JP4699105B2 - Gold recovery method and apparatus - Google Patents

Gold recovery method and apparatus Download PDF

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JP4699105B2
JP4699105B2 JP2005184904A JP2005184904A JP4699105B2 JP 4699105 B2 JP4699105 B2 JP 4699105B2 JP 2005184904 A JP2005184904 A JP 2005184904A JP 2005184904 A JP2005184904 A JP 2005184904A JP 4699105 B2 JP4699105 B2 JP 4699105B2
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JP2007002310A (en
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光 阿部
征樹 福島
義彦 大川
敏郎 下房
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
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    • C25C7/08—Separating of deposited metals from the cathode
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Description

本発明は、水溶性硫黄含有金化合物を含む水性廃液から金を回収する方法、および該方法で金を回収するための装置に関するものである。   The present invention relates to a method for recovering gold from an aqueous waste liquid containing a water-soluble sulfur-containing gold compound, and an apparatus for recovering gold by the method.

金メッキは、装身具等の装飾用としての用途以外にも、優れた耐食性や耐摩耗性、適度な硬さ等を生かして、例えばプリント配線板上に形成された銀や銅からなる導体パターンのコーティング膜として利用したり、各種電子機器の接点部分に利用されている。   Gold plating is not only used for decorative purposes such as jewelry, but also has excellent corrosion resistance, wear resistance, moderate hardness, etc., for example, coating a conductive pattern made of silver or copper formed on a printed wiring board It is used as a film or as a contact part of various electronic devices.

金メッキ法には、電解金メッキ法と無電解金メッキ法があり、これらの金メッキ法で用いられる金メッキ液（金メッキ浴）としては、シアン系の金メッキ液とノンシアン系の金メッキ液が知られている。ノンシアン系の金メッキ液としては、例えば水溶性硫黄含有金化合物（例えば、チオ硫酸金化合物や亜硫酸金化合物など）を含む金メッキ液や、塩化金化合物を含む金メッキ液が挙げられる。   The gold plating method includes an electrolytic gold plating method and an electroless gold plating method. As gold plating solutions (gold plating baths) used in these gold plating methods, cyan gold plating solutions and non-cyan gold plating solutions are known. Examples of the non-cyanide gold plating solution include a gold plating solution containing a water-soluble sulfur-containing gold compound (for example, a gold thiosulfate compound or a gold sulfite compound) or a gold plating solution containing a gold chloride compound.

ところで金メッキ後に排出される水性のメッキ廃液や、洗浄液には、金メッキ液程ではないが、相当量の金が含まれており、例えば、金メッキ液には一般的に２０〜３０ｇ／Ｌ程度の金が含まれているのに対し、金メッキ後の水性廃液には１０〜１５ｇ／Ｌ程度の金が含まれている。金は非常に高価な金属であるから、こうした水性廃液に残留している金は効率よく回収する必要がある。   By the way, the aqueous plating waste liquid and the cleaning liquid discharged after the gold plating contain a considerable amount of gold, although not as much as the gold plating liquid. For example, the gold plating liquid generally has a gold content of about 20 to 30 g / L. In contrast, the aqueous waste liquid after gold plating contains about 10 to 15 g / L of gold. Since gold is a very expensive metal, it is necessary to efficiently recover the gold remaining in such aqueous waste liquid.

金を含む水性廃液から金を回収する方法としては、例えば化学還元法や電気分解法が知られている。化学還元法は、水性廃液に還元剤として水素化ホウ素ナトリウムや亜硫酸ソーダ、ヒドラジン等を添加し、金を還元・沈殿させて回収する方法である。ところが化学還元法には、還元剤の使用に伴うコストの問題があるほか、水性廃液に含まれる金以外の金属成分も同時に還元されるため、金を選択的に還元・回収できない。従って金を選択的に回収するには、化学還元法で回収された回収物を精製しなければならず、操作が煩雑である。   As a method for recovering gold from an aqueous waste liquid containing gold, for example, a chemical reduction method or an electrolysis method is known. The chemical reduction method is a method in which sodium borohydride, sodium sulfite, hydrazine or the like is added to an aqueous waste liquid as a reducing agent, and gold is reduced and precipitated to be recovered. However, the chemical reduction method has a cost problem associated with the use of a reducing agent, and metal components other than gold contained in the aqueous waste liquid are also reduced at the same time, so that gold cannot be selectively reduced and recovered. Therefore, in order to selectively recover gold, the recovered material recovered by the chemical reduction method must be purified, and the operation is complicated.

一方、電気分解法は、金を含む水性廃液を電気分解して陰極表面に金を析出させて回収する方法である。電気分解法によれば、還元電位を調整することで水性廃液から金を選択的に回収できる。ところが陰極表面に析出した金の一部が電解の途中で剥がれ落ちることがある。そして剥離脱落した金が電解槽の底に堆積すると、水性廃液の排出口や排水ポンプを閉塞することがあった。また陰極表面から剥離脱落した金が電解槽の底に散乱状態で堆積していると、回収が煩雑になる。そこで陰極表面に析出した金の剥離脱落を防止する技術として、例えば特許文献１には、金の剥離脱落の原因となる陰極（Ｔｉ電極）表面に形成された酸化膜を除去することが提案されている。ところが酸化膜を如何に除去しても金の剥離脱落を完全に防止することは難しい。そのため金の一部は電極に析出したものとして回収し、一部は電解槽の底に堆積したものとして回収しなければならなかった。   On the other hand, the electrolysis method is a method in which an aqueous waste liquid containing gold is electrolyzed to deposit gold on the cathode surface and recovered. According to the electrolysis method, gold can be selectively recovered from the aqueous waste liquid by adjusting the reduction potential. However, some of the gold deposited on the cathode surface may be peeled off during electrolysis. When the peeled and dropped gold accumulates at the bottom of the electrolytic cell, the aqueous waste liquid discharge port and the drain pump may be blocked. Further, if gold peeled off from the cathode surface is deposited in a scattered state on the bottom of the electrolytic cell, recovery becomes complicated. Therefore, as a technique for preventing gold from peeling off on the cathode surface, for example, Patent Document 1 proposes removing an oxide film formed on the surface of the cathode (Ti electrode) which causes gold peeling off. ing. However, it is difficult to completely prevent the gold from coming off even if the oxide film is removed. Therefore, some of the gold had to be collected as deposited on the electrode, and some had to be collected as deposited on the bottom of the electrolytic cell.

また上記水溶性硫黄含有金化合物（例えば、チオ硫酸金化合物や亜硫酸金化合物など）を含む水性廃液は非常に不安定であり、貯槽等に貯留している間に金が容器の壁面に自然析出することがある。また、水溶性硫黄含有金化合物を含む水性廃液を電気分解する際にも、陰極以外の陽極表面や電解槽の壁面にも金が自然析出する。そして陽極と陰極が析出し成長した金によって短絡したり、陰極と電解槽の壁面や、陽極と電解槽の壁面が短絡し、電解不能になることがあった。   In addition, aqueous waste liquids containing the above water-soluble sulfur-containing gold compounds (for example, gold thiosulfate compounds and gold sulfite compounds) are very unstable, and gold is naturally deposited on the wall of the container while it is stored in a storage tank. There are things to do. Also, when electrolyzing an aqueous waste liquid containing a water-soluble sulfur-containing gold compound, gold spontaneously deposits on the anode surface other than the cathode and on the wall of the electrolytic cell. Then, the anode and the cathode may be short-circuited by the deposited gold and the wall surface of the cathode and the electrolytic cell, or the wall surface of the anode and the electrolytic cell may be short-circuited, and the electrolysis may become impossible.

この様な理由もあって、水溶性硫黄含有金化合物を含む水性廃液からの金の回収には、化学還元法が使用されてきたのであるが、化学還元法には、上述したような問題があるため、電気分解法による効率的な金回収の開発が望まれている。
特開平１１−９２９８５号公報（特許請求の範囲、段落０００３、００１３） For these reasons, the chemical reduction method has been used for the recovery of gold from an aqueous waste solution containing a water-soluble sulfur-containing gold compound. However, the chemical reduction method has the problems described above. Therefore, the development of efficient gold recovery by electrolysis is desired.
JP-A-11-92985 (Claims, paragraphs 0003 and 0013)

本発明は、この様な状況に鑑みてなされたものであり、その目的は、水溶性硫黄含有金化合物を含む水性廃液から金を回収するにあたり、電気分解法を採用しても効率よく簡便に金を回収できる方法を提供することにある。また、本発明の他の目的は、この方法で金を回収するために用いる装置を提供することにある。   The present invention has been made in view of such a situation, and the object thereof is to efficiently and easily adopt an electrolysis method for recovering gold from an aqueous waste liquid containing a water-soluble sulfur-containing gold compound. It is to provide a method for recovering gold. Another object of the present invention is to provide an apparatus used for recovering gold by this method.

