JP4788998B2 - Method for recovering gold from etching waste liquid - Google Patents
Method for recovering gold from etching waste liquid Download PDFInfo
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- JP4788998B2 JP4788998B2 JP2005377319A JP2005377319A JP4788998B2 JP 4788998 B2 JP4788998 B2 JP 4788998B2 JP 2005377319 A JP2005377319 A JP 2005377319A JP 2005377319 A JP2005377319 A JP 2005377319A JP 4788998 B2 JP4788998 B2 JP 4788998B2
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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
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Description
本発明は使用済みのエッチング廃液から、金を回収する方法に関するものであり、更に詳しく述べるならば、金のエッチングに使用した後のよう素系エッチング液の廃液から金を回収するに際し、亜硫酸塩により、よう素を還元した後、金属粉を添加し残りの金を還元、回収することを特徴とするエッチング廃液からの金の回収方法に関するものである。 The present invention relates to a method for recovering gold from spent etching waste liquid. More specifically, the present invention relates to a process for recovering gold from an iodine-based etchant waste liquid after use in gold etching. Thus, after reducing iodine, a metal powder is added, and the remaining gold is reduced and recovered.
電子工業分野では例えば半導体基板の金薄膜の微細加工に、扱いやすさ、エッチング速度の制御性が良いこと等の理由から、よう素系のエッチング液が用いられている。
使用済みのエッチング廃液は高価な金を含むため、各種の還元剤による化学還元、金属粉による置換析出、あるいは電解採取法等により金を析出して回収している。
Since the used etching waste liquid contains expensive gold, gold is deposited and recovered by chemical reduction with various reducing agents, displacement deposition with metal powder, or electrolytic collection.
上記の金回収方法で電解採取法は直流電源や電解槽といった高価な設備を必要とする。 In the gold recovery method described above, the electrolytic collection method requires expensive equipment such as a DC power source and an electrolytic cell.
また、金属粉による置換析出では、例えば亜鉛粉では金との置換反応の他、エッチング廃液に含まれるよう素との反応が優先して起きるため高価な亜鉛粉を多量に消費する上、処理後液に亜鉛が多量に含まれるため排水処理にも労力、費用を必要とする。 In addition, in substitution deposition with metal powder, for example, in zinc powder, in addition to the substitution reaction with gold, the reaction with iodine contained in the etching waste liquid is preferentially caused, so a large amount of expensive zinc powder is consumed and after treatment Since the liquid contains a large amount of zinc, drainage treatment requires labor and cost.
還元剤による化学的還元では、金はよう素と安定な錯体を生成するため、エッチング廃液中の金の還元、析出が不充分で回収率が良くない。 In chemical reduction with a reducing agent, gold forms a stable complex with iodine, so that the reduction and precipitation of gold in the etching waste liquid is insufficient and the recovery rate is not good.
本発明は、上記問題を解決し、簡単な操作で、経済的に効率よく、エッチング廃液中の金を回収する方法を提供しようとするものである。 The present invention is intended to solve the above problems and provide a method for recovering gold in an etching waste liquid with simple operation and economical efficiency.
以下本発明を示す。
（１）金のエッチングに使用した後のよう素系エッチング液の廃液に亜硫酸塩溶液を添加し、よう素を還元した後、
金属粉を添加し廃液中の残りの金を還元し、固液分離するエッチング廃液からの金の回収方法。
The present invention is shown below.
(1) After adding a sulfite solution to the waste liquid of iodine-based etching solution after being used for gold etching, and reducing iodine,
A method for recovering gold from an etching waste liquid in which metal powder is added to reduce the remaining gold in the waste liquid, and solid-liquid separation is performed.
（２）上記（１）記載の亜硫酸塩溶液の添加における終点を、エッチング廃液中のよう素の濃褐色が消失するまでとするエッチング廃液からの金の回収方法。 (2) A method for recovering gold from the etching waste liquid, wherein the end point in the addition of the sulfite solution according to the above (1) is until the dark brown of iodine in the etching waste liquid disappears.
本発明によれば、特別な設備を必要とせずに、簡単な操作で、経済的に効率よく、金のエッチングに使用した後のよう素系エッチング廃液から金を回収することができる。 According to the present invention, gold can be recovered from iodine-based etching waste liquid after being used for gold etching with simple operation and economical efficiency without requiring special equipment.
金のエッチング液にはシアン系、王水系、よう素系等があるが、電子工業分野では扱いやすさ、エッチング速度の制御性を良好にする等の理由から、半導体基板の金薄膜の微細加工等に用いられている。よう素系エッチング液はよう素とよう化アルカリ（又はアンモニウム）といったよう化物の溶液で、エッチング特性向上のため有機添加剤が添加されている。
本発明の処理の対象は金のエッチングに使用した後のよう素系エッチング廃液で、特に限定はされないが廃液１リットル当り１００ｍｇ〜２０００ｍｇ程度の金を含んでいる。
Gold etching solutions include cyan, aqua regia, iodine, etc. In the electronics industry, fine processing of gold thin films on semiconductor substrates for reasons such as ease of handling and better control of etching rate. Etc. are used. The iodine-based etching solution is a solution of iodide such as iodine and alkali iodide (or ammonium), and an organic additive is added to improve etching characteristics.
