JP2012091968A - Method of recovering germanium from germanium-containing intermediate - Google Patents
Method of recovering germanium from germanium-containing intermediate Download PDFInfo
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- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 94
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 45
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims abstract description 39
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 34
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 19
- 239000011701 zinc Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000013067 intermediate product Substances 0.000 claims abstract description 5
- 238000011084 recovery Methods 0.000 claims description 37
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 13
- 238000003723 Smelting Methods 0.000 claims description 9
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000004821 distillation Methods 0.000 description 16
- 239000002994 raw material Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- 239000012141 concentrate Substances 0.000 description 9
- 238000002386 leaching Methods 0.000 description 9
- 239000002699 waste material Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- -1 polyethylene terephthalate Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229940119177 germanium dioxide Drugs 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000013307 optical fiber Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002290 germanium Chemical class 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229940056932 lead sulfide Drugs 0.000 description 1
- 229910052981 lead sulfide Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
Classifications
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
本発明は、ゲルマニウムを含有する中間物からゲルマニウムを回収する方法に関する。 The present invention relates to a method for recovering germanium from an intermediate containing germanium.
ゲルマニウム（Ｇｅ）は、光ファイバーや太陽電池等のいわゆるハイテク産業用の材料開発、ポリエチレンテレフタレート樹脂の重合促進触媒、更には、有機ゲルマニウム化合物（例えば、ポリ−トランス−［（２−カルボキシエチル）ゲルマセスキオキサン]）の製造のための原料などとして、様々な分野における不可欠な元素である。
特に最近は、磁気ディスク材料等のエレクトロニクス材料としてのゲルマニウムの利用が増加しており、砒素及び非鉄金属の含有量が少ない、高品位のゲルマニウムの需要が高まっている。
Germanium (Ge) is a material for high-tech industries such as optical fibers and solar cells, a polymerization accelerating catalyst for polyethylene terephthalate resin, and an organic germanium compound (for example, poly-trans-[(2-carboxyethyl) germaseski). Oxane]) is an indispensable element in various fields as a raw material for production.
Particularly recently, the use of germanium as an electronic material such as a magnetic disk material has increased, and the demand for high-quality germanium with a low content of arsenic and non-ferrous metals has increased.
しかし、近年、ゲルマニウムの供給がその需要に追いつかず、需要−供給がアンバランスな状態が続くために問題視されている。そこで、主に亜鉛製錬の副産物として製錬されている高品位のゲルマニウムを、高い回収率で、効率よく且つ安価に回収することができれば、需要−供給のバランスが改善されると共に、資源の節約の観点からも好ましい。 However, in recent years, the supply of germanium has not been able to keep up with the demand, and it has been regarded as a problem because the demand-supply balance continues to be unbalanced. Therefore, if high-quality germanium, which is mainly smelted as a byproduct of zinc smelting, can be recovered efficiently and inexpensively at a high recovery rate, the balance between demand and supply will be improved. It is also preferable from the viewpoint of saving.
従来、亜鉛精鉱に含まれるゲルマニウムの回収方法としては、亜鉛精鉱を焙焼し、酸で浸出した後の浸出残渣を乾燥し、加熱した後に塩酸により塩化したゲルマニウムを回収する方法（Ｅａｇｌｅ−Ｐｉｃｈｅｒ法）が知られている（非特許文献１参照）。
しかしながら、この文献による方法には、亜鉛精鉱からのゲルマニウムの回収率が低い上に、安定して回収できないという問題がある。
Conventionally, as a method for recovering germanium contained in zinc concentrate, zinc concentrate is roasted, the leaching residue after leaching with acid is dried, heated, and then germanium salified with hydrochloric acid is recovered (Eagle- (Picher method) is known (see Non-Patent Document 1).
However, the method according to this document has a problem that the recovery rate of germanium from the zinc concentrate is low and it cannot be stably recovered.