本発明者らは、前記課題を解決するために鋭意研究を重ねた結果、水性廃液を強塩基性に調整すれば水溶性硫黄含有金化合物を含んでいても液が安定化し、電気分解法によって金を効率よく回収できることを見出した。   As a result of intensive research to solve the above problems, the present inventors have stabilized the liquid even if it contains a water-soluble sulfur-containing gold compound by adjusting the aqueous waste liquid to be strongly basic, and by electrolysis. It was found that gold can be recovered efficiently.

また、従来では、陰極に金を析出させることにより金を回収していたため、陰極に析出した金の剥離を如何にして防止するかという観点から種々検討が重ねられてきた。これに対し、本発明者らは、陰極に析出した金を積極的に剥離脱落させ、金を電解槽の底部に堆積させて回収する方法を採用すれば、より簡単に回収できるのではないか、という従来とは逆の発想に基づいて検討を重ねてきた。その結果、水性廃液を強塩基性に調整すれば、水溶性硫黄含有金化合物を含む水性廃液が安定化し、電解槽壁面等への金の析出が防止されるばかりでなく、陰極に析出した金は剥がれ易くなって陰極の下方に落下すること、従って該陰極表面から剥がれ落ちた金を回収するための受け部を設けてやれば、効率よく金を回収できることを見出し、本発明を完成した。   Conventionally, since gold was collected by precipitating gold on the cathode, various studies have been repeated from the viewpoint of how to prevent peeling of gold deposited on the cathode. On the other hand, the present inventors can recover more easily by adopting a method in which the gold deposited on the cathode is positively peeled and dropped and gold is deposited on the bottom of the electrolytic cell and recovered. We have been studying it based on the idea opposite to the conventional one. As a result, if the aqueous waste liquid is adjusted to be strongly basic, the aqueous waste liquid containing the water-soluble sulfur-containing gold compound is stabilized, and not only gold is prevented from depositing on the wall of the electrolytic cell, but also gold deposited on the cathode. It has been found that gold can be efficiently recovered if it is easily peeled off and falls below the cathode, and therefore a receiving portion for recovering gold that has peeled off from the cathode surface can be provided.

即ち、本発明に係る金の回収方法は、水溶性硫黄含有金化合物を含む水性廃液から金を回収するにあたり、前記水性廃液を強塩基性に調整した後、該水性廃液を電気分解することにより陰極表面に析出する金の全部または一部を下方へ落下させて回収することに要旨を有するものである。前記水性廃液としては、アルカリ金属の水酸化物によって強塩基性に調整された液を使用することが好ましい。   That is, in the gold recovery method according to the present invention, in recovering gold from an aqueous waste liquid containing a water-soluble sulfur-containing gold compound, after adjusting the aqueous waste liquid to be strongly basic, the aqueous waste liquid is electrolyzed. The gist is that all or part of the gold deposited on the cathode surface is dropped and recovered. As the aqueous waste liquid, it is preferable to use a liquid adjusted to be strongly basic with an alkali metal hydroxide.

本発明に係る金の回収装置は、上記水性廃液を強塩基性に調整する調整手段、電解槽、該電解槽内に設けられた少なくとも１対の電極（即ち、陽極と陰極）、および前記陰極の下方に陰極表面から剥がれ落ちた金を回収するための受け部を有すると共に、前記受け部には堆積した金を前記電解槽の外へ取り出すための取り出し口を備えており、且つ前記電解槽の下方は、前記受け部に向かって下り勾配の傾斜面で構成されている点に要旨を有するものである。前記受け部の底面は、前記取り出し口に向かって下り勾配に形成されていることが好ましい。また、前記受け部には、金を回収するための受け器を設けておき、該受け器は前記回収装置に対し出し入れ可能に構成しておくのがよい。更に、前記陰極表面に析出した金を掻き落とす機構を備えることも好ましい構成である。   The gold recovery apparatus according to the present invention includes an adjusting means for adjusting the aqueous waste liquid to be strongly basic, an electrolytic cell, at least one pair of electrodes (that is, an anode and a cathode) provided in the electrolytic cell, and the cathode And a receiving portion for collecting gold peeled off from the surface of the cathode, the receiving portion having a takeout port for taking out the deposited gold out of the electrolytic cell, and the electrolytic cell The lower part of the above has a gist in that it is constituted by an inclined surface having a downward slope toward the receiving part. It is preferable that the bottom surface of the receiving portion is formed with a downward slope toward the take-out port. In addition, it is preferable that the receiving portion is provided with a receiver for collecting gold, and the receiver is configured to be able to be taken in and out of the collecting device. Furthermore, it is also preferable to provide a mechanism for scraping off gold deposited on the cathode surface.

本発明の金の回収方法によれば、水性廃液を強塩基性に調整しているため水溶性硫黄含有金化合物を含む水性廃液が安定化し、貯槽や電解槽等の壁面などに金が析出するのを防止できる。従って金の回収に電気分解法を採用することが可能となる。このとき金は陰極表面に析出し、析出した金は容易に剥離脱落する。従って本発明の金の回収装置では、陰極の下方に陰極表面から剥がれ落ちた金を回収するための受け部を設けることによって、効率よく金を回収できる。   According to the gold recovery method of the present invention, since the aqueous waste liquid is adjusted to be strongly basic, the aqueous waste liquid containing the water-soluble sulfur-containing gold compound is stabilized, and gold is deposited on the wall surface of a storage tank or an electrolytic tank. Can be prevented. Therefore, it is possible to employ an electrolysis method for gold recovery. At this time, gold is deposited on the cathode surface, and the deposited gold easily peels off. Therefore, in the gold recovery apparatus of the present invention, gold can be efficiently recovered by providing a receiving portion for recovering gold peeled off from the cathode surface below the cathode.

本発明に係る金の回収方法では、水溶性硫黄含有金化合物を含む水性廃液（以下、単に「水性廃液」ということがある）を強塩基性に調整することが重要である。前記水性廃液を強塩基性に調整することで、水性廃液に含まれる水溶性硫黄含有金化合物を安定化できる。そのため水溶性硫黄含有金化合物を含む水性廃液を電気分解しても陽極や電解槽の壁面に金が自然析出することがなく、金を陰極のみに析出させて効率よく回収することが可能となる。   In the gold recovery method according to the present invention, it is important to adjust an aqueous waste liquid containing a water-soluble sulfur-containing gold compound (hereinafter, simply referred to as “aqueous waste liquid”) to be strongly basic. The water-soluble sulfur-containing gold compound contained in the aqueous waste liquid can be stabilized by adjusting the aqueous waste liquid to be strongly basic. Therefore, even when electrolyzing an aqueous waste liquid containing a water-soluble sulfur-containing gold compound, gold does not spontaneously deposit on the anode or electrolytic cell wall, and gold can be efficiently recovered by depositing only on the cathode. .

前記水溶性硫黄含有金化合物が水性廃液中で安定化する機構については、まだ充分には解明できていないが、後述する実施例から明らかなように、前記水性廃液にＨＣｌやＨ2ＳＯ4等の酸を添加して水性廃液を酸性とし、或いは前記水性廃液にＮａＣｌＯやＨ2Ｏ2等の酸化剤を添加し、もしくは前記水性廃液にチオ尿素等の還元剤を添加しても前記水性廃液からの金の自然析出は防止できないことが判明している。これに対し前記水性廃液にアルカリ金属の水酸化物やアンモニア等の塩基を添加して水性廃液を塩基性の液としてやれば、前記水性廃液からの金の自然析出を阻止できる。 Although the mechanism by which the water-soluble sulfur-containing gold compound is stabilized in an aqueous waste liquid has not yet been fully clarified, as is clear from the examples described later, HCl, H 2 SO 4, etc. Even if an acid such as NaClO or H 2 O 2 is added to the aqueous waste liquid or a reducing agent such as thiourea is added to the aqueous waste liquid, It has been found that the spontaneous precipitation of gold from can not be prevented. On the other hand, if a base such as an alkali metal hydroxide or ammonia is added to the aqueous waste liquid to make the aqueous waste liquid a basic liquid, it is possible to prevent spontaneous precipitation of gold from the aqueous waste liquid.

