JP3806258B2 - Ga, In solvent extraction method - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、Ｇａ，Ｉｎを含有する被抽出溶液に抽出用有機溶媒を加えてＧａ，Ｉｎを有機相に抽出して分離するＧａ，Ｉｎの溶媒抽出方法に関する。
【０００２】
【従来の技術】
Ｇａは亜鉛やアルミニウムの製錬副産物として微量得られる金属元素で、化合物半導体に多く使用されている。化合物半導体分野では６Ｎ（９９．９９９９％）以上に精製された高純度ＧａがＧａＡｓ，ＧａＰ製造に使用され、これらは発光ダイオード、ＩＣ、ＬＳＩなどに利用されている。一方、ＩｎはＧａ同様、亜鉛やアルミニウムの製錬副産物として微量得られる金属元素で、大部分が液晶の透明電極膜であるＩＴＯに使用されている。
【０００３】
従来、Ｇａ，Ｉｎを含む溶液（被抽出溶液）からＧａ，Ｉｎを選択的に分離、濃縮する方法として、溶媒抽出法がある。その原理は、有機溶剤としてカルボン酸系または燐酸系キレート抽出薬剤を加え、これを有機相とし、前記被抽出溶液の水相のｐＨを調整し、前記有機相と十分に接触させることにより、水相中のＧａ，Ｉｎを選択的に有機相中にキレート化合物として抽出することである。この際、Ｇａ，Ｉｎ等の抽出反応が進むと有機相のキレート剤のプロトン（Ｈ＋）が抽出元素であるＧａ，Ｉｎ等に置換され、水相に放出される。そのため水相のｐＨが低下してくるため、抽出反応を継続させるには接触反応時にアルカリ剤を添加することで水相のｐＨを調整する必要がある。
【０００４】
有機相に抽出されたＧａ，Ｉｎ等は次工程において高濃度の酸を含む水溶液との接触により、ストリップされ、回収工程に送られる。一方、高濃度の酸と接触した有機相はＧａ，Ｉｎ等のイオンを離すと同時にプロトンを得て、再度抽出工程に戻され循環利用される。
【０００５】
【発明が解決しようとする課題】
しかしながら、前記方法では溶媒抽出時、水相のｐＨを維持するためアルカリ剤の添加が必要であるが、添加されたアルカリ剤によって瞬間的にまたは局所的にｐＨが非常に高くなり、鉄、亜鉛およびアルミニウム等の不純物が有機相に移行してしまう割合が高く、次工程でのこれらの分離が必要で手間とコストがかかった。
【０００６】
本発明は、上述の背景のもとでなされたものであり、鉄、亜鉛およびアルミニウム等の不純物の有機相への移行を押さえながら、Ｇａ，Ｉｎを効率よく抽出することができるＧａ，Ｉｎの溶媒抽出方法を提供することを目的とする。
【０００７】
【課題を解決するための手段】
上述の課題を解決するために、本発明者らが鋭意研究した結果、Ｇａ，Ｉｎ等の抽出時に水相のｐＨの低下を抑えるには、プロトンが水相中に放出されないようにすることが必要であること、また、そのためには、あらかじめ有機相中に含有させたキレート剤のプロトンをアルカリ土類金属元素で置換しておくことが必要であることが解明された。本発明は、この解明結果に基づいてなされたものであり、第１の発明は、
Ｇａ，Ｉｎを含有する被抽出溶液に抽出用有機溶媒を加えてＧａ，Ｉｎを有機相に抽出して分離するにおいて、
前記被抽出溶液は、そのｐＨが２．４〜３．６に調整されたものであり、
前記抽出用有機溶媒は、有機溶剤にキレート剤が加えられ、さらに、このキレート剤のプロトンの一部がアルカリ土類元素で置換された有機相を有するものであり、
前記被抽出溶液と前記抽出用有機溶媒とを混合することによって前記被抽出溶液中のＧａ，Ｉｎを有機相中に抽出することを特徴とするＧａ，Ｉｎの溶媒抽出方法である。
【０００８】
第２の発明は、
第１の発明にかかるＧａ，Ｉｎの溶媒抽出方法において、
前記被抽出溶液と前記抽出用有機溶媒との混合工程は、両液の温度を７０℃以下に維持し、撹拌または振とうする処理を行うものであることを特徴とするＧａ，Ｉｎの溶媒抽出方法である。
【０００９】
第３の発明は、
第１又は第２の発明にかかるＧａ，Ｉｎの溶媒抽出方法において、