一方、ポリエチレンテレフタレート、光ファイバー、半導体などの製造過程において、大量のゲルマニウム含有物が使用されているが、その大部分が廃棄されていることに注目し、ゲルマニウム含有廃棄物から、ゲルマニウムを回収する方法が提案されている。
例えば、ポリエチレンテレフタレート及びこれを主体とするポリエステルの製造する際には、ゲルマニウムが重合促進剤（触媒）として使用されており、その廃液からゲルマニウムを回収する方法が提案されている（特許文献１参照）。しかしながら、この提案では、前記廃液を焼却して得られた灰を塩酸を用いて蒸留し、四塩化ゲルマニウムを回収する方法であり、前記Ｅａｇｌｅ−Ｐｉｃｈｅｒ法と同様、ゲルマニウムの回収率が低い上に、安定して回収できないという問題がある。
また、光ファイバーのような光導波路材料の製造において用いられる改良化学気相成長法（ＭＣＶＤ）では、大量の高純度四塩化ゲルマニウムが使用されるおり、ＭＣＶＤ加工廃棄物からゲルマニウムを回収する方法が提案されている（特許文献２参照）。この提案によれば、ＭＣＶＤ加工廃棄物から、塩化水素ガスとＭＣＶＤ廃棄物（フィルターケーキ）との直接反応により、ゲルマニウム塩の迅速で完全な塩素化が行われ、四塩化ゲルマニウムが生成され、回収される。しかしながら、この提案では、ゲルマニウム以外の不要物も同時に回収されるため、最終的に得られたゲルマニウムにおける不純物の含有率が高いという問題がある。
On the other hand, in the manufacturing process of polyethylene terephthalate, optical fiber, semiconductor, etc., a large amount of germanium-containing material is used, but paying attention to the fact that most of it is discarded, a method for recovering germanium from germanium-containing material Has been proposed.
For example, germanium is used as a polymerization accelerator (catalyst) in the production of polyethylene terephthalate and polyester mainly composed thereof, and a method for recovering germanium from the waste liquid has been proposed (see Patent Document 1). ). However, in this proposal, the ash obtained by incineration of the waste liquid is distilled using hydrochloric acid, and germanium tetrachloride is recovered. Like the Eagle-Picher method, the recovery rate of germanium is low. There is a problem that it cannot be recovered stably.
In the improved chemical vapor deposition method (MCVD) used in the production of optical waveguide materials such as optical fibers, a large amount of high-purity germanium tetrachloride is used, and a method for recovering germanium from MCVD processing waste is proposed. (See Patent Document 2). According to this proposal, germanium salt is rapidly and completely chlorinated from MCVD processing waste by direct reaction of hydrogen chloride gas with MCVD waste (filter cake) to produce and recover germanium tetrachloride. Is done. However, this proposal has a problem in that the content of impurities in the finally obtained germanium is high because unnecessary substances other than germanium are also recovered at the same time.
したがって、高品位のゲルマニウムを、高い回収率で、効率よく且つ安価に、ゲルマニウムを含有する中間物から回収する方法は、未だ提供されておらず、その速やかな提供が強く求められているのが現状である。 Therefore, a method for recovering high-grade germanium from an intermediate containing germanium at a high recovery rate, efficiently and inexpensively has not yet been provided, and its prompt provision is strongly demanded. Currently.
本発明は、従来における前記諸問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、高品位のゲルマニウムを、高い回収率で、効率よく且つ安価に、ゲルマニウムを含有する中間物から回収する方法を提供することを目的とする。 An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a method for recovering high-quality germanium from an intermediate containing germanium efficiently and inexpensively at a high recovery rate.