また、水性廃液に塩基を添加して強塩基性の水性廃液とすれば、陰極に析出した金が剥がれ易くなる。その機構は不明であるが、後述する実施例からも明らかなように、強塩基性の水性廃液を電気分解することによって、陰極に析出する金は綿状（ポーラス状）であり、陰極表面と金の接点が少なくなったことも一因と考えられる。   Further, if a base is added to the aqueous waste liquid to form a strongly basic aqueous waste liquid, the gold deposited on the cathode is easily peeled off. The mechanism is unknown, but as is clear from the examples described later, the gold deposited on the cathode by electrolyzing the strongly basic aqueous waste liquid is cotton-like (porous), and the surface of the cathode One possible reason is the lack of gold contacts.

更に、強塩基性の水性廃液を電気分解すると、該水性廃液中に含まれる塩基が電解質として作用し、電極間の電気の流れが良好となる。そのため水性廃液に含まれる水溶性硫黄含有金化合物に起因する金イオンが、陰極方向へ誘導され、陰極表面に金を析出させることができる。   Further, when the strongly basic aqueous waste liquid is electrolyzed, the base contained in the aqueous waste liquid acts as an electrolyte, and the flow of electricity between the electrodes is improved. Therefore, gold ions derived from the water-soluble sulfur-containing gold compound contained in the aqueous waste liquid are induced toward the cathode, and gold can be deposited on the cathode surface.

本発明の金の回収方法では、陰極表面に析出した金の全部または一部を電極の下方に落下させて電解槽の下方から金を回収する。即ち、従来のように陰極からの金の剥離をできるだけ防止し、陰極に金を固着させて回収するのではなく、本発明では、陰極に析出した金を積極的に陰極から剥離落下させ、電解槽の下方から回収する。なお、電解槽の下方から回収する金を「全部または一部」としたのは、全部の金を電解槽の下方から回収するのが好ましいが、陰極表面にも析出した金の一部が多少残る場合があるからである。   In the gold recovery method of the present invention, all or part of the gold deposited on the cathode surface is dropped below the electrode, and gold is recovered from below the electrolytic cell. That is, it prevents gold from peeling from the cathode as much as possible, and does not collect gold by fixing it to the cathode. In the present invention, the gold deposited on the cathode is positively peeled and dropped from the cathode, Collect from the bottom of the tank. Note that “all or part of” the gold recovered from the lower part of the electrolytic cell is preferably recovered from the lower part of the electrolytic cell, but some of the gold deposited on the cathode surface is somewhat This is because it may remain.

陰極表面に析出した金を積極的に剥離落下させるには、水性廃液を強塩基性の液に調整する他、例えば、陰極の表面に酸化皮膜を形成することも有効である。酸化皮膜を形成しておけば、陰極表面に金が密着し難くなり、金が陰極表面から剥離し易くなる。   In order to positively peel and drop the gold deposited on the cathode surface, it is effective to form an oxide film on the cathode surface, for example, in addition to adjusting the aqueous waste solution to a strongly basic solution. If an oxide film is formed, it becomes difficult for gold to adhere to the cathode surface, and gold is easily peeled off from the cathode surface.

上記強塩基性の水性廃液とは、ｐＨが１１．０以上の水性廃液である。水性廃液のｐＨが１１．０未満では、水溶性硫黄含有金化合物が充分に安定化しない。水性廃液のｐＨは１２以上であることが好ましい。   The strongly basic aqueous waste liquid is an aqueous waste liquid having a pH of 11.0 or higher. When the pH of the aqueous waste liquid is less than 11.0, the water-soluble sulfur-containing gold compound is not sufficiently stabilized. The pH of the aqueous waste liquid is preferably 12 or more.

上記水性廃液を強塩基性に調整するには、前記水性廃液に塩基としてアルカリ金属の水酸化物やアンモニア等を添加すればよい。アルカリ金属の水酸化物としては、例えばＮａＯＨやＫＯＨ等を用いることができる。特に、アルカリ金属の水酸化物は、アンモニアと比べて臭気が殆どないため、作業環境が良好となり、好適に用いることができる。   In order to adjust the aqueous waste liquid to be strongly basic, an alkali metal hydroxide, ammonia or the like may be added to the aqueous waste liquid as a base. As the alkali metal hydroxide, for example, NaOH or KOH can be used. In particular, an alkali metal hydroxide has almost no odor compared to ammonia, so that the working environment is good and can be suitably used.

上記水性廃液を強塩基性の液にするには、例えば水性廃液のＮａＯＨ濃度を０．４質量％以上とするのがよい。ＮａＯＨ濃度の上限は特に限定されないが、経済性を考慮して１０質量％程度である。ＫＯＨの場合は０．５質量％以上とすればよい。上限は特に限定されないが、経済性を考慮して１０質量％程度である。アンモニアの場合は１．０質量％以上とすればよい。上限は特に限定されないが、経済性を考慮して５質量％程度である。   In order to make the aqueous waste liquid into a strongly basic liquid, for example, the NaOH concentration of the aqueous waste liquid is preferably 0.4% by mass or more. The upper limit of the NaOH concentration is not particularly limited, but is about 10% by mass in consideration of economy. In the case of KOH, it may be 0.5% by mass or more. Although an upper limit is not specifically limited, Considering economical efficiency, it is about 10 mass%. In the case of ammonia, it may be 1.0% by mass or more. Although an upper limit is not specifically limited, Considering economical efficiency, it is about 5 mass%.

次に、上記金の回収方法で金を回収するために用いる装置について説明する。本発明に係る金の回収装置は、電解槽、該電解槽内に設けられた少なくとも１対の陽極と陰極、および前記陰極の下方に陰極表面から剥がれ落ちた金を回収するための受け部を有すると共に、前記受け部には堆積した金を前記電解槽の外へ取り出すための取り出し口を備えており、且つ前記電解槽の下方は、前記受け部に向かって下り勾配の傾斜面で構成されている。これを図面を用いて説明する。但し、下記に示す図面は本発明を限定する性質のものではなく、前・後記の趣旨に適合し得る範囲で適当に設計変更して実施することも可能であり、それらはいずれも本発明の技術的範囲に含まれる。   Next, an apparatus used for recovering gold by the gold recovery method will be described. The gold recovery apparatus according to the present invention includes an electrolytic cell, at least a pair of an anode and a cathode provided in the electrolytic cell, and a receiving unit for recovering gold peeled off from the cathode surface below the cathode. And the receiving part is provided with a take-out port for taking out the deposited gold to the outside of the electrolytic cell, and the lower part of the electrolytic cell is composed of an inclined surface with a downward slope toward the receiving part. ing. This will be described with reference to the drawings. However, the drawings shown below are not intended to limit the present invention, and can be implemented with appropriate modifications within the scope that can be adapted to the purpose described above and below. Included in the technical scope.

図１は、本発明に係る金の回収装置の一構成例を示す断面図、図２は、図１におけるＡ−Ａ’矢視図である。図中、１は電解槽、２は受け部、２ａは受け部の底面、３は電極、４は取り出し口、５は水性廃液の供給口、６は水性廃液の排出口、７は循環用水性廃液供給口、８は循環用水性廃液排出口、９はオーバーフローした水性廃液の排出口、１１はテーパ、１２はスクレーパー、２１は金、を夫々示している。なお、図１および図２において、水性廃液を強塩基性に調整する調整手段（以下、単に「調整手段」ということがある）は図示していない。また、図１において、電極３のうち斜線で示した部分は水性廃液に浸漬していることを表している。図２において、３ａは陽極、３ｂは陰極を夫々示している。   FIG. 1 is a cross-sectional view showing a configuration example of a gold recovery apparatus according to the present invention, and FIG. 2 is a view taken along the line A-A ′ in FIG. 1. In the figure, 1 is an electrolytic cell, 2 is a receiving part, 2a is a bottom surface of the receiving part, 3 is an electrode, 4 is an outlet, 5 is a supply port for aqueous waste liquid, 6 is a discharge port for aqueous waste liquid, and 7 is aqueous for circulation The waste liquid supply port, 8 is an aqueous waste liquid discharge port for circulation, 9 is a discharge port for overflowing aqueous waste liquid, 11 is a taper, 12 is a scraper, and 21 is gold. In FIG. 1 and FIG. 2, adjustment means for adjusting the aqueous waste liquid to strong basicity (hereinafter simply referred to as “adjustment means”) is not shown. Moreover, in FIG. 1, the part shown with the oblique line among the electrodes 3 represents being immersed in the aqueous waste liquid. In FIG. 2, 3a indicates an anode, and 3b indicates a cathode.

