混合物を銅熔錬工程に導入してセレンおよびテルルと銅を合金化し、これを銅電解して電気銅を回収する一方、セレンおよびテルルを銅電解スライムに蓄積させ、この銅電解スライムを硫酸酸化浸出してテルルを溶出させる上記（１）に記載するセレンテルルの処理方法。
（３）セレンテルル白金族含有物を蒸留処理した残物に苛性ソーダと硝酸ソーダの混合物を加え、該混合物の溶融（共晶）温度以上に加熱してセレンテルルを溶解し、これを水浸出してセレンテルルを含む浸出液と白金族を含む浸出残渣とに分離し、このアルカリ溶融工程において得た浸出液をセレンテルル白金族含有物のアルカリ浸出工程に加えてアルカリ浸出を行い、この浸出液に硫酸または塩酸を加えて中和し、生じたセレンテルル混合物を銅熔錬工程に導入してセレンおよびテルルと銅を合金化し、これを銅電解して電気銅を回収する一方、セレンおよびテルルを銅電解スライムに蓄積させ、この銅電解スライムを硫酸酸化浸出してテルルを溶出させる上記（１）または（２）に記載するセレンテルルの処理方法。
（４）セレンテルル白金族含有物が金抽出後液に亜硫酸ガスを導入し、還元処理して生じた還元滓である上記（１）、（２）または（３）に記載するセレンテルルの処理方法。
（５）上記（１）〜（４）の何れかに記載する処理方法において、銅電解スライムを硫酸酸化浸出してテルルを溶出させた後に、この浸出液を金属銅に接触させて生成したテルル化銅を回収するセレンテルルの処理方法。
【００１１】
【具体的な説明】
以下、本発明を具体的に説明する。
本発明の処理方法は、セレンテルル混合物を銅熔錬工程に導入してセレンおよびテルルと銅を合金化し、これを銅電解して電気銅を回収する一方、セレンおよびテルルを銅電解スライムに蓄積させ、この銅電解スライムを硫酸酸化浸出してテルルを溶出させることによって、テルルを浸出残渣に残るセレンと分離することを特徴とするセレンテルルの処理方法である。
【００１２】
本発明の具体的な処理工程の一例を図１に示す。図示する処理方法は、セレンテルル混合物としてセレンテルル白金族含有物を用い、これを高温下でアルカリ浸出し、セレンテルルを含む浸出液と白金族を含む浸出残渣とに分離するアルカリ浸出工程の後に、この浸出液に硫酸または塩酸を加えて中和し、セレンテルル混合物を沈殿させ、この混合物を銅熔錬工程に導入してセレンおよびテルルと銅を合金化し、これを銅電解して電気銅を回収する一方、セレンおよびテルルを銅電解スライムに蓄積させ、この銅電解スライムを硫酸酸化浸出してテルルを溶出させることによって、テルルを浸出残渣に残るセレンから分離する。
【００１３】
〔セレンテルル混合物〕
本発明の処理方法は、セレンテルル混合物として銅製錬工程で有られるセレンテルル白金族含有物を処理したものを用いることができる。具体的には、セレンテルル白金族含有物として例えば、脱銅電解精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還元処理滓などを原料として用いることができる。この脱銅電解スライムにはロジウム、ルテニウム、パラジウム、イリジウム、白金などの白金族元素、金、銀、セレン、テルルなどの有価金属が多量に含まれている。具体的には、セレンテルル白金族含有物は、例えば脱銅精錬スライムを次のように処理して得られる。まず、脱銅精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する。次に、この浸出液の液性を調整し、ＤＢＣ等を用いた溶媒抽出によって浸出液から金を分離する。このようにして金を分離した抽出残液には白金族元素およびセレン、テルルが液中に溶存している。そこで、この抽出残液に二酸化イオウ、具体的には例えば亜硫酸ガスを液中のセレン濃度を３ｇ／Ｌ以上に保つ量で導入し、セレンを還元して沈殿させ、抽出残液から分離する。セレンを分離した濾液にさらに二酸化イオウを導入し、残りのセレンと共にテルルを還元して沈澱させ、濾別する。
【００１４】
本発明はセレンテルル白金族含有物として上記金抽出後液の還元処理滓やさらに蒸留処理した蒸留滓を用いることができる。この他に、セレンテルル白金族含有液として、例えばメッキ工場の排水や製錬排水などのセレンテルルおよび白金族を含有する溶液を用いることができる。
【００１５】
なお、上記金抽出後液の還元処理において、セレンとテルルを還元して沈澱させる際、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セレンとテルルを分離回収することができる。この還元により白金族元素はセレン、テルルと共に沈殿する。
【００１６】
このようにして得たセレンテルル白金族含有物を次のアルカリ浸出工程およびアルカリ溶融工程において処理する。この場合、上記抽出残液の還元によって先に沈澱したセレン滓を蒸留して高純度のセレンを回収し、残物（蒸留残）をアルカリ溶融処理し、その後に沈澱したテルル滓をアルカリ浸出処理するのが好ましい。この蒸留残はセレン化パラジウム等の化合物を形成しており、安定であるためアルカリ浸出してもセレンの溶出が進まない。蒸留滓をアルカリ溶融処理することによってセレンを効率よく処理することができる。一方、テルル滓中のロジウムおよびルテニウムはセレン滓中に含まれる場合よりも相対的に品位が高く、このためアルカリ溶融すると難溶性の酸化物になりやすく、後の塩酸浸出が難しくなる。従って、テルル滓はアルカリ浸出処理するのが好ましい。
【００１７】
〔アルカリ浸出工程〕
セレンテルル白金族含有物をアルカリ浸出処理する。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良く、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ってｐＨ１４以上の強アルカリ性となり、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。
【００１８】