前記課題を解決するための手段としては、以下の通りである。即ち、
＜１＞ 金属回収工程における、ゲルマニウムを含有する中間物から、塩酸と過酸化水素とを併用して、ゲルマニウムを塩化物として回収するゲルマニウム塩化物回収工程を含むことを特徴とするゲルマニウムの回収方法である。
＜２＞ 過酸化水素の添加量が、ゲルマニウムに対して２モル当量以上である前記＜１＞に記載のゲルマニウムの回収方法である。
＜３＞ ゲルマニウム塩化物回収工程で回収したゲルマニウム塩化物を加水分解して、ゲルマニウムを酸化物として回収するゲルマニウム酸化物回収工程を含む前記＜１＞から＜２＞のいずれかに記載のゲルマニウムの回収方法である。
＜４＞ 中間物が亜鉛製錬の中間産物である前記＜１＞から＜３＞のいずれかに記載のゲルマニウムの回収方法である。
Means for solving the problems are as follows. That is,
<1> A method for recovering germanium, comprising a germanium chloride recovery step of recovering germanium as chloride from a germanium-containing intermediate in a metal recovery step by using hydrochloric acid and hydrogen peroxide in combination. It is.
<2> The method for recovering germanium according to <1>, wherein the addition amount of hydrogen peroxide is 2 molar equivalents or more with respect to germanium.
<3> The germanium chloride according to any one of <1> to <2>, further including a germanium oxide recovery step of hydrolyzing the germanium chloride recovered in the germanium chloride recovery step and recovering germanium as an oxide. It is a collection method.
<4> The method for recovering germanium according to any one of <1> to <3>, wherein the intermediate is an intermediate product of zinc smelting.
本発明によると、従来の諸問題を解決することができ、高品位のゲルマニウムを、高い回収率で、効率よく且つ安価に、ゲルマニウムを含有する中間物から回収する方法を提供することができる。 According to the present invention, conventional problems can be solved, and a method for recovering high-quality germanium from an intermediate containing germanium at a high recovery rate, efficiently and inexpensively can be provided.
本発明のゲルマニウムの回収方法は、公知の金属回収工程（処理）において得られるゲルマニウムを含有する中間物から、塩酸と過酸化水素とを併用して、ゲルマニウムを塩化物として回収するゲルマニウム塩化物回収工程を含んでなり、更に必要に応じてその他の工程を含む。 The germanium recovery method of the present invention is a germanium chloride recovery in which germanium is recovered as a chloride from a germanium-containing intermediate obtained in a known metal recovery step (treatment) using hydrochloric acid and hydrogen peroxide in combination. It includes a process, and further includes other processes as necessary.
本発明のゲルマニウムを回収する方法については、従来から一般的に知られているＥａｇｌｅ−Ｐｉｔｃｈｅｒ法（レアメタルハンドブック２００８、金属時評、ｐ．１６４参照）において、塩酸と過酸化水素とを併用してゲルマニウムを塩化物として回収するゲルマニウム塩化物回収工程を例に説明する。
亜鉛製錬においては、一般的に、硫化物精鉱を焙焼し、酸による浸出及び中和処理などにより各種金属を残渣や液に分離する。このような亜鉛製錬プロセスからゲルマニウムが濃縮された残渣を発生させることが可能である。特に、亜鉛製錬プロセスから派生したインジウム回収プロセスにおいて生ずる中間産物である残渣中にゲルマニウムが比較的高濃度に含まれており、これを本発明の原料として利用することが可能である。
As for the method for recovering germanium of the present invention, germanium is used in combination with hydrochloric acid and hydrogen peroxide in the conventionally known Eagle-Pitcher method (see rare metal handbook 2008, metal reviews, p.164). An example of a germanium chloride recovery process for recovering as a chloride will be described.
In zinc smelting, sulfide concentrate is generally roasted and various metals are separated into residues and liquids by leaching with acid and neutralization treatment. It is possible to generate a germanium enriched residue from such a zinc smelting process. In particular, germanium is contained at a relatively high concentration in the residue that is an intermediate product generated in the indium recovery process derived from the zinc smelting process, and this can be used as a raw material of the present invention.