前記有機相のキレート剤のプロトンとアルカリ土類元素を置換する方法が、キレート剤を含む有機相に、アルカリ土類元素水酸化物のパルプを加えることであることを特徴とするＧａ，Ｉｎの溶媒抽出方法である。
【００１０】
第４の発明は、
第１ないし第３のいずれかの発明にかかるＧａ，Ｉｎの溶媒抽出方法において、
前記有機相のキレート剤のプロトンと置換するアルカリ土類元素がカルシウムであり、その置換方法が、キレート剤を含む有機相に９０〜１１０ｇ／Ｌの消石灰パルプを有機相の容量に対して０．５〜２．５容量％を加えることであることを特徴とするＧａ，Ｉｎの溶媒抽出方法である。
【００１１】
第５の発明は、
第１ないし第４のいずれかの発明にかかるＧａ，Ｉｎの溶媒抽出方法において、
前記キレート剤がカルボン酸系の抽出試薬であることを特徴とするＧａ，Ｉｎの溶媒抽出方法である。
【００１２】
第６の発明は、第１ないし第５の発明のいずれかの発明に係るＧａ，Ｉｎの溶媒抽出方法において、前記抽出操作における抽出用有機溶媒／被抽出溶液を、容量比で０．５〜ｌ．５とし、当該抽出用有機溶媒中に抽出されたＧａ，Ｉｎを、５〜１２Ｎの塩酸による逆抽出工程でストリップして濃縮することを特徴とするＧａ，Ｉｎの溶媒抽出方法である。
【００１３】
【発明の実施の形態】
図１は本発明の一実施の形態にかかるＧａ，Ｉｎの溶媒抽出方法の概略構成を示すフロー図である。以下、図１を参照にしながら本発明の一実施の形態にかかるＧａ，Ｉｎの溶媒抽出方法を説明する。なお、この実施の形態は、Ｇａ，Ｉｎを含む溶液である被抽出溶液として、湿式亜鉛製錬における亜鉛浸出残渣処理工程で得られる溶液を用いる例である。
【００１４】
この実施の形態の方法は、（１）Ｇａ，Ｉｎを含む溶液である被抽出溶液を得る工程、（２）被抽出溶液のｐＨを調整する工程、（３）有機溶媒を得る工程、（４）被抽出液と有機溶媒とを混合する工程、（５）有機相を分離して取り出す工程、（６）有機相からＧａ，Ｉｎを分離する工程（逆抽出）とを有する。
【００１５】
（１）被抽出溶液を得る工程
Ｇａ，Ｉｎを含む溶液である被抽出溶液は、図１に示される湿式亜鉛製錬における亜鉛浸出残渣処理工程の２段中和工程で得られる。すなわち、図１に示されるように、湿式亜鉛製錬における亜鉛浸出残渣処理は、焼鉱に戻り硫酸を加えて亜鉛浸出を行った後の亜鉛浸出残渣に、まず、ＳＯ2 と電解尾液とを加えてＳＯ2 浸出を行う。このＳＯ2 浸出処理によって、亜鉛浸出残渣から、Ｐｂ、Ａｕ、Ａｇ等が残渣として取り除かれる。
【００１６】
次に、ＳＯ2 浸出によってＰｂ、Ａｕ、Ａｇ等が取り除かれた液に、炭酸カルシウム（ＣａＣＯ3 ）を加えて第一段中和を行う。これにより、石膏が析出して遊離硫酸が取り除かれる。
【００１７】
次に、１段中和がなされた液に亜鉛粉末を加えて脱砒素処理を行う。この脱砒素処理の際に、砒化銅パルプが析出される。次に、脱砒素処理が施された後の液に炭酸カルシウムが加えられて２段中和がなされる。この２段中和の際に、石膏、Ｇａ、Ｉｎ等が取り除かれる。本発明は、この２段中和の際に取り除かれるＧａ、Ｉｎ等を含む２段中和残渣の酸浸出溶液を被抽出溶液として用いる。なお、２段中和後には、Ｏ2 及び蒸気が加えられて脱鉄処理がなされてヘマタイトとして取り除かれ、残りの液は、最初の浸出液に戻されて同様の処理がなされる。
【００１８】
（２）被抽出溶液のｐＨを調整する工程
この工程は、被抽出溶液にアルカリ剤又は鉱酸を加えて被抽出溶液のｐＨを調整する工程である。特にキレート系の溶媒抽出を行う際、溶液のｐＨは非常に大きな影響を抽出に与える。ｐＨが２．４〜３．６が好ましい。カルボン酸系キレート試薬でＧａ，Ｉｎイオンを同時に抽出する場合は、ｐＨが２．４を下回ると、Ｇａ，Ｉｎイオンともに抽出率が８０％未満であり、ｐＨが３．６を超えるとＧａイオンの抽出率が８０％を割り始め、かつ亜鉛、鉄、アルミニウム等の不純物イオンが多く抽出されてしまう。Ｇａ，Ｉｎ両イオンの抽出率を８５〜９５％とし、不純物イオンを最低に抑える好ましいｐＨ範囲は２．６〜３．２である。従って溶液中のｐＨが２．４〜３．６外の場合は鉱酸あるいはアルカリ剤を用いてこのｐＨ範囲に調整する。