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浸出液と、白金族元素を含む固形分とに分離する。
【００１９】
上記アルカリ浸出は、セレンテルル白金族含有物を蒸留処理した残物をアルカリ溶融して得た浸出液を加えて行っても良い。セレンテルル白金族含有物を還元処理して得たセレン滓またはこの還元セレン滓を蒸留処理して得た残物に、苛性ソーダ（ＮａＯＨ）と硝酸ソーダ（ＮａＮＯ３）の混合物からなるフラックスを添加し、これをフラックスの溶融温度（共晶温度）以上に加熱して溶融する。この加熱溶融によってセレンは主に４価になり、亜セレン酸ソーダ（Ｎａ２ＳｅＯ３）を生じて溶解する。このアルカリ溶融によってセレンテルルが溶解し、これを水浸出してセレンテルルを含む浸出液と白金族を含む浸出残渣とに分離する。この浸出液をセレンテルル白金族含有物のアルカリ浸出工程に加えて前述のアルカリ浸出を行うことができる。このアルカリ溶融工程から得た浸出液を用いることによって、処理工程全体のセレンテルルの回収率を高めることができる。
【００２０】
上記アルカリ浸出の固液分離後、セレンテルルを含む濾液に、硫酸または塩酸を加えて中和すると金属セレンないし金属テルルの黒色沈澱を生じ、溶液の色が濃紫色から次第に薄くなり、ｐＨ７付近で液は透明になる。これを固液分離することによって金属テルルおよび金属セレンの混合物を回収することができる。この混合物のセレンとテルルの品位は概ね９９％以上であり、高品位の金属セレンないし金属テルルを回収することができる。なお、硫酸や塩酸に代えて硝酸を用いると、硝酸の酸化力によってセレンやテルルは酸化溶解するので沈殿化することができない。また、液温は６０〜８０℃が好ましい。この液温で中和すれば濾過性の良いセレンテルル混合物を得ることができる。
【００２１】
本発明の処理方法は、上記セレンテルル混合物を銅熔錬工程に導入してセレンおよびテルルを銅と合金化し、この合金化した銅（粗銅）を電解工程に導入して電気銅を回収し、一方、セレンおよびテルルを他の不溶成分と共に銅電解スライムに蓄積させる。この銅電解は通常の銅電解条件下で実施することができる。銅電解によって高純度の電気銅を得る一方、セレンおよびテルルは粗銅に含まれる他の不溶成分と共に銅電解スライムになる。この銅電解スライムを硫酸で空気酸化して浸出処理（脱銅浸出）すると、スライムに含まれる銅とテルルの大部分が溶出する。この硫酸としては硫酸性電解液を用いることができる。溶出したテルルを含む脱銅浸出液を金属銅に接触させるとテルル化銅を形成するので、テルルをテルル化銅として回収することができる。工業的には溶出したテルルを含む脱銅浸出液を銅チップ塔に通液してテルル化銅を回収するとよい。一方、セレンは浸出残渣（脱銅スライム）中に残るので、この脱銅浸出によってセレンとテルルを分離することができる。
【００２２】
上記脱銅浸出の後に、銅とセレンを含む浸出液は銅電解工程に戻して銅を電気銅として回収する。セレンは先に述べたように銅電解スライムに蓄積するので、この銅電解スライムの硫酸酸化浸出（脱銅浸出）を繰り返すことによって、セレンは脱銅スライムに濃縮される。また、この脱銅スライムには金、銀、白金族元素、鉛などの貴金属が多く含まれているので、この脱銅スライムに過酸化水素などの酸化剤と共に塩素ガス、塩酸などを導入して塩化浸出を行うことによって、これらの貴金属を溶解し、各貴金属元素に対応した処理工程を経て回収することができる。
【００２３】
上記貴金属の回収工程の一例としては、上記塩化浸出によってスライム中の銀および鉛を塩化物に転じて不溶化する一方、金、白金族元素、セレン、テルルは浸出液中を溶解させ、この浸出液を金および白金族元素などを含有する浸出濾液と銀、鉛を含有する浸出濾滓（銀鉛含有滓）とに固液分離し、先に述べた処理工程などによって銀鉛含有滓から銀と鉛を分離回収する。また、テルルおよび白金族元素を含む浸出濾液から溶媒抽出によって金を分離し、還元して金を回収し、一方、その抽出残液を蒸留処理してセレン、テルルを還元し、この還元滓を用いて本発明の処理を繰り返すことによって、セレンおよびテルルを濃縮して効率よく回収することができる。
【００２４】
【実施例】
セレンテルル還元澱物であるセレン白金族含有物（Ｓｅ６５％、Ｔｅ３０％、Ｐｄ５％、ＰｔＯ．５％、Ｒｈ０．２％、ＲｕＯ．４％）１ｋｇに、５モル／Ｌの苛性ソーダ溶液１０Ｌを混合し、８０℃に保持してアルカリ浸出したところ、セレンおよびテルルの大部分は液中に溶解して液は濃い紫色になった。冷却後、濾過して残渣６５ｇを回収した。この濾液の組成はＳｅ：６５ｇ／Ｌ、Ｔｅ：３０ｇ／Ｌであり、白金族元素は検出されなかった。この濾液を８０℃に保持して硫酸（５０％濃度）を加えｐＨ１まで中和したところ、黒色粉末が沈殿した。この沈殿物の組成はＳｅ：６８．５％、Ｔｅ：３１．５％であった。また、濾液中のＳｅおよびＴｅの濃度はそれぞれ５３０ｐｐｍおよび２１０ｐｐｍであった。この沈殿物を銅熔錬工程に導入して電解精製し、生じたアノードスライムを硫酸性電解液で空気を吹き込んで浸出した。アノードスライム中のＴｅの大部分が溶け出すので浸出後のスライム中のＴｅ品位は０．５％であった。また、Ｓｅは溶け出さないため浸出液中にＳｅは検出されず、浸出後のスライム中のＳｅ品位は８．３％であつた。この浸出液を銅チップ塔に通液して、液中のＴｅをテルル化銅として回収した。またスライムに残留したＳｅや金を塩酸酸化浸出によって溶出させ、金を溶媒抽出した後に、この抽出後液に亜硫酸ガスを導入してセレンを還元し回収した。一方、先のアルカリ浸出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２Ｌ、水５００ｍＬでリパルプし、液温を７０℃に保ちながら、過酸化水素３６０ｍＬを徐々に添加した。過酸化水素の添加終了後に冷却して濾過し、この濾液を分析したところ、Ｐｄ８１ｇ／Ｌ、Ｐｔ７ｇ／Ｌ、Ｒｈ２．１ｇ／Ｌ、Ｒｕ２．４ｇ／Ｌであった。
【００２５】
【発明の効果】