なお、前記原料は、本願発明に利用できる中間物の一例を示したものにすぎず、これに限定されるものではない。本発明の原料として利用できる中間物としては、金属回収工程（処理）において得られるものであって、ゲルマニウムを含有している限り、特に制限はなく、公知のものの中から適宜選択することができ、例えば、前述した亜鉛鉱石などのゲルマニウム含有鉱石を酸化、酸浸出するなどの製錬工程により発生する残渣等の非鉄製錬中間産物、ポリエチレンテレフタレート及びこれを主体とするポリエステルを製造する際の廃液を焼却して得られた灰、ＭＣＶＤ加工廃棄物、半導体材料として用いられた後のその材料乃至その製造において発生する廃棄物等のレアメタル回収等の中間産物などが挙げられる。前記中間物の形態としては、塩酸と反応できる形態であれば、特に制限はなく、例えば、金属化合物の形態であってもよいし、無機物以外の有機物も含む複雑化合物の形態でもよい。 In addition, the said raw material is only what showed an example of the intermediate body which can be utilized for this invention, and is not limited to this. The intermediate that can be used as the raw material of the present invention is not particularly limited as long as it is obtained in the metal recovery step (treatment) and contains germanium, and can be appropriately selected from known ones. For example, non-ferrous smelting intermediate products such as residues generated by smelting processes such as oxidation and acid leaching of germanium-containing ores such as zinc ore described above, waste liquid when producing polyethylene terephthalate and polyester mainly composed thereof Ash obtained by incineration, MCVD processing waste, intermediate materials such as recovery of rare metals such as the material after being used as a semiconductor material or waste generated in the production thereof. The form of the intermediate is not particularly limited as long as it can react with hydrochloric acid, and may be, for example, a form of a metal compound or a form of a complex compound including an organic substance other than an inorganic substance.
前記Ｅａｇｌｅ−Ｐｉｔｃｈｅｒ法においては、先ず、ゲルマニウムを含有する亜鉛精鉱（ゲルマニウムの含有比率は、通常、０．０１質量％〜０．０１５質量％）を酸化焙焼し、得られた焼鉱に塩及び石炭を混ぜて、焼結させる。焼結させた残滓は亜鉛製錬の原料となるが、焼結の際に生じる揮発物（煙灰）には、ゲルマニウム、カドミウム、銅及び鉛などが含まれる。
次に、前記揮発物を硫酸で浸出し、ろ過することで、硫化鉛を除去し、得られたろ液に亜鉛粉末を添加する。これにより、ゲルマニウム及び銅が亜鉛と置換されるため、カドミウムを溶液に残したまま、ゲルマニウム及び銅を凝集させて、沈殿させる。
更に、得られた沈殿物に硫酸と亜鉛粉末を加えることで、銅を溶液に残し、ゲルマニウムを凝集させて、沈殿させる。この沈殿物をろ過して回収した後、該ろ過物を乾燥及び加熱させ、得られたものを前記ゲルマニウム塩化物回収工程の原料とする。以上は、前記Ｅａｇｌｅ−Ｐｉｔｃｈｅｒ法における通常の工程である。
In the Eagle-Pitcher method, first, zinc concentrate containing germanium (the content ratio of germanium is usually 0.01% by mass to 0.015% by mass) is oxidized and roasted. Mix salt and coal and sinter. The sintered residue becomes a raw material for zinc smelting, but volatiles (smoke ash) generated during sintering include germanium, cadmium, copper, lead, and the like.
Next, the volatiles are leached with sulfuric acid and filtered to remove lead sulfide, and zinc powder is added to the obtained filtrate. Thereby, since germanium and copper are substituted with zinc, germanium and copper are aggregated and precipitated while cadmium remains in the solution.
Furthermore, by adding sulfuric acid and zinc powder to the obtained precipitate, copper is left in the solution, and germanium is aggregated and precipitated. After the precipitate is collected by filtration, the filtrate is dried and heated, and the resultant is used as a raw material for the germanium chloride collecting step. The above is a normal process in the Eagle-Pitcher method.