【００１９】
（３）抽出用有機溶媒を得る工程
上記被抽出溶液を得る工程と平行して、有機溶媒を得る工程が行なわれる。抽出用有機溶媒（抽出用有機相）は、キレート剤の一種であるカルボン酸系の抽出試薬（Ｒ一ＣＯＯＨ）をケロシン等の有機溶剤を用いて容量で３０〜５０％に希釈したものを用いる。抽出試薬が３０％未満ではＧａ，Ｉｎの抽出率が落ち、５０％より多い場合でもＧａ，Ｉｎの抽出率は変わらないので経済的ではない。またキレート抽出剤として燐酸系を用いることもできる。
【００２０】
次に、上記キレート剤のプロトンの一部をアルカリ土類金属元素で置換する。この処理操作は、上記有機相に９０〜１１０ｇ／Ｌのアルカリ土類水酸化物パルプを有機相容量に対して０．５〜２．５容量％添加し、緩やかに撹拌する事で行う。この操作で有機相中のキレート剤のプロトンはアルカリ土類元素に置換される。添加するアルカリ土類水酸化物としては消石灰が操作性、コストの面で最適である。添加された消石灰パルプ（９０〜１１０ｇ／Ｌ）は速やかに有機溶媒に溶解され、透明な溶液となる。混合当初は消石灰がイオン化してないので白濁しているが、消石灰中のカルシウムが有機溶媒中のキレートに置換されることによって濁りがなくなる。
【００２１】
（４）被抽出液と有機溶媒とを混合する工程
ｐＨ調整された被抽出溶液と前記調製した抽出用有機溶媒とを、有機相／水相比、が容量比で０．５〜１．５となるようにそれぞれの液を撹拌機付き反応槽に給液し、７０℃以下で１５分以上激しく撹拌する。有機相／水相比が容量比で０．５より小さい場合には溶液中にアルミニウム等不純物が多量に含まれていると有機相に抽出され、有機溶媒の粘度があがり抽出効率が低下する。逆にｌ．５を超えるとかなり不純物成分の多い溶液についても抽出可能であるが分離濃縮という点で経済的ではない。さらに好ましくは、０．９〜１．０がよい。また、混合時の温度は、７０℃以下が好ましい。７０℃を超えると、Ｉｎの抽出効率が極端に低下し、３０％を割ることもある。
【００２２】
（５）有機相を分離して取り出す工程
撹拌抽出後、有機相と水相を分離するためにセットラーにて静置する。この際、溶液が硫酸酸性の場合は石膏（ＣａＳＯ4 ・２Ｈ2 ０）が発生し、セットラー下部に蓄積する。連続操業をするためにはセットラーの抜き出し部はコーン状にし、セットラーヘの石膏の蓄積を防止する。
【００２３】
（６）有機相からＧａ，Ｉｎを分離する工程（逆抽出）
有機相中に抽出されたＧａ，Ｉｎは次工程の強酸による逆抽出工程でストリップされる。強酸としては５〜１２Ｎ塩酸が一般的でその量としては有機相の容量の３０分の１程度で行う。従ってこの塩酸溶液中のＧａ，Ｉｎ濃度は処理前の溶液の２０〜６０倍濃縮されたことになる。又、濃塩酸と接触した有機相はプロトンを得て、再度抽出工程に戻され循環利用される。
【００２４】
（実施例）
被抽出溶液として、亜鉛製錬の亜鉛浸出残査処理工程における２段中和処理によって得られた溶液から石膏を浸出し、あらかじめ大部分のＩｎを除いた後の溶液を用いた。この被抽出溶液の主な成分は、Ｇａ １００ｍ ｇ／Ｌ，Ｉｎ ２００ｍ ｇ／Ｌ，不純物として、Ｆｅ １５ｇ／Ｌ、Ｚｎ ３０ｇ／Ｌ、Ａ１１５ｇ／Ｌであった。この溶液は硫酸酸性であったので、炭カル添加でｐＨを３．４とした。
【００２５】
抽出用有機溶液としては、抽出用有機相としてカルボン酸系の抽出試薬バーサチック１０（シェル化学株式会社の商品名）を用い、これを灯油系の有機溶剤であるケロシンで容量で５０％に希釈したものを用いた。この抽出用有機溶液に消石灰を水で１００ｇ／Ｌ程度のパルプにしたものを容量で有機相の２％加え、バーサチックのプロトンをカルシウムイオンに置換した。添加された消石灰パルプ（１００ｇ／Ｌ）は速やかに有機溶媒に溶解され、透明な溶液となった。
【００２６】