本発明の処理方法によれば、セレンテルル混合物を銅熔錬工程に導入してセレンおよびテルルを銅と合金化し、この銅合金を電解することによって高純度の電気銅を回収し、一方、セレンおよびテルルは銅電解スライムに蓄積されるので、これを硫酸酸化浸出（脱銅浸出）して、テルルを液中に浸出させてセレンと分離し、溶出したテルルを金属銅に接触させてテルル化銅として分離回収することができる。また、脱銅浸出残渣に残るセレンは、この残渣に含まれる金等の貴金属回収工程、例えば、金抽出五の還元処理工程において、分離回収することができる。
【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。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a treatment method for efficiently separating selenium and tellurium from a mixture of selenium and tellurium. The treatment method of the present invention is a process for recovering a noble metal from copper electrolytic slime, in a process of separating and recovering selenium and platinum group from reduced slag obtained by reducing the solution after gold extraction, separation of selenium and tellurium It is suitable as a method. In the present invention, the selenium and tellurium mixture means a mixture of selenium and tellurium, for example, a precipitate formed by neutralizing a filtrate obtained by filtering a platinum group-containing residue from a solution after gold extraction from decoppered slime and the like. . In addition, the selenium tellurium platinum group-containing substance means a substance containing at least one of selenium and tellurium and a platinum group element, and selenium tellurium means selenium and / or tellurium.
[0002]
[Prior art]
In the copper electrolysis step of copper smelting, impurities insoluble in the electrolytic solution are by-produced as residues. The by-products contain a considerable amount of platinum group elements such as Pt, Rh, and Ir, selenium, tellurium, gold, silver, and copper. Many methods for separating and recovering these metals have been proposed. I have. For example, platinum group elements are recovered from silver anode slime obtained from a silver refining process, slime obtained by leaching metal 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, in the case of selenium or tellurium containing selenium and tellurium together with the platinum group element, if this is reduced and precipitated, the platinum group element will form a compound with selenium and the aqua regia, hydrochloric acid and hydrogen peroxide However, there is a disadvantage that it is difficult to dissolve and separate and collect it. In particular, hydrogen peroxide decomposes on the surface of a compound such as selenide, and thus can hardly exhibit the effect as an oxidizing agent. Further, there is a method in which such a compound is roasted and vaporized and separated in the form of selenium oxide or tellurium oxide, but there is a problem of environmental pollution due to its toxicity.