水溶性硫黄含有金化合物を含む水性廃液を、図示しない調整手段で強塩基性に調整した後、供給口５から回収装置内へ供給する。供給口５から供給された水性廃液は、電解槽１で電気分解して金を回収した後、取り出し口４に設けられた排出口６から系外へ排出される。このとき水性廃液を電解槽１で電気分解すると、陰極３ｂ表面に金が析出する。この析出した金は、自重で陰極３ｂ表面から剥がれ落ちる。そこで本発明に係る金の回収装置では、図１や図２に示すように、電極３（特に、陰極３ｂ）の下方に受け部２を有しているため、陰極３ｂ表面から剥がれ落ちた金は受け部２に堆積し、効率よく回収できる。また、図示する如く受け部２の底面積（即ち受け部２の開口面積）を電解槽１の底面積より小さくできる。従って金２１の堆積領域を狭くすることができる。   An aqueous waste liquid containing a water-soluble sulfur-containing gold compound is adjusted to strong basicity by an adjusting means (not shown) and then supplied from the supply port 5 into the recovery device. The aqueous waste liquid supplied from the supply port 5 is electrolyzed in the electrolytic cell 1 to recover gold, and then discharged from the discharge port 6 provided in the discharge port 4 to the outside of the system. At this time, when the aqueous waste liquid is electrolyzed in the electrolytic cell 1, gold is deposited on the surface of the cathode 3b. The deposited gold peels off from the surface of the cathode 3b by its own weight. Accordingly, in the gold recovery apparatus according to the present invention, as shown in FIGS. 1 and 2, since the receiving portion 2 is provided below the electrode 3 (particularly, the cathode 3b), the gold peeled off from the surface of the cathode 3b. Accumulates in the receiving part 2 and can be efficiently recovered. Further, as shown in the drawing, the bottom area of the receiving portion 2 (that is, the opening area of the receiving portion 2) can be made smaller than the bottom area of the electrolytic cell 1. Therefore, the deposition region of the gold 21 can be narrowed.

また本発明の回収装置では、陰極３ｂから剥がれ落ちた金を確実に受け部２で回収するために、電解槽１の下方を、前記電解槽１の壁面側から前記受け部２に向かって下り勾配の傾斜面で構成する。即ち、上記図２に示すように、電解槽１の下方にテーパ１１を設ける。テーパ１１を設けることで、該テーパ１１の上方に陰極３ｂを配置しても受け部２の開口面積を小さくでき、陰極３ｂ表面から剥がれ落ちた金を確実に回収できる。なお、テーパ１１の傾斜は、陰極３ｂから剥がれ落ちた金がテーパ１１上に堆積せず、受け部２へスムーズに送られる程度とすればよい。テーパ１１の傾斜は、例えば３０°以上（好ましくは４０°以上）である。   Further, in the recovery device of the present invention, in order to reliably recover the gold peeled off from the cathode 3b by the receiving part 2, the lower part of the electrolytic cell 1 is lowered from the wall surface side of the electrolytic cell 1 toward the receiving part 2. Consists of a sloped surface. That is, as shown in FIG. 2, the taper 11 is provided below the electrolytic cell 1. By providing the taper 11, even if the cathode 3b is disposed above the taper 11, the opening area of the receiving portion 2 can be reduced, and gold peeled off from the surface of the cathode 3b can be reliably recovered. The inclination of the taper 11 may be such that the gold peeled off from the cathode 3b is not deposited on the taper 11 and is smoothly sent to the receiving part 2. The inclination of the taper 11 is, for example, 30 ° or more (preferably 40 ° or more).

上記受け部２に堆積した金２１は、金を電解槽１の外へ取り出すための取り出し口４から系外へ取り出すことで回収できる。なお、前記受け部２は、堆積した金を濾取する構造を備えており、金２１を取り出し口４から系外へ取り出すに先立って、金回収装置内の水性廃液を例えば排出口６から系外へ排出する。前記堆積した金を濾取する構造としては、前記排出口６に例えば開閉弁やフィルター等を備えればよく、受け部２に堆積した金２１が排出口６から系外へ排出されないように構成する（図示しない）。   The gold 21 deposited on the receiving part 2 can be recovered by taking it out of the system from the take-out port 4 for taking the gold out of the electrolytic cell 1. The receiving portion 2 has a structure for filtering the deposited gold, and prior to taking out the gold 21 from the takeout port 4 to the outside of the system, the aqueous waste liquid in the gold recovery device is discharged from the discharge port 6 to the system, for example. Drain out. As the structure for collecting the deposited gold, the discharge port 6 may be provided with, for example, an on-off valve or a filter, and the gold 21 deposited on the receiving portion 2 is not discharged from the discharge port 6 to the outside of the system. (Not shown).

前記受け部２の底面２ａは、受け部２に堆積した金を電解槽１の外へ取り出し易くするために、上記図１に示すように、前記取り出し口４の対面側から前記取り出し口４に向かって下り勾配に形成することが好ましい。下り勾配に形成することで、陰極３ｂ表面から剥がれ落ちた金が斜面を転がって、受け部２近傍に自然に集中するため金を回収し易くなる。なお、前記受け部２の底面２ａは、平面で構成しても構わない。   As shown in FIG. 1, the bottom surface 2 a of the receiving portion 2 extends from the facing side of the extraction port 4 to the extraction port 4 so that the gold deposited on the receiving portion 2 can be easily taken out of the electrolytic cell 1. It is preferable to form a downward slope. By forming it in a downward gradient, the gold peeled off from the surface of the cathode 3b rolls on the slope and naturally concentrates in the vicinity of the receiving portion 2, so that it becomes easy to collect the gold. In addition, you may comprise the bottom face 2a of the said receiving part 2 with a plane.

ところで受け部２に堆積した金２１を取り出し口４から取り出すタイプでは、堆積した金２１が排出口６を閉塞しないように、該排出口６を例えば取り出し口４や受け部２の壁面に設けなければならない。そこで前記受け部２は、金を回収するための受け器を備え、該受け器は前記回収装置に対し出し入れ可能に構成することが好ましい。このことを図面を用いて説明する。図３は、本発明に係る金の回収装置の他の構成例を示す断面図であり、前記図１に示した構成に対し、受け器１３を備えている。なお、前記図１と同じ部分には同一の符合を付すことで重複説明を避ける。   By the way, in the type in which the gold 21 deposited on the receiving portion 2 is taken out from the take-out port 4, the discharge port 6 must be provided on the wall of the take-out port 4 or the receiving portion 2 so that the deposited gold 21 does not block the discharge port 6. I must. Therefore, it is preferable that the receiving portion 2 includes a receiver for recovering gold, and the receiver is configured to be able to be taken in and out of the recovery device. This will be described with reference to the drawings. FIG. 3 is a cross-sectional view showing another configuration example of the gold recovery apparatus according to the present invention, which is provided with a receiver 13 with respect to the configuration shown in FIG. Note that the same parts as those in FIG.

図３に示すように、受け部２の内側に、陰極３ｂ表面から剥がれ落ちた金２１を回収するための受け器１３を備えることで、金２１を受け器１３内に捕集することができる。そのため排出口６を受け部２の底面に設けても堆積した金２１が排出口６を閉塞せず、しかもこの受け器１３は回収装置に対して出し入れ可能に構成しておけば、金２１を回収装置から簡便に取り出すことができる。   As shown in FIG. 3, the gold 21 can be collected in the receiver 13 by providing the receiver 13 for collecting the gold 21 peeled off from the surface of the cathode 3 b inside the receiver 2. . Therefore, even if the discharge port 6 is provided on the bottom surface of the receiving portion 2, the deposited gold 21 does not block the discharge port 6, and if the receiver 13 is configured to be able to be taken in and out of the recovery device, the gold 21 can be removed. It can be easily removed from the collection device.