次に、上記ｐＨを３．４に調整した被抽出溶液と前記調製した有機溶媒とを有機相／水相比が容量比１．０となるようにそれぞれの液を１リットルの撹拌機（プロペラ式）付き反応槽に給液し、４０℃で３０分間、撹拌速度３００ｒｐｍで撹拌した。撹拌抽出後、有機相と水相を分離するためにセットラーにて静置した。この際、溶液が硫酸酸性であったので石膏（ＣａＳＯ4 ・２Ｈ2 ０）が発生し、セットラー下部に蓄積した。セットラ一の抜き出し部をコーン状とし、逐次セットラーから石膏を抜き出した。抽出終了時、水相のｐＨを測定したところ３．３で抽出前とほぼ変わらなかった。
【００２７】
次に、上記分離した有機相を９Ｎ塩酸を用いたで逆抽出工程でストリップした。用いた９Ｎ塩酸容量は、有機相容量の３０分の１程度としたので、Ｇａ，Ｉｎの濃縮度は処理前の溶液の３０倍になる。なお、プロトンを得た有機相は、再度抽出工程に戻し循環利用した。
【００２８】
以上得られた結果から、抽出対象成分であるＧａ，Ｉｎの抽出率（回収率）と同時に混入した不純物であるＦｅ，Ｚｎ，Ａ１の抽出率を算出した結果を本発明法として図２の表１に示す。
【００２９】
（比較例）
この比較例は、消石灰によるプロトンーカルシウムの置換を行わなかった点を除き、上記実施例１とほとんど同じ工程により、抽出操作を行った。すなわち、被抽出溶液を実施例１と同じものを使用し、被抽出溶液のｐＨ調整も実施例の操作と同様に行い３．４に調整した。有機相の調製はバーサチックーケロシンまで実施例１と同様で、ｐＨを３．４に調整した溶液と前記調製した有機溶媒を有機相／水相比が容量比１．０となるようにそれぞれの液を１リットルの撹拌機（プロペラ式）付き反応槽に給液し、４０℃で３０分間，撹拌速度３００ｒｐｍで撹拌した。この問、ｐＨが下がらないように撹拌抽出中に、ＮａＯＨ溶液の添加を行い、ｐＨ３．４を維持した。以下実施例と同操作を行い、その結果を従来法として表１に示した。
【００３０】
実施例と比較例とを比較すると、Ｇａ，Ｉｎの回収率についてはほとんど差はなく、Ｇａが実施例８５％に対して比較例が８４％、Ｉｎが実施例９２％に対して比較例が９１％であった。しかしながら、不純物の混入については、アルミニウムで、比較例１２％に対して実施例が４％，鉄で、比較例１１％に対して実施例が２％，同様に、亜鉛についても、比較例８％に対して実施例２％と、比較例に対して実施例は有機相の不純物の混入を押さえることができた。
【００３１】
【発明の効果】
以上詳述したように、本発明は、Ｇａ，Ｉｎを含有する被抽出溶液に抽出用有機溶媒を加えてＧａ，Ｉｎを有機相に抽出して分離するＧａ，Ｉｎの溶媒抽出方法において、前記被抽出溶液は、そのｐＨが２．４〜３．６に調整されたものであり、前記抽出用有機溶媒は、有機溶剤にキレート剤が加えられ、さらに、このキレート剤のプロトンの一部がアルカリ土類元素で置換された有機相を有するものであり、 前記被抽出溶液と前記抽出用有機溶媒とを混合することによって前記被抽出溶液中のＧａ，Ｉｎを有機相中に抽出することを特徴とする。これにより、鉄、亜鉛およびアルミニウム等の不純物の有機相への移行を押さえながら、Ｇａ，Ｉｎを効率よく抽出することができるＧａ，Ｉｎの溶媒抽出方法を得ている。
【図面の簡単な説明】
【図１】本発明の一実施の形態にかかるＧａ，Ｉｎの溶媒抽出方法の概略構成を示すフロー図である。
【図２】実施例１及び比較例１の回収率をまとめて表にして比較して示した図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a Ga, In solvent extraction method in which an extraction organic solvent is added to a solution to be extracted containing Ga, In to extract and separate Ga and In into an organic phase.