[0004]
As a method for separating the platinum group element and selentellur 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, and the solution is heated to 8 to 10 mol / L at a temperature of 60 to 90 ° C. A method in which a sulfuric acid gas having a concentration of 12% is blown into a liquid to reduce and precipitate a platinum group element (JP-A-2001-316735), or an extraction in which gold and a platinum group are recovered by solvent extraction from a hydrochloric acid leaching solution of copper electrolytic slime. A method is known in which sulfur dioxide is introduced into the residual liquid to reduce and precipitate selentellur (Japanese Patent No. 3087758, Japanese Patent Application Laid-Open No. 2001-207223).
[0005]
However, in these methods, there are many parameters to be controlled at the time of selenium reduction, such as hydrochloric acid concentration, temperature, sulfurous acid gas concentration, and sulfurous acid gas amount, so that control is difficult, and there is a problem that the recovery rate of the platinum group element and selenium is reduced. . Further, in the two-step reduction treatment with sulfur dioxide, it is very difficult to control the process, and furthermore, in any precipitation, the incorporation of selentellur or a platinum group element is unavoidable, and the separation by sulfur dioxide alone is insufficient. Further, the method of separating the platinum group and selentellurium by solvent extraction is expensive, and the recovery process after the extraction is complicated and troublesome.
[0006]
Furthermore, instead of treating copper electrolytic slime with hydrochloric acid and sulfur dioxide, a method of leaching with a sulfuric acid acidic solution under an oxygen-enriched gas under a pressurized condition (Japanese Patent Laid-Open No. 5-31258). A method has also been proposed in which leaching is carried out under a pressure of enriched gas, followed by treatment with a solution of chlorine ions and sodium thiosulfate to remove silver, and then adding copper (Japanese Patent Laid-Open No. 5-31264). However, such a method of using copper under the oxygen-enriched gas pressurized condition has disadvantages in that process control is difficult, cost is extremely high, and practicality is poor.
[0007]
In addition, a method of oxidizing metal selenium using an oxidizing agent and neutralizing the same with an alkali metal carbonate or hydroxide to produce an alkali metal selenate (Japanese Patent Application Laid-Open No. 60-176908), A method in which a selenium-containing substance is reacted with an alkali metal carbonate to form a water-soluble slurry, which is roasted in an oxidizing atmosphere into pellets and then leached with water (JP-A-56-5306). A method of dissolving in a mineral acid in the presence of an oxidizing agent, adding an alkali thereto to precipitate and separate copper, and then neutralizing to precipitate tellurium (JP-A-56-84428); And a method using a butyl carbitol as a tellurium extraction solvent using a compound containing a compound with a strong acid such as hydrochloric acid and an oxidizing agent such as chlorine (JP-A-2000-239753). That. However, these methods have many steps, and the recovery efficiency of selentell is low.
[0008]
Further, as a method of recovering tellurium, the anode slime obtained by electrolytic refining of copper or nickel is subjected to wet treatment to separate a sparingly soluble silver compound, which is leached with ammonia or the like to separate silver, and contains tellurium. A method of leaching the residue with sodium carbonate (Japanese Patent Application Laid-Open No. 2001-11547), in which a tellurium-containing filtrate obtained by extracting gold as a solvent is reduced to precipitate selenium, and then returned to sulfuric acid pressure leaching to be leached into a decopperized leaching solution. Methods (establishment of wet processing technology for copper deposits, resources and materials, Vol. 116, p. 484, 2000) and the like. However, the method of recovering tellurium from a poorly soluble silver compound has a problem that the transfer rate of tellurium is low. Further, the method of returning the filtrate containing tellurium to pressure leaching has a problem that if the tellurium is in a metal state, the leaching becomes insufficient and the amount of stagnation in the process increases.
[0009]
[Problems to be solved by the invention]
The present invention has solved the problem of the above-mentioned conventional processing method, and, for a mixture of selenium and terrel, alloys selenium and terrel with copper, and further performs electrolysis of the copper to recover electrolytic copper, while selenium and selenium are recovered. An object of the present invention is to provide a treatment method in which tellurium is converted into slime and tellurium is eluted and separated from selenium by the leaching treatment of the copper electrolytic slime so that selenium and tellurium can be treated efficiently.
[0010]
[Means for Solving the Problems]
That is, the present invention relates to a method for treating selentellur having the following constitution.
(1) A selenium / tellurium mixture is introduced into a copper smelting process to alloy selenium and tellurium with copper, and this is electrolyzed with copper to recover electrolytic copper. A method for treating selenium tellurium, comprising separating out tellurium from selenium remaining in a leaching residue by leaching slime by sulfuric acid oxidation and leaching tellurium.