上記受け器１３は、陰極３ｂ表面から剥がれ落ちた金を捕捉できるように構成されていれば特に限定されないが、金２１を含む水性廃液から金２１を濾別できるように構成するのがよい。例えば、受け器１３を２層構造とし、内側は金２１を捕捉するために網目の細かいメッシュ層、外側はメッシュ層を支持するための補強層とすれば、金はメッシュ層で捕捉される。メッシュ層の素材としては、例えばポリプロピレンやポリエチレン、テフロン（登録商標）、塩化ビニル等を選択し、このメッシュの網目を５０〜２００メッシュ（好ましくは７０メッシュ以上、１４０メッシュ以下、より好ましくは８０メッシュ以上、１００メッシュ以下）とし、目開きを７５〜３００μｍ（好ましくは１００μｍ以上、２００μｍ以下、より好ましくは１５０μｍ以上、１８０μｍ以下）とすれば金２１を捕捉できる。補強層の素材としては、例えば塩化ビニルやポリエチレン、ポリプロピレン、テフロン（登録商標）等を選択すればよい。補強層はメッシュ状にする必要はなく、水性廃液を通すための孔が適当に空けられていればよい。なお、受け器１３は２層構造のものに限定されず、１層構造でもよいし、３層以上の積層構造でもよい。   The receiver 13 is not particularly limited as long as it is configured to capture gold peeled off from the surface of the cathode 3b. However, the receiver 13 may be configured to filter the gold 21 from the aqueous waste liquid containing the gold 21. For example, if the receptacle 13 has a two-layer structure, the inside is a fine mesh layer for capturing the gold 21 and the outside is a reinforcing layer for supporting the mesh layer, the gold is captured by the mesh layer. As a material of the mesh layer, for example, polypropylene, polyethylene, Teflon (registered trademark), vinyl chloride or the like is selected, and the mesh network is 50 to 200 mesh (preferably 70 mesh or more, 140 mesh or less, more preferably 80 mesh). As described above, the gold 21 can be captured by setting the mesh to 75 to 300 μm (preferably 100 μm to 200 μm, more preferably 150 μm to 180 μm). As the material for the reinforcing layer, for example, vinyl chloride, polyethylene, polypropylene, Teflon (registered trademark) or the like may be selected. The reinforcing layer does not need to be in a mesh shape, and it is only necessary that a hole for passing the aqueous waste liquid is appropriately formed. Note that the receiver 13 is not limited to a two-layer structure, and may be a one-layer structure or a three-layer structure or more.

上記受け部２の上方には、少なくとも１対の陽極と陰極を設ければよく、上記図２では、陽極３ａを２枚、陰極３ｂを１枚備えた例を示した。本発明の装置はこの図２に限定されるものではなく、例えば、陽極３ａをｎ枚、陰極３ｂをｎ枚（ｎは自然数。以下同じ）としてもよいし、陽極３ａをｎ＋１枚、陰極３ｂをｎ枚とし、陰極３ｂを陽極３ａで挟むように構成してもよい。電解効率を高め、回収効率を高めるには、陰極３ｂの表面と裏面に金を析出させることが好ましく、陽極３ａをｎ＋１枚、陰極３ｂをｎ枚とするのがよい。   It is only necessary to provide at least one pair of anode and cathode above the receiving portion 2, and FIG. 2 shows an example in which two anodes 3a and one cathode 3b are provided. The apparatus of the present invention is not limited to this FIG. 2. For example, n anodes 3a and n cathodes 3b (n is a natural number; the same shall apply hereinafter), or n + 1 anodes 3a and cathodes 3b may be used. May be composed of n sheets, and the cathode 3b may be sandwiched between the anodes 3a. In order to increase the electrolysis efficiency and increase the recovery efficiency, it is preferable to deposit gold on the front and back surfaces of the cathode 3b, and it is preferable to have n + 1 anodes 3a and n cathodes 3b.

上記陽極３ａとしては、例えばステンレス製（例えばＳＵＳ３１６製）の電極を用いることができる。一方、上記陰極３ｂとしては、例えばチタン製の電極を用いることができる。   As the anode 3a, for example, an electrode made of stainless steel (for example, made of SUS316) can be used. On the other hand, as the cathode 3b, for example, an electrode made of titanium can be used.

本発明の回収装置では、陰極３ｂ表面に析出した金を全て掻き落とすために、陰極３ｂ表面に析出した金を掻き落とす機構を備えてもよい。陰極３ｂ表面に析出した金を掻き落とす機構としては、例えば前記図２に示したように、陰極３ｂの表面近傍にスクレーパー１２を備えればよい。   The recovery apparatus of the present invention may be provided with a mechanism for scraping off the gold deposited on the surface of the cathode 3b in order to scrape off all the gold deposited on the surface of the cathode 3b. As a mechanism for scraping off gold deposited on the surface of the cathode 3b, for example, as shown in FIG. 2, a scraper 12 may be provided in the vicinity of the surface of the cathode 3b.

陰極３ｂ表面に析出した金を掻き落とすには、例えばスクレーパー１２を上下方向に移動するように構成して掻き落としてもよいし、スクレーパー１２を固定しておき、陰極３ｂを上下方向に移動させて掻き落としてもよい。なお、陰極３ｂ表面に析出した金は、もちろん手動で掻き落としても構わない。   In order to scrape the gold deposited on the surface of the cathode 3b, for example, the scraper 12 may be configured to move up and down and scraped off, or the scraper 12 may be fixed and the cathode 3b moved up and down. You can scrape it off. Of course, the gold deposited on the surface of the cathode 3b may be manually scraped off.

供給口５から供給された水性廃液は、電解槽１で電気分解されるが、電気分解を安定して効率よく行うために、回収装置内で水性廃液を循環させることが好ましい。水性廃液を回収装置内で循環させるには、例えば上記図１に示すように、循環用水性廃液排出口８から水性廃液の一部を図示しないポンプを用いて抜き出し、抜き出した水性廃液を循環用水性廃液供給口７から供給すればよい。循環用水性廃液供給口７と循環用水性廃液排出口８を設ける位置は図１に示した配置に限定されず、例えば循環用水性廃液供給口７を設けている同じ壁面に循環用水性廃液排出口８を設けてもよい。   The aqueous waste liquid supplied from the supply port 5 is electrolyzed in the electrolytic cell 1, but it is preferable to circulate the aqueous waste liquid in the recovery device in order to perform electrolysis stably and efficiently. In order to circulate the aqueous waste liquid in the recovery device, for example, as shown in FIG. 1, a part of the aqueous waste liquid is extracted from the circulation aqueous waste liquid discharge port 8 using a pump (not shown), and the extracted aqueous waste liquid is used for circulation. What is necessary is just to supply from the aqueous waste liquid supply port 7. FIG. The position where the circulating aqueous waste liquid supply port 7 and the circulating aqueous waste liquid discharge port 8 are provided is not limited to the arrangement shown in FIG. 1. For example, the circulating aqueous waste liquid discharge port is disposed on the same wall surface where the circulating aqueous waste liquid supply port 7 is provided. An outlet 8 may be provided.

また、オーバーフローした水性廃液は、上記図１に示すように、排出口９から系外へ排出することが好ましい。なお、電気分解が進むに連れて水性廃液自体が電気分解され、水素等のガスが発生することがある。そのため回収装置内で発生したガスを、系外へ排出するための排気口を設けることが好ましい（図示しない）。   Further, the overflowed aqueous waste liquid is preferably discharged out of the system from the discharge port 9 as shown in FIG. As the electrolysis proceeds, the aqueous waste liquid itself may be electrolyzed to generate a gas such as hydrogen. Therefore, it is preferable to provide an exhaust port for exhausting the gas generated in the recovery device to the outside of the system (not shown).

次に、本発明に係る金の回収装置を用い、水溶性硫黄含有金化合物を含む水性廃液から金を回収する手順について図面を用いて説明する。図４は、金を回収するためのフロー図であり、３１は貯留槽（ストックタンク）、３２は金回収装置、３３はバッファータンク、３４は塩基貯留槽、４１〜４４はポンプ、５１〜５７は経路を夫々示している。なお、塩基貯留槽３４とポンプ４１をまとめて調整手段ということがある。   Next, a procedure for recovering gold from an aqueous waste liquid containing a water-soluble sulfur-containing gold compound using the gold recovery apparatus according to the present invention will be described with reference to the drawings. FIG. 4 is a flowchart for recovering gold, 31 is a storage tank (stock tank), 32 is a gold recovery apparatus, 33 is a buffer tank, 34 is a base storage tank, 41-44 are pumps, 51-57. Indicates routes. The base storage tank 34 and the pump 41 may be collectively referred to as adjusting means.