[0002]
[Prior art]
Ga is a metal element obtained in a trace amount as a smelting byproduct of zinc and aluminum, and is often used in compound semiconductors. In the compound semiconductor field, high-purity Ga purified to 6N (99.9999%) or more is used for GaAs and GaP production, and these are used for light-emitting diodes, ICs, LSIs, and the like. On the other hand, In, like Ga, is a metal element obtained in a trace amount as a smelting by-product of zinc and aluminum, and most of it is used in ITO which is a transparent electrode film of liquid crystal.
[0003]
Conventionally, there is a solvent extraction method as a method for selectively separating and concentrating Ga and In from a solution containing Ga and In (solution to be extracted). The principle is that a carboxylic acid-based or phosphoric acid-based chelate extraction agent is added as an organic solvent, this is used as an organic phase, the pH of the aqueous phase of the solution to be extracted is adjusted, and the water is sufficiently brought into contact with the organic phase. This is to selectively extract Ga and In in the phase into the organic phase as a chelate compound. At this time, when the extraction reaction of Ga, In, etc. proceeds, protons (H + ) of the chelating agent in the organic phase are replaced with Ga, In, etc., which are extraction elements, and released into the aqueous phase. Therefore, since the pH of the aqueous phase is lowered, it is necessary to adjust the pH of the aqueous phase by adding an alkaline agent during the contact reaction in order to continue the extraction reaction.
[0004]
Ga, In and the like extracted in the organic phase are stripped by contact with an aqueous solution containing a high concentration acid in the next step and sent to the recovery step. On the other hand, the organic phase that has been in contact with the high-concentration acid releases protons such as Ga and In, and at the same time obtains protons, and is returned to the extraction process and recycled.
[0005]
[Problems to be solved by the invention]
However, in the above method, it is necessary to add an alkaline agent in order to maintain the pH of the aqueous phase at the time of solvent extraction, but the pH becomes very high instantaneously or locally by the added alkaline agent, and iron, zinc In addition, the rate at which impurities such as aluminum migrate to the organic phase is high, and it is necessary to separate them in the next step, which takes time and cost.
[0006]
The present invention has been made under the above-mentioned background, and is capable of efficiently extracting Ga and In while suppressing the transition of impurities such as iron, zinc and aluminum to the organic phase. An object is to provide a solvent extraction method.
[0007]
[Means for Solving the Problems]
As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, in order to suppress a decrease in pH of the aqueous phase during extraction of Ga, In, etc., it is necessary to prevent protons from being released into the aqueous phase. It has been clarified that this is necessary, and for that purpose, it is necessary to replace the proton of the chelating agent previously contained in the organic phase with an alkaline earth metal element. The present invention has been made based on the results of this elucidation.
In extracting and separating Ga and In into an organic phase by adding an extraction organic solvent to an extraction solution containing Ga and In,
The to-be-extracted solution has its pH adjusted to 2.4-3.6,
The organic solvent for extraction has an organic phase in which a chelating agent is added to the organic solvent, and a part of protons of the chelating agent is substituted with an alkaline earth element,
The Ga and In solvent extraction method is characterized in that Ga and In in the extraction solution are extracted into an organic phase by mixing the extraction solution and the organic solvent for extraction.
[0008]
The second invention is
In the Ga, In solvent extraction method according to the first invention,
Ga and In solvent extraction characterized in that the mixing step of the solution to be extracted and the organic solvent for extraction performs a process of stirring or shaking while maintaining the temperature of both solutions at 70 ° C. or lower. Is the method.
[0009]
The third invention is
In the Ga or In solvent extraction method according to the first or second invention,
The method for replacing protons and alkaline earth elements of the chelating agent in the organic phase is to add pulp of alkaline earth element hydroxide to the organic phase containing the chelating agent. Solvent extraction method.
[0010]
The fourth invention is:
In the Ga, In solvent extraction method according to any one of the first to third inventions,
The alkaline earth element that replaces the proton of the chelating agent in the organic phase is calcium, and the substitution method is performed by adding 90 to 110 g / L of slaked lime pulp to the organic phase containing the chelating agent in an amount of 0. The solvent extraction method for Ga and In is characterized by adding 5 to 2.5% by volume.
[0011]
The fifth invention is:
In the Ga, In solvent extraction method according to any one of the first to fourth inventions,
It is a Ga, In solvent extraction method, wherein the chelating agent is a carboxylic acid-based extraction reagent.