(2) Alkaline leaching of the selentellurium platinum group-containing substance at a high temperature, and after an alkali leaching step of separating into a leachate containing selentellur and a leach residue containing the platinum group, neutralize the leachate by adding sulfuric acid or hydrochloric acid, Precipitating a selenium tellurium mixture, introducing this mixture into a copper smelting process to alloy selenium and tellurium with copper, and electrolyzing this to recover electrolytic copper, while accumulating selenium and tellurium in copper electrolytic slime; The method for treating selenium tellur as described in (1) above, wherein the copper electrolytic slime is leached by sulfuric acid oxidation to elute tellurium.
(3) A mixture of caustic soda and sodium nitrate was added to the residue obtained by distilling the selentellurium-containing substance, and the mixture was heated to a temperature higher than the melting (eutectic) temperature of the mixture to dissolve the selentellurium. Is separated into a leachate containing Pt and a leach residue containing a platinum group, and the leachate obtained in the alkali melting step is added to the alkali leach step of the selentellurium platinum group-containing substance to perform alkali leach, and sulfuric acid or hydrochloric acid is added to the leachate. Neutralized, the resulting selenium tellurium mixture is introduced into a copper smelting process to alloy selenium and tellurium with copper, and copper is electrolyzed to recover electrolytic copper, while selenium and tellurium are accumulated in copper electrolytic slime, The method of treating selentellur as described in (1) or (2) above, wherein the copper electrolytic slime is leached by sulfuric acid oxidation to elute tellurium.
(4) The method for treating selentellur as described in (1), (2) or (3) above, wherein the platinum group containing selentellurium is reduced slag generated by introducing a sulfurous acid gas into the liquid after gold extraction and performing a reduction treatment.
(5) In the treatment method according to any one of (1) to (4), after the copper electrolytic slime is leached by sulfuric acid oxidation to elute tellurium, the leachate is contacted with metallic copper to form tellurium. A method for treating selentellur for recovering copper.
[0011]
[Specific explanation]
Hereinafter, the present invention will be described specifically.
In the treatment method of the present invention, a selenium tellurium mixture is introduced into a copper smelting step to alloy selenium and tellurium with copper, and this is electrolyzed with copper to recover electrolytic copper, while selenium and tellurium are accumulated in copper electrolytic slime. A method for treating selenium tellurium, characterized by separating out tellurium from selenium remaining in the leaching residue by leaching the tellurium by leaching the copper electrolytic slime by sulfuric acid oxidation.
[0012]
FIG. 1 shows an example of a specific processing step of the present invention. The processing method shown in the figure uses a selentellurium-containing substance as a selentellur mixture, and is alkali-leached at a high temperature, and after an alkali leaching step of separating into a leachate containing selentellur and a leach residue containing a platinum group, the leachate is added to the leachate. The mixture is neutralized by adding sulfuric acid or hydrochloric acid to precipitate a selenium tellurium mixture, and the mixture is introduced into a copper smelting process to alloy selenium and tellurium with copper. And tellurium is accumulated in the copper electrolytic slime, and the copper electrolytic slime is leached by sulfuric acid oxidization to elute tellurium, thereby separating tellurium from selenium remaining in the leach residue.
[0013]
(Selentellurium mixture)
In the treatment method of the present invention, it is possible to use a mixture obtained by treating a selentellurium platinum group-containing material in a copper smelting process as a selentellur mixture. Specifically, as the selentellurium platinum group-containing material, for example, a reduction slag of an extraction residue obtained by separating gold from a hydrochloric acid leachate of a copper-free electrolytic refining slime by solvent extraction can be used as a raw material. This copper-free electrolytic slime contains a large amount of platinum group elements such as rhodium, ruthenium, palladium, iridium and platinum, and valuable metals such as gold, silver, selenium and tellurium. Specifically, the selentellurium platinum group-containing material can be obtained, for example, by treating copper-free refining slime as follows. First, the copper-free refining slime is slurried with hydrochloric acid and hydrogen peroxide, and then filtered to separate into a leach slag containing mainly silver and a leach liquor containing gold, a platinum group element and selenium and tellurium. Next, the liquid property of the leachate is adjusted, and gold is separated from the leachate by solvent extraction using DBC or the like. The platinum group element, selenium, and tellurium are dissolved in the extraction residue from which gold has been separated in this manner. Therefore, sulfur dioxide, specifically, for example, sulfur dioxide gas is introduced into the extraction residue in an amount that keeps the selenium concentration in the solution at 3 g / L or more, selenium is reduced and precipitated, and separated from the extraction residue. Sulfur dioxide is further introduced into the filtrate from which selenium has been separated, and tellurium is reduced and precipitated together with the remaining selenium, followed by filtration.
[0014]
In the present invention, as the selentellurium platinum group-containing material, a reduced slag of the above-mentioned solution after gold extraction or a distilled slag subjected to a further distillation treatment can be used. In addition, as the selentellurium platinum group-containing solution, for example, a solution containing selentellurium and a platinum group, such as wastewater from a plating plant or smelting wastewater, can be used.