The object of the treatment of the present invention is an iodine-based etching waste liquid after being used for gold etching, which is not particularly limited, but contains about 100 mg to 2000 mg of gold per liter of the waste liquid.
金は還元性が強いため、通常各種の還元剤で液中の金を容易に還元、析出して回収できるが、表１に示す標準酸化還元電位より、金のよう化物錯体は他のハロゲン化物錯体より標準酸化還元電位が低く、安定で還元しにくいことがわかる。
また、還元力の強い金属粉を用いたときは、金濃度を充分に低下させることが可能であるが、金の還元の他、よう素の還元にも高価な金属粉が必要であり、金回収後の廃液も多量の金属成分が溶解するため排水処理に労力、費用がかかる。 In addition, when a metal powder having a strong reducing power is used, the gold concentration can be sufficiently reduced. However, in addition to the reduction of gold, an expensive metal powder is required for the reduction of iodine. Since a large amount of metal components dissolves in the waste liquid after recovery, the wastewater treatment takes labor and cost.
そこで種々検討の結果、よう素系エッチング廃液から金を回収するには、まず亜硫酸塩溶液を添加してよう素を還元した後、金属粉を添加して廃液中の残りの金を還元、析出し、固液分離するのが良いとの結論に達した。 As a result of various studies, in order to recover gold from iodine-based etching waste liquid, first, sulfite solution was added to reduce iodine, then metal powder was added to reduce and deposit the remaining gold in the waste liquid. The conclusion was reached that solid-liquid separation is better.
エッチング廃液に亜硫酸塩溶液を添加すると、次式によりまずよう素の還元が起こる。亜硫酸塩溶液の添加量は廃液中のよう素の濃褐色が消失するので容易に判断できる。
続いてこれに金属粉を添加する。金属粉としては亜鉛粉、アルミニウム粉、鉄粉、マグネシウム粉等が使えるが、銅粉はよう素と難溶性化合物を生成し沈殿するので好ましくない。亜鉛末を使用したときの金還元の反応式を次式に示す。
還元、析出した金は固液分離を行い回収する。還元後液は中和処理後廃棄するが、よう素回収のために使用することも可能である。 The reduced and precipitated gold is recovered by solid-liquid separation. The post-reduction solution is discarded after neutralization, but can also be used for iodine recovery.
以下、実施例により更に詳しく本発明を説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
（実施例）
試験液は金のエッチングに使用した後のよう素系エッチング廃液で分析の結果、廃液１リットル当りヨウ素を１１０ｇ、よう化物をＫＩで２６０ｇ、金を２１００ｍｇ含んでいた。特に規程はされないが、試験ではこのエッチング廃液を２倍に希釈して使用した。
エッチング廃液５０ｍｌをビーカーにとり２倍に希釈した後、撹拌しながら０．５M亜硫酸ナトリウム溶液を少しずつ添加した。添加量が４８ｍｌになったところでエッチング廃液の色が濃褐色からほぼ透明になったので、添加をやめ、ろ液の分析を行ったところ金濃度は６５０ｍｇ／ｌであった。続いて、亜鉛粉５０ｍｇ（金に対して約２．８当量）を添加し１５分間撹拌を行ったところ金の析出がみられ、ろ液の分析を行ったところ金濃度は１．５ｍｇ／ｌに低下していた。さらに亜鉛粉２５ｍｇ（金に対して約１．４当量）を添加し１５分間撹拌を行い、ろ液の分析を行ったところ金濃度は１ｍｇ／ｌ以下になった。以上のように、亜硫酸ナトリウム溶液でよう素を還元した後、亜鉛粉を添加することにより、容易にかつ効率的にエッチング廃液中の金を回収することが可能である。
(Example)
The test solution was an iodine-based etching waste solution after being used for etching gold, and as a result of analysis, it contained 110 g of iodine, 260 g of iodide and 2100 mg of gold per liter of the waste solution. Although there is no particular rule, in the test, this etching waste solution was used after being diluted twice.
50 ml of the etching waste solution was placed in a beaker and diluted twice, and then 0.5 M sodium sulfite solution was added little by little while stirring. When the added amount reached 48 ml, the color of the etching waste liquid became almost transparent from dark brown. When the addition was stopped and the filtrate was analyzed, the gold concentration was 650 mg / l. Subsequently, 50 mg of zinc powder (about 2.8 equivalents relative to gold) was added and stirred for 15 minutes. As a result, precipitation of gold was observed, and analysis of the filtrate revealed that the gold concentration was 1.5 mg / l. It had fallen to. Further, 25 mg of zinc powder (about 1.4 equivalents relative to gold) was added and stirred for 15 minutes, and analysis of the filtrate revealed that the gold concentration was 1 mg / l or less. As described above, after reducing iodine with a sodium sulfite solution, it is possible to easily and efficiently recover gold in the etching waste liquid by adding zinc powder.