本発明のゲルマニウムを回収する方法では、前記ゲルマニウム塩化物回収工程において、前記原料に塩酸を混合して混合液を調整し、該混合液に更に過酸化水素を添加して、これを蒸留装置により蒸留することで、塩化物としてゲルマニウム（四塩化ゲルマニウム）を回収する。
前記ゲルマニウム塩化物回収工程において、塩酸と過酸化水素とを併用することにより、ゲルマニウムの回収率を大幅に改善することができる。塩酸と過酸化水素の併用は、特に添加順序に制限はなく、また、これらの酸の効果を促進するのであれば別の薬剤を更に添加してもよい。
In the method for recovering germanium according to the present invention, in the germanium chloride recovery step, hydrochloric acid is mixed with the raw material to prepare a mixed solution, hydrogen peroxide is further added to the mixed solution, and this is added to a distillation apparatus. By distillation, germanium (germanium tetrachloride) is recovered as chloride.
In the germanium chloride recovery step, the recovery rate of germanium can be greatly improved by using hydrochloric acid and hydrogen peroxide in combination. In the combined use of hydrochloric acid and hydrogen peroxide, the order of addition is not particularly limited, and another agent may be further added as long as the effect of these acids is promoted.
前記混合液の塩酸濃度（規定度）としては、四塩化ゲルマニウムの溶解性の安定の点で、６Ｎ〜１２Ｎが好ましく、８Ｎ〜１０Ｎがより好ましい。また、前記混合液において塩酸の量としては、四塩化ゲルマニウムの溶解性の点で、ゲルマニウム(４価)に対して１モル当量〜１００モル当量が好ましく、４モル当量〜１０モル当量がより好ましい。
前記過酸化水素の添加量としては、四塩化ゲルマニウムの回収率の点で、ゲルマニウムに対して２モル当量以上が好ましく、２モル当量〜３モル当量がより好ましい。前記添加量が、ゲルマニウムに対して２モル当量未満であると、四塩化ゲルマニウムの回収率が低下することがある。
The hydrochloric acid concentration (normality) of the mixed solution is preferably 6N to 12N, more preferably 8N to 10N in terms of stable solubility of germanium tetrachloride. The amount of hydrochloric acid in the mixed solution is preferably 1 to 100 molar equivalents, more preferably 4 to 10 molar equivalents with respect to germanium (tetravalent), from the viewpoint of germanium tetrachloride solubility. .
The addition amount of the hydrogen peroxide is preferably 2 molar equivalents or more, more preferably 2 molar equivalents to 3 molar equivalents with respect to germanium in terms of the recovery rate of germanium tetrachloride. When the addition amount is less than 2 molar equivalents with respect to germanium, the recovery rate of germanium tetrachloride may be reduced.
前記蒸留装置としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、エバポレーター、ジムロート冷却器、アリーン冷却器などを使用することができる。該蒸留装置の市販品としては、例えば、石英ガラス製の蒸留器が挙げられる。
前記蒸留としては、精留効率の良さの点で、蒸留温度が９５℃〜１２０℃であり、蒸留時間が０．５時間〜１２時間が好ましく、蒸留温度が１００℃〜１２０℃であり、蒸留時間が１時間〜６時間がより好ましい。
There is no restriction | limiting in particular as said distillation apparatus, According to the objective, it can select suitably, For example, an evaporator, a Dimroth cooler, an Allen cooler etc. can be used. As a commercial item of this distillation apparatus, the distiller made from quartz glass is mentioned, for example.
As the distillation, the distillation temperature is 95 ° C. to 120 ° C., the distillation time is preferably 0.5 hours to 12 hours, the distillation temperature is 100 ° C. to 120 ° C. The time is more preferably 1 to 6 hours.
前記Ｅａｇｌｅ−Ｐｉｔｃｈｅｒ法における通常の工程であるゲルマニウム酸化物回収工程では、前記回収された四塩化ゲルマニウムに水を加えて、加水分解することにより、酸化物としてゲルマニウム（二酸化ゲルマニウム）を回収する。
前記加水分解において、四塩化ゲルマニウムに対する水の量は、反応を十分に行わせる観点から、２倍質量〜１００倍質量が好ましく、２倍質量〜５倍質量がより好ましい。また、前記加水分解は、１０℃〜３０℃で行うことが好ましい。
In the germanium oxide recovery step, which is a normal step in the Eagle-Pitcher method, water is added to the recovered germanium tetrachloride and hydrolyzed to recover germanium (germanium dioxide) as an oxide.