[0015]
In the reduction treatment of the solution after gold extraction, when reducing and precipitating selenium and tellurium, tellurium has a lower reduction potential than selenium, and tellurium precipitates after selenium precipitates. By further adding sulfur dioxide to the filtrate to precipitate tellurium, selenium and tellurium can be separated and recovered. This reduction causes the platinum group element to precipitate together with selenium and tellurium.
[0016]
The thus obtained selentellurium platinum group-containing material is treated in the following alkali leaching step and alkali melting step. In this case, the selenium slag previously precipitated by the reduction of the extraction residue is distilled to recover selenium of high purity, the residue (distillation residue) is subjected to alkali melting treatment, and then the precipitated tellurium slag is subjected to alkali leaching treatment. Is preferred. This distillation residue forms a compound such as palladium selenide and is stable, so that selenium does not elute even with alkaline leaching. Selenium can be efficiently treated by subjecting the distillation slag to alkali melting treatment. On the other hand, rhodium and ruthenium in tellurium slag are relatively higher in quality than those contained in selenium slag, so that they become easily insoluble oxides when alkali-melted, and subsequent leaching of hydrochloric acid becomes difficult. Therefore, the tellurium residue is preferably subjected to an alkali leaching treatment.
[0017]
[Alkali leaching process]
Alkaline leaching treatment of the selentellurium platinum group-containing material. The alkali leaching is preferably performed under an alkali concentration of 1 mol / L or more, for example, preferably in the range of 5 mol / L to 8 mol / L. By making the alkali concentration 1 mol / L or more, it becomes strongly alkaline at pH 14 or more, the oxidation-reduction potential of selenium or tellurium is lowered, and selenium and tellurium are eluted in an alkaline solution without using an oxidizing agent under normal pressure. Can be. 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.
[0018]
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 into a selenium or tellurium leachate and a solid containing a platinum group element.
[0019]
The above-mentioned alkali leaching may be performed by adding a leaching solution obtained by alkali-melting the residue obtained by subjecting the selentellurium-containing substance to a distillation treatment. A flux composed of a mixture of caustic soda (NaOH) and sodium nitrate (NaNO 3 ) is added to the selenium slag obtained by reducing the selentellurium platinum group-containing substance or the residue obtained by distilling the reduced selenium slag, This is heated above the melting temperature (eutectic temperature) of the flux and melted. By this heating and melting, selenium becomes mainly tetravalent and generates and dissolves sodium selenite (Na 2 SeO 3 ). Selentell is dissolved by the alkali melting, and is leached with water to be separated into a leaching solution containing selentell and a leaching residue containing a platinum group. This leaching solution can be added to the alkali leaching step of the substance containing the selentellurium platinum group to perform the above-described alkali leaching. By using the leachate obtained from the alkali melting step, the recovery rate of selentellur in the entire treatment step can be increased.
[0020]
After the solid-liquid separation of the alkali leaching, the filtrate containing selenium tellurium is neutralized by adding sulfuric acid or hydrochloric acid to form a black precipitate of selenium metal or tellurium metal, and the color of the solution gradually decreases from dark purple to near pH 7, and the solution becomes liquid at around pH 7. Becomes transparent. By subjecting the mixture to solid-liquid separation, a mixture of metallic tellurium and metallic selenium can be recovered. The grade of selenium and tellurium in this mixture is about 99% or more, and high-grade metallic selenium or metallic tellurium can be recovered. If nitric acid is used instead of sulfuric acid or hydrochloric acid, selenium or tellurium is oxidized and dissolved by the oxidizing power of nitric acid, so that precipitation cannot be performed. The liquid temperature is preferably from 60 to 80C. If the solution is neutralized at this liquid temperature, a selentelluric mixture having good filterability can be obtained.
[0021]
In the treatment method of the present invention, the selenium tellurium mixture is introduced into a copper smelting step to alloy selenium and tellurium with copper, and the alloyed copper (blister copper) is introduced into an electrolytic step to recover electrolytic copper. , Selenium and tellurium are accumulated in the copper electrolytic slime together with other insoluble components. This copper electrolysis can be performed under ordinary copper electrolysis conditions. While high purity electrolytic copper is obtained by copper electrolysis, selenium and tellurium together with other insoluble components contained in blister copper become copper electrolytic slime. When this copper electrolytic slime is air-oxidized with sulfuric acid and leached (decopper leaching), most of copper and tellurium contained in the slime are eluted. As this sulfuric acid, a sulfuric acid electrolytic solution can be used. When the decoppered leachate containing the eluted tellurium is brought into contact with metallic copper, copper telluride is formed, so that tellurium can be recovered as copper telluride. Industrially, it is advisable to recover the copper telluride by passing the decoppered leachate containing the eluted tellurium through a copper chip tower. On the other hand, since selenium remains in the leaching residue (decopperized slime), selenium and tellurium can be separated by the decoppered leaching.