（比較例１）
実施例と同じエッチング廃液５０ｍｌをビーカーにとり２倍に希釈した後、撹拌しながら０．５M亜硫酸ナトリウム溶液を少しずつ添加した。添加量が４５ｍｌになったところでエッチング廃液の色が濃褐色からほぼ透明になったので、添加をやめ、ろ液の分析を行ったところ金濃度は６６０ｍｇ／ｌであった。このまま１５分間撹拌を続けたところ金の析出がみられたので、再度ろ液の分析を行ったところ金濃度は３８０ｍｇ／ｌであった。さらに０．５M亜硫酸ナトリウム溶液１０ｍｌを徐々に添加し４５分間撹拌した後、ろ液の分析を行ったところ金濃度は４１ｍｇ／ｌであった。以上のように亜硫酸ナトリウムだけではエッチング廃液中の金濃度を充分に低下させることはできなかった。
(Comparative Example 1)
After 50 ml of the same etching waste solution as in the example was placed in a beaker and diluted 2 times, 0.5 M sodium sulfite solution was added little by little while stirring. When the addition amount reached 45 ml, the color of the etching waste liquid became almost transparent from dark brown, and when the addition was stopped and the filtrate was analyzed, the gold concentration was 660 mg / l. When stirring was continued for 15 minutes, gold was precipitated, and the filtrate was analyzed again. The gold concentration was 380 mg / l. Further, 10 ml of 0.5 M sodium sulfite solution was gradually added and stirred for 45 minutes, and then the filtrate was analyzed. As a result, the gold concentration was 41 mg / l. As described above, it was not possible to sufficiently reduce the gold concentration in the etching waste liquid only with sodium sulfite.
（比較例２）
実施例と同じエッチング廃液５０ｍｌをビーカーにとり２倍に希釈した後、撹拌しながら亜鉛末を少量ずつ添加した。このとき、亜鉛末の添加に伴い液のｐＨが上昇し水酸化亜鉛が生成するため、希塩酸を加えてｐＨ１〜３に調整するようにした。亜鉛末１５００ｍｇを添加したところでエッチング廃液の色が薄くなり始めたので、ろ液の分析を行ったところ金濃度は８１０ｍｇ／ｌであった。この間、ｐＨ調整に希塩酸（１：９）を２０ｍｌ添加した。さらに亜鉛末６００ｍｇ（合計２１００ｍｇ）を添加したところで液がほぼ透明になったので、１５分間撹拌を続けた後、ろ液の分析を行ったところ金濃度は１ｍｇ／ｌ以下であった。以上のように亜鉛末を使うとエッチング廃液中の金濃度を充分に低下させることができ金を回収できるが、高価な亜鉛末の使用量が多く、還元後液に亜鉛が溶解するため排水処理に労力、費用を要することになり好ましい方法とはいえない。
(Comparative Example 2)
50 ml of the same etching waste solution as in the example was placed in a beaker and diluted twice, and then zinc dust was added little by little while stirring. At this time, since the pH of the liquid increased with the addition of zinc powder and zinc hydroxide was produced, diluted hydrochloric acid was added to adjust the pH to 1-3. When 1500 mg of zinc powder was added, the color of the etching waste liquid began to lighten. When the filtrate was analyzed, the gold concentration was 810 mg / l. During this time, 20 ml of dilute hydrochloric acid (1: 9) was added for pH adjustment. Further, when 600 mg of zinc powder (2100 mg in total) was added, the liquid became almost transparent. After stirring for 15 minutes, the filtrate was analyzed, and the gold concentration was 1 mg / l or less. As mentioned above, the use of zinc dust can sufficiently reduce the gold concentration in the etching waste liquid, but it can recover the gold. However, the amount of expensive zinc dust used is large, and the zinc is dissolved in the solution after reduction, so the wastewater treatment. However, this method is not preferable because it requires labor and cost.
Claims (2)
金属粉を添加し廃液中の残りの金を還元し、固液分離することを特徴とするエッチング廃液からの金の回収方法。 After adding a sulfite solution to the waste liquid of iodine-based etchant after being used for gold etching and reducing iodine,
A method for recovering gold from an etching waste liquid, comprising adding metal powder, reducing the remaining gold in the waste liquid, and solid-liquid separation.
A method for recovering gold from an etching waste solution, wherein the end point in the addition of the sulfite solution according to claim 1 is until the dark brown color of iodine in the etching waste solution disappears.
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| US3957505A (en) * | 1974-08-05 | 1976-05-18 | Bayside Refining And Chemical Company | Gold reclamation process |
| AU577173B2 (en) * | 1985-12-06 | 1988-09-15 | In-Situ Inc. | An electrolytic process for the simultaneous deposition of gold and replenishment of elemental iodine |
| JP2619893B2 (en) * | 1988-01-12 | 1997-06-11 | 田中貴金属工業株式会社 | Precious metal recovery method |
| JP3975901B2 (en) * | 2002-12-09 | 2007-09-12 | 住友金属鉱山株式会社 | Iridium separation and purification method |
| JP4524593B2 (en) * | 2003-10-27 | 2010-08-18 | 三菱化学株式会社 | Noble metal solution and method for dissolving and recovering noble metal using this solution |
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