[0012]
According to a sixth invention, in the Ga, In solvent extraction method according to any one of the first to fifth inventions, the extraction organic solvent / extracted solution in the extraction operation is 0.5 to l. The Ga and In solvent extraction method is characterized in that Ga and In extracted in the organic solvent for extraction are stripped and concentrated in a back extraction step with 5 to 12N hydrochloric acid.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is a flowchart showing a schematic configuration of a Ga, In solvent extraction method according to an embodiment of the present invention. Hereinafter, a Ga, In solvent extraction method according to an embodiment of the present invention will be described with reference to FIG. This embodiment is an example in which a solution obtained in a zinc leaching residue treatment step in wet zinc smelting is used as a solution to be extracted which is a solution containing Ga and In.
[0014]
The method of this embodiment includes (1) a step of obtaining an extraction solution that is a solution containing Ga, In, (2) a step of adjusting the pH of the extraction solution, (3) a step of obtaining an organic solvent, (4 ) A step of mixing the liquid to be extracted and an organic solvent, (5) a step of separating and taking out the organic phase, and (6) a step of separating Ga and In from the organic phase (back extraction).
[0015]
(1) Step of obtaining solution to be extracted The solution to be extracted, which is a solution containing Ga and In, is obtained in the two-step neutralization step of the zinc leaching residue treatment step in wet zinc smelting shown in FIG. That is, as shown in FIG. 1, the zinc leach residue processing in wet zinc smelting, zinc leach residue after the zinc leaching by adding sulfuric acid to return to burn ore, firstly, the SO 2 and the electrolyte tail solution To perform SO 2 leaching. By this SO 2 leaching treatment, Pb, Au, Ag, etc. are removed as residues from the zinc leaching residue.
[0016]
Next, first stage neutralization is performed by adding calcium carbonate (CaCO 3 ) to the liquid from which Pb, Au, Ag and the like have been removed by SO 2 leaching. Thereby, gypsum precipitates and free sulfuric acid is removed.
[0017]
Next, a zinc powder is added to the liquid that has been neutralized by one stage to perform a dearsenic treatment. During this dearsenic treatment, copper arsenide pulp is deposited. Next, calcium carbonate is added to the liquid after the dearsenic treatment, and two-stage neutralization is performed. In the two-stage neutralization, gypsum, Ga, In and the like are removed. In the present invention, an acid leaching solution of a two-stage neutralization residue containing Ga, In and the like removed during the two-stage neutralization is used as an extraction solution. After the two-stage neutralization, O 2 and steam are added to remove iron to remove it as hematite, and the remaining liquid is returned to the first leachate and subjected to the same treatment.
[0018]
(2) Step of adjusting the pH of the solution to be extracted This step is a step of adjusting the pH of the solution to be extracted by adding an alkaline agent or mineral acid to the solution to be extracted. In particular, when performing chelate-based solvent extraction, the pH of the solution has a very large influence on the extraction. The pH is preferably 2.4 to 3.6. When Ga and In ions are simultaneously extracted with a carboxylic acid chelating reagent, if the pH is less than 2.4, the extraction rate of both Ga and In ions is less than 80%, and if the pH exceeds 3.6, Ga ions are extracted. The extraction rate starts to be less than 80%, and many impurity ions such as zinc, iron, and aluminum are extracted. A preferable pH range in which the extraction rate of both Ga and In ions is 85 to 95% and impurity ions are minimized is 2.6 to 3.2. Therefore, when the pH in the solution is outside 2.4 to 3.6, the pH is adjusted to this pH range using a mineral acid or an alkali agent.
[0019]
(3) Step of obtaining organic solvent for extraction A step of obtaining an organic solvent is performed in parallel with the step of obtaining the solution to be extracted. As the organic solvent for extraction (organic phase for extraction), a carboxylic acid type extraction reagent (R-COOH), which is a kind of chelating agent, is diluted to 30 to 50% by volume with an organic solvent such as kerosene. . If the extraction reagent is less than 30%, the extraction rate of Ga and In decreases, and if it is more than 50%, the extraction rate of Ga and In does not change, which is not economical. Moreover, a phosphoric acid type can also be used as a chelate extractant.