In the hydrolysis, the amount of water with respect to germanium tetrachloride is preferably 2 to 100 times, more preferably 2 to 5 times, from the viewpoint of sufficiently performing the reaction. Moreover, it is preferable to perform the said hydrolysis at 10 to 30 degreeC.
以下、本発明の実施例を説明するが、本発明は、これらの実施例に何ら限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
（実施例１）
＜原料＞
前記ゲルマニウムを回収する原料としては、海外輸入により入手した亜鉛精鉱（該亜鉛精鉱に含まれるゲルマニウムの含有量は０．０１質量％〜０．０１５質量％程度）を酸化焙焼し、酸により亜鉛を浸出させた後の残渣に処理を行い、得られたものを用いた。これは、従来技術と同様に、該残渣を酸浸出及び中和処理することによりカドミニウム等を除去した後、亜鉛粉末によりゲルマニウムを凝集沈殿させ、回収した沈殿残渣を塩酸浸出してできた金属ゲルマニウム含有物である。
前記原料の成分を表１に示す。前記成分は、乾燥時の質量％で示す。なお、前記成分のそれぞれの含有量はＩＣＰ発光分光分析を用いて測定した。
Example 1
<Raw material>
As the raw material for recovering germanium, zinc concentrate obtained by importing overseas (germanium content in the zinc concentrate is about 0.01% to 0.015% by mass) is oxidized and roasted, and then acidified. The residue after leaching zinc was processed by using the obtained one. This is the same as in the prior art, in which the residue is acid leached and neutralized to remove cadmium and the like, then coagulate and precipitate germanium with zinc powder, and the recovered precipitation residue is leached with hydrochloric acid. Inclusions.
The ingredients of the raw material are shown in Table 1. The said component is shown by the mass% at the time of drying. In addition, each content of the said component was measured using ICP emission spectral analysis.
＜塩酸浸出及び蒸留条件＞
前記原料２９０ｇ(乾燥重量)、水１００ｍＬ、３５質量％塩酸４５０ｍＬの混合溶液(塩酸規定度９．８Ｎ)を調製し、該混合液の温度を７０℃まで上昇させた。その後、３０質量％過酸化水素水を少量ずつ添加し、合計１００ｍＬ（ゲルマニウムに対して２．１モル当量）添加し、蒸留温度１０５度（液温）で３０分間保持し、合計２時間の蒸留をした。なお、過酸化水素水の添加量（ゲルマニウムに対するモル当量）は、下記化学式を前提とし、ゲルマニウム１ｍｏｌに対し、２ｍｏｌの過酸化水素を使用するものと想定した。
〔化１〕
Ｇｅ＋２Ｈ２Ｏ２→ＧｅＯ２＋２Ｈ２Ｏ
<Hydrochloric acid leaching and distillation conditions>
A mixed solution (hydrochloric acid normality 9.8 N) of 290 g (dry weight) of the raw material, 100 mL of water and 450 mL of 35 mass% hydrochloric acid was prepared, and the temperature of the mixed solution was raised to 70 ° C. Thereafter, 30% by mass of hydrogen peroxide solution was added little by little, and a total of 100 mL (2.1 molar equivalents with respect to germanium) was added and kept at a distillation temperature of 105 ° C. (liquid temperature) for 30 minutes. Did. The amount of hydrogen peroxide added (molar equivalent with respect to germanium) was based on the following chemical formula, and it was assumed that 2 mol of hydrogen peroxide was used per 1 mol of germanium.