[0022]
After the leaching from copper, the leachate containing copper and selenium is returned to the copper electrolysis step to recover copper as electrolytic copper. Since selenium accumulates in the copper electrolytic slime as described above, selenium is concentrated into the copper-free slime by repeating the sulfuric acid oxidizing leaching (copper leaching) of the copper electrolytic slime. In addition, since this decoppered slime contains a lot of precious metals such as gold, silver, platinum group elements and lead, chlorine gas and hydrochloric acid are introduced into this decoppered slime together with an oxidizing agent such as hydrogen peroxide. By performing chlorination leaching, these noble metals can be dissolved and recovered through processing steps corresponding to each noble metal element.
[0023]
As an example of the precious metal recovery step, silver and lead in the slime are converted to chlorides and insolubilized by the chlorination leaching, while gold, platinum group elements, selenium, and tellurium are dissolved in the leaching solution, and the leaching solution is treated with gold. And a leach filtrate containing a platinum group element and the like and a leach filtrate containing silver and lead (silver-lead slag) are separated into solid and liquid, and silver and lead are separated from the silver-lead slag by the processing steps described above. Separate and collect. In addition, gold is separated from the leaching filtrate containing tellurium and a platinum group element by solvent extraction, and reduced to recover gold.On the other hand, selenium and tellurium are reduced by distillation of the extraction residue, and the reduced slag is removed. By repeating the treatment of the present invention using selenium and selenium, selenium and tellurium can be concentrated and recovered efficiently.
[0024]
【Example】
10 mol of a 5 mol / L caustic soda solution is mixed with 1 kg of a selenium platinum group-containing substance (Se65%, Te30%, Pd5%, PtO.5%, Rh0.2%, RuO.4%) which is a selentellurium reduced precipitate. When the alkaline leaching was carried out at 80 ° C., most of selenium and tellurium were dissolved in the liquid, and the liquid turned deep purple. After cooling, the mixture was filtered to recover 65 g of a residue. The composition of this filtrate was 65 g / L for Se and 30 g / L for Te, and no platinum group element was detected. The filtrate was kept at 80 ° C. and neutralized to pH 1 by adding sulfuric acid (50% concentration), whereby a black powder precipitated. The composition of this precipitate was Se: 68.5% and Te: 31.5%. The concentrations of Se and Te in the filtrate were 530 ppm and 210 ppm, respectively. The precipitate was introduced into a copper smelting step for electrolytic purification, and the resulting anode slime was leached by blowing air with a sulfuric acid electrolyte. Since most of the Te in the anode slime elutes, the Te grade in the slime after leaching was 0.5%. Further, Se did not elute, so that Se was not detected in the leachate, and the Se quality in the slime after leaching was 8.3%. This leachate was passed through a copper chip tower, and Te in the liquid was recovered as copper telluride. Se and gold remaining in the slime were eluted by oxidative leaching with hydrochloric acid, and after extracting gold with a solvent, selenium gas was introduced into the liquid after the extraction to reduce and collect selenium. On the other hand, when the alkali leaching residue was analyzed, the 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 2 L of hydrochloric acid and 500 mL of water, and 360 mL of hydrogen peroxide was gradually added while maintaining the liquid temperature at 70 ° C. After completion of the addition of hydrogen peroxide, the mixture was cooled and filtered, and the filtrate was analyzed. As a result, Pd was 81 g / L, Pt was 7 g / L, Rh was 2.1 g / L, and Ru was 2.4 g / L.
[0025]
【The invention's effect】
According to the treatment method of the present invention, a selenium tellurium mixture is introduced into a copper smelting step to alloy selenium and tellurium with copper, and high-purity electrolytic copper is recovered by electrolyzing the copper alloy. Since tellurium is accumulated in copper electrolytic slime, it is oxidized and leached with sulfuric acid (decopper leaching), so that tellurium is leached into the liquid to separate it from selenium, and the eluted tellurium is brought into contact with metallic copper to form copper telluride. Can be separated and collected. In addition, selenium remaining in the copper removal leaching residue can be separated and recovered in a step of recovering a noble metal such as gold contained in the residue, for example, in a reduction treatment step of gold extraction.
[Brief description of the drawings]
FIG. 1 is a process chart showing an outline of a processing method of the present invention.