[0020]
Next, a part of protons of the chelating agent is replaced with an alkaline earth metal element. This treatment operation is performed by adding 90 to 110 g / L of alkaline earth hydroxide pulp to the organic phase in an amount of 0.5 to 2.5% by volume based on the volume of the organic phase and gently stirring. By this operation, protons of the chelating agent in the organic phase are replaced with alkaline earth elements. As the alkaline earth hydroxide to be added, slaked lime is optimal in terms of operability and cost. The added slaked lime pulp (90 to 110 g / L) is quickly dissolved in an organic solvent to become a transparent solution. Since slaked lime is not ionized at the beginning of mixing, it is cloudy. However, turbidity is eliminated by replacing calcium in slaked lime with chelate in an organic solvent.
[0021]
(4) Step of mixing the solution to be extracted and the organic solvent The pH-adjusted solution to be extracted and the prepared organic solvent for extraction have an organic phase / water phase ratio of 0.5 to 1.5 in volume ratio. Then, each solution is fed into a reaction tank equipped with a stirrer and stirred vigorously at 70 ° C. or lower for 15 minutes or longer. When the organic phase / aqueous phase ratio is smaller than 0.5 by volume, if the solution contains a large amount of impurities such as aluminum, it is extracted into the organic phase, the viscosity of the organic solvent increases, and the extraction efficiency decreases. Conversely, l. If it exceeds 5, it is possible to extract a solution having a large amount of impurity components, but it is not economical in terms of separation and concentration. More preferably, 0.9-1.0 is good. The temperature during mixing is preferably 70 ° C. or lower. If it exceeds 70 ° C., the extraction efficiency of In is extremely reduced, and may be 30%.
[0022]
(5) Step of separating and taking out the organic phase After stirring and extraction, the organic phase and the aqueous phase are allowed to stand with a setter in order to separate them. At this time, if the solution is sulfuric acid acid, gypsum (CaSO 4 .2H 2 0) is generated and accumulated in the lower part of the setler. In order to perform continuous operation, the extraction part of the setler should be shaped like a cone to prevent the plaster from accumulating on the setler.
[0023]
(6) Step of separating Ga and In from the organic phase (back extraction)
Ga and In extracted in the organic phase are stripped in the back extraction step with a strong acid in the next step. As the strong acid, 5-12N hydrochloric acid is generally used, and the amount is about 1/30 of the capacity of the organic phase. Therefore, the Ga and In concentrations in this hydrochloric acid solution are concentrated 20 to 60 times that of the solution before the treatment. In addition, the organic phase that has come into contact with concentrated hydrochloric acid obtains protons, and is returned to the extraction step for recycling.
[0024]
(Example)
As the solution to be extracted, a solution obtained by leaching gypsum from the solution obtained by the two-step neutralization treatment in the zinc leaching residue treatment process of zinc smelting and removing most of In beforehand was used. Main components of this solution to be extracted were Ga 100 mg / L, In 200 mg / L, and impurities were Fe 15 g / L, Zn 30 g / L, and A 115 g / L. Since this solution was acidic with sulfuric acid, the pH was adjusted to 3.4 by adding charcoal calcium.
[0025]
As an organic solution for extraction, a carboxylic acid-based extraction reagent Versatic 10 (trade name of Shell Chemical Co., Ltd.) was used as an organic phase for extraction, and this was diluted to 50% by volume with kerosene, a kerosene-based organic solvent. A thing was used. 2% of the organic phase was added to the organic solution for extraction with pulp of about 100 g / L slaked lime with water to replace the versatic protons with calcium ions. The added slaked lime pulp (100 g / L) was quickly dissolved in an organic solvent to become a transparent solution.
[0026]
Next, the solution to be extracted whose pH is adjusted to 3.4 and the prepared organic solvent are mixed with a 1 liter stirrer (propeller) so that the organic phase / water phase ratio is 1.0. The solution was fed to a reaction vessel equipped with a formula) and stirred at 40 ° C. for 30 minutes at a stirring speed of 300 rpm. After stirring and extracting, the mixture was allowed to stand with a setter in order to separate the organic phase and the aqueous phase. At this time, since the solution was acidic with sulfuric acid, gypsum (CaSO 4 .2H 2 0) was generated and accumulated in the lower part of the setler. The extraction part of the setler was made into a cone shape, and the gypsum was sequentially extracted from the setler. At the end of the extraction, the pH of the aqueous phase was measured and was almost the same as before extraction at 3.3.
[0027]
Next, the separated organic phase was stripped in a back extraction step using 9N hydrochloric acid. Since the 9N hydrochloric acid capacity used was about 1/30 of the organic phase capacity, the concentration of Ga and In was 30 times that of the solution before treatment. The organic phase from which protons were obtained was recycled back to the extraction step.
[0028]
From the results obtained above, the results of calculating the extraction rates of impurities Fe, Zn, and A1 mixed at the same time as the extraction rate (recovery rate) of Ga and In that are the extraction target components are shown in FIG. It is shown in 1.