[Chemical formula 1]
Ge + 2H 2 O 2 → GeO 2 + 2H 2 O
前記蒸留に用いた装置としては、容積が１，０００ｍＬであり、蒸留経路に冷却管を備えた市販の蒸留器（ガラス製ジムロート冷却器）を用いた。該蒸留器により蒸発した四塩化ゲルマニウムを冷却し、捕集容器にて回収した。これにより得られた四塩化ゲルマニウムの回収率を表２に示す。なお、四塩化ゲルマニウムの回収率は、下記数式により求めた。
〔式１〕
四塩化ゲルマニウムの回収率（質量％）＝回収後の四塩化ゲルマニウム溶液中のゲルマニウム質量／原料中のゲルマニウム質量×１００
As the apparatus used for the distillation, a commercially available distiller (glass Dimroth cooler) having a volume of 1,000 mL and equipped with a cooling pipe in the distillation path was used. The germanium tetrachloride evaporated by the distiller was cooled and recovered in a collection container. Table 2 shows the recovery rate of germanium tetrachloride thus obtained. In addition, the recovery rate of germanium tetrachloride was calculated | required by the following numerical formula.
[Formula 1]
Recovery rate (mass%) of germanium tetrachloride = mass of germanium in germanium tetrachloride solution after recovery / mass of germanium in raw material × 100
なお、本塩酸浸出においては、新たに化合された不溶解残物が発生することはなく、また、前記原料を前記塩酸に溶解させた際に容器内壁へゲルマニウムが飛散して付着することもなかった。したがって、本塩酸浸出においては、ゲルマニウムが浸出液に確実に溶解し、前記原料中に溶残りとしてある以外のロスが全くないと考えられる。 In this hydrochloric acid leaching, a newly combined insoluble residue is not generated, and germanium is not scattered and attached to the inner wall of the container when the raw material is dissolved in the hydrochloric acid. It was. Therefore, in the hydrochloric acid leaching, germanium is surely dissolved in the leaching solution, and it is considered that there is no loss other than that which remains as a dissolved residue in the raw material.
＜加水分解＞
前記回収された四塩化ゲルマニウムを水１，０００ｍＬに加え、撹拌して加水分解し、二酸化ゲルマニウムを精製した。該二酸化ゲルマニウムの品位を表２に示す。
<Hydrolysis>
The recovered germanium tetrachloride was added to 1,000 mL of water, stirred and hydrolyzed to purify germanium dioxide. Table 2 shows the quality of the germanium dioxide.
（実施例２）
実施例１において、過酸化水素水の添加量を１００ｍＬ（ゲルマニウムに対して２．１モル当量）から９１ｍＬ（ゲルマニウムに対して１．９モル当量）に変更した以外は、実施例１と同じ方法を用いて、ゲルマニウムの回収を行った。結果を表２に示す。
(Example 2)
In Example 1, the same method as in Example 1 except that the amount of hydrogen peroxide added was changed from 100 mL (2.1 molar equivalents to germanium) to 91 mL (1.9 molar equivalents to germanium). Was used to recover germanium. The results are shown in Table 2.
（比較例１）
実施例１において、過酸化水素水を添加しなかった以外は、前記実施例１と同じ方法を用いて、ゲルマニウムの回収を行った。結果を表２に示す。
(Comparative Example 1)
In Example 1, germanium was recovered using the same method as in Example 1 except that no hydrogen peroxide solution was added. The results are shown in Table 2.