経路５１から貯留槽３１に供給された水溶性硫黄含有金化合物を含む水性廃液は、経路５３上に設けられたポンプ４２を動作させることにより金回収装置３２へ供給される。ここで本発明では、水性廃液を調整手段で予め強塩基性に調整しておく。即ち、貯留槽３１に蓄えられた水溶性硫黄含有化合物を含む水性廃液へ、塩基貯留槽３４から経路５２を通して塩基が供給され、前記水性廃液は強塩基性に調整される。なお、経路５２上にはポンプ４１が設けられており、該ポンプ４１の動作を制御することで塩基の供給量を調整できる。   The aqueous waste liquid containing the water-soluble sulfur-containing gold compound supplied from the path 51 to the storage tank 31 is supplied to the gold recovery device 32 by operating the pump 42 provided on the path 53. Here, in the present invention, the aqueous waste liquid is adjusted to be strongly basic in advance by the adjusting means. That is, the base is supplied from the base storage tank 34 to the aqueous waste liquid containing the water-soluble sulfur-containing compound stored in the storage tank 31 through the path 52, and the aqueous waste liquid is adjusted to be strongly basic. A pump 41 is provided on the path 52, and the amount of base supplied can be adjusted by controlling the operation of the pump 41.

上記水溶性硫黄含有金化合物を含む水性廃液としては、例えば水溶性硫黄含有金化合物を含むメッキ液を用いて金メッキした後に排出される水性廃液や、金メッキ時に洗浄に使用されて排出される水性廃液などが挙げられる。前記水溶性硫黄含有金化合物としては、例えばチオ硫酸金化合物や亜硫酸金化合物などが挙げられる。   Examples of the aqueous waste liquid containing the water-soluble sulfur-containing gold compound include an aqueous waste liquid discharged after gold plating using a plating liquid containing a water-soluble sulfur-containing gold compound, and an aqueous waste liquid discharged after being used for cleaning during gold plating. Etc. Examples of the water-soluble sulfur-containing gold compound include gold thiosulfate compounds and gold sulfite compounds.

金回収装置３２に供給された上記水性廃液は、電気分解によって金が回収される。このとき金回収装置３２には循環経路５７が設けられており、該経路５７上に設けられたポンプ４３を動作させることで、金回収装置３２内の水性廃液を適宜循環させることができる。また、金回収装置３２には貯留槽３１と接続された経路５６が設けられており、金回収装置３２でオーバーフローした水性廃液は貯留槽３１へ返送される。なお、電気分解条件は特に限定されず、公知の条件を採用できる。   The aqueous waste liquid supplied to the gold recovery device 32 recovers gold by electrolysis. At this time, a circulation path 57 is provided in the gold recovery apparatus 32, and the aqueous waste liquid in the gold recovery apparatus 32 can be appropriately circulated by operating the pump 43 provided on the path 57. Further, the gold recovery device 32 is provided with a path 56 connected to the storage tank 31, and the aqueous waste liquid overflowed by the gold recovery device 32 is returned to the storage tank 31. In addition, electrolysis conditions are not specifically limited, A well-known condition is employable.

金回収後の水性廃液は、経路５４上に設けられたポンプ４４を動作させることにより一旦バッファータンクに貯留され、廃液として経路５５から系外へ排出される。   The aqueous waste liquid after the gold recovery is temporarily stored in the buffer tank by operating the pump 44 provided on the path 54, and is discharged out of the system as a waste liquid from the path 55.

上記図４では、貯留槽３１に調整手段（即ち、塩基貯留槽３４とポンプ４１）を設けて水溶性硫黄含有金化合物を含む水性廃液を強塩基性に調整する例を示したが、本発明はこれに限定されず、例えば金メッキ終了後に排出された水性廃液に直ぐに塩基を添加して強塩基性に調整した後、これを電気分解してもよい。金メッキ終了直後の水性廃液に塩基を添加することで液が安定化するため、容器内における自然析出を防止できる。   FIG. 4 shows an example in which adjusting means (that is, the base storage tank 34 and the pump 41) is provided in the storage tank 31 to adjust the aqueous waste liquid containing the water-soluble sulfur-containing gold compound to be strongly basic. Is not limited thereto, and for example, a base may be immediately added to the aqueous waste liquid discharged after the completion of gold plating to adjust to strong basicity, followed by electrolysis. Since the solution is stabilized by adding a base to the aqueous waste solution immediately after the end of gold plating, spontaneous precipitation in the container can be prevented.

以下、本発明を実施例によって更に詳細に説明するが、下記実施例は本発明を限定する性質のものではなく、前・後記の趣旨に適合し得る範囲で適当に変更して実施することも可能であり、それらはいずれも本発明の技術的範囲に含まれる。   Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are not intended to limit the present invention, and may be implemented with appropriate modifications within a range that can meet the purpose described above and below. These are all possible and are within the scope of the present invention.

実験例１
水溶性硫黄含有金化合物を含む水性廃液（以下、原料廃液という）の安定性について調べた。原料廃液は、水溶性硫黄含有化合物として亜硫酸金化合物を含むメッキ廃液を用いた（金の量は１５．５ｇ／Ｌ）。前記原料廃液３０ｍＬをガラス製の容器に入れ、これに下記表１に示した添加物を濃度が４．８質量％となるように添加し、撹拌した後、４８時間静置した。 Experimental example 1
The stability of an aqueous waste liquid containing a water-soluble sulfur-containing gold compound (hereinafter referred to as a raw material waste liquid) was examined. As the raw material waste liquid, a plating waste liquid containing a gold sulfite compound as a water-soluble sulfur-containing compound was used (the amount of gold was 15.5 g / L). 30 mL of the raw material waste liquid was placed in a glass container, and the additives shown in Table 1 below were added thereto so as to have a concentration of 4.8% by mass. After stirring, the mixture was allowed to stand for 48 hours.

撹拌後の原料廃液のｐＨをｐＨメーターで測定し、結果を下記表１に示す。また、静置前後で、原料水溶液の様子を目視で観察し、金の析出の有無を調べた。結果を下記表１に示す。表１では、液に懸濁が認められた場合を「微粉末析出あり」とし、容器壁面に金の析出が認められた場合を「析出あり」とし、液に懸濁が認められず、容器壁面に金の析出が認められなかった場合を「析出なし」と表記した。また、４８時間経過後における原料水溶液の臭気についても調べた。   The pH of the raw material waste liquid after stirring was measured with a pH meter, and the results are shown in Table 1 below. In addition, before and after standing, the state of the raw material aqueous solution was visually observed to examine the presence or absence of gold deposition. The results are shown in Table 1 below. In Table 1, the case where suspension was observed in the liquid was defined as “with fine powder precipitation”, and the case where gold deposition was observed on the container wall surface was defined as “with precipitation”. The case where no gold deposition was observed on the wall surface was described as “no deposition”. Further, the odor of the raw material aqueous solution after 48 hours was also examined.

Figure 0004699105
Figure 0004699105

表１から明らかなように、Ｎｏ．１とＮｏ．２は本発明で規定する要件を満足する例であり、上記原料廃液に塩基を添加して強塩基性の水性廃液に調整したため、亜硫酸金化合物が安定化し、４８時間経過しても容器の壁面に金の析出は認められなかった。これに対し、Ｎｏ．３〜７は、本発明で規定する要件を満たさない例であり、Ｎｏ．３と４は酸を添加した例、Ｎｏ．５と６は酸化剤を添加した例、Ｎｏ．７は還元剤を添加した例である。これら何れも４８時間経過後には容器の壁面に金が析出していた。   As is apparent from Table 1, No. 1 and No. No. 2 is an example that satisfies the requirements defined in the present invention. Since a base was added to the above raw material waste liquid to prepare a strongly basic aqueous waste liquid, the gold sulfite compound was stabilized and the wall surface of the container even after 48 hours had passed. No gold deposition was observed. In contrast, no. Nos. 3 to 7 are examples that do not satisfy the requirements defined in the present invention. 3 and 4 are examples in which an acid was added. Nos. 5 and 6 are examples in which an oxidizing agent was added. 7 is an example in which a reducing agent is added. In any case, gold was deposited on the wall of the container after 48 hours.