Claims (5)
Priority Applications (14)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003006391A JP4269693B2 (en) | 2003-01-14 | 2003-01-14 | Process for treating selenium mixture |
| KR20047014284A KR100956050B1 (en) | 2002-03-15 | 2003-03-14 | Platinum Group Element Separation Method |
| US10/506,613 US7479262B2 (en) | 2002-03-15 | 2003-03-14 | Method for separating platinum group element |
| PCT/JP2003/003108 WO2003078670A1 (en) | 2002-03-15 | 2003-03-14 | Method for separating platinum group element |
| KR1020107002024A KR20100019577A (en) | 2002-03-15 | 2003-03-14 | Method for separating platinum group element |
| CN038106884A CN1653198B (en) | 2002-03-15 | 2003-03-14 | Method for separating platinum group elements |
| DE2003192375 DE10392375T5 (en) | 2002-03-15 | 2003-03-14 | Separation process for platinum group elements |
| CA 2507370 CA2507370C (en) | 2002-11-29 | 2003-08-28 | Separation process for platinum group elements |
| ES03812271T ES2316871T5 (en) | 2002-11-29 | 2003-08-28 | Methods to separate platinum group elements from materials containing selenium / tellurium |
| DE60325639T DE60325639D1 (en) | 2002-11-29 | 2003-08-28 | METHOD FOR SEPARATING ELEMENTS OF THE PLATING GROUP FROM SELEN / TELLUR CONTAINING MATERIALS |
| EP03812271.9A EP1577408B2 (en) | 2002-11-29 | 2003-08-28 | Method for separating platinum group elements from selenum/tellurium bearing materials |
| AU2003264343A AU2003264343A1 (en) | 2002-11-29 | 2003-08-28 | Method for separating platinum group element |
| PCT/JP2003/010950 WO2004050927A1 (en) | 2002-11-29 | 2003-08-28 | Method for separating platinum group element |
| CA 2730558 CA2730558C (en) | 2002-11-29 | 2003-08-28 | Separation process for platinum group elements |
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| JP2003006391A JP4269693B2 (en) | 2003-01-14 | 2003-01-14 | Process for treating selenium mixture |
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| JP4269693B2 JP4269693B2 (en) | 2009-05-27 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2377334C1 (en) * | 2008-04-22 | 2009-12-27 | Учреждение Российской академии наук Институт физики твердого тела РАН | Method of extracting tellurium |
| JP2011068528A (en) * | 2009-09-28 | 2011-04-07 | Jx Nippon Mining & Metals Corp | Method for recovering tellurium from copper electrolysis precipitation |
| JP2017203207A (en) * | 2016-05-13 | 2017-11-16 | 一般財団法人電力中央研究所 | Recovery method of selenium and tellurium from molten chloride |
| CN112442601A (en) * | 2020-12-08 | 2021-03-05 | 山东黄金归来庄矿业有限公司 | Process for improving leaching rate of carbon-containing tellurium-containing refractory limestone type gold ore |
| CN113044815A (en) * | 2021-03-22 | 2021-06-29 | 江西华赣瑞林稀贵金属科技有限公司 | Method and system for comprehensively treating selenium-tellurium-containing waste |
| JP2021105195A (en) * | 2019-12-26 | 2021-07-26 | 三菱マテリアル株式会社 | Method for recovering selenium |
| CN114892007A (en) * | 2022-05-18 | 2022-08-12 | 云南锡业股份有限公司铜业分公司 | Method for recovering valuable metals from selenium steaming slag of complex copper anode slime |
| CN116179863A (en) * | 2022-09-07 | 2023-05-30 | 金川集团股份有限公司 | A method for enriching and recovering silver-selenium from low-nickel and high-nickel copper anode slime |
| CN116253296A (en) * | 2023-01-06 | 2023-06-13 | 永兴县鸿福金属有限公司 | Method for extracting tellurium from matte |
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- 2003-01-14 JP JP2003006391A patent/JP4269693B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2377334C1 (en) * | 2008-04-22 | 2009-12-27 | Учреждение Российской академии наук Институт физики твердого тела РАН | Method of extracting tellurium |
| JP2011068528A (en) * | 2009-09-28 | 2011-04-07 | Jx Nippon Mining & Metals Corp | Method for recovering tellurium from copper electrolysis precipitation |
| JP2017203207A (en) * | 2016-05-13 | 2017-11-16 | 一般財団法人電力中央研究所 | Recovery method of selenium and tellurium from molten chloride |
| JP2021105195A (en) * | 2019-12-26 | 2021-07-26 | 三菱マテリアル株式会社 | Method for recovering selenium |
| JP7338462B2 (en) | 2019-12-26 | 2023-09-05 | 三菱マテリアル株式会社 | Selenium recovery method |
| CN112442601A (en) * | 2020-12-08 | 2021-03-05 | 山东黄金归来庄矿业有限公司 | Process for improving leaching rate of carbon-containing tellurium-containing refractory limestone type gold ore |
| CN113044815A (en) * | 2021-03-22 | 2021-06-29 | 江西华赣瑞林稀贵金属科技有限公司 | Method and system for comprehensively treating selenium-tellurium-containing waste |
| CN114892007A (en) * | 2022-05-18 | 2022-08-12 | 云南锡业股份有限公司铜业分公司 | Method for recovering valuable metals from selenium steaming slag of complex copper anode slime |
| CN116179863A (en) * | 2022-09-07 | 2023-05-30 | 金川集团股份有限公司 | A method for enriching and recovering silver-selenium from low-nickel and high-nickel copper anode slime |
| CN116253296A (en) * | 2023-01-06 | 2023-06-13 | 永兴县鸿福金属有限公司 | Method for extracting tellurium from matte |
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