＜蒸留結果＞
実施例１では、前記蒸留により、四塩化ゲルマニウムと揮発した塩酸溶液を１００ｍＬ回収でき、うち四塩化ゲルマニウム溶液としては４５ｍＬ得た。前記蒸留により回収されたゲルマニウムの重量は、四塩化ゲルマニウム量で８４ｇ、ゲルマニウム量で２９ｇであった。前記四塩化ゲルマニウムとしての回収率は、８２％であった。
また、前記四塩化ゲルマニウム溶液の加水分解により得られた二酸化ゲルマニウムは、９９．９質量％以上の品位であり、忌避される不純物である砒素は確実に除去されていた。
実施例２では、前記蒸留により回収されたゲルマニウムの重量は、四塩化ゲルマニウム量で７１ｇ、ゲルマニウム量で２４ｇであった。前記四塩化ゲルマニウムとしての回収率は、７５％であり、前記二酸化ゲルマニウムは、９９．９質量％以上の品位であった。
他方、塩酸に過酸化水素水を添加しない従来の方法を用いた比較例１では、四塩化ゲルマニウム量で１０ｇ、ゲルマニウム量で３ｇであった。前記四塩化ゲルマニウムとしての回収率は、１０％であり、四塩化ゲルマニウムを殆ど回収できなかった。
<Distillation results>
In Example 1, 100 mL of germanium tetrachloride and volatilized hydrochloric acid solution could be recovered by the distillation, and 45 mL of germanium tetrachloride solution was obtained. The weight of germanium recovered by the distillation was 84 g in terms of germanium tetrachloride and 29 g in terms of germanium. The recovery rate as germanium tetrachloride was 82%.
Further, germanium dioxide obtained by hydrolysis of the germanium tetrachloride solution has a quality of 99.9% by mass or more, and arsenic, which is an impurity to be avoided, has been reliably removed.
In Example 2, the weight of germanium recovered by the distillation was 71 g in terms of germanium tetrachloride and 24 g in terms of germanium. The recovery rate as germanium tetrachloride was 75%, and the germanium dioxide had a quality of 99.9% by mass or more.
On the other hand, in Comparative Example 1 using a conventional method in which hydrogen peroxide was not added to hydrochloric acid, the amount of germanium tetrachloride was 10 g and the amount of germanium was 3 g. The recovery rate as germanium tetrachloride was 10%, and germanium tetrachloride was hardly recovered.
前記実施例１の結果から、本発明の亜鉛精鉱からゲルマニウムを回収する方法は、高品位のゲルマニウムを高い回収率で、効率よく且つ安価に回収できることがわかった。 From the results of Example 1, it was found that the method for recovering germanium from the zinc concentrate of the present invention can recover high-grade germanium efficiently and inexpensively with a high recovery rate.
本発明の亜鉛精鉱からゲルマニウムを回収する方法は、高品位のゲルマニウムを、高い回収率で、効率よく且つ安価に回収できるので、光ファイバーや太陽電池等のいわゆるハイテク産業用の材料開発、ポリエチレンテレフタレート樹脂の重合促進触媒、ダイオード及びトランジスター等の半導体素子、相変化磁気ディスク材料等のエレクトロニクス材料、触媒、その他の加工用原料などに使用可能なゲルマニウムを回収する方法として好適に用いられる。 The method of recovering germanium from the zinc concentrate according to the present invention can recover high-quality germanium at a high recovery rate efficiently and inexpensively, so that development of materials for so-called high-tech industries such as optical fibers and solar cells, polyethylene terephthalate It is suitably used as a method for recovering germanium that can be used as a resin polymerization promotion catalyst, semiconductor elements such as diodes and transistors, electronic materials such as phase change magnetic disk materials, catalysts, and other processing raw materials.
Claims (4)
The method for recovering germanium according to any one of claims 1 to 3, wherein the intermediate is an intermediate product in zinc smelting.
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| JP2014162648A (en) * | 2013-02-21 | 2014-09-08 | Dowa Metals & Mining Co Ltd | Method for producing germanium oxide |
| CN104073636A (en) * | 2014-06-23 | 2014-10-01 | 贵州顶效开发区宏达金属综合回收有限公司 | Method for extracting germanium concentrate from germanium-containing reverse extraction alkaline liquor |
| JP2015048525A (en) * | 2013-09-04 | 2015-03-16 | Ｄｏｗａメタルマイン株式会社 | Recovery method of germanium |
| JP2015105226A (en) * | 2013-12-03 | 2015-06-08 | 三菱マテリアル株式会社 | Method for producing germanium oxide |
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