実験例２
上記実験例１で用いた原料廃液１００ｍＬに、濃度が４．８質量％となるようにＮａＯＨを添加した液を電気分解し、金を回収した。なお、液のｐＨは１３．３であった。 Experimental example 2
A solution obtained by adding NaOH to 100 mL of the raw material waste liquid used in Experimental Example 1 so as to have a concentration of 4.8% by mass was electrolyzed to recover gold. The pH of the solution was 13.3.

金の回収には前記図１に示した回収装置を用いた。陽極はステンレス製の電極（ＳＵＳ３１６製の電極）を用い、陰極はチタン製の電極を用いた。電極の大きさは、横２０ｍｍ×縦１５０ｍｍ×厚み２ｍｍである。なお、陽極と陰極は夫々１枚とした。電解条件は次の通りである。電源の制御は定電流制御とし、電流密度を０．０３３Ａ／ｃｍ2として電気分解した。 For the recovery of gold, the recovery device shown in FIG. 1 was used. The anode was a stainless steel electrode (SUS316 electrode), and the cathode was a titanium electrode. The size of the electrode is 20 mm wide × 150 mm long × 2 mm thick. One anode and one cathode were used. The electrolysis conditions are as follows. The power source was controlled at a constant current, and electrolysis was performed with a current density of 0.033 A / cm 2 .

電気分解した結果、陰極表面には金が析出していたが、一部は陰極表面から剥がれ落ち、剥がれ落ちた金が受け部に堆積していた。剥がれ落ちた金は、脆く、ポーラス状であった。剥がれ落ちた金を液中で１２時間放置したが、再溶解していなかった。   As a result of the electrolysis, gold was deposited on the cathode surface, but part of the gold was peeled off from the cathode surface, and the gold that was peeled off was deposited on the receiving part. The gold that peeled off was brittle and porous. The gold that was peeled off was left in the liquid for 12 hours, but was not re-dissolved.

実験例３
上記実験例１で用いた原料廃液１００ｍＬに、下記表２に示す濃度となるようにＮａＯＨを添加した液を調製し、この液を電解液として用い、電気分解して金を回収した。金の回収には前記図１に示した回収装置を用い、回収条件は上記実験例２と同じ条件とした。 Experimental example 3
A solution was prepared by adding NaOH to 100 mL of the raw material waste solution used in Experimental Example 1 so as to have the concentration shown in Table 2 below, and this solution was used as an electrolytic solution to recover gold by electrolysis. The recovery apparatus shown in FIG. 1 was used for recovery of gold, and the recovery conditions were the same as in Experimental Example 2 above.

電気分解後、回収装置内を目視で観察し、金の析出の有無を観察した。結果を下記表２に示す。表２では、金の析出が認められない場合を○、金の析出が認められる場合を×で示している。   After electrolysis, the inside of the recovery device was visually observed to observe the presence or absence of gold deposition. The results are shown in Table 2 below. In Table 2, the case where gold deposition is not observed is indicated by ◯, and the case where gold deposition is observed is indicated by x.

Figure 0004699105
Figure 0004699105

表２から明らかなように、Ｎｏ．１は本発明で規定する要件を満たさない例であり、水性廃液が強塩基性ではないため、電解槽の内壁面や電極等に金の析出が認められた。これに対し、Ｎｏ．２〜５は、本発明で規定する要件を満たす例であり、電気分解後、金は陰極表面に析出しているか、陰極の下方に堆積しており、陽極や電解槽の内壁面等には金の析出は認められなかった。   As can be seen from Table 2, no. No. 1 is an example that does not satisfy the requirements defined in the present invention. Since the aqueous waste liquid is not strongly basic, gold deposition was observed on the inner wall surface and electrodes of the electrolytic cell. In contrast, no. Nos. 2 to 5 are examples that satisfy the requirements defined in the present invention, and after electrolysis, gold is deposited on the cathode surface or deposited below the cathode. No gold deposition was observed.

実験例４
上記実験例１で用いた原料廃液１６０Ｌに、濃度が１．９２質量％となるようにＮａＯＨを添加した液を電気分解し、金を回収した。なお、液のｐＨは１２．５であった。 Experimental Example 4
A liquid obtained by adding NaOH to the raw material waste liquid 160L used in Experimental Example 1 so as to have a concentration of 1.92% by mass was electrolyzed to recover gold. The pH of the liquid was 12.5.

金の回収には前記図３に示した回収装置を用いた。陽極はステンレス製の電極（ＳＵＳ３１６製の電極）、陰極はチタン製の電極を用いた。電極の大きさは、横７５０ｍｍ×縦６８０ｍｍ×厚み３ｍｍである。なお、陰極は１枚、陽極は２枚用い、陰極を陽極で挟んだ。陰極と陽極の電極間距離は３５ｍｍである。   For the recovery of gold, the recovery device shown in FIG. 3 was used. The anode was a stainless steel electrode (SUS316 electrode), and the cathode was a titanium electrode. The size of the electrode is 750 mm wide × 680 mm long × 3 mm thick. One cathode and two anodes were used, and the cathode was sandwiched between the anodes. The distance between the cathode and the anode is 35 mm.

電極の最下端から受け部の上端までの距離は１００ｍｍであり、受け部には受け器を備えている。   The distance from the lowest end of the electrode to the upper end of the receiving part is 100 mm, and the receiving part is provided with a receptacle.

受け器は２層構造であり、内側はポリプロピレン製のメッシュ層と外側は塩化ビニル製の補強層との積層体である。前記メッシュ層の網目は８０〜１００メッシュ、目開きは１５０〜１８０μｍである。前記補強層は径が１０ｍｍ程度の孔が空いており、水性廃液を透過し易くしている。   The receptacle has a two-layer structure, and a laminated body of a polypropylene mesh layer on the inner side and a reinforcing layer made of vinyl chloride on the outer side. The mesh layer has a mesh of 80 to 100 mesh and an opening of 150 to 180 μm. The reinforcing layer has a hole having a diameter of about 10 mm, and allows the aqueous waste liquid to pass therethrough.

電解条件は次の通りである。電源の制御は定電流制御とし、電流密度を０．００４Ａ／ｃｍ2として２４時間電気分解した。 The electrolysis conditions are as follows. The power source was controlled at a constant current, and electrolysis was performed for 24 hours with a current density of 0.004 A / cm 2 .

電気分解の途中で陰極表面を観察すると、表面には綿状（ポーラス状）の金が付着していたが、電気分解の終了間際では、陰極表面に付着していた金の一部は剥がれ落ちていた。また、電気分解の終了間際では、水が電気分解されたことにより水素ガスが発生していた。   When the surface of the cathode was observed during electrolysis, cotton-like (porous) gold was attached to the surface, but at the end of electrolysis, a part of the gold attached to the cathode surface was peeled off. It was. Further, just before the end of electrolysis, hydrogen gas was generated due to electrolysis of water.

電気分解終了後、陰極表面から回収できた金の質量と、受け器から回収できた金の質量の比は、おおよそ３〜４：７〜６であった。陰極表面に付着した金をヘラで削ぎ落としたところ簡単に剥がれ落ちた。   After completion of the electrolysis, the ratio of the mass of gold collected from the cathode surface to the mass of gold collected from the receiver was approximately 3-4: 7-6. When the gold adhering to the cathode surface was scraped off with a spatula, it was easily peeled off.

陰極表面と受け器から回収できた金の質量は２４７９．５ｇであった（電気分解後の液中の金の濃度は３．１ｍｇ／Ｌ）。従って、上記原料廃液に含まれる金の質量は２４８０ｇであるから（電気分解前の金の濃度は１５．５ｇ／Ｌ）、金の回収率は９９．９８％であった。   The mass of gold recovered from the cathode surface and the receiver was 2479.5 g (the concentration of gold in the liquid after electrolysis was 3.1 mg / L). Therefore, since the mass of gold contained in the raw material waste liquid is 2480 g (the gold concentration before electrolysis is 15.5 g / L), the gold recovery rate was 99.98%.

実験例５
上記実験例４において、陰極表面に析出した金を掻き落とす機構としてスクレーパーを備えた回収装置を用い、上記実験例４と同じ条件で電気分解して金を回収した。 Experimental Example 5
In Experimental Example 4, gold was recovered by electrolysis under the same conditions as in Experimental Example 4 using a recovery device equipped with a scraper as a mechanism for scraping gold deposited on the cathode surface.

電気分解終了後、陰極表面から回収できた金の質量と、受け器から回収できた金の質量の比は、おおよそ３：７であったが、スクレーパーの刃を陰極表面に接触させて、該スクレーパーを昇降させたところ、陰極表面に付着した金をほぼ全て掻き落とすことができた。   After the electrolysis, the ratio of the mass of gold recovered from the cathode surface to the mass of gold recovered from the receiver was approximately 3: 7, but the scraper blade was brought into contact with the cathode surface, When the scraper was moved up and down, almost all the gold adhering to the cathode surface could be scraped off.

実験例６
上記実験例４において、ＮａＯＨの濃度を１．９２質量％とする代わりに、ＫＯＨの濃度を１．９２質量％とする以外は、上記実験例４と同じ条件で電気分解して金を回収した。なお、液のｐＨは１２．０であった。 Experimental Example 6
In Experimental Example 4, gold was recovered by electrolysis under the same conditions as in Experimental Example 4 except that the concentration of NaOH was 1.92% by mass instead of 1.92% by mass. . The pH of the liquid was 12.0.

その結果、陰極表面と受け器から回収できた金の質量は２４７９ｇであった（電気分解後の液中の金の濃度は６．２ｍｇ／Ｌ）。従って、上記原料廃液に含まれる金の質量は２４８０ｇであるから（電気分解前の金の濃度は１５．５ｇ／Ｌ）、金の回収率は９９．９５％であった。   As a result, the mass of gold recovered from the cathode surface and the receiver was 2479 g (the concentration of gold in the liquid after electrolysis was 6.2 mg / L). Therefore, since the mass of gold contained in the raw material waste liquid is 2480 g (the gold concentration before electrolysis is 15.5 g / L), the gold recovery rate was 99.95%.

実験例７（比較例１）
上記実験例４において、ＮａＯＨの濃度を０．２４質量％とする以外は、上記実験例４と同じ条件で電気分解して金を回収した。なお、液のｐＨは１０．５であった。 Experimental Example 7 (Comparative Example 1)
In Experimental Example 4, gold was recovered by electrolysis under the same conditions as in Experimental Example 4 except that the NaOH concentration was 0.24 mass%. The pH of the liquid was 10.5.

その結果、陰極表面には黒色の金が付着していた。また、陽極の表面や回収装置の内壁面にも金が付着もしくはメッキされた状態で析出していた。陰極や陽極、回収装置の内壁面等に付着した金は、ヘラやスクレーパーを用いても剥がし落とすことができず、金を回収できなかった。   As a result, black gold adhered to the cathode surface. Further, gold was deposited on the surface of the anode and the inner wall surface of the recovery device in a state of being attached or plated. The gold adhering to the cathode, the anode, the inner wall surface of the recovery device, etc. could not be removed even using a spatula or a scraper, and the gold could not be recovered.

実験例８（比較例２）
上記実験例４において、原料廃液にＮａＯＨを添加せず、また電流密度を０．０３３Ａ／ｃｍ2に変更する以外は、上記実験例４と同じ条件で電気分解して金を回収した。なお、液のｐＨは７．０であった。 Experimental Example 8 (Comparative Example 2)
In Experimental Example 4, gold was recovered by electrolysis under the same conditions as in Experimental Example 4 except that NaOH was not added to the raw material waste liquid and the current density was changed to 0.033 A / cm 2 . The pH of the solution was 7.0.

その結果、陰極表面には黒色の金が付着していた。また、陽極の表面や回収装置の内壁面にも金が付着もしくはメッキされた状態で析出していた。陰極や陽極、回収装置の内壁面等に付着した金は、ヘラやスクレーパーを用いても剥がし落とすことができず、金を回収できなかった。   As a result, black gold adhered to the cathode surface. Further, gold was deposited on the surface of the anode and the inner wall surface of the recovery device in a state of being attached or plated. The gold adhering to the cathode, the anode, the inner wall surface of the recovery device, etc. could not be removed even using a spatula or a scraper, and the gold could not be recovered.

図１は、本発明に係る金の回収装置の一構成例を示す断面図である。FIG. 1 is a cross-sectional view showing an example of the configuration of a gold recovery apparatus according to the present invention. 図２は、上記図１におけるＡ−Ａ’矢視図である。FIG. 2 is a view taken along the line A-A ′ in FIG. 図３は、本発明に係る金の回収装置の他の構成例を示す断面図である。FIG. 3 is a sectional view showing another configuration example of the gold recovery apparatus according to the present invention. 図４は、本発明に係る金の回収装置を用い、水溶性硫黄含有金化合物を含む水性廃液から金を回収する手順を説明するためのフロー図である。FIG. 4 is a flowchart for explaining a procedure for recovering gold from an aqueous waste liquid containing a water-soluble sulfur-containing gold compound using the gold recovery apparatus according to the present invention.

符号の説明Explanation of symbols

１ 電解槽
２ 受け部
３ 電極
４ 取り出し口
５ 水性廃液の供給口
６ 水性廃液の排出口
７ 循環用水性廃液供給口
８ 循環用水性廃液排出口
９ オーバーフローした水性廃液の排出口
１１ テーパ
１２ スクレーパー
２１ 金
３１ 貯留槽（ストックタンク）
３２ 金回収装置
３３ バッファータンク
３４ 塩基貯留槽
４１〜４４ ポンプ
５１〜５７ 経路 DESCRIPTION OF SYMBOLS 1 Electrolysis tank 2 Receiving part 3 Electrode 4 Outlet 5 Aqueous waste liquid supply port 6 Aqueous waste liquid discharge port 7 Circulating aqueous waste liquid supply port 8 Circulating aqueous waste liquid discharge port 9 Overflowing aqueous waste liquid discharge port 11 Taper 12 Scraper 21 Gold 31 storage tank (stock tank)
32 Gold recovery device 33 Buffer tank 34 Base storage tanks 41 to 44 Pumps 51 to 57 Route

Claims (6)

水溶性硫黄含有金化合物を含む水性廃液から金を回収するにあたり、前記水性廃液を強塩基性に調整した後、該水性廃液を電気分解することにより陰極表面に析出する金の全部または一部を下方へ落下させて回収することを特徴とする金の回収方法。   In recovering gold from an aqueous waste liquid containing a water-soluble sulfur-containing gold compound, after adjusting the aqueous waste liquid to be strongly basic, all or part of the gold deposited on the cathode surface by electrolyzing the aqueous waste liquid A method for collecting gold, wherein the gold is dropped and collected. 前記水性廃液を強塩基性に調整するにあたりアルカリ金属の水酸化物を使用する請求項１に記載の回収方法。   The recovery method according to claim 1, wherein an alkali metal hydroxide is used to adjust the aqueous waste liquid to be strongly basic. 請求項１または２に記載の方法で金を回収するための装置であって、水性廃液を強塩基性に調整する調整手段、電解槽、該電解槽内に設けられた少なくとも１対の陽極と陰極、および前記陰極の下方に陰極表面から剥がれ落ちた金を回収するための受け部を有すると共に、前記受け部には堆積した金を前記電解槽の外へ取り出すための取り出し口を備えており、且つ前記電解槽の下方は、前記受け部に向かって下り勾配の傾斜面で構成されていることを特徴とする金の回収装置。   An apparatus for recovering gold by the method according to claim 1 or 2, comprising an adjusting means for adjusting aqueous waste liquid to strong basicity, an electrolytic cell, and at least one pair of anodes provided in the electrolytic cell; The cathode has a receiving portion for recovering gold peeled off from the cathode surface below the cathode, and the receiving portion has a takeout port for taking out the deposited gold out of the electrolytic cell. And the lower part of the said electrolytic vessel is comprised by the inclined surface of a downward slope toward the said receiving part, The gold | metal collection | recovery apparatus characterized by the above-mentioned. 前記受け部の底面は、前記取り出し口に向かって下り勾配に形成されている請求項３に記載の回収装置。   The recovery device according to claim 3, wherein a bottom surface of the receiving portion is formed in a downward slope toward the take-out port. 前記受け部は、金を回収するための受け器を備え、該受け器は前記回収装置に対し出し入れ可能に構成されている請求項３に記載の回収装置。   The said receiving part is provided with the receptacle for collect | recovering gold | metal | money, This collection | recovery apparatus is a collection | recovery apparatus of Claim 3 comprised so that withdrawing / inserting with respect to the said collection | recovery apparatus. 前記陰極表面に析出した金を掻き落とす機構を備えている請求項３〜５のいずれかに記載の回収装置。   The recovery device according to any one of claims 3 to 5, further comprising a mechanism for scraping gold deposited on the cathode surface.
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