[0029]
(Comparative example)
In this comparative example, the extraction operation was performed by almost the same steps as in Example 1 except that the substitution of proton-calcium with slaked lime was not performed. That is, the same extraction solution as in Example 1 was used, and the pH of the extraction solution was adjusted to 3.4 by performing the same adjustment as in the operation of the example. The organic phase was prepared in the same manner as in Example 1 up to versatic kerosene, and the solution prepared by adjusting the pH to 3.4 and the prepared organic solvent were adjusted so that the organic phase / water phase ratio was 1.0. The solution was fed into a 1 liter reactor equipped with a stirrer (propeller type), and stirred at 40 ° C. for 30 minutes at a stirring speed of 300 rpm. During this stirring extraction, NaOH solution was added to maintain the pH of 3.4 so that the pH did not drop. Thereafter, the same operation as in the Examples was performed, and the results are shown in Table 1 as a conventional method.
[0030]
When the Examples and Comparative Examples are compared, there is almost no difference in the recovery rates of Ga and In. Ga is 85% of the Comparative Example with 84% of the Comparative Example, and In is the Comparative Example with the Comparative Example of 92%. It was 91%. However, with regard to the mixing of impurities, aluminum was 4% in the example compared to 12% of the comparative example, iron was 2% in the example of 11% of the comparative example, and similarly zinc was also in the comparative example 8 Example 2 was able to suppress contamination of impurities in the organic phase compared to Example 2% with respect to%.
[0031]
【The invention's effect】
As described in detail above, the present invention provides a solvent extraction method for Ga and In, in which an extraction organic solvent is added to a solution to be extracted containing Ga and In, and Ga and In are extracted and separated into an organic phase. The extraction solution has a pH adjusted to 2.4 to 3.6, and the organic solvent for extraction is obtained by adding a chelating agent to the organic solvent, and further, a part of protons of the chelating agent is added. And having an organic phase substituted with an alkaline earth element, and extracting Ga and In in the solution to be extracted into the organic phase by mixing the solution to be extracted and the organic solvent for extraction. Features. Thereby, the solvent extraction method of Ga and In is obtained that can efficiently extract Ga and In while suppressing the migration of impurities such as iron, zinc, and aluminum to the organic phase.
[Brief description of the drawings]
FIG. 1 is a flowchart showing a schematic configuration of a Ga, In solvent extraction method according to an embodiment of the present invention.
FIG. 2 is a table showing the recovery rates of Example 1 and Comparative Example 1 in a table and compared.
Claims (6)
前記抽出操作における抽出用有機溶媒／被抽出溶液を、容量比で０．５〜ｌ．５とし、
当該抽出用有機溶媒中に抽出されたＧａ，Ｉｎを、５〜１２Ｎの塩酸による逆抽出工程でストリップして濃縮することを特徴とするＧａ，Ｉｎの溶媒抽出方法。 In the Ga, In solvent extraction method according to any one of claims 1 to 5,
In the extraction operation, the organic solvent for extraction / the solution to be extracted is 0.5 to 1 by volume ratio. 5 and
A Ga, In solvent extraction method comprising stripping and concentrating Ga, In extracted in the extraction organic solvent in a back extraction step with 5-12 N hydrochloric acid.
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| WO2006006497A1 (en) | 2004-07-09 | 2006-01-19 | Aquatech Corporation | Indium adsorbing agent and method for separating indium |
| JP5367862B2 (en) | 2012-03-13 | 2013-12-11 | 国立大学法人九州大学 | Scandium extractant and method for extracting scandium using the extractant |
| JP5442080B2 (en) | 2012-08-20 | 2014-03-12 | 国立大学法人九州大学 | Valuable metal separation method |
| JP5398885B1 (en) | 2012-08-20 | 2014-01-29 | 国立大学法人九州大学 | Gallium extraction method |
| JP5420033B1 (en) | 2012-08-20 | 2014-02-19 | 国立大学法人九州大学 | Indium extractant and method for extracting indium using the extractant |
| JP5734268B2 (en) | 2012-12-12 | 2015-06-17 | 国立大学法人九州大学 | Nickel extraction method |
| JP5595554B1 (en) | 2013-03-18 | 2014-09-24 | 国立大学法人九州大学 | Method for separating impurities from an acidic solution containing nickel, cobalt and / or scandium |
| JP5940688B1 (en) | 2015-01-20 | 2016-06-29 | 国立大学法人九州大学 | Zirconium extractant and zirconium extraction